CN103467690A - Wet polyurethane resin with high tear strength and hydrolysis resistance for impregnation and preparation method of wet polyurethane resin - Google Patents
Wet polyurethane resin with high tear strength and hydrolysis resistance for impregnation and preparation method of wet polyurethane resin Download PDFInfo
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- CN103467690A CN103467690A CN2013104302379A CN201310430237A CN103467690A CN 103467690 A CN103467690 A CN 103467690A CN 2013104302379 A CN2013104302379 A CN 2013104302379A CN 201310430237 A CN201310430237 A CN 201310430237A CN 103467690 A CN103467690 A CN 103467690A
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- polyurethane resin
- polyol
- tear strength
- polyol compound
- urethane resin
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- 238000006460 hydrolysis reaction Methods 0.000 title claims abstract description 20
- 230000007062 hydrolysis Effects 0.000 title claims abstract description 19
- 229920005749 polyurethane resin Polymers 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000005470 impregnation Methods 0.000 title claims abstract description 12
- -1 polyol compound Chemical class 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 229920005862 polyol Polymers 0.000 claims abstract description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000004970 Chain extender Substances 0.000 claims abstract description 14
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 6
- 150000003077 polyols Chemical group 0.000 claims abstract description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 34
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 25
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims description 16
- 229920005906 polyester polyol Polymers 0.000 claims description 12
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 11
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 229920000570 polyether Polymers 0.000 claims description 10
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical group C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 150000002148 esters Chemical class 0.000 claims description 8
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 7
- 229920001451 polypropylene glycol Polymers 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 5
- 239000003112 inhibitor Substances 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- 239000012467 final product Substances 0.000 claims description 4
- 239000013589 supplement Substances 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 125000002462 isocyano group Chemical group *[N+]#[C-] 0.000 claims description 2
- 229920005989 resin Polymers 0.000 abstract description 14
- 239000011347 resin Substances 0.000 abstract description 14
- 239000003054 catalyst Substances 0.000 abstract description 5
- 229910052797 bismuth Inorganic materials 0.000 abstract description 4
- 230000000704 physical effect Effects 0.000 abstract description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 abstract 2
- 239000003963 antioxidant agent Substances 0.000 abstract 1
- 230000003078 antioxidant effect Effects 0.000 abstract 1
- 239000012948 isocyanate Substances 0.000 abstract 1
- 150000002513 isocyanates Chemical class 0.000 abstract 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 239000002649 leather substitute Substances 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 5
- 229910052731 fluorine Inorganic materials 0.000 description 5
- 239000011737 fluorine Substances 0.000 description 5
- 239000010985 leather Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 230000003301 hydrolyzing effect Effects 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- 239000012752 auxiliary agent Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 230000008595 infiltration Effects 0.000 description 2
- 238000001764 infiltration Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 239000000057 synthetic resin Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000007719 peel strength test Methods 0.000 description 1
- SNGREZUHAYWORS-UHFFFAOYSA-N perfluorooctanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F SNGREZUHAYWORS-UHFFFAOYSA-N 0.000 description 1
- 230000000176 photostabilization Effects 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
Abstract
The invention discloses wet polyurethane resin with high tear strength and hydrolysis resistance for impregnation and a preparation method of the wet polyurethane resin. The polyurethane resin comprises the following components in parts by mass: 6-10 parts of isocyanate, 16-26 parts of polyol compound, 1-3 parts of polyol chain extender, 0-0.3 part of antioxidant, 0-0.05 part of reaction terminator methanol, and an organic tin or organic bismuth catalyst, wherein the dosage of the organic tin or organic bismuth catalyst is 0.001-0.05 percent of the mass of the polyol compound. The polyurethane resin can be used for greatly improving and increasing physical properties, such as peel strength, tear strength and hydrolysis resistance, of resins, is durable, and has 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 Wet-type polyurethane resin and preparation method thereof for impregnation 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, class is high-quality good.Fast containing resin pickup general requirement excellent hydrolysis resistance, impregnation, the suitable infiltration that is conducive to coating material of film-forming properties simultaneously, strengthen the combination of coating material and fabricbase, and finished leather has higher tear strength.Existing hydrolysis, containing resin pickup, is selected the polytetrahydrofuran dibasic alcohol usually, but because of its cost higher, modulus is prone to the tear strength fast-descending when slightly high, in recent years the dibasic alcohol of poly(propylene oxide) and polytetrahydrofuran copolymerization occurs, tear and increase, but the finished leather stripping strength is unstable.
Chinese invention patent application 201010145366.X discloses polyester high-hydrolysis resistance and high-peeling strength polyurethane resin and preparation method thereof for a kind of wet-method synthetic leather, the 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 the synthetic urethane resin hydrolysis of chainextender by Diethylene Glycol generally all poor altogether.The anti-hydrolytic performance of this invention is to be realized by 0.1% hydrolysis auxiliary agent (fluorine surface-modifying agent) fully, therefore the feature of environmental protection of fluorine surface-modifying agent causes that people pay close attention to (relevant report of seeing Perfluorocaprylic Acid and derivative thereof) day by day in recent years, and developing the urethane resin that resin itself has anti-hydrolytic performance is industry development trend.This invention is to not statement of tear strength, but the synthetic resin of its whole polyester type polyvalent alcohol should not have advantage aspect tear strength.
Chinese invention patent application 201010610958.4 discloses a kind of wet type impregnating polyurethane resin and preparation method thereof, wet type impregnating with the high modulus polyurethane resin by selecting multiple polyether glycol and chainextender to be used in conjunction with (not adding the hydrolysis auxiliary agent), make the modulus of resin high, tear strength is high, hydrolytic resistance, the reaction later stage adds the photostabilization auxiliary agent to improve anti-xanthochromia.This invention has overcome the problem opposed between anti-hydrolytic performance, modulus and the tear strength of existing wet type hydrolysis resistance chemical leather with the urethane resin existence.This invention polyvalent alcohol is the polyether glycol that hydrophobicity is strong, is unfavorable for infiltration and the cohesion moulding of coating material in the process hides 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 the polytetrahydrofuran material to meet the anti-hydrolytic performance of urethane resin, select the polarity of the polyester diol material raising resin that polarity is stronger simultaneously, binding strength with raising with fabricbase, strengthen its amount of impregnation to fabricbase, added the fluorine surface-modifying agent when reaction finishes in addition.This invention is not paid close attention to the raising of tear strength, has selected organic fluorine simultaneously, does not possess the feature of environmental protection.
Three, summary of the invention
The present invention aims to provide a kind of Wet-type polyurethane resin and preparation method thereof for impregnation with high-tear strength, hydrolysis, and technical problem to be solved is to improve stripping strength, tear strength and the anti-hydrolytic performance of Synthetic Leather.In addition, urethane resin of the present invention does not add the 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, the 0.001-0.05% that addition is the polyol compound quality.
Described isocyanic ester is 4,4 '-diphenylmethanediisocyanate (MDI);
Described polyol compound consists 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 dibasic alcohol chainextender is ethylene glycol and/or BDO.
Described polyester polyol is that hexanodioic acid is polyester polyol;
Described polyether glycol is polytetrahydrofuran polyvalent alcohol, polyoxypropylene polyol and polyoxyethylene polyvalent alcohol; Wherein the quality of polytetrahydrofuran polyvalent alcohol, polyoxypropylene polyol and polyoxyethylene polyvalent alcohol is 1-2:2:1.5.
The functionality of described polyester polyol is 2; The functionality of described polyether glycol is 2.
The ratio of the hydroxyl integral molar quantity in described isocyanic ester in the molar weight of isocyano and described polyol compound and described dibasic alcohol chainextender is 0.9-1:1.
The mol ratio of described polyol compound and described dibasic alcohol chainextender is 1:1.7-2.1.
The present invention has the preparation method of the impregnation of high-tear strength, hydrolysis with the Wet-type polyurethane resin, operation according to the following steps:
1) polyol compound and oxidation inhibitor are added in organic solvent, control solid content at 45-55%, add the isocyanic ester of organic tin or organo-bismuth class catalyzer and 30-40% after stirring, in 75-85 ℃ of reaction 1-3 hour, obtain prepolymer; The solid content of described prepolymer is controlled at 45-60%, and viscosity controller is at 50000-10000cps/75 ℃.
2) isocyanic ester that adds dibasic alcohol chainextender and surplus in the prepolymer prepared to step 1), after stirring, continue reaction 2-5h in 75-85 ℃, in the process of reaction, along with the increase of system viscosity constantly supplements organic solvent, make final viscosity be controlled at 40000-80000cps/25 ℃, after having reacted, add reaction terminating agent methyl alcohol to get final product.
The preferred N of described organic solvent, N '-dimethyl formamide (DMF).
The impregnation made by above-mentioned formula is applied to synthetic leather production with the Wet-type polyurethane resin, and the leather goods of making have excellent stripping strength, tear strength and anti-hydrolytic performance.
Urethane resin of the present invention has been improved more greatly the physical property of stripping strength, tear strength and the hydrolysis aspect of resin, and product is durable in use, and product specification is high, has the market competitiveness.
Four, embodiment
Below in conjunction with specific embodiment, the present invention is further explained to explanation.
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, the preparation method is referring to urethane resin and application thereof, Chemical Industry Press (2011.11), Liu Yijun, the production method of 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 dibasic alcohol 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 to be better than organotin be to know altogether in industry to the feature of environmental protection of organo-bismuth;
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 production of MDI and the organo-bismuth class catalyst B iCAT8106(U.S. after stirring), in 75-85 ℃ of reaction 1-3 hour, obtain the prepolymer of solid content 55%;
2) MDI that adds dibasic alcohol chainextender EG and BG and surplus in the prepolymer prepared to step 1), after stirring, continue reaction 2-5h in 75-85 ℃, in the process of reaction, along with the increase of system viscosity constantly supplements organic solvent, make final viscosity be controlled at 40000-80000cps/25 ℃, after having reacted, add reaction terminating agent methyl alcohol 0.5-2kg to get final product.
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 production of MDI and the organo-bismuth class catalyst B iCAT8106(U.S. after stirring), in 75-85 ℃ of reaction 1-3 hour, obtain the prepolymer of solid content 55%;
2) MDI that adds dibasic alcohol chainextender EG and BG and surplus in the prepolymer prepared to step 1), after stirring, continue reaction 2-5h in 75-85 ℃, in the process of reaction, along with the increase of system viscosity constantly supplements organic solvent, make final viscosity be controlled at 40000-80000cps/25 ℃, after having reacted, add reaction terminating agent methyl alcohol 0.5-2kg to get final product.
Urethane resin and the ordinary resin of basic inventive embodiments 1 and embodiment 2 preparations 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 Amway urethane novel material company limited produces.
As can be seen from Table 1, urethane resin of the present invention is all substantially exceeding ordinary resin aspect stripping strength, tear strength and hydrolytic resistance.Wherein the synthetic resin modulus of embodiment 2 will be higher than embodiment 1.Modulus refers to the soft or hard degree of resin, generally with 100%, surely stretches modulus and means, the modulus of the urethane resin of embodiment 1,2 preparation is respectively 2.5,3.5MPa, and the soft section hard tear strength of the same terms calculating modulus high resin descends.
Claims (8)
1. the impregnation Wet-type polyurethane resin with high-tear strength, hydrolysis is characterized in that its raw material and proportioning are:
Organic tin or organo-bismuth class catalyzer, the 0.001-0.05% that addition is the polyol compound quality.
2. urethane resin according to claim 1 is characterized in that:
Described isocyanic ester is 4,4 '-diphenylmethanediisocyanate;
Described polyol compound consists 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 dibasic alcohol chainextender is ethylene glycol and/or BDO.
3. urethane resin according to claim 2 is characterized in that:
Described polyester polyol is that hexanodioic acid is polyester polyol;
Described polyether glycol is polytetrahydrofuran polyvalent alcohol, polyoxypropylene polyol and polyoxyethylene polyvalent alcohol; Wherein the quality of polytetrahydrofuran polyvalent alcohol, polyoxypropylene polyol and polyoxyethylene polyvalent alcohol is 1-2:2:1.5.
4. urethane resin according to claim 1 and 2 is characterized in that:
The ratio of the hydroxyl integral molar quantity in described isocyanic ester in the molar weight of isocyano and described polyol compound and described dibasic alcohol chainextender is 0.9-1:1.
5. urethane resin according to claim 1 and 2 is characterized in that:
The mol ratio of described polyol compound and described dibasic alcohol chainextender is 1:1.7-2.1.
6. according to the described urethane resin of claim 2 or 3, it is characterized in that:
The functionality of described polyester polyol is 2;
The functionality of described polyether glycol is 2.
7. the preparation method of Wet-type polyurethane resin for the impregnation with high-tear strength, hydrolysis claimed in 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%, add the isocyanic ester of organic tin or organo-bismuth class catalyzer and 30-40% after stirring, in 75-85 ℃ of reaction 1-3 hour, obtain prepolymer;
2) isocyanic ester that adds dibasic alcohol chainextender and surplus in the prepolymer prepared to step 1), after stirring, continue reaction 2-5h in 75-85 ℃, in the process of reaction, along with the increase of system viscosity constantly supplements organic solvent, make final viscosity be controlled at 40000-80000cps/25 ℃, after having reacted, add reaction terminating agent methyl alcohol to get final product.
8. preparation method according to claim 7 is characterized in that:
The solid content of prepolymer described in step 1) is controlled at 45-60%, and viscosity controller is at 50000-10000cps/75 ℃.
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| CN201310430237.9A CN103467690B (en) | 2013-09-18 | 2013-09-18 | A kind of impregnation Wet-type polyurethane resin and preparation method thereof with high-tear strength, hydrolysis |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN105837774A (en) * | 2016-06-02 | 2016-08-10 | 台州禾欣高分子新材料有限公司 | High stripping hydrolysis-resistant polyurethane resin, and preparation method and application 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 |
| 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 |
| 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 |
| 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 |
| CN111087566A (en) * | 2019-09-29 | 2020-05-01 | 扬州工业职业技术学院 | Preparation method of polyester modified biomass hydrolysis-resistant high-peel-resistance PU wet resin |
| CN112079980A (en) * | 2020-09-10 | 2020-12-15 | 浙江华峰合成树脂有限公司 | Polyurethane composite catalyst, solvent-free polyurethane resin thereof and preparation method |
| CN117843906A (en) * | 2023-12-01 | 2024-04-09 | 四川东树新材料有限公司 | A hydrolysis-resistant high-strength polyurethane composition for photovoltaic frames |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
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| 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 |
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| 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 |
| CN117843906A (en) * | 2023-12-01 | 2024-04-09 | 四川东树新材料有限公司 | A hydrolysis-resistant high-strength polyurethane composition for photovoltaic frames |
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