A polyester elastomer / styrene elastomer composite and its preparation and application

Abstract

The present invention relates to a polyester elastomer / styrene elastomer composite and its preparation and application. The composite components include, by weight: 55-95 parts of a thermoplastic polyester elastomer composite; 8-42 parts of a styrene elastomer; and 5-15 parts of a styrene-acrylonitrile-glycidyl acrylate copolymer composite. The composite has good adhesion to a non-woven fabric at low temperatures.

Description

Technical Field

[0001] The invention belongs to the technical field of elastomers, and particularly relates to a polyester elastomer / styrene elastomer composite and a preparation method and application thereof. Background Art

[0002] Thermoplastic polyester elastomer materials have excellent mechanical properties, excellent chemical solvent resistance, high moisture and air permeability, etc., and have been increasingly used in clothing, jackets, outdoor tents, etc. Especially in the field of jackets, the isolation layer made of thermoplastic polyester elastomer has the advantages of high moisture permeability, high air permeability, good thermal insulation effect, etc., and can be used in high-end jackets.

[0003] Jackets are generally multi-layered, with the outer layer being generally non-woven fabric and the middle layer being a moisture-permeable and heat-insulating layer. The moisture-permeable and heat-insulating layer and the non-woven fabric layer are bonded together with glue or double-sided tape. The production process includes extrusion casting to produce non-woven fabric, extrusion casting to produce thermoplastic polyester elastomer isolation film, applying glue or double-sided tape on the surface of non-woven fabric, and bonding the non-woven fabric layer and the isolation layer. The production process has many steps, a long process, and cannot be produced continuously.

[0004] Non-woven fabrics are generally made of polypropylene, which is a non-polar material, while thermoplastic polyester elastomers are polar materials, and the two are not compatible. Cast film made directly by multi-layer co-extrusion has no adhesion between the non-woven fabric layer and the isolation layer, resulting in the detachment of the two layers and the inability to form a composite film.

[0005] When people wear jackets for outdoor sports, they may encounter low temperature environments. At present, under low temperature conditions, the moisture permeable insulation layer and the non-woven fabric layer are easy to debond, which deteriorates the user experience. Summary of the invention

[0006] The technical problem to be solved by the present invention is to provide a polyester elastomer / styrene elastomer composite and its preparation and application, so as to overcome the defect of poor adhesion between thermoplastic elastomer and non-woven fabric at low temperature in the prior art.

[0007] The present invention provides a polyester elastomer / styrene elastomer composite, wherein the composite components include, by weight:

[0008] 55-95 parts of thermoplastic polyester elastomer compound;

[0009] 8-42 parts of styrene elastomer;

[0010] 5-15 parts of styrene-acrylonitrile-glycidyl methacrylate copolymer compound;

[0011] The thermoplastic polyester elastomer compound comprises a thermoplastic polyester elastomer 1 and a thermoplastic polyester elastomer 2 at a weight ratio of 7:2 to 3:11; the thermoplastic polyester elastomer 1 is a copolymer of terephthalic acid, isophthalic acid, ethylene glycol and polyethylene glycol; the thermoplastic polyester elastomer 2 is a copolymer of cyclohexanedicarboxylic acid, adipic acid, propylene glycol and polyethylene glycol;

[0012] The styrene-acrylonitrile-glycidyl methacrylate copolymer compound is a compound of styrene-acrylonitrile-glycidyl methacrylate copolymers with different contents of glycidyl methacrylate.

[0013] Preferably, the composite components include, by weight:

[0014] 58-88 parts of thermoplastic polyester elastomer compound;

[0015] Styrene elastomer 12-38 parts;

[0016] 6-12 parts of styrene-acrylonitrile-glycidyl acrylate copolymer compound.

[0017] Preferably, the styrene elastomer is a diblock copolymer; the diblock copolymer includes one or more of hydrogenated styrene-butadiene copolymer and hydrogenated styrene-isoprene copolymer.

