CN115417946A - Preparation method and application of organic silicon acrylate resin monomer composition - Google Patents
Preparation method and application of organic silicon acrylate resin monomer composition Download PDFInfo
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- CN115417946A CN115417946A CN202211148060.9A CN202211148060A CN115417946A CN 115417946 A CN115417946 A CN 115417946A CN 202211148060 A CN202211148060 A CN 202211148060A CN 115417946 A CN115417946 A CN 115417946A
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- acrylate resin
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- 239000004925 Acrylic resin Substances 0.000 title claims abstract description 72
- 239000000178 monomer Substances 0.000 title claims abstract description 62
- 239000000203 mixture Substances 0.000 title claims abstract description 54
- SOGFHWHHBILCSX-UHFFFAOYSA-J prop-2-enoate silicon(4+) Chemical compound [Si+4].[O-]C(=O)C=C.[O-]C(=O)C=C.[O-]C(=O)C=C.[O-]C(=O)C=C SOGFHWHHBILCSX-UHFFFAOYSA-J 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 49
- 239000000839 emulsion Substances 0.000 claims abstract description 40
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 20
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 41
- 238000003756 stirring Methods 0.000 claims description 40
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 36
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 29
- 239000000126 substance Substances 0.000 claims description 25
- 229920001296 polysiloxane Polymers 0.000 claims description 24
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 22
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 18
- 238000006116 polymerization reaction Methods 0.000 claims description 18
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 18
- 238000010992 reflux Methods 0.000 claims description 17
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical group C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- 229910052710 silicon Inorganic materials 0.000 claims description 12
- 239000010703 silicon Substances 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 10
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 10
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 10
- CYEJMVLDXAUOPN-UHFFFAOYSA-N 2-dodecylphenol Chemical compound CCCCCCCCCCCCC1=CC=CC=C1O CYEJMVLDXAUOPN-UHFFFAOYSA-N 0.000 claims description 9
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 9
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 9
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 8
- 239000003377 acid catalyst Substances 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 8
- 238000004945 emulsification Methods 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 claims description 5
- 230000001804 emulsifying effect Effects 0.000 claims description 5
- -1 silicon modified acrylate Chemical class 0.000 claims description 5
- URDOJQUSEUXVRP-UHFFFAOYSA-N 3-triethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C(C)=C URDOJQUSEUXVRP-UHFFFAOYSA-N 0.000 claims description 4
- XDQWJFXZTAWJST-UHFFFAOYSA-N 3-triethoxysilylpropyl prop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C=C XDQWJFXZTAWJST-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 4
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
- 238000005580 one pot reaction Methods 0.000 claims description 3
- 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 description 2
- RMKZLFMHXZAGTM-UHFFFAOYSA-N [dimethoxy(propyl)silyl]oxymethyl prop-2-enoate Chemical compound CCC[Si](OC)(OC)OCOC(=O)C=C RMKZLFMHXZAGTM-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 239000003729 cation exchange resin Substances 0.000 claims description 2
- 239000004927 clay Substances 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 230000003472 neutralizing effect Effects 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000007858 starting material Substances 0.000 claims description 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 239000002981 blocking agent Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 8
- 230000007062 hydrolysis Effects 0.000 abstract description 4
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 4
- 239000004908 Emulsion polymer Substances 0.000 abstract 1
- 238000001035 drying Methods 0.000 description 21
- 239000007864 aqueous solution Substances 0.000 description 13
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 12
- 238000001914 filtration Methods 0.000 description 12
- 239000007787 solid Substances 0.000 description 12
- 238000012512 characterization method Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 239000007789 gas Substances 0.000 description 10
- 125000004429 atom Chemical group 0.000 description 6
- 238000007720 emulsion polymerization reaction Methods 0.000 description 6
- 238000004817 gas chromatography Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000007385 chemical modification Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- 229920000058 polyacrylate Polymers 0.000 description 3
- KBQVDAIIQCXKPI-UHFFFAOYSA-N 3-trimethoxysilylpropyl prop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C=C KBQVDAIIQCXKPI-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- MWGMEGAYPPQWFG-UHFFFAOYSA-N [SiH4].OC(=O)C=C Chemical compound [SiH4].OC(=O)C=C MWGMEGAYPPQWFG-UHFFFAOYSA-N 0.000 description 2
- 229920006243 acrylic copolymer Polymers 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 150000001282 organosilanes Chemical class 0.000 description 2
- 238000002464 physical blending Methods 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
- C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
- C08F230/085—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon the monomer being a polymerisable silane, e.g. (meth)acryloyloxy trialkoxy silanes or vinyl trialkoxysilanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/42—Introducing metal atoms or metal-containing groups
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D143/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
- C09D143/04—Homopolymers or copolymers of monomers containing silicon
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- Polymers & Plastics (AREA)
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- General Chemical & Material Sciences (AREA)
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Abstract
The invention discloses an organic silicon acrylate resin monomer composition and a preparation method and application of an emulsion polymer thereof. The organosilicon acrylic resin copolymer emulsion prepared by adopting the organosilicon acrylic resin monomer composition has good reaction activity, and fundamentally solves the problem that the silane coupling agent is easy to generate gel due to hydrolysis in the reaction process. The emulsion prepared by the method has good hydrophobicity and has more remarkable technical and cost advantages.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a preparation method and application of an organic silicon acrylate resin monomer composition and emulsion.
Background
Acrylic resin is widely applied to the industries of paint, adhesive, leather finishing, textile treatment and the like due to excellent film forming property, good gloss retention and excellent mechanical property, but most acrylic resin molecules are linear structures and lack crosslinking points, so that the water resistance, weather resistance and heat resistance are relatively poor, and the use of the acrylic resin is limited. The organic silicon resin structure has Si-O bonds with high covalent bond energy, and the molecular skeleton is flexible to endow the organic silicon resin structure with excellent high and low temperature resistance, weather aging resistance, hydrophobicity and the like. The acrylic resin modified by organic silicon can have the advantages of both.
The method for modifying the acrylic resin by the organic silicon comprises a physical blending method and a chemical modification method. The chemical modification method is characterized in that an organic silicon monomer is introduced to a molecular chain of an acrylate polymer through a chemical reaction, so that chemical bonds are formed among polymer molecules with greatly different polarities, and the acrylate polymer is modified structurally and compositionally, so that the effect of molecular modification is achieved. The chemical modification obviously improves the compatibility between two phases, controls the surface migration of organic silicon molecular chains and the microscopic form of organic silicon to a certain extent, and has various excellent performances which cannot be achieved by simple physical blending of polysiloxane/polyacrylate, so the chemical modification has more application prospects.
However, in the prior art, an organosilane coupling agent is usually used as an initial monomer to be copolymerized with an acrylate monomer to prepare an emulsion, alkoxy in molecules of the organosilane coupling agent is easily hydrolyzed in water, gel is easily generated in the reaction process, and the preparation of high-performance organosilicon modified silicone-acrylate resin is difficult. Chinese patent application CN103342782A discloses a preparation method of an organosilicon acrylic resin emulsion, which specifically comprises the following steps: (1) preparation of a silicone intermediate emulsion; (2) preparing a silicon-acrylic copolymer nuclear emulsion; and (3) preparing a silicone-acrylic copolymer shell emulsion. The silicone acrylic resin emulsion molecule with special core-shell structure design is prepared by firstly preparing siloxane intermediate emulsion, taking part of the intermediate emulsion as seed reaction, emulsifying and dripping monomers in two steps. However, the method has a complex process, and in the reaction process, methoxy in gamma-methacryloxypropyltrimethoxysilane (KH 570) can be hydrolyzed to generate molecular cross-linking and generate a large amount of waste methanol, so that the method has no utilization value, influences the stability of the emulsion, has low atom economy and causes raw material waste.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a preparation method of an organic silicon acrylate resin monomer composition, which solves the problems of hydrolysis and gel generation of a silane coupling agent in the reaction process, effectively improves the atom utilization rate, realizes atom economy and saves the raw material cost. The organosilicon modified acrylate resin monomer composition prepared by the method has good reaction activity in emulsion polymerization, and can be used as a new raw material for emulsion polymerization.
The invention is realized by the following technical scheme:
a preparation method of a silicone acrylate resin monomer composition comprises the following steps: adding an acrylate silane coupling agent, an acid catalyst, an acrylic acid monomer and an end-capping reagent into a reaction container, carrying out one-pot reaction under the condition of heating reflux, standing, cooling, neutralizing, washing, standing and layering, and collecting an upper-layer oily substance to obtain the organic silicon acrylate resin monomer composition.
Further, an acrylate type silane coupling agent: acrylic acid monomer: the mol ratio of the end capping agent is 1 (3-7) to 3; preferably 1 (3 to 4) to 3. The dosage of the acid catalyst is 1-6wt% of the total mass of the starting materials.
The structural formula of the acrylate silane coupling agent is as follows:
Preferably, the acrylate type silane coupling agent is selected from any one or more of methacryloxypropyltrimethoxysilane, acryloxypropyltrimethoxysilane, methacryloxypropyltriethoxysilane or acryloxypropyltriethoxysilane.
The structural formula of the end capping agent is as follows:
The preferred endcapping agent is hexamethyldisiloxane.
Preferably, the acid catalyst is selected from any one or more of sulfuric acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, hydrochloric acid, phosphoric acid, cation exchange resin or acid clay.
Preferably, the acrylic monomer is selected from any one or more of acrylic acid or methacrylic acid.
Further, in the neutralization step of the post-treatment, the concentrated sulfuric acid is neutralized by adding a carbonate aqueous solution. Preferably, the carbonate is sodium carbonate or potassium carbonate.
According to the preparation method, the end-capping treatment is carried out on the acrylic silane coupling agent by breaking the end-capping agent (hexamethyldisiloxane) through an acid catalyst in the reaction process, so that the hydrolysis of the acrylic silane coupling agent is effectively prevented, and meanwhile, under the condition of acid catalysis, alkoxy in the acrylic silane coupling agent is combined with an acrylic monomer through an esterification reaction to generate an acrylate compound, so that the full utilization of atoms is realized, and the organic silicon acrylate resin monomer composition with good reaction activity is prepared.
In the preparation method of the present invention, the reaction temperature is preferably 50 to 70 ℃, preferably 55 to 65 ℃. The reaction time is 1 to 10 hours, preferably 3 to 5 hours.
The invention also provides a silicone acrylate resin monomer composition, which is prepared by the preparation method of the silicone acrylate resin monomer composition.
The invention also provides application of the organic silicon acrylate resin monomer composition, and the organic silicon acrylate resin monomer composition can be specifically used for preparing organic silicon acrylate resin emulsion.
The organic silicon acrylic resin emulsion comprises the following components in percentage by mass:
the invention also provides a preparation method of the organic silicon acrylate resin emulsion, which comprises the following steps:
s1, weighing the components according to a ratio, sequentially adding part of dodecyl phenol polyoxyethylene ether, lauryl sodium sulfate and ammonium persulfate into a pre-emulsification kettle, then adding part of deionized water, and stirring for dissolving; adding the organosilicon modified acrylic monomer composition, stirring and emulsifying for 15-20 min to obtain pre-emulsion;
s2, sequentially adding the rest sodium dodecyl sulfate, the rest dodecyl phenol polyoxyethylene ether, the rest sodium carbonate and the rest deionized water into a polymerization kettle provided with a stirring and refluxing condenser pipe, stirring for dissolving, and placing in a water bath at 50-55 ℃; weighing part of the pre-emulsion and adding the pre-emulsion into a polymerization kettle; dissolving the rest ammonium persulfate in deionized water, slowly adding into a polymerization kettle, and setting the water bath temperature to be 80-85 ℃ to slowly raise the temperature;
s3, after the water bath temperature is raised to the set temperature, slowly dripping the residual pre-emulsion into the polymerization kettle for 2-2.5 hours through a constant-pressure dropping funnel; preserving the heat for 1.5-2 h; after cooling, adjusting the pH value to about 7; discharging to obtain the organic silicon acrylic resin emulsion.
The invention has the following beneficial effects:
according to the invention, the acrylate type silane coupling agent, the acrylic monomer, the end capping agent and the acid catalyst are directly blended and then subjected to one-pot reaction at a certain temperature, so that the hydrolysis of the acrylate type silane coupling agent can be effectively prevented, the atom utilization rate is improved, the full utilization of atoms is realized, and the prepared organosilicon acrylate resin monomer composition with good reaction activity can be used as a new raw material for emulsion polymerization.
The organosilicon acrylic resin monomer composition is used for preparing organosilicon acrylic resin emulsion, has good reaction activity in emulsion polymerization, and effectively saves the raw material cost.
Drawings
FIG. 1 is a gas chromatogram of a silicone acrylate resin monomer composition prepared in example 1;
FIG. 2 is a gas chromatogram of a silicone acrylate resin monomer composition prepared in example 9;
FIG. 3 is a gas chromatogram of a silicone acrylate resin monomer composition prepared in example 10;
FIG. 4 is a gas chromatogram of a silicone acrylate resin composition prepared in comparative example 1;
FIG. 5 is a gas chromatogram of a silicone acrylate resin composition prepared in comparative example 2;
FIG. 6 is an infrared spectrum of a silicone acrylate resin composition prepared in example 1.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
The reagents used in the examples of the present invention and comparative examples are commercially available, but are not limited to these materials.
Example 1
Adding 24.8g of methacryloxypropyl trimethoxy silane, 1.0g of concentrated sulfuric acid, 25.8g of methacrylic acid and 48.7g of hexamethyldisiloxane into a reaction bottle provided with a reflux condenser and a stirring device, reacting for 5 hours under the stirring condition of 60 ℃, standing the product after the reaction is finished, cooling to room temperature, adding a sodium carbonate aqueous solution to neutralize the concentrated sulfuric acid, washing with water, standing for layering, collecting the upper oily substance, adding anhydrous sodium sulfate for drying treatment, drying for 2-3 hours, filtering to remove white solids, and collecting colorless transparent oily substances to obtain the organic silicon acrylate resin monomer composition.
Respectively carrying out gas chromatography characterization and infrared characterization on the prepared organic silicon acrylate resin monomer composition:
fig. 1 is a gas chromatogram of example 1, and the characterization results are shown in table 1, which shows that the esterification reaction and the capping reaction are effectively performed in the preparation method of the present invention, and the product conversion rate is high.
TABLE 1
FIG. 6 is an infrared spectrum of example 1, in which the infrared detection result shows that an acrylic ester compound is generated, indicating that methoxy groups are efficiently converted into ester bonds during the reaction.
Example 2
Adding 24.8g of methacryloxypropyl trimethoxy silane, 0.95g of concentrated sulfuric acid, 21.6g of acrylic acid and 48.7g of hexamethyldisiloxane into a reaction bottle provided with a reflux condenser and a stirring device, reacting for 5 hours under the stirring condition of 60 ℃, standing the product after the reaction is finished, cooling to room temperature, adding a sodium carbonate aqueous solution to neutralize the concentrated sulfuric acid, washing with water, standing for layering, collecting the upper oily substance, adding anhydrous sodium sulfate for drying treatment, drying for 2-3 hours, filtering to remove white solids, and collecting the colorless transparent oily substance to obtain the organic silicon acrylate resin monomer composition.
Example 3
Adding 23.4g of acryloyloxypropyl trimethoxysilane, 0.98g of concentrated sulfuric acid, 25.8g of methacrylic acid and 48.7g of hexamethyldisiloxane into a reaction bottle provided with a reflux condenser and a stirring device, reacting for 5 hours under the stirring condition of 60 ℃, standing the product after the reaction is finished, cooling to room temperature, adding a sodium carbonate aqueous solution to neutralize the concentrated sulfuric acid, washing with water, standing for layering, collecting the upper oily substance, adding anhydrous sodium sulfate for drying treatment, drying for 2-3 hours, filtering to remove white solids, and collecting the colorless transparent oily substance to obtain the organic silicon acrylate resin monomer composition.
Example 4
Adding 23.4g of acryloyloxypropyl trimethoxysilane, 0.94g of concentrated sulfuric acid, 21.6g of acrylic acid and 48.7g of hexamethyldisiloxane into a reaction bottle provided with a reflux condenser and a stirring device, reacting for 5 hours under the stirring condition of 60 ℃, standing the product after the reaction is finished, cooling to room temperature, adding a sodium carbonate aqueous solution to neutralize the concentrated sulfuric acid, washing with water, standing for layering, collecting the upper oily substance, adding anhydrous sodium sulfate for drying treatment, drying for 2-3 hours, filtering to remove white solids, and collecting the colorless transparent oily substance to obtain the organosilicone acrylate resin monomer composition.
Example 5
Adding 29.04g of methacryloxypropyltriethoxysilane, 1.03g of concentrated sulfuric acid, 25.8g of methacrylic acid and 48.7g of hexamethyldisiloxane into a reaction bottle provided with a reflux condenser and a stirring device, reacting for 5 hours under the stirring condition at 60 ℃, standing the product after the reaction is finished, cooling to room temperature, adding a sodium carbonate aqueous solution to neutralize the concentrated sulfuric acid, washing with water, standing for layering, collecting the upper oily substance, adding anhydrous sodium sulfate for drying treatment, drying for 2-3 hours, filtering to remove the white solid, and collecting the colorless transparent oily substance to obtain the organic silicon acrylate resin monomer composition.
Example 6
Adding 29.04g of methacryloxypropyltriethoxysilane, 0.99g of concentrated sulfuric acid, 21.6g of acrylic acid and 48.7g of hexamethyldisiloxane into a reaction bottle provided with a reflux condenser and a stirring device, reacting for 5 hours under the stirring condition of 60 ℃, standing the product after the reaction is finished, cooling to room temperature, adding a sodium carbonate aqueous solution to neutralize the concentrated sulfuric acid, washing with water, standing for layering, collecting the upper oily substance, adding anhydrous sodium sulfate, drying for 2-3 hours, filtering to remove the white solid, and collecting the colorless transparent oily substance to obtain the organic silicon acrylate resin monomer composition.
Example 7
Adding 27.6g of acryloyloxypropyltriethoxysilane, 1.02g of concentrated sulfuric acid as a catalyst, 25.8g of methacrylic acid and 48.7g of hexamethyldisiloxane into a reaction bottle provided with a reflux condenser and a stirring device, reacting for 5 hours under the stirring condition at 60 ℃, standing the product after the reaction is finished, cooling to room temperature, adding a sodium carbonate aqueous solution to neutralize the concentrated sulfuric acid, standing for layering, collecting upper-layer oily substances, adding anhydrous sodium sulfate, drying for 2-3 hours, filtering to remove white solids, and collecting colorless transparent oily substances to obtain the organic silicon acrylate resin monomer composition.
Example 8
Adding 27.6g of acryloyloxypropyltriethoxysilane, 1.12g of concentrated sulfuric acid, 21.6g of acrylic acid and 48.7g of hexamethyldisiloxane into a reaction bottle provided with a reflux condenser and a stirring device, reacting for 5 hours under the stirring condition of 60 ℃, standing the product after the reaction is finished, cooling to room temperature, adding a sodium carbonate aqueous solution to neutralize the concentrated sulfuric acid, standing for layering, collecting upper-layer oily matter, adding anhydrous sodium sulfate for drying treatment for 2-3 hours, filtering to remove white solid, and collecting colorless transparent oily matter to obtain the organic silicon acrylate resin monomer composition.
Example 9
Adding 24.8g of methacryloxypropyl trimethoxy silane, 1.0g of concentrated sulfuric acid, 25.8g of methacrylic acid and 48.7g of hexamethyldisiloxane into a reaction bottle provided with a reflux condenser and a stirring device, reacting for 5 hours under the stirring condition of 50 ℃, standing the product after the reaction is finished, cooling to room temperature, adding a sodium carbonate aqueous solution to neutralize the concentrated sulfuric acid, washing with water, standing for layering, collecting the upper oily substance, adding anhydrous sodium sulfate for drying treatment, drying for 2-3 hours, filtering to remove white solids, and collecting colorless transparent oily substances to obtain the organic silicon acrylate resin monomer composition.
And (3) carrying out gas chromatography characterization on the prepared organic silicon acrylate resin monomer composition:
FIG. 2 is a gas chromatogram of example 9, with the characterization results shown in Table 2.
Table 2:
example 10:
adding 24.8g of methacryloxypropyl trimethoxy silane, 1.0g of concentrated sulfuric acid, 25.8g of methacrylic acid and 48.7g of hexamethyldisiloxane into a reaction bottle provided with a reflux condenser and a stirring device, reacting for 5 hours under the stirring condition of 70 ℃, standing the product after the reaction is finished, cooling to room temperature, adding a sodium carbonate aqueous solution to neutralize the concentrated sulfuric acid, washing with water, standing for layering, collecting the upper oily substance, adding anhydrous sodium sulfate for drying treatment, drying for 2-3 hours, filtering to remove the white solid, and collecting the colorless transparent oily substance to obtain the organic silicon acrylate resin monomer composition.
And (3) carrying out gas chromatography characterization on the prepared organic silicon acrylate resin monomer composition:
FIG. 3 is a gas chromatogram of example 10, with the characterization results shown in Table 3.
Table 3:
comparative example 1:
adding 24.8g of methacryloxypropyl trimethoxy silane, 1.0g of concentrated sulfuric acid, 25.8g of methacrylic acid and 48.7g of hexamethyldisiloxane into a reaction bottle provided with a reflux condenser and a stirring device, reacting for 5 hours under the stirring condition of 80 ℃, standing the product after the reaction is finished, cooling to room temperature, adding a sodium carbonate aqueous solution to neutralize the concentrated sulfuric acid, washing with water, standing for layering, collecting the upper oily substance, adding anhydrous sodium sulfate for drying treatment, drying for 2-3 hours, filtering to remove white solids, and collecting colorless transparent oily substances to obtain the organic silicon acrylate resin monomer composition.
And (3) carrying out gas chromatography characterization on the prepared organic silicon acrylate resin monomer composition:
FIG. 4 is a gas chromatogram of comparative example 1, and the results of the characterization are shown in Table 4, in which the reaction temperature was too high, the end-capping agent (hexamethyldisiloxane) was easily volatilized, the end-capping reaction effect was poor, and the product conversion rate was low.
Table 4:
comparative example 2:
adding 24.8g of methacryloxypropyl trimethoxy silane, 1.0g of concentrated sulfuric acid, 25.8g of methacrylic acid and 48.7g of hexamethyldisiloxane into a reaction bottle provided with a reflux condenser and a stirring device, reacting for 5 hours under the stirring condition of 40 ℃, standing the product after the reaction is finished, cooling to room temperature, adding a sodium carbonate aqueous solution to neutralize the concentrated sulfuric acid, washing with water, standing for layering, collecting the upper oily substance, adding anhydrous sodium sulfate for drying treatment, drying for 2-3 hours, filtering to remove white solids, and collecting colorless transparent oily substances to obtain the organic silicon acrylate resin monomer composition.
And (3) carrying out gas chromatography characterization on the prepared organic silicon acrylate resin monomer composition:
FIG. 5 is a gas chromatogram of comparative example 2, wherein the results are shown in Table 5, and if the reaction temperature is too low, the esterification reaction is not complete, the number of side reactions is large, and the conversion rate of the product is low.
Table 5:
application example 1
S1, weighing the components according to a ratio, sequentially adding 0.30g of dodecyl phenol polyoxyethylene ether, 0.30g of lauryl sodium sulfate and 1.5g of ammonium persulfate into a pre-emulsification kettle, then adding 15g of deionized water, and stirring for dissolving; adding the organic silicon modified acrylate resin monomer composition, stirring and emulsifying for 15min to obtain a pre-emulsion;
s2, sequentially adding 0.6g of sodium dodecyl sulfate, 0.6g of dodecylphenol polyoxyethylene ether, 0.4g of sodium carbonate and 25g of deionized water into a polymerization kettle provided with a stirring and refluxing condenser pipe, stirring for dissolving, and placing in a water bath at 50 ℃; weighing 5g of pre-emulsion, and adding into a polymerization kettle; dissolving 2.5g of ammonium persulfate in 7.4g of deionized water, slowly adding into a polymerization kettle, and setting the water bath temperature to 82 ℃ for slow heating;
s3, after the water bath temperature is raised to the set temperature, slowly dripping the residual pre-emulsion into the polymerization kettle through a constant-pressure dropping funnel for about 2 hours; then 7.4g of deionized water is taken to wash the pre-emulsification kettle and is dripped into the polymerization kettle; preserving the heat for 2 hours; after cooling, adjusting the pH value to about 7; discharging to prepare the organosilicon acrylic resin copolymer emulsion.
Comparative application example 2
S1, weighing the components according to a ratio, sequentially adding 0.30g of dodecyl phenol polyoxyethylene ether, 0.30g of lauryl sodium sulfate and 1.5g of ammonium persulfate into a pre-emulsification kettle, then adding 15g of deionized water, and stirring for dissolving; adding acrylic acid, butyl acrylate, styrene and methyl methacrylate, stirring and emulsifying for 15min to obtain a pre-emulsion;
s2, sequentially adding 0.6g of residual lauryl sodium sulfate, 0.6g of lauryl phenol polyoxyethylene ether, 0.4g of sodium carbonate and 25g of deionized water into a polymerization kettle provided with a stirring and refluxing condenser pipe, stirring for dissolving, and placing in a water bath at 50 ℃; weighing 5g of pre-emulsion, and adding into a polymerization kettle; dissolving 2.5g of the rest ammonium persulfate into 7.4g of deionized water, slowly adding into a polymerization kettle, and setting the water bath temperature to 82 ℃ for slow heating;
s3, after the water bath temperature is raised to the set temperature, slowly dripping the residual pre-emulsion into the polymerization kettle through a constant-pressure dropping funnel for about 2 hours; then 7.4g of deionized water is taken to wash the pre-emulsification kettle and is dripped into the polymerization kettle; preserving the heat for 2 hours; after cooling, adjusting the pH value to about 7; discharging to obtain the acrylic resin emulsion.
And (4) relevant performance test:
according to the measurement of the contact angle of the GB/T30693-2014 plastic film with water, the contact angles of the acrylic resin emulsions prepared in the application example 1 and the application comparative example 2 are measured by using a water drop projection contact angle measuring instrument, and the measurement results are shown in Table 6.
Table 6: results of contact Angle test of acrylic resin emulsions of application example 1 and application comparative example 2
The results show that the organosilicon acrylic resin composition prepared by the method has good reaction activity in emulsion polymerization, can obviously improve the characteristics of products after emulsion polymerization, and obviously improves the hydrophobicity of the prepared emulsion.
Claims (9)
1. A preparation method of a silicone acrylate resin monomer composition is characterized by comprising the following steps: adding an acrylic silane coupling agent, an acid catalyst, an acrylic monomer and an end-capping agent into a reaction vessel, carrying out one-pot reaction under a heating condition, standing, cooling, neutralizing, washing, standing and layering, and collecting an upper oily substance to obtain the organic silicon acrylate resin monomer composition.
2. The method for preparing a silicone acrylate resin monomer composition according to claim 1, wherein the acrylate type silane coupling agent has the following structural formula:
3. The method of claim 1, wherein the end-capping agent has the following formula:
preferably, the blocking agent is selected from hexamethyldisiloxane.
4. The method for preparing a silicone acrylate resin monomer composition according to claim 1, wherein the acid catalyst is selected from any one or more of sulfuric acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, hydrochloric acid, phosphoric acid, cation exchange resin or acid clay; the acrylic monomer is selected from any one or two of acrylic acid or methacrylic acid.
5. The method for producing a silicone acrylate resin monomer composition according to claim 1, characterized in that the acrylate type silane coupling agent: acrylic acid monomer: the molar ratio of the end-capping reagent is 1 (3~7): 3; preferably 1 (3~4): 3;
the dosage of the acid catalyst is 1-6wt% of the total mass of the starting materials.
6. The method for preparing a silicone acrylate resin monomer composition according to claim 1, wherein the reaction temperature is 50-70 ℃, preferably 55-65 ℃; the reaction time is 1 to 10 hours, preferably 3 to 5 hours.
7. A silicone acrylate resin monomer composition, characterized by being produced by the method for producing the silicone acrylate resin monomer composition according to any one of claims 1 to 6.
8. The use of the silicone acrylic monomer composition of claim 7 for the preparation of a silicone acrylic emulsion; the organic silicon acrylic resin emulsion comprises the following components in percentage by mass:
39% to 42.8% of the silicone acrylate resin monomer composition of claim 7;
3.1 to 4 percent of ammonium persulfate;
0.2 to 0.4 percent of sodium carbonate;
0.4 to 0.9 percent of sodium dodecyl sulfate;
0.4 to 0.9 percent of dodecyl phenol polyoxyethylene ether;
47 to 54.8 percent of deionized water.
9. The use of the silicone acrylate resin monomer composition according to claim 8, wherein the preparation method of the silicone acrylate resin emulsion comprises the following steps:
s1, weighing the components according to a ratio, sequentially adding part of dodecyl phenol polyoxyethylene ether, lauryl sodium sulfate and ammonium persulfate into a pre-emulsification kettle, then adding part of deionized water, and stirring for dissolving; adding the organic silicon modified acrylate monomer composition, stirring and emulsifying for 15min-20min to obtain a pre-emulsion;
s2, sequentially adding the rest sodium dodecyl sulfate, the rest dodecyl phenol polyoxyethylene ether, the rest sodium carbonate and the rest deionized water into a polymerization kettle provided with a stirring and refluxing condenser pipe, stirring for dissolving, and placing in a water bath at 50-55 ℃; weighing part of the pre-emulsion and adding the pre-emulsion into a polymerization kettle; dissolving the rest ammonium persulfate in deionized water, slowly adding into a polymerization kettle, and setting the water bath temperature to be 80-85 ℃ to slowly raise the temperature;
s3, after the water bath temperature rises to the set temperature, slowly dripping the residual pre-emulsion into the polymerization kettle through a constant-pressure dropping funnel, and finishing dripping within 2-2.5 hours; preserving the heat for 1.5-2 h; after cooling, adjusting the pH value to 7; discharging to prepare the organosilicon acrylic resin copolymer emulsion.
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| CN1221756A (en) * | 1997-12-31 | 1999-07-07 | 中国石化齐鲁石油化工公司 | Method for preparing organic silicon modified acrylic resin |
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| WO2022114097A1 (en) * | 2020-11-27 | 2022-06-02 | 三菱ケミカル株式会社 | Adhesive composition, adhesive, adhesive sheet, and adhesive sheet for image display device |
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| CN1221756A (en) * | 1997-12-31 | 1999-07-07 | 中国石化齐鲁石油化工公司 | Method for preparing organic silicon modified acrylic resin |
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| CN103194166A (en) * | 2013-05-06 | 2013-07-10 | 哈尔滨工业大学 | Photo-thermal double-curing conductive adhesive and preparation method thereof |
| WO2022114097A1 (en) * | 2020-11-27 | 2022-06-02 | 三菱ケミカル株式会社 | Adhesive composition, adhesive, adhesive sheet, and adhesive sheet for image display device |
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