CN101693759A - polyurethane resin with intelligent moisture permeating function for synthetic leather surface coating and preparation method thereof - Google Patents
polyurethane resin with intelligent moisture permeating function for synthetic leather surface coating and preparation method thereof Download PDFInfo
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- CN101693759A CN101693759A CN200910153507A CN200910153507A CN101693759A CN 101693759 A CN101693759 A CN 101693759A CN 200910153507 A CN200910153507 A CN 200910153507A CN 200910153507 A CN200910153507 A CN 200910153507A CN 101693759 A CN101693759 A CN 101693759A
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Abstract
The invention relates to a polyurethane resin with an intelligent moisture permeating function for a synthetic leather surface coating, wherein an organic polyalcohol polymer is a mixture of polyester diol and polyether diol, and the mass ratio of the polyester diol and the polyether diol is 1:0.2-4; diisocyanate is 4,4'-methylene diphenyl diisocyanate, toluene diisocyanate or isophorone diisocyanate; and the extending chain is 1,4-butanediol, ethanediol or diglycol. The invention combines the advantages of polyurethane adopting the polyester diol as a soft segment and polyurethane adopting polyethylene glycol as a soft segment and learns from strong points to offset weakness, and the obtained polyurethane has better moisture permeability and favorable mechanical performance; the intelligent moisture permeating conversion temperature of the polyurethane resin ranges from 20 DEG C to 50 DEG C and can be controlled by adjusting the molecular weight and proportion of the polyester diol and the polyethylene glycol.
Description
Technical field
The present invention relates to a kind of urethane resin, relate in particular to a kind of synthetic leather surface daub on a wall with intelligent moisture-permeable function with urethane resin and preparation method.
Background technology
Along with improving constantly of standard of living, people not only are satisfied with covering of clothes, footwear and resisting cold function, and are also more and more higher to the requirement of its snugness of fit.In people's physiological activity, human body is by the evaporation of perspiration that does not perceive partly body temperature to be descended and equilibrated.If the water vapour permeability of clothes, footwear is not good,, can make the people feel stuffy because sweat can't be discharged with vapor form.Long-time dress at clothes, the inner water of condensation that forms of shoes, makes the people feel moist, feel bad the easy breed bacteria of the sweat that gathers simultaneously.Considering wearer's comfortableness, is different for the water vapour permeability of clothes in the requirement under the varying environment, and demanding water vapour permeability then requires lower moisture vapor permeability to guarantee heat retention to guarantee good heat extraction perspire under the high temperature during low temperature.Yet general synthetic leather can't reach this functional requirement.
The used organic multicomponent alkoxide polymer of urethane resin can be divided into pure and mild polyether Glycols two classes of polyester binary.Polyoxyethylene glycol in the polyether Glycols, the ehter bond in its molecule are typical non-ionic hydrophilic groups, and water molecules moves easily betwixt, rate of perviousness is big, is that soft section urethane has higher water vapour permeability, elongation with polyoxyethylene glycol, and price is lower, hydrolytic resistance is good, but intensity is lower.And be soft section urethane resin good mechanical performance with polyester diol, film forming properties is good, and is heat-resisting, fast light, but water vapour permeability and hydrolytic resistance are bad, and price is higher.If simultaneously with polyester and polyethers as soft segment of polyurethane, learn from other's strong points to offset one's weaknesses, be expected to obtain the urethane resin of high comprehensive performance.
Summary of the invention
The objective of the invention is to overcome the defective of prior art, a kind of synthetic leather surface daub on a wall urethane resin and preparation method thereof with intelligent moisture-permeable function is provided.
For achieving the above object, the present invention adopts a kind of synthetic leather surface daub on a wall urethane resin with intelligent moisture-permeable function, comprise that organic polyhydric alcohol polymer, vulcabond, chainextender reaction obtain, the proportioning of organic multicomponent alkoxide polymer, vulcabond, chainextender is by mass:
20 ~ 120 parts of organic multicomponent alkoxide polymers;
10 ~ 30 parts of vulcabond;
2 ~ 9 parts of chainextenders.
The organic multicomponent alkoxide polymer is the mixture of the pure and mild polyether Glycols of polyester binary, and the ratio of the amount of substance of the pure and mild polyether Glycols of polyester binary is 1: 0.2 ~ 4.Vulcabond is 4,4 '-diphenylmethanediisocyanate, tolylene diisocyanate or isophorone diisocyanate; Described chainextender is 1,4-butyleneglycol, ethylene glycol or glycol ether.
It is 2000～3000 polyethylene glycol adipate or poly adipate succinic acid ester for the number average relative molecular mass that the present invention further is set to polyester diol; Described polyether Glycols is 1000～6000 polyoxyethylene glycol for the number average relative molecular mass.
The preparation method of above-mentioned urethane resin is:
(1) 20 ~ 120 parts of organic multicomponent alkoxide polymers is joined in the reaction vessel, heat up and vacuumize,, be cooled to 60 ℃ then, feed nitrogen and remove vacuum, add 20 ~ 100 parts organic solvent, stir 110 ℃ ~ 120 ℃ dehydrations 2 ~ 4 hours down;
(2) prepolymerization reaction: add 5 ~ 20 parts vulcabond, under 60 ℃ ~ 80 ℃ temperature, reacted 2 ~ 4 hours,, add 30 ~ 200 parts organic solvent according to the viscosity of reactant;
(3) after pre-polymerization is finished, add 2 ~ 9 parts chainextender, after stirring, the vulcabond that adds 0 ~ 25 part again under 60 ℃ ~ 80 ℃ temperature, reacted 2 ~ 4 hours, as requested solid content adds 50 ~ 350 parts organic solvent, obtains solid content and be 20 ~ 35% polyurethane solution.
6, the preparation method of urethane resin according to claim 5 is characterized in that described organic solvent is at least a in dimethyl formamide, N,N-DIMETHYLACETAMIDE, methyl-2-pyrrolidone, the dimethyl sulfoxide (DMSO).
The invention has the advantages that:
(1) combines with polyester diol and be soft section urethane and be the advantage of soft section urethane that learn from other's strong points to offset one's weaknesses, the existing water vapour permeability preferably of the urethane that obtains has the favorable mechanical performance again with polyoxyethylene glycol.
(2) the intelligent moisture-permeable transition temperature of urethane resin of the present invention is in 20 ~ 50 ℃ of scopes, and transition temperature can be controlled by molecular weight and the ratio of adjusting the pure and mild polyoxyethylene glycol of polyester binary.
Embodiment
If the urethane resin in that surface daub on a wall one deck of common synthetic leather has the intelligent moisture-permeable function then can make the water vapour permeability of synthetic leather change with the variation of outside temperature, regulate the microclimate in the human clothing better.1
Urethane resin is a kind of high molecular polymer with block structure that is obtained by organic multicomponent alkoxide polymer, vulcabond and chainextender reaction.Organic multicomponent alkoxide polymer in the polymer molecule is very submissive, is called soft section, gives material with flexible, saturating performance such as wet, ventilative; And that carbamate groups that is generated by the reaction of isocyanic ester and chainextender or urea groups are extended at normal temperatures is bar-shaped, and chain is its conformation of malleable not, and this segment is more stiff, generally is referred to as hard section, gives material with performances such as high mechanical strength.Soft section incompatible on thermodynamics with hard section, can form the two-phase separated structures, the soft section formation crystallization that flocks together.When envrionment temperature was lower than soft section crystalline fusing point, because intracrystalline segment is arranged closely, water molecules was difficult for passing through, and rate of perviousness is lower; When temperature surpasses soft section crystalline fusing point, soft section crystal fusion, the amorphous structure of formation short texture, water molecules very easily passes through, and rate of perviousness increases rapidly, shows as intelligent moisture-permeable.By adjusting the kind and the ratio of organic multicomponent alkoxide polymer, chainextender, vulcabond, just can controlling polymers soft section fusing point, thereby control the transition temperature of intelligent moisture-permeable
Embodiment 1
With 60g number average relative molecular mass is that 6000 polyoxyethylene glycol and 20g number average relative molecular mass are that 2000 polyethylene glycol adipate joins in the there-necked flask of the 1000mL that has agitator, be warming up to 110 ℃, start and stir and vacuumize dehydration 3h, be cooled to 60 ℃ then, feed nitrogen and remove vacuum, add the 40g dimethyl formamide, stir.Add 5g 4,4 '-diphenylmethanediisocyanate again, react 4h down,, add the 80g dimethyl formamide according to the viscosity of reactant at 60 ℃.After pre-polymerization is finished, add 4.5g1 successively, 4-butyleneglycol, 12.5g 4,4 '-diphenylmethanediisocyanate at 70 ℃ down behind the reaction 3h, add the 118g dimethyl formamide, obtain solid content and be 30% polyurethane solution.
The polyurethane solution that obtains is coated on the synthetic leather bass, and the vapor transfer rate under each temperature is as shown in table 1 after tested.
The synthetic leather rate of perviousness after table 1 is covered with paint, lacquer, colour wash, etc. and the relation of temperature
Embodiment 2
With 60g number average relative molecular mass is that 6000 polyoxyethylene glycol and 20g number average relative molecular mass are that 2000 poly adipate succinic acid ester joins in the there-necked flask of the 1000mL that has agitator, be warming up to 110 ℃, start and stir and vacuumize dehydration 3h, be cooled to 80 ℃ then, feed nitrogen and remove vacuum, add the 30g N,N-DIMETHYLACETAMIDE, stir.Add 5g 4,4 '-diphenylmethanediisocyanate again, react 2h down,, add the 100g N,N-DIMETHYLACETAMIDE according to the viscosity of reactant at 80 ℃.After pre-polymerization is finished, add 4.9g1 successively, 4-butyleneglycol, 13.5g 4,4 '-diphenylmethanediisocyanate at 80 ℃ down behind the reaction 2h, add the 62g N,N-DIMETHYLACETAMIDE, obtain solid content and be 35% polyurethane solution.
The polyurethane solution that obtains is coated on the synthetic leather bass, and the vapor transfer rate under each temperature is as shown in table 2 after tested.
The synthetic leather rate of perviousness after table 2 is covered with paint, lacquer, colour wash, etc. and the relation of temperature
Claims (4)
1. the synthetic leather surface daub on a wall urethane resin with intelligent moisture-permeable function comprises that organic polyhydric alcohol polymer, vulcabond, chainextender reaction obtain, and the proportioning of organic multicomponent alkoxide polymer, vulcabond, chainextender is by mass:
20 ~ 120 parts of organic multicomponent alkoxide polymers;
10 ~ 30 parts of vulcabond;
2 ~ 9 parts of chainextenders;
It is characterized in that: described organic multicomponent alkoxide polymer is the mixture of the pure and mild polyether Glycols of polyester binary, and the ratio of the amount of substance of the pure and mild polyether Glycols of polyester binary is 1: 0.2 ~ 4; Described vulcabond is 4,4 '-diphenylmethanediisocyanate, tolylene diisocyanate or isophorone diisocyanate; Described chainextender is 1,4-butyleneglycol, ethylene glycol or glycol ether.
2. the urethane resin of stating according to claim 1, it is characterized in that: described polyester diol is 2000～3000 polyethylene glycol adipate or poly adipate succinic acid ester for the number average relative molecular mass; Described polyether Glycols is 1000～6000 polyoxyethylene glycol for the number average relative molecular mass.
3. the preparation method of urethane resin according to claim 1 is:
(1) 20 ~ 120 parts of organic multicomponent alkoxide polymers is joined in the reaction vessel, heat up and vacuumize,, be cooled to 60 ℃ then, feed nitrogen and remove vacuum, add 20 ~ 100 parts organic solvent, stir 110 ℃ ~ 120 ℃ dehydrations 2 ~ 4 hours down;
(2) prepolymerization reaction: add 5 ~ 20 parts vulcabond, under 60 ℃ ~ 80 ℃ temperature, reacted 2 ~ 4 hours,, add 30 ~ 200 parts organic solvent according to the viscosity of reactant;
(3) after pre-polymerization is finished, add 2 ~ 9 parts chainextender, after stirring, the vulcabond that adds 0 ~ 25 part again under 60 ℃ ~ 80 ℃ temperature, reacted 2 ~ 4 hours, as requested solid content adds 50 ~ 350 parts organic solvent, obtains solid content and be 20 ~ 35% polyurethane solution.
4. the preparation method of urethane resin according to claim 3 is characterized in that described organic solvent is at least a in dimethyl formamide, N,N-DIMETHYLACETAMIDE, methyl-2-pyrrolidone, the dimethyl sulfoxide (DMSO).
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| Application Number | Priority Date | Filing Date | Title |
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| CN200910153507XA CN101693759B (en) | 2009-09-28 | 2009-09-28 | polyurethane resin with intelligent moisture permeating function for synthetic leather surface coating and preparation method thereof |
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| CN200910153507XA CN101693759B (en) | 2009-09-28 | 2009-09-28 | polyurethane resin with intelligent moisture permeating function for synthetic leather surface coating and preparation method thereof |
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| CN101693759A true CN101693759A (en) | 2010-04-14 |
| CN101693759B CN101693759B (en) | 2012-07-04 |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102775577A (en) * | 2012-08-02 | 2012-11-14 | 烟台万华超纤股份有限公司 | Hydrolysis-resistant powdered polyurethane and preparation method thereof |
| CN102898816A (en) * | 2012-10-19 | 2013-01-30 | 奥斯汀新材料（张家港）有限公司 | Preparation method of moisture-permeable thermoplastic polyurethane elastomer |
| CN103741489A (en) * | 2013-12-30 | 2014-04-23 | 辽宁恒星精细化工有限公司 | Heat-accumulating, temperature-regulating, cold-resistant and moisture-permeable coating adhesive for textile and preparation method |
| CN104358130A (en) * | 2014-11-14 | 2015-02-18 | 江苏宝泽高分子材料股份有限公司 | Bright Yangbuck blow-molding treating agent for synthetic leather and preparation method thereof |
| CN105061721A (en) * | 2015-07-22 | 2015-11-18 | 东莞市吉鑫高分子科技有限公司 | Temperature-sensitive intelligent thermoplastic polyurethane elastomer and preparation method thereof |
| CN105461887A (en) * | 2016-01-13 | 2016-04-06 | 江苏东邦科技有限公司 | Method for preparing PU film for high-grade sportswear |
| CN108624276A (en) * | 2018-04-27 | 2018-10-09 | 广东多正树脂科技有限公司 | A kind of preparation method of polyurethane moisture-curable clothing glue |
| CN113817134A (en) * | 2021-09-25 | 2021-12-21 | 华大化学(安徽)有限公司 | Polyurethane resin for air-permeable and moisture-permeable labor protection gloves and preparation method thereof |
-
2009
- 2009-09-28 CN CN200910153507XA patent/CN101693759B/en not_active Expired - Fee Related
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102775577A (en) * | 2012-08-02 | 2012-11-14 | 烟台万华超纤股份有限公司 | Hydrolysis-resistant powdered polyurethane and preparation method thereof |
| CN102898816A (en) * | 2012-10-19 | 2013-01-30 | 奥斯汀新材料（张家港）有限公司 | Preparation method of moisture-permeable thermoplastic polyurethane elastomer |
| CN102898816B (en) * | 2012-10-19 | 2014-04-30 | 奥斯汀新材料（张家港）有限公司 | Preparation method of moisture-permeable thermoplastic polyurethane elastomer |
| CN103741489A (en) * | 2013-12-30 | 2014-04-23 | 辽宁恒星精细化工有限公司 | Heat-accumulating, temperature-regulating, cold-resistant and moisture-permeable coating adhesive for textile and preparation method |
| CN103741489B (en) * | 2013-12-30 | 2015-10-28 | 辽宁恒星精细化工有限公司 | Heat-accumulation temperature-adjustment used for textiles resists cold moisture permeable coating glue and preparation method |
| CN104358130A (en) * | 2014-11-14 | 2015-02-18 | 江苏宝泽高分子材料股份有限公司 | Bright Yangbuck blow-molding treating agent for synthetic leather and preparation method thereof |
| CN105061721A (en) * | 2015-07-22 | 2015-11-18 | 东莞市吉鑫高分子科技有限公司 | Temperature-sensitive intelligent thermoplastic polyurethane elastomer and preparation method thereof |
| CN105061721B (en) * | 2015-07-22 | 2018-06-19 | 东莞市吉鑫高分子科技有限公司 | A kind of temperature sensitive intelligent thermoplastic polyurethane elastomer and preparation method thereof |
| CN105461887A (en) * | 2016-01-13 | 2016-04-06 | 江苏东邦科技有限公司 | Method for preparing PU film for high-grade sportswear |
| CN108624276A (en) * | 2018-04-27 | 2018-10-09 | 广东多正树脂科技有限公司 | A kind of preparation method of polyurethane moisture-curable clothing glue |
| CN113817134A (en) * | 2021-09-25 | 2021-12-21 | 华大化学(安徽)有限公司 | Polyurethane resin for air-permeable and moisture-permeable labor protection gloves and preparation method thereof |
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| CN101693759B (en) | 2012-07-04 |
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Effective date of registration: 20180702 Address after: 352000 Zhangwu industrial concentration area, Ningde, Fujian Patentee after: FUJIAN DONGTAI HIGH POLYMER MATERIAL CO., LTD. Address before: 325000 Wenzhou tea mountain high education park in Zhejiang Province Patentee before: Wenzhou University |
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Granted publication date: 20120704 Termination date: 20200928 |