CN104045804A - Preparation method of aqueous light-curable polyurethane paper surface reinforcing agent - Google Patents
Preparation method of aqueous light-curable polyurethane paper surface reinforcing agent Download PDFInfo
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Abstract
The invention discloses a preparation method of an aqueous light-curable polyurethane paper surface reinforcing agent. The preparation method comprises the following steps: carrying out a prepolymer polymerization process on raw materials comprising polymeric polyol, polyisocyanate, an epoxy resin and a hydrophilic chain extender under the action of a catalyst to prepare a series of isocyanate terminated polyurethane prepolymer; and introducing a polyvinyl monomer with a responsive group to carry out a reaction of the polyvinyl monomer and the isocyanate terminated polyurethane in order to prepare vinyl terminated polyurethane, neutralizing, and adding water for self-emulsification in order to form the aqueous light-curable polyurethane dispersion. The emulsion particles of the above product obtained in the invention are nanometer particles, and the product is used for paper surface glue applying, can penetrate into paper fibers, and can also form a polymer film on the paper surface in order to comprehensively improve the dry/wet tenacity, the folding strength and the water resistance of the paper. The product has the advantages of fast light curing technology like curing rate, small pollution and automatic operation. Additionally, the product can be used for coating wood ware and metal surfaces.
Description
Technical field
The present invention relates to a kind of preparation method of paper surface reinforcing agent, particularly a kind of preparation method of aqueous photo-curing polyurethane paper surface reinforcing agent.
Background technology
UV-curing technology has that solidification rate soon, does not need heating, pollutes less, expense is low, can single component use, can automated operation etc. advantage, develop rapidly and widespread use.Be applied at present multiple fields such as paint, coating, ink and tackiness agent, but on paper, had no report as the application of paper surface sizing agent.Contemporary society's industry develops rapidly, more strict to the requirement of speciality paper performance, shows especially enhanced water resistance and physical strength etc.What traditional Surface Size was the most frequently used is starch and modifier thereof, later stage has engendered polyacrylamide resin, polyvinyl alcohol, modification AKD etc., but generally their molecular weight is larger, be difficult for penetrating into paper fibre, be difficult to form strong cross-linked network at paper surface and inside, intensity and the water tolerance of paper still need further improvement.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art part, a kind of preparation method of aqueous photo-curing polyurethane paper surface reinforcing agent is provided, can significantly improve water tolerance and the intensity of paper.
For achieving the above object, the technical solution used in the present invention is:
A. first, according to the mass fraction, in dry reactor, add 20～50 parts of polymer polyatomic alcohols, 25～55 parts of diisocyanate cpds, 1～10 part of epoxy resin, 2～15 parts of wetting ability chainextenders and 0.10～0.35 part of catalyzer, temperature of reaction is constant is 60～85 DEG C, react 2～3 hours, make isocyanate-terminated base polyurethane prepolymer for use as; Or
First, according to the mass fraction, in dry reactor, add 20～50 parts of polymer polyatomic alcohols, 25～55 parts of diisocyanate cpds, 2～15 parts of wetting ability chainextenders and 0.10～0.35 part of catalyzer, temperature of reaction is constant is 60～85 DEG C, react 2～3 hours, add again 1～10 part of epoxy resin and at 60～85 DEG C, react 2 hours, making isocyanate-terminated base polyurethane prepolymer for use as;
B. be then cooled to 50～60 DEG C, add 2～20 parts of multi-vinyl monomer and 0.10～0.20 part of catalyzer with reactive group, react after 3～5 hours, make the urethane of ethenyl blocking;
C. last, be cooled to 30～50 DEG C, add 1～10 part of neutralizing agent to neutralize, neutralization reaction, after 0.5～1 hour, under agitation adds 100～300 parts of water, stirs after 1～2 hour, makes aqueous photo-curing polyurethane paper surface reinforcing agent.
Described polymer polyatomic alcohol is the mixture of one or both arbitrary proportions in the poly-hexanodioic acid hexylene glycol ester of molecular weight between 1000～2000, poly adipate succinic acid ester, polycaprolactone glycol, polycarbonate diol, polytetrahydrofuran diol.
Described diisocyanate cpd is the mixture of one or both arbitrary proportions in hexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate, diphenylmethanediisocyanate.
Described wetting ability chainextender is the mixture of one or more arbitrary proportions in dimethylol propionic acid, dimethylolpropionic acid, dihydroxyl propanesulfonate, 2-aminoethylamino ethyl sulfonic acid sodium, diamino benzene sulfonic acid sodium.
Described epoxy resin is the mixture of a kind of, two or more arbitrary proportion in propane type epoxy resin of di phenolic group 55, E51, E44.
The described multi-vinyl monomer with reactive group is the one in pentaerythritol triacrylate, tripropylene glycol diacrylate.
Described catalyzer is the one in dibutyl tin laurate, dibutyltin diacetate, stannous octoate.
Described neutralizing agent is the one in ammoniacal liquor, triethylamine.
Compared with prior art, the beneficial effect that the present invention has: the present invention is using epoxy resin as crosslinked chainextender, has prepared serial aqueous photo-curing polyurethane paper surface reinforcing agent.Preparation process of the present invention is simple, containing organic solvent, not environmentally friendly.The product that the present invention makes, VOC free, has nontoxic, safety, curing speed is high, water-tolerant, intensity advantages of higher.The present invention is by aqueous photo-curing polyurethane system for paper for surface sizing, and it has the advantage of photocuring technology and water-based cross-linked polymer concurrently.Be nano level through the aqueous photo-curing polyurethane product of epoxy chain extension-crosslinking modification, the synchronous curing mechanism of photocuring and oxidative cure can further improve products solidifying speed.In the time of paper for surface sizing, the permeable paper inside that enters of its nano level emulsion particle forms cross-linked network structure between fiber, and in addition, it also can form fine and close polymeric film at paper surface, thereby significantly improves water tolerance and the intensity of sized paper.The present invention combines UV-curing technology with aqueous polyurethane, product is nano level, when penetrating into paper inside, also can form uniform polymeric film at paper surface, significantly improves the rate of drying of paper, water tolerance and intensity.By to paper for surface sizing, can make the sized paper with good water resistance and intensity.Product of the present invention also can be widely used in decoration and the protection on timber-work and metal products surface.
Embodiment
Below by specific embodiment, the present invention is described in detail.
Embodiment 1
The preparation process of aqueous photo-curing polyurethane paper surface reinforcing agent is as follows:
A. first, in dry reactor, add 20 parts of polymer polyatomic alcohols, 26 parts of diisocyanate cpds, 3 parts of epoxy resin, 3.5 parts of wetting ability chainextenders and 0.10 part of catalyzer, temperature of reaction is constant is 80 DEG C, the reaction times is within 2 hours, to make isocyanate-terminated base polyurethane prepolymer for use as;
B. be then cooled to 50 DEG C, add 3.5 parts of multi-vinyl monomer and 0.10 part of catalyzer with reactive group, react after 4 hours, add 10 parts of acetone to reduce reaction system concentration, make the urethane of ethenyl blocking;
C. last, be cooled to 30 DEG C, add 1.6 parts of neutralizing agents to neutralize, neutralization reaction, after 0.5 hour, slowly adds 120 parts of water under high-speed stirring, stirs after 1 hour, takes off place's acetone by underpressure distillation, makes aqueous photo-curing polyurethane paper surface reinforcing agent.
Described polymer polyatomic alcohol is the polycaprolactone glycol of molecular weight 1000; Described diisocyanate cpd is isophorone diisocyanate; Described wetting ability chainextender is dimethylolpropionic acid; Described epoxy resin is propane type epoxy resin of di phenolic group E44; The described multi-vinyl monomer with reactive group is pentaerythritol triacrylate; Described catalyzer is dibutyl tin laurate; Described neutralizing agent is triethylamine.
Embodiment 2
The preparation process of aqueous photo-curing polyurethane paper surface reinforcing agent is as follows:
A. first, in dry reactor, add 23 parts of polymer polyatomic alcohols, 29 parts of diisocyanate cpds, 4 parts of epoxy resin, 4.5 parts of wetting ability chainextenders and 0.20 part of catalyzer, temperature of reaction is constant is 80 DEG C, the reaction times is within 3 hours, to make isocyanate-terminated base polyurethane prepolymer for use as;
B. be then cooled to 60 DEG C, add 4.8 parts of multi-vinyl monomer and 0.15 part of catalyzer with reactive group, react after 5 hours, add 12 parts of acetone to reduce reaction system concentration, make the urethane of ethenyl blocking;
C. last, be cooled to 40 DEG C, add 2 parts of neutralizing agents to neutralize, neutralization reaction, after 1 hour, slowly adds 160 parts of water under high-speed stirring, stirs after 1 hour, takes off place's acetone by underpressure distillation, makes aqueous photo-curing polyurethane paper surface reinforcing agent.
Described polymer polyatomic alcohol is the poly-hexanodioic acid hexylene glycol ester of molecular weight 1000; Described diisocyanate cpd is that mass ratio is the hexamethylene diisocyanate of 1:1 and the mixture of isophorone diisocyanate; Described wetting ability chainextender is dimethylolpropionic acid; Described epoxy resin is propane type epoxy resin of di phenolic group E51; The described multi-vinyl monomer with reactive group is pentaerythritol triacrylate; Described catalyzer is stannous octoate; Described neutralizing agent is triethylamine.
Embodiment 3
The preparation process of aqueous photo-curing polyurethane paper surface reinforcing agent is as follows:
A. first, in dry reactor, add 40 parts of polymer polyatomic alcohols, 30 parts of diisocyanate cpds, 5 parts of wetting ability chainextenders and 0.20 part of catalyzer, temperature of reaction is constant is 80 DEG C, and the reaction times is within 2 hours, to make isocyanate-terminated base polyurethane prepolymer for use as; Continue to add 4 parts of epoxy resin to carry out chain extending reaction, and react 2 hours at 80 DEG C;
B. be then cooled to 60 DEG C, add 5 parts of multi-vinyl monomer and 0.20 part of catalyzer with reactive group, react after 4 hours, add 18 parts of acetone to reduce reaction system concentration, make the urethane of ethenyl blocking;
C. last, be cooled to 40 DEG C, add 3 parts of neutralizing agents to neutralize, neutralization reaction, after 1 hour, slowly adds 200 parts of water under high-speed stirring, stirs after 1 hour, takes off place's acetone by underpressure distillation, makes aqueous photo-curing polyurethane paper surface reinforcing agent.
Described polymer polyatomic alcohol is the poly-hexanodioic acid hexylene glycol ester of molecular weight 2000; Described diisocyanate cpd is that mass ratio is the hexamethylene diisocyanate of 1:1 and the mixture of isophorone diisocyanate; Described wetting ability chainextender is that mass ratio is the dimethylolpropionic acid of 1:1 and the mixture of dihydroxyl propanesulfonate; Described epoxy resin is propane type epoxy resin of di phenolic group E44; The described multi-vinyl monomer with reactive group is pentaerythritol triacrylate; Described catalyzer is dibutyl tin laurate; Described neutralizing agent is triethylamine.
Three kinds of aqueous photo-curing polyurethane paper surface reinforcing agents that embodiment 1-3 is obtained are for paper for surface sizing, and resin added is 10 ± 0.36g/m
2, and the salient features of applying glue and sized paper is not detected, result is as table 1.
Table 1 performance test results
| Test item | Unsized paper sample | Example 1 | Example 2 | Example 3 |
| Cobb value (g/m 2) | 172 | 25.5 | 22.5 | 19.8 |
| Dry tensile strength (N.m.g -1) | 32.1 | 49.6 | 48.7 | 49.8 |
| Wet tensile strength (N.m.g -1) | 5.72 | 17.5 | 17.9 | 18.5 |
| Folding endurance (inferior) | 42 | 87 | 96 | 86 |
| Surface strength (m.s -1) | 1.3 | 2.7 | 2.8 | 3.0 |
As can be seen from Table 1, compared with water leaf paper, the Cobb value of sized paper is lower, and dry tensile strength and wet tensile strength obviously increase compared with water leaf paper, and folding endurance and surface strength all improve a lot.
Embodiment 4
The preparation process of aqueous photo-curing polyurethane paper surface reinforcing agent is as follows:
A. first, in dry reactor, add 30 parts of polymer polyatomic alcohols, 55 parts of diisocyanate cpds, 1 part of epoxy resin, 15 parts of wetting ability chainextenders and 0.15 part of catalyzer, temperature of reaction is constant is 60 DEG C, and the reaction times is 2.5 hours, makes isocyanate-terminated base polyurethane prepolymer for use as;
B. be then cooled to 50 DEG C, add 10 parts of multi-vinyl monomer and 0.10 part of catalyzer with reactive group, react after 3 hours, add 15 parts of acetone to reduce reaction system concentration, make the urethane of ethenyl blocking;
C. last, be cooled to 35 DEG C, add 5 parts of neutralizing agents to neutralize, neutralization reaction, after 0.4 hour, slowly adds 300 parts of water under high-speed stirring, stirs after 1.5 hours, takes off place's acetone by underpressure distillation, makes aqueous photo-curing polyurethane paper surface reinforcing agent.
Described polymer polyatomic alcohol is the poly adipate succinic acid ester of molecular weight 1200; Described diisocyanate cpd is tolylene diisocyanate; Described wetting ability chainextender is 2-aminoethylamino ethyl sulfonic acid sodium; Described epoxy resin is propane type epoxy resin of di phenolic group E55; The described multi-vinyl monomer with reactive group is tripropylene glycol diacrylate; Described catalyzer is stannous octoate; Described neutralizing agent is ammoniacal liquor.
Embodiment 5
The preparation process of aqueous photo-curing polyurethane paper surface reinforcing agent is as follows:
A. first, in dry reactor, add 50 parts of polymer polyatomic alcohols, 25 parts of diisocyanate cpds, 7 parts of epoxy resin, 2 parts of wetting ability chainextenders and 0.25 part of catalyzer, temperature of reaction is constant is 85 DEG C, and the reaction times is 3 hours, makes isocyanate-terminated base polyurethane prepolymer for use as;
B. be then cooled to 60 DEG C, add 2 parts of multi-vinyl monomer and 0.20 part of catalyzer with reactive group, react after 4 hours, add 16 parts of acetone to reduce reaction system concentration, make the urethane of ethenyl blocking;
C. last, be cooled to 50 DEG C, add 1 part of neutralizing agent to neutralize, neutralization reaction, after 0.1 hour, slowly adds 240 parts of water under high-speed stirring, stirs after 2 hours, takes off place's acetone by underpressure distillation, makes aqueous photo-curing polyurethane paper surface reinforcing agent.
Described polymer polyatomic alcohol is the mixture of the polycaprolactone glycol of molecular weight 1500 and the polycarbonate diol arbitrary proportion of molecular weight 1500; Described diisocyanate cpd is the mixture of isophorone diisocyanate and tolylene diisocyanate arbitrary proportion; Described wetting ability chainextender is the mixture of dimethylolpropionic acid and diamino benzene sulfonic acid sodium arbitrary proportion; Described epoxy resin is the mixture of the arbitrary proportion of propane type epoxy resin of di phenolic group E44, E55; The described multi-vinyl monomer with reactive group is tripropylene glycol diacrylate; Described catalyzer is dibutyltin diacetate; Described neutralizing agent is ammoniacal liquor.
Embodiment 6
The preparation process of aqueous photo-curing polyurethane paper surface reinforcing agent is as follows:
A. first, in dry reactor, add 35 parts of polymer polyatomic alcohols, 42 parts of diisocyanate cpds, 10 parts of epoxy resin, 9 parts of wetting ability chainextenders and 0.3 part of catalyzer, temperature of reaction is constant is 70 DEG C, and the reaction times is 2 hours, makes isocyanate-terminated base polyurethane prepolymer for use as;
B. be then cooled to 55 DEG C, add 20 parts of multi-vinyl monomer and 0.15 part of catalyzer with reactive group, react after 3.5 hours, add 10 parts of acetone to reduce reaction system concentration, make the urethane of ethenyl blocking;
C. last, be cooled to 45 DEG C, add 10 parts of neutralizing agents to neutralize, neutralization reaction, after 0.8 hour, slowly adds 100 parts of water under high-speed stirring, stirs after 1.5 hours, takes off place's acetone by underpressure distillation, makes aqueous photo-curing polyurethane paper surface reinforcing agent.
Described polymer polyatomic alcohol is the mixture of the arbitrary proportion of polycarbonate diol, molecular weight 1800 polytetrahydrofuran diols of molecular weight 1800; Described diisocyanate cpd is the mixture of tolylene diisocyanate and diphenylmethanediisocyanate arbitrary proportion; Described wetting ability chainextender is the mixture of dimethylolpropionic acid and diamino benzene sulfonic acid sodium arbitrary proportion; Described epoxy resin is the mixture of propane type epoxy resin of di phenolic group E44, E55 and E51 arbitrary proportion; The described multi-vinyl monomer with reactive group is tripropylene glycol diacrylate; Described catalyzer is dibutyltin diacetate; Described neutralizing agent is triethylamine.
Embodiment 7
The preparation process of aqueous photo-curing polyurethane paper surface reinforcing agent is as follows:
A. first, in dry reactor, add 44 parts of polymer polyatomic alcohols, 36 parts of diisocyanate cpds, 12 parts of wetting ability chainextenders and 0.35 part of catalyzer, temperature of reaction is constant is 80 DEG C, reaction times is 2.5 hours, add again 6 parts of epoxy resin and at 60 DEG C, react 3 hours, making isocyanate-terminated base polyurethane prepolymer for use as;
B. be then cooled to 55 DEG C, add 15 parts of multi-vinyl monomer and 0.10 part of catalyzer with reactive group, react after 4.5 hours, add 20 parts of acetone to reduce reaction system concentration, make the urethane of ethenyl blocking;
C. last, be cooled to 30 DEG C, add 7 parts of neutralizing agents to neutralize, neutralization reaction, after 1 hour, slowly adds 270 parts of water under high-speed stirring, stirs after 2 hours, takes off place's acetone by underpressure distillation, makes aqueous photo-curing polyurethane paper surface reinforcing agent.
Described polymer polyatomic alcohol is the polycarbonate diol of molecular weight 2000; Described diisocyanate cpd is tolylene diisocyanate; Described wetting ability chainextender is 2-aminoethylamino ethyl sulfonic acid sodium; Described epoxy resin is propane type epoxy resin of di phenolic group E44; The described multi-vinyl monomer with reactive group is pentaerythritol triacrylate; Described catalyzer is dibutyltin diacetate; Described neutralizing agent is triethylamine.
Embodiment 8
The preparation process of aqueous photo-curing polyurethane paper surface reinforcing agent is as follows:
A.a. first, in dry reactor, add 40 parts of polymer polyatomic alcohols, 30 parts of diisocyanate cpds, 5 parts of wetting ability chainextenders and 0.20 part of catalyzer, temperature of reaction is constant is 80 DEG C, and the reaction times is within 2 hours, to make isocyanate-terminated base polyurethane prepolymer for use as; Continue to add 1 part of epoxy resin to carry out chain extending reaction, and react 2 hours at 85 DEG C;
B. be then cooled to 55 DEG C, add 15 parts of multi-vinyl monomer and 0.10 part of catalyzer with reactive group, react after 4.5 hours, make the urethane of ethenyl blocking;
C. last, be cooled to 30 DEG C, add 7 parts of neutralizing agents to neutralize, neutralization reaction, after 1 hour, slowly adds 270 parts of water under high-speed stirring, stirs after 2 hours, makes aqueous photo-curing polyurethane paper surface reinforcing agent.
Described polymer polyatomic alcohol is the polycarbonate diol of molecular weight 2000; Described diisocyanate cpd is tolylene diisocyanate; Described wetting ability chainextender is 2-aminoethylamino ethyl sulfonic acid sodium; Described epoxy resin is propane type epoxy resin of di phenolic group E44; The described multi-vinyl monomer with reactive group is pentaerythritol triacrylate; Described catalyzer is dibutyltin diacetate; Described neutralizing agent is triethylamine.
Embodiment 9
The preparation process of aqueous photo-curing polyurethane paper surface reinforcing agent is as follows:
A. first, in dry reactor, add 40 parts of polymer polyatomic alcohols, 30 parts of diisocyanate cpds, 5 parts of wetting ability chainextenders and 0.20 part of catalyzer, temperature of reaction is constant is 80 DEG C, and the reaction times is within 2 hours, to make isocyanate-terminated base polyurethane prepolymer for use as; Continue to add 10 parts of epoxy resin to carry out chain extending reaction, and react 2 hours at 75 DEG C;
B. be then cooled to 60 DEG C, add 5 parts of multi-vinyl monomer and 0.20 part of catalyzer with reactive group, react after 4 hours, make the urethane of ethenyl blocking;
C. last, be cooled to 40 DEG C, add 3 parts of neutralizing agents to neutralize, neutralization reaction, after 1 hour, slowly adds 200 parts of water under high-speed stirring, stirs after 1 hour, makes aqueous photo-curing polyurethane paper surface reinforcing agent.
Described polymer polyatomic alcohol is the poly-hexanodioic acid hexylene glycol ester of molecular weight 2000; Described diisocyanate cpd is that mass ratio is the hexamethylene diisocyanate of 1:1 and the mixture of isophorone diisocyanate; Described wetting ability chainextender is that mass ratio is the dimethylolpropionic acid of 1:1 and the mixture of dihydroxyl propanesulfonate; Described epoxy resin is propane type epoxy resin of di phenolic group E44; The described multi-vinyl monomer with reactive group is pentaerythritol triacrylate; Described catalyzer is dibutyl tin laurate; Described neutralizing agent is triethylamine.
Epoxy resin in the present invention is the mixture of a kind of, two or more arbitrary proportion in propane type epoxy resin of di phenolic group (abbreviation bisphenol A type epoxy resin) E55, E51, E44 (trade mark being divided into according to the difference of the viscosity of bisphenol A type epoxy resin and oxirane value).
The present invention introduces epoxy resin in polyurethane molecular chain and realizes by two kinds of modes: the one, in the time preparing isocyanate-terminated base polyurethane prepolymer for use as, epoxy resin is incorporated on polymkeric substance polymer by the mode of chain extension; The 2nd, making after isocyanate-terminated base polyurethane prepolymer for use as, add epoxy resin, it is reacted with the isocyanate groups on base polyurethane prepolymer for use as, further improve the molecular weight of urethane, and react 1-2 hour at 80 DEG C.
The present invention adopts performed polymer polymerization, under the effect of catalyzer, first prepares series isocyanates blocked polyurethane performed polymer taking polymer polyatomic alcohol, polyisocyanates, epoxy resin, hydrophilic chain extender as raw material.Then introduce multi-vinyl monomer and the isocyanate-terminated polyurethane reaction with reactive group, make ethenyl blocking urethane, after neutralization, the self-emulsifying that adds water, form aqueous photo-curing polyurethane dispersion liquid.Product emulsion particle of the present invention is nano level, and for paper for surface sizing, permeable entering in paper fiber, also can form polymeric film at paper surface, comprehensively to improve do/wet tenacity, folding endurance and the water tolerance of paper.This product also has advantages of that photocuring technology is as fast in solidification rate, pollutes little and operable automatically.In addition, product of the present invention also can be used for the coating of woodenware, metallic surface.
Key of the present invention is that by aqueous photo-curing polyurethane system, for paper for surface sizing, it has the advantage of photocuring technology and water-based cross-linked polymer concurrently.Be nano level through the aqueous photo-curing polyurethane product of epoxy chain extension-crosslinking modification, the synchronous curing mechanism of photocuring and oxidative cure can further improve products solidifying speed.In the time of paper for surface sizing, the permeable paper inside that enters of its nano level emulsion particle forms cross-linked network structure between fiber, and in addition, it also can form fine and close polymeric film at paper surface, thereby significantly improves water tolerance and the intensity of sized paper.Product preparation process of the present invention is simple, containing organic solvent, not environmentally friendly.
Claims (8)
1. a preparation method for aqueous photo-curing polyurethane paper surface reinforcing agent, is characterized in that, comprises the following steps:
A. first, according to the mass fraction, in dry reactor, add 20～50 parts of polymer polyatomic alcohols, 25～55 parts of diisocyanate cpds, 1～10 part of epoxy resin, 2～15 parts of wetting ability chainextenders and 0.10～0.35 part of catalyzer, temperature of reaction is constant is 60～85 DEG C, react 2～3 hours, make isocyanate-terminated base polyurethane prepolymer for use as; Or
First, according to the mass fraction, in dry reactor, add 20～50 parts of polymer polyatomic alcohols, 25～55 parts of diisocyanate cpds, 2～15 parts of wetting ability chainextenders and 0.10～0.35 part of catalyzer, temperature of reaction is constant is 60～85 DEG C, react 2～3 hours, add again 1～10 part of epoxy resin and at 60～85 DEG C, react 2 hours, making isocyanate-terminated base polyurethane prepolymer for use as;
B. be then cooled to 50～60 DEG C, add 2～20 parts of multi-vinyl monomer and 0.10～0.20 part of catalyzer with reactive group, react after 3～5 hours, make the urethane of ethenyl blocking;
C. last, be cooled to 30～50 DEG C, add 1～10 part of neutralizing agent to neutralize, neutralization reaction, after 0.5～1 hour, under agitation adds 100～300 parts of water, stirs after 1～2 hour, makes aqueous photo-curing polyurethane paper surface reinforcing agent.
2. the preparation method of a kind of aqueous photo-curing polyurethane paper surface reinforcing agent according to claim 1, it is characterized in that, described polymer polyatomic alcohol is the mixture of one or both arbitrary proportions in the poly-hexanodioic acid hexylene glycol ester of molecular weight between 1000～2000, poly adipate succinic acid ester, polycaprolactone glycol, polycarbonate diol, polytetrahydrofuran diol.
3. the preparation method of a kind of aqueous photo-curing polyurethane paper surface reinforcing agent according to claim 1, it is characterized in that, described diisocyanate cpd is the mixture of one or both arbitrary proportions in hexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate, diphenylmethanediisocyanate.
4. the preparation method of a kind of aqueous photo-curing polyurethane paper surface reinforcing agent according to claim 1, it is characterized in that, described wetting ability chainextender is the mixture of one or more arbitrary proportions in dimethylol propionic acid, dimethylolpropionic acid, dihydroxyl propanesulfonate, 2-aminoethylamino ethyl sulfonic acid sodium, diamino benzene sulfonic acid sodium.
5. the preparation method of a kind of aqueous photo-curing polyurethane paper surface reinforcing agent according to claim 1, it is characterized in that, described epoxy resin is the mixture of a kind of, two or more arbitrary proportion in propane type epoxy resin of di phenolic group 55, E51, E44.
6. the preparation method of a kind of aqueous photo-curing polyurethane paper surface reinforcing agent according to claim 1, is characterized in that, the described multi-vinyl monomer with reactive group is the one in pentaerythritol triacrylate, tripropylene glycol diacrylate.
7. the preparation method of a kind of aqueous photo-curing polyurethane paper surface reinforcing agent according to claim 1, is characterized in that, described catalyzer is the one in dibutyl tin laurate, dibutyltin diacetate, stannous octoate.
8. the preparation method of a kind of aqueous photo-curing polyurethane paper surface reinforcing agent according to claim 1, is characterized in that: described neutralizing agent is the one in ammoniacal liquor, triethylamine.
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| CN110172861A (en) * | 2019-05-16 | 2019-08-27 | 浙江恒达新材料股份有限公司 | A kind of no chlorine wet strength agent and preparation method thereof |
| CN110284363A (en) * | 2019-05-05 | 2019-09-27 | 苏州恒康新材料有限公司 | High surface strength high waterproof sizing agent and preparation method thereof |
| CN116751344A (en) * | 2023-08-18 | 2023-09-15 | 成都飞机工业（集团）有限责任公司 | Reinforcing agent for acrylic plate, preparation method of reinforcing agent and acrylic plate assembling method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110284363A (en) * | 2019-05-05 | 2019-09-27 | 苏州恒康新材料有限公司 | High surface strength high waterproof sizing agent and preparation method thereof |
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| CN116751344B (en) * | 2023-08-18 | 2023-12-08 | 成都飞机工业（集团）有限责任公司 | Reinforcing agent for acrylic plate, preparation method of reinforcing agent and acrylic plate assembling method |
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