CN105542108B - Superfine fiber chemical leather easy dyeing polyurethane resin and preparation method thereof - Google Patents
Superfine fiber chemical leather easy dyeing polyurethane resin and preparation method thereof Download PDFInfo
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- CN105542108B CN105542108B CN201510971522.0A CN201510971522A CN105542108B CN 105542108 B CN105542108 B CN 105542108B CN 201510971522 A CN201510971522 A CN 201510971522A CN 105542108 B CN105542108 B CN 105542108B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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- 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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- 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
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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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3271—Hydroxyamines
- C08G18/3275—Hydroxyamines containing two hydroxy 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
- C08G18/3823—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing -N-C=O groups
- C08G18/3825—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing -N-C=O groups containing amide groups
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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
- C08G18/40—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
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers 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
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6603—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
- C08G18/28—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
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- 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
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Polyurethanes Or Polyureas (AREA)
- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
Abstract
The invention discloses a kind of superfine fiber chemical leather easy dyeing polyurethane resin and preparation method thereof, preparation method comprises the following steps：Using isocyanates, polyalcohol and chain extender as initiation material, reacted, then diluted reaction product, obtain described superfine fiber chemical leather easy dyeing polyurethane resin, wherein, one or more of polyalcohol and chain extender, amide groups, secondary amino group or tertiary amino group are contained.Polyurethane dye-uptake of the present invention is high, and base fabric level dyeing is good, and the color fastness after colouring is high, and bright in luster, dyestuff usage amount is low, can substantially reduce production cost, has actual application value.
Description
Technical field
The present invention relates to a kind of polyurethane resin and preparation method thereof.
Background technology
At present, superfine fiber chemical leather is divided into not island ultrafine fiber and island ultrafine fiber synthetic leather, is that instead of natural
The ideal material of leather.Its basalis is the composite non woven cloth material of superfine fibre and polyurethane (PU) elastomer, ultra-fine
Fibre three-dimensional is crosslinked together, plays skeleton and supporting role, and polyurethane is distributed in the surrounding of fiber, makes whole synthetic leather base cloth
Form an entirety.Surface layer also makes face using polyurethane resin, no matter products obtained therefrom is from internal microcellular structure, or outward appearance matter
Sense, physical characteristic and snugness of fit etc., can compare favourably with advanced natural leather, be widely used in clothes
The fields such as dress, shoemaking, automobile.
Nylon superfine fiber and polyurethane (PU) resin in superfine fiber chemical leather, structure is different, and dyeing difference is big, from
And cause the difficult point of microfiber synthetic leather dyeing.Island ultrafine fiber is compared to not island ultrafine fiber simultaneously, and dye-uptake is higher, such as
Fruit dyes heterogeneity, base fabric is grown dim after making dyeing using conventional polyurethane resin.
The content of the invention
A kind of preparation method it is an object of the invention to provide superfine fiber chemical leather with easy dyeing polyurethane resin, solution
The defects of certainly existing polyurethane resin hardly possible dyeing, level-dyeing property difference and poor color fastness.
The preparation method of the present invention, comprises the following steps：
Using isocyanates, polyalcohol and chain extender as initiation material, reacted, then diluted reaction product, obtained
Described superfine fiber chemical leather easy dyeing polyurethane resin, wherein, one or more of polyalcohol and chain extender, contain acyl
Amido, secondary amino group or tertiary amino group；
Specifically, the method for the present invention, comprises the following steps：
(1) isocyanates is added in polynary alcohol and solvent, 65~75 DEG C of 80~100min of pre-polymerization；
The mol ratio of isocyanates and polyalcohol is：Isocyanates: polyalcohol=2:1~8:1
In solvent, the weight content of polyalcohol is 40%~80%；
Described polyalcohol is one or more of PEPA or PPG；
Wherein, described PPG be two functional group's polyetheramines (PEA) or two functional group's polyetheramines (PEA) and
Polytetrahydrofuran diol (PTMG)；
When from two functional group's polyetheramines (PEA) and polytetrahydrofuran diol (PTMG), weight ratio is：
Polytetrahydrofuran diol: two functional group polyetheramine=4~6: 1；
(2) and then addition has the chain extender, small molecule chain extender and solvent that can contaminate group, and isocyanic acid is added portionwise
Ester, 50~100 DEG C, preferably 65~75 DEG C reactions, the addition of isocyanates, the viscosity for making reactant is 80~200Pas
(25 DEG C), then add solvent and be diluted to viscosity as (25 DEG C) 20~40min of addition terminators reaction of 60~180Pas, you can
Obtain described superfine fiber chemical leather easy dyeing polyurethane resin；
Weight consumption with the chain extender that can contaminate group is the 0.1%~10% of polyalcohol, 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 polyalcohol in step (1), in solvent, the weight content of polyalcohol is 45%~70%；
It is 230~5000, preferably D230 (molecular weight that two functional group's polyetheramines (PEA), which commonly use molecular weight,：230)、D2000
(molecular weight：2000)；
The conventional molecular weight of polytetrahydrofuran diol (PTMG) is 850~3000, preferably PTMG2000 (molecular weight：
2000)；
The preferred polyester-diol of PEPA, described polyester-diol are adipic acid system PEPA, such as：Oneself two
PBA1000, PBA2000, PBA3000 etc. obtained by acid and butanediol reaction, or for obtained by adipic acid and glycol reaction
PEA1000, PEA2000, PEA3000 etc., or PHA1000, PHA2000, PHA3000 that adipic acid and hexylene glycol reaction form
Deng；
The preferred methyl diphenylene diisocyanate MDI of above-mentioned isocyanates；
Described there is the chain extender that can contaminate group to be selected from N- tertiarybutyldiethanolamines (TBDEA), double (the 2- hydroxyl second of N, N'-
Base) terephthalamide (HETA), N, N'- bis- (2- ethoxys) oxamides (HEOA) or N, N'- bis- (2- ethoxys) succinyl
One kind in amine (HEDA)；
One kind in the preferred ethylene glycol of described small molecule chain extender (EG) or butanediol (BG)；
Described solvent is selected from N,N-dimethylformamide (DMF), toluene, butanone, isopropanol, one kind or more of isobutanol
Kind；
One or more in described end-capping reagent methanol and ethanol；
Using the easy dyeing polyurethane resin for preparing of the present invention, in molecule soft and hard segments region, introducing can contaminate group, introduce acyl
One or more in amido, secondary amino group or tertiary amino group；
Polyetheramine is introduced, improves the dye-uptake in soft segment region；Amide groups is introduced, makes resin that there is knot similar with fiber
Structure；Tertiary amino is introduced, improves the binding strength with dyestuff.
The present invention makes product meet that basic performance will by introducing the group that can be combined with dyestuff in polyurethane resin
While asking, dyeability is also improved.Compared with the dyeing polyurethane resin of existing report, it is applied to that to determine island, indefinite island ultra-fine
In fiber synthetic leather dyeing course, polyurethane dye-uptake is high, and base fabric level dyeing is good, and the color fastness after colouring is high, color
Bright-coloured, dyestuff usage amount is low, can substantially reduce production cost, has actual application value.
Embodiment
Present invention is further described with reference to specific embodiment, experimental condition of the invention can be according to need
Adjust accordingly, and be not limited to the experimental condition of the present embodiment.
Embodiment 1
(1) by polytetrahydrofuran diol (PTMG2000) (100g), two functional group's polyetheramine (PEA) D2000 (20g), molten
In agent DMF (DMF) (100g) input reaction bulb, it is well mixed, puts into MDI (12g) 70 DEG C of pre-polymerization 80min；
(2) after the completion of pre-polymerization, ethylene glycol EG (11g), N- tertiarybutyldiethanolamines TBDEA (1.5g) and DMF are added
(280g), is added portionwise MDI (51g), 80 DEG C of reactions, after MDI react, adds MDI and viscosity is increased to (25 DEG C) of 90Pas and glue
When spending, stop adding；
Then the viscosity 60Pas (25 DEG C) that DMF (80g) is diluted to reactant is added, it is anti-to add methanol 0.05g terminators
30min is answered, is discharged after being cooled to 50 DEG C, you can obtains described superfine fiber chemical leather easy dyeing polyurethane resin, resin
Mass fraction of solids is (30 ± 1) %.
Use on synthetic leather base cloth, detected using GB/T 29865-2013 methods, Datacolors F650 Computer color testings
Instrument SCT- batch mixings transmission color measuring and matching system of matching colors is tested, and is compared with normal dyeing base fabric, as a result as follows：Dye-uptake can improve
More than 30%, dyeing is homogeneous, and color fastness improves 1 grade, and dyestuff usage amount reduces 30%.
Embodiment 2
(1) by polytetrahydrofuran diol (PTMG2000) (120g), two functional group's polyetheramine (PEA) D230 (10g) and DMF
In (100g) input reaction bulb, stirring makes it well mixed, input MDI (20g), is warming up to 60 DEG C of pre-polymerization 90min；
(2) after the completion of pre-polymerization, ethylene glycol (EG) (10g), N, N'- bis- (2- ethoxys) succinamide (HEDA) are added
(5g), DMF (320g) put into MDI (52g) in batches into reaction bulb, keep 70 DEG C of reactions, after MDI has reacted, adding MDI makes
When viscosity increases to 100Pas (25 DEG C) viscosity, stop adding；
Add DMF (80g) and be diluted to viscosity 80Pas (25 DEG C), add methanol (0.05g) terminator reaction 30min, drop
Discharged after warm to 50 DEG C, resulting resin solid mass fraction is (30 ± 1) %.
Use on synthetic leather base cloth, detected using GB/T 29865-2013 methods, Datacolors F650 Computer color testings
Instrument SCT- batch mixings transmission color measuring and matching system of matching colors is tested, as a result as follows：Dye-uptake can improve more than 20%, and dyeing is homogeneous,
Color fastness improves 1 grade, and dyestuff usage amount reduces 20%.
Embodiment 3
(1) by polytetrahydrofuran diol (PTMG) 2000 (120g), two functional group's polyetheramine (PEA) D2000 (30g), DMF
In (100g) input reaction bulb, stirring makes it well mixed, input MDI (14g), is warming up to 80 DEG C of pre-polymerization 60min；
(2) ethylene glycol (EG) (14g), N- tertiarybutyldiethanolamines (TBDEA) (1g) and DMF (380g), N, N'- bis- are added
(2- ethoxys) oxamides (HEOA) (4g), MDI (70g) is added portionwise, keeps 75 DEG C of reactions, after MDI has reacted, add MDI
When making the viscosity increase to 140Pas (25 DEG C) viscosity, stop adding；
Add DMF (80g) and be diluted to viscosity 120Pas (25 DEG C), add methanol (0.05g) terminator reaction 30min,
Discharged after being down to 50 DEG C, obtained resin solid mass fraction is (30 ± 1) %.
Use on synthetic leather base cloth, detected using GB/T 29865-2013 methods, Datacolors F650 Computer color testings
Instrument SCT- batch mixings transmission color measuring and matching system of matching colors is tested, as a result as follows：Dye-uptake can improve more than 60%, and dyeing is homogeneous,
Color fastness improves 1.5 grades, and dyestuff usage amount reduces 60%.
Embodiment 4
(1) by erythritan (PTMG2000) (100g), two functional group's polyetheramine (PEA) D2000 (20g), oneself two
Stirred in acid and adipic acid system PEPA PHA2000 (30g), DMF (100g) the input reaction bulb of hexylene glycol reaction generation
Make it well mixed, input MDI (14g), be warming up to 70 DEG C of pre-polymerization 90min；
(2) after the completion of pre-polymerization, ethylene glycol EG (8g), N- tertiarybutyldiethanolamines (TBDEA) (4g), double (2- hydroxyl second are added
Base) terephthalamide HETA (3g), DMF (320g) stir evenly into reaction bulb, puts into MDI (46g) in batches, keep 70 DEG C it is anti-
Should, after MDI react, when adding MDI makes the viscosity increase to 160Pas (25 DEG C) viscosity, stop addition；
Add DMF (80g) and be diluted to viscosity 140Pas (25 DEG C), add methanol (0.05g) terminator reaction 30min,
Discharged after being cooled to 50 DEG C, resulting resin solid mass fraction is (30 ± 1) %.
Use on synthetic leather base cloth, detected using GB/T 29865-2013 methods, Datacolors F650 Computer color testings
Instrument SCT- batch mixings transmission color measuring and matching system of matching colors is tested, as a result as follows：Dye-uptake can improve more than 50%, and dyeing is homogeneous,
Color fastness improves 1.5 grades, and dyestuff usage amount reduces 50%.
Claims (6)
1. the superfine fiber chemical leather preparation method of easy dyeing polyurethane resin, it is characterised in that comprise the following steps：(1)
Isocyanates is added into pre-polymerization in polynary alcohol and solvent；
Described polyalcohol is one or more of PEPA or PPG；
Wherein, described PPG is two functional group's polyetheramines either two functional group's polyetheramines and PolyTHF two
Alcohol；
(2) and then add with the chain extender, small molecule chain extender and solvent that can contaminate group, reaction, add solvent dilution, add
Terminator reacts 20~40min, you can obtains described superfine fiber chemical leather easy dyeing polyurethane resin；
Described small molecule chain extender is selected from ethylene glycol or butanediol；
Described there is the chain extender that can contaminate group to be selected from N, N'- double (2- ethoxys) terephthalamide, (the 2- hydroxyls of N, N'- bis-
Ethyl) one kind in oxamides or N, N'- bis- (2- ethoxys) succinamide；
Weight consumption with the chain extender that can contaminate group is the 0.1%~10% of polyalcohol, and the weight of small molecule chain extender is used
Measure as 1~15 times with the chain extender that can contaminate group.
2. according to the method for claim 1, it is characterised in that when from two functional group's polyetheramines and polytetrahydrofuran diol
When, weight ratio is：Polytetrahydrofuran diol: two functional group polyetheramine=4~6: 1.
3. according to the method for claim 1, it is characterised in that two functional group's polyetheramine molecular weight are 230~5000；Poly- four
Hydrogen furans glycol molecular weight is 850~3000.
4. according to the method for claim 1, it is characterised in that the PEPA is polyester-diol.
5. according to the method for claim 1, it is characterised in that described isocyanates is methyl diphenylene diisocyanate
MDI。
6. the superfine fiber chemical leather easy dyeing polyurethane resin prepared according to any one of Claims 1 to 5 methods described.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510971522.0A CN105542108B (en) | 2015-12-22 | 2015-12-22 | Superfine fiber chemical leather easy dyeing polyurethane resin and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510971522.0A CN105542108B (en) | 2015-12-22 | 2015-12-22 | Superfine fiber chemical leather easy dyeing polyurethane resin and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
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| CN105542108A CN105542108A (en) | 2016-05-04 |
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| CN105821678A (en) * | 2016-06-07 | 2016-08-03 | 耿云花 | Preparation technology of easy-to-dye synthetic leather |
| CN106073089A (en) * | 2016-06-07 | 2016-11-09 | 耿云花 | A kind of easy dyeing processing suitcase |
| CN106397716A (en) * | 2016-09-06 | 2017-02-15 | 上海华峰超纤材料股份有限公司 | Moisture absorption dyeable polyurethane resin and preparation method thereof |
| CN109749043B (en) * | 2018-12-29 | 2021-07-16 | 浙江华峰合成树脂有限公司 | Solvent-free polyurethane resin for high-stripping leather and preparation method and application thereof |
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| CN102532468B (en) * | 2011-12-23 | 2013-08-28 | 上海汇得化工有限公司 | Chromatophilous aromatic polyurethane resin and preparation method thereof |
| CN102532462B (en) * | 2011-12-23 | 2013-10-16 | 上海汇得化工有限公司 | Easily-dyed aliphatic polyurethane resin and preparation method thereof |
| CN102746484A (en) * | 2012-06-18 | 2012-10-24 | 福建华阳超纤有限公司 | Preparation method of solvent-based dyeable wet polyurethane resin |
| CN104356350B (en) * | 2014-11-12 | 2017-01-11 | 超然(福建)新材料科技有限公司 | High-dyeability polyurethane resin and preparation method thereof |
| CN104693405B (en) * | 2015-03-27 | 2019-07-09 | 陕西科技大学 | A kind of super branched polyurethane and preparation method thereof containing active amino |
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Address after: 201508, No. 888 Ting Wei Road, Shanghai, Jinshan District Patentee after: Shanghai Huafeng Super Fiber Technology Co.,Ltd. Address before: 201508, No. 888 Ting Wei Road, Shanghai, Jinshan District Patentee before: HUAFON MICROFIBRE (SHANGHAI) Co.,Ltd. |