CN112940203A - Organosilicon modified acrylic acid secondary dispersion and preparation method thereof - Google Patents
Organosilicon modified acrylic acid secondary dispersion and preparation method thereof Download PDFInfo
- Publication number
- CN112940203A CN112940203A CN202110358228.8A CN202110358228A CN112940203A CN 112940203 A CN112940203 A CN 112940203A CN 202110358228 A CN202110358228 A CN 202110358228A CN 112940203 A CN112940203 A CN 112940203A
- Authority
- CN
- China
- Prior art keywords
- acrylate
- modified acrylic
- secondary dispersion
- parts
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/04—Polymerisation in solution
- C08F2/06—Organic solvent
Abstract
The invention discloses an organosilicon modified acrylic acid secondary dispersion and a preparation method thereof, wherein the dispersion is prepared from 15-25 parts by weight of (methyl) acrylate monomer, 0.5-3 parts by weight of monomer containing carboxyl, 8-15 parts by weight of hydroxyl (methyl) acrylate and 2-6 parts by weight of organosilicon modified monomer. The organic silicon modified acrylic acid secondary dispersion has high organic silicon grafting rate and good emulsion stability, does not have the phenomena of floating oil, gel, phase separation and the like after being placed for 6 months, and has excellent scratch resistance, weather resistance, aging resistance, hydrophobicity, heat resistance and the like after a paint film is cured.
Description
Technical Field
The invention relates to a modified resin, which has remarkable effects on stain resistance, heat resistance, sweat resistance, fingerprint resistance and scratch resistance of high-end 3C equipment such as electronic products of mobile phones, computers, earphones, new energy automobile accessories, interior trims and the like.
Technical Field
In recent years, the theory and technology of emulsion polymerization are continuously developed and perfected, and people have higher and higher demands on environment-friendly chemical products. The acrylate paint film has good adhesiveness, acid and alkali resistance, chemical corrosion resistance and other properties. But the paint film formed by the acrylate emulsion still has defects in water resistance; the disadvantages of brittleness at low temperature and stickiness at high temperature also limit the use of acrylate emulsions. To solve this problem, the research on various composite structure emulsions, such as polyorganosiloxane PDMS modified silicone-acrylic emulsion, is now a hot research focus in high performance water-borne coatings. However, in the process of synthesizing the organosilicon modified acrylate emulsion, due to poor compatibility between PDMS and polyacrylate, phase separation is very easy to occur during synthesis and film formation, so that floating oil or coagulation is caused, the effective binding capacity is not high, and meanwhile, the large-scale phase separation causes low light transmittance of a coating film, so that the organosilicon property cannot be well reflected.
The vinyl silicone oil has good weather resistance, aging resistance, ultraviolet resistance and flexibility, and can react with various organic materials such as polyurethane, acrylic acid and the like to prepare a high-performance anti-corrosion weather-resistant coating.
Patent CN105801769B describes a method for improving the anti-graffiti property of the surface by introducing vinyl silicone oil through emulsion polymerization, but the vinyl silicone oil has lower reactivity of double bonds, and the emulsion polymerization mode cannot obtain higher grafting efficiency, and has a certain risk to the stability of the coating.
Patent CN109111554A describes an anti-wear vinyl silicone oil modified acrylic emulsion and a preparation method thereof, which further improves the grafting rate of vinyl silicone oil by adopting solution polymerization and mercapto-click chemistry, thereby obtaining an emulsion with good anti-wear performance. However, the reaction accelerator contains sulfur groups, has special odor and high boiling point, is difficult to volatilize at room temperature, causes chest pain, headache, nausea and pulmonary edema when inhaled, is harmful to the environment and workers, and is not beneficial to long-term development.
Patent CN107383278A describes a method for preparing cationic polymer emulsion by soap-free emulsion polymerization, which uses gamma-ray radiation to prepare pure cationic polymer emulsion under the conditions of normal temperature and without initiator, but for vinyl silicone oil with low reactivity, the grafting ratio is difficult to be improved, and the application is limited.
Disclosure of Invention
In order to solve the problems in the prior art, the invention aims to disclose an organosilicon modified acrylic acid secondary dispersion and a preparation method thereof, the secondary dispersion has high silicone oil grafting rate and good emulsion stability, no phenomena of floating oil, gel, phase separation and the like occur after being placed for 6 months, and a paint film has excellent scratch resistance, weather resistance, aging resistance, hydrophobicity, heat resistance and the like after being cured.
An organosilicon modified acrylic secondary dispersion prepared by reacting raw materials comprising:
15 to 25 parts by weight of a (meth) acrylate monomer, 0.5 to 3 parts by weight of a monomer containing a carboxyl group, 8 to 15 parts by weight of a hydroxyl (meth) acrylate, and 2 to 6 parts by weight of a silicone-modified monomer including an organopolysiloxane having a radical-polymerizable unsaturated group, the radical-polymerizable unsaturated group in the polysiloxane having a radical-polymerizable unsaturated group being a (meth) acrylate group.
Preferably, the silicone-modified monomer comprises a polysiloxane having only one end cap group with a free-radically polymerizable unsaturated group.
Preferably, the number average molecular weight of the organosilicon modified monomer is 1000-5000.
Preferably, the polysiloxane with the free radical polymerizable unsaturated group is prepared by reacting (methyl) acrylate with alkenyl of C2-C5 and organopolysiloxane with at least one hydrogen bond connected with silicon, the molecular structure of the (methyl) acrylate with the alkenyl of C2-C5 is at least provided with one alkenyl of C2-C5 and at least one (methyl) acrylate group, and the reaction is addition reaction of carbon-carbon double bond in the alkenyl of C2-C5 and Si-H.
Further, the method for preparing the polysiloxane having a radical polymerizable unsaturated group includes the steps of:
under the protection of inert gas, (methyl) acrylate with C2-C5 alkenyl is mixed with organopolysiloxane with at least one silicon-bonded hydrogen group, polymerization inhibitor and catalyst, and then the mixture is heated to react to obtain polysiloxane with free radical polymerizable unsaturated groups;
the (meth) acrylate having an alkenyl group of C2-C5 is a compound having at least one alkenyl group of C2-C5 in a molecular structure and at least one (meth) acrylate group.
The (meth) acrylate having an alkenyl group of C2 to C5 is a compound having at least one alkenyl group of C2 to C5 and at least one (meth) acrylate group in the molecular structure, and examples of the alkenyl group of C2 to C5 include allyl, propenyl, vinyl, isobutenyl and the like, preferably allyl.
The addition reaction of Si — H with C ═ C is the prior art, the catalyst is an addition reaction catalyst of Si-H with C ═ C, is not particularly limited, and includes a platinum catalyst, and preferably, the catalyst is used in an amount of 0.5 to 6.5% by mass of the (meth) acrylate having an alkenyl group of C2 to C5.
The inert gas atmosphere is not particularly limited and includes nitrogen. Preferably, the temperature of the temperature rise reaction is 40-60 ℃, and the reaction time is 4-10 h. In the temperature range, the reaction probability of the double bond of the (meth) acrylate group in the (meth) acrylate having the alkenyl group of C2 to C5 can be reduced, the occurrence of side reactions can be reduced, and the reaction efficiency can be improved.
Preferably, the temperature is reduced after the temperature-increasing reaction, an organic layer is separated, and then the organic layer is washed with water and then distilled under reduced pressure to remove the solvent, unreacted reactants, low-molecular by-products, and the like, thereby obtaining a polysiloxane having a radical-polymerizable unsaturated group.
In order to secure the reactivity, the molar ratio of the alkenyl group of C2 to C5 in the (meth) acrylate having an alkenyl group of C2 to C5 to the hydrogen bond to silicon in the organopolysiloxane having one hydrogen bond to silicon is (1 to 1.05): 1, thereby allowing complete reaction of hydrogen bonds with silicon attachment. Whether the addition reaction of Si-H and C ═ C is complete and whether side reactions occur can be judged by testing the hydrosilation content and the double bond content of the reaction product.
The polymerization inhibitor is used for preventing the (methyl) acrylate group from generating self-polymerization reaction. Preferably, the polymerization inhibitor is p-hydroxyanisole, 2, 6-di-tert-butyl-p-cresol, 2, 5-di-tert-butylhydroquinone, 2-tert-butylhydroquinone or hydroquinone. Preferably, the mass of the polymerization inhibitor is 0.004 to 0.25% of the sum of the mass of the (meth) acrylate having an alkenyl group of C2 to C5 and the mass of the organopolysiloxane having at least one silicon-bonded hydrogen group.
The (meth) acrylate having an alkenyl group of C2 to C5 can be obtained in the prior art by esterification of (meth) acrylic acid with an alcohol having an alkenyl group of C2 to C5. Preferably, the (meth) acrylate having an alkenyl group of C2 to C5 is allyl (meth) acrylate.
The (meth) acrylate group of the present invention is a methacrylate group and/or an acrylate group, and the (meth) acrylate having an alkenyl group of C2 to C5 preferably has the same meaning as (meth) in the compound.
Preferably, the organopolysiloxane having at least one silicon-bonded hydrogen group has a number average molecular weight of 200-. Too low a molecular weight results in the final modified acrylic resin not exhibiting silicone properties such as poor anti-fouling properties, while too high a molecular weight product is susceptible to phase separation.
Preferably, the organopolysiloxane having at least one hydrogen bond with silicon includes a compound having a structural formula shown in formula 1:
in formula 1, m is an integer greater than 1, and R is the same or different alkyl, cycloalkyl, aryl, aralkyl, alkoxy, or haloalkyl.
The above-mentioned R's are the same or different alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, alkoxy groups or haloalkyl groups, the alkyl groups include methyl, ethyl, propyl or butyl groups, the cycloalkyl groups include cyclohexyl and cyclopentyl groups, the aryl groups include phenyl, tolyl and xylyl groups, the aralkyl groups include benzyl and phenethyl groups, the haloalkyl groups include 3, 3, 3-trifluoropropyl groups, and the alkoxy groups include methoxy, ethoxy and propoxy groups. The R is preferably methyl or phenyl.
The preparation of the compound having the formula shown in formula 1 can be performed with reference to the prior art. Preferably, the compound having the structural formula shown in formula 1 is prepared by the following method: mixing cyclosiloxane, an acid catalyst and an organic solvent 1, heating to 65-75 ℃ for reaction for 2-4 h, adding trialkylsiloxide and the organic solvent 2, heating to 75-80 ℃ for reaction for 8-12 h, and adding dialkyl monohalosilane at 0 +/-5 ℃ for reaction for 18-24 h to obtain the compound with the structural formula shown in formula 1.
In the preparation method of the compound with the structural formula shown in the formula 1, the structural formula of the cyclosiloxane is shown in the specification
Wherein n is an integer from 3 to 6, R is as previously described and is selected, identically or differently, from alkyl, cycloalkyl, aryl, aralkyl, alkoxy or haloalkyl.
In the preparation method of the compound with the structural formula shown in the formula 1, alkyl in trialkylsiloxide is R as described above and is selected from alkyl, cycloalkyl, aryl, aralkyl, alkoxy or halogenated alkyl, trialkylsiloxide is selected from lithium trialkylsiloxide, sodium trialkylsiloxide or potassium trialkylsiloxide, and preferably, trialkylsiloxide is potassium trialkylsiloxide. Preferably, the mass ratio of the cyclosiloxane to the trialkylsiloxy salt is (6-20): 1, trialkylsilyloxidates as blocking agents, the amount used influencing the molecular weight of the final polysiloxane.
In the preparation method of the compound having the structural formula shown in formula 1, the acid catalyst can catalyze ring-opening polymerization of cyclosiloxane, and the specific substance is not particularly limited, and is preferably concentrated sulfuric acid, hydrochloric acid or trifluoromethanesulfonic acid, and preferably, the mass of the acid catalyst is 0.3% -1.8% of that of the cyclosiloxane.
In the preparation method of the compound with the structural formula shown in the formula 1, the halogenated group of the dialkyl monohalogenated silane is chlorine or bromine, preferably the dialkyl monohalogenated silane, and the alkyl in the dialkyl monohalogenated silane is R as described above and is selected from alkyl, cycloalkyl, aryl, aralkyl, alkoxy or halogenated alkyl. Preferably, in the method for preparing the compound having the structural formula shown in formula 1, the molar ratio of the dialkyl monohalosilane to the trialkylsilyloxide is (1-1.1): 1.
preferably, in the preparation method of the compound having the structural formula shown in formula 1, in the operation of mixing the cyclosiloxane, the acid catalyst and the organic solvent 1, the organic solvent 1 is a nonpolar solvent, such as toluene, xylene or cyclohexane, and the mass ratio of the organic solvent 1 to the cyclosiloxane is (0.3-2): 1.
preferably, in the preparation method of the compound having the structural formula shown in formula 1, in the operation of adding the trialkylsilyl silicon alkoxide and the organic solvent 2, the organic solvent 2 is a polar non-alcoholic solvent, and may be one or more of tetrahydrofuran and acetonitrile, and the mass ratio of the organic solvent 2 to the trialkylsilyl silicon alkoxide is (1-6): 1.
preferably, in the preparation method of the compound with the structural formula shown in formula 1, dialkyl monohalosilane is added to react for 18-24 hours, then the mixture is filtered, and then the organic solvent and low-boiling-point substances such as low molecules are removed by reduced pressure distillation at 80-90 ℃ to obtain the compound with the structural formula shown in formula 1, wherein the low molecules comprise low-molecular-weight side reaction products, unreacted reactants and the like.
In the raw materials for preparing the silicone-modified acrylic secondary dispersion, the (meth) acrylate ester monomer includes at least one compound selected from the group consisting of methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, cyclohexyl (meth) acrylate, butyl (meth) acrylate, isobornyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and isooctyl (meth) acrylate.
In the raw material for preparing the silicone-modified acrylic secondary dispersion, preferably, the monomer containing a carboxyl group is at least one compound selected from the group consisting of maleic anhydride, fumaric acid, crotonic acid, itaconic acid, acrylic acid, and methacrylic acid.
In the raw materials for preparing the organosilicon modified acrylic secondary dispersion, the hydroxyl (methyl) acrylate is a monomer simultaneously having hydroxyl and (methyl) acrylate groups, and preferably one or more of hydroxyethyl (methyl) acrylate, hydroxypropyl (methyl) acrylate and caprolactone modified acrylate. More preferably, the caprolactone-modified acrylate is caprolactone-modified acrylate of xylonite chemical industry co, and the product model is FA1DDM or FA 2D.
The preparation method of the organic silicon modified acrylic acid secondary dispersion comprises the following steps:
mixing 15-25 parts by weight of (methyl) acrylate monomer, 0.5-3 parts by weight of monomer containing carboxyl, 2-6 parts by weight of organosilicon modified monomer, 8-15 parts by weight of hydroxyl (methyl) acrylate, chain transfer agent and first part of free radical initiator to obtain a mixture;
mixing part of the mixture with a second part of the free radical initiator and the cosolvent, heating to 140-160 ℃ for reaction, adding the rest mixture, continuing to react at 155-165 ℃, then cooling to 125-130 ℃ for neutralization, cooling to 100-110 ℃, adding water for first emulsification, continuing to cool to 80-85 ℃, adding water for second emulsification, and cooling to obtain the organic silicon modified acrylic acid secondary dispersion.
The radical reaction initiator may be selected from at least one of ammonium persulfate or alkali metal persulfate and hydrogen peroxide, t-amyl peroxyacetate, t-butyl peroxybenzoate, dicumyl peroxide, and di-t-amyl peroxide.
Preferably, in the preparation method, the total amount of the free radical initiator is 0.8 to 4 parts by weight. Preferably, the mass of the first part of the free radical initiator is 70-85% of the total mass of the free radical initiator, the initiator is added in two parts, the content of the initiator in the solution in the former stage is high, the molecular weight of the polymer can be controlled, and the phenomena of overhigh viscosity, poor dispersion and emulsification effects and the like caused by overhigh molecular weight in the later stage are avoided.
Preferably, the cosolvent is one or more of propylene glycol methyl ether, propylene glycol butyl ether, dipropylene glycol methyl ether, dipropylene glycol butyl ether, tripropylene glycol methyl ether, propylene glycol methyl ether acetate, ethylene glycol butyl ether acetate and diethylene glycol butyl ether acetate. Preferably, the cosolvent is used in an amount of 3-6 parts by weight.
The chain transfer agent is not particularly limited, and is preferably 2, 4-diphenyl-4-methyl-1-pentene (AMSD), EMMP (from kao shogao sho new materials science and technology ltd, guangzhou), n-dodecyl mercaptan (NDM), in an amount of 0.5 to 1.5 parts by weight.
Preferably, the neutralizing agent used for neutralization is triethylamine, N-dimethylethanolamine or industrial ammonia water, and the neutralizing agent is preferably N, N-dimethylethanolamine. The amount of the neutralizing agent is not particularly limited, and the pH of the reaction solution may be adjusted to 7 to 8.
Preferably, the partial mixture accounts for 10-15% of the total mass of the mixture, and the reaction progress and the molecular weight of the product are controlled by controlling the using amount of the reactants.
Preferably, the amount of the water added in the first emulsification is 60-80% of the total amount of water in the preparation method. Preferably, the water is added in one time for the first emulsification, so that the system viscosity can be reduced, the water is added in the second emulsification for dropwise addition for phase transition emulsification, the later-stage overlarge resin viscosity can be avoided, the dispersion uniformity and stability are improved, the use amount of the cosolvent is effectively reduced, and the atmospheric pollution caused by VOC is reduced. Preferably, the stirring speed is 500-1000 r/min when the temperature is reduced to 100-110 ℃ and water is added for the first emulsification.
Preferably, the reaction time of heating to 140-160 ℃ is 15-20 min, the reaction time of adding the rest mixture is 1-2 h at 155-165 ℃, the high-temperature reaction condition can reduce the viscosity of the resin, improve the reaction efficiency and uniformity, and ensure the performance of the final resin.
Preferably, the silicone-modified acrylic secondary dispersion has a solid content of 35 to 50%.
Preferably, the silicone-modified acrylic secondary dispersion has a viscosity of 200-.
Preferably, the average particle diameter of the organosilicon modified acrylic secondary dispersion is 50-200 nm.
The application method of the organic silicon modified acrylic acid secondary dispersion comprises the steps of uniformly mixing the dispersion with water, an auxiliary agent and a water-based isocyanate curing agent according to a certain proportion to obtain a coating, and coating and drying the coating. The auxiliary and the aqueous isocyanate curing agent are not particularly limited.
Compared with the prior art, the invention has the advantages that:
1. compared with the conventional low-molecular silane coupling agent and double-end or multi-end vinyl silicone oil, the polysiloxane modified acrylic resin with the free-radical polymerizable unsaturated group has the advantages that after the polysiloxane modified acrylic resin is grafted onto a molecular chain, a chain segment capable of moving freely is longer, the polysiloxane modified acrylic resin is not easy to wrap inside molecules and can be transferred to the surface of the molecules more easily, and a thin protective oil layer can be formed on the surface of a paint film after curing, so that the paint film has excellent hydrophobicity, scratch resistance and silkiness of hand feeling like baby skin.
2. The preparation method of the emulsion adopts a high-temperature solution polymerization process, greatly improves the grafting rate of the modified silicone oil compared with the conventional polymerization technology, and has smaller particle size of the prepared emulsion, less oil floating phenomenon and improved production efficiency.
3. The preparation process of the modified acrylic resin adopts a process of injecting most of water at 100-110 ℃ at one time, and effectively avoids the phenomena of high viscosity and poor dispersion of the resin at the later stage, thereby effectively reducing the dosage of the cosolvent and avoiding the atmospheric pollution caused by VOC.
4. The acrylic resin provided by the invention has the advantages of non-toxic and environment-friendly raw materials, no toxic solvent, no spontaneous combustion, single component, convenience in construction and excellent comprehensive performance.
Detailed Description
The following specific examples are given to further illustrate the present invention.
Examples of the preparation of silicone-modified monomers are given below, where the viscosity is a dynamic viscosity value at 25 ℃ according to test methods described in GB/T2794-1995; the vinyl content is the mass percentage content of vinyl, and the test of the vinyl content adopts a titration method to determine, referring to national standards GB/T1676-; and meanwhile, the hydrogen content of the reaction product is tested, and the reaction rate of hydrosilation is examined, wherein the test method is HG-T4658-2014 determination of the content of active hydrogen in the hydrogen-containing silicone oil as the textile dyeing and finishing auxiliary.
In the embodiment, the molecular weights of the organosilicon modified monomer and the silicone oil containing silicon-hydrogen groups at one end are measured and calculated by gel permeation chromatography, the equipment is water1525, the company of waters in America, toluene is used as a mobile phase, the flow rate is 1.0ml/min, polysiloxane is used as a standard sample, the temperature of a column box is 35 ℃, the model of a separation column is Stry-agleo HT4, the size of the column is 7.8 multiplied by 300mm, and the test is carried out at room temperature; the hydrogen content is the mass percentage content of hydrogen base connected with silicon, and the test method is HG-T4658-2014 determination of the content of active hydrogen in hydrogen-containing silicone oil as textile dyeing and finishing auxiliary.
Example 1
Under the condition of nitrogen protection, 12.7g of allyl methacrylate, 100g of silicone oil with one silicon-hydrogen containing group at one end, 0.006g of polymerization inhibitor p-hydroxyanisole and 0.6g of 5000ppm of Kansted platinum catalyst are mixed, reacted at 40 ℃ for 10 hours, and subjected to reduced pressure distillation to obtain an organic silicon modified monomer, wherein the yield is 99%, the viscosity is 13mPa.s, the number average molecular weight is 1130, the vinyl content is 2.3%, and the hydrogen content is 0;
the preparation method of the silicone oil containing silicon-hydrogen group at one end comprises the following steps:
adding 300g of octamethylcyclotetrasiloxane into a 1L three-neck flask, adding 5.4g of concentrated sulfuric acid and 600g of toluene, slowly heating to 75 ℃, reacting for 3 hours, adding 45g of potassium trimethylsilanolate and 270g of THF, heating to 80 ℃, reacting for 10 hours, cooling to room temperature, dropwise adding 33g of dimethylchlorosilane under an ice bath condition, reacting for 20 hours while keeping the temperature, filtering, distilling the filtrate under reduced pressure at 90 ℃ to remove low-boiling-point substances, obtaining silicone oil with silylhydride at one end, and testing that the silicone oil has the number average molecular weight of 1000 and the hydrogen content of 0.10%.
Example 2
Under the protection of nitrogen, 11.3g of allyl acrylate, 100g of silicone oil with one silicon-hydrogen containing group at one end, 0.006g of polymerization inhibitor p-hydroxyanisole and 0.7g of 5000ppm of Kansted platinum catalyst are mixed, reacted at 40 ℃ for 8 hours, and subjected to reduced pressure distillation to obtain an organic silicon modified monomer, wherein the yield is 99%, the viscosity is 12mPa.s, the number average molecular weight is 1112, the vinyl content is 2.4%, and the hydrogen content is 0;
the silicone oil having silylhydride at one end was prepared in the same manner as in example 1.
Example 3
Under the condition of nitrogen protection, 4.7g of allyl methacrylate, 100g of silicone oil with one silicon-hydrogen containing group at one end, 0.25g of polymerization inhibitor p-hydroxyanisole and 0.27g of 5000ppm of Kansted platinum catalyst are mixed, reacted for 8 hours at 60 ℃, and then subjected to reduced pressure distillation to obtain an organic silicon modified monomer, wherein the yield is 99%, the viscosity is 30mPa.s, the number average molecular weight is 2830, the vinyl content is 0.91%, and the hydrogen content is 0;
the preparation method of the silicone oil containing silicon-hydrogen group at one end comprises the following steps:
adding 300g of octamethylcyclotetrasiloxane into a 1L three-neck flask, adding 0.9g of trifluoromethanesulfonic acid and 90g of toluene, slowly heating to 75 ℃, reacting for 3h, adding 15g of potassium trimethylsilanolate and 45g of THF, heating to 80 ℃, reacting for 10h, cooling to room temperature, dropwise adding 11g of dimethylchlorosilane under an ice bath condition, reacting for 20h while keeping the temperature, filtering, distilling the filtrate under reduced pressure at 90 ℃ to remove low-boiling-point substances, obtaining silicone oil with silylhydride at one end, and testing that the silicone oil has the number average molecular weight of 2700 and the hydrogen content of 0.037%.
Example 4
Under the protection of nitrogen, 4.2g of allyl acrylate, 100g of silicone oil with one silicon-hydrogen containing group at one end, 0.25g of polymerization inhibitor p-hydroxyanisole and 0.24g of 5000ppm of Kanster platinum catalyst are mixed, reacted at 60 ℃ for 10 hours, and then subjected to reduced pressure distillation to obtain an organic silicon modified monomer, wherein the yield is 99%, the viscosity is 29mPa.s, the number average molecular weight is 2820, the vinyl content is 0.95%, and the hydrogen content is 0; the silicone oil having silylhydride at one end was prepared in the same manner as in example 3.
Example 5
Under the condition of nitrogen protection, 7.5g of allyl methacrylate, 100g of silicone oil with one silicon-hydrogen containing group at one end, 0.1g of polymerization inhibitor p-hydroxyanisole and 0.22g of 5000ppm of Kanster platinum catalyst are mixed, reacted for 6 hours at 50 ℃, and then subjected to reduced pressure distillation to obtain an organic silicon modified monomer, wherein the yield is 99%, the viscosity is 20mPa.s, the number average molecular weight is 1830, the double bond content is 1.4%, and the hydrogen content is 0; the preparation method of the silicone oil containing silicon-hydrogen group at one end comprises the following steps:
adding 300g of octamethylcyclotetrasiloxane into a 1L three-neck flask, adding 1.5g of concentrated sulfuric acid and 300g of toluene, slowly heating to 75 ℃, reacting for 3 hours, adding 25g of potassium trimethylsilanolate and 25g of THF, heating to 80 ℃, reacting for 10 hours, cooling to room temperature, dropwise adding 18.5g of dimethylchlorosilane under an ice bath condition, reacting for 20 hours while keeping the temperature, filtering, distilling the filtrate under reduced pressure at 90 ℃ to remove low-boiling-point substances, obtaining silicone oil with one end containing silylhydride, and testing that the silicone oil has the number average molecular weight of 1700 and the hydrogen content of 0.059%.
Examples of the preparation of silicone-modified acrylic secondary dispersions are given below.
Example 6
The preparation steps of the organosilicon modified acrylic acid secondary dispersion are as follows:
21.6g of dicumyl peroxide, 125g of isobornyl methacrylate, 30g of methyl methacrylate, 35g of isooctyl methacrylate, 12g of acrylic acid and 100g of methacrylic acidHydroxyethyl ester, 35g of the silicone-modified monomer prepared in example 1 and 8g of 2, 4-diphenyl-4-methyl-1-pentadiene (AMSD) were charged into a single-neck flask and dispersed at high speed for 40 minutes to obtain a mixtureAn agent; will 55Mixing propylene glycol methyl ether acetate (g), dicumyl peroxide (4 g) and a mixture (38.1 g), stirring and heating to 140 ℃, carrying out heat preservation reaction for 20min, then beginning to dropwise add the rest mixture, heating to 155 ℃ after 3.5 hours, continuing to carry out heat preservation reaction for 1 hour, cooling to 125 ℃, adding dimethylethanolamine (10.2 g), cooling to 110 ℃ after 15min of neutralization, increasing the stirring speed to 1000r/min, adding 368g of deionized water at one time, slowly dropwise adding the rest 225g of deionized water when the temperature is reduced to 80 ℃, continuing to stir for 20min, cooling to below 45 ℃, and filtering to obtain the organic silicon modified acrylic acid secondary dispersion.
Example 7
The preparation steps of the organosilicon modified acrylic acid secondary dispersion are as follows:
24g of t-amyl peroxyacetate, 80g of isobornyl methacrylate, 40g of methyl methacrylate, 50g of cyclohexyl methacrylate, 40g of t-butyl methacrylate, 25g of methacrylic acid, 115g of hydroxyacrylate (FA1DDM), 55g of the silicone-modified monomer prepared in example 3 and 14g of n-dodecyl mercaptan (NDM) were placed in a single-neck flask and dispersed at high speed for 30 minutes to obtain a mixtureAn agent; will 40A mixture of dipropylene glycol dimethyl ether as co-solvent, 6g t-amyl peroxyacetate and 44.3gMixing the materialsStirring, heating to 145 ℃, reacting for 20min under heat preservation, and then beginning to drop and mix the restArticle (A)And after finishing dripping within 3 hours, heating to 155 ℃, continuing to perform heat preservation reaction for 1 hour, cooling to 130 ℃, adding 21.25g of dimethylethanolamine, cooling to 105 ℃ after neutralizing for 20 minutes, increasing the stirring speed to 800r/min, adding 426.4g of deionized water at one time, dripping the rest 182.8g of deionized water when the temperature is reduced to 80 ℃, finishing dripping within 30 minutes, continuing to stir for 30 minutes, cooling to below 45 ℃, filtering and discharging to obtain the organic silicon modified acrylic acid secondary dispersion.
Example 8
The preparation steps of the organosilicon modified acrylic acid secondary dispersion are as follows:
12g of tert-butyl peroxybenzoateThe ester, 120g of isobornyl acrylate, 70g of methyl methacrylate, 50g of isobutyl methacrylate, 8g of itaconic acid, 138g of hydroxyacrylate (FA2D), 28g of the silicone-modified monomer prepared in example 5 and 7g of EMMP were placed in a single-neck flask and dispersed at high speed for 35 minutes to obtain a mixed solutionAn agent; will 46A mixture of diethylene glycol monobutyl ether acetate co-solvent, 4g t-butyl peroxybenzoate initiator, and 43.3gMixing the materialsStirring and heating to 145 ℃, carrying out heat preservation reaction for 20min, then beginning to dropwise add the rest mixture, finishing dropwise adding after 2.5 hours, heating to 160 ℃, continuing to carry out heat preservation reaction for 1 hour, cooling to 125 ℃, adding 6.8g of dimethylethanolamine, cooling to 110 ℃ after 15min of neutralization, increasing the stirring speed to 1400r/min, adding 356.3g of deionized water at one time, finishing dropwise adding the rest 118.7g of deionized water after the temperature is reduced to 85 ℃, continuing to stir for 20min, cooling to below 45 ℃, filtering and discharging to obtain the organosilicon modified acrylic acid secondary dispersion.
Comparative examples
12g of t-butyl peroxybenzoate, 120g of isobornyl acrylate, 70g of methyl methacrylate, 50g of isobutyl methacrylate, 8g of itaconic acid, 138g of hydroxyacrylate (FA2D), 28g of the silicone-modified monomer prepared in example 5 and 7g of EMMP were placed in a single-neck flask and dispersed at high speed for 35 minutes to obtain a mixtureAn agent; will 46A mixture of diethylene glycol monobutyl ether acetate co-solvent, 4g t-butyl peroxybenzoate initiator, and 43.3gMixing the materialsStirring, heating to 145 ℃, reacting for 20min under heat preservation, and then beginning to drop and mix the restArticle (A)After dripping for 2.5 hours, heating to 160 ℃, continuing to perform heat preservation reaction for 1 hour, cooling to 125 ℃, adding 6.8g of dimethylethanolamine, neutralizing for 15 minutes, cooling to 110 ℃, increasing the stirring speed to 1400r/min, slowly dripping 475g of deionized water, boiling the liquid surface, seriously refluxing, continuously dripping the rest deionized water when the temperature is reduced to 90 ℃, ensuring that the solution viscosity is overlarge and the liquid surface is basically not stirred, cooling to room temperature, filtering and discharging to obtain a comparative organic silicon modified acrylic acid secondary dispersion, and collecting more massive flocculates on a filter screen.
Test examples
The performance test of the organosilicon modified acrylic acid secondary dispersion prepared in examples 6-8 and comparative examples is carried out by the following method:
1. testing solid content according to GB1725-79, and testing particle size according to a laser particle size analyzer; testing the hydroxyl content according to a chemical titration method;
2. the viscosity was measured according to GBT 2794-1995-determination of the viscosity of the adhesive ";
3. testing the storage stability of the organic silicon modified acrylic acid secondary dispersion according to GB/T11175-2002 synthetic resin emulsion test method;
4. heat resistance: a thermal gravimetric analyzer TGA 7 model manufactured by Perkin-Elmer company in USA is adopted: weighing 10mg of organic silicon modified acrylic acid secondary dispersion, measuring the thermal decomposition temperature T with the weight loss of 5% under the nitrogen atmosphere at the heating rate of 20 ℃/min and the heating speed of 20 ℃/min from 50-500 ℃ and the flow rate of 20mL/min5(DEG C) and a thermal decomposition temperature T at which 10% of the weight is lost10(℃)。
The test results are shown in Table 1.
TABLE 1
The application performance test of the organosilicon modified acrylic acid secondary dispersion prepared in examples 6-8 and comparative example is carried out by the following method:
weighing 80g of organic silicon modified acrylic acid secondary dispersion, respectively adding 0.3g of waterborne defoaming agent TEGO-902W, 0.5g of substrate wetting agent BYK-346, 5g of film forming additive PMA and 14.2g of deionized water under high-speed stirring, uniformly stirring at high speed to obtain varnish, adding DNW-5500 isocyanate curing agent accounting for 25% of the mass of the varnish, and uniformly stirring to obtain the waterborne coating. On a clean glass plate, 20g of the aqueous coating was uniformly applied to the glass using a 20 × 5 wet film maker (50 μm), allowed to stand at room temperature for 30 minutes, continuously blade-coated in the same manner for a second time, and then placed in a drying oven at 80 ℃ to dry for 4 hours, to obtain a coating film, and then subjected to a hydrophobicity test, a hardness test, and a scratch resistance test. Wherein, the hydrophobicity test is to adopt a full-automatic water drop angle tester to measure the contact angle between a water drop and a coating; the hardness is measured according to GB/T6739-2006, and the scratch resistance is measured according to ISO 12137-1: 1997 the paint films were tested for scratch resistance. The test data are shown in Table 2.
TABLE 2
| Examples | Hydrophobicity | Scratch resistance/200 g | Hardness of |
| Example 6 | 92° | Has no influence on | HB |
| Example 7 | 94° | Has no influence on | HB |
| Example 8 | 97° | Has no influence on | HB |
| Comparative examples | 79° | Obvious cohesive cracks | HB |
As can be seen from the data in tables 1 and 2, the organosilicone modified acrylic acid secondary dispersion prepared by the invention has good heat resistance and stability, and the coating prepared by the organosilicone modified acrylic acid secondary dispersion has excellent hydrophobicity, stability and scratch resistance after being formed into a film, and has good application prospect in application occasions with special requirements on surface hydrophobicity.
The foregoing is a more detailed description of the invention in connection with specific preferred embodiments and it is not intended that the invention be limited to these specific details. For those skilled in the art to which the invention pertains, several simple deductions or substitutions can be made without departing from the spirit of the invention, and all shall be considered as belonging to the protection scope of the invention.
Claims (10)
1. An organosilicon modified acrylic secondary dispersion, which is characterized by being prepared by reacting raw materials comprising the following substances:
15 to 25 parts by weight of a (meth) acrylate monomer, 0.5 to 3 parts by weight of a monomer containing a carboxyl group, 8 to 15 parts by weight of a hydroxyl (meth) acrylate, and 2 to 6 parts by weight of a silicone-modified monomer including an organopolysiloxane having a radical-polymerizable unsaturated group, the radical-polymerizable unsaturated group in the polysiloxane having a radical-polymerizable unsaturated group being a (meth) acrylate group.
2. The silicone-modified acrylic secondary dispersion of claim 1, wherein the polysiloxane having free-radically polymerizable unsaturated groups is prepared by reacting a (meth) acrylate having an alkenyl group of C2-C5 with an organopolysiloxane having at least one hydrogen bond with silicon.
3. The silicone-modified acrylic secondary dispersion of claim 2, wherein the polysiloxane having a free-radically polymerizable unsaturated group is prepared by a method comprising the steps of:
under the protection of inert gas, (methyl) acrylate with C2-C5 alkenyl is mixed with organopolysiloxane with at least one silicon-bonded hydrogen group, polymerization inhibitor and catalyst, and then the mixture is heated to react to obtain polysiloxane with free radical polymerizable unsaturated groups;
the (meth) acrylate having an alkenyl group of C2-C5 is a compound having at least one alkenyl group of C2-C5 in a molecular structure and at least one (meth) acrylate group.
4. The silicone-modified acrylic secondary dispersion of any of claims 1-3, wherein the organopolysiloxane having at least one hydrogen bond to silicon comprises a compound having a formula shown in formula 1:
in formula 1, m is an integer greater than 1, and R is the same or different alkyl, cycloalkyl, aryl, aralkyl, alkoxy, or haloalkyl.
5. The silicone-modified acrylic secondary dispersion of claim 4, wherein the compound having the formula of formula 1 is prepared by the following method: mixing cyclosiloxane, an acid catalyst and an organic solvent 1, heating to 65-75 ℃ for reaction for 2-4 h, adding trialkylsiloxide and the organic solvent 2, heating to 75-80 ℃ for reaction for 8-12 h, and adding dialkyl monohalosilane at 0 +/-5 ℃ for reaction for 18-24 h to obtain the compound with the structural formula shown in formula 1.
6. The process for preparing the silicone-modified acrylic secondary dispersion as claimed in any of claims 1 to 3, comprising the steps of:
mixing 15-25 parts by weight of (methyl) acrylate monomer, 0.5-3 parts by weight of monomer containing carboxyl, 2-6 parts by weight of organosilicon modified monomer, 8-15 parts by weight of hydroxyl (methyl) acrylate, chain transfer agent and first part of free radical initiator to obtain a mixture;
mixing part of the mixture with a second part of the free radical initiator and the cosolvent, heating to 140-160 ℃ for reaction, adding the rest mixture, continuing to react at 155-165 ℃, then cooling to 125-130 ℃ for neutralization, cooling to 100-110 ℃, adding water for first emulsification, continuing to cool to 80-85 ℃, adding water for second emulsification, and cooling to obtain the organic silicon modified acrylic acid secondary dispersion.
7. The method of claim 6, wherein the total amount of free radical initiator is 0.8-4 parts, and the mass of the first portion of free radical initiator is 70-85% of the total mass of free radical initiator.
8. The method of preparing the silicone-modified acrylic secondary dispersion of claim 6, wherein the portion of the mixture is 10 to 15% by mass of the total mass of the mixture.
9. The method of claim 6, wherein the amount of water added for the first emulsification is 60-80% of the total amount of water in the method, the water added for the first emulsification is added at one time, and the water added for the second emulsification is added dropwise.
10. The method of preparing the silicone-modified acrylic secondary dispersion of claim 6, wherein the silicone-modified acrylic secondary dispersion has a solid content of 35 to 50%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110358228.8A CN112940203A (en) | 2021-04-01 | 2021-04-01 | Organosilicon modified acrylic acid secondary dispersion and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110358228.8A CN112940203A (en) | 2021-04-01 | 2021-04-01 | Organosilicon modified acrylic acid secondary dispersion and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112940203A true CN112940203A (en) | 2021-06-11 |
Family
ID=76232119
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110358228.8A Pending CN112940203A (en) | 2021-04-01 | 2021-04-01 | Organosilicon modified acrylic acid secondary dispersion and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112940203A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114292485A (en) * | 2022-02-18 | 2022-04-08 | 常州大学 | Antibacterial adhesion-resistant hydrophobic anti-reflection material and preparation method and application thereof |
| CN114891166A (en) * | 2021-10-29 | 2022-08-12 | 江苏科技大学 | Organic silicon oil composite acrylic latex and preparation method thereof |
| CN114716680B (en) * | 2021-06-23 | 2023-08-25 | 浙江赢科新材料股份有限公司 | Preparation method of single-end gamma-methacryloxypropyl functional group-terminated polydimethylsiloxane |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101649098A (en) * | 2009-09-21 | 2010-02-17 | 浙江环达漆业集团有限公司 | Method for preparing acrylic aqueous dispersion with hydroxyl through two-step polymerization |
| CN101691466A (en) * | 2009-09-15 | 2010-04-07 | 中国船舶重工集团公司第七二五研究所 | Method for preparing antifouling material with surface of spherically raised microstructure |
| CN108997582A (en) * | 2018-06-01 | 2018-12-14 | 杭州师范大学 | A kind of preparation method of the single-ended polysiloxane fluid containing active hydrogen |
| CN109608575A (en) * | 2018-12-18 | 2019-04-12 | 三棵树涂料股份有限公司 | A kind of hydroxyl polyacrylate second level aqueous dispersion and preparation method thereof |
-
2021
- 2021-04-01 CN CN202110358228.8A patent/CN112940203A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101691466A (en) * | 2009-09-15 | 2010-04-07 | 中国船舶重工集团公司第七二五研究所 | Method for preparing antifouling material with surface of spherically raised microstructure |
| CN101649098A (en) * | 2009-09-21 | 2010-02-17 | 浙江环达漆业集团有限公司 | Method for preparing acrylic aqueous dispersion with hydroxyl through two-step polymerization |
| CN108997582A (en) * | 2018-06-01 | 2018-12-14 | 杭州师范大学 | A kind of preparation method of the single-ended polysiloxane fluid containing active hydrogen |
| CN109608575A (en) * | 2018-12-18 | 2019-04-12 | 三棵树涂料股份有限公司 | A kind of hydroxyl polyacrylate second level aqueous dispersion and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 耿耀宗 等 主编: "《合成聚合物乳液制造与应用技术》", 30 June 1990, 北京：中国轻工业出版社 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114716680B (en) * | 2021-06-23 | 2023-08-25 | 浙江赢科新材料股份有限公司 | Preparation method of single-end gamma-methacryloxypropyl functional group-terminated polydimethylsiloxane |
| CN114891166A (en) * | 2021-10-29 | 2022-08-12 | 江苏科技大学 | Organic silicon oil composite acrylic latex and preparation method thereof |
| CN114292485A (en) * | 2022-02-18 | 2022-04-08 | 常州大学 | Antibacterial adhesion-resistant hydrophobic anti-reflection material and preparation method and application thereof |
| CN114292485B (en) * | 2022-02-18 | 2023-09-22 | 常州大学 | Antibacterial adhesion-resistant hydrophobic anti-reflection material, and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112940203A (en) | Organosilicon modified acrylic acid secondary dispersion and preparation method thereof | |
| CN109868026B (en) | Organic silicon modified acrylate resin, preparation method thereof and hydrophobic weather-resistant slow-release modified acrylic resin coating | |
| CN107075341B (en) | Stripping film is with re-releasing additive and stripping film organopolysiloxane composition and stripping film | |
| US6534590B1 (en) | Silicone-grafted vinyl copolymer emulsion composition | |
| KR20100114046A (en) | Copolymers of nanoparticles, vinyl monomers and silicone | |
| CN111234136B (en) | Photo-curing organic silicon resin system and preparation method of photo-curing film | |
| CN109735144B (en) | Photocuring POSS/fluorocarbon siloxane modified polyacrylate coating composition and application thereof | |
| CN109666111B (en) | Nano SiO2Organosilicon modified acrylate emulsion | |
| CN105111360B (en) | The preparation method of multiple cross-linked water-based acrylic resin | |
| CN106928410B (en) | Organic silicon modified acrylic resin with high solid content and low viscosity, preparation method and application | |
| CN108728023A (en) | Pressure-sensitive adhesive composition and the film formed using the composition | |
| CN109337518A (en) | A kind of aqueous epoxide resin paint and preparation method thereof | |
| CN107936746A (en) | A kind of organic-silicon-modified cation photocuring cycloaliphatic epoxy resin coating and its application | |
| CN102731558A (en) | Organosilicone oligomer and preparation method thereof, and bi-component system and application thereof | |
| CN104011130A (en) | Photocurable fluorine-containing copolymer composition | |
| EP0816404B1 (en) | Methods for preparing silicone-modified vinyl polymers | |
| CN107254037A (en) | A kind of epoxy resin and organic-silicon-modified aqueous alkide resin and preparation method | |
| CN113105592A (en) | Modified acrylic resin emulsion and preparation method thereof | |
| CN110452490B (en) | Dual POSS polyether hybrid water-based acrylic resin dispersion, preparation method and composition for preparing resin coating film | |
| JP6994562B2 (en) | A coating film containing a coating resin composition and a cured product thereof as a coating layer. | |
| He et al. | Fluorinated polyacrylates containing amino side chains for the surface modification of waterborne epoxy resin | |
| Vitry et al. | Hybrid copolymer latexes cross-linked with methacryloxy propyl trimethoxy silane. Film formation and mechanical properties | |
| CN114835901B (en) | Epoxy modified vinyl silicone rubber and preparation method and application thereof | |
| CN106188120A (en) | A kind of bifunctionality acrylate monomer of silicone-containing structure and preparation method thereof | |
| CN113968973A (en) | Epoxy siloxane, epoxy polysiloxane-silicon rubber compound, preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |