Thermoplastic elastomer material, process for its preparation and use

Abstract

The application discloses a thermoplastic elastomer material and a preparation method and application thereof, and belongs to the technical field of polymer materials. The thermoplastic elastomer material comprises the following components in parts by weight: 5-30 parts of a thermoplastic elastomer; 5-40 parts of a plasticizer; 1-10 parts of a compatilizer; 0.1-10 parts of an epoxy resin; 0-20 parts of a general plastic; 10-50 parts of glass fiber; and 0-5 parts of a processing aid. The compatilizer is a hydrogenated styrene-polyurethane block copolymer; and the impregnating agent of the glass fiber is one or more of an aqueous polyurethane emulsion, a polyvinyl acetate emulsion, an ester silane coupling agent or a polyester emulsion. The thermoplastic elastomer and the impregnated glass fiber form a good compatibility effect by synergistic effect of the compatilizer and the epoxy resin, so that the tensile strength and the impact strength of the material can be significantly improved.

Description

Technical Field

[0001] This invention relates to the field of polymer materials technology, and more specifically, to a thermoplastic elastomer material, its preparation method, and its application. Background Technology

[0002] Thermoplastic elastomers (TPEs) are a new type of polymer material that lies between rubber and resin. They can not only replace some rubber but also modify plastics, and are increasingly used in the automotive industry, electronics, wire and cable industries.

[0003] Styrene-based thermoplastic elastomers are gaining increasing attention due to the readily available raw materials, wide range of formulation design options, and large hardness adjustment range. However, the inherent low strength and poor heat resistance of styrene-based thermoplastic elastomers significantly limit their application in other fields. Adding fillers such as glass fibers can generally significantly improve the strength and rigidity of the polymer. However, because styrene-based thermoplastic elastomers have weak polarity and poor compatibility with glass fibers, glass fibers are difficult to disperse uniformly within them. Therefore, even with the addition of large amounts of glass fibers, especially when the weight ratio of glass fibers exceeds 30% of the raw material, the mechanical properties of styrene-based thermoplastic elastomers cannot be significantly improved.

[0004] Due to the complex working conditions and heavy load, the base of a power tool bench drill is susceptible to various impacts and collisions. The motor generates a lot of heat and operates at a high temperature. It also vibrates a lot and is prone to noise. In order to reduce safety risks and environmental noise, the material of the new generation of power tool bench drill bases needs to have stronger tensile strength, impact strength, heat resistance and better shock absorption.

[0005] Existing technology discloses a TPE comprising 100 parts by weight of SEBS, 20-40 parts by weight of PP, 50-80 parts by weight of white oil, 20-80 parts by weight of LLDPE, 1-10 parts by weight of sulfonated phenylmethyl silicone oil, 0.1-1 parts by weight of antioxidant, 0.1-0.3 parts by weight of slip agent, and 10-40 parts by weight of filler, wherein the filler is nano-magnesium hydroxide or glass fiber. However, while the sulfonated phenylmethyl silicone oil improves the burst resistance of the TPE, it does not improve the impact strength and heat resistance of the material. Moreover, the tensile strength of this material does not meet the requirements of the base of a bench drill press for power tools. Summary of the Invention

[0006] The technical problem to be solved by the present invention is to overcome the defects and shortcomings of the low tensile strength of existing styrene-based thermoplastic elastomers, and to provide a thermoplastic elastomer material that, through the synergistic effect of compatibilizer and epoxy resin, effectively improves the dispersion effect of impregnated glass fiber in the system, so that the thermoplastic elastomer and impregnated glass fiber form a better compatibility effect, thereby significantly improving the tensile strength, impact strength and heat resistance of the material.

[0007] Another object of the present invention is to provide a method for preparing a thermoplastic elastomer material.

[0008] Another object of the present invention is to provide an application of a thermoplastic elastomer material in the preparation of a bench drill base.

[0009] The above-mentioned objective of this invention is achieved through the following technical solution:

[0010] A thermoplastic elastomer material, comprising the following components by weight:

[0011]

[0012] The compatibilizer is a hydrogenated styrene-polyurethane block copolymer;

[0013] The impregnating agent for the glass fiber is one or more of the following: waterborne polyurethane emulsion, polyvinyl acetate emulsion, ester-based silane coupling agent, or polyester emulsion.

[0014] This invention utilizes the synergistic effect of compatibilizer and epoxy resin. The epoxy groups react with the terminal amino groups of polyurethane and the ester groups on the surface of impregnated glass fibers, respectively, which improves the dispersion effect of impregnated glass fibers in the system. This results in better compatibility between thermoplastic elastomer and impregnated glass fibers, thereby significantly improving the tensile strength and impact strength of the material. Furthermore, the interface between the thermoplastic elastomer molecular chains and the impregnated glass fibers is a flexible connection, allowing the material to maintain good flexibility and reduce the magnitude of hardness increase.

[0015] Furthermore, since impregnated glass fibers can restrict the free movement volume of styrene segments in thermoplastic elastomers within the molecular chain, requiring the absorption of more heat to enable the molecular chain to move, the heat resistance of thermoplastic elastomer materials is significantly improved.

[0016] Preferably, the general-purpose plastic is a non-polar plastic.

[0017] More preferably, the general-purpose plastic is one or more of polyethylene, polypropylene, or POE.

[0018] Preferably,

[0019] By weight, it includes the following components:

[0020]

[0021] Preferably, the epoxy resin has an epoxy equivalent of 0.1 to 0.5 (100 g / g) and the test standard is GB / T1677-2008 hydrochloric acid acetone method.

[0022] More preferably, the epoxy resin has an epoxy equivