CN101974147A - Polyester polyol and polyurethane resin for superfine fiber synthetic leather - Google Patents
Polyester polyol and polyurethane resin for superfine fiber synthetic leather Download PDFInfo
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- CN101974147A CN101974147A CN 201010281872 CN201010281872A CN101974147A CN 101974147 A CN101974147 A CN 101974147A CN 201010281872 CN201010281872 CN 201010281872 CN 201010281872 A CN201010281872 A CN 201010281872A CN 101974147 A CN101974147 A CN 101974147A
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- polyester polyol
- urethane resin
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- polyurethane resin
- superfine fiber
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Abstract
The invention relates to polyester polyol for synthesizing a polyurethane resin for superfine fiber synthetic leather and the polyurethane resin synthesized by polyester polyol. The polyester polyol comprises the following starting materials: 5-15wt% of polyethylene glycol, 50-65wt% of mixed dicarboxylic acid and 15-35wt% of mixed diols. The assistants adopted during synthesis include a catalyst and an antioxidant. The polyurethane resin synthesized by polyester polyol obtained by adopting the technical scheme is especially suitable for processing the superfine fiber post-dyed synthetic leathers, the degree of dyeing of the polyurethane resin for superfine resins is improved, the polyurethane resin is not easy to decolor and polyester polyol has high moisture absorption, thus ensuring the final superfine resin products to have good handfeel.
Description
Technical field
The present invention relates to a kind of superfine fiber chemical leather urethane resin and preparation method thereof.
Background technology
In recent years, along with the chemistry and the development of composite technology, obtain fast development as the synthetic leather technology of new industry.Utilize the synthetic leather of super-fine fiber material processing to have the characteristics of high emulation skin, all exceed corium in each side such as physicals, material structure, ventilation properties.General superfine fiber chemical leather working method is: after the ultra-fine fibre process urethane resin impregnation of blend spinning, utilize again solvent or alkali with a component of fiber molten from, obtain super-fine fiber material, again through obtaining superfine fiber chemical leather after the technologies such as veneer, ornamenting.
At present, superfine fiber chemical leather is later relatively with urethane resin development, exist technically and ultra-fine fibre nonsynchronous phenomenon that dyes, in addition itself and combination of dyes power a little less than, the phenomenon of colour fastness difference appears again easily.The difficult problem of the dyeing of superfine fiber chemical leather has perplexed the sector for a long time, and it is highly beneficial to the development of ultra-fine fibre to synthesize the good urethane resin of poststaining, also can promote the development of emulation synthetic leather.
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 improved polyester polyol is provided, and urethane resin prepared therefrom is particularly suitable for preparing superfine fiber chemical leather.
The present invention also will provide a kind of superfine fiber chemical leather urethane resin simultaneously.
For solving above technical problem, a kind of technical scheme that the present invention takes is: a kind of polyester polyol that is used for the synthesizing superfine fiber synthetic leather with urethane resin, it is polymerized by di-carboxylic acid and polyvalent alcohol, the reaction starting raw material of described polyester polyol is by the poly ethylene glycol 5wt%～15wt% of molecular weight 300～1000, mix dibasic alcohol 15wt%～35wt% and mix di-carboxylic acid 50wt%～65wt% composition, wherein, described mixing dibasic alcohol is by Diethylene Glycol 13wt%～18wt%, neopentyl glycol 3wt%～9wt% and 1,6-hexylene glycol 2wt%～8wt% forms; Described mixing di-carboxylic acid hexanodioic acid 31wt%～39wt%, terephthalic acid 14wt%～15wt%, phthalic acid or anhydride phthalic acid 5wt%～9wt% forms, and the acid number of described polyester polyol＜1, hydroxyl value are 53～59.
Among the present invention, the reaction starting raw material is meant that the reactive material that participates in polyreaction is di-carboxylic acid component and polyol component.
According to an aspect of the present invention, the preparation process of described polyester polyol is as follows: at first feed nitrogen in reactor, with adding reaction starting raw material and weight after the air displacement in the still is the oxidation inhibitor of the 0.4wt%～0.6wt% of described reaction starting raw material weight, heat, when rising to 150 ℃～160 ℃, temperature of reaction kettle begins to dewater, constant temperature 3.5～4.5 hours, after continuing to be warming up to 195 ℃～210 ℃ then, keep constant temperature, in thermostatic process, constantly carry out the acid number test, when acid number is reduced to 4.5～5, add catalyzer, continue again to react to acid number less than 1, and hydroxyl value is 53～59, continue insulation after 3～5 hours, cooling, stopped reaction.
Described oxidation inhibitor can be 2,6 ditertiary butyl p cresol (BHT), and institute's catalyzer can be stannous octoate, tetra isopropyl titanate or the mixture of the two, and the add-on of catalyzer is generally 20～30PPM (is benchmark with reaction starting raw material gross weight).
Another technical scheme provided by the invention is: a kind of superfine fiber chemical leather urethane resin, in weight part, the composition of raw materials of described urethane resin is: above-mentioned polyester polyol 13wt%～15wt%, isocyanic ester 8wt%～10wt%, chainextender 2wt%～3wt%, N, dinethylformamide 72wt%～78wt%.The preparation method of urethane resin is as follows: polyester polyol, isocyanic ester and the chainextender of above-mentioned recipe ratio are dispersed in N, in the dinethylformamide, under 70 ℃～90 ℃ conditions, react, after reaching suitable polymerization viscosity, reduce to room temperature and promptly get described urethane resin.
Described isocyanic ester is preferably 4,4 '-diphenylmethanediisocyanate (MDI).Described chainextender is 1, the 4-butyleneglycol.
Because the employing of technique scheme, the present invention compared with prior art has the following advantages:
The contriver discovers that adopting specific mixing dibasic alcohol and mixed dibasic acid and poly ethylene glycol is raw material, and the polyester polyol synthetic urethane resin that obtains is particularly suitable for the processing of super long and slender dimension poststaining synthetic leather.At first, be improved with urethane resin colouring speed with this polyvalent alcohol synthetic ultra-fine fibre; Secondly, approaching with the dyeing speed of this polyvalent alcohol synthetic urethane resin and fiber, reduced the phenomenon that dyeing is grown dim; In addition, this polyester polyol synthetic urethane has and the good associativity of dyestuff, is not easy to occur the decolouring phenomenon in last handling process and the use; At last, polyester polyol has high water absorbability, causes this polyester polyol synthetic urethane resin to have this characteristic equally, makes final ultra-fine fibre product have good feel.
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 1～6
Polyester polyol according to embodiment 1～6 adopts the listed composition of raw materials of table 1, and obtains by being prepared as follows method:
(1), in reactor, feeds nitrogen, poly ethylene glycol, Diethylene Glycol, the neopentyl glycol, 1 of formula ratio will be added after the air displacement, 6-hexylene glycol, hexanodioic acid, terephthalic acid, phthalic acid and quality are the 0.4wt%～0.6wt% antioxidant BHT of described raw material gross weight, begin dehydration when being warming up to 150～160 ℃, after constant temperature dewatered about 4 hours, continue to be warming up to 200 ℃ of constant temperature.
(2), constantly carry out the acid number test in the thermostatic process, treat that acid number was reduced at 5 o'clock, adding quality is the catalyzer of 20～30PPM of described raw material gross weight, continue to react to acid number＜1, after the hydroxyl value 53～59, continue insulation cooling afterwards in 4 hours again, promptly get described polyester polyol.
The composition of raw materials of the polyester polyol of table 1 embodiment 1～6
Embodiment 7～12
Embodiment 7～12 provides the superfine fiber chemical leather urethane resin, they adopt the polyester polyol of embodiment 1～6 respectively, composition of raw materials according to table 2, and prepare by the following method: in reactor, charge into nitrogen, the DMF, the polyester polyol, 1 that add formula ratio successively, 4-butyleneglycol and MDI are 75 ℃ of reactions down, as the polymerization viscosity Z that reaches regulation
3～Z
4The back cooling promptly gets urethane resin.
The composition of raw materials of the urethane resin of table 2 embodiment 7～12
The performance of the superfine fiber chemical leather that the urethane resin of embodiment 7-12 is processed is tested, and the results are shown in Table 3.
Table 3 The performance test results
As seen from Table 3, adopt polyvalent alcohol synthetic ultra-fine fibre of the present invention approaching with the dyeing speed of the time of half dyeing of urethane resin and starting time and fiber, thereby improved the dye uptake of urethane resin and reduced the phenomenon that dyeing is grown dim, made final product have good performance.
More than the present invention has been done detailed description; its purpose is to allow the personage that is familiar with this art can understand content of the present invention and is implemented; 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 (5)
1. one kind is used for the polyester polyol that the synthesizing superfine fiber synthetic leather is used urethane resin, it is polymerized by di-carboxylic acid and polyvalent alcohol, it is characterized in that: the reaction starting raw material of described polyester polyol is made up of poly ethylene glycol 5wt%～15wt%, mixing dibasic alcohol 15wt%～35wt% and the mixing di-carboxylic acid 50wt%～65wt% of molecular weight 300～1000, wherein, described mixing dibasic alcohol is by Diethylene Glycol 13wt%～18wt%, neopentyl glycol 3wt%～9wt% and 1, and 6-hexylene glycol 2wt%～8wt% forms; Described mixing di-carboxylic acid hexanodioic acid 31wt%～39wt%, terephthalic acid 14wt%～15wt%, phthalic acid or anhydride phthalic acid 5wt%～9wt% forms, and the acid number of described polyester polyol＜1, hydroxyl value are 53～59.
2. polyester polyol according to claim 1, it is characterized in that: the preparation process of described polyester polyol is as follows: at first feed nitrogen in reactor, with adding reaction starting raw material and weight after the air displacement in the still is the oxidation inhibitor of the 0.4wt%～0.6wt% of described reaction starting raw material weight, heat, when temperature of reaction kettle rises to 150 ℃～160 ℃, constant temperature 3.5～4.5 hours, after continuing to be warming up to 195 ℃～210 ℃ then, keep constant temperature, in thermostatic process, constantly carry out the acid number test, when acid number is reduced to 4.5～5, add catalyzer, continue again to react to acid number less than 1, and hydroxyl value is 53～59, continue insulation after 3～5 hours, cooling, stopped reaction.
3. polyester polyol according to claim 1 is characterized in that: described oxidation inhibitor is 2,6 ditertiary butyl p cresol, and described catalyzer is stannous octoate, tetra isopropyl titanate or the mixture of the two.
4. superfine fiber chemical leather urethane resin, it is characterized in that: in weight part, the composition of raw materials of described urethane resin is: each described polyester polyol 13wt%～15wt% in the claim 1 to 3, isocyanic ester 8wt%～10wt%, chainextender 2wt%～3wt%, N, dinethylformamide 72wt%～78wt%, the preparation method of described urethane resin is as follows: with the polyester polyol of described recipe ratio, isocyanic ester and chainextender are dispersed in N, in the dinethylformamide, under 70 ℃～90 ℃ conditions, react, after reaching suitable polymerization viscosity, reduce to room temperature and promptly get described urethane resin.
5. urethane resin according to claim 4 is characterized in that: described isocyanic ester is 4,4 '-diphenylmethanediisocyanate; Described chainextender is 1, the 4-butyleneglycol.
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| CN2010102818721A CN101974147B (en) | 2010-09-15 | 2010-09-15 | Polyester polyol and polyurethane resin for superfine fiber synthetic leather |
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| CN2010102818721A CN101974147B (en) | 2010-09-15 | 2010-09-15 | Polyester polyol and polyurethane resin for superfine fiber synthetic leather |
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| CN101974147B CN101974147B (en) | 2012-01-11 |
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Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102212183A (en) * | 2011-05-03 | 2011-10-12 | 烟台华大化学工业有限公司 | Polyurethane resin used for skin-imitated superfine fiber synthetic leather, and preparation method thereof |
| CN102276783A (en) * | 2011-06-15 | 2011-12-14 | 浙江华峰合成树脂有限公司 | Non-yellowing alkali deweighting wet method dyeing polyurethane resin for superfine fiber synthetic leather and preparation method thereof |
| CN102329410A (en) * | 2011-08-17 | 2012-01-25 | 浙江恒泰源聚氨酯有限公司 | Preparation method of polyester and polyether mixed type polyurethane material with high fluidity |
| CN102532462A (en) * | 2011-12-23 | 2012-07-04 | 上海汇得化工有限公司 | Easily-dyed aliphatic polyurethane resin and preparation method thereof |
| CN102532468A (en) * | 2011-12-23 | 2012-07-04 | 上海汇得化工有限公司 | Chromatophilous aromatic polyurethane resin and preparation method thereof |
| CN103030778A (en) * | 2012-12-24 | 2013-04-10 | 建德市顺发化工助剂有限公司 | Chromatophilous polyurethane resin for synthetic leather and preparation method of polyurethane resin |
| CN103694458A (en) * | 2013-12-11 | 2014-04-02 | 高鼎精细化工(昆山)有限公司 | Biology base polyester polyol well as preparation method and application thereof |
| CN104650330A (en) * | 2013-11-18 | 2015-05-27 | 上海凯众材料科技股份有限公司 | Preparation method of polyester dihydric alcohol and microcellular polyurethane elastomer |
| CN104650330B (en) * | 2013-11-18 | 2016-11-30 | 上海凯众材料科技股份有限公司 | Polyester diol and the preparation method of microcellular polyurethane elastomer |
| CN109762151A (en) * | 2018-12-26 | 2019-05-17 | 浙江吉仑高分子材料股份有限公司 | A kind of polyester polyol and preparation method thereof for melt spun spandex |
| KR102058153B1 (en) * | 2019-07-16 | 2019-12-20 | 강대권 | Manufacturing Method Of Polyesther Polyol Using Terephthalic Acid |
| KR102058148B1 (en) * | 2019-07-16 | 2019-12-20 | 박인식 | Manufacturing Method Of Polyol Mixture |
| CN110869405A (en) * | 2017-07-13 | 2020-03-06 | 汉高股份有限及两合公司 | Semi-crystalline mixtures of polyester polyols and use thereof |
| CN113480923A (en) * | 2021-07-24 | 2021-10-08 | 宁波恒大防护用品有限公司 | Ultra-soft polyurethane and preparation method and application thereof |
| TWI802219B (en) * | 2022-01-12 | 2023-05-11 | 三晃股份有限公司 | Thermoplastic polyurethane foam and impact-resistant composite layer comprising same |
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| KR101826976B1 (en) | 2017-04-12 | 2018-02-07 | (주)엔나노텍 | Manufacturing method of polyester polyol at low temperature using perovskite catalyst |
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| US20090197094A1 (en) * | 2004-06-11 | 2009-08-06 | Shuichi Nakahara | Polyester resin and thermosetting water-borne coating compositions |
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Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102212183A (en) * | 2011-05-03 | 2011-10-12 | 烟台华大化学工业有限公司 | Polyurethane resin used for skin-imitated superfine fiber synthetic leather, and preparation method thereof |
| CN102276783A (en) * | 2011-06-15 | 2011-12-14 | 浙江华峰合成树脂有限公司 | Non-yellowing alkali deweighting wet method dyeing polyurethane resin for superfine fiber synthetic leather and preparation method thereof |
| CN102329410A (en) * | 2011-08-17 | 2012-01-25 | 浙江恒泰源聚氨酯有限公司 | Preparation method of polyester and polyether mixed type polyurethane material with high fluidity |
| CN102329410B (en) * | 2011-08-17 | 2012-09-19 | 浙江恒泰源聚氨酯有限公司 | Preparation method of polyester and polyether mixed type polyurethane material with high fluidity |
| CN102532462B (en) * | 2011-12-23 | 2013-10-16 | 上海汇得化工有限公司 | Easily-dyed aliphatic polyurethane resin and preparation method thereof |
| CN102532462A (en) * | 2011-12-23 | 2012-07-04 | 上海汇得化工有限公司 | Easily-dyed aliphatic polyurethane resin and preparation method thereof |
| CN102532468A (en) * | 2011-12-23 | 2012-07-04 | 上海汇得化工有限公司 | Chromatophilous aromatic polyurethane resin and preparation method thereof |
| CN103030778B (en) * | 2012-12-24 | 2015-06-17 | 建德市顺发化工助剂有限公司 | Chromatophilous polyurethane resin for synthetic leather and preparation method of polyurethane resin |
| CN103030778A (en) * | 2012-12-24 | 2013-04-10 | 建德市顺发化工助剂有限公司 | Chromatophilous polyurethane resin for synthetic leather and preparation method of polyurethane resin |
| CN104650330A (en) * | 2013-11-18 | 2015-05-27 | 上海凯众材料科技股份有限公司 | Preparation method of polyester dihydric alcohol and microcellular polyurethane elastomer |
| CN104650330B (en) * | 2013-11-18 | 2016-11-30 | 上海凯众材料科技股份有限公司 | Polyester diol and the preparation method of microcellular polyurethane elastomer |
| CN103694458A (en) * | 2013-12-11 | 2014-04-02 | 高鼎精细化工(昆山)有限公司 | Biology base polyester polyol well as preparation method and application thereof |
| CN103694458B (en) * | 2013-12-11 | 2016-06-01 | 高鼎精细化工(昆山)有限公司 | A kind of biological poly ester polyol and its preparation method and application |
| CN110869405A (en) * | 2017-07-13 | 2020-03-06 | 汉高股份有限及两合公司 | Semi-crystalline mixtures of polyester polyols and use thereof |
| US11807714B2 (en) | 2017-07-13 | 2023-11-07 | Henkel Ag & Co. Kgaa | Semi-crystalline mixture of polyester polyols, and the use thereof |
| CN109762151A (en) * | 2018-12-26 | 2019-05-17 | 浙江吉仑高分子材料股份有限公司 | A kind of polyester polyol and preparation method thereof for melt spun spandex |
| KR102058153B1 (en) * | 2019-07-16 | 2019-12-20 | 강대권 | Manufacturing Method Of Polyesther Polyol Using Terephthalic Acid |
| KR102058148B1 (en) * | 2019-07-16 | 2019-12-20 | 박인식 | Manufacturing Method Of Polyol Mixture |
| CN113480923A (en) * | 2021-07-24 | 2021-10-08 | 宁波恒大防护用品有限公司 | Ultra-soft polyurethane and preparation method and application thereof |
| TWI802219B (en) * | 2022-01-12 | 2023-05-11 | 三晃股份有限公司 | Thermoplastic polyurethane foam and impact-resistant composite layer comprising same |
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