CN109134810A - A kind of hydrolysis resistant polyurethane resin and preparation method thereof, the method that shoes leather is prepared using the hydrolysis resistant polyurethane resin - Google Patents
A kind of hydrolysis resistant polyurethane resin and preparation method thereof, the method that shoes leather is prepared using the hydrolysis resistant polyurethane resin Download PDFInfo
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- CN109134810A CN109134810A CN201710499477.2A CN201710499477A CN109134810A CN 109134810 A CN109134810 A CN 109134810A CN 201710499477 A CN201710499477 A CN 201710499477A CN 109134810 A CN109134810 A CN 109134810A
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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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
-
- A—HUMAN NECESSITIES
- A43—FOOTWEAR
- A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
- A43B1/00—Footwear characterised by the material
- A43B1/14—Footwear characterised by the material made of plastics
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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
- C08G18/65—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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/06—Polyurethanes from polyesters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
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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)
- Treatment And Processing Of Natural Fur Or Leather (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a kind of hydrolysis resistant polyurethane resins, belong to technical field of chemical products, be made of the components of following parts: 5-25 parts of isocyanate ester compound, 10-20 parts of polyester polyol compound, hydroxyl 50-90 parts of 1-10 parts of 1-10 parts of 0.2-1.0 parts of low molecular weight compound, auxiliary agent, other additives, organic solvent.The method of shoes leather is prepared the invention also discloses preparation method, using the hydrolysis resistant polyurethane resin.A kind of hydrolysis resistant polyurethane resin of the invention, considerably increases the anti-hydrolytic performance of polyurethane resin, effectively increases the service life of shoes leather；Preparation method substantially improves the folding line of synthesis shoes leather goods, reaches the effect similar to corium, simple process, low in cost；The method that the present invention prepares shoes leather using the hydrolysis resistant polyurethane resin can substantially reduce the cost of hydrolysis synthesis shoes leather, have good market prospects.
Description
Technical field
The invention belongs to technical field of chemical products, in particular to a kind of hydrolysis resistant polyurethane resin and preparation method thereof,
The method for preparing shoes leather using the hydrolysis resistant polyurethane resin.
Background technique
At present in shoes with leather in the market, corium resource is increasingly in short supply, expensive.With synthetic leather technology in recent years
Development, synthetic leather no matter in terms of style, feel all very close to the effect of corium, or even surmount corium in some aspects.Meanwhile
Since synthetic leather clothes are cheap, a great variety of models, the most important part for the leather-like clothes that synthesis shoes leather already takes up,
The deep favor by external consumer.
Shoes leather is generally divided into two major classes according to its usage, and one kind is fashionable recreation type shoes, and one kind is fashion sports type
Shoes, general playshoes use condition is milder, of less demanding for the physical property for synthesizing leather goods, usually there is a 1-2 service life
, and sports type shoes leather is violent because of resource-user cost method, the corrosion by sweat gas and sweat is more, therefore it is required that very high resistance to
Hydrolysis property.
In order to improve the anti-hydrolytic performance of synthesis leather goods, it is common practice to use polytetrahydrofuran ether in polyalcohol
Dihydric alcohol reduces the dosage of polyester polyol, because ester bond is easily broken off by the attack of hydrone, and ehter bond will not be broken.
But since the price of polytetrahydrofuran ether is usually twice of the price of polyester polyol, hydrolysis type synthetic leather at
This can be much higher than the cost of plain edition synthetic leather.In addition, the synthesis generally existing folding line of leather goods is big, the feature of folding line depth, and
The folding line of real leather products is thin and small.
Summary of the invention
Goal of the invention: the purpose of the present invention is overcoming problems of the prior art, a kind of hydrolysis resistant polyurethane is provided
Resin；It is a further object of the present invention to provide the preparation methods of the hydrolysis resistant polyurethane resin；Another object of the present invention is to mention
Method for preparing shoes leather using the hydrolysis resistant polyurethane resin.
Technical solution: for achieving the above object, the present invention adopts the following technical scheme:
A kind of hydrolysis resistant polyurethane resin, is made of the components of following parts: 5-25 parts of isocyanate ester compound,
10-20 parts of polyester polyol compound, hydroxyl 1-10 parts of 0.2-1.0 parts of low molecular weight compound, auxiliary agent, other add
Add 1-10 parts of agent, 50-90 parts of organic solvent；Wherein, the auxiliary agent includes containing-COOY ,-SO3Y、-PO(OY)2、-NR2、-
NR3The compound of group, wherein Y H, NH4 +Or metal cation, R H, alkyl or aryl；Other additives include neutralizing
Agent, defoaming agent and thickener.
The isocyanate ester compound includes aliphatic isocyanates class compound or aromatic isocyanate class chemical combination
Object；Wherein, aliphatic isocyanates class compound is selected from 1, hexamethylene-diisocyanate, benzene dimethylene diisocyanate and different Buddhist
That ketone diisocyanate；Aromatic diisocyanate class compound is selected from 4,4- methyl diphenylene diisocyanate and toluene two is different
Cyanate.
The polyester polyol compound is polyadipate neopentyl glycol and/or polyadipate ethylene glycol, molecule
Amount is 400-5000；Preferably, the polyester polyol compound includes the polyadipate that weight percent is 20%-80%
The polyadipate ethylene glycol of neopentyl glycol and 20%-80%.
The low molecular weight compound of the hydroxyl is selected from one of ethylene glycol, butanediol and neopentyl glycol or several
Kind, molecular weight 20-200.
The auxiliary agent is selected from diamino sulfonic acid salt, dihydromethyl propionic acid, dimethylolpropionic acid, the pungent valeric acid of hydroxyl, N- bis-
One or more of ethanol amine or Cyclohexylamino propane sulfonic acid.
The additive is that row is commonly used in the trade, and neutralizer is selected from sodium hydroxide, potassium hydroxide, dimethylethanolamine, sulphur
Dimethyl phthalate and hydrochloric acid；Defoaming agent is organic silicon modified by polyether class compound, and typical organic silicon modified by polyether class compound has
BYK-020 (commercial name)；Thickener is that association type aqueous polyurethane or alkali soluble rise type polyacrylate emulsion, typical association type water
Property polyurethane has UH-420 (commercial name), and typical alkali swelling type polyacrylate emulsion has ASE-60 (commercial name).
The organic solvent is dimethylformamide.
The method for preparing hydrolysis resistant polyurethane resin, comprising the following steps:
1) performed polymer is prepared
Polyester polyol compound and isocyanate ester compound are mixed and are incorporated in 60-90 DEG C of reaction 3-5h, obtains performed polymer；
2) hydrolysis resistant polyurethane resin is prepared
Low molecular weight compound and the dimethylformamide chain extension at 80-100 DEG C that hydroxyl is added into performed polymer are anti-
After answering 7-10h, auxiliary agent and other additives is added to get hydrolysis resistant polyurethane resin.
The method for preparing shoes leather using the hydrolysis resistant polyurethane resin, comprising the following steps:
1) hydrolysis resistant polyurethane resin and calcium carbonate are dissolved in dimethylformamide, stirred evenly, obtain feed liquid；
2) feed liquid is coated on to be placed in solidification liquid on cloth and is solidified, obtain molding mass；
3) by molding mass through hot water wash, drying to get.
In step 1), the weight ratio of the hydrolysis resistant polyurethane resin, calcium carbonate and dimethylformamide is (3-6): (3-
6): (5-8)；In step 2), coating thickness 0.5mm-2mm；Solidification liquid is DMF aqueous solution, and wherein DMF content is 5-30%；
In step 3), drying temperature is 100-150 DEG C.
The utility model has the advantages that compared with prior art, a kind of hydrolysis resistant polyurethane resin of the invention, by introducing in the feed
The polyester polyol synthesized by neopentyl glycol and adipic acid achievees the effect that considerably increase poly- similar to polytetrahydrofuran ether
The anti-hydrolytic performance of urethane resin effectively increases the service life of shoes leather, and the polyester synthesized by neopentyl glycol and adipic acid
The cost price of dihydric alcohol is only the half of polytetrahydrofuran ether dihydric alcohol；Preparation method, in small molecular alcohol chain extender
It is middle to use 1,4-butanediol, the folding line of synthesis shoes leather goods can be substantially improved, the effect similar to corium, technique are reached
Simply, low in cost；The method that the present invention prepares shoes leather using the hydrolysis resistant polyurethane resin can substantially reduce hydrolysis conjunction
At the cost that shoes are removed from office, there are good market prospects.
Specific embodiment
According to following embodiments, the present invention may be better understood.However, as it will be easily appreciated by one skilled in the art that real
It applies specific material proportion, process conditions and its result described in example and is merely to illustrate the present invention, without that should will not limit
The present invention described in detail in claims processed.
A kind of hydrolysis resistant polyurethane resin, is made of the components of following parts: 5-25 parts of isocyanate ester compound,
10-20 parts of polyester polyol compound, hydroxyl 1-10 parts of 0.2-1.0 parts of low molecular weight compound, auxiliary agent, other add
Add 1-10 parts of agent, 50-90 parts of organic solvent；Wherein, auxiliary agent includes containing-COOY ,-SO3Y、-PO(OY)2、-NR2、-NR3Group
Compound, wherein Y H, NH4 +Or metal cation, R H, alkyl or aryl；Other additives include neutralizer, defoaming
Agent and thickener.
Isocyanate ester compound includes aliphatic isocyanates class compound or aromatic isocyanate class compound；Its
In, aliphatic isocyanates class compound is selected from 1, hexamethylene-diisocyanate, benzene dimethylene diisocyanate and isophorone
Diisocyanate；Aromatic diisocyanate class compound is selected from 4,4- methyl diphenylene diisocyanate and toluene diisocynate
Ester.
Polyester polyol compound is polyadipate neopentyl glycol and/or polyadipate ethylene glycol, molecular weight are
400-5000；Preferably, the polyester polyol compound includes the polyadipate new penta that weight percent is 20%-80%
The polyadipate ethylene glycol of two pure and mild 20%-80%.
The low molecular weight compound of hydroxyl is selected from one or more of ethylene glycol, butanediol and neopentyl glycol, point
Son amount is 20-200.
Auxiliary agent is selected from diamino sulfonic acid salt, dihydromethyl propionic acid, dimethylolpropionic acid, the pungent valeric acid of hydroxyl, N- diethanol amine
Or one or more of Cyclohexylamino propane sulfonic acid.
Additive is that row is commonly used in the trade, and neutralizer is selected from sodium hydroxide, potassium hydroxide, dimethylethanolamine, dimethyl sulfate
Ester and hydrochloric acid；Defoaming agent is organic silicon modified by polyether class compound, and typical organic silicon modified by polyether class compound has BYK-020
(commercial name)；Thickener is that association type aqueous polyurethane or alkali soluble rise type polyacrylate emulsion, the typical aqueous poly- ammonia of association type
Ester has UH-420 (commercial name), and typical alkali swelling type polyacrylate emulsion has ASE-60 (commercial name).
Organic solvent is dimethylformamide.
The method for preparing hydrolysis resistant polyurethane resin, comprising the following steps:
1) performed polymer is prepared
Polyester polyol compound and isocyanate ester compound are mixed and are incorporated in 60-90 DEG C of reaction 3-5h, obtains performed polymer；
2) hydrolysis resistant polyurethane resin is prepared
Low molecular weight compound and the dimethylformamide chain extension at 80-100 DEG C that hydroxyl is added into performed polymer are anti-
After answering 7-10h, auxiliary agent and other additives is added to get hydrolysis resistant polyurethane resin.
The method for preparing shoes leather using the hydrolysis resistant polyurethane resin, comprising the following steps:
1) hydrolysis resistant polyurethane resin and calcium carbonate are dissolved in dimethylformamide, stirred evenly, obtain feed liquid；
2) feed liquid is coated on to be placed in solidification liquid on cloth and is solidified, obtain molding mass；
3) by molding mass through hot water wash, drying to get.
In step 1), the weight ratio of hydrolysis resistant polyurethane resin, calcium carbonate and dimethylformamide is (3-6): (3-6):
(5-8)；In step 2), coating thickness 0.5mm-2mm；Solidification liquid is DMF aqueous solution, and wherein DMF content is 5-30%；Step
3) in, drying temperature is 100-150 DEG C.
Embodiment 1
Hydrolysis resistant polyurethane resin, is made of the components of following parts:
4,4- 10 parts of methyl diphenylene diisocyanates, 15 parts of toluene di-isocyanate(TDI)；Molecular weight is 2500 to gather oneself two
15 parts of sour neopentyl glycol；Molecular weight is 4 parts of polyadipate ethylene glycol of 2500；0.4 part of ethylene glycol, 0.3 part of butanediol and new penta
0.3 part of glycol；1 part of diamino sulfonic acid salt；Other additives include: 4 parts of neutralizer, and any reasonable neutralizer may be selected, excellent
Selection of land, including sodium hydroxide, potassium hydroxide, dimethylethanolamine, dimethyl suflfate or hydrochloric acid；It 3 parts of defoaming agent, may be selected any
Reasonable organic silicon modified by polyether class compound, it is preferable that be BYK-020；3 parts of thickener, any reasonable association may be selected
Type aqueous polyurethane or alkali soluble rise type polyacrylate emulsion, it is preferable that including UH-420 or ASE-60；Dimethylformamide 90
Part.
The preparation method of hydrolysis resistant polyurethane resin, comprising the following steps:
1) performed polymer is prepared: by the polyadipate neopentyl glycol, polyadipate ethylene glycol, 4,4- diphenyl methane of above-mentioned amount
Diisocyanate and toluene di-isocyanate(TDI), which mix, is incorporated in 75 DEG C of reaction 4h, obtains performed polymer；
2) it prepares hydrolysis resistant polyurethane resin: butanediol and the dimethylformamide chain extension at 90 DEG C being added in performed polymer
After reacting 8.5h, be added auxiliary agent and additive to get.
The method for preparing shoes leather using the hydrolysis resistant polyurethane resin, comprising the following steps:
1) 45 parts of hydrolysis resistant polyurethane resins and 15 parts of lignocellulosics are dissolved in 65 parts of dimethylformamides, are stirred evenly,
Obtain feed liquid；
2) feed liquid is coated on to be placed on cloth in the DMF aqueous solution that content is 20% and is solidified, coating thickness 0.5mm-
2mm obtains molding mass；
3) molding mass through hot water wash, 120 DEG C drying to get.
Embodiment 2
Hydrolysis resistant polyurethane resin, is made of the components of following parts: 4,4- methyl diphenylene diisocyanates 15
Part, 10 parts of toluene di-isocyanate(TDI)；Molecular weight is 20 parts of polybutyleneadipate of 2000；The polyadipate that molecular weight is 2000
6 parts of ethylene glycol；0.3 part of ethylene glycol, 0.3 part of butanediol and 0.3 part of neopentyl glycol；5 parts of dihydromethyl propionic acid；Other additive packets
It includes: 3 parts of neutralizer, any reasonable neutralizer may be selected, it is preferable that including sodium hydroxide, potassium hydroxide, dimethyl ethanol
Amine, dimethyl suflfate or hydrochloric acid；3 parts of defoaming agent, any reasonable organic silicon modified by polyether class compound may be selected, it is preferable that
For BYK-020；4 parts of thickener, it may be selected any reasonable association type aqueous polyurethane or alkali soluble rise type polyacrylate emulsion, it is excellent
Selection of land, including UH-420 or ASE-60；90 parts of dimethylformamide.
The preparation method of hydrolysis resistant polyurethane resin, comprising the following steps:
1) performed polymer is prepared: by the polyadipate neopentyl glycol, polyadipate ethylene glycol, 4,4- diphenyl methane of above-mentioned amount
Diisocyanate and toluene di-isocyanate(TDI), which mix, is incorporated in 75 DEG C of reaction 4h, obtains performed polymer；
2) it prepares hydrolysis resistant polyurethane resin: butanediol is added in performed polymer and dimethylformamide chain extension at 90 DEG C is anti-
After answering 8.5h, be added auxiliary agent and additive to get.
The method for preparing shoes leather using the hydrolysis resistant polyurethane resin, comprising the following steps:
1) 45 parts of hydrolysis resistant polyurethane resins and 15 parts of lignocellulosics are dissolved in 65 parts of dimethylformamides, are stirred evenly,
Obtain feed liquid；
2) feed liquid is coated on to be placed on cloth in the DMF aqueous solution that content is 20% and is solidified, coating thickness 0.5mm-
2mm obtains molding mass；
3) molding mass through hot water wash, 120 DEG C drying to get.
Embodiment 3
Hydrolysis resistant polyurethane resin, is made of the components of following parts:
20 parts of 4,4- methyl diphenylene diisocyanate；Molecular weight is 20 parts of polyadipate neopentyl glycol of 3000；Molecule
Amount is 4 parts of polyadipate ethylene glycol of 4000；0.4 part of ethylene glycol；0.4 part of butanediol；10 parts of dimethylolpropionic acid；Additive packet
It includes: 2.5 parts of neutralizer, any reasonable neutralizer may be selected, it is preferable that including sodium hydroxide, potassium hydroxide, dimethyl ethanol
Amine, dimethyl suflfate or hydrochloric acid；2.5 parts of defoaming agent, any reasonable organic silicon modified by polyether class compound may be selected, preferably
Ground is BYK-020；2.5 parts of thickener, it may be selected any reasonable association type aqueous polyurethane or alkali soluble rise type polyacrylic acid
Lotion, it is preferable that including UH-420 or ASE-60；80 parts of dimethylformamide.
The preparation method of hydrolysis resistant polyurethane resin, comprising the following steps:
1) performed polymer is prepared: by the polyadipate neopentyl glycol, polyadipate ethylene glycol and 4,4- diphenylmethyl of above-mentioned amount
Alkane diisocyanate is mixed to be incorporated in 80 DEG C of reaction 3.5h, obtains performed polymer；
2) it prepares hydrolysis resistant polyurethane resin: butanediol is added in performed polymer and dimethylformamide chain extension at 85 DEG C is anti-
After answering 9h, be added auxiliary agent and additive to get.
The method for preparing clothing leather using the hydrolysis resistant polyurethane resin, comprising the following steps:
1) 60 parts of hydrolysis resistant polyurethane resins and 20 parts of lignocellulosics are dissolved in 60 parts of dimethylformamides, are stirred evenly,
Obtain feed liquid；
2) feed liquid is coated on to be placed on cloth in the DMF aqueous solution that content is 10% and is solidified, coating thickness 0.5mm-
2mm obtains molding mass；
3) molding mass through hot water wash, 120 DEG C drying to get.
Above-described embodiment 3 prepares clothing leather using hydrolysis resistant polyurethane resin, it is clear that it can also apply water-fast depolymerization ammonia
Ester resin prepares other synthetic leather such as shoes leather.
4 test case of embodiment
One, resistance to sodium hydroxide detection
Reagent: 10% sodium hydrate aqueous solution, instrument: AI-7000S puller system.
Method: patent resin is done into shoes leather goods obtained and cuts two pieces, one piece of original peel strength of test, one piece is put into
It 25 DEG C, impregnates 12 hours in 10% sodium hydrate aqueous solution, then takes out, clean residual sodium hydroxide solution, water is tested in drying
Peel strength after solution.
The shoes that normal polyester type resin is done are removed from office, and after 10% soaking with sodium hydroxide 12 hours, leather surface dusting is not removed strong
Degree；The shoes that the application resin is done are removed from office, after 10% soaking with sodium hydroxide 12 hours, the relatively primitive removing of peel strength, and conservation rate
80%.
Two, ageing-resistant detection
Instrument: KTHA-010TBS climatic chamber, AI-7000S puller system.
Method: patent resin is done into shoes leather goods obtained and cuts two pieces, one piece of original peel strength of test, one piece is put into
In climatic chamber, standing time is 14 days, and climatic chamber condition is set as 95 DEG C of temperature, humidity 70%.After 14 days, it will remove from office
Sample takes out, and tests peel strength after drying.
The shoes leather that normal polyester type resin is done, after constant temperature and humidity 14 days, peel strength is relative to original removing, conservation rate
About 50%；The shoes leather that the application resin is done, after constant temperature and humidity 14 days, peel strength is about relative to original removing, conservation rate
95%.
Three, resistance to tortuous detection
Instrument: KTHA-010TBS climatic chamber, GT-7071-B complications tester.
Method: leather sample obtained by patent resin is placed 14 days in climatic chamber, the setting of climatic chamber condition
It is 95 DEG C of temperature, humidity 70% after 14 days, is taken out leather sample, dried, and resistance to tortuous number is then tested.
The shoes leather that normal polyester type resin is done, after constant temperature and humidity 14 days, resistance to complications number is at 50,000 times or so；The application
The shoes leather that resin is done, after constant temperature and humidity 14 days, resistance to complications number is at 180,000 times.
Claims (10)
1. a kind of hydrolysis resistant polyurethane resin, it is characterised in that: be made of the components of following parts: isocyanate ester compound
5-25 parts, 10-20 parts of polyester polyol compound, hydroxyl 1-10 parts of 0.2-1.0 parts of low molecular weight compound, auxiliary agent,
1-10 parts of other additives, 50-90 parts of organic solvent；Wherein, the auxiliary agent includes containing-COOY ,-SO3Y、-PO(OY)2、-
NR2、-NR3The compound of group, wherein Y H, NH4 +Or metal cation, R H, alkyl or aryl；Other additives include
Neutralizer, defoaming agent and thickener.
2. a kind of hydrolysis resistant polyurethane resin according to claim 1, it is characterised in that: the isocyanates chemical combination
Object includes aliphatic isocyanates class compound or aromatic isocyanate class compound；Wherein, aliphatic isocyanates class
It closes object and is selected from 1, hexamethylene-diisocyanate, benzene dimethylene diisocyanate and isophorone diisocyanate；Aromatic series two is different
Cyanate compound is selected from 4,4- methyl diphenylene diisocyanate and toluene di-isocyanate(TDI).
3. a kind of hydrolysis resistant polyurethane resin according to claim 1, it is characterised in that: the polyester polyol
Closing object is polyadipate neopentyl glycol and/or polyadipate ethylene glycol, molecular weight 400-5000.
4. a kind of hydrolysis resistant polyurethane resin according to claim 1, it is characterised in that: the low molecule of the hydroxyl
It measures compound and is selected from one or more of ethylene glycol, butanediol and neopentyl glycol, molecular weight 20-200.
5. a kind of hydrolysis resistant polyurethane resin according to claim 1, it is characterised in that: the auxiliary agent is selected from diamino
In the pungent valeric acid of sulfonate, dihydromethyl propionic acid, dimethylolpropionic acid, hydroxyl, N- diethanol amine or Cyclohexylamino propane sulfonic acid
It is one or more of.
6. a kind of hydrolysis resistant polyurethane resin according to claim 1, it is characterised in that: the neutralizer is selected from hydrogen-oxygen
Change sodium, potassium hydroxide, dimethylethanolamine, dimethyl suflfate and hydrochloric acid；The defoaming agent is organic silicon modified by polyether class
Close object；The thickener is that association type aqueous polyurethane or alkali soluble rise type polyacrylate emulsion.
7. a kind of hydrolysis resistant polyurethane resin according to claim 1, it is characterised in that: the organic solvent is dimethyl
Formamide.
8. the method for preparing hydrolysis resistant polyurethane resin described in any one of claim 1-7, it is characterised in that: including with
Lower step:
1) performed polymer is prepared
Polyester polyol compound and isocyanate ester compound are mixed and are incorporated in 60-90 DEG C of reaction 3-5h, obtains performed polymer；
2) hydrolysis resistant polyurethane resin is prepared
Low molecular weight compound and dimethylformamide the chain extending reaction 7- at 80-100 DEG C of hydroxyl are added into performed polymer
After 10h, auxiliary agent and other additives is added to get hydrolysis resistant polyurethane resin.
9. the method that hydrolysis resistant polyurethane resin described in application claim 1-7 prepares shoes leather, comprising the following steps:
1) hydrolysis resistant polyurethane resin and calcium carbonate are dissolved in dimethylformamide, stirred evenly, obtain feed liquid；
2) feed liquid is coated on to be placed in solidification liquid on cloth and is solidified, obtain molding mass；
3) by molding mass through hot water wash, drying to get.
10. the method according to claim 9 for preparing shoes leather using hydrolysis resistant polyurethane resin, it is characterised in that: step
1) in, the weight ratio of the hydrolysis resistant polyurethane resin, calcium carbonate and dimethylformamide is (3-6): (3-6): (5-8)；Step
It is rapid 2) in, coating thickness 0.5mm-2mm；Solidification liquid is DMF aqueous solution, and wherein DMF content is 5-30%；In step 3), dry
Dry temperature is 100-150 DEG C.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710499477.2A CN109134810A (en) | 2017-06-27 | 2017-06-27 | A kind of hydrolysis resistant polyurethane resin and preparation method thereof, the method that shoes leather is prepared using the hydrolysis resistant polyurethane resin |
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| CN201710499477.2A CN109134810A (en) | 2017-06-27 | 2017-06-27 | A kind of hydrolysis resistant polyurethane resin and preparation method thereof, the method that shoes leather is prepared using the hydrolysis resistant polyurethane resin |
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|---|---|---|---|
| CN201710499477.2A Pending CN109134810A (en) | 2017-06-27 | 2017-06-27 | A kind of hydrolysis resistant polyurethane resin and preparation method thereof, the method that shoes leather is prepared using the hydrolysis resistant polyurethane resin |
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| CN (1) | CN109134810A (en) |
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| CN110205077A (en) * | 2019-06-19 | 2019-09-06 | 南宝树脂（佛山）有限公司 | A kind of hydrolysis solvent borne polyurethane adhesive |
| CN110483724A (en) * | 2019-08-08 | 2019-11-22 | 合肥安利聚氨酯新材料有限公司 | A kind of high branched structure hydrolysis wet polyurethane resin and preparation method thereof |
| CN115181238A (en) * | 2022-07-07 | 2022-10-14 | 上海华峰新材料研发科技有限公司 | Wear-resistant hydrolysis-resistant polyurethane resin and preparation method and application thereof |
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Application publication date: 20190104 |