CN115073709A - High-moisture-permeability breathable thermoplastic polyurethane elastomer and preparation method thereof - Google Patents
High-moisture-permeability breathable thermoplastic polyurethane elastomer and preparation method thereof Download PDFInfo
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/797—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing carbodiimide and/or uretone-imine groups
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6607—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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Abstract
The invention relates to the field of C08L75/04, in particular to a high moisture permeable and breathable thermoplastic polyurethane elastomer and a preparation method thereof. The high moisture permeable and breathable thermoplastic polyurethane elastomer is prepared from 50-60 parts of modified isocyanate, 30-40 parts of polyether polyol, 30-40 parts of polyester polyol, 5-15 parts of a small molecular chain extender, 2-5 parts of an anti-aging agent, 5-10 parts of a porous material and 4-8 parts of a compatilizer, has proper hardness and toughness, has excellent waterproof, moisture permeable and breathable properties, and meets the high practical application requirement in the field of clothing films. By controlling the mass ratio of the modified isocyanate, the porous material and the compatilizer, on one hand, the polyurethane elastomer is ensured to have excellent waterproof, moisture permeable and air permeable performances, and simultaneously, the toxicity of diisocyanate to human bodies and the environment is greatly reduced, and the mechanical requirements in the field of clothing films are met by controlling the mass ratio of the polyol and the micromolecule chain extender.
Description
Technical Field
The invention relates to the field of C08L75/04, in particular to a high-moisture-permeability breathable thermoplastic polyurethane elastomer and a preparation method thereof.
Background
At present, polyurethane in the market adopts isocyanate, polyester polyol and a micromolecular chain extender as main raw materials to synthesize a thermoplastic polyurethane elastomer, but polyester chain segments in the polyester polyol are easy to break after hydrolysis and are not suitable for being used in clothing films, and the isocyanate has high activity and vapor pressure, generates great toxic action on human bodies and the environment and cannot meet the actual use requirements of the clothing films.
In order to improve the moisture permeability of the polyurethane elastomer, Chinese patent CN111171554A discloses an ultrahigh moisture permeability matte thermoplastic polyurethane composition and a preparation method thereof, wherein the thermoplastic polyurethane elastomer and the moisture permeability matte master batch are used as main raw materials to prepare the thermoplastic polyurethane composition with high moisture permeability, but the thermoplastic polyurethane composition is processed again on the basis of a semi-finished product, so that the production cost is improved; chinese patent CN112480361A discloses a method for preparing a moisture permeable thermoplastic polyurethane film, wherein a hyperbranched polyester polyol having a large number of hydrophilic groups is obtained by performing hydrophilic modification on polyester polyol to prepare a hydrophilic TPU film, which has good moisture permeability and cannot guarantee high requirements for waterproof performance and air permeability when applied to the field of garment films.
Therefore, the thermoplastic polyurethane elastomer with proper hardness and toughness and excellent waterproof, breathable and moisture-permeable performances is provided, and can meet higher practical application requirements in the field of clothing films, so that the thermoplastic polyurethane elastomer has important practical research and application significance.
Disclosure of Invention
The invention provides a high moisture permeable and breathable thermoplastic polyurethane elastomer which at least comprises the following components in parts by weight: 50-60 parts of modified isocyanate, 30-40 parts of polyether polyol, 30-40 parts of polyester polyol, 5-15 parts of small molecular chain extender, 2-5 parts of anti-aging agent, 5-10 parts of porous material and 4-8 parts of compatilizer.
At present, in the production process of polyurethane elastomer, diphenylmethane diisocyanate and hexamethylene diisocyanate are used as main raw materials, but isocyanate monomers have lower boiling points and higher vapor pressure, so that the isocyanate monomers can cause human beings to have higher steam pressureIn order to make the prepared thermoplastic polyurethane elastomer be better applied to the field of clothing films, as a preferable technical scheme, the modified isocyanate is selected from at least one of urethane modified polyisocyanate, biuret modified isocyanate and carbodiimide modified isocyanate; in the occasion of long-term water contact or overtime, the polyester chain segment of the polyester polyurethane which is the leading in the market can be broken due to hydrolysis, so that the service life of the thermoplastic polyurethane elastomer is greatly shortened, and in order to improve the hydrolysis resistance of the thermoplastic polyurethane elastomer, as a preferable technical scheme, the modified isocyanate is carbodiimide modified isocyanate, preferably, the carbodiimide modified isocyanate is carbodiimide modified 4, 4-diphenylmethane diisocyanate (carbodiimide modified MDI), unreacted carboxyl in a system can be removed, the hydrolysis of the polyester chain segment is inhibited, the hydrolysis resistance of the thermoplastic polyurethane elastomer is obviously improved, and the service life is prolonged; on the other hand, the isocyanate is subjected to hydrophilic modification by carbodiimide, and the microporous thermoplastic polyurethane elastomer is provided in cooperation with the porous material in the system under the condition that the compatilizer exists, so that the moisture permeability and air permeability of the polyurethane elastomer are remarkably improved, and the actual use of the clothing film is better met; in addition, the content and the vapor pressure of highly unsaturated groups-NCO in an isocyanate structure are reduced by modifying isocyanate through carbodiimide, and the inventor finds that the content of the-NCO in MDI modified by the carbodiimide is 25-30 percent, and the vapor pressure is at 25 DEG in the research process<10 -5 And in mmHg, the carbodiimide modified MDI can be ensured to have good reactivity with polyether polyol, polyester polyol and micromolecular chain extender in the system, the toxicity of diisocyanate to human bodies and the environment is greatly reduced, and the actual use requirements of the field of clothing films on the thermoplastic polyurethane elastomer are better met.
The carbodiimide modified MDI has 29 percent of-NCO content and vapor pressure at 25 DEG C<10 -5 mmHg, model Henscman 2020 available from Jiangyin bamboo Green chemical Co., Ltd.
As a preferred technical scheme, the porous material is at least one of zeolite powder, nano-silica and nano-silica aerogel; preferably, the porous material is zeolite powder, on one hand, the porous material effectively toughens the polyurethane elastomer, improves the mechanical property of the polyurethane elastomer, and simultaneously provides a porous channel for water vapor molecules, so that the moisture permeability and the air permeability of the polyurethane elastomer are improved, preferably, the zeolite powder has a particle size of 150-200 meshes, the porosity is not less than 48%, and the zeolite powder can be well dispersed in a system and cooperate with modified isocyanate in the system in the presence of a compatilizer, so that the prepared polyurethane elastomer has high moisture permeability and air permeability and excellent waterproof property.
The zeolite powder has the particle size of 200 meshes and the porosity of 48 percent, and is purchased from Qingdaxin and Source Filter Material Co., Ltd;
as a preferred technical scheme, the compatilizer is selected from at least one of polyethylene glycol-200, polyethylene glycol-400, polyethylene glycol-600 and polyethylene glycol-800; preferably, the compatilizer is polyethylene glycol-400, so that the compatibility between the zeolite powder and the modified isocyanate is improved, the zeolite powder is favorably dispersed in the isocyanate, and the system is favorably stabilized.
During the research process, the applicant finds that when the mass ratio of the modified isocyanate, the porous material and the compatilizer is controlled to be (53-58): (7-10): (5-8), on one hand, the polyurethane elastomer is ensured to have excellent waterproof, moisture permeable and air permeable performances, and on the other hand, the stable reaction between the modified isocyanate and the polyether polyol and the polyester polyol is maintained, and the mechanical property of the polyurethane elastomer is improved.
The polyethylene glycol 400 has a CAS number of 25322-68-3, available from Sigma Aldrich trade company, Inc.;
as a preferred technical scheme, the polyester polyol is polyethylene glycol adipate, particularly the polyethylene glycol adipate with the average molecular weight of 10000, so that the processing of a polyurethane elastomer is prevented from being influenced by overhigh viscosity of a system, and the production efficiency and the product quality are improved; as a preferred technical solution, the polyether polyol is selected from one or more of polyoxypropylene diol, polytetrahydrofuran diol, and tetrahydrofuran-oxypropylene copolymerized diol, preferably, the polyether polyol is polyoxypropylene diol, and the polyoxypropylene diol is selected from at least one of polyoxypropylene diol 200, polyoxypropylene diol 600, polyoxypropylene diol 1000, polyoxypropylene diol 2000, and polyoxypropylene diol 4000, preferably, the polyoxypropylene diol is polyoxypropylene diol 1000, and the applicant has found in the research process that the introduction of polyoxypropylene diol 1000 into the system improves the toughness and tear strength of the polyurethane elastomer on one hand, so that the obtained polyurethane elastomer can be better suitable for the actual use requirements of the clothing film; on the other hand, the polyether soft segment in the polyurethane elastomer has certain hydrophilicity, and the moisture permeability and the air permeability of the polyurethane elastomer are improved.
Polyether polyol and polyester polyol serve as long-chain polyol compounds to form soft segments in polyurethane in the preparation process of polyurethane, micromolecule chain extenders serve as hard segments in polyurethane, the selection and proportion of polyether polyol and micromolecule chain extenders directly influence the mechanical property of polyurethane elastomers, and as a preferable technical scheme, the micromolecule chain extenders are 1, 4-butanediol, and the applicant finds that when the mass ratio of the polyether polyol, the polyester polyol and the micromolecule chain extenders is controlled to be (35-40): (30-35): (8-12), the provided polyurethane elastomer has the most appropriate hardness and toughness, and meets the mechanical property requirements of the field of clothing films for the polyurethane elastomer.
The polyethylene adipate has a CAS number of 24938-37-2 and a cat number of 181919, and was purchased from sigma aldrich (shanghai) trade company, ltd; the CAS number of the polyoxypropylene diol 1000 is 25322-69-4, and the polyoxypropylene diol is purchased from Henan Wittig chemical technology Co., Ltd; the CAS number of the 1, 4-butanediol is 110-63-4, and the 1, 4-butanediol is purchased from Shanghai Aladdin Biotechnology GmbH;
as a preferred technical scheme, the anti-aging agent is selected from at least one of anti-aging agent 4020, antioxidant 1076, UV-531, UV-9, UVP-327 and RMB; preferably, the anti-aging agent is a combination of an anti-aging agent 4020, an antioxidant 1076 and UV-531, and the mass ratio of the anti-aging agent 4020 to the antioxidant 1076 to the UV-531 is (1-2): (1-1.5): (0.8-1.2), the aging resistance of the polyurethane elastomer is effectively improved, the service life of the thermoplastic polyurethane elastomer is prolonged, and the thermoplastic polyurethane elastomer is better suitable for the field of clothing films.
The CAS number of the anti-aging agent 4020 is 793-24-8, and the anti-aging agent is purchased from Tianjin Xiansi Biotechnology Co., Ltd; the CAS number of the antioxidant 1076 is 2082-79-3, and the antioxidant is purchased from Hangzhou landscape optimizer, Co.Ltd; the CAS number of the UV-531 is 1843-05-6, and the CAS is purchased from Fujian emperor science and technology Co., Ltd;
the invention also provides a preparation method of the thermoplastic polyurethane elastomer with high moisture and air permeability, which at least comprises the following steps:
(1) putting the anti-aging agent, polyether polyol and polyester polyol into a reaction kettle according to the parts by weight, mixing, controlling the temperature to be 80-100 ℃, and stirring for 30-60min to obtain a polyol mixture;
(2) then controlling the temperature to be 100-120 ℃, adding the modified isocyanate, the porous material and the compatilizer into a reaction kettle according to the weight part to react with the polyol mixture obtained in the step (1) to prepare a polyurethane prepolymer, adjusting the temperature to be 80-100 ℃, and pumping the polyurethane prepolymer in vacuum for 4-6 hours;
(3) and (3) putting the polyurethane prepolymer after vacuum water pumping in the step (2) and the micromolecule chain extender into a double-screw extruder for reaction according to the parts by weight, controlling the reaction temperature to be 150-.
Has the advantages that:
1. the invention provides a high moisture permeable and breathable thermoplastic polyurethane elastomer, which not only has proper hardness and toughness, but also has excellent waterproof, moisture permeable and breathable performances, and meets higher practical application requirements in the field of clothing films;
2. the carbodiimide is adopted to modify the isocyanate, so that the hydrolysis resistance, moisture permeability and air permeability of the thermoplastic polyurethane elastomer are obviously improved, and the service life is prolonged; meanwhile, the toxicity of diisocyanate to human bodies and the environment is greatly reduced, and the practical use requirements of the field of clothing films on the thermoplastic polyurethane elastomers are better met. (ii) a
3. The zeolite powder porous material with specific particle size and porosity is adopted, so that the polyurethane elastomer is effectively toughened, the mechanical property of the polyurethane elastomer is improved, a porous channel is provided for water vapor molecules, and the moisture permeability and the air permeability of the polyurethane elastomer are improved.
4. Controlling the mass ratio of the modified isocyanate to the porous material to the compatilizer to be (53-58): (7-10): (5-8), on one hand, the polyurethane elastomer is ensured to have excellent waterproof, moisture permeable and air permeable performances, and on the other hand, the stable reaction between the modified isocyanate and the polyether polyol and the polyester polyol is maintained, and the mechanical property of the polyurethane elastomer is improved.
5. By controlling the ratio of the polyether polyol to the polyester polyol to the micromolecular chain extender to be (35-40): (30-35): (8-12), the provided polyurethane elastomer has the most appropriate hardness and toughness, and meets the mechanical property requirements of the field of clothing films for the polyurethane elastomer.
Detailed Description
Example 1
Embodiment 1 of the present invention provides a highly moisture-permeable and air-permeable thermoplastic polyurethane elastomer, which at least comprises the following components in parts by weight: 55 parts of modified isocyanate, 38 parts of polyether polyol, 32 parts of polyester polyol, 10 parts of micromolecular chain extender, 3 parts of anti-aging agent, 8 parts of porous material and 6 parts of compatilizer.
The modified isocyanate is carbodiimide modified isocyanate, the carbodiimide modified isocyanate is carbodiimide modified 4, 4-diphenylmethane diisocyanate, the content of-NCO in the carbodiimide modified MDI is 29%, and the vapor pressure is at 25 DEG C<10 -5 mmHg, model Henscman 2020 available from Jiangyin bamboo Green chemical Co., Ltd.
The porous material is zeolite powder, the particle size of the zeolite powder is 200 meshes, the porosity is 48%, and the porous material is purchased from Qingdao Xin and Source Filter Material Co., Ltd;
the compatibilizer is polyethylene glycol-400, and the polyethylene glycol 400 has a CAS number of 25322-68-3 and is purchased from sigma aldrich (shanghai) trade company, ltd.
The mass ratio of the modified isocyanate to the porous material to the compatilizer is 55: 8: 6.
the polyester polyol is polyethylene glycol adipate, and the average molecular weight of the polyethylene glycol adipate is 10000.
The polyether polyol is polyoxypropylene diol, and the polyoxypropylene diol is polyoxypropylene diol 1000.
The micromolecular chain extender is 1, 4-butanediol.
The mass ratio of the polyether polyol to the polyester polyol to the micromolecule chain extender is 38: 32: 10.
the polyethylene adipate has a CAS number of 24938-37-2 and a cat number of 181919, and was purchased from sigma aldrich (shanghai) trade company, ltd; the CAS number of the polyoxypropylene glycol 1000 is 25322-69-4, and the polyoxypropylene glycol is purchased from Henan Wittig chemical technology Co., Ltd; the 1, 4-butanediol has a CAS number of 110-63-4 and is purchased from Shanghai Allantin Biotechnology Ltd.
The anti-aging agent is a combination of an anti-aging agent 4020, an antioxidant 1076 and UV-531, and the mass ratio of the anti-aging agent 4020 to the antioxidant 1076 to the UV-531 is 1.5: 1.2: 1.
the CAS number of the anti-aging agent 4020 is 793-24-8, and the anti-aging agent is purchased from Tianjin Xiansi Biotechnology Co., Ltd; the CAS number of the antioxidant 1076 is 2082-79-3, and the antioxidant is purchased from Hangzhou landscape optimizer, Co.Ltd; the CAS number for UV-531 is 1843-05-6, which is available from Fujian emperor science and technology Co.
In another aspect, embodiment 1 of the present invention provides a method for preparing a thermoplastic polyurethane elastomer with high moisture and air permeability, which at least comprises the following steps:
(1) putting the anti-aging agent, polyether polyol and polyester polyol into a reaction kettle according to the parts by weight, mixing, controlling the temperature to be 100 ℃, and stirring for 40min to obtain a polyol mixture;
(2) then controlling the temperature to be 120 ℃, adding the modified isocyanate, the porous material and the compatilizer into a reaction kettle according to the weight part, reacting with the polyol mixture obtained in the step (1) to prepare a polyurethane prepolymer, adjusting the temperature to be 100 ℃, and pumping water for the polyurethane prepolymer in vacuum for 5 hours;
(3) and (3) putting the polyurethane prepolymer after vacuum water pumping in the step (2) and the micromolecule chain extender into a double-screw extruder for reaction according to the parts by weight, controlling the reaction temperature to be 200 ℃, controlling the rotating speed of the screw to be 300rpm, carrying out underwater granulation and dehydration after reacting for 90s, dehumidifying and drying at 60 ℃ for 5h, and finally packaging to obtain the high-moisture-permeability breathable thermoplastic polyurethane elastomer.
Example 2
Embodiment 2 of the present invention provides a highly moisture-permeable and air-permeable thermoplastic polyurethane elastomer, which at least comprises the following components in parts by weight: 58 parts of modified isocyanate, 40 parts of polyether polyol, 35 parts of polyester polyol, 12 parts of micromolecular chain extender, 5 parts of anti-aging agent, 10 parts of porous material and 8 parts of compatilizer.
The modified isocyanate is carbodiimide modified isocyanate, the carbodiimide modified isocyanate is carbodiimide modified 4, 4-diphenylmethane diisocyanate, the content of-NCO in the carbodiimide modified MDI is 29%, and the vapor pressure is at 25 DEG C<10 -5 mmHg, model Henstmann 2020, available from Jiangyin Zhuqing chemical Co.
The porous material is zeolite powder, the particle size of the zeolite powder is 200 meshes, the porosity is 48%, and the porous material is purchased from Qingdao Xin and Source Filter Material Co., Ltd;
the compatibilizer is polyethylene glycol-400, and the polyethylene glycol 400 has a CAS number of 25322-68-3 and is available from sigma aldrich (shanghai) trade, ltd.
The mass ratio of the modified isocyanate to the porous material to the compatilizer is 58: 10: 8.
the polyester polyol is polyethylene glycol adipate, and the average molecular weight of the polyethylene glycol adipate is 10000.
The polyether polyol is polyoxypropylene diol, and the polyoxypropylene diol is polyoxypropylene diol 1000.
The micromolecular chain extender is 1, 4-butanediol.
The mass ratio of the polyether polyol to the polyester polyol to the micromolecular chain extender is 40: 35: 12.
the polyethylene adipate has a CAS number of 24938-37-2 and a cat number of 181919, and was purchased from sigma aldrich (shanghai) trade company, ltd; the CAS number of the polyoxypropylene glycol 1000 is 25322-69-4, and the polyoxypropylene glycol is purchased from Henan Wittig chemical technology Co., Ltd; the 1, 4-butanediol has a CAS number of 110-63-4 and is purchased from Shanghai Allantin Biotechnology Ltd.
The anti-aging agent is a combination of an anti-aging agent 4020, an antioxidant 1076 and UV-531, and the mass ratio of the anti-aging agent 4020 to the antioxidant 1076 to the UV-531 is 2: 1.5: 1.2.
the CAS number of the anti-aging agent 4020 is 793-24-8, and the anti-aging agent is purchased from Tianjin Xiansi Biotechnology Co., Ltd; the CAS number of the antioxidant 1076 is 2082-79-3, and the antioxidant is purchased from Hangzhou landscape optimizer, Co.Ltd; the CAS number for UV-531 is 1843-05-6, which is available from Fujian emperor science and technology Co.
In another aspect, embodiment 2 of the present invention provides a method for preparing a thermoplastic polyurethane elastomer with high moisture and air permeability, which at least comprises the following steps:
(1) putting the anti-aging agent, polyether polyol and polyester polyol into a reaction kettle according to the parts by weight, mixing, controlling the temperature to be 100 ℃, and stirring for 40min to obtain a polyol mixture;
(2) then controlling the temperature to be 120 ℃, adding the modified isocyanate, the porous material and the compatilizer into a reaction kettle according to the weight part, reacting with the polyol mixture obtained in the step (1) to prepare a polyurethane prepolymer, adjusting the temperature to be 100 ℃, and pumping water for the polyurethane prepolymer in vacuum for 5 hours;
(3) and (3) putting the polyurethane prepolymer after vacuum water pumping in the step (2) and the micromolecule chain extender into a double-screw extruder for reaction according to the parts by weight, controlling the reaction temperature to be 200 ℃, controlling the rotating speed of the screw to be 300rpm, carrying out underwater granulation and dehydration after the reaction for 90s, dehumidifying and drying at 60 ℃ for 5h, and finally packaging to obtain the high-moisture-permeability breathable thermoplastic polyurethane elastomer.
Example 3
Embodiment 3 of the present invention provides a highly moisture-permeable and air-permeable thermoplastic polyurethane elastomer, which at least comprises the following components in parts by weight: 53 parts of modified isocyanate, 30 parts of polyether polyol, 35 parts of polyester polyol, 8 parts of small molecular chain extender, 2 parts of anti-aging agent, 7 parts of porous material and 5 parts of compatilizer.
The modified isocyanate is carbodiimide modified isocyanate, the carbodiimide modified isocyanate is carbodiimide modified 4, 4-diphenylmethane diisocyanate, the content of-NCO in the carbodiimide modified MDI is 29%, and the vapor pressure is at 25 DEG C<10 -5 mmHg, model Henscman 2020 available from Jiangyin bamboo Green chemical Co., Ltd.
The porous material is zeolite powder, the particle size of the zeolite powder is 200 meshes, the porosity is 48%, and the porous material is purchased from Qingdao Xin and Source Filter Material Co., Ltd;
the compatibilizer is polyethylene glycol-400, and the polyethylene glycol 400 has a CAS number of 25322-68-3 and is purchased from sigma aldrich (shanghai) trade company, ltd.
The mass ratio of the modified isocyanate to the porous material to the compatilizer is 53: 7: 5.
the polyester polyol is polyethylene glycol adipate, and the average molecular weight of the polyethylene glycol adipate is 10000.
The polyether polyol is polyoxypropylene diol, and the polyoxypropylene diol is polyoxypropylene diol 1000.
The micromolecular chain extender is 1, 4-butanediol.
The mass ratio of the polyether polyol to the polyester polyol to the micromolecule chain extender is 35: 30: 8.
the polyethylene adipate has a CAS number of 24938-37-2 and a cat number of 181919, and was purchased from sigma aldrich (shanghai) trade company, ltd; the CAS number of the polyoxypropylene glycol 1000 is 25322-69-4, and the polyoxypropylene glycol is purchased from Henan Wittig chemical technology Co., Ltd; the 1, 4-butanediol has a CAS number of 110-63-4 and is purchased from Shanghai Allantin Biotechnology Ltd.
The anti-aging agent is a combination of an anti-aging agent 4020, an antioxidant 1076 and UV-531, and the mass ratio of the anti-aging agent 4020 to the antioxidant 1076 to the UV-531 is 1: 1: 0.8.
the CAS number of the anti-aging agent 4020 is 793-24-8, and the anti-aging agent is purchased from Tianjin Xiansi Biotechnology Co., Ltd; the CAS number of the antioxidant 1076 is 2082-79-3, and the antioxidant is purchased from Hangzhou landscape optimizer, Co.Ltd; the CAS number for UV-531 is 1843-05-6, which is available from Fujian emperor science and technology Co.
In another aspect, embodiment 3 of the present invention provides a method for preparing a thermoplastic polyurethane elastomer with high moisture and air permeability, which at least comprises the following steps:
(1) putting the anti-aging agent, polyether polyol and polyester polyol into a reaction kettle according to the parts by weight, mixing, controlling the temperature to be 100 ℃, and stirring for 40min to obtain a polyol mixture;
(2) then controlling the temperature to be 120 ℃, adding the modified isocyanate, the porous material and the compatilizer into a reaction kettle according to the weight part, reacting with the polyol mixture obtained in the step (1) to prepare a polyurethane prepolymer, adjusting the temperature to be 100 ℃, and pumping water for the polyurethane prepolymer in vacuum for 5 hours;
(3) and (3) putting the polyurethane prepolymer after vacuum water pumping in the step (2) and the micromolecule chain extender into a double-screw extruder for reaction according to the parts by weight, controlling the reaction temperature to be 200 ℃, controlling the rotating speed of the screw to be 300rpm, carrying out underwater granulation and dehydration after reacting for 90s, dehumidifying and drying at 60 ℃ for 5h, and finally packaging to obtain the high-moisture-permeability breathable thermoplastic polyurethane elastomer.
Comparative example 1
Comparative example 1 of the present invention provides a highly moisture permeable and breathable thermoplastic polyurethane elastomer, which is the same as example 1 except that the modified isocyanate is diphenylmethane diisocyanate having a CAS number of 101-68-8, which is available from shanghai alatin biotechnology, ltd.
Comparative example 2
Comparative example 2 of the present invention provides a highly moisture-permeable and breathable thermoplastic polyurethane elastomer, which is the same as example 1 except that the raw material for preparing the highly moisture-permeable and breathable thermoplastic polyurethane elastomer does not include a porous material.
Comparative example 3
Comparative example 3 of the present invention provides a highly moisture permeable and breathable thermoplastic polyurethane elastomer, which is similar to example 1, except that the mass ratio of the modified isocyanate, the porous material and the compatibilizer is 50: 5: 1.
comparative example 4
Comparative example 4 of the present invention provides a highly moisture-permeable, breathable thermoplastic polyurethane elastomer, which is the same as example 1 except that the raw material for preparing the highly moisture-permeable, breathable thermoplastic polyurethane elastomer does not include polyether polyol.
Comparative example 5
The comparative example 5 of the invention provides a thermoplastic polyurethane elastomer with high moisture and air permeability, and the specific implementation manner is the same as that in example 1, except that the mass ratio of the polyether polyol to the polyester polyol to the small-molecule chain extender is 30: 25: 15.
performance test method
(1) Mechanical properties: (1) hardness: the shore hardness of the thermoplastic polyurethane elastomers obtained in the examples and comparative examples was measured by the method described in ASTM D2240; (2) elongation at break: the elongation at break of the thermoplastic polyurethane elastomers prepared in the examples and comparative examples was measured with reference to ASTM D412.
(2) Moisture permeability: the moisture permeability of the thermoplastic polyurethane elastomers obtained in examples and comparative examples was measured with reference to JIS L1099-2006 (method B-1).
Performance test data
The thermoplastic polyurethane elastomers obtained in examples 1 to 3 and comparative examples 1 to 5 were evaluated for their properties.
Referring to Table 1, Table 1 shows the data of the performance tests of the thermoplastic polyurethane elastomers prepared in examples 1 to 3 and comparative examples 1 to 5.
Claims (10)
1. The high moisture-permeable breathable thermoplastic polyurethane elastomer is characterized by comprising the following raw materials in parts by weight: 50-60 parts of modified isocyanate, 30-40 parts of polyether polyol, 30-40 parts of polyester polyol, 5-15 parts of small molecular chain extender, 2-5 parts of anti-aging agent, 5-10 parts of porous material and 4-8 parts of compatilizer.
2. The thermoplastic polyurethane elastomer with high moisture and air permeability as claimed in claim 1, wherein the mass ratio of the modified isocyanate, the porous material and the compatilizer is (53-58): (7-10): (5-8).
3. The thermoplastic polyurethane elastomer with high moisture and air permeability as claimed in claim 1 or 2, wherein the modified isocyanate is selected from at least one of urethane modified polyisocyanate, biuret modified isocyanate, and carbodiimide modified isocyanate.
4. The thermoplastic polyurethane elastomer with high moisture and gas permeability as claimed in claim 1 or 2, wherein the porous material is at least one of zeolite powder, nano silica and nano silica aerogel.
5. The thermoplastic polyurethane elastomer with high moisture and air permeability as claimed in claim 1 or 2, wherein the compatibilizer is at least one selected from polyethylene glycol-200, polyethylene glycol-400, polyethylene glycol-600, and polyethylene glycol-800.
6. The thermoplastic polyurethane elastomer with high moisture and air permeability as claimed in claim 1, wherein the mass ratio of the polyether polyol to the polyester polyol to the small-molecule chain extender is (35-40): (30-35): (8-12).
7. The thermoplastic polyurethane elastomer with high moisture and air permeability as claimed in claim 6, wherein the polyether polyol is selected from one or more of polyoxypropylene glycol, polytetrahydrofuran glycol and tetrahydrofuran-propylene oxide copolymerized glycol.
8. The thermoplastic polyurethane elastomer with high moisture and air permeability as claimed in claim 7, wherein the polyether polyol is polyoxypropylene glycol.
9. The thermoplastic polyurethane elastomer with high moisture and air permeability as claimed in claim 1, wherein the antioxidant is at least one selected from antioxidant 4020, antioxidant 1076, UV-531, UV-9, UVP-327 and RMB.
10. A process for preparing a thermoplastic polyurethane elastomer with high moisture and air permeability according to any one of claims 1 to 9, characterized in that it comprises at least the following steps:
(1) putting the anti-aging agent, polyether polyol and polyester polyol into a reaction kettle according to the parts by weight, mixing, controlling the temperature to be 80-100 ℃, and stirring for 30-60min to obtain a polyol mixture;
(2) then controlling the temperature to be 100-120 ℃, adding the modified isocyanate, the porous material and the compatilizer into a reaction kettle according to the weight part to react with the polyol mixture obtained in the step (1) to prepare a polyurethane prepolymer, adjusting the temperature to be 80-100 ℃, and pumping the polyurethane prepolymer in vacuum for 4-6 hours;
(3) and (3) putting the polyurethane prepolymer after vacuum pumping in the step (2) and the micromolecule chain extender into a double-screw extruder for reaction according to the parts by weight, controlling the reaction temperature to be 150-200 ℃, controlling the rotation speed of the screw to be 200-300rpm, carrying out underwater granulation and dehydration after the reaction for 60-90s, dehumidifying and drying at 40-60 ℃ for 4-7h, and finally packaging to obtain the high-moisture-permeability breathable thermoplastic polyurethane elastomer.
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