CN113185636A - 一种短氟碳链丙烯酸酯聚合物及其制备方法与在脱模剂中的应用 - Google Patents
一种短氟碳链丙烯酸酯聚合物及其制备方法与在脱模剂中的应用 Download PDFInfo
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- CN113185636A CN113185636A CN202110421995.9A CN202110421995A CN113185636A CN 113185636 A CN113185636 A CN 113185636A CN 202110421995 A CN202110421995 A CN 202110421995A CN 113185636 A CN113185636 A CN 113185636A
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- monomer
- mold release
- silicone oil
- parts
- methyl
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- 229920000058 polyacrylate Polymers 0.000 title claims abstract description 32
- 239000006082 mold release agent Substances 0.000 title abstract description 19
- 238000002360 preparation method Methods 0.000 title description 8
- 239000000178 monomer Substances 0.000 claims abstract description 79
- 239000000203 mixture Substances 0.000 claims abstract description 46
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical group FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 claims abstract description 37
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 19
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 19
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 5
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 5
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 34
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical group N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 31
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 30
- 229920002545 silicone oil Polymers 0.000 claims description 30
- 239000003505 polymerization initiator Substances 0.000 claims description 22
- 239000002904 solvent Substances 0.000 claims description 22
- -1 2-tetrafluoroethyl ethyl Chemical group 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 21
- 239000012298 atmosphere Substances 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 14
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 8
