CN105175641A - Silane coupling agent modified polyurethane-acrylate composite emulsion and preparation method thereof - Google Patents
Silane coupling agent modified polyurethane-acrylate composite emulsion and preparation method thereof Download PDFInfo
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- CN105175641A CN105175641A CN201510622001.4A CN201510622001A CN105175641A CN 105175641 A CN105175641 A CN 105175641A CN 201510622001 A CN201510622001 A CN 201510622001A CN 105175641 A CN105175641 A CN 105175641A
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Abstract
The invention relates to silane coupling agent modified polyurethane-acrylate composite emulsion and a preparation method thereof. The emulsion is prepared from polyester polyol, isophorone diisocyanate, reactive diluents, a hydrophilic chain-extending agent, trimethylolpropane, dihydric alcohol, dibutyltin dilaurate, neutralizer, water, ethidene diamine, a silane coupling agent, initiator and an initiator dissolving solvent. The silane coupling agent modified polyurethane-acrylate composite emulsion and the preparation method thereof have the following advantages that the problem that water resistance is lowered due to the fact that emulgator is added is solved; pollution caused by an organic solvent and the trouble of the process of extracting organic solvents in the later period are avoided; the emulsion is provided with a stereoscopic net (Si-O-Si) crosslinking structure, chemical crosslinking points are increased, crosslinking density is correspondingly increased, the function of enhancing the density of a glue film surface layer is achieved, and finally the mechanical performance and tolerance of a glue film are improved.
Description
Technical field
The present invention relates to technical field of aqueous paint, be specifically related to a kind of silane coupler modified polyurethane-acrylate composite emulsion and preparation method thereof.
Background technology
Along with the reinforcement day by day of countries in the world environmental consciousness, in succession formulated some environmental regulations both at home and abroad to limit volatile organic compounds (VOC) to airborne release, high-performance, environmental protection have become the direction of paint development.Therefore the technician of current almost whole coating circle is at the content paying close attention to solvent, the research and development of solventless coatings.Water-borne coatings as a kind of coating taking water as solvent, already be familiar with by people.Various water-borne coatings is also come out one after another and is accepted by market soon.
The advantages such as urethane has that film-forming temperature is low, wear resistance good, chemical resistance is excellent, pliable and tough, strong adhesion, are described as the resin that best performance is different.At present, on market, polyurethane industries among others is still based on solvent based product, and in product, free toluene diisocyanate (TDI) content is higher, and containing volatile organic solvent, the health of harmful to human.Up to now, water-borne wood latex is on the market mainly based on ACRYLIC EMULSION and aqueous polyurethane emulsion.Aqueous polyurethane emulsion has fabulous low-temperature performance and wear resistance, chemicals-resistant corrodibility, and performance also has many weak points compared with solvent borne polyurethane, and as low in solid content, poor water resistance, stability are bad.
In order to effectively promote the fast development of Polyurethane Industry, promoting high-performance, the environmental protection of urethane resin, the technical problems such as aqueous polyurethane solid content is low, poor water resistance, poor solvent resistance, stability are bad must be solved.For solving the problem, modification must be carried out to it.At present acrylic acid modified, organic-silicon-modified and epoxy resin modification etc. are mainly contained for waterborne polyurethane modified method.Acrylic ester polymer has excellent mechanical property, and ageing-resistant and yellowing resistance good, luster performance is excellent.The characteristic of urethane and acrylic ester polymer has certain complementarity, and therefore for realizing the diversification of performance, letex polymerization also changes from the unicity of component to compound direction.By forming the means such as nucleocapsid structure or interpenetrating(polymer)networks, acrylate being incorporated in polyurethane structural, forming Acrylic-PU Composition Latex, thus give the performance of resin excellence.
Summary of the invention
The invention provides a kind of silane coupler modified polyurethane-acrylate composite emulsion and preparation method thereof, its aqueous polyurethane emulsion not only solved on market can not have that film-forming temperature is low, wear resistance good, chemical resistance is excellent concurrently and sticking power, water tolerance, solvent resistance, satisfactory mechanical property technical problem, and solve and with an organic solvent cause polluting and the later stage extracts the loaded down with trivial details technical problem of organic solvent technique out.The present invention has and to have below: using intermediate product urethane as self-emulsifier, avoid the water tolerance decline problem that additional emulsifying agent causes; Take acrylate monomer as the thinner of urethane, avoid pollution that organic solvent causes and the later stage deviates from the loaded down with trivial details of organic solvent technique.In addition, the present invention introduces silane coupling agent in the process of synthesis of polyurethane prepolymer, silane coupling agent hydrolysis under certain condition forms silanol, the active group condensation on silanol and polymeric inner or surface forms cubic network (Si-O-Si) crosslinking structure, chemically crosslinked point increases, the corresponding increase of cross-linking density, has enhancement to the density on glued membrane top layer, and final mechanical property and the patience improving glued membrane.
Technical solution of the present invention is as follows:
One) scheme one:
A kind of silane coupling agent modified polyurethane-acrylate composite emulsion, it is formulated by following ratio of weight and number by following component:
The present invention, using intermediate product urethane as self-emulsifier, avoids the water tolerance decline problem that additional emulsifying agent causes.
Further, described reactive thinner be methyl methacrylate (MMA), butyl methacrylate (BMA), vinylformic acid isooctyl (2-EHA) or butyl acrylate (BA) etc. containing can with the acrylic ester monomer of the group of polyurethane reaction.This programme take acrylate monomer as the thinner of urethane, avoids pollution that organic solvent causes and the later stage deviates from the loaded down with trivial details of organic solvent technique.
Further, described dibasic alcohol is the one in ethylene glycol, propylene glycol, BDO, pentanediol, glycol ether or neopentyl glycol.
Further, described silane coupling agent adopts the one in ammonia propylene triethoxyl silane, N-2-aminoethyl-3-aminopropyl triethoxysilane or two [3-(triethoxysilicane) propyl group] amine.
Further, described initiator adopts the one in Diisopropyl azodicarboxylate, benzoyl peroxide or 2,2'-Azobis(2,4-dimethylvaleronitrile).
Further, the solvent of described initiator dilution adopts the one in acetone, butanone or N-Methyl pyrrolidone.
Two) scheme two: a kind of preparation of silane coupling agent modified polyurethane-acrylate composite emulsion, it is prepared from according to following step of sequentially carrying out by the raw material of following weight proportioning:
A preparation method for silane coupling agent modified polyurethane-acrylate composite emulsion, it is prepared from according to following step of sequentially carrying out by the raw material of following weight proportioning:
1) preparation of polyurethane prepolymer:
Polyester polyol 24.00-26.00 part and isoflurane chalcone diisocyanate 25.36-30.18 part are joined in reactor, 80-85 DEG C is heated under 300-500rpm mixing speed and nitrogen protection, then ,-NCO content is measured, until measured-NCO content reaches theoretical value;
Then above-mentioned rotating speed and temperature is kept, add the reactive thinner regulation system viscosity of 42.00-46.00 part, then the dibutyl tin laurate of the hydrophilic chain extender of 4.00-5.00 part, the TriMethylolPropane(TMP) of 0.50-1.00 part, the dibasic alcohol of 2.66-3.27 part and 0.04-0.08 part is added, start afterwards to measure-NCO content, until when-NCO content reaches theoretical value, namely obtain polyurethane prepolymer;
2) neutralization of polyurethane prepolymer, emulsification, aqueous phase chain extension and silane coupler modified:
Keep above-mentioned rotating speed, by step 1) after obtained polyurethane prepolymer cools to 40-45 DEG C, add the neutralizing agent of 2.73-3.78 part, in and 5-6min;
Then add 131.00-192.00 part water, improve rotating speed to 1000-1500rpm, after dilution emulsification 20-30min, reduce mixing speed to 300-500rpm;
Then after the quadrol of 1.19-2.30 part being joined the water dilution of 24.00-26.00 part, the ethylenediamine solution after dilution was added drop-wise in reactor in 9-11 minute, reaction 4-6 minute;
Afterwards the silane coupling agent of 0.59-1.27 part is joined the water dilution of 24.00-26.00 part, the silane coupler solution after dilution was added drop-wise in reactor, at aqueous phase chain extending reaction 1-2 hour in 9-11 minute;
3) preparation of nucleocapsid structure urethane acrylate composite emulsion:
Then by step 2) obtained reaction system is warmed up to 80-85 DEG C, the initiator diluting solvent of 4.00-6.00 part is added in the initiator of 0.24-0.27 part, then the initiator 20-30 minute after dilution is added drop-wise in the reaction system after intensification, keep 80-85 DEG C of thermotonus 3-4 hour, termination reaction.
Further, the measuring method of described-NCO content is Di-n-Butyl Amine back titration method.
Inventive principle of the present invention is as follows:
This research is by butyl methacrylate, methyl methacrylate is as the thinner of polyurethane prepolymer, adopt method prepared by carboxylic acid type negatively charged ion, dimethylol propionic acid (DMPA) is selected to be hydrophilic chain extender, carboxyl is introduced in polyurethane structural, in addition, silane coupling agent is introduced in the process of synthesis of polyurethane prepolymer, silane coupling agent hydrolysis under certain condition forms silanol, the active group condensation on silanol and polymeric inner or surface forms cubic network (Si-O-Si) crosslinking structure, chemically crosslinked point increases, the corresponding increase of cross-linking density, enhancement is had to the density on glued membrane top layer, and final mechanical property and the patience improving glued membrane.The polyurethane aqueous dispersion body of synthesis self-emulsifying, heats up after emulsification and carries out the radical polymerization of Acrylic Acid Monomer, prepared silane coupling agent modified polyurethane-acrylate composite emulsion copolymerization latex of urethane acrylate.
The present invention compared with prior art, has the following advantages:
1) this preparation method is using polyurethane prepolymer as self-emulsifier, avoids the water tolerance decline problem that additional emulsifying agent causes;
2) take acrylate monomer as the thinner of polyurethane prepolymer, the copolyreaction of later stage urethane acrylate can be participated in, avoid pollution that organic solvent causes and the later stage extracts the loaded down with trivial details of organic solvent technique out.
3) copolymerization latex of urethane acrylate prepared of the present invention, silane coupling agent is introduced in the process of synthesis of polyurethane prepolymer, silane coupling agent hydrolysis under certain condition forms silanol, the active group condensation on silanol and polymeric inner or surface forms cubic network (Si-O-Si) crosslinking structure, chemically crosslinked point increases, the corresponding increase of cross-linking density, has enhancement to the density on glued membrane top layer, and final mechanical property and the patience improving glued membrane.
Embodiment
Below in conjunction with embodiment, embodiment, content of the present invention is described in detail:
(1) embodiment
A kind of silane coupling agent modified polyurethane-acrylate composite emulsion, it is formulated by following ratio of weight and number by following component:
A preparation method for silane coupling agent modified polyurethane-acrylate composite emulsion, it is prepared from according to following step of sequentially carrying out by the raw material of following weight proportioning:
1) preparation of polyurethane prepolymer:
Polyester polyol 24.00-26.00 part and isoflurane chalcone diisocyanate 25.36-30.18 part are joined in reactor, 80-85 DEG C is heated under 300-500rpm mixing speed and nitrogen protection, then ,-NCO content is measured, until measured-NCO content reaches theoretical value;
Then above-mentioned rotating speed and temperature is kept, add the reactive thinner regulation system viscosity of 42.00-46.00 part, then the dibutyl tin laurate of the hydrophilic chain extender of 4.00-5.00 part, the TriMethylolPropane(TMP) of 0.50-1.00 part, the dibasic alcohol of 2.66-3.27 part and 0.04-0.08 part is added, start afterwards to measure-NCO content, until when-NCO content reaches theoretical value, namely obtain polyurethane prepolymer;
2) neutralization of polyurethane prepolymer, emulsification, aqueous phase chain extension and silane coupler modified:
Keep above-mentioned rotating speed, by step 1) after obtained polyurethane prepolymer cools to 40-45 DEG C, add the neutralizing agent of 2.73-3.78 part, in and 5-6min;
Then add 131.00-192.00 part water, improve rotating speed to 1000-1500rpm, after dilution emulsification 20-30min, reduce mixing speed to 300-500rpm;
Then after the quadrol of 1.19-2.30 part being joined the water dilution of 24.00-26.00 part, the ethylenediamine solution after dilution was added drop-wise in reactor in 9-11 minute, reaction 4-6 minute;
Afterwards the silane coupling agent of 0.59-1.27 part is joined the water dilution of 24.00-26.00 part, the silane coupler solution after dilution was added drop-wise in reactor, at aqueous phase chain extending reaction 1-2 hour in 9-11 minute;
3) preparation of nucleocapsid structure urethane acrylate composite emulsion:
Then by step 2) obtained reaction system is warmed up to 80-85 DEG C, the initiator diluting solvent of 4.00-6.00 part is added in the initiator of 0.24-0.27 part, then the initiator 20-30 minute after dilution is added drop-wise in the reaction system after intensification, keep 80-85 DEG C of thermotonus 3-4 hour, termination reaction.
The measuring method of described-NCO content is Di-n-Butyl Amine back titration method.
(2) embodiment:
Embodiment 1
A kind of silane coupling agent modified polyurethane-acrylate composite emulsion, it is formulated by following ratio of weight and number by following component:
A preparation for silane coupling agent modified polyurethane-acrylate composite emulsion, it is prepared from according to following step of sequentially carrying out by the raw material of following weight proportioning:
1) preparation of polyurethane prepolymer:
Agitator is being housed, thermometer, in the 500mL four-hole boiling flask of prolong, add polyester polyol 24.00 parts and isoflurane chalcone diisocyanate 25.36 parts, mixing speed is at 500rpm, be heated to 85 DEG C under nitrogen protection, reaction to measured-NCO content reaches theoretical value (16.94%), then the methyl methacrylate of 12.2 parts is added, the butyl methacrylate regulation system viscosity of 29.8 parts, add the hydrophilic chain extender 2 of 5 parts subsequently, 2-dimethylol propionic acid (DMPA), the TriMethylolPropane(TMP) (TMP) of 0.5 part, 2.66 parts 1, 4-butyleneglycol, the dibutyl tin laurate (T-12) of 0.04 part, react under the condition of 85 DEG C,-NCO content (2.39%) is measured with Di-n-Butyl Amine back titration method, when reaching theoretical value, namely polyurethane prepolymer is obtained.
2) neutralization of polyurethane prepolymer, emulsification, aqueous phase chain extension and silane coupler modified:
Polyurethane prepolymer is cooled to 40 DEG C, adds the neutralizing agent triethylamine of 3.78 parts, in and after 5min, add 192 parts of water dilution emulsifications, improve rotating speed to 1500rpm, emulsification 20min.Reduce mixing speed to 500rpm, the quadrol of 1.34 parts is dissolved in the water of 24 parts, is added drop-wise in reactor, drip 10 minutes, react after 5 minutes, the aminopropyl triethoxysilane of 0.59 part is dissolved in 24 parts of water, be added drop-wise in reactor with 10 minutes, aqueous phase chain extending reaction 1 hour.Carry out next step reaction.
3) preparation of nucleocapsid structure urethane acrylate composite emulsion:
Be warmed up to 80 DEG C, the initiator of 0.24 part added the solvent cut of 5 parts, be added drop-wise in reaction flask with 20 minutes, 80 DEG C of reactions 4 hours, discharging.
Embodiment 2
A kind of silane coupling agent modified polyurethane-acrylate composite emulsion, it is formulated by following ratio of weight and number by following component:
A preparation for silane coupling agent modified polyurethane-acrylate composite emulsion, it is prepared from according to following step of sequentially carrying out by the raw material of following weight proportioning:
1) preparation of polyurethane prepolymer:
Agitator is being housed, thermometer, in the 500mL four-hole boiling flask of prolong, add polyester polyol 26 parts and isoflurane chalcone diisocyanate 30.18 parts, mixing speed is at 500rpm, be heated to 85 DEG C under nitrogen protection, reaction to measured-NCO content reaches theoretical value (18.76%), then the methyl methacrylate of 14.2 parts is added, the butyl methacrylate regulation system viscosity of 31.8 parts, add the hydrophilic chain extender 2 of 4 parts subsequently, 2-dimethylol propionic acid (DMPA), the TriMethylolPropane(TMP) (TMP) of 0.5 part, 2.66 parts 1, 4-butyleneglycol, the dibutyl tin laurate (T-12) of 0.06 part, react under the condition of 85 DEG C,-NCO content is measured with Di-n-Butyl Amine back titration method, when reaching theoretical value (3.98%), namely polyurethane prepolymer is obtained.
2) neutralization of polyurethane prepolymer, emulsification, aqueous phase chain extension and silane coupler modified:
Polyurethane prepolymer is cooled to 40 DEG C, adds the neutralizing agent triethylamine of 3.78 parts, in and after 5min, add 142 parts of water dilution emulsifications, improve rotating speed to 1500rpm, emulsification 20min.Reduce mixing speed to 500rpm, the quadrol of 2.30 parts is dissolved in the water of 26 parts, is added drop-wise in reactor, drip 10 minutes, react after 5 minutes, the aminopropyl triethoxysilane of 1.27 parts is dissolved in 26 parts of water, be added drop-wise in reactor with 10 minutes, aqueous phase chain extending reaction 1 hour.Carry out next step reaction.
3) preparation of nucleocapsid structure urethane acrylate composite emulsion:
Be warmed up to 80 DEG C, the initiator of 0.27 part added the solvent cut of 5 parts, be added drop-wise in reaction flask with 20 minutes, 80 DEG C of reactions 4 hours, discharging.
Embodiment 3
A kind of silane coupling agent modified polyurethane-acrylate composite emulsion, it is formulated by following ratio of weight and number by following component:
A preparation for silane coupling agent modified polyurethane-acrylate composite emulsion, it is prepared from according to following step of sequentially carrying out by the raw material of following weight proportioning:
1) preparation of polyurethane prepolymer:
Agitator is being housed, thermometer, in the 500mL four-hole boiling flask of prolong, add polyester polyol 25.00 parts and isoflurane chalcone diisocyanate 30.18 parts, mixing speed is at 500rpm, be heated to 85 DEG C under nitrogen protection, reaction to measured-NCO content reaches theoretical value (18.76%), then the methyl methacrylate of 17.50 parts is added, the butyl methacrylate regulation system viscosity of 26.50 parts, add the hydrophilic chain extender 2 of 5.00 parts subsequently, 2-dimethylol propionic acid (DMPA), the TriMethylolPropane(TMP) (TMP) of 0.50 part, 2.66 parts 1, 4-butyleneglycol, the dibutyl tin laurate (T-12) of 0.06 part, react under the condition of 85 DEG C,-NCO content is measured with Di-n-Butyl Amine back titration method, when reaching theoretical value (3.98%), namely polyurethane prepolymer is obtained.
2) neutralization of polyurethane prepolymer, emulsification, aqueous phase chain extension and silane coupler modified:
Polyurethane prepolymer is cooled to 40 DEG C, adds the neutralizing agent triethylamine of 3.78 parts, in and after 5min, add 192.00 parts of water dilution emulsifications, improve rotating speed to 1500rpm, emulsification 20min.Reduce mixing speed to 500rpm, the quadrol of 2.30 parts is dissolved in the water of 25 parts, be added drop-wise in reactor, drip 10 minutes, react after 5 minutes, the aminopropyl triethoxysilane of 1.27 parts is dissolved in 25.00 parts of water, was added drop-wise in reactor with 10 minutes, aqueous phase chain extending reaction 1 hour.Carry out next step reaction.
3) preparation of nucleocapsid structure urethane acrylate composite emulsion:
Be warmed up to 80 DEG C, the initiator of 0.26 part added the solvent cut of 5.00 parts, be added drop-wise in reaction flask with 20 minutes, 80 DEG C of reactions 4 hours, discharging.
Embodiment 4
A kind of silane coupling agent modified polyurethane-acrylate composite emulsion, it is formulated by following ratio of weight and number by following component:
A preparation for silane coupling agent modified polyurethane-acrylate composite emulsion, it is prepared from according to following step of sequentially carrying out by the raw material of following weight proportioning:
1) preparation of polyurethane prepolymer:
Agitator is being housed, thermometer, in the 500mL four-hole boiling flask of prolong, add polyester polyol 25.00 parts and isoflurane chalcone diisocyanate 27.17 parts, mixing speed is at 500rpm, be heated to 85 DEG C under nitrogen protection, reaction to measured-NCO content reaches theoretical value (17.70%), then the methyl methacrylate of 20.10 parts is added, the butyl methacrylate regulation system viscosity of 23.90 parts, add the hydrophilic chain extender 2 of 4.00 parts subsequently, 2-dimethylol propionic acid (DMPA), the TriMethylolPropane(TMP) (TMP) of 0.50 part, 3.27 parts 1, 4-butyleneglycol, the dibutyl tin laurate (T-12) of 0.06 part, react under the condition of 85 DEG C,-NCO content is measured with Di-n-Butyl Amine back titration method, when reaching theoretical value (3.07%), namely polyurethane prepolymer is obtained.
2) neutralization of polyurethane prepolymer, emulsification, aqueous phase chain extension and silane coupler modified:
Polyurethane prepolymer is cooled to 40 DEG C, adds the neutralizing agent triethylamine of 2.73 parts, in and after 5min, add 166.00 parts of water dilution emulsifications, improve rotating speed to 1500rpm, emulsification 20min.Reduce mixing speed to 500rpm, the quadrol of 1.76 parts is dissolved in the water of 25 parts, is added drop-wise in reactor, drip 10 minutes, react after 5 minutes, the aminopropyl triethoxysilane of 0.63 part is dissolved in 25 parts of water, be added drop-wise in reactor with 10 minutes, aqueous phase chain extending reaction 1 hour.Carry out next step reaction.
3) preparation of nucleocapsid structure urethane acrylate composite emulsion:
Be warmed up to 80 DEG C, the initiator of 0.26 part added the solvent cut of 5 parts, be added drop-wise in reaction flask with 20 minutes, 80 DEG C of reactions 4 hours, discharging.
Embodiment 5
A kind of silane coupling agent modified polyurethane-acrylate composite emulsion, it is formulated by following ratio of weight and number by following component:
A preparation for silane coupling agent modified polyurethane-acrylate composite emulsion, it is prepared from according to following step of sequentially carrying out by the raw material of following weight proportioning:
1) preparation of polyurethane prepolymer:
Agitator is being housed, thermometer, in the 500mL four-hole boiling flask of prolong, add polyester polyol 25 parts and isoflurane chalcone diisocyanate 27.17 parts, mixing speed is at 500rpm, be heated to 85 DEG C under nitrogen protection, reaction to measured-NCO content reaches theoretical value (17.70%), then the methyl methacrylate of 17.50 parts is added, the butyl methacrylate regulation system viscosity of 26.5 parts, add the hydrophilic chain extender 2 of 5.00 parts subsequently, 2-dimethylol propionic acid (DMPA), the TriMethylolPropane(TMP) (TMP) of 1 part, 3.16 parts 1, 4-butyleneglycol, the dibutyl tin laurate (T-12) of 0.06 part, react under the condition of 85 DEG C,-NCO content is measured with Di-n-Butyl Amine back titration method, when reaching theoretical value (2.09%), namely polyurethane prepolymer is obtained.
2) neutralization of polyurethane prepolymer, emulsification, aqueous phase chain extension and silane coupler modified:
Polyurethane prepolymer is cooled to 40 DEG C, adds the neutralizing agent triethylamine of 3.78 parts, in and after 5min, add 131.00 parts of water dilution emulsifications, improve rotating speed to 1500rpm, emulsification 20min.Reduce mixing speed to 500rpm, the quadrol of 1.19 parts is dissolved in the water of 25 parts, is added drop-wise in reactor, drip 10 minutes, react after 5 minutes, the aminopropyl triethoxysilane of 0.65 part is dissolved in 25 parts of water, be added drop-wise in reactor with 10 minutes, aqueous phase chain extending reaction 1 hour.Carry out next step reaction.
3) preparation of nucleocapsid structure urethane acrylate composite emulsion:
Be warmed up to 80 DEG C, the initiator of 0.26 part added the solvent cut of 5 parts, be added drop-wise in reaction flask with 20 minutes, 80 DEG C of reactions 4 hours, discharging.
In above each embodiment:
The CMA-44 of the preferred Hua Da chemistry of described polyester polyol;
Described isoflurane chalcone diisocyanate is preferably the IPDI that Bayer is produced;
Described methyl methacrylate, butyl methacrylate, 2,2-dimethylol propionic acids, TriMethylolPropane(TMP), BDO, Diisopropyl azodicarboxylate, butanone, quadrol are preferably Aladdin reagent.
Described dibutyl tin laurate is preferably the product of the triumphant auspicious chemical Science and Technology Ltd. in Changzhou.
The KH550 (ammonia propylene triethoxyl silane) of the preferred Guangzhou Long Kai Chemical Co., Ltd. of described silane coupling agent.
Silane coupling agent modified polyurethane-acrylate composite emulsion is carried out to the performance tests such as size, hardness, film-forming temperature, water tolerance, resistance to vinegar, alcohol resistance.
Sreen analysis: adopt Malvern company 3000SHA type nano-particle size analysis instrument test emulsion particle diameter.
Gloss (60 DEG C): according to the test of GB/T9754 regulation.
Hardness: test according to GB/T6739 regulation.
Sticking power: test according to GB/T9286-1998 regulation, drawing compartment distance is 2mm.
Water tolerance: test according to GB/T4893.1-2005 regulation.Water-fast 24 hours, whether paint film there is exception.
Alcohol resistance: testing method is identical with water tolerance, test solution is the ethanolic soln of 50% (volume fraction), and experimental period is 1h, tests after 1 hour, whether normally observes paint film.
Resistance to vinegar: select making vinegar, tested after 1 hour, whether normally observed paint film.
Film-forming temperature: adopt Britain RHOPOINT company MFFTBar-60 minimum film forming temperature tester, the minimum film-forming temperature of test emulsion.
Can obviously find out from table one, various embodiments of the present invention all have good water tolerance, alcohol resistance and stain resistance under difficult environmental conditions, and size distribution, all at about 100nm, has very high sticking power and hardness, has good using value.
In sum, the silane coupling agent modified polyurethane-acrylate composite emulsion of various embodiments of the present invention has very high hardness and sticking power, has good water tolerance, alcohol resistance and stain resistance.
Above-mentioned embodiment is just explained in detail technical scheme of the present invention; the present invention has more than and is only confined to above-described embodiment; those skilled in the art should be understood that; every improvement on basis of the present invention according to above-mentioned principle and spirit, substitute, all should within protection scope of the present invention.
The experimental data of each embodiment test of table one polyurethane-acrylate composite emulsion
Claims (10)
1. silane coupling agent modified polyurethane-acrylate composite emulsion, is characterized in that: it is formulated by following ratio of weight and number by following component:
2. a kind of silane coupling agent modified polyurethane-acrylate composite emulsion according to claim 1, is characterized in that: described reactive thinner be not containing can with the acrylic ester monomer of the group of polyurethane reaction.
3. a kind of silane coupling agent modified polyurethane-acrylate composite emulsion according to claim 1, is characterized in that: the polyester polyol of described polyester polyol to be molecular weight be 1000-2000.
4. polyurethane-acrylate composite emulsion according to claim 1, is characterized in that: described dibasic alcohol is the one in ethylene glycol, propylene glycol, BDO, pentanediol, glycol ether or neopentyl glycol.
5. a kind of silane coupling agent modified polyurethane-acrylate composite emulsion according to claim 1, is characterized in that: described silane coupling agent adopts the one in ammonia propylene triethoxyl silane, N-2-aminoethyl-3-aminopropyl triethoxysilane or two [3-(triethoxysilicane) propyl group] amine.
6. a kind of silane coupling agent modified polyurethane-acrylate composite emulsion according to claim 1, is characterized in that: described initiator adopts the one in Diisopropyl azodicarboxylate, benzoyl peroxide or 2,2'-Azobis(2,4-dimethylvaleronitrile).
7. a kind of silane coupling agent modified polyurethane-acrylate composite emulsion according to claim 1, is characterized in that: described initiator diluting solvent adopts the one in acetone, butanone or N-Methyl pyrrolidone.
8. a kind of silane coupling agent modified polyurethane-acrylate composite emulsion according to claim 1, is characterized in that: described hydrophilic chain extender is 2,2-dimethylol propionic acid; Described neutralizing agent is triethylamine.
9. a preparation method for silane coupling agent modified polyurethane-acrylate composite emulsion, is characterized in that: it is prepared from according to following step of sequentially carrying out by the raw material of following weight proportioning:
1) preparation of polyurethane prepolymer:
Polyester polyol 24.00-26.00 part and isoflurane chalcone diisocyanate 25.36-30.18 part are joined in reactor, 80-85 DEG C is heated under 300-500rpm mixing speed and nitrogen protection, then ,-NCO content is measured, until measured-NCO content reaches theoretical value;
Then above-mentioned rotating speed and temperature is kept, add the reactive thinner regulation system viscosity of 42.00-46.00 part, then the dibutyl tin laurate of the hydrophilic chain extender of 4.00-5.00 part, the TriMethylolPropane(TMP) of 0.50-1.00 part, the dibasic alcohol of 2.66-3.27 part and 0.04-0.08 part is added, start afterwards to measure-NCO content, until when-NCO content reaches theoretical value, namely obtain polyurethane prepolymer;
2) neutralization of polyurethane prepolymer, emulsification, aqueous phase chain extension and silane coupler modified:
Keep above-mentioned rotating speed, by step 1) after obtained polyurethane prepolymer cools to 40-45 DEG C, add the neutralizing agent of 2.73-3.78 part, in and 5-6min;
Then add 131.00-192.00 part water, improve rotating speed to 1000-1500rpm, after dilution emulsification 20-30min, reduce mixing speed to 300-500rpm;
Then the quadrol of 1.19-2.30 part is joined the water dilution of 24.00-26.00 part, the ethylenediamine solution after dilution was added drop-wise in reactor in 9-11 minute, reaction 4-6 minute;
Afterwards the silane coupling agent of 0.59-1.27 part is joined the water dilution of 24.00-26.00 part, the silane coupler solution after dilution was added drop-wise in reactor, at aqueous phase chain extending reaction 1-2 hour in 9-11 minute;
3) preparation of nucleocapsid structure urethane acrylate composite emulsion:
Then, keep above-mentioned rotating speed, by step 2) obtained reaction system is warmed up to 80-85 DEG C, the initiator diluting solvent of 4.00-6.00 part is added in the initiator of 0.24-0.27 part, then the initiator 20-30 minute after dilution is added drop-wise in the reaction system after intensification, keep 80-85 DEG C of thermotonus 3-4 hour, termination reaction.
10. the preparation method of a kind of silane coupling agent modified polyurethane-acrylate composite emulsion according to claim 1, is characterized in that: the measuring method of described-NCO content is Di-n-Butyl Amine back titration method.
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| CN108034392A (en) * | 2016-07-28 | 2018-05-15 | 南安市品龙新材料科技有限公司 | A kind of high bond strength, ageing-resistant binding agent and preparation method and application |
| CN108130057A (en) * | 2017-12-30 | 2018-06-08 | 周益铭 | A kind of preparation method of heat resistant type fluid loss additive |
| CN109422855A (en) * | 2017-07-20 | 2019-03-05 | 蚌埠金黄山凹版印刷有限公司 | A kind of line gravure UV gloss oil resin and its preparation method and application |
| CN109651559A (en) * | 2018-12-11 | 2019-04-19 | 上海绘兰材料科技有限公司 | A kind of release-free scalds cloth anodized aluminium acrylic resin and its preparation method and application |
| CN110078868A (en) * | 2019-05-08 | 2019-08-02 | 广东伟明涂料有限公司 | A kind of synthetic method of silane-modified water-borne polyurethane-acrylate resin |
| CN111057210A (en) * | 2019-12-31 | 2020-04-24 | 阜阳欣奕华材料科技有限公司 | Waterborne polyurethane coating agent and preparation method and application thereof |
| CN111072882A (en) * | 2019-12-31 | 2020-04-28 | 深圳市安品有机硅材料有限公司 | Modified waterborne polyurethane resin, coating and preparation method thereof |
| CN111087549A (en) * | 2019-12-31 | 2020-05-01 | 惠州市安品新材料有限公司 | Waterborne polyurethane resin, coating and preparation method thereof |
| CN111979791A (en) * | 2020-08-11 | 2020-11-24 | 南通金秋服装辅料有限公司 | Polyurethane modified silicone rubber and preparation method thereof |
| CN112011200A (en) * | 2020-08-27 | 2020-12-01 | 山东韩师傅新材料有限公司 | High-weather-resistance self-cleaning inorganic building coating and preparation method thereof |
| CN112680094A (en) * | 2020-12-28 | 2021-04-20 | 成都启铎弗涂料科技有限公司 | Preparation method of waterborne polyurethane acrylate waterborne paint |
| CN112759999A (en) * | 2021-01-21 | 2021-05-07 | 浙江锶通净新材料有限公司 | Preparation method of organic silicon modified water-based acrylic polyurethane anticorrosive paint |
| CN117025111A (en) * | 2023-08-09 | 2023-11-10 | 广东派尔新材料科技有限公司 | Environment-friendly super-elastic acrylic protective film and preparation process thereof |
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| CN108034392A (en) * | 2016-07-28 | 2018-05-15 | 南安市品龙新材料科技有限公司 | A kind of high bond strength, ageing-resistant binding agent and preparation method and application |
| CN108034392B (en) * | 2016-07-28 | 2020-04-28 | 烟台长盈电子科技有限公司 | High-bonding-strength and anti-aging bonding agent and preparation method and application thereof |
| CN109422855A (en) * | 2017-07-20 | 2019-03-05 | 蚌埠金黄山凹版印刷有限公司 | A kind of line gravure UV gloss oil resin and its preparation method and application |
| CN108130057A (en) * | 2017-12-30 | 2018-06-08 | 周益铭 | A kind of preparation method of heat resistant type fluid loss additive |
| CN109651559A (en) * | 2018-12-11 | 2019-04-19 | 上海绘兰材料科技有限公司 | A kind of release-free scalds cloth anodized aluminium acrylic resin and its preparation method and application |
| CN109651559B (en) * | 2018-12-11 | 2021-11-09 | 上海绘兰材料科技有限公司 | Acrylic resin for release-free ironing cloth electrochemical aluminum and preparation method and application thereof |
| CN110078868A (en) * | 2019-05-08 | 2019-08-02 | 广东伟明涂料有限公司 | A kind of synthetic method of silane-modified water-borne polyurethane-acrylate resin |
| CN111087549A (en) * | 2019-12-31 | 2020-05-01 | 惠州市安品新材料有限公司 | Waterborne polyurethane resin, coating and preparation method thereof |
| CN111072882A (en) * | 2019-12-31 | 2020-04-28 | 深圳市安品有机硅材料有限公司 | Modified waterborne polyurethane resin, coating and preparation method thereof |
| CN111057210A (en) * | 2019-12-31 | 2020-04-24 | 阜阳欣奕华材料科技有限公司 | Waterborne polyurethane coating agent and preparation method and application thereof |
| CN111979791A (en) * | 2020-08-11 | 2020-11-24 | 南通金秋服装辅料有限公司 | Polyurethane modified silicone rubber and preparation method thereof |
| CN112011200A (en) * | 2020-08-27 | 2020-12-01 | 山东韩师傅新材料有限公司 | High-weather-resistance self-cleaning inorganic building coating and preparation method thereof |
| CN112680094A (en) * | 2020-12-28 | 2021-04-20 | 成都启铎弗涂料科技有限公司 | Preparation method of waterborne polyurethane acrylate waterborne paint |
| CN112759999A (en) * | 2021-01-21 | 2021-05-07 | 浙江锶通净新材料有限公司 | Preparation method of organic silicon modified water-based acrylic polyurethane anticorrosive paint |
| CN117025111A (en) * | 2023-08-09 | 2023-11-10 | 广东派尔新材料科技有限公司 | Environment-friendly super-elastic acrylic protective film and preparation process thereof |
| CN117025111B (en) * | 2023-08-09 | 2024-01-23 | 广东派尔新材料科技有限公司 | Environment-friendly super-elastic acrylic protective film and preparation process thereof |
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