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    • 专利摘要:
    silicone - acrylic copolymer. the present invention relates to a new silicone-acrylic copolymer comprising a poly = silicone polymer covalently bonded with an acrylic polymer via -s-i-o-si- bonding is described. the silicone - acrylic copolymer is a reaction product of (a) a silicone polymer, (bi) a mixture of acrylic monomers where at least one acrylic monomer comprises a (met) acrylic silane monomer and / or a siloxane (met) macromer acrylic with a radical initiator to form an acrylic prepolymer or (bii) acrylic polymer comprising a silane or siloxane functional group; and (c) a mixing catalyst, where the ratio of the silicone polymer (a) and the mixture of acrylic monomers (bi) or polymer (bii) is 50: 1 to 1:50. the silicone - acrylic copolymer is useful as an adhesive, sealant, coating, and the like.
    公开号:BR112012027110B1
    申请号:R112012027110-5
    申请日:2011-04-15
    公开日:2020-05-12
    发明作者:Yuxia Liu
    申请人:Henkel IP & Holding GmbH；
    IPC主号:
    专利说明:

    Descriptive Report of the Invention Patent for SILICONE-ACRYLIC COPOLYMER, ARTICLE AND COMPOSITION UNDERSTANDING SILICONE-ACRYLIC COPOLYMER. Reference - Cross to request related patent [001] This application claims the benefit of provisional application for patent No. US. 61/327 141 deposited on April 23, 2010, the contents of which are incorporated herein by reference.
    Field of the Invention [002] The invention relates to silicone - acrylic copolymers and compositions comprising copolymers and their end use applications.
    Background of the Invention [003] Acrylic-based polymers have been widely used as adhesives, coatings and sealants since they are relatively low cost, adhere well to a variety of different surfaces and, if necessary, can be formulated for adhesion development to a surface. The disadvantages of acrylic-based polymers include poor performance at high temperature, poor performance at low temperature, inability to adhere to substrates with low surface energies and the potential to develop excessive adhesion to substrates with high surface energies.
    [004] Polymers based on silicone exhibit good performance at high and low temperature as adhesives, coatings and sealants. Silicone-based polymers have excellent chemical inertia, electrical insulating properties, biocompatibility, and the ability to adhere to low surface energy substrates. A primary disadvantage of silicone-based polymers is their high cost compared to other types of technologies. Other limitations include less grip
    Petition 870190128908, of 12/06/2019, p. 5/46
    2/22 josice and limited adhesion development, when necessary, compared to acrylic based polymers.
    [005] Although individual silicone adhesive and acrylic polymer have distinct advantages, and although they can be physically combined to form a hybrid polymer system, the combination is thermodynamically unstable and ultimately leads to macroscopic phase separation and separation and change in the properties of combination with time.
    [006] An attempt to overcome this incompatibility was addressed in WO 2007/145996, which forms a silicone adhesive grafted with acrylic through a complex process. However, this complex process makes removal of residual monomer difficult and the level of crosslinking cannot be well controlled. If any unreacted silicone and acrylic components remain, these unreacted components lead to phase separation over time, even if the rest of the components are covalently grafted.
    [007] Covalent silicone and acrylic grafts can be formed through the reaction of a silicone polymer and an acrylic polymer, however, a silicone resin is necessary to form a hybrid polymer system. The resulting hybrid polymer system forms silicone resin as the core domain and silicone and acrylic polymer are linked to this domain. Therefore, the resulting hybrid polymer system requires silicone resin as the center domain to form a lattice-like polymer.
    [008] There is a need in the technique of adhesives, coatings and sealants that exhibit the advantages of technologies based on acrylic and silicone without the inherent disadvantages of the prior art.
    [009] This invention is addressed to this need.
    Summary of the Invention
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    3/22 [0010] The present invention describes a new silicone copolymer
    - acrylic comprising a silicone polymer covalently bonded with an acrylic polymer via the -Si-O-Si- bond.
    [0011] One modality is directed to a silicone copolymer
    - acrylic comprising a silicone polymer and an acrylic polymer that are covalently bonded via a -Si-O- bond, where the ratio of the silicone polymer to the acrylic monomer is 50: 1 to 1:50, and the acrylic polymer contains at least one silane or siloxane functional group.
    [0012] Still in one embodiment, a silicone - acrylic copolymer comprising a reaction product of a silicone polymer, a mixture of acrylic monomers where at least one acrylic monomer comprises an (meth) acrylic monomer and / or a siloxane (meth) macromer ) acrylic, a radical initiator, and a mixing catalyst, where the ratio of the silicone polymer to the acrylic monomer is 50: 1 to 1:50.
    [0013] Still in one embodiment, an acrylic silicone copolymer comprises a reaction product of a silicone polymer, an acrylic polymer comprising a silane or siloxane functional group, and a mixing catalyst, where the ratio of the silicone polymer to the acrylic polymer is 50: 1 to 1:50.
    [0014] Another modality is directed to a process of manufacturing a silicone - acrylic copolymer comprising the reaction steps of a silane (met) acrylic monomer and / or a siloxane (met) acrylic macromer in the presence of a radical initiator and a solvent to form an acrylic prepolymer, adding a silicone polymer and mixing catalyst in the solvent, and removing the solvent.
    [0015] Still in one embodiment, an acrylic silicone copolymer is prepared by reacting a silicone polymer with
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    4/22 an acrylic polymer that contains at least one silane and / or siloxane functional group in the presence of a mixing catalyst and a solvent.
    [0016] Yet another embodiment is directed to a composition comprising the silicone - acrylic copolymer.
    [0017] Another modality is directed to an article comprising the silicone - acrylic copolymer. The article can be formed into a solution adhesive, a water-borne adhesive or a hot melt adhesive.
    Brief Description of the Figures [0018] Figure 1 are GPC chromatograms of silicone polymer ( ...... ), acrylic polymer (----) and silicone - acrylic copolymer ( __ ).
    [0019] Figure 2 are GPC chromatograms of adhesives made from (1) silicone copolymer - acrylic with MQ resin (----) and (2) silicone polymer, acrylic polymer and MQ resin ( ----- ).
    [0020] Figure 3 is a photograph of an adhesive made of silicone - acrylic copolymer with MQ resin (left, clear solution) and an adhesive made of silicone polymer, acrylic polymer and MQ resin (right, opaque solution).
    Detailed Description of the Invention [0021] Weight percentage means, unless expressly stated otherwise, percentage in dry weight.
    [0022] The invention provides a silicone-acrylic copolymer comprising a silicone polymer covalently bonded with an acrylic polymer via -Si-O-Si- bonding, and the acrylic polymer contains at least one (meth) acrylic and / or silane monomer or a (meth) acrylic siloxane macromer. Copolymer comprising a silicone polymer covalently bonded with an acrylic polymer via -Si-O-Si- bonding.
    [0023] The copolymer is prepared by reaction of a mixture
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    5/22 of silicone polymer and mixtures of acrylic monomers comprising at least one (meth) acrylic silane monomer and / or a (meth) acrylic siloxane macromer, with a radical initiator and a mixing catalyst. The ratio of the silicone polymer to the acrylic monomer is 50: 1 to 1:50.
    [0024] The copolymer is also prepared by reacting a mixture of a silicone polymer and an acrylic polymer comprising at least one (meth) acrylic silane monomer and / or a (meth) acrylic siloxane monomer with a mixing catalyst. The ratio of the silicone polymer to the acrylic monomer is also 50: 1 to 1:50.
    [0025] Useful silicone polymers that can be used in the practice of the invention include silicone polymers that comprise an organo substituted poly siloxane. Diorgan substitutes include, for example, dimethyl, methyl vinyl, methyl phenyl, diphenyl, methyl ethyl, and 3,3,3trifluorine propyl. In one embodiment, the diorgan substitutes are all dimethyl substituents. The silicone polymer will typically be capped at the end with functional groups such as hydroxyl, alkoxy, hydride, vinyl functional groups, and the like. In one embodiment, functional groups capped at the end are hydroxyl groups, alkoxy functional groups, hydride functional groups, vinyl functional groups, or mixtures thereof. The molecular weight of the poly diorgan siloxane will typically vary from about 100 to about 2,000,000, preferably from about 20,000 to about 150,000 g / mol.
    [0026] Acrylic monomers of the invention include at least one silane (meth) acrylic monomer and / or a siloxane (meth) acrylic macromer.
    [0027] Examples of (meth) acrylic silane monomer include trialoxy silyl (meth) acrylates, silyl (meth) dialkoxy acrylates, and the like. The silane (meth) acrylic monomer will typically be used in
    Petition 870190128908, of 12/06/2019, p. 9/46
    6/22 amounts from 0.2 to 50 weight percent of the total weight of the acrylic polymer, more preferably the amount of silane (meth) acrylic monomer will vary from about 1.0 to about 10 weight percent of the acrylic polymer.
    [0028] Examples of (meth) acrylic siloxane macromer include polydimethyl siloxane mono (meth) acrylate, for example, trialoxy silyl (meth) acrylates, silyl dialoxy (meth) acrylates or methacrylates. Preferred (meth) acrylic siloxane macromers are trimethoxy silyl and dimethoxy methyl silyl acrylates or methacrylates. An example of such a monomer is methacryloxy propyl trimethoxy silane. The (meth) acrylic siloxane macromer has a content of about 0.2 to 50 weight percent based on the total weight of acrylic monomers.
    [0029] Other acrylic monomers are selected from the group of alkyl (meth) acrylate monomers. Preferred (Met) alkyl acrylates that can be used to practice the invention have up to about 18 carbon atoms in the alkyl group, preferably from 1 to about 12 carbon atoms in the alkyl group. These acrylic polymer components may comprise a glass transition low temperature alkyl acrylate (Tg) monomer. Low Tg monomers are those having a homopolymer Tg of less than about 0 o C. Preferred low Tg alkyl acrylates for use in the invention have from about 4 to about 10 carbon atoms in the alkyl group and include butyl, methyl acrylate, methyl methacrylate, acrylate tocyl, ethyl hydroxy acrylate and acrylic acid, hydroxy propyl acrylate, hydroxy propyl methacrylate, amyl acrylate, hexyl acrylate, 2-ethyl hexyl acrylate, octyl acrylate, isooctyl acrylate, decyl aceylate, their isomers, and their combinations. Butyl acrylate, 2-ethyl hexyl acrylate and isooctyl acrylate are particularly preferred.
    [0030] Low Tg acrylic monomers are preferably
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    7/22 but not necessarily present in amounts greater than about 40% by weight based on the total weight of the acrylic polymer monomer. The acrylic polymer components can still comprise (meth) acrylate monomers having a high glass transition temperature. Non-limiting examples include methyl acrylate, ethyl acrylate, methyl methacrylate, and isobutyl methacrylate. It will be understood by those skilled in the art that the choice of monomers is dictated by consideration of adhesive properties, compatibility with the other adhesive matrix components, drug solubility and so on. Thus, the monomer Tg is only one of many variables to be taken into account in any particular polymer project.
    [0031] Useful acrylic monomers can be a nitrogen compound, in particular N-substituted acrylamides or methacrylamides. Examples include N-vinyl pyrrolidone, N-vinyl caprolactam, octyl N-tertiary acrylamide, dimethyl acrylamide, diacetone acrylamide, N-butyl tertiary acrylamide, N-isopropyl acrylamide, cyano ethyl acrylate, N-vinyl acetamide and N-vinyl formamide.
    [0032] Useful acrylic monomers can also be selected from a group of one or more hydroxyl-containing functionality monomers such as 2-hydroxy ethyl acrylate, 2-hydroxy ethyl methacrylate, propyl hydroxy acrylate and / or propyl hydroxy methacrylate. Such hydroxy functional monomers are generally used in amounts of up to about 40% by weight, more typically from about 0.5 to about 10% by weight, based on the total weight of the acrylic polymer monomer.
    [0033] Useful acrylic monomers, if desired, can be selected from a group of carboxylic acid functionality monomers. Useful carboxylic acids preferably contain from about 3 to about 6 carbon atoms and include, among others, acrylic acid,
    Petition 870190128908, of 12/06/2019, p. 11/46
    8/22 methacrylic acid, itaconic acid, ethyl beta-carboxy acrylate and the like. Acrylic acid is particularly preferred. Such carboxy-functional monomers are generally used in amounts of up to about 25% by weight, more typically from about 0.5 to about 10% by weight, based on the total weight of the acrylic polymer monomer.
    [0034] Comonomers can be added to acrylic monomers. Useful comonomers include vinyl acetate, styrene, alkyl di (meth) acrylates, glycidyl methacrylate and allyl glycidyl ether, as well as macromers such as, for example, poly (styryl) methacrylate.
    [0035] Radical initiators are added with acrylic monomers to form an acrylic prepolymer. Although a particular polymerization process is described in the examples, the acrylic polymer component of the present invention can be prepared by conventional polymerization processes familiar to those skilled in the art. These processes include, without limitation, solution polymerization, suspension polymerization, volume polymerization, and emulsion polymerization. In the practice of the invention, it may be advantageous to reduce the residual monomer content, or to remove or reduce levels of solvent and / or other volatiles, following polymerization using processes that are known and conventional in the art. The adhesive can be applied from organic solution, aqueous dispersion, or from a melt.
    [0036] Acrylic prepolymer can be formed as described above, or acrylic polymer can be used directly to form the silicone - acrylic copolymer. The acrylic polymer of the invention contains at least one monomer of alkoxy silyl functionality and / or a polysiloxane-containing macromer. Examples of polymers containing polysiloxane include polydimethyl monoacrylates or mono methacrylates
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    9/22 siloxane.
    [0037] The amount of (meth) acrylic macromer containing poly siloxane will typically be used in amounts of 0.2 to 50 weight percent, more preferably 1 to 15 weight percent of the acrylic polymer.
    [0038] Other acrylic polymers that can be advantageously used in the practice of the invention are acrylic polymers comprising end capped alkoxy functional groups or copolymers blocked or grafted with polysiloxane. Examples of the alkoxy silyl functional groups capped at the end are trialkoxy silyl, dialkoxy silyl functional groups. Preferred end capped alkoxy silyl functional groups are trimethoxy silyl, dimethoxy methyl silyl, triethoxy silyl and / or diethyloxy methyl silyl. Examples of such polymers are polymer-MS (Kaneka). Block copolymers are also useful. An example of a polysiloxane block copolymer is poly dimethyl siloxane - acrylic block copolymer. The preferred amount of siloxane block is 10 to 50 weight percent of the total block polymer.
    [0039] An acrylic polymer component that can be used in the practice of the invention is an acrylic polymer comprising from about 90 to about 99.5% by weight of 2-ethyl hexyl acrylate and from about 0.5 to about 10% by weight of dimethoxy methyl silyl methacrylate.
    [0040] It has been found that polymers comprising more than about 0.2% by weight of silyl alkoxy functional monomers are particularly well suited for use in the adhesive compositions of the invention and can be used in the production of adhesive articles such as, for example, tapes adhesive sheets and sheets by applying an adhesive or adhesive composition to a base material such as paper, cloth or plastic film.
    [0041] The ratio of the silicone polymer and the monomer and / or acrylic polymer is 50: 1 to 1:50.
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    10/22 [0042] A preferable polymerization process is to form the silicone - acrylic copolymer through the initiation of polymerization of acrylic monomers in the presence of a radical initiator, a solvent and the silicone polymer. At the end of radical polymerization, a mixing catalyst is introduced and the acrylic polymer reacts with the silicone polymer in the same reaction vessel to produce the copolymer. The alkoxy silyl monomers, once incorporated on the acrylic polymer backbone, undergo condensation reactions with OH functional groups capped at the end of the silicone polymer and quickly rebalanced with a -Si-O-Si-dynamic bond cleavage and reforming in the presence of water / moisture and an acid catalyst or strong base. This step is called a mixing reaction, since it leads to completely miscible of the two intrinsically immiscible polymers: silicone polymer and acrylic polymer. The alkoxy silyl groups of the acrylic polymer undergo a self-crosslinking reaction in the presence of water / moisture and the catalyst of the mixing reaction.
    [0043] In another preferred polymerization process, the mixing catalyst is introduced into the silicone polymer and acrylic polymer in the same reaction vessel to produce the copolymer. Again, the mixing reaction occurs and results in the copolymer.
    [0044] Useful mixing catalysts have a pKa value of less than or equal to -6 or greater than or equal to 15.
    [0045] Examples of the mixing catalyst are KOH, NaOH,
    LiOH, lithium organo reagents, Grignard reagents, methane sulfonic acid, sulfuric acid, acid clay, acid ion exchange resins and mixtures thereof. Other examples of the catalyst include organic metal salts of metals such as tin, titanium, aluminum, bismuth. Combination of more than one type of catalyst above can also be used.
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    11/22 [0046] Mixing reaction can take place at room temperature, a preferred process is to conduct any reaction with heating to 50-160 o C. The preferred temperature for the mixing step is between 100-150 o C. The mixing reaction is preferably left to proceed at least until the rate of evolution of condensation by-products, such as water, alcohol and carbon dioxide, is substantially removed. Heating is continued until the desired physical properties such as viscosity, clarity of the solution, and adhesion values are obtained. Typically, the mixture from each step will be allowed to react for about 1 to about 24 hours.
    [0047] The preferred solvent or co-solvent is selected from the group consisting of aliphatic hydrocarbons, aromatic hydrocarbons, ether, tetrahydrofuran, ethyl acetate, methyl ethyl ketone, water and mixtures thereof.
    [0048] Another modality is directed to a composition comprising the silicone - acrylic copolymer. The silicone - acrylic copolymer can be formulated into a variety of adhesives including a solution adhesive, emulsion adhesive and hot melt adhesive. Additional components can be added to the silicone - acrylic copolymer to form desired properties.
    [0049] The silicone - acrylic copolymer can be combined with additional components to form a composition such as an adhesive, coating, sealant, and the like. Additional components can be combined with the copolymer of the invention to further increase or decrease the desired property of the composition. Such components include silicone resin, tackiness agents, solubilizing agents, additives, antioxidants, polyether polyester, polyurethane, natural rubber, synthetic rubber, viscosity modifying agents, fillers, and the like.
    Petition 870190128908, of 12/06/2019, p. 15/46
    12/22 [0050] Useful silicone resin components that can be used in the practice of the invention include silicone resins that contain 0.05 to 5 weight percent of the hydroxyl group bonded to silicone and comprise R3SO1 / 2 triorgan siloxide units and units SiO4 / 2 siloxyl in a molar ratio of 0.5-1.5 R3SO1 / 2 units for each SiO4 / 2. The silicone resin can be combined with the silicone - acrylic copolymer, in a solid form or in a solution with toluene, xylene or heptane, and the like. Preferred organic R groups of the silicone resin are methyl, hydroxyl, vinyl, phenyl, (meth) acryloxy, and mixtures thereof. A preferred R group is a methyl group. Resins can also be treated with Me3SiOSiMe3, ViMe2SiOSiMe2Vi, MeViPhSiOSiPhViMe, Me3SiNHSiMe3 or triorgan silane such as triorganosilane Me3SiCl, Me2ViSiCl or MeViPhSiCl to reduce the amount of silicone.
    [0051] The addition of a silicone resin to the copolymer of the invention results in a different composition than the addition of silicon resin to silicone polymer and acrylic polymer that did not form into a copolymer. Although not bound by any theory, in the latter composition, silicone resin forms the center domain that bridges the silicone polymer and acrylic polymer. These compositions are thermally unstable and will ultimately lead to microscopic, or even macroscopic, phase separation over time. For composition made with the copolymer, the reactive sites on the silicone polymer have already reacted with acrylic monomers / polymers, and therefore, the silicone resin does not form the center domains or bridge domains for connecting acrylic polymer and silicone polymer in the hybrid adhesive of the invention.
    [0052] The addition of silicone resin to the silicone-acrylic copolymer is considered as a body-forming reaction and is conducted in the presence of a body-forming catalyst. Exem
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    13/22 plos of the body-forming catalyst for this body-forming reaction is (NH4) 2CÜ3 (s), ammonium carbamate, NH4OH (aq.), Methane sulfonic acid, sulfuric acid, acid clay, resin exchange resins Amberlyst acid ions (Rohm and Haas), KOH, NaOH, LiOH, n-BuLi, and mixtures thereof. Although body-forming reactions can occur at room temperature, a preferred process is to conduct the reaction with heating to 50-160 o C. The preferable temperature of the body-forming step is between 40-150 o C.
    [0053] The body-forming reaction is preferably left to proceed at least until the rate of evolution of condensation by-products, such as water, alcohol, and carbon dioxide, is substantially removed. Heating can be continued until the desired physical properties such as viscosity, clarity of the solution, and adhesion values are obtained. Typically the mixture from each step will be allowed to react for about 1 to about 24 hours. When the reaction body formation step is complete, the solids content of the resulting composition can be adjusted by adding or removing solvent.
    [0054] Suitable tackifying agents are those known in the art including: (1) aliphatic hydrocarbons; (2) mixed aliphatic and aromatic hydrocarbons; (3) aromatic hydrocarbons; (4) substituted aromatic hydrocarbons; (5) hydrogenated esters; (6) polyterpenes; (7) mineral oils; and (8) wood resins or rosin and their hydrogenated forms. Useful levels of tackiness builders are generally from about 1% by weight to about 30% by weight based on the weight of the total composition.
    [0055] The copolymers of the invention can also be combined with additional polymers to improve desired properties. Examples of polymers useful for combination include, but are not limited to, other acrylates, polysiloxanes, poly
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    14/22 isobutylene, polyester, PPO, polyisoprene, polybutadiene, styrenic block polymers, and the like. Examples of styrenic block copolymers include, but are not limited to, styrene - isoprene - styrene (SIS) block copolymer, styrene - butadiene styrene (SBS) copolymer, styrene - ethylene butene - styrene (SEBS) copolymers, and theirs diblock analogues.
    [0056] The compositions of the invention can include other additives known to those skilled in the art. These additives may include, but are not limited to, pigments, fillers, fluorescent additives, leveling and flow additives, wetting agents, surfactants, antifoaming agents, rheology modifiers, permeation enhancers, stabilizers, and antioxidants.
    [0057] Antioxidants can be added alone or in combination to protect components from degradation during preparation and use of the adhesive compositions, and to ensure long-term thermal stability. In general up to about 1% by weight of one or more antioxidants can be included in the adhesive compositions, usually from about 0.1% to about 0.5% by weight.
    [0058] Additional polymers can still be combined with silicone - acrylic copolymers. Examples of such polymers include polyester, polyether, polyurethane, natural rubber, synthetic rubber, and the like.
    Examples
    Example 1 [0059] An initial charge containing 20.0 g of butyl acrylate, 5.0 g of methyl methacrylate, 0.5 g of trimethoxy silyl propyl acrylate, 40.8 g of silicone polymer (Wacker Elastomer 80N) , 0.05 g of Vazo67 (2,2'-azo di- (2-methyl butyryl nitrile)), and 50.0 g of xylene were mixed and loaded into a 4-neck round bottom flask of
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    15/22
    500 mL, equipped with stainless steel stirrer, thermometer, condenser, water bath, and slowly added funnels. The initial charge was heated to reflux while stirring. After 15 minutes of reflux, 30 g of xylene and 0.3 g of Vazo-67 were added over a period of 2 hours. At the end of the addition, 0.1 g of KOH (1.0 N in water) was added and the mixture was stirred at reflux for 4 hours. At the end of the maintenance period, the contents were cooled to room temperature and the polymer solution was discharged. Xylene was removed by rotary vacuum evaporation and heptane was added to achieve a 50% solid content.
    Example 2 [0060] An initial charge containing 98.0 g of 2-EHA, 2.0 g of silyl propyl trimethoxy acrylate, 400.0 g of silicone polymer (Wacker Elastomer 80N), 0.07 g of Vazo-67 , and 650.0 g of heptane were mixed and loaded into a 2-neck, 4-neck, round-bottom flask equipped with a stainless steel stirrer, thermometer, condenser, water bath, and slow-adding funnels. The initial charge was heated to reflux while stirring. After 15 minutes of reflux, 50 g of heptane and 0.5 g of Vazo-67 were added over a period of 2 hours. At the end of the addition, 0.2 g of KOH (1.0 N in water) was added and the mixture was stirred at reflux for 4 hours. At the end of the retention time, the contents were cooled to room temperature and the polymer solution was discharged. Part of the heptane was removed by rotary evaporation under vacuum, adjusting the solids content to 50% Example 3 [0061] An initial charge containing 20.0 g of 2-EHA, 5.0 g of methyl arylate, 0.5 g of trimethoxy silyl propyl acrylate, 0.05 g of Vazo67, and 50.0 g of xylene was mixed and loaded into a round bottom flask, 4 necks, 500 mL, equipped with stainless steel stirrer, thermometer, condenser, bath water, and adding funnels
    Petition 870190128908, of 12/06/2019, p. 19/46
    16/22 slow motion. The initial charge was heated to reflux while stirring. After 15 minutes of reflux, 30 g of xylene and 0.3 g of Vazo-67 were added over a period of 2 hours. At the end of the addition, 0.1 g of KOH (1 N in water), and 40.8 g of silicone polymer (Wacker Elastomer 80N) were added and the mixture was stirred at reflux for 4 hours. At the end of the retention period, the contents were cooled to room temperature and the polymer solution was discharged. Xylene was removed by rotary vacuum evaporation and heptane was added, adjusting the solids content to 50%.
    Example 4 [0062] An initial charge containing 98.0 g of 2-EHA, 2.0 g of trimethoxy silyl propyl acrylate, 0.07 g of Vazo-67, and 1.0 L of heptane was mixed and charged to a 2-L, round neck, 4-neck flask equipped with a stainless steel stirrer, thermometer, condenser, water bath, and slow-adding funnels. The initial charge was heated to reflux with stirring. After 15 minutes of reflux, 50 g of heptane and 0.5 g of Vazo-67 were added over a period of 2 hours. At the end of the addition, 0.2 g of KOH (1.0 N in water) and 400.0 g of silicone polymer (Wacker Elastomer 80N) were added and the mixture was stirred at reflux for 4 hours. At the end of the retention period, the contents were cooled to room temperature and the polymer solution was discharged. Some heptane was removed by rotary evaporation under vacuum, adjusting the solids content to 50%.
    Example 5 [0063] An initial charge containing 98.0 g of 2-EHA, 2.0 g of trimethoxy silyl propyl acrylate, 0.07 g of Vazo-67, and 80.0 g of heptane was mixed and charged to a 500 ml 4-neck round-bottom flask equipped with a stainless steel stirrer, thermometer, condenser, water bath, and slow-adding funnels. The initial charge was heated to reflux while stirring. After 15 minutes of reflux,
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    17/22 g of heptane and 0.5 g of Vazo-67 were added over a 2 hour period. At the end of the addition, the contents of the flask were kept at reflux for 2 hours. At the end of the retention period, the contents were cooled to room temperature and the polymer solution was discharged. Heptane was added, adjusting the solids content to 50%.
    Example 6 [0064] A mixture of silicone - acrylic copolymer of Example 2 (50 g), methyl MQ resin (20 g), catalyst (NH4) 2CO3 (0.5 g), and heptane (30 g) was stirred at 60 o C for 2 hours. The reaction mixture was then heated to heptane reflux for 2 hours under a slow flow of nitrogen gas. Hexamethyl disilazane (2.0 g) was added and the reaction continued at reflux for 2 hours. The product was cooled to room temperature and filled in a glass jar.
    Example 7 [0065] A mixture of Example 2 silicone - acrylic copolymer (50 g), MQ methyl resin (20 g), NH4OH (aq.) Catalyst (30% NH3, 0.2 g), and heptane (30 g) was stirred at reflux for 3 hours under a slow flow of nitrogen gas. Hexamethyl disilazane (2.0 g) was added and the reaction continued at reflux for 2 hours. The product was cooled to room temperature and filled in a glass jar. Example 8 [0066] A mixture of Example 1 silicone - acrylic copolymer (50 g), methyl MQ resin (20 g), KOH (aq.) Catalyst (0.1 g), and heptane (200 g) was stirred at 100 o C for 3 hours under a slow flow of nitrogen gas. Hexa methyl disilazane (2.0 g) was added and the reaction continued at reflux for 2 hours. The product was cooled to room temperature and filled in a glass jar.
    Example 9 [0067] A mixture of silicone - acrylic copolymer of Example 3 (50 g), methyl MQ resin (20 g), KOH catalyst (0.1 g), and heptane
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    18/22 (30 g) was stirred at 100 o C for 3 hours under a slow flow of nitrogen gas. Hexamethyl disilazane (2.0 g) was added and the reaction continued at reflux for 2 hours. The product was cooled to room temperature and filled in a glass jar.
    Example 10 [0068] A mixture of Example 4 silicone - acrylic copolymer (50 g), methyl MQ resin (20 g), NH4OH catalyst (aq.) (30% NH3, 0.2 g), and heptane (30 g) was stirred at reflux for 3 hours under a slow flow of nitrogen gas. Hexamethyl disilazane (2.0 g) was added and the reaction continued at reflux for 2 hours. The product was cooled to room temperature and filled in a glass jar. Example 11 [0069] A mixture of acrylic copolymer of Example 5 (50 g), silicone polymer (Wacker Elastomer 80N, 50 g), KOH catalyst (aq.) (1.0 N in water) (0.2 g), and heptane (300 g) was stirred at reflux for 4 hours under a slow flow of nitrogen gas. Then methyl resin MQ (50 g) and KOH (aq.) (1.0 N in water) (0.1 g) were added and the mixture was stirred at reflux for 2 hours. Acetic acid (0.03 g) was added and the mixture was stirred at reflux for 0.5 hour. NH4OH (aq.) (30% NH3, 0.05 g) was added and the mixture was stirred under reflux for 0.5 h. Hexamethyl disilazane (2.0 g) was added and the reaction continued at reflux for 1 hour. The heptane solvent was removed by rotary evaporation and the resulting hot melt adhesive was filled into a glass jar.
    Example 12 [0070] A mixture of acrylic copolymer of Example 5 (50 g), silica polymer (Wacker Elastomer 80N, 50 g), KOH catalyst (aq.) (1.0 N in water) (0.2 g) , and heptane (300 g) was stirred at reflux for 4 hours under a slow flow of nitrogen gas. Acetic acid (0.03 g) was added and the mixture was stirred at reflux for 0.5 hour. O
    Petition 870190128908, of 12/06/2019, p. 22/46
    The product was cooled to room temperature and filled in a glass jar.
    Example 13: Comparative example [0071] A mixture of acrylic copolymer of Example 5 (50 g), silicone polymer (Wacker Elastomer 80N, 50g), methyl MQ resin (50 g), KOH catalyst (aq.) (1.0 N in water) (0.2 g), and heptane (300 g) was stirred at reflux for 4 hours under a slow flow of nitrogen gas. Acetic acid (0.03 g) was added and the mixture was stirred at reflux for 0.5 hour. Hexamethyl disilazane (5.0 g) was added and the reaction continued at reflux for 1 hour. The product was cooled to room temperature and filled in a glass jar.
    Example 14 [0072] A mixture of acrylic copolymer of Example 5 (50 g), silicone polymer (Wacker Elastomer 80N, 50 g), KOH catalyst (aq.) (1.0 N in water) (0.2 g), and heptane (300 g) was stirred at reflux for 4 hours under a slow flow of nitrogen gas. Acetic acid (0.03 g) was added and the mixture was stirred at reflux for 0.5 hour. NH4OH (aq.) (30% NH3, 0.2 g) and then methyl resin MQ (50 g) were added and the mixture was stirred at reflux for 3 hours. Hexamethyl disilazane (5.0 g) was added and the reaction continued at reflux for 1 hour. The product was cooled to room temperature and filled in a glass jar.
    Example 15 [0073] A mixture of Example 5 acrylic copolymer (50 g), silicone polymer (Wacker Elastomer 80N, 50 g), KOH catalyst (aq.) (1.0 N in water) (0.2 g) , and heptane (300 g) was stirred at reflux for 4 hours under a slow flow of nitrogen gas. (NH4) 2CO3 (0.5 g) and then methyl MQ resin (50 g) were added and the mixture was stirred at 60 o C for 3 hours and then reflux for 1 hour. Hexamethyl disilazane (5.0 g) was added and the reaction continued at reflux for 1 hour. O
    Petition 870190128908, of 12/06/2019, p. 23/46
    The product was cooled to room temperature and filled in a glass jar.
    Example 16 [0074] An initial charge containing 24.5 g of 2-EHA, 0.5 g of silyl propyl trimethoxy acrylate, 50.0 g of silicone polymer (Wacker Elastomer 80N), 0.03 g of Vazo-67 , and 250.0 g of heptane was mixed and loaded into a round neck, 4-neck, 1 L flask equipped with a stainless steel stirrer, thermometer, condenser, water bath, and slow-adding funnels. The initial charge was heated to reflux while stirring. After 15 minutes of reflux, 50 g of heptane and 0.5 g of Vazo-67 were added over a period of 2 hours. At the end of the addition, 0.2 g of KOH (aq.) (1.0 N in water) was added and the mixture was stirred at reflux for 4 hours. Acetic acid (0.03 g) was added and the mixture was stirred at reflux for 0.5 hour. NH4OH (aq.) (30% NH3, 0.2 g) and then methyl resin MQ (50 g) were added and the mixture was stirred at reflux for 4 hours. Hexamethyl disilazane (5.0 g) was added and the reaction continued at reflux for 1 hour. The product was cooled to room temperature and filled in a glass jar.
    Example 17 [0075] An initial charge containing 24.5 g of 2-EHA, 0.5 g of trimethoxy silyl propyl acrylate, 50.0 g of silicone polymer (Wacker Elastomer 80N), 0.03 g of Vazo-67 , and 250.0 g of heptane was mixed and loaded into a 4-neck, 1 L round-bottom flask equipped with a stainless steel stirrer, thermometer, condenser, water bath, and slow addition funnels. The initial charge was heated to reflux while stirring. After 15 minutes of reflux, 50 g of heptane and 0.5 g of Vazo-67 were added over a period of 2 hours. At the end of the addition, 0.2 g of KOH (aq.) (1.0 N in water) was added and the mixture was stirred at reflux for 4 hours. (NH4) 2CO3 (0.5 g),
    Petition 870190128908, of 12/06/2019, p. 24/46
    21/22
    NaHCOs (0.1 g) and methyl MQ resin (50 g) were added and the mixture was stirred at 60 o C for 3 hours and then at reflux for 1 hour. Hexamethyl disilazane (5.0 g) was added and the reaction continued at reflux for 1 hour. The product was cooled to room temperature and filled in a glass jar.
    Example 18 [0076] An initial charge containing 24.5 g of 2-EHA, 0.5 g of trimethoxy silyl propyl acrylate, 0.03 g of Vazo-67, and 50.0 g of heptane was mixed and charged to a 4-neck, 1 L round-bottom flask equipped with a stainless steel stirrer, thermometer, condenser, water bath, and slow-adding funnels. The initial charge was heated to reflux while stirring. After 15 minutes of reflux, 50 g of heptane and 0.5 g of Vazo-67 were added over a period of 2 hours. At the end of the addition, 50.0 g of silicone polymer (Wacker Elastomer 80N), 0.2 g of KOH (aq.) (1.0 N in water) and 200 g of heptane were added and the mixture was stirred at reflux for 4 hours. Acetic acid (0.03 g) was added and the mixture was stirred at reflux for 0.5 hour. NH4OH (aq.) (30% NH3, 0.2 g) and methyl MQ resin (50 g) were added and the mixture was stirred at reflux for 4 hours. Hexamethyl disilazane (5.0 g) was added and the reaction continued at reflux for 1 hour. The product was cooled to room temperature and filled in a glass jar.
    Example 19 [0077] The GPC (Waters Alliance 2695 GPC) chromatograms of silicone polymer (Wacker Elastomer 80N) ( ...... ), acrylic polymer (Example 5) (----), and the silicone copolymer - Example 12 acrylic ( ---- ) are shown in Figure 1.
    [0078] Figure 1 shows that the silicone - acrylic copolymer has a higher molecular weight than the individual polymers, indicating the formation of a silicone - acrylic copolymer.
    Petition 870190128908, of 12/06/2019, p. 25/46
    22/22
    Example 20: GPC graph [0079] GPC (Waters Alliance 2695 GPC) chromatograms of adhesives made from (1) silicone - acrylic copolymer with MQ resin, Example 14 (-) and (2) silicone polymer, acrylic polymer and MQ resin, Example 13 (-) are shown in Figure 2.
    [0080] Figure 2 shows that the two adhesives have different GPC characteristics. The adhesive made from the silicone - acrylic copolymer (Example 14) has a wider and larger molecular weight distribution and peaks than the adhesive made from Example 13.
    Example 21: Photography [0081] The samples above Example 20 were photographed with a Sony Cyber-Shot DSC-S85, 4.0 Mega Pixels.
    [0082] The hybrid silicone-acrylic adhesive of the invention (Example 14) is a clear solution in heptane (left). Example adhesive 13 is an opaque heptane solution. This adhesive is thermodynamically unstable and will ultimately lead to microscopic or even macroscopic phase separation over time.
    [0083] Many modifications and variations of this invention can be made without departing from its spirit and scope, as will be visible to those skilled in the art. The specific realizations described herein are offered by way of example only, and the invention is to be limited only by the terms of the claims affixed, along with the entire scope of equivalents to which such claims are entitled.
    权利要求:
    Claims (10)
    [1]
    1. Silicone-acrylic copolymer, characterized by the fact that it comprises a silicone polymer and an acrylic polymer that are covalently linked through a -Si-O- bond, where the ratio of the silicone polymer and the acrylic polymer is of 50: 1 to 1:50;
    wherein the acrylic polymer is functionalized along its structure with at least one silane or siloxane functional group which is an alkoxy sily functional group that is selected from the trimethoxy sily group, dimethoxy methyl sily group, triethoxy sily group, diethoxy methyl group silyl or mixtures thereof;
    wherein the acrylic polymer is prepared from acrylic monomers selected from butyl acrylate, 2-ethyl hexyl acrylate, isooctyl acrylate, methyl acrylate, methyl methacrylate, t-octyl acrylamide, ethyl hydroxy acrylate and acrylic acid, acrylate hydroxy propyl, hydroxy propyl methacrylate, a monomer containing nitrogen or mixtures thereof;
    wherein the silicone-acrylic copolymer is a branched structure with a plurality of silicone polymers grafted onto the acrylic polymer structure; and wherein the silicone-acrylic copolymer forms a single phase in an organic solvent.
    [2]
    2. Silicone-acrylic copolymer according to claim 1, characterized in that the silicone polymer is a disubstituted poly siloxane organo which is capped at the terminal end with a hydroxyl functional group, alkoxy functional group, hydride functional group , functional group vinyl or their mixtures.
    [3]
    3. Silicone-acrylic copolymer according to claim 1, characterized by the fact that the silicone polymer has an average molecular weight of 100 g / mol to 2,000,000 g / mol.
    Petition 870190128908, of 12/06/2019, p. 27/46
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    [4]
    4. Silicone-acrylic copolymer according to claim 1, characterized by the fact that the nitrogen-containing monomer is selected from the group consisting of N-vinyl pyrrolidone, N-vinyl caprolactam, octyl N-tertiary acrylamide, dimethyl acrylamide, acrylamide diacetone , N-butyl tertiary acrylamide, N-isopropyl acrylamide, cyano ethyl acrylate, N-vinyl acetamide, N-vinyl formamide and mixtures thereof.
    [5]
    5. Article, characterized by the fact that it comprises the silicone-acrylic copolymer as defined in claim 1.
    [6]
    6. Article according to claim 5, characterized by the fact that it is a coating, sealant or adhesive.
    [7]
    7. Article according to claim 6, characterized in that the adhesive is an adhesive in solution, an adhesive carried in water or a hot melt adhesive.
    [8]
    8. Composition, characterized by the fact that it comprises (1) a silicone resin and (2) a silicone-acrylic copolymer that is covalently bonded with an acrylic polymer through Si-O-Si- bonding;
    wherein the silicone resin comprises at least one unit of R3SiOi / 2 siloxy triorgan, where R is methyl, hydroxyl, vinyl, phenyl, (meth) acryloxy, or mixtures thereof, and a 1: 2 molar ratio to 2: 1 R3SíOi / 2 units for each SiO4 / 2;
    wherein the molar ratio of silicone polymers and acrylic polymers is 50: 1 to 1:50;
    wherein the acrylic polymer contains at least one silane or siloxane functional group;
    wherein the silicone-acrylic copolymer is a branched structure with a plurality of silicone polymers grafted onto the acrylic polymer structure; and wherein the siliconeacrylic copolymer forms a single phase in an organic solvent.
    Petition 870190128908, of 12/06/2019, p. 28/46
    3/3
    [9]
    Composition according to claim 8, characterized in that it additionally comprises a tackiness builder, solubilizing agents, polyester, polyether, polyurethane, natural rubber, synthetic rubber, antioxidant, viscosity modifying agent, filler material or its mixtures.
    [10]
    10. Composition according to claim 8, characterized in that the amount of R groups is 0.05% by weight to 10% by weight based on the total weight of the silicone resin.
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    同族专利:
    公开号 | 公开日
    US8664329B2|2014-03-04|
    KR101535847B1|2015-07-13|
    CN102947370B|2016-05-11|
    KR20140141724A|2014-12-10|
    US20140128539A1|2014-05-08|
    US8962748B2|2015-02-24|
    JP5826826B2|2015-12-02|
    WO2011133408A2|2011-10-27|
    WO2011133408A3|2012-02-16|
    US20150119536A1|2015-04-30|
    EP2561008A4|2013-11-06|
    CN102947370A|2013-02-27|
    JP2013525543A|2013-06-20|
    WO2011133408A4|2012-04-12|
    RU2012149840A|2014-05-27|
    US20130012653A1|2013-01-10|
    RU2570574C2|2015-12-10|
    KR101644349B1|2016-08-01|
    KR20130064066A|2013-06-17|
    EP2561008A2|2013-02-27|
    BR112012027110A2|2016-07-26|
    EP2561008B1|2018-02-28|
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    法律状态:
    2018-02-14| B25A| Requested transfer of rights approved|Owner name: HENKEL US IP LLC (US) |
    2018-03-06| B25A| Requested transfer of rights approved|Owner name: HENKEL IP AND HOLDING GMBH (DE) |
    2018-04-10| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|
    2019-09-10| B06U| Preliminary requirement: requests with searches performed by other patent offices: suspension of the patent application procedure|
    2020-03-10| B09A| Decision: intention to grant|
    2020-05-12| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 15/04/2011, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US32714110P| true| 2010-04-23|2010-04-23|
    US61/327,141|2010-04-23|
    PCT/US2011/032609|WO2011133408A2|2010-04-23|2011-04-15|Silicone-acrylic copolymer|
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