CN102504189B - Polyurethane for high-resilience clothing leather and preparation method thereof - Google Patents
Polyurethane for high-resilience clothing leather and preparation method thereof Download PDFInfo
- Publication number
- CN102504189B CN102504189B CN 201110349862 CN201110349862A CN102504189B CN 102504189 B CN102504189 B CN 102504189B CN 201110349862 CN201110349862 CN 201110349862 CN 201110349862 A CN201110349862 A CN 201110349862A CN 102504189 B CN102504189 B CN 102504189B
- Authority
- CN
- China
- Prior art keywords
- urethane
- resilience
- mixture
- clothing leather
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
The invention relates to polyurethane for high-resilience clothing leather and a preparation method thereof. The polyurethane is prepared from the following raw materials in percentage by weight: 16 to 24 percent of poly(ethylene glycol adipate)diol with a number-average molecular weight of 2,000 to 6,000, 0.8 to 1.5 percent of 1,3-propanediol, 5 to 9 percent of 4,4'-diphenylmethane diisocyanate and the balance of dimethylformamide. The preparation method of the polyurethane comprises: adding poly(ethylene glycol adipate)diol and 1,3-propanediol into a reaction kettle according to a formula ratio, heating the mixture to 100 to 110 DEG C, dehydrating the mixture till the mixture contains no water, cooling the mixture to 40 to 50 DEG C, adding 4,4'-diphenylmethane diisocyanate according to a formula ratio, heating the mixture to 70 to 90 DEG C, performing bulk polymerization, monitoring the viscosity in a reaction process till the viscosity reaches 1.2MCps/25DEG C, adding the dimethylformamide according to a formula ratio, stirring uniformly, filtering the mixture and packaging the mixture. The polyurethane is suitable for high-resilience clothing leather and has high resilience and drape resilience.
Description
Technical field
The present invention relates to a kind of urethane resin, particularly a kind of high resilience clothing leather urethane.
Background technology
It is soft, soft that urethane (PU) synthetic leather has gloss, the characteristics such as good mechanical performance, and it is the ideal substitute of natural leather.Synthetic Leather has passed through the development of many decades, has been widely used at present a plurality of fields such as clothes, case and bag, footwear leather, furniture and automobile.In recent years, the synthetic leather technology has obtained development at a high speed, and especially the tempo of clothing leather use synthetic leather is far ahead of other field.The wet processing that is processed as routine of Synthetic Leather, the urethane resin that is about to contain dimethyl formamide (DMF) is coated on the surface of base cloth, adopt the method for DMF exchange in water and resin make urethane resin obtain solidifying because of, formation has the layer of polyurethane of microvoid structure.Usually the character of leather and feel are all that resin by its use determines, the variation of resin kind can obtain the synthetic leather goods of different varieties.
The mixed system that existing clothing leather normally adopts the pure and mild polyether glycol of polyester polyols with urethane is as polyol component, with oxalyl or butyleneglycol etc. as chainextender.For example, the disclosed clothing leather urethane of Chinese invention patent ZL200810107274.5, its composition of raw materials comprises the polyoxyethylene glycol butyleneglycol hexanodioic acid copolyesters glycol 8%～10% of molecular weight 2000, the polyglycol ether 8%～10% of molecular weight 2000, ethylene glycol 0.6～0.8% etc.The purpose of the performances such as other patent is also by the improvement to the component of the polyvalent alcohol that consists of the urethane main body, reached to improve the clothing leather wear behavior and for example endure hardships, and is wear-resisting.But so far, using the clothing leather that existing these urethane make generally relatively is being short of aspect elasticity and recovering of folds.
Summary of the invention
Technical problem to be solved by this invention is to overcome the deficiencies in the prior art, and a kind of high resilience clothing leather urethane is provided.
The present invention also will provide the preparation method of a kind of high resilience clothing leather with urethane simultaneously.
For solving above technical problem, a kind of technical scheme that the present invention takes is:
A kind of high resilience clothing leather urethane, in weight percentage, the composition of raw materials of this urethane is: the polyethylene glycol adipate glycol 16%～24%, 1 of number-average molecular weight 2000～6000, ammediol 0.8%～1.5%, 4,4 '-diphenylmethanediisocyanate 5%～9% and surplus dimethyl formamide.
According to a preferred aspect of the present invention, the composition of raw materials of described urethane is: the polyethylene glycol adipate glycol 18%～22%, 1 of number-average molecular weight 3000～6000, ammediol 0.8%～1.5%, 4,4 '-'-diphenylmethane diisocyanate 5%～7% and surplus are dimethyl formamide.
Preferably, the number-average molecular weight of described polyethylene glycol adipate glycol is 4000～6000.
the another technical scheme that the present invention takes is: a kind of above-mentioned high resilience clothing leather preparation method of urethane, it is the polyethylene glycol adipate two pure and mild 1 with formula ratio, ammediol is added in reactor, be heated to 100 ℃～110 ℃, carry out processed to anhydrous state, be cooled to 40 ℃～50 ℃, add 4 of formula ratio, 4 '-diphenylmethanediisocyanate, then be warming up to 70 ℃～90 ℃ and carry out bulk polymerization, monitoring viscosity in reaction process, reach 1.2MCps/25 ℃ to viscosity, the dimethyl formamide that adds formula ratio, stir, filter and package to get described high resilience clothing leather urethane.
Due to the employing of technique scheme, the present invention compared with prior art has the following advantages:
From traditional make in formula spent glycol or butyleneglycol different as chainextender, urethane of the present invention adopts 1,3-PD as chainextender, and carries out rational proportion in conjunction with the specific pure and mild isocyanate component of polyester polyols and to the consumption of each component.Use the clothing leather of urethane processing of the present invention, have high resilience and excellent recovering of folds.In addition, polyurethane formulations of the present invention is simple, can adopt the mass polymerization preparation, and production cost is low.
The preparation method of urethane of the present invention is simple to operate, does not need separation and the purification of high complexity, just can obtain the high urethane of purity, uses the clothing leather of this urethane processing, has high resilience and excellent recovering of folds.
Embodiment
The present invention will be further described in detail below in conjunction with specific embodiment, but the invention is not restricted to these embodiment.
Embodiment 1
The clothing leather of the present embodiment consists of with the composition of raw materials of urethane: the polyethylene glycol adipate glycol of number-average molecular weight 4500 (directly commercially available) 20 weight parts, 1, ammediol 1.2 weight parts, 4,4 '-diphenylmethanediisocyanate, 5.1 weight parts and dimethyl formamide 73.7 weight parts.
Described urethane prepares through following steps: with the polyethylene glycol adipate glycol, 1,3-PD adds reactor, be warming up to 110 ℃ of processed to anhydrous state, add 4 after being cooled to 40 ℃, then 4 '-diphenylmethanediisocyanate is warming up to 90 ℃ and carries out bulk polymerization, monitoring viscosity in reaction process, treat that viscosity is 1.2MCps/25 ℃, stopped reaction adds dimethyl formamide, after stirring, can filter and package and get final product.
Embodiment 2
The clothing leather of the present embodiment consists of with the composition of raw materials of urethane: the polyethylene glycol adipate glycol of number-average molecular weight 5000 (directly commercially available) 21 weight parts, 1, ammediol 1.3 weight parts, 4,4 '-diphenylmethanediisocyanate, 5.3 weight parts and dimethyl formamide 72.4 weight parts.
Described urethane prepares through following steps: with the polyethylene glycol adipate glycol, 1,3-PD adds reactor, be warming up to 110 ℃ of processed to anhydrous state, add 4 after being cooled to 45 ℃, then 4 '-diphenylmethanediisocyanate is warming up to 90 ℃ and carries out bulk polymerization, monitoring viscosity in reaction process, treat that viscosity is 1.2MCps/25 ℃, stopped reaction adds dimethyl formamide, after stirring, can filter and package and get final product.
Embodiment 3
The clothing leather of the present embodiment consists of with the composition of raw materials of urethane: the polyethylene glycol adipate glycol of number-average molecular weight 5500 (directly commercially available) 19 weight parts, 1, ammediol 1.35 weight parts, 4,4 '-diphenylmethanediisocyanate, 5.3 weight parts and dimethyl formamide 74.35 weight parts.
Described urethane prepares through following steps: with the polyethylene glycol adipate glycol, 1,3-PD adds reactor, be warming up to 105 ℃ of processed to anhydrous state, add 4 after being cooled to 40 ℃, then 4 '-diphenylmethanediisocyanate is warming up to 80 ℃ and carries out bulk polymerization, monitoring viscosity in reaction process, treat that viscosity is 1.2MCps/25 ℃, stopped reaction adds dimethyl formamide, after stirring, can filter and package and get final product.
Embodiment 4
The clothing leather of the present embodiment consists of with the composition of raw materials of urethane: the polyethylene glycol adipate glycol of number-average molecular weight 6000 (directly commercially available) 18 weight parts, 1, ammediol 1.5 weight parts, 4,4 '-'-diphenylmethane diisocyanate, 5.7 weight parts and dimethyl formamide 74.8 weight parts.
Described urethane prepares through following steps: with the polyethylene glycol adipate glycol, 1,3-PD adds reactor, be warming up to 100 ℃ of processed to anhydrous state, add 4 after being cooled to 40 ℃, then 4 '-diphenylmethanediisocyanate is warming up to 75 ℃ and carries out bulk polymerization, monitoring viscosity in reaction process, treat that viscosity is 1.2MCps/25 ℃, stopped reaction adds dimethyl formamide, after stirring, can filter and package and get final product.
Embodiment 5
The clothing leather of the present embodiment consists of with the composition of raw materials of urethane: the polyethylene glycol adipate glycol of number-average molecular weight 4000 (directly commercially available) 21 weight parts, 1, ammediol 1.3 weight parts, 4,4 '-diphenylmethanediisocyanate, 5.6 weight parts and dimethyl formamide 72.1 weight parts.
Described urethane prepares through following steps: with the polyethylene glycol adipate glycol, 1,3-PD adds reactor, be warming up to 110 ℃ of processed to anhydrous state, add 4 after being cooled to 50 ℃, then 4 '-diphenylmethanediisocyanate is warming up to 75 ℃ and carries out bulk polymerization, monitoring viscosity in reaction process, treat that viscosity is 1.2MCps/25 ℃, stopped reaction adds dimethyl formamide, after stirring, can filter and package and get final product.
Comparative Examples 1
The raw material of the urethane of this Comparative Examples consists of: the polyethylene glycol adipate glycol of number-average molecular weight 5000 (directly commercially available) 20 weight parts, ethylene glycol 1.2 weight parts, 4,4 '-diphenylmethanediisocyanate, 5.8 weight parts and dimethyl formamide 73 weight parts.The preparation method is with embodiment 1.
Comparative Examples 2
The raw material of the urethane of this Comparative Examples consists of: the polyethylene glycol adipate glycol of number-average molecular weight 5000 (directly commercially available) 20 weight parts, butyleneglycol 1.6 weight parts, 4,4 '-diphenylmethanediisocyanate, 6 weight parts and dimethyl formamide 72.4 weight parts.The preparation method is with embodiment 1.
Urethane to embodiment 1～5 and Comparative Examples 1～2 carries out the test of rebound resilience and recovering of folds, and test result is referring to table 1.
Table 1 Synthetic Leather rebound resilience and recovering of folds property testing result
As seen from Table 1, when other component is identical, adopt 1,3-PD to have higher rebound resilience and recovering of folds as chainextender than the urethane that adopts ethylene glycol or butyleneglycol to make as chainextender.
Above the present invention has been done detailed description; its purpose is to allow the personage who is familiar with this art can understand content of the present invention and be implemented; can not limit protection scope of the present invention with this; the equivalence that all spirit according to the present invention are done changes or modifies, and all should be encompassed in protection scope of the present invention.
Claims (3)
1. a resilience clothing leather is with the preparation method of urethane, it is characterized in that: in weight percentage, the composition of raw materials of described urethane is: the polyethylene glycol adipate glycol 16%～24% of number-average molecular weight 2000～6000, 1, ammediol 0.8%～1.5%, 4, 4 '-diphenylmethanediisocyanate 5%～9% and surplus dimethyl formamide, described method is the polyethylene glycol adipate two pure and mild 1 with formula ratio, ammediol is added in reactor, be heated to 100 ℃～110 ℃, carry out processed to anhydrous state, be cooled to 40 ℃～50 ℃, add 4 of formula ratio, 4 '-diphenylmethanediisocyanate, then be warming up to 70 ℃～90 ℃ and carry out bulk polymerization, monitoring viscosity in reaction process, reach 1.2MCps/25 ℃ to viscosity, the dimethyl formamide that adds formula ratio, stir, filter and package to get described resilience clothing leather urethane.
2. resilience clothing leather according to claim 1 is with the preparation method of urethane, it is characterized in that: the composition of raw materials of described urethane is: the polyethylene glycol adipate glycol 18%～22%, 1 of number-average molecular weight 2000～6000, ammediol 0.8%～1.5%, 4,4 '-diphenylmethanediisocyanate 5%～7% and surplus are dimethyl formamide.
3. resilience clothing leather according to claim 1 is with the preparation method of urethane, and it is characterized in that: the number-average molecular weight of described polyethylene glycol adipate glycol is 4000～6000.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110349862 CN102504189B (en) | 2011-11-08 | 2011-11-08 | Polyurethane for high-resilience clothing leather and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110349862 CN102504189B (en) | 2011-11-08 | 2011-11-08 | Polyurethane for high-resilience clothing leather and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102504189A CN102504189A (en) | 2012-06-20 |
| CN102504189B true CN102504189B (en) | 2013-06-05 |
Family
ID=46216328
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201110349862 Active CN102504189B (en) | 2011-11-08 | 2011-11-08 | Polyurethane for high-resilience clothing leather and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102504189B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101619636B1 (en) | 2014-11-07 | 2016-05-10 | 현대자동차주식회사 | Synthetic Leather For Steering Wheel Covering improved Durability And Preparation Method Thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1445390A (en) * | 2003-05-06 | 2003-10-01 | 东华大学 | Method and equipment for making elastic nonwovens from polyurethane by melting and jetting material to form mesh |
| CN101016407A (en) * | 2007-01-26 | 2007-08-15 | 东莞市宏达聚氨酯有限公司 | Polyurethane resin composition and its preparing process |
| CN101580635A (en) * | 2009-04-15 | 2009-11-18 | 浙江华峰合成树脂有限公司 | High-performance anti-hydrolysis and high-density resin material for coining polyurethane leather and preparing method thereof |
| CN101665675A (en) * | 2009-09-22 | 2010-03-10 | 烟台华大化学工业有限公司 | Method for preparing aqueous polyurethane adhesive and superfine fiber synthetic leather |
| CN101942767A (en) * | 2010-07-28 | 2011-01-12 | 丽水市优耐克水性树脂科技有限公司 | Interior wall adornment leather and preparation method |
-
2011
- 2011-11-08 CN CN 201110349862 patent/CN102504189B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1445390A (en) * | 2003-05-06 | 2003-10-01 | 东华大学 | Method and equipment for making elastic nonwovens from polyurethane by melting and jetting material to form mesh |
| CN101016407A (en) * | 2007-01-26 | 2007-08-15 | 东莞市宏达聚氨酯有限公司 | Polyurethane resin composition and its preparing process |
| CN101580635A (en) * | 2009-04-15 | 2009-11-18 | 浙江华峰合成树脂有限公司 | High-performance anti-hydrolysis and high-density resin material for coining polyurethane leather and preparing method thereof |
| CN101665675A (en) * | 2009-09-22 | 2010-03-10 | 烟台华大化学工业有限公司 | Method for preparing aqueous polyurethane adhesive and superfine fiber synthetic leather |
| CN101942767A (en) * | 2010-07-28 | 2011-01-12 | 丽水市优耐克水性树脂科技有限公司 | Interior wall adornment leather and preparation method |
Non-Patent Citations (4)
| Title |
|---|
| IPDI/PEPA型热塑性聚氨酯的合成及表征;廖肃然,罗运军,卢赟,等;《合成纤维工业》;20061031;第29卷(第5期);第1-3页 * |
| PEPA/MDI体系聚氨酯弹性体力学性能的研究;刘凉冰,贾林才,刘红梅;《弹性体》;20071225;第17卷(第6期);第34-36页 * |
| 刘凉冰,贾林才,刘红梅.PEPA/MDI体系聚氨酯弹性体力学性能的研究.《弹性体》.2007,第17卷(第6期), |
| 廖肃然,罗运军,卢赟,等.IPDI/PEPA型热塑性聚氨酯的合成及表征.《合成纤维工业》.2006,第29卷(第5期), |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102504189A (en) | 2012-06-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105585701B (en) | A kind of polyether-modified copolyesters continuous preparation method | |
| CN102181031B (en) | Durable polyurethane resin for sofa leather and preparation method of the durable polyurethane resin | |
| CN101381449B (en) | Polyurethane resin for artificial leather | |
| CN101481449B (en) | Wet impregnated polyurethane resin for high hydrolysis resistance synthetic leather and preparation thereof | |
| CN101338016B (en) | High springback wet method polyurethane resin for superfine fiber chemical leather | |
| CN103450436A (en) | Polyurethane resin, and preparation method and application thereof | |
| CN104163909B (en) | Polyurethane resin for hydrolysis-resistant sofa leather and preparation method thereof | |
| CN101628964B (en) | Bi-components for manufacturing polyurethane sole materials | |
| CN108048020B (en) | Single-component moisture-curing reaction type polyurethane hot melt adhesive and preparation method thereof | |
| CN108864404A (en) | A kind of coffee grounds composite material and preparation method of isocyanates enhancing | |
| CN102964564B (en) | Low-foam and anti-ageing wet type polyurethane resin for synthetic leather and preparation method thereof | |
| CN106496514A (en) | A kind of waterborne polyurethane resin | |
| CN103755917A (en) | Polyurethane bonding layer resin for clothing leather, and preparation method and application thereof | |
| CN102181259B (en) | Polyurethane hot melt adhesive for bookbinding of books and magazines and preparation method thereof | |
| CN102504189B (en) | Polyurethane for high-resilience clothing leather and preparation method thereof | |
| CN105295817A (en) | Preparation method for high-solid-content aqueous polyurethane adhesive | |
| CN106117493A (en) | A kind of preparation method of heat resistant type TPU film | |
| CN108903529A (en) | A kind of memory sponge quilt | |
| CN109293876A (en) | A kind of novel body building apparatus material and preparation method thereof | |
| CN111253544B (en) | Environment-friendly chain extender and preparation method thereof | |
| CN103865467A (en) | Nonyellowing-type high-performance polyurethane adhesive and preparation method thereof | |
| CN102504216B (en) | Preparation method of phthalic anhydride polyalcohol for synthesis of thermoplastic polyurethane (TPU) | |
| CN104448221A (en) | Polyurethane high-resilience leather clothes and preparation method thereof | |
| CN101628963B (en) | Bicomponent for manufacturing polyester polyurethane woodlike material | |
| CN105273170B (en) | Ultralow-chroma PEHA for TPU and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |