CN107722219A - A kind of clothing leather wet polyurethane resin and preparation method thereof - Google Patents
A kind of clothing leather wet polyurethane resin and preparation method thereof Download PDFInfo
- Publication number
- CN107722219A CN107722219A CN201711008689.2A CN201711008689A CN107722219A CN 107722219 A CN107722219 A CN 107722219A CN 201711008689 A CN201711008689 A CN 201711008689A CN 107722219 A CN107722219 A CN 107722219A
- Authority
- CN
- China
- Prior art keywords
- polyurethane resin
- clothing leather
- wet polyurethane
- diisocyanate
- leather wet
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6607—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
- C08G18/6611—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
-
- 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
-
- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- 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
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
-
- 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
-
- 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
-
- 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
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
- D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
Abstract
The invention discloses a kind of clothing leather wet polyurethane resin and preparation method thereof, clothing leather wet polyurethane resin is prepared by polyalcohol and its mixture, diisocyanate, small molecule glycol chain extender, crosslinking agent, catalyst, solvent;Polyalcohol and its mixture are first carried out appropriate prepolymerization reaction by the inventive method, and the size of performed polymer molecular weight is controlled by the pre-polymerization viscosity size under high temperature;Pre-polymerization adds small molecule dihydric alcohol and carries out chain extending reaction after terminating;Participate in reacting jointly using two kinds of diisocyanate;Final resin viscosity control terminates reaction in critical field.Clothing leather wet polyurethane resin prepared by the present invention, substantially increase the anti-hydrolytic performance of clothing leather wet polyurethane resin, use not only soft, the plentiful, low elasticity, and the requirement such as 5 years anti-hydrolytic performances, wear-resisting scratch resistance performance and durability can be met of clothing leather made of 5 years hydrolyzation resisting clothing leather wet polyurethane resins of ultra-soft matter of the present invention.
Description
Technical field
The present invention relates to polyurethane resin field, specifically a kind of clothing leather wet polyurethane resin and preparation method thereof.
Background technology
Because the natural resources of corium product is limited, price is high, can not meet the growing market demand.And polyurethane
Synthetic leather products material wide material sources, cheap, processing characteristics is good, the comprehensive close even more than natural leather of physical property, completely
The life pursuit of people can be met.Application of the polyurethane resin in terms of synthetic leather is mainly reflected in clothes, case and bag, footwear, family
The multiple fields such as tool, automobile.At present in clothing leather in the market, corium resource is increasingly in short supply, expensive.Synthetic leather clothes valency
Lattice are cheap, a great variety of models, surmounted corium also close to the effect of corium, or even some aspect performances in terms of feel.However, one
As synthetic leather clothes service life there was only 2 years or so, at present, in the market major part clothing leather wet polyurethane resin, in height
Easily degraded under temperature, moist environment, hydraulic performance decline, cause clothing leather encounter water wet etc., cracking, efflorescence easily occurs, it is resistance to
Long property is poor, it is difficult to meets the market demand of consumer.
The content of the invention is existing to solve it is an object of the invention to provide a kind of clothing leather wet polyurethane resin and preparation method thereof
There is the problem of facile hydrolysis, poor durability existing for technology clothes polyurethane resin synthetic leather.
In order to achieve the above object, the technical solution adopted in the present invention is:
A kind of clothing leather wet polyurethane resin, it is characterised in that:By polyalcohol and its mixture, diisocyanate, small molecule
Glycol chain extender, crosslinking agent, catalyst, solvent are prepared, wherein:
The mole ratio of polyalcohol and its mixture and small molecule glycol chain extender is 1:Between 0.9 ~ 1.0;
Diisocyanate is with polyalcohol and its mole ratio of mixture and small molecule glycol chain extender 1.0 ~ 1.08:
Between 1;
Catalyst amount is 0.2 ‰ ~ the 1 ‰ of polyol compound weight;
Dosage of crosslinking agent is 0.4 ~ the 0.6 ‰ of polyol compound weight;
Solvent load is the 74% ~ 76% of system gross weight.
A kind of described clothing leather wet polyurethane resin, it is characterised in that:Described polyalcohol and its group of mixture
Into as follows:
Polyadipate ethylene glycol BDO esterdiol, number-average molecular weight are 4000 ± 300g/mol;
Polytetrahydrofuran diol, number-average molecular weight are 2000 ± 200g/mol;
PCDL, number-average molecular weight are 2000 ± 200g/mol.
A kind of described clothing leather wet polyurethane resin, it is characterised in that:Described diisocyanate is 4,4 '-hexichol
Dicyclohexylmethane diisocyanate MDI-100, and 2,4 '-methyl diphenylene diisocyanate and 4, the isocyanide of 4 '-diphenyl methane two
The mixture M DI-50 of acid esters is formed, i.e., diisocyanate is that MDI-100 and MDI-50 is formed, and both participate in reacting jointly, its
Middle MDI-50 provides more preferable flexibility and low elasticity for clothing leather wet polyurethane resin.
A kind of described clothing leather wet polyurethane resin, it is characterised in that:Described small molecule glycol chain extender point
Son amount is 62 ~ 200g/mol, and small molecule glycol chain extender is in ethylene glycol, BDO, neopentyl glycol, 1,6- hexylene glycols
One or two.
A kind of described clothing leather wet polyurethane resin, it is characterised in that:Described catalyst is catalyzed for organo-bismuth class
Agent MB20.
A kind of described clothing leather wet polyurethane resin, it is characterised in that:Described crosslinking agent is trimethylolpropane
TMP。
A kind of described clothing leather wet polyurethane resin, it is characterised in that:Described solvent is organic solvent DMF.
A kind of preparation method of clothing leather wet polyurethane resin, it is characterised in that:Comprise the following steps:
(1), put into polyalcohol and its mixture, crosslinking agent, the solvent for the 35-40% for accounting for solvent total amount in a kettle and fully stir
After even, the diisocyanate MDI-100 for accounting for total amount 54-58% is added, prepolymerization reaction is carried out under the conditions of existing for catalyst,
Pre-polymerization viscosity is controlled by 6-8 ten thousand or so, and 40% ~ 50%, reaction temperature is controlled at 70-80 DEG C for solid content control during pre-polymerization;
(2), pre-polymerization terminate after again into reactor add small molecule glycol chain extender and diisocyanate MDI-100 and two it is different
Chain extending reaction occurs for cyanate MDI-50, with being continuously increased for system viscosity, is gradually added and remaining accounts for solvent total amount 60-
65% solvent, at 70 ~ 80 DEG C, final viscosity is controlled in 80 ~ 120Pa S/25 DEG C for reaction temperature control.
A kind of preparation method of described clothing leather wet polyurethane resin, it is characterised in that:Step(1)、(2)In it is more
First alcohol and its mixture, diisocyanate, small molecule glycol chain extender, crosslinking agent, solvent are required to moisture content and are less than
500ppm。
The present invention reaction mechanism be:In polyurethane resin building-up process, soft segment uses three kinds of polyester, polyethers and poly- carbon
Polyalcohol and its mixture copolymerization, substantially increase the anti-hydrolytic performance of clothing leather wet polyurethane resin, meet 5 years it is water-fast
The requirement of solution;Hard section quotes two kinds of diisocyanate(MDI-100 and MDI-50)Common to participate in reaction, wherein MDI-50 is clothes
Remove from office wet polyurethane resin and more preferable flexibility and low elasticity are provided.
The present invention solves existing ordinary soft clothing leather wet polyurethane resin hydrolysis, durability etc. difference
The defects of.Using made of 5 years hydrolyzation resisting clothing leather wet polyurethane resins of ultra-soft matter of the present invention, not only feel is soft for clothing leather
It is soft, plentiful, elastic low.And the requirement such as 5 years anti-hydrolytic performances, wear-resisting scratch resistance performance and durability can be met.
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.
Embodiment 1:
Material name weight(Unit K g)
Polyadipate ethylene glycol BDO esterdiol 520
Polytetrahydrofuran diol 200
PCDL 300
Ethylene glycol 22
MDI-100 168
MDI-50 17
Crosslinking agent TMP 0.5
Catalyst MB20 0.5
N,N-dimethylformamide 3685
Polyadipate ethylene glycol BDO esterdiol:4000 ± 300g/mol of number-average molecular weight PEPA,
Polytetrahydrofuran diol:2000 ± 200g/mol of number-average molecular weight PPG,
PCDL:2000 ± 200g/mol of number-average molecular weight PEPA.
5 years hydrolyzation resisting clothing leather wet polyurethane resins of ultra-soft matter of the present invention are prepared according to the following steps:
1st, various polyalcohols and its mixture are put into a kettle, micro crosslinking agent, part DMF are mixed, stirring 10 ~
Again by appropriate diisocyanate after 15 minutes(MDI-100)It is added in reactor, under the conditions of adding existing for catalyst
Prepolymerization reaction is carried out, pre-polymerization viscosity controlled by 6-8 ten thousand or so, and 40% ~ 50%, kettle temperature is controlled 70 for solid content control during pre-polymerization
℃~80℃;
2nd, small molecule ethylene glycol chain extender is added after pre-polymerization terminates, after stirring 20 minutes, adds diisocyanate(MDI-
100 and MDI-50)Generation chain extending reaction;
3rd, midway progressively adds MDI and continues to react, and being continuously increased with system viscosity, is gradually added required solvent DMF.
Final viscosity control is controlled between 70 ~ 80 DEG C in 80 ~ 120Pa S/25 DEG C, kettle temperature;
4th, reaction cools to less than 60 DEG C after terminating and carries out rushing down material, metering packing.
Embodiment 2:
Material name weight(Unit K g)
Polyadipate ethylene glycol BDO esterdiol 520
Polytetrahydrofuran diol 100
PCDL 400
Ethylene glycol 20
Neopentyl glycol 3.5
MDI-100 172
MDI-50 13
Crosslinking agent TMP 0.5
Catalyst MB20 0.5
N,N-dimethylformamide 3690
Polyadipate ethylene glycol BDO esterdiol:4000 ± 300g/mol of number-average molecular weight PEPA,
Polytetrahydrofuran diol:2000 ± 200g/mol of number-average molecular weight PPG,
PCDL:2000 ± 200g/mol of number-average molecular weight PEPA.
5 years hydrolyzation resisting clothing leather wet polyurethane resins of ultra-soft matter of the present invention, are prepared according to the following steps:
1st, various polyalcohols and its mixture are put into a kettle, micro crosslinking agent, part DMF are mixed, stirring 10 ~
Again by appropriate diisocyanate after 15 minutes(MDI-100)It is added in reactor, under the conditions of adding existing for catalyst
Prepolymerization reaction is carried out, pre-polymerization viscosity controlled by 6-8 ten thousand or so, and 40% ~ 50%, kettle temperature is controlled 70 for solid content control during pre-polymerization
℃~80℃;
2nd, small molecule ethylene glycol and neopentyl glycol chain extender are added after pre-polymerization terminates, 20 minutes is stirred again and adds two isocyanic acids
Ester(MDI-100 and MDI-50)Generation chain extending reaction;
3rd, midway progressively adds MDI and continues to react, and being continuously increased with system viscosity, is gradually added required solvent DMF.
Final viscosity control is controlled between 70 ~ 80 DEG C in 80 ~ 120Pa S/25 DEG C, kettle temperature.
4th, reaction cools to less than 60 DEG C after terminating and carries out rushing down material, metering packing.
Embodiment 3:
Material name weight(Unit K g)
Polyadipate ethylene glycol BDO esterdiol 520
Polytetrahydrofuran diol 400
PCDL 100
Ethylene glycol 19
BDO 5
MDI-100 170
MDI-50 15.5
Crosslinking agent TMP 0.5
Catalyst MB20 0.5
N,N-dimethylformamide 3693
Polyadipate ethylene glycol BDO esterdiol:4000 ± 300g/mol of number-average molecular weight PEPA,
Polytetrahydrofuran diol:2000 ± 200g/mol of number-average molecular weight PPG,
PCDL:2000 ± 200g/mol of number-average molecular weight PEPA.
5 years hydrolyzation resisting clothing leather wet polyurethane resins of ultra-soft matter of the present invention, are prepared according to the following steps:
1st, various polyalcohols and its mixture are put into a kettle, micro crosslinking agent, part DMF are mixed, stirring 10 ~
Again by appropriate diisocyanate after 15 minutes(MDI-100)It is added in reactor, under the conditions of adding existing for catalyst
Prepolymerization reaction is carried out, pre-polymerization viscosity controlled by 6-8 ten thousand or so, and 40% ~ 50%, kettle temperature is controlled 70 for solid content control during pre-polymerization
℃~80℃;
2nd, small molecule ethylene glycol and BDO chain extender are added after pre-polymerization terminates, 20 minutes is stirred again and adds two isocyanides
Acid esters(MDI-100 and MDI-50)Generation chain extending reaction;
3rd, midway progressively adds MDI and continues to react, and being continuously increased with system viscosity, is gradually added required solvent DMF.
Final viscosity control is controlled between 70 ~ 80 DEG C in 80 ~ 120Pa S/25 DEG C, kettle temperature.
4th, reaction cools to less than 60 DEG C after terminating and carries out rushing down material, metering packing.
Verification the verifying results scheme 4:
In order to verify that clothing leather is not only made of a kind of 5 years hydrolyzation resisting clothing leather wet polyurethane resins of ultra-soft matter of the present invention
Soft, plentiful, low elasticity.And the requirement such as 5 years anti-hydrolytic performances, wear-resisting scratch resistance performance and durability can be met.
Prepared resin and the contrast of ordinary soft Wet-type polyurethane resin in the embodiment above, according to known to synthetic leather industry
Method is drawn a design.The general method of process hides is:100 parts of resins, 100 parts of DMF, 8-10 part lignin and wet method usual auxiliaries stir evenly,
Vacuum defoamation must apply and scrape feed liquid;Then painting is scraped into feed liquid coated on cloth, is placed in the 15-20% DMF aqueous solution and solidifies 10 points
Clock, clothing leather crust leather is can obtain through washing, drying after coagulation forming.
Through examination survey, with the embodiment above 1,2,3 prepare resin made by wet method crust leather, feel it is super it is soft, plentiful,
Elasticity is low.And wet method crust leather made of the low modulus Wet-type polyurethane resin of ordinary soft, soft degree, richness and elasticity are equal
Typically.Equally, the wet method crust leather made by resin prepared with the embodiment above 1,2,3, before and after detecting its hydrolysis respectively
Peel strength retention rate be significantly larger than wet method crust leather made of ordinary soft Wet-type polyurethane resin.Meanwhile by made from
Wearability and constant temperature and humidity durability are detected after wet method crust leather dry method veneer, the resin institute prepared with the embodiment above 1,2,3
Manufactured wet method crust leather wearability and constant temperature and humidity durability are wet significantly better than made of ordinary soft Wet-type polyurethane resin
Method crust leather.
The so-called system of the present invention, refers to whole reaction system, is exactly the total amount of all substances.The present invention is not by above-mentioned implementation
Merely illustrating the principles of the invention described in the limitation of case, the embodiment above and specification, essence of the invention is not being departed from
Various changes and modifications of the present invention are possible on the premise of god and scope, and these changes and improvements belong to present invention scope
Within.
Claims (9)
- A kind of 1. clothing leather wet polyurethane resin, it is characterised in that:By polyalcohol and its mixture, diisocyanate, small point Sub- glycol chain extender, crosslinking agent, catalyst, solvent are prepared, wherein:The mole ratio of polyalcohol and its mixture and small molecule glycol chain extender is 1:Between 0.9 ~ 1.0;Diisocyanate is with polyalcohol and its mole ratio of mixture and small molecule glycol chain extender 1.0 ~ 1.08: Between 1;Catalyst amount is 0.2 ‰ ~ the 1 ‰ of polyol compound weight;Dosage of crosslinking agent is 0.4 ~ the 0.6 ‰ of polyol compound weight;Solvent load is the 74% ~ 76% of system gross weight.
- A kind of 2. clothing leather wet polyurethane resin according to claim 1, it is characterised in that:Described polyalcohol and its The composition of mixture is as follows:Polyadipate ethylene glycol BDO esterdiol, number-average molecular weight are 4000 ± 300g/mol;Polytetrahydrofuran diol, number-average molecular weight are 2000 ± 200g/mol;PCDL, number-average molecular weight are 2000 ± 200g/mol.
- A kind of 3. clothing leather wet polyurethane resin according to claim 1, it is characterised in that:Described diisocyanate For 4,4 '-methyl diphenylene diisocyanate MDI-100, and 2,4 '-methyl diphenylene diisocyanate and 4,4 '-diphenyl The mixture M DI-50 of methane diisocyanate is formed, i.e., diisocyanate is that MDI-100 and MDI-50 is formed, and both join jointly With reaction, wherein MDI-50 provides more preferable flexibility and low elasticity for clothing leather wet polyurethane resin.
- A kind of 4. clothing leather wet polyurethane resin according to claim 1, it is characterised in that:Described small molecule binary Alcohol chain extender molecular weight is 62 ~ 200g/mol, and small molecule glycol chain extender is ethylene glycol, BDO, neopentyl glycol, 1, One or both of 6- hexylene glycols.
- A kind of 5. clothing leather wet polyurethane resin according to claim 1, it is characterised in that:Described catalyst is to have Machine bismuth class catalyst MB20.
- A kind of 6. clothing leather wet polyurethane resin according to claim 1, it is characterised in that:Described crosslinking agent is three Hydroxymethyl-propane TMP.
- A kind of 7. clothing leather wet polyurethane resin according to claim 1, it is characterised in that:Described solvent is organic Solvent DMF.
- A kind of 8. preparation method of clothing leather wet polyurethane resin, it is characterised in that:Comprise the following steps:(1), put into polyalcohol and its mixture, crosslinking agent, the solvent for the 35-40% for accounting for solvent total amount in a kettle and fully stir After even, the diisocyanate MDI-100 for accounting for total amount 54-58% is added, prepolymerization reaction is carried out under the conditions of existing for catalyst, Pre-polymerization viscosity is controlled by 6-8 ten thousand or so, and 40% ~ 50%, reaction temperature is controlled at 70-80 DEG C for solid content control during pre-polymerization;(2), pre-polymerization terminate after again into reactor add small molecule glycol chain extender and diisocyanate MDI-100 and two it is different Chain extending reaction occurs for cyanate MDI-50, with being continuously increased for system viscosity, is gradually added and remaining accounts for solvent total amount 60- 65% solvent, at 70 ~ 80 DEG C, final viscosity is controlled in 80 ~ 120Pa S/25 DEG C for reaction temperature control.
- A kind of 9. preparation method of clothing leather wet polyurethane resin according to claim 8, it is characterised in that:Step (1)、(2)In polyalcohol and its mixture, diisocyanate, small molecule glycol chain extender, crosslinking agent, solvent be required to contain Water rate is less than 500ppm.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201711008689.2A CN107722219A (en) | 2017-10-25 | 2017-10-25 | A kind of clothing leather wet polyurethane resin and preparation method thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201711008689.2A CN107722219A (en) | 2017-10-25 | 2017-10-25 | A kind of clothing leather wet polyurethane resin and preparation method thereof |
Publications (1)
Publication Number | Publication Date |
---|---|
CN107722219A true CN107722219A (en) | 2018-02-23 |
Family
ID=61213942
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201711008689.2A Pending CN107722219A (en) | 2017-10-25 | 2017-10-25 | A kind of clothing leather wet polyurethane resin and preparation method thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN107722219A (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109853254A (en) * | 2019-02-28 | 2019-06-07 | 扬州工业职业技术学院 | A kind of middle hard mirror surface polyurethane wet bass and preparation method thereof |
CN113106764A (en) * | 2020-01-13 | 2021-07-13 | 浙江诚迅新材料有限公司 | Super-fiber super-soft scratch-resistant wear-resistant surface layer resin and preparation method thereof |
CN115873204A (en) * | 2022-12-14 | 2023-03-31 | 合肥安利聚氨酯新材料有限公司 | High-wear-resistance polyurethane resin for velvet foamed leather and preparation method and application thereof |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5166299A (en) * | 1991-09-09 | 1992-11-24 | Ethyl Corporation | Polyurethanes comprising the reaction product of an isocyanate prepolymer and isomers of di(methylthio)-diaminotoluene |
CN102181031A (en) * | 2010-10-20 | 2011-09-14 | 上海汇得化工有限公司 | Durable polyurethane resin for sofa leather and preparation method of the durable polyurethane resin |
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 |
CN104004159A (en) * | 2014-06-16 | 2014-08-27 | 旭川化学(苏州)有限公司 | Polyurethane resin and preparation method and application thereof |
CN104163909A (en) * | 2014-08-06 | 2014-11-26 | 合肥安利聚氨酯新材料有限公司 | Polyurethane resin for hydrolysis-resistant sofa leather and preparation method thereof |
CN105111412A (en) * | 2015-09-29 | 2015-12-02 | 合肥安利聚氨酯新材料有限公司 | Soft hydrolysis resistance composite polyether type high peeling wet process polyurethane resin and preparing method thereof |
-
2017
- 2017-10-25 CN CN201711008689.2A patent/CN107722219A/en active Pending
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5166299A (en) * | 1991-09-09 | 1992-11-24 | Ethyl Corporation | Polyurethanes comprising the reaction product of an isocyanate prepolymer and isomers of di(methylthio)-diaminotoluene |
CN102181031A (en) * | 2010-10-20 | 2011-09-14 | 上海汇得化工有限公司 | Durable polyurethane resin for sofa leather and preparation method of the durable polyurethane resin |
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 |
CN104004159A (en) * | 2014-06-16 | 2014-08-27 | 旭川化学(苏州)有限公司 | Polyurethane resin and preparation method and application thereof |
CN104163909A (en) * | 2014-08-06 | 2014-11-26 | 合肥安利聚氨酯新材料有限公司 | Polyurethane resin for hydrolysis-resistant sofa leather and preparation method thereof |
CN105111412A (en) * | 2015-09-29 | 2015-12-02 | 合肥安利聚氨酯新材料有限公司 | Soft hydrolysis resistance composite polyether type high peeling wet process polyurethane resin and preparing method thereof |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109853254A (en) * | 2019-02-28 | 2019-06-07 | 扬州工业职业技术学院 | A kind of middle hard mirror surface polyurethane wet bass and preparation method thereof |
CN109853254B (en) * | 2019-02-28 | 2021-08-03 | 扬州工业职业技术学院 | Medium-hard mirror polyurethane wet base and preparation method thereof |
CN113106764A (en) * | 2020-01-13 | 2021-07-13 | 浙江诚迅新材料有限公司 | Super-fiber super-soft scratch-resistant wear-resistant surface layer resin and preparation method thereof |
CN115873204A (en) * | 2022-12-14 | 2023-03-31 | 合肥安利聚氨酯新材料有限公司 | High-wear-resistance polyurethane resin for velvet foamed leather and preparation method and application thereof |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN101381449B (en) | Polyurethane resin for artificial leather | |
CN100383178C (en) | Bicompenent high solid content aqueous polyurethane, its preparation method and application | |
CN103467696B (en) | A kind of preparation method of soft high-elasticity embossing sofa leather wet-method polyurethane resin | |
TWI529196B (en) | Polycarbonate diol, production method thereof, polyurethane using the same and production method thereof | |
CN101824294B (en) | Preparation method of tetrabasic copolymerized waterborne polyurethane automotive interior adhesive | |
CN107722219A (en) | A kind of clothing leather wet polyurethane resin and preparation method thereof | |
CN101759841B (en) | Core-shell type aqueous polyurethane-acrylic ester emulsion original position radiation polymerization method | |
CN101974141A (en) | Preparation method of water-based polyacrylate modified polyurethane dispersion (PUD) | |
CN101503498B (en) | Wet-type high cracking resistance, high wear resistance and high peel strength polyurethane resin and preparation thereof | |
CN106883592A (en) | A kind of super abrasive color inhibition easy dyeing super fiber leather polyurethane resin | |
CN104163909A (en) | Polyurethane resin for hydrolysis-resistant sofa leather and preparation method thereof | |
CN110835401A (en) | Waterborne polyurethane surface layer resin and preparation method thereof | |
CN112482045B (en) | Polylactic acid biodegradable polyurethane synthetic leather and preparation method thereof | |
CN114085353B (en) | Photo-thermal dual-curing resin and preparation method thereof | |
CN109554153A (en) | A kind of preparation method and application of collagen base adhesive | |
CN101503861A (en) | Two-liquid type rapid stripping synthetic leather composite overlay | |
CN106753171A (en) | polyurethane binder and preparation method thereof | |
CN106188478A (en) | A kind of modified polyurethane emulsion film former and its preparation method and application | |
CN105646838B (en) | A kind of preparation method of newtrex based polyurethanes performed polymer | |
CN111269647A (en) | Preparation method and application of epoxy resin modified polyurethane coating agent | |
CN109468112B (en) | Low-residue high-temperature-resistant high-strength polyether polyurethane adhesive for high-speed compounding and preparation method thereof | |
CN102617826B (en) | Soft non-adhesive wet polyurethane resin and preparation method thereof | |
Li et al. | Thermal-driven cationic waterborne polyurethane crosslinker with oxime-based and catechol structure for the preparation of soybean protein-based adhesive with excellent adhesion properties | |
CN108948320A (en) | It is a kind of for manufacturing the combination material of polyurethane sole materials | |
CN101184792A (en) | Use of solid pigment preparations for dyeing composite cellulose/polymer materials |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
RJ01 | Rejection of invention patent application after publication | ||
RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180223 |