CN109705310B - Polyurethane resin for waterproof breathable leather and preparation method thereof - Google Patents
Polyurethane resin for waterproof breathable leather and preparation method thereof Download PDFInfo
- Publication number
- CN109705310B CN109705310B CN201811554389.9A CN201811554389A CN109705310B CN 109705310 B CN109705310 B CN 109705310B CN 201811554389 A CN201811554389 A CN 201811554389A CN 109705310 B CN109705310 B CN 109705310B
- Authority
- CN
- China
- Prior art keywords
- polyol
- polyurethane resin
- solvent
- leather
- waterproof
- 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
Landscapes
- Polyurethanes Or Polyureas (AREA)
- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
Abstract
The invention discloses a polyurethane resin for waterproof and vapor-permeable leather and a preparation method thereof, wherein the polyurethane resin is prepared from the following raw materials in parts by weight: the molar ratio of the polyol A to the polyol B is 1: 1-50: 1; the ratio of the chain extender to the number of moles of the polyol A and the polyol B is 1.5:1 to 5: 1; the mole number of the terminating agent is 2 times of the difference value between the mole number of the diisocyanate and the mole numbers of the polyol A, the polyol B and the chain extender; the dosage of the solvent is 65-80% of the total weight of the polyol A, the polyol B, the diisocyanate, the chain extender, the terminator and the solvent. The invention has excellent hydrophobicity, simultaneously ensures that the resin part forms a three-dimensional interpenetrating hole structure in the wet solidification process, has smaller hole diameter and meets the requirement that water vapor easily passes through; when the superfine fiber suede leather is used for superfine fiber suede leather, the superfine fiber suede leather has excellent suede and meat feeling, and the production has the characteristics of simple and easy operation.
Description
Technical Field
The invention relates to polyurethane resin for leather and a preparation method thereof, in particular to polyurethane resin which can be used as a raw material of superfine fiber synthetic leather base cloth with excellent waterproof, vapor permeability and mechanical properties.
Background
At present, the superfine fiber synthetic leather can be comparable to high-grade natural leather in aspects of appearance texture, physical properties, wearing comfort and the like, and is widely applied to the fields of clothes, shoes, automobiles and the like. The superfine fiber synthetic leather mainly comprises polyurethane and fibers, wherein a compact resin film is arranged on the surface of conventional veneered leather, so that the superfine fiber synthetic leather has good waterproofness but poor vapor permeability, and the suede leather is opposite to the conventional veneered leather, so that the superfine fiber synthetic leather needs to have excellent waterproof and vapor permeability when being applied to various sports goods, industrial safety goods, military goods and the like.
The polyurethane is a block-type high polymer material with alternating soft and hard sections, and the unique molecular structure enables the comprehensive performance of the polyurethane to be very excellent and the application to be wide. However, polyurethane has a disadvantage of poor hydrophobicity due to a large amount of ester groups, urea groups, and the like contained in the chain. A hydrophobic film of fluorosilane modified polyurethane and its preparing process (CN 107446151A) features that the hydrophobic group containing fluorine is introduced to the chain segment of polyurethane, and the prepared polyurethane is used for dry film.
At present, the moisture permeability of microfiber synthetic leather is mainly measured by testing the permeation condition of water vapor, the permeation of water vapor and the absorption coefficient. The superfine fiber suede leather has good moisture permeability but no waterproof effect, and the fluorine waterproof agent is padded through after-finishing, so that the waterproof effect is good but the vapor permeability is reduced.
Disclosure of Invention
The invention aims to provide a polyurethane resin for waterproof and vapor-permeable leather and a preparation method thereof, so as to overcome the defects in the prior art.
The polyurethane resin for the waterproof and vapor-permeable leather is prepared from the following raw materials in parts by weight:
the molar ratio of the polyol A to the polyol B is 1: 1-50: 1, preferably 10: 1-20: 1;
the ratio of the chain extender to the number of moles of polyol A and polyol B is 1.5:1 to 5:1, preferably 2:1 to 3: 1;
the mole number of the terminating agent is 2 times of the difference value between the mole number of the diisocyanate and the mole numbers of the polyol A, the polyol B and the chain extender;
the dosage of the solvent is 65 to 80 percent of the total weight of the polyol A, the polyol B, the diisocyanate, the chain extender, the terminator and the solvent, and is preferably 70 percent;
the polyol A is selected from at least one of polybutylene adipate glycol (PBA), neopentyl glycol adipate glycol (PNA), polyhexamethylene glycol adipate glycol (PHA), polycaprolactone glycol (PCL), 3-methylpentanediol adipate glycol (PMA), polyethylene glycol (PEG), polypropylene glycol (PPG) and polytetrahydrofuran ether glycol (PTMG), preferably at least one of polybutylene adipate glycol (PBA), polyhexamethylene glycol adipate (PHA), polypropylene glycol (PPG) and polytetrahydrofuran ether glycol (PTMG), and the number average molecular weight of the polyol A is 1000-3000, preferably 2000.
The polyol B is at least one of hydroxyl-terminated long-chain alkyl silicone oil (PAPS) and hydroxyl-terminated polytrifluoropropylmethylsiloxane (PMTFPS); the number average molecular weight of the polyol B is 1000-3000, and the molecular weight is preferably 2000.
The diisocyanate is 4,4' -diphenylmethane diisocyanate (MDI);
the chain extender A is one or two of Ethylene Glycol (EG) and Butanediol (BG);
one or more of methanol and ethanol as the terminating agent;
the solvent is selected from N, N-Dimethylformamide (DMF);
the preparation method of the polyurethane resin for the waterproof and vapor-permeable leather comprises the following steps:
(1) uniformly mixing polyol A, polyol B and a part of solvent at 50-60 ℃;
(2) then adding diisocyanate at 60-80 ℃, preferably 70 ℃, and reacting at normal pressure until the content of isocyanate groups is constant;
(3) adding a chain extender and the balance of a solvent, and uniformly mixing at 50-60 ℃;
(4) continuously adding diisocyanate, reacting at 60-80 ℃ under normal pressure to increase the viscosity of the reactant to 80-160 Pa.s (25 ℃), and adding a terminator to react for 20-40 min to obtain the polyurethane resin;
according to the invention, long-chain alkyl silicone oil with low surface energy and hydrophobicity and siloxane with fluorine-containing side chains are introduced into a polyurethane structure, and the polyurethane prepared by the method has excellent hydrophobicity; meanwhile, a three-dimensional interpenetrating hole structure is formed on the resin part in the wet solidification process, and the diameter of the hole is small, so that the condition that water vapor easily passes through is met; and the resin and the fiber are adhered to avoid the existence of macropores. When the product is used for the superfine fiber suede leather, the combination of waterproofness and vapor permeability is realized, the product has excellent suede feeling and meat feeling, and the production has the characteristics of simple and easy operation.
Detailed Description
The present invention is further described with reference to the following specific examples, and the test conditions of the present invention can be adjusted accordingly as needed, but are not limited to the test conditions of the present embodiment.
Example 1
(1) Mixing polybutylene adipate glycol (0.05mol), polytetrahydrofuran ether glycol (0.05mol), double-end hydroxyl long-chain alkyl silicone oil (0.01mol) and N, N-dimethylformamide (100ml) serving as a solvent, adding 4,4' -diphenylmethane diisocyanate (0.088mol), and reacting at 75 ℃ until the content of isocyanate groups is constant;
(2) ethylene glycol (0.23mol) and N, N-dimethylformamide (80ml) were added thereto, 4 '-diphenylmethane diisocyanate (0.224mol) was added thereto, and the mixture was reacted at 75 ℃ for 1 hour, followed by addition of N, N-dimethylformamide (194ml) as a solvent, and further addition of 4,4' -diphenylmethane diisocyanate (0.032mol) was stopped when the viscosity had risen to 120 pas (25 ℃ C.). Adding a methanol (0.003mol) terminator for reaction, cooling to 50 ℃ after 30min, and discharging to obtain the polyurethane resin, wherein the solid mass fraction of the resin is 30%.
Example 2
(1) Putting poly (hexamethylene adipate) glycol (0.08mol), polypropylene glycol (0.02mol), hydroxyl-terminated long-chain alkyl silicone oil (0.003mol), hydroxyl-terminated polytrifluoropropylmethylsiloxane (0.002mol) and N, N-dimethylformamide (100ml) serving as a solvent into a reaction bottle, uniformly mixing, putting 4,4' -diphenylmethane diisocyanate (0.08mol), and reacting at 75 ℃ until the content of isocyanate groups is constant;
(2) after the completion of the prepolymerization, ethylene glycol (0.316mol) and N, N-dimethylformamide (80ml) as a solvent were added thereto, 4 '-diphenylmethane diisocyanate (0.32mol) was added thereto, the reaction was carried out at 75 ℃ for 1 hour, and N, N-dimethylformamide (210g) as a solvent was added in the rest amount, and the addition was stopped when 4,4' -diphenylmethane diisocyanate (0.02mol) was further added and the viscosity increased to 100 pas (25 ℃). Adding a methanol (0.003mol) terminator for reaction, cooling to 50 ℃ after 30min, and discharging to obtain the polyurethane resin, wherein the solid mass fraction of the resin is 30%.
Example 3
(1) Putting polybutylene adipate glycol (0.04mol), polytetrahydrofuran ether glycol (0.06mol), hydroxyl-terminated long-chain alkyl silicone oil (0.006mol), hydroxyl-terminated polytrifluoropropylmethylsiloxane (0.002mol) and N, N-dimethylformamide (100ml) serving as a solvent into a reaction bottle, uniformly mixing, putting 4,4' -diphenylmethane diisocyanate (0.339mol), and reacting at 75 ℃ until the content of isocyanate groups is constant;
(2) after the completion of the prepolymerization, ethylene glycol (0.271mol) and N, N-dimethylformamide (80ml) as a solvent were added thereto, 4 '-diphenylmethane diisocyanate (0.272mol) was added thereto, the reaction was carried out at 75 ℃ for 1 hour, N-dimethylformamide (200g) as a solvent was added in the rest amount, and the addition was stopped when 4,4' -diphenylmethane diisocyanate (0.016mol) was further added and the viscosity increased to 80 pas (25 ℃). Adding a methanol (0.003mol) terminator for reaction, cooling to 50 ℃ after 30min, and discharging to obtain the polyurethane resin, wherein the solid mass fraction of the resin is 30%.
Example 4
To further illustrate the technical innovation of the invention, the resin obtained in the examples 1 to 3 is selected to prepare the superfine fiber synthetic leather base cloth through the following conventional process steps: preparing working solution according to the weight portion ratio of 100 portions of polyurethane and 58 portions of solvent DMF, taking the needle-punched non-woven fabric as a substrate, saturating and soaking the working solution in fiber gaps, and carrying out coagulation, water washing, decrement, drying, buffing and dyeing to obtain the polyurethane fiber, wherein the polyurethane fiber is prepared by the following steps: "synthetic technology" (Qujiabo et al. synthetic leather technology [ M ]. Beijing: chemical industry Press, 2010.). The waterproof and vapor-permeable superfine fiber suede leather can be obtained. The waterproof and vapor-permeable superfine fiber suede leather prepared by the resins in the examples 1, 2 and 3 and the existing suede leather obtained by post-processing fluorine waterproofing agent are respectively tested for waterproof and moisture-permeable performances (QB/T4044-.
As can be seen from the above table, the microfiber suede leather prepared by using the polyurethane resin of the present invention has excellent water resistance and vapor permeability.
Claims (2)
1. The preparation method of the polyurethane resin for the waterproof and vapor-permeable leather is characterized by comprising the following steps:
(1) 0.08mol of polyhexamethylene glycol adipate glycol, 0.02mol of polypropylene glycol, 0.003mol of double-end hydroxyl long-chain alkyl silicone oil, 0.002mol of double-end hydroxyl polytrifluoropropylmethylsiloxane and 100ml of solvent N, N-dimethylformamide are put into a reaction bottle and mixed uniformly, 0.08mol of 4,4' -diphenylmethane diisocyanate is added, and the reaction is carried out at 75 ℃ until the content of isocyanate groups is constant;
(2) after the prepolymerization is finished, adding 0.316mol of ethylene glycol and 80ml of solvent N, N-dimethylformamide, adding 0.32mol of 4,4 '-diphenylmethane diisocyanate, reacting for 1 hour at 75 ℃, adding the solvent 210g N, N-dimethylformamide, continuously adding 0.02mol of 4,4' -diphenylmethane diisocyanate, stopping adding when the viscosity is increased to 100 Pa.s/25 ℃, adding 0.003mol of methanol to stop the reaction, cooling to 50 ℃ after 30min, and discharging to obtain the polyurethane resin, wherein the mass fraction of the resin solid is 30%.
2. The polyurethane resin for waterproof vapor-permeable leather prepared by the preparation method according to claim 1, wherein the polyurethane resin for waterproof vapor-permeable leather has a water penetration amount of 0.0211 g and a water vapor permeability coefficient of 112.8352 mg/cm2。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811554389.9A CN109705310B (en) | 2018-12-18 | 2018-12-18 | Polyurethane resin for waterproof breathable leather and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811554389.9A CN109705310B (en) | 2018-12-18 | 2018-12-18 | Polyurethane resin for waterproof breathable leather and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109705310A CN109705310A (en) | 2019-05-03 |
| CN109705310B true CN109705310B (en) | 2021-09-10 |
Family
ID=66256765
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811554389.9A Active CN109705310B (en) | 2018-12-18 | 2018-12-18 | Polyurethane resin for waterproof breathable leather and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109705310B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110818880B (en) * | 2019-11-19 | 2021-12-31 | 江苏华大新材料有限公司 | Solvent type polyurethane resin, preparation method thereof and fluorine-free clothes with lotus leaf effect |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101386682A (en) * | 2007-09-11 | 2009-03-18 | 嘉兴联合化学有限公司 | Hydroxyl alkyl-terminated polysiloxane and use thereof as additive agent of polyurethane artificial leather |
| CN103435773A (en) * | 2013-09-11 | 2013-12-11 | 侯马飞 | Polyurethane resin for synthetic leather with high water pressure resistance |
| CN104004159A (en) * | 2014-06-16 | 2014-08-27 | 旭川化学（苏州）有限公司 | Polyurethane resin and preparation method and application thereof |
| CN106397728A (en) * | 2016-08-31 | 2017-02-15 | 合肥安利聚氨酯新材料有限公司 | Environment-friendly low-VOC two-component polyurethane resin for totally-dry-bonding bonding layer of synthetic leather and preparation method thereof |
| CN106977686A (en) * | 2017-03-24 | 2017-07-25 | 中山市聚力有机硅技术有限公司 | A kind of urethane acrylate copolymer containing poly- fluorosilicone block and preparation method thereof |
| CN108948319A (en) * | 2018-07-20 | 2018-12-07 | 张家港市东方高新聚氨酯有限公司 | The cold-resistant Niu Bage polyurethane resin and preparation method thereof of hydrolysis |
-
2018
- 2018-12-18 CN CN201811554389.9A patent/CN109705310B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101386682A (en) * | 2007-09-11 | 2009-03-18 | 嘉兴联合化学有限公司 | Hydroxyl alkyl-terminated polysiloxane and use thereof as additive agent of polyurethane artificial leather |
| CN103435773A (en) * | 2013-09-11 | 2013-12-11 | 侯马飞 | Polyurethane resin for synthetic leather with high water pressure resistance |
| CN104004159A (en) * | 2014-06-16 | 2014-08-27 | 旭川化学（苏州）有限公司 | Polyurethane resin and preparation method and application thereof |
| CN106397728A (en) * | 2016-08-31 | 2017-02-15 | 合肥安利聚氨酯新材料有限公司 | Environment-friendly low-VOC two-component polyurethane resin for totally-dry-bonding bonding layer of synthetic leather and preparation method thereof |
| CN106977686A (en) * | 2017-03-24 | 2017-07-25 | 中山市聚力有机硅技术有限公司 | A kind of urethane acrylate copolymer containing poly- fluorosilicone block and preparation method thereof |
| CN108948319A (en) * | 2018-07-20 | 2018-12-07 | 张家港市东方高新聚氨酯有限公司 | The cold-resistant Niu Bage polyurethane resin and preparation method thereof of hydrolysis |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109705310A (en) | 2019-05-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US7202322B2 (en) | Heat resistant high moisture vapor transmission thermoplastic polyurethane | |
| CN104479102B (en) | Environment-friendly polyurethane clothing leather and preparation method thereof | |
| KR101776539B1 (en) | Leather-like sheet | |
| CN101381448B (en) | Polyurethane resin for water proof and breathable clothing leather | |
| CN105111724B (en) | A kind of high Waterproof Breathable TPU film and preparation method thereof | |
| US3180853A (en) | Polyurethane prepolymer chain-extended with an n-lower alkyl amino-bislower alkyl amine | |
| US3664979A (en) | Polyurethane elastomer and method for preparation of same | |
| CN106496514A (en) | A kind of waterborne polyurethane resin | |
| CN115354505B (en) | Bio-based solvent-free polyurethane surface layer resin for synthetic leather and preparation method thereof | |
| JPH11131373A (en) | Moisture-permeable and waterproof fabric and its production | |
| CN109705310B (en) | Polyurethane resin for waterproof breathable leather and preparation method thereof | |
| CN101381962A (en) | Water proof and moisture permeable artificial leather and method for making same | |
| CN1303124C (en) | Water base block polyurethane, its preparing method and water-proof, heat insulation and wet permeable material made thereof | |
| JP3810479B2 (en) | Method for producing coated fabric | |
| Jassal et al. | Waterproof breathable polymeric coatings based on polyurethanes | |
| CN111171266B (en) | Polyurethane resin for high-water-pressure-resistant high-moisture-permeability clothes and preparation method thereof | |
| CN112626640A (en) | Waterproof and anti-radiation fabric and preparation method thereof | |
| US3575894A (en) | Process for making water vapor permeable microporous sheeting | |
| KR101492728B1 (en) | polyurethane resin composition for artificial leather impregnation | |
| CN110685159A (en) | Production method of water-based microfiber synthetic leather | |
| CN110106714A (en) | A kind of waterproof weather-resistant pu textile coating agent and preparation method thereof | |
| US3540916A (en) | Process for manufacturing artificial leathers | |
| CN109763337B (en) | Waterproof and breathable superfine fiber suede leather and preparation method and application thereof | |
| CN103993483A (en) | Tear-resistant coated fabric and preparation technology thereof | |
| CN101171276A (en) | Spandex from poly(tetramethylene-co-ethyleneether) glycols having high ethyleneether content |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information |
Address after: 201508, No. 888 Ting Wei Road, Shanghai, Jinshan District Applicant after: Shanghai Huafeng Super Fiber Technology Co.,Ltd. Address before: 201508, No. 888 Ting Wei Road, Shanghai, Jinshan District Applicant before: HUAFON MICROFIBRE (SHANGHAI) Co.,Ltd. |
|
| CB02 | Change of applicant information | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |