CN115368569B - Branched polysiloxane and preparation method and application thereof - Google Patents
Branched polysiloxane and preparation method and application thereof Download PDFInfo
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- CN115368569B CN115368569B CN202211096485.XA CN202211096485A CN115368569B CN 115368569 B CN115368569 B CN 115368569B CN 202211096485 A CN202211096485 A CN 202211096485A CN 115368569 B CN115368569 B CN 115368569B
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- -1 polysiloxane Polymers 0.000 title claims abstract description 132
- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 113
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 78
- 238000006243 chemical reaction Methods 0.000 claims abstract description 61
- 230000032683 aging Effects 0.000 claims abstract description 47
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 38
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000013067 intermediate product Substances 0.000 claims abstract description 23
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 19
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract description 15
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910000077 silane Inorganic materials 0.000 claims abstract description 15
- 230000007062 hydrolysis Effects 0.000 claims abstract description 11
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 11
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims description 45
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 34
- 239000003054 catalyst Substances 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 12
- 238000004821 distillation Methods 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 230000002378 acidificating effect Effects 0.000 claims description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- FSIJKGMIQTVTNP-UHFFFAOYSA-N bis(ethenyl)-methyl-trimethylsilyloxysilane Chemical compound C[Si](C)(C)O[Si](C)(C=C)C=C FSIJKGMIQTVTNP-UHFFFAOYSA-N 0.000 claims description 8
- 230000003301 hydrolyzing effect Effects 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 claims description 5
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical group CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- 238000011067 equilibration Methods 0.000 claims description 4
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 4
- 239000003456 ion exchange resin Substances 0.000 claims description 4
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 4
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 3
- 125000002947 alkylene group Chemical group 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- 235000010216 calcium carbonate Nutrition 0.000 claims description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 2
- 239000011736 potassium bicarbonate Substances 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 235000011181 potassium carbonates Nutrition 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- UHUUYVZLXJHWDV-UHFFFAOYSA-N trimethyl(methylsilyloxy)silane Chemical compound C[SiH2]O[Si](C)(C)C UHUUYVZLXJHWDV-UHFFFAOYSA-N 0.000 claims description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims 2
- 125000003545 alkoxy group Chemical group 0.000 abstract description 22
- 230000009194 climbing Effects 0.000 abstract description 5
- 230000000052 comparative effect Effects 0.000 description 11
- 239000007788 liquid Substances 0.000 description 10
- 239000000123 paper Substances 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 238000005266 casting Methods 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000012528 membrane Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000002131 composite material Substances 0.000 description 5
- 239000002537 cosmetic Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 230000001276 controlling effect Effects 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000003377 acid catalyst Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- DRDRYGIIYOPBBZ-XBXARRHUSA-N Licochalcone B Chemical compound COC1=C(O)C(O)=CC=C1\C=C\C(=O)C1=CC=C(O)C=C1 DRDRYGIIYOPBBZ-XBXARRHUSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000002431 foraging effect Effects 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000011268 mixed slurry Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- FHHAJIAWQMSOLD-YFKPBYRVSA-N (2r)-2-amino-3-prop-2-enylselanylpropanoic acid Chemical compound OC(=O)[C@@H](N)C[Se]CC=C FHHAJIAWQMSOLD-YFKPBYRVSA-N 0.000 description 1
- IIZPXYDJLKNOIY-JXPKJXOSSA-N 1-palmitoyl-2-arachidonoyl-sn-glycero-3-phosphocholine Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCC\C=C/C\C=C/C\C=C/C\C=C/CCCCC IIZPXYDJLKNOIY-JXPKJXOSSA-N 0.000 description 1
- GTCLFEMMPGBNOI-UHFFFAOYSA-N 2-phenylethynamine Chemical group NC#CC1=CC=CC=C1 GTCLFEMMPGBNOI-UHFFFAOYSA-N 0.000 description 1
- ILQJHONKKBBPOK-UHFFFAOYSA-N C(=O)(O)CCC[SiH]([Si](C)(C)C)C Chemical compound C(=O)(O)CCC[SiH]([Si](C)(C)C)C ILQJHONKKBBPOK-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- BITPLIXHRASDQB-UHFFFAOYSA-N ethenyl-[ethenyl(dimethyl)silyl]oxy-dimethylsilane Chemical compound C=C[Si](C)(C)O[Si](C)(C)C=C BITPLIXHRASDQB-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011086 glassine Substances 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000000787 lecithin Substances 0.000 description 1
- 229940067606 lecithin Drugs 0.000 description 1
- 235000010445 lecithin Nutrition 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000005373 pervaporation Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/06—Preparatory processes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
- C08G77/18—Polysiloxanes containing silicon bound to oxygen-containing groups to alkoxy or aryloxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
- D21H27/001—Release paper
Abstract
The invention provides branched polysiloxane, and a preparation method and application thereof. The branched polysiloxane has a structure shown in the following formula I; the preparation method comprises the following steps: (1) Carrying out hydrolysis polycondensation reaction on the end-capped silane and silicate, and distilling at high temperature to obtain an intermediate product; (2) Aging the intermediate product obtained in the step (1) with acetic acid to obtain siloxane; (3) And (3) after the siloxane and the siloxane ring body obtained in the step (2) are subjected to an equilibrium reaction, adding a neutralizing agent, and stopping the reaction to obtain the polysiloxane. The molar percentage content of alkoxy in the branched polysiloxane is less than or equal to 0.05mol percent, the branched polysiloxane is suitable for preparing a release agent, and the prepared release agent has lower ageing release force climbing.
Description
Technical Field
The invention belongs to the technical field of polymer materials, and particularly relates to branched polysiloxane and a preparation method and application thereof.
Background
Branched polysiloxanes have been widely used in industry, cosmetics, detergents, release agents, etc. at present because of their low viscosity and high reactivity.
CN105879699a discloses a hyperbranched polysiloxane multilayer composite film and a preparation method thereof. The preparation method comprises the following steps of: (1) 1.5-2 parts of hyperbranched polysiloxane, 86-89 parts of solvent, 7.5-10 parts of 107 glue and 0.5-1.0 part of catalyst react for 12 hours at 60-80 ℃ to form casting film liquid, the casting film liquid is coated on a polyvinylidene fluoride porous base film, the casting film liquid is left to stand in air for vulcanization for 2 hours, and then the casting film liquid is transferred into an air blast drying box to be dried for 12 hours at 80 ℃ to obtain the hyperbranched polysiloxane composite film; (2) And (3) reacting 1.5-2 parts of vinyl triethoxysilane, 86-89 parts of solvent, 7.5-10 parts of 107 glue and 0.5-1.0 part of catalyst at 60-80 ℃ for 6 hours to form casting film liquid, coating the obtained casting film liquid on the hyperbranched polysiloxane film, standing for 2 hours in air for vulcanization, and then transferring into an air blast drying box for drying at 80 ℃ for 12 hours to obtain the hyperbranched polysiloxane multilayer composite film. The hyperbranched polysiloxane multilayer composite membrane prepared by the technical scheme has a three-layer membrane structure, wherein the bottom layer is a polyvinylidene fluoride ultrafiltration membrane with a non-woven fabric support, the middle layer is a hyperbranched polysiloxane membrane, and the top separation layer is an extremely thin polysiloxane membrane. According to the hyperbranched polysiloxane multilayer composite membrane provided by the technical scheme, the porosity degree is distributed in a gradient manner from top to bottom, and the performance of separating butanol in water by pervaporation is greatly improved.
CN107722266a discloses a hyperbranched polysiloxane/cyanate resin and a preparation method thereof. The preparation method comprises the following steps: (1) 1 part of aminophenylacetylene and 1 part of isocyanic propyl triethoxysilane are dissolved in 100 to 400 parts of aromatic or haloform solvent according to mol, and fully mixed; reflux-treating for 8-24 h at 60-100 ℃ in inert gas atmosphere and stirring condition; after the reaction is finished, removing the solvent to obtain an intermediate; (2) Dissolving the intermediate prepared in the step (1) in 100-400 parts of alcohol solvent, adding 1-2 parts of water, and carrying out reflux treatment for 4-12 h at the temperature of 40-80 ℃; after removing the solvent, washing and drying to obtain yellow liquid hyperbranched polysiloxane; (3) Uniformly mixing 100 parts of molten cyanate with 5.3-25.0 parts of hyperbranched polysiloxane prepared in the step (2), and curing to obtain the hyperbranched polysiloxane/cyanate resin. The hyperbranched polysiloxane/cyanate resin provided by the technical scheme has better heat resistance, flame retardance, toughness and rigidity.
CN111419738A discloses a solid powder cosmetic and a preparation method thereof. The solid powder cosmetic comprises the following components in parts by weight: 5-10 parts of 1, 3-bis (3-carboxypropyl) tetramethyl disilane/dihydroxyceramide polycondensate, 25-40 parts of alpha-semi-lactic glycosyl-C16-ceramide/lecithin/licochalcone B/3- (2-propenyl seleno) -L-alanine/hyperbranched polysiloxane copolymer powder, 10-15 parts of liquid oil and 8-12 parts of surface modified inorganic powder. The solid powder cosmetic disclosed in the technical proposal has excellent impact resistance and usability, good stability and cosmetic durability, and good ductility, lubrication feeling and affinity during application.
In the prior art, the branched polysiloxane has less research on preparing the release agent, and the release agent prepared from the branched polysiloxane has poorer aging release force due to the excessively high content of alkoxy in the branched polysiloxane. Therefore, how to provide branched polysiloxane with low alkoxy content has become a technical problem to be solved at present.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide branched polysiloxane and a preparation method and application thereof. According to the invention, the molar percentage content of alkoxy in the branched polysiloxane is controlled to be less than or equal to 0.05mol%, and the prepared branched polysiloxane has excellent performance, so that the prepared release agent has low aging release force climbing.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a branched polysiloxane having the structure of formula I:
(R 1 R 2 2 SiO 1/2 ) a (R 3 2 SiO) b (R 4 SiO 3/2 ) c (SiO 2 ) d a formula I;
wherein R is 1 Is C2-C4 alkylene, R 2 、R 3 Each independently selected from C1-C4 hydrocarbyl radicals, R 4 Selected from methoxy or ethoxy;
a is selected from integers of 2-50, b is selected from integers of 1-500, c is selected from integers of 1-5, and d is selected from integers of 1-20;
r in the branched polysiloxane 4 SiO 3/2 The mol percent of the groups is less than or equal to 0.05mol percent.
According to the invention, the molar percentage content of alkoxy in the branched polysiloxane is controlled to be less than or equal to 0.05mol%, and the prepared branched polysiloxane has excellent performance, so that the prepared release agent has low aging release force climbing.
In the present invention, R 1 C2-C4 alkylene (e.g. ethenyl, propenyl, butenyl), R 2 、R 3 Each independently selected from C1-C4 (e.g., C1, C2, C3, or C4) hydrocarbyl groups.
a is an integer of 2 to 50 (for example, 2, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, etc.), b is an integer of 1 to 500 (for example, 1, 2, 5, 10, 20, 50, 100, 200, 300, 400, 500, etc.), c is an integer of 1 to 5 (for example, 1, 2, 3, 4, 5, etc.), and d is an integer of 1 to 20 (for example, 1, 2, 4, 6, 8, 10, 12, 14, 16, 18, 20, etc.).
R in the branched polysiloxane 4 SiO 3/2 The molar percentage of the groups is not more than 0.05mol%, for example, 0.002mol%, 0.005mol%, 0.01mol%, 0.02mol%, 0.03mol%, 0.04mol% or 0.05mol%, etc.
In the present invention, the alkoxy group means R 4 SiO 3/2 A group.
The following is a preferred technical scheme of the present invention, but not a limitation of the technical scheme provided by the present invention, and the following preferred technical scheme can better achieve and achieve the objects and advantages of the present invention.
In a preferred embodiment of the present invention, the branched polysiloxane has a number average molecular weight of 500 to 50000, and may be 500, 1000, 5000, 10000, 15000, 20000, 25000, 30000, 35000, 40000, 45000, 50000, or the like, for example.
Preferably, the branched polysiloxane has a viscosity of 10 to 2000cP at 25℃and may be, for example, 10cP, 50cP, 100cP, 200cP, 400cP, 600cP, 800cP, 1000cP, 1200cP, 1400cP, 1600cP, 1800cP, 2000cP, etc.
In a second aspect, the present invention provides a process for the preparation of a branched polysiloxane according to the first aspect, the process comprising the steps of:
(1) Carrying out hydrolysis polycondensation reaction on the end-capped silane and silicate, and distilling at high temperature to obtain an intermediate product;
(2) Aging the intermediate product obtained in the step (1) with acetic acid to obtain siloxane;
(3) And (3) after the siloxane and the siloxane ring body obtained in the step (2) are subjected to an equilibrium reaction, adding a neutralizing agent, and stopping the reaction to obtain the polysiloxane.
According to the invention, through designing the preparation raw materials and the preparation method of the branched polysiloxane, and further through carrying out an aging reaction on the intermediate product obtained in the step (1) and acetic acid, the mole percentage content of alkoxy in the branched polysiloxane can be controlled to be less than or equal to 0.05mol%, the prepared branched polysiloxane has excellent performance, and the prepared release agent has low aging release force climbing.
As a preferred embodiment of the present invention, the blocked silane is selected from any one or a combination of at least two of divinyl tetramethyl disiloxane and hexamethyldisiloxane, divinyl tetramethyl disiloxane and tetramethyl disiloxane, and divinyl tetramethyl disiloxane.
Preferably, the silicate is selected from methyl orthosilicate and/or ethyl orthosilicate.
Preferably, the molar ratio of blocked silane to silicate is (1-3): 1, which may be, for example, 1:1, 1.2:1, 1.4:1, 1.6:1, 1.8:1, 2:1, 2.2:1, 2.4:1, 2.6:1, 2.8:1, or 3:1, etc.
Preferably, the catalyst is selected from any one or a combination of at least two of sulfuric acid, hydrochloric acid or trifluoromethanesulfonic acid.
Preferably, the catalyst is 0.05 to 0.2% by mass, based on 100% by mass of the sum of the blocked silane and silicate, and may be, for example, 0.05%, 0.06%, 0.07%, 0.08%, 0.09%, 0.1%, 0.11%, 0.12%, 0.13%, 0.14%, 0.15%, 0.16%, 0.17%, 0.18%, 0.19% or 0.2%.
Preferably, the hydrolytic polycondensation reaction is carried out in the presence of a shielding gas.
Preferably, the shielding gas comprises nitrogen.
Preferably, the hydrolytic polycondensation reaction is carried out in the presence of deionized water.
Preferably, the deionized water is 3 to 10% by mass, for example, 3%, 4%, 5%, 6%, 7%, 8%, 9% or 10% by mass, based on 100% by mass of the sum of the blocked silane and the silicate.
As a preferred embodiment of the present invention, the temperature of the hydrolytic polycondensation reaction is 50 to 90 ℃ (for example, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃ or the like can be used), and more preferably 60 to 80 ℃.
The hydrolysis polycondensation reaction time is preferably 1 to 6 hours (for example, 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, etc.), and more preferably 2 to 4 hours.
Preferably, the temperature of the high-temperature distillation is 60 to 100 ℃, and may be 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃, or the like, for example.
In the invention, the micromolecular product generated after the hydrolysis polycondensation reaction is removed by high-temperature distillation.
In a preferred embodiment of the present invention, the mass percentage of the acetic acid is 2 to 10% based on 100% of the mass of the intermediate product, and may be, for example, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10% or the like.
According to the invention, the content of alkoxy in the branched polysiloxane can be regulated and controlled by controlling the dosage of acetic acid within a specific range, so that the molar percentage content of the alkoxy in the branched polysiloxane is less than or equal to 0.05mol percent, and the branched polysiloxane suitable for preparing the release agent is prepared. If the consumption of the acetic acid is too small, the content of the alkoxy in the prepared branched polysiloxane is too high, so that the aging release force of the prepared release agent climbs more; if the amount of acetic acid is too large, the content of alkoxy in the branched polysiloxane is not further reduced, and the waste of raw materials is caused.
The mass of the intermediate product is considered as the sum of the masses of the blocked silane and the silicate in the present invention.
Preferably, the temperature of the aging reaction is 50 to 100 ℃, and may be, for example, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃, or the like.
Preferably, the aging reaction is carried out for 1 to 4 hours, for example, 1 hour, 2 hours, 3 hours, 4 hours, or the like.
According to the invention, by controlling the temperature and time of the aging reaction within specific ranges, acetic acid can fully react with the intermediate product, and the branched polysiloxane with low alkoxy content is finally prepared. If the reaction temperature is too low or the reaction time is too short, the content of alkoxy in the prepared branched polysiloxane is too high, and the aging release force of the release agent climbs more; if the aging reaction temperature is too high or the reaction time is too long, the production efficiency is low.
Preferably, the aging reaction is carried out in the presence of a catalyst.
Preferably, the catalyst is selected from any one or a combination of at least two of sulfuric acid, hydrochloric acid or trifluoromethanesulfonic acid.
The catalyst is preferably contained in an amount of 0.001 to 0.5% by mass (for example, 0.001%, 0.002%, 0.005%, 0.1%, 0.2%, 0.3%, 0.4% or 0.5% by mass based on 100% by mass of the intermediate product), and more preferably 0.05 to 0.3% by mass.
Preferably, the aging reaction further comprises a post-treatment step.
Preferably, the post-treatment method comprises water washing and distillation.
In the invention, the small molecular compound in the aging reaction product can be removed by washing, and the aging reaction product is purified.
As a preferred embodiment of the present invention, the siloxane has the structure shown in the following formula II:
(R 1 R 2 2 SiO 1/2 ) a (R 4 SiO 3/2 ) c (SiO 2 ) d a formula II;
R 1 、R 2 、R 4 the a, b, c, d have the same protective scope as the first aspect.
In a preferred embodiment of the present invention, the mass percentage of the siloxane is 0.5 to 10% (for example, 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10% or the like, and preferably 1 to 6%) based on 100% of the mass of the siloxane ring.
Preferably, the siloxane ring is selected from octamethyl cyclotetrasiloxane and/or dimethylsiloxane hybrid ring (DMC).
Preferably, the equilibration reaction is carried out in the presence of an acidic catalyst.
Preferably, the acidic catalyst is selected from any one or a combination of at least two of sulfuric acid, hydrochloric acid, trifluoromethanesulfonic acid or acidic ion exchange resins, and more preferably any one or a combination of at least two of sulfuric acid, trifluoromethanesulfonic acid or acidic ion exchange resins.
Preferably, the acid catalyst is 0.005 to 0.2% by mass, based on 100% by mass of the siloxane ring, and may be, for example, 0.005%, 0.007%, 0.01%, 0.02%, 0.05%, 0.1%, 0.12%, 0.15%, 0.18% or 0.2%.
Preferably, the temperature of the equilibrium reaction is 50 to 100 ℃, and may be, for example, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃, or the like.
Preferably, the time of the equilibrium reaction is 2 to 10 hours, and may be, for example, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, or the like.
As a preferred embodiment of the present invention, the neutralizing agent is selected from any one or a combination of at least two of calcium carbonate, sodium carbonate, potassium carbonate, sodium bicarbonate and potassium bicarbonate.
Preferably, the neutralizing agent is 0.025 to 10% by mass, based on 100% by mass of the siloxane ring, and may be, for example, 0.025%, 0.05%, 0.1%, 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% or 10% by mass, etc.
The reaction temperature of the termination reaction is preferably 50 to 60℃and may be, for example, 50℃and 51℃and 52℃and 53℃and 54℃and 55℃and 56℃and 57℃and 58℃and 59℃and 60 ℃.
Preferably, the reaction time for terminating the reaction is 1 to 2 hours, and may be 60min, 70min, 80min, 90min, 100min, 110min, 120min, or the like, for example.
Preferably, the termination reaction further comprises a post-treatment step.
Preferably, the post-treatment method comprises filtration and distillation.
