CN105237727A - Highly-waterproof water-soluble polyurethane resin and preparation method thereof - Google Patents
Highly-waterproof water-soluble polyurethane resin and preparation method thereof Download PDFInfo
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- CN105237727A CN105237727A CN201510595465.0A CN201510595465A CN105237727A CN 105237727 A CN105237727 A CN 105237727A CN 201510595465 A CN201510595465 A CN 201510595465A CN 105237727 A CN105237727 A CN 105237727A
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/281—Monocarboxylic acid compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3271—Hydroxyamines
- C08G18/3275—Hydroxyamines containing two hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4202—Two or more polyesters of different physical or chemical nature
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
- C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
- C08G18/423—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing cycloaliphatic groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/54—Polycondensates of aldehydes
- C08G18/544—Polycondensates of aldehydes with nitrogen compounds
Abstract
The invention discloses a preparation method of highly-waterproof water-soluble polyurethane resin. The method comprises the following steps: heating terephthalic anhydride polyester diol and poly(1,4-cyclohexanedimethanol adipate) diol for melting, carrying out heat insulation, and carrying out vacuum dehydration to obtain a material a; adding tetramethyl phenyldimethylene diisocyanate to the material a, heating, carrying out heat insulation, cooling, adding 1,5-pentanediol, melamine-formaldehyde resin and N-methyl pyrrolidone, adding cobalt octoate, heating, and carrying out heat insulation to obtain a material b; cooling the material b, adding a N-propyldiethanolamine and bis(2-hydroxyethyl)aniline mixed solution in a dropwise manner, heating, and carrying out heat insulation to obtain a material c; and adding propionic acid to the material c to neutralize, and carrying out vacuum distillation to obtain the highly-waterproof water-soluble polyurethane resin. The invention also discloses the highly-waterproof water-soluble polyurethane resin. The highly-waterproof water-soluble polyurethane resin has excellent waterproof property and hardness, and the method is stable and is easy to control.
Description
Technical field
The present invention relates to water soluble polyurethane resin technical field, particularly relate to a kind of enhanced water resistance water soluble polyurethane resin and preparation method thereof.
Background technology
Urethane as a kind of macromolecular material with high strength, anti tear, the characteristic such as wear-resisting, in field widespread uses such as daily life, industrial and agricultural production, medical science.Traditional urethane is generally solvent-borne type, and the discharge of its volatile organic compounds is large, and environmental pollution is comparatively serious.Along with the increasingly stringent of environmental regulation and the enhancing gradually of people's environmental consciousness, aqueous polyurethane replaces the emphasis that solvent borne product has become people's research.Aqueous polyurethane has excellent physical and mechanical properties, containing or containing a small amount of volatilizable organism, production and construction safety, to environment and human body substantially harmless, meet environmental requirement.
The preparation method generally used now is internal emulsification method, namely on polyurethane molecular chain, introduce some hydrophilic radicals, make polyurethane molecular have certain wetting ability, then under high speed dispersion, make it spontaneously be scattered in water by means of these hydrophilic radicals, thus obtain aqueous polyurethane.But hydrophilic radical be introduced in the water tolerance improving and but to reduce it while polyurethane hydrophilic.
Summary of the invention
Based on the technical problem that background technology exists, the present invention proposes a kind of enhanced water resistance water soluble polyurethane resin and preparation method thereof, there is excellent water resistance and hardness, and method process stabilizing, reaction is easy to control, and production risk is little.
A kind of enhanced water resistance water soluble polyurethane resin preparation method that the present invention proposes, comprises the following steps:
S1, by terephthalic anhydride polyester diol and poly-hexanodioic acid-1,4 cyclohexane dimethanol esterdiol intensification melting, insulation, then vacuum hydro-extraction obtains material a;
S2, add in material a by tetramethylxylylene diisocyanate, heat up, insulation, adds 1,5-PD, melamine formaldehyde resin and N-Methyl pyrrolidone, then adds cobalt octoate after cooling, heats up, and insulation, obtains material b;
S3, material b is lowered the temperature after, then drip the mixing solutions containing N-propyl group diethanolamine and two (2-hydroxyethyl) aniline, heat up, insulation obtains material c;
S4, drip after propionic acid neutralizes in material c, vacuum distilling obtains enhanced water resistance water soluble polyurethane resin.
Preferably, in S1, terephthalic anhydride polyester diol and poly-hexanodioic acid-1,4 cyclohexane dimethanol esterdiol are warming up to 130 ~ 160 DEG C, insulation 3 ~ 4.5h, then vacuum hydro-extraction obtains material a.
Preferably, in S2, tetramethylxylylene diisocyanate is added in material a, be warming up to 90 ~ 100 DEG C, insulation 2 ~ 3h, 1 is added after being cooled to 45 ~ 55 DEG C, 5-pentanediol, melamine formaldehyde resin and N-Methyl pyrrolidone, then add cobalt octoate, be warming up to 87 ~ 90 DEG C, insulation 2.5 ~ 3.2h, obtains material b.
Preferably, in S3, after material b is cooled to 40 ~ 45 DEG C, then drip the mixing solutions containing N-propyl group diethanolamine and two (2-hydroxyethyl) aniline, time for adding is 4 ~ 8h, is warming up to 82 ~ 85 DEG C, and insulation 1.5 ~ 3h obtains material c.
Preferably, the weight ratio of terephthalic anhydride polyester diol and poly-hexanodioic acid-1,4 cyclohexane dimethanol esterdiol is 30 ~ 33:13 ~ 16.
Preferably, the weight ratio of terephthalic anhydride polyester diol and tetramethylxylylene diisocyanate, 1,5-PD, melamine formaldehyde resin, cobalt octoate, N-Methyl pyrrolidone is 30 ~ 33:25 ~ 28:4 ~ 6:2 ~ 3:0.1 ~ 0.2:25 ~ 28.
Preferably, in S3, mixing solutions by N-propyl group diethanolamine, two (2-hydroxyethyl) aniline, N-Methyl pyrrolidone be that 2 ~ 3:5 ~ 8:15 ~ 20 are mixed to get by weight.
Preferably, the weight ratio of cobalt octoate and N-propyl group diethanolamine is 0.1 ~ 0.2:2 ~ 3.
Preferably, the weight ratio of two (2-hydroxyethyl) aniline, propionic acid and water is 5 ~ 8:3 ~ 6:285 ~ 300.
A kind of enhanced water resistance water soluble polyurethane resin that the present invention also proposes, adopts above-mentioned enhanced water resistance water soluble polyurethane resin preparation method to obtain.
Because the water-borne polyurethane bond film hardness of terephthalic anhydride polyester diol synthesis under equal conditions is higher, the present invention adopts the terephthalic anhydride polyester diol of high rigidity to be soft section, zwitterion mixing hydrophilic chain extender, it is high that the mode that segmentation is progressively polymerized has synthesized hardness, strong adhesion, closure is good, and impervious oil and anti-pigment ooze out superior performance, the waterborne polyurethane resin of water-tolerant.
In addition in order to overcome the defect of easily sudden and violent coagel in cation aqueous polyurethane production process, the present invention creatively adopts positively charged ion coupling and two kinds of cationic hydrophilics to expand the method joining agent coupling and controls speed of response, and improves emulsion intercalation method and solid content.
Compared with prior art, the present invention has the following advantages:
1) hardness of the present invention is high, strong adhesion, and closure is good, and impervious oil and anti-pigment ooze out superior performance, water-tolerant;
2) wettability of the present invention is good, does not need additionally to add wetting agent, prevents wetting agent on the impact of oil impregnate;
3) film forming speed of the present invention is fast, and paint film is transparent, and pencil hardness reaches H ~ 2H, and water-fast 48h is without exception, and sticking power is 0 grade;
4) perviousness of the present invention is strong, and impervious oiliness is good, coating surface and other resin compatibles good;
5) preparation method's process stabilizing of the present invention, reaction is easy to control, and production risk is little.
Accompanying drawing explanation
Fig. 1 is the schematic flow sheet of a kind of enhanced water resistance water soluble polyurethane resin preparation method that the present invention proposes.
Embodiment
As shown in Figure 1, Fig. 1 is the schematic flow sheet of a kind of enhanced water resistance water soluble polyurethane resin preparation method that the present invention proposes.
With reference to Fig. 1, a kind of enhanced water resistance water soluble polyurethane resin preparation method that the present invention proposes, comprises the following steps:
S1, by terephthalic anhydride polyester diol and poly-hexanodioic acid-1,4 cyclohexane dimethanol esterdiol intensification melting, insulation, then vacuum hydro-extraction obtains material a;
S2, add in material a by tetramethylxylylene diisocyanate, heat up, insulation, adds 1,5-PD, melamine formaldehyde resin and N-Methyl pyrrolidone, then adds cobalt octoate after cooling, heats up, and insulation, obtains material b;
S3, material b is lowered the temperature after, then drip the mixing solutions containing N-propyl group diethanolamine and two (2-hydroxyethyl) aniline, heat up, insulation obtains material c;
S4, drip after propionic acid neutralizes in material c, vacuum distilling obtains enhanced water resistance water soluble polyurethane resin.
Below, by specific embodiment, technical scheme of the present invention is described in detail.
Embodiment 1
A kind of enhanced water resistance water soluble polyurethane resin preparation method that the present invention proposes, comprises the following steps:
S1, by weight 30 parts of terephthalic anhydride polyester diol and 16 parts of poly-hexanodioic acid-1,4 cyclohexane dimethanol esterdiols are warming up to 130 DEG C, insulation 4.5h, then vacuum hydro-extraction obtains material a;
S2,25 parts of tetramethylxylylene diisocyanate are added in material a, be warming up to 100 DEG C, insulation 2h, 4 part 1 is added after being cooled to 55 DEG C, 5-pentanediol, 3 parts of melamine formaldehyde resins and 25 parts of N-Methyl pyrrolidone, then add 0.2 part of cobalt octoate, be warming up to 87 DEG C, insulation 3.2h, obtains material b;
S3, material b is cooled to 40 DEG C after, drip the mixing solutions containing N-propyl group diethanolamine and two (2-hydroxyethyl) aniline again, wherein mixing solutions is mixed to get by 3 parts of N-propyl group diethanolamine, 5 parts of two (2-hydroxyethyl) aniline, 20 parts of N-Methyl pyrrolidone, time for adding is 4h, be warming up to 85 DEG C, insulation 1.5h obtains material c;
S4, drip after 6 parts of propionic acid neutralize in material c, vacuum distilling obtains enhanced water resistance water soluble polyurethane resin.
Embodiment 2
A kind of enhanced water resistance water soluble polyurethane resin preparation method that the present invention proposes, comprises the following steps:
S1, by weight 33 parts of terephthalic anhydride polyester diol and 13 parts of poly-hexanodioic acid-1,4 cyclohexane dimethanol esterdiols are warming up to 160 DEG C, insulation 3h, then vacuum hydro-extraction obtains material a;
S2,28 parts of tetramethylxylylene diisocyanate are added in material a, be warming up to 90 DEG C, insulation 3h, 6 part 1 is added after being cooled to 45 DEG C, 5-pentanediol, 2 parts of melamine formaldehyde resins and 28 parts of N-Methyl pyrrolidone, then add 0.1 part of cobalt octoate, be warming up to 90 DEG C, insulation 2.5h, obtains material b;
S3, material b is cooled to 45 DEG C after, drip the mixing solutions containing N-propyl group diethanolamine and two (2-hydroxyethyl) aniline again, wherein mixing solutions is mixed to get by 2 parts of N-propyl group diethanolamine, 8 parts of two (2-hydroxyethyl) aniline, 15 parts of N-Methyl pyrrolidone, time for adding is 8h, be warming up to 82 DEG C, insulation 3h obtains material c;
S4, drip after 3 parts of propionic acid neutralize in material c, vacuum distilling obtains enhanced water resistance water soluble polyurethane resin.
Embodiment 3
A kind of enhanced water resistance water soluble polyurethane resin preparation method that the present invention proposes, comprises the following steps:
S1, by weight 31 parts of terephthalic anhydride polyester diol and 15 parts of poly-hexanodioic acid-1,4 cyclohexane dimethanol esterdiols are warming up to 140 DEG C, insulation 4h, then vacuum hydro-extraction obtains material a;
S2,26 parts of tetramethylxylylene diisocyanate are added in material a, be warming up to 95 DEG C, insulation 2.3h, 4.5 part 1 is added after being cooled to 52 DEG C, 5-pentanediol, 2.8 parts of melamine formaldehyde resins and 26 parts of N-Methyl pyrrolidone, then add 0.18 part of cobalt octoate, be warming up to 88 DEG C, insulation 3h, obtains material b;
S3, material b is cooled to 42 DEG C after, drip the mixing solutions containing N-propyl group diethanolamine and two (2-hydroxyethyl) aniline again, wherein mixing solutions is mixed to get by 2.8 parts of N-propyl group diethanolamine, 6 parts of two (2-hydroxyethyl) aniline, 18 parts of N-Methyl pyrrolidone, time for adding is 6h, be warming up to 84 DEG C, insulation 2h obtains material c;
S4, drip after 5 parts of propionic acid neutralize in material c, vacuum distilling obtains enhanced water resistance water soluble polyurethane resin.
Embodiment 4
A kind of enhanced water resistance water soluble polyurethane resin preparation method that the present invention proposes, comprises the following steps:
S1, by weight 32 parts of terephthalic anhydride polyester diol and 14 parts of poly-hexanodioic acid-1,4 cyclohexane dimethanol esterdiols are warming up to 150 DEG C, insulation 3.5h, then vacuum hydro-extraction obtains material a;
S2,27 parts of tetramethylxylylene diisocyanate are added in material a, be warming up to 92 DEG C, insulation 2.6h, 5.5 part 1 is added after being cooled to 48 DEG C, 5-pentanediol, 2.5 parts of melamine formaldehyde resins and 27 parts of N-Methyl pyrrolidone, then add 0.12 part of cobalt octoate, be warming up to 89 DEG C, insulation 2.8h, obtains material b;
S3, material b is cooled to 43 DEG C after, drip the mixing solutions containing N-propyl group diethanolamine and two (2-hydroxyethyl) aniline again, wherein mixing solutions is mixed to get by 2.3 parts of N-propyl group diethanolamine, 7 parts of two (2-hydroxyethyl) aniline, 16 parts of N-Methyl pyrrolidone, time for adding is 7h, be warming up to 83 DEG C, insulation 2.5h obtains material c;
S4, drip after 4 parts of propionic acid neutralize in material c, vacuum distilling obtains enhanced water resistance water soluble polyurethane resin.
The above; be only the present invention's preferably embodiment; but protection scope of the present invention is not limited thereto; anyly be familiar with those skilled in the art in the technical scope that the present invention discloses; be equal to according to technical scheme of the present invention and inventive concept thereof and replace or change, all should be encompassed within protection scope of the present invention.
Claims (10)
1. an enhanced water resistance water soluble polyurethane resin preparation method, is characterized in that, comprises the following steps:
S1, by terephthalic anhydride polyester diol and poly-hexanodioic acid-1,4 cyclohexane dimethanol esterdiol intensification melting, insulation, then vacuum hydro-extraction obtains material a;
S2, add in material a by tetramethylxylylene diisocyanate, heat up, insulation, adds 1,5-PD, melamine formaldehyde resin and N-Methyl pyrrolidone, then adds cobalt octoate after cooling, heats up, and insulation, obtains material b;
S3, material b is lowered the temperature after, then drip the mixing solutions containing N-propyl group diethanolamine and two (2-hydroxyethyl) aniline, heat up, insulation obtains material c;
S4, drip after propionic acid neutralizes in material c, vacuum distilling obtains enhanced water resistance water soluble polyurethane resin.
2. enhanced water resistance water soluble polyurethane resin preparation method according to claim 1, is characterized in that, in S1, by terephthalic anhydride polyester diol and poly-hexanodioic acid-1,4-cyclohexanedimethanoester ester glycol is warming up to 130 ~ 160 DEG C, and insulation 3 ~ 4.5h, then vacuum hydro-extraction obtains material a.
3. enhanced water resistance water soluble polyurethane resin preparation method according to claim 1 or 2, it is characterized in that, in S2, tetramethylxylylene diisocyanate is added in material a, be warming up to 90 ~ 100 DEG C, insulation 2 ~ 3h, adds 1,5-PD, melamine formaldehyde resin and N-Methyl pyrrolidone after being cooled to 45 ~ 55 DEG C, add cobalt octoate again, be warming up to 87 ~ 90 DEG C, insulation 2.5 ~ 3.2h, obtains material b.
4. enhanced water resistance water soluble polyurethane resin preparation method according to any one of claim 1-3, it is characterized in that, in S3, after material b is cooled to 40 ~ 45 DEG C, drip the mixing solutions containing N-propyl group diethanolamine and two (2-hydroxyethyl) aniline again, time for adding is 4 ~ 8h, is warming up to 82 ~ 85 DEG C, and insulation 1.5 ~ 3h obtains material c.
5. enhanced water resistance water soluble polyurethane resin preparation method according to any one of claim 1-4, is characterized in that, the weight ratio of terephthalic anhydride polyester diol and poly-hexanodioic acid-1,4 cyclohexane dimethanol esterdiol is 30 ~ 33:13 ~ 16.
6. enhanced water resistance water soluble polyurethane resin preparation method according to any one of claim 1-5, it is characterized in that, the weight ratio of terephthalic anhydride polyester diol and tetramethylxylylene diisocyanate, 1,5-PD, melamine formaldehyde resin, cobalt octoate, N-Methyl pyrrolidone is 30 ~ 33:25 ~ 28:4 ~ 6:2 ~ 3:0.1 ~ 0.2:25 ~ 28.
7. enhanced water resistance water soluble polyurethane resin preparation method according to any one of claim 1-6, it is characterized in that, in S3, mixing solutions by N-propyl group diethanolamine, two (2-hydroxyethyl) aniline, N-Methyl pyrrolidone be that 2 ~ 3:5 ~ 8:15 ~ 20 are mixed to get by weight.
8. according to any one of claim 1-7 item described enhanced water resistance water soluble polyurethane resin preparation method, it is characterized in that, the weight ratio of cobalt octoate and N-propyl group diethanolamine is 0.1 ~ 0.2:2 ~ 3.
9. enhanced water resistance water soluble polyurethane resin preparation method according to any one of claim 1-8, is characterized in that, the weight ratio of two (2-hydroxyethyl) aniline, propionic acid and water is 5 ~ 8:3 ~ 6:285 ~ 300.
10. an enhanced water resistance water soluble polyurethane resin, is characterized in that, adopts enhanced water resistance water soluble polyurethane resin preparation method described in any one of claim 1-9 to obtain.
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| CN101235248A (en) * | 2008-03-12 | 2008-08-06 | 北京瑞京乳胶制品有限公司 | Latex glove with inner coat and pockmark surface |
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