CN107190511B - A kind of AS resin modified polyurethane resin textile slurry and preparation method thereof - Google Patents
A kind of AS resin modified polyurethane resin textile slurry and preparation method thereof Download PDFInfo
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- CN107190511B CN107190511B CN201710462387.6A CN201710462387A CN107190511B CN 107190511 B CN107190511 B CN 107190511B CN 201710462387 A CN201710462387 A CN 201710462387A CN 107190511 B CN107190511 B CN 107190511B
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
- D06M15/572—Reaction products of isocyanates with polyesters or polyesteramides
-
- 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
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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
- C08G18/4009—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
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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
- C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
- C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
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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
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
- C08G18/4277—Caprolactone and/or substituted caprolactone
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- C—CHEMISTRY; METALLURGY
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- 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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- 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
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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
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
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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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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/31—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated nitriles
Abstract
A kind of wet polyurethane resin textile slurry, component including following dosage: 2000~2500 parts of polyester polyols alcohol mixture, 1500~1800 parts of diisocyanate, 300~450 parts of polyetherdiol, 230~280 parts of AS resin, glycol chain extender, 5000~8000 parts of DMAC, 10~13 parts of 2,6-di-tert-butyl p-cresol, 4~6 parts of dibutyl tin dilaurate, 0.05~0.1Kg/1000Kg of reaction terminating agent, 20~30 parts of cell modifiers, 3~8 parts of CA-630；The molar ratio of polyester polyols alcohol mixture and glycol chain extender is 1:1.5~2.0.Wet polyurethane resin textile slurry of the present invention, is re-introduced into AS resin system, not only increases the intensity, gas permeability and stripping performance of resin, and improves its modulus and improve its physical property, and it is dry and comfortable to improve cloth cover.
Description
Technical field
The present invention relates to textile raw material technical fields, more particularly, to a kind of AS resin modified polyurethane resin textile
Slurry and preparation method thereof.
Background technique
Currently, corium good permeability is soft, but it is expensive, resource has in fields such as footwear, textiles
Limit, being synthesized leather substitution has been trend of the times.Synthetic leather production technology is divided into three step of wet process, dry method and back-end processing, wherein
The wet process that wet processing is produced is synthetic leather base material, usually the synthetic leather, then is logical on the surface of wet process substrate
It crosses dry method and post-processing process is made, being formed largely containing soaking technology at the cloth base back side in wet-method synthetic leather process
Microcellular structure, with leather effect, this microcellular structure of wet-method synthetic leather proposes the various aspects of performance of resin
Higher requirement.Currently, the high hydrolysis resistance polyurethane resin of corium material can be replaced usually all to select polyether polyurethane body
System, but the system polarity is weaker, and the fastness in conjunction with base fabric is poor, causes the peel strength of product relatively low.
Polyurethane resin systems are the quasi polymers for containing-NHCOO- constitutional repeating unit on main chain, have for one kind
The high molecular material of the characteristics such as high intensity, tear-proof, wear-resisting.Synthetic Leather made by wet polyurethane resin slurry,
With soft glossy, naturally, soft, appearance kishke feel is strong, although it is preferable with base fabric binding strength, solves system
The relatively low problem of product peel strength, but its hydrolytic resistance can meet the requirement of product.Polyurethane in the prior art
Resin system is usually to be reacted to be formed in the case where DMF is solvent with polyester polyol by diisocyanate, DMF also known as diformazan
Base formamide is both a kind of industrial chemicals that purposes is extremely wide and a kind of excellent solvent having many uses, is mainly used for skin
Leather, the sterilization of processes such as production, storage, transport of footwear and textile and mould proof etc., dimethylformamide is to a variety of high polymers
Such as polyethylene, polyvinyl chloride, polyacrylonitrile, polyamide are good solvent, and it is fine to can be used for the synthesis such as polyacrylonitrile fibre
The synthesis of the wet spinning silk, polyurethane of dimension.But in recent years, with the improvement of people's environmental awareness, finding after study, DMF in
After human body proximity contact, to liver, kidney has certain damage, belongs to moderate toxicity.Although at home, also using DMF in large quantities
As polyurethane resin systems solvent, but early from May 1st, 2009, DMF is individually listed by European Union member countries as more
Stringent regulation, EU member country, which must assure that, forbids the product containing DMF to put goods on the market；Contain to market is already present on
The product of DMF must be recalled from market, and be recalled from consumer；Consumer must know the risk of the product.Currently, grinding
Issue the demand that a kind of water resistance is good, heat-resisting, ventilative and environmentally friendly synthesis leather has become market.
Application No. is the patent of invention of CN201310655926.X, a kind of leather Polyurethane resin slurry and its system are disclosed
Preparation Method preparation method includes the following steps: (1) by the N of polyester polyol A and total weight 15%~30%, N- dimethyl formyl
Amine (DMF) is uniformly mixed, then puts into the diisocyanate of total weight 50%~80%, is reacted；(2) C2~C4 binary is then added
The DMF of pure and mild total weight 30%~60%, then surplus is added portionwise at 70~85 DEG C in the diisocyanate of investment surplus in batches
DMF, react to product viscosity be 70~130Pas/25 DEG C, cooling, terminate reaction discharging.Its leather developed is used
Polyurethane resin slurry is a kind of preferable synthetic leather of heat resistance, but which are added the N of total weight 15%~30%, N- diformazans
Base formamide (DMF), to human body, there are toxic hidden danger.
Summary of the invention
In order to overcome the shortcomings in the background art, the invention discloses a kind of AS resin modified polyurethane resin textile slurries
Material.
In order to realize the goal of the invention, the present invention adopts the following technical scheme: a kind of AS resin modified polyurethane resin
Textile slurry, the component including following dosage: 2000~2500 parts of polyester polyols alcohol mixture, diisocyanate 1500~
1800 parts, 300~450 parts of polyetherdiol, 230~280 parts of AS resin, glycol chain extender, 5000~8000 parts of DMAC, 2,
10~13 parts of 6- di-tert-butyl p-cresol, 4~6 parts of dibutyl tin dilaurate, 0.05~0.1Kg/1000Kg of reaction terminating agent,
20~30 parts of cell modifiers, 3~8 parts of CA-630；The molar ratio of polyester polyols alcohol mixture and glycol chain extender is 1:
1.5~2.0；The polyester polyol is phthalic anhydride polyester diol, polycaprolactone polyol and polyethylene glycol adipate binary
The compounding blend of alcohol.
In order to be further improved technical solution, polyetherdiol of the present invention is the poly- of 1000~2000g/mol of molecular weight
Tetrahydrofuran ether glycol.
In order to be further improved technical solution, chain extender of the present invention is 1,4-butanediol, ethylene glycol, 1,2- the third two
In alcohol, 1,5- pentanediol, 1,6-HD or ethanol amine any one or it is two or more.
In order to be further improved technical solution, diisocyanate of the present invention be '-diphenylmethane diisocyanate (MDI),
4,4- dicyclohexyl methyl hydride diisocyanate (HMDI), tetramethyl xylylene diisocyanate m-TMXDI, isophorone two are different
One of cyanate or 1,6- hexamethylene diisocyanate (HDI).
In order to be further improved technical solution, 2,6-di-tert-butyl p-cresol of the present invention is by BHT Hinered phenols antioxygen
One of agent 245,1790, triphenyl phosphite, GA-80 or Chinox 30N replacement.
In order to be further improved technical solution, dibutyl tin dilaurate of the present invention is by butyl titanate, phosphorous acid
Triphenylmethyl methacrylate, stannous octoate or organic bismuth catalyst replacement.
In order to be further improved technical solution, cell modifiers of the present invention be wood powder, frosted resin, calcium carbonate,
One or more of calcium sulfate, wollastonite or white carbon black；The mesh number of the wood powder is 400 mesh or more.
In order to be further improved technical solution, reaction terminating agent of the present invention is methanol, in n-propanolamine, isopropanolamine
One or more.
A kind of preparation method of AS resin modified polyurethane resin textile slurry, preparation step are as follows:
(1) cell modifiers are added in organic solvent DMAC first by formula rate, and 10min is sufficiently stirred to bubble
Pore regulator is well dispersed in organic solvent DMAC；Simultaneously in organic solvent by the dissolution of AS resin；
(2) in cell modifiers under organic solvent DMAC dispersity, by phthalic anhydride polyester diol, polycaprolactone polyol
Alcohol and polyethylene glycol adipate dihydric alcohol compound blend and the organic molten of total weight 15%~30% is added in polyetherdiol
It is uniformly mixed in agent DMAC, and is heated to 60 DEG C；Then it is added and has distilled part chain extender that is dry and accurately measuring, 2,
6- di-tert-butyl p-cresol, CA-630 and dibutyl tin dilaurate, stirring keep it mixed with organic solvent mixed liquor substantially uniformity
It closes, control solid content is controlled in 35-45%, viscosity at 60-80Pa.S/75 DEG C；Be stirring evenly and then adding into total weight 50%~
80% diisocyanate reacts 1 hour in 75-85 DEG C, and prepolymer is made；
(3) chain extender of surplus is added in the prepolymer prepared to step 2), adds diisocyanate in batches after mixing evenly
Ester thickening, the reaction was continued 1-3 hours in 75-85 DEG C, as DMAC is continuously replenished in the increase of system viscosity during reaction
So that final solid content is 25~30%, viscosity is 50-110Pa.S/25 DEG C, reaction terminating agent is added after the reaction was completed；
(4) it is stirred evenly after mixing the reaction solution in step (3) with dissolved AS resin in step (1)；
(5) on the cloth of ready A4 size, prepared mixed slurry in step (4) in coating, afterwards with 150 DEG C
Baking oven drying, take out cooling.
By adopting the above-described technical solution, the invention has the following beneficial effects: solvent dimethyl used herein
Acetamide is a kind of colourless transparent liquid, can be mixed with organic solvents such as water, alcohol, ethers, is a kind of polar solvent.Dimethylacetamide
The thermal stability of amine is good, stable even if boiling point not decompose, and can be refined by distillation；It is stable in aqueous solution, but have acid,
It can promote to hydrolyze in the presence of alkali.Due to introducing ethyl in the molecular structure, the boiling point of dimethyl acetamide is than dimethyl formyl
High 10 DEG C of amine (DMF) or more (boiling point of dimethylformamide is 153 DEG C), therefore have better heat steady than dimethylformamide
Qualitative and chemical stability.
In addition, AS resin modified polyurethane resin textile slurry of the present invention, using phthalic anhydride polyester diol, gathers oneself
The blend that compounds of lactone polyols and polyethylene glycol adipate dihydric alcohol, and preparation is blended with polytetrahydrofuran ether glycol
It forms, is re-introduced into AS resin system, not only increase the intensity, gas permeability and stripping performance of resin, and improve its modulus
And improve its physical property, it is dry and comfortable to improve cloth cover.Use the gas permeability for the synthetic leather base cloth that impregnant made of slurry modulation produces
And stripping performance is also greatly improved, and is the compound synthetic leather base cloth of the soft hydrolysis of one kind, surface dry.
Specific embodiment
By the following examples can the detailed explanation present invention, the open purpose of the present invention is intended to protect model of the present invention
Enclose all interior technological improvements.
Embodiment one
AS resin modified polyurethane resin textile slurry, including following material component (parts by weight, similarly hereinafter): phthalic anhydride polyester
800 parts of dihydric alcohol, 500 parts of polycaprolactone polyol, 700 parts of polyethylene glycol adipate dihydric alcohol, diphenylmethane diisocyanates
1500 parts of ester, 300 parts of the polytetrahydrofuran ether glycol of 1000~2000g/mol of molecular weight, 230 parts of AS resin, 1,4-butanediol,
5000 parts of DMAC, 10 parts of DBPC 2,6 ditertiary butyl p cresol, 4 parts of dibutyl tin dilaurate, methanol 0.05Kg/1000Kg, 400
20 parts of purpose wood powder, 3 parts of CA-630.
When preparation, the wood powder of 400 mesh is added in organic solvent DMAC by formula rate first, and is sufficiently stirred
10min is well dispersed in organic solvent DMAC to cell modifiers；Simultaneously in organic solvent by the dissolution of AS resin；
In cell modifiers under organic solvent DMAC dispersity, by phthalic anhydride polyester diol, polycaprolactone polyol
Total weight 15%~30% is added with compound blend and the polytetrahydrofuran ether glycol of polyethylene glycol adipate dihydric alcohol
It is uniformly mixed in organic solvent DMAC, and is heated to 60 DEG C；Then it is added and has distilled part 1 that is dry and accurately measuring,
4- butanediol, 2,6-di-tert-butyl p-cresol, CA-630 and dibutyl tin dilaurate, stirring make itself and organic solvent mixed liquor
Substantially uniformity mixing, control solid content are controlled in 35-45%, viscosity at 60-80Pa.S/75 DEG C；It is stirring evenly and then adding into gross weight
The '-diphenylmethane diisocyanate of amount 50% reacts 1 hour in 75-85 DEG C, and prepolymer is made；
Then the 1,4-butanediol of surplus is added into the prepolymer of preparation, adds diphenyl-methane two in batches after mixing evenly
Isocyanates thickening, the reaction was continued 1-3 hours in 75-85 DEG C, as the increase of system viscosity is constantly mended during reaction
It fills that DMAC makes final solid content be 25%, viscosity is 70Pa.S/25 DEG C, methanol is added after the reaction was completed and terminates reaction, then
Obtained mixed slurry is stirred evenly after reaction solution is mixed with dissolved AS resin；Then in the cloth of ready A4 size
On material, prepared mixed slurry in coating is rear to be dried with 150 DEG C of baking oven, takes out cooling.
Embodiment two
AS resin modified polyurethane resin textile slurry, including following material component (parts by weight, similarly hereinafter): phthalic anhydride polyester
850 parts of dihydric alcohol, 900 parts of polycaprolactone polyol, 750 parts of polyethylene glycol adipate dihydric alcohol, 4,4- dicyclohexyl methyl hydride
1800 parts of diisocyanate, 400 parts of the polytetrahydrofuran ether glycol of 1000~2000g/mol of molecular weight, 240 parts of AS resin, 1,
4- butanediol, 6500 parts of DMAC, 13 parts of DBPC 2,6 ditertiary butyl p cresol, 6 parts of dibutyl tin dilaurate, methanol 0.05Kg/
1000Kg, 10 parts of wood powder, 15 parts of frosted resin, 7 parts of CA-630.
When preparation, wood powder and frosted resin are added in organic solvent DMAC by formula rate first, and sufficiently stirs
It mixes 10min and is well dispersed in organic solvent DMAC to cell modifiers；Simultaneously in organic solvent by the dissolution of AS resin；
In cell modifiers under organic solvent DMAC dispersity, by phthalic anhydride polyester diol, polycaprolactone polyol
Total weight 15%~30% is added with compound blend and the polytetrahydrofuran ether glycol of polyethylene glycol adipate dihydric alcohol
It is uniformly mixed in organic solvent DMAC, and is heated to 60 DEG C；Then it is added and has distilled part 1 that is dry and accurately measuring,
4- butanediol, 2,6-di-tert-butyl p-cresol, CA-630 and dibutyl tin dilaurate, stirring make itself and organic solvent mixed liquor
Substantially uniformity mixing, control solid content are controlled in 35-45%, viscosity at 60-80Pa.S/75 DEG C；It is stirring evenly and then adding into gross weight
4, the 4- dicyclohexyl methyl hydride diisocyanate 1 of amount 50% reacts 1 hour in 75-85 DEG C, and prepolymer is made；
Then the 1,4-butanediol of surplus is added into the prepolymer of preparation, adds 4,4-, bis- hexamethylene in batches after mixing evenly
Dicyclohexylmethane diisocyanate thickening, the reaction was continued 1-3 hours in 75-85 DEG C, with the increasing of system viscosity during reaction
Add and be continuously replenished that DMAC makes final solid content be 25%, viscosity is 70Pa.S/25 DEG C, be added after the reaction was completed methanol terminate it is anti-
It answers, stirs evenly obtained mixed slurry after then mixing reaction solution with dissolved AS resin；Then in ready A4
On the cloth of size, prepared mixed slurry in coating is rear to be dried with 150 DEG C of baking oven, takes out cooling., after mixing evenly
It can blanking packaging.
Embodiment three
AS resin modified polyurethane resin textile slurry, including following material component (parts by weight, similarly hereinafter): phthalic anhydride polyester
900 parts of dihydric alcohol, 800 parts of polycaprolactone polyol, 650 parts of polyethylene glycol adipate dihydric alcohol, durol dimethyl two
1700 parts of isocyanates, 450 parts of the polytetrahydrofuran ether glycol of 1000~2000g/mol of molecular weight, 280 parts of AS resin, 1,5-
Pentanediol, DMAC8000 parts, it is triphenyl phosphite, 6 parts of dibutyl tin dilaurate, isopropanolamine 0.1Kg/1000Kg, wooden
30 parts of powder, 8 parts of CA-630.
When preparation, wood powder is added in organic solvent DMAC by formula rate first, and 10min is sufficiently stirred to wood
Matter powder is well dispersed in organic solvent DMAC；Simultaneously in organic solvent by the dissolution of AS resin；
In cell modifiers under organic solvent DMAC dispersity, by phthalic anhydride polyester diol, polycaprolactone polyol
Total weight 15%~30% is added with compound blend and the polytetrahydrofuran ether glycol of polyethylene glycol adipate dihydric alcohol
It is uniformly mixed in organic solvent DMAC, and is heated to 60 DEG C；Then it is added and has distilled part 1 that is dry and accurately measuring,
5- pentanediol, triphenyl phosphite, CA-630 and triphenyl phosphite, stirring keep it mixed with organic solvent mixed liquor substantially uniformity
It closes, control solid content is controlled in 35-45%, viscosity at 60-80Pa.S/75 DEG C；It is stirring evenly and then adding into the four of total weight 50%
Xylylene diisocyanate reacts 1 hour in 75-85 DEG C, and prepolymer is made；
Then the 1,5-PD of surplus is added into the prepolymer of preparation, adds durol two in batches after mixing evenly
Methyl diisocyanate thickening, the reaction was continued 1-3 hours in 75-85 DEG C, with the increase of system viscosity during reaction
It is continuously replenished that DMAC makes final solid content be 25%, viscosity is 70Pa.S/25 DEG C, isopropanolamine is added after the reaction was completed and terminates
Reaction, stirs evenly obtained mixed slurry after then mixing reaction solution with dissolved AS resin；Then ready
On the cloth of A4 size, prepared mixed slurry in coating is rear to be dried with 150 DEG C of baking oven, takes out cooling., stir evenly
After can blanking packaging.
Example IV
AS resin modified polyurethane resin textile slurry, including following material component (parts by weight, similarly hereinafter): phthalic anhydride polyester
650 parts of dihydric alcohol, 850 parts of polycaprolactone polyol, 750 parts of polyethylene glycol adipate dihydric alcohol, 4,4- dicyclohexyl methyl hydride
1650 parts of diisocyanate, 380 parts of the polytetrahydrofuran ether glycol of 1000~2000g/mol of molecular weight, 250 parts of AS resin, 1,
2- propylene glycol, DMAC6800 parts, BHT Hinered phenols antioxidant 245,5 parts of organic bismuth catalyst, methanol 0.08Kg/1000Kg, mill
25 parts of sand resin, 6 parts of CA-630.
When preparation, frosted resin is added in organic solvent DMAC by formula rate first, and 10min is sufficiently stirred extremely
Cell modifiers are well dispersed in organic solvent DMAC；Simultaneously in organic solvent by the dissolution of AS resin；
In cell modifiers under organic solvent DMAC dispersity, by phthalic anhydride polyester diol, polycaprolactone polyol
Total weight 15%~30% is added with compound blend and the polytetrahydrofuran ether glycol of polyethylene glycol adipate dihydric alcohol
It is uniformly mixed in organic solvent DMAC, and is heated to 60 DEG C；Then it is added and has distilled part 1 that is dry and accurately measuring,
2- propylene glycol, BHT Hinered phenols antioxidant 245, CA-630 and organic bismuth catalyst, stirring keep it complete with organic solvent mixed liquor
Complete uniformly mixing, control solid content are controlled in 35-45%, viscosity at 60-80Pa.S/75 DEG C；It is stirring evenly and then adding into total weight
50% 4,4- dicyclohexyl methyl hydride diisocyanate reacts 1 hour in 75-85 DEG C, and prepolymer is made；
Then the 1,2-PD of surplus is added into the prepolymer of preparation, adds 4,4-, bis- hexamethylene in batches after mixing evenly
Dicyclohexylmethane diisocyanate thickening, the reaction was continued 1-3 hours in 75-85 DEG C, with the increasing of system viscosity during reaction
Add and be continuously replenished that DMAC makes final solid content be 25%, viscosity is 70Pa.S/25 DEG C, be added after the reaction was completed methanol terminate it is anti-
It answers, stirs evenly obtained mixed slurry after then mixing reaction solution with dissolved AS resin；Then in ready A4
On the cloth of size, prepared mixed slurry in coating is rear to be dried with 150 DEG C of baking oven, takes out cooling.
Claims (8)
1. a kind of AS resin modified polyurethane resin textile slurry, it is characterized in that: including the component of following dosage: polyester polyols
2000~2500 parts of alcohol mixture, 1500~1800 parts of diisocyanate, 300~450 parts of polyetherdiol, AS resin 230~280
Part, glycol chain extender, 5000~8000 parts of DMAC, 10~13 parts of DBPC 2,6 ditertiary butyl p cresol, dibutyl tin dilaurate
4~6 parts, 0.05~0.1Kg/1000Kg of reaction terminating agent, 20~30 parts of cell modifiers, 3~8 parts of CA-630；Polyester polyols
The molar ratio of alcohol mixture and glycol chain extender is 1:1.5~2.0；The polyester polyol is phthalic anhydride polyester diol, gathers
Caprolactone polyol compounds blend with polyethylene glycol adipate dihydric alcohol；The polyetherdiol be molecular weight 1000~
The polytetrahydrofuran ether glycol of 2000g/mol.
2. AS resin modified polyurethane resin textile slurry as described in claim 1, it is characterized in that: the chain extender is 1,
In 4- butanediol, ethylene glycol, 1,5- pentanediol, 1,6-HD or ethanol amine any one or it is two or more.
3. AS resin modified polyurethane resin textile slurry as described in claim 1, it is characterized in that: the diisocyanate
It is different for '-diphenylmethane diisocyanate (MDI), 4,4- dicyclohexyl methyl hydride diisocyanate (HMDI), durol dimethyl two
One of cyanate m-TMXDI, isophorone diisocyanate or 1,6- hexamethylene diisocyanate (HDI).
4. AS resin modified polyurethane resin textile slurry as described in claim 1, it is characterized in that: the tertiary fourth of 2, the 6- bis-
Base paracresol is replaced by one of BHT Hinered phenols antioxidant 245,1790, triphenyl phosphite, GA-80 or Chinox 30N
It changes.
5. AS resin modified polyurethane resin textile slurry as described in claim 1, it is characterized in that: dibutyl tin cinnamic acid
Tin is replaced by butyl titanate, triphenyl phosphite, stannous octoate or organic bismuth catalyst.
6. AS resin modified polyurethane resin textile slurry as described in claim 1, it is characterized in that: the cell modifiers
For one or more of wood powder, frosted resin, calcium carbonate, calcium sulfate, wollastonite or white carbon black；The mesh number of the wood powder
More than 400 mesh.
7. AS resin modified polyurethane resin textile slurry as described in claim 1, it is characterized in that: the reaction terminating agent
For one or more of methanol, n-propanolamine, isopropanolamine.
8. a kind of preparation method of AS resin modified polyurethane resin textile slurry as described in claim 1, it is characterized in that: its
Preparation step are as follows:
(1) cell modifiers are added in organic solvent DMAC first by formula rate, and 10min is sufficiently stirred to abscess tune
Section agent is well dispersed in organic solvent DMAC；Simultaneously in organic solvent by the dissolution of AS resin；
(2) in cell modifiers under organic solvent DMAC dispersity, by phthalic anhydride polyester diol, polycaprolactone polyol with
The organic solvent of total weight 15%~30% is added in the compounding blend and polyetherdiol of polyethylene glycol adipate dihydric alcohol
It is uniformly mixed in DMAC, and is heated to 60 DEG C；Then it is added and has distilled part chain extender, 2,6- dry and accurately measure
Di-tert-butyl p-cresol, CA-630 and dibutyl tin dilaurate, stirring mix it with organic solvent mixed liquor substantially uniformity,
Solid content is controlled in 35-45%, viscosity is controlled at 60-80Pa.S/75 DEG C；It is stirring evenly and then adding into total weight 50%~80%
Diisocyanate reacts 1 hour in 75-85 DEG C, and prepolymer is made；
(3) chain extender of surplus is added in the prepolymer prepared to step 2), adds diisocyanate increasing in batches after mixing evenly
Viscous, the reaction was continued 1-3 hours in 75-85 DEG C, and increase during reaction with system viscosity is continuously replenished DMAC and makes
Final solid content is 25~30%, viscosity is 50-110Pa.S/25 DEG C, and reaction terminating agent is added after the reaction was completed；
(4) obtained mixing slurry is stirred evenly after mixing the reaction solution in step (3) with dissolved AS resin in step (1)
Material；
(5) on the cloth of ready A4 size, prepared mixed slurry in step (4) in coating, afterwards with 150 DEG C of baking
Case drying, takes out cooling.
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| CN1174212A (en) * | 1996-08-20 | 1998-02-25 | 中国石油化工总公司 | Polyurethane-containing thermoplastic binary composition |
| CN101787242A (en) * | 2010-01-19 | 2010-07-28 | 华南师范大学 | Wear-resistant waterborne two-component polyurethane coating and preparation method thereof |
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| CN106753160A (en) * | 2016-11-29 | 2017-05-31 | 上海华峰材料科技研究院（有限合伙） | Aqueous polyurethane Flock Adhesive and preparation method thereof |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1174212A (en) * | 1996-08-20 | 1998-02-25 | 中国石油化工总公司 | Polyurethane-containing thermoplastic binary composition |
| CN101787242A (en) * | 2010-01-19 | 2010-07-28 | 华南师范大学 | Wear-resistant waterborne two-component polyurethane coating and preparation method thereof |
| CN102070766A (en) * | 2010-12-27 | 2011-05-25 | 沈阳化工大学 | Method for preparing novel polyether-polyester polyurethane material |
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