CN106397716A - Moisture absorption dyeable polyurethane resin and preparation method thereof - Google Patents

Moisture absorption dyeable polyurethane resin and preparation method thereof Download PDF

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Publication number
CN106397716A
CN106397716A CN201610803760.5A CN201610803760A CN106397716A CN 106397716 A CN106397716 A CN 106397716A CN 201610803760 A CN201610803760 A CN 201610803760A CN 106397716 A CN106397716 A CN 106397716A
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China
Prior art keywords
chain extender
dyeing
polyhydric alcohol
pepa
polyurethane resin
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Inventor
杜明兵
张其斌
杨银龙
韩芹
吴勇
诸葛磊
胡忠杰
刘国
彭超豪
胡雪丽
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SHANGHAI HUAFON MICREOFIBRE TECHNOLOGY Co Ltd
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SHANGHAI HUAFON MICREOFIBRE TECHNOLOGY Co Ltd
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Priority to CN201610803760.5A priority Critical patent/CN106397716A/en
Publication of CN106397716A publication Critical patent/CN106397716A/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
    • 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
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/46—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen
    • C08G18/4676—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen containing sulfur
    • 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
    • C08G18/4804—Two or more polyethers of different physical or chemical nature
    • C08G18/4808—Mixtures of two or more polyetherdiols
    • 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
    • C08G18/4825—Polyethers containing two 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
    • C08G18/28—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
    • C08G18/4833—Polyethers containing oxyethylene units
    • 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
    • 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
    • C08G18/6614—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 C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38
    • C08G18/6622—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 C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3271
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
    • C08G18/6688—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3271
    • 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
    • D06M15/568—Reaction products of isocyanates with polyethers
    • 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

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The invention discloses a moisture absorption dyeable polyurethane resin and a preparation method thereof. The preparation method comprises the following steps: (1) pre-polymerizing isocyanate and polyhydric alcohol in a solvent; (2) adding a dyeing assisting chain extender, a small-molecular chain extender and the solvent, then adding the isocyanate in batches for reaction, putting into the solvent for dilution, adding an end-capping reagent for reaction to obtain the moisture absorption dyeable polyurethane resin for ultrafine fiber synthesis leather, wherein the use amount of the small-molecular chain extender is 1 to 15 times that of the dyeing assisting chain extender by weight; the dyeing assisting chain extender is selected from one of N-tert-butyl diethanolamine, N-methyldiethanolamine and methylene diphenylamine. The ultrafine fiber synthesis leather prepared from the moisture absorption dyeable polyurethane resin can quickly absorb moisture; when the moisture absorption dyeable polyurethane resin is used in a process for dyeing figured-sea-island and unfigured-sea-island ultrafine fiber synthesis leather, the dyeing time can be shortened, and the dye-uptake can be increased, so that the dyeing speed of base cloth dyeing can be increased, the base cloth dyeing time can be shortened, the efficiency is improved, and the cost is reduced.

Description

Moisture-absorbing dyed color polyurethane resin and preparation method thereof
Technical field
The present invention relates to a kind of polyurethane resin, more particularly, to a kind of superfine fiber chemical leather is with moisture-absorbing dyed color polyurethane And its manufacture method.
Background technology
Sea-island Composite Fiber Synthetic Leather, is made up of nylon fiber and polyurethane resin, because of its unique structure and excellent Performance, make the high-end product in synthetic leather field, its product is had and compared favourably with natural leather, simultaneously in physical property side Face is better than natural leather, and it is the product having merged the multinomial professional technique such as chemical fibre, non-woven fabrics, process hides, chemical industry, dyeing and finishing, this Kind of fabric is lightweight, soft comfortable, designs and varieties many it is easy to maintenance etc., performance surmounts corium better than woollen higher than cotton.Simultaneously There is good antibacterial, mould proof, mothproof environmental-protecting performance and plentiful fine hair, numerous patterns and be on various fabrics, Can be widely used for the fields such as glove for golf game, sofa, recreational men and women's footwear, decoration, dress ornament.
With regard to dyeing, absorptive polyurethane resin patent report, for example：A kind of elastic water absorption basketball leather wet method Polyurethane resin and preparation method (number of patent application：201110440156.8), patent obtains suction by introducing Polyethylene Glycol Aqueouss energy, but easily there is a problem of swelling；Superfine fiber chemical leather easy dyeing polyurethane resin and preparation method thereof is (specially Sharp application number：2015109715220) very well, hygroscopicity is general, the microfiber synthetic leather made for the resin dyeability that, patent system obtains Base fabric big production dyeing time is long, and dyeing rate is general.
Content of the invention
It is an object of the invention to provide a kind of preparation method of moisture-absorbing dyed color polyurethane resin, solve existing polyurethane tree The difficult dyeing of fat, the defect of moisture absorption difference.
The method of the present invention, comprises the steps：
(1) by isocyanates and polyhydric alcohol, in a solvent, 65～75 DEG C of pre-polymerization 80～100min；
Isocyanates with the mol ratio of polyhydric alcohol are：Isocyanates: polyhydric alcohol=2:1～8:1
In solvent, the weight content of polyhydric alcohol is 40%～80%；
Described polyhydric alcohol is one or more of PEPA or polyether polyol；
Wherein：
Described polyether polyol is polyethylene glycol oxide-propylene oxide copolymerization dihydroxylic alcohols P (EO/PO), polyethylene glycol oxide two First alcohol PEG, Polyoxypropylene diol PPG, at least one in PolyTHF dihydroxylic alcohols PTMG, molecular weight be 400～ 4000；
Described PEPA is sulfonate grafted polyester polyhydric alcohol, and molecular weight is 1000-4000, preferably such as：BY- 3301st, BY-3305B (Beijing one hundred source Chemical Co., Ltd.), adipic acid system PEPA, such as：Adipic acid and butanediol reaction Obtained by PBA1000, PBA2000, PBA3000 etc., or for adipic acid and PEA1000 obtained by glycol reaction, PEA2000, PEA3000 etc., or PHA1000, PHA2000, PHA3000 of adipic acid and hexanediol reaction etc.；
Preferably, when described polyhydric alcohol is the mixture of PEPA or polyether polyols, weight ratio is：
Polyether polyol: PEPA=2～6: 1；
Preferably, described polyhydric alcohol is PolyTHF dihydroxylic alcohols (PTMG2000) and Polyoxypropylene diol (PPG2000) mixture, weight ratio is：PolyTHF dihydroxylic alcohols：Polyoxypropylene diol=5～3:1；, preferably 5: 1；
Or it is：
The mixing of PolyTHF dihydroxylic alcohols 2000, PEPA BY-3305B and Polyoxypropylene diol 2000 Thing, weight ratio is：
PolyTHF dihydroxylic alcohols 2000:PEPA BY-3305B:Polyoxypropylene diol 2000=10:1.5 ～2.5:2.5～3.5, preferably 10:2:3；
(2) it is subsequently adding assisting-dyeing chain extender, small molecule chain extender and solvent, and point 3～8 batches of addition isocyanates, 50～ 100 DEG C, preferably 65～75 DEG C reactions, the addition of isocyanates, the viscosity making reactant is 80～200Pa s (25 DEG C), so Solvent dilution to viscosity is added to be that (25 DEG C) of 60～180Pa s adds end-capping reagent to react 20～40min afterwards, you can to obtain described Superfine fiber chemical leather with moisture-absorbing dyed color polyurethane resin；
The weight consumption of assisting-dyeing chain extender is the 0.1%～10% of polyhydric alcohol, preferably 1～5%；
The weight consumption of small molecule chain extender is 1～15 times with the chain extender that can contaminate group；
On the basis of the polyhydric alcohol in step (1), in solvent, the weight content of polyhydric alcohol is 45%～70%；
The conventional molecular weight of polytetrahydrofuran diol (PTMG) is 850～3000, preferably PTMG2000 (molecular weight： 2000)；
Above-mentioned isocyanates preferred methyl diphenylene diisocyanate MDI, HDI；
Described assisting-dyeing chain extender is selected from N- tertiarybutyldiethanolamine (TBDEA), N methyldiethanol amine (MDEA) and two One of phenylmethane diamidogen (MDA)；
(BY-3306D, Beijing one hundred source chemical industry has described small molecule chain extender preferred small molecule sulfonate polyester polyol Limit company), one of ethylene glycol (EG) or butanediol (BG)；
Described solvent is selected from N,N-dimethylformamide (DMF)；
One or more of described end-capping reagent methanol and ethanol；
Using the moisture-absorbing dyed color polyurethane resin of the present invention, prepared microfiber synthetic leather, there is quick moisture absorption, and will not Swelling occurs, be applied to determine island, not in island ultrafine fiber synthetic leather dyeing course, because polyurethane resin has preferably Dyeability, hygroscopicity, can shortening dyeing time, improve dye-uptake, thus improving base fabric dyeing dyeing speed, shortening base fabric Dyeing time, improves efficiency cost-effective.
Specific embodiment
With reference to specific embodiment, present invention is further described, the experimental condition of the present invention can be according to need Adjust accordingly, and be not limited to the experimental condition of the present embodiment.
In embodiment, what each abbreviation represented is：
Polyether polyol：
PEG- polyoxyethylene glycol, PTMG- polytetrahydrofuran diol, PPG- Polyoxypropylene diol；
PEPA is sulfonate grafted polyester polyhydric alcohol：
BY-3301- sulfonate grafted polyester polyhydric alcohol, BY-3306D
MDI- methyl diphenylene diisocyanate
Assisting-dyeing chain extender：TBDEA-N- tertiarybutyldiethanolamine (TBDEA), MDEA-N- methyl diethanolamine, MDA- hexichol Methylmethane diamidogen；
Small molecule chain extender：Sulfonate polyester polyol-BY-3306D, EG- ethylene glycol, BG-1,4 butanediol；
Solvent：N,N-dimethylformamide (DMF)；
Embodiment 1
(1) polyether polyol PTMG2000 (100g), PEPA BY-3301 (20g), solvent DMF (100g) are thrown Enter mixing in reaction bulb, put into isocyanates MDI (12g), 70 DEG C of pre-polymerization 90min；
(2) small molecule chain extender EG (11g), assisting-dyeing chain extender TBDEA (1.5g), solvent DMF (280g) is added to arrive reaction Stir evenly in bottle, point 5 batches of inputs isocyanates MDI (51g), 80 DEG C of reactions, and the viscosity according to reactant, add isocyanates When MDI makes viscosity increase to 90Pa s (25 DEG C) viscosity, stop adding；
It is subsequently adding solvent DMF (80g), is diluted to the viscosity 60Pa s (25 DEG C) of reactant, add methanol 0.05g eventually Only agent reaction 30min, discharging after being cooled to 50 DEG C, you can obtain the moisture-absorbing dyed color polyurethane of described superfine fiber chemical leather Resin, resin solid mass fraction is 30%.
Embodiment 2
(1) polyether polyol PTMG2000 (100g), polyether polyol PPG2000 (20g) and solvent DMF (100g) are thrown Enter mixing in reaction bulb, put into MDI (12g), 70 DEG C of pre-polymerization 90min；
(2) small molecule chain extender EG (10g), assisting-dyeing chain extender MDEA (0.5g), small molecule chain extender BY-3306D are added (10g), solvent DMF (280g) stirs evenly in reaction bulb, point 3 batches of inputs MDI (50g), keeps 70 DEG C of reactions, and according to reactant Viscosity, when adding MDI and making viscosity increase to 130Pa s (25 DEG C) viscosity, stop adding；
It is subsequently adding the viscosity 100Pa s (25 DEG C) that DMF (80g) is diluted to reactant, add methanol 0.05g terminator Reaction 30min, discharging after being cooled to 50 DEG C, you can obtain described superfine fiber chemical leather with moisture-absorbing dyed color polyurethane tree Fat, resin solid mass fraction is 31%.
Embodiment 3
(1) polyether polyol PTMG2000 (120g), PEPA BY-3305B (30g), DMF (100g) are put into instead Answer mixing in bottle, put into MDI (14g), 70 DEG C of pre-polymerization 90min；
(2), after the completion of pre-polymerization, polyether polyol EG (14g), small molecule chain extender BY-3306D (5g), assisting-dyeing chain extension are added Agent MDA (5g), DMF (360g) stir evenly in reaction bulb, point 8 batches of inputs MDI (71g), keep 80 DEG C of reactions, and according to reactant Viscosity, when adding MDI and making viscosity increase to 160Pa s (25 DEG C) viscosity, stop adding；
It is subsequently adding the viscosity 120Pa s (25 DEG C) that DMF (100) is diluted to reactant, add methanol 0.05g terminator Reaction 30min, discharging after being cooled to 50 DEG C, you can obtain described superfine fiber chemical leather with moisture-absorbing dyed color polyurethane tree Fat, resin solid mass fraction is 29%.
Embodiment 4
(1) by polyether polyol PTMG2000 (100g), PEPA BY-3305B (20g), polyether polyol PPG2000 (30g), solvent DMF (100g) put in reaction bulb, and mixing puts into MDI (14g), 70 DEG C of pre-polymerization 90min；
(2) small molecule chain extender EG (8g), assisting-dyeing chain extender MDA (3g), DMF (300g) is added to stir evenly in reaction bulb, Divide 3 batches to put into MDI (40g), keep 70 DEG C of reactions, and the viscosity according to reactant, adding MDI makes viscosity increase to 200Pa s During (25 DEG C) viscosity, stop adding；
It is subsequently adding the viscosity 180Pa s (25 DEG C) that DMF (80g) is diluted to reactant, add methanol 0.05g terminator Reaction 30min, discharging after being cooled to 50 DEG C, you can obtain described superfine fiber chemical leather with moisture-absorbing dyed color polyurethane tree Fat, resin solid mass fraction is 30%.
Polyurethane resin obtained by aforementioned four example is obtained superfine fibre synthesis by following Conventional process steps Leather base cloth：By 100 parts of polyurethane, the weight that 58 parts of solvent DMF prepares working solution, with needle punched non-woven fabrics as base, Its fiber gap saturation impregnates working solution, forms through solidification, washing, decrement, drying and shaping, such as document：《Synthesis technique》(bent Build ripple etc. synthetic leather technology [M]. Beijing：Chemical Industry Press, 2010.).
Above-mentioned obtained base fabric is dyeed, compared with normal dyeing base fabric, above-mentioned prepared base fabric dye uptake is extremely Few high by more than 30%, color fastness is at least high 1 grade, and dyeing time at least shortens 1/3rd.

Claims (10)

1. the preparation method of moisture-absorbing dyed color polyurethane resin is it is characterised in that comprise the steps：
(1) by isocyanates and polyhydric alcohol, in a solvent, pre-polymerization；
(2) it is subsequently adding assisting-dyeing chain extender, small molecule chain extender and solvent, be dividedly in some parts isocyanates, reaction, then enter solvent Dilution, adds end-capping reagent reaction, you can obtain the moisture-absorbing dyed color polyurethane resin of described superfine fiber chemical leather；
The weight consumption of small molecule chain extender is 1～15 times of assisting-dyeing chain extender；
Described assisting-dyeing chain extender is selected from N- tertiarybutyldiethanolamine (TBDEA), N methyldiethanol amine (MDEA) and diphenyl One of methane diamidogen (MDA).
2. method according to claim 1 is it is characterised in that in step (1), by isocyanates and polyhydric alcohol, in solvent In, 65～75 DEG C of pre-polymerization 80～100min.
3. method according to claim 1 is it is characterised in that isocyanates with the mol ratio of polyhydric alcohol are：Isocyanates: Polyhydric alcohol=2:1～8:1.
4. method according to claim 1 is it is characterised in that described polyhydric alcohol is PEPA or polyether polyol One or more of.
5. method according to claim 4 is it is characterised in that described polyether polyol is polyethylene glycol oxide-oxidation third Alkene copolymerization dihydroxylic alcohols P (EO/PO), polyoxyethylene glycol PEG, Polyoxypropylene diol PPG, PolyTHF dihydroxylic alcohols At least one in PTMG, molecular weight is 400～4000.
6. method according to claim 5 is it is characterised in that described PEPA is molecular weight 1000-4000's Sulfonate grafted polyester polyhydric alcohol, adipic acid system PEPA, adipic acid and PEA1000 obtained by glycol reaction, PEA2000, PEA3000 or PHA1000, PHA2000 or PHA3000 of adipic acid and hexanediol reaction.
7. method according to claim 5 is it is characterised in that described polyhydric alcohol is PEPA or polyether polyols During mixture, weight ratio is：Polyether polyol: PEPA=2～6: 1.
8. method according to claim 5 is it is characterised in that described polyhydric alcohol is PolyTHF dihydroxylic alcohols (PTMG2000) and Polyoxypropylene diol (PPG2000) mixture, weight ratio is：PolyTHF dihydroxylic alcohols：Polyoxy Change propylene dihydroxylic alcohols=5～3:1；Preferably 5:1；
Or it is：
The mixture of PolyTHF dihydroxylic alcohols 2000, PEPA BY-3305B and Polyoxypropylene diol 2000, weight Measuring ratio is：
PolyTHF dihydroxylic alcohols 2000:PEPA BY-3305B:Polyoxypropylene diol 2000=10:1.5～ 2.5:2.5～3.5, preferably 10:2:3.
9. the method according to any one of claim 1～8 is it is characterised in that described small molecule chain extender is selected from sulfonic acid One of salt PEPA, ethylene glycol (EG) or butanediol (BG).
10. the moisture-absorbing dyed color polyurethane resin of the method preparation according to any one of claim 1～9.
CN201610803760.5A 2016-09-06 2016-09-06 Moisture absorption dyeable polyurethane resin and preparation method thereof Pending CN106397716A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102212183A (en) * 2011-05-03 2011-10-12 烟台华大化学工业有限公司 Polyurethane resin used for skin-imitated superfine fiber synthetic leather, and preparation method thereof
CN103467696A (en) * 2013-08-16 2013-12-25 合肥安利聚氨酯新材料有限公司 Preparation method of soft high-elasticity embossed sofa leather wet-method polyurethane resin
CN105542108A (en) * 2015-12-22 2016-05-04 上海华峰超纤材料股份有限公司 Easily-dyeable polyurethane resin used for superfine fiber synthetic leather and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102212183A (en) * 2011-05-03 2011-10-12 烟台华大化学工业有限公司 Polyurethane resin used for skin-imitated superfine fiber synthetic leather, and preparation method thereof
CN103467696A (en) * 2013-08-16 2013-12-25 合肥安利聚氨酯新材料有限公司 Preparation method of soft high-elasticity embossed sofa leather wet-method polyurethane resin
CN105542108A (en) * 2015-12-22 2016-05-04 上海华峰超纤材料股份有限公司 Easily-dyeable polyurethane resin used for superfine fiber synthetic leather and preparation method thereof

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