In the invention, the preparation method of the branched polysiloxane specifically comprises the following steps:
(1) In a protective gas atmosphere, after mixing end-capped silane, silicate and a catalyst at 50-90 ℃, adding deionized water into the mixture to carry out hydrolytic polycondensation reaction for 1-6 h, and then carrying out high-temperature distillation at 60-100 ℃ to remove micromolecular products, thus obtaining an intermediate product; wherein the mol ratio of the end-capped silane to the silicate is (1-3) 1, the mass percent of the catalyst is 0.05-0.2% and the mass percent of the deionized water is 3-10% based on 100% of the sum of the masses of the end-capped silane and the silicate;
(2) In the presence of a catalyst, aging the intermediate product obtained in the step (1) and acetic acid for 1-4 hours at 60-80 ℃, washing with water to remove small molecular products, and distilling to obtain siloxane shown in a formula II; wherein, the mass percentage of the acetic acid is 2 to 10 percent and the mass percentage of the catalyst is 0.001 to 0.5 percent based on 100 percent of the mass of the intermediate product, and the siloxane has the structure shown in the following formula II:
(R 1 R 2 2 SiO 1/2 ) a (R 4 SiO 3/2 ) c (SiO 2 ) d a formula II;
R 1 、R 2 、R 4 a, b, c, d have the same scope of protection as the first aspect;
(3) In the presence of an acid catalyst, carrying out a balance reaction on the siloxane and the siloxane ring body obtained in the step (2) for 2-10 h at 50-100 ℃, adding a neutralizing agent, reacting for 1-2 h at 50-60 ℃, terminating the reaction, filtering, and distilling to obtain polysiloxane; wherein, the mass percent of the siloxane is 0.5 to 10 percent, the mass percent of the acid catalyst is 0.005 to 0.2 percent and the mass percent of the neutralizer is 0.025 to 10 percent based on 100 percent of the mass of the siloxane ring body.
In a third aspect, the present invention provides the use of a branched polysiloxane according to the first aspect in a release agent having an aged release force climb of < 200%, for example 50%, 70%, 90%, 100%, 120%, 140%, 160%, 180% or 200% etc.
Branched polysiloxane has the characteristics of high content of reactive functional groups and low viscosity, and is often used as a main agent of a release agent. The main properties of the release agent comprise a rigid-drop release force and an aging release agent, wherein the rigid-drop release force is the expression of the initial property of the release agent, and the aging release force is the expression of the storage stability of the release agent. The existence of the alkoxy in the branched polysiloxane is decomposed to generate hydroxyl along with the aging process of the release agent, so that the hydroxyl can interact with the release agent colloid, and the aging release force of the release agent is greatly improved. According to the invention, the ageing release force of the release agent product can climb less than 200% by controlling the mole percentage content in the branched polysiloxane to be less than or equal to 0.05mol%, so that the release agent product has good storage stability.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, through designing the preparation raw materials and the preparation method of the branched polysiloxane, the molar percentage content of alkoxy in the branched polysiloxane is less than or equal to 0.05mol% by controlling the consumption of acetic acid in the aging reaction process and the time and the temperature of the aging reaction within specific ranges, the prepared branched polysiloxane has excellent performance, and the prepared release agent has good storage stability and the aging release force is up to less than 200%.
Drawings
FIG. 1 is a nuclear magnetic resonance spectrum of a branched polysiloxane provided in example 1 of the present invention.
Detailed Description
The technical scheme of the invention is further described below by the specific embodiments with reference to the accompanying drawings. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
The amounts of the respective substances added in the following examples and comparative examples were parts by weight.
Example 1
The embodiment provides branched polysiloxane and a preparation method thereof, wherein the preparation method comprises the following steps:
(1) Under the nitrogen atmosphere, adding 33 parts of tetraethoxysilane, 50 parts of tetramethyl divinyl disiloxane and 0.1 part of trifluoromethanesulfonic acid into a three-port bottle, stirring at 70 ℃ for 3 hours, adding 5 parts of deionized water into the mixture, performing hydrolytic polycondensation reaction for 3 hours, raising the temperature to 100 ℃ after the polycondensation reaction reaches equilibrium, and distilling out ethanol generated by hydrolysis to obtain an intermediate product;
(2) Cooling the reaction system of the intermediate product obtained in the step (1) to 70 ℃, adding 0.1 part of trifluoromethanesulfonic acid and 5 parts of acetic acid into the reaction system, carrying out aging reaction for 2 hours, washing with water to remove the trifluoromethanesulfonic acid and the residual acetic acid, and then carrying out reduced pressure distillation under the conditions of 80 ℃ and minus 0.09MPa to obtain siloxane;
(3) Mixing 30 parts of siloxane obtained in the step (2), 740 parts of octamethyl cyclotetrasiloxane and 0.5 part of trifluoromethanesulfonic acid at 60 ℃, carrying out equilibrium reaction for 5 hours, cooling to 50-60 ℃, adding 10 parts of calcium carbonate into the mixture to carry out reaction for 1-2 hours, neutralizing trifluoromethanesulfonic acid in a reaction system, terminating the reaction, filtering to obtain clear transparent oily liquid, carrying out reduced pressure distillation for 2 hours at 160 ℃ and minus 0.095MPa, and removing unreacted siloxane rings and micromolecular siloxane to obtain the branched polysiloxane, wherein a nuclear magnetic spectrum chart of the branched polysiloxane is shown as figure 1.
The viscosity of the branched polysiloxane prepared was tested at 25℃using a Brookfield DV2T rotational viscometer and it was 360cP.
The mass percent of vinyl in the branched polysiloxane is 0.52 percent by a chemical titration method;
the mole percent of alkoxy (ethoxy) in the branched polysiloxane is 0.03 percent through nuclear magnetic resonance spectrum test.
Example 2
The present example provides a branched polysiloxane and a method of making the same, the method of making the branched polysiloxane is as follows:
(1) Under the nitrogen atmosphere, 45 parts of divinyl tetramethyl disiloxane, 5 parts of hexamethyldisiloxane, 27 parts of methyl orthosilicate and 0.1 part of sulfuric acid are added into a three-mouth bottle, after stirring is carried out for 4 hours at 60 ℃, 5 parts of deionized water is added into the three-mouth bottle, hydrolysis polycondensation is carried out for 4 hours, the temperature is increased to 90 ℃ after the polycondensation reaches equilibrium, and ethanol generated by hydrolysis is distilled out, so that an intermediate product is obtained; wherein the molar ratio of the hexamethyldisiloxane to the methyl orthosilicate is 1:1, and the mass percentage of the sulfuric acid is 0.13 percent (the sulfuric acid is a sulfuric acid solution with the mass percentage of 98 percent, and the following is the same) based on 100 percent of the total mass of the divinyl tetramethyl disiloxane, the hexamethyldisiloxane and the methyl orthosilicate;
(2) Cooling the reaction system of the intermediate product obtained in the step (1) to 70 ℃, adding 0.1 part of sulfuric acid and 5 parts of acetic acid into the reaction system for aging reaction for 1h, and then washing the reaction system with water to remove the sulfuric acid and the residual ethanol to obtain siloxane; wherein, the mass percentage of the acetic acid is 5 percent and the mass percentage of the sulfuric acid is 0.1 percent based on 100 percent of the mass of the intermediate product;
(3) Mixing 740 parts of siloxane obtained in the step (2) with 0.5 part of sulfuric acid at 80 ℃, carrying out equilibrium reaction for 6 hours, cooling to 60 ℃, adding 20 parts of sodium carbonate into the mixture to react for 1 hour, neutralizing sulfuric acid in a reaction system, terminating the reaction, filtering to obtain clear and transparent oily liquid, carrying out reduced pressure distillation for 2 hours under the conditions of 160 ℃ and minus 0.095MPa, and removing unreacted siloxane ring and micromolecular siloxane to obtain the branched polysiloxane; wherein, the mass percent of the siloxane is 5 percent, the mass percent of the sulfuric acid is 0.1 percent and the mass percent of the sodium carbonate is 3 percent based on 100 percent of the mass of the octamethyl cyclotetrasiloxane.
Example 3
This example provides a branched polysiloxane and a method for preparing the same, which differ from example 1 only in that in step (2), the weight part of the acetic acid is 2 parts, and the other conditions are the same as in example 1.
Example 4
This example provides a branched polysiloxane and a method for preparing the same, which differ from example 1 only in that in step (2), the weight part of the acetic acid is 9 parts, and the other conditions are the same as in example 1.
Example 5
This example provides a branched polysiloxane and a method for preparing the same, which differ from example 1 only in that in step (2), the weight part of the acetic acid is 1 part, and the other conditions are the same as in example 1.
Example 6
This example provides a branched polysiloxane and a method for preparing the same, which differ from example 1 only in that in step (2), the weight part of the acetic acid is 12 parts, and the other conditions are the same as in example 1.
Example 7
This example provides a branched polysiloxane and a method for preparing the same, which differ from example 1 only in that in step (2), the temperature of the aging reaction is 50℃and the other conditions are the same as in example 1.
Example 8
This example provides a branched polysiloxane and a method for preparing the same, which differ from example 1 only in that in step (2), the temperature of the aging reaction is 100℃and the other conditions are the same as in example 1.
Example 9
This example provides a branched polysiloxane and a method for preparing the same, which differ from example 1 only in that in step (2), the temperature of the aging reaction is 40℃and the other conditions are the same as in example 1.
Example 10
This example provides a branched polysiloxane and a method for preparing the same, which differ from example 1 only in that in step (2), the temperature of the aging reaction is 120℃and the other conditions are the same as in example 1.
Comparative example 1
This comparative example provides a branched polysiloxane and method of making the same, differing from example 1 only in that step (2) is not performed, with the other conditions being the same as example 1.
The viscosity of the branched polysiloxane provided in comparative example 1 was tested at 25℃using a Brookfield DV2T rotational viscometer and was 370cP.
The mass percentage of vinyl in the branched polysiloxane is 0.55 percent by a chemical titration method;
the mole percent of alkoxy (ethoxy) in the branched polysiloxane is 0.06 percent through nuclear magnetic resonance spectrum test.
Application example 1
Application example 1 provides release paper, and the preparation method of the release paper comprises the following steps:
(1) 100 parts of branched polysiloxane provided in example 1, 3.2 parts of hydrogen-containing silicone oil (available from Dow Corning, MHX-1107) and a platinum catalyst (Pt content: 5000 ppm) were mixed to obtain a mixed slurry;
(2) The mixed slurry was coated on glassine paper using a coater to a thickness of 1.5 μm, and cured in an oven at 150 ℃ for 10s, to obtain the release paper.
Application examples 2 to 11
Application examples 2 to 11 each provide a release paper differing from application example 1 only in that the branched polysiloxane provided in example 1 was replaced with the branched polysiloxane provided in examples 2 to 11 in order, with the other conditions being the same as application example 1.
Comparative example 1 was used
Application comparative example 1 provides a release paper differing from application example 1 only in that the branched polysiloxane provided in example 1 is replaced with the branched polysiloxane provided in comparative example 1 in order, with the other conditions being the same as application example 1.
The branched polysiloxane used in the above application examples and application comparative examples and the release paper provided in the application examples and application comparative examples were subjected to performance test by the following specific test methods:
viscosity of branched polysiloxanes: the branched polysiloxanes used in the above application examples and comparative examples were tested for viscosity using a Brookfield DV2T rotational viscometer at 25 ℃;
mole percent of alkoxy groups: the molar percentage of alkoxy groups in the branched polysiloxanes used in the above application examples and comparative examples were tested by nuclear magnetic resonance spectroscopy;
normal temperature release force: the sample was then placed on release paper using 7475 tape, placed in a constant temperature cabinet and pressed against the sample using standard pressure strips for 20h. And (3) carrying out a tensile test at a speed of 300mm/min by using a tensile machine (model AR-2000), wherein the test result is normal-temperature release force.
Aged release force: and (3) placing the sample in a baking oven at 70 ℃ for aging for 20 hours, then taking down the pressing bar, placing for 4 hours at normal temperature, and testing the peeling force to obtain the aging release force.
Aging release force climbing: aging release force climb= (aging release force-normal temperature release force)/normal temperature release force.
The results of the above test are shown in table 1 below:
TABLE 1
As can be seen from the contents of Table 1, in the invention, the molar percentage of alkoxy in the branched polysiloxane is less than or equal to 0.05mol% by designing the preparation raw materials and the preparation method of the branched polysiloxane, and the prepared branched polysiloxane has excellent performance, so that the prepared release agent has good storage stability, and the aged release force climb of the release agent is less than 200%, specifically 39.1-111.1%.
Compared with application example 1, if the amount of acetic acid used in the preparation process of the branched polysiloxane is too small (application example 5), the content of siloxane in the prepared branched polysiloxane is higher, so that the prepared release paper has poorer performance; if the branched polysiloxane is used in the preparation process, the content of the alkoxy in the branched polysiloxane is not further reduced and the waste of raw materials is caused even if the amount of the acetic acid is excessive (application example 6).
Compared with application example 1, if the branched polysiloxane used is too low or too high in temperature in the aging range (application examples 9 to 10) during the preparation process, the prepared release paper has poor performance.
In summary, in the invention, the preparation raw materials and the preparation method of the branched polysiloxane are designed, and the consumption of acetic acid in the aging reaction process, the time and the temperature of the aging reaction are controlled within a specific range, so that the molar percentage of alkoxy in the branched polysiloxane is controlled to be less than or equal to 0.05mol percent, the branched polysiloxane has excellent performance, and the prepared release agent has good storage stability.
The applicant states that the detailed process flow of the present invention is illustrated by the above examples, but the present invention is not limited to the above detailed process flow, i.e. it does not mean that the present invention must be implemented depending on the above detailed process flow. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.
Claims (35)
1. A branched polysiloxane, characterized in that the branched polysiloxane has the structure of formula I:
(R 1 R 2 2 SiO 1/2 ) a (R 3 2 SiO) b (R 4 SiO 3/2 ) c (SiO 2 ) d a formula I;
wherein R is 1 Is C2-C4 alkylene, R 2 、R 3 Each independently selected from C1-C4 hydrocarbyl radicals, R 4 Selected from methoxy or ethoxy;
a is an integer of 2 to 50, b is an integer of 1 to 500, c is an integer of 1 to 5, and d is an integer of 1 to 20;
r in the branched polysiloxane 4 SiO 3/2 The mol percent of the groups is less than or equal to 0.04mol percent;
the branched polysiloxane is prepared by a method comprising the following steps:
(1) Carrying out hydrolysis polycondensation reaction on the end-capped silane and silicate, and distilling at high temperature to obtain an intermediate product;
(2) Aging the intermediate product obtained in the step (1) with acetic acid to obtain siloxane;
(3) After the siloxane and the siloxane ring body obtained in the step (2) are subjected to an equilibrium reaction, adding a neutralizing agent, and stopping the reaction to obtain the polysiloxane;
the mass percentage of the acetic acid is 2-10% based on 100% of the mass of the intermediate product;
the temperature of the aging reaction is 50-100 ℃, and the time of the aging reaction is 1-4 hours.
2. The branched polysiloxane of claim 1, wherein the branched polysiloxane has a number average molecular weight of 500 to 50000.
3. The branched polysiloxane of claim 1, wherein the branched polysiloxane has a viscosity of 10 to 2000cP at 25 ℃.
4. A process for the preparation of a branched polysiloxane according to any one of claims 1 to 3, comprising the steps of:
(1) Carrying out hydrolysis polycondensation reaction on the end-capped silane and silicate, and distilling at high temperature to obtain an intermediate product;
(2) Aging the intermediate product obtained in the step (1) with acetic acid to obtain siloxane;
(3) After the siloxane and the siloxane ring body obtained in the step (2) are subjected to an equilibrium reaction, adding a neutralizing agent, and stopping the reaction to obtain the polysiloxane;
the mass percentage of the acetic acid is 2-10% based on 100% of the mass of the intermediate product;
the temperature of the aging reaction is 50-100 ℃, and the time of the aging reaction is 1-4 hours.
5. The method according to claim 4, wherein the blocked silane is selected from any one or a combination of at least two of divinyl tetramethyl disiloxane and hexamethyldisiloxane, divinyl tetramethyl disiloxane and tetramethyl disiloxane, and divinyl tetramethyl disiloxane.
6. The process according to claim 4, wherein the silicate is selected from methyl orthosilicate and/or ethyl orthosilicate.
7. The method according to claim 4, wherein the molar ratio of the blocked silane to the silicate is (1-3): 1.
8. The process according to claim 4, wherein the hydrolytic polycondensation is carried out in the presence of a catalyst.
9. The method according to claim 8, wherein the catalyst is selected from any one or a combination of at least two of sulfuric acid, hydrochloric acid and trifluoromethanesulfonic acid.
10. The method according to claim 8, wherein the catalyst is 0.05 to 0.2% by mass based on 100% by mass of the sum of the blocked silane and the silicate.
11. The method according to claim 4, wherein the temperature of the hydrolytic polycondensation reaction is 50 to 90 ℃.
12. The method according to claim 11, wherein the temperature of the hydrolytic polycondensation reaction is 60 to 80 ℃.
13. The method according to claim 4, wherein the hydrolysis polycondensation reaction time is 1 to 6 hours.
14. The method according to claim 13, wherein the hydrolysis polycondensation reaction time is 2 to 4 hours.
15. The method according to claim 4, wherein the high temperature distillation is carried out at a temperature of 60 to 100 ℃.
16. The process of claim 4, wherein the aging reaction is carried out in the presence of a catalyst.
17. The method of claim 4, wherein the aging reaction is followed by a post-treatment step.
18. The method of claim 17, wherein the post-treatment comprises water washing and distillation.
19. The method of claim 4, wherein the siloxane has the structure of formula II:
(R 1 R 2 2 SiO 1/2 ) a (R 4 SiO 3/2 ) c (SiO 2 ) d a formula II;
R 1 、R 2 、R 4 a, b, c, d have the following characteristicsThe same protection scope as in claim 1.
20. The method according to claim 4, wherein the mass percentage of the siloxane is 0.5 to 10% based on 100% of the mass of the siloxane ring.
21. The preparation method according to claim 20, wherein the mass percentage of the siloxane is 1-6% based on 100% of the mass of the siloxane ring.
22. The method according to claim 4, wherein the siloxane ring is selected from octamethyl cyclotetrasiloxane and/or dimethylsiloxane hybrid ring.
23. The process of claim 4, wherein the equilibration reaction is carried out in the presence of an acidic catalyst.
24. The method of claim 23, wherein the acidic catalyst is selected from any one or a combination of at least two of sulfuric acid, hydrochloric acid, trifluoromethanesulfonic acid, or an acidic ion exchange resin.
25. The method of claim 24, wherein the acidic catalyst is selected from any one or a combination of at least two of sulfuric acid, trifluoromethanesulfonic acid, or an acidic ion exchange resin.
26. The method according to claim 23, wherein the acidic catalyst is 0.005 to 0.2% by mass based on 100% by mass of the siloxane ring.
27. The method according to claim 4, wherein the temperature of the equilibration reaction is 50-100 ℃.
28. The method according to claim 4, wherein the time for the equilibration reaction is 2 to 10 hours.
29. The method according to claim 4, wherein the neutralizing agent is selected from any one or a combination of at least two of calcium carbonate, sodium carbonate, potassium carbonate, sodium bicarbonate and potassium bicarbonate.
30. The preparation method according to claim 4, wherein the mass percentage of the neutralizing agent is 0.025-10% based on 100% of the mass of the siloxane ring.
31. The method according to claim 4, wherein the reaction temperature for terminating the reaction is 50 to 60 ℃.
32. The method according to claim 4, wherein the reaction time for terminating the reaction is 1 to 2 hours.
33. The method according to claim 4, wherein the step of post-treatment is further included after the termination reaction.
34. The method of claim 33, wherein the post-treatment comprises filtration and distillation.
35. Use of a branched polysiloxane according to any one of claims 1 to 3 in a release agent wherein the release agent has an aged release force climb < 200%.
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