CN104552688B - Curable fluorine resin demoulding agent and preparation method - Google Patents
Curable fluorine resin demoulding agent and preparation method Download PDFInfo
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- CN104552688B CN104552688B CN201510012665.9A CN201510012665A CN104552688B CN 104552688 B CN104552688 B CN 104552688B CN 201510012665 A CN201510012665 A CN 201510012665A CN 104552688 B CN104552688 B CN 104552688B
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- curing agent
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- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 130
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 61
- 239000011737 fluorine Substances 0.000 title claims abstract description 61
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000011347 resin Substances 0.000 title abstract description 10
- 229920005989 resin Polymers 0.000 title abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 39
- 239000003960 organic solvent Substances 0.000 claims abstract description 36
- 239000000178 monomer Substances 0.000 claims abstract description 29
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 claims abstract description 16
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 9
- 229920001577 copolymer Polymers 0.000 claims description 23
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 21
- -1 pentyl ester Chemical class 0.000 claims description 18
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 16
- 229910000077 silane Inorganic materials 0.000 claims description 16
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- 238000009835 boiling Methods 0.000 claims description 8
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 8
- XUPYJHCZDLZNFP-UHFFFAOYSA-N butyl butanoate Chemical compound CCCCOC(=O)CCC XUPYJHCZDLZNFP-UHFFFAOYSA-N 0.000 claims description 8
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 8
- SHZIWNPUGXLXDT-UHFFFAOYSA-N ethyl hexanoate Chemical compound CCCCCC(=O)OCC SHZIWNPUGXLXDT-UHFFFAOYSA-N 0.000 claims description 8
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 150000008282 halocarbons Chemical class 0.000 claims description 6
- 150000002576 ketones Chemical class 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 5
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 5
- 231100000419 toxicity Toxicity 0.000 claims description 5
- 230000001988 toxicity Effects 0.000 claims description 5
- 239000004698 Polyethylene Substances 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 150000002170 ethers Chemical class 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- WMOVHXAZOJBABW-UHFFFAOYSA-N tert-butyl acetate Chemical compound CC(=O)OC(C)(C)C WMOVHXAZOJBABW-UHFFFAOYSA-N 0.000 claims description 4
- HFZLSTDPRQSZCQ-UHFFFAOYSA-N 1-pyrrolidin-3-ylpyrrolidine Chemical compound C1CCCN1C1CNCC1 HFZLSTDPRQSZCQ-UHFFFAOYSA-N 0.000 claims description 3
- GHUXAYLZEGLXDA-UHFFFAOYSA-N 8-azido-5-ethyl-6-phenylphenanthridin-5-ium-3-amine;bromide Chemical compound [Br-].C12=CC(N=[N+]=[N-])=CC=C2C2=CC=C(N)C=C2[N+](CC)=C1C1=CC=CC=C1 GHUXAYLZEGLXDA-UHFFFAOYSA-N 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 150000002632 lipids Chemical class 0.000 claims description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 2
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims description 2
- 229940090181 propyl acetate Drugs 0.000 claims description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 2
- 241000790917 Dioxys <bee> Species 0.000 claims 1
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- 150000002118 epoxides Chemical class 0.000 claims 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims 1
- 231100000053 low toxicity Toxicity 0.000 abstract description 3
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- 235000019000 fluorine Nutrition 0.000 description 50
- 239000000243 solution Substances 0.000 description 22
- 238000003756 stirring Methods 0.000 description 19
- 229920003023 plastic Polymers 0.000 description 17
- 239000004033 plastic Substances 0.000 description 17
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 15
- 230000000694 effects Effects 0.000 description 11
- 239000011435 rock Substances 0.000 description 11
- 229920001971 elastomer Polymers 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 238000007493 shaping process Methods 0.000 description 9
- PGMYKACGEOXYJE-UHFFFAOYSA-N pentyl acetate Chemical compound CCCCCOC(C)=O PGMYKACGEOXYJE-UHFFFAOYSA-N 0.000 description 8
- 150000002148 esters Chemical class 0.000 description 7
- 238000007689 inspection Methods 0.000 description 7
- 238000007711 solidification Methods 0.000 description 7
- 230000008023 solidification Effects 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical group COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 239000007822 coupling agent Substances 0.000 description 5
- 239000004814 polyurethane Substances 0.000 description 5
- 229920002635 polyurethane Polymers 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000002270 dispersing agent Substances 0.000 description 4
- 239000003995 emulsifying agent Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 3
- 125000001153 fluoro group Chemical group F* 0.000 description 3
- 229920000578 graft copolymer Polymers 0.000 description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 239000002562 thickening agent Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- HNAGHMKIPMKKBB-UHFFFAOYSA-N 1-benzylpyrrolidine-3-carboxamide Chemical compound C1C(C(=O)N)CCN1CC1=CC=CC=C1 HNAGHMKIPMKKBB-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- OBNCKNCVKJNDBV-UHFFFAOYSA-N butanoic acid ethyl ester Natural products CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 238000003754 machining Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 230000000284 resting effect Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 1
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 241001062009 Indigofera Species 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- FQBWIAATJXZQKY-UHFFFAOYSA-N [S].[S].[Na] Chemical compound [S].[S].[Na] FQBWIAATJXZQKY-UHFFFAOYSA-N 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 238000004378 air conditioning Methods 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000013028 medium composition Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920003225 polyurethane elastomer Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000007115 recruitment Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000019574 salt enhancing Nutrition 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 238000007592 spray painting technique Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
- 229940099259 vaseline Drugs 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
Abstract
The invention discloses a curable fluorine resin demoulding agent and a preparation method. According to the curing fluorine resin demoulding agent, two fluorine resin copolymers of which the polymerization degree is not less than 500 are mixed; the fluorine resin copolymers are prepared by polymerizing vinylidene difluoride monomers and chlorotrifluoroethylene monomers. A curable low-toxicity fluorine resin demoulding agent composition with high film-forming property, high demoulding property and difficulty in gumming and thinning under a high temperature can be prepared under cooperation of organic solvents and a proper quantity of curing agents.
