thermoplastic, thermoplastic block, thermoplastic statistic, asphalt binder, adhesive or sealant, ti

专利摘要:
POLY(acrylated POLYOL) AND METHOD FOR PREPARING AND USING THE SAME AS MODIFIERS, ADHESIVES, FRACTIONING ADDITIVES, OR ASPHALT RUBBER FRACTIONING FLUIDS. The present invention relates to a thermoplastic copolymer, block copolymer, and statistical copolymer comprising plural acrylated polyol monomer units with different degrees of acrylation of hydroxyl groups. Acrylated polyol monomeric units have an average degree of acrylation greater than 1 and less than the number of hydroxyl groups in the polyol. The present invention also relates to a method of preparing thermoplastic copolymer, block copolymer, and statistical copolymer, and using them in various applications, such as modifiers, asphalt rubber adhesives, or an additive in a tracking fluid for oil tracking.
公开号:BR112016026839B1
申请号:R112016026839-3
申请日:2015-05-20
公开日:2021-07-06
发明作者:Eric W. Cochran；R. Christopher Williams；Nacu HERNANDEZ；Elvira Joana Ferreira Peralta；Michael John Forrester
申请人:Iowa State University Research Foundation, Inc；
IPC主号:

专利说明:

[001] This application claims the benefit of provisional patent application US 62/001,444, filed May 21, 2014, incorporated herein by reference in its entirety. FIELD OF THE INVENTION
[002] The present invention relates to a new thermoplastic polymer composition and methods of preparing and using the same. In particular, the present invention relates to the successful application of controlled free radical polymerization in an acrylated polyol composition to prepare novel thermoplastic copolymers, block copolymers and statistical copolymers and to use the same in various applications as rubber modifiers. asphalt, adhesives or additives in fractionation fluids for the fractionation industry. BACKGROUND OF THE INVENTION
[003] The global asphalt market is expected to reach 118.4 million tons by 2015, according to a January 2011 report by industry analysts Global, Inc. The asphalt paving industry accounts for the largest market segment in utilization asphalt end. With growth in the developing markets of China, India and Eastern Europe increasing, asphalt will be increasingly needed to build road infrastructure for the next decade. The increased demand for asphalt, coupled with the need for improved asphalt pavement/materials performance, creates the opportunity for an asphalt modifier.
[004] Asphalt grade governs the performance of paving mixes at service temperatures. In many cases the characteristics of bitumen need to be changed to improve its recovery/elastic ductility at low temperatures for sufficient crack strength also to increase its shear strength, for sustained loads and/or at high temperatures for grooving strength. Thus, to provide the durable pavements, polymer modifiers are added to impart the desired physical properties to the asphalt. Typical polymer modifiers used include a suspended semi-crystalline solid (eg, polyethylene) or a dispersed SBS-type thermoplastic elastomer (eg, various SBS products from the Kraton® family).
[005] In the last decade, there has been an increase in the use of recycled tire rubber in asphalt binders as an alternative to polymer modifiers in the asphalt paving industry due to its good performance and competitive economic opportunity. The use of soil strip rubber (GTR) as an asphalt modifier is an environmentally sustainable means of enhancing pavement quality while simultaneously recycling large amounts of waste material. Asphalt rubber (AR) binders have been applied since the 1960s. However, AR production and storage presents some challenges. It is important to have the rubber particles evenly distributed in the asphalt matrix for the asphalt rubber. Because the rubber in GTR is cross-linked, it does not completely melt into the asphalt at commonly used mixing and production temperatures. Thus, AR binders require higher mixing and compaction temperatures than conventional binders. Furthermore, AR binders typically have some degree of separation during storage due to the immiscibility of GTR with asphalt and the disparity in specific gravities. To increase the performance of rubber on asphalt and maintain the storage stability of rubber after it is reacted on the asphalt, stabilizers/compatibilizers have been commonly used to swell rubber particles and form physical or chemical bonds between the particle and GTR fillers and binder of asphalt.
[006] There are several stabilizers on the market for asphalt rubbers. For example, an additive widely used in AR production to reduce mixing and compaction temperatures and to prevent separation is polyoctanamer (often referred to as Vestenamer®, by Evonik Industries/Degussa). However, conventional binders are expensive and offer no environmental benefits. With the forecast increasing demand for asphalt paving and AR binders over the next decade, there is still a strong need for new types of polymers that are cost-effective, and environmentally friendly, viable polymers that can be used as AR binders instead. of standard rubber-asphalt binders.
[007] Adhesives are materials that can be fluid, semi-fluid or materials that can become fluid with external assistance such as heating (for example, hot melt adhesives). When applied between two objects, the solidification of adhesives binds the objects together. The adhesives industry is divided into the packaging industry, with a 37% share of the total market, the construction industry, with a 20% share (eg carpet placement, roofing, pre-finished panels, etc.). ), with a 19% share of the automobile industry, the laminated industry with a 12% share (for example, labeling, veneers, laminates), the footwear industry, with a 5% share, the consumer industry, with a share of 4% and other markets that constitute the remaining 3% share.
[008] The global market for adhesives in 2013 has been estimated by the Adhesive and Sealant Council to be US$40.5 billion in sales (approximately 9,000 kilo tons) and is expected to reach US$58 billion in sales by 2018 (approximately 12,400 kilo tons) . There remains, therefore, a strong need in the art for new types of cost-effective, environmentally friendly, viable polymers that can be used as adhesives.
[009] "Fracking", or hydraulic fracturing, is a process for extracting in solution natural gas, oil or uranium from deep shale formations. The process involves the fracturing of shale rock deposits by a pressurized liquid. Liquid fractionation is a mixture of water, sand and other chemical additives. The typical recipe for fluid fractionation consists of 90% water and 8-9% sand and 1-2% other chemicals such as biocides, acids, inhibitors, stabilizers, crosslinkers, friction reducers, pH adjusting agents, control of iron, surfactants and gelling agents. Because fractionation can consume millions of gallons of fractionation fluids, 1-2% of the fractionation fluids (ie 1-2% chemicals among the fractionation fluids) can still amount to hundreds of tons. This can be very toxic to the soil and can attribute to deep water contamination. Thus, there is a need in the art to develop a polymer as a substitute for gelling agents such as guar gum, which can serve as a gelling agent for water, as a cross-linking agent, as a pH adjusting agent, as a drying agent. breaks and as a biocide.
[0010] Polymers based on glycerol have been used in the last decade in the manufacture of matrices for drug release, structures in tissue engineering, in addition to many other applications. Similar chemicals were applied to sorbitol to create polymers. For example, Liu et al, "Preparation and characterization of a thermoplastic poly(glycerol sebacate) elastomer by two-step method," Journal of Applied Polymer Science 103(3):1412-19 (2007), synthesized a thermoplastic elastomer prepared using poly(glycerolosebacate) and sebacic acid in a two-step method. Cai et al., "Shape-memory effect of poly(glycerol-sebacate) elastomer," Materials Letters 62(14):2171-73 (2008), were able to synthesize a poly(glycerol-sebacate) elastomer with memory capabilities in excellent ways.
[0011] However, these latest efforts have focused on the acid/alcohol condensation chemistry between glycerol or sorbitol monomer and another monomer. None of them have explored biopolymers based on the polymerization of a polyol monomer or its derivatives. Thus, there is a need in the art to use a monomer derived from an inexpensive natural biomaterial or petrochemical raw materials to develop a highly processable thermoplastic and elastomeric polymer with a wide range of applications and physical properties.
[0012] The present invention is directed to satisfy these needs in the art. SUMMARY OF THE INVENTION
[0013] One aspect of the present invention relates to a thermoplastic copolymer comprising plural acrylated polyol monomeric units, with different degrees of acrylation of hydroxyl groups. Acrylated polyol monomeric units have an average degree of acrylation greater than 1 and less than the number of hydroxyl groups in the polyol.
[0014] Another aspect of the invention relates to a thermoplastic block copolymer comprising at least one PA block and at least one PB block. PA represents a polymer block comprising one or more A monomer units and PB represents a polymer block comprising one or more B monomer units. A monomer is an acrylated polyol monomeric unit with different degrees of acrylation of hydroxyl groups . The acrylated polyol monomeric unit has an average degree of acrylation greater than 1 and less than the number of hydroxyl groups in the polyol. Monomer B is a radically polymerizable monomer.
[0015] Another aspect of the invention relates to a thermoplastic statistical copolymer having a general formula of: [Ai-Bj-Ck]q. A represents monomer A, which is an acrylated polyol monomeric unit with different degrees of acrylation of hydroxyl groups. The acrylated polyol monomeric unit has an average degree of acrylation greater than 1 and less than the number of hydroxyl groups in the polyol. B represents monomer B, which is a radically polymerizable monomer. C represents monomer C, which is a radically polymerizable monomer. Monomer B is different than monomer A, and monomer C is different than monomer A or monomer B. i, j and k are the average number of repeating units of monomer A , monomer B and monomer C, respectively, of so that i and j are each greater than 0 and less than 1, k is 0 to less than 1, provided that i + j + k = 1. q represents the average number of the degree of polymerization and ranges from 10 to 100,000.
[0016] These thermoplastic copolymers, block copolymers and statistical copolymers can be partially or fully hydrophilic and therefore fully or partially soluble in water and can be partially or fully biodegradable.
[0017] One aspect of the present invention relates to a method of preparing a thermoplastic copolymer or block copolymer. The method comprises providing an acrylated polyol composition comprising plural acrylated polyol monomeric units having different degrees of acrylation of hydroxyl groups. The acrylated polyol composition has an average degree of acrylation greater than 1 and less than the number of hydroxyl groups in the polyol. The method also comprises polymerizing the acrylated polyol composition through controlled radical polymerization to form the thermoplastic copolymer or block copolymer.
[0018] Another aspect of the invention relates to a method of preparing a thermoplastic statistical copolymer. The method comprises providing monomer A, which is an acrylated polyol monomeric unit having different degrees of acrylation of hydroxyl groups, in which the acrylated polyol monomeric unit has an average degree of acrylation greater than 1 and less than the number of hydroxyl groups of the polyol. The method also comprises providing a radically polymerizable monomer, represented by B. The method further comprises polymerizing monomer A and monomer B simultaneously, through reverse addition fragmentation chain transfer polymerization (RAFT), in the presence of a radical initiator and a chain transfer agent to form the thermoplastic statistical copolymer.
[0019] Another aspect of the present invention relates to an asphalt composition. The asphalt composition comprises: i) an asphalt component; ii) a rubber bran having a weight percentage in the range of 1% to 15%; and iii) a thermoplastic copolymer, block copolymer or statistical copolymer as an asphalt additive, modifier, and/or filler having a weight percentage in the range of 0.01% to 1.05%.
[0020] Another aspect of the present invention relates to a method for preparing a homogeneous asphalt composition. The method comprises mixing a thermoplastic copolymer, block copolymer or statistical copolymer as an asphalt additive, modifier and/or filler, with a weight percentage in the range of 0.01% to 1.05%, in an asphalt composition. to form a homogeneous asphalt composition. The asphalt composition comprises: i) an asphalt component and ii) a rubber bran having a weight percentage in the range of 1% to 15%.
[0021] Another aspect of the present invention relates to a method for preparing an adhesive or sealant composition. The method comprises mixing thermoplastic copolymer, statistical copolymer or block copolymer with a thickener, and/or a plasticizer and/or a solvent.
[0022] Another aspect of the present invention relates to a method for preparing a fractionation liquid. The method comprises mixing thermoplastic copolymer, statistical copolymer or block copolymer as an additive chemical with water and sand.
[0023] For each of the above aspects of asphalt composition, the method for preparing a homogeneous asphalt composition and the method for preparing a fractionating liquid, thermoplastic copolymer, statistical copolymer, block copolymer are discussed as below. The thermoplastic copolymer comprises plural acrylated polyol monomeric units with different degrees of acrylation of hydroxyl groups. Acrylated polyol monomeric units have an average degree of acrylation greater than 1 and less than the number of hydroxyl groups in the polyol. The thermoplastic statistical copolymer has a general formula of: [Ai-Bj-Ck]q. A represents monomer A, which is an acrylated polyol monomeric unit with different degrees of acrylation of hydroxyl groups. The acrylated polyol monomeric unit has an average degree of acrylation greater than 1 and less than the number of hydroxyl groups in the polyol. B represents monomer B, which is a radically polymerizable monomer. C represents monomer C, which is a radically polymerizable monomer. Monomer B is different than monomer A, and monomer C is different than monomer A or monomer B. i, j and k are the average number of repeating units of monomer A, monomer B and monomer C, respectively, of so that i + j are each greater than 0 and less than 1, k is 0 to less than 1, provided that i + j + k = 1. q represents the average number of degrees of polymerization and ranges from 10 to 100,000. The thermoplastic block copolymer comprising at least one PA block and at least one PB block. PA represents a polymer block comprising one or more A monomer units and PB represents a polymer block comprising one or more B monomer units. A monomer is an acrylated polyol monomeric unit with different degrees of acrylation of hydroxyl groups . The acrylated polyol monomeric unit has an average degree of acrylation greater than 1 and less than the number of hydroxyl groups in the polyol. Monomer B is a radically polymerizable monomer.
[0024] The present invention involves the successful application of controlled free-radical polymerization to multifunctional polyols, which can be derived from natural biomaterials or petrochemical raw materials, for example, glycerol and sorbitol, producing thermoplastic rubbers.
[0025] Glycerol (1,2,3-propanetriol) is generally derived from natural and petrochemical raw materials (for example, it is a co-product of biodiesel production, through soybean oil and other raw materials) and is considered a of the most versatile chemicals for its wide range of applications. It is the backbone of all animal and vegetable triglycerides, constituting an average of 10% by weight of the fat portion. With the recent explosion in biofuel production, glycerol quickly became a market surplus, as it is created as a by-product in biodiesel manufacturing by transesterification of vegetable oils with methanol using NaOH as a catalyst (Pagliaro et al., "The future of Glycerol: 2nd Edition RSC Green Chemistry,"(The Royal Society of Chemistry, 2nd ed. 2010), which is hereby incorporated by reference in its entirety). Sorbitol ((2S,3R,4R,5R)-hexane-1,2,3,4,5,6-hexol) is commonly produced from corn syrup or other biomass sources. Dextrose is a simple monosaccharide found in plants. These small polyols currently represent some of the cheapest chemical commodities available, ranging from $0.15 to $0.30 per pound. Thus, glycerol, sorbitol and dextrose are "green", inexpensive and offer several functional sites that can be exploited to alter their properties to be incorporated into biologically based polymers.
[0026] Polyols are converted by standard acid or base catalyzed condensation chemistry to contain the readily polymerizable conjugate acrylic fraction (C-C=C=O). The resulting acrylated polyol can be represented by APx, where x represents the average number of acrylic groups per molecule. At least one and as many as the maximum number of hydroxyl functionalities on the polyol can be arylated. Free radical controlled polymerization techniques such as radical atom transfer polymerization (ATRP) and reversible addition fragmentation chain transfer polymerization (RAFT) can be applied to these acrylated polyol monomers to produce thermoplastic rubbers or elastomers.
[0027] The distinguishing feature of this polymerization is that it allows the design of the molecular architecture of the resulting polymers such that they are predominantly non-lightly branched chains or linear non-crosslinked that behave like rubbers/elastomers at room temperature, but melt reversibly and are susceptible to common processing techniques at elevated temperatures. The success of technology on polyols such as glycerol, sorbitol or dextrose is surprising, as the multifunctional nature of polyols such as glycerol, sorbitol or dextrose has likely eliminated them as they are considered candidates for the basis of chain-growth polymerization chemistries — even AG1 (acrylated glycerol having an average of one acrylic group per molecule) contains a significant fraction of di- and even tri-acrylate fractions. Thus, it is reasonably expected that it would be quite difficult to polymerize these monomers to result in a high molar mass thermoplastic polymer without gelling. However, the inventors found that under certain conditions, ATRP and RAFT polymerizations can be successfully applied to polymerize acrylated polyols to achieve a high molecular weight and conversion rate.
[0028] The resulting acrylated polyol or poly(acrylated polyol) have properties capable of reducing mixing and compacting temperatures and prevent rubber separation during AR storage. Thus, acrylated polyol or poly(acrylated polyol), such as acrylated glycerol, poly(acrylated glycerol), acrylated sorbitol, or poly(acrylated sorbitol), can be formulated as biologically based additives for the modification of asphalt cements. Furthermore, the inventors have found that certain specific formulations of poly(acrylated polyols) - for example, poly(acrylated glycerol) or poly(acrylated sorbitol) - have excellent properties as AR modifiers. For example, when added to an asphalt rubber composition, certain poly(acrylated polyols) formulations can reduce the mixing and compaction temperature in asphalt cements and can be used as "hot mix" additive properties; certain poly(acrylated polyols) formulations can extend the service temperature and can be used as a "grade range extender"; certain poly(acrylated polyols) formulations can prevent separation during AR storage and can be used as a "stabilizer/compatibilizer"; and certain poly(acrylated polyols) formulations can smooth otherwise impractical asphalts, such as those at the bottom of the vacuum tower and therefore can be used as "fluxes", ie the additives used to smooth the asphalts at the bottom of the vacuum tower. vacuum.
[0029] This technology allows the development of "green" and economical alternatives to petrochemically derived thermoplastic polymers. The resulting poly(acrylated polyol) based thermoplastic copolymer can be used in thermoplastic rubber or elastomeric compositions for a variety of applications such as adhesives (eg pressure sensitive adhesives, hot melt adhesives or water soluble adhesives) , sealants, tire components, shoes, electronics, bitumen modifiers or viscosity modifiers for consumer care products or the petroleum fractionating industry. BRIEF DESCRIPTION OF THE DRAWINGS
[0030] Figure 1 shows the chemical structures for exemplary glycerol, sorbitol and acrylated glycerol (AGx) and exemplary acrylated sorbitol (ASx) that may be present in monomeric acrylated polyols, where x is the number of acrylic groups. Acrylic groups were attached to glycerol or sorbitol through acid or base catalyzed condensation of glycerol or sorbitol with acrylic acid.
[0031] Figure 2A is a graph showing 13C-NMR results for glycerol using deuterated DMSO as solvent. Figures 2B-2D are graphs showing 13C NMR results for acrylated glycerol (AG) using deuterated DMSO as a solvent. The sample in Figure 2B shows 0.85 acrylic groups per glycerol molecule. The example in Figure 2C shows 0.91 acrylic groups per glycerol molecule. The example in Figure 2D shows 2.15 acrylic groups per glycerol molecule.
[0032] Figure 3 is a graph showing the results of differential scanning calorimetry (DSC) for a sample of poly(acrylated glycerol) ("P(AG)") synthesized from polymerization for 12 hours.
[0033] Figures 4A-4B are graphs showing the curves of P(AG) rheology samples synthesized using two different strand transfer agents: EMP (Figure 4A) and ETMP (Figure 4B), respectively. Reference temperature was 20°C.
[0034] Figure 5 is a graph showing the result of 1H-NMR proton for AG and P(AG).
[0035] Figure 6 is a graph showing the DSC results of a P(AG) sample (ghrmf82, see table 3). A glass transition temperature is shown in the graph at -30°C.
[0036] Figures 7A-7B are graphs showing rheology curves for P(AG) samples with a low molecular weight (reference temperature was 50°C) (Figure 7A) and an average molecular weight (reference temperature was 80°C) (Figure 7B).
[0037] Figures 8A - 8C are graphs showing the results of viscosities at different temperatures for asphalt binders (AR) and residual AR for the three samples in example 3, experiment 1: AR control (Figure 8A); AR-V (Figure 8B); and AR-AG (Figure 8C).
[0038] Figures 9A - 9C are graphs showing the rheology results measured by the DSR under various conditions (aged, aged RTFO and aged PAV) for the AR and residual AR binders for the three samples in example 3, experiment 1: AR control (Figure 9A); AR-V (Figure 9B); and AR-AG (Figure 9C).
[0039] Figures 10A - 10C are graphs showing the classification results for the AR and residual AR ligands for the three samples in example 3, experiment 1: AR control; AR-V; and AR-AG. Figure 10A presents the results of G*/sinδ. Figure 10B presents the results for G*. Figure 10 presents the results for δ.
[0040] Figures 11A - 11C are graphs showing the separation results for AR and residual AR binders for the three samples in example 3, experiment 1: control AR (Figure 11A); AR-V (Fig. 11B); and AR-AG (Figure 11).
[0041] Figures 12A - 12C are graphs showing the results of viscosities at different temperatures for the AR and residual AR binders for the three oven-cured samples in example 3, experiment 2: AR control (Figure 12A); AR-V (Figure 12B); and AR-AG (Figure 12C).
[0042] Figures 13A - 13C are graphs showing the rheology results measured by the DSR for the AR and residual AR binders for three oven-cured samples in example 3, experiment 2: AR control (Figure 13A); AR-V (Figure 13B); and AR-AG (Figure 13C).
[0043] Figures 14A - 14C are graphs showing the separation results for AR and residual AR binders for the three samples in example 3, experiment 2: control AR (Figure 14A); AR-V (Figure 14B); and AR-AG (Figure 14C).
[0044] Figures 15A-15F are graphs showing the comparison results between the samples in experiment 1 and experiment 2 in example 3. Figure 15A compares the classification results (G*/sinδ) for the AR and residual AR ligands. Figure 15B compares the classification results (G*) for the AR and residual AR ligands. Figure 15C compares the classification results (δ) of AR and residual AR ligands. Figure 15D-15F compares the results of AR and residual AR binder viscosities for control AR (Figure 15D), AR-V (Figure 15E), and AR-AG (Figure 15F), respectively.
[0045] Figure 16 shows tables and graphs summarizing the continuous degree of high temperature for P(AG)-modified unaged AR binders, compared to the results of an unstabilized AR (control), stabilized AR binders with Vestenamer® and a 5% Kraton® modified asphalt binder.
[0046] Figure 17 shows tables and graphs summarizing the continuous degree of high temperature for AR binders aged with RTFO modified by P(AG), compared to the results of an unstabilized AR (control), stabilized AR binders with Vestenamer® and a 5% Kraton® modified asphalt binder.
[0047] Figure 18 shows tables and graphs summarizing the percentage of mass loss during the residual binder RTFO test.
[0048] Figure 19 shows tables and graphs summarizing the continuous degree of intermediate temperature for RTFO + AR binders aged with PAV modified by P(AG), compared to the results of an unstabilized AR (control), AR binders stabilized with Vestenamer® and a 5% Kraton® modified asphalt binder.
[0049] Figure 20 shows tables and graphs, summarizing the continuous degree of low temperature for RTFO + AR binders aged with PAV modified by P(AG), compared to the results of an unstabilized AR (control), binders of AR stabilized with Vestenamer® and a 5% Kraton® modified asphalt binder.
[0050] Figure 21A is a graph showing the viscosities results for the P(AG) modified AR binders, compared to the results for an unstabilized AR (control) and the Vestenamer® stabilized AR binders. Viscosities were measured at 20 rpm. Figure 21B is a graph showing viscosities results for residual AR binders measured at 20 rpm.
[0051] Figure 22 shows tables and graphs summarizing the percent difference in storage stability of DSR for P(AG) modified AR binders compared to the results of an unstabilized AR (control), stabilized AR binders with Vestenamer® and a 5% Kraton® modified asphalt binder.
[0052] Figure 23 shows tables and graphs, summarizing the grade range for P(AG) modified AR binders, compared to the results of an unstabilized AR (control), AR binders stabilized with Vestenamer® and a binder of asphalt modified with 5% Kraton®.
[0053] Figure 24 shows tables and graphs, summarizing the minimum mixing temperatures for AR binders modified by P(AG), compared to the results of an unstabilized AR (control), AR binders stabilized with Vestenamer® and a 5% Kraton® modified asphalt binder.
[0054] Figure 25 shows tables and graphs, summarizing the minimum compaction temperatures for AR binders modified by P(AG), compared to the results of an unstabilized AR (control), AR binders stabilized with Vestenamer® and a 5% Kraton® modified asphalt binder.
[0055] Figure 26 shows tables and Figures summarizing the mean difference between AR and residual viscosities for P(AG) modified AR binders, compared to the results of an unstabilized AR (control), Vestenamer stabilized AR binders ® and a 5% Kraton® modified asphalt binder.
[0056] Figure 27 shows tables and graphs, summarizing the final percentage classification of AR ligands stabilized with P(AG) and Vestenamer®, analyzed against the control AR (not stabilized).
[0057] Figure 28 shows tables and graphs, summarizing the final percentage classification of AR ligands stabilized with P(AG), analyzed against AR modified with Vestenamer®.
[0058] Figure 29 is a graph showing the results of trace gel permeation chromatography of three polymers of poly(acrylated glycerol) ("PAG"), having molecular weights ranging from 1 million Daltons to 10,000 Daltons.
[0059] Figures 30A-C show the images of the polymer poly(acrylated glycerol) with molecular weight of 10k Daltons (Figure 30A), 100k Daltons (Figure 30B) and 1 million Daltons (Figure 30C). DETAILED DESCRIPTION OF THE INVENTION
[0060] One aspect of the present invention relates to a thermoplastic copolymer comprising plural acrylated polyol monomer units, with different degrees of acrylation of hydroxyl groups. Acrylated polyol monomeric units have an average degree of acrylation greater than 1 and less than the number of hydroxyl groups in the polyol.
[0061] Another aspect of the invention relates to a thermoplastic block copolymer comprising at least one PA block and at least one PB block. PA represents a polymer block comprising one or more A monomer units and PB represents a polymer block comprising one or more B monomer units. A monomer is an acrylated polyol monomeric unit with different degrees of acrylation of hydroxyl groups . The acrylated polyol monomeric unit has an average degree of acrylation greater than 1 and less than the number of hydroxyl groups in the polyol. Monomer B is a radically polymerizable monomer.
[0062] Another aspect of the invention relates to a thermoplastic statistical copolymer having a general formula of: [Ai-Bj-Ck]q. A represents monomer A, which is an acrylated polyol monomeric unit with different degrees of acrylation of hydroxyl groups. The acrylated polyol monomeric unit has an average degree of acrylation greater than 1 and less than the number of hydroxyl groups in the polyol. B represents monomer B, which is a radically polymerizable monomer. C represents monomer C, which is a radically polymerizable monomer. Monomer B is different than monomer A, and monomer C is different than monomer A or monomer B. i, j and k are the average number of repeating units of monomer A, monomer B and monomer C, respectively, of so that i + j are each greater than 0 and less than 1, k is 0 to less than 1, provided that i + j + k = 1. q represents the average number of degrees of polymerization and ranges from 10 to 100,000.
[0063] Polyols that can be used in thermoplastic copolymer, block copolymer, or statistical copolymer include any polyols readily derived from natural biomaterial or petrochemical raw materials, as well as saccharides that contain various hydroxyl functional groups. Suitable polyols include, but are not limited to ethylene glycol, propylene glycol, dipropylene glycol, 1,2,4-butanetriol, 1,7-heptanediol, glycerol, panaxatriol, panaxitriol, thalose, balsaminol B, momordol, erythritol, enterodiol, xylitol , miglitol, sorbitol, mannitol, galactitol, isomalt, maltitol and mixtures thereof. Suitable polyols may also include saccharides such as aldohexose, aldopentose, aldotetrose, aldotriose, aldose, alose, altrose, arabinose, amylopectin, amylose, dextrose, erythrose, fructose, galactose, glucose, glutouse, hexose, fructosehexose, ketose , lactose, garbagese, maltose, mannose, pentose, ribose, sucrose, sucrose, talose, tetrose, triose, xylose, as well as their respective stereoisomers. Exemplary and subtilized polyols are glucose, sorbitol and glycerol.
[0064] The acrylated polyol monomeric unit can be represented by AGx, where x represents the average number of acrylic groups per acrylated polyol molecule. At least one or as many as the maximum number of hydroxyl functionalities on the polyol molecule can be arylated on the acrylated polyol monomeric unit. For example, glycerol contains 3 hydroxyl groups, and thus, in acrylated glycerol represented by AGx, x can range from greater than 0 to 3. Likewise, sorbitol contains 6 hydroxyl groups, and thus, in acrylated sorbitol represented by ASx, x can range from greater than 0 to 6. In the APx monomeric acrylated polyol, there can be a mixture of various acrylated polyols with different degrees of acrylation. For example, in the case of acrylated glycerol, while most of AG1's acrylated polyol monomer unit may be mono-acrylated glycerol, there may also be small populations of acrylated polyol monomer unit which are unacylated glycerol and di-acrylated glycerol (or ie, 2 hydroxyl groups of glycerol are acrylated) as well. In addition, monomeric APx may also have a small number of aryl polyol oligomers, as the self-polymerization of acrylic groups cannot be completely suppressed. Accordingly, while APx is referred to as "monomers" herein, it is to be understood that such monomeric units may contain mixtures having a distribution of varying degrees of arcylation and varying molecular weights. Because the acrylated polyol monomeric unit is a mixture of several acrylated polyols, the resulting thermoplastic polymer is considered to be a copolymer.
[0065] Exemplary acrylated polyol monomer units are acrylated glycerol, acrylated sorbitol and acrylated dextrose. The average degree of acrylation in acrylated glycerol can range from 0.01 to 3. Typically, the average degree of acrylation in acrylated glycerol ranges from 1.001 to 2.9, for example from 1.001 to 1.25. The average degree of acrylation in acrylated sorbitol can range from 0.01 to 6. Typically, the average degree of acrylation in acrylated sorbitol ranges from 1.001 to 3. The average degree of acrylation in acrylated glucose can range from 0.01 to 5. Typically, the average degree of acrylation in acrylated dextrose ranges from 1.001 to 3. Structures of glycerol, sorbitol and exemplary monomeric acrylated glycerol and acrylated sorbitol with different degrees of acrylation are shown in Figure 1.
[0066] The structure of an exemplary poly(acrylated glycerol) molecule is shown in scheme 1. Scheme 1 shows that the copolymer is a mixture of X mono-acrylated glycerol units and Y diacrylated glycerol units and Z units of triacrylated glycerol, and resulting x, the average degree of acrylation of the poly(acrylated glycerol) molecule can theoretically be calculated as (X + Y + Z)/3. Scheme 1

[0067] The thermoplastic copolymer has a straight or branched chain structure and has properties characteristic of thermoplastic substances, in which it has the necessary stability for processing at elevated temperatures and still has strength well below the temperature at which it softens. The thermoplastic copolymer has a glass transition temperature (Tg) below 0°C, for example from -60°C to 0°C, from -60°C to -15°C or from -45°C to -20 °C. The thermoplastic copolymer has a molecular weight of at least 1KDa, for example, a molecular weight of 1KDa to 10MDa, 10KDa to 1MDa, 50KDa to 10MDa, or 50KDa to 200KDa.
[0068] The acrylated polyol monomeric unit may contain one or more conjugated sites that can increase the reactivity of acrylated polyol for propagation reactions in radical-controlled polymerization.
[0069] In thermoplastic block copolymer, the PA block represents a polymer block comprising one or more A monomer units, with A monomer being an acrylated polyol monomeric unit with different degrees of acrylation of hydroxyl groups, in which the acrylated polyol monomeric unit has an average degree of acrylation greater than 1 and less than the number of hydroxyl groups in the polyol. Monomer A was discussed in the above embodiments in the thermoplastic copolymer based on acrylated polyol.
[0070] The PB block can be polymerized from one or more radically polymerizable monomers, which include a kind of variety of monomers such as vinyl (such as vinyl aromatic), acrylic (such as methacrylates, acrylates, methacrylamides, acrylamides, etc.) , diolefin, nitrile, dinitrile, acrylonitrile monomer, a monomer with reactive functionality and a crosslinking monomer.
[0071] Aromatic vinyl monomers are exemplary vinyl monomers that can be used in the block copolymer and include any aromatic vinyls optionally having one or more substituents on the aromatic moiety. The aromatic fraction can be either mono- or polycyclic. Exemplary vinyl aromatic monomers for the PB block include styrene, α-methyl styrene, t-butyl styrene, vinyl xylene, vinyl naphthalene, vinyl pyridine, divinyl benzene, N-vinyl heteroaromatics (such as 4-vinylimidazole (Vim), N-vinylcarbazole (NVC), N-vinylpyrrolidone, etc.). Other examples of vinyls include vinyl esters (such as vinyl acetate (VAc), vinyl butyrate (VB), vinyl benzoate (VBz)), N-vinyl amides and imides (such as N-vinylcaprolactam (NVCL), N- vinylpyrrolidone (NVP), N-vinylphthalimide (NVPI), etc.), vinylsulfonates (such as 1-butyl ethenesulfonate (BES), Neopentyl ethenesulfonate (NES), etc.), vinylphosphonic acid (VPA), halo-olefins (such as vinylidene fluoride (VF2)), etc. Exemplary methacrylates include C1-C6 (meth)acrylate (ie, methyl methacrylate, ethyl methacrylate, propyl acrylate (methamphetamine), butyl acrylate (meth)acrylate, isobutyl methacrylate, heptyl (meth)acrylate, or hexyl(meth) acrylate), 2-(acetoacetoxy)ethyl methacrylate (AAEMA), 2-aminoethyl methacrylate (hydrochloride) (AEMA), allyl methacrylate (AMA), cholesteryl methacrylate (CMA), t-butyldimethylsilyl methacrylate (BDSMA), (diethylene glycol monomethyl ether ) methacrylate (DEGMA), 2-(dimethylamino)ethyl methacrylate (DMAEMA), (ethylene glycol monomethyl ether) methacrylate (EGMA), 2-hydroxyethyl methacrylate (HEMA), dodecyl methacrylate (LMA), methacryloyloxyethyl phosphorylcholine (MPC), (ether poly(ethylene glycol) monomethyl) methacrylate (PEGMA), pentafluorophenyl methacrylate (PFPMA), 2-(trimethylammonium)ethyl methacrylate (TMAEMA), 3-(trimethylammonium) propyl methacrylate (TMAPMA), triphenylmethyl methacrylate (TPMMA), etc. Other exemplary acrylates include 2-(acryloyloxy)ethyl phosphate (AEP), butyl acrylate (BA), 3-chloropropyl acrylate (CPA), dodecyl acrylate (DA), di(ethylene glycol) 2-ethylhexyl ether acrylate (DEHEA ), 2-(dimethylamino) ethyl acrylate (DMAEA), ethyl acrylate (EA) ethyl α-acetoxyacrylate (EAA), ethoxy-heethyl acrylate (EEa), 2-ethylhexyl acrylate (EHA), isobornyl acrylate (iBoA) , methyl acrylate (MA), propargyl acrylate (PA), (poly(ethylene glycol) monomethyl ether) acrylate (PEGA), tert-butyl acrylate (tBA), etc. Exemplary methacrylamides include N-(2-aminoethyl) methacrylamide (hydrochloride) (AEMAm) and N-(3-aminopropyl) methacrylamide (hydrochloride) (APMAm), N-(2-(dimethylamino)ethyl) acrylamide (DEAPMAm), N- (3-(dimethylamino)propyl)methacrylamide (hydrochloride) (DMAPMAm), etc. Other exemplary acrylamides include acrylamide (Am) 2-acrylamido-2-methylpropanesulfonic acid sodium salt (AMPS), N-benzylacrylamide (BzAm), N-cyclohexylacrylamide (CHAm), diacetone acrylamide (N-(1,1- dimethyl-3-oxobutyl)acrylamide) (DAAm), N,N-diethylacrylamide (DEAm), N,N-dimethylacrylamide (DMAm), N-(2-(dimethylamino)ethyl)acrylamide (DMAEAm), N-isopropylacrylamide (NIPAm ), N-octylacrylamide (OAm), etc. Exemplary nitriles include acrylonitrile, adiponitrile, methacrylonitrile, etc. Exemplary diolefins include butadiene, isoprene, etc.
[0072] Radially polymerizable monomers suitable for use herein also include monomers with reactive functionality, eg a 'clickable' functionality so that the monomers are incorporated into blocks, these 'clickable' functional groups can be used as a precursor to a polymer brush or copolymerizer to provide sites for functionality bonding or crosslinking. Exemplary of reactive functionality include functional groups suitable for 1,3-dipolar azide-alkyne cycloaddition, such as azide functionality; "active ester" functional groups that are particular active with primary amine functionality; functional groups with protected thiol, hydrazide or amino functionality; functional groups with isocyanate or isothiocyanate functionality, etc.
[0073] Radially polymerizable monomers suitable for use herein may also include the crosslinking monomers that are commonly used in both the synthesis of microgels and polymer networks (see below). Monomers can include degradable crosslinks such as an acetal bond, or disulfide bonds, resulting in the formation of degradable crosslinks. Examples of crosslinking monomers of diethylene glycol dimethacrylate (DEGDMA), triethylene glycol dimethacrylate (TEGDMA), ethylene glycol dimethacrylate (EGDMA), hexane-1,6-diol diacrylate (HDDA), methylene-bis-acrylamide (MBAm), divinylbenzene (DVB) , etc.
[0074] A more extensive list of exemplary methacrylate monomers, acrylate monomers, methacrylamide monomers, acrylamide monomers, styrenic monomers, diene monomers, vinyl monomers, monomers with reactive functionality and crosslinking monomers, which are suitable for use as the radically polymerizable monomers, described herein in Moad et al., "Living Radical Polymerization by the Raft Process - the Third Update," Australian Journal of Chemistry 65:985-1076 (2012), which is hereby incorporated by reference , in your totality.
[0075] Furthermore, two or more different monomers can be used together in forming PB block or different PB block in block copolymer. A typical radically polymerizable B monomer used herein is styrene, and the resulting PB block is a homopolymer of styrene. Another typical radically polymerizable B monomer used herein is methyl acrylate, and the resulting PB block is a homopolymer of methyl acrylate.
[0076] The PB block can also be polymerized from one or more monomeric triglycerides, usually derived from a vegetable oil, animal fat or a synthetic triglyceride. This polymerized vegetable oil or animal oil can be further partially or fully saturated through a catalytic hydrogenation post-polymerization. Monomeric oils used in the block copolymer can be any triglycerides or mixtures of triglycerides that are radically polymerizable. These triglycerides or triglyceride mixtures are usually vegetable oils. Suitable vegetable oils include, but are not limited to, a variety of vegetable oils such as soybean oil, peanut oil, walnut oil, palm oil, palm kernel oil, sesame oil, sunflower oil, safflower oil, safflower oil. rapeseed oil, linseed oil, linseed oil, rapeseed oil, coconut oil, corn oil, sunflower oil, olive oil, castor oil, false linseed oil, hemp oil, mustard oil, radish oil, oil of ramtyl, rice bran oil, salicornia oil, tigernut oil, tung oil, etc. and its mixtures. Typical vegetable oil used herein includes soybean oil, linseed oil, corn oil, linseed oil or rapeseed oil, and the resulting PB block is polymerized triglyceride or triglyceride derivatives.
[0077] The thermoplastic block copolymer may further include at least one PC block. The PC block can be polymerized from one or more radically polymerizable monomers. Any monomer that is suitable to form the PB block can be used to form the PC block.
[0078] The structure of an exemplary poly(acrylated glycerol) block copolymer is shown in scheme 2. Scheme 2 shows that the copolymer is a mixture of X monoacrylated glycerol units, Y diacrylated glycerol units, Z tri-acrylated glycerol units, and the resulting x, the average degree of acrylation of the poly(acrylated glycerol) molecule can theoretically be calculated as (X + Y + Z)/3. R1 and R2 are polymer blocks (eg PB block and PC block, respectively), different from poly(acrylated glycerol) block. Scheme 2

[0079] The thermoplastic block copolymer has a molecular weight ranging from 5 to 10 MDa, for example, from 5 to 500 kDa, from about 15 to 300 kDa, from about 40 to about 100 kDa, or from about from 80 to about 100 kDa. The PA block has a glass transition temperature (Tg) below 0°C or below -15°C, eg from -60°C to 0°C, from -60°C to -15°C or from -45°C to -20°C. Typically, the PA block, PB block and PC block, if present, each have a straight-chain or branched structure.
[0080] In the thermoplastic statistical copolymer [Ai-Bj-Ck]q, monomer A is based on an acrylated polyol monomeric unit with different degrees of acrylation of hydroxyl groups. Monomer A was discussed in the above embodiments in thermoplastic copolymer based on acrylated polyol.
[0081] Monomer B or monomer C can each independently be vinyl, acryl, diolefin, nitrile, dinitrile, acrylonitrile monomer, or monomer with reactive functionality or crosslinking monomer. The exemplary embodiments of monomer B and monomer C suitable for use in the thermoplastic statistical copolymer are the same as the exemplary embodiments for monomer B, as described above in the thermoplastic block copolymer. Exemplary B monomer and C monomer include styrene, α-methyl styrene, t-butyl-styrene, vinyl xylene, vinyl naphthalene, vinyl pyridine, divinyl benzene, vinyl acetate, N-vinylpyrrolidone, methyl acrylate, C1-C6 (met )acrylate (ie, methyl acrylate, ethyl methacrylate, propyl(meth)acrylate acrylate, butyl(meth)acrylate, heptyl(meth)acrylate or hexyl(meth)acrylate), acrylonitrile, adiponitrile, methacrylonitrile, butadiene, isoprene, oils radically polymerizable vegetables, or mixtures thereof. For example, monomer B and monomer C are each independently an aromatic vinyl monomer, such as a styrene; an acrylate monomer such as a methyl (meth)acrylate; or a radically polymerizable vegetable oil such as soybean oil, linseed oil, corn oil, linseed oil or rapeseed oil.
[0082] In one embodiment, the C monomer is absent.
[0083] One or more acrylated polyol monomer units in the thermoplastic copolymer, block copolymer, or statistical copolymer may also contain one or more alkoxy groups, which may be derived from esterification of the non-acrylated hydroxy groups in the acrylated polyol. For example, one or more acrylated polyol monomer units in the thermoplastic copolymer contain one or more methoxy or ethoxy groups.
[0084] Exemplary applications of thermoplastic copolymers based on poly(acrylated polyol), block copolymers, and statistical copolymers include their use as "green" and cost-effective alternatives to petrochemically derived thermoplastic polymers. For example, thermoplastic copolymers, block copolymers or statistical copolymers can be used as rubbers or elastomers; as consumer electronics components such as shock/impact protection component or cover components; as asphalt modifiers; as resin modifiers; as engineering resins; as leather and cement modifiers; in footwear, such as in rubber shoe heels, rubber soles; in automobiles, such as tires, hoses, feed belts, conveyor belts, printing rollers, rubber presses, automobile mats, truck fenders, ball mill liners and weather strips; as sealants or adhesives (such as pressure sensitive adhesives, hot melt adhesives or water-soluble adhesives); in aerospace equipment; as viscosity modifiers for consumer care products such as viscosity index improvers; as detergents; as diagnostic agents and their support; as dispersants; as emulsifiers; as lubricants and/or surfactants; as paper additives and coating agents; as additives for the fractionation industry, as fractionation fluid; and in packaging, such as food and beverage packaging materials.
[0085] In some embodiments, thermoplastic copolymers based on poly(acrylated polyol), block copolymers and statistical copolymers can be used as a major component in a thermoplastic elastomer composition, to improve the thermoplastic and elastic properties of the composition. To form an elastomeric composition, thermoplastic copolymers based on poly(acrylated polyol), block copolymers, statistical copolymers can be further vulcanized, cross-linked, compatibilized, or combined with one or more other materials, such as other elastomers, additive, modifier and /or filling. The resulting elastomer can be used as a rubber composition, in various industries, such as in footwear, automobiles, packaging, or as an additive in the fractionation industry, etc.
[0086] In one embodiment, thermoplastic copolymers based on poly(acrylated polyol), block copolymers or statistical copolymers can be used in an automobile, such as in vehicle tires, hoses, feed belts, conveyor belts, printing rollers , rubber squeezers, automobile mats, truck fenders, ball mill liners and weather strips. The automobile composition (e.g., vehicle tires) may further include a rubber compound. Thermoplastic copolymers, block copolymers or statistical copolymers can serve as a major component in a thermoplastic composition to improve the thermoplastic and elastic properties of automobile compositions. The resulting compositions can be further vulcanized, cross-linked, compatibilized, or combined with one or more other materials, such as other elastomers, additive, modifier and/or filler.
[0087] In one embodiment, thermoplastic copolymers based on poly(acrylated polyol), block copolymers or statistical copolymers can be used in an asphalt binder composition, as an asphalt additive, modifier and/or filler. The asphalt binder composition may further include a rubber bran.
[0088] In one embodiment, thermoplastic copolymers based on poly(acrylated polyol), block copolymers or statistical copolymers can be used in an adhesive or sealant composition. The adhesive or sealant composition may further include a thickener or plasticizer, and/or a solvent. Suitable solvents include, but are not limited to, water and an organic solvent such as dimethylsulfoxide (DMSO), dimethylformamide (DMF), benzene, dioxane, toluene, chloroform, hexane, cyclohexane, xylene, carbon tetrachloride, acetone, acetonitrile, butanol , heptane and ethanol. Suitable thickeners include, but are not limited to, dinitrate-based thickeners; Piccotac™ 1095 and Piccotac™ 8095; glycerol ester thickeners such as Staybelite™ 10-E hydrogenated rosin ester and Staybelite™ 3-E hydrogenated rosin ester; Floral™ AX-E pitch fully hydrogenated; phenolic resins; polyester terpenes; polyterpenes; rosin esters; phenolic terpenes; and monomeric resins. Suitable plasticizers include, but are not limited to benzoflex 2088 (DEGD); abietic acid; Eastman™ Triacetin; Eastman 168™ non-phthalate plasticizer; polyalkylene esters such as polyethylene glycol, polytetramethylene glycol, polypropylene glycol and mixtures thereof; glyceryl monostearate; octyl epoxy soate, epoxidized soybean oil, epoxy talate and epoxidized linseed oil; polyhydroxyalkanoat; glycols such as ethylene glycol, pentamethylene glycol and hexamethylene glycol; anionic or cationic plasticizers such as dioctyl sulfosuccinate, alkane sulphonate and sulphonated fatty acids; phthalate or trimellitate plasticizers; polyethylene glycol di-(2-ethylhexoate); citrate esters; naphthenic oil and dioctyl phthalate; white oil; esters of citric, sebacic or lauric acids; non-fugitive polyoxyethylene aryl ether; ethylene and carbon monoxide copolymer; unsaturated light-curing liquid plasticizer; and sorbitol.
[0089] In one embodiment, thermoplastic copolymers based on poly(acrylated polyol), block copolymers or statistical copolymers can be used as an additive in the fractionation fluid or as a fractionation fluid. Fractionation fluid can also include water and sand. A typical recipe for a fractionating fluid comprises about 90% water, about 8-9% sand and about 1-2% other chemicals such as biocides, acids, inhibitors, stabilizers, crosslinkers, friction reducers, pH regulating agents, iron control, surfactants and gelling agents. Thermoplastic copolymers based on poly(acrylated polyol), block copolymers or statistical copolymers can be used as a substitute for gelling agents like guar gum, can serve as a thickening agent for water, as a crosslinking agent, as a curing agent. pH adjustment, as a breaking agent or as a biocide. The fractionation fluid composition may also include a thermoplastic polymer block added to impart a desired fluid property to the thermoplastic copolymer, statistical copolymer, or block copolymer. Suitable thermoplastic polymer block that can be added to the thermoplastic copolymers based on poly(acrylated polyol), block copolymers or statistical copolymers discussed in embodiments above can also be used here.
[0090] Another aspect of the present invention relates to a method of preparing a thermoplastic copolymer or block copolymer. The method comprises providing an acrylated polyol composition comprising plural acrylated polyol monomeric units having different degrees of acrylation of hydroxyl groups. The acrylated polyol composition has an average degree of acrylation greater than 1 and less than the number of hydroxyl groups in the polyol. The method also comprises polymerizing the acrylated polyol composition through radical controlled polymerization to form the thermoplastic copolymer or block copolymer.
[0091] An acrylated polyol composition can be prepared by reacting one or more polyols with an acrylic reagent. Polyols are acrylated through a standard acid- or base-catalyzed condensation reaction. This reaction usually takes place at a mild temperature and produces water as the recyclable waste product. The reaction imparts acrylic functionality to the polyol molecule, making it readily polymerized and to interact with other polymers such as rubber like polymers having backbones that contain tire rubber.
[0092] The acrylic reagent used can be an unsaturated carboxylic acid or an acid halide. Suitable acrylic reagents include, but are not limited to, acrylic acid, acryloyl chloride, methacrylic acid, or other vinyl-terminated acid or acid halides.
[0093] The acrylic reagent is usually added in excess of the polyol. The amount of acrylic reagent added may depend on the desired degree of acrylation: the more excessive the acrylic reagent in relation to the polyol, the greater the degree of acrylation will be achieved. Typically, the stoichiometric ratio of acrylic reagent to polyol can range from 1 to the maximum number of hydroxyl functionalities on the polyol molecule. For example, the stoichiometric ratio of acrylic reagent to glycerol typically ranges from 1 to 3.
[0094] The acrylation reaction is usually carried out at a temperature from 30°C to 130°C, at a temperature from 50°C to 110°C or at a temperature from 90°C to 110°C. The acrylation reaction can be carried out in the presence of a catalyst. Suitable catalysts include, but are not limited to, a homogeneous catalyst such as triphenyl phosphine or triamine pyrophosphate or a heterogeneous polyanionic resin such as the Amberlyst™ family (eg, amberlyst 15). The acrylation reaction can be carried out in the presence of an inhibitor. Exemplary inhibitors include, but are not limited to, phenothiazine, hydroquinone or antioxidant inhibitors such as the ETANOX family (for example, ETANOX 330TM).
[0095] The resulting aryl polyol can be represented by APx, where x represents the average number of acrylic groups per aryl polyol molecule. At least one or as many as the maximum number of hydroxyl functionalities on the polyol molecule can be arylated. For example, glycerol contains 3 hydroxyl groups before it is acrylated. Glycerol acrylation results in AGx, x can range from greater than 0 to 3. Likewise, sorbitol contains 6 hydroxyl groups before being acrylated. Sorbitol acrylation results in ASx, where x ranges from greater than 0 to 6. In the resulting aryl polyol, APx, there can be a distribution of all possible reaction products. For example, in the case of acrylated glycerol, while AG1 may be composed mainly of mono-acylated glycerol, there may also be small populations of non-acylated glycerol and dia-acrylated glycerol as well.
[0096] Furthermore, self-polymerization of acrylic groups cannot be completely suppressed. Thus, APx may also have a small number of aryl polyol oligomers. In this regard, while APx is referred to as "monomers" herein, it is to be understood that such monomeric units may contain mixtures having a distribution of varying degrees of arcylation and varying molecular weights.
Suitable polyols for acrylation include, but are not limited to ethylene glycol, propylene glycol, dipropylene glycol, 1,2,4-butanetriol, 1,7-heptanediol, glycerol, panaxatriol, panaxitriol, talose, balsaminol B, momordol, erythritol, enterodiol, xylitol, miglitol, sorbitol, mannitol, galactitol, isomalt and maltitol. Suitable polyols may also include saccharides such as aldohexose, aldopentose, aldotetrose, aldotriose, aldose, alose, altrose, arabinose, amylopectin, amylose, dextrose, erythrose, fructose, galactose, glucose, glutouse, hexose, fructosehexose, ketose , lactose, garbagese, maltose, mannose, pentose, ribose, sucrose, sucrose, talose, tetrose, triose, xylose, as well as their respective stereoisomers. Exemplary polyols used are glucose, sorbitol and dextrose. The average degree of acrylation for glycerol can range from 0.01 to 3. Typically, the average degree of acrylation for glycerin ranges from 1.001 to 2.9, for example from 1.001 to 1.25. The average degree of acrylation for sorbitol can range from 0.01 to 6. Typically, the average degree of acrylation for sorbitol ranges from 1.001 to 3.
[0098] The acrylated polyol composition then can be polymerized by, for example, free radical, anionic or radical controlled polymerization. Typically, controlled radical polymerization is conducted over the acrylated polyol composition to form a thermoplastic copolymer, block copolymer, or statistical copolymer. The polymerization step is carried out under conditions effective to produce the thermoplastic copolymer, block copolymer or statistical copolymer with a molecular weight of at least 1 KDa without gelling. The resulting thermoplastic copolymer, block copolymer or statistical copolymer has a straight or branched chain structure.
[0099] Side reactions in the acrylation process can promote the joining of mono-acrylated polyol, di-acrylated polyol or other multi-acrylated polyol to form larger molecules, known as oligomers. Acrylated glycerol monomer or oligomers can be further polymerized.
[00100] The polymerization step is carried out by means of live free radical polymerization which involves live/controlled polymerization with free radicals, as the end of the active polymer chain (Moad et al., "The Chemistry of Radical Polymerization - Secind Fully Revised Edition," Elsevier Science Ltd. (2006), which is incorporated in its entirety by reference). This form of polymerization is a form of addition polymerization, where the ability of a growing polymer chain to terminate and terminate has been removed. The chain initiation rate is therefore much greater than the chain propagation rate. The result is that polymer chains grow at a more constant rate than seen in traditional chain polymerization and their lengths remain very similar. Typically, the polymerization step takes place in the presence of a free radical initiator and a catalyst or a chain transfer agent to form the thermoplastic copolymer.
[00101] One form of living free radical polymerization is atom transfer radical polymerization. Atom transfer radical polymerization (ATRP) is a reversible catalyzed redox process that achieves controlled polymerization via easy transfer of labile radicals (eg, halide radicals) between rising polymer streams and a catalyst (Davis et al., " Atom Transfer Radical Polymerization of tert-Butyl Acrylate and Preparation of Block Copolymers," Macromolecules 33:4039-4047 (2000); Matyjaszewski et al., "Atom Transfer Radical Polymerization," Chemical Reviews 101:2921-2990 (2001), which hereby are incorporated by reference in their entirety). In ATRP, chain termination and transfer reactions are essentially eliminated by keeping the concentration of free radicals small. Briefly, the mechanism by which ATRP operates can be summarized as:

[00102] In equation (1), the labile radical X can be a halogen (eg Br, Cl) attached to the end of a polymer P. The catalyst, CuIBr, reversibly abstracts this halogen, forming a polymer free radical ( P^). The balance achieved between inert polymers and active polymer free radicals strongly favors the left side (K << 10-8). Equation (2) is the standard free radical propagation reaction between a polymer of length ie a monomer M. The concentration of small free radicals ensured by equation (1) practically eliminates the termination reactions, and the halogen functionality is retained in produced polymers, which allows the production of copolymers of almost any monomer amenable to conventional free radical polymerization.
[00103] The ATRP polymerization reaction starts with initiation. Initiation is achieved by adding an agent capable of decomposition to form free radicals; the decomposed free radical fragment of the initiator attacks a monomer generating a free radical monomer and finally produces an intermediate capable of propagating polymerization. These agents are often referred to as "initiators". Initiation is usually based on the reversible formation of rising radicals in a redox reaction between various transition metal compounds and an initiator.
[00104] Appropriate initiators depend largely on the details of the polymerization, including the types of monomers being used, the type of catalyst system, the solvent system and the reaction conditions. Simple organic halides are commonly used as template halogen atom transfer initiators. Exemplary initiators are aralkyl halides or aryl halides, such as benzyl bromide or benzyl chloride.
[00105] In ATRP, the introduction of a catalyst system to the reaction medium is necessary to establish the balance between active (free radicals of active polymer for polymer growth) and dormant (the inert polymer formed) states. The catalyst is typically a transition metal compound being able to participate in a redox cycle with the initiator and a dormant polymer chain. The transition metal compound used here is a transition metal halide. Any transition metal that can participate in a redox cycle with the initiator and the dormant polymer chain, but does not form a direct C-metal bond with the polymer chain, is suitable in the present invention. Exemplary transition metal includes Cu1+, Cu2+, Fe2+, Fe3+, Ru2+, Ru3+, Ru4+, Ru5+, Ru6+, Cr2+, Cr3+, Mo0, Mo+, Mo2+, Mo3+, W2+, W3+, Mn3+, Mn4+, Rh+, Rh2+, Rh3+, Rh4+, Re2+, Re3+, Re4+, Co+, Co2+, Co3+, V2+, V3+, V4+, V5+, Zn+, Zn2+, Au+, Au2+, Au3+, Hg+, Hg2+, Pd0, Pd+, Pd2+, Pt0, Pt+, Pt+ Pt4+, Ir0, Ir+, Ir2+, Ir3+, Ir4+, Os2+, Os3+, Os 4+, Nb2+, Nb3+, Nb4+, Nb5+, Ta3+, Ta4+, Ta5+, Ni0, Ni+, Ni2+, Ni3+, Nd0, Nd+, Nd2+, Nd2+ Ag+, and Ag2+. A typical transition metal catalyst system used here is CuCl/CuCl2.
[00106] The binder serves to coordinate with the transition metal compound such that direct bonds between the transition metal and crescent polymer radicals are not formed and the formed copolymer is isolated. The ligand can be any compound containing N, O, P, or S that coordinates with the transition metal to form a bond to, any compound that contains C that coordinates with the transition metal to form a π bond, or any compound that contains C which coordinates with the transition metal to form a C-transition metal α bond, but does not form a CC bond with the monomers under polymerization conditions. A typical binder used here is pentamethyldiethylenetriamine (PMDETA).
The state of the art of ATRP has been reviewed by Matyjaszewski (Matyjaszewski et al., "Atom Transfer Radical Polymerization," Chemical Reviews 101:2921-2990 (2001), which is hereby incorporated by reference in its entirety) . Further details for selection of initiators and catalyst/binder system for ATRP reaction can be found in US Patent No. 5,763,548 to Matyjaszewski et al and US Patent No. 6,538,091 to Matyjaszewski et al, which are incorporated herein by reference, in your totality. Detailed descriptions for ATRP polymerization of a similar system, vegetable oil-based thermoplastic copolymer conjugate can be found in U.S. Patent Application No. 13/744,733 to Cochran et al., incorporated herein by reference in its entirety.
[00108] Thus, some embodiments of the present invention relate to a method of preparing a thermoplastic copolymer or thermoplastic block copolymer through ATRP. The method comprises providing an acrylated polyol composition comprising plural acrylated polyol monomeric units having different degrees of acrylation of hydroxyl groups. The acrylated polyol composition has an average degree of acrylation greater than 1 and less than the number of hydroxyl groups in the polyol. The method also comprises polymerizing the acrylated polyol composition through ATRP, in the presence of a solvent, a catalyst, a countercatalyst, an initiator and a binder.
[00109] In some other embodiments, the present invention relates to a method of preparing a thermoplastic block copolymer. The method comprises providing an acrylated polyol composition comprising plural acrylated polyol monomeric units having different degrees of acrylation of hydroxyl groups. The acrylated polyol composition has an average degree of acrylation greater than 1 and less than the number of hydroxyl groups in the polyol. The method also comprises polymerizing the acrylated polyol composition through controlled radical polymerization in the presence of a solvent, a catalyst, a countercatalyst, a macromolecular initiator and a binder to form the thermoplastic block copolymer. The method may further encompass providing a radically polymerizable monomer other than the acrylated polyol monomer unit; and polymerizing the radically polymerizable monomer through atom transfer radical polymerization (ATRP) with the thermoplastic block copolymer formed as a macromolecular free radical initiator to add an additional block to the thermoplastic block copolymer.
[00110] Thermoplastic block copolymer formed based on poly(acrylated polyol) can be used as a macromolecular free radical initiator to add additional block polymer. Thus, the method may further include providing a radically polymerizable monomer other than the acrylated polyol monomeric unit; and polymerizing the radically polymerizable monomer with the thermoplastic block copolymer formed as a free radical macromolecular initiator to add an additional block to the thermoplastic block copolymer. The radically polymerizable monomer suitable for use in the method are the same as the exemplary embodiments for the B monomer as described above in the thermoplastic block copolymer.
[00111] One form of living free radical polymerization is Addition of Radical-Fragmentation Chain Transfer (RAFT). Radical Addition-Fragment Chain Transfer (RAFT) polymerization is a type of live polymerization or controlled polymerization using a chain transfer agent (CTA). Mechanism of conventional RAFT polymerization, which consists of a sequence of addition-fragmentation equilibria, is shown in Moad et al., "Living Radical Polymerization by the Raft Process—a First Update," Australian Journal of Chemistry 59: 669 - 92 ( 2006), which is incorporated herein by reference in its entirety. The RAFT polymerization reaction starts with initiation. Initiation is achieved by adding an agent capable of decomposition to form free radicals; the decomposed free-radical fragment of the initiator attacks a monomer generating a propagating radical (Pl), whereupon additional monomers are added producing a growing polymer chain. In the propagation step, the propagating radical (P’n) adds to a chain transfer agent (CTA), followed by the fragmentation of the intermediate radical forming a dormant polymer chain and a new radical (R^). This radical (R^) reacts with a new monomer molecule forming a new propagating radical (Pm). In the chain propagation step, (P^n) and (Pm) reach equilibrium and the dormant polymer chain provides an equal probability for all polymer chains to grow at the same rate, allowing the polymers to be synthesized with narrow polydispersity. Termination is limited in RAFT, and, if it does occur, it is negligible. Targeting a specific molecular weight in RAFT can be calculated by multiplying the proportion of monomer consumed by the concentration of CTA used by the molecular weight of the monomer.
[00112] Initiating agents are often referred to as "initiators". Appropriate initiators are highly dependent on the details of the polymerization, including the types of monomers being used, the type of catalyst system, solvent system and reaction conditions. A typical radical initiator can be azo compounds, which provide a centered radical of two carbon atoms. Radical initiators such as benzoyl peroxide, azobisisobutyronitrile (AIBN), 1,1'-azobis(cyclohexanecarbonitrile) or (ABCN), or 4,4'-Azobis(4-cyanovaleric acid) (ACVA); redox initiators such as benzoyl peroxide/N,N-dimethylaniline; microwave heating initiator; photoinitiator such as (2,4,6-trimethylbenzoyl)-diphenylphosphine oxide; gamma radiation initiator; or Lewis acids such as scandium(III) triflate or yttrium(III) triflate are commonly used in RAFT polymerization.
[00113] RAFT polymerization can use a wide variety of CTA agents. Suitable CTA agents must be able to initiate the polymerization of monomers (styrene and AESO) and achieve a tight polydispersity in the process. For a RAFT polymerization to be efficient, the CTA starting agents and the polymer RAFT agent must have a C = S reactive double bond; the intermediate radical must break up quickly without side reactions; the intermediate must partition in favor of products, and the scavenging radicals (R^) must efficiently restart polymerization. Suitable CTA agent is usually a thiocarbonylthio compound (ZC(=S)
where R is the free radical leaving group and Z is a group that modifies addition and fragmentation rates of RAFT polymerization. Exemplary CTA agents include, but are not limited to, a dithioester compound (where Z = aryl, heteraryl, or alkyl), a trithiocarbonate compound (where Z = alkylthio, arylthio, or heteroarylthio), a dithiocarbamate compound (where Z = arylamine or heteroarylamine or alkylamine) and a xanthate compound (where Z = alkoxy, aryloxy or heteroaryloxy), which are capable of reversible association with polymerizable free radicals. Z can also be sulfonyl, phosphonate or phosphine. A more extensive list of suitable CTA agents (or RAFT agents) can be found in Moad et al., "Living Radical Polymerization by the Raft Process - A First Update," Australian Journal of Chemistry 59: 669 - 92 (2006); Moad et al., "Living Radical Polymerization by the Raft Process—A Second Update," Australian Journal of Chemistry 62 (11): 1402 - 72 (2009); Moad et al., "Raying Life Radical Polymerization - The Third Update," Australian Journal of Chemistry 65:985-1076 (2012); Skey et al., "Facilitate one pot synthesis of a range of reversible addition-fragmentation chain transfer (RAFT) agents." Chemical Communications 35: 4183-85 (2008), which are hereby incorporated by reference in their entirety. Effectiveness of the CTA agent depends on the monomer being used and is determined by the properties of the free radical leaving group R and group Z. These groups activate and deactivate the thiocarbonyl double bond of the RAFT agent and modify the stability of the intermediate radicals (Moad et al. al., "Living Radical Polymerization by the Raft Process-a Second Update," Australian Journal of Chemistry 62 (11): 1402 - 72 (2009), which is hereby incorporated by reference in its entirety). Typical CTA agents used are 1-phenylethyl benzodithioate or 1-phenylethyl 2-phenylpropanedithioate.
[00114] More details for selection of initiators, chain transfer agents and other reaction conditions for RAFT reaction, as well as detailed descriptions for RAFT polymerization of a similar system, vegetable oil based thermoplastic copolymer conjugates, can be found in US Patent No. 61/825,241, filed May 20, 2013, to Cochran et al., incorporated herein by reference in its entirety.
[00115] Thus, some embodiments of the present invention relate to a method of preparing a thermoplastic copolymer or thermoplastic block copolymer through RAFT. The method comprises providing an acrylated polyol composition comprising plural acrylated polyol monomeric units having different degrees of acrylation of hydroxyl groups. The acrylated polyol composition has an average degree of acrylation greater than 1 and less than the number of hydroxyl groups in the polyol. The method also comprises polymerizing the acrylated polyol composition via RAFT, in the presence of a free radical initiator, a solvent and a chain transfer agent.
[00116] In one embodiment, polymerization of the acrylated polyol is carried out by polymerization of RAFT. In RAFT polymerization, reaction time, temperature and solvent concentration must be chosen appropriately to ensure the production of non-crosslinked thermoplastic elastomers. Reaction time is closely related to the temperature the reaction is carried out at: higher temperature requires shorter reaction times and lower temperature requires longer reaction times. Monitoring the polymerization time of the acrylated polyol is crucial since reacting the acrylated polyol too long causes the polymer to crosslink; whereas reacting the acrylated polyol to very little causes polymer conversion to be very slow.
[00117] Temperatures for polymerization of RAFT in acrylated polyols can range from room temperature up to 180°C. Typical reaction temperatures for an acrylated polyol RAFT reaction is 120°C or less, for example, 50 to 120°C, or 50°C to 85°C.
[00118] The ratio of monomeric acrylated polyol to CTA may vary depending on the desired molecular weight. In the polymerization of acrylated polyols, the multifunctional character of the monomer tends to crosslink. This crosslinking can be attenuated by using too much CTA. In one embodiment, RAFT polymerization is performed at a molar ratio of chain transfer agent to monomer ranging from 1:1 to 1:10,000.
[00119] Solvent is selected based on the solubility requirements of acrylated polyol and a normal boiling point compatible with the polymerization temperature. The solvent used in the RAFT polymerization of the acrylated polyol can be toluene, dioxane, THF, chloroform, cyclohexane, dimethylsulfoxide, dimethyl formamide, acetone, acetonitrile, n-butanol, n-pentanol, chlorobenzene, dichloromethane, diethyl ether, tert-butanol , 1,2,-dichloroethylene, diisopropylether, ethanol, ethylacetate, ethylmethylketone, heptane, hexane, isopropyl alcohol, Isoamyl alcohol, methanol, pentane, n-propyl alcohol, pentachlorethane, 1,1,2,2,-tetrachloroethane, 1,1,1,-trichloroethane, tetrachloroethylene, tetrachloromethane, trichloroethylene, water, xylene, benzene, nitromethane, glycerol or a mixture thereof. A typical solvent used for RAFT acrylated polyols is methanol, glycerol or a mixture of these.
[00120] The concentrations of the monomeric acrylated polyol used in the reactions depend partially on the solubility of the monomer and the polymer products, as well as the evaporation temperature of the solvent. Solvent concentration can affect polymer gelation. Insufficient solvent in the RAFT reaction can cause the polymer to crosslink in a short period of time without ever achieving high enough conversions. Therefore, the solvent is usually added in excess to allow the polymer chains to grow and achieve an 80% conversion rate without risking the polymer reaching the gel point. The concentration of monomeric acrylated polyol dissolved in the solvent in RAFT reactions can range from 5% to 100% weight percent monomer. Usually, a monomer concentration of less than 90% by weight is adequate to guarantee the solubility of the resulting polymers and, in addition, to prevent premature gelling.
[00121] In one embodiment, the method is performed in the presence of a solvent, with the acrylated polyol monomer having a concentration, when dissolved in the solvent, ranging from 1% by weight to 90% by weight, for example, 1% by weight to 40% by weight, from 1% by weight to 10% by weight, or from 20% by weight to 30% by weight.
[00122] In one embodiment, RAFT polymerization of the acrylated polyol is carried out with a free radical initiator selected from the group consisting of benzoyl peroxide and azobisisobutyronitrile.
[00123] In one embodiment, RAFT polymerization of the acrylated polyol is carried out in the presence of a chain transfer agent. The chain transfer agent used can be a thiocarbonylthio compound, a dithioester compound, a trithiocarbonate compound, a dithiocarbamate compound, or a xanthate compound capable of reversibly associating with polymerizable free radicals. Typically, the chain transfer agent is 1-phenylethyl benzodithioate, 1-phenylethyl 2-phenylpropanedithioate or dibenzyl carbontrithioate.
[00124] In some other embodiments, the present invention relates to a method of preparing a thermoplastic block copolymer. The method comprises providing an acrylated polyol composition comprising plural acrylated polyol monomeric units having different degrees of acrylation of hydroxyl groups. The acrylated polyol composition has an average degree of acrylation greater than 1 and less than the number of hydroxyl groups in the polyol. The method also comprises polymerizing the acrylated polyol composition through controlled radical polymerization in the presence of a free radical initiator, a solvent and a macromolecular chain transfer agent to form the thermoplastic block copolymer. The method may further include providing a radically polymerizable monomer different than the acrylated polyol monomer unit and polymerizing the radically polymerizable monomer through reversible fragmentation-addition chain transfer polymerization (RAFT) with the thermoplastic block copolymer formed as an agent of macromolecular chain transfer to add an additional block to the thermoplastic block copolymer.
[00125] Thermoplastic block copolymer formed based on poly(acrylated polyol) can be used as a macromolecular free radical initiator to add additional block polymer. Thus, the method may further include providing a radically polymerizable monomer other than the acrylated polyol monomeric unit; and polymerizing the radically polymerizable monomer with thermoplastic block copolymer formed as a macromolecular chain transfer agent to add an additional block to the thermoplastic block copolymer. The radically polymerizable monomer suitable for use in the method are the same as the exemplary embodiments for the B monomer as described above in the thermoplastic block copolymer.
[00126] Another aspect of the invention relates to a method of preparing a statistical thermoplastic copolymer. The method comprises providing monomer A, which is an acrylated polyol monomeric unit having different degrees of acrylation of hydroxyl groups, wherein the acrylated polyol monomeric unit has an average degree of acrylation greater than 1 and less than the number of hydroxyl groups of the polyol. The method also comprises providing a radically polymerizable monomer, represented by B. The method further comprises polymerizing monomer A and monomer B simultaneously, through reversible fragmentation addition chain transfer polymerization (RAFT), in the presence of a free radical initiator and a chain transfer agent to form the thermoplastic statistical copolymer. The polymerization step can be carried out under conditions effective to achieve a number average degree of polymerization (Nn) for the thermoplastic statistical copolymer of up to 100,000 without gelling.
[00127] The method can be used to simultaneously polymerize three or more different monomeric units. For example, another radically polymerizable monomer, represented by C, can also be supplied, in addition to monomer A and monomer B. Monomer C is different from monomer A or monomer B. Monomer A, monomer B and monomer C are then polymerized simultaneously through RAFT, in the presence of the free radical initiator and the chain transfer agent to form the thermoplastic statistical copolymer. The polymerization step can be carried out under conditions effective to achieve an average number of degree of polymerization (Nn) for the thermoplastic statistical copolymer of up to 100,000 without gelling.
[00128] Suitable conditions of polymerization, reaction reagents and monomers A, B and C for the RAFT statistical thermoplastic copolymer preparation method are the same as those discussed in the above modalities.
[00129] The radical-controlled polymerization described above can be used to polymerize acrylated polyol, under the above-described reaction conditions effective to produce thermoplastic copolymer, block copolymer and statistical copolymer with molecular weight ranging from 1 KDa to 10 MKDa without gelling, for example, a molecular weight of 50 KDa to 200 KDa without gelation or a molecular weight of 50 KDa to 10 MKDa without gelation.
[00130] Thermoplastic copolymer, block copolymer or statistical copolymer can be further reacted with an organic acid to esterify one or more remaining acrylated hydroxy groups in one or more acrylated polyol monomer units to change the solvent compatibility of the thermoplastic copolymer, block copolymer or statistical copolymer. Alternatively, the acrylated polyol monomer, prior to polymerization, can be treated with the organic acid to esterify one or more remaining unacrylated hydroxy groups of the acrylated polyol monomer. Suitable organic acid includes any organic acid capable of converting the free hydroxy groups in the acrylated polyol to alkoxy groups, such as methoxy or ethoxy. Commonly used organic acids are formic acid, acetic acid, hexanoic acid, ethanoic acid, propanoic acid, among others.
[00131] The thermoplastic copolymer, block copolymer or statistical copolymer, when containing unreacted acrylate groups, can undergo a crosslinking reaction at a high temperature. Furthermore, the thermoplastic copolymer, block copolymer or statistical copolymer can be further chemically modified with a crosslinking agent to undergo a crosslinking reaction at an elevated temperature.
[00132] The crosslinking agent used to chemically modify thermoplastic copolymer, block copolymer or statistical copolymer may include those that are normally used in the synthesis of microgels and polymer networks, for example, degradable crosslinks such as an acetal bond, or disulfide bonds, resulting in the formation of degradable crosslinks. Exemplary crosslinking agents used to modify thermoplastic copolymer, block copolymer, and statistical copolymer include diethylene glycol dimethacrylate (DEGDMA) diethylene glycol diacrylate, triethylene glycol dimethacrylate (TEGDMA), ethylene glycol dimethacrylate (EGDMA), hexane-1,6-diol diacrylate (HDDA) ), methylene-bis-acrylamide (MBAm), divinylbenzene (DVB), p-divinylbenzene (p-DVB), sulfur, 1,4-cyclohexanedimethanol divinyl ether, N,N'-(1,2-dihydroxyethylene )bisacrylamide, ethylene glycol diacrylate, ethylene glycol dimethacrylate, 4,4'-Methylenebis(cyclohexyl isocyanate), 1,4-Phenylenediacryloyl chloride, poly(ethylene glycol) diacrylate, poly(ethylene glycol) dimethacrylate, tetra(ethylene glycol) diacrylate, tetraethylene glycol dimethyl ether, triethylene glycol dimethacrylate, potassium metaborate, triethanolamine zirconate, sodium tetraborate, boric acid, zirconium complexes, borate salts, methanol, etc.
[00133] Thermoplastic copolymer, block copolymer or statistical copolymer can be further chemically modified with a reagent to impart an acidic or basic functionality of thermoplastic copolymer, block copolymer, statistical copolymer, making thermoplastic copolymer, block copolymer or copolymer statistic a pH regulating agent. Non-reactive hydroxyl groups in polyols can be modified with a diacid such as oxalic acid, malonic acid, succinic acid, glutatic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanoic acid, dodecanoic acid; or a dicarboxylic acid such as ortho-phthalic acid, isophthalic acid, terephthalic acid, to provide an acidic environment. Non-reactive hydroxyl groups can also be modified with a dibasic salt, such as glyphosate, hydroquinone, resorcinol, to provide a basic environment.
[00134] Thermoplastic copolymer, block copolymer or statistical copolymer can be further chemically modified with a reagent to impart a biocidal functionality to the thermoplastic copolymer, block copolymer or statistical copolymer, making the thermoplastic copolymer, block copolymer or statistical copolymer a biocidal agent. The reagent can be a quaternary ammonium, glutaraldehyde, tetrakis hydroxymethyl sulphate phosphonium, etc.
[00135] Another aspect of the present invention relates to an asphalt composition. The asphalt composition comprises: i) an asphalt component; ii) a rubber bran having a weight percentage in the range of 1% to 15%; and iii) a thermoplastic copolymer, block copolymer or statistical copolymer as an asphalt additive, modifier, and/or filler having a weight percentage in the range of 0.01% to 1.05%. Any of the thermoplastic, block copolymer, and statistical copolymer discussed in the above embodiments can be used here.
[00136] A typical source of rubber crumb is tire ground rubber (GTR). Two basic types of GTR are available based on GTR preparation processes: Cryogenic GTR is produced by breaking up the tire into relatively large pieces and then subjecting the rubber to grinding under cryogenic conditions; Ambient or hot milled GTR is produced under a warm or ambient milling procedure. Shredding and separating the rubber from the tire at room temperature produces irregular particles having a high surface area which desirably increases the number of reactive sites available for bonding or crosslinking with the acrylated polyol based thermoplastic copolymer. There are many sources of GTR and the material can be used in either vulcanized or devulcanized form. Devulcanized GTR produced by an oxidative or reducing process can be used.
[00137] GTR of various particle sizes can be incorporated into an asphalt cement. Typically, any GTR having particle sizes less than 10 mesh can be used. Exemplary ground tire rubbers have particle sizes capable of passing through 20 mesh to 80 mesh, eg 30 mesh to 40 mesh.
[00138] Another suitable source of rubber meal is ground industrial rubber waste. These materials can be produced by ambient grinding or cryogenic grinding. Different types of rubber crumbs can be mixed to achieve the desired properties.
[00139] The aggregate used to prepare the asphalt component can be one or a mixture of the various standard aggregates used in the art, including gravel, gravel, stone, quarry gravel and recycled paving material.
[00140] To enhance certain performance specifications, other asphalt modifiers or additives can be incorporated into the asphalt composition. For example, mineral oil, heating oils, vegetable oils, or light petroleum distillates can be added to an asphalt binder to keep the PG value within an acceptable range.
[00141] In asphalt rubber formulations containing thermoplastic copolymer based on poly(acrylated polyol), block copolymer, or statistical copolymer, varied parameters, such as the concentration of thermoplastic copolymer based on poly(acrylated polyol), copolymer block, or statistical copolymers, the average degree of acrylation in poly(acrylated polyol) and the molecular weight of poly(acrylated polyol) can affect the performance of the resulting asphalt rubber.
[00142] For thermoplastic copolymer based on poly(acrylated polyol), normally, the thermoplastic copolymer, block copolymer or statistical copolymer can have a weight percentage in the range of 0.1% by weight to 30% by weight relative to the weight of the rubber bran, for example, a range of 0.1% by weight to 7% by weight, or 2.5% by weight to 6.5% by weight relative to the weight of the rubber bran. The degree of acrylation for thermoplastic copolymer based on poly(acrylated polyol) typically can range from 1.001 to 2.9. Typically, a low degree of acrylation is desirable for the asphalt formulation, which ranges from 1.001 to 1.25, from 1.001 to 1.17, or from 1.001 to 1.05. The molecular weight for thermoplastic copolymer based on poly(acrylated polyol), block copolymer or statistical copolymer can range from 1 KDa to 10 KDa M, from 0 to 50 KDa, from 50 KDa to 10 M KDa, from 50 KDa to 200 KDa or 200 KDa to 10 M KDa. Typically, an average molecular weight of thermoplastic copolymer based on acrylated glycerol, block copolymer or statistical copolymer is desirable for the asphalt formulation, ranging from 200 KDa to 10 M KDa.
[00143] Detailed formulations for thermoplastic copolymer based on poly(acrylated polyol), block copolymer, or statistical copolymer in terms of average degree of acrylation in poly(acrylated polyol), molecular weight of poly(acrylated polyol) and the concentration of poly(acrylated polyol) relative to rubber bran, and resulting performances of asphalt rubbers are exemplified in examples 3 and 4. The use of poly(acrylated glycerol) in asphalt rubber improves performance on all characteristics of asphalt rubber. asphalt rubbers, for example, reduce the continuous low performance grade of asphalt rubber, reduce the viscosity sensitivity of asphalt rubber to temperature, reduce the binder modulus of low temperature asphalt rubber, and reduce the separation between rubbers of asphalt after curing.
[00144] In one embodiment, the polyol in thermoplastic copolymer based on poly(acrylated polyol), block copolymer, or statistical copolymer is glycerol; the average degree of acrylation ranges from 1.001 to 1.25; the thermoplastic copolymer, block copolymer or statistical copolymer has a molecular weight ranging from 50 KDa to 200 KDa; and the weight concentration of thermoplastic copolymer, block copolymer or statistical copolymer in relation to the weight of rubber bran is 4.5%. The resulting asphalt composition has one or more of the following properties: a high temperature degree greater than 78°C, a low temperature degree greater than -29°C, a degree range greater than 107°C, a minimum temperature of mixing less than 171°C and a minimum compaction temperature of less than 161°C.
[00145] In one embodiment, the polyol in thermoplastic copolymer based on poly(acrylated polyol), block copolymer, or statistical copolymer is glycerol; the average degree of acrylation ranges from 1.001 to 1.25; the thermoplastic copolymer, block copolymer or statistical copolymer has a molecular weight ranging from 50 KDa to 200 KDa; and the concentration of thermoplastic copolymer weight in relation to the rubber bran weight is 6.5%. The resulting asphalt composition has one or more of the following properties: a high temperature degree greater than 82°C, a low temperature degree greater than -28.5°C, a degree range greater than 110°C, a minimum mixing temperature less than 179°C and a minimum compaction temperature less than 168°C.
[00146] The resulting asphalt composition prepared from the above modalities can be homogeneous and stable for at least 3 days under a temperature of 130°C to 180°C.
[00147] Another aspect of the present invention relates to a method for preparing a homogeneous asphalt composition. The method comprises mixing a thermoplastic copolymer, block copolymer or statistical copolymer as an asphalt additive, modifier, and/or filler, with a weight percentage in the range of 0.01 to 1.05%, in an asphalt composition. to form a homogeneous asphalt composition. The asphalt composition comprises: i) an asphalt component and ii) a rubber bran having a weight percentage in the range of 1 to 15%. Any of the thermoplastic copolymer, block copolymer, or statistical copolymer discussed in the above embodiments can be used here.
[00148] Appropriate rubber crumbs, rubber crumb sizes, aggregates used to prepare the asphalt component, other asphalt modifiers or additives and detailed formulations of asphalt rubber containing the poly(acrylated polyol) varying the average degree of acrylation, the molecular weight and concentration of poly(acrylated polyol) have been described in the above embodiments relating to the asphalt composition and are also suitable for the method of preparing the homogeneous asphalt composition here.
[00149] One way to blend thermoplastic copolymer, block copolymer or statistical copolymer into an asphalt composition is by pre-mixing GTR and thermoplastic copolymer, block copolymer or statistical copolymer, then adding the premix to a component of asphalt, typically a hot liquefied asphalt cement and continuing mixing on the same temperature scale.
[00150] Alternatively, the GTR can be mixed with an asphalt component, typically a hot liquefied asphalt cement. Thermoplastic copolymer, block copolymer, statistical copolymer is added into the mix, and mixing is continued on the same temperature scale.
[00151] The mixing temperature can depend on the qualities and characteristics of the asphalt cement. The blending of thermoplastic copolymer based on acrylated polyol, block copolymer, or statistical copolymer with the asphalt rubber composition is normally carried out in the temperature range of 130°C to 180°C.
[00152] The use of poly(acrylated glycerol) in an asphalt rubber reduces mixing and compaction temperatures and reduces the separation of the asphalt rubber after curing. Thus, mixing can take place at a location remote from where the homogeneous asphalt composition is used. The resulting asphalt composition is homogeneous and stable for at least 3 days at a temperature of 130°C to 180°C. EXAMPLES
[00153] The following examples are for illustrative purposes only and are not intended to limit the scope of the present invention in any way. Example 1 - Synthesis of Poly(Acrylated Glycerol) (P(AG)) by Reversible Fragmentation-Addition Chain Transfer Polymerization (RAFT) Glycerol Acrylation
[00154] Glycerol was mixed with hydroquinone (inhibitor, 0.5% by weight of glycerol), thiamine pyrophosphate (TPP, catalyst) in a mass ratio 0.06:1 of glycerol, acrylic acid, in the mass ratio of 1.5:1 for glycerol and DMSO in a 1:1 mass ratio for glycerol. The reaction was stirred and bubbled for 20 minutes and then heated to 90°C. The reaction was allowed to proceed for a minimum period of 12 hours and was terminated by cooling to room temperature. The final acrylated glycerol was mixed with cyclohexane to remove DMSO and dried overnight in vacuum ovens at room temperature. RAFT polymerization of acrylated glycerol
[00155] RAFT synthesis was performed similarly to the procedure described in Moad et al., "Living Radical Polymerization by the Raft Process - the First Update," Australian Journal of Chemistry 59:669-92 (2006); Moad et al., "Living Radical Polymerization by the Raft Process - the Second Update," Australian Journal of Chemistry 62 (11): 1402 - 72 (2009), which are incorporated herein by reference in their entirety. Briefly, azobisisobutyronitrile (AIBN) was used as the initiator, 1-phenylethyl benzodithioate (PBT) was used as the chain transfer agent (CTA).
[00156] Monomer (acrylated glycerol), initiator, CTA and solvent (DMSO) were mixed under argon in a 100 mL round bottom flask with various mass ratios of monomer to solvent, 1:5 molar ratio of initiator to CTA and 10:1 molar ratio of monomer to CTA. The reaction flask was bubbled with argon for 30 minutes to remove oxygen from the system before the temperature was increased. The reaction was carried out at 95°C, and the reaction time varied according to the desired molecular weight (Mn). The polymer was precipitated by dropwise addition of isopropanol and then dried in a vacuum oven at room temperature for 24 hours. Procedure for calculating the number of acrylic groups per molecule
[00157] 13C-NMR was used to calculate the number of acrylic groups per molecule. The peak integral at ~74 was defined as a value of 1. Then the peak integral at ~64 would be approximately 2. The integrals over both peaks at ~130 were then combined. These are the carbon peaks of the acrylic groups. The integral was then divided by 2 to get the average number of acrylic groups per molecule, because there are two carbons per acrylic group. The peak integral at ~168 (carboxyl carbon) was calculated.
[00158] Different proportions of reagents, the amount of solvent and the reaction time may vary with the average number of acrylic groups per molecule. 13C-NMR results are shown in Figures 2A-2D. The correlation between the average number of acrylic groups per molecule and various reaction conditions are shown in table 1. The results demonstrate that glycerol's primary alcohols were all acrylated, although not all secondary alcohols were acrylated. These findings are in agreement with the reactivity of alcohols (1° > 2° > 3°), suggesting that a longer reaction time, an increased temperature or an increase in the concentration of acrylic acid are desirable to further acrylate the secondary alcohols.

viscoelastic/thermal characterization
[00159] Differential scanning calorimetry (DSC) experiments showed a glass transition temperature (Tg) for P(AG) at 14°C. See Figure 3.
[00160] It was also found that the viscosity of the product was affected by the degree of acrylation — as the degree of acrylation increased the product became more viscous.
[00161] Rheology samples were mixed with butylated hydroxytoluene (BHT) to prevent crosslinking of the polymer. Figure 4 shows the rheology curves of two different P(AG) polymers synthesized using two different CTAs: 2-ethylsulfanylthiocarbonylsulfanyl)-2-methylpropionic acid (EMP) and ethyl 2-((ethoxycarbonothioyl)thio)-2-methylpropanoate (ETMP ), respectively. The results showed a low modulus of elasticity and liquid-like behavior at high temperatures, which are the characteristics of thermoplastic elastomers. These curves also showed a rubbery plateau, signaling an elevated system of tangles.
[00162] All these findings proved that these P(AG) polymers can be used as replacements for petroleum-based elastomers. Example 2 - Synthesis of Poly(Acrylated Glycerol) (P(AG)) or Poly(Acrylated Sorbitol) (P(AS)) via RAFT Synthesis of AGx or ASx
[00163] Synthesis of AGx or ASx can be performed following the general procedures described below.
[00164] Process 1: G moles of glycerol (sorbitol) are combined with 1-5% by mass of hydroquinone or Ethanox 330TM (oxidative inhibitors), Triphenylphosphine (TPP) or Amberlyst 15 (catalyst) at a mass ratio of 0.05 :1 glycerol and xG mol acrylic acid (x is the molar ratio of acrylic acid to glycerol or sorbitol). The mixture is stirred and sparged with air for 36 hours at 127°C (TPP) or 120°C (Amberlyst). Inhibitor and air spray (O2) help to reduce self-polymerization (which will otherwise lead to gelling). After 36 hours, the reaction is terminated by cooling to room temperature. The monomer contains up to 20% of the initial charge of acrylic acid.
[00165] Process 2: G moles of glycerol (sorbitol) are combined with 1-5% by mass of hydroquinone or Ethanox 330TM, 0.05:1 mass ratio of Triphenylphosphine (TPP) or Amberlyst 15 (catalyst) to glycerol and xEG soft acrylic acid. Here, xE is the molar ratio of acrylic acid to glycerol or sorbitol and means an excess stoichiometric ratio ranging from 1 to 3. The reaction is stirred and sparged with air for 8 hours at 90°C - 110°C.
[00166] In contrast to process 1, the lower temperature in process 2 substantially reduces self-polymerization; the use of a molar excess of acrylic acid allows the desired functionality to be achieved within the shortened time frame. After 8 hours the reaction is quenched with 50%/50% water/acetone. Excess acrylic, water and acetone are then removed under vacuum.
[00167] The characteristics of a representative set of poly(acrylated glycerol) P(AG)x produced according to the above processes are shown in table 2 below. TABLE 2. Representative table of acrylated polyol monomers.
RAFT polymerization of acrylated glycerol
[00168] RAFT polymerization was performed similarly to the procedure described in Moad et al., "Living Radical Polymerization by the Raft Process - the First Update," Australian Journal of Chemistry 59:669-92 (2006); Moad et al., "Living Radical Polymerization by the Raft Process - the Second Update," Australian Journal of Chemistry 62 (11): 1402 - 72 (2009), which are incorporated by reference in their entirety. Briefly, azobisisobutyronitrile (AIBN) was used as initiator, dibenzylcarbonotrithioate (DBCT) as chain transfer agent (CTA).
[00169] Monomer, initiator, CTA and solvent (methanol and/or glycerol) were mixed under argon in a 100 mL round bottom flask with various mass ratios of solvent monomer, 0.05 mass ratio of initiator to monomer and varying proportions of monomer to CTA, depending on the desired molecular weight of the resulting polymer. The reaction flask was purged with argon for 30 minutes to remove oxygen from the system before the temperature was increased. The reaction was conducted at 71°C, and the reaction time was controlled to allow maximum conversion without crosslinking the sample. The polymer was then precipitated by the addition of a 50%/50% mixture of acetone and hexane. The solvent was then decanted and acetone was mixed with the polymer still cleaning the polymer.
[00170] The characteristics of a representative set of poly(acrylated glycerol) P(AG)x produced in this way are shown in table 3.

Procedure for calculating the conversion of acrylic acid to acrylic groups
[00171] Proton nuclear magnetic resonance was used to calculate the average number of acrylic groups per molecule. The results are shown in Figure 5. The integral of the peak over 5.746.02 in deuterated DMSO was defined as a value of 1. The integral over both peaks at 5.74-5.82 was then combined. The peak integral was calculated at 5.90-6.02. The peak between 5.74-5.82 measured unreacted acrylic acid. The peak between 5.90-6.02 measured the acrylic groups reacted. The integral over the reacted acrylic groups provides the conversion of acrylic acid to acrylic groups in the polymer.
[00172] It was found that, to acrylate the secondary alcohols to glycerol, a higher concentration of acrylic acid or an increase in temperature was necessary. These results agree with the reactivity of alcohols (1st > 2nd > 3rd). Molecular characterization
[00173] DSC experiments showed glass transition temperature (Tg) for P(AG) between -45°C (ghrmf30 sample) to -20°C (ghrmf59 sample). See Table 3. Figure 6 shows an example of the DSC results for P(AG) (sample ghrmf82) demonstrating that the Tg was -30°C.
[00174] It was also found that the viscosity of the product was affected by the degree of acrylation — as the degree of acrylation increased the product became more viscous.
[00175] Rheology samples were mixed with butylated hydroxytoluene (BHT) to prevent crosslinking of the polymer. Figure 7 shows the rheology curves of different P(AG) polymers with different target molecular weights. Example 3 - modification of asphalt rubber with polymers derived from RAFT polymerization of acrylated glycerol
[00176] The glycerol from the biodiesel industry was acrylated and polymerized to different extents, and the resulting materials were then used in the production of rubber from the asphalt. Asphalt rubber binders "stabilized" by polymerized acrylated glycerol were tested and the results were compared with an asphalt rubber (GTR) without any stabilizer, and an asphalt rubber stabilized with Vestenamer®.
[00177] The performances of asphalt rubber without any stabilizer, stabilized by poly(acrylated glycerol) and stabilized by Vestenamer® (AR) were compared in terms of rheology, viscosity and the mixing and compaction temperatures of AR, the effect on the separation during AR storage and the effect of AR and residual AR. Materials and Equipment
[00178] Poly(acrylated glycerol)(P(AG)) with different degrees of acrylation and polymerization was prepared based on procedures in the same way as the procedures described in example 1 or 2.
[00179] The asphalt base used was PG 58-28 (Seneca Petroleum), and ambient ground tire rubber (ambGTR) prepared by mechanical destruction provided by Seneca Petroleum (030 mesh). Vestenamer® was used as a commercially available asphalt modifier to compare with the performance of P(AG) as the asphalt modifier. The. Experiment 1
[00180] The asphalt and rubber bran were mixed under the following conditions: • Controlled speed - 3000 rpm • Controlled interaction temperature - 180°C • Interaction time - 1 hour • Rubber concentration - 15% by weight of the asphalt-mixture rubber • Concentration of additives - 4.5% by weight of rubber
[00181] The rubber asphalt was then centrifuged at a controlled speed (1500 rpm) at 180°C for 3 minutes.
[00182] Three AR samples were produced: • PG58-28 + 15% by weight ambGTR (known as "AR" control) • PG58-28 + 15% by weight (ambGTR + 4.5% Vestenamer® by weight of ambGTR) (referred to as "AR-V") • PG58-28 + 15% by weight (ambGTR + 4.5% poly(acrylated glycerol) by weight of ambGTR) - (referred to as "AR-AG").
[00183] The samples were tested in the rotational viscometer (RV) to characterize their viscosities, in the dynamic shear rheometer (DSR) and/or bending beam rheometer (BBR) to characterize their rheologies. Sample separation was tested by the Cigar Tube Separation Method (CTS) (ASTM D 7173). The binders were aged using Rolling Thin Film Furnace (RTFO) to simulate short term aging and further aged using pressurized aging vessel (PAV) to simulate long term aging. Assays performed on residual AR and AR ligand samples are shown in table 4.

[00184] The results of viscosity at various temperatures for the rubber-asphalt binders and residual AR for the three samples are shown in Figures 8A - 8C.
[00185] The results of rheology measured by the DSR for the AR and residual AR binders for the three samples under different conditions (aged, aged RTFO and aged PAV) are shown in Figures 9A - 9c.
[00186] The classification results for AR and residual AR binders for the three samples under various conditions (aged, aged RTFO and aged PAV) are shown in Figures 10A - 10C.
[00187] The results of separation of AR binders (top and bottom, ie, the binding material in the top and bottom 1/3 of the cigar tube as specified in ASTM D 7173) for the three samples are shown in Figures 11A - 11C.
[00188] All results were analyzed and summarized in Tables 5-6.

B. Experiment 2
[00189] The experimental conditions were similar to the experimental conditions in Experiment 1 in this example, except that the three AR samples were produced and cured (covered containers) in the oven at 163°C for 72 hours and then centrifuged: • PG58-28 + 15% ambGTR (known as "AR" control) • PG58-28 + 15% by weight (ambGTR + 4.5% Vestenamer® by weight, of ambGTR) (referred to as "AR-V") • PG58-28 + 15% by weight (ambGTR + 4.5% poly(acrylated glycerol) by weight of ambGTR) - (referred to as "AR-AG").
[00190] The samples were tested in the dynamic shear rheometer (DSR) to characterize their rheology for total AR and residual materials. Sample separations were tested by CT for total AR and residual materials.
[00191] The results of viscosity at various temperatures for the rubber-asphalt binders and residual AR for the three samples are shown in Figures 12A - 12C.
[00192] The rheology results measured by the DSR for the rubber asphalt binders (top and bottom) for the three samples are shown in Figures 13A - 13C.
[00193] The separation results for the asphalt-rubber binders for the three samples are shown in Figures 14A - 14C. ç. Comparison
[00194] The test results for the three samples in Experiment 1 (not aged) and Experiment 2 (oven-cured) were compared. The results of the comparison are shown in Figures 15A-15F and summarized in Tables 7-9.

* Mixing and compaction temperatures above 180°C have been extrapolated
[00195] The results show that the rubber particles added to the asphalt affected the AR viscosity, which would have affected the accurate determination of the mixing and compaction temperatures.
[00196] Compared to AR (control, without additives) and AR with Vestenamer®, the use of poly (acrylated glycerol) in AR improved performance in all AR characteristics, that is, it reduced the degree of continuous performance low AR, reduced the sensitivity of AR viscosity to temperature, reduced AR binder modulus at low temperature, and reduced AR separation after cure (72 hours at 163°C). Example 4 - modification of asphalt rubber with polymers derived from RAFT polymerization of acrylated glycerol
[00197] The glycerol from the biodiesel industry was acrylated and polymerized to different extents, and the resulting materials were then used in the production of rubber from the asphalt. AR binders "stabilized" by polymerized acrylated glycerol were tested, and the results were compared with an asphalt rubber (GTR) without any stabilizer, an AR stabilized with Kraton® D1101 and an asphalt rubber stabilized with Vestenamer®.
[00198] The overall performance of the Vestenamer® stabilized AR was better than the unstabilized control AR. However, the best performance was achieved by AR stabilized using 4.5% by weight of poly(acrylated glycerol) with a low degree of acrylation and average molecular weight (the weight percentage was in relation to the weight of the rubber binder ). Materials and equipment
[00199] Poly(acrylated glycerol)(P(AG)) with different degrees of acrylation and polymerization was prepared based on procedures in the same way as the procedures described in example 1 or 2.
[00200] The base asphalt used was PG 58-28 (Seneca Petroleum), and rubber was ambient ground tire rubber (ambGTR) made by mechanical destruction provided by Seneca Petroleum (030 mesh). Kraton® D1101 and Vestenamer® were used as commercially available asphalt modifiers to compare with the performance of P(AG) as the AR modifier.
[00201] The following equipment was used to prepare AR binders and characterize the modified AR. • Silverson Shear Mill • Accelerated Binder Separator - BAS (this method separates expanded rubber from residual AR binder) • Rotational viscometer • Dynamic Shear Rheometer • Thin Film Rolling Furnace • Pressure Aging Vessel • Beam Rheometer bending • Degassing furnace Experimental Procedures
[00202] Six samples of P(AG) with different degrees of acrylation and polymerization were used in the production of ARs at three different concentrations (2.5%, 4.5% and 6.5%, by weight of the GTR) as summarized in table 10 below. Only 6.5% concentration levels were used for the 37 and 64 experimental blocks of acrylated glycerol and resulting in 14 experimental compositions for the acrylated glycerol being evaluated. Table 10. The Vestanamer® sample was mixed at the same three concentrations with the GTR without any stabilizer and resulted in a total of 18 experimental compositions being evaluated.
[00203] The polymer/GTR was added to the asphalt base at 12% by weight of the total AR binder. Table 10. Materials tested for three degrees of acrylation and polymerization (molecular weight) for different P(AG) contents

[00204] All samples were tested in the dynamic shear rheometer (DSR), bending beam rheometer (BBR) and in the viscometer (RV) to obtain their continuous high notes grades, between medium and low. All AR ligands were also tested for separation susceptibility (for 48 hours at 163°C). The binders were aged using Rolling Thin Film Oven (RTFO) to simulate short term aging and further aged using pressurized aging vessel (PAV) to simulate long term aging. All classification tests on the binders were performed as specified in Superpave®: Asphalt Binder Specification Rated Performance and Tests (2003) (Asphalt Institute), as well as in AASHTO R 29-08 and AASHTO M 320-05. The determination of the rheological properties of the asphalt binder using a dynamic shear rheometer was conducted in accordance with ASTM D 7175-08. Experimental results
[00205] The results of each test are presented in a summary table (Figures 16-28), where the results of RA stabilized with P(AG) were compared with the unstabilized RA (control), the RA stabilized with Vestenamer® and additionally a 5% Kraton® modified binder.
[00206] The shaded cells in the summary tables about Vestenamer® stabilized binders indicate the values that ideally can be achieved or exceeded using poly (acrylated glycerol) — these values are also shaded in the summary tables with respect to the binders stabilized with P(AG) in dark grey. The light gray in the summary tables with respect to the P(AG) stabilized binders are those that perform similarly to the Vestenamer® stabilized binders, taking into account the test variability. The. Continuous High Temperature Grade for Aged Binders - DSR
[00207] AR binders have been aged. The samples were tested on the DSR to obtain their continuous high temperature grades. The results for the P(AG)-modified unaged AR binders are summarized in the table and compared with the results for an unstabilized AR (control), AR binders stabilized with Vestenamer® and a 5% Kraton modified asphalt binder ®, as shown in Figure 16.
[00208] The addition of rubber to the asphalt increased the high temperature grade of the AR from 58° to 76°, and the high performance grade (PG) of the residual binder was nearly 70°. These results were improved by the addition of Vestenamer®, which performed better than asphalt modified with 5% ®Kraton D1101.
[00209] The PG of the stabilized AR ligands, with P(AG) or Vestenamer®, was always better than the non-stabilized AR (control). The addition of poly(acrylated glycerol) improved the high PG of the binders at least to the same extent as Vestenamer® and in some cases (eg 6.5% AG82 and 6.5% AG54) better than Vestenamer®. B. Continuous high temperature grade for binders aged with RTFO - DSR
[00210] AR binders were aged using RTFO, to simulate short term aging. The samples were tested on the DSR to obtain their continuous grades at high temperature. Tests were performed in accordance with ASTM D 2872-04. The results for the aged AR binders with P(AG)-modified RTFO are summarized in the table and compared with the results for an unstabilized AR (control), AR binders stabilized with Vestenamer® and a 5% Kraton modified asphalt binder ®, as shown in Figure 17.
[00211] After aging with RTFO, all binders (except 2.5% AG78) produced to the same grade, which is the normal behavior for asphalt binders. The table in Figure 18 summarizes the percent mass loss achieved during the RTFO test.
[00212] The RTFO aging process can result in variable results, and 1% mass loss is the acceptable criterion. Thus, the AR residues stabilized with AG showed an acceptable mass loss value (except for 6.5% of AG 37, 59 and 64). AR stabilized with 2.5% AG54 and 4.5% AG82 performed better than AR stabilized with Vestenamer®. Absolute mass loss values for the AR binder could not be measured because the bottles overflowed during the test. ç. Continuous degree of intermediate temperature for binders aged with RTFO + PAV-DSR
[00213] AR binders were aged using RTFO and again aged using PAV to simulate long-term aging. The aging of the PAV was performed according to AASHTO R 28. The samples were tested in the DSR to obtain their continuous degrees of intermediate temperature. The results for AR binders aged by RTFO + PAV modified by P(AG) are summarized in the table and compared with the results for an unstabilized AR (control), AR binders stabilized with Vestenamer® and an asphalt binder modified with 5% Kraton® as shown in Figure 19.
[00214] For intermediate temperatures, the weaker behavior of Kraton® D1101 was noticeable when compared to the other binders, especially the non-stabilized AR (control). Vestenamer® sample improved the AR binder but had the opposite effect on the residual. The same trend was observed for P(AG), but the performance improvements for the AR binder using P(AG) were more substantial than Vestenamer®. These more substantial improvements than the Vestenamer® sample using P(AG) were observed for the AR binders and for the residual binder. d. Continuous low temperature grade for binders aged by RTFO + PAV-BBR
[00215] AR binders were aged using RTFO and again aged using PAV to simulate long-term aging. The samples were tested at BBR to obtain their continuous low temperature grades. Testing was performed in accordance with ASTM D 6648-08. The results for AR binders aged by RTFO + PAV modified by P(AG) are summarized in the table and compared with the results for an unstabilized AR (control), AR binders stabilized with Vestenamer® and a modified asphalt binder with 5 % Kraton® as shown in Figure 20.
[00216] Similar to the results at the continuous grades of intermediate temperature, Kraton® had the weakest performance at the low temperature PG. The most significant result is that the stabilization of AR binders with P(AG) was very significant, even when compared to AR binders modified by Vestenamer®. and. Determination of viscosity for unaged binders - RV
[00217] The viscosity test was performed on the RV in accordance with ASTM D 4402-06. The results are illustrated in Figures 21A and 21B.
[00218] The viscosity test revealed the excellent performance of AR binders stabilized with P(AG). These binders showed improved performance with regard to high, intermediate and low temperature grades. Typically, it is expected that a relatively high level of temperature sensitivity would result. However, Figure 21A mainly shows the opposite, especially for the AR ligand stabilized with 6.5% and 4.5% AG82 and 4.5% AG78. The addition of the Vestenamer® sample increased the viscosity of the AR binder when compared to the unstabilized AR (control). Using P(AG) to modify AR, most binders showed lower viscosities than Vestenamer® modified AR binders and some P(AG) modified AR binders showed even lower viscosity than AR from control.
[00219] Residual viscosities were also evaluated for AR binders modified with P(AG), and a reduction in viscosity was observed when compared to AR, even with the Vestenamer® sample. However, temperature sensitivity was quite similar among all binders, which suggests that P(AG) acts in conjunction with rubber particles. See Figure 21B. f. Storage stability of asphalt rubber binders -DSR
[00220] Storage stability has been tested on the DSR in accordance with ASTM D 7173-05. The DSR storage stability percent difference results for the P(AG) modified AR binders are summarized in the table and compared with the results for an unstabilized AR (control), AR binders stabilized with Vestenamer® and a Vestenamer® binder. asphalt modified with 5% Kraton®, as shown in Figure 22.
[00221] The results showed that Vestenamer® stabilized the AR ligand. The storage stability of the P(AG)-modified AR binders was significantly improved for most of the tested samples compared to the AR control binders. g. grade range
[00222] The improvement of the degree of high and low temperature is desirable and indicates under what conditions the binder can be used successfully. It is also desirable to have a binder that can be used over a wide range of weather conditions. This is determined by the grade range.
[00223] The grade range results for the P(AG) modified AR binders are summarized in the table and compared with the results for an unstabilized AR (control), AR binders stabilized with Vestenamer® and an asphalt binder modified with 5% Kraton® as shown in Figure 23.
[00224] Similar to results in continuous grades of intermediate and low temperature, Kraton ® D1101 showed the weakest performance in the grade range. The addition of the GTR alone widened the grade range by 16°C. After the AR was modified with Vestenamer®, an extra 6°C was obtained. The best performance was obtained by the AR modified by P(AG), which achieved a grade range of 113°C (27°C above the original PG58-28 without the GTR and 5°C above the AR modified with Vestenamer®). H. Mixing and compaction temperatures
[00225] Mixing and compaction temperatures were determined as specified in Superpave® Mix Design. Superpave Serial No. 2 (SP-02) (Asphalt Institute, Lexington, KY, 2001). The results of the minimum mixing temperatures and minimum compaction temperatures for the P(AG)-modified AR binders are summarized in the tables and compared with the results of an unstabilized AR (control), Vestenamer® stabilized AR binders and a 5% Kraton® modified asphalt binder as shown in Figure 24 and Figure 25, respectively.
[00226] The viscosity of a material is very susceptible to the presence of particles; the particles dramatically increase the viscosity of the composite material, and this phenomenon is reflected in the mixing temperature — a higher mixing temperature is needed to achieve the desired viscosity for the composite material containing particles. This is well illustrated in the tables in Figure 24 and Figure 25.
[00227] The control asphalt rubber showed the smallest increase in the temperature of the mixture. The addition of the Vestenamer® sample increased the mixing temperature by 6°C, but the SBS Kraton® modified asphalt showed an even greater increase of 7°C. However, the addition of P(AG) only increased the temperature of the mixture by 4°C (eg using 4.5% AG82). See Figure 24.
[00228] The performance of P(AG) was excellent in relation to the compaction temperatures. Compaction temperatures 6°C lower than the control AR were achieved by AR modified with P(AG). In fact, the overall performance of AR modified with P(AG) at almost all concentrations, degrees of acrylation and molecular weights was better than AR stabilized with AR modified with Vestenamer® and asphalt modified with Kraton®. See Figure 25. i. Average difference between AR and Residual viscosities
[00229] It is often difficult and time-consuming to determine whether an asphalt binder is or is not stable during storage. However, comparing the viscosities of AR and residual binders can provide an indication of this characteristic.
[00230] The average viscosity of AR was compared with the residual, subtracting the latter from the former, and a smaller value of the difference between the two indicates a more stable material. The results of the mean difference between AR and residual viscosities for AR binders modified by P(AG) are summarized in the table and compared with the results for an unstabilized AR (control), AR binders stabilized with Vestenamer® and a 5% Kraton® modified asphalt binder as shown in Figure 26.
[00231] The results show a remarkable similarity between the viscosities of AR and residual binders of materials stabilized with P(AG). Analysis and discussion
[00232] Almost all poly(acrylated glycerol) stabilizers synthesized performed well at the three concentrations tested. To optimize the production process for P(AG) and the AR binder formulation containing the P(AG), different tested parameters were categorized, analyzed and ranked to assign relative weights to each parameter, as shown below: • PG High Temperature not aged 1.75 • PG High temperature RTFO 0.75 • Mass loss RTFO 0.50 • PG intermediate temperature 0.75 • PG low temperature 1.25 • Grade range 1.50 • viscosity 1.25 • Minimum temperature mixing temperature 1.00 • Minimum compaction temperature 1.00 • Storage stability 2.00 • Viscosity difference (AR-Residual) 1.25
[00233] Before applying the relative weight, each parameter was converted to a percentage, where the highest value was 100% and the lowest possible value was -100%. In the first comparison, the control AR values were set to 0%. The final percentage rating of AR binders stabilized with P(AG) and Vestenamer® was analyzed against the control AR (not stabilized), as shown in the table in Figure 27.
[00234] Almost all AR stabilized with P(AG) and Vestenamer® performed better than unstabilized control AR. The highlighted cell in the table shows the combination where P(AG) performed best in the weighted ranking.
[00235] In the second comparison, the AR values modified with Vestenamer® were set at 0%. The final percent rating of AR ligands stabilized with P(AG) was analyzed against AR modified with Vestenamer®, as shown in the table in Figure 28.
[00236] When compared to Vestemamer®, P(AG) commonly showed better performance. The highlighted cell in the table shows the combination where P(AG) performed best in the weighted ranking.
[00237] The AR binder modified by P(AG) which in general showed a 27% better performance than the AR binder modified by Vestenamer® was the P(AG) with a low degree of acrylation and a medium molecular weight (grade of polymerization), added at a concentration of 6.5% by weight of the GTR (for a modified asphalt with 12% by weight of ambient GTR).
[00238] The AR binder modified by P(AG) with a low degree of acrylation and an average molecular weight, added at a concentration of 4.5% by weight of the GTR (for a modified asphalt with 12% by weight of Ambient GTR) showed an exceptional result - 44% better performance than the AR control. Example 5 - Synthesis of poly(acrylated glycerol) Acrylation of glycerol
[00239] Glycerol was mixed with phenothiazine or hydroquinone (inhibitor, 0.5% by weight of glycerol), Amberlyst 15 or thiamine pyrophosphate (TPP) as the catalyst in a mass ratio of 0.06:1 to glycerol, acrylic acid at a 1.5:1 mass ratio for glycerol and DMSO at a 1:1 mass ratio for glycerol. The reaction was stirred and bubbled for 20 minutes and then heated to 90°C. The reaction was allowed to proceed for a minimum period of 12 hours and was terminated by cooling to room temperature. The final acrylated glycerol was mixed with cyclohexane to remove DMSO and dried overnight in vacuum ovens at room temperature. Acrylated glycerol polymerization
[00240] Polymerization of acrylated glycerol was carried out in accordance with the procedures referred to in Example 1. The resulting three poly(acrylated glycerol) polymers having molecular weights ranging from 1 million Daltons to 10,000 Daltons are shown in Figure 30, with the gel permeation chromatography traces shown in Figure 29.
[00241] Although preferred embodiments have been described and detailed herein, it will be apparent to those skilled in the art that various modifications, additions, substitutions and the like will be made without departing from the spirit of the present invention and are therefore considered within the scope of the present invention. invention as defined in the claims which follow.

权利要求:
Claims (32)
[0001]
1. Thermoplastic copolymer, characterized in that it comprises plural acrylated polyol monomeric units with different degrees of acrylation of hydroxyl groups, wherein the acrylated polyol monomeric units have an average degree of acrylation greater than 1 and less than the number of groups hydroxyl of the polyol, in which the polymer chain of the thermoplastic copolymer is based on the polymerization of radically polymerizable acrylic moieties (O=CC=C).
[0002]
2. Thermoplastic copolymer according to claim 1, characterized in that the thermoplastic copolymer has: a) a linear or branched chain structure; or b) a molecular weight of at least 1 KDa, optionally wherein the thermoplastic copolymer has a molecular weight ranging from 50 KDa to 10 MDa; or c) a transition temperature (Tg) below 0°C, optionally wherein the thermoplastic copolymer has a Tg ranging from -60°C to -15°C.
[0003]
3. Thermoplastic copolymer according to claim 1, characterized in that the polyol is selected from the group consisting of ethylene glycol, propylene glycol, dipropylene glycol, 1,2,4-butanetriol, 1,7-heptanediol , glycerol, panaxatriol, panaxitriol, thalose, balsaminol B, momordol, erythritol, enterodiol, xylitol, miglitol, sorbitol, mannitol, galactitol, isomalt, maltitol, aldohexose, aldopentose, aldotetrose, aldomyldose, aldothyrose, aldothyrose amylose, dextrose, erythrose, fructose, galactose, glucose, gluteus, hexose, indose, ketohexose, ketose, lactose, garbagese, maltose, mannose, pentose, ribose, sucrose, sucrose, talose, tetrose, triose, xylose and stereoisomers thereof; and optionally wherein the polyol is glycerol, optionally wherein the average degree of acrylation ranges from 1.001 to 2.9, or wherein the average degree of acrylation ranges from 1.001 to 1.25; or wherein the polyol is sorbitol, optionally wherein the average degree of acrylation ranges from 1.001 to 3; or where the polyol is dextrose, optionally where the average degree of acrylation ranges from 1.001 to 3.
[0004]
4. Thermoplastic copolymer according to claim 1, characterized in that one or more acrylated polyol monomeric units contain one or more alkoxy groups derived from esterification of non-acrylated hydroxy groups, optionally wherein one or more polyol monomeric units acrylates contain one or more methoxy or ethoxy groups.
[0005]
5. Thermoplastic block copolymer, characterized in that it comprises at least one PA block and at least one PB block, wherein PA represents a polymer block comprising one or more A monomer units and PB represents a block of polymer comprising one or more monomer B units, with monomer A being an acrylated polyol monomeric unit with different degrees of acrylation of hydroxyl groups, wherein the acrylated polyol monomeric unit has an average degree of acrylation greater than 1 and less than number of hydroxyl groups of the polyol, and monomer B being a radically polymerizable monomer.
[0006]
6. Thermoplastic block copolymer according to claim 5, characterized in that the PA block and PB block each have a linear or branched chain structure; and optionally wherein one or more PA block acrylated polyol monomer units contain one or more alkoxy groups derived from esterification of the non-acrylated hydroxy groups; or further comprising at least one PC block, wherein PC represents a polymer block comprising one or more C monomer units, with the C monomer being a radically polymerizable monomer; or wherein the block copolymer has a molecular weight ranging from 5 to 10 MDa; or where the PA block has a glass transition temperature (Tg) below 0 °C.
[0007]
7. Thermoplastic block copolymer according to claim 5, characterized in that the monomer A polyol is selected from the group consisting of ethylene glycol, propylene glycol, dipropylene glycol, 1,2,4-butanetriol, 1 ,7-heptanediol, glycerol, panaxatriol, panaxitriol, thalose, balsaminol B, momordol, erythritol, enterodiol, xylitol, miglitol, sorbitol, mannitol, galactitol, isomalt, maltitol, aldohexose, aldopentose, aldose, aldose altrose, arabinose, amylopectin, amylose, dextrose, erythrose, fructose, galactose, glucose, glucose, hexose, indose, ketohexose, ketose, lactose, garbagese, maltose, mannose, pentose, ribose, sucrose, sucrose, tetrose, triose, x respective stereoisomers; and optionally wherein the A monomer polyol is glycerol, or sorbitol, or dextrose.
[0008]
8. Thermoplastic block copolymer according to claim 5, characterized in that one or more acrylated polyol monomeric units of the PA block contain one or more alkoxy groups derived from the esterification of non-acrylated hydroxy groups.
[0009]
9. Thermoplastic block copolymer according to claim 5, characterized in that the B monomer is a vinyl, acrylic, diolefin, nitrile, dinitrile, acrylonitrile monomer, a monomer with reactive functionality, or a crosslinking monomer; optionally selected from the group consisting of styrene, α-methyl styrene, t-butyl-styrene, vinyl xylene, vinyl naphthalene, vinyl pyridine, divinyl benzene, methyl acrylate, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, heptyl (meth)acrylate, hexyl (meth)acrylate, acrylonitrile, adiponitrile, methacrylonitrile, butadiene, isoprene, radically polymerizable vegetable oils, and mixtures thereof; optionally wherein the B monomer is a radically polymerizable vegetable oil selected from the group consisting of soybean oil, linseed oil, corn oil, linseed oil, and rapeseed oil.
[0010]
10. Thermoplastic block copolymer according to claim 9, characterized in that it further comprises at least one PC block, wherein the PC represents a polymer block comprising one or more C monomer units, being C monomer a radically polymerizable monomer.
[0011]
11. Thermoplastic block copolymer according to claim 5, characterized in that the block copolymer has a molecular weight ranging from 5 to 10 MDa.
[0012]
12. Thermoplastic block copolymer according to claim 5, characterized in that the PA block has a glass transition temperature (Tg) below 0 °C.
[0013]
13. Thermoplastic statistical copolymer, characterized by the fact that it has a general formula of: [Ai-Bj-Ck]q, where: A represents the monomer A, which is a monomeric unit of acrylated polyol with different degrees of acrylation of groups hydroxyl, wherein the acrylated polyol monomeric unit has an average degree of acrylation greater than 1 and less than the number of hydroxyl groups on the polyol; B represents monomer B, which is a radically polymerizable monomer; C represents monomer C, which is a radically polymerizable monomer; provided that monomer B is different than monomer A, and monomer C is different than monomer A or monomer B; i, j and k are the average number of repeating units of monomer A, monomer B, and monomer C, respectively, so that i and j are each greater than 0 and less than 1, k is 0 to less than 1, as long as i + j + k = 1; and q represents the average degree of polymerization number and ranges from 10 to 100,000, where the polymer chain of the thermoplastic copolymer is based on the polymerization of radically polymerizable acrylic moieties (O=C-C=C).
[0014]
14. Thermoplastic statistical copolymer, according to claim 13, characterized in that the acrylated polyol monomeric unit contains one or more conjugated sites; optionally wherein one or more acrylated polyol monomer units of the A monomer contain one or more alkoxy groups derived from esterification of the non-acrylated hydroxy groups.
[0015]
15. Thermoplastic statistical copolymer according to claim 13, characterized in that the monomer A polyol is selected from the group consisting of ethylene glycol, propylene glycol, dipropylene glycol, 1,2,4-butanetriol, 1 ,7-heptanediol, glycerol, panaxitriol, thalose, Balsaminol B, momordol, erythritol, enterodiol, xylitol, miglitol, sorbitol, mannitol, galactitol, isomalt, maltitol, aldohexose, aldopose, aldetrose, amylose, amylope, altrose dextrose, erythrose, fructose, galactose, glucose, sugar, hexose, idose, ketohexose, ketosis, lactose, garbagese, maltose, mannose, pentose, ribose, sucrose, sucrose, tetrose, triose, xylose and their stereoisomers; and optionally wherein the A monomer polyol is glycerol, or sorbitol, or dextrose.
[0016]
16. Thermoplastic statistical copolymer according to claim 13, characterized in that one or more acrylated polyol monomer units of monomer A contain one or more alkoxy groups derived from the esterification of non-acrylated hydroxy groups.
[0017]
17. Thermoplastic statistical copolymer according to claim 13, characterized in that monomer B and monomer C, if present, are each independently vinyl, acrylic, diolefin, nitrile, dinitrile monomers, of acrylonitrile, a monomer with reactive functionality or a crosslinking monomer; optionally each independently styrene, α-methyl styrene, t-butyl styrene, vinyl xylene, vinyl naphthalene, vinyl pyridine, divinyl benzene, methyl acrylate, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl ( meth)acrylate, heptyl(meth)acrylate, hexyl(meth)acrylate, acrylonitrile, adiponitrile, methacrylonitrile, butadiene, isoprene, radically polymerizable vegetable oils, or mixtures thereof; optionally wherein the radically polymerizable vegetable oil is selected from the group consisting of soybean oil, linseed oil, corn oil, linseed oil and rapeseed oil.
[0018]
18. Asphalt binder composition, characterized in that it comprises: the thermoplastic copolymer as defined in claim 1, the thermoplastic block copolymer as defined in claim 5, or the thermoplastic statistical copolymer as defined in claim 13; and a rubber crumb.
[0019]
19. Adhesive or sealant composition, characterized in that it comprises: the thermoplastic copolymer as defined in claim 1, the thermoplastic block copolymer as defined in claim 5, or the thermoplastic statistical copolymer as defined in claim 13; and a thickener, and/or a plasticizer, and/or a solvent.
[0020]
20. Tire composition, characterized in that it comprises: the thermoplastic copolymer as defined in claim 1, the thermoplastic block copolymer as defined in claim 5, or the thermoplastic statistical copolymer as defined in claim 13; and a rubber compound
[0021]
21. Fractionation fluid composition, characterized by the fact that it comprises: water; sand; the thermoplastic copolymer as defined in claim 1, the thermoplastic block copolymer as defined in claim 5, or the thermoplastic statistical copolymer as defined in claim 13, as a chemical additive; and optionally, a thermoplastic polymer block added to impart a desired fluid property to the thermoplastic copolymer, statistical thermoplastic copolymer, or thermoplastic block copolymer.
[0022]
22. Method of preparing a thermoplastic copolymer or block copolymer, characterized in that it comprises: providing an acrylated polyol composition comprising plural acrylated polyol monomer units with different degrees of acrylation of hydroxyl groups, wherein the acrylated polyol composition has an average degree of acrylation greater than 1 and less than the number of hydroxyl groups in the polyol; and polymerizing the acrylated polyol composition through controlled radical polymerization to form the thermoplastic copolymer or block copolymer.
[0023]
23. The method of claim 22, further comprising: a) wherein said providing an acrylated polyol composition comprises: reacting a polyol with an acrylic reagent in a stoichiometric ratio of the acrylic reagent to the polyol ranging from 1 to 3; optionally wherein said reaction is carried out at a temperature of 30 to 130 °C, or wherein said acrylic reagent is an unsaturated carboxylic acid or acid halide selected from the group consisting of acrylic acid, acryloyl chloride, methacrylic acid and other acids or acidic halides terminated with a vinyl; or b) wherein said polymerization is carried out to produce the thermoplastic copolymer or block copolymer having a straight-chain or branched structure; or c) wherein said polymerization is carried out under conditions effective to produce the thermoplastic copolymer or block copolymer having a molecular weight of at least 1 KDa without gelling; or optionally wherein said polymerization is carried out under conditions effective to produce the thermoplastic copolymer having a molecular weight of 50 KDa to 10 MDa without gelling; or d) wherein said polymerization is carried out by atom transfer radical polymerization (ATRP), in the presence of a solvent, a catalyst, a countercatalyst, an initiator and a binder; or e) wherein said polymerization is carried out by reversible fragmentation addition chain transfer polymerization (RAFT), in the presence of a free radical initiator, a solvent, and a chain transfer agent; optionally wherein said polymerization is carried out at a temperature of 50 to 120 °C, or wherein said solvent is selected from the group consisting of toluene, THF, chloroform, cyclohexane, dioxane, dimethylsulfoxide, dimethyl formamide, acetone, acetonitrile, n-butanol, n-pentanol, chlorobenzene, dichloromethane, diethyl ether, tert-butanol, 1,2,-dichloroethylene, diisopropyl ether ethanol, ethylacetate, ethylmethylketone, heptane, hexane, isopropyl alcohol, isoamyl alcohol, methanol, pentane , n-propyl alcohol, pentachlorethane, 1,1,2,2,-tetrachloroethane, 1,1,1-trichloroethane, tetrachloroethylene, tetrachloromethane, trichloroethylene, water, xylene, benzene, nitromethane, glycerol, and a mixture thereof; optionally methanol, glycerol, or a mixture thereof, or wherein said polymerization is carried out in a solvent with the monomer having a concentration, when dissolved in the solvent, ranging from 1% to 90%, or wherein the free radical initiator is selected from the group consisting of benzoyl peroxide and azobisisobutyronitrile, or wherein the chain transfer agent is a thiocarbonylthio compound, a dithioester compound, a trithiocarbonate compound, a dithiocarbamate compound, or a xanthate compound capable of reversible association with polymerizable free radicals, optionally 1-phenylethyl benzodithioate, 1-phenylethyl 2-phenylpropanedithioate, or dibenzyl carbontrithioate; or f) wherein the polyol is selected from the group consisting of ethylene glycol, propylene glycol, dipropylene glycol, 1,2,4-butanetriol, 1,7-heptanediol, glycerol, panaxatriol, panaxitriol, talose, Balsaminol B, momordol, erythritol, enterodiol, xylitol, miglitol, sorbitol, mannitol, galactitol, isomalt, maltitol, aldohexose, aldopentose, aldotetrose, aldotriose, aldose, alose, altrose, arabinose, amylopectin, fructose, amylose, and dextrose glutose, hexose, idose, ketohexose, ketose, lactose, garbagese, maltose, mannose, pentose, ribose, sucrose, sucrose, tetrose, triose, xylose and their stereoisomers; optionally wherein the polyol is glycerol, optionally wherein the average degree of acrylation ranges from 1.001 to 2.9, optionally wherein the average degree of acrylation ranges from 1.001 to 1.25, or wherein the polyol is sorbitol, optionally that the average degree of acrylation ranges from 1.001 to 3, or wherein the polyol is dextrose, optionally wherein the average degree of acrylation ranges from 1.001 to 3; or g) further comprises reacting the thermoplastic copolymer or block copolymer with organic acid to esterify the unacrylated hydroxy groups into one or more acrylated polyol monomeric units, optionally wherein the organic acid is formic acid, acetic acid, hexanoic acid, acid ethanoic or propanoic acid; or h) wherein said polymerization is carried out in the presence of a solvent, a catalyst, a countercatalyst, a macromolecular initiator, and a binder to form the thermoplastic block copolymer; and optionally further comprising providing a different radically polymerizable monomer than the acrylated polyol monomeric unit; and polymerizing the radically polymerizable monomer through atom transfer radical polymerization (ATRP) with the thermoplastic block copolymer formed as a macromolecular free radical initiator to add an additional block to the thermoplastic block copolymer; or i) wherein said polymerization is carried out in the presence of a free radical initiator, a solvent, and a macromolecular chain transfer agent to form the thermoplastic block copolymer; and optionally further comprising providing a different radically polymerizable monomer than the acrylated polyol monomeric unit; and polymerizing the radically polymerizable monomer through reversible fragmentation addition chain transfer polymerization (RAFT) with the formed thermoplastic block copolymer as a macromolecular chain transfer agent to add an additional block to the thermoplastic block copolymer; or j) further comprising chemically modifying the thermoplastic copolymer or block copolymer with a crosslinking agent, allowing the thermoplastic copolymer or block copolymer to undergo a crosslinking reaction at an elevated temperature; or k) further comprising chemically modifying the thermoplastic copolymer or block copolymer with a reagent to impart acidic or basic functionality to the thermoplastic copolymer or block copolymer, making the thermoplastic copolymer or block copolymer a pH regulating agent; or l) further comprising chemically modifying the thermoplastic copolymer or block copolymer with a reagent to impart a biocidal functionality to the thermoplastic copolymer or block copolymer, making the thermoplastic copolymer or block copolymer a biocidal agent.
[0024]
24. Method of preparing a statistical thermoplastic copolymer, characterized in that it comprises: providing the monomer A, which is a monomeric unit of acrylated polyol with different degrees of acrylation of hydroxyl groups, in which the monomeric unit of acrylated polyol has a average degree of acrylation greater than 1 and less than the number of hydroxyl groups in the polyol; provide a radically polymerizable monomer, represented by B; and polymerize monomer A and monomer B simultaneously, through reversible fragmentation addition chain transfer polymerization (RAFT), in the presence of a free radical initiator and a chain transfer agent to form the thermoplastic statistical copolymer.
[0025]
25. Method according to claim 24, characterized in that it further comprises: a) before said polymerization: providing a radically polymerizable monomer, represented by C, in which the C monomer is different from monomer A or monomer B, wherein said polymerization comprises polymerization of monomer A, monomer B and monomer C simultaneously, through RAFT, in the presence of the free radical initiator and the chain transfer agent to form the thermoplastic statistical copolymer, and optionally wherein the C monomer is radically polymerizable plant oil selected from the group consisting of soybean oil, linseed oil, corn oil, linseed oil and rapeseed oil; or b) wherein the polyol of monomer A is glycerol, or sorbitol, or dextrose; or c) wherein the B monomer is a vinyl, acrylic, diolefin, nitrile, dinitrile, acrylonitrile monomer, a reactive functionality monomer or a crosslinking monomer, optionally selected from the group consisting of styrene, α-methyl styrene, t-butyl styrene, vinyl xylene, vinyl naphthalene, vinyl pyridine, divinyl benzene, methyl acrylate, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, heptyl (meth)acrylate, hexyl (meth)acrylate, acrylonitrile, adiponitrile, methacrylonitrile, butadiene, isoprene, and mixtures thereof; or d) reacting the thermoplastic statistical copolymer with an organic acid to esterify the unacrylated hydroxy groups into one or more acrylated polyol monomeric units, optionally wherein the organic acid is formic acid, acetic acid, hexanoic acid, ethanoic acid or propanoic acid .
[0026]
26. Method according to claim 24, characterized in that the C monomer is a radically polymerizable vegetable oil selected from the group consisting of soybean oil, linseed oil, corn oil, linseed oil and rapeseed oil.
[0027]
27. Asphalt composition, characterized by the fact that it comprises: i) an asphalt component; ii) a rubber bran having a weight percentage in the range of 1 to 15%; optionally wherein the rubber bran is a ground tire rubber, optionally comprising particles capable of passing through a 30 mesh screen; and iii) the thermoplastic copolymer as defined in claim 1, the thermoplastic block copolymer as defined in claim 5, or the thermoplastic statistical copolymer as defined in claim 13, as an asphalt additive, modifier, and/or filler having a weight percentage in the range of 0.01 to 1.05%.
[0028]
28. Asphalt composition according to claim 26, characterized in that the weight concentration of thermoplastic copolymer, block copolymer or statistical copolymer in relation to the weight of rubber bran has a range of 2.5% to 6 .5%; and optionally wherein the polyol is glycerol and the average degree of acrylation ranges from 1.001 to 1.25, the thermoplastic copolymer, block copolymer or statistical copolymer has a molecular weight ranging from 50 KDa to 200 KDa, and the concentration by weight of the thermoplastic copolymer in relation to the weight of rubber bran is 4.5%, optionally wherein said asphalt composition has one or more of the following properties: a high temperature degree greater than 78°C, a low temperature degree not greater at -29 °C, a degree range greater than 107 °C, a minimum mixing temperature less than 171 °C and a minimum compaction temperature less than 161 °C; or where the polyol is glycerol and the average degree of acrylation ranges from 1.001 to 1.25, the thermoplastic copolymer, block copolymer or statistical copolymer has a molecular weight ranging from 50 KDa to 200 KDa, and the weight concentration of the thermoplastic copolymer with respect to the weight of rubber bran is 6.5%, optionally wherein said asphalt composition has one or more of the following properties: a high temperature degree greater than 82°C, a low temperature degree not greater at -28.5 °C, a degree range greater than 110 °C, a minimum mixing temperature less than 179 °C, and a minimum compaction temperature less than 168 °C.
[0029]
29. Asphalt composition according to claim 27, characterized in that said asphalt composition is homogeneous and stable for at least 3 days at a temperature of 130 °C to 180 °C.
[0030]
30. Method for the preparation of a homogeneous asphalt composition, characterized in that it comprises: mixing the thermoplastic copolymer as defined in claim 1, the thermoplastic block copolymer as defined in claim 5, or the thermoplastic statistical copolymer as defined in the claim 13, as an asphalt additive, modifier, and/or filler, with a weight percentage in the range of 0.01% to 1.05%, in an asphalt composition comprising i) an asphalt component and ii) a rubber bran having a weight percentage in the range of 1% to 15%, to form a homogeneous asphalt composition; and optionally further comprising: a) wherein the rubber bran is a ground tire rubber, optionally comprising particles capable of passing through a 30 mesh screen; or b) wherein the weight concentration of thermoplastic copolymer, block copolymer or statistical copolymer in relation to the weight of rubber bran ranges from 2.5% to 6.5%; optionally wherein the polyol is glycerol and the average degree of acrylation ranges from 1.001 to about 1.25, the thermoplastic copolymer, block copolymer or statistical copolymer has a molecular weight ranging from 50 KDa to 200 KDa, and the concentration in weight of the thermoplastic copolymer in relation to the weight of the rubber bran is 4.5%, or where the polyol is glycerol and the average degree of acrylation ranges from 1.001 to about 1.25, the thermoplastic copolymer, block copolymer or copolymer statistician has a molecular weight ranging from 50 KDa to 200 KDa, and the concentration in weight of the thermoplastic copolymer in relation to the weight of the rubber bran is 6.5%; or c) wherein said mixing is made at a temperature of 130°C to 180°C; or d) wherein said mixing takes place at a location remote from where the homogeneous asphalt composition is used, and wherein the asphalt composition is homogeneous and stable for at least 3 days at a temperature of 130 °C to 180 ° Ç.
[0031]
31. Method for preparing a fractionation fluid, characterized in that it comprises: mixing the thermoplastic copolymer as defined in claim 1, the thermoplastic block copolymer as defined in claim 5, or the thermoplastic statistical copolymer as defined in claim 13, as a chemical additive, with water, and sand.
[0032]
32. Method for the preparation of an adhesive or sealant composition, characterized in that it comprises: mixing the thermoplastic copolymer as defined in claim 1, the thermoplastic block copolymer as defined in claim 5, or the thermoplastic statistical copolymer as defined in claim 13, with a thickener, and/or a plasticizer, and/or a solvent.

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同族专利:

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MX2016014977A|2017-03-31|

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WO2015179553A3|2016-01-07|

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BR112016026839A2|2017-08-15|

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JP2017522398A|2017-08-10|

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EA201692352A1|2017-04-28|

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BR112016026839A8|2021-05-04|

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KR20170012234A|2017-02-02|

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SG11201609358QA|2016-12-29|

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US20190135971A1|2019-05-09|

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US20150337078A1|2015-11-26|

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US10066051B2|2018-09-04|

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PH12016502144A1|2016-12-19|

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CA2946797A1|2015-11-26|

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