CN105801776A - Aqueous polysiloxane resin and preparation method thereof - Google Patents
Aqueous polysiloxane resin and preparation method thereof Download PDFInfo
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- CN105801776A CN105801776A CN201610315742.2A CN201610315742A CN105801776A CN 105801776 A CN105801776 A CN 105801776A CN 201610315742 A CN201610315742 A CN 201610315742A CN 105801776 A CN105801776 A CN 105801776A
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- silicone resin
- acrylate
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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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/10—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
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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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
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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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
- C08F283/124—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes on to polysiloxanes having carbon-to-carbon double bonds
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- 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
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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
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C09D151/085—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds on to polysiloxanes
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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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
Abstract
The invention discloses aqueous polysiloxane resin and a preparation method thereof. The aqueous polysiloxane resin is prepared from a pre-emulsion A, an emulsion B and a solution C as raw materials. The preparation method comprises the following steps: 1) preparing the pre-emulsion A; 2) preparing the emulsion B; 3) preparing the solution C; 4) pouring a part of the pre-emulsion A into a reaction container, dripping a part of the emulsion B, and at the same time heating the reaction container to 55-65 DEG C to react for 0.5-1 hour so as to prepare a light blue fluorescent seed emulsion; 5) simultaneously dripping the rest pre-emulsion A and the emulsion B into the fluorescent seed emulsion, heating to 55-65 DEG C to react for 2-3 hours, after the reaction is completed, cooling to the room temperature, adjusting the pH value to be 7-8, dripping the solution C, stirring for 10-30 minutes, and filtering, thereby obtaining a filtrate, that is, the aqueous polysiloxane resin. The aqueous polysiloxane resin is good in storage stability and flexibility, good in adhesion property, high in hardness and good in impact resistance, water resistance, salt water resistance, artificial aging resistance and chemical corrosion resistance. The aqueous polysiloxane resin is simple in preparation method, gentle in reaction condition and stable in process procedure.
Description
Technical field
The invention belongs to fine chemistry industry technical field of coatings, be specifically related to a kind of water based silicone resin and preparation side thereof
Method.
Background technology
The organosilicon acrylic resin that acrylate monomer is prepared with organosilicon copolymerization, the features such as its wearability is bad, hardness is inadequate are difficult
To be applied in the fields such as water-based metal finish paint, aqueous woodware paint.Tradition prepares aqueous polyurethane organic siliconresin, utilizes hydroxyl
Base silicone oil (Si-OH) reacts with polyurethane (-NCO), and the Si-O-C key facile hydrolysis of generation, prepared stability of emulsion is poor.
The recipe ratio that the most domestic acrylic monomers, epoxy resin compound modified organic silicon prepare waterborne organic silicon resin is less, and
And similar products are the most fewer.
Summary of the invention
For solving the problem that above-mentioned prior art exists, the invention provides a kind of water based silicone resin and preparation thereof
Method, this resin storage stability and flexibility are good, and adhesive force is big, and hardness is high, and have good resistance to impact, water-fast
Property, resistance to salt water, artificial ageing resistance and chemical resistance.
This preparation method is simple, does not the most utilize organic solvent, and reaction condition is gentle, and technical process is more steady
Fixed.
Realizing the technical scheme that above-mentioned purpose of the present invention used is:
A kind of water based silicone resin, is that raw material is prepared from by A pre-emulsion, B emulsion and C solution:
A pre-emulsion is prepared from by the raw material of following mass parts:
B emulsion is prepared from by the raw material of following mass parts:
C solution is prepared from by the raw material of following mass parts:
Adipic dihydrazide 0.8-1.8 part
Deionized water 5-10 part.
Described waterborne epoxy acrylate is that the TJ157-70 of Liangshan Tian Jia Chemical Co., Ltd. is aqueous acrylic modified
Epoxy ester resin and TJ153-70 waterborne organic silicon epoxy acrylic resin.
Described aqueous polyurethane acrylate emulsion is that Nanjing Jia Zhong Chemical Industry Science Co., Ltd JAZO type aqueous UV is gathered
Urethane acrylate.
Described acrylic ester monomer is acrylic acid, methacrylic acid, methyl methacrylate, methacrylic acid second
Ester, n propyl methacrylate, n-BMA, acrylic acid methyl ester., ethyl acrylate, n-butyl acrylate, propylene
Any one in acid hydroxyl ethyl ester, Hydroxypropyl acrylate, lauryl acrylate and acrylic acid-2-ethyl caproite, or the most several
The combination planted.
Described emulsifying agent is made up of sodium lauryl sulphate and NPE, sodium lauryl sulphate and nonyl
The mass ratio of both base phenol polyethenoxy ethers is 1:2-2:1.
Described silane coupler is allyltrimethoxysilanis, vinyltrimethoxy silane, vinyl three isopropyl
TMOS, dimethoxymethylvinylchlane, methylvinyldimethoxysilane, methacrylic diethoxy silane
With any one in γ-(methacryloxypropyl) propyl trimethoxy silicane, or the most several combination.
Described initiator is made up of with sodium sulfite potassium peroxydisulfate, and the ratio of potassium peroxydisulfate and sodium sulfite is
1.2:1。
Described buffer agent is sodium bicarbonate.
The preparation method of a kind of water based silicone resin, comprises the steps:
1) waterborne epoxy acrylate resin, aqueous polyurethane acrylate emulsion, propylene are weighed according to above-mentioned proportioning
Esters of gallic acid monomer, styrene, N-[2-(2-methyl-4-oxopentyl), emulsifying agent, buffer agent and deionized water, after mixing, high-speed stirred carries out breast
Change, prepare A pre-emulsion；
2) octamethylcy-clotetrasiloxane, emulsifying agent, silane coupler, styrene, acrylic acid are weighed according to above-mentioned proportioning
Esters monomer, N-[2-(2-methyl-4-oxopentyl), initiator and deionized water, by octamethylcy-clotetrasiloxane, emulsifying agent and deionized water
Mix homogeneously, during with sulfuric acid solution regulation pH value to 3-4, continues dropping silane coupler, is heated to 75-80 DEG C, and 3-4 is little in reaction
Shi Hou, is cooled to room temperature, with ammonia regulation pH value to 7-8, continuously adds styrene, acrylic ester monomer, diacetone acrylamide
Amide and initiator, high-speed stirred carries out emulsifying, prepares B emulsion；
3) weigh adipic dihydrazide and deionized water according to the proportioning described in claim 1, adipic dihydrazide is dissolved in deionization
In water, prepare C solution；
4) taking and account for the A pre-emulsion of gross mass 10%-20% and pour in reaction vessel, then dropping accounts for gross mass 10%
B emulsion, reacting by heating container is to 55-65 DEG C simultaneously, reacts 0.5-1 hour, prepares fluorescent seeds emulsion azury；
5) remaining A pre-emulsion, B emulsion are simultaneously added dropwise in fluorescent seeds emulsion, after being heated to 55-65 DEG C, instead
Answering 2-3 hour, question response completes, and is cooled to room temperature, drips C solution, stir 10-30 minute, mistake after ammonia regulation pH to 7-8
Filter off except filtering residue, take filtrate, obtain water based silicone resin.
Compared with prior art, advantages of the present invention and having the beneficial effects that:
1) resin stability prepared by the present invention is good, after drying and forming-film, its hardness, adhesive force, impact resistance, pliable and tough
Property, organic solvent-resistant, resistance to water, artificial ageing resistance, alkali resistance and freeze-thawing resistant cycle performance are the most all good.
2) resin prepared by the present invention has nontoxic, harmless, odorlessness and the advantage such as environmentally friendly.
3) present invention uses mutual network polymerization emulsifying INP, takes partial cross-linked thing A pre-emulsion conduct " seed " emulsion, with
Time add the quantitative B pre-emulsion containing organosilicon and initiator, in-situ polymerization, formed and intert emulsion；Prepared by this invention
INP emulsion, due to the connection of different chemical structures, is cross-linked interspersed by general nucleocapsid structure further, and relatively continuity method emulsion is gathered
For conjunction, semicontinuous pre-emulsifying method, nucleocapsid emulsion process, prepared water based silicone resin, performance possesses preferably coordination
With complementary advantage, the resin such as the present invention all has greatly improved in resistance to water, pliability, hardness, stability etc..
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in detail.
Embodiment 1
A kind of water based silicone resin, is that raw material is prepared from by A pre-emulsion, B emulsion and C solution:
A pre-emulsion is prepared from by the raw material of following mass parts:
B emulsion is prepared from by the raw material of following mass parts:
C solution is prepared from by the raw material of following mass parts:
Adipic dihydrazide 0.8 part
Deionized water 5 parts.
Described waterborne epoxy acrylate is that the TJ157-70 of Liangshan Tian Jia Chemical Co., Ltd. is aqueous acrylic modified
Epoxy ester resin.
Described aqueous polyurethane acrylate emulsion is that Nanjing Jia Zhong Chemical Industry Science Co., Ltd JAZO type aqueous UV is gathered
Urethane acrylate.
Described emulsifying agent is made up of sodium lauryl sulphate and NPE, sodium lauryl sulphate and nonyl
The mass ratio of both base phenol polyethenoxy ethers is 1:2.
Described initiator is made up of with sodium sulfite potassium peroxydisulfate, and the ratio of potassium peroxydisulfate and sodium sulfite is
1.2:1。
The preparation method of above-mentioned water based silicone resin, the steps include:
1) waterborne epoxy acrylate resin, aqueous polyurethane acrylate emulsion, methyl are weighed according to above-mentioned proportioning
Acrylic acid methyl ester., styrene, n-butyl acrylate, lauryl acrylate, acrylic acid-2-ethyl caproite, acrylic acid, acrylic acid hydroxyl
Ethyl ester, N-[2-(2-methyl-4-oxopentyl), emulsifying agent, sodium bicarbonate and deionized water, high-speed stirred after mixing (rotating speed 2000r/min, is stirred
Mix 10min) carry out emulsifying, prepare A pre-emulsion
2) octamethylcy-clotetrasiloxane, emulsifying agent, allyltrimethoxysilanis, methyl-prop are weighed according to above-mentioned proportioning
E pioic acid methyl ester, styrene, n-butyl acrylate, N-[2-(2-methyl-4-oxopentyl), initiator and deionized water, by prestox ring four silica
Alkane, emulsifying agent and deionized water mix homogeneously, when regulating pH value to 3 with the sulfuric acid solution of 0.1mol/L, continue dropping pi-allyl
Trimethoxy silane, is heated to 75 DEG C, after reacting 3 hours, is cooled to room temperature (20-30 DEG C), with ammonia regulation pH value to 8, continues
Continuous addition methyl methacrylate, styrene, n-butyl acrylate, N-[2-(2-methyl-4-oxopentyl) and initiator, high-speed stirred (rotating speed
2000r/min, stirring 10min) carry out emulsifying, prepare B emulsion；
3) weigh adipic dihydrazide and deionized water according to above-mentioned proportioning, adipic dihydrazide is dissolved in deionized water, prepare C
Solution；
4) taking and account for the A pre-emulsion of gross mass 10% and pour in reaction vessel, then dropping accounts for the B breast of gross mass 10%
Liquid, reacting by heating container is to after 65 DEG C simultaneously, reacts 0.5 hour, prepares fluorescent seeds emulsion azury；
5) by remaining A pre-emulsion, B emulsion (time of A pre-emulsion, B emulsion dropping is all higher than half an hour) together
Time be added dropwise in fluorescent seeds emulsion, after being heated to 65 DEG C, react 3 hours, question response completes, and is cooled to room temperature (20-30 DEG C),
Drip C solution, stirring (rotating speed 600r/min) 20 minutes with after ammonia regulation pH to 8, with the nylon net filter of 200 mesh, remove
Filtering residue, takes filtrate, obtains water based silicone resin.
Embodiment 2
A kind of water based silicone resin, is that raw material is prepared from by A pre-emulsion, B emulsion and C solution:
A pre-emulsion is prepared from by the raw material of following mass parts:
B emulsion is prepared from by the raw material of following mass parts:
C solution is prepared from by the raw material of following mass parts:
Adipic dihydrazide 0.8 part
Deionized water 10 parts.
Described waterborne epoxy acrylate is that the TJ153-70 of Liangshan Tian Jia Chemical Co., Ltd. is aqueous acrylic modified
Epoxy ester resin.
Described aqueous polyurethane acrylate emulsion is that Nanjing Jia Zhong Chemical Industry Science Co., Ltd JAZO type aqueous UV is gathered
Urethane acrylate.
Described emulsifying agent is made up of sodium lauryl sulphate and NPE, sodium lauryl sulphate and nonyl
The mass ratio of both base phenol polyethenoxy ethers is 1:2.
Described initiator is made up of with sodium sulfite potassium peroxydisulfate, and the mass ratio of potassium peroxydisulfate and sodium sulfite is
1.2:1。
The preparation method of above-mentioned water based silicone resin, the steps include:
1) waterborne epoxy acrylate resin, aqueous polyurethane acrylate emulsion, methyl are weighed according to above-mentioned proportioning
Acrylic acid methyl ester., styrene, n-butyl acrylate, ethyl acrylate, acrylic acid, 2-(Acryloyloxy)ethanol, N-[2-(2-methyl-4-oxopentyl),
Emulsifying agent, sodium bicarbonate and deionized water, after mixing, high-speed stirred (rotating speed 2000r/min, stirring 10min) carries out emulsifying, system
Standby A pre-emulsion；
2) octamethylcy-clotetrasiloxane, emulsifying agent, methacrylic diethoxy silane, first are weighed according to above-mentioned proportioning
Base acrylic acid methyl ester., styrene, n-butyl acrylate, N-[2-(2-methyl-4-oxopentyl), initiator and deionized water, by prestox ring four
Siloxanes, emulsifying agent and deionized water mix homogeneously, when regulating pH value to 3 with the sulfuric acid solution of 0.1mol/L, continue dropping first
Base pi-allyl diethoxy silane, is heated to 80 DEG C, after reacting 4 hours, is cooled to room temperature (20-30 DEG C), regulates pH with ammonia
Value, to 7, continuously adds methyl methacrylate, styrene, n-butyl acrylate, N-[2-(2-methyl-4-oxopentyl) and initiator, at a high speed
Stirring (rotating speed 2000r/min, stirring 10min) carries out emulsifying, prepares B emulsion；
3) weigh adipic dihydrazide and deionized water according to above-mentioned proportioning, adipic dihydrazide is dissolved in deionized water, prepare C
Solution；
4) taking and account for the A pre-emulsion of A pre-emulsion gross mass 20% and pour in reaction vessel, then to account for B emulsion total in dropping
The B emulsion of quality 10%, reacting by heating container is to after 60 DEG C simultaneously, reacts 0.5 hour, prepares fluorescent seeds azury breast
Liquid；
5) by remaining A pre-emulsion, B emulsion (time of A pre-emulsion, B emulsion dropping is more than half an hour) simultaneously
Being added dropwise in fluorescent seeds emulsion, after being heated to 65 DEG C, react 2.5 hours, question response completes, and is cooled to room temperature (20-30 DEG C),
Drip C solution, stirring (rotating speed 600r/min) 20 minutes with after ammonia regulation pH to 7, with the nylon net filter of 200 mesh, remove
Filtering residue, takes filtrate, obtains water based silicone resin.
Embodiment 3
A kind of water based silicone resin, is that raw material is prepared from by A pre-emulsion, B emulsion and C solution:
A pre-emulsion is prepared from by the raw material of following mass parts:
B emulsion is prepared from by the raw material of following mass parts:
C solution is prepared from by the raw material of following mass parts:
Adipic dihydrazide 1.5 parts
Deionized water 10 parts.
Described waterborne epoxy acrylate is that the TJ153-70 of Liangshan Tian Jia Chemical Co., Ltd. is aqueous acrylic modified
Epoxy ester resin.
Described aqueous polyurethane acrylate emulsion is that Nanjing Jia Zhong Chemical Industry Science Co., Ltd JAZO type aqueous UV is gathered
Urethane acrylate.
Described emulsifying agent is made up of sodium lauryl sulphate and NPE, sodium lauryl sulphate and nonyl
The mass ratio of both base phenol polyethenoxy ethers is 1:2.
Described initiator is made up of with sodium sulfite potassium peroxydisulfate, and the mass ratio of potassium peroxydisulfate and sodium sulfite is
1.2:1。
The preparation method of above-mentioned water based silicone resin, the steps include:
1) waterborne epoxy acrylate resin, aqueous polyurethane acrylate emulsion, methyl are weighed according to above-mentioned proportioning
Acrylic acid methyl ester., styrene, n-butyl acrylate, lauryl acrylate, acrylic acid, N-[2-(2-methyl-4-oxopentyl), emulsifying agent, carbonic acid
Hydrogen sodium and deionized water, high-speed stirred (rotating speed 2000r/min, stirring 10min) carries out emulsifying, prepares A pre-emulsion；
2) octamethylcy-clotetrasiloxane, emulsifying agent, methacrylic diethoxy silane, first are weighed according to above-mentioned proportioning
Base acrylic acid methyl ester., styrene, n-butyl acrylate, N-[2-(2-methyl-4-oxopentyl), initiator and deionized water, by prestox ring four
Siloxanes, emulsifying agent and deionized water mix homogeneously, when regulating pH value to 3 with the sulfuric acid solution of 0.1mol/L, continue dropping first
Base pi-allyl diethoxy silane, is heated to 75 DEG C, after reacting 3 hours, is cooled to room temperature (20-30 DEG C), regulates pH with ammonia
Value, to 7.5, continuously adds methyl methacrylate, styrene, n-butyl acrylate, N-[2-(2-methyl-4-oxopentyl) and initiator, system
Obtain B emulsion；
3) weigh adipic dihydrazide and deionized water according to above-mentioned proportioning, adipic dihydrazide is dissolved in deionized water, prepare C
Solution；
4) taking and account for the A pre-emulsion of A pre-emulsion gross mass 20% and pour in reaction vessel, then to account for B emulsion total in dropping
The B emulsion of quality 10%, reacting by heating container is to after 60 DEG C simultaneously, reacts 0.5 hour, prepares fluorescent seeds azury breast
Liquid；
5) by remaining A pre-emulsion, B emulsion (time of A pre-emulsion, B emulsion dropping is more than half an hour) simultaneously
Being added dropwise in fluorescent seeds emulsion, after being heated to 65 DEG C, react 3 hours, question response completes, and is cooled to room temperature (20-30 DEG C), uses
Drip C solution, stirring (rotating speed 600r/min) 20 minutes after ammonia regulation pH to 8, with the nylon net filter of 200 mesh, take filtrate,
Obtain water based silicone resin.
Embodiment 4
A kind of water based silicone resin, is that raw material is prepared from by A pre-emulsion, B emulsion and C solution:
A pre-emulsion is prepared from by the raw material of following mass parts:
B emulsion is prepared from by the raw material of following mass parts:
C solution is prepared from by the raw material of following mass parts:
Adipic dihydrazide 0.8 part
Deionized water 10 parts.
Described waterborne epoxy acrylate is that the TJ153-70 of Liangshan Tian Jia Chemical Co., Ltd. is aqueous acrylic modified
Epoxy ester resin.
Described aqueous polyurethane acrylate emulsion is that Nanjing Jia Zhong Chemical Industry Science Co., Ltd JAZO type aqueous UV is gathered
Urethane acrylate.
Described emulsifying agent is made up of sodium lauryl sulphate and NPE, sodium lauryl sulphate and nonyl
The mass ratio of both base phenol polyethenoxy ethers is 1:2.
Described initiator is made up of with sodium sulfite potassium peroxydisulfate, and the mass ratio of potassium peroxydisulfate and sodium sulfite is
1.2:1。
The preparation method of above-mentioned water based silicone resin, the steps include:
1) waterborne epoxy acrylate resin, aqueous polyurethane acrylate emulsion, methyl are weighed according to above-mentioned proportioning
Acrylic acid methyl ester., styrene, n-butyl acrylate, lauryl acrylate, acrylic acid, N-[2-(2-methyl-4-oxopentyl), emulsifying agent, carbonic acid
Hydrogen sodium and deionized water, high-speed stirred (rotating speed 2000r/min, stirring 10min) carries out emulsifying, prepares A pre-emulsion；
2) octamethylcy-clotetrasiloxane, emulsifying agent, methacrylic diethoxy silane, first are weighed according to above-mentioned proportioning
Base acrylic acid methyl ester., styrene, n-butyl acrylate, N-[2-(2-methyl-4-oxopentyl), initiator and deionized water, by prestox ring four
Siloxanes, emulsifying agent and deionized water mix homogeneously, when regulating pH value to 3 with the sulfuric acid solution of 0.1mol/L, continue dropping first
Base pi-allyl diethoxy silane, is heated to 80 DEG C, after reacting 3 hours, is cooled to room temperature (20-30 DEG C), regulates pH with ammonia
Value, to 8, continuously adds methyl methacrylate, styrene, n-butyl acrylate, N-[2-(2-methyl-4-oxopentyl) and initiator, at a high speed
Stirring (rotating speed 2000r/min, stirring 10min) carries out emulsifying, prepares B emulsion；
3) weigh adipic dihydrazide and deionized water according to above-mentioned proportioning, adipic dihydrazide is dissolved in deionized water, prepare C
Solution；
4) taking and account for the A pre-emulsion of A pre-emulsion gross mass 15% and pour in reaction vessel, then to account for B emulsion total in dropping
The B emulsion of quality 10%, reacting by heating container is to after 55 DEG C simultaneously, reacts 0.5 hour, prepares fluorescent seeds azury breast
Liquid；
5) by remaining A pre-emulsion, B emulsion (A pre-emulsion, the time for adding of B emulsion are more than half an hour) simultaneously
Being added dropwise in fluorescent seeds emulsion, after being heated to 65 DEG C, react 2 hours, question response completes, and is cooled to room temperature (20-30 DEG C), uses
Drip C solution, stirring (rotating speed 600r/min) 20 minutes after ammonia regulation pH to 7, with the nylon net filter of 200 mesh, remove filter
Slag, takes filtrate, obtains water based silicone resin.
Embodiment 5
A kind of water based silicone resin, is that raw material is prepared from by A pre-emulsion, B emulsion and C solution:
A pre-emulsion is prepared from by the raw material of following mass parts:
B emulsion is prepared from by the raw material of following mass parts:
C solution is prepared from by the raw material of following mass parts:
Adipic dihydrazide 1.5 parts
Deionized water 10 parts.
Described waterborne epoxy acrylate is that the TJ157-70 of Liangshan Tian Jia Chemical Co., Ltd. is aqueous acrylic modified
Epoxy ester resin.
Described aqueous polyurethane acrylate emulsion is JAZO type aqueous UV of Nanjing Jia Zhong Chemical Industry Science Co., Ltd
Urethane acrylate.
Described emulsifying agent is made up of sodium lauryl sulphate and NPE, sodium lauryl sulphate and nonyl
The mass ratio of both base phenol polyethenoxy ethers is 1:2.
Described initiator is made up of with sodium sulfite potassium peroxydisulfate, and the mass ratio of potassium peroxydisulfate and sodium sulfite is
1.2:1。
The preparation method of above-mentioned water based silicone resin, the steps include:
1) waterborne epoxy acrylate resin, aqueous polyurethane acrylate emulsion, methyl are weighed according to above-mentioned proportioning
Acrylic acid methyl ester., styrene, n-butyl acrylate, ethyl acrylate, acrylic acid, 2-(Acryloyloxy)ethanol, N-[2-(2-methyl-4-oxopentyl),
Emulsifying agent, sodium bicarbonate and deionized water, high-speed stirred (rotating speed 2000r/min, stirring 10min) carries out emulsifying, prepares the pre-breast of A
Change liquid；
2) octamethylcy-clotetrasiloxane, emulsifying agent, methacrylic diethoxy silane, first are weighed according to above-mentioned proportioning
Base acrylic acid methyl ester., styrene, n-butyl acrylate, N-[2-(2-methyl-4-oxopentyl), initiator and deionized water, by prestox ring four
Siloxanes, emulsifying agent and deionized water mix homogeneously, when regulating pH value to 3 with the sulfuric acid solution of 0.1mol/L, continue dropping first
Base pi-allyl diethoxy silane, is heated to 75 DEG C, after reacting 4 hours, is cooled to room temperature, with ammonia regulation pH value to 8, continues
Add methyl methacrylate, styrene, n-butyl acrylate, N-[2-(2-methyl-4-oxopentyl) and initiator, high-speed stirred (rotating speed
2000r/min, stirring 10min) carry out emulsifying, prepare B emulsion；
3) weigh adipic dihydrazide and deionized water according to above-mentioned proportioning, adipic dihydrazide is dissolved in deionized water, prepare C
Solution；
4) taking and account for the A pre-emulsion of A pre-emulsion gross mass 20% and pour in reaction vessel, then to account for B emulsion total in dropping
The B emulsion of quality 10%, reacting by heating container is to after 60 DEG C simultaneously, reacts 0.5 hour, prepares fluorescent seeds azury breast
Liquid；
5) by remaining A pre-emulsion, B emulsion (time of A pre-emulsion, B emulsion dropping is more than half an hour) simultaneously
Being added dropwise in fluorescent seeds emulsion, after being heated to 65 DEG C, react 2.5 hours, question response completes, and is cooled to room temperature (20-30 DEG C),
Drip C solution, stirring (rotating speed 600r/min) 20 minutes with after ammonia regulation pH to 7, with the nylon net filter of 200 mesh, remove
Filtering residue, takes filtrate, obtains water based silicone resin.
Water based silicone resin embodiment 1-5 prepared detects, and examination criteria is as follows: adhesive force, GB/
T6739-2006 " paint and varnish pencil method measures hardness of paint film "；Impact resistance, GB/T 1,732 1993 paint film impact resistance measures
Method；Hardness, GB/T 6,739 2006 paint and varnish pencil method measures hardness of paint film；Resistance to water, GB/T1733 1993 paint film
Resistance to water algoscopy；Alcohol resistance, the mensuration of GB/T11547-2008 plastics resistant to liquid chemical reagent performance；Pliability, GB/T
1731 1993 paint film flexibility algoscopys；Artificial ageing resistance, paint and varnish artificial weathering aging and man-made radiation expose to the open air；Resistance to
Alkalescence, the mensuration of GB/T11547-2008 plastics resistant to liquid chemical reagent performance；Storage stability, GB/T11175 2002 (closes
Resin Emulsion Test Method)；Freeze-thawing resistant circulation GB/T11175 2002 (synthetic resin emulsion test method).
Test result is as shown in the table:
Claims (9)
1. a water based silicone resin, it is characterised in that be that raw material is prepared from by A pre-emulsion, B emulsion and C solution:
A pre-emulsion is prepared from by the raw material of following mass parts:
B emulsion is prepared from by the raw material of following mass parts:
C solution is prepared from by the raw material of following mass parts:
Adipic dihydrazide 0.8-1.8 part
Deionized water 5-10 part.
Water based silicone resin the most according to claim 1, it is characterised in that: described waterborne epoxy acrylate is
The TJ157-70 aqueous acrylic modified epoxy ester resin of Liangshan Tian Jia Chemical Co., Ltd. and TJ153-70 waterborne organic silicon ring
Oxypropylene acid resin.
Water based silicone resin the most according to claim 1, it is characterised in that: described aqueous polyurethane acrylate
Emulsion is Nanjing Jia Zhong Chemical Industry Science Co., Ltd JAZO type aqueous UV urethane acrylate.
Water based silicone resin the most according to claim 1, it is characterised in that: described acrylic ester monomer is third
The positive fourth of olefin(e) acid, methacrylic acid, methyl methacrylate, ethyl methacrylate, n propyl methacrylate, methacrylic acid
Ester, acrylic acid methyl ester., ethyl acrylate, n-butyl acrylate, 2-(Acryloyloxy)ethanol, Hydroxypropyl acrylate, lauryl acrylate
With any one in acrylic acid-2-ethyl caproite, or the most several combination.
Water based silicone resin the most according to claim 1, it is characterised in that: described emulsifying agent is by dodecyl sulfur
Acid sodium and NPE composition, the mass ratio of sodium lauryl sulphate and NPE is 1:
2-2:1。
Water based silicone resin the most according to claim 1, it is characterised in that: described silane coupler is pi-allyl
Trimethoxy silane, vinyltrimethoxy silane, vinyl silane triisopropoxide, dimethoxymethylvinylchlane,
Methylvinyldimethoxysilane, methacrylic diethoxy silane and γ-(methacryloxypropyl) propyl trimethoxy
Any one in silane, or the most several combinations.
Water based silicone resin the most according to claim 1, it is characterised in that: described initiator by potassium peroxydisulfate with
Sodium sulfite forms, and the ratio of potassium peroxydisulfate and sodium sulfite is 1.2:1.
Water based silicone resin the most according to claim 1, it is characterised in that: described buffer agent is sodium bicarbonate.
9. the preparation method of a water based silicone resin, it is characterised in that comprise the steps:
1) according to the proportioning described in claim 1 weigh waterborne epoxy acrylate resin, aqueous polyurethane acrylate emulsion,
Acrylic ester monomer, styrene, N-[2-(2-methyl-4-oxopentyl), emulsifying agent, buffer agent and deionized water, after mixing, stirring carries out breast
Change, prepare A pre-emulsion；
2) according to the proportioning described in claim 1 weigh octamethylcy-clotetrasiloxane, emulsifying agent, silane coupler, styrene, third
Olefin(e) acid esters monomer, N-[2-(2-methyl-4-oxopentyl), initiator and deionized water, by octamethylcy-clotetrasiloxane, emulsifying agent and go from
Sub-water mix homogeneously, during with sulfuric acid solution regulation pH value to 3-4, continues dropping silane coupler, is heated to 75-80 DEG C, reaction
After 3-4 hour, it is cooled to room temperature, with ammonia regulation pH value to 7-8, continuously adds styrene, acrylic ester monomer, diacetone
Acrylamide and initiator, stirring carries out emulsifying, prepares B emulsion；
3) weigh adipic dihydrazide and deionized water according to the proportioning described in claim 1, adipic dihydrazide be dissolved in deionized water,
Prepare C solution；
4) taking and account for the A pre-emulsion of gross mass 10%-20% and pour in reaction vessel, then dropping accounts for the B breast of gross mass 10%
Liquid, reacting by heating container is to 55-65 DEG C simultaneously, reacts 0.5-1 hour, prepares fluorescent seeds emulsion azury；
5) remaining A pre-emulsion, B emulsion are simultaneously added dropwise in fluorescent seeds emulsion, after being heated to 55-65 DEG C, react 2-3
Hour, question response completes, and is cooled to room temperature, drips C solution, stir 10-30 minute, cross and filter off after ammonia regulation pH to 7-8
Except filtering residue, take filtrate, obtain water based silicone resin.
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| CN115043996A (en) * | 2021-03-08 | 2022-09-13 | 中国石油天然气股份有限公司 | Method for preparing high-weather-resistance thermoplastic resin by emulsion polymerization and prepared silicon-containing thermoplastic resin |
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