Description
Technical field
The present invention relates to a kind of curable fluororesin releasing agent is and in particular to a kind of hypotoxicity fluorine tree coordinating curing agent
Fat releasing agent and preparation method thereof.
Background technology
In polymeric material manufacture field, because releasing agent can prevent the products such as rubber, plastics to be bonded on mould, lead
Cause products appearance bad, the situation that qualification rate declines, and there is very important effect.But, the releasing agent such as talcum of early stage
Using inconvenience, the releasing agent such as vaseline, low molecular weight polyethylene, silicone oil is easy to remain the releasing agents such as powder, mica powder, soap
Oily face and affect the outward appearance of product, after the demoulding, product is difficult to directly to carry out secondary operation such as spray painting, printing, pastes etc.；Promote
Develop some new fluorine-containing demoulding agents in recent years, to solve the deficiency of early stage releasing agent.
The patent document of Patent No. CN103878910A discloses one kind with polytetrafluoroethylene (PTFE), stearic acid, carbon black and sulphur
Sulphur sodium, the rubber releasing agent of distilled water preparation.The patent document of Patent No. CN102782075A disclose a kind of by containing
Fluo-copolymer and the releasing agent of medium composition, this fluorinated copolymer contains the monomer based on the Polyfluoroalkyl with carbon number 1～6
The Component units of (a), the Component units of (methyl) acrylate (b) based on the alkyl with carbon number 18～30.Patent No.
The patent document of CN102596382A discloses poly- fluoroalkyl phosphonate emulsifying agent and taking off using this emulsifying agent as active ingredient
Mould agent.The patent document of Patent No. CN102458789A discloses a kind of graft copolymer and the demoulding with it as main component
Agent, this graft copolymer is to make formula CnF2n+1(CH2CF2)a(CF2CF2)bCH=CH2(wherein n is 1～6 integer, and a is 1
～4 integer, b is 1～3 integer) shown in how fluoro- 1-1 alkene carry out grafting altogether with PAG or its alkyl ether
Obtained by poly-.A kind of open novel noninflammability demoulding for mould of plastics of knowing clearly of the patent document of Patent No. CN1799805A
Agent composition, said composition comprises：(a) hydrofluoroether, (b) fluorocarbon oil, (c) fluorine based surfactant.Patent No. CN87102964A
Patent document disclose a kind of mold release compositions, including (a) at least perfluoroalkyl of a 4-20 carbon atom and 4-
The mixture of the perfluorinated alkenyl of 20 carbon atoms or polymer, and a kind of (b) ladder polymer of organic sesqui siloxane.Specially
The patent document for CN101186665A for the profit number disclose using vinylidene and trichlorine PVF mol ratio be 10～
30mol%：The monomer of 70～90mol% and organic peroxide carry out suspension polymerisation, obtain number-average molecular weight 5 ten thousand to 45 ten thousand
Fluororesin, and adopt ethanol, acetone equal solvent, the dispersant such as calcium carbonate, talcum powder and stearic acid dispersion aids make each
Plant corrosion resistant coating, direct construction usage can be passed through.
As described above, existing fluorine-containing demoulding agent needs particular monomers (as fluorinated acrylate, fluorine-containing alkyl phosphoric acid at present
Ester or phosphate) and be difficult to prepare containing fluorine graft copolymer, under thermoplastic fluorocarbon resin high temperature can gummosis thinning；Fluorine resin coating
Do not have solidification, under high temperature can gummosis it is difficult to meet the demand of demoulding during high-temperature molding；In such as polyurethanes and its derivative
Thing (concrete such as polyurethane plastics, polyurethane elastomer and foamed material), unsaturated polyester plastic, micro-nano slaine strengthen rubber
Have such problems as during the shaping such as moulding material that mould adhesion, the demoulding are difficult.
And, the present inventor finds under study for action, when polyurethane plastics and micro-nano slaine strengthen rubber-plastics material shaping
There is very strong stickness, be all difficult to obtain satisfaction using silicone releasing agent GMT457, MA2020 fluorine-containing demoulding agent etc.
High temperature release effect.
Content of the invention
[technical problem to be solved]
Present invention aim to address the problem that above-mentioned prior art exists, provide a kind of organic fluorine releasing agent, should
Releasing agent can be coated in die surface and dry solidification forms one layer of fluoropolymer material being difficult high temperature gummosis, and is to have
The hypotoxicity fluororesin releasing agent of good stripping result.
[technical scheme]
In order to reach above-mentioned technique effect, the present invention takes technical scheme below：
, by the degree of polymerization is not less than 500 two kinds of fluororesin copolymer mixing, this fluororesin copolymer is by inclined for the present invention
Fluoride monomers are polymerized with CTFE monomer；Under organic solvent, appropriate curing agent coordinate, it is obtained in that film forming
Property good, high temperature under be difficult the curable hypotoxicity fluororesin mold release compositions that gummosis is thinning, release property is good.
A kind of curable fluororesin releasing agent, it includes the component of following mass parts：
23 0.1～30 part of type organic fluorine mixtures；
70～99.9 parts of organic solvent；
0～5 part of curing agent；
Described 23 type organic fluorine mixtures be the material by vinylidene fluoride monomers Yu CTFE monomer amount it
Than for 1：The copolymer of (0.5～2) and vinylidene fluoride monomers are 1 with the ratio of the amount of the material of CTFE monomer：(2.2
～9) copolymer mixes.
In 23 type organic fluorine mixtures of the present invention, the amount of vinylidene fluoride monomers and CTFE monomeric substance
Ratio be 1：The content of the copolymer of (2.2～9) is 0～99%.
Organic solvent of the present invention is one or more organic solvent selected from ethers, lipid or halogenated hydrocarbon, ketone；
The toxicity of described organic solvent is not less than 2000mg/kg, boiling point between 50～170 DEG C for LD50.
Organic solvent of the present invention is to be selected from oxolane, methyl acetate, ethyl acetate, acetic acid third one or more
Ester, n-butyl acetate, sec-butyl acetate, tert-butyl acetate, pentyl acetate, butyl propionate, butyl butyrate, ethyl hexanoate, methyl
The organic solvent of methyl acrylate, EMA, chloroform, dioxane, acetone or cyclohexanone.
Curing agent of the present invention is the tri-alkoxy or dialkoxy silicane containing amino.
Curing agent of the present invention be one or more be selected from γ-aminopropyl-trialkoxy silane, N- (β-aminoethyl)-
γ-aminopropyl-trialkoxy silane, N- (β-aminoethyl)-γ-aminopropyltriethoxy dialkoxy silicane, γ-ureido-propyl-three
The consolidating of alkoxy silane, γ-(polyethylene amino) propyl trialkoxy silane or γ-amidino groups sulfopropyl trialkoxy silane
Agent；The alkoxyl of described curing agent is methoxy or ethoxy.
The preparation method of foregoing curable fluororesin releasing agent, it comprises the following steps：
A, the preparation of 23 type organic fluorine solution
23 type organic fluorine mixtures are dissolved in organic solvent, obtain 23 described type organic fluorine solution；
B, the mixing of curing agent
The 23 type organic fluorine solution that step A is obtained add curing agent, mix, and obtain described curable fluorine
Resin releasing agent.
The temperature of curing reaction of the present invention is 80～200 DEG C, and the time is no less than 30min.
Will be described in detail the present invention below.
A kind of curable fluororesin releasing agent, it includes the component of following mass parts：
23 0.1～30 part of type organic fluorine mixtures；
70～99.9 parts of organic solvent；
0～5 part of curing agent；
Described 23 type organic fluorine mixtures be the material by vinylidene fluoride monomers Yu CTFE monomer amount it
Than for 1：The copolymer of (0.5～2) and vinylidene fluoride monomers are 1 with the ratio of the amount of the material of CTFE monomer：(2.2
～9) copolymer mixes.
23 type organic fluorine mixtures of the present invention are the polymeric matrix material of fluororesin releasing agent, its polymerization
Monomer is vinylidene and CTFE, and its average composition is as shown in formula (I)：
(CH2CF2)n(CF2CFCl)m(I)
In average compositional formula (I), n, m represent vinylidene fluoride monomers and the degree of polymerization of CTFE monomer respectively,
It is respectively 1 in the n/m ratio of two kind of 23 type organic fluorine copolymer of the application：(0.5～2) and 1：(2.2～9).
23 type organic fluorine mixtures, can be using vinylidene fluoride monomers and CTFE monomer in normal temperature and pressurization bar
Obtained by free radical suspensioning polymerization under part.
The number-average degree of polymerization of 23 type organic fluorine mixtures of the present invention is n+m, is not less than 500, and is not more than
10000；
The number-average degree of polymerization preferably more than 1000, less than 5000 of 23 type organic fluorine mixtures of the present invention.
As long as the number-average degree of polymerization of 23 type organic fluorine mixtures is in the range of 500～10000,23 type organic fluorines
Mixture will have preferable dissolubility, mobility, good mechanical strength.
In the present invention 23 type organic fluorine mixture, the condition determination of molecular weight n or m of repetitive is to adopt the U.S.
Waters company produces M244 type ALC/GPC instrument, and mobile phase is ethyl acetate, and flow velocity is 1.0mL/min.
23 type organic fluorine n/m ratios of the present invention are 1：The copolymer of (0.5～2) scope, preferably n/m ratio is
1：1 or 1：2 copolymer；More preferably n/m ratio is 1：1 copolymer.
23 type organic fluorine n/m ratios of the present invention are 1：The copolymer of (2.2～9) scope, preferably n/m ratio is
(1：3)、(1：4) or (1：9) copolymer；More preferably 1：3 or 1：4 copolymer.
In 23 type organic fluorine mixtures of the present invention, the amount of vinylidene fluoride monomers and CTFE monomeric substance
Ratio be 1：The content of the copolymer of (2.2～9) is 0～99%.
In 23 type organic fluorine mixtures of the present invention, the amount of vinylidene fluoride monomers and CTFE monomeric substance
Ratio be 1：The content of the copolymer of (2.2～9) more preferably 30～70%.
As long as the n/m ratio of copolymer is respectively 1 in 23 type organic fluorine mixtures：(0.5～2) and 1：(2.2～
, and the ratio of content vinylidene fluoride monomers and the amount of CTFE monomeric substance is 1 9)：The content of the copolymer of (2.2～9)
During for 0～99%, this mixture will have preferable dissolubility, mobility, good mechanical strength, in high temperature film forming and
Mobility aspect keeps good effect.
23 type organic fluorine mixtures of the present invention to be calculated by 100 parts with the mass parts sum of organic solvent；Institute
State 23 type organic fluorine mixture preferably 0.1～30 mass parts, preferably 1～10 mass parts；Described 23 type organic fluorines mix
Compound more preferably 2～7 mass parts.Described organic solvent preferably 70～99.9 mass parts, preferably 90～99 mass parts, more preferably 93
～98 mass parts.As long as the mass parts of described 23 type organic fluorine mixtures and organic solvent are within this range, fluororesin takes off
The construction effect of mould agent just can obtain good guarantee.
Organic solvent of the present invention is one or more organic solvent selected from ethers, lipid or halogenated hydrocarbon, ketone；
The toxicity of described organic solvent is not less than 2000mg/kg, boiling point between 50～170 DEG C for LD50.
Organic solvent of the present invention is to be selected from oxolane, methyl acetate, ethyl acetate, acetic acid third one or more
Ester, n-butyl acetate, sec-butyl acetate, tert-butyl acetate, pentyl acetate, butyl propionate, butyl butyrate, ethyl hexanoate, methyl
The organic solvent of methyl acrylate, EMA, chloroform, dioxane, acetone or cyclohexanone.
The boiling point of organic solvent that the present invention uses and toxicity LD50 are as follows：
Oxolane (66 DEG C, 3000mg/kg), methyl acetate (57.8 DEG C, 5450mg/kg), ethyl acetate (77.1 DEG C,
5620mg/kg), propyl acetate (101 DEG C, 9370mg/kg), n-butyl acetate (126.5 DEG C, 13100mg/kg), acetic acid Zhong Ding
Ester (116 DEG C, 3200mg/kg), tert-butyl acetate (97.8 DEG C, 4100mg/kg), pentyl acetate (149.3 DEG C, 16600mg/
Kg), ethyl propionate (99.1 DEG C, 3500mg/kg), ethyl butyrate (121.3 DEG C, 13050mg/kg), butyl butyrate (166.6 DEG C,
9520mg/kg), ethyl hexanoate (168 DEG C, 5000mg/kg) and methyl methacrylate (101 DEG C, 7872mg/kg), methyl-prop
Olefin(e) acid ethyl ester (119 DEG C, 14800mg/kg), Isobutyl methacrylate (155 DEG C, 6400mg/kg), n-BMA
(163 DEG C, 12900mg/kg), chloroform (61.2 DEG C, 2180mg/kg), dioxane (101 DEG C, 6000mg/kg), acetone (56.5
DEG C, 9750mg/kg), cyclohexanone (155 DEG C, 3460mg/kg).
Organic solvent of the present invention is preferably LD50 and is not less than 3000mg/kg, and boiling point is in 60 DEG C～160 DEG C of ester
Class, ethers, halogenated hydrocarbon, one or more of organic solvent of ketone；More preferably LD50 is not less than 5000mg/kg, and boiling point is 60
DEG C～160 DEG C of ester, ether, halogenated hydrocarbons, one or more of the organic solvent of the micro- toxicity of ketone.Specifically, organic solvent is preferred
Oxolane, methyl acetate, ethyl acetate, acetic acid (just) butyl ester, pentyl acetate, acetone, one or more of ethyl butyrate.
The present invention does not have special restriction to the specification of organic solvent and purity, as long as after organic solvent volatilization no substantially
Residual, products surface quality and stripping result are no significantly affected, even technical grade, the pure organic solvent of chemistry
Can also.
As can be seen here, the material when present invention is all hypotoxic, and the fluororesin releasing agent preparing also is low toxicity
Property fluororesin releasing agent.
Curing agent of the present invention is the tri-alkoxy or dialkoxy silicane containing amino.
Curing agent of the present invention be one or more be selected from γ-aminopropyl-trialkoxy silane, N- (β-aminoethyl)-
γ-aminopropyl-trialkoxy silane, N- (β-aminoethyl)-γ-aminopropyltriethoxy dialkoxy silicane, γ-ureido-propyl-three
The consolidating of alkoxy silane, γ-(polyethylene amino) propyl trialkoxy silane or γ-amidino groups sulfopropyl trialkoxy silane
Agent；The alkoxyl of described curing agent is methoxy or ethoxy.
The alkoxyl of described curing agent is to ensure that the fluorine tree obtaining suitable stripping result for methoxy or ethoxy
Fat releasing agent.
Preferred γ-aminopropyl-the trialkoxy silane of curing agent of the present invention and/or N- (β-aminoethyl)-γ-ammonia third
Base-trialkoxy silane.
Hardener dose of the present invention is 0～5 mass parts；Preferably 0.01～3.0 mass parts；More preferably 0.2～1.0 matter
Amount part.
As long as the consumption of aminoalkoxysilane is in the range of 0～5 mass parts, just can obtain that solidification effect is good, have
The fluororesin releasing agent of good stripping result.That is, the present invention can add curing agent, use after fully crosslinked,
Curing agent can be added without use after releasing agent drying and forming-film.The fluororesin releasing agent of the present invention making after adding curing agent
With time or resting period, it is not particularly limited.
Fluororesin releasing agent of the present invention may also include levelling agent, thickener, anti-extension agent, dispersant, diluent, divides
Powder, emulsifying agent, one or more of water.
Levelling agent of the present invention such as moral is modest 466, EFKA3700, EFKA3770 etc..Such as YK-P104s, moral is modest for dispersant
D904S.Thickener such as SiO 2 powder.Levelling agent, thickener, anti-extension agent, the species of dispersant and consumption be not specific
Limit, be advisable with the using effect that disclosure satisfy that releasing agent.The species of emulsifying agent and consumption are existed with disclosure satisfy that fluorine-containing demoulding agent
In water, good emulsion dispersion, long-time stable are advisable.Special restriction, hydro carbons, ether are had no to diluent kind and specification, consumption
Class, halogenated hydrocarbon, esters, ketone, if boiling point in the range of 50～170 DEG C, LD50 in more than 2000mg/kg and
23 type fluororesin releasing agents mixing are significantly separated and incompatible situation occurs, the concentration of fluororesin keeps after dilution
More than 0.1%, disclosure satisfy that the use requirement of releasing agent.
The preparation method of foregoing curable fluororesin releasing agent, it comprises the following steps：
A, the preparation of 23 type organic fluorine solution
23 type organic fluorine mixtures are dissolved in organic solvent, obtain 23 described type organic fluorine solution；
23 type organic fluorine solution of the present invention are transparent, clarification solution.
B, the mixing of curing agent
The 23 type organic fluorine solution that step A is obtained add curing agent, mix, and obtain described curable fluorine
Resin releasing agent.
C, the application of fluororesin releasing agent
The curable fluororesin releasing agent that step B is obtained, coats the mold cavity surface of cleaning, drying, no rusty stain,
After its dry tack free, heat its surface so as to surface is fully cured.
In stepb, described mixing refers to gentle agitation so as to mix.
The temperature of curing reaction of the present invention is 80～200 DEG C, and the time is no less than 30min.
In the 23 type organic fluorine release agent solution preparation processes of the present invention, the concrete grammar of fluororesin dissolving is no clear and definite
Restriction, either long-time standing dissolving, stirring and dissolving or be heated to reflux dissolving etc. under room temperature.And the present invention is to room
The rotating speed of the time of the lower standing of temperature and addition temperature, stirring all no clearly limits, as long as its time, temperature and rotating speed reach 23
Type organic fluorine is completely dissolved.To time of the static dissolving of room temperature to be advisable no less than 2 days, preferably 3～20 days, more excellent
Select 7～14 days, as long as within this range, the dissolving of fluororesin is achieved with gratifying effect.
In stepb, curing agent can be added to use after fully crosslinked, also can be added without curing agent and be dried in releasing agent
Use after film.The fluororesin releasing agent of the present invention add curing agent after use time or the resting period, not special
Limit.
In step C, the solidification mode of heating of the fluororesin releasing agent of the present invention does not have special restriction.It is coated with the demoulding
The moulds of industrial equipment of agent, can may also be employed Far-infrared Heating, electric furnace heating wire heating, or even heat using air-conditioning constant temperature, baking oven heating
Metal plate heats.The solidification temperature of the fluororesin releasing agent of the present invention is advisable with 50 DEG C～250 DEG C, as long as releasing agent is in mould
Using at a temperature of temperature even more high not gummosis thinning.The solidification temperature condition of the fluororesin releasing agent of the present invention, preferably
140 DEG C ± 60 DEG C, as long as solidification temperature falls within the range so that it may obtain good crosslinking curing effect.
In step C, the hardening time of the fluororesin releasing agent of the present invention does not specifically limit, with fluororesin releasing agent
It is fully cured, gummosis or liquefaction are not advisable under high temperature.The hardening time condition of the fluororesin releasing agent of the present invention, preferably 140
Solidify at DEG C ± 60 DEG C and be advisable no less than 30min, as long as falling within the range so that it may obtain good cross-linking effect.
The material of the fluororesin releasing agent preparation of the present invention, even if also can smoothly obtain outward appearance under the conditions of pressurized, heated
The second best in quality product of rubber and plastic, is not required to pass through machining, you can obtain accurate size and good appearance again, exempts
Unnecessary operation.
The fluororesin releasing agent of the present invention, applies in rubber-plastics material shaping not only as releasing agent, also can be further
It is applied to the fields such as anti-corrosion material, coat, good protective action is played to various devices and material.
[beneficial effect]
The present invention compared with prior art, has following beneficial effect：
The material low toxicity that the present invention uses, simple and easy to get；It is thinning that the fluororesin releasing agent preparing is difficult high temperature gummosis.
And the fluororesin releasing agent stripping result of the present invention is good, products appearance quality good it may be unnecessary to extra machining, just
Accurate size and good appearance can be obtained.
According to the raw material of the present invention and its mass parts of use, no matter adopt the method such as organic solution or emulsion, all
The good organic fluorine releasing agent of release property can be obtained.
The releasing agent of the present invention is widely used, and also can further apply the fields such as anti-corrosion material, coat, to various devices
Part and material play good protective action.
Specific embodiment
With reference to embodiments of the invention, the invention will be further elaborated.Use a series of embodiments below
With comparative example, the present invention is specifically described, but the present invention is limited by following examples never in any form.Following
In embodiment, " part " refers to " mass parts ".
Embodiment 1：
First, by 3.5 number average molecular weights about 16 × 10423 type organic fluorine (CH2CF2)1(CF2CFCl)1(middle indigo plant
Morning twilight chemical research institute produces, trade mark F2311), with 3.5 number average molecular weights about 42 × 10423 type organic fluorines
(CH2CF2)1(CF2CFCl)4(Zhonglan Chenguang Chemical Inst produces, trade mark F2314) adds in sealable glass container, then
Add the oxolane (chemistry is pure) of 46.5 parts of butyl acetates (chemistry is pure) and 46.5 parts and seal up lid, in slight wobble stirring
Afterwards, place at room temperature, rock stirring once in 1～2d, treat that it naturally dissolves, becomes colourless or slightly yellow transparent solution.
Then, 0.2 part of KH550 coupling agent is added in fluororesin release agent solution, and rock stir, stand-by.
Finally, strengthen the mould of rubber-plastics material shaping for polyurethanes (foam) plastics or micro-nano carboxylic metallic salt
Tool mold cavity surface removes rusty stain, greasy dirt, and with absolute alcohol equal solvent cleaning, after surface is completely dried, is dipped with gauze
State fluorine-containing demoulding agent solution coating in mold cavity surface, after its dry tack free, heat its surface 60min at 140 DEG C, make
Its surface is fully cured film forming.
Molding mode according to polyurethanes (foam) plastics is molded and the demoulding using ready mould, according to
According to HB5479-91《The non-silicon mold release agent of composite》The effect that carries out of the stripping result method of inspection in aerospace industry standard is commented
Fixed.And the method according to micro-nano carboxylic metallic salt enhancing rubber-plastics material, carry out high temperature vulcanized crosslinking and stripping result grading, comment
Level standard is as follows：A- smooth in appearance, the demoulding is easy；B- smooth in appearance, sticking to mould area are less than the 5% of product surface, gently
Micro- sticking to mould, somewhat firmly can the smoothly demoulding；Rough complete, the sticking to mould area of C- outward appearance, more than the 10% of product surface, recruitment
Tool could the demoulding；D- product surface heavy damage, the demoulding is difficult.
Embodiment 2
First, 2.5 number F2311 are added in sealable glass container, be subsequently added into 97.5 parts of ethyl acetate, and seal
Upper lid, after slight wobble stirring, places at room temperature, rocks stirring once in 1～2d, treat that it naturally dissolves, becomes colourless
Or slightly yellow transparent solution.
Then, curing agent need not be added, similarly to Example 1 process mould, smearing release agent but be not required to carry out mould
Heat treatment；After releasing agent dry tack free, carry out the shaping of product of rubber and plastic, and the inspection of stripping result, grading evaluation.
Embodiment 3
First, by 10 parts of F2311, add in sealable glass container with 10 parts of F2314, be subsequently added into 40 parts of acetic acid fourths
The oxolane of ester and 40 parts simultaneously seals up lid, after slight wobble stirring, places at room temperature, rocks stirring one in 1～2d
Secondary, treat that it naturally dissolves, becomes colourless or slightly yellow transparent solution.
Then, 1.0 parts of KH550 coupling agent is added in fluororesin release agent solution, and rock stir, stand-by.
Finally, process mould, smearing release agent similarly to Example 1 and carry out die ＆ mold treatment；In releasing agent film forming
Afterwards, carry out the shaping of product of rubber and plastic, and the inspection of stripping result, grading evaluation.
Embodiment 4
First, 0.5 part of F2311 and 0.5 part of F2314 is added in sealable glass container, be subsequently added into 49.5 parts of second
The oxolane of acid butyl ester and 49.5 parts simultaneously seals up lid, after slight wobble stirring, places at room temperature, rocks in 1～2d and stir
Mix once, treat that it naturally dissolves, becomes colourless or slightly yellow transparent solution.
Then, 0.05 part of KH550 coupling agent is added in fluororesin release agent solution, and rock stir, stand-by.
Finally, process mould, smearing release agent similarly to Example 1 and carry out die ＆ mold treatment；On releasing agent surface
After drying and forming-film, carry out the shaping of product of rubber and plastic, and the inspection of stripping result, grading evaluation.
Comparative example 1
First, 0.02 part of F2311 and 0.02 part of F2314 is added in sealable glass container, be subsequently added into 40 parts of second
The oxolane of acid butyl ester and 49.96 parts simultaneously seals up lid, after slight wobble stirring, places at room temperature, rocks in 1～2d
Stirring once, treats that it naturally dissolves, becomes colourless or slightly yellow transparent solution.
Then, 0.05 part of KH550 coupling agent is added in fluororesin release agent solution, and rock stir, stand-by.
Finally, process mould, smearing release agent similarly to Example 1, carry out die ＆ mold treatment；Do on releasing agent surface
After dry, carry out the shaping of product of rubber and plastic, and the inspection of stripping result, grading evaluation.
Comparative example 2
First, 10 parts of F2311 and 10 part of F2314 are added in sealable glass container, be subsequently added into 40 parts of hexamethylenes
The oxolane of (80.7 DEG C of boiling point, LD50 value is 813mg/kg) and 40 parts simultaneously seals up lid, after slight wobble stirring, places
At room temperature, rock stirring once in 1～2d, treat that it naturally dissolves, becomes colourless or slightly yellow transparent solution.
Then, 6 parts of KH550 coupling agent is added in fluororesin release agent solution, and rock stir, stand-by.
Finally, process mould, smearing release agent similarly to Example 1, carry out die ＆ mold treatment；Do on releasing agent surface
After dry, carry out the shaping of product of rubber and plastic, and the inspection of stripping result, grading evaluation.
The stripping result inspection of each embodiment releasing agent of table 1, grading evaluation
From table 1, when organic solvent be added beyond 70～99.9 scope, obtained releasing agent stripping result
Difference, article outer surface are of poor quality；In addition, when curing agent adds excessive, also stripping result is poor for obtained releasing agent, outside product
Surface quality is poor.As can be seen here, only in appropriate organic solvent, the curing agent of arranging in pairs or groups, preferable releasing agent could be obtained.
Although reference be made herein to invention has been described for the explanatory embodiment of the present invention, and above-described embodiment is only this
Bright preferably embodiment, embodiments of the present invention are simultaneously not restricted to the described embodiments it should be appreciated that people in the art
Member can be designed that a lot of other modifications and embodiment, and these modifications and embodiment will fall in principle disclosed in the present application
Within scope and spirit.
Claims (6)
1. a kind of curable fluororesin releasing agent is it is characterised in that it includes the component of following mass parts：
23 0.1～30 part of type organic fluorine mixtures；
70～99.9 parts of organic solvent；
0～5 part of curing agent；
Described 23 type organic fluorine mixtures are that the ratio by vinylidene fluoride monomers and the amount of the material of CTFE monomer is
1：The copolymer of (0.5～2) and vinylidene fluoride monomers are 1 with the ratio of the amount of the material of CTFE monomer：(2.2～9)
Copolymer mix；
In described 23 type organic fluorine mixtures, vinylidene fluoride monomers are 1 with the ratio of the amount of CTFE monomeric substance：
The content of the copolymer of (2.2～9) is 0～99%；
Number-average degree of polymerization in described 23 type organic fluorine mixtures is not less than 500, and no more than 10000；
Described curing agent is the tri-alkoxy or dialkoxy silicane containing amino.
2. curable fluororesin releasing agent according to claim 1 is it is characterised in that described organic solvent is a kind of or many
Plant the organic solvent selected from ethers, lipid or halogenated hydrocarbon, ketone；The toxicity of described organic solvent is not less than for LD50
2000mg/kg, boiling point are between 50～170 DEG C.
3. curable fluororesin releasing agent according to claim 2 is it is characterised in that described organic solvent is a kind of or many
Plant and be selected from oxolane, methyl acetate, ethyl acetate, propyl acetate, n-butyl acetate, sec-butyl acetate, tert-butyl acetate, second
Sour pentyl ester, butyl propionate, butyl butyrate, ethyl hexanoate, methyl methacrylate, EMA, chloroform, dioxy six
The organic solvent of ring, acetone or cyclohexanone.
4. curable fluororesin releasing agent according to claim 1 is it is characterised in that described curing agent is one or more
Selected from γ-aminopropyl-trialkoxy silane, N- (β-aminoethyl)-γ-aminopropyl-trialkoxy silane, N- (β-aminoethyl)-
γ-aminopropyltriethoxy dialkoxy silicane, γ-ureido-propyl-trialkoxy silane, γ-(polyethylene amino) propyl group three alkane
TMOS or the curing agent of γ-amidino groups sulfopropyl trialkoxy silane；The alkoxyl of described curing agent is methoxyl group or second
Epoxide.
5. the curable fluororesin releasing agent according to Claims 1 to 4 any one preparation method it is characterised in that it
Comprise the following steps：
A, the preparation of 23 type organic fluorine solution
23 type organic fluorine mixtures are dissolved in organic solvent, obtain 23 described type organic fluorine solution；
B, the mixing of curing agent
The 23 type organic fluorine solution that step A is obtained add curing agent, mix, and obtain described curable fluororesin
Releasing agent.
6. the preparation method of fluororesin releasing agent according to claim 4 is it is characterised in that the temperature of described curing reaction
For 80～200 DEG C, the time is no less than 30min.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0803337A2 (en) * | 1996-04-26 | 1997-10-29 | Hoechst Japan Limited | Release agent compositions |
| CN101659817A (en) * | 2009-10-12 | 2010-03-03 | 胡小林 | Fluoroelastomer coating with high fluorine content and low-temperature solidification |
| JP2012066447A (en) * | 2010-09-22 | 2012-04-05 | Shin Etsu Polymer Co Ltd | Mold release film |
| EP2537907A1 (en) * | 2010-02-15 | 2012-12-26 | Asahi Glass Company, Limited | Release agent composition |
| CN103878910A (en) * | 2014-04-14 | 2014-06-25 | 柳州市颖航汽配有限公司 | Rubber product demolding agent and preparation method thereof |
-
2015
- 2015-01-09 CN CN201510012665.9A patent/CN104552688B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0803337A2 (en) * | 1996-04-26 | 1997-10-29 | Hoechst Japan Limited | Release agent compositions |
| CN101659817A (en) * | 2009-10-12 | 2010-03-03 | 胡小林 | Fluoroelastomer coating with high fluorine content and low-temperature solidification |
| EP2537907A1 (en) * | 2010-02-15 | 2012-12-26 | Asahi Glass Company, Limited | Release agent composition |
| JP2012066447A (en) * | 2010-09-22 | 2012-04-05 | Shin Etsu Polymer Co Ltd | Mold release film |
| CN103878910A (en) * | 2014-04-14 | 2014-06-25 | 柳州市颖航汽配有限公司 | Rubber product demolding agent and preparation method thereof |
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