CN101503499A - Wet low modulus ultra-soft high peel strength polyurethane resin for synthetic leather and preparation thereof - Google Patents
Wet low modulus ultra-soft high peel strength polyurethane resin for synthetic leather and preparation thereof Download PDFInfo
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- CN101503499A CN101503499A CNA2009101163310A CN200910116331A CN101503499A CN 101503499 A CN101503499 A CN 101503499A CN A2009101163310 A CNA2009101163310 A CN A2009101163310A CN 200910116331 A CN200910116331 A CN 200910116331A CN 101503499 A CN101503499 A CN 101503499A
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- polyurethane resin
- low modulus
- synthetic leather
- peel strength
- polyol compound
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Abstract
The invention discloses a wet polyurethane resin with low modulus, super softness and high peeling strength, and a preparation method thereof. The polyurethane resin comprises the following raw materials: 4,4'-diphenylmethane diisocyanate; two polyester diol compounds with 2000-4000g/mol molecular weight; a diol chain extender mixed with glycol and 1,4-butanediol; a catalyst; an additive; and a solvent and the like. The wet polyurethane resin with low modulus, super softness and high peeling strength fully solves the peeling strength problem of synthetic leather products formed by processing the existing wet polyurethane resin with low modulus and super softness, and meets high peeling property requirement of super soft shoe leather products.
Description
Technical field
The present invention relates to a kind of manufacture method of low modulus ultra-soft high peel strength polyurethane resin, specifically, relate to a kind of low modulus ultra-soft high peel strength polyurethane resin and preparation method thereof.
Background technology
At present, aspect the footwear leather, in order to satisfy the requirement of strength of synthetic leather product, generally select the harder high modulus polyurethane resin of feel for use, and common polyurethane resin is when being used to make the synthetic leather product, because the hardness height, feel is harder, and sense comfortable and easy to wear is poor, and existence must limitation; And super soft type urethane resin adds man-hour being used for synthetic leather, because himself intensity is lower, the intensity of big its leather goods of elongation is also low, tensile deformation takes place easily, the size conservation rate is low, can not satisfy high strength, height is peeled off requirement, is not suitable for being used to produce footwear leather product.
Summary of the invention
The object of the present invention is to provide a kind of use for synthetic leather low modulus ultra-soft high peel strength polyurethane resin and preparation method thereof, its working method is according to prepolymerization process step-by-step polymerization method: add various raw materials by the control condition requirement, in proportion, be sequentially added into the method synthetic macromolecule polyurethane material that carries out polymer condensation chain extending reaction in the reactor.By putting in order and block structure of various raw materials in the regular arrangement polyurethane molecular structure, the crystallinity of control polyurethane high molecule, regularity etc. improve the rerum natura of polyurethane material.
Technical solution of the present invention is as follows:
A kind of use for synthetic leather wet low modulus ultra-soft high peel strength polyurethane resin is characterized in that, takes the technology of various raw material step-by-step polymerizations, and the proportioning of each feed composition is:
Vulcabond;
Polyol compound;
The dibasic alcohol chainextender; Consumption accounts for 2～3% of system gross weight;
Catalyzer;
Auxiliary agent;
Solvent;
Wherein, ratio 1:3～5 of polyol compound and the amount of substance of dibasic alcohol chainextender;
In the described vulcabond in diisocyanate based and polyol compound and the dibasic alcohol chainextender ratio of the molar weight of hydroxyl be: 0.98～1.05:1;
Described catalyzer is phosphoric acid, organo-bismuth class catalyzer or its compound, and consumption is 0.1 ‰ of polyol compound weight～1 ‰;
Described auxiliary agent is one or more the mixture in oxidation inhibitor, weather-proof stablizer, flow agent, the pore-creating agent;
Described solvent is water-soluble organic solvent.
Described use for synthetic leather wet low modulus ultra-soft high peel strength polyurethane resin is characterized in that: described solvent load is 70 ± 1% of a system gross weight; Described auxiliary dosage is 0.2 ‰ of system gross weight～1 ‰.
Described use for synthetic leather wet low modulus ultra-soft high peel strength polyurethane resin is characterized in that: described solvent is N, dinethylformamide; Described vulcabond is 4,4 '-diphenylmethanediisocyanate.
Described use for synthetic leather wet low modulus ultra-soft high peel strength polyurethane resin is characterized in that: described oxidation inhibitor is oxidation inhibitor I-1010 or other similar oxidation inhibitor; Described polyol compound is meant that number-average molecular weight is the polyester polyol of 2000～4000g/mol, one or more the mixing in the polyether glycol; Described dibasic alcohol chainextender is an ethylene glycol, 1, the mixture of 4-butyleneglycol, and based on ethylene glycol, by 1, the 4-butyleneglycol is adjusted the crystalline polyurethane resin performance, and 1, the 4-butyleneglycol accounts for 10%～20% of dibasic alcohol chainextender integral molar quantity.
Described use for synthetic leather wet low modulus ultra-soft high peel strength polyurethane resin is characterized in that: described polyol compound is meant the mixture of adipate glycol-butanediol ester, tetramethylene adipate, and the mol ratio of the two is 3:7.
The preparation method of described use for synthetic leather wet low modulus ultra-soft high peel strength polyurethane resin is characterized in that: preparation according to the following steps:
A, polyol compound carry out drying and dewater, and water ratio is less than 300ppm;
B, the solvent that adds the reaction needed in early stage in reactor, polyol compound, catalyzer etc. fully stir and control 35～65 ℃ of certain temperatures;
C, elder generation add vulcabond in batches in reactor, form polyol compound and isocyanate reaction and form soft chain segment; After dropping into the dibasic alcohol chainextender again, add vulcabond more in batches, carry out block reaction, form hard segment, strictness is controlled the temperature of reaction system less than 80 ℃, and constantly increases solvent according to the viscosity situation of reaction system, and final viscosity is controlled at 120～220Pa.s/25 ℃; Finish the back in reaction process and add auxiliary agent;
D, the postcooling that reacts completely, metering, packing.
The preparation method of described use for synthetic leather wet low modulus ultra-soft high peel strength polyurethane resin, it is characterized in that: adopt gradation in batches to drop into polyol compound, and the time sequence of dibasic alcohol chainextender, control the reaction block order of various structures in macromolecular chain, after being the polymerization in advance of polyvalent alcohol and isocyanic ester, add the chainextender dibasic alcohol again, and then by isocyanic ester link formation macromolecular structure, in the high molecular polymer molecular chain, the soft or hard section forms the block arrangement structure that needs successively.
The preparation process of synthetic leather is produced according to common wet method leather production technique, repeats no more here.
The major equipment that adopts is as follows:
Dry water removal device, reactor, drying room (baking oven) etc.
The low modulus ultra-soft high peel strength polyurethane resin of preparation of the present invention possesses the finished leather processing characteristics of common wet polyurethane resin, and made leather goods have super softness, high-intensity characteristic simultaneously.Stripping strength obtains the intensity index of hard product greater than 120N/3cm.
Embodiment
For technique means, creation characteristic that the present invention is realized, reach purpose and effect is easy to understand, below in conjunction with embodiment, further set forth the present invention.
Embodiment 1:
Material name weight (unit K g)
Poly-adipate glycol-butanediol ester glycol (molecular weight 4000) 30
Poly adipate succinic acid ester glycol (molecular weight 2000) 70
Ethylene glycol 9.3
1,4-butyleneglycol 1.8
4,4 '-diphenylmethanediisocyanate 55
Phosphoric acid 0.001
Organo-bismuth 0.01
Oxidation inhibitor I-1010 1.0
N, dinethylformamide 390
Use for synthetic leather low modulus ultra-soft high peel strength polyurethane resin of the present invention prepares according to the following steps:
1, in reactor, drop into various polyol compounds, oxidation inhibitor I-1010 stirs, and is warming up to 100 ℃, vacuumizes drying and dewaters 1 hour, detect water ratio and be cooled to 30 ℃ after less than 300ppm.
2, drop into N, dinethylformamide stirs and drops into phosphoric acid stirring 20 minutes after 10 minutes, and the still temperature control is at 35～65 ℃, and the control temperature of reaction kettle is at 70～80 ℃ in the reaction process.
3, according to the formulating of recipe amount drop into 4,4 '-diphenylmethanediisocyanate, drop into ethylene glycol, 1, the 4-mixture of butanediols after the reaction specified time.
4, continue reaction, at the appointed time in the formulating of recipe ratio drop into 4,4 step by step '-diphenylmethanediisocyanate, and constantly increase N, dinethylformamide according to the viscosity situation of reaction system.Final viscosity is controlled at 120～220Pa.s/25 ℃, and amount of solid content is controlled to be 30 ± 1%, finishes the back in reaction process and adds auxiliary agent.
5, react completely postcooling, metering, packing.
Embodiment 2:
In order to verify that low modulus ultra-soft high peel strength polyurethane resin of the present invention has the characteristic of ultra-soft high peel, the resin that above-mentioned case study on implementation is prepared is made synthetic leather by following wet method finished leather complete processing prescription, concrete process hides prescription is as follows:
Material name weight (unit K g)
Resin 100
DMF 50
Pore-creating agent 2
Black cream 4
Blue cream 0.2
Purple cream 0.2
After testing, soft with the Synthetic Leather that the prescription of above-mentioned enforcement is made, contain the porosity height, stripping strength can reach the product design requirement greater than 120N/3cm simultaneously.
Claims (7)
1, a kind of use for synthetic leather wet low modulus ultra-soft high peel strength polyurethane resin is characterized in that, takes the technology of various raw material step-by-step polymerizations, and the proportioning of each feed composition is:
Vulcabond;
Polyol compound;
The dibasic alcohol chainextender; Consumption accounts for 2～3% of system gross weight;
Catalyzer;
Auxiliary agent;
Solvent;
Wherein, ratio 1:3～5 of polyol compound and the amount of substance of dibasic alcohol chainextender;
In the described vulcabond in diisocyanate based and polyol compound and the dibasic alcohol chainextender ratio of the molar weight of hydroxyl be: 0.98～1.05:1;
Described catalyzer is phosphoric acid, organo-bismuth class catalyzer or its compound, and consumption is 0.1 ‰ of polyol compound weight～1 ‰;
Described auxiliary agent is one or more the mixture in oxidation inhibitor, weather-proof stablizer, flow agent, the pore-creating agent;
Described solvent is water-soluble organic solvent.
2, use for synthetic leather wet low modulus ultra-soft high peel strength polyurethane resin according to claim 1 is characterized in that: described solvent load is 70 ± 1% of a system gross weight; Described auxiliary dosage is 0.2 ‰ of system gross weight～1 ‰.
3, use for synthetic leather wet low modulus ultra-soft high peel strength polyurethane resin according to claim 1 is characterized in that: described solvent is N, dinethylformamide; Described vulcabond is 4,4 '-diphenylmethanediisocyanate.
4, use for synthetic leather wet low modulus ultra-soft high peel strength polyurethane resin according to claim 1 is characterized in that: described oxidation inhibitor is oxidation inhibitor I-1010 or other similar oxidation inhibitor; Described polyol compound is meant that number-average molecular weight is the polyester polyol of 2000～4000g/mol, one or more the mixing in the polyether glycol; Described dibasic alcohol chainextender is an ethylene glycol, 1, the mixture of 4-butyleneglycol, and based on ethylene glycol, by 1, the 4-butyleneglycol is adjusted the crystalline polyurethane resin performance, and 1, the 4-butyleneglycol accounts for 10%～20% of dibasic alcohol chainextender integral molar quantity.
5, use for synthetic leather wet low modulus ultra-soft high peel strength polyurethane resin according to claim 4, it is characterized in that: described polyol compound is meant the mixture of adipate glycol-butanediol ester, tetramethylene adipate, and the mol ratio of the two is 3:7.
6, the preparation method of use for synthetic leather wet low modulus ultra-soft high peel strength polyurethane resin according to claim 1 is characterized in that: preparation according to the following steps:
A, polyol compound carry out drying and dewater, and water ratio is less than 300ppm;
B, the solvent that adds the reaction needed in early stage in reactor, polyol compound, catalyzer etc. fully stir and control 35～65 ℃ of certain temperatures;
C, elder generation add vulcabond in batches in reactor, form polyol compound and isocyanate reaction and form soft chain segment; After dropping into the dibasic alcohol chainextender again, add vulcabond more in batches, carry out block reaction, form hard segment, strictness is controlled the temperature of reaction system less than 80 ℃, and constantly increases solvent according to the viscosity situation of reaction system, and final viscosity is controlled at 120～220Pa.s/25 ℃; Finish the back in reaction process and add auxiliary agent;
D, the postcooling that reacts completely, metering, packing.
7, the preparation method of use for synthetic leather wet low modulus ultra-soft high peel strength polyurethane resin according to claim 6, it is characterized in that: adopt gradation in batches to drop into polyol compound, and the time sequence of dibasic alcohol chainextender, control the reaction block order of various structures in macromolecular chain, after being the polymerization in advance of polyvalent alcohol and isocyanic ester, add the chainextender dibasic alcohol again, and then by isocyanic ester link formation macromolecular structure, in the high molecular polymer molecular chain, the soft or hard section forms the block arrangement structure that needs successively.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2009101163310A CN101503499A (en) | 2009-03-11 | 2009-03-11 | Wet low modulus ultra-soft high peel strength polyurethane resin for synthetic leather and preparation thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2009101163310A CN101503499A (en) | 2009-03-11 | 2009-03-11 | Wet low modulus ultra-soft high peel strength polyurethane resin for synthetic leather and preparation thereof |
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| CN101503499A true CN101503499A (en) | 2009-08-12 |
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| CNA2009101163310A Pending CN101503499A (en) | 2009-03-11 | 2009-03-11 | Wet low modulus ultra-soft high peel strength polyurethane resin for synthetic leather and preparation thereof |
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Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102094331A (en) * | 2010-12-29 | 2011-06-15 | 浙江华峰合成树脂有限公司 | Wet type impregnating polyurethane resin and preparation method thereof |
| CN102391462A (en) * | 2011-08-29 | 2012-03-28 | 旭川化学（苏州）有限公司 | Polyurethane surface layer resin for shoe lining leather and preparation method thereof |
| CN102617826A (en) * | 2012-03-26 | 2012-08-01 | 合肥安利聚氨酯新材料有限公司 | Soft non-adhesive wet polyurethane resin and preparation method thereof |
| CN102875774A (en) * | 2012-10-12 | 2013-01-16 | 合肥安利聚氨酯新材料有限公司 | High-peel strength and anti-hydrolysis wet polyurethane resin and preparation method thereof |
| CN104844780A (en) * | 2015-05-22 | 2015-08-19 | 佛山市高明恒祥化工树脂有限公司 | Environment-friendly low-temperature wet stamping-discoloring polyurethane resin and preparation method for same |
| CN104892883A (en) * | 2015-05-26 | 2015-09-09 | 温州日胜新材料科技有限公司 | Preparation method of clothing leather resin |
| CN105153397A (en) * | 2015-09-21 | 2015-12-16 | 合肥安利聚氨酯新材料有限公司 | Preparation method of dry, comfortable and cold-resistant surface-layer polyurethane resin for elastic leather |
| CN106279599A (en) * | 2015-05-26 | 2017-01-04 | 温州日胜新材料科技有限公司 | A kind of hydrolysis process for preparing resins |
| CN106753163A (en) * | 2016-12-27 | 2017-05-31 | 丽水学院 | A kind of footwear kind of flocked leather can be molded aqueous polyurethane flock glue and preparation method thereof |
| CN108623780A (en) * | 2018-05-25 | 2018-10-09 | 清远市番亿聚氨酯有限公司 | A kind of low modulus, the preparation method of rill hole wet method resin |
| CN109666114A (en) * | 2018-12-11 | 2019-04-23 | 无锡双象超纤材料股份有限公司 | A kind of preparation method of Cambodia's sense woven fabric sofa artificial leather wet polyurethane resin |
| CN109853254A (en) * | 2019-02-28 | 2019-06-07 | 扬州工业职业技术学院 | A kind of middle hard mirror surface polyurethane wet bass and preparation method thereof |
| CN109912761A (en) * | 2019-01-24 | 2019-06-21 | 扬州工业职业技术学院 | A kind of extra soft polyurethane wet process bass and preparation method thereof |
| CN110437409A (en) * | 2019-07-05 | 2019-11-12 | 浙江旭川树脂有限公司 | It is a kind of it is high rebound without abscess polyurethane wet resin and its preparation method and application |
| CN111117549A (en) * | 2019-12-27 | 2020-05-08 | 雨中情防水技术集团有限责任公司 | Single-component polyurethane sealant prepared by using PAPI (polymethylacrylate polyimide) |
-
2009
- 2009-03-11 CN CNA2009101163310A patent/CN101503499A/en active Pending
Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102094331A (en) * | 2010-12-29 | 2011-06-15 | 浙江华峰合成树脂有限公司 | Wet type impregnating polyurethane resin and preparation method thereof |
| CN102391462A (en) * | 2011-08-29 | 2012-03-28 | 旭川化学（苏州）有限公司 | Polyurethane surface layer resin for shoe lining leather and preparation method thereof |
| CN102617826A (en) * | 2012-03-26 | 2012-08-01 | 合肥安利聚氨酯新材料有限公司 | Soft non-adhesive wet polyurethane resin and preparation method thereof |
| CN102875774A (en) * | 2012-10-12 | 2013-01-16 | 合肥安利聚氨酯新材料有限公司 | High-peel strength and anti-hydrolysis wet polyurethane resin and preparation method thereof |
| CN102875774B (en) * | 2012-10-12 | 2014-06-11 | 合肥安利聚氨酯新材料有限公司 | High-peel strength and anti-hydrolysis wet polyurethane resin and preparation method thereof |
| CN104844780B (en) * | 2015-05-22 | 2018-04-24 | 佛山市高明恒祥化工树脂有限公司 | A kind of environment-friendly type leather low temperature wet method buckling polyurethane resin and preparation method thereof |
| CN104844780A (en) * | 2015-05-22 | 2015-08-19 | 佛山市高明恒祥化工树脂有限公司 | Environment-friendly low-temperature wet stamping-discoloring polyurethane resin and preparation method for same |
| CN106279599A (en) * | 2015-05-26 | 2017-01-04 | 温州日胜新材料科技有限公司 | A kind of hydrolysis process for preparing resins |
| CN104892883A (en) * | 2015-05-26 | 2015-09-09 | 温州日胜新材料科技有限公司 | Preparation method of clothing leather resin |
| CN105153397A (en) * | 2015-09-21 | 2015-12-16 | 合肥安利聚氨酯新材料有限公司 | Preparation method of dry, comfortable and cold-resistant surface-layer polyurethane resin for elastic leather |
| CN106753163B (en) * | 2016-12-27 | 2020-06-16 | 丽水学院 | Flocking leather injection-moldable waterborne polyurethane flocking glue for shoes and preparation method thereof |
| CN106753163A (en) * | 2016-12-27 | 2017-05-31 | 丽水学院 | A kind of footwear kind of flocked leather can be molded aqueous polyurethane flock glue and preparation method thereof |
| CN108623780A (en) * | 2018-05-25 | 2018-10-09 | 清远市番亿聚氨酯有限公司 | A kind of low modulus, the preparation method of rill hole wet method resin |
| CN109666114A (en) * | 2018-12-11 | 2019-04-23 | 无锡双象超纤材料股份有限公司 | A kind of preparation method of Cambodia's sense woven fabric sofa artificial leather wet polyurethane resin |
| CN109912761A (en) * | 2019-01-24 | 2019-06-21 | 扬州工业职业技术学院 | A kind of extra soft polyurethane wet process bass and preparation method thereof |
| CN109912761B (en) * | 2019-01-24 | 2021-10-08 | 扬州工业职业技术学院 | Super-soft polyurethane wet base and preparation method thereof |
| CN109853254A (en) * | 2019-02-28 | 2019-06-07 | 扬州工业职业技术学院 | A kind of middle hard mirror surface polyurethane wet bass and preparation method thereof |
| CN109853254B (en) * | 2019-02-28 | 2021-08-03 | 扬州工业职业技术学院 | Medium-hard mirror polyurethane wet base and preparation method thereof |
| CN110437409A (en) * | 2019-07-05 | 2019-11-12 | 浙江旭川树脂有限公司 | It is a kind of it is high rebound without abscess polyurethane wet resin and its preparation method and application |
| CN111117549A (en) * | 2019-12-27 | 2020-05-08 | 雨中情防水技术集团有限责任公司 | Single-component polyurethane sealant prepared by using PAPI (polymethylacrylate polyimide) |
| CN111117549B (en) * | 2019-12-27 | 2022-01-28 | 雨中情防水技术集团股份有限公司 | Single-component polyurethane sealant prepared by using PAPI (polymethylacrylate polyimide) |
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