CN105153397A - Preparation method of dry, comfortable and cold-resistant surface-layer polyurethane resin for elastic leather - Google Patents
Preparation method of dry, comfortable and cold-resistant surface-layer polyurethane resin for elastic leather Download PDFInfo
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- CN105153397A CN105153397A CN201510601774.4A CN201510601774A CN105153397A CN 105153397 A CN105153397 A CN 105153397A CN 201510601774 A CN201510601774 A CN 201510601774A CN 105153397 A CN105153397 A CN 105153397A
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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
- C08G18/70—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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- 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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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- 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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- 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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- 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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- 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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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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- 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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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/06—Polyurethanes from polyesters
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/08—Polyurethanes from polyethers
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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
- D06N3/147—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 characterised by the isocyanates used
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- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/90—Applications
- C08G2261/93—Applications in textiles, fabrics and yarns
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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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
- D06N2211/00—Specially adapted uses
- D06N2211/12—Decorative or sun protection articles
- D06N2211/28—Artificial leather
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- Polymers & Plastics (AREA)
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- Treatment And Processing Of Natural Fur Or Leather (AREA)
Abstract
The invention discloses a preparation method of dry, comfortable and cold-resistant surface-layer polyurethane resin for elastic leather. The method comprises the steps that a polyatomic alcohol compound, an antioxidant and solvent are put into a reaction kettle and stirred for 10-20 minutes, then diisocyanate is put into the reaction kettle, and a pre-polymerization reaction is performed for 1-1.5 hours at the temperature of 70 DEG C-80 DEG C, wherein the mole ratio of the diisocyanate to the polyatomic alcohol compound is 1.2-1.5:1; after the pre-polymerization reaction is finished, a micromolecular dihydric alcohol chain extender and diisocyanate are sequentially added, the reaction is continuously performed, and the polyurethane resin is obtained. According to the preparation method, a quantitative pre-polymerization method is adopted, the phase separation degree of soft segments and hard segments is improved, and the characteristics, such as the softness and low-temperature deflection properties, of the soft segments of the resin can be embodied; the leather surface of the finished leather is dry and comfortable, and the leather is soft, high in fullness and excellent in low-temperature deflection property.
Description
Technical field
The present invention relates to synthetic leather and manufacture field, specifically a kind of Stretch leather preparation method that is dry-ness, winter hardiness surface layer urethane resin.
Background technology
At present for guaranteeing footwear leather and luggage leather surface dry, general way improves the modulus of finished leather resin, but drawback is that after finished leather, feel is stiff, soft not, sense of fullness is strong, and deflect performance particularly low temperature deflect poor-performing, cause the range of application of Stretch leather limited, class is not high.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of Stretch leather preparation method that is dry-ness, winter hardiness surface layer urethane resin, and solve resin modulus prepared by existing polyurethane Preparation Method higher, after finished leather, feel is stiff, and low temperature deflects the problem of poor performance.
Technical scheme of the present invention is:
A Stretch leather preparation method that is dry-ness, winter hardiness surface layer urethane resin, specifically includes following steps:
(1) drop into polyol compound, in a kettle., oxidation inhibitor, solvent drop into vulcabond after carrying out stirring 10-20 minute and carry out prepolymerization reaction, the reaction times is 1-1.5 hour, and temperature is 70-80 DEG C; Wherein, the mol ratio of vulcabond and polyol compound is 1.2-1.5:1;
(2), after prepolymerization reaction terminates, in the reaction solution of step (1), continue to add small molecules glycol chain extender react, the reaction times is 1-1.5 hour, and temperature is 70-80 DEG C;
(3), under catalyzer existent condition, continue to add vulcabond in reactor to react, temperature is 70-80 DEG C, along with the continuous increase of system viscosity, progressively add required solvent, final viscosity controls at 80,000-12 ten thousand cps, adds appropriate terminator methyl alcohol, obtain urethane resin after reaction terminates;
Wherein, the mol ratio 1:4-8 of described polyol compound and small molecules glycol chain extender; In described step (1) and step (3), in vulcabond, in ester group and polyol compound, small molecules glycol chain extender, the mol ratio of hydroxyl is: 1-1.05:1.
Described vulcabond is 4,4 '-diphenylmethanediisocyanate.
Described polyol compound is one or both the mixing in polyester polyol, polyether glycol.
Described polyether glycol is polytetramethylene ether diol.
The molecular weight of described small molecules glycol chain extender is 62-200g/mol, and small molecules glycol chain extender is one or both the mixing in ethylene glycol, BDO, 1,6-hexylene glycol.
Described catalyzer is organo-bismuth class catalyzer MB20, and consumption accounts for 0.01 ‰-0.1 ‰ of polyol compound weight.
Add auxiliary agent in urethane resin prepared by described step (3), auxiliary agent is at least one in UV light absorber, weathering stabilizers and flow agent, and auxiliary dosage is the 0.1%-0.5% accounting for system gross weight.
Described solvent is DMF, and consumption is the 69%-71% of system gross weight.
The water content of described vulcabond, polyol compound, small molecules glycol chain extender and solvent is all less than 500ppm.
Advantage of the present invention:
After finished leather of the present invention, leather surface is dry and comfortable, and leather is soft, and sense of fullness is strong, and has the low temperature with excellence to deflect performance.Its particular content is in urethane (PU) resin synthesis process, adopt the method for quantitative pre-polymerization, improve the degree that is separated of soft, hard section, because in common synthetic methods, resin is soft, hard section is blocked distribution, in the higher i.e. resin of resin modulus, hard segment content is higher, when content of soft segmer is lower, resin is more the characteristic showing the hard section occupied the majority, the characteristic that resin is soft section can not get embodying, adopt quantitative pre-polymerization method, to allow in resin the characteristic-softness of soft section, low temperature deflect performance etc. and embodied.
Embodiment
The technique means realized for making the present invention, creation characteristic, reaching object and effect is easy to understand, below in conjunction with embodiment, setting forth the present invention further.
embodiment 1
A Stretch leather preparation method that is dry-ness, winter hardiness surface layer urethane resin, is characterized in that: specifically include following steps:
(1), 270KgPET-1,890KgPTMG-2,12Kg oxidation inhibitor, 2000KgN is dropped in a kettle., dinethylformamide (DMF) solvent drops into 188Kg4 after carrying out stirring 10-20 minute, 4-diphenylmethanediisocyanate (MDI) carries out prepolymerization reaction, reaction times is 1-1.5 hour, and temperature is 70-80 DEG C;
(2), after prepolymerization reaction terminates, in the reaction solution of step (1), continue to add 200Kg ethylene glycol react, the reaction times is 1-1.5 hour, and temperature is 70-80 DEG C;
(3), continue to add 790KgMDI and 0.2Kg catalyzer in reactor, react under catalyzer existent condition, temperature is 70-80 DEG C, along with the continuous increase of system viscosity, progressively add 3257KgDMF solvent, final viscosity controls at 80,000-12 ten thousand cps, adds appropriate terminator methyl alcohol after reaction terminates, and adds 4.0Kg UV light absorber UV-328;
(4), be cooled to less than 60 DEG C and carry out rushing down material, metering packing, obtain dry-ness, the winter hardiness surface layer urethane resin finished product of Stretch leather.
Wherein, above-mentioned PET-1 is the polyester polyol of molecular weight 1000, and raw materials used and formula is hexanodioic acid 4000Kg, ethylene glycol 1300Kg, BDO 900Kg, catalyzer TPT0.5Kg; PTMG-2 is the polytetramethylene ether diol of molecular weight 2000.
embodiment 2
A Stretch leather preparation method that is dry-ness, winter hardiness surface layer urethane resin, is characterized in that: specifically include following steps:
(1), 210KgPET-1,900KgPET-2,12Kg oxidation inhibitor, 2000KgN is dropped in a kettle., dinethylformamide (DMF) solvent drops into 170Kg4 after carrying out stirring 10-20 minute, 4-diphenylmethanediisocyanate (MDI) carries out prepolymerization reaction, reaction times is 1-1.5 hour, and temperature is 70-80 DEG C;
(2), after prepolymerization reaction terminates, continue to add 280Kg1 in the reaction solution of step (1), 4 butyleneglycols react, and the reaction times is 1-1.5 hour, and temperature is 70-80 DEG C;
(3), continue to add 735KgMDI and 0.3Kg catalyzer in reactor, react under catalyzer existent condition, temperature is 70-80 DEG C, along with the continuous increase of system viscosity, progressively add 3355KgDMF solvent, final viscosity controls at 80,000-12 ten thousand cps, adds appropriate terminator methyl alcohol after reaction terminates, and adds 4.0Kg UV light absorber UV-328;
(4), be cooled to less than 60 DEG C and carry out rushing down material, metering packing, obtain dry-ness, the winter hardiness surface layer urethane resin finished product of Stretch leather.
Wherein, above-mentioned PET-1 is the polyester polyol of molecular weight 1000, and raw materials used and formula is hexanodioic acid 4000Kg, ethylene glycol 1300Kg, BDO 900Kg, catalyzer TPT0.5Kg; PET-2 is the polyester polyol of molecular weight 2000, and raw materials used and formula is hexanodioic acid 3000Kg, ethylene glycol 200Kg, BDO 1800Kg, catalyzer TPT0.4Kg.
In order to verify that Stretch leather of the present invention dry-ness and low temperature that is dry-ness, winter hardiness surface layer urethane resin deflects performance, the according to the following formulation and at present dry method veneer normal process finished leather of the resin prepared by above-described embodiment scheme, concrete formula and as follows:
Resin 100,
DMF60，
Colorant 15,
Flow agent 1,
Help stripper 0.5.
After testing, the dry type polyurethane synthetic leather made with above-mentioned formula, surface dry, soft and sense of fullness is strong, has excellent low temperature and deflects performance.
In claims of this specification sheets and the application, so-called system, refers to whole reaction system, and system gross weight is the total amount of all substances.What describe in above-mentioned embodiment and specification sheets just illustrates principle of the present invention, and the present invention also has various changes and modifications without departing from the spirit and scope of the present invention, and these changes and improvements all fall in the claimed scope of the invention.Application claims protection domain is defined by appending claims and jljl thereof.
Claims (9)
1. a Stretch leather preparation method that is dry-ness, winter hardiness surface layer urethane resin, is characterized in that: specifically include following steps:
(1) drop into polyol compound, in a kettle., oxidation inhibitor, solvent drop into vulcabond after carrying out stirring 10-20 minute and carry out prepolymerization reaction, the reaction times is 1-1.5 hour, and temperature is 70-80 DEG C; Wherein, the mol ratio of vulcabond and polyol compound is 1.2-1.5:1;
(2), after prepolymerization reaction terminates, in the reaction solution of step (1), continue to add small molecules glycol chain extender react, the reaction times is 1-1.5 hour, and temperature is 70-80 DEG C;
(3), under catalyzer existent condition, continue to add vulcabond in reactor to react, temperature is 70-80 DEG C, along with the continuous increase of system viscosity, progressively add required solvent, final viscosity controls at 80,000-12 ten thousand cps, adds appropriate terminator methyl alcohol, obtain urethane resin after reaction terminates;
Wherein, the mol ratio 1:4-8 of described polyol compound and small molecules glycol chain extender; In described step (1) and step (3), in vulcabond, in ester group and polyol compound, small molecules glycol chain extender, the mol ratio of hydroxyl is: 1-1.05:1.
2. a kind of Stretch leather according to claim 1 preparation method that is dry-ness, winter hardiness surface layer urethane resin, is characterized in that: described vulcabond is 4,4 '-diphenylmethanediisocyanate.
3. a kind of Stretch leather according to claim 1 preparation method that is dry-ness, winter hardiness surface layer urethane resin, is characterized in that: described polyol compound is one or both the mixing in polyester polyol, polyether glycol.
4. a kind of Stretch leather according to claim 3 preparation method that is dry-ness, winter hardiness surface layer urethane resin, is characterized in that: described polyether glycol is polytetramethylene ether diol.
5. a kind of Stretch leather according to claim 1 preparation method that is dry-ness, winter hardiness surface layer urethane resin, it is characterized in that: the molecular weight of described small molecules glycol chain extender is 62-200g/mol, small molecules glycol chain extender is ethylene glycol, 1, one or both mixing in 4-butyleneglycol, 1,6-hexylene glycol.
6. a kind of Stretch leather according to claim 1 preparation method that is dry-ness, winter hardiness surface layer urethane resin, is characterized in that: described catalyzer is organo-bismuth class catalyzer MB20, and consumption accounts for 0.01 ‰-0.1 ‰ of polyol compound weight.
7. a kind of Stretch leather according to claim 1 preparation method that is dry-ness, winter hardiness surface layer urethane resin, it is characterized in that: in urethane resin prepared by described step (3), add auxiliary agent, auxiliary agent is at least one in UV light absorber, weathering stabilizers and flow agent, and auxiliary dosage is the 0.1%-0.5% accounting for system gross weight.
8. a kind of Stretch leather according to claim 1 preparation method that is dry-ness, winter hardiness surface layer urethane resin, it is characterized in that: described solvent is DMF, consumption is the 69%-71% of system gross weight.
9. a kind of Stretch leather according to claim 1 preparation method that is dry-ness, winter hardiness surface layer urethane resin, is characterized in that: the water content of described vulcabond, polyol compound, small molecules glycol chain extender and solvent is all less than 500ppm.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510601774.4A CN105153397A (en) | 2015-09-21 | 2015-09-21 | Preparation method of dry, comfortable and cold-resistant surface-layer polyurethane resin for elastic leather |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201510601774.4A CN105153397A (en) | 2015-09-21 | 2015-09-21 | Preparation method of dry, comfortable and cold-resistant surface-layer polyurethane resin for elastic leather |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106366290A (en) * | 2016-08-31 | 2017-02-01 | 合肥安利聚氨酯新材料有限公司 | Two-component full-dry adhesive layer polyurethane resin for TPU (thermoplastic polyurethane) film compound synthetic leather and preparation method of resin |
| CN106832187A (en) * | 2017-01-10 | 2017-06-13 | 合肥安利聚氨酯新材料有限公司 | A kind of cold-resistant solvent resistant color inhibition surface layer polyurethane resin and preparation method thereof |
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| CN106366290A (en) * | 2016-08-31 | 2017-02-01 | 合肥安利聚氨酯新材料有限公司 | Two-component full-dry adhesive layer polyurethane resin for TPU (thermoplastic polyurethane) film compound synthetic leather and preparation method of resin |
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| CN112194777A (en) * | 2020-10-12 | 2021-01-08 | 浙江华峰合成树脂有限公司 | Polyurethane surface layer resin for PVC sole injection molding and preparation method thereof |
| CN112409563A (en) * | 2020-11-21 | 2021-02-26 | 华大化学(安徽)有限公司 | Surface layer polyurethane resin for dry-method direct-sticking four-side elastic clothing leather and preparation method thereof |
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