CN111303593A - Thermoplastic polymer composition for waterproof moisture-permeable film - Google Patents
Thermoplastic polymer composition for waterproof moisture-permeable film Download PDFInfo
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- CN111303593A CN111303593A CN202010210007.1A CN202010210007A CN111303593A CN 111303593 A CN111303593 A CN 111303593A CN 202010210007 A CN202010210007 A CN 202010210007A CN 111303593 A CN111303593 A CN 111303593A
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- polymer composition
- permeable film
- thermoplastic polymer
- waterproof moisture
- nylon
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
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- Polymers & Plastics (AREA)
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Abstract
The invention relates to a thermoplastic polymer composition for a waterproof moisture-permeable film, which comprises the following raw materials in percentage by weight: 60-95% copolyester, which is polymerized by aromatic dicarboxylic acid or derivative ester thereof, alkylene glycol and hydrophilic polymeric polyol; 3-35% of copolymerized nylon; 3-10% of polymer containing maleic anhydride groups. In the invention, the water absorption of the copolyester material can be greatly improved by only adding a small amount of copolymerized nylon, nano-scale micropores are generated between the copolymerized nylon and the copolymerized nylon in the film forming process, and the copolyester has good tearing strength and high moisture permeability, is mainly used for manufacturing a waterproof moisture-permeable film, and is also suitable for manufacturing moisture-absorbing elastic fibers because the polyester also has good flexibility, rebound resilience and heat resistance.
Description
The technical field is as follows:
the invention relates to a thermoplastic polymer composition for a waterproof moisture-permeable film.
Background art:
CN 100460440C discloses a block copolyether ester elastomer having a molecular weight of at least 25000g/mol formed by hard segments formed from aromatic dicarboxylic acids or their derived esters and soft segments formed from poly (oxyalkylene) polyols which are polyoxypropylene block copolyethers terminated with oxyethylene groups.
The waterproof moisture-permeable film made of the polyether ester elastomer has obviously insufficient moisture permeability, and if the moisture permeability is improved, more hydrophilic polyether polyol needs to be added, but the tearing strength of the film is insufficient.
The invention content is as follows:
in order to overcome the disadvantages and shortcomings of the prior art, the present invention provides a method for preparing a thermoplastic polymer composition with high water absorption and high moisture permeability by using a composition comprising hydrophilic copolyester, hydrophilic copolymer nylon and Maleic Anhydride (MAH) group-containing polymer.
The invention is realized by the following technical scheme:
a thermoplastic polymer composition for a waterproof moisture-permeable film, which comprises:
(1) copolyester is polymerized by aromatic dicarboxylic acid or derivative ester thereof, at least one alkylene glycol and hydrophilic poly (oxyalkylene) polyol, and accounts for 60-95% of the weight of the polymer composition;
(2) copolymerized nylon, the copolymer accounts for at least 3-35% of the weight of the high molecular composition;
(3) the polymer containing Maleic Anhydride (MAH) group accounts for 3-10% of the weight of the high molecular composition, and the soaking water absorption rate in 24 hours is more than 30%.
The copolyester contains Ethylene Oxide (EO) units, and the weight percentage is at least more than 30%.
The copolymerized nylon is a nylon-based elastomer which takes nylon 5/nylon 6/nylon 11/nylon 12 as a hard segment, contains Ethylene Oxide (EO) units and takes (alkylene oxide) polyol with the weight percentage of at least 30 percent as a soft segment.
The polymer containing Maleic Anhydride (MAH) groups comprises maleic acid rod-acrylic acid copolymer, maleic acid rod-styrene-ethylene/butylene-styrene-block copolymer, maleic acid rod-polyolefin copolymer and maleic acid rod-polyether ester copolymer.
The grafting rate of Maleic Anhydride (MAH) groups of the maleic anhydride group polymer reaches more than 1.0 percent; the soaking water absorption rate of the polymer composition in 24 hours is more than 40 percent; the tearing strength of the polymer composition is more than 100 KN/m; the tensile breaking strength of the polymer composition is more than 20 Mpa; the Shaw hardness of the polymer composition is between 33 and 50D; the moisture-permeable waterproof film (30um) prepared from the polymer composition has a moisture permeability rate (MVTR) of at least 10000g/m2 × day.
The high polymer is obtained by increasing hydrophilic functional groups of the copolymer in order to achieve better moisture permeability and water absorption; however, the more hydrophilic functional groups, the lower the strength, heat resistance and UV resistance of the copolymer. In the case where sufficient tear strength cannot be satisfied, thinner water-resistant tear-through films and better fiber strength cannot be obtained.
The invention is characterized in that the copolymer mixture of the poly (oxyalkylene) polyol is used less, so that the high water absorption and the high moisture permeability can be achieved, and the elongation is higher and the tearing strength is better.
Preferably, poly (oxyalkylene) polyols having an oxyethylene content of 30% to 100%, more preferably 50% to 100%, are used in the copolyester composition. According to the invention, the polyester obtained by using a high ethylene oxide content has a higher water absorption, but when the ethylene oxide content is greater than 80%, the mechanical properties and heat resistance thereof are significantly reduced.
In addition to the above, poly (oxyalkylene) polyols having a molecular weight of 2000-6000g/mol are preferably used, and poly (oxyalkylene) polyols having a molecular weight of 3000-5000g/mol are more preferably used. According to the present invention, polyesters obtained using higher molecular weight poly (oxyalkylene) polyols have better flexibility and elasticity. When a poly (oxyalkylene) polyol having a molecular weight of more than 6000g/mol is used for polymerization, phase separation occurs and the polymerization reaction is difficult.
Examples of optional aromatic dicarboxylic acids or their derived esters in the present invention are: terephthalic acid, 2, 6-naphthalenedicarboxylic acid, 4, 4' -diphenyletherdicarboxylic acid. Preferably, terephthalic acid is used. Examples of alternative alkylene glycols are: 1, 4-butanediol, 1, 3-propanediol, ethylene glycol, 1, 4-butanediol is preferably used.
Poly (oxyalkylene) polyols having an oxyethylene content of 30% to 100% are preferably used in the copolymerized nylon composition, except that conventional polyether polyols are used, such as amide group-capped polyols which are used in condensation copolymerization processes or chain extension polymerization processes.
The polymer composition of the present invention contains at least one conventional additive, such as: heat stabilizers, anti-UV stabilizers, antioxidants, mold release agents, rheology modifiers, mineral fillers or combinations thereof. Generally the total amount of additive combination should be less than 5% by weight of the total composition, preferably from 0.1% to 3%.
The invention can be used for preparing the polymer composition of the waterproof moisture-permeable film. The waterproof moisture permeable film is a novel high-molecular waterproof material, and the surface of the film is free of micropores, so that the film can prevent wind and repel water. The film has hydrophilic groups, so that the film has a moisture permeability function through moisture absorption and conduction. In addition, nanometer micropores are generated between the copolyester and the copolymerized nylon in the film forming process, and the moisture permeability is increased, so that when the polyester obtained according to the invention is applied to a waterproof moisture permeable film, the high water absorption and the water absorption rate of the polyester enable the polyester to rapidly conduct water vapor formed in the material to the outside of the film.
The invention has the beneficial effects that: in the invention, the water absorption of the copolyester material can be greatly improved by only adding a small amount of copolymerized nylon, nano-scale micropores are generated between the copolymerized nylon and the copolymerized nylon in the film forming process, and the copolyester has good tearing strength and high moisture permeability, is mainly used for manufacturing a waterproof moisture-permeable film, and is also suitable for manufacturing moisture-absorbing elastic fibers because the polyester also has good flexibility, rebound resilience and heat resistance.
Detailed Description
The invention is further illustrated by reference to the following examples and comparative examples.
Copolyester A, polybutylene terephthalate 43%, ethylene oxide 100%, poly (alkylene oxide) polyol molecular weight 2000, 57%;
copolyester B, polybutylene terephthalate accounts for 60%, the content of ethylene oxide is 100%, and the molecular weight of poly (alkylene oxide) polyol is 2000, accounts for 40%;
copolymerized nylon C, 50% of nylon 6, 100% of ethylene oxide content and 50% of poly (alkylene oxide) polyol molecular weight of 2000;
maleic acid rod-styrene-ethylene/butylene-styrene-block copolymer D (SEBS-g-MAH), Maleic Anhydride (MAH) group graft rate 1.8%.
Detailed description of the preferred embodiments
Polymer composition
The copolyester, the copolymerized nylon and the maleic acid rod-styrene-ethylene/butylene-styrene-block copolymer in weight percentage are premixed in different ratios, and then put into a double-screw extruder for mixing granulation, wherein the screw extrusion temperature is 200-220 ℃.
Waterproof moisture-permeable film of polymer composition
The polymer composition was melted by a single screw, the melting temperature was 230 ℃, and a film was formed by a casting method, the thickness of the cast film was 30 μm.
The performance test method comprises the following steps:
surface hardness was measured according to ISO 868 Shore D hardness.
Water absorption% for 24 hours: the water absorption of the polyester was determined according to ISO62 method one, method for water absorption test in water at 23 ℃. The test pieces used were 6mm by 2mm test pieces and the soaking time was 24 hours.
Tensile breaking strength MPa,% tensile breaking elongation: the test specimens were of type 5A and the tensile rate was 50mm/min, tested according to ISO527 method.
Tear Strength KN/m measured according to ISO34-1 method, tensile Rate 50 mm/min.
Moisture vapor transmission rate MVTR was tested according to E96BW-94 at 38 deg.C, 50% R.H.
The test results are shown in Table 1.
Table 1: comparative example and comparative example Performance comparison Table
The waterproof moisture-permeable films with high moisture-permeable rate are obtained in the embodiment 1 and the embodiment 2, and have higher strength, the higher tearing strength can ensure that the films are not easy to tear in use, and even thinner waterproof moisture-permeable films can be manufactured.
The polymer composition obtained in comparative example 1 had a very high water absorption rate, but was extremely poor in strength and low in elongation due to compatibility, and was not easily formed into a film, and the moisture permeability could not be measured.
The waterproof moisture-permeable film prepared in the comparative example 2 has good strength performance, but the moisture-permeable rate of the film is obviously insufficient.
The waterproof moisture-permeable film prepared in comparative example 3 has a high moisture-permeable rate, but the film strength is significantly insufficient.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art will understand that: any person skilled in the art can modify or easily conceive the technical solutions described in the foregoing embodiments or equivalent substitutes for some technical features within the technical scope of the present disclosure; such modifications, changes or substitutions do not depart from the spirit and scope of the embodiments of the present invention, and they should be construed as being included therein. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (8)
1. A thermoplastic polymer composition for a waterproof moisture-permeable film is characterized by comprising the following raw materials in percentage by weight:
60-95% copolyester, which is polymerized by aromatic dicarboxylic acid or derivative ester thereof, alkylene glycol and hydrophilic polymeric polyol;
3-35% of copolymerized nylon;
3-10% of polymer containing maleic anhydride groups.
2. The thermoplastic polymer composition for waterproof moisture-permeable film according to claim 1, wherein: the copolyester contains ethylene oxide units, and the weight percentage of the ethylene oxide accounts for at least more than 30% of the copolyester.
3. The thermoplastic polymer composition for waterproof moisture-permeable film according to claim 1, wherein: the copolymerized nylon is a nylon-based elastomer which takes nylon 5/nylon 6/nylon 11/nylon 12 as a hard segment, contains ethylene oxide units and takes polylol with the weight percentage of at least 30 percent as a soft segment.
4. The thermoplastic polymer composition for waterproof moisture-permeable film according to claim 1, wherein: the polymer containing maleic anhydride groups comprises maleic acid rod-acrylic acid copolymer, maleic acid rod-styrene-ethylene/butylene-styrene-segmented copolymer, maleic acid rod-polyolefin copolymer and maleic acid rod-polyether ester copolymer.
5. The thermoplastic polymer composition for waterproof moisture-permeable film according to claim 1, wherein: the grafting rate of the maleic anhydride group of the polymer containing the maleic anhydride group reaches more than 1.0 percent.
6. The thermoplastic polymer composition for waterproof moisture-permeable film according to claim 1, wherein: the aromatic dicarboxylic acid or its derivative ester is terephthalic acid, 2, 6-naphthalene dicarboxylic acid, 4, 4' -diphenyl ether dicarboxylic acid.
7. The thermoplastic polymer composition for waterproof moisture-permeable film according to claim 1, wherein: the alkylene glycol adopts 1, 4-butanediol, 1, 3-propanediol and ethylene glycol.
8. The thermoplastic polymer composition for waterproof moisture-permeable film according to claim 1, wherein: the thermoplastic polymer composition also comprises 0.1-3% of additive, wherein the additive is a heat stabilizer, an anti-UV stabilizer, an antioxidant, a mold release agent, a rheology modifier, a mineral filler or a composition thereof.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202010210007.1A CN111303593B (en) | 2020-03-23 | 2020-03-23 | Thermoplastic polymer composition for waterproof moisture-permeable film |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202010210007.1A CN111303593B (en) | 2020-03-23 | 2020-03-23 | Thermoplastic polymer composition for waterproof moisture-permeable film |
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| CN111303593A true CN111303593A (en) | 2020-06-19 |
| CN111303593B CN111303593B (en) | 2022-04-12 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113214613A (en) * | 2021-05-19 | 2021-08-06 | 佛山金万达科技股份有限公司 | Film and laminate formed from waste thermoplastic elastomer and recycled polyester |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1111267A (en) * | 1994-03-29 | 1995-11-08 | 德国埃尔夫·阿托谢姆有限公司 | A polymer mixture and films prepared therefrom |
| TWI558764B (en) * | 2015-12-23 | 2016-11-21 | 財團法人紡織產業綜合研究所 | Polymer composition and high moisture permeable elastic film made by the same and polymer material including isolated pore |
-
2020
- 2020-03-23 CN CN202010210007.1A patent/CN111303593B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1111267A (en) * | 1994-03-29 | 1995-11-08 | 德国埃尔夫·阿托谢姆有限公司 | A polymer mixture and films prepared therefrom |
| TWI558764B (en) * | 2015-12-23 | 2016-11-21 | 財團法人紡織產業綜合研究所 | Polymer composition and high moisture permeable elastic film made by the same and polymer material including isolated pore |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113214613A (en) * | 2021-05-19 | 2021-08-06 | 佛山金万达科技股份有限公司 | Film and laminate formed from waste thermoplastic elastomer and recycled polyester |
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| CN111303593B (en) | 2022-04-12 |
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