CN112724333B - Water-based phosphorus-containing organic silicon resin and preparation method thereof - Google Patents
Water-based phosphorus-containing organic silicon resin and preparation method thereof Download PDFInfo
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- CN112724333B CN112724333B CN202011520461.3A CN202011520461A CN112724333B CN 112724333 B CN112724333 B CN 112724333B CN 202011520461 A CN202011520461 A CN 202011520461A CN 112724333 B CN112724333 B CN 112724333B
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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
- C09D5/18—Fireproof paints including high temperature resistant paints
Abstract
The invention discloses a water-based phosphorus-containing organic silicon resin which is obtained by emulsion polymerization of raw materials comprising cyclic organopolysiloxane and modified phosphate ester, wherein the modified phosphate ester is prepared by esterification reaction of glycidyl (meth) acrylate and phosphoric acid, the resin does not contain organic solvent, can play a role in sealing, insulation, heat-resistant protection, flame retardance and the like, and has high paint film strength and good permeability.
Description
Technical Field
The invention relates to a water-based phosphorus-containing 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 existing organic silicon emulsion on the market is poor in flame retardant effect, in order to improve the flame retardance, a large amount of halogen-containing powder flame retardant is added, so that 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.
Disclosure of Invention
In order to solve the problems in the prior art, the invention aims to provide the water-based phosphorus-containing organic silicon resin and the preparation method thereof, which do not contain organic solvents, are environment-friendly, can achieve the functions of sealing, insulation, heat-resistant protection, flame retardance and the like, and have high paint film strength and good permeability.
The technical scheme of the invention is as follows:
the water-based phosphorus-containing organic silicon resin is prepared by emulsion polymerization of raw materials comprising cyclic organopolysiloxane A, modified phosphate ester and cyclic organopolysiloxane B, wherein the modified phosphate ester is prepared by esterification reaction of glycidyl (meth) acrylate and phosphoric acid;
the cyclic organopolysiloxane a is a compound represented by formula 1: [ -R 1 R 2 SiO-]n (formula 1), n is an integer of 3 to 9, R 1 、R 2 Alkyl, cycloalkyl, aryl, aralkyl or haloalkyl, which may be the same or different;
the cyclic organopolysiloxane B is a compound represented by formula 2: [ -R 3 R 4 SiO-]m (formula 2), wherein m is an integer of 3 to 9, R 3 、R 4 The same or different are an aliphatic unsaturated hydrocarbon group, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or a halogenated alkyl group, and the cyclic organopolysiloxane B has at least 1 aliphatic unsaturated hydrocarbon group in the molecular structure.
Preferably, the preparation method of the modified phosphate ester comprises the following steps:
mixing a polymerization inhibitor and a cosolvent, simultaneously dripping glycidyl (meth) acrylate and phosphoric acid at 0 +/-5 ℃ under the stirring condition, heating to 60-70 ℃ for esterification reaction, cooling, and distilling under reduced pressure to obtain the modified phosphate.
The glycidyl (meth) acrylate is glycidyl acrylate and/or glycidyl methacrylate. Preferably, the molar ratio of the glycidyl (meth) acrylate to the phosphoric acid is (1.5-3): 1, and the content of the phosphoric acid monoester and the phosphoric acid diester in the reaction product is adjusted by controlling the molar ratio.
The modified phosphate ester is a mixture, contains phosphate monoester, phosphate diester, unreacted phosphoric acid, polymerization inhibitor and the like, does not need to be separated, and is preferably selected, wherein the mass fraction of the phosphate monoester in the modified phosphate ester is 45-65%, the mass percentage of the phosphate diester is 30-45%, the esterification rate cannot reach 100% due to the influence of reaction balance, and the sum of the mass percentages of the phosphate monoester and the phosphate diester is less than 100%. 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 time for raising the temperature to 60-70 ℃ for reaction is 3-6h.
The reduced pressure distillation is to remove the cosolvent. The cosolvent is acetone, methanol or ethanol, and preferably accounts for 10-25% of the mass of the glycidyl (meth) acrylate.
Preferably, the polymerization inhibitor is one or two of p-methoxyphenol, tert-butylcatechol and hydroquinone, and the mass fraction of the polymerization inhibitor is 0.02-0.1%, namely the percentage of the polymerization inhibitor in the glycidyl (meth) acrylate, the polymerization inhibitor, the cosolvent and the phosphoric acid is 0.02-0.1%.
It is to be noted that the cyclic organopolysiloxane a is known in the art as a compound represented by formula 1: [ -R 1 R 2 SiO-]n (formula 1), n is an integer of 3 to 9, R 1 、R 2 Identical or different hydrogen radicals, alkyl radicals,Cycloalkyl, aryl, aralkyl, or haloalkyl. 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: [ -R 3 R 4 SiO-]m, wherein m is an integer of 3 to 9, R 3 、R 4 And 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 tetramethyltetravinylcyclotetrakisA siloxane.
Preferably, the modified phosphate ester is used in an amount of 50 to 120 parts by weight based on 100 parts by weight of the cyclic organopolysiloxane a. Preferably, the amount of the cyclic organopolysiloxane B is 300-600 parts based on 100 parts by weight of the cyclic organopolysiloxane A, the amount of the modified phosphate directly affects the reaction process and the state of the final polymer, and the application performance of the resin, the excessive amount of the modified phosphate can cause self-polymerization and even gelation, and the insufficient amount of the modified phosphate can cause instability of the reaction system and poor storage performance.
The preparation method of the water-based phosphorus-containing organic silicon resin comprises the following steps:
mixing the cyclic organopolysiloxane A and the cyclic organopolysiloxane B, heating, adding a free radical initiator, water, modified phosphate and an emulsifier, stirring for reaction at 60-85 ℃, heating to 120-150 ℃, continuing to react, cooling and neutralizing to obtain the water-based phosphorus-containing organic silicon resin.
Preferably, the stirring speed of the stirring reaction at the temperature of between 60 and 85 ℃ is 1500 to 3000r/min.
Preferably, the stirring rate for continuously reacting when the temperature is increased to 120-150 ℃ is 100-500r/min.
Preferably, the stirring reaction time at 60-85 ℃ is 4-10 h. Preferably, the time for continuing the reaction after the temperature is raised to 120-150 ℃ is 0.5-3 h.
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 6 parts by weight, based on 100 parts by weight of the cyclic organopolysiloxane a. The emulsifier is not particularly limited, and is preferably an anionic surfactant such as sodium C12-C18 alkyl sulfate, sodium C12-C18 alkylbenzene sulfonate, polyoxyethylene alkylphenol ether sulfate, succinic acid-modified polyoxyethylene alkylphenol ether, or sodium dodecylbenzenesulfonate.
Preferably, the water is used in an amount of 600 to 3000 parts by weight based on 100 parts by weight of the cyclic organopolysiloxane a.
Preferably, the number average molecular weight of the water-based phosphorus-containing organic silicon resin is 5000-12000.
Preferably, the solid content of the water-based phosphorus-containing organic silicon resin is 15-48%, and the kinematic viscosity at 25 ℃ is 4000-30000mPa & 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 temperature for drying and curing 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 the preparation method of the water-based phosphorus-containing 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 the reference is as follows: the improved synthesis process of phosphate ester and the detection of the content of monoester and diester of the leather in western province, no. 2 of No. 29 book of 2.2007, 31-34.
Example 1
The preparation method of the modified phosphate ester comprises the following steps:
adding 0.15g of hydroquinone polymerization inhibitor and 30.6g of acetone into a four-neck flask provided with a stirrer, a thermometer and a constant pressure dropping funnel, placing the flask in an ice water bath at (0 +/-1) DEG C, simultaneously dropwise adding 255.6g of glycidyl methacrylate and 98g of concentrated phosphoric acid (the mass fraction is 98%) while stirring, completing dropwise adding for 2h, heating to 68 ℃ for reaction for 4h, cooling to 45 ℃, carrying out reduced pressure distillation by using a rotary evaporator to separate and remove the acetone to obtain modified phosphate, testing the mass fraction of the phosphate diester to be 33.5%, the mass fraction of the phosphate monoester to be 61.2%, and testing the method to be a 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, 605g of deionized water, 65g of modified phosphate and 3.8g of sodium dodecyl benzene sulfonate are put into the reaction kettle, the mixture is stirred and reacted for 5 hours at 75 ℃ and on a JB-90D digital display constant speed stirrer at 1600r/min, the stirring speed is reduced to 300r/min, the temperature is raised to 125 ℃, the mixture is continuously stirred and reacted for 1 hour on the JB-90D digital display constant speed stirrer, the temperature is reduced to 45 ℃,20 g of sodium bicarbonate is put into the reaction kettle to adjust the pH value to be neutral, and the water-based phosphorus-containing organic silicon resin is obtained after filtration and packaging.
Example 2
The preparation method of the modified phosphate ester comprises the following steps:
adding 0.26g of hydroquinone polymerization inhibitor and 59.6g of ethanol into a four-neck flask provided with a stirrer, a thermometer and a constant pressure dropping funnel, placing the flask in an ice water bath at (0 +/-1) DEG C, simultaneously dropwise adding 298.2g of glycidyl methacrylate and 98g of concentrated phosphoric acid (the mass fraction is 98%) while stirring, completing dropwise adding for 2h, heating to 65 ℃ for reaction for 5h, cooling to 45 ℃, carrying out reduced pressure distillation by using a rotary evaporator to remove the ethanol to obtain modified phosphate, testing that the mass percentage of the diester phosphate is 37.7%, the mass percentage of the monoester phosphate is 56.4%, and testing by adopting a bromocresol green-phenolphthalein mixed indicator method.
68g of dodecamethylcyclohexasiloxane monomer, 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 ℃, after cyclosiloxane crystals are completely dissolved, 19g of tert-butyl peroxybenzoate, 2006g of deionized water, 57.8g of modified phosphate and 3.4g of sodium dodecyl benzene sulfonate are put into the pressure-resistant reaction kettle, the temperature is kept at 75 ℃, the mixture is stirred and reacted for 8 hours at a high speed of 2200r/min on a JB-90D digital display constant speed stirrer, the stirring speed is reduced to 200r/min, the mixture is heated to 135 ℃ on the JB-90D digital display constant speed stirrer, the stirring and the reaction are continued for 2 hours, the temperature is reduced to 40 ℃, 19g of sodium bicarbonate is put into the pressure-resistant reaction kettle to adjust the pH value to be neutral, and the aqueous organic silicon resin material is obtained through filtering and packaging.
Example 3
Preparation of modified phosphate ester:
0.38g of hydroquinone polymerization inhibitor and 44.3g of methanol are added into a four-neck flask provided with a stirrer, a thermometer and a constant pressure dropping funnel, the flask is placed in an ice water bath at (0 +/-1) DEG C, 340.8g of glycidyl methacrylate and 98g of concentrated phosphoric acid (the mass fraction is 98%) are simultaneously dropped while stirring, the dropping is finished for 2h, the temperature is raised to 70 ℃ for reaction for 5h, the temperature is reduced to 45 ℃, a rotary evaporator is used for carrying out reduced pressure distillation and separation to remove the methanol, modified phosphate is obtained, the mass percentage of the phosphoric acid diester is tested to be 40.4%, the mass percentage of the phosphoric acid monoester is tested to be 52.5%, and the test method is a bromocresol green-phenolphthalein mixed indicator method.
100g of hexamethylcyclotrisiloxane monomer, 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, 115.4g of modified phosphate and 5.4g of sodium dodecyl benzene sulfonate are put into the reaction kettle, the temperature is kept at 75 ℃, the mixture is stirred and reacted for 7.5 hours at a high speed of 2850r/min on a JB-90D digital display constant speed stirrer, the stirring speed is reduced to 150r/min, the temperature is raised to 130 ℃, the mixture is stirred and reacted for 2.5 hours on the JB-90D digital display constant speed stirrer continuously, the temperature is reduced to 35 ℃, 26g of sodium bicarbonate is put into the reaction kettle to adjust the PH value to be neutral, and the mixture is filtered and packaged to obtain the water-based phosphorus-containing organic silicon resin material.
Example 4 (comparative example)
Preparation of modified phosphate ester:
adding 0.26g of hydroquinone polymerization inhibitor and 59.6g of ethanol into a four-neck flask provided with a stirrer, a thermometer and a constant pressure dropping funnel, placing the flask in an ice water bath at (0 +/-1) DEG C, simultaneously dropwise adding 298.2g of glycidyl methacrylate and 98g of concentrated phosphoric acid (the mass fraction is 98%) while stirring, completing dropwise adding for 2h, heating to 65 ℃ for reaction for 5h, cooling to 45 ℃, carrying out reduced pressure distillation by using a rotary evaporator to remove the ethanol to obtain modified phosphate, testing that the mass percentage of the diester phosphate is 37.7%, the mass percentage of the monoester phosphate is 56.4%, and testing by adopting 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, 35.4g of modified phosphate and 5.4g of sodium dodecyl benzene sulfonate are put into the pressure-resistant reaction kettle, 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 digital display constant speed stirrer, the stirring speed is reduced to 150r/min, the temperature is raised to 130 ℃ on the JB-90D digital display constant speed stirrer, the stirring and reaction are continued for 2.5 hours, the temperature is reduced to 35 ℃, 22g of sodium bicarbonate is put into the pressure-resistant reaction kettle to adjust the pH value to be neutral, and the aqueous phosphorus-containing organic silicon resin is obtained after filtering and packaging.
Test examples
The performance test is carried out on the 1-4# water-based phosphorus-containing organic silicon resin, and the specific steps are as follows:
1. solid content and viscosity: the solids content is tested with reference to GB/T8077-2012, and the viscosity at 25 ℃ is measured with a rotational viscometer NDJ-4.
2. Storage stability: 150g of water-based phosphorus-containing organic silicon resin is filled into a closed conical flask, transferred into a baking oven with the temperature of 50 +/-2 ℃, and taken out after 30 days to observe the appearance state.
3. Uniformly spraying 50g of water-based phosphorus-containing organic silicon resin on a blank PVC (polyvinyl chloride) mould plate with the specification of 400mm × 200mm × 3mm, drying for 4 hours at room temperature, transferring into a 50 ℃ drying oven for drying for 8 hours, heating to 80 ℃ for continuously drying for 8 hours, taking out the dried product, standing at room temperature 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: and testing by referring to the standard GB/T2408-2008.
Breakdown voltage: refer to GB/T1695-2005.
Gloss: refer to GBT4893.6.
Tensile strength: reference is made 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: at 40 ℃; pump flow rate: 1ml/min; isoconcentrate elution is used.
High temperature aging resistance: and (3) taking a 50mm paint film, putting the paint film into a 150 ℃ oven, baking the paint film for 1000 hours, taking the paint film out, cooling the paint film, and observing the change of the appearance of the paint film.
The test results are shown in Table 1.
TABLE 1
As can be seen from the data in Table 1, the water-based phosphorus-containing organic silicon resin prepared by reacting cyclosiloxane and modified 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 (6)
1. The water-based phosphorus-containing organic silicon resin is characterized by being obtained by emulsion polymerization of raw materials including cyclic organic polysiloxane A, modified phosphate ester and cyclic organic polysiloxane B, wherein the modified phosphate ester is prepared by esterification of glycidyl (meth) acrylate and phosphoric acid, the molar ratio of the glycidyl (meth) acrylate to the phosphoric acid is (1.5-3): 1, the mass fraction of the phosphate monoester in the modified phosphate ester is 40-60%, and the mass fraction of the phosphate diester is 30-45%;
based on 100 parts by weight of cyclic organopolysiloxane A, the use amount of the modified phosphate ester is 50-120 parts, and based on 100 parts by weight of cyclic organopolysiloxane A, the use amount of cyclic organopolysiloxane B is 300-600 parts;
the cyclic organopolysiloxane a is a compound represented by formula 1: [ -R 1 R 2 SiO-]n (formula 1), n is an integer of 3 to 9, R 1 、R 2 Alkyl, cycloalkyl, aryl, aralkyl or haloalkyl, which may be the same or different;
the cyclic organopolysiloxane B is a compound represented by formula 2: [ -R 3 R 4 SiO-]m (formula 2) wherein m is an integer of 3 to 9, R 3 、R 4 And 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 phosphorus-containing silicone resin of claim 1, wherein the modified phosphate ester is prepared by a method comprising the steps of:
mixing a polymerization inhibitor and a cosolvent, simultaneously dripping glycidyl (meth) acrylate and phosphoric acid at 0 +/-5 ℃ under the stirring condition, heating to 60-70 ℃ for esterification reaction, cooling, and distilling under reduced pressure to obtain the modified phosphate.
3. The method for producing the aqueous phosphorus-containing silicone resin according to claim 1 or 2, characterized by comprising the steps of:
mixing and heating the cyclic organopolysiloxane A and the cyclic organopolysiloxane B, adding a free radical initiator, water, modified phosphate ester and an emulsifier, stirring and reacting at 60-85 ℃, heating to 120-150 ℃ for continuous reaction, and cooling and neutralizing to obtain the water-based phosphorus-containing organic silicon resin.
4. The method for preparing the aqueous phosphorus-containing silicone resin according to claim 3, wherein the stirring rate for the stirring reaction at 60-85 ℃ is 1500-3000r/min, and the stirring rate for the continuous reaction when the temperature is increased to 120-150 ℃ is 100-500r/min.
5. The method of claim 3, wherein the aqueous phosphorus-containing silicone resin has a solid content of 15% to 48% and a kinematic viscosity at 25 ℃ of 4000 to 30000 mPas.
6. A coating prepared from the water-based phosphorus-containing organic silicon resin of claim 1 or 2, wherein the water-based phosphorus-containing organic silicon resin of claim 1 or 2 is coated and then dried and cured to obtain the coating.
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| CN103183703A (en) * | 2012-12-11 | 2013-07-03 | 湖南农业大学 | Dimethyl acrylic acid glyceride phosphate and synthetic method thereof |
| 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 |
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| CN103183703A (en) * | 2012-12-11 | 2013-07-03 | 湖南农业大学 | Dimethyl acrylic acid glyceride phosphate and synthetic method thereof |
| 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 |
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