CN103467690B - A kind of impregnation Wet-type polyurethane resin and preparation method thereof with high-tear strength, hydrolysis - Google Patents
A kind of impregnation Wet-type polyurethane resin and preparation method thereof with high-tear strength, hydrolysis Download PDFInfo
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- CN103467690B CN103467690B CN201310430237.9A CN201310430237A CN103467690B CN 103467690 B CN103467690 B CN 103467690B CN 201310430237 A CN201310430237 A CN 201310430237A CN 103467690 B CN103467690 B CN 103467690B
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Abstract
The invention discloses a kind of impregnation Wet-type polyurethane resin and preparation method thereof with high-tear strength, hydrolysis, the raw material of this urethane resin is configured to by mass fraction: isocyanic ester 6-10 part, polyol compound 16-26 part, glycol chain extender 1-3 part, oxidation inhibitor 0-0.3 part, reaction terminating agent methyl alcohol 0-0.05 part, organic tin or organo-bismuth class catalyzer, addition is the 0.001-0.05% of polyol amount.Urethane resin of the present invention has improved more greatly the physical property of the stripping strength of resin, tear strength and hydrolysis aspect, and product is durable in use, has the market competitiveness.
Description
One, technical field
The present invention relates to a kind of functional urethane resin and preparation method thereof, specifically a kind of impregnation Wet-type polyurethane resin and preparation method thereof with high-tear strength, hydrolysis.
Two, background technology
Synthetic Leather is by making the fabricbase back side have material to have skin emulation effect containing soaking technology, and class high-quality is good.Containing resin pickup general requirement excellent hydrolysis resistance, impregnation soon, film-forming properties is suitable for the infiltration being conducive to coating material simultaneously, and strengthen the combination of coating material and fabricbase, finished leather has higher tear strength.Existing hydrolysis containing resin pickup, selects polytetrahydrofuran dibasic alcohol usually, but because of its cost higher, modulus slightly Gao Shiyi occurs that tear strength declines fast, in recent years occur the dibasic alcohol of poly(propylene oxide) and polytetrahydrofuran copolymerization, tear and increase, but finished leather stripping strength is unstable.
Chinese invention patent application 201010145366.X discloses a kind of wet-method synthetic leather polyester high-hydrolysis resistance and high-peeling strength polyurethane resin and preparation method thereof, urethane synthesis phase is raw materials used is conventional polyester type polyvalent alcohol, do not have an anti-hydrolytic performance of excellence, and chainextender preferably 1,4-butyleneglycol, Diethylene Glycol, know in industry that to make by Diethylene Glycol the urethane resin hydrolysis that chainextender synthesizes general all poor altogether.The anti-hydrolytic performance of this invention is realized by the hydrolysis auxiliary agent of 0.1% (fluorine surface-modifying agent) completely, the feature of environmental protection of fluorine surface-modifying agent causes people to pay close attention to (relevant report see Perfluorocaprylic Acid and derivative thereof) day by day in recent years, and therefore developing the urethane resin that resin itself has an anti-hydrolytic performance is industry development trend.This invention is not stated tear strength, but the resin of its whole polyester type polyvalent alcohol synthesis should not have advantage in tear strength.
Chinese invention patent application 201010610958.4 discloses a kind of wet type impregnating polyurethane resin and preparation method thereof, wet type impregnating high modulus polyurethane resin is by selecting multiple polyether glycol and chainextender with the use of (not adding hydrolysis auxiliary agent), make that the modulus of resin is high, tear strength is high, hydrolytic resistance, the reaction later stage adds photostabilization auxiliary agent to improve color inhibition.This invention overcomes the anti-hydrolytic performance that existing wet type hydrolysis resistance chemical leather urethane resin exists, the problem opposed between modulus and tear strength.This invention polyvalent alcohol is the polyether glycol that hydrophobicity is strong, is unfavorable for the infiltration of coating material and condenses shaping in leather making process, and high expensive.
Chinese invention patent application 200910116140.4 discloses a kind of wet type impregnated polyurethane resin for high hydrolysis resistance synthetic leather and manufacture method thereof, by adopting polytetrahydrofuran material to meet the anti-hydrolytic performance of urethane resin, the polyester diol material simultaneously selecting polarity stronger improves the polarity of resin, to improve the binding strength with fabricbase, strengthen its impregnation amount to fabricbase, with the addition of fluorine surface-modifying agent at the end of reaction in addition.The raising of this invention to tear strength is not paid close attention to, and has selected organic fluorine simultaneously, has not possessed the feature of environmental protection.
Three, summary of the invention
The present invention aims to provide a kind of impregnation Wet-type polyurethane resin and preparation method thereof with high-tear strength, hydrolysis, and technical problem to be solved improves the stripping strength of Synthetic Leather, tear strength and anti-hydrolytic performance.In addition, urethane resin of the present invention does not add fluorine surface-modifying agent, and the feature of environmental protection is better.
Technical solution problem of the present invention adopts following technical scheme:
The present invention has the impregnation Wet-type polyurethane resin of high-tear strength, hydrolysis, and its raw material and proportioning are:
Organic tin or organo-bismuth class catalyzer, addition is the 0.001-0.05% of polyol amount.
Described isocyanic ester is 4,4 '-diphenylmethanediisocyanate (MDI);
Described polyol compound is made up of polyester polyol and polyether glycol, and wherein the mass ratio of polyester polyol and polyether glycol is 1:1.5-1.7; The number-average molecular weight of described polyol compound is 1000-3000, preferably 2000;
Described glycol chain extender is ethylene glycol and/or BDO.
Described polyester polyol is hexanodioic acid system polyester polyol;
Described polyether glycol is polytetrahydrofuran polyol, polyoxypropylene polyol and polyoxyethylated polyols; Wherein the quality of polytetrahydrofuran polyol, polyoxypropylene polyol and polyoxyethylated polyols is 1-2:2:1.5.
The functionality of described polyester polyol is 2; The functionality of described polyether glycol is 2.
In described isocyanic ester, the molar weight of isocyano is 0.9-1:1 with the ratio of the hydroxyl integral molar quantity in described polyol compound and described glycol chain extender.
The mol ratio of described polyol compound and described glycol chain extender is 1:1.7-2.1.
The present invention has the preparation method of impregnation Wet-type polyurethane resin of high-tear strength, hydrolysis, operates according to the following steps:
1) polyol compound and oxidation inhibitor are added in organic solvent, control solid content at 45-55%, after stirring, add the isocyanic ester of organic tin or organo-bismuth class catalyzer and 30-40%, in 75-85 DEG C of reaction 1-3 hour, obtain prepolymer; The solid content of described prepolymer controls at 45-60%, and viscosity controller is at 50000-10000cps/75 DEG C.
2) isocyanic ester of glycol chain extender and surplus is added in the prepolymer prepared to step 1), after stirring, reaction 2-5h is continued in 75-85 DEG C, in the process of reaction, make final viscosity control at 40000-80000cps/25 DEG C along with the increase of system viscosity constantly supplements organic solvent, after having reacted, add reaction terminating agent methyl alcohol.
Described organic solvent preferred N, N '-dimethyl formamide (DMF).
Be applied to synthetic leather by the impregnation Wet-type polyurethane resin that above-mentioned formula is obtained to produce, the leather goods made have excellent stripping strength, tear strength and anti-hydrolytic performance.
Urethane resin of the present invention has improved more greatly the physical property of the stripping strength of resin, tear strength and hydrolysis aspect, and product is durable in use, and product specification is high, has the market competitiveness.
Four, embodiment
Below in conjunction with specific embodiment, explanation is further explained to the present invention.
SP-1, SP-2 are respectively the polyester polyol that homemade molecular weight is 1000,2000, raw materials used and formula is hexanodioic acid 8000kg, ethylene glycol 2500kg, 1,4-butyleneglycol or Diethylene Glycol 2000kg, preparation method is see urethane resin and application thereof, Chemical Industry Press (2011.11), the production method of Liu Yijun, P62 polyester polyol and Material calculation;
EG is ethylene glycol;
BG is BDO;
PPG-1, PPG-2 are respectively the Polyoxypropylene diol that molecular weight is 1000,2000;
PTMG-1, PTMG-2 are respectively the polytetrahydrofuran dibasic alcohol that molecular weight is 1000,2000;
PEG-1, PEG-2 are respectively the polyoxyethylene glycol that molecular weight is 1000,2000;
PCL-1, PCL-2 are respectively the polycaprolactone diols that molecular weight is 1000,2000;
I-1010 is commercially available oxidation inhibitor, entirely four [β-(3,5-di-t-butyl-4 hydroxy phenyl) propionic acid] pentaerythritol ester by name;
MDI is 4,4 '-diphenylmethanediisocyanate;
Organo-bismuth is catalysts, and wherein the feature of environmental protection of organo-bismuth is better than organotin is know altogether in industry;
DMF is solvent N, N '-dimethyl formamide, and methyl alcohol is reaction terminating agent.
Embodiment 1:
1, raw material and proportioning:
2, preparation method:
1) polyol compound PCL-2, PTMEG-2, PPG-2 and PEG-2 and oxidation inhibitor I-1010 are added in solvent DMF, add the leading chemical company of MDI and the organo-bismuth class catalyst B iCAT8106(U.S. after stirring to produce), in 75-85 DEG C of reaction 1-3 hour, obtain the prepolymer of solid content 55%;
2) MDI of glycol chain extender EG and BG and surplus is added in the prepolymer prepared to step 1), after stirring, reaction 2-5h is continued in 75-85 DEG C, in the process of reaction, make final viscosity control at 40000-80000cps/25 DEG C along with the increase of system viscosity constantly supplements organic solvent, after having reacted, add reaction terminating agent methyl alcohol 0.5-2kg.
Embodiment 2:
1, raw material and proportioning:
2, preparation method:
1) polyol compound SP-1, PTMEG-2, PPG-2 and PEG-2 and oxidation inhibitor I-1010 are added in solvent DMF, add the leading chemical company of MDI and the organo-bismuth class catalyst B iCAT8106(U.S. after stirring to produce), in 75-85 DEG C of reaction 1-3 hour, obtain the prepolymer of solid content 55%;
2) MDI of glycol chain extender EG and BG and surplus is added in the prepolymer prepared to step 1), after stirring, reaction 2-5h is continued in 75-85 DEG C, in the process of reaction, make final viscosity control at 40000-80000cps/25 DEG C along with the increase of system viscosity constantly supplements organic solvent, after having reacted, add reaction terminating agent methyl alcohol 0.5-2kg.
The urethane resin prepare basic inventive embodiments 1 and embodiment 2 and ordinary resin are drawn a design according to synthetic leather industry ordinary method, carry out the test of stripping strength, tear strength and hydrolytic resistance, testing method refers to synthetic leather technology, Qu Jianbo etc. write, Chemical Industry Press (2010.3), P127-158 finished leather complete processing, P368 peel strength test method, P367 tear strength detection method, P369 hydrolysis detection method, adopt quick alkaline-resisting survey to peel off.Test result sees the following form 1.
Table 1
| Physicals | Embodiment 1 | Embodiment 2 | Ordinary resin SW-5025 |
| Resin state | Transparent liquid | Transparent liquid | Light yellow transparent liquid |
| Stripping strength N/3cm | 140 | 135 | 127 |
| Tear strength N | 110 | 100 | 60 |
| Hydrolytic resistance N/3cm | 100 | 110 | 63 |
* ordinary resin SW-5025 is that Hefei Anli New Material Polyurethane Co., Ltd. produces.
As can be seen from Table 1, urethane resin of the present invention all greatly exceed ordinary resin in stripping strength, tear strength and hydrolytic resistance.Wherein the resin modulus of the 2-in-1 one-tenth of embodiment is higher than embodiment 1.Modulus refers to the soft or hard degree of resin, and generally surely stretching modulus with 100% represents, the modulus of urethane resin prepared by embodiment 1,2 is respectively 2.5,3.5MPa, the soft section of hard tear strength decline of the same terms calculating modulus high resin.
Claims (2)
1. there is an impregnation Wet-type polyurethane resin for high-tear strength, hydrolysis, it is characterized in that its raw material and proportioning are:
Organic tin or organo-bismuth class catalyzer, addition is the 0.001-0.05% of polyol amount;
Described isocyanic ester is 4,4 '-diphenylmethanediisocyanate;
Described polyol compound is made up of polyester polyol and polyether glycol, and wherein the mass ratio of polyester polyol and polyether glycol is 1:1.5-1.7; The number-average molecular weight of described polyol compound is 1000-3000;
Described glycol chain extender is ethylene glycol and/or BDO;
Described polyester polyol is hexanodioic acid system polyester polyol;
Described polyether glycol is polytetrahydrofuran polyol, polyoxypropylene polyol and polyoxyethylated polyols; Wherein the quality of polytetrahydrofuran polyol, polyoxypropylene polyol and polyoxyethylated polyols is 1-2:2:1.5;
In described isocyanic ester, the molar weight of isocyano is 0.9-1:1 with the ratio of the hydroxyl integral molar quantity in described polyol compound and described glycol chain extender;
The mol ratio of described polyol compound and described glycol chain extender is 1:1.7-2.1;
The functionality of described polyester polyol is 2;
The functionality of described polyether glycol is 2.
2. the preparation method of impregnation Wet-type polyurethane resin with high-tear strength, hydrolysis according to claim 1, is characterized in that operating according to the following steps:
1) polyol compound and oxidation inhibitor are added in organic solvent, control solid content at 45-55%, after stirring, add the isocyanic ester of organic tin or organo-bismuth class catalyzer and 30-40%, in 75-85 DEG C of reaction 1-3 hour, obtain prepolymer; The solid content of prepolymer controls at 45-60%, and viscosity controller is at 50000-10000cps/75 DEG C;
2) to step 1) add the isocyanic ester of glycol chain extender and surplus in the prepolymer prepared, after stirring, reaction 2-5h is continued in 75-85 DEG C, in the process of reaction, make final viscosity control at 40000-80000cps/25 DEG C along with the increase of system viscosity constantly supplements organic solvent, after having reacted, add reaction terminating agent methyl alcohol.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104448221A (en) * | 2014-11-24 | 2015-03-25 | 晋江市闽高纺织科技有限公司 | Polyurethane high-resilience leather clothes and preparation method thereof |
| CN105801813B (en) * | 2016-04-29 | 2019-10-08 | 浙江枧洋高分子科技有限公司 | Polyurethane resin for superfine fibre soaking and preparation method thereof |
| CN105837774B (en) * | 2016-06-02 | 2021-04-27 | 台州禾欣高分子新材料有限公司 | High-peel hydrolysis-resistant polyurethane resin and preparation method and application thereof |
| CN106397728A (en) * | 2016-08-31 | 2017-02-15 | 合肥安利聚氨酯新材料有限公司 | Environment-friendly low-VOC two-component polyurethane resin for totally-dry-bonding bonding layer of synthetic leather and preparation method thereof |
| CN106366290A (en) * | 2016-08-31 | 2017-02-01 | 合肥安利聚氨酯新材料有限公司 | Two-component full-dry adhesive layer polyurethane resin for TPU (thermoplastic polyurethane) film compound synthetic leather and preparation method of resin |
| CN109776752A (en) * | 2019-01-22 | 2019-05-21 | 华大化学(安徽)有限公司 | A kind of ultra-soft matter skin sense dry method surface layer resin and its preparation method and application |
| CN111087566B (en) * | 2019-09-29 | 2021-10-29 | 扬州工业职业技术学院 | Preparation method of polyester modified biomass hydrolysis-resistant high-peel-resistance PU wet resin |
| CN112079980B (en) * | 2020-09-10 | 2022-05-03 | 浙江华峰合成树脂有限公司 | Polyurethane composite catalyst, solvent-free polyurethane resin thereof and preparation method |
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| CN101475742A (en) * | 2009-01-23 | 2009-07-08 | 合肥安利化工有限公司 | Aromatic yellow-stain resistant polyurethane resin for synthetic leather and preparation thereof |
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| CN102875774A (en) * | 2012-10-12 | 2013-01-16 | 合肥安利聚氨酯新材料有限公司 | High-peel strength and anti-hydrolysis wet polyurethane resin and preparation method thereof |
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Patent Citations (4)
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| JPH07149869A (en) * | 1993-11-30 | 1995-06-13 | Dainippon Ink & Chem Inc | Production of polyurethane resin |
| CN101475742A (en) * | 2009-01-23 | 2009-07-08 | 合肥安利化工有限公司 | Aromatic yellow-stain resistant polyurethane resin for synthetic leather and preparation thereof |
| CN101481449A (en) * | 2009-01-23 | 2009-07-15 | 合肥安利化工有限公司 | Wet impregnated polyurethane resin for high hydrolysis resistance synthetic leather and preparation thereof |
| CN102875774A (en) * | 2012-10-12 | 2013-01-16 | 合肥安利聚氨酯新材料有限公司 | High-peel strength and anti-hydrolysis wet polyurethane resin and preparation method thereof |
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