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 8
- 125000001931 aliphatic group Chemical group 0.000 claims description 8
- 239000007810 chemical reaction solvent Substances 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims description 4
- 125000004122 cyclic group Chemical group 0.000 claims description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 4
- VNXYDFNVQBICRO-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoro-2-methoxypropane Chemical compound COC(C(F)(F)F)C(F)(F)F VNXYDFNVQBICRO-UHFFFAOYSA-N 0.000 claims description 3
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 3
- CBEFDCMSEZEGCX-UHFFFAOYSA-N 1,1,2,2,2-pentafluoro-n,n-bis(1,1,2,2,2-pentafluoroethyl)ethanamine Chemical compound FC(F)(F)C(F)(F)N(C(F)(F)C(F)(F)F)C(F)(F)C(F)(F)F CBEFDCMSEZEGCX-UHFFFAOYSA-N 0.000 claims description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- LGJCFVYMIJLQJO-UHFFFAOYSA-N 1-dodecylperoxydodecane Chemical compound CCCCCCCCCCCCOOCCCCCCCCCCCC LGJCFVYMIJLQJO-UHFFFAOYSA-N 0.000 claims description 2
- DFUYAWQUODQGFF-UHFFFAOYSA-N 1-ethoxy-1,1,2,2,3,3,4,4,4-nonafluorobutane Chemical compound CCOC(F)(F)C(F)(F)C(F)(F)C(F)(F)F DFUYAWQUODQGFF-UHFFFAOYSA-N 0.000 claims description 2
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- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 2
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 claims description 2
- CHPNMYQJQQGAJS-UHFFFAOYSA-N 3-tri(propan-2-yloxy)silylpropyl 2-methylprop-2-enoate Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)CCCOC(=O)C(C)=C CHPNMYQJQQGAJS-UHFFFAOYSA-N 0.000 claims description 2
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 2
- HIHIPCDUFKZOSL-UHFFFAOYSA-N ethenyl(methyl)silicon Chemical compound C[Si]C=C HIHIPCDUFKZOSL-UHFFFAOYSA-N 0.000 claims description 2
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 2
- DBOFMRQAMAZKQY-UHFFFAOYSA-N ethyl 2,2,3,3,3-pentafluoropropanoate Chemical compound CCOC(=O)C(F)(F)C(F)(F)F DBOFMRQAMAZKQY-UHFFFAOYSA-N 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- XGLLQDIWQRQROJ-UHFFFAOYSA-N methyl 3,3,3-trifluoro-2-oxopropanoate Chemical compound COC(=O)C(=O)C(F)(F)F XGLLQDIWQRQROJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
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- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 2
- LGUZHRODIJCVOC-UHFFFAOYSA-N perfluoroheptane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F LGUZHRODIJCVOC-UHFFFAOYSA-N 0.000 claims description 2
- ZJIJAJXFLBMLCK-UHFFFAOYSA-N perfluorohexane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F ZJIJAJXFLBMLCK-UHFFFAOYSA-N 0.000 claims description 2
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
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- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 24
- 229910052731 fluorine Inorganic materials 0.000 abstract description 24
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- YFSUTJLHUFNCNZ-UHFFFAOYSA-N perfluorooctane-1-sulfonic acid Chemical compound OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YFSUTJLHUFNCNZ-UHFFFAOYSA-N 0.000 abstract description 3
- SNGREZUHAYWORS-UHFFFAOYSA-N perfluorooctanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F SNGREZUHAYWORS-UHFFFAOYSA-N 0.000 abstract description 3
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 14
- 239000003795 chemical substances by application Substances 0.000 description 14
- 238000009472 formulation Methods 0.000 description 13
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 description 12
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Classifications
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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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1818—C13or longer chain (meth)acrylate, e.g. stearyl (meth)acrylate
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- 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
- B29C33/00—Moulds or cores; Details thereof or accessories therefor
- B29C33/56—Coatings, e.g. enameled or galvanised; Releasing, lubricating or separating agents
- B29C33/60—Releasing, lubricating or separating agents
- B29C33/62—Releasing, lubricating or separating agents based on polymers or oligomers
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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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
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Abstract
本发明提供了一种短氟碳链丙烯酸酯聚合物,由短氟碳链丙烯酸酯单体、丙烯酸酯单体、含乙烯基的有机硅单体、丙烯酸单体通过溶液聚合得到;本发明还提供了一种以短氟碳链丙烯酸酯聚合物为主体的含氟树脂脱模剂组合物,其具有很好的降解性,避免了PFOA/PFOS类物质的使用;本发明脱模剂组合物在模具表面成膜均匀,脱模时间短,脱模寿命长,不易高温流胶,容易从待脱模成品表面脱除,具有优异的脱模性能,可运用于热固性树脂、热塑性树脂和各种橡胶制件等脱模技术领域。
Description
技术领域
本发明涉及热固性树脂、热塑性树脂和各种橡胶制件等脱模技术领域,特别涉及一种短氟碳链丙烯酸酯聚合物及其制备方法,以及在高性能脱模剂组合物中的应用。
背景技术
脱模剂是一种介于模具与成型加工物之间的功能性物质,常用于金属压铸、聚氨酯泡沫和弹性体、玻璃纤维增强塑料、注塑热塑性塑料、真空发泡片材和挤压型材等各种模压操作中,以防止模制品、层压制品等粘结到模具或其他板面,起到易于脱离作用的一类加工助剂。
在高分子聚合物的成型加工领域内,脱模剂的使用是必不可少的,传统用作脱模剂的物质主要为碳氢类表面活性剂或聚硅氧烷类的有机硅表面活性剂。利用碳氢类的酯化物(如磷脂类化合物)配制的脱模剂,其脱模后的产品可直接进行二次加工,但长期使用后将会在模具表面形成棕色结焦物而污染模具。选用有机硅类(如硅油、硅橡胶)物质配成的脱模剂,其脱模效果要比前一类优越,但对脱模后的产品表面产生一定的油状污染,使该产品无法进行二次加工。
随着对模制品质量要求的提高,模制品加工方式及注塑、挤出、压延、模压、层压等工艺的迅速发展,传统的蜡类和硅油类脱模剂已难以适应,近年来利用含氟表面活性剂(FS)配制成新一代高效含氟脱模剂成为众多企业研究的热点。其主要优点为:使用浓度低,使用寿命长,对高黏度的原料有良好的脱模性,对制品表面污染性小,制品可直接进行二次加工,对模具表面无污染性,制备后的脱模剂产品质量稳定,存储时间长。
含氟丙烯酸酯聚合物具有独特的氟链烷基结构,含氟烷基(Rf)向外扩展延伸,并定向排列,大大降低聚合物的表面能。因此,使用含氟丙烯酸酯聚合物作为含氟脱模剂的主体得到了广泛的研究。日本专利5060847号公开了由丙烯酸全氟烷基酯、含磷酸基的丙烯酸酯和丙烯酸改性有机硅油共聚而得的共聚化合物形成的脱模剂,但是研究发现磷酸基的存在会与成型材料发生反应,损害脱模性。专利CN102782075A公开了一种由含氟共聚物和介质构成的脱模剂,该含氟共聚物含有碳数1~6的多氟烷基的单体(a)的构成单元、碳数18~30的烷基的(甲基)丙烯酸酯(b)的构成单元,但该脱模剂难以满足高温成型时脱模的需求。
长氟碳链(C≥8)丙烯酸酯聚合物由于较长的氟碳链段,运动性强,从而使氟链可稳定迁移排列于表面,可显著降低脱模剂表面的表面能;但是长碳氟链化合物具有环境持久性、长距离迁移性和生物累积性以及潜在的健康风险,国际社会已出台相应法案和行动措施对PFOA/PFOS类物质进行淘汰和限制。短氟碳链(C≤6)丙烯酸酯聚合物具有很好的降解性,故已成为目前研发的热点。但与长氟碳链丙烯酸酯聚合物相比,由于氟碳链较短,氟链难于迁移并稳定排列于表面,因而其表面性能不佳。为进一步提高短氟碳链丙烯酸酯聚合物的表面性能,在聚合体系中引入长链丙烯酸酯单体,利用其长链优异的运动迁移性能,带动短氟碳链迁移,并将含氟短链有效稳定存在于表面。
发明内容
针对现有技术中存在的问题,本发明提供了一种短氟碳链丙烯酸酯聚合物及其制备方法,和以短氟碳链丙烯酸酯聚合物为主体的脱模剂组合物,该脱模剂具有优异的脱模性能。
本发明提出以短氟碳链丙烯酸酯聚合物作为脱模剂组合物的主体,该脱模剂组合物可运用于热固性树脂、热塑性树脂和各种橡胶制件等脱模技术领域,在模具表面成膜均匀,脱模时间短,脱模寿命长,不易高温流胶,容易从待脱模成品表面脱除,具有优异的脱模性能。
本发明的技术方案如下:
一种短氟碳链丙烯酸酯聚合物,由以下重量份的单体共聚而成:
(A)短氟碳链丙烯酸酯单体20~80份;
(B)丙烯酸酯单体20~60份;
(C)含乙烯基的有机硅单体5~20份;
(D)丙烯酸单体5~20份。
优选的,所述短氟碳链丙烯酸酯聚合物由以下重量份的单体共聚而成:
(A)短氟碳链丙烯酸酯单体40~60份;
(B)丙烯酸酯单体20~40份;
(C)含乙烯基的有机硅单体5~14份;
(D)丙烯酸单体1~14份。
单体(A)如通式(I)所示:
式(I)中:
R1为氢或甲基;
R2为-O-、-S-或-NH-;
R3为碳数1~8的二价脂肪族烃基、碳数6~12的二价芳香族烃基或环状脂肪族烃基;
Rf为全氟烷基,可以是直链或支链状,碳数优选为1~6,特别是4~6;具体的,Rf例如:-CF3、-CF2CF3、-CF2CF2CF3、-CF(CF3)2、-CF2CF2CF2CF3、-CF2CF(CF3)2、-C(CF3)3、-(CF2)4CF3、-(CF2)2CF(CF3)2、-CF2C(CF3)3、-CF(CF3)CF2CF2CF3、-(CF2)5CF3、-(CF2)3CF(CF3)2等;
作为上述通式(I)所示的短氟碳链(C≤6)丙烯酸酯单体的具体物质,例举如下(但不限于这些):
H2C=C(CH3)COO(CH2)2(CF2)5CF3
H2C=C(CH3)COO(CH2)2CF(CF3)CF2CF2CF3
H2C=C(CH3)CONH(CH2)2(CF2)5CF3
H2C=C(CH3)CONH(CH2)2(CF2)2CF(CF3)2
H2C=C(CH3)COS(CH2)2(CF2)5CF3
H2C=C(CH3)COS(CH2)2CF2CF2CF2CF2CF3
单体(B)如通式(II)所示:
式(II)中:
R4为氢或甲基;
R5为直链或支链状的一价脂肪族烃基、一价芳香族烃基或一价环状脂肪族烃基,R5碳数1~30,优选12~30;
作为上述通式(II)所示的丙烯酸酯单体的具体物质,例举如下(但不限于这些):
(甲基)丙烯酸十三烷基酯、(甲基)丙烯酸十四烷基酯、(甲基)丙烯酸十六烷基酯、(甲基)丙烯酸十八烷基酯、(甲基)丙烯酸硬脂酯、(甲基)丙烯酸二十二烷基酯等。
单体(C)例如为:乙烯基三甲氧基硅烷、乙烯基三乙氧基硅烷、甲基丙烯酰氧丙基三(异丙氧基)硅烷、甲基丙烯酰氧丙基三(甲氧基)硅烷等。
本发明所述短氟碳链丙烯酸酯聚合物由单体(A)、单体(B)、单体(C)、单体(D)通过溶液聚合得到,其制备方法为:
按照各单体的重量配比备料,N2气氛下,将单体(B)、单体(D)加到反应溶剂中,开启搅拌并升温至65℃,待单体全部溶解后,滴加聚合引发剂的溶液,滴加完毕后反应1h,接着于65℃下加入单体(A)和单体(C),反应6h,再升温至75℃反应2h,之后冷却至室温(20~30℃),得到所述短氟碳链丙烯酸酯聚合物(溶液形式);
所述反应溶剂为丙酮、甲乙酮、甲基异丁基甲酮、氯仿、异丙醇、戊烷、已烷、庚烷、辛烷、环己烷、苯、甲苯、二甲苯、石油醚、四氢呋喃、乙酸乙酯、乙酸丁酯中的任意一种;
所述反应溶剂的质量与单体(A)、单体(B)、单体(C)、单体(D)合计质量之比为0.5~2:1;
所述聚合引发剂为偶氮二异丁腈、苯甲酰基过氧化物、二叔丁基过氧化物、月桂基过氧化物、过氧化氢异丙苯、过氧化新戊酸叔丁酯、过氧化二碳酸二异丙酯或偶氮双甲基丙酸酯等;
所述聚合引发剂与单体(A)、单体(B)、单体(C)、单体(D)合计质量之比为0.1~2:100;
聚合引发剂溶液中的溶剂与反应溶剂相同。
本发明还提供了一种脱模剂组合物,由以下重量份的组分组成:
1~20份短氟碳链丙烯酸酯聚合物,10~30份硅油,30~80份溶剂A,1~20份溶剂B。
优选的,所述脱模剂组合物由以下重量份的组分组成:
5~15份短氟碳链丙烯酸酯聚合物,10~20份硅油,50~80份溶剂A,1~10份溶剂B。
所述脱模剂组合物中:
短氟碳链丙烯酸酯聚合物的数均分子量为5000~100000,优选20000~50000;
硅油无特殊的限制,可选自甲基硅油、乙基硅油、苯基硅油、甲基含氢硅油、甲基苯基硅油、甲基氯苯基硅油、甲基乙氧基硅油、甲基三氟丙基硅油、甲基乙烯基硅油、甲基羟基硅油、乙基含氢硅油、羟基含氢硅油中的任意一种;
溶剂A、溶剂B没有特殊的含义,标记为“A”、“B”只是用于区分不同类型的溶剂;其中,溶剂A选自乙酸甲酯、乙酸乙酯、乙酸丙酯、乙酸正丁酯、丙酸丁酯、乙二醇甲醚、二氧六环、丙酮、环己酮、戊烷、已烷、庚烷、辛烷、环己烷中的任意一种;溶剂B选自全氟己烷、全氟庚烷、全氟三乙胺、六氟异丙基甲醚、1,1,2,2-四氟乙基-2,2,2-三氟乙基醚、1,1,2,2-四氟乙基乙基醚、乙基九氟丁基醚、三氟丙酮酸甲酯、五氟丙酸乙酯中的任意一种。
所述脱模剂组合物的制备方法为:
按照配方,取短氟碳链丙烯酸酯聚合物,然后加入硅油、溶剂A、溶剂B,混合均匀后备用。
所述脱模剂组合物可作为内脱模剂或外脱模剂使用,优选作为外脱模剂使用。
与现有技术相比,本发明的有益效果是:
本发明提供了一种短氟碳链(C≤6)丙烯酸酯聚合物,和一种以短氟碳链丙烯酸酯聚合物为主体的含氟树脂脱模剂组合物,其具有很好的降解性,避免了PFOA/PFOS类物质的使用;本发明脱模剂组合物在模具表面成膜均匀,脱模时间短,脱模寿命长,不易高温流胶,容易从待脱模成品表面脱除,具有优异的脱模性能,可运用于热固性树脂、热塑性树脂和各种橡胶制件等脱模技术领域。
具体实施方式
下面通过具体实施例进一步描述本发明,但本发明的保护范围并不仅限于此。
实施例1
N2气氛下,将30g甲基丙烯酸十八烷基酯、5g丙烯酸加到80g乙酸丁酯中,开启搅拌并升温至65℃,待单体全部溶解后,滴加0.2g偶氮二异丁腈溶于5mL乙酸丁酯的聚合引发剂溶液,滴加完毕后反应1h,然后于65℃下加入10g CH2=C(CH3)COO(CH2)2(CF2)5CF3和5g乙烯基三乙氧基硅烷,反应6.0h,再升温至75℃反应2h。冷却至室温,得均匀的含氟丙烯酸酯共聚物溶液。
脱模剂组合物的配制:取5.0g上述制备得到的含氟丙烯酸酯共聚物溶液,加入20g甲基硅油、70g丙酮、5.0g六氟异丙基甲基醚,混合均匀后备用。
之后利用下述测试方法,测试脱模性能,结果请参阅表1。
脱模性能测试方法
(1)脱模持续力
首先将每边长为25mm*25mm*5mm的立方体模具型腔表面去除锈迹、油污,并用无水乙醇等溶剂清洁,在表面完全干燥后,将脱模剂组合物利用喷雾枪在相同条件(喷嘴与物面距离为200~300mm、喷枪移动速度15~30cm/s)下涂布于保温在180℃的模具(3片型)的圆筒形的中间模具的孔,该孔里填充硫加硫型的EPDM化合物(催化剂:茂金属)。然后,对上述EPDM化合物以180℃×10min进行压制成型。压制成型后,用压力表(0~200N)测定中间模具的圆柱成型物的阻力。然后,在不涂布脱模剂组合物的情况下进行成型,重复阻力的测定。阻力越大则脱模所需的力越大,阻力越小则脱模所需的力越小。即,阻力越小则脱模性越优异,阻力越大则脱模性越差。
将该阻力维持20N以下的次数作为持续次数,将其作为脱模持续力。
(2)依据HB5479-91《复合材料用非硅脱模剂》航天工业标准中的脱模效果检验方法进行效果评定。脱模效果评级标准如下所示:
A—外观光滑,脱模容易;
B—外观光滑,粘模面积小于制品表明的5%,轻微粘模、稍微用力可顺利脱模;
C—外观不光滑、不完整,粘模面积小于制品表明的10%,要用工具才能脱模;
D—制品表明严重破坏,脱模困难。
实施例2
N2气氛下,将20g甲基丙烯酸十八烷基酯、5g丙烯酸加到80g乙酸丁酯中,开启搅拌并升温至65℃,待单体全部溶解后,滴加0.2g偶氮二异丁腈溶于5mL乙酸丁酯的聚合引发剂溶液,滴加完毕后反应1h,然后于65℃下加入20g CH2=C(CH3)COO(CH2)2(CF2)5CF3和5g乙烯基三乙氧基硅烷,反应6.0h,再升温至75℃反应2h。冷却至室温,得均匀的含氟丙烯酸酯共聚物溶液。
脱模剂组合物的配制和脱模性能测试方法与实施例1相同,测试结果见表1。
实施例3
N2气氛下,将10g甲基丙烯酸十八烷基酯、5g丙烯酸加到80g乙酸丁酯中,开启搅拌并升温至65℃,待单体全部溶解后,滴加0.2g偶氮二异丁腈溶于5mL乙酸丁酯的聚合引发剂溶液,滴加完毕后反应1h,然后于65℃下加入30g CH2=C(CH3)COO(CH2)2(CF2)5CF3和5g乙烯基三乙氧基硅烷,反应6.0h,再升温至75℃反应2h。冷却至室温,得均匀的含氟丙烯酸酯共聚物溶液。
脱模剂组合物的配制和脱模性能测试方法与实施例1相同,测试结果见表1。
实施例4
N2气氛下,将20g甲基丙烯酸十八烷基酯、3g丙烯酸加到80g乙酸丁酯中,开启搅拌并升温至65℃,待单体全部溶解后,滴加0.2g偶氮二异丁腈溶于5mL乙酸丁酯的聚合引发剂溶液,滴加完毕后反应1h,然后于65℃下加入20g CH2=C(CH3)COO(CH2)2(CF2)5CF3和7g乙烯基三乙氧基硅烷,反应6.0h,再升温至75℃反应2h。冷却至室温,得均匀的含氟丙烯酸酯共聚物溶液。
脱模剂组合物的配制和脱模性能测试方法与实施例1相同,测试结果见表1。
实施例5
N2气氛下,将20g甲基丙烯酸十八烷基酯、7g丙烯酸加到80g乙酸丁酯中,开启搅拌并升温至65℃,待单体全部溶解后,滴加0.2g偶氮二异丁腈溶于5mL乙酸丁酯的聚合引发剂溶液,滴加完毕后反应1h,然后于65℃下加入20g CH2=C(CH3)COO(CH2)2(CF2)5CF3和3g乙烯基三乙氧基硅烷,反应6.0h,再升温至75℃反应2h。冷却至室温,得均匀的含氟丙烯酸酯共聚物溶液。
脱模剂组合物的配制和脱模性能测试方法与实施例1相同,测试结果见表1。
实施例6
N2气氛下,将20g甲基丙烯酸十八烷基酯、5g丙烯酸加到80g乙酸丁酯中,开启搅拌并升温至65℃,待单体全部溶解后,滴加1.0g偶氮二异丁腈溶于5mL乙酸丁酯的聚合引发剂溶液,滴加完毕后反应1h,然后于65℃下加入20g CH2=C(CH3)COO(CH2)2(CF2)5CF3和5g乙烯基三乙氧基硅烷,反应6.0h,再升温至75℃反应2h。冷却至室温,得均匀的含氟丙烯酸酯共聚物溶液。
脱模剂组合物的配制和脱模性能测试方法与实施例1相同,测试结果见表1。
实施例7
N2气氛下,将20g甲基丙烯酸十八烷基酯、5g丙烯酸加到80g乙酸丁酯中,开启搅拌并升温至65℃,待单体全部溶解后,滴加0.2g偶氮二异丁腈溶于5mL乙酸丁酯的聚合引发剂溶液,滴加完毕后反应1h,然后于65℃下加入20g CH2=C(CH3)COO(CH2)2(CF2)2CF3和5g乙烯基三乙氧基硅烷,反应6.0h,再升温至75℃反应2h。冷却至室温,得均匀的含氟丙烯酸酯共聚物溶液。
脱模剂组合物的配制和脱模性能测试方法与实施例1相同,测试结果见表1。
实施例8
N2气氛下,将20g甲基丙烯酸十八烷基酯、5g丙烯酸加到80g乙酸丁酯中,开启搅拌并升温至65℃,待单体全部溶解后,滴加0.2g偶氮二异丁腈溶于5mL乙酸丁酯的聚合引发剂溶液,滴加完毕后反应1h,然后于65℃下加入20g CH2=C(CH3)CONH(CH2)2(CF2)5CF3和5g乙烯基三乙氧基硅烷,反应6.0h,再升温至75℃反应2h。冷却至室温,得均匀的含氟丙烯酸酯共聚物溶液。
脱模剂组合物的配制和脱模性能测试方法与实施例1相同,测试结果见表1。
实施例9
N2气氛下,将20g甲基丙烯酸十八烷基酯、5g丙烯酸加到80g乙酸丁酯中,开启搅拌并升温至65℃,待单体全部溶解后,滴加0.2g偶氮二异丁腈溶于5mL乙酸丁酯的聚合引发剂溶液,滴加完毕后反应1h,然后于65℃下加入20g CH2=C(CH3)COS(CH2)2(CF2)5CF3和5g乙烯基三乙氧基硅烷,反应6.0h,再升温至75℃反应2h。冷却至室温,得均匀的含氟丙烯酸酯共聚物溶液。
脱模剂组合物的配制和脱模性能测试方法与实施例1相同,测试结果见表1。
实施例10
N2气氛下,将20g甲基丙烯酸十二烷基酯、5g丙烯酸加到80g乙酸丁酯中,开启搅拌并升温至65℃,待单体全部溶解后,滴加0.2g偶氮二异丁腈溶于5mL乙酸丁酯的聚合引发剂溶液,滴加完毕后反应1h,然后于65℃下加入20g CH2=C(CH3)COO(CH2)2(CF2)5CF3和5g乙烯基三乙氧基硅烷,反应6.0h,再升温至75℃反应2h。冷却至室温,得均匀的含氟丙烯酸酯共聚物溶液。
脱模剂组合物的配制和脱模性能测试方法与实施例1相同,测试结果见表1。
实施例11
N2气氛下,将20g甲基丙烯酸十八烷基酯、5g丙烯酸加到80g乙酸丁酯中,开启搅拌并升温至65℃,待单体全部溶解后,滴加0.2g偶氮二异丁腈溶于5mL乙酸丁酯的聚合引发剂溶液,滴加完毕后反应1h,然后于65℃下加入20g CH2=C(CH3)COO(CH2)2(CF2)5CF3和5g甲基丙烯酰氧丙基三(甲氧基)硅烷,反应6.0h,再升温至75℃反应2h。冷却至室温,得均匀的含氟丙烯酸酯共聚物溶液。
脱模剂组合物的配制和脱模性能测试方法与实施例1相同,测试结果见表1。
对比例1
N2气氛下,将40g甲基丙烯酸十八烷基酯、5g丙烯酸加到80g乙酸丁酯中,开启搅拌并升温至65℃,待单体全部溶解后,滴加0.2g偶氮二异丁腈溶于5mL乙酸丁酯的聚合引发剂溶液,滴加完毕后反应1h,然后于65℃下加入5g乙烯基三乙氧基硅烷,反应6.0h,再升温至75℃反应2h。冷却至室温,得均匀的丙烯酸酯共聚物溶液。
脱模剂组合物的配制和脱模性能测试方法与实施例1相同,测试结果见表1。
对比例2
N2气氛下,将5g丙烯酸加到80g乙酸丁酯中,开启搅拌并升温至65℃,待单体全部溶解后,滴加0.2g偶氮二异丁腈溶于5mL乙酸丁酯的聚合引发剂溶液,滴加完毕后反应1h,然后于65℃下加入40g CH2=C(CH3)COO(CH2)2(CF2)5CF3和5g乙烯基三乙氧基硅烷,反应6.0h,再升温至75℃反应2h。冷却至室温,得均匀的含氟丙烯酸酯共聚物溶液。
脱模剂组合物的配制和脱模性能测试方法与实施例1相同,测试结果见表1。
对比例3
N2气氛下,将20g甲基丙烯酸十八烷基酯、10g丙烯酸加到80g乙酸丁酯中,开启搅拌并升温至65℃,待单体全部溶解后,滴加0.2g偶氮二异丁腈溶于5mL乙酸丁酯的聚合引发剂溶液,滴加完毕后反应1h,然后于65℃下加入20g CH2=C(CH3)COO(CH2)2(CF2)5CF3,反应6.0h,再升温至75℃反应2h。冷却至室温,得均匀的含氟丙烯酸酯共聚物溶液。
脱模剂组合物的配制和脱模性能测试方法与实施例1相同,测试结果见表1。
表1脱模剂组合物脱模性能
此外,应当理解,虽然本说明书按照实施方式加以描述,但并非每个实施方式仅包含一个独立的技术方案,说明书的这种叙述方式仅仅是为清楚起见,本领域技术人员应当将说明书作为一个整体,各实施例中的技术方案也可以经适当组合,形成本领域技术人员可以理解的其他实施方式。
Claims (8)
1.一种短氟碳链丙烯酸酯聚合物,其特征在于,由以下重量份的单体共聚而成:
(A)短氟碳链丙烯酸酯单体20~80份;
(B)丙烯酸酯单体20~60份;
(C)含乙烯基的有机硅单体5~20份;
(D)丙烯酸单体5~20份;
单体(A)如通式(I)所示:
式(I)中:
R1为氢或甲基;
R2为-O-、-S-或-NH-;
R3为碳数1~8的二价脂肪族烃基、碳数6~12的二价芳香族烃基或二价环状脂肪族烃基;
Rf为直链或支链状的全氟烷基,碳数为1~6;
单体(B)如通式(II)所示:
式(II)中:
R4为氢或甲基;
R5为直链或支链状的一价脂肪族烃基、一价芳香族烃基或一价环状脂肪族烃基,R5碳数1~30;
单体(C)为:乙烯基三甲氧基硅烷、乙烯基三乙氧基硅烷、甲基丙烯酰氧丙基三(异丙氧基)硅烷或甲基丙烯酰氧丙基三(甲氧基)硅烷。
2.如权利要求1所述短氟碳链丙烯酸酯聚合物,其特征在于,由以下重量份的单体共聚而成:
(A)短氟碳链丙烯酸酯单体40~60份;
(B)丙烯酸酯单体20~40份;
(C)含乙烯基的有机硅单体5~14份;
(D)丙烯酸单体1~14份。
3.如权利要求1所述短氟碳链丙烯酸酯聚合物的制备方法,其特征在于,所述制备方法为:
按照各单体的重量配比备料,N2气氛下,将单体(B)、单体(D)加到反应溶剂中,开启搅拌并升温至65℃,待单体全部溶解后,滴加聚合引发剂的溶液,滴加完毕后反应1h,接着于65℃下加入单体(A)和单体(C),反应6h,再升温至75℃反应2h,之后冷却至室温,得到所述短氟碳链丙烯酸酯聚合物;
所述反应溶剂为丙酮、甲乙酮、甲基异丁基甲酮、氯仿、异丙醇、戊烷、已烷、庚烷、辛烷、环己烷、苯、甲苯、二甲苯、石油醚、四氢呋喃、乙酸乙酯、乙酸丁酯中的任意一种;
所述反应溶剂的质量与单体(A)、单体(B)、单体(C)、单体(D)合计质量之比为0.5~2:1。
4.如权利要求3所述的制备方法,其特征在于,所述聚合引发剂为偶氮二异丁腈、苯甲酰基过氧化物、二叔丁基过氧化物、月桂基过氧化物、过氧化氢异丙苯、过氧化新戊酸叔丁酯、过氧化二碳酸二异丙酯或偶氮双甲基丙酸酯。
5.如权利要求4所述的制备方法,其特征在于,所述聚合引发剂与单体(A)、单体(B)、单体(C)、单体(D)合计质量之比为0.1~2:100;聚合引发剂溶液中的溶剂与反应溶剂相同。
6.一种包含权利要求1所述短氟碳链丙烯酸酯聚合物的脱模剂组合物,其特征在于,所述脱模剂组合物由以下重量份的组分组成:
1~20份短氟碳链丙烯酸酯聚合物,10~30份硅油,30~80份溶剂A,1~20份溶剂B;
所述溶剂A选自乙酸甲酯、乙酸乙酯、乙酸丙酯、乙酸正丁酯、丙酸丁酯、乙二醇甲醚、二氧六环、丙酮、环己酮、戊烷、已烷、庚烷、辛烷、环己烷中的任意一种;
所述溶剂B选自全氟己烷、全氟庚烷、全氟三乙胺、六氟异丙基甲醚、1,1,2,2-四氟乙基-2,2,2-三氟乙基醚、1,1,2,2-四氟乙基乙基醚、乙基九氟丁基醚、三氟丙酮酸甲酯、五氟丙酸乙酯中的任意一种。
7.如权利要求6所述脱模剂组合物,其特征在于,所述硅油选自甲基硅油、乙基硅油、苯基硅油、甲基含氢硅油、甲基苯基硅油、甲基氯苯基硅油、甲基乙氧基硅油、甲基三氟丙基硅油、甲基乙烯基硅油、甲基羟基硅油、乙基含氢硅油、羟基含氢硅油中的任意一种。
8.如权利要求6所述脱模剂组合物的制备方法,其特征在于,所述制备方法为:
按照配方,取短氟碳链丙烯酸酯聚合物,然后加入硅油、溶剂A、溶剂B,混合均匀后备用。
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