CN102094331A - Wet type impregnating polyurethane resin and preparation method thereof - Google Patents
Wet type impregnating polyurethane resin and preparation method thereof Download PDFInfo
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- CN102094331A CN102094331A CN 201010610958 CN201010610958A CN102094331A CN 102094331 A CN102094331 A CN 102094331A CN 201010610958 CN201010610958 CN 201010610958 CN 201010610958 A CN201010610958 A CN 201010610958A CN 102094331 A CN102094331 A CN 102094331A
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Abstract
The invention relates to a wet type impregnating polyurethane resin and a preparation method thereof. The wet type impregnating polyurethane resin comprises the following components: 12-18 percent of polyether polyol, 4-7 percent of chain extender, 10-15 percent of isocyanate, 60-70 percent of organic solvent, 0.05-0.1 percent of antioxidant, 0.05-0.1 percent of light-resistant auxiliary agent and 0.05-0.1 percent of chain terminator. The preparation method comprises the following steps of: (1) adding the polyether polyol, the organic solvent, the antioxidant and part of the isocyanate into a reactor according to a prescription and reacting for 90-120 minutes at the temperature of 70-90 DEG C under normal pressure to obtain a prepolymer; (2) adding the chain extender based on prescription dosage into the prepolymer and continuously reacting; (3) putting the rest isocyanate into the reactor in batch, strictly controlling the reaction system temperature to be smaller than 100 DEG C, continuously adding the used organic solvent according to the viscosity condition of a reaction system, controlling the final viscosity to 80-160 Pa.s/25 DEG C and adding a terminator for terminating reaction; and (4) adding the light-resistant auxiliary agent after the reaction process is finished.
Description
Technical field
The present invention relates to a kind of wet type impregnation polyurethane resin and manufacture method thereof.
Background technology
At present, the application of Synthetic Leather on clothing leather, luggage leather, footwear leather is extensive especially, and performance has surpassed corium, because the resource of corium is limited especially, and costs an arm and a leg, can not satisfy current demand.Containing soaking technology and making base cloth reach leather effect of synthetic leather, along with fashion trend constantly changes, more and more higher to the requirement of use for synthetic leather polyurethane resin.Must to select polyethers for use be first-selected to polyurethane resin in order to satisfy anti-hydrolytic performance, with maximum be PolyTHF, but PolyTHF costs an arm and a leg, and is also bad with the adhesion of base cloth, and synthetic resin modulus is generally lower, the test piece tearing strength of making is not high yet, can not satisfy the requirement of high-tear strength, adding the anti tear resin can improve tearing strength limitedly, but costs an arm and a leg, addition is big, and can be influential to the hydrolysis of resin.The common polyester polyol and the adhesion of base cloth are good, the test piece tearing strength height that makes, but do not reach the anti-hydrolytic performance requirement.
Summary of the invention
The objective of the invention is to overcome the problem that opposes between anti-hydrolytic performance, modulus and the tearing strength of existing wet type hydrolysis resistance chemical leather with the polyurethane resin existence, a kind of novel Wet-type polyurethane resin and the preparation method of this material are provided.
Technical solution of the present invention is as follows: a kind of wet type impregnation polyurethane resin is characterized in that: include polyether polyol, chain extender, isocyanates, organic solvent, antioxidant, light resistance auxiliary agent and chain terminating agent, the mass ratio of above-mentioned raw materials is:
Polyether polyol 12-18%;
Isocyanates 10-15%;
Chain extender 4-7%;
Organic solvent 60-70%;
Antioxidant 0.05-0.1%;
Light resistance auxiliary agent 0.05-0.1%;
Chain terminating agent 0.05-0.1%.
The wet type impregnation that makes by above-mentioned prescription has high modulus with polyurethane resin, and anti-hydrolytic performance is excellent especially.
Preparation method's of the present invention technical scheme is: may further comprise the steps successively:
(1), in reactor, add polyether polyol, organic solvent, antioxidant and part isocyanates, in reaction 90-120 minute down of temperature 70-90 ℃ normal pressure, obtain performed polymer by prescription;
(2), in above-mentioned performed polymer, add the chain extender of formula ratio, continue stirring reaction;
(3), remaining isocyanates is dropped into reactor in batches, the temperature of strict control reaction system is less than 100 ℃, viscosity situation according to reaction system constantly increases used organic solvent, and final viscosity is controlled at 80-160Pa.s/25 ℃, adds the terminator cessation reaction;
(4), finishing the back in course of reaction adds the light resistance auxiliary agent, the continuation stirring.
The specific embodiment
Below be specific embodiments of the invention, technical scheme of the present invention is done some explanations, but the invention is not restricted to these embodiment.
Embodiment one
With weight average molecular weight is 2000, degree of functionality is that 2 PolyTHF ethoxylated polyhydric alcohol 18.0kg, weight average molecular weight are 4000, degree of functionality is that 2 PolyTHF ethoxylated polyhydric alcohol 4.5kg, weight average molecular weight are 2000, degree of functionality is 2 polypropylene oxide ethoxylated polyhydric alcohol 8.0kg, antioxidant 0.05kg, N, dinethylformamide 55kg adds in the reactor together, stirs in 55-60 ℃ to mix in 30 minutes; Add 4,4-methyl diphenylene diisocyanate 1.675kg was in 70-80 ℃ of reaction 90 minutes; Add solvent N, dinethylformamide 10kg, 1,4-butanediol and special chain extender A amount to 8.42kg, stirring reaction 30-60 minute; Drop into 4,4-methyl diphenylene diisocyanate 18kg is in 70-90 ℃ of reaction in batches, add solvent N, dinethylformamide dilutes in batches, and final viscosity is controlled at 80-160 Pa.s/25 ℃, add chain terminating agent and light resistance auxiliary agent, back cooling packing stirs.
Embodiment two
With weight average molecular weight is 2000, degree of functionality is that 2 PolyTHF ethoxylated polyhydric alcohol 19.5kg, weight average molecular weight are 2000, degree of functionality is 2 polypropylene oxide ethoxylated polyhydric alcohol 14.0kg, antioxidant 0.05kg, N, dinethylformamide 59kg adds in the reactor together, stirs in 55-60 ℃ to mix in 30 minutes; Add 4,4-methyl diphenylene diisocyanate 1.75kg was in 70-80 ℃ of reaction 90 minutes; Add solvent N, dinethylformamide 10kg, 1,4-butanediol and special chain extender B amount to 8.36kg, stirring reaction 30-60 minute; Drop into 4,4-methyl diphenylene diisocyanate 19kg is in 70-90 ℃ of reaction in batches, add solvent N, dinethylformamide dilutes in batches, and final viscosity is controlled at 80-160 Pa.s/25 ℃, add chain terminating agent and light resistance auxiliary agent, back cooling packing stirs.
Embodiment three
With weight average molecular weight is 2000, degree of functionality is that 2 PolyTHF ethoxylated polyhydric alcohol 19.5kg, weight average molecular weight are 2000, degree of functionality is 2 polypropylene oxide ethoxylated polyhydric alcohol 14.0kg, antioxidant 0.05kg, N, dinethylformamide 57kg adds in the reactor together, stirs in 55-60 ℃ to mix in 30 minutes; Add 4,4-methyl diphenylene diisocyanate 1.75kg was in 70-80 ℃ of reaction 90 minutes; Add solvent N, dinethylformamide 10kg, 1,4-butanediol 6.75kg, stirring reaction 30-60 minute; Drop into 4,4-methyl diphenylene diisocyanate 19.5kg is in 70-90 ℃ of reaction in batches, add solvent N, dinethylformamide dilutes in batches, and final viscosity is controlled at 80-160 Pa.s/25 ℃, add chain terminating agent and light resistance auxiliary agent, back cooling packing stirs.
Embodiment four
With weight average molecular weight is 2000, degree of functionality is that 2 PolyTHF ethoxylated polyhydric alcohol 18.0kg, weight average molecular weight are 4000, degree of functionality is that 2 oxolane-propylene oxide polyol 4.5kg, weight average molecular weight are 2000, degree of functionality is 2 polypropylene oxide ethoxylated polyhydric alcohol 8.0kg, weight average molecular weight is 1000, degree of functionality is 3 extraordinary polyether polyol 0.3kg, antioxidant 0.05kg, N, dinethylformamide 55kg adds in the reactor together, stirs in 55-60 ℃ to mix in 30 minutes; Add 4,4-methyl diphenylene diisocyanate 1.675kg was in 70-80 ℃ of reaction 90 minutes; Add solvent N, dinethylformamide 10kg, 1,4-butanediol and special chain extender B8.36kg, stirring reaction 30-60 minute; Drop into 4,4-methyl diphenylene diisocyanate 16kg is in 70-90 ℃ of reaction in batches, add solvent N, dinethylformamide dilutes in batches, and final viscosity is controlled at 80-160 Pa.s/25 ℃, add chain terminating agent and light resistance auxiliary agent, back cooling packing stirs.
We carry out performance comparison by the above embodiments: draw following contrast table:
The invention solves high-modulus as can be known from the above table and contain the low problem of resin pickup tearing strength, by selecting for use multiple polyether polyol and chain extender to be used, improved modulus, the tearing strength of resin, hydrolytic resistance is also better, solves market technical bottleneck in this regard.
Claims (6)
1. wet type impregnation polyurethane resin, it is characterized in that: include polyether polyol, chain extender, isocyanates, organic solvent, antioxidant, light resistance auxiliary agent and chain terminating agent, the mass ratio of above-mentioned raw materials is:
Polyether polyol 12-18%;
Isocyanates 10-15%;
Chain extender 4-7%;
Organic solvent 60-70%;
Antioxidant 0.05-0.1%;
Light resistance auxiliary agent 0.05-0.1%;
Chain terminating agent 0.05-0.1%.
2. a kind of wet type impregnation polyurethane resin according to claim 1, it is characterized in that: described polyether polyol includes that weight average molecular weight is 1000 ~ 10000, degree of functionality is the PolyTHF ethoxylated polyhydric alcohol of 2-4, weight average molecular weight is 1000 ~ 10000, degree of functionality is the polypropylene oxide ethoxylated polyhydric alcohol of 2-4, weight average molecular weight is 1000 ~ 10000, degree of functionality is oxolane-propylene oxide polyol of 2-4, one or more mixing in the extraordinary polyether polyol that weight average molecular weight is 1000 ~ 10000, degree of functionality is 2-4; Described isocyanates is 4,4-methyl diphenylene diisocyanate, 4, the mixing of one or more in 4-dicyclohexyl methyl hydride diisocyanate, the isophorone diisocyanate; Described chain extender is the dihydroxylic alcohols chain extender of 62-200g/mol, it is an ethylene glycol, 1,2-propylene glycol, 1, ammediol, 1,4-butanediol, diglycol, dipropylene glycol, neopentyl glycol, methyl propanediol ethylene glycol, 1,6-hexylene glycol 1,4 cyclohexane dimethanol, one or more kinds of the mixing in quinhydrones-two (beta-hydroxyethyl) ether.
3. a kind of wet type impregnation polyurethane resin according to claim 1 and 2, it is characterized in that: described organic solvent is N, dinethylformamide.
4. a kind of wet type impregnation polyurethane resin according to claim 1 and 2, it is characterized in that: described antioxidant is 2,6-di-tert-butyl-4-methy phenol, antioxidant 1010, the mixing of one or more in the phosphite ester; Described light resistance auxiliary agent is the one or more kinds of mixing in benzotriazole, salicylate class and the benzophenone compound; Described chain terminating agent is a methyl alcohol.
5. a kind of wet type impregnation polyurethane resin according to claim 3, it is characterized in that: described antioxidant is 2,6-di-tert-butyl-4-methy phenol, antioxidant 1010, the mixing of one or more in the phosphite ester; Described light resistance auxiliary agent is the one or more kinds of mixing in benzotriazole, salicylate class and the benzophenone compound; Described chain terminating agent is a methyl alcohol.
6. according to the preparation method of the wet type impregnation in the claim 1, it is characterized in that: may further comprise the steps successively with polyurethane resin:
(1), in reactor, add polyether polyol, organic solvent, antioxidant and part isocyanates, in reaction 90-120 minute down of temperature 70-90 ℃ normal pressure, obtain performed polymer by prescription;
(2), in above-mentioned performed polymer, add the chain extender of formula ratio, continue stirring reaction;
(3), remaining isocyanates is dropped into reactor in batches, the temperature of strict control reaction system is less than 100 ℃, viscosity situation according to reaction system constantly increases used organic solvent, and final viscosity is controlled at 80-160Pa.s/25 ℃, adds the terminator cessation reaction;
(4), finishing the back in course of reaction adds the light resistance auxiliary agent, the continuation stirring.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2010106109584A CN102094331B (en) | 2010-12-29 | 2010-12-29 | Wet type impregnating polyurethane resin and preparation method thereof |
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| CN2010106109584A CN102094331B (en) | 2010-12-29 | 2010-12-29 | Wet type impregnating polyurethane resin and preparation method thereof |
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| CN102094331B CN102094331B (en) | 2012-06-27 |
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Cited By (3)
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| CN104987489A (en) * | 2015-07-14 | 2015-10-21 | 福建国邦树脂有限公司 | Highly-wear-resistant, low-temperature-resistant, folding-resistant, hydrolysis-resistant polyurethane surfacing resin |
| CN105968288A (en) * | 2016-06-02 | 2016-09-28 | 台州禾欣高分子新材料有限公司 | High-modulus high-resilience polyurethane resin and preparation method and application thereof |
| CN107938376A (en) * | 2017-12-26 | 2018-04-20 | 泉州静杰企业管理咨询有限公司 | A kind of production method for frivolous synthetic leather of breathing freely |
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| CN101503595A (en) * | 2008-12-01 | 2009-08-12 | 无锡双象化学工业有限公司 | Yellowing-resistant solvent type polyurethane leather coating agent and preparation thereof |
| CN101857721A (en) * | 2010-06-30 | 2010-10-13 | 合肥安利聚氨酯新材料有限公司 | Cold-resistant, solvent-resistant and yellowing-resistant polyurethane resin and preparation method thereof |
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| US4242463A (en) * | 1979-12-19 | 1980-12-30 | Sheller-Globe Corporation | Color stable integral skin foam |
| US20070129524A1 (en) * | 2005-12-06 | 2007-06-07 | Sunkara Hari B | Thermoplastic polyurethanes comprising polytrimethylene ether soft segments |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104987489A (en) * | 2015-07-14 | 2015-10-21 | 福建国邦树脂有限公司 | Highly-wear-resistant, low-temperature-resistant, folding-resistant, hydrolysis-resistant polyurethane surfacing resin |
| CN105968288A (en) * | 2016-06-02 | 2016-09-28 | 台州禾欣高分子新材料有限公司 | High-modulus high-resilience polyurethane resin and preparation method and application thereof |
| CN107938376A (en) * | 2017-12-26 | 2018-04-20 | 泉州静杰企业管理咨询有限公司 | A kind of production method for frivolous synthetic leather of breathing freely |
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| CN102094331B (en) | 2012-06-27 |
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