[0018] Preferably, the mass fraction of styrene in the styrene elastomer is 10-15%. 1 HNMR method test. 1 In the H NMR spectrum, δ at 6.1-7.6 ppm is the proton on the benzene ring of the styrene segment, and 0.8-3.0 ppm is the proton on the methylene group of the EB segment. The mass fraction of styrene is calculated by the integrated area ratio of the two.

[0019] Preferably, the styrene elastomer is free of mineral oil.

[0020] Preferably, the thermoplastic polyester elastomer 1 comprises, by weight percentage, 20-40% terephthalic acid residues, 1-10% isophthalic acid residues, 30-50% polyethylene glycol residues, and 10%-49% ethylene glycol residues. The weight percentage is obtained by nuclear magnetic resonance H spectrum.

[0021] Preferably, the preparation method of the thermoplastic polyester elastomer 1 comprises: esterifying 20-40% terephthalic acid, 1-10% isophthalic acid, 30-50% polyethylene glycol and 10%-49% ethylene glycol at 210-240°C for 2-4 hours under normal pressure to 130 kPa, heating to 245-260°C, carrying out polycondensation reaction for 3-5 hours under pressure less than 200 Pa, charging high-purity nitrogen into the reaction system, extruding the melt through a mouth mold, and pelletizing to obtain the product.

[0022] Preferably, the thermoplastic polyester elastomer 2 comprises, by weight percentage, 10-30% of p-cyclohexanedicarboxylic acid residues, 15-25% of adipic acid residues, 30-50% of polyethylene glycol residues, and 15-45% of propylene glycol residues. The weight percentages are obtained by nuclear magnetic resonance H spectrum.

[0023] Preferably, the preparation method of the thermoplastic polyester elastomer 2 comprises: esterifying 10-30% cyclohexanedicarboxylic acid, 15-25% adipic acid, 30-50% polyethylene glycol and 15-45% propylene glycol at 200-230°C for 2-4 hours under normal pressure to 80 kPa, heating to 240-270°C, carrying out polycondensation reaction for 3-5 hours under pressure less than 200 Pa, charging the reaction system with high-purity nitrogen, extruding the melt through a mouth mold, and pelletizing to obtain the product.

[0024] Preferably, the number average molecular weight of the polyethylene glycol in the thermoplastic polyester elastomer 1 is 3000-6000.

[0025] Preferably, the number average molecular weight of polyethylene glycol in the thermoplastic polyester elastomer 2 is 250-2500.

[0026] Preferably, the styrene-acrylonitrile-glycidyl methacrylate copolymer compound comprises styrene-acrylonitrile-glycidyl methacrylate copolymer 1 and styrene-acrylonitrile-glycidyl methacrylate copolymer 2 in a weight ratio of 10:1-1:10.

[0027] Preferably, the mass fraction of glycidyl methacrylate in the styrene-acrylonitrile-glycidyl methacrylate copolymer 1 is 25-30%. The test standard for the mass fraction of glycidyl methacrylate is the hydrochloric acid-acetone method in GB / T 1677-2008.

[0028] Preferably, the mass fraction of glycidyl methacrylate in the styrene-acrylonitrile-glycidyl methacrylate copolymer 2 is 1-6%. The test standard for the mass fraction of glycidyl methacrylate is the hydrochloric acid-acetone method in GB / T 1677-2008.

[0029] Preferably, the compound further comprises 0-15 parts of additives.

[0030] Preferably, the additives include one or more of flame retardants, antioxidants, UV resistant agents, carbon black, pigments, dyes, and mineral powders.

[0031] Preferably, the flame retardant includes one or more of aluminum hypophosphite, melamine cyanurate, and brominated polystyrene.

[0032] Preferably, the antioxidant includes one or more of hindered phenol antioxidants, phosphite antioxidants, aniline antioxidants, and thioester antioxidants.

[0033] Preferably, the UV-resistant agent includes one or more of benzophenone-based UV-resistant agents, benzotriazole-based UV-resistant agents, and hindered amine-based UV-resistant agents.

[0034] Preferably, the pigment includes one or more of titanium dioxide, zinc sulfide and barium sulfate.

[0035] Preferably, the dye includes one or more of ultramarine blue, red iron oxide and titanium yellow.

[0036] Preferably, the mineral powder includes one or more of talc, calcium carbonate and kaolin.

[0037] The present invention also provides a method for preparing a polyester elastomer / styrene elastomer composite, comprising the following steps:

[0038] The components are mixed, and the obtained material is fed into a twin-screw extruder for extrusion, and the polyester elastomer / styrene elastomer composite is obtained after granulation and drying.

[0039] Preferably, the extrusion temperature is 170-240° C.; the aspect ratio of the twin-screw extruder is 36-60:1; and the residence time of the material in the screw is 45-95 s.

[0040] The invention also provides application of a polyester elastomer / styrene elastomer composite in a jacket.

[0041] When thermoplastic polyester elastomer 1 or thermoplastic polyester elastomer 2 is used alone, at low temperature (such as -35°C), the phase separation degree of thermoplastic polyester elastomer and styrene elastomer is serious, resulting in a larger phase region between the two, which leads to uneven bonding between the composite and the non-woven fabric, and changes from surface bonding to point bonding, thereby reducing the bonding effect. When thermoplastic polyester elastomer 1 and thermoplastic polyester elastomer 2 of the present invention are used in combination, at low temperature (such as -35°C), the microphase morphology of the composite remains stable, so as to meet the effect of high bonding performance.

[0042] In the present invention, the styrene-acrylonitrile-methacrylate glycidyl copolymer is a multi-component copolymer, and has good compatibility with the thermoplastic polyester elastomer compound and the styrene elastomer, and can improve the compatibility of the two. When a copolymer with a low methacrylate glycidyl content is used alone, the cross-linking point density formed by the reaction with the end group of the thermoplastic polyester elastomer is low, and the melt viscosity is greatly affected by the shear rate. When the composite is extruded and flows through the die, due to the difference in shear rate between the middle and edge of the die, the melt viscosity of the middle and edge parts is different, and the thickness difference is large, and a film material with uniform thickness cannot be obtained. In the process of bonding with the non-woven fabric, the phenomenon of uneven bonding effect between the middle and the edge will occur. When a copolymer with a high methacrylate glycidyl content is used alone, the cross-linking point density formed by the reaction with the end group of the thermoplastic polyester elastomer is high, and the melt viscosity is less affected by the shear rate, which is conducive to obtaining a film material with uniform thickness. At this time, the viscosity of the thermoplastic polyester elastomer is high, making it difficult to disperse in the composite with the styrene elastomer, and the phase size is large, resulting in uneven bonding with the non-woven fabric. The use of two copolymers with different glycidyl methacrylate contents can achieve uniform thickness and uniform bonding strength with non-woven fabrics.

[0043] Beneficial Effects

[0044] The present invention uses a compound of thermoplastic polyester elastomer 1 and thermoplastic polyester elastomer 2 to significantly improve the bonding strength between the composite and the non-woven fabric at low temperatures. The use of styrene-acrylonitrile-glycidyl acrylate copolymers with different contents of glycidyl methacrylate can further improve the bonding strength between the composite and the non-woven fabric at low temperatures. DETAILED DESCRIPTION

[0045] The present invention will be further described below in conjunction with specific embodiments. It should be understood that these embodiments are only used to illustrate the present invention and are not intended to limit the scope of the present invention. In addition, it should be understood that after reading the content taught by the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms fall within the scope limited by the appended claims of the application equally.

[0046] Source of reagents:

[0047] Thermoplastic polyester elastomer 1:

[0048] Thermoplastic polyester elastomer 1-1: a copolymer of terephthalic acid, isophthalic acid, ethylene glycol and polyethylene glycol. The preparation method of the copolymer is as follows: 20% of terephthalic acid, 10% of isophthalic acid, 30% of polyethylene glycol (PEG-4000, the number average molecular weight of polyethylene glycol is 4000) and 40% of ethylene glycol are put into a reactor, after being stirred evenly at normal pressure, the pressure is increased to 120 kPa within half an hour, esterification reaction is carried out at 210° C. for 4 hours, the temperature is raised to 245° C., the pressure is reduced to 100 Pa within one hour, and polycondensation reaction is continued for 4 hours, high-purity nitrogen is filled into the reactor, the melt is extruded from the reactor through a mouth mold, and pelletized to obtain the copolymer, wherein the raw material percentage is the percentage of the raw material mass to the total raw material mass; the raw materials used are purchased from Sinopharm Group, and the analytically pure reagents;

[0049] Thermoplastic polyester elastomer 1-2: a copolymer of terephthalic acid, isophthalic acid, ethylene glycol and polyethylene glycol, the preparation method thereof is the same as the preparation method of thermoplastic polyester elastomer 1-1, except that the number average molecular weight of polyethylene glycol is 1500, PEG-1500, purchased from Sinopharm Group, analytically pure reagent;

[0050] Thermoplastic polyester elastomer 2-1: a copolymer of cyclohexanedicarboxylic acid, adipic acid, propylene glycol and polyethylene glycol. The preparation method of the copolymer is as follows: 10% of cyclohexanedicarboxylic acid, 15% of adipic acid, 30% of polyethylene glycol (PEG-2000, the number average molecular weight of polyethylene glycol is 2000) and 45% of propylene glycol are put into a reactor, and after being stirred evenly at normal pressure, the pressure is reduced to 80 kPa within half an hour, and the esterification reaction is carried out at 230°C for 3 hours, and the temperature is raised to 250°C, and the pressure is reduced to 70 Pa within half an hour, and the polycondensation reaction is carried out for 4 hours. High-purity nitrogen is filled into the reactor, and the melt is molded out of the reactor through the mouth, and pelletized to obtain the product, wherein the percentage of raw materials is the percentage of the raw material mass to the total raw material mass, and the raw materials used are purchased from Sinopharm Group, and the analytically pure reagents;

[0051] Thermoplastic polyester elastomer 2-2: a copolymer of cyclohexanedicarboxylic acid, adipic acid, propylene glycol and polyethylene glycol, the preparation method thereof is the same as the preparation method of thermoplastic polyester elastomer 2-1 except that the number average molecular weight of polyethylene glycol is 4000 (PEG-4000, Sinopharm Group);

[0052] Styrene elastomer 1: hydrogenated styrene-butadiene diblock copolymer (styrene mass fraction is 13%), brand Kraton G1645, does not contain mineral oil, Kraton;

[0053] Styrene elastomer 2: hydrogenated styrene-butadiene-styrene triblock copolymer (styrene mass fraction is 20%), brand Kraton G1642, does not contain mineral oil, Kraton;

[0054] Styrene elastomer 3: hydrogenated styrene-butadiene diblock copolymer (styrene mass fraction is 19%), brand name Kraton G1643, does not contain mineral oil, Kraton;

[0055] Styrene-acrylonitrile-glycidyl methacrylate copolymer:

[0056] Synthesize as follows:

[0057] Add styrene (commercially available), acrylonitrile (commercially available), and glycidyl methacrylate (commercially available) into a reaction kettle containing toluene and stir evenly. At 40°C, slowly drip a small amount of azobisisobutyronitrile, react for 3 hours, raise the temperature to 85°C, and continue to react for 1 hour. After cooling to room temperature, wash with hot water to obtain styrene-acrylonitrile-glycidyl methacrylate copolymer. Adjust the addition ratio of glycidyl methacrylate to obtain copolymers with different glycidyl methacrylate contents. (The following styrene-acrylonitrile-glycidyl methacrylate copolymers are synthesized according to the above method)

[0058] Styrene-acrylonitrile-glycidyl methacrylate copolymer 1:

[0059] Styrene-acrylonitrile-glycidyl methacrylate copolymer 1-1: the mass fraction of glycidyl methacrylate is 27.7%. During the preparation of the copolymer, the amount of styrene added is 580 g, the amount of acrylonitrile added is 150 g, and the amount of glycidyl methacrylate added is 280 g;

[0060] Styrene-acrylonitrile-glycidyl methacrylate copolymer 1-2: the mass fraction of glycidyl methacrylate is 23%. During the preparation of the copolymer, the amount of styrene added is 500g, the amount of acrylonitrile added is 270g, and the amount of glycidyl methacrylate added is 230g;

[0061] Styrene-acrylonitrile-glycidyl methacrylate copolymer 2:

[0062] Styrene-acrylonitrile-glycidyl methacrylate copolymer 2-1: the mass fraction of glycidyl methacrylate is 5%. During the preparation of the copolymer, the amount of styrene added is 550g, the amount of acrylonitrile added is 450g, and the amount of glycidyl methacrylate added is 50g;

[0063] Styrene-acrylonitrile-glycidyl methacrylate copolymer 2-2: the mass fraction of glycidyl methacrylate is 8%. During the preparation of the copolymer, the amount of styrene added is 620 g, the amount of acrylonitrile added is 300 g, and the amount of glycidyl methacrylate added is 80 g;

[0064] Ethylene-glycidyl methacrylate: glycidyl methacrylate mass fraction is 20%, brand 4170, DuPont; Additives:

[0065] Antioxidant: Hindered phenol antioxidant, commercially available;

[0066] The additives (antioxidants) used in the examples and comparative examples are the same commercially available products.

[0067] The preparation method of the polyester elastomer / styrene elastomer composite is as follows:

[0068] According to the proportions in Table 1, Table 2 and Table 3, the components are mixed, and the obtained material is fed into a twin-screw extruder for extrusion, and a polyester elastomer / styrene elastomer composite is obtained after granulation and drying. The extrusion temperature is 170-240°C, the aspect ratio of the twin-screw extruder is 36-60:1, and the residence time of the material in the screw is 45-95s.

[0069] Performance Test:

[0070] The thermoplastic polyester elastomer compound and non-woven fabric special material (PP T30S, Sinopec) were co-extruded in two layers to prepare a composite film, wherein the extrusion temperature of PP T30S was 210°C and the film thickness was 1.0 mm, and the extrusion temperature of the thermoplastic polyester elastomer was 220°C and the film thickness was 0.9 mm. The composite film was cut into a width of 60 mm and tested for 180-degree peel force at -35°C using a universal testing machine Zwick / Roell Z020 with a displacement speed of 250 mm / min.

[0071] Table 1 Example 1-9 Proportions (parts by weight)

[0072]

[0073]

[0074]

[0075] Table 2 Proportions of Examples 10-18 (parts by weight)

[0076]

[0077]

[0078] Table 3 Comparative proportions (parts by weight)

[0079]

[0080]

[0081] As shown in Table 1-3, in Comparative Example 1, only thermoplastic polyester elastomer 1-1 is added, and thermoplastic polyester elastomer 2-1 is not added. In Comparative Example 2, only thermoplastic polyester elastomer 2-1 is added, and thermoplastic polyester elastomer 1-1 is not added. The adhesion between the composite and the non-woven fabric at low temperature in Comparative Examples 1 and 2 is less than that in Example 1. The weight ratio of thermoplastic polyester elastomer 1-1 and thermoplastic polyester elastomer 2-1 added in Comparative Examples 6 and 7 is not within the scope of the present invention. The adhesion between the composite and the non-woven fabric at low temperature in Comparative Examples 6 and 7 is less than that in Example 1. It can be seen that the present invention adopts thermoplastic polyester elastomer 1-1 and thermoplastic polyester elastomer 2-1 compounding, and adding them in proportion can significantly improve the adhesion between the composite and the non-woven fabric at low temperature.

[0082] Comparative Example 3 only adds styrene-acrylonitrile-glycidyl acrylate copolymer 1-1, and Comparative Example 4 only adds styrene-acrylonitrile-glycidyl acrylate copolymer 2-1. The adhesion between the composite and the non-woven fabric at low temperature in Comparative Example 3 and Comparative Example 4 is less than that in Example 1. Comparative Example 5 adds ethylene-glycidyl methacrylate, and the adhesion between the composite and the non-woven fabric at low temperature is less than that in Example 1. It can be seen that the present invention uses a styrene-acrylonitrile-glycidyl acrylate copolymer compound to further improve the adhesion between the composite and the non-woven fabric at low temperature.

Claims

1. A polyester elastomer / styrene elastomer composite, characterized in that: The composite components include, by weight: 55-95 parts of a thermoplastic polyester elastomer compound; 8-42 parts of styrene elastomer; 5-15 parts of styrene-acrylonitrile-glycidyl methacrylate copolymer compound; The thermoplastic polyester elastomer compound comprises a thermoplastic polyester elastomer 1 and a thermoplastic polyester elastomer 2 in a weight ratio of 7:2 to 3:11; the thermoplastic polyester elastomer 1 comprises, by weight percentage, 20-40% of terephthalic acid residues, 1-10% of isophthalic acid residues, 30-50% of polyethylene glycol residues, and 10%-49% of ethylene glycol residues; the thermoplastic polyester elastomer 2 comprises, by weight percentage, 10-30% of cyclohexanedicarboxylic acid residues, 15-25% of adipic acid residues, 30-50% of polyethylene glycol residues, and 15-45% of propylene glycol residues; The styrene-acrylonitrile-glycidyl methacrylate copolymer compound comprises a styrene-acrylonitrile-glycidyl methacrylate copolymer 1 and a styrene-acrylonitrile-glycidyl methacrylate copolymer 2 in a weight ratio of 10:1-1:10; the mass fraction of glycidyl methacrylate in the styrene-acrylonitrile-glycidyl methacrylate copolymer 1 is 25-30%; the mass fraction of glycidyl methacrylate in the styrene-acrylonitrile-glycidyl methacrylate copolymer 2 is 1-6%.

2. The polyester elastomer / styrene elastomer composite according to claim 1, characterized in that: The composite components include, by weight: 58-88 parts of thermoplastic polyester elastomer compound; Styrene elastomer 12-38 parts; 6-12 parts of styrene-acrylonitrile-glycidyl acrylate copolymer compound.

3. The polyester elastomer / styrene elastomer composite according to claim 1, characterized in that: The styrene elastomer is a diblock copolymer; the diblock copolymer includes one or more of hydrogenated styrene-butadiene copolymer and hydrogenated styrene-isoprene copolymer.

4. The polyester elastomer / styrene elastomer composite according to claim 1, characterized in that: The mass fraction of styrene in the styrene elastomer is 10-15%; the styrene elastomer does not contain mineral oil; the number average molecular weight of polyethylene glycol in the thermoplastic polyester elastomer 1 is 3000-6000; and the number average molecular weight of polyethylene glycol in the thermoplastic polyester elastomer 2 is 250-2500.

5. The polyester elastomer / styrene elastomer composite according to claim 1, characterized in that: The compound further comprises 0-15 parts of additives; the additives comprise one or more of flame retardants, antioxidants, UV resistant agents, carbon black, pigments, dyes, and mineral powders.

6. A method for preparing the polyester elastomer / styrene elastomer composite as claimed in any one of claims 1 to 5, comprising the following steps: The components are mixed, and the obtained material is fed into a twin-screw extruder for extrusion, and the polyester elastomer / styrene elastomer composite is obtained after granulation and drying.

7. The preparation method according to claim 6, characterized in that: The extrusion temperature is 170-240° C.; the length-to-diameter ratio of the twin-screw extruder is 36-60:1; and the residence time of the material in the screw is 45-95 seconds.

8. Use of the polyester elastomer / styrene elastomer composite as claimed in any one of claims 1 to 5 in a jacket.

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