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    公开号:ES2598630T9
    申请号:ES12169704.9T
    申请日:2007-12-11
    公开日:2017-09-12
    发明作者:John M. Brown；Michael A. Smith；Nathan E. Stacy；Carleton E. Stouffer；John D. Wilkey
    申请人:Chevron Phillips Chemical Co LP；
    IPC主号:
    专利说明:

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    DESCRIPTION
    Copolymers in butadiene styrene block for film applications BACKGROUND OF THE INVENTION
    The present invention relates, in general, to the field of block copolymers. More particularly, it refers to conjugated diene-monovinylarene copolymers useful in shrink film applications, especially in mixtures with polystyrene.
    Articles formed from conjugated diene-monovinylarene copolymers, such as styrene-butadiene copolymers, for example K-Resin® (Chevron Phillips Chemical Company LP, The Woodlands, TX), generally have improved physical properties compared to the articles formed from general purpose polystyrenes. However, in the case of articles for which heat shrinkage behavior is important, new conjugated diene-monovinyrene copolymers are necessary to provide the desired shrinkage behavior for this growing market. As an example, typical conjugated diene-monivinilarene copolymers have glass transition temperatures (Tg), which are the main controller of shrinkage behavior, which are typically in the range of 95 ° C to 108 ° C. This relatively high Tg does not have a good reception in the market since a relatively high temperature is required to start the retraction. US5587425 and US20070173605 describe block copolymer compositions based on diene units and monovinyl linkages.
    In addition, polystyrene is usually mixed with conjugated diene copolymers-monivinilarene for a wide variety of reasons, including increasing the stiffness of the film and reducing costs. Articles formed from mixtures of polystyrene and copolymers of conjugated diene-monivinilarene can also be used in applications where retraction behavior is important.
    Therefore, it would be desirable to have butadiene-monivinylrene copolymers with lower Tg and improved heat shrinkage behavior, either alone or mixed with polystyrene.
    SUMMARY OF THE INVENTION
    The present invention relates to a copolymer of conjugated diene-monivinilarene blocks containing a plurality of mixed conjugated diene-monivinilarene blocks, wherein each mixed block contains conjugated diene units and monovinylarene units in a weight ratio of 0, 05 to 0.33.
    In another embodiment, the present invention relates to a composition containing (a) from 50 parts by weight to 95 parts by weight of a copolymer of conjugated diene-monivinilarene blocks comprising a plurality of mixed blocks of conjugated diene-monivinilarene, wherein each mixed block contains conjugated diene units and monovinyrene units in a weight ratio of 0.05 to 0.33; and (b) from 5 parts by weight to 50 parts by weight polystyrene; wherein the copolymer of conjugated diene-monivinilarene blocks and polystyrene make a total of 100 parts by weight.
    In another embodiment, the present invention relates to a wrapping method by retracting an object or a group of objects by wrapping the object or group of objects with a film containing the composition, to provide an object or a group of objects wrapped, and heating the object or group of objects wrapped at a temperature and for a time sufficient to retract the film in at least a first direction, to provide an object or a group of objects wrapped by retraction.
    The copolymer and the composition can be used in the production of shrink films.
    DESCRIPTION OF THE ILLUSTRATIVE EMBODIMENTS
    The present invention relates to a copolymer of conjugated diene-monivinilarene blocks containing a plurality of mixed conjugated diene-monivinilarene blocks, wherein each mixed block contains conjugated diene units and monovinylarene units in a weight ratio of 0, 05 to 0.33. The weight ratio can be defined as phm (parts per cent of monomer, especially the monovinylrene and conjugated diene monomer charged to the polymer during polymerization) of conjugated diene units per phm of monovinylrene units. The amounts of monomers and monomer units expressed herein are normally in terms of parts per cent of monomer (phm) based on the total weight of monovinylarene monomer and conjugated diene monomer charged during polymerization.
    The basic starting materials and the polymerization conditions for preparing monovinylrene / conjugated diene block copolymers are described in US Pat. Nos. 4,091,053; 4,584,346; 4,704,434; 4,704,435; 5,227,419; 5,545,690 and 6,096,828.
    "Conjugated diene," as used herein, refers to an organic compound containing conjugated carbon-carbon double bonds and a total of 4 to 12 carbon atoms, such as 4 to 8 carbon atoms. Exemplary conjugated dienes include butadiene, 2-methyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 2,3-dimethyl-1,3-
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    butadiene, 1,3-pentadiene, 3-butyl-1,3-octadiene and mixtures thereof. In one embodiment, the conjugated diene may be 1,3-butadiene or isoprene. In a further embodiment, the conjugated diene may be 1,3-butadiene. A unit of a polymer, wherein the unit is derived from the polymerization of a conjugated diene monomer, is a "conjugated diene unit."
    "Monovinylarene," as used herein, refers to an organic compound that contains a single carbon-carbon double bond, at least one aromatic moiety and a total of 8 to 18 carbon atoms, such as 8 to 12 atoms. carbon Exemplary monovinylarenes include styrene, alpha-methylstyrene, 2-methylstyrene, 3- methylstyrene, 4-methylstyrene, 2-ethylstyrene, 3-ethylstyrene, 4-ethylstyrene, 4-n-propylstyrene, 4-t-butyl styrene, 2,4-dimethylstyrene , 4-cyclohexylstyrene, 4-decylstyrene, 2-ethyl-4-benzylstyrene, 4- (4-phenyl-n-butyl) styrene, 1-vinylnaphthalene, 2-vinylnaphthalene and mixtures thereof. In one embodiment, the monovinylarene is styrene. A unit of a polymer, where the unit is derived from the polymerization of a monovinylrene monomer, is a "monovinylrene unit."
    In the polymer of the present invention, the conjugated diene-monivinilarene blocks contain conjugated diene units and monovinylarene units. The mixed conjugated diene and monovinylarene blocks may be random or progressive variation. The mixed block is of "progressive variation" when (a) the molar fraction of conjugated diene units in a first section of the block is greater than the molar fraction of conjugated diene units in a second section of the block, where the second section of the block is close to a given end of the block and (b) condition (a) is true for substantially all sections of the block. (Depending on the size of the sections to be considered, the condition (a) may not be true for all sections, but if so, it will not be true to no more than approximately the level expected by chance).
    In one embodiment, each mixed block contains conjugated diene units and monovinyrene units in a weight ratio of 0.06 to 0.28. In another embodiment, each mixed block contains conjugated diene units and monovinyrene units in a weight ratio of 0.08 to 0.26. In another embodiment, each mixed block contains conjugated diene units and monovinyrene units in a weight ratio of 0.05 to 0.09. Without pretending to be limited by the theory, it is believed that having each mixed block content containing the specified weight ratios of conjugated diene units and monovinylarene units provides conjugated diene-monivinylrene copolymers having a glass transition temperature below 100 ° C that are suitable for applications that require heat shrinkage aptitude.
    In one embodiment, the copolymer of conjugated diene-monivinilarene blocks contains at least three mixed blocks of conjugated diene-monivinilarene. In a further embodiment, the copolymer of conjugated diene-monivinilarene blocks contains four or five mixed blocks of conjugated diene-monivinilarene.
    In one embodiment, the copolymer of conjugated diene-monivinilarene blocks contains four consecutive mixed blocks of conjugated diene-monivinilarene. In a further embodiment, the copolymer of conjugated diene-monivinilarene blocks contains five consecutive mixed blocks of conjugated diene-monivinilarene.
    In addition to the plurality of mixed blocks described above, the copolymer of conjugated diene-monivinilarene blocks may additionally contain blocks of monovinylarene units, conjugated diene units, random conjugated diene-monivinilarene, conjugated diene-monivinilarene gradual, conjugated diene-monivinilarene mixed containing more conjugated diene units than a weight ratio of a conjugated diene / monovinylarene of 0.33, and other monomers, either alone, in copolymer blocks, or in combination with monovinylarene units, conjugated diene units, or both .
    In one embodiment, the conjugated diene-monivinilarene block copolymer also contains a proximal conjugated diene block. In this context, "proximal" refers to a position closer to the terminal end of the block copolymer than to the initial end. In one embodiment, the proximal conjugated diene block contains from 5 phm of conjugated diene units to 50 phm of conjugated diene units, relative to the total amount of monovinylarene units and conjugated diene units in the diene block copolymer. conjugate-monivinilarene. In another embodiment, the proximal conjugated diene block contains from 10 phm of conjugated diene units to 35 phm of conjugated diene units. In a further embodiment, the proximal conjugated diene block contains 11 phm of conjugated diene units to 25 phm of conjugated diene units. Without pretending to be limited by the theory, it is believed that having a proximal conjugated diene block containing the specified amount of conjugated diene units provides impact resistance to the conjugated diene copolymer-monivinilarene and mixtures thereof.
    In another embodiment, the conjugated diene-monivinilarene block copolymer also contains a distal monovinylarene block. In this context, "distal" refers to a position closer to the initial end of the block copolymer than to the terminal end. In one embodiment, the distal monovinylarene block contains from 10 phm of monovinylarene units to 40 phm of monovinyrene units, relative to the total amount of monovinylarene units and conjugated diene units in the conjugated diene monolynilarene block copolymer. . In a further embodiment, the distal monovinylarene block contains 15 phm of monovinylarene units to 35 phm of monovinylarene units.
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    In one embodiment, the conjugated diene copolymer-monivinilarene is a block copolymer comprising styrene blocks and butadiene blocks (a "styrene-butadiene block copolymer"). Exemplary styrene-butadiene copolymers are commercially available under the name K-Resin® (Chevron Phillips Chemical Company, Lp, The Woodlands, TX).
    The conjugated diene-monivinilarene copolymer can have any proportion of monovinylarene units and conjugated diene units. In one embodiment, the conjugated diene-monivinylrene copolymer has 50% by weight: 50% by weight of monovinylarene units: conjugated diene units to 90% by weight: 10% by weight of monovinylarene units: conjugated diene units . In one embodiment, the conjugated diene copolymer-monivinilarene has 65% by weight: 35% by weight of monovinylarene units: conjugated diene units to 85% by weight: 15% by weight of monovinylarene units: conjugated diene units .
    The conjugated diene-monivinilarene copolymer may additionally comprise other monomers known in the art by inclusion in conjugated diene-monivinilarene copolymers.
    Generally, each block is formed by the polymerization of the monomer or the mixture of monomers from which the desired units of the block are derived. The polymerization process will be susceptible to a relative loss of change in the process parameters between the different blocks, but the person skilled in the art, who has the benefit of the present disclosure, can make some minor changes in the process parameters between the Different blocks as a matter of routine experimentation. The following descriptions of the polymerization process will generally apply to the formation of all types of blocks in the inventive polymer, although some descriptions may be of greater or lesser value to form one or more of the types of blocks in the inventive polymer.
    The polymerization process can be carried out in a hydrocarbon diluent at any suitable temperature in the range of -100 ° C to 150 ° C, such as from 0 ° C to 150 ° C, and at a pressure to keep the reaction mixture substantially in The liquid phase. In one embodiment, the hydrocarbon diluent may be a linear or cyclic paraffin, or mixtures thereof. Exemplary linear or cyclic paraffins include, but are not limited to, pentane, hexane, octane, cyclopentane, cyclohexane and mixtures thereof, among others. In one embodiment, the paraffin is cyclohexane.
    The polymerization process can be carried out in the substantial absence of oxygen and water, such as in an inert gas atmosphere.
    The polymerization process can be performed in the presence of an initiator. In one embodiment, the initiator can be any organomonoalkali metal compound known for use as an initiator. In a further embodiment, the initiator may have the formula RM, wherein R is an alkyl, cycloalkyl, or aryl radical containing 4 to 8 carbon atoms, such as an n-butyl radical and M is an alkali metal, such as lithium. In a particular embodiment, the initiator is n-butyllithium.
    The amount of initiator used depends on the molecular weight of the desired block or polymer, and is known in the art and is easily determinable, taking due account of the traces of toxic substances in the feed streams.
    An initiator can be charged to the polymerization process one or more than once. When multiple initiator charges are charged in the polymerization process, a particular initiator compound can be used in one, several or all initiator charges. The loading of multiple initiator charges to the polymerization process can modify the modality of the final polymer, as will be discussed below.
    The polymerization process may also involve the use of a randomizer. In one embodiment, the randomizer can be a polar organic compound, such as an ether, a thioether, or a tertiary amine. In another embodiment, the randomizer may be a potassium salt or a sodium salt of an alcohol. The randomizer may be included in the hydrocarbon diluent to improve the effectiveness of the initiator, to randomize at least part of the monovinylrene monomer in a mixed monomer charge, to modify the mixture in a mixed monomer charge or two or more thereof. The inclusion of a randomizer can be of value when a mixed conjugated diene-monivinilarene block of the present polymer is formed. Exemplary randomizers include dimethyl ether, diethyl ether, ethyl methyl ether, ethyl propyl ether, di-n-propyl ether, di-n-octyl ether, anisole, dioxane, 1,2-dimethoxyethane, 1,2-diethoxypropane, dibenzyl ether, diphenyl ether, 1,2-dimethoxybenzene, tetramethylene oxide (tetrahydrofuran or THF), potassium tert-amylate (KTA), dimethyl sulfide, diethyl sulfide, di-n-propyl sulfide, di-n-butyl sulfide , methyl ethyl sulfide, dimethylethylamine, tri-n-ethylamine, tri-n-propylamine, tri-n-butylamine, trimethylamine, triethylamine, tetramethylethylenediamine, tetraethylethylenediamine, N, N-di-methylaniline, N-methyl-N-ethylaniline, N-methylmorpholine and mixtures, among others.
    In one embodiment, the randomizer is tetrahydrofuran. When tetrahydrofuran is used, tetrahydrofuran is generally present in an amount in the range of from 0.01 phm to 1.0 phm, such as from 0.02 phm to 1.0 phm.
    In another embodiment, the randomizer is potassium tert-amylate (KTA). When KTA is used, the KTA is generally present in an amount in the range of from 0.001 phm to 1.0 phm, such as from 0.004 phm to 0.4 phm.
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    When a particular block is formed, each monomer charge or monomer mixture charge can be polymerized under dissolution polymerization conditions such that the polymerization of each monomer charge or each monomer mixture charge, to form the particular block , is substantially completed before a subsequent load is loaded. "Charging," as used herein, refers to the introduction of a compound into a reaction zone, such as the inside of a reactor vessel.
    Without pretending to be linked to any theory, if an initiator is included in a load, a block of new origin will be typically formed or by addition to the end of an unfinished, previously formed block. In addition to not being linked to theory, if an initiator is not included in a load, only one block will be formed typically by adding to the end of an unfinished, previously formed block.
    A coupling agent can be added after the polymerization is complete. Suitable coupling agents include di- or multivinilarene compounds; di- or multiepoxides; di- or multialkoxysilanes; di- or multiisocyanates; di- or multi-mines; di- or multialdehldos; di- or multi-ketones; alkoxystane compounds; multi-halides, such as silicon halides and halosilanes; mono-, di-, or multi-hydride; di- or multi-esters, such as the esters of monoalcohols with polycarboxylic acids; diesters that are esters of monohydric alcohols with dicarboxylic acids; diesters that are esters of monobasic acids with polyalcohols such as glycerol; and mixtures of two or more such compounds, among others.
    Useful multifunctional coupling agents include, but are not limited to, epoxidized vegetable oils such as epoxidized soybean oil, epoxidized flaxseed oil, and mixtures thereof among others. In one embodiment, the coupling agent is epoxidized soybean oil. Epoxidized vegetable oils are commercially available under the Vikoflex® trademark of Arkema Inc. (Philadelphia, PA).
    If the coupling is to be performed, any effective amount of the coupling agent can be used. In one embodiment, a stoichiometric amount of the coupling agent relative to alkali metal-active polymer tends to promote maximum coupling. However, more or less stoichiometric amounts can be used to vary the efficiency of the coupling when desired for particular products.
    After completion of the coupling reaction, if any, the polymerization reaction mixture can be treated with a terminating agent such as water, carbon dioxide, alcohol, phenols, saturated aliphatic mono-dicarboxylic acids, or mixtures thereof. same, to remove the alkali metal from the block copolymer or to control the color.
    After completion, if any, the polymer cement (polymer in the polymerization solvent) normally contains 10 to 40 percent by weight solids, more usually 20 to 35 percent solids. The polymer cement can be subjected to instant evaporation to evaporate a part of the solvent to increase the solids content to a concentration of 50 to 99 percent by weight solids, followed by drying in a vacuum oven, a devolatilization extruder, a stirred film evaporator, or other methods of elimination of the remaining solvent.
    The block copolymer can be recovered and worked in a desired manner, such as extrusion of sheets, extrusion of film by molding, blown film or injection molding. The block copolymer may also contain additives such as antioxidants, anti-blocking agents, release agents, fillers, extenders and dyes.
    In one embodiment, the conjugated diene copolymer-monivinilarene further comprises a rubber modified polystyrene. An exemplary rubber modified polystyrene is a high impact polystyrene (HIPS). A rubber modified polystyrene is a composition comprising any graft copolymer of styrene and rubber. By "graft copolymer" is meant polystyrene produced by polymerization of styrene in the presence of an unsaturated rubber where some amount of free radicals reacts with the polystyrene chains that produce rubber that are covalently bonded to the rubber. During this process the rubber, grafted with polystyrene, is dispersed through the polystyrene in the form of discrete fields. In one embodiment the unsaturated rubber is polybutadiene. A suitable high impact polystyrene is available from Chevron Phillips Chemical Company LP (The Woodlands, TX) with the designation EA8100. Generally, a composition that additionally comprises a rubber modified polystyrene may contain from 0.1 phm of rubber modified polystyrene to 5 phm of rubber modified polystyrene, such as 2 phm of rubber modified polystyrene. The rubber modified polystyrene can be used in some embodiments as an anti-blocking agent.
    In the present invention, the conjugated diene block monolynilarene copolymer can be monomodal, that is, a population of copolymer molecules, it can have a peak in a histogram of the molecular weight distribution of the population, or it can be polymodal, that is, having two or more peaks in a histogram of the molecular weight distribution of the population of copolymer molecules. Without pretending to be linked to theory, the load of multiple initiator charges will tend to provide polymer chains of different lengths and so on! It will tend to have different molecular weights. In addition, and again without pretending to be linked to theorist, the use of an agent of
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    coupling will tend to provide coupled chains formed by coupling different numbers of chains of the same or different length, and thus the coupled chains will tend to have different molecular weights.
    In the present invention, the conjugated diene-monivinylrene copolymer can be coupled or uncoupled, as described above.
    In specific polymerization processes, the typical initiator, mixing sequences of monomer and monomer mixes include, but are not limited to, loading orders selected from the group consisting of iCCiCB-CA, iCCCiCCB-CA, iACCCCB-CA, iAiCCCCB -CA, iAiCCCC-CA, iAiCCCCCB-CA, and iAC- CiCCB-CA, where i is a polymerization initiator charge, A is a monovinylarene charge, B is a conjugated diene charge, C is a monovinylarene charge and conjugated diene, and CA is a coupling agent. In a further realization, the load order is selected from the group consisting of i-C-C-i-C-B- CA, i-C-C-C-i-C-C-B-CA, i-A-C-C-C-C-B-CA, i-A-i-C-C-C-C-B-CA, i-A-i-C-C-C-C-C-B-CA, and i-A-C-C-i-C-C-B-CA.
    In one embodiment, the conjugated diene-monovinylarene block copolymer can be formed into a film or a sheet. A typical extruded sheet can have a thickness of 10 mils (0.254 mm). In a further embodiment, a sheet can be stretched in at least one direction at a temperature of 50 ° C to 100 ° C, such as 90 ° C to form a film having a thickness of 0.5 thousand to 3 thousand (0 , 0127 mm to 0.076 mm) such as 2 mil (0.051 mm). In this embodiment, the film formed from the conjugated diene-monovinylarene block copolymer can have a retraction in at least one direction of at least 40% at 100 ° C. In one embodiment, the film formed from the conjugated diene-monovinylarene block copolymer can have a retraction in at least one direction of at least 60% at 100 ° C, such as at least 70% at 100 ° C, such as from 71% to 76% at 100 ° C. Also, the film formed from the conjugated diene-monovinylarene block copolymer can have a turbidity of less than 10%. In one embodiment, the film formed from the conjugated diene-monovinylarene block copolymer can have a turbidity of less than 6%. Also, the film formed from the conjugated diene-monovinylarene block copolymer can have a natural shrinkage of less than 10% after 7 days. In one embodiment, the film formed from the conjugated diene-monovinylarene block copolymer can have a natural shrinkage of less than 7% after 7 days.
    In another embodiment, the present invention relates to a composition containing (a) from 50 parts by weight to 95 parts by weight of a conjugated diene-monivinilarene block copolymer comprising a plurality of mixed conjugated diene-monivinilarene blocks, wherein each mixed block contains conjugated diene and monovinylarene in a weight ratio of 0.05 to 0.33; and (b) from 5 parts by weight to 50 parts by weight polystyrene; wherein the copolymer of conjugated diene-monivinilarene blocks and polystyrene make a total of 100 parts by weight.
    The block copolymer can be as described above. As used herein, "polystyrene" or "PS" refers to any homopolymer containing styrene units and does not include HIPS as described above. Suitable polystyrenes are available from Chevron Phillips Chemical Company LP (The Woodlands, TX) with the designations D4049, EA3400, eA3710, MC3200 and MC3600.
    In one embodiment, the composition contains from 70 parts by weight to 95 parts by weight of the conjugated diene-monivinilarene block copolymer and from 5 parts by weight to 30 parts by weight of polystyrene.
    In one embodiment, the composition may further comprise a rubber modified polystyrene as described above. The rubber modified polystyrene can be used in some embodiments as an anti-blocking agent.
    In one embodiment, the composition can be shaped into a film or a sheet. A typical extruded sheet can have a thickness of 10 mils (0.254 mm). In a further embodiment, a sheet can be stretched in at least one direction at a temperature of 50 ° C to 100 ° C, such as 90 ° C to form a film having a thickness of 0.5 thousand to 3 thousand (0 , 0127 mm to 0.076 mm) such as 2 mil (0.051 mm). In this embodiment, the film formed from the composition may have a retraction in at least one direction of at least 40% at 100 ° C. Also, the film formed from the composition may have a turbidity of less than 10%. Also, the film formed from the composition may have a natural shrinkage of less than 5% after 7 days.
    The film or sheet can be produced by any technique known in the technique of monolayers and coextrusion. Such techniques include extrusion of films by molding, extrusion of film by blowing and extrusion of sheets; either as a single extruded layer or a plurality of coextruded layers. Generally, the film can be produced by film casting or extrusion film techniques. For example, the film can be produced using conventional extrusion techniques such as a coextruded molding film. In coextrusion, two or more polymers are extruded simultaneously through a nozzle. Two or more extruders are used simultaneously to feed the nozzle. In this process, various polymer melts are introduced into the nozzle under laminar flow conditions in such a way that there is no intermingling, but the union occurs at the interface between the layers of the film.
    In a molded film extrusion process, the molten material of an extruder flows through a flat nozzle directly onto a molding roller, which cools in molten material. Generally, the processes of
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    Molded film produces films with an average thickness of 10 mils (0.254 mm) or less, however the process can be used to produce films with thickness greater than 20 mils (0.51 mm). In one embodiment, the orientation in the film can be introduced before winding it over the final drum. In another embodiment, the film can be wound on a rolling mill and the orientation can be introduced into the film by passing the film through a separate orientation process line.
    In a sheet extrusion process, the molten material of an extruder flows through a flat nozzle to form a sheet that is passed through a set of cold rollers. The fried roller assembly typically consists of at least three cooled rollers. Typically, the sheet process differs from the molded film process in that the sheet produced is between 5 mils (0.127 mm) and 20 mils (0.51 mm) thick. This thickness allows the resulting sheet to be oriented both in the transverse direction and in the machining direction.
    In a blown film extrusion process, while the extrusion process above the nozzle is similar to the molding process, the nozzle and arc below are different. In the blown film process, the nozzle is annular (circular) and typically the polymer exits in an upward direction. This produces a cylindrical tube, which can then be closed (collapsed) at the top between drag rollers, resulting in a flattened tube. Subsequently, the film tube can be reheated, re-inflated, and stretched to introduce orientation in the transverse direction and in the machine direction. This tube can then be cut and then rolled into one or more film rolls. This is often referred to as a double bubble blown film process.
    Generally, the film has a machining direction, which is parallel to the direction in which the polymer leaves the nozzle, and a transverse direction that is perpendicular to the machining direction.
    The preparation of retractable films requires the introduction of orientation in the polymer film by any technique known in the art. Without pretending to be linked to any theory, it is widely believed that the orientation process introduces and fixes tension in the film which is then recovered as retraction when the film is subsequently heated. The orientation can be introduced in a stage or series of stages immediately after the production of the sheet or the initial film (i.e., in line) or as a separate post-processing stage or stages (i.e., out of line) that may occur at a later date. The orientation can be entered in at least one direction. One technique for entering the orientation is the use of a widening structure, generally used to introduce orientation in the transverse direction, often referred to as a TDO machine. The widening structure achieves this by pushing the film in the transverse direction using a series of clips mounted on a chain that traps the edges of the film. The chain clips stretch the film in the transverse direction, due to the mounting of the film on divergent chain glues, while the film is heated in a long oven. An alternative orientation technique is the use of a series of temperature-controlled rollers, generally used to introduce orientation in the machining direction, often referred to as an MDO machine. The roller series introduces orientation by having one or more intermediate pairs of these rollers rotating at different speeds. The film is stretched in the direction of the machine in the space between the pairs of rollers. In some cases it may be desirable to introduce orientation in both directions. Both techniques can be used in combination to produce a film oriented both in the machining direction and in the transverse direction. The production of the oriented film through molded film extrusion or sheet extrusion techniques, together with a TDO machine and, optionally, an MDO machine, is often referred to as a tensioning and molding process.
    In another embodiment, a shrink label of the present invention may be formed from a film containing (a) from 50 parts by weight to 95 parts by weight of a conjugated diene-monivinilarene block copolymer comprising a plurality of blocks mixed conjugated diene-monivinilarene, wherein each mixed block contains conjugated diene units and monovinyrene units in a weight ratio of 0.05 to 0.33; and optionally (b) from 5 parts by weight to 50 parts by weight polystyrene; wherein the copolymer of conjugated diene-monivinilarene blocks and polystyrene total 100 parts by weight, to provide a shrink label.
    A shrink label is a shrink film having a length, width and thickness, where the length and width are each at least an order of magnitude greater than the thickness and at least one of the length or width will decrease after Exposure to heat. The term "shrink label" encompasses such part of the film before, during, or after exposure to heat and decreases in length or width. Prior to exposure to heat, the shrink label may be referred to as a "non-retractable shrink label. "Although it is also a shrink label according to the definition given above. The length and width of the shrink label are not critical; the thickness can be any suitable thickness, such as 0.1 mil (0.00254 mm) to 10 mil ( 0.254 mm).
    The shrink label can have a cylindrical structure. When the shrink label has a cylindrical structure, the term shrink sleeve can be applied.
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    Any geometry of the shrink label is contemplated, in terms of size, shape, number of faces, radius or the like, and will be a matter of routine experimentation for the person skilled in the art who has the benefit of the present description.
    Generally, a retractable tag oriented on the TD can be referred to as a "sleeve tag". In one embodiment, the sleeve tag can be printed and cut in the MD direction. Solvent bonding can be used to form a seam parallel to the TD and obtain a sleeve. The sleeve can be applied from the top of a container, resulting in the direction TD of the film around the circumference of the container. Materials that constitute a sleeve tag can be chosen to have a desirable degree of retraction.
    Generally, a retractable label oriented in the MD can be referred to as a "roller-fed" label. A roller-fed label can be fed in the machining direction from a roller in a labeling machine. The labeling machine can wrap the roller-fed label around a container, cut the roller-fed label, and solvent-join the roller-fed label, with the MD direction of the film around the circumference of the container.
    In another embodiment, the present invention relates to a wrapping method by retraction of an object or a group of objects by wrapping the object or group of objects with a film containing (a) 50 parts by weight to 95 parts in weight of a copolymer of conjugated diene-monivinilarene blocks comprising a plurality of mixed conjugated diene-monivinilarene blocks, wherein each mixed block contains conjugated diene and monovinylarene in a weight ratio of 0.05 to 0.33; and optionally (b) from 5 parts by weight to 50 parts by weight polystyrene; wherein the copolymer of conjugated diene-monivinilarene blocks and polystyrene total 100 parts by weight, to provide a wrapped object or group of objects, and heat the object or group of wrapped objects at a temperature and for a time to retract the film in at least a first address, to provide an object or group of objects wrapped by retraction.
    The film can be as described above. In one embodiment, the film has a greater retraction in a first direction than in a second direction. If it is oriented in one direction, the first direction may be the machining direction or the transverse direction. The second direction would then be the other one of the machining direction or the transverse direction.
    In another embodiment, the film has a substantially similar retraction in both a first direction and a second direction. ("Substantially similar retraction" in this embodiment means that the ratio of the retraction in the first direction to the retraction in the second direction is 0.5 to 2).
    Any object or group of objects for which the envelope is desired can be used in this method. In one embodiment, the object or group of objects is a group of bottles, cans, or other discrete objects, optionally contained in a tray.
    In the wrapping stage, the film may be arranged in a suitable manner around the object or group of objects. For example, if the object or group of objects defines a cuboid, the film may be arranged around the object or group of objects such that it makes contact with at least two pairs of parallel faces, such as two or three pairs of parallel faces. . The disposition address can be chosen as a routine matter for the person skilled in the art who has the benefit of the present description, depending on the objects, the structure of the film, and the desired structure of the object or group of objects wrapped by retraction. .
    The result of the wrapping stage is an object or group of wrapped objects.
    After wrapping, the object or group of wrapped objects can be heated to a temperature and for a time to retract the film. Temperature and duration are a matter of routine experimentation for the person skilled in the art who has the benefit of the present description. The retraction proceeds typically until the film has retracted in at least the first direction and, if the film has a similar retraction in the second direction, also the second direction, to make contact with the object or group of objects.
    The following examples are included to demonstrate preferred embodiments of the invention. It should be appreciated by those skilled in the art that the techniques described in the examples below represent techniques discovered by the inventor to function well in the practice of the invention and therefore may be considered preferred modes of practice.
    EXAMPLES
    Materials:
    Cyclohexane was dried on activated alumina and stored under nitrogen. The n-butyllithium ("Li") initiator was received at approximately 15% by weight in cyclohexane and diluted with cyclohexane to approximately 2% by weight. Tetrahydrofunan (THF) is stored on activated alumina under nitrogen. Styrene and butadiene were purified on activated alumina. Epoxidized soybean oil was used as received. Reagent quantities are expressed
    5
    10
    fifteen
    twenty
    25
    30
    usually in parts per cent of monomer (phm) based on the total weight of monovinylarene and conjugated diene used.
    Example 1
    Polymer Recipe A - X
    The polymerizations were carried out in a 2 gallon stainless steel reactor (7.57 l). The reactor was equipped with a jacket for temperature control, a double screw screw impeller and baffles. Generally, each block is formed by the polymerization of the monomer or the mixture of monomers from which the desired units of the block are derived.
    Cyclohexane is initially charged to the reactor, followed by THF (0.10 PHM). The temperature is adjusted to approximately 60 ° C and the initiator is charged, followed by the first monomer charge. After the polymerization is completed, a sample of the first polymerization block in isopropanol with nitrogen bubbling is coagulated, filtered, dried and analyzed by Gel Permeation Chromatograph. Continuous polymerization by sequential loading of monomers and / or initiators as desired. The coupling agent is charged and reacted at approximately 100 ° C for approximately 15 minutes. The polymer was recovered by evaporation with solvents and pelletized with a spindle extruder.
    Polymer recipes Y - OO
    Y-OO styrene / butadiene mixed block copolymers were prepared using sequential solution polymerization under nitrogen. The polymerization processes were carried out in a stirred reactor of 100 gallon (378.5 l) carbon steel with internal cooling coils and essentially anhydrous reagents and conditions were employed.
    The cyclohexane was initially charged to the reactor, followed by THF. The temperature was set at 60 ° C and the initiator was charged, followed by the first charge. The lines were purged with approximately 0.5 kg of cyclohexane after each load. Polymerization was allowed to continue until complete after each monomer charge or monomer mixture. The polymerization temperature ranged from about 38 ° C to about 120 ° C and the pressure ranged from about 2 psig (13789.5 Pa) to about 60 psig (413685.4 Pa). The total weight of the monomer was approximately 90 kg. After completion of the sequential polymerizations, a coupling agent is charged to the reactor. The coupling agent was reacted at approximately 100 ° C for approximately 15 minutes. After the coupling was completed, the reaction was terminated by adding CO2 and approximately 0.2 phm of water.
    Table 1 shows the sequence of charges and a partial characterization of each polymer. All quantities of the loaded materials are given in phm. Blank cells indicate that no material was charged or that a value was not determined. The abbreviations in the table are as follows: THF, tetrahydrofuran; i, n-butyllithium initiator; S, styrene; B, butadiene; CA, coupling agent (Vikoflex 7170, epoxidized soybean oil, Arkema, Inc.).
     Table 1
     #Ex.  THF ii So l2 (B1 / Si) (B2 / S2) (B3 / S3) i3 (B 4 / S4) (B5 / S5) Bs CA1 CA2 Fusion flow
     TO  0.10 0.08 2.01 17.00 2.01 17.00 2.01 17.00 0.080 0.60 10.8 0.6 10.8 20.10 0.40 40.0
     B  0.10 0.08 2.01 15.66 2.01 15.66 2.01 15.66 0.080 0.60 10.4 0.6 10.4 25.00 0.40 23.0
     C  0.04 0.08 1.33 17.00 1.33 17.00 1.33 17.00 0.080 0.40 10.8 0.4 10.8 22.60 0.14 0.27 17.0
     D  0.04 0.08 0.67 17.00 0.67 17.00 0.67 17.00 0.080 0.20 10.8 0.2 10.8 25.00 0.14 0.27 11.0
     AND  0.10 0.08 1.33 17.00 1.33 17.00 1.33 17.00 0.080 0.40 10.8 0.4 10.8 22.60 0.14 0.27 15.9
     F  0.04 0.08 1.60 38.40 0.54 12.46 0.080 0.90 21.1 25.00 0.14 0.27 14.6
     G  0.10 0.08 0.67 26.50 0.67 26.50 0.080 0.55 22 23.12 0.14 0.27 14.2
     H  0.04 0.095 20 2.1 12 2.1 12 2.1 12 2.1 12 2.1 12 9.5 0.25 8.7
     I  0.10 0.100 20 1.7 13.75 1.7 13.75 1.7 13.75 1.7 13.75 18.2 0.28 5.3
     J  0.10 0.090 25 1.7 13.75 1.7 13.75 1.7 13.75 1.7 13.75 13.2 0.28 8.6
     K  0.10 0.085 25 2.1 13.75 2.1 13.75 2.1 13.75 2.1 13.75 11.6 0.28 8.7
     L  0.10 0.100 20 2.1 13.75 2.1 13.75 2.1 13.75 2.1 13.75 16.6 0.28 6.7
     M  0.10 0.105 25 1.6 12.5 1.6 12.5 1.6 12.5 1.6 12.5 18.6 0.28 6.47
     N  0.10 0.115 25 1.9 12.5 1.9 12.5 1.9 12.5 1.9 12.5 17.4 0.28 7.3
     0  0.10 0.115 30 1.4 11.25 1.4 11.25 1.4 11.25 1.4 11.25 19.4 0.28 9
     P  0.10 0.100 30 1.7 11.25 1.7 11.25 1.7 11.25 1.7 11.25 18.2 0.28 11
     Q  0.10 0.090 30 2 11.25 2 11.25 2 11.25 2 11.25 17 0.28 9.5
     R  0.10 0.115 30 2.3 11.25 2.3 11.25 2.3 11.25 2.3 11.25 15.8 0.28 12
     S  0.10 0.085 30 2.8 11.25 2.8 11.25 2.8 11.25 2.8 11.25 13.8 0.28 8.6
     T  0.04 0.066 32 0.025 1.89 13.5 1.89 13.5 10.11 9 9.11 9 0.4 5.2
     OR  0.04 0.065 32 0.025 1.62 13.5 1.62 13.5 10.38 9 9.38 9 0.4 5.7
     V  0.04 0.065 32 0.025 1.62 13.5 2.15 13.5 10.12 9 9.11 9 0.4 6.5
     w  0.04 0.065 32 0.023 2.15 13.5 2.15 13.5 9.9 9 8.8 9 0.4 6.1
     X  0.04 0.065 32 0.022 2.15 13.5 1.62 13.5 10.12 9 9.11 9 0.4 4.5
     Y  0.10 0.0844 2.00 17.00 2.00 17.00 2.00 17.00 0.077 1.27 10.80 1.27 10.80 18.86 0.10 0.30 15.1
     z  0.10 0.085 2.00 17.00 2.00 17.00 2.00 17.00 0.040 1.27 10.80 1.27 10.80 18.86 0.20 0.20 12.8
     AA  0.10 0.085 2.00 17.00 2.00 17.00 2.00 17.00 0.038 1.27 10.80 1.27 10.80 18.86 0.40 14.4
     Table 1
     # Ex.  THF h So l2 (B1 / Si) (B 2 / S2) (B3 / Ss) i3 (B 4 / S4) (Bs / S5) Bs CA1 CA2 Fusion flow
     BB  0.10 0.085 1.70 17.00 1.70 17.00 1.70 17.00 0.040 1.09 10.80 1.09 10.80 20.10 0.10 0.30 11.9
     DC  0.10 0.085 1.36 17.00 1.36 17.00 1.36 17.00 0.040 0.79 10.80 0.79 10.80 22.60 0.10 0.30 10.5
     DD  0.10 0.085 2.00 17.00 2.00 17.00 2.00 17.00 0.035 1.27 10.80 1.27 10.80 18.86 0.40 8.8
     EE  0.10 0.080 1.00 17.00 1.00 17.00 1.00 17.00 0.062 0.65 10.80 0.65 10.80 23.00 0.10 0.30 11.5
     FF  0.10 0.085 1.19 17.00 1.19 17.00 1.19 17.00 0.060 0.76 10.80 0.76 10.00 22.30 0.40 11
     GG  0.10 0.085 1.28 17.00 1.28 17.00 1.28 17.00 0.060 0.81 10.80 0.81 10.00 21.90 0.40 11.8
     H H  0.10 0.085 1.36 17.00 1.36 17.00 1.36 17.00 0.060 0.86 10.80 0.86 10.00 21.60 0.40 13.3
     II  0.10 0.077 1.36 17.00 1.36 17.00 1.36 17.00 0.044 0.86 10.80 0.86 10.00 21.60 0.40 12.6
     JJ  0.10 0.077 17.00 1.36 17.00 1.36 17.00 0.044 0.86 10.80 0.86 10.00 22.96 0.40 11.4
     Kk  0.04 0.085 20 1.88 15 1.88 15 1.88 15 1.88 15 12.5 0.23 6.4
     LL  0.10 0.083 20 2.1 13.75 2.1 13.75 2.1 13.75 2.1 13.75 16.6 0.28 7.8
     MM  0.10 0.087 30 2.3 11.25 2.3 11.25 2.3 11.25 2.3 11.25 15.6 0.28 8.5
     NN  0.04 0.053 32 0.022 2.15 13.5 2.15 13.5 9.9 9 8.8 9 0.4 8.4
     00  0.04 0.055 32 0.022 1.89 13.5 1.89 13.5 10.11 9 9.11 9 0.4 8.1
    Example 2
    A) Shrink films A - S:
    In Table 2, pelletized products were extruded into sheets of approximately 8 "width (20.3 cm) and approximately 10 thousand thickness (0.254 mm) (thickness on a Davis Standard 150S extruder equipped with a 5-line Killion sheet. Plates of approximately 12 cm x approximately 12 cm were punched out from sheet samples of approximately 10 thousand (0.254 mm) to serve as film samples Using a biaxial orientation machine manufactured by Bruckner Maschinenbau, the films were uniaxially stretched normally in the transverse direction to the extrusion direction at the lowest temperature necessary to reach a 5: 1 extension. This temperature appears in Table 2 in the column labeled "Stretch T." The 10-sheet samples were stretched at a constant rate of approximately 3 cm / s
    B) Y-KK shrink films:
    In Table 2, the pelletized products were extruded into sheets of approximately 10 "wide (25.4 cm) and approximately 10 thousand (0.254 mm) thick on a Killion sheet extruder and line. The laminators were then fed to a Marshall & Williams Plastics widening structure and stretched uniaxially in the transverse direction at the lowest temperature that allowed an extension of approximately 5: 1.
    Representative physical properties of shrink films are given in Table 2, which include turbidity, retraction in the transverse direction (TD) at the given temperature (° C), retraction in the machining direction (MD) at the given temperature ( ° C), and natural retraction. Blank cells indicate that a value has not been determined. The heat shrinkage was determined by immersion of the oriented films in an oil bath at a temperature for approximately 30 seconds, after which the heat shrinkage was calculated. Natural retraction was determined by placing the oriented films in an oven set at approximately 40 ° C for the given number of days. Turbidity was measured as% turbidity using a Haze-Gard® Plus instrument from BYK-Gardner USA (Columbia, MD). The measurements were made in accordance with the operating instructions of this instrument.
     TD Retraction MD Retraction Natural Retraction
     Ex.  Stretching T Turbidity 60 70 80 90 100 120 60 70 80 90 100 120 1 2 3 7 14
     TO  65 6.3 4.9 30.0 56.3 70.8 72.2 74.9 0.0 -1.0 -2.2 -1.3 10.5 11.5
     B  65 12.7 6.2 37.0 54.5 68.6 72.1 71.1 0.0 -6.3 -2.9 -3.5 0.5 5.3
     C  80 9.4 0.5 9.9 35.0 68.6 69.6 75.4 0.0 -0.7 -4.0 -5.8 6.5 6.7
     D  95 5.1 0.0 0.0 2.7 13.0 39.2 66.2 0.0 0.0 -0.3 0.0 -1.8 17.0
     AND  80 10.9 0.0 4.3 23.3 48.5 65.5 75.3 0.0 0.0 -1.7 -2.3 -6.8 7.8
     F  90 9.5 0.0 0.7 7.3 22.3 42.8 69.7 0.0 0.0 0.0 -0.7 -1.3 16.2
     G  105 9.7 0.0 0.0 0.0 2.8 20.5 66.7 0.0 0.0 0.0 0.0 -2.0 -5.8
     H  70 10.6 15.0 40.0 68.0 73.0 75.0 77.0 0.0 -3.0 -8.0 -8.0 -7.0 2.0
     one  70 6.16 7.5 35.0 59.2 73.3 75.0 75.0 0.0 -0.8 -5.0 -1.7 4.2 12.5
     J  75 2.35 0.0 5.0 22.5 69.2 75.8 77.5 0.0 0.0 0.8 -5.0 -0.8 1.7
     K  80 7.33 0.0 7.5 39.2 71.7 75.8 77.5 0.0 0.0 0.0 -10.8 -8.3 -6.7
     L  70 2.56 8.3 34.2 65.8 75.0 75.0 76.7 -0.8 -1.7 -8.3 9.2 0.0 10.0
     M  75 0.86 0.0 9.2 38.3 61.7 75.0 77.5 0.0 0.0 -0.8 -4.2 -3.3 0.0
     N  70 2.48 1.7 16.7 45.0 70.0 75.8 75.8 0.0 0.0 4.2 -3.3 -0.8 5.8
     0  70 3.14 0.0 25.0 51.7 71.7 74.2 75.0 0.0 -1.7 -5.0 -4.2 -3.3 1.7
     P  70 1.97 3.3 28.3 55.0 71.7 74.2 75.0 0.0 -1.7 -3.3 -5.8 -4.2 0.8
     Q  70 0.75 3.3 15.8 49.2 72.5 75.0 77.5 0.0 0.0 -3.3 -7.5 -5.0 -4.2
     R  70 2.33 1.7 26.7 57.5 73.3 75.0 75.8 0.0 -1.7 -7.5 -9.2 -5.8 2.5
     S  70 4.79 9.2 41.7 58.3 69.2 72.5 74.2 0.0 -1.7 -9.2 -0.8 -1.7 11.7
     Y  70 5.9 12.0 60.0 70.0 73.0 75.0 77.0 0 3.0 10.0 25.0 18.0 32
     Z  60 4.7 25.0 50.0 67.0 73.0 73.0 75.0 0 2.0 5.0 12.0 22.0 28
     AA  60 5.3 30.0 52.0 65.0 70.0 73.0 75.0 5 2.0 7.0 17.0 12.0 18
     BB  70 4.3 13.0 38.0 65.0 72.0 73.0 75.0 0 2.0 3.0 10.0 15.0 23
     DC  75 3.0 7.0 23.0 50.0 70.0 73.0 75.0 0 3.0 7.0 18.0 22.0 32 8.66 10.2 11.4 13.78 15, 35
     DD  65 5.7 26.7 54.2 68.3 72.5 75.0 75.0 0 1.7 5.0 14.2 19.2 27.5 20.63 25.3 27.7 32.61
     EE  95 3.6 0.0 1.7 14.2 42.5 65.8 75.8 0 0.0 3.3 8.3 22.5 40.8 1.77 2.4 2.8 3.73
     FF  85 3.35 0.0 19.2 39.2 60.0 70.0 75.0 0 0.0 3.3 7.5 19.2 36.7 8.5
     GG  85 3.57 0.8 9.2 37.5 65.0 74.2 75.0 0 0.8 2.5 2.5 14.2 20.8 7.7
     H H  85 4.03 3.3 19.2 45.8 67.5 74.2 75.0 0 0.0 1.7 4.2 16.7 25.8 11.4
     TD Retraction MD Retraction Natural Retraction
     Kk  85 1.5 0.0 14.2 38.3 58.3 74.2 79.2 0.0 0.8 6.7 13.3 25.8 35.8 3.7 4.5 4.9 6 , 9 7.5
    Example 3
    Shrink films containing Polymer and Polystyrene
    Shrink films (nominal thickness approximately 2 mil, 0.51 mm) were obtained from the I-OO polymers, mixed with approximately 0% by weight or approximately 20% by weight polystyrene and 5 approximately 0% by weight or approximately 2 % by weight of high impact polystyrene (HIPS) as an anti-blocking agent. The polystyrene used was EA3710 and the HIPS used was EA8100, both available from Chevron Phillips Chemical Company LP, The Woodlands, TX. Retractable I-X films were prepared and tested using the same methods used for the unmixed resins described in Example 2A). DD-OO shrink films were prepared and tested using the same methods used for the unmixed resins described in Example 2B).
     TD Retraction MD Retraction Natural Retraction
     # Ex.  % by weight S% HIPS Stretch T Turbidity 60 70 80 90 100 120 60 70 80 90 100 120 1 2 3 7 14
     one  20 0 95 1.51 0.0 0.0 12.5 35.0 58.3 70.8 0.0 0.0 -0.8 -4.2 -5.0 13.3
     J  20 0 95 1.07 0.0 0.0 5.0 17.5 50.0 75.0 0.0 0.0 0.0 1.7 0.0 -1.7
     K  20 0 90 3.02 0.0 0.0 8.3 31.7 63.3 75.0 0.0 0.0 0.0 0.0 -7.5 -2.5
     L  20 0 85 2.54 0.0 9.2 37.5 61.7 69.2 75.0 0.0 0.0 -3.3 -9.2 -5.0 -4.2
     M  20 0 100 0.92 0.0 0.0 0.0 14.2 40.8 70.8 0.0 0.0 0.0 2.5 -0.8 0.0
     N  20 0 95 1.21 0.0 0.8 4.2 26.7 49.2 72.5 0.0 0.0 0.0 0.0 -5.0 8.3
     0  20 0 100 1.13 0.0 0.0 2.5 15.8 46.7 70.8 0.0 0.0 0.0 0.8 -5.0 -7.5
     P  20 0 95 2.73 0.0 0.0 5.0 27.5 56.7 74.2 0.0 0.0 0.0 0.0 -8.3 -5.8
     Q  20 0 95 3.19 0.0 1.7 11.7 35.8 46.7 71.7 0.0 0.8 0.0 -4.2 -4.2 -7.5
     R  20 0 85 2.44 0.0 5.0 17.5 47.5 61.7 75.0 0.0 0.0 0.0 -4.2 -4.2 -2.5
     S  20 0 85 6.6 0.0 5.8 29.2 55.0 60.8 72.5 0.0 0.0 -0.8 -4.2 -4.2 0.0
     T  20 0 75 4.51 2.5 18.3 40.0 60.0 70.0 74.2 0.0 0.0 -3.3 -5.0 -5.0 0.0
     OR  20 0 90 5.5 0.8 7.5 20.0 41.7 60.8 72.5 0.0 0.0 -1.7 -4.2 -4.2 -2.5
     V  20 0 90 3.58 0.0 5.0 20.0 36.7 64.2 70.0 0.0 0.0 -0.8 -2.5 -5.0 -3.3
     w  20 0 75 4.01 3.3 15.8 37.5 55.0 70.8 75.0 0.0 0.0 -0.8 -3.3 -3.3 0.0
     X  20 0 90 5.54 1.7 5.8 21.7 40.0 56.7 74.2 0.0 0.0 0.0 -2.5 -3.3 -0.8
     DD  20 2 75 33.6 10 25.8 45 63.3 72.5 75 0 0 0 -2.5 0 10 12.55 15.69 17.65 20.98
     EE  20 2 100 12.4 0 0 8.3 39.2 57.5 74.2 0 0 0 0 6.7 25.8 0.98 1.18 1.38 1.96
     FF  20 2 90 15.9 0 7.5 26.7 50.8 68.3 75.8 0 0 2.5 2.5 -1.7 9.2 7.23
     GG  20 2 95 18.8 0 9.2 25.8 48.3 66.7 73.3 0 0 0 0.8 2.5 30.8 5.7
     H H  20 2 95 24.3 0 7.5 25.8 50 69.2 74.2 0 0 0.8 0.8 0.8 17.5 6.08
     II  0 2 85 3.2 0 5.0 33.0 54.0 68.0 75.0 3.0 22.0 4.0
     JJ  0 2 88 2.2 0 3 27 47 66 75 5 23 3
     JJ  20 2 99 10.1 0.0 2.0 9.0 20.0 48.0 73.0 2.0 11.0 2.0
     Kk  20 2 90 7.2 0.0 6.7 25.0 47.5 68.3 75.8 0.0 0.0 3.3 5.0 8.3 23.3 2.4 2.9 3, 1 4.5 5.1
     LL  20 2 91 8 0.0 13.0 24.0 56.0 71.0 77.0 3.0 3.0 3.0
     MM  20 2 85 7.6 0.0 14.0 38.0 66.0 72.0 78.0 0.0 0.0 6.0
     NN  20 2 77 8.3 12.0 28.0 50.0 68.0 73.0 75.0 -2.0 1.0 19.0
     00  20 2 74 4.7 4.0 15.0 35.0 48.0 63.0 73.0 -1.0 9.0 13.0
    All compositions described and claimed herein can be obtained and executed without undue experimentation in view of the present description.
    权利要求:
    Claims (13)
    [1]
    5
    10
    fifteen
    twenty
    25
    30
    35
    40
    Four. Five
    1. A copolymer of conjugated diene-monivinilarene blocks, comprising:
    a proximal conjugated diene block comprising from 5 phm units of conjugated diene to 50 phm units of conjugated diene; Y
    a plurality of mixed conjugated diene-monivinilarene blocks, wherein each mixed conjugated diene-monivinilarene block contains conjugated diene units and monovinylarene units with a weight ratio of conjugated diene units to monovinylarene units of 0.05 to 0 , 33;
    wherein the block copolymer is formed through a load order selected from the group consisting of iC-CiCB-CA, iCCCiCCB-CA, iACCCCB-CA, iAiCCCCB-CA, iAiCCCCCB-CA, and iACCiCCB-CA, where i is a polymerization initiator charge, A is a monovinylarene charge, B is a conjugated diene charge, C is a monovinylarene and conjugated diene charge and CA is a coupling agent;
    [2]
    2. The conjugated diene-monivinylrene block copolymer of claim 1, wherein the weight ratio of conjugated diene units to monovinylrene units within each mixed block is 0.06 to 0.28
    [3]
    3. The conjugated diene-monivinylrene block copolymer of claim 1, wherein the weight ratio of conjugated diene units to monovinylrene units within each mixed block is 0.08 to 0.26.
    [4]
    4. The conjugated diene-monivinylrene block copolymer of claim 1, wherein the block copolymer comprises at least three mixed blocks of conjugated diene-monivinilarene, or wherein the block copolymer comprises at least four consecutive mixed blocks of diene conjugate-monivinilarene.
    [5]
    5. The conjugated diene-monivinylrene block copolymer of claim 1, further comprising a distal monovinylarene block containing from 10 phm units of monovinylarene to 40 phm units of monovinylarene.
    [6]
    6. The conjugated diene-monivinilarene block copolymer of claim 1, in the form of a film having a thickness of 0.5 thousand to 3 thousand (13-75 pm) and which has been oriented at approximately 90 ° C , wherein the block copolymer has a retraction of at least 40% at about 100 ° C and a natural retraction of less than 10% after 7 days; or in the form of a film that is 0.5 thousand to 3 thousand (13-75 pm) thick and has been oriented at approximately 90 ° C, where the block copolymer has a turbidity of less than 10%.
    [7]
    7. A composition, comprising a conjugated diene-monivinylrene block copolymer of claim 1 and a rubber modified polystyrene.
    [8]
    8. A composition, comprising:
    (a) from 50 parts by weight to 95 parts by weight of a conjugated diene-monovinylarene block copolymer according to any one of claims 1 to 6; Y
    (b) from 5 parts by weight to 50 parts by weight of a polystyrene; wherein the conjugated diene block monolynilarene copolymer and polystyrene make a total of 100 parts by weight.
    [9]
    9. The composition of claim 8, comprising from 70 parts by weight to 95 parts by weight of the conjugated diene-monovinylarene block copolymer and from 5 parts by weight to 30 parts by weight of the polystyrene.
    [10]
    10. The composition of claim 8, in the form of a film having a thickness of 0.5 thousand to 3 thousand (13-75 pm) and which has been oriented at approximately 90 ° C, wherein the composition has a retraction at least 40% at about 100 ° C and a natural shrinkage of less than 5% after 7 days; or in the form of a film that is 0.5 thousand to 3 thousand (13-75 pm) thick and has been oriented at approximately 90 ° C, where the composition has a turbidity of less than 10%.
    [11]
    11. The composition of claim 8, which further comprises a rubber modified polystyrene.
    [12]
    12. A wrapping method by retraction of an object or a group of objects, comprising:
    wrapping the object or group of objects with a film comprising (a) from 50 parts by weight to 95 parts by weight of a copolymer of conjugated diene-monivinilarene blocks comprising a proximal conjugated diene block containing 5 phm units of conjugated diene at 50 phm conjugated diene units; and a plurality of mixed conjugated diene-monivinilarene blocks, wherein each mixed block contains conjugated diene units and
    monovinyrene units in a weight ratio of 0.05 to 0.33; and (b) from 5 parts by weight to 50 parts by weight of a polystyrene; wherein the copolymer of conjugated diene-monivinilarene blocks and polystyrene total 100 parts by weight, to provide an object or a group of wrapped objects, and
    heating the object or group of objects wrapped at a temperature and for a time sufficient to retract film 5 in at least a first direction, to provide an object or group of objects wrapped by retraction;
    wherein the block copolymer is formed through a load order selected from the group consisting of iC-CiCB-CA, iCCCiCCB-CA, iACCCCB-CA, iAiCCCCB-CA, iAiCCCCCB-CA, and iACCiCCB-CA, where i is a polymerization initiator charge, A is a monovinylarene charge, B is a conjugated diene charge, C is a monovinylarene and conjugated diene charge and CA is a coupling agent;
    10 13. A retractable film, comprising:
    a copolymer of conjugated diene-monivinilarene blocks according to any one of claims 1-5 or 7, or a composition according to any one of claims 8, 9 or 11, the film having a thickness of 0.5 thousand to 3 thousand ( 13-75 pm) and having been oriented at approximately 90 ° C, where the film has a retraction of at least 40% at approximately 100 ° C, a turbidity of less than 10%, and a natural retraction of less than 6% 15 after 3 days;
    [14]
    14. The shrink film of claim 13, formed in a shrink label.
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    同族专利:
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    US609159|2006-12-11|
    US11/609,159|US8415429B2|2006-12-11|2006-12-11|Styrene butadiene block copolymers for film applications|
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