CN105153399B - A kind of wet wax sense dry method surface layer resin of hydrolysis ultra-soft matter and preparation method thereof - Google Patents
A kind of wet wax sense dry method surface layer resin of hydrolysis ultra-soft matter and preparation method thereof Download PDFInfo
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- CN105153399B CN105153399B CN201510634184.1A CN201510634184A CN105153399B CN 105153399 B CN105153399 B CN 105153399B CN 201510634184 A CN201510634184 A CN 201510634184A CN 105153399 B CN105153399 B CN 105153399B
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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
- C08G18/70—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
- C08G18/40—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
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
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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
- C08G18/44—Polycarbonates
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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
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene 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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/134—Phenols containing ester groups
- C08K5/1345—Carboxylic esters of phenolcarboxylic acids
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
- Treatment And Processing Of Natural Fur Or Leather (AREA)
- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
Abstract
The invention discloses wet wax sense dry method surface layer resin of a kind of hydrolysis ultra-soft matter and preparation method thereof, polyol compound, chain extender and antioxidant are added in organic solvent first, it is stirring evenly and then adding into 80% 85% isocyanates and is reacted 1 hour in 60 80 DEG C, add the isocyanates and organic tin or organo-bismuth class catalyst of surplus, stir and continue to react 2 5h after 75 85 DEG C, final viscosity control is at 80 120Pas/25 DEG C, solid content is 30%, and reaction terminating agent methanol is added after the completion of reaction and produces polyurethane resin.Polyurethane resin of the present invention is under conditions of without using oily wax additives, it is simple to adjust the sense of touch and its anti-hydrolytic performance of the wet wax of soft resin with the control of when product modulus using between polyalcohol, product defects caused by the migration of silicone oil analog assistant can be fundamentally prevented compared with similar products, and there is very big value of the product.
Description
First, technical field
The present invention relates to a kind of functional urethane resin and preparation method thereof, and in particular to a kind of hydrolysis ultra-soft matter is wet
Wax sense dry method surface layer resin and preparation method thereof.
2nd, background technology
In the product category of synthetic leather industry, imitate the synthetic leather with wet wax leather effect and account for synthetic leather total amount very
Big share, but various silicone oil or silicone oil performed polymers are always added in actual production to realize the leather effect of wet wax, this causes this
The problem of silicone oil precipitation, in industry being referred to as after (hot and humid) placement of complex environment, is easily occurring in class product
To send out mist.Product quality is influenceed, causes many quality accidents.In addition similar soft resin is to meet that resin has normal decorative pattern
Fixed effect and polyester material can only be used, so anti-hydrolytic performance is generally poor, this is again undoubtedly for the product of high-quality
One it is huge the defects of.
3rd, the content of the invention
The present invention is intended to provide a kind of wet wax sense dry method surface layer resin of hydrolysis ultra-soft matter and preparation method thereof, soft to be lifted
The anti-hydrolytic performance of matter dry method surface layer resin and wet wax sense of touch.
The wet wax sense dry method surface layer resin of hydrolysis ultra-soft matter of the present invention, its raw material and proportioning form as follows：
Isocyanates
Polyol compound
Chain extender
Antioxidant
Reaction terminating agent methanol
Organic tin or organo-bismuth class catalyst, addition are the 0.001-0.05% of polyol amount of substance；
The polyol compound is PEPA, PPG or polycarbonate polyol, the polynary alcoholization
The number-average molecular weight of compound is 2000-4000；
Isocyano and total hydroxyl mol ratio in polyol compound and chain extender are 0.9-1 in the isocyanates:
1；
The mol ratio of the polyol compound and chain extender is 1:0.8-1.5.
The isocyanates is 4,4 '-methyl diphenylene diisocyanate.
The polyol compound is adipic acid system PEPA, PPG or the makrolon that degree of functionality is 2
Polyalcohol；
Adipic acid system PEPA is by ethylene glycol, 1,4- butanediols, diethylene glycol, 1,3- propane diols, 3- first
One or more and adipic acid in the pentanediol of base -1,5 are 1.02-1.2 in molar ratio:1 proportioning and using isopropyl titanate as
Catalyst synthesis, wherein catalyst is acid, the 0.2%-1% of alcohol gross mass；
The PPG is polytetrahydrofuran polyol and/or polyoxypropylene polyol；
It is poly- with dimethyl carbonate copolymerization that the polycarbonate polyol is 1,5- pentanediols and/or 1,6-HD
Carbonate polyol and its product for being grafted or compounding with PPG.
The chain extender be ethylene glycol, 1,4- butanediols, 1,6-HD, diethylene glycol, 1,3- propane diols, 3- methyl-
One or more in 1,5 pentanediols.
The antioxidant is four (β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid) pentaerythritol ester (antioxidant 1-
1010) or 2,2'- di-2-ethylhexylphosphine oxide (4- methyl-6-tert-butylphenols) (antioxidant 2246), the addition of antioxidant are total for raw material
The 0.5 ‰ -3 ‰ of quality.
The addition of reaction terminating agent methanol is the 0-0.5 ‰ of raw material gross mass.
The preparation method of the wet wax sense dry method surface layer resin of hydrolysis ultra-soft matter of the present invention, including following process：
Polyol compound, chain extender and antioxidant are added in organic solvent, it is the molten of 60-65% to form solid content
Liquid, it is stirring evenly and then adding into 80%-85% isocyanates and is reacted 1 hour in 60-80 DEG C, add the isocyanates of surplus
And organic tin or organo-bismuth class catalyst, stir continue after 75-85 DEG C react 2-5h, during reaction with
The increase of system viscosity is continuously replenished organic solvent and make it that solid content is at 80-120Pas/25 DEG C for final viscosity control
30%, reaction terminating agent methanol is added after the completion of reaction and produces polyurethane resin.
Formula design and synthesis focus in whole course of reaction and the auxiliary agent that wet wax sense can be brought to resin are not used,
Realized from polyalcohol proportioning merely, in the absence of hidden danger of quality such as silicone oil precipitations.
The polyol compound, isocyanates, the moisture content of chain extender are respectively less than 500ppm；The organic solvent is N,
N '-dimethylformamide or butanone.
There is table by dry method release liners shifting process, manufactured leather goods by polyurethane resin made from above-mentioned formula
The advantages that sense of touch wet wax sense in face is strong, excellent hydrolysis resistance, small hair mist hidden danger.Have compared with other like products obvious excellent
Gesture, there is larger market value.
4th, embodiment
To be easy to understand the technical means, the inventive features, the objects and the advantages of the present invention, with reference to
Embodiment, the present invention is expanded on further.
Each component difference is as follows in example below：
EG is ethylene glycol；
SP-1 is the adipic acid butanediol system PEPA that molecular weight is 3000；
SP-2 is the polytetrahydrofuran polyol that molecular weight is 2000；
SP-3 is the 1,6 hexylene glycol makrolon that molecular weight is 2000；
SP-4 is the poly- carbonic acid of 1,5- pentanediols, 1,6-HD and dimethyl carbonate copolymerization that molecular weight is 2000
Ester polyol；
SP-5 is the poly- carbonic acid of 1,5- pentanediols, 1,6-HD and dimethyl carbonate copolymerization that molecular weight is 4000
Ester polyol and the dihydric alcohol of polytetrahydrofuran polyol copolymerization；
SP-6 be molecular weight be 3000 adipic acid butanediol, 3- methyl isophthalic acids, 5 pentanediol system PEPAs；
Above-mentioned raw materials are purchased from Hefei Anli New Material Polyurethane Co., Ltd..
I-1010 is commercially available antioxidant, complete entitled four [β-(hydroxy phenyl of 3,5- di-t-butyl -4) propionic acid] pentaerythrite
Ester；
MDI is 4,4 '-methyl diphenylene diisocyanate；
Organo-bismuth is catalysts, and wherein the feature of environmental protection of organo-bismuth is to know altogether in industry better than organotin；
DMF is solvent N, N '-dimethylformamide, and methanol is reaction terminating agent.
Embodiment 1：
Raw material and proportioning：
First by 250kg SP-1,370kg SP-2,50kg SP-3,160kg SP-4,110kg SP-5,100kg
SP-6,55kgEG and 3kg antioxidant I-1010 add in organic solvent DMF, forms solution of the solid content for 60-65%；Stir
Mix uniformly after add 80%-85% MDI in 60-80 DEG C react 1 hour, add surplus MDI and organo-bismuth class catalyst (8106, the leading chemical company production in the U.S.) 0.2kg, after stirring, continue to react 2-5h in 75-85 DEG C,
Cause final viscosity control in 80-120Pas/ as organic solvent is continuously replenished in the increase of system viscosity during reaction
25 DEG C, solid content 30%, reaction terminating agent methanol is added after the completion of reaction and produces polyurethane resin.
Embodiment 2：
Raw material and proportioning：
First by 150kg SP-1,270kg SP-2,150kg SP-3,100kg SP-4,70kg SP-5,210kg
SP-6,55kgEG and 3kg antioxidant I-1010 add in organic solvent DMF, forms solution of the solid content for 60-65%；Stir
Mix uniformly after add 80%-85% MDI in 60-80 DEG C react 1 hour, add surplus MDI and organo-bismuth class catalyst (8106, the leading chemical company production in the U.S.) 0.2kg, after stirring, continue to react 2-5h in 75-85 DEG C,
Cause final viscosity control in 80-120Pas/ as organic solvent is continuously replenished in the increase of system viscosity during reaction
25 DEG C, solid content 30%, reaction terminating agent methanol is added after the completion of reaction and produces polyurethane resin.
Comparative example 1：
In order to verify of the present invention have the wet wax sense of surface touch strong, excellent hydrolysis resistance, hair mist hidden danger small
Advantage, by the wet wax sense dry method surface layer resin of the hydrolysis resistance soft prepared, synthetic leather, specific process hides is made by existing method
Formula is as follows：
ST-30A 100kg
DMF 70kg
Appropriate mill base
Polyurethane resin prepared by Example 1 and Example 2 of the present invention is prepared into polyurethane wet slurry according to comparative example
Material, draws a design according to synthetic leather industry conventional method, hydrolysis test, sense of touch evaluation and anti-hair mist performance test.Sample preparation and
Method of testing refers to synthetic leather technology, and Qu Jianbo etc. writes, Chemical Industry Press (2010.3), and feel, sense of touch evaluation please
The engineer of long campaigns synthetic leather production judges, as a result see the table below 1.
Table 1
From table 1 it follows that polyurethane resin of the present invention is in anti-hydrolytic performance, sense of touch, feel, anti-hair mist aspect of performance
Surmount ordinary resin completely.
After testing, the Synthetic Leather made of the formula of above-mentioned implementation, there is good physical property and outstanding
Sense of touch, feel.Had a clear superiority relative to common synthetic leather.
In this specification and following claims, so-called system, refer to whole reaction system, be exactly all substances
Total amount.Merely illustrating the principles of the invention described in the embodiment above and specification, do not depart from spirit of the invention and
Various changes and modifications of the present invention are possible on the premise of scope, and these changes and improvements both fall within claimed invention model
In enclosing.The claimed scope of the invention is defined by appended claims and its jljl.
Claims (4)
1. a kind of wet wax sense dry method surface layer resin of hydrolysis ultra-soft matter, it is characterised in that raw material and proportioning composition are as follows：
SP-1 is the adipic acid butanediol system PEPA that molecular weight is 3000；
SP-2 is the polytetrahydrofuran polyol that molecular weight is 2000；
SP-3 is the 1,6- hexylene glycol makrolon that molecular weight is 2000；
SP-4 is that the makrolon of 1,5- pentanediols, 1,6-HD and dimethyl carbonate copolymerization that molecular weight is 2000 is more
First alcohol；
SP-5 is that the makrolon of 1,5- pentanediols, 1,6-HD and dimethyl carbonate copolymerization that molecular weight is 4000 is more
First alcohol and the dihydric alcohol of polytetrahydrofuran polyol copolymerization；
SP-6 be molecular weight be 3000 adipic acid butanediol, 3- methyl isophthalic acids, 5- pentanediols system PEPA；
I-1010 is four [β-(hydroxy phenyl of 3,5- di-t-butyls -4) propionic acid] pentaerythritol esters.
A kind of 2. preparation method of the wet wax sense dry method surface layer resin of hydrolysis ultra-soft matter described in claim 1, it is characterised in that
Comprise the following steps：
First by 250kg SP-1,370kg SP-2,50kg SP-3,160kg SP-4,110kg SP-5,100kg SP-
6th, 55kgEG and 3kg antioxidant I-1010 is added in organic solvent DMF, forms the solution that solid content is 60-65%；Stir
The MDI for adding 80%-85% afterwards reacts 1 hour in 60-80 DEG C, adds the MDI and organo-bismuth class catalyst 0.2kg of surplus,
After stirring, continue in 75-85 DEG C react 2-5h, during reaction with the increase of system viscosity be continuously replenished it is organic
Solvent causes final viscosity control at 80-120Pas/25 DEG C, solid content 30%, reaction terminating agent to be added after the completion of reaction
Methanol produces polyurethane resin.
3. a kind of wet wax sense dry method surface layer resin of hydrolysis ultra-soft matter, it is characterised in that raw material and proportioning composition are as follows：
SP-1 is the adipic acid butanediol system PEPA that molecular weight is 3000；
SP-2 is the polytetrahydrofuran polyol that molecular weight is 2000；
SP-3 is the 1,6- hexylene glycol makrolon that molecular weight is 2000；
SP-4 is that the makrolon of 1,5- pentanediols, 1,6-HD and dimethyl carbonate copolymerization that molecular weight is 2000 is more
First alcohol；
SP-5 is that the makrolon of 1,5- pentanediols, 1,6-HD and dimethyl carbonate copolymerization that molecular weight is 4000 is more
First alcohol and the dihydric alcohol of polytetrahydrofuran polyol copolymerization；
SP-6 be molecular weight be 3000 adipic acid butanediol, 3- methyl isophthalic acids, 5- pentanediols system PEPA；
I-1010 is four [β-(hydroxy phenyl of 3,5- di-t-butyls -4) propionic acid] pentaerythritol esters.
A kind of 4. preparation method of the wet wax sense dry method surface layer resin of hydrolysis ultra-soft matter described in claim 3, it is characterised in that
Comprise the following steps：
First by 150kg SP-1,270kg SP-2,150kg SP-3,100kg SP-4,70kg SP-5,210kg SP-
6th, 55kgEG and 3kg antioxidant I-1010 is added in organic solvent DMF, forms the solution that solid content is 60-65%；Stir
The MDI for adding 80%-85% afterwards reacts 1 hour in 60-80 DEG C, adds the MDI and organo-bismuth class catalyst 0.2kg of surplus,
After stirring, continue in 75-85 DEG C react 2-5h, during reaction with the increase of system viscosity be continuously replenished it is organic
Solvent causes final viscosity control at 80-120Pas/25 DEG C, solid content 30%, reaction terminating agent to be added after the completion of reaction
Methanol produces polyurethane resin.
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| 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 |
| CN108707220A (en) * | 2018-06-15 | 2018-10-26 | 合肥安利聚氨酯新材料有限公司 | A kind of leather pigment compatibility improvement dry method face layer polyurethane resin and preparation method |
| CN109575213B (en) * | 2018-12-07 | 2021-04-16 | 福建华普树脂有限公司 | Dry-process foaming polyurethane resin and preparation method thereof |
| US20220251379A1 (en) * | 2019-08-07 | 2022-08-11 | Mitsui Chemicals, Inc. | Polyurethane resin composition and molded article |
| CN114316771B (en) * | 2021-12-29 | 2023-06-02 | 雅涂科技(张家港)有限公司 | Polyurethane coating and preparation method and application thereof |
| CN114805725A (en) * | 2022-03-26 | 2022-07-29 | 浙江禾欣科技有限公司 | TPU resin with good processing performance and preparation method thereof |
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| CN103467696A (en) * | 2013-08-16 | 2013-12-25 | 合肥安利聚氨酯新材料有限公司 | Preparation method of soft high-elasticity embossed sofa leather wet-method polyurethane resin |
| CN104140520A (en) * | 2014-08-06 | 2014-11-12 | 合肥安利聚氨酯新材料有限公司 | Super-soft high-elasticity hydrolysis resistance high-stripping wet polyurethane resin and preparation method thereof |
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| YU14397A (en) * | 1997-04-11 | 1998-09-18 | Jovan Kerešić | Procedure for the manufacturing of matresse for judo sport and play and matresse manufactured by such procedure |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102617826A (en) * | 2012-03-26 | 2012-08-01 | 合肥安利聚氨酯新材料有限公司 | Soft non-adhesive wet polyurethane resin and preparation method 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 |
| CN103467696A (en) * | 2013-08-16 | 2013-12-25 | 合肥安利聚氨酯新材料有限公司 | Preparation method of soft high-elasticity embossed sofa leather wet-method polyurethane resin |
| CN104140520A (en) * | 2014-08-06 | 2014-11-12 | 合肥安利聚氨酯新材料有限公司 | Super-soft high-elasticity hydrolysis resistance high-stripping wet polyurethane resin and preparation method thereof |
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| CN105153399A (en) | 2015-12-16 |
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