CN113166332A - 由支化聚合物形成橡胶胶乳的方法 - Google Patents
由支化聚合物形成橡胶胶乳的方法 Download PDFInfo
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- CN113166332A CN113166332A CN201980080344.9A CN201980080344A CN113166332A CN 113166332 A CN113166332 A CN 113166332A CN 201980080344 A CN201980080344 A CN 201980080344A CN 113166332 A CN113166332 A CN 113166332A
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- rubber cement
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- 238000000034 method Methods 0.000 title claims description 25
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- 239000005060 rubber Substances 0.000 claims abstract description 34
- 229920001195 polyisoprene Polymers 0.000 claims abstract description 33
- 229920001400 block copolymer Polymers 0.000 claims abstract description 32
- 239000004568 cement Substances 0.000 claims abstract description 26
- 229920001519 homopolymer Polymers 0.000 claims abstract description 25
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000007787 solid Substances 0.000 claims abstract description 13
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- LLVWLCAZSOLOTF-UHFFFAOYSA-N 1-methyl-4-[1,4,4-tris(4-methylphenyl)buta-1,3-dienyl]benzene Chemical compound C1=CC(C)=CC=C1C(C=1C=CC(C)=CC=1)=CC=C(C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 LLVWLCAZSOLOTF-UHFFFAOYSA-N 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
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- 239000001257 hydrogen Substances 0.000 claims 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 4
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims 2
- 239000000178 monomer Substances 0.000 abstract description 18
- 238000006243 chemical reaction Methods 0.000 abstract description 10
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- 125000000129 anionic group Chemical group 0.000 abstract description 5
- 239000003999 initiator Substances 0.000 abstract description 4
- 125000002947 alkylene group Chemical group 0.000 abstract description 3
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- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 5
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- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 5
- JSNRRGGBADWTMC-UHFFFAOYSA-N (6E)-7,11-dimethyl-3-methylene-1,6,10-dodecatriene Chemical compound CC(C)=CCCC(C)=CCCC(=C)C=C JSNRRGGBADWTMC-UHFFFAOYSA-N 0.000 description 4
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 4
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- 150000001993 dienes Chemical class 0.000 description 3
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- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 2
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- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- VYBREYKSZAROCT-UHFFFAOYSA-N alpha-myrcene Natural products CC(=C)CCCC(=C)C=C VYBREYKSZAROCT-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 229920005605 branched copolymer Polymers 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
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- 238000007598 dipping method Methods 0.000 description 2
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- 235000010413 sodium alginate Nutrition 0.000 description 2
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- 229920006132 styrene block copolymer Polymers 0.000 description 2
- HBXWUCXDUUJDRB-UHFFFAOYSA-N 1-octadecoxyoctadecane Chemical compound CCCCCCCCCCCCCCCCCCOCCCCCCCCCCCCCCCCCC HBXWUCXDUUJDRB-UHFFFAOYSA-N 0.000 description 1
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 1
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- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
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- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
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- 125000003545 alkoxy group Chemical group 0.000 description 1
- 150000008055 alkyl aryl sulfonates Chemical class 0.000 description 1
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- 230000008901 benefit Effects 0.000 description 1
- 229940071167 c14 olefin sulfonate Drugs 0.000 description 1
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- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
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- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
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- 239000004615 ingredient Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 229920005684 linear copolymer Polymers 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- CETVQRFGPOGIQJ-UHFFFAOYSA-N lithium;hexane Chemical compound [Li+].CCCCC[CH2-] CETVQRFGPOGIQJ-UHFFFAOYSA-N 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
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- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
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- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- RLEFZEWKMQQZOA-UHFFFAOYSA-M potassium;octanoate Chemical compound [K+].CCCCCCCC([O-])=O RLEFZEWKMQQZOA-UHFFFAOYSA-M 0.000 description 1
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- 239000003784 tall oil Substances 0.000 description 1
- IZRJPHXTEXTLHY-UHFFFAOYSA-N triethoxy(2-triethoxysilylethyl)silane Chemical compound CCO[Si](OCC)(OCC)CC[Si](OCC)(OCC)OCC IZRJPHXTEXTLHY-UHFFFAOYSA-N 0.000 description 1
- JCGDCINCKDQXDX-UHFFFAOYSA-N trimethoxy(2-trimethoxysilylethyl)silane Chemical group CO[Si](OC)(OC)CC[Si](OC)(OC)OC JCGDCINCKDQXDX-UHFFFAOYSA-N 0.000 description 1
- LTOKKZDSYQQAHL-UHFFFAOYSA-N trimethoxy-[4-(oxiran-2-yl)butyl]silane Chemical compound CO[Si](OC)(OC)CCCCC1CO1 LTOKKZDSYQQAHL-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/25—Incorporating silicon atoms into the molecule
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
- C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
- C08F297/04—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
- B29C41/02—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of definite length, i.e. discrete articles
- B29C41/14—Dipping a core
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F136/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F136/02—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F136/04—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F136/08—Isoprene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/10—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated with vinyl-aromatic monomers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
- C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
- C08F297/04—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes
- C08F297/044—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes using a coupling agent
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
- C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
- C08F297/04—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes
- C08F297/046—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes polymerising vinyl aromatic monomers and isoprene, optionally with other conjugated dienes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/42—Introducing metal atoms or metal-containing groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/07—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media from polymer solutions
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/02—Direct processing of dispersions, e.g. latex, to articles
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- C—CHEMISTRY; METALLURGY
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Abstract
本发明涉及由以下任意支化聚合物形成的橡胶胶乳:衍生自烯基芳烃‑1,3‑二烯单体体系的支化嵌段共聚物和衍生自异戊二烯的支化聚异戊二烯均聚物。在实施方案中,聚合物的获得是通过在阴离子引发剂存在下于0‑100℃的温度进行聚合,接着与式(R1O)3Si‑Y‑Si(OR2)3的多官能偶联剂偶联,其中R1和R2独立地为C1‑C6烷基,Y是C2‑C8亚烷基。获得的聚合物为具有高固体含量和低零切粘度的橡胶胶浆。所述橡胶胶浆对于制造可用于更多应用的胶乳很有价值。
Description
相关申请
本申请要求2018年12月5日提交的美国临时申请No.62/775624和2019年8月21日提交的美国临时申请No.62/889785的优先权,通过引用并入本文。
发明领域
本发明涉及形成包含使用多官能偶联剂制成的支化聚合物的胶乳的方法。
发明背景
弹性体嵌段共聚物和均聚物对于众多终端用途是有价值的合成材料。具有聚合型共轭二烯嵌段的一或多个嵌段的均聚物和嵌段共聚物是这类材料的实例。实例包括苯乙烯嵌段共聚物如苯乙烯-丁二烯嵌段共聚物以及聚丁二烯和聚异戊二烯均聚物。通常使用阴离子聚合来制备具有较窄分子量分布的苯乙烯嵌段共聚物和聚异戊二烯。合成的聚异戊二烯也可以通过使用Ziegler Natta催化剂将异戊二烯聚合来生产。聚异戊二烯均聚物是合成的,主要为立构规整聚合物,其在分子结构和性能上与天然橡胶极为相似。聚合物最初是在有机溶液中产生的,随后将其凝固并干燥成固体橡胶,或转化成水性胶乳形式。
对于制备包含新型嵌段共聚物和均聚物的具有增强性能的改进胶乳和胶乳制品例如浸渍制品的方法有持续需求,且还需要进一步改进制备胶乳和由其形成的胶乳制品的方法的生产力。
发明概述
本发明的一个方面是制备橡胶胶乳和胶乳制品的方法,包括提供包含支化嵌段共聚物的橡胶胶浆和将橡胶胶浆乳化以形成橡胶胶乳。所述支化嵌段共聚物包含一或多个聚合物嵌段A和一或多个聚合物嵌段B且具有式(A-B)m(R1O)3-mSi-Y-Si(R2O)3-n(B-A)n。每个A嵌段独立地包含至少90摩尔%的烯基芳烃且重均分子量为9-15kg/mol;其中一或多个A嵌段占嵌段共聚物总重量的8-13重量%。每个B嵌段独立地是包含至少90摩尔%的一或多种1,3-二烯且重均分子量为75-150kg/mol的聚(1,3-二烯)嵌段。R1和R2独立地是H或C1-C6烷基,Y是C2-C8亚烷基,m和n独立地是值为1-3的整数。所述嵌段共聚物的偶联效率(CE)为至少40%、优选大于80%。
本发明另一个方面是制备橡胶胶乳和胶乳制品的方法,包括提供包含支化聚异戊二烯均聚物的橡胶胶浆和将橡胶胶浆乳化以形成橡胶胶乳。所述支化聚异戊二烯均聚物具有式(C)m(R1O)3-mSi-Y-Si(R2O)3-n(C)n,其中每个C段是独立地具有400-1000kg/mol、优选500-700kg/mol重均分子量的聚异戊二烯段。R1和R2独立地是H或C1-C6烷基;Y是C2-C8亚烷基;m和n独立地是值为1-3的整数。所述均聚物的偶联效率(CE)为至少40%、优选大于80%。
发明详述
以下术语用于本说明书并具有以下含义。
术语“活性的”用于描述在增长末端具有反应性碳阴离子中心的聚合物链。
术语“偶联效率”(CE)用于定量化由GPC测定的未偶联聚合物与偶联聚合物的比例。
术语“支化度”是指每个支化嵌段共聚物分子中存在的总聚合物臂数的平均值。
多官能偶联剂:支化嵌段共聚物和支化聚异戊二烯均聚物是使用通式(I)表示的多官能偶联剂制备的:
(R1O)3Si-Y-Si(R2O)3 (I);
其中R1和R2独立地是H或C1-C6烷基,且Y是C2-C8亚烷基。具有碳阴离子链端的活性聚合物链与偶联剂(I)的2个硅中心反应形成偶联的嵌段共聚物和偶联的均聚物。由于式(I)具有6个离去基团(烷氧基),所以偶联剂是六官能的,因此理论上每个硅上可以有1-3个聚合物链。任何包含式(I)的六官能有机硅化合物都可以用作偶联剂。在一个实施方案中,优选的多官能偶联剂选自1,2-双(三甲氧基甲硅烷基)乙烷(BTMSE)、1,2-双(三乙氧基甲硅烷基)乙烷(BTESE)或其混合物。
支化嵌段共聚物和支化聚异戊二烯均聚物:用式(I)的多官能偶联剂制备的支化嵌段共聚物包含一或多个聚合物嵌段A、一或多个聚合物嵌段B,由通式(II)表示:
(A-B)m(R1O)3-mSi-Y-Si(R2O)3-n(B-A)n (II);
其中R1、R2和Y如上式(I)所定义,且m和n是支化度测定给出的整数,如下文进一步解释。在实施方案中,支化的嵌段共聚物(II)中R1和R2独立地选自H、甲基或乙基,且Y是-CH2-CH2-基团。
A嵌段是主要由衍生自一或多种烯基芳烃的重复单元构成的芳族嵌段。在实施方案中,A嵌段包含至少90摩尔%、90-95摩尔%或至少95摩尔%的烯基芳烃。在整个嵌段共聚物中,A嵌段(多个)的重量百分比通常小于15重量%。在实施方案中,A嵌段(多个)占8-13重量%、或者8-10重量%、或者10-13重量%。A嵌段的重均分子量为9-15kg/mol。在另一些实施方案中,A嵌段的分子量为9-12kg/mol、或为12-15kg/mol。可使用本领域已知的任何烯基芳烃,例如苯乙烯、α-甲基苯乙烯、对甲基苯乙烯、乙烯基萘等。苯乙烯是优选的单体。
B嵌段是主要由衍生自一或多种共轭二烯(1,3-二烯)的重复单元构成的弹性体嵌段。在实施方案中,B嵌段包含至少90摩尔%、90-95摩尔%或至少95摩尔%的1,3-二烯。每个B嵌段的重均分子量为75-150kg/mol。在另一些实施方案中,B嵌段分子量可以为75-100kg/mol、100-125kg/mol或125-150kg/mol。适合用于制备B嵌段的1,3-二烯的非限制性实例包括丁二烯、异戊二烯、间戊二烯、环己二烯、2,3-二甲基-1,3-丁二烯、月桂烯、法尼烯等。
式(II)中m和n独立地在1-3范围。随着m和n的值从1增加至3,整个共聚物中更高支化的共聚物的量将相应增加。在实施方案中,式(II)中的m和n的值分别可以为1,2;1,3;2,2;2,3;3,2;3,1和3,3。当活性聚合物链与多官能偶联剂偶联时,依据化学计量和反应条件,m和n值范围在1-3范围内的支化嵌段共聚物的混合物是可能的。因此,理论上讲,由偶联反应得到的总产物可以通过m和n的平均值以及总支化度来表征,可测量出产物中支化嵌段共聚物的总量。这进而会影响共聚物的物理和/或化学性质。在一个方面,支化嵌段共聚物(II)的m和n值可在1-3之间,使得(m+n)大于2但小于或等于6,数学上可表示为:2<(m+n)≤6。
支化聚异戊二烯均聚物包含一种或多个聚合物嵌段C,并由通式(III)表示:
(C)m(R1O)3-mSi-Y-Si(R2O)3-n(C)n (III);
其中R1、R2和Y如上式(I)所定义,且m和n如上式(II)所定义。C段主要由衍生自一或多种共轭二烯(1,3-二烯)的重复单元构成。适合用于制备C段的1,3-二烯的非限制性实例包括丁二烯、异戊二烯、间戊二烯、环己二烯,2,3-二甲基-1,3-丁二烯、月桂烯、法尼烯等。C段独立地具有400-1000kg/mol、优选500-700kg/mol的重均分子量。支化均聚物(III)中的支化度取决于m和n的值,且可按上述支化嵌段共聚物(II)类似的方式变动。在一个实施方案中,m和n的值为1或1。在另一个实施方案中,m和n的值在1-3之间,使得(m+n)大于2但小于或等于6,数学上可表示为:2<(m+n)≤6。m+n的值可以是3-6。在实施方案中,式(III)中的m和n的值可以分别为1,2;1,3;2,2;2,3;3,2;3,1和3,3。在优选的实施方案中,R1和R2独立地选自H、甲基或乙基;Y为-CH2-CH2-基团。
制备支化共聚物的方法:通过首先构建聚合物嵌段A然后构建嵌段B,之后将活性链末端与多官能偶联剂(I)偶联的方法,获得式(II)的支化嵌段共聚物。嵌段A是通过使用阴离子引发剂将第一单体聚合而形成,该第一单体可以是一或多种包含至少90摩尔%烯基芳烃的烯基芳烃。在第一单体中可以存在少量(至多10摩尔%)的其它可阴离子聚合的单体,例如1,3-二烯。然后加入包含至少90摩尔%一或多种1,3-二烯的第二单体,聚合得到嵌段B。第二种单体可包含少量(至多10摩尔%)另一种阴离子可聚合单体,例如烯基芳烃。所述反应在惰性气体(氮气或氩气)气氛下进行。阴离子引发剂通常是烷基锂,例如正丁基锂、仲丁基锂、正己基锂等。适用溶剂是液态烃溶剂,例如液态低级烃溶剂,如正戊烷、环戊烷、正己烷、环己烷、正庚烷等。所述反应可在-50℃至150℃或20℃至100℃的温度下进行。异戊二烯主要以线形方式聚合而形成具有“活性”阴离子链端的聚异戊二烯链。在达到所期望的单体转化率之后,通过加入式(I)的多官能偶联剂来终止聚合。所得产品(II)包含期望的支化嵌段共聚物,它如果需要可凝结成固体橡胶产物,或转化成含水胶乳形式。
支化聚异戊二烯均聚物(III)是通过使用阴离子引发剂在类似上述条件下将异戊二烯聚合,然后活性链末端与多官能偶联剂(I)进行偶联而获得的。在达到所期望的单体转化率之后,通过与试剂(I)偶联终止聚合。所得的支化嵌段共聚物可凝结成固体橡胶产物,或转化成含水胶乳形式。
上面得到的橡胶胶浆的固含量通常为5%-35重量%,或为15%-25重量%。在实施方案中,聚合物(II)和(III)中聚异戊二烯链的顺式含量范围为70%-95%。
动力粘度随温度变化的曲线表明,对于给定的重量%浓度,在相近分子量条件下,共聚物(II)和均聚物(III)的粘度显著小于没有偶联剂情况下制备的相应线性共聚物和均聚物的粘度。在实施方案中,固含量15%-35%(重量)的含聚合物(II)的橡胶胶浆具有70%-95%的顺式含量,零切粘度小于25000mPa、或小于20000mPa、或小于15000mPa,重均分子量为350-700kg/mol。在另一实施例中,固体含量15%-25%(重量)的含聚合物(III)的橡胶胶浆具有70-95%的顺式含量,零切粘度小于80000mPa、或小于75000mPa、或小于70000mPa,且重均分子量为1000-3500kg/mol。在生产装置中中橡胶胶浆的粘度降低能提供有价值的益处,因为这样就能允许在不必升级工艺设备尺寸条件下处理高达100%甚至更高产能的橡胶胶浆。
由聚合步骤得到的在有机溶剂中的偶联聚合物(II)或(III)的橡胶溶液可通过使用高剪切混合器与表面活性剂水溶液混合而转化为水基胶乳。随后将溶剂从所得乳液中除去,至残留溶剂<0.1%。得到的稀水性胶乳可通过离心或膏化法浓缩至60重量%橡胶。
乳化过程中使用的表面活性剂也使即时形成的胶乳稳定。表面活性剂的用量通常为干基聚异戊二烯重量计的0.5-2.0重量%范围。阴离子表面活性剂是优选的。阴离子表面活性剂的例子包括十二烷基苯磺酸钠、其它烷基芳基磺酸盐、烷基磺酸盐、烯烃磺酸盐(例如C14烯烃磺酸盐)、醇硫酸盐如十二烷基硫酸钠,任选与一或多种其它表面活性剂如辛酸钾、聚氧乙烯十六烷基/硬脂基醚等组合使用。在一个实施方案中,表面活性剂也可以是包括松香、二聚松香、歧化松香和氢化松香的松香类材料的碱金属盐。在另一实施方案中,表面活性剂还可以是一或多种选自妥尔油脂肪酸、长链例如有12-20个碳原子的脂肪酸的碱金属盐,等等。
性能:支化均聚物(II)和共聚物(III)的胶乳形成质量非常好的浸渍膜。由此形成的固化膜表现出改善的性能。在实施方案中,固化膜表现出20-40MPa、或至少25MPa、或至少30MPa的拉伸强度。在实施方案中,膜还表现出500-1250%、或从750-1250%、或至少750%的断裂伸长率。在实施方案中,所述膜还表现出15-35kN/m或至少20kN/m的撕裂强度。还可以形成具有所有上述范围内三个性能的膜。
支化聚合物(II)和(III)的用途:包含聚合物(II)或(III)的胶乳对于生产制品是有价值的。方法包含将无凝固剂或涂有凝固剂的模型浸入水性胶乳乳液中至少一次,以在模型表面上形成具有偶合的聚异戊二烯单一粒子的胶乳膜薄层。可以使用本领域中已知的任何模型。该技术还可用于在模型上层叠一层以上的胶乳粒子膜来生产诸如手套,避孕套等制品,然后从模型上剥离胶乳膜。
实施例。聚合物分子量(在本文中称为“重均分子量”或“GPC分子量”)可以通过HMW-GPC(凝胶渗透色谱法)采用聚苯乙烯校准标准物来确定。胶乳的中值粒径是用BeckmanCoulter LS13320通过激光衍射进行测定的。固含量可用Sartorius MA35水分天平进行测定。
与多官能偶联剂反应的偶联效率可通过GPC由未偶联的聚合物相对于更高分子量的偶联聚合物的峰积分比来确定。
通过在60℃并同时搅拌条件下将Ca(NO3)2.4H2O(~14%)和CaCO3(~5%)在水中溶解/分散来制备凝固剂溶液/分散液。将包括参比样品在内的所有胶乳与5重量份市售母胶组合物(含有硫、促进剂和抗氧剂)混合,并用市售表面活性剂稳定。将这些化合物用软化水稀以获得所期望的30%固含量。加入1M KOH溶液将pH调节至11-11.5并将化合物在搅拌下于环境温度中储存。
对于凝固剂浸渍操作,使用金属板并采用标准浸渍程序。在熟成1、3和6天后浸渍薄膜。按照ASTM D412/ISO37(模片C),使用配备500N载荷传感器和长行程引伸计的Instron3365拉伸工作台,测定浸渍膜的机械性能。拉伸性能示于表5。
实施例1-5.制备支化聚异戊二烯均聚物。
在氮气氛下,于配有搅拌器、冷却、温度探针、压力探针和用于加入/排出溶剂、单体和其它试剂的辅助设备的10L不锈钢反应器中进行聚合。使用前,将溶剂和单体通过Alcoa(活性氧化铝)纯化。作为通用步骤,向反应器中加入5L干燥溶剂和450g异戊二烯并加热至60℃。向混合物中加入稀s-BuLi溶液(0.04M)来引发聚合。在将所需量的单体转化为所期望的分子量后,通过按活性链/偶联剂摩尔比为4/1的量加入偶联剂(BTMSE或BTESE)来终止反应。在某些情况下,重复此步骤一或两次,直到单体完全转化。
在异戊二烯聚合反应中于不同活性链浓度下对BTMSE和BTESE进行了评估。结果总结在表1中。数据显示BTMSE和BTSE具有相近的偶联表现。
表1.BTMSE和BTESE与不同浓度的活性聚异戊二烯链的偶联反应。
实施例6-8:制备支化聚异戊二烯均聚物。采用上述步骤将它们制备成橡胶胶浆。结果示于表2。参比样品是不使用偶联剂制备的线形(无支化)聚异戊二烯。
表2.制备的支化聚异戊二烯。
实施例9-11:制备支化聚异戊二烯橡胶胶乳。将橡胶胶浆样品转移至实验室规模的胶乳生产装置,该装置配备带有聚合物和皂液计量泵的在线高剪切混合装置。在标准化乳化条件下,由固定比例的胶浆和歧化松香酸钾盐水溶液生产乳液。随后对乳液进行溶剂脱除而获得稀乳液,加入海藻酸钠后通过膏化将其浓缩。结果见表3。参比-2是由上述参比-1橡胶胶浆制备的参比聚异戊二烯胶乳。
表3.制备的支化聚异戊二烯胶乳。
R/S比:橡胶/皂的比例PSmed:中值粒径
表4.固化膜的拉伸性能。
表4显示,由使用多官能偶联剂制备的支化聚异戊二烯(实施例12和13)制成的浸渍膜的拉伸性能非常好,且与参比样品膜(参比-3)所观察到的拉伸性能相当。
实施例14.制备支化苯乙烯-异戊二烯嵌段共聚物。
在氮气氛下,于配有搅拌器、冷却、温度探针、压力探针和用于加入/排出溶剂、单体和其它试剂的辅助设备的10L不锈钢反应器中进行聚合。使用前,将溶剂和单体通过Alcoa(活性氧化铝)纯化。向反应器中加入5L干燥溶剂和400g苯乙烯并加热至60℃。向混合物中加入稀s-BuLi溶液(0.04M)来引发聚合。苯乙烯转化后,加入3kg异戊二烯单体。在第二单体转化至所期望的分子量后,通过按活性链/偶联剂摩尔比为4/1的量加入BTMSE偶联剂来终止反应。结果示于表5。参比-4是使用GPTS(缩水甘油基丙基三甲氧基硅烷)作为偶联剂制备的聚异戊二烯市售批样。
表5.CE表示偶联效率。DoB表示支化度。
实施例15:制备支化苯乙烯-异戊二烯嵌段共聚物胶乳。
将来自实施例14的橡胶胶浆样品转移至实验室规模的胶乳生产装置,该装置配备带有聚合物和皂液计量泵的在线高剪切混合装置。在标准化乳化条件下,由固定比例的胶浆和歧化松香酸钾盐水溶液生产乳液。随后对乳液进行溶剂脱除而获得稀乳液,加入海藻酸钠后通过膏化将其浓缩。结果示于表6。
表6.
R/S比:橡胶/皂的比例PSmed:中值粒径
实施例16代表由实施例15的支化苯乙烯-异戊二烯嵌段共聚物胶乳制成的浸渍膜。参比5代表由衍生自参比4的嵌段共聚物的支化苯乙烯-异戊二烯嵌段共聚物胶乳制成的浸渍膜。表7显示,由使用多官能偶联剂制备的支化苯乙烯-异戊二烯嵌段共聚物制成的浸渍膜(实施例16)的拉伸性能非常好,且与参比样品膜(参比-5)所观察到的拉伸性能相当。
表7.
实施例 | 拉伸强度 | 模量500% | 伸长率 | 撕裂强度 |
参比5 | 21.4 | 1.62 | 1089 | 24.7 |
16 | 20.4 | 1.43 | 1113 | 27.3 |
对于本说明书和所附权利要求书,除非另行指明,说明书和权利要求书中所用的表示量、百分比或比例的所有数字和其它数值应被理解为在所有情况下都被术语“大约”修饰。因此,除非有相反的指示,下列说明书和所附权利要求书中所列的数字参数是近似值,其可以根据寻求获得的所期望特性而变动。注意,如在本说明书和所附权利要求书中所使用的,单数形式“一”、“一个(种)”和“该”包括复数指代,除非明确指明是单数指代。如本文所用,术语“包括”及其语法变体旨在为非限制性的,从而列表中列举的项目不排斥其它类似项目可以代替或加入该列表项目中。
如本文所使用的,术语“包含”意味着包括跟着该术语后指出的元素或步骤,但是任何这样的元素或步骤都不是穷尽的,并且实施例可以包括其它元素或步骤。尽管本文已使用术语“包含”和“包括”来描述各个方面,但可以使用术语“基本由...组成”和“由...组成”来代替“包含”和“包括”以提供本公开内容的更具体方面并且也是公开的。
除非另有说明,否则本文所用的所有技术和科学术语具有本公开发明所属领域技术人员通常所理解的相同含义,与本公开内容所述元素,材料或其它组分的种类均由该类,材料或其它成分组成。可以选择单独的组分或组分的混合物,旨在包含所列组分及其混合物的所有可能的亚通用组合。元素、材料或其它组分的种属列举,可以选择单个组分或混合组分,旨在包括所列举的组分及其混合物的所有可能的亚属组合。
可专利范围由权利要求书限定,并且可以包括本领域技术人员想到的其它实施例,只要它们的结构元素与权利要求书的文字语言没有区别,或者如果它们包括与权利要求书的文字语言没有实质性区别的等效结构元素。在与本申请不矛盾的程度内,本文提及的所有参考文献均通过引用并入本申请。
Claims (24)
1.由包含支化嵌段共聚物的胶乳制成的膜制品,所述支化嵌段共聚物包含一或多个聚合物嵌段A和一或多个聚合物嵌段B且具有式(A-B)m(R1O)3-mSi-Y-Si(R2O)3-n(B-A)n,
其中
每个A嵌段独立地包含至少90摩尔%的烯基芳烃,其中一或多个A嵌段占嵌段共聚物总重量的8-13重量%;
每个B嵌段独立地是包含至少90摩尔%的一或多种1,3-二烯的聚(1,3-二烯)嵌段;
每个A嵌段独立地具有9-15kg/mol的重均分子量,且每个B嵌段独立地具有75-150kg/mol的重均分子量;
R1和R2独立地是H或C1-C6烷基,Y是C2-C8亚烷基,m和n独立地是值为1-3的整数;和
所述嵌段共聚物的偶联效率(CE)为至少40%;和
其中
所述膜制品表现出至少20MPa的拉伸强度。
2.权利要求1的膜制品,其中(m+n)的值为3-6。
3.权利要求1的膜制品,其中Y是-CH2CH2-,且R1和R2是氢、甲基或乙基。
4.权利要求1的膜制品,其中1,3-二烯是异戊二烯且烯基芳烃是苯乙烯。
5.权利要求1-4任一项的膜制品,其中所述膜制品表现出以下至少一项性能:至少20Mpa的拉伸强度,至少500%的断裂伸长率和至少15kN/m的撕裂强度。
6.权利要求1-4任一项的膜制品,其中所述膜制品是选自避孕套和手套的浸渍制品。
7.由包含式(C)m(R1O)3-mSi-Y-Si(R2O)3-n(C)n的支化聚异戊二烯均聚物的胶乳制成的膜制品,
其中
每个C嵌段是独立地具有400-1000kg/mol重均分子量的聚异戊二烯嵌段;
R1和R2独立地是H或C1-C6烷基,Y是C2-C8亚烷基,m和n独立地是值为1-3的整数;
所述支化聚异戊二烯均聚物的偶联效率(CE)为至少40%;和
其中
所述膜制品表现出至少20MPa的拉伸强度。
8.权利要求7的膜制品,其中(m+n)的值为3-6。
9.权利要求7的膜制品,其中Y是-CH2CH2-,且R1和R2是氢、甲基或乙基。
10.权利要求7的膜制品,其中C嵌段的重均分子量为500-700kg/mol。
11.权利要求7-10任一项的膜制品,其中所述膜制品表现出以下至少一项性能:500%的断裂伸长率和至少15kN/m的撕裂强度。
12.一种形成橡胶胶乳的方法,包括:
提供一种橡胶胶浆,包含
偶联效率(CE)至少为40%的支化嵌段共聚物,所述支化嵌段共聚物包含一或多个聚合物嵌段A和一或多个聚合物嵌段B且具有式(A-B)m(R1O)3-mSi-Y-Si(R2O)3-n(B-A)n,其中
每个A嵌段独立地包含至少90摩尔%的烯基芳烃,其中一或多个A嵌段占嵌段共聚物总重量的8-13重量%;
每个B嵌段独立地是包含至少90摩尔%的一或多种1,3-二烯的聚(1,3-二烯)嵌段;
每个A嵌段独立地具有9-15kg/mol的重均分子量,且每个B嵌段独立地具有75-150kg/mol的重均分子量;
R1和R2独立地是H或C1-C6烷基,Y是C2-C8亚烷基,m和n独立地是值为1-3的整数;和
将橡胶胶浆乳化以形成橡胶胶乳。
13.权利要求12的方法,其中所述橡胶胶浆中所述支化嵌段共聚物的(m+n)值为3-6。
14.权利要求12的方法,其中所述橡胶胶浆中所述支化嵌段共聚物的Y是-CH2CH2-,且R1和R2是氢、甲基或乙基。
15.权利要求12的方法,其中所述橡胶胶浆中支所述化嵌段共聚物中的1,3-二烯是异戊二烯,且所述支化嵌段共聚物中的所述烯基芳烃是苯乙烯。
16.权利要求12-15任一项的方法,其中固含量在15-25重量%范围的所述橡胶胶浆的零剪切粘度小于25000mPas。
17.通过权利要求12-15任一项方法形成的胶乳。
18.一种形成橡胶胶乳的方法,包括:
提供一种橡胶胶浆,其包含具有式(C)m(R1O)3-mSi-Y-Si(R2O)3-n(C)n的偶联效率(CE)至少为40%的支化聚异戊二烯均聚物,其中
每个C嵌段是独立地具有400-1000kg/mol重均分子量的聚异戊二烯嵌段;
R1和R2独立地是H或C1-C6烷基,Y是C2-C8亚烷基,m和n独立地是值为1-3的整数;和
将橡胶胶浆乳化以形成橡胶胶乳。
19.权利要求18的方法,其中所述支化聚异戊二烯均聚物的(m+n)值为3-6。
20.权利要求18的方法,其中所述支化聚异戊二烯中的Y是-CH2CH2-,且R1和R2是氢、甲基或乙基。
21.权利要求18的方法,其中所述支化聚异戊二烯均聚物中的C段具有500-700kg/mol的重均分子量。
22.权利要求18-21任一项的方法,其中固含量范围在15-25重量%的所述橡胶胶浆的零剪切粘度小于80000mPas。
23.权利要求18-21任一项的方法,其中所述橡胶胶浆的固含量为5-25重量%。
24.权利要求18的方法,其中所述橡胶胶浆具有
固含量范围在15-25重量%下的零剪切粘度小于80000mPas;
顺式含量为70%至95%;和
重均分子量为1000-3500kg/mol。
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JP7376586B6 (ja) | 2023-11-27 |
BR112021010922A2 (pt) | 2021-08-24 |
JP2022509737A (ja) | 2022-01-24 |
US20220010126A1 (en) | 2022-01-13 |
EP3867289A4 (en) | 2022-08-31 |
CN113166332B (zh) | 2024-02-09 |
EP3867289A1 (en) | 2021-08-25 |
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