CN112724406A - Water-based organic silicon resin and preparation method thereof - Google Patents
Water-based organic silicon resin and preparation method thereof Download PDFInfo
- Publication number
- CN112724406A CN112724406A CN202011502991.5A CN202011502991A CN112724406A CN 112724406 A CN112724406 A CN 112724406A CN 202011502991 A CN202011502991 A CN 202011502991A CN 112724406 A CN112724406 A CN 112724406A
- Authority
- CN
- China
- Prior art keywords
- water
- cyclic organopolysiloxane
- modified phosphate
- silicone resin
- reaction
- 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.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/30—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen phosphorus-containing groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/06—Preparatory processes
-
- 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
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
- C09D183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Silicon Polymers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a water-based organic silicon resin and a preparation method thereof, wherein the water-based organic silicon resin is prepared by emulsion polymerization of raw materials comprising cyclic organic polysiloxane and modified phosphate ester, and the modified phosphate ester is prepared by esterification reaction of (methyl) hydroxyalkyl acrylate and phosphorus pentoxide. The water-based organic silicon resin does not contain organic solvent, is environment-friendly, does not self-ignite, has high film strength and good permeability, and can be used for a long time at the temperature of 150 ℃.
Description
Technical Field
The invention relates to a water-based organic silicon resin and a preparation method thereof, in particular to an environment-friendly protective material with the performances of flame retardance, insulation, high and low temperature resistance and the like for protecting important parts of new energy automobiles such as motor coils, igniters, battery wire sheaths, spark plug sheaths and the like.
Technical Field
The air port of the automobile industry is located in a new energy automobile at present and is a future development direction. The plug-in hybrid and battery-powered Electric Vehicle (EV) markets are expected to grow exponentially in the coming years. There has been a great deal of research by silicone practitioners as to whether they can be used in power cells. The organic silicon is widely applied to the field of automobiles as a novel chemical material, and the shadow of the organic silicon is visible everywhere on a plurality of automobile parts such as interior trimming parts, air bag coatings, windscreen wipers and turbo-charging sleeves. The application field of the vehicle organic silicon can be described as 'bloom all over the world' by virtue of the advantages of high adhesion, strong sealing property, vibration damping property, insulation property and the like. With the continuous innovation of various technologies in the automobile industry, the application potential of the organic silicon is deeply excavated to a greater extent.
At present, the organic silicon material applied to the market is mainly a solvent system, and the high VOC content has great influence on constructors and environment. The organic silicon modified polyurethane, acrylic acid, alkyd resin and the like are partially used, the silicon content is low, the characteristics of organic silicon cannot be fully exerted, the flame retardant effect of the existing organic silicon emulsion on the market is poor, in order to improve the flame retardance, a large amount of halogen-containing powder flame retardant is added, the environment and the human health are harmed, and the permeability and the strength of a paint film are greatly influenced due to the excessive powder introduction.
Disclosure of Invention
In order to solve the problems in the prior art, the invention aims to provide the water-based organic silicon resin and the preparation method thereof, the water-based organic silicon resin does not contain organic solvents, is environment-friendly, does not spontaneously combust, is convenient and fast to construct, has excellent comprehensive performance, can achieve sealing, insulation, corrosion prevention, heat-resistant protection, flame retardance and the like, has high paint film strength and good permeability, and can be used for a long time at the temperature of up to 150 ℃.
The technical scheme of the invention is as follows:
the water-based organic silicon resin is prepared by carrying out emulsion polymerization on raw materials comprising cyclic organopolysiloxane A, modified phosphate ester and cyclic organopolysiloxane B, wherein the modified phosphate ester is prepared by carrying out esterification reaction on hydroxyalkyl (meth) acrylate and phosphorus pentoxide;
the cyclic organic compoundPolysiloxane A is a compound represented by formula 1: [ -R1R2SiO-]n (formula 1), n is an integer of 3 to 9, R1、R2Alkyl, cycloalkyl, aryl, aralkyl or haloalkyl, which may be the same or different;
the cyclic organopolysiloxane B is a compound represented by formula 2: [ -R3R4SiO-]m (formula 2), wherein m is an integer of 3 to 9, R3、R4And the same or different aliphatic unsaturated hydrocarbon groups, alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups or halogenated alkyl groups, and the cyclic organopolysiloxane B has at least 1 aliphatic unsaturated hydrocarbon group in its molecular structure.
Preferably, the preparation method of the modified phosphate ester comprises the following steps:
mixing and stirring (methyl) hydroxyalkyl acrylate and a polymerization inhibitor, adding phosphorus pentoxide in several times, reacting at 65-85 ℃ for 1-3 h, heating to 90-100 ℃ for reacting for 2-3 h, cooling to 75-90 ℃, adding water, reacting at 75-90 ℃ for 1-2 h, cooling, and discharging to obtain the modified phosphate.
The modified phosphate ester is a mixture, contains phosphate monoester, phosphate diester, polyphosphate ester, water and the like, does not need to be separated, is preferable, and the mass fraction of the phosphate monoester in the modified phosphate ester is 60-80 percent and is adjusted by controlling the material proportion and the reaction condition.
The method for testing the mass fraction of the phosphate monoester in the modified phosphate is a bromocresol green-phenolphthalein mixed indicator method, and the reference documents are as follows: plum jun, improvement of a phosphate ester synthesis process and detection of the content of monoester and diester, western leather, volume 2 of 2.29 in 2007, 31-34.
Preferably, the hydroxyalkyl (meth) acrylate is a hydroxyalkyl acrylate and/or hydroxyalkyl methacrylate, the alkyl is a C1-C5 alkyl, and preferably, the alkyl is propyl.
Preferably, the hydroxyalkyl (meth) acrylate and the polymerization inhibitor are mixed and stirred, the temperature is raised to 50-65 ℃, and then phosphorus pentoxide is added in several times to melt reactants and promote the esterification reaction.
Preferably, the molar ratio of the phosphorus pentoxide to the hydroxyalkyl (meth) acrylate is (0.2-0.6):1, and the mass fractions of the phosphoric monoester and phosphoric diester in the modified phosphoric ester can be controlled by adjusting the material ratio. The reaction is carried out for 1-3 h at 65-85 ℃, the temperature is raised to 90-100 ℃ and the reaction is carried out for 2-3 h, namely, the esterification reaction is carried out in two steps, so that reactants are fully melted and mixed, and the esterification rate can be improved.
Preferably, the mass fraction of the water is 4-8%, that is, the mass percentage of the water in the total mass of the hydroxyalkyl (meth) acrylate, the polymerization inhibitor, the phosphorus pentoxide and the water is 4-8%.
Preferably, the polymerization inhibitor is one or two of p-methoxyphenol, tert-butyl catechol and hydroquinone, and the mass fraction of the polymerization inhibitor is 0.1-0.3%, namely the mass percentage of the polymerization inhibitor in the total mass of the hydroxyalkyl (meth) acrylate, the polymerization inhibitor, the phosphorus pentoxide and the water is 0.1-0.3%.
It is to be noted that the cyclic organopolysiloxane a is known in the art as a compound represented by formula 1: [ -R1R2SiO-]n (formula 1), n is an integer of 3 to 9, R1、R2Identical or different hydrogen radicals, alkyl radicals, cycloalkyl radicals, aryl radicals, aralkyl radicals or haloalkyl radicals. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group, and a methyl group is preferable; examples of the cycloalkyl group include cyclohexyl and cyclopentyl, and examples of the aryl group include phenyl, tolyl and xylyl; examples of the aralkyl group include benzyl and phenethyl, and preferably phenyl; as the haloalkyl group, 3, 3, 3-trifluoropropyl group can be mentioned. More specifically, examples of the cyclic organopolysiloxane a include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, 1-diethylhexamethylcyclotetrasiloxane, phenylheptamethylcyclotetrasiloxane, 1-diphenylhexamethylcyclotetrasiloxane, 1, 2, 3, 4-tetramethylcyclotetrasiloxane, dodecamethylcyclohexasiloxane, 1, 2, 3, 4-tetraphenyl-1, 2, 3, 4-tetramethylcyclotetrasiloxane and the like. Among them, the cyclic organopolysiloxane a is preferably octamethylcyclotetrasiloxane.
The cyclic organopolysiloxane B is known in the art and is a compound represented by formula 2: [ -R3R4SiO-]m, wherein m is an integer of 3 to 9, R3、R4And the same or different aliphatic unsaturated hydrocarbon groups, alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups or halogenated alkyl groups, and the cyclic organopolysiloxane B has at least 1 aliphatic unsaturated hydrocarbon group in its molecular structure. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group, and a methyl group is preferable; examples of the cycloalkyl group include cyclohexyl and cyclopentyl, and examples of the aryl group include phenyl, tolyl and xylyl; examples of the aralkyl group include benzyl and phenethyl, and preferably phenyl; examples of the haloalkyl group include a 3, 3, 3-trifluoropropyl group; the aliphatic unsaturated alkyl has free radical reaction activity, and can generate free radicals through the initiation of a free radical initiator so as to generate reaction. The aliphatic unsaturated hydrocarbon group includes a silicon-bonded alkenyl group, wherein the alkenyl group may be a vinyl group, an allyl group, a butenyl group, or a pentenyl group, preferably a vinyl group or an allyl group. Examples of the cyclic organopolysiloxane B include tetramethyltetravinylcyclotetrasiloxane and methylvinylcyclosiloxane. Among them, the cyclic organopolysiloxane B is preferably tetramethyltetravinylcyclotetrasiloxane.
Preferably, the modified phosphate is used in an amount of 80 to 150 parts based on 100 parts by weight of the cyclic organopolysiloxane a. Preferably, the cyclic organopolysiloxane B is used in an amount of 300-600 parts based on 100 parts by weight of the cyclic organopolysiloxane A. The use level of the modified phosphate directly affects the reaction process, the state of the final polymer and the application performance of the resin, the modified phosphate can be self-polymerized and even gelatinized if the use level is too high, and the reaction system is unstable and has poor storage performance if the use level of the modified phosphate is insufficient.
The preparation method of the water-based organic silicon resin comprises the following steps:
mixing the cyclic organopolysiloxane A and the cyclic organopolysiloxane B, heating, adding a free radical initiator, water, an acid catalyst, modified phosphate ester and an emulsifier, stirring for reaction at 60-85 ℃, heating to 120-150 ℃, continuing to react, cooling and neutralizing to obtain the water-based organic silicon resin.
Preferably, the stirring speed of the stirring reaction at the temperature of 60-85 ℃ is 800-1500 r/min.
Preferably, the stirring rate for continuing the reaction when the temperature is raised to 120-150 ℃ is 100-500 r/min.
Preferably, the stirring reaction time at 60-85 ℃ is 4-10 h. Preferably, the time for continuing the reaction when the temperature is raised to 120-150 ℃ is 0.5-3 h.
The acid catalyst is a common catalyst for ring-opening reaction of cyclic organopolysiloxane, is not particularly limited, and can be one or more of hydrochloric acid, phosphoric acid, nitric acid and boric acid. Because the added modified phosphate also has acidity, the added acid catalyst can be reduced, and the pH value of the reaction system can reach 1-3.
The radical initiator is not particularly limited, and examples thereof include organic peroxides such as cumene hydroperoxide, tert-butyl hydroperoxide, perbenzoic acid, tert-butyl peroxyisopropyl carbonate, di-tert-butyl peroxide, tert-butyl peroxylaurate, p-menthane hydroperoxide, tert-hexyl hydroperoxide, lauroyl peroxide, succinic peroxide, cyclohexanone peroxide, and acetylacetone peroxide; inorganic peroxides such as potassium persulfate and ammonium persulfate; azo compounds such as 2, 2 '-azobisisobutyronitrile and 2, 2' -azobis-2, 4-dimethylvaleronitrile. Among them, the radical initiator is preferably an organic peroxide and/or an inorganic peroxide.
Preferably, the free radical initiator is one or more of tert-amyl peroxyacetate, tert-butyl peroxybenzoate, dicumyl peroxide and di-tert-amyl peroxide. Preferably, the radical initiator is used in an amount of 20 to 30 parts by weight based on 100 parts by weight of the cyclic organopolysiloxane a.
Preferably, the emulsifier is used in an amount of 3 to 8 parts by weight based on 100 parts by weight of the cyclic organopolysiloxane a. The emulsifier is not particularly limited, but is preferably an anionic surfactant such as sodium alkyl sulfate of C12-C18, sodium alkyl benzene sulfonate of C12-C18, succinic acid-modified polyoxyethylene alkyl phenol ether or dodecylbenzene sulfonic acid.
Preferably, the amount of the water is 700-5000 parts by weight based on 100 parts by weight of the cyclic organopolysiloxane A.
Preferably, the number average molecular weight of the water-based silicone resin is 3500-10000.
Preferably, the solid content of the water-based organic silicon resin is 15-50%, and the kinematic viscosity at 25 ℃ is 3000-30000mPa & s.
A coating is prepared from the water-based organic silicon resin, and the water-based organic silicon resin is dried and solidified after being coated to obtain the coating.
Preferably, the drying and curing temperature is 40-80 ℃.
Compared with the prior art, the invention has the following beneficial effects:
1. the addition of the modified phosphate can not only improve the flame retardance of the paint film, but also serve as a surfactant, so that the dosage of the small molecular emulsifier is reduced, and the prepared resin paint film has low water absorption and good yellowing resistance;
2. the reaction system of the invention adopts free radical initiation reaction, which can effectively improve the grafting and polymerization rate of the cyclosiloxane, thereby improving the physical and mechanical strength of the material.
3. The water-based organic silicon modified material disclosed by the invention does not contain a toxic solvent, is environment-friendly, does not contain halogen elements, is safe and environment-friendly, does not spontaneously combust, is convenient to construct and has excellent comprehensive performance.
Detailed Description
The following examples are given as preparation method examples of the water-based organic silicon resin material, and the method for testing the mass fraction of the phosphoric monoester and the phosphoric diester in the following examples is a bromocresol green-phenolphthalein mixed indicator method, and references are as follows: plum jun, improvement of a phosphate ester synthesis process and detection of the content of monoester and diester, western leather, volume 2 of 2.29 in 2007, 31-34.
Example 1
The preparation method of the modified phosphate ester comprises the following steps:
uniformly mixing 1000g of hydroxypropyl methacrylate and 2.5g of tert-butyl catechol in a closed reaction kettle with a stirring device, stirring and heating to 55 ℃, uniformly adding 260g of phosphorus pentoxide into 5 batches within 1.5h, controlling the temperature to be 75 ℃, continuing to perform heat preservation reaction for 1.5h, heating to 95 ℃, continuing to perform reaction for 3h, cooling to 80 ℃, slowly adding 62g of deionized water, continuing to perform heat preservation reaction for 1.5h, cooling to room temperature, discharging to obtain modified phosphate, testing the solid content of the modified phosphate to be 95.3%, testing the monoester phosphate rate to be 62.6%, and testing the monoester rate testing method to be bromocresol green-phenolphthalein mixed indicator method.
100g of octamethylcyclotetrasiloxane and 350g of tetramethyltetravinylcyclotetrasiloxane (D4-vi) are put into a closed pressure-resistant reaction kettle with a stirring device, the temperature is raised to 75 ℃, after cyclosiloxane crystals are completely dissolved, 23g of tert-butyl peroxybenzoate, 718g of deionized water, 1.8g of hydrochloric acid (the mass percentage is 37%), 90g of modified phosphate and 4.5g of sodium dodecyl benzene sulfonate are put into the reaction kettle, the pH value of the reaction solution is 3, the temperature is kept at 75 ℃, the reaction solution is stirred and reacted for 5 hours on a JB-90D digital display constant speed stirrer at 1500r/min, the stirring speed is reduced to 300r/min on the JB-90D constant speed stirrer, the temperature is raised to 125 ℃, the reaction solution is continued for 1 hour, the temperature is reduced to 45 ℃, 20g of sodium bicarbonate is put into the reaction kettle to adjust the pH value to be neutral, and the aqueous organic silicon.
Example 2
The preparation method of the modified phosphate ester comprises the following steps:
uniformly mixing 1000g of hydroxyethyl acrylate and 4.5g of p-methoxyphenol in a closed reaction kettle with a stirring device, stirring and heating to 60 ℃, uniformly dividing 5 batches of p-methoxyphenol into 5 batches of phosphorus pentoxide and adding 550g in 2h, controlling the temperature to be 80 ℃, continuing to perform heat preservation reaction for 2h, heating to 100 ℃, continuing to perform reaction for 2.5h, cooling to 75 ℃, slowly adding 94g of deionized water, continuing to perform heat preservation reaction for 2h, cooling to room temperature, discharging to obtain modified phosphate, testing the solid content to be 94.3%, testing the obtained phosphate monoester rate to be 69.4%, wherein the monoester rate testing method is a bromocresol green-phenolphthalein mixed indicator method.
68g of dodecamethylcyclohexasiloxane, 382g of tetramethyltetravinylcyclotetrasiloxane (D4-vi) are put into a pressure-resistant reaction kettle which is closed and provided with a stirring device, the temperature is raised to 75 ℃, 19g of tert-butyl peroxybenzoate, 3084g of deionized water, 0.8g of hydrochloric acid (the mass percentage is 37%), 95.2g of phosphate monomer and 3.4g of sodium dodecyl benzene sulfonate are put into the pressure-resistant reaction kettle after cyclosiloxane crystals are completely dissolved, the pH value of reaction liquid is 2, the temperature is kept at 75 ℃, the reaction liquid is stirred at a high speed of 1200r/min on a JB-90D digital display constant speed stirrer for 8 hours, the stirring speed is reduced to 200r/min on the JB-90D digital display constant speed stirrer, the temperature is raised to 135 ℃, the reaction liquid is continuously stirred for 2 hours, the temperature is reduced to 40 ℃, 19g of sodium bicarbonate is put into the pressure-resistant reaction kettle for regulating the pH.
Example 3
Preparation of modified phosphate ester:
the preparation method comprises the steps of uniformly mixing 1000g of hydroxyethyl methacrylate and 3.8g of hydroquinone in a closed reaction kettle with a stirring device, stirring and heating to 65 ℃, uniformly dividing 5 batches of phosphorus pentoxide into 5g in 2h, controlling the temperature to be 80 ℃, continuing to perform heat preservation reaction for 2h, heating to 90 ℃, continuing to perform reaction for 2.5h, cooling to 75 ℃, slowly adding 95g of deionized water, continuing to perform heat preservation reaction for 2h, cooling to room temperature, discharging to obtain modified phosphate, testing the modified phosphate to obtain 93.7% of solid content, testing the modified phosphate to obtain 67.8% of monoester phosphate, wherein the monoester rate testing method is a bromocresol green-phenolphthalein mixed indicator method.
100g of hexamethylcyclotrisiloxane and 460g of tetramethyltetravinylcyclotetrasiloxane (D4-vi) are put into a closed pressure-resistant reaction kettle with a stirring device, the temperature is raised to 75 ℃, after cyclosiloxane crystals are completely dissolved, 25g of tert-butyl peroxybenzoate, 1548g of deionized water, 0.5g of hydrochloric acid (37 percent by mass), 102.4g of phosphate monomer and 5.4g of sodium dodecyl benzene sulfonate are put into the reaction kettle, the pH value of the reaction solution is 3, the temperature is kept at 75 ℃, the reaction solution is stirred at a high speed of 850r/min on a JB-90D digital display constant speed stirrer for 7.5 hours, the stirring speed is reduced to 150r/min on a JB-90D digital display constant speed stirrer, the reaction solution is continuously stirred for 2.5 hours when the temperature is raised to 130 ℃, 22g of sodium bicarbonate is put into the reaction solution for regulating the pH value to be neutral, and the aqueous organosilicon resin material is obtained through filtration and packaging.
Example 4 (comparative example)
Preparation of modified phosphate ester:
uniformly mixing 1000g of hydroxyethyl methacrylate and 3.8g of hydroquinone in a closed reaction kettle with a stirring device, stirring and heating to 65 ℃, uniformly dividing 5 batches of phosphorus pentoxide into 5 batches within 2 hours, controlling the temperature to be 80 ℃, continuing to perform heat preservation reaction for 2 hours, heating to 90 ℃ after the viscosity of the solution is not changed any more, continuing to perform reaction for 2.5 hours, cooling to 75 ℃, slowly adding 95g of deionized water, continuing to perform heat preservation reaction for 2 hours, cooling to room temperature, discharging to obtain modified phosphate, testing the solid content to be 93.7%, testing to obtain the phosphate monoester rate to be 67.8%, wherein the monoester rate testing method is a bromocresol green-phenolphthalein mixed indicator method.
115g of hexamethylcyclotrisiloxane and 522g of tetramethyltetravinylcyclotetrasiloxane are put into a closed pressure-resistant reaction kettle with a stirring device, the temperature is raised to 75 ℃, after cyclosiloxane crystals are completely dissolved, 25g of tert-butyl peroxybenzoate, 1548g of deionized water, 0.5g of hydrochloric acid (the mass percent is 37%), 35.4g of modified phosphate and 5.4g of sodium dodecyl benzene sulfonate are put into the pressure-resistant reaction kettle, the pH value of reaction liquid is 3, the temperature is kept at 75 ℃, the mixture is stirred and reacted for 7.5 hours at a high speed of 850r/min on a JB-90D constant speed stirrer, the stirring speed is reduced to 150r/min on the JB-90D constant speed stirrer, the temperature is raised to 130 ℃, the reaction is continued for 2.5 hours, the temperature is reduced to 35 ℃, 22g of sodium bicarbonate is put into the mixture to adjust the pH value to be neutral, and the mixture is filtered and packaged to.
Test examples
The performance test is carried out on the 1-4# water-based organic silicon resin, and the specific steps are as follows:
1. solid content and viscosity: the solid content is tested according to GB/T8077-.
2. Storage stability: 150g of water-based organic silicon resin is filled into a closed conical flask, transferred into a baking oven at 50 +/-2 ℃, taken out after 30 days and observed for the appearance state.
3. Uniformly spraying 50g of water-based organic silicon resin on a blank PVC (polyvinyl chloride) mould plate with the specification of 400mm x 200mm x 3mm, drying for 4 hours at room temperature, transferring into a 50 ℃ drying oven for drying for 8 hours, heating to 80 ℃, continuing to dry for 8 hours, taking out the dried product at room temperature, standing for 2 hours, and taking out a paint film to obtain a test sample for testing flame retardant property, breakdown voltage, glossiness, tensile strength, number average molecular weight and high-temperature aging resistance, wherein the specific test method comprises the following steps:
flame retardant property: the test is carried out according to the standard GB/T2408-2008.
Breakdown voltage: reference is made to GB/T1695-2005.
Gloss: refer to GBT 4893.6.
Tensile strength: refer to GB/T528-2009.
Number average molecular weight: after a paint film is fully dissolved by toluene, the gel permeation chromatography is adopted for determination, the model of the instrument is SW-105, the used mobile phase is tetrahydrofuran, the standard sample is polystyrene, the sample concentration is 10mg/ml, and the basic parameters are set as follows: temperature of the column oven: 40 ℃; pump flow rate: 1 ml/min; isoconcentrate elution is used.
High temperature aging resistance: and (3) taking a paint film of 50mm by 50mm, putting the paint film into a baking oven of 150 ℃ for baking for 1000h, taking out the paint film, cooling, and observing the appearance change.
The test results are shown in Table 1.
TABLE 1
As can be seen from the data in Table 1, the water-based organic silicon resin prepared by the reaction of cyclosiloxane and phosphate ester has good storage stability, good comprehensive application performance and good application prospect.
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 (9)
1. The water-based organic silicon resin is characterized by being prepared by carrying out emulsion polymerization on raw materials comprising cyclic organopolysiloxane A, modified phosphate ester and cyclic organopolysiloxane B, wherein the modified phosphate ester is prepared by carrying out esterification reaction on hydroxyalkyl (meth) acrylate and phosphorus pentoxide;
the cyclic organopolysiloxane a is a compound represented by formula 1: [ -R1R2SiO-]n (formula 1), n is an integer of 3 to 9, R1、R2Alkyl, cycloalkyl, aryl, aralkyl or haloalkyl, which may be the same or different;
the cyclic organopolysiloxane B is a compound represented by formula 2: [ -R3R4SiO-]m (formula 2), wherein m is an integer of 3 to 9, R3、R4And the same or different aliphatic unsaturated hydrocarbon groups, alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups or halogenated alkyl groups, and the cyclic organopolysiloxane B has at least 1 aliphatic unsaturated hydrocarbon group in its molecular structure.
2. The aqueous silicone resin according to claim 1, wherein the modified phosphate ester is prepared by a method comprising the steps of:
mixing and stirring (methyl) hydroxyalkyl acrylate and a polymerization inhibitor, adding phosphorus pentoxide in several times, controlling the temperature to be 65-85 ℃, reacting for 1-3 h, heating to 90-100 ℃, reacting for 2-3 h, cooling to 75-90 ℃, adding water, reacting for 1-2 h at 75-90 ℃, cooling, and discharging to obtain the modified phosphate.
3. The aqueous silicone resin according to claim 2, wherein the modified phosphate ester has a mass fraction of the phosphate monoester of 60% to 80%.
4. The aqueous silicone resin according to claim 2, wherein the modified phosphate ester is used in an amount of 80 to 150 parts based on 100 parts by weight of the cyclic organopolysiloxane a.
5. The aqueous silicone resin according to claim 2, wherein the amount of the cyclic organopolysiloxane B is 300-600 parts based on 100 parts by weight of the cyclic organopolysiloxane a.
6. The method for preparing the aqueous silicone resin according to claim 2, comprising the steps of:
mixing the cyclic organopolysiloxane A and the cyclic organopolysiloxane B, heating, adding a free radical initiator, water, an acid catalyst, modified phosphate ester and an emulsifier, stirring for reaction at 60-85 ℃, heating to 120-150 ℃, continuing to react, cooling and neutralizing to obtain the water-based organic silicon resin.
7. The method as claimed in claim 6, wherein the stirring rate of the stirring reaction at 60-85 ℃ is 800-1500r/min, and the stirring rate of the continuous reaction at 120-150 ℃ is 100-500 r/min.
8. The method for producing an aqueous silicone resin according to claim 6, wherein the kinematic viscosity at 25 ℃ of the aqueous silicone resin is 3000-30000 mPas.
9. A coating layer prepared from the water-based silicone resin of claim 1 or 2, wherein the water-based silicone resin of claim 1 or 2 is coated and then dried and cured to obtain the coating layer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011502991.5A CN112724406B (en) | 2020-12-17 | 2020-12-17 | Water-based organic silicon resin and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011502991.5A CN112724406B (en) | 2020-12-17 | 2020-12-17 | Water-based organic silicon resin and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112724406A true CN112724406A (en) | 2021-04-30 |
| CN112724406B CN112724406B (en) | 2022-11-11 |
Family
ID=75602969
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011502991.5A Active CN112724406B (en) | 2020-12-17 | 2020-12-17 | Water-based organic silicon resin and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112724406B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102924667A (en) * | 2012-10-26 | 2013-02-13 | 武汉海源九天新材料有限公司 | Single-component self-phosphatizing antirust acrylic emulsion, and preparation method and application thereof |
| CN103130948A (en) * | 2013-02-28 | 2013-06-05 | 广东工业大学 | Room temperature crosslinkage and curable styrene-acrylate emulsion, and its preparation method |
| CN104877141A (en) * | 2015-06-11 | 2015-09-02 | 深圳市安品有机硅材料有限公司 | Preparation method of polymerizable modifier |
| CN106146755A (en) * | 2015-04-09 | 2016-11-23 | 泉州市合创涂料科技有限公司 | A kind of preparation method of high solids content silicone acrylic emulsion |
-
2020
- 2020-12-17 CN CN202011502991.5A patent/CN112724406B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102924667A (en) * | 2012-10-26 | 2013-02-13 | 武汉海源九天新材料有限公司 | Single-component self-phosphatizing antirust acrylic emulsion, and preparation method and application thereof |
| CN103130948A (en) * | 2013-02-28 | 2013-06-05 | 广东工业大学 | Room temperature crosslinkage and curable styrene-acrylate emulsion, and its preparation method |
| CN106146755A (en) * | 2015-04-09 | 2016-11-23 | 泉州市合创涂料科技有限公司 | A kind of preparation method of high solids content silicone acrylic emulsion |
| CN104877141A (en) * | 2015-06-11 | 2015-09-02 | 深圳市安品有机硅材料有限公司 | Preparation method of polymerizable modifier |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112724406B (en) | 2022-11-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103214628B (en) | A kind of acrylic resin modified and preparation method thereof for weatherability coating | |
| CN104098736B (en) | Hybrid silicon-containing modified acrylate emulsion and application thereof and preparation method | |
| CN103189422B (en) | Siloxane graft co-polymers for mold release | |
| US20070213474A1 (en) | Polysiloxane graft polymer | |
| CN103145994A (en) | Trapezoidal polysiloxane and preparation method thereof | |
| EP2057202A1 (en) | Crosslinkable reactive silicone organic copolymers and method for the production and use thereof | |
| CN103421324A (en) | Crosslinked polysiloxane/acrylic ester compound emulsion, and preparation method and application thereof | |
| CN108034051A (en) | A kind of vinyl polysiloxane and preparation method and application | |
| CN110818860A (en) | Preparation method of acrylate modified organic silicon resin | |
| CN112940203A (en) | Organosilicon modified acrylic acid secondary dispersion and preparation method thereof | |
| US5605983A (en) | Soluble organopolysiloxane free-radical macroinitators for graft copolymerization | |
| JPH0579248B2 (en) | ||
| US3932555A (en) | Silicone elastomers | |
| CN112724406B (en) | Water-based organic silicon resin and preparation method thereof | |
| US8637613B2 (en) | Self-dispersible silicone copolymers and method for the production and use thereof | |
| CN112724333B (en) | Water-based phosphorus-containing organic silicon resin and preparation method thereof | |
| CN105601845B (en) | A kind of synthesis of high molecular weight nitrile group-containing polysiloxanes and the preparation method of peroxide type heat cure nitrile silicone rubber | |
| JPS62116605A (en) | Nonaqueous dispersion of polymer particle | |
| KR20120008322A (en) | Acrylic emulsion resin having high weather resistance and paint composition comprising the same | |
| CN108424488B (en) | Anti-fouling and water-resistant silicone-acrylate emulsion and preparation method thereof | |
| CN113980201B (en) | Slump-retaining water reducer and preparation method thereof | |
| CN102911418B (en) | Method for preparing polyacrylate-organic P fire retardant through concentrated emulsion | |
| KR101757676B1 (en) | Silicone elastomer composition, silicone elastomer and silicone paste prepared using the same | |
| CN108659156A (en) | The preparation method of automobile coating thermoplastic acrylic resin | |
| CN112175521B (en) | Elastic exterior wall waterproof coating and preparation method 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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |