CN103319680B - Preparation method of composite emulsion of cation-nonionic waterborne polyurethane-polyacrylate - Google Patents
Preparation method of composite emulsion of cation-nonionic waterborne polyurethane-polyacrylate Download PDFInfo
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Abstract
The invention relates to a preparation method of composite emulsion of cation-nonionic waterborne polyurethane-polyacrylate. The method comprises the following steps of: in synthesis polyurethane reaction, accessing polyacrylate containing terminated hydroxyl into a polyurethane molecular chain through the contained terminated hydroxyl, and forming a side chain of a polyurethane molecule, so as to obtain the composite emulsion combined with a chemical bond, wherein the side chain of the polyacrylate containing the terminated hydroxyl includes a cationic hydrophilic group, a non-ionic segment and a large-resistance group; preparing the polyacrylate containing terminated hydroxyl by using a uniform dripping method in preparation, and then neutralizing and emulsifying to obtain the composite emulsion of cation-nonionic waterborne polyurethane-polyacrylate after reacting with common high-molecular polyol, isocyanate, a crosslinking agent and a common chain extender. The prepared composite emulsion integrates dual advantages of the polyurethane and polyacrylate materials, especially has excellent storage stability and electrolyte resistance, simultaneously has good water resistance and excellent mechanical property, and can be widely applied to the fields such as painting, ink, a binder and the like.
Description
Technical field
The present invention relates to a kind of method for making of positively charged ion-non-ion aqueous polyurethane-poly acrylate composite emulsion.This emulsion is applicable to the fields such as coating, ink and tackiness agent.
Background technology
Water-base polyurethane material, due to the performance of its excellence and environmental protection feature, has been widely used in the fields such as coating, ink and sizing agent at present, but due to the price of raw materials isocyanic ester higher, limit its application to a great extent.ACRYLIC EMULSION has good ageing resistance and Bao Se gloss retention, and cost is lower simultaneously, well compensate for the weak point of polyurethane material.Therefore, aqueous polyurethane and water polyacrylic acid are combined, prepares aquosity polyurethane-polyacrylate composite emulsion, the product of high performance-price ratio can be obtained.In recent years, aquosity polyurethane-polyacrylate composite emulsion (hereinafter referred to as PUA composite emulsion) is comparatively fast developed.The method of the current PUA of preparation composite emulsion mainly comprises two kinds: aqueous polyurethane and water polyacrylic acid resin are prepared by " cold spelling " by one; It is two on the basis of aqueous polyurethane emulsion, drips acrylate monomer polymerization, preparation " core-shell structure copolymer " type composite emulsion.The PUA composite emulsion prepared of above two kinds of methods essentially its main body is still the physical mixed body of urethane and polyacrylic ester two component, and the problem of consistency is there is only by the composite emulsion of physical blending, the advantage of two components cannot be played to greatest extent.Current research emphasis how urethane and polyacrylate component to be combined by the mode of chemical bond.Although existing multiple method is open, but, performance and the cost of obtained PUA composite emulsion are difficult to take into account, particularly the electrolyte-resistant of PUA composite emulsion and stability in storage Shortcomings, and the water tolerance after emulsion film forming and mechanical property can not meet application requiring.On the other hand, by carrying out functional modification to the side chain of PUA hybrid emulsion resins, prepared product can be made to obtain some specific performances, and then meet product some particular demands in actual applications.But still can not provide reliable preparation method at present.
Summary of the invention
The object of the invention is: a kind of preparation method with the positively charged ion-non-ion aqueous polyurethane-poly acrylate composite emulsion of excellent storage stability, good electrolyte-resistant and alkali resistance is provided.
The technical scheme realizing the object of the invention is: a kind of method for making of positively charged ion-non-ion aqueous polyurethane-poly acrylate composite emulsion, it is characterized in that, in synthesis of polyurethane reaction, polyacrylic ester containing terminal hydroxy group is accessed polyurethane molecular chain by contained terminal hydroxy group and becomes the side chain of polyurethane molecular, obtain urethane and the polyacrylic ester composite emulsion by chemical bonds, its side chain containing the polyacrylic ester of terminal hydroxy group has cationic hydrophilic groups, non-ionic segments and larger steric group, and concrete preparation process is as follows:
1. preparation is containing the polyacrylic ester of terminal hydroxy group
By the mixture of whole monomer, chain-transfer agent and initiator, to be evenly added drop-wise in solvent and to carry out radical polymerization formation, concrete operations are as follows:
In reaction vessel, the solvent adding 20 ~ 50wt% is bed material, at 50 ~ 130 DEG C, by the vinyl monomer of 10 ~ 20wt% cation type hydrophilic radical, 14 ~ 35wt% contains the acrylate monomer of non-ionic segments, 6 ~ 25wt% contains the acrylate monomer of larger steric group, other monomers containing vinyl structure of 2 ~ 15wt%, 0.5 ~ 8wt% mixes and the mixture stirred containing sulfydryl dibasic alcohol chain-transfer agent and 0.05 ~ 3wt% initiator, evenly be added drop-wise in the solvent in reaction vessel in 3 ~ 5 hours, drip after terminating at 50 ~ 130 DEG C, be incubated 3 ~ 10 hours obtained polyacrylic ester containing terminal hydroxy group, above-mentioned each raw material dosage sum is 100%, wherein, the vinyl monomer of cation type hydrophilic radical is (methyl) dimethylaminoethyl acrylate, (methyl) acrylate propyl ester, (methyl) vinylformic acid lignocaine ethyl ester, vinylformic acid diethylin propyl ester, methacrylic acid-2-t-butylaminoethyl, (methyl) acrylyl oxy-ethyl-trimethyl salmiac, one or more in (methyl) acryloxyethyldimethyl benzyl ammonium chloride, acrylate monomer containing larger steric group is one or more in (methyl) isobornyl acrylate, (methyl) vinylformic acid methylcyclopentyl ester, (methyl) cyclohexyl acrylate, (methyl) t-butylcyclohexyl base ester, (methyl) vinylformic acid trimethylcyclohexylidene base ester, other monomers containing vinyl structure are one or more in (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) butyl acrylate, (methyl) propyl acrylate, the own monooctyl ester of (methyl) vinylformic acid, ethyl acrylate, (methyl) n-octyl, benzyl acrylate, vinylbenzene, alpha-methyl styrene, be one or more in 3-Mercapto-1，2-propanediol, Isosorbide-5-Nitrae-DTT containing sulfydryl dibasic alcohol chain-transfer agent, initiator is one or more in Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), 2,2'-Azobis(2,4-dimethylvaleronitrile), azo-bis-iso-dimethyl, azo dicyclohexyl formonitrile HCN, hydrogen peroxide, dibenzoyl peroxide, tert-butyl peroxide, solvent is one or more in acetone, butanone, 1-Methyl-2-Pyrrolidone, DMF, 1-Methoxy-2-propyl acetate, acrylate monomer containing non-ionic segments has following structure:
Wherein R
1for H or CH
3, R
2for methyl or ethyl or butyl, the scope of n is 7 ~ 35;
2. positively charged ion-non-ion aqueous polyurethane-poly acrylate composite emulsion is prepared
In reaction vessel, add the polyacrylic ester containing terminal hydroxy group that 10 ~ 30wt% step is 1. obtained, 2 ~ 10wt% general macromolecular polyvalent alcohol and 5 ~ 20wt% isocyanic ester, at 80 ~ 90 DEG C, 2 ~ 3h is reacted after mixing, then 0.2 ~ 4wt% linking agent is added successively, the common chainextender of 0.1 ~ 5wt%, 5 ~ 20wt% solvent, 2 ~ 4h is reacted at 70 ~ 80 DEG C, add 0.005 ~ 0.3wt% catalyzer again, polyurethane prepolymer solution is obtained react 3 ~ 5h at 60 ~ 70 DEG C after, reactant is moved in dispersion machine, under the stirring velocity of 2000 revs/min, add the neutralization of 1 ~ 8wt% neutralizing agent, add after 40 ~ 70wt% deionized water and stirring is uniformly dispersed again, except desolventizing after underpressure distillation, obtain positively charged ion-non-ion aqueous polyurethane-poly acrylate composite emulsion, above-mentioned each raw material dosage sum is 100%.
In the method for making of above-mentioned composite emulsion, 1. step prepares polyacrylic ester containing the terminal hydroxy group acrylate monomer containing non-ionic segments used is one or more in methoxy poly (ethylene glycol) list (methyl) acrylate, oxyethyl group polyethyleneglycol (methyl) acrylate, butoxy polyethyleneglycol (methyl) acrylate.
In the method for making of above-mentioned composite emulsion, 2. step is prepared in the raw material of positively charged ion-non-ion aqueous polyurethane-poly acrylate composite emulsion, and described general macromolecular polyvalent alcohol is one or more in polycaprolactone polyol, polycarbonate polyol, polytetrahydrofuran ethoxylated polyhydric alcohol, polyethylene oxide polyol, polyoxypropylene polyol, hydroxy-terminated polybutadienes polyvalent alcohol, polyester polyol; Described isocyanic ester is isophorone diisocyanate, 1, hexamethylene-diisocyanate, 4, one or more in 4 '-dicyclohexyl methyl hydride-vulcabond, xylylene diisocyanate, tetramethyl-xylylene diisocyanate, tolylene diisocyanate, diphenylmethanediisocyanate, 1,5-naphthalene diisocyanate, poly methylene poly phenyl poly isocyanate; Described linking agent is one or more in TriMethylolPropane(TMP), glycerol, tetramethylolmethane, Dipentaerythritol, Sorbitol Powder; Described common chainextender is one or more in ethylene glycol, glycol ether, BDO, 2,3-butanediol, 1,6-hexylene glycol, neopentyl glycol, glycol ether, hydroxymethyl-cyclohexane; Described solvent is one or more in acetone, butanone, 1-Methyl-2-Pyrrolidone, DMF; Described catalyzer is one or more in triethylamine, triethylene diamine, dibutyl tin laurate, stannous octoate; Described neutralizing agent is one or more in lactic acid, acetic acid, phosphoric acid.
Technique effect of the present invention is: the method preparing aquosity polyurethane-polyacrylate composite emulsion in technical solution of the present invention compared with prior art, has following advantage:
(1) 1. step is prepared in the polyacrylic ester monomer used containing terminal hydroxy group, contains 3 kinds of functional monomers namely simultaneously: the vinyl monomer of cation type hydrophilic radical, the acrylate monomer containing non-ionic segments, containing the acrylate monomer of larger steric group.Like this, the side chain of the obtained polyacrylic ester containing terminal hydroxy group is simultaneously containing non-ionic segments, cationic hydrophilic groups and larger steric group.Containing the cationic hydrophilic groups in the polyacrylic ester of terminal hydroxy group, make to prepare subsequently in urethane process just can realize Water-borne modification without the need to the additional hydrophilic monomer for self-emulsifying or hydrophilic chain extender, make formula for a product simpler; Be positioned at the side chain of polyurethane molecular containing the non-ionic segments in the polyacrylic ester of terminal hydroxy group and distribute comparatively concentrated, therefore, the synergy of non-ionic segments can be played, more excellent electrolyte-resistant is provided, in addition, the price of the acrylate monomer containing non-ionic segments that the present invention is used is lower than usually introducing side chain non-ionic segments polyether Glycols used; The reactive force between molecular chain is weakened containing the larger steric group in the polyacrylic ester of terminal hydroxy group, polyacrylate solution viscosity containing terminal hydroxy group is reduced, also simplify the operation of subsequent polyurethane synthesis, in addition, larger steric group has preferably water tolerance after can also ensureing emulsion film forming;
(2) when 1. step prepares the polyacrylic ester containing terminal hydroxy group, adopt and the mode that each monomer mixture evenly drips is fed intake, the composition of the polyacrylic ester that can ensure containing terminal hydroxy group forms consistent with raw material, and then effectively can improve the performance of corresponding urethane.Overcome the polymkeric substance composition that the difference of the reactivity ratio because of different monomers that prior art adopts a step feeding mode to cause causes and form inconsistent shortcoming with monomer used;
(3) step urethane synthetic reaction process 2., polyacrylic ester containing terminal hydroxy group is accessed polyurethane molecular chain by contained terminal hydroxy group and becomes the side chain of polyurethane molecular, obtained urethane and polyacrylic ester are by the composite emulsion of chemical bonds, composite emulsion is made to have both the advantage of two kinds of components, and make the side chain of PUA hybrid emulsion resins obtain functional modification, overcome the shortcoming that the poor and application performance of composite emulsion component compatibility that adopts physical cold to spell preparation is restricted;
(4) step urethane building-up process 2., introduces linking agent, makes the composite emulsion molecule of preparation have crosslinking structure, effectively raises the mechanical property after emulsion film forming, solve the problem that pectination material mechanical performance is poor.
Embodiment
Below in conjunction with embodiment, the present invention is described further, but is not limited to this.
Embodiment and comparative example raw materials are unless otherwise indicated commercially available industrial goods, buy by commercial channel.
Embodiment 1 ~ 3
1. preparation is containing the polyacrylic ester of terminal hydroxy group
By the mixture of whole monomer, chain-transfer agent and initiator, to be evenly added drop-wise in solvent and to carry out radical polymerization formation.
A) formula is in table 1.
Table 1
B) concrete operations
By the formula that table 1 provides, agitator is being housed, thermometer, adding solvent in the four-hole boiling flask of drying nitrogen conduit and reflux condensing tube is bed material, by the vinyl monomer of cation type hydrophilic radical at 75 ~ 85 DEG C, acrylate monomer containing non-ionic segments, acrylate monomer containing larger steric group, other are containing the monomer of vinyl structure, mix and the mixture stirred containing sulfydryl dibasic alcohol chain-transfer agent and initiator, evenly be added drop-wise in the solvent in four-hole boiling flask in 3 hours, at 80 DEG C, 5 hours are incubated after dropping terminates, the polyacrylic ester containing terminal hydroxy group of obtained embodiment 1 ~ 3 respectively, its solids content is 66.67wt%, save backup.
2. positively charged ion-non-ion aqueous polyurethane-poly acrylate composite emulsion is prepared
A) formula is in table 2.
Table 2
B) concrete operations
In the container that agitator, thermometer and condenser are housed, add containing the polyacrylic ester of terminal hydroxy group, general macromolecular polyvalent alcohol and isocyanic ester by table 2 formula ratio, at 90 DEG C, 2h is reacted after mixing, then linking agent, common chainextender, solvent is added successively, 3h is reacted at 70 ~ 80 DEG C, add catalyzer again, react 4h at 60 ~ 70 DEG C after, obtain polyurethane prepolymer solution.Reactant is moved in high speed shear dispersion machine, with under the stirring velocity of 2000 revs/min, add neutralizing agent neutralization, add after deionized water and stirring is uniformly dispersed again, except desolventizing after underpressure distillation, obtain the positively charged ion-non-ion aqueous polyurethane-poly acrylate composite emulsion of embodiment 1 ~ 3 respectively, its solids content is 33.3wt%, and pH value is 6 ~ 7.
Comparative example 1 ~ 3
1. preparation is containing the polyacrylic ester of terminal hydroxy group
A) formula is in table 3.
Table 3
B) concrete operations
Except formula difference, all the other all obtain the polyacrylic ester containing terminal hydroxy group of comparative example 1 ~ 3 respectively by the method for embodiment, for subsequent use.
2. positively charged ion-non-ion aqueous polyurethane-poly acrylate composite emulsion is prepared
A) formula is in table 4.
Table 4
B) concrete operations
Except formula difference, all the other all obtain the positively charged ion-non-ion aqueous polyurethane-poly acrylate composite emulsion of comparative example 1 ~ 3 respectively by the method for embodiment.
detect the performance of the positively charged ion-non-ion aqueous polyurethane-poly acrylate composite emulsion of embodiment and comparative example
(1) detection method
1. viscosity
Measure the viscosity of the polyacrylic ester containing terminal hydroxy group.At 25 DEG C, adopt model to be that NDJ-1 rotational viscosimeter is measured.
2. electrolyte-resistant
Get composite emulsion 20 grams, slowly adding 10 grams more can Chemical Co., Ltd.'s product containing electrolyte solution YK-L360(Shanghai) be uniformly mixed after, to be positioned in 50 DEG C of baking ovens 3 months, to observe with or without precipitation and throw out generation.Electrolyte-resistant is divided into 3 grades: 1 grade for homogeneous solution, without precipitation, without layering; 2 grades is micro-turbid solution, without precipitation, without layering; 3 grades is flocculation, and precipitation is arranged at bottom, layering.1 grade best, and 3 grades the poorest.
3. stability in storage
Get 20 grams of composite emulsion to pour in airtight vial, to be positioned in 50 DEG C of baking ovens 3 months, observe with or without precipitation and throw out generation.
4. water tolerance
Be sprayed on by composite emulsion on the steel plate galvanized after polishing, film thickness monitoring, between 15 ~ 20 μm, under room temperature after surface drying, is put into 80 DEG C of oven dryings and is obtained model to be measured in 30 minutes.Model to be measured is immersed in the water of 25 DEG C, after 48 hours, observe model changing conditions.According to the visual condition soaking rear model, 3 grades: 1 grade water tolerance is divided into be that model is substantially unchanged; 2 grades is that specimen surface bubbles, and micro-ly turns white; 3 grades is that on model, film comes off, and turns white completely.1 grade best, and 3 grades the poorest.
5. tensile strength
Composite emulsion is poured into film forming on polyfluortetraethylene plate, film thickness monitoring, between 1 ~ 2mm, is tested according to American Society Testing and Materials standard A STMD412-87 after glued membrane complete drying.
(2) detected result is in table 5
Table 5
In table 5, A is the polyacrylic ester containing terminal hydroxy group
From the test result of table 5, the polyacrylic ester modest viscosity containing terminal hydroxy group prepared in the embodiment of the present invention 1 ~ 3, is conducive to the synthesis of subsequent polyurethane.Positively charged ion-non-ionic water polyurethane-acrylate composite emulsion prepared in the embodiment of the present invention 1 ~ 3 combines the two-fold advantage of urethane and polyacrylate material, particularly there is preferably stability in storage and electrolyte res is tance, there is good water tolerance and excellent mechanical property simultaneously, the fields such as coating, ink and tackiness agent can be widely used in.
From table 5 detected result also, compare with the embodiment of the present invention 1 ~ 3, because comparative example 1 does not add the acrylate monomer containing non-ionic segments in the polyacrylic ester preparation process containing terminal hydroxy group, therefore, the Stability towards electrolytes of comparative example 1 composite emulsion and stability in storage are obviously deteriorated; Because comparative example 2 does not add the acrylate monomer containing larger steric group in containing the polyacrylic ester preparation process of terminal hydroxy group, therefore, the viscosity of the polyacrylic ester containing terminal hydroxy group of comparative example 2 is higher, is unfavorable for that follow-up polyurethane is standby.Meanwhile, the water tolerance of corresponding composite emulsion is also poor; Because comparative example 3 does not add linking agent preparing in urethane process, therefore, the tensile strength of the compound emulsion film of comparative example 3 correspondence is lower, and mechanical property is obviously poor.Demonstrate the present invention thus when preparing the polyacrylic ester containing terminal hydroxy group, using the acrylate monomer containing non-ionic segments, containing the acrylate monomer of larger steric group and adopting linking agent when preparing urethane, to the performance after improving composite emulsion and film forming, there is positive effect.
Claims (2)
1. the method for making of positively charged ion-non-ion aqueous polyurethane-poly acrylate composite emulsion, it is characterized in that, in synthesis of polyurethane reaction, polyacrylic ester containing terminal hydroxy group is accessed polyurethane molecular chain by contained terminal hydroxy group and becomes the side chain of polyurethane molecular, obtain urethane and the polyacrylic ester composite emulsion by chemical bonds, its side chain containing the polyacrylic ester of terminal hydroxy group has cationic hydrophilic groups, non-ionic segments and larger steric group, and concrete preparation process is as follows:
1. preparation is containing the polyacrylic ester of terminal hydroxy group
By the mixture of whole monomer, chain-transfer agent and initiator, to be evenly added drop-wise in solvent and to carry out radical polymerization formation, concrete operations are as follows:
In reaction vessel, the solvent adding 20 ~ 50wt% is bed material, at 50 ~ 130 DEG C, by the vinyl monomer of 10 ~ 20wt% cation type hydrophilic radical, 14 ~ 35wt% contains the acrylate monomer of non-ionic segments, 6 ~ 25wt% contains the acrylate monomer of larger steric group, other monomers containing vinyl structure of 2 ~ 15wt%, 0.5 ~ 8wt% mixes and the mixture stirred containing sulfydryl dibasic alcohol chain-transfer agent and 0.05 ~ 3wt% initiator, evenly be added drop-wise in the solvent in reaction vessel in 3 ~ 5 hours, drip after terminating at 50 ~ 130 DEG C, be incubated 3 ~ 10 hours obtained polyacrylic ester containing terminal hydroxy group, above-mentioned each raw material dosage sum is 100%, wherein, the vinyl monomer of cation type hydrophilic radical is (methyl) dimethylaminoethyl acrylate, (methyl) acrylate propyl ester, (methyl) vinylformic acid lignocaine ethyl ester, vinylformic acid diethylin propyl ester, methacrylic acid-2-t-butylaminoethyl, (methyl) acrylyl oxy-ethyl-trimethyl salmiac, one or more in (methyl) acryloxyethyldimethyl benzyl ammonium chloride, acrylate monomer containing larger steric group is one or more in (methyl) isobornyl acrylate, (methyl) vinylformic acid methylcyclopentyl ester, (methyl) cyclohexyl acrylate, (methyl) t-butylcyclohexyl base ester, other monomers containing vinyl structure are one or more in (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) butyl acrylate, (methyl) propyl acrylate, ethyl acrylate, (methyl) n-octyl, benzyl acrylate, vinylbenzene, alpha-methyl styrene, be one or more in 3-Mercapto-1，2-propanediol, Isosorbide-5-Nitrae-DTT containing sulfydryl dibasic alcohol chain-transfer agent, initiator is one or more in Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), 2,2'-Azobis(2,4-dimethylvaleronitrile), azo-bis-iso-dimethyl, azo dicyclohexyl formonitrile HCN, hydrogen peroxide, dibenzoyl peroxide, tert-butyl peroxide, solvent is one or more in acetone, butanone, 1-Methyl-2-Pyrrolidone, DMF, 1-Methoxy-2-propyl acetate, acrylate monomer containing non-ionic segments is one or more in methoxy poly (ethylene glycol) list (methyl) acrylate, oxyethyl group polyethyleneglycol (methyl) acrylate, butoxy polyethyleneglycol (methyl) acrylate,
2. positively charged ion-non-ion aqueous polyurethane-poly acrylate composite emulsion is prepared
In reaction vessel, add the polyacrylic ester containing terminal hydroxy group that 10 ~ 30wt% step is 1. obtained, 2 ~ 10wt% general macromolecular polyvalent alcohol and 5 ~ 20wt% isocyanic ester, at 80 ~ 90 DEG C, 2 ~ 3h is reacted after mixing, then 0.2 ~ 4wt% linking agent is added successively, the common chainextender of 0.1 ~ 5wt%, 5 ~ 20wt% solvent, 2 ~ 4h is reacted at 70 ~ 80 DEG C, add 0.005 ~ 0.3wt% catalyzer again, polyurethane prepolymer solution is obtained react 3 ~ 5h at 60 ~ 70 DEG C after, reactant is moved in dispersion machine, under the stirring velocity of 2000 revs/min, add the neutralization of 1 ~ 8wt% neutralizing agent, add after 40 ~ 70wt% deionized water and stirring is uniformly dispersed again, except desolventizing after underpressure distillation, obtain positively charged ion-non-ion aqueous polyurethane-poly acrylate composite emulsion, above-mentioned each raw material dosage sum is 100%.
2. the method for making of composite emulsion according to claim 1, it is characterized in that, 2. step is prepared in the raw material of positively charged ion-non-ion aqueous polyurethane-poly acrylate composite emulsion, and described general macromolecular polyvalent alcohol is one or more in polycaprolactone polyol, polycarbonate polyol, polytetrahydrofuran ethoxylated polyhydric alcohol, polyethylene oxide polyol, polyoxypropylene polyol, hydroxy-terminated polybutadienes polyvalent alcohol, polyester polyol; Described isocyanic ester is isophorone diisocyanate, 1, hexamethylene-diisocyanate, 4, one or more in 4 '-dicyclohexyl methyl hydride-vulcabond, xylylene diisocyanate, tetramethyl-xylylene diisocyanate, tolylene diisocyanate, diphenylmethanediisocyanate, 1,5-naphthalene diisocyanate, poly methylene poly phenyl poly isocyanate; Described linking agent is one or more in TriMethylolPropane(TMP), glycerol, tetramethylolmethane, Dipentaerythritol, Sorbitol Powder; Described common chainextender is one or more in ethylene glycol, glycol ether, BDO, 2,3-butanediol, 1,6-hexylene glycol, neopentyl glycol, hydroxymethyl-cyclohexane; Described solvent is one or more in acetone, butanone, 1-Methyl-2-Pyrrolidone, DMF; Described catalyzer is one or more in triethylamine, triethylene diamine, dibutyl tin laurate, stannous octoate; Described neutralizing agent is one or more in lactic acid, acetic acid, phosphoric acid.
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| CN104725588B (en) * | 2015-02-02 | 2017-09-26 | 雅图高新材料有限公司 | The preparation method of solvent-free the moon/non-ion aqueous polyurethane acrylate graft copolymers with IPN structures |
| CN105255338B (en) * | 2015-10-27 | 2018-10-02 | 宝山钢铁股份有限公司 | Galvanized steel plain sheet with excellent surface wear resistance, corrosion resistance and resistance to acid and alkali and aqueous surface-treating agent |
| CN106753177A (en) * | 2016-12-26 | 2017-05-31 | 天津博苑高新材料有限公司 | The adhesive and preparation method of effectively bonding can be realized to card stock at low temperature |
| CN107459618B (en) * | 2017-08-24 | 2018-06-22 | 广州至然科技应用有限公司 | A kind of preparation method of woodcare paint water-based acrylic resin and the product of acquisition |
| CN108003775A (en) * | 2017-11-30 | 2018-05-08 | 浙江工业大学 | A kind of water-soluble compound resin emulsion and preparation method and application |
| CN109337632B (en) * | 2018-09-11 | 2020-12-15 | 万华化学（宁波）有限公司 | Water-based single-component adhesive and application thereof in automobile interior decoration bonding |
| CN111620984B (en) * | 2020-06-12 | 2022-11-08 | 湖南湘江关西涂料有限公司 | Modified polyurethane resin and preparation method thereof, water-based paint and coating product |
| CN113461868B (en) * | 2021-06-08 | 2023-07-25 | 广州市雅欧森姆皮革原料有限公司 | Polyurethane-fluorine-containing acrylate emulsion and preparation method and application thereof |
| CN117720703A (en) * | 2023-12-22 | 2024-03-19 | 珠海市金团化学品有限公司 | Comb-type polyurethane hyperdispersant and preparation method and application thereof |
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