CN102504189A - Polyurethane for high-resilience clothing leather and preparation method thereof - Google Patents
Polyurethane for high-resilience clothing leather and preparation method thereof Download PDFInfo
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- CN102504189A CN102504189A CN2011103498621A CN201110349862A CN102504189A CN 102504189 A CN102504189 A CN 102504189A CN 2011103498621 A CN2011103498621 A CN 2011103498621A CN 201110349862 A CN201110349862 A CN 201110349862A CN 102504189 A CN102504189 A CN 102504189A
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- Prior art keywords
- urethane
- clothing leather
- mixture
- resilience
- polyurethane
- 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.)
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- 239000010985 leather Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000004814 polyurethane Substances 0.000 title abstract description 10
- 229920002635 polyurethane Polymers 0.000 title abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 239000000203 mixture Substances 0.000 claims abstract description 19
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 238000012662 bulk polymerization Methods 0.000 claims abstract description 9
- 238000012544 monitoring process Methods 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 44
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 37
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 22
- 239000002202 Polyethylene glycol Substances 0.000 claims description 20
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 claims description 20
- 229920001223 polyethylene glycol Polymers 0.000 claims description 20
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 claims description 18
- 238000010792 warming Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 abstract description 15
- -1 poly(ethylene glycol adipate) Polymers 0.000 abstract description 8
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 abstract 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 abstract 2
- 150000002009 diols Chemical class 0.000 abstract 2
- 238000010438 heat treatment Methods 0.000 abstract 2
- 229920000166 polytrimethylene carbonate Polymers 0.000 abstract 2
- 238000001816 cooling Methods 0.000 abstract 1
- 238000001914 filtration Methods 0.000 abstract 1
- 238000004806 packaging method and process Methods 0.000 abstract 1
- 239000002649 leather substitute Substances 0.000 description 6
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 5
- 239000004970 Chain extender Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000012545 processing Methods 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229920005906 polyester polyol Polymers 0.000 description 2
- 150000003673 urethanes Chemical class 0.000 description 2
- 229920001634 Copolyester Polymers 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 241000009298 Trigla lyra Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- IYWCBYFJFZCCGV-UHFFFAOYSA-N formamide;hydrate Chemical group O.NC=O IYWCBYFJFZCCGV-UHFFFAOYSA-N 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000003431 oxalo group Chemical group 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
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 is used urethane.
Background technology
It is soft, soft that urethane (PU) synthetic leather has gloss, 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 in a plurality of fields such as clothes, case and bag, footwear leather, furniture and automobile at present.In recent years, the synthetic leather technology has obtained the high speed development, especially clothing leather with the tempo of synthetic leather far ahead of other field.PU synthetic leather processing as a conventional wet process, ie containing dimethylformamide (DMF) of a polyurethane resin is coated on the base fabric Xun surface of the resin with water and DMF exchange method to obtain the polyurethane coagulation basket for carrying soil tree Guo , to form a polyurethane layer having a porous structure.Usually Piper and feel of the leather are determined by the resin used, the resin can be different kinds of changes in species composition leather Link
The mixed system that existing clothing leather normally adopts the pure and mild polyether glycol of polyester polyols with
ammonia
is as polyol component, with oxalyl or butyleneglycol etc. as chainextender.For example; The disclosed clothing leather of Chinese invention patent ZL200810107274.5 is used urethane; 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, terepthaloyl moietie 0.6～0.8% etc.The purpose of performances such as other patent is also through the improvement to the component of the polyvalent alcohol that constitutes 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 clothing leather that existing these urethane process generally relatively is short of aspect restorative at elasticity and fold.
Summary of the invention
Technical problem to be solved by this invention is the deficiency that overcomes prior art, provides a kind of high resilience clothing leather to use urethane.
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 is used 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 N.
According to a preferred aspect of the present invention; The composition of raw materials of said 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 N.
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 is with the preparation method of urethane, and it is that the polyethylene glycol adipate of formula ratio two is pure and mild 1, and ammediol is added in the reaction kettle; Be heated to 100 ℃～110 ℃, carry out processed to anhydrous state, be cooled to 40 ℃～50 ℃; Add 4 of formula ratio, the 4-diphenylmethanediisocyanate is warming up to 70 ℃～90 ℃ then and carries out bulk polymerization; Monitoring viscosity in the reaction process reaches 1.2MCps/25 ℃ to viscosity, adds the N of formula ratio; Stir, filter and package to such an extent that said high resilience clothing leather is used urethane.
Because the employing of technique scheme, the present invention compared with prior art has the following advantages:
Different as chainextender with traditional spent glycol or butyleneglycol of in prescription, making, urethane of the present invention adopts 1, and ammediol is as chainextender, and combines the pure and mild isocyanate component of specific polyester polyols and the consumption of each component is carried out rational proportion.Use the clothing leather of urethane processing of the present invention, the fold with high resilience and excellence is restorative.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 the separation and the purification of high complexity, just can obtain the high urethane of purity, uses the clothing leather of this urethane processing, and the fold with high resilience and excellence is restorative.
Embodiment
Below in conjunction with concrete embodiment the present invention is done further detailed explanation, but the invention is not restricted to these embodiment.
Embodiment 1
The clothing leather of present embodiment consists of with the composition of raw materials of urethane: the polyethylene glycol adipate glycol of number-average molecular weight 4500 (directly being purchased acquisition) 20 weight parts, 1; Ammediol 1.2 weight parts, 4,4-diphenylmethanediisocyanate 5.1 weight parts and N 73.7 weight parts.
Said urethane prepares through following steps: with the polyethylene glycol adipate glycol, and 1, ammediol adds reaction kettle, is warming up to 110 ℃ of processed to anhydrous state; Add 4 after being cooled to 40 ℃, the 4-diphenylmethanediisocyanate is warming up to 90 ℃ then and carries out bulk polymerization; Monitoring viscosity in the reaction process treats that viscosity is 1.2MCps/25 ℃, stopped reaction; Add N, after stirring, can filter and package promptly and get.
Embodiment 2
The clothing leather of present embodiment consists of with the composition of raw materials of urethane: the polyethylene glycol adipate glycol of number-average molecular weight 5000 (directly being purchased acquisition) 21 weight parts, 1; Ammediol 1.3 weight parts, 4,4-diphenylmethanediisocyanate 5.3 weight parts and N 72.4 weight parts.
Said urethane prepares through following steps: with the polyethylene glycol adipate glycol, and 1, ammediol adds reaction kettle, is warming up to 110 ℃ of processed to anhydrous state; Add 4 after being cooled to 45 ℃, the 4-diphenylmethanediisocyanate is warming up to 90 ℃ then and carries out bulk polymerization; Monitoring viscosity in the reaction process treats that viscosity is 1.2MCps/25 ℃, stopped reaction; Add N, after stirring, can filter and package promptly and get.
Embodiment 3
The clothing leather of present embodiment consists of with the composition of raw materials of urethane: the polyethylene glycol adipate glycol of number-average molecular weight 5500 (directly being purchased acquisition) 19 weight parts, 1; Ammediol 1.35 weight parts, 4,4-diphenylmethanediisocyanate 5.3 weight parts and N 74.35 weight parts.
Said urethane prepares through following steps: with the polyethylene glycol adipate glycol, and 1, ammediol adds reaction kettle, is warming up to 105 ℃ of processed to anhydrous state; Add 4 after being cooled to 40 ℃, the 4-diphenylmethanediisocyanate is warming up to 80 ℃ then and carries out bulk polymerization; Monitoring viscosity in the reaction process treats that viscosity is 1.2MCps/25 ℃, stopped reaction; Add N, after stirring, can filter and package promptly and get.
Embodiment 4
The clothing leather of present embodiment consists of with the composition of raw materials of urethane: the polyethylene glycol adipate glycol of number-average molecular weight 6000 (directly being purchased acquisition) 18 weight parts, 1; Ammediol 1.5 weight parts, 4,4-'-diphenylmethane diisocyanate 5.7 weight parts and N 74.8 weight parts.
Said urethane prepares through following steps: with the polyethylene glycol adipate glycol, and 1, ammediol adds reaction kettle, is warming up to 100 ℃ of processed to anhydrous state; Add 4 after being cooled to 40 ℃, the 4-diphenylmethanediisocyanate is warming up to 75 ℃ then and carries out bulk polymerization; Monitoring viscosity in the reaction process treats that viscosity is 1.2MCps/25 ℃, stopped reaction; Add N, after stirring, can filter and package promptly and get.
Embodiment 5
The clothing leather of present embodiment consists of with the composition of raw materials of urethane: the polyethylene glycol adipate glycol of number-average molecular weight 4000 (directly being purchased acquisition) 21 weight parts, 1; Ammediol 1.3 weight parts, 4,4-diphenylmethanediisocyanate 5.6 weight parts and N 72.1 weight parts.
Said urethane prepares through following steps: with the polyethylene glycol adipate glycol, and 1, ammediol adds reaction kettle, is warming up to 110 ℃ of processed to anhydrous state; Add 4 after being cooled to 50 ℃, the 4-diphenylmethanediisocyanate is warming up to 75 ℃ then and carries out bulk polymerization; Monitoring viscosity in the reaction process treats that viscosity is 1.2MCps/25 ℃, stopped reaction; Add N, after stirring, can filter and package promptly and get.
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 being purchased acquisition) 20 weight parts, terepthaloyl moietie 1.2 weight parts, 4,4-diphenylmethanediisocyanate 5.8 weight parts and N 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 being purchased acquisition) 20 weight parts, butyleneglycol 1.6 weight parts, 4,4-diphenylmethanediisocyanate 6 weight parts and N 72.4 weight parts.The preparation method is with embodiment 1.
Urethane to embodiment 1～5 and Comparative Examples 1～2 carries out rebound resilience and the restorative test of fold, and test result is referring to table 1.
The restorative test result of table 1 Synthetic Leather rebound resilience and fold
Visible from table 1, when other component is identical, adopt 1, ammediol have higher rebound resilience as chainextender than the urethane that adopts terepthaloyl moietie or butyleneglycol to process as chainextender and fold restorative.
More than the present invention has been done detailed description; Its purpose is to let the personage that is familiar with this art can understand content of the present invention and implements; Can not limit protection scope of the present invention with this; All equivalences of doing according to spirit of the present invention change or modify, and all should be encompassed in protection scope of the present invention.
Claims (4)
1. one kind high resilience clothing leather is used urethane; It is characterized in that: in weight percentage; The composition of raw materials of said 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 N.
2. high resilience clothing leather according to claim 1 is used 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 N.
3. high resilience clothing leather according to claim 1 is used urethane, it is characterized in that: the number-average molecular weight of described polyethylene glycol adipate glycol is 4000～6000.
4. the described high resilience clothing leather of each claim is characterized in that with the preparation method of urethane in the claim 1 to 3: this method is that the polyethylene glycol adipate of formula ratio two is pure and mild 1, and ammediol is added in the reaction kettle; Be heated to 100 ℃～110 ℃, carry out processed to anhydrous state, be cooled to 40 ℃～50 ℃; Add 4 of formula ratio, the 4-diphenylmethanediisocyanate is warming up to 70 ℃～90 ℃ then and carries out bulk polymerization; Monitoring viscosity in the reaction process reaches 1.2MCps/25 ℃ to viscosity, adds the N of formula ratio; Stir, filter and package to such an extent that said high resilience clothing leather is used urethane.
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 |
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| CN102504189A true CN102504189A (en) | 2012-06-20 |
| CN102504189B CN102504189B (en) | 2013-06-05 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN 201110349862 Active CN102504189B (en) | 2011-11-08 | 2011-11-08 | Polyurethane for high-resilience clothing leather and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105586783A (en) * | 2014-11-07 | 2016-05-18 | 现代自动车株式会社 | Synthetic leather for steering wheel cover having improved durability and method for preparing the same |
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Cited By (3)
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| CN105586783A (en) * | 2014-11-07 | 2016-05-18 | 现代自动车株式会社 | Synthetic leather for steering wheel cover having improved durability and method for preparing the same |
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| US11628647B2 (en) | 2014-11-07 | 2023-04-18 | Hyundai Motor Company | Synthetic leather for steering wheel cover having improved durability and method for preparing the same |
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| CN102504189B (en) | 2013-06-05 |
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