COMPOSITE MATERIAL AND PROCESS FOR MANUFACTURING A COMPOSITE MATERIAL

专利摘要:
polymeric composition, composite material, and, process for making a polymeric composition or composite material. a polymeric composition comprising at least one covalently cross-linked siloxanyl polymer agglomerate which is further cross-linked by a boron compound, wherein the boron concentration is in the range of 0.005 to 0.160% by weight.
公开号:BR112015027755B1
申请号:R112015027755-1
申请日:2014-05-02
公开日:2022-02-01
发明作者:Jonas Modell；Staffan Thuresson；Krister Thuresson
申请人:Delta Of Sweden Ab；
IPC主号:

专利说明:

Field of Invention
[001] The present invention relates to silicon-containing polymeric compositions characterized by low boron content. These compositions have the properties of a class of substance described as, for example, a bouncing clay, bouncing clay, or modeling clay. The invention further relates to a composite material comprising the polymeric silicon-containing composition and further comprising a particulate or granular material in amounts ranging from small additions, to additions such that the particulate or granular material forms the vast majority by volume of the composite material. . The invention also relates to methods for producing silicon-containing polymeric compositions and composite materials. Materials comprising or consisting of the compositions of the invention are also provided. Fundamentals
[002] Polydimethylsiloxane-based materials with hydroxyl termination cross-linked through a boron-containing compound have wide use and can be found in various patents and patent applications. Applications for these materials range from the automotive industry, for example, as resonance absorbers, through therapeutic and rehabilitation uses, to uses as toys for children. They are also used in homes and by hobbyists to remove dirt from various surfaces and as a masking means when spray painting.
[003] US 2,541,851 represents early work in the field and describes the use of various boron compounds, including pyroboric acid, boric anhydride, boric acid, borax, and hydrolyzed esters of boric acid to form a solid, elastic product with a dimethyl silicon compound having two hydrolysable groups which have been hydrolyzed. Another material is described in US 5,607,993 which discloses a bouncing clay. The bouncing clay contains a proportion of particles having a filler function in order to reduce the density of the clay product. Another known material is described in WO 2008/020800 A1 which discloses a particulate or granular material with a silicone-based binder which is arranged as a coating on the particles or grains.
[004] However, it has recently been concluded that compounds containing boron may have an adverse effect on the health of humans. These compounds are therefore now classified as toxic for reproduction in the European Union, and the following boron-containing compounds have been added to the European Chemicals Agency (ECHA) candidate list: Diboron trioxide (CAS: 1303-86-2); Disodium tetraboron heptoxide, hydrate (CAS: 12267-73-1); Boric acid (CAS: 10043-35-3, 11113-50-1); Disodium tetraborate, anhydrous (CAS: 1303-96-4, 1330-43-4, 12179-04-3).
[005] If a substance on this list is present in a product in a concentration greater than 0.1% by weight then that product will be subject to certain restrictions and the supplier will have obligations regarding its safe use. Since some of the substances in the product may be difficult to analyze by common analytical techniques, it is useful to recalculate the limitation in terms of corresponding amounts of boron. An elemental analysis of boron content is generally simple to perform.
[006] 0.1% by weight diboron trioxide (CAS: 1303-86-2); disodium tetraboron heptaoxide, hydrate (CAS: 12267-73-1); Boric acid (CAS: 10043-35-3, 11113-50-1); Disodium tetraborate, anhydrous (CAS: 130396-4, 1330-43-4, 12179-04-3) corresponds to 0.031% by weight; 0.020% by weight; 0.017% by weight; 0.021 wt% boron, respectively.
[007] Also, following the European Toy Safety Directive (2009/48/EC), boron is not allowed above 0.03% by weight in certain product classes and not above 0.12% in weight in other product classes. Altogether, recalculated for boron, the most stringent limitation (boric acid) corresponds to 0.017 wt% boron.
[008] These limitations greatly hamper the use of hydroxy-terminated polydimethylsiloxane-based materials cross-linked through boron-containing compounds in many applications, and preclude their use in other applications since boron levels are too high. For example, US 2,541,851 claims a boron compound working range of between 5-25% by weight based on the weight of the polymeric dimethylsiloxane and US 3,177,176 claims 1-10% by weight.
[009] Thus, it is of great concern to find a silicon-containing composition having a boron content that can meet the regulations, ie, be below the stipulated amounts, while maintaining the necessary properties of the compounds currently used in the art.
[0010] Various ways of manufacturing the composite materials of the art, all of which are characterized by having a boron content outside the scope of the new regulations, are known to the expert. Often, the process involves “cooking” the mixture for several hours. During the cooking operation, a blanket of nitrogen is spread over the mixture to prevent volatiles from burning or exploding. However, retention of the volatile compounds can result in a product that cannot demonstrate the necessary physical properties, for example, having inadequate strength and/or rebound ability.
[0011] US 4,371,493 describes a process based on dimethyl silicone gum that is claimed to result in low rejection frequency. However, this process also requires heating to 150-260 °C for several hours, and the addition of boron compound in the range of 4-15% by weight, which is above the amounts granted by the new European regulations.
[0012] US 3,177,176 describes that it is preferred to first mix all components in a low viscosity state, followed by an increase in temperature to between 90-250°C until there is a sudden and substantial increase in viscosity. The working range of boron compounds is between 1-10% by weight, which is again clearly above the amounts allowed by the new European regulations.
[0013] US2012/0329896 discloses a process comprising adding low levels of a boron-containing crosslinking agent to a polyorganosiloxane to form a borosilicon compound, crosslinking the resulting composition with a siloxane crosslinking agent, and curing the resulting mixture to form a viscoelastic silicone rubber composition approx. However, described compositions have a permanent equilibrium shape, meaning they will return to an equilibrium shape after being deformed. In addition, the curing time for these compositions is a period of several days.
[0014] Another general disadvantage with previously known manufacturing processes is the excessive heating and prolonged reaction time that is required before the reaction is complete. It would be a substantial advantage if the viscosity increase could be initiated in a controlled and convenient manner. It would also be desirable for the viscosity increase to start soon after the start of the process and without excessive heating. Summary of the Invention
[0015] The present invention relates to the development of new polymeric compositions, composite materials comprising said compositions, and methods for their preparation and uses.
[0016] Viewed from a first aspect, the invention thus provides a polymeric composition comprising at least one covalently cross-linked siloxanyl polymer agglomerate which is further cross-linked by a boron compound, wherein the boron concentration is in the range of 0.005-0.160% in weight. Preferably, the agglomerate, prior to crosslinking with boron, may comprise, on average, more than one hydroxyl moiety per molecule, preferably at least two. The average molecular weight between branch points within the cluster preferably can be in the range of 480 kD, more preferably 8-40 kD.
[0017] In one embodiment, applicable to all aspects of the invention, the agglomerate, before further crosslinking with boron, may comprise hydroxyl fractions at a concentration equivalent to 1-100 μmol [OH] per g of the agglomerate, preferably 5- 50 μmol [OH] per g of agglomerate. Preferably, the agglomerate, prior to boron crosslinking, may comprise hydroxyl fractions at an average concentration corresponding to 10-1000 kD of agglomerated polymer per hydroxyl fraction.
[0018] Preferably, said polymer agglomerate may comprise at least one covalently cross-linked linear or branched siloxanyl polymer. Preferably, said siloxanil polymers, prior to covalent cross-linking, may comprise on average more than one hydroxyl fraction per molecule, preferably at least two, as well as at least three.
[0019] In one embodiment, the polymer agglomerate may have a shear viscosity of between 10 and 2000 Pas at 23°C, preferably between 50 and 1000 Pas, all measured at a shear rate of 10 s-1. In another embodiment, the polymer agglomerate may have a shear modulus (G'') greater than its modulus of elasticity (G') over a range of shear rates from 1 Hz to 10 Hz, preferably over an entire range from 0.1 Hz to 30 Hz (at 23°C).
[0020] In one embodiment, applicable to all aspects of the invention, the siloxanil polymer, prior to covalent cross-linking to form said agglomerate, may comprise hydroxyl fractions at a concentration equivalent to 20-2000 μmol [OH] per g of polymer , and/or may comprise hydroxyl moieties at an average concentration corresponding to 0.5-50 kD of polymer per hydroxyl moiety.
[0021] In a preferred embodiment, applicable to all aspects of the invention, the polymer agglomerate may comprise at least one siloxanyl polymer covalently cross-linked with at least one siloxy-containing compound.
[0022] It is preferred that before covalent cross-linking the siloxanyl polymer has the structure: 123 45 678 (R )(R )(R )Si[OSi(R )(R )]NOSi(R )(R )(R ) in that N is an integer and preferably is in the range of 30-1000, more preferably 40-650, especially about 50 to about 500; and wherein each of R1-R8 may be the same or different and is independently selected from the group consisting of hydrogen, methyl, ethyl, propyl, butyl, phenyl, vinyl and hydroxyl, preferably hydrogen, methyl, vinyl and hydroxyl, especially methyl and hydroxyl; and wherein at least one of R1-R8 is hydroxyl, preferably at least two. More preferably at least one of R1 , R2 , R3 , R6 , R7 and R8 is hydroxyl. In a preferred embodiment, applicable to all aspects of the invention, at least one of R1, R2 and R3, and at least one of R6, R7 and R8 are hydroxyl.
[0023] For example, said siloxanyl polymer may be selected from the group consisting of polydiphenylsiloxane, polydibutylsiloxane, polydipropylsiloxane, polydibutylsiloxane, polydiethylsiloxane, polydimethylsiloxane, and hydroxy-functionalized compounds thereof, preferably the group consisting of polydimethylsiloxane and hydroxy-functionalized compounds of the same. It is preferred that the hydroxy-functionalized compounds comprise at least one terminal hydroxyl group.
[0024] Preferably, the siloxy-containing compound may be selected from the group consisting of polymers acetoxysilanes, oxymosilanes, alkoxysilanes, isopropenoxysilanes, amidosilanes, aminosilanes, aminooxysilanes and siloxanyl functionalized with at least one of these groups, preferably the group consisting of acetoxysilanes, alkoxysilanes , acetoxy-functionalized polymers and alkoxy-functionalized siloxanyl polymers. More preferably said siloxy-containing compound is selected from the group consisting of tetraacetoxysilane, triacetoxy methylsilane, triacetoxy ethylsilane, tetraethyl silicate, acetoxy-functionalized polydimethylsiloxane and alkoxy-functionalized polydimethylsiloxane.
[0025] It is preferred that the boron compound is selected from triethyl borate, diboron trioxide, disodium tetraboron heptoxide, disodium tetraborate and boric acid.
[0026] Preferably the compositions of the invention have a boron concentration that is less than 0.12% by weight, preferably less than 0.03% by weight, more preferably less than 0.017% by weight. For example, in the range 0.005-0.11% by weight, preferably 0.010-0.016% by weight.
[0027] In one aspect, the compositions of the invention may comprise at least two siloxanyl polymers, each of which is covalently cross-linked with at least one siloxy-containing compound. The siloxy-containing compounds may be independently selected for each siloxanil polymer and may be the same or different.
[0028] It is preferred that, in all aspects and embodiments, the compositions of the invention have a Shore hardness on the Shore OO scale in the range of 20 to 80, preferably 20 to 75, more preferably 20 to 60.
[0029] Preferably the compositions of the invention, in all aspects and embodiments, skip. For example, a formed 0.4 g ball bounces to a height of at least 20 cm when dropped from a height of 2 m onto a flat glass surface.
[0030] Viewed from another aspect, the invention further provides a composite material, comprising the polymeric composition of the invention. Preferably, the composite materials of the invention may comprise at least 2% by volume of the polymeric composition according to the invention, preferably 2-99% by volume.
[0031] In a preferred embodiment applicable to all aspects of the invention, the composite material may further comprise at least 1% by volume, for example 1-98% by volume of a particulate or granular material.
[0032] In one embodiment, the composite material may comprise at least 80% by volume of said particulate or granular material, for example 80-98% by volume, preferably 88-95% by volume.
[0033] In a further embodiment, which is equally preferred, the composite material may comprise less than 80% by volume of the particulate or granular material, preferably less than 75% by volume, more preferably less than 50% by volume. For example 174% by volume, preferably 5-49% by volume, for example 10-40% by volume.
[0034] Preferably, in all embodiments, the particulate or granular material has an average particle size in the range of 0.020.5 mm, preferably 0.05-0.25 mm, such as 0.075-0.15 mm.
[0035] It is preferred that the particulate or granular material be selected from the group consisting of borosilicate glass granules, sand, ground marble, polymer grains or balls, cenospheres, plastic, ceramic or glass microspheres, or mixtures of these materials.
[0036] In all embodiments, the polymeric composition or composite material of the invention may further comprise at least one additive selected from the group consisting of softeners, plasticizers, lubricants, pigments and dyes. Additives such as polyglycol or oleic acid can also be added.
[0037] Preferably these additives may be present in total in a maximum of 10% by weight by weight of the polymeric composition or by weight of the composite material.
[0038] Viewed from another aspect, the invention provides a bouncing dough or modeling clay comprising the polymeric composition or composite material according to the invention.
[0039] Viewed from another aspect, the invention provides a process for manufacturing the polymeric compositions and composite materials of the invention.
[0040] In one aspect, the invention provides a process for manufacturing a polymeric composition or composite material, comprising the steps of: (i) reacting at least one siloxanyl polymer with a siloxy-containing crosslinking agent to form covalent crosslinks; (ii) reacting the covalently cross-linked polymer with a boron compound; and optionally (iii) adding a particulate material.
[0041] In another aspect, the invention provides a process for manufacturing a composite material, said process comprising the steps of: a. reacting at least one siloxanil polymer with a siloxy-containing crosslinking agent to form covalent crosslinks; B. adding a borosilicate particulate material; and c. adjust the pH of the mixture.
[0042] The pH adjustment of the mixture can be carried out using an acid, preferably selected from carboxylic acids and HCl, more preferably HCl.
[0043] In a preferred embodiment applicable to all aspects of the invention, step (i) may be carried out at a temperature in the range of 20200°C, preferably 20-150°C, for example 130°C, more preferably at range of 20-100°C, for example 60-90°C. Preferably, step (i) may have a reaction duration in the range of 5 minutes to 5 hours, more preferably approximately 15-90 minutes, for example 30-60 minutes.
[0044] Preferably, step (i) may be a condensation reaction completed before all hydroxyl moieties are consumed.
[0045] In a preferred embodiment applicable to all aspects of the invention, the ratio of siloxy-containing crosslinking agent to siloxanil polymer in step (i) may be a molar ratio in the range of 0.7:1 to 1.30:1, preferably 0.8:1 to 1.2:1, such as 0.9:1 to 1.1:1, especially approximately 1:1. Preferably said siloxy-containing cross-linking agent may be trifunctional and/or said siloxanyl polymer may be end-capped with OH.
[0046] Preferably the siloxanil polymer, before step (i) comprises on average more than one hydroxyl fraction per molecule, preferably at least two.
[0047] Alternatively, or in addition, the siloxanyl polymer may preferably comprise at least one hydrolysable group per molecule. Preferably such hydrolysable groups can be hydrolyzed after step (i), preferably under acid hydrolysis conditions. Usually suitable hydrolysable groups can be selected from amide groups and ester groups.
[0048] Preferably, step (ii) may be carried out at a temperature in the range of 5-200°C, preferably 10-150°C, more preferably in the range of 20-80°C, for example about 50°C Ç. Preferably, step (ii) has a reaction duration in the range of 5 seconds to 1 hour, preferably approximately 30 seconds to 10 minutes, for example 1-5 minutes.
[0049] Preferably, the processes of the invention provide polymeric compositions and/or composite materials having a boron concentration in the range of 0.005-0.160% by weight.
[0050] It is preferred that the particulate material forms 1-98% by volume of the composite material product produced by the processes of the invention.
[0051] In one embodiment, the composite material may comprise at least 80% by volume of the particulate or granular material, for example 80-98% by volume, preferably 88-95% by volume.
[0052] In another embodiment, which is equally preferred, the composite material produced may comprise less than 80% by volume of the particulate or granular material, preferably less than 75% by volume, more preferably less than 50% by volume. For example 174% by volume, preferably 5-49% by volume, for example 10-40% by volume.
[0053] The processes of the invention can provide polymeric compositions and/or composite materials according to the invention, having the characteristics disclosed and described herein.
[0054] Viewed from another aspect, the invention provides a polymeric composition or composite materials obtainable by the processes of the invention.
[0055] Viewed from yet another aspect, the invention provides the use of covalent cross-linking for the reduction of boron content in a polymeric composition or composite materials, preferably a polymeric composition or composite material as defined herein.
[0056] In another aspect, the invention provides the use of a covalently cross-linked siloxanyl polymer in the provision of a polymeric composition or composite material having reduced boron content, preferably wherein said polymer, polymeric composition and composite material are as defined herein. Said compositions and/or composite materials preferably have properties as described herein, for example in relation to bounce and/or viscosity. Detailed Description of the Invention
[0057] Aspects and embodiments of the invention are described and defined in detail below. Where preferred embodiments or aspects of the invention are described, these are disclosed individually and in combination with any other preferred embodiments and/or aspects of the invention. For example, if components A, B, C and D are disclosed as the components of a composition, and preferred embodiments thereof A1, B1, C1 and D1 are also disclosed, then compositions comprising any and all combinations and permutations of A , B, C, D, A1, B1, C1 and D1 are also disclosed. crosslinks
[0058] Crosslinking is used in synthetic polymer chemistry to refer to the “linking of polymer chains”. The extent of cross-linking and specifics of the cross-linking agents may vary. In the present invention, there are two different types of crosslinks required.
[0059] For the class of materials known as bouncing clays, modeling clays or bouncing putties, there is a known type of crosslinks that normally form between hydroxyl fractions attached to the various siloxane-based arrangements and boron compounds such as boric acid. . These crosslinks are essential to achieve the physical properties required for this class of materials. For example, the ability to exhibit elastic properties on short timescales but flow under gravity on longer timescales. This type of crosslinking is referred to herein as being non-permanent or dynamic about. Such crosslinks can form at "crosslink points", normally provided by hydroxyl moieties in the polymer chains.
[0060] Dynamic crosslinks are normally formed between a boron compound and the hydroxyl groups of the siloxanyl polymer.
[0061] The other type of crosslinking relevant to the present invention is characterized by being covalent. Such crosslinks are referred to as covalent crosslinks or permanent crosslinks. This type of crosslinking, for example, is the result of a condensation reaction between polydimethylsiloxane (PDMS) based structures comprising hydroxyl moieties, and crosslinking agents exemplified by acetoxysilanes and alkoxysilanes.
[0062] Traditionally a bouncy mass is based on hydroxy-terminated PDMS cross-linked through boric acid, ie, containing dynamic cross-links through boron. Linear and branched PDMS can be used, as for example in US 2,431,878. Without being bound by theory, it is believed that the essential properties of these materials depend on the dynamic character of boron-based crosslinks. These act as permanent bonds on a short timescale, but on a longer timescale they allow materials to have liquid properties and to flow under stress because the crosslinks can be reformed. Dynamic cross-linking by boric acid, therefore, allows materials to simultaneously be strongly cohesive, self-repair, and in part have fluid-like properties, and therefore flow under gravity. As indicated by the name, these materials have elastic properties on a shorter time scale and bounce when dropped on a hard surface. As discussed above, however, the boron content of known materials of this type is higher than that allowed by new European regulations.
[0063] In theory, various ways to reduce the boron content of materials known in the art can be presented. For example: i) Reduce the amount of boron-containing compound. However, as shown in Example 1, simply reducing the boron content within existing compositions simply results in loss of necessary properties before the boron-containing substance content is low enough to meet regulatory standards. ii) Decrease the number of cross-linking points needed to increase the length of the PDMS chain between terminating hydroxyl groups, for example by choosing a hydroxy-terminated PDMS with a higher molecular weight as the starting material. In theory, this would decrease the amount of boron-containing substance needed because the number of cross-linking points depends on the concentration of hydroxyl groups attached to the PDMS chains. Again, however, the material loses its desired properties before the boron content is sufficiently low, as demonstrated in example 2. iii) Increase the total weight of the material by adding inactive filler. However, again the material loses the necessary properties before the boron-containing substance content is low enough. See Example 3, for example.
[0064] The present inventors have surprisingly found that it is possible to provide a material with a significantly reduced boron content while maintaining the desired physical properties. Thus, a siloxanil polymer agglomerate comprising covalent crosslinks, further crosslinked with boron to provide dynamic crosslinks, in accordance with the present invention, can meet regulatory requirements and maintain the desired properties.
[0065] The covalent cross-links introduced into the siloxanil polymer agglomerate do not have the dynamic properties that characterize cross-links between boron and hydroxyl fractions, for example, cross-links between boric acid and hydroxy-terminated PDMS.
[0066] Without being bound by theory, it is believed that the covalently cross-linked siloxanyl crosslinked polymer cluster comprises a partially covalently linked network, where the remaining hydroxyl groups form a functional part of the covalently linked network. The remaining hydroxyl groups are therefore at least partially accessible for traditional cross-linking and dynamic cross-linking through a boron-containing substance. Siloxanil polymer agglomerate
[0067] Agglomerates of siloxanil polymer (also referred to as "agglomerate" or "polymer agglomerate" herein) suitable in the polymeric compositions of the invention can be obtained by a variety of methods. For example, agglomerates can be formed by the reaction of the primary units of silicones (polysiloxanes). Silicones are oligomeric or polymeric compounds in which silicon atoms are bonded through oxygen and in which silicon atoms have one or more organic substituents. The silicone structure therefore comprises alternating Si-O-Si bonds. The diversity of molecular structures in silicone chemistry is derived from the many different ways in which the various structural units can be combined.
[0068] Structural units are designated M (monofunctional structural unit at the end of the chain), D (linear difunctional structural unit within the chain), T (trifunctional structural unit with three-dimensional branching) and Q (tetrafunctional structural unit with four-dimensional branching) . Siliones or polysiloxanes composed of D units (difunctional structural fractions) can be linear or cyclic, while combinations of T and Q units can produce densely branched network structures. Branched polysiloxanes may comprise a combination of M, D and T units.
[0069] Typically, siloxanyl polymer agglomerates suitable in the polymeric compositions of the invention can be formed by covalent cross-linking of siloxanyl polymers (polysiloxanes). Crosslinking with a siloxy-containing compound via condensation reaction, radical crosslinking, and Pt-catalyzed reactions between vinyl-containing siloxanyl polymers are examples of typical methods for obtaining suitable covalently crosslinked siloxanyl polymer agglomerates.
[0070] US 2,568,672, for example, discloses peroxide-induced free radical cross-linking. Peroxides can be vinyl specific (DTBP, DTBPH, DCB) or non-specific (TBB, DBP, DCLBP). The former react with vinyl groups, while the latter also attack methyl groups.
[0071] Other examples of suitable covalent crosslinking methods include: - Addition-cure (or hydrosilylation), which normally can be based on a Pt-catalyzed reaction between alkenyl polysiloxanes and Si-H oligosiloxanes (crosslinkers) - Example 8 here based on similar dehydrocondensation where hydrogen gas is released when SiH is reacted with Si-OH; - Condensation-cure, as used in many of the examples here; - Sulfur vulcanization of polysiloxanes rich in vinyl groups; - Radiation-induced healing; - Photoinitiated curing, which needs chromophore groups within the polysiloxane or an initiator that can be photoinitiated.
[0072] Covalently cross-linked siloxanyl polymer agglomerates can be supplied by one or more of addition-cure, condensation-cure, vulcanization, radiation-induced curing and/or photoinitiated curing. Preferably, condensation-cure and/or addition-cure can be used to prepare the siloxanil polymer agglomerates.
[0073] The covalently cross-linked siloxanyl polymer agglomerates according to the invention contain at least one branch point. A branch point is defined herein as the junction of siloxanyl polymer chains or branches, i.e. the point at which at least three chains or branches are joined, preferably by covalent cross-linking. For example, a siloxanil polymer agglomerate may comprise on average at least two branch points, such as 310 branch points, for example 4, 5 or 6 branch points.
[0074] Typical siloxanil polymer agglomerates may have average molecular weight between branch points within said agglomerate in the range of 4-80 kD, for example a range of 15-60 kD. A range of 5-50 kD, such as 8-40 kD, may be preferred.
[0075] Agglomerates of siloxanil polymer according to the invention may comprise, on average, more than one hydroxyl fraction per agglomerate, preferably at least two hydroxyl fractions per agglomerate. For example, suitable agglomerates may comprise at least three hydroxyl moieties.
[0076] In one embodiment, applicable to all aspects of the invention, the polymer agglomerate, before further crosslinking with boron, may comprise hydroxyl fractions at a concentration equivalent to 1-100 μmol [OH] per g of agglomerate, preferably 5-50 μmol [OH] per g of agglomerate.
[0077] Preferably, the agglomerate, prior to crosslinking with boron, may comprise hydroxyl fractions at an average concentration corresponding to 10-1000 kD of agglomerated polymer per hydroxyl fraction. For example, 50-500 kD of polymer agglomerate per hydroxyl fraction. siloxanil polymer
[0078] Preferably, said polymer agglomerate may comprise at least one linear or branched siloxanyl polymer. Preferably, said siloxanil polymers, prior to crosslinking to form said agglomerate, may comprise on average more than one hydroxyl fraction per molecule, preferably at least two, at least three.
[0079] In one embodiment, applicable to all aspects of the invention, the siloxanil polymer, prior to crosslinking to form said agglomerate, may comprise hydroxyl fractions at a concentration equivalent to 20-2000 μmol [OH] per g of polymer, and/or may comprise hydroxyl moieties at an average concentration corresponding to 0.5-50 kD of the polymer per hydroxyl moiety.
[0080] Preferably, the concentration of hydroxyl fractions can be in the range of 22-500 μmol [OH] per g of polymer, for example, 25-250 μmol [OH] per g of polymer, and/or hydroxyl fractions in an average concentration corresponding to 2-45 kD of polymer per hydroxyl fraction, eg 4-40 kD of polymer per hydroxyl fraction.
[0081] Preferably, suitable siloxanyl polymers may have a number average molecular weight (MN) in the range of 2 kD to 100 kD. More preferably, MN can be in the range of 3 kD to 50 kD, for example, 4 kD to 40 kD, preferably 10-25 kD, such as about 15-20 kD.
[0082] Suitable siloxanyl polymers, prior to crosslinking, may normally have a viscosity in the range of 0.025-20 Pas at 20°C (25-20000 cP), preferably 0.100-18 Pas at 20°C (100-18000 cP).
[0083] Prior to cross-linking, suitable polymers normally comprise on average more than one hydroxyl fraction per molecule, preferably at least two hydroxyl fractions per molecule. Suitable polymers may be end capped with -OH moieties and/or may comprise non-terminal -OH groups.
[0084] Preferably, a suitable linear siloxanyl polymer, prior to crosslinking, may have the structure: 123 45 678 (R )(R )(R )Si[OSi(R )(R )]NOSi(R )(R )( R) wherein N is an integer and preferably is in the range of 30-1000, and wherein each of R1-R8 may be the same or different and is independently selected from the group consisting of hydrogen, methyl, ethyl, propyl, butyl, phenyl, vinyl, trifluoropropyl and hydroxyl, wherein at least one of R1-R8 is hydroxyl.
[0085] A typical branched siloxanyl polymer, before crosslinking, may have the formula: 1 2 3 4 5 4' 5' 6 7 8 (R )(R )(R )Si[OSi(R )(R )]NX [OSi(R )(R )]XOSi(R )(R )(R ) where N is an integer and preferably is in the range of 30-1000 and X is an integer and is preferably in the range of 1-20 . Units of formula [OSi(R4')(R5')] may be adjacent in the polymer backbone and/or may be interspersed with units of formula [OSi(R4)(R5)]. Preferably, that each unit [OSi(R4')(R5')] is separated by at least one unit [OSi(R4)(R5)], more preferably by 1-500 units [OSi(R4)(R5)], for example, 1-50 units [OSi(R')(R5)]. Each of R1-R8 may be the same or different and is independently selected from the group consisting of hydrogen, methyl, ethyl, propyl, butyl, phenyl, vinyl, trifluoropropyl and hydroxyl. At least one of R1-R8 is hydroxyl. At least one of R4' and R5' is a polymer chain, the other being selected from the group consisting of hydrogen, methyl, ethyl, propyl, butyl, phenyl, vinyl, trifluoropropyl and hydroxyl, preferably hydrogen and methyl. Preferably, at least one of R4' and R5' is a polymer chain with a repeating unit of the formula [OSi(R4)(R5)] where R4 and R5 are as previously defined.
[0086] In one embodiment, applicable to all aspects of the invention, the branched siloxanyl polymer, prior to crosslinking, may have the formula: 1 2 3 4 5 4' 5' 6 7 8 (R )(R )(R ) Si{[OSi(R )(R )]P[OSi(R )(R )]}QOSi(R )(R )(R ) where Q is an integer and preferably is in the range 1-20, and P has a mean value equal to [(30-1000)/Q]. Each of R1-R8 may be the same or different and is independently selected from the group consisting of hydrogen, methyl, ethyl, propyl, butyl, phenyl, vinyl, trifluoropropyl and hydroxyl. At least one of R1-R8 is hydroxyl. At least one of R4' and R5' is a polymer chain, the other being selected from the group consisting of hydrogen, methyl, ethyl, propyl, butyl, phenyl, vinyl, trifluoropropyl and hydroxyl, preferably hydrogen and methyl. Preferably, at least one of R4' and R5' is a polymer chain with a repeating unit of the formula [OSi(R4)(R5)] where R4 and R5 are as previously defined.
[0087] It is preferred that N is in the range of 40-650, especially about 50 to about 500.
[0088] For branched siloxanyl polymers, it is preferred that X can be in the range of 5-10.
[0089] It is preferred that each of R1-R8 may be independently selected from the group consisting of hydrogen, methyl, vinyl and hydroxyl, preferably methyl and hydroxyl. At least one of R1-R8 is hydroxyl, preferably at least two.
[0090] In a preferred embodiment, applicable to all aspects of the invention, R4 and R5 are methyl.
[0091] Preferably at least one of R1, R2, R3, R6, R7 and R8 is hydroxyl.
[0092] In a preferred embodiment applicable to all aspects of the invention, at least one of R1, R2 and R3, and/or at least one of R6, R7 and R8 is hydroxyl.
[0093] Preferably said siloxanyl polymer may be selected from the group consisting of polydiphenylsiloxane, polydibutylsiloxane, polydipropylsiloxane, polydibutylsiloxane, polydiethylsiloxane, polydimethylsiloxane, and hydroxy-functionalized compounds thereof, preferably the group consisting of polydimethylsiloxane and hydroxy-functionalized compounds thereof .
[0094] In a preferred embodiment applicable to all aspects of the invention, the siloxanyl polymer may be linear or branched polydimethylsiloxane comprising at least one terminal hydroxyl group, and/or at least one hydroxyl side group. For example, at least one of R1, R2 and R3, and/or at least one of R6, R7 and R8 is hydroxyl, and additionally at least one of R4 and R5 is hydroxyl.
[0095] Any siloxanil-based molecular arrangement characterized by having hydroxyl functionality, which is at least partially accessible for cross-linking through a boron-containing substance, can be functional to produce the compositions of the invention. In a preferred embodiment applicable to all aspects of the invention, the siloxanyl polymer is a linear PDMS terminated with at least one hydroxyl group.
[0096] Alternatively or additionally, the functional groups may be hydrolysable groups which are hydrolyzed prior to cross-linking through a boron-containing substance. Preferably, the siloxanyl polymer covalently cross-linked with the siloxy-containing compound comprises at least one hydrolysable group in place of or in addition to at least one hydroxyl group.
[0097] The properties of the polymeric composition can be influenced by the characteristics of the siloxanil polymer that is used as a raw material. For example, a hydroxyl-terminated siloxanyl polymer having short chains or a high level of hydroxyl substituents relative to alkyl substituents can result in a relatively hard and cohesive or sometimes brittle end product. A long chain hydroxyl-terminated siloxanyl polymer, or a siloxanyl polymer having a low level of hydroxyl substituents relative to alkyl substituents, can result in a relatively soft and sometimes sticky end product.
[0098] In an embodiment applicable to all aspects of the invention, a mixture of long-chain and short-chain siloxanyl polymers can be used. For example, at least one polymer where N is in the range of 300-500, in combination with at least one polymer where N is in the range of 30-150.
[0099] Alternatively or additionally, in an equally preferred embodiment, applicable to all aspects of the invention, a mixture of intermediate chain polymers may be used, such as at least two polymers having N values in the range of 150-300. For example, at least one polymer where N is in the range 170-230, in combination with at least one polymer where N is in the range 230-290, such as a polymer where N is approximately 200 and another where N is approximately 270.
[00100] The polymeric composition of the invention may comprise at least two siloxanyl polymers as defined above, each of which is covalently cross-linked with at least one siloxy-containing compound. The siloxy-containing compounds may be independently selected for each siloxanil polymer and may be the same or different. Preferably, the polymeric composition may comprise a mixture of long-chain and short-chain siloxanyl polymers, for example at least one long-chain and at least one short-chain siloxanyl polymer. Alternatively or additionally, and equally preferably, the polymeric composition may comprise or further comprise a mixture of intermediate chain siloxanyl polymers. Compounds containing siloxy
[00101] Various siloxy-containing compounds that give covalent cross-links can be used. The siloxy-containing compound must be capable of forming covalent cross-links, as defined herein, with the siloxanil polymer. Siloxy-containing compounds are also referred to herein as siloxy-containing cross-linking agents.
[00102] A preferred combination of siloxanyl polymer and siloxy-containing compound is characterized by having the ability to form at least partial networks, or branched structures with hydroxyl functionality, rather than combinations that can only form linear polysiloxane structures having hydroxyl ends.
[00103] In a preferred embodiment applicable to all aspects of the invention, the siloxy-containing compound may be trifunctional or tetrafunctional.
[00104] Suitable siloxy-containing compounds acting as covalent cross-linking agents can be exemplified by low molecular weight siloxy-containing compounds (acetoxysilanes and alkoxysilanes such as; tetraacetoxysilane, triacetoxy methylsilane; triacetoxy ethylsilane, or tetraethyl silicate), or by molecular weight siloxy-containing compounds higher (such as a PDMS with acetoxy or alkoxy functional groups).
[00105] Preferably, the siloxy-containing compound is selected from the group consisting of acetoxysilanes, alkoxysilanes, acetoxy functionalized siloxanyl polymers and alkoxy functionalized siloxanyl polymers.
[00106] More preferably, the siloxy-containing compound is selected from the group consisting of tetraacetoxysilane, triacetoxy methylsilane, triacetoxy ethylsilane, tetraethyl silicate, acetoxy-functionalized polydimethylsilane and alkoxy-functionalized polydimethylsiloxane.
[00107] Crosslinking between the siloxanil polymer and the siloxy-containing compound preferably occurs through the condensation reaction.
[00108] In the examples herein, a triacetoxy ethylsilane, supplied by Wacker Chemie AG under the tradename RETICULANTE WACKER® ES 23 is used as the siloxy-containing cross-linking agent. The crosslinker is trifunctional and reacts with the hydroxyl groups of the hydroxyl-terminated PDMS in a condensation reaction releasing acetic acid.
[00109] Preferably about 0.5-15% by weight, for example approximately 0.9% by weight or approximately 3.9% by weight, preferably 1-10% by weight, for example 2-5% by weight, such as about 4% by weight, of the siloxy-containing compound can be used to form the covalently cross-linked siloxanyl polymer. Preferably, the amount of the siloxy-containing compound may be sufficient to provide a covalently cross-linked siloxanyl polymer having the proper concentration of hydroxyl groups to obtain the desired properties in the polymeric composition and requiring a low concentration of boron. For example, sufficient to provide a crosslinked polymer agglomerate having a concentration of hydroxyl moieties as defined herein.
[00110] An indication of when the level of covalent crosslinking between the siloxanil polymer and the siloxy-containing compound approaches a phase that is useful for further processing through boron crosslinking can be indicated by a marked increase in viscosity. For example, viscosity may increase from a value of below or about 1 Pas to values of at least a factor of 5, for example a factor of 10 or more.
[00111] Preferably, the ratio of siloxy-containing compound to siloxanil polymer may correspond to a molar ratio of siloxy-containing compound: siloxanil polymer in the range of 0.7:1 to 1.30:1, preferably 0.8:1 to 1 .2:1, such as 0.9:1 to 1.1:1. Ratios of approximately 1:1 are especially preferred.
[00112] Preferably, the molar ratio of the siloxy-containing compound: siloxanyl polymer may correspond to a theoretical excess of cross-linking functional groups in the siloxy-containing compound of about 50% compared to the cross-linking groups in the siloxanyl polymer, for example, hydroxyl groups. For example, there may be an excess of about 30-70%, preferably about 40-60%. boron compounds
[00113] The boron compound must be able to form dynamic cross-links, as defined herein, with the covalently cross-linked siloxanyl polymer.
[00114] Preferably the boron compound is selected from triethyl borate, diboron trioxide, disodium tetraboron heptoxide, disodium tetraborate and boric acid.
[00115] The boron concentration within the polymeric compositions of the invention is in the range of 0.005-0.160% by weight, by weight of the total composition. Preferably, the boron concentration is less than 0.12% by weight, preferably less than 0.03% by weight, more preferably less than 0.017% by weight. Typical ranges of boron content would, for example, be in the range of 0.007-0.11% by weight, preferably 0.010-0.016% by weight. polymeric composition
[00116] The polymeric compositions of the invention preferably have a Shore hardness measured using a Shore OO durometer in accordance with ISO-868 in the range of 20 to 80.
[00117] The viscosity of polymeric compositions can normally be higher than the siloxanil polymer, siloxy-containing compound and boron-containing compound used in their production. For example, the final viscosity of the polymeric composition may be in the range of 30-2000 Pas at 20°C (30000-2000000 cP). Typical polymeric compositions according to the invention have similar viscosity at 20°C to BASF Oppanol® B10N.
[00118] The polymeric compositions of the invention may themselves be suitable for use as bouncing putties, modeling clays and/or bouncing clays, i.e. without the addition of a particulate or granular material, or other additives. Typically, the compositions of the invention may have a bounce height of at least 20 cm, preferably at least 35 cm, more preferably at least 50 cm, when a 0.4 g ball formed therefrom falls from a height of 2 m into a flat glass surface. Composite materials
[00119] The present invention provides a composite material comprising the polymeric composition as defined herein.
[00120] Preferably, the composite materials of the invention may comprise at least 2% by volume of the polymeric composition of the invention, for example 2-99% by volume.
[00121] Preferably, the composite material further comprises at least 1% by volume of a particulate or granular material, for example 1-98% by volume of a particulate or granular material.
[00122] In one embodiment, applicable in all aspects of the invention, the composite material may comprise at least 80% by volume of the particulate or granular material, for example 80-98% by volume, preferably 88-95% by volume.
[00123] In another embodiment, which is equally applicable in all aspects of the invention, the composite material may comprise less than 80% by volume of the particulate or granular material, preferably less than 75% by volume, more preferably less than 50% by volume. volume. For example 1-74% by volume, preferably 5-49% by volume, for example 10-40% by volume.
[00124] Preferably, in all embodiments, the particulate or granular material has an average particle size in the range of 0.020.5 mm, 0.05-0.35, more preferably 0.075-0.35 mm, for example 0. 10-0.15 mm.
[00125] It is preferred that the particulate or granular material is selected from the group consisting of borosilicate glass granules, sand, ground marble, polymer grains or balls, cenospheres, plastic, ceramic or glass microspheres, or mixtures of these materials.
[00126] The particles contained in the preferred embodiment consist of natural sand, which is sold under the designation GA39. Another suitable particle is 3M K37, a synthetically produced hollow spherical glass bead. Another usable particle is SL 150, which consists of so-called cenospheres that are produced together with ash in the combustion of coal. They are white or gray in color and are hollow.
[00127] Yet another particulate material that was used in practical tests is Mikroperl AF, which consists of solid, completely round glass spheres. A preferred size is 75 to 150 μm. They are transparent, which can be used to achieve interesting and attractive aesthetic effects in the composition of the finished material. The polymeric compositions of the invention exhibit extremely good adhesion to these particles, which is why no modification or surface initiation is required.
[00128] In testing different types of particles, it was observed that completely round particles increase the pasty property of the composition, which implies that the polymeric composition can be prepared drier and the need for a plasticizer can be reduced.
[00129] Particles that create purely aesthetic effects, such as mica particles, can be added. Surface modification may be necessary for the polymeric composition to adhere to it.
[00130] When the particulate or granular material forms the majority of the composite material by volume, the polymeric composition of the invention acts as a binder, coating the particles or grains so that they adhere to each other, but in many places small pockets of air are formed. among them. These air pockets can be defined as “voids” and where the volume% of the fill is greater than 74% by volume, this can include the combined volume of voids and particulate or granular material.
[00131] In embodiments where the polymeric composition of the invention is acting as a binder, for example where the particulate or granular material forms more than 50% by volume of the composite material, it may form the aforementioned layers on the particles or grains with a thickness layer which is in the order of magnitude of 0.1 to 10 μm, preferably 0.5 to 5 μm and even more preferably 1 to 2 μm. This layer thickness is sufficient to allow adhesion between the particles or grains, but it is still not so great that the interstices between the coated particles or grains run the risk of being completely filled by the polymeric composition so that the granular structure of the material compound is lost. When the particles or grains have finally been covered by the polymeric composition, it should, as mentioned above, have those chemical or physical properties that remain in the particles or grains to a high degree. Treatment or modification of the surface of the particles or grains can be used to improve the adhesion of the polymeric compositions and the surface of the particles or grains.
[00132] Another important property of the polymeric composition is that of low adhesion, that is, the low adhesion to the surrounding environment, with the exception of particles or grains. By these means, residues of binder do not remain on hands, clothing, molds, work surfaces or the like when the composite material is handled. For the composite material to maintain its integrity and not be too brittle, it is important that the polymeric composition has a good level of internal adhesion, and is soft and flexible enough to maintain cohesion as a whole that is easily manipulated, not disordered.
[00133] The composite material preferably shows poor adhesion to one or more other surfaces that may occur in its surroundings, with the exception of silicone and silicone rubber. Preferably the composite material does not stick and smear, for example, tables and hands when used. Internal adhesion of composite material is good, which contributes to its internal integrity and non-breaking property. The particulate structure of the composite material makes it pleasant to handle. Additions
[00134] Various additives can also optionally be added to the polymeric composition or composite material of the invention to improve or vary its properties in some way.
[00135] A plasticizer acts as a lubricant between the polymer chains included in the polymeric composition, and imparts a more pasty consistency to the composition or composite material. Suitable plasticizers include, for example, stearic acid and oleic acid.
[00136] The use may advantageously be carried out of adhesion reducing agents such as Vaseline, which is a highly viscous paraffin oil in the semi-solid phase. Glycols such as polyglycols can also be used for this purpose.
[00137] Various pigments can be added in order to change the color of the composite material.
[00138] In all embodiments, the polymeric composition or composite material of the invention may further comprise at least one additive, preferably selected from the group consisting of softeners, tack reducers, plasticizers, lubricants, pigments and dyes. Additives such as polyglycols, eg ethoxylated fatty acid esters, or oleic acid may also be added. Suitable additives include esters of monoglycerides such as acetic acid esters of monoglycerides such as sold as "Soft & Safe". Alcohols such as octyldodecanol and Isofol20 are also suitable additives. Stearic acid can also be added.
[00139] Preferably these additives may be present in total in a maximum of 10% by weight by weight of the polymeric composition or by weight of the composite material. Bouncy Dough or Modeling Dough
[00140] The polymer compositions and composite materials of the invention are preferably suitable for use as a bouncing dough or modeling clay, alone or in combination with suitable additives as stated above. Doughs are familiar to those skilled in the art about In this context, a dough means a fluid composition that exhibits viscous properties on long timescales, but can show elastic properties on short timescales. Compositions of the invention are viscous over longer time scales (seconds to minutes, for example, for periods longer than 1 second, such as longer than 1 second to 10 minutes or longer) and can be reformed into different ways. Generally, compositions of the invention are elastic over shorter time scales (particularly for periods of less than 1 second, particularly for periods of less than 0.1 seconds (e.g. less than 0.02 seconds such as 0.02 to 0.02 seconds). 0001 second). Normally, compositions of the invention will bounce and retain their shape when dropped onto a hard surface, but will deform over longer time scales. Masses such as compositions of the invention have the property that they do not have a permanent equilibrium shape. , and will not revert to their original shape if deformed.
[00141] As a general indication, in an oscillatory shear experiment when the elastic modulus (G') exceeds the viscous modulus (G'') this corresponds to a transition from viscous to elastic behavior. Masses of the invention will exhibit viscous behavior at low shear rates. In a preferred embodiment, masses of the invention exhibit viscous behavior at low oscillatory shear rates, that is, G'' > G' at low shear rates, such as below 1 s-1 or below 0.5 s-1.
[00142] G', G'' and complex viscosity are measured with the rheometer in oscillatory shear mode. Shear viscosity is measured as a function of shear rate with the rheometer in continuous shear mode.
[00143] The viscosity of the final mass should preferably be above 102 Pas, as above 103 Pas. Polymer compositions and putties may have a viscosity below 108 or 106 Pas, preferably below 105 Pas when measured at a shear rate of 0.015 -2 s -1 under continuous shear mode. Preferred ranges are 102-106 Pas and especially 103-105 Pas when measured at a shear rate of 0.015-2 s-1.
[00144] Typically, for polymeric compositions and masses (as well as all appropriate embodiments) of the invention, the crossover point for elastic behavior, i.e. where G' > G'' will occur with an oscillatory shear rate in the range of 1 to 20 Hz, preferably between 1 and 10 Hz. Thus, in one embodiment, the compositions (and other embodiments such as masses) of the invention will show elastic behavior (G' > G'') at shear rates above 1 s -1 , especially above 2 s -1 and particularly above 10 s-1 (for example, at 2 to 10,000 s-1). Correspondingly, in one embodiment, the compositions (and other embodiments such as masses) of the invention will show viscous behavior (G'' > G') at shear rates below 1 s-1, especially below 0.5 s-1 and particularly below 0.2 s-1 (for example, at 0.2 to 0.0001 s-1). All viscosity and shear parameters refer to measurements at 20-25°C (eg 23°C) unless otherwise noted. Law Suit
[00145] Processes for making polymeric compositions according to the present invention are further provided.
[00146] In one aspect, a process for manufacturing a polymeric composition or composite material is provided, said process comprising the steps of: (i) reacting at least one siloxanil polymer with a siloxy-containing crosslinking agent to form covalent crosslinks; (ii) reacting the covalently cross-linked polymer with a boron compound; and optionally (iii) adding a particulate material.
[00147] In another aspect, a process for manufacturing a composite material is provided, said process comprising the steps of: a. reacting at least one siloxanil polymer with a siloxy-containing crosslinking agent to form covalent crosslinks; B. adding a borosilicate particulate material; and c. adjust the pH of the mixture.
[00148] In all aspects of the invention it is preferred that step (i) is a condensation reaction completed before all hydroxyl fractions are consumed.
[00149] The invention is not limited to structures obtained using linear PDMS molecules terminated with hydroxyl groups as a raw material. Any siloxanil-based polymers characterized by having hydroxyl functionality, which at least in part are accessible for cross-linking through a boron-containing substance, would be functional as raw materials to produce the compositions of the invention. Alternatively or additionally, the functional groups may be hydrolysable groups which are hydrolyzed prior to cross-linking through a boron-containing substance.
[00150] The reaction of the siloxanil polymer and siloxy-containing compound in step (i) can normally be achieved by mixing at a temperature in the range of 20-200°C, for example 20-150°C, for example about 130°C. More preferably, the temperature is in the range of 20100°C, for example 60-90°C.
[00151] Step (i) can normally have a reaction duration in the range of 5 minutes to 5 hours, preferably approximately 15-90 minutes, for example 30-60 minutes.
[00152] The ratio of siloxy-containing cross-linking agent to siloxanil polymer in step (i) preferably may correspond to a molar ratio of siloxy-containing cross-linking agent: siloxanil polymer in the range of 0.7:1 to 1.30:1, preferably 0 .8:1 to 1.2:1, such as 0.9:1 to 1.1:1, especially approximately 1:1.
[00153] In a preferred embodiment, applicable to all aspects of the invention, said siloxy-containing crosslinking agent is trifunctional and/or said siloxyanil polymer is end-protected with OH.
[00154] Preferably, said siloxanil polymer before step (i) comprises on average more than one hydroxyl fraction per molecule, preferably at least two. Alternatively or additionally, said siloxanyl polymer may comprise at least one hydrolysable group per molecule.
[00155] Hydrolyzable groups, when present, may be hydrolyzed after step (i) to provide additional hydroxyl moieties to serve as cross-linking points for step (ii). Preferably, said hydrolysis may be under acid hydrolysis conditions.
[00156] Suitable hydrolyzable groups may be selected from amide groups and ester groups.
[00157] Normally, the reaction between the covalently cross-linked siloxanyl polymer agglomerate formed in step (i) and boron compound in step (ii) is carried out at a temperature in the range of 5-200°C, preferably 10-150°C , more preferably in the range of 20-80°C, for example 50°C.
[00158] Preferably, step (ii) has a reaction duration in the range of 5 seconds to 1 hour, preferably approximately 30 seconds to 10 minutes, for example 1-5 minutes.
[00159] Usually, the boron compound can be added in the form of a saturated aqueous solution. A suitable concentration may be in the range of 1-10% by weight, for example about 5-6% by weight, for example 5.4% by weight. Cross-linking through boron can be achieved by mixing, for example, by continuous stirring. For example, an aqueous solution of boric acid can be used.
[00160] An increase in temperature in step (ii) can advantageously accelerate the reaction due to an increase in the rate at which water is evaporated.
[00161] In one embodiment, applicable to all aspects of the invention, crosslinking through hydroxyl groups of covalently crosslinked siloxanyl polymers such as PDMS, for example, terminating groups in linear polymers, functional side groups in linear or branched polymers, or groups functional in a covalently bonded polymer network, or other related arrangements, can be achieved without the direct addition of a boron-containing chemical such as boric acid.
[00162] In this embodiment, dynamic crosslinks can be initiated by activating the borosilicate based glass granules by adjusting the pH of the material. Preferably, the pH is adjusted below 8, for example below 7.5.
[00163] This allows for a convenient manufacturing process and easy production scaling since blending can be done in the low viscosity state. After mixing, dynamic crosslinks, and an increase in viscosity, can be triggered in the final stage of production by pH adjustment. Furthermore, this crosslinking reaction is fast and there is no need for excessive heating for extended periods of time. Instead, a high viscosity material with elastic properties is obtained after simple evaporation of residual water from the acid used for pH adjustment.
[00164] Suitable acids for pH adjustment include carboxylic acids, such as oxalic acid, and HCl. Preferably, HCl can be used. The acids can be added as an aqueous solution to the dry material, which, optionally, can be kneaded.
[00165] Normally, the pH adjustment initiating the reaction between the cross-linked siloxanyl polymer agglomerate formed in step (i) and the borosilicate material is conducted near room temperature, for example, a temperature in the range of 5-90°C , preferably 10-80°C, more preferably in the range of 20-70°C, for example around 50°C.
[00166] Preferably, the boron crosslinking step has a reaction duration in the range of 5 seconds to 1 hour, preferably approximately 30 seconds to 10 minutes, for example 1-5 minutes.
[00167] The processes of the invention provide polymeric compositions and/or composite materials as discussed above. Preferably, the formed product has a boron concentration in the range of 0.005-0.160% by weight.
[00168] The invention further provides a polymeric composition or composite materials obtainable by the processes of the invention. Preferred Modalities
[00169] The preferred embodiments described herein are applicable to all aspects of the invention.
[00170] Normally in a first step (step (i)), PDMS molecules characterized by containing an average of more than one hydroxyl group per molecule are reacted with a crosslinking agent containing siloxy to form covalent crosslinks. The siloxy-containing cross-linking agent is characterized by not containing boron in any form, and by forming cross-links that are not dynamic in character, i.e., that are covalent.
[00171] The material then goes through a second step (step (ii)), characterized by the formation of dynamic crosslinks that are important to obtain a product with the properties of a modeling clay. Dynamic crosslinks are the result of crosslinking between hydroxyl moieties linked to various molecular arrangements based on siloxane and boron compounds, as described above.
[00172] The covalent cross-linking of step (i) reduces the amount of boron compound required to perform sufficient dynamic cross-linking to obtain the required properties. In this way, new materials are provided that comply with the new European regulations and still have the properties of a modeling clay.
[00173] The properties of the final material can be influenced by the characteristics of the siloxanil-containing polymer that is used as a raw material. For example, a short-chain hydroxyl-terminated PDMS, or a PDMS with a high hydroxyl content relative to dimethylsiloxane content, can result in a relatively hard and cohesive or sometimes brittle end product. A long-chain hydroxyl-terminated PDMS, or a PDMS with a low hydroxyl content relative to dimethylsiloxane content, can result in a relatively soft and sometimes sticky end product. The ability to manipulate the length of the chain can be useful in achieving certain properties in the product.
[00174] For example, WACKER® POLYMER CDS 100 (molecular weight of about 4000 Dalton and viscosity of about 100cP as determined by the manufacturer Wacker Chemie AG) and WACKER® POLYMER C 2 T (molecular weight of about 25000Dalton and viscosity of about 2000cP, as determined by the manufacturer Wacker Chemie AG), can be compared in Example 1 and Example 2. Mixtures of long-chain and short-chain PDMS may be advantageous.
[00175] Various siloxy-containing compounds that give covalent cross-links can be used. A preferred combination of PDMS and cross-linking agent is characterized by having the ability to form network (partial) or branched structures with hydroxyl functionality, rather than combinations that can only form linear PDMS structures with hydroxyl ends. For example, the siloxy-containing compound functioning as a cross-linking agent may form two more, for example three or more covalent bonds to PDMS.
[00176] Crosslinking agents can be exemplified by low molecular weight siloxy-containing compounds (acetoxysilanes such as; triacetoxy methylsilane; triacetoxy ethylsilane, or tetraethyl silicate), or by higher molecular weight siloxy-containing compounds (such as a PDMS with alkoxy functional groups) .
[00177] In the examples herein, a triacetoxy ethylsilane, supplied by Wacker Chemie AG under the tradename RETICULANTE WACKER® ES 23 is used as the siloxy-containing cross-linking agent. The crosslinker is trifunctional and reacts with the hydroxyl groups of the hydroxyl-terminated PDMS in a condensation reaction releasing acetic acid.
[00178] An amount of about 1% by weight ES 23 may be suitable for crosslinking WACKER® C 2 T POLYMER to obtain a web for further processing. A smaller amount of ES 23 can give a network with also a high concentration of hydroxyl groups, which consumes a lot of boric acid to obtain a product with the desired properties, while a larger amount of ES 23 can provide a covalent network that is too hard to be useful. . See Example 4.
[00179] An indication of when the conversion is approaching a phase that is useful for further processing is indicated by a marked increase in viscosity.
[00180] For C 2 T, the experimentally found weight ratio converts to a molar ratio of about 1:1 for the siloxy-containing compound and the siloxanil polymer (ES 23:C 2T), which corresponds to a theoretical excess of about 50% of the ES 23 functional groups to PDMS hydroxyl groups.
[00181] Likewise, appropriate amounts of ES 23 to WACKER® CDS100 POLYMER, WACKER® CDS750 POLYMER (viscosity about 750cP), and WACKER® POLYMER C 1 T (viscosity about 750cP) corresponds to 3.9% by weight, 1.5% by weight, and 1.1% by weight.
[00182] Instead of using a boron-containing compound, eg boric acid for the final crosslinking reaction in which dynamic crosslinks are obtained, borosilicate glass microspheres can be used. In many applications, microspheres are added as a filler anyway.
[00183] This may allow the formation of cross-links through hydroxyl groups belonging to PDMS-based structures, such as: terminating groups in linear PDMS; functional side groups in linear or branched PDMS; or functional groups in a covalently linked PDMS network; or other related arrangements, without any addition of a boron-containing compound per se.
[00184] In these systems, crosslinking can be achieved by adjusting the pH of the material. Since the associated increase in the viscosity of the polymer composition can now be controlled and deferred to a later production stage, this allows for greater control and convenience in the production process and easy scaling of manufacturing.
[00185] Another advantage is that crosslinking now creates stems from positions within the polymer composition and surfaces of borosilicate based microspheres. Thus, no particular care has to be taken to uniformly distribute the crosslinking agent throughout the polymeric composition, as it is already perfectly distributed through the mixture of the microspheres (acting as the filler) and the covalently crosslinked siloxanyl polymer, which may have relatively low viscosity before pH adjustment and dynamic crosslinking. See Example 5.
[00186] When added in small amounts, the particulate material acts as the filler. However, the examples cover a scale up to and including the particulate material forming the major component by volume. Thus, the polymeric composition acts as a binder that covers the particles with a thin individual layer thereof.
[00187] To obtain a final product with properties expected from a bouncy dough, and with a boric acid content that is below the levels stipulated by the European Chemicals Agency (ECHA) candidate list, a certain amount of WACKER® CDS 100 POLYMER, POLYMER WACKER® C 2 T, fabric softener, and fillers can be added to the formula. It has also been found that it can sometimes be useful to mix different preparations of covalently cross-linked networks. See Example 6.
[00188] Other additives such as fillers, softeners, and chemicals reducing product adhesion can optionally be added to obtain the final material with the desired properties. In particular, the properties for the currently invented dough are improved by adding polyglycols such as ethoxylated fatty acid esters. See Example 7.
[00189] The invention is further demonstrated and described in the following non-limiting examples and the attached Figures, in which:
[00190] Figure 1 shows the viscosity of a modeling clay at different shear rates at 23°C.
[00191] Figure 2 shows the modulus of elasticity (G') and the viscous modulus (G'') of a modeling clay at different shear rates.
[00192] Figure 3 shows the viscosity of a polymer agglomerate (before boron addition) at different shear rates.
[00193] Figure 4 shows the modulus of elasticity (G') and the viscous modulus (G'') of a polymer agglomerate (before boron addition) at different shear rates. Examples
[00194] EXAMPLE 1. Reducing the amount of boron-containing compounds results in loss of desired properties well before the boron-containing substance content is below the levels set by the European Union. A series of modeling clays in which the boric acid content was varied were prepared as follows: A saturated aqueous solution of boric acid was prepared, which at 25°C has a concentration corresponding to 5.4% by weight. The saturated boric acid solution was mixed with a hydroxyl-terminated polydimethylsiloxane; WACKER® CDS 100 POLYMER (molecular weight about 4000Dalton and viscosity about 100cP, as determined by the manufacturer Wacker Chemie AG). Water that was evaporated during continuous mixing of the mixture and the properties of the final mixture were evaluated. The bouncing property was evaluated by dropping a ball (0.4 g) from a height of 2 m onto a flat glass surface. Table 1 shows that the loss of properties was observed below a 1:1 molar ratio (boric acid:PDMS) corresponding to 1.6% by weight. It is clear that the desired properties are lost well before the boric acid content is low enough.Table 1.


[00195] EXAMPLE 2. An increase in the molecular weight of the polydimethylsiloxane (PDMS) chain used as a raw material results in a loss of the desired properties before the boron-containing substance content is sufficiently low. A series of bouncy doughs, prepared as described in Example 1, with WACKER ® C 2 T POLYMER (molecular weight of about 25000Dalton and viscosity of about 2000cP, as determined by the manufacturer Wacker Chemie AG) shows that essential properties are already lost in the molecular weight at and above 25000 as none of the samples in Table 2 have desired properties. However, the concentration of boric acid is above the levels set by the European Union. Table 2.


[00196] EXAMPLE 3. Addition of inactive filler material results in loss of desired properties before the boron-containing substance content is sufficiently low. A series of bouncy doughs with higher filler content show a loss of properties in filler content above 40% by weight. All samples were based on WACKER® POLYMER CDS 100 with a 1:1 molar ratio (boric acid: CDS 100), and hydrophilic amorphous fumed silica was used as filler; WACKER® HDK® N20. The doughs were prepared as described in Example 1, and the filling was added by kneading. Sometimes, a small amount of ethanol was used as the processing liquid, which was evaporated in the final stages. Through the preparation of samples with or without ethanol, it was verified that mass properties were not affected by the use of the processing solvent. Table 3 shows the loss of properties well before the boric acid content is low enough. Table 3.

[00197] EXAMPLE 4. A marked increase in viscosity during the final stages of crosslinking hydroxy-terminated PDMS with CROSSlinking WACKER® ES 23 is an indication of a desired crosslink density for further processing. For POLYMER WACKER ® C 2 T this is obtained with an amount of about 0.9% by weight ES 23. A smaller amount of ES 23 gives a network with (very) high concentration of hydroxyl groups that consumes a very high amount of boric acid to obtain a product with the desired properties, while a higher amount of ES 23 gives a (too) hard and less flexible matrix to be useful, see Table 4. Likewise, appropriate amounts of ES 23 for WACKER® POLYMER CDS100, WACKER® POLYMER CDS750, and WACKER® POLYMER C 1 T correspond to 3.9% by weight, 1.5% by weight, and 1.1% by weight. Table 4.

[00198] EXAMPLE 5. Dynamic crosslinks and a final product with desired properties of a bouncy mass can be obtained without adding boric acid, but using a borosilicate glass microsphere filler (3M™ Glass Bubbles K37) to form the dynamic crosslinks . In a first stage, the binder is conveniently mixed with the filler in a low-viscous solution, after which the pH is reduced by the addition of hydrochloric acid. Addition of HCl activates dynamic cross-linking, binder/material viscosity increases strongly and final bouncy mass properties are achieved. From the three samples with 0.38g K37 per gram CDS 100 it can be seen that at a given amount of acid added there is no further gain in properties, and from about 8% by weight of HCl (30%) based on the weight of K37 was used as a standard addition. From the table, it can be concluded that K37 can replace boric acid addition and, in addition, provides a convenient route for processing. Table 5.
*) Noting that the sample containing 0.51g K37 and 1g CDS 100 has similar properties to the sample in Table 1 with a 1:1 molar ratio (boric acid: CDS 100), 1 g of K37 appears to replace 0.5mmol of boric acid . The number in the parentheses refers to the boric acid concentration with the calculation based on the binder weight and omitting the filler weight. #) Estimated in calculation using a density of K37 of 0.37 g/mL, and assuming that the space filled by K37 has a volume fraction of 0.74 in closed packaging.
[00199] EXAMPLE 6. To obtain a final product with properties expected from a bouncy mass, and with a boric acid content that is below the levels stipulated by the European Chemicals Agency (ECHA) candidate list, a certain amount of WACKER® CDS POLYMER 100, and fillers can be added to the formula. The first five partially different covalently cross-linked networks were prepared using the method described above, Table 6. These were then used to prepare the doughs in Table 7.
[00200] In Table 8 preparations with very high volume content particles are given. This is to show that the silicone-based binder can be laid out in a thin layer as a coating over the particles, or the grains, which is the main component (by volume). The preparation has similar properties to the paste.Table 6.
Table 7.

*) Noting that the sample containing 0.51g K37 and 1g CDS 100 has similar properties to the sample in Table 1 with a 1:1 molar ratio (boric acid: CDS 100), 1 g of K37 appears to replace 0.5mmol of boric acid . In the last two examples, boric acid was added via a saturated aqueous solution of boric acid (5.4% by weight) and therefore the “true” value was indicated. Table 8.
#) Estimated in calculation using a K37 density of 0.37 g/mL, a density of 2.6g/mL for quartz sand, and assuming the fill-filled space has a volume fraction of 0.74 in packaging closed.
[00201] EXAMPLE 7. The alcohol ethoxylate “C12-13 Pareth-12” supplied by Croda under the trade name BRIJ™ LT12-SO-(RB) was added in an amount corresponding to 1, 2 or 4 parts to 100 parts of organosiloxane. Polyglycol may improve properties after extended kneading and use. Intermediate amounts gave a slightly less sticky dough while still maintaining the bounce, compared to a dough without polyglycol. Table 9.

*) Noting that the sample containing 0.51g K37 and 1g CDS 100 has similar properties to the sample in Table 1 with a 1:1 molar ratio (boric acid: CDS 100), 1g of K37 appears to replace 0.5mmol of boric acid.
[00202] EXAMPLE 8. 11.1g Wacker CDS100 was mixed with 0.104g Wacker Crosslinker V24 (Si-H oligo-siloxane) and 0.020g Wacker OL Catalyst (Pt-catalyst in PDMS). On heating, hydrogen gas was released and the solution became thick like a syrup. With the addition of boric acid through a saturated solution corresponding to a final concentration of 0.21% by weight of boron, a cohesive modeling clay-like material was obtained. Despite being above the limits given by the new European legislation, this is in contrast to the result obtained by adding the same amount of boric acid to CDS100 itself (compare Table 1 in Example 1) which gives a syrup-like texture. The observation was repeated using another Si-H oligosiloxane crosslinker (Wacker V88) and mixing 9.8g CDS100 with 0.14 V88 and 0.030g Catalyst OL.
[00203] EXAMPLE 9. The rheological properties of a commercial sample of Modeling Putty (“Intelligent Knete” or “Thinking Putty” from Crazy Aaron's putty world) was investigated with a Bohlin CVO 100 Digital voltage controlled rheometer equipped with a plate 20 mm parallel. The clearance was kept constant at 250 micrometers. The results are shown in Figure 1 and Figure 2. The properties of this dough are representative of the doughs of the invention.
[00204] In continuous shear mode the investigated shear stress ranged up to above 44 kPa resulting in a shear rate of 2s-1. In this shear rate range (0.015s-1a 2s-1) the sample behaved practically Newtonian with a viscosity of about 1*104 Pas to 1*105 Pas. The data clearly show that the sample flows with viscous properties dominating the elastic ones on these time scales. In the hands of a user, this viscous property manifests itself in that the sample can be molded and reshaped into new shapes without returning to its original shape.
[00205] The viscosity behavior at higher shear rates was obtained through the empirical Cox-Mertz rule and complex viscosity data as a function of angular frequency are included in the figure. These data were obtained with the rheometer in oscillatory shear mode and the frequency was swept from 0.05 Hz to 100 Hz. Viscosity decreases at higher angular frequencies with a cross along Newtonian behavior located in the range 1 s-1 to 100 s-1. Deviation from Newtonian behavior indicates that on shorter time scales (higher angular frequencies) the sample does not have time to relax to an equilibrium position.
[00206] EXAMPLE 10. The rheological properties of the sample in Table 4, which was judged to have the most appropriate crosslink density, with a 0.96:1 molar ratio of ES 23 crosslinker to C 2 T polymer, was investigated with a Bohlin CVO 100 Digital controlled voltage rheometer equipped with a 20 mm parallel plate. The clearance was kept constant at 250 micrometers. In an oscillatory shear experiment the viscous property is dominating and G'' (the viscous modulus) exceeds G' (the elastic modulus) in virtually every frequency domain accessible with the rheometer present. The results are shown in Figure 3.
[00207] With the rheometer in continuous shear mode the Newtonian plateau viscosity is about 100 Pas. The results are shown in Figure 4. This is much lower than in a final modeling clay sample (see example 9) and demonstrates the influence of additional (dynamic) crosslinks with a boron compound.

权利要求:
Claims (21)
[0001]
1. Composite material, characterized in that it comprises at least 2% by volume of a polymeric composition comprising at least one covalently cross-linked siloxanyl polymer agglomerate which is further cross-linked by a boron compound, wherein the composite material has a concentration of boron in the range of 0.005 to 0.160% by weight; and at least 1% by volume of a granular or particulate material; and wherein the composite material does not return to its original shape when deformed and wherein prior to covalent cross-linking said siloxanyl polymer has the structure: 123 45 678 (R )(R )(R )Si[OSi(R )(R ) ]nOSi(R )(R )(R ) where N is an integer in the range from 30 to 1000; and wherein each R1-R8 may be the same or different and is independently selected from the group consisting of hydrogen, methyl, ethyl, propyl, butyl, phenyl, vinyl and hydroxyl, and wherein at least one of R1-R8 is hydroxyl.
[0002]
2. Composite material according to claim 1, characterized in that said polymer comprises, on average, at least two hydroxyl fractions per molecule.
[0003]
3. Composite material according to any one of the preceding claims, characterized in that said agglomerate comprises at least one siloxanyl polymer covalently cross-linked with at least one siloxy-containing compound.
[0004]
4. Composite material according to any one of the preceding claims, characterized in that at least one of R1, R2, R3, R6, R7 and R8 is hydroxyl.
[0005]
5. Composite material according to any one of claims 1 to 4, characterized in that said siloxanyl polymer is selected from the group consisting of hydroxy-functionalized compounds of polydiphenylsiloxane, polydibutylsiloxane, polydipropylsiloxane, polydibutylsiloxane, polydiethylsiloxane, polydimethylsiloxane.
[0006]
6. Composite material according to any one of claims 3 to 5, characterized in that said siloxy-containing compound is selected from the group consisting of acetoxysilanes, oxymosilanes, alkoxysilanes, isopropeneoxysilanes, amidosilanes, aminosilanes, aminooxysilanes and functionalized siloxanyl polymers with at least one of these groups.
[0007]
7. Composite material according to any one of the preceding claims, characterized in that said boron compound is selected from triethyl borate, diboron trioxide, disodium tetraboron heptoxide, disodium tetraborate and boric acid.
[0008]
8. Composite material according to any one of the preceding claims, characterized in that the boron concentration is less than 0.12% by weight.
[0009]
9. Composite material according to any one of the preceding claims, characterized in that it comprises at least two siloxanyl polymers each of which is covalently cross-linked with at least one siloxy-containing compound.
[0010]
10. Composite material according to any one of the preceding claims, characterized in that it has a Shore OO hardness in the range of 20 to 80.
[0011]
11. Composite material according to any one of the preceding claims, characterized in that it comprises 1-98% by volume of said particulate or granular material.
[0012]
12. Composite material according to claim 11, characterized in that it comprises 1 to 75% by volume of a particulate or granular material.
[0013]
13. Process for manufacturing a composite material, as defined in any one of claims 1 to 12, having a boron concentration in the range of 0.005 to 0.160% by weight, said process characterized in that it comprises the steps of: (i) reacting at least one siloxanil polymer with a siloxy-containing crosslinking agent to form covalent crosslinks, wherein prior to covalent crosslinking said siloxanil polymer has the structure: 123 45 678 (R )(R )(R )Si[OSi (R )(R )]nOSi(R )(R )(R ), where N is an integer in the range from 30 to 1000; and wherein each R1-R8 may be the same or different and is independently selected from the group consisting of hydrogen, methyl, ethyl, propyl, butyl, phenyl, vinyl and hydroxyl; and wherein at least one of R1-R8 is hydroxyl, (ii) reacting the covalently cross-linked polymer with a boron compound; and (iii) adding a particulate material.
[0014]
14. Process for manufacturing a composite material, as defined in any one of claims 1 to 12, having a boron concentration in the range of 0.005 to 0.160% by weight, said process characterized by the fact that it comprises the steps of: ( i) reacting at least one siloxanil polymer with a siloxy-containing crosslinking agent to form covalent crosslinks, wherein prior to covalent crosslinking said siloxanil polymer has the structure: 123 45 678 (R )(R )(R )Si[OSi( R )(R )]nOSi(R )(R )(R ), where N is an integer in the range from 30 to 1000; and wherein each R1-R8 may be the same or different and is independently selected from the group consisting of hydrogen, methyl, ethyl, propyl, butyl, phenyl, vinyl and hydroxyl, and wherein at least one of R1-R8 is hydroxyl, (ii) adding a borosilicate particulate material; and (iii) adjusting the pH of the mixture.
[0015]
15. Process according to claim 14, characterized in that in step (iii) the pH is adjusted using an acid.
[0016]
16. Process according to any one of claims 13 to 15, characterized in that step (i) is carried out at a temperature in the range of 20 to 200°C.
[0017]
17. Process according to any one of claims 13 to 16, characterized in that step (i) is a condensation reaction completed before all hydroxyl fractions are consumed.
[0018]
Process according to any one of claims 13 to 17, characterized in that the ratio of siloxy-containing cross-linking agent to siloxanil polymer in step (i) corresponds to a molar ratio of siloxy-containing cross-linking agent: siloxanil polymer in range from 0.7:1 to 1.30:1.
[0019]
Process according to any one of claims 13 to 18, characterized in that said siloxy-containing crosslinking agent is trifunctional and/or said siloxanil polymer is capped at the OH end.
[0020]
Process according to any one of claims 13 to 19, characterized in that said siloxanyl polymer comprises at least one hydrolysable group per molecule.
[0021]
21. Process according to any one of claims 13 and 16 to 20, characterized in that step (ii) is carried out at a temperature in the range of 5 to 200°C.

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同族专利:

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公开号 | 公开日

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CA2911331C|2021-02-16|

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WO2014177710A1|2014-11-06|

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RU2680827C2|2019-02-28|

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KR102344551B1|2021-12-29|

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CN105492501B|2021-05-07|

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KR20160041851A|2016-04-18|

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BR112015027755A2|2014-11-06|

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MX2015015191A|2016-06-06|

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EP2992040A1|2016-03-09|

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AU2014261363B2|2017-03-30|

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GB201308072D0|2013-06-12|

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RU2015149341A|2017-06-08|

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CA2911331A1|2014-11-06|

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JP2016520690A|2016-07-14|

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AU2014261363A1|2015-12-10|

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US10266659B2|2019-04-23|

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CN105492501A|2016-04-13|

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US20160130405A1|2016-05-12|

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JP6577457B2|2019-09-18|

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法律状态:
2018-02-27| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2019-06-04| B25A| Requested transfer of rights approved|Owner name: DELTA OF SWEDEN AB (SE) |

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2019-12-24| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2020-10-06| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|

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2021-11-09| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2022-02-01| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 02/05/2014, OBSERVADAS AS CONDICOES LEGAIS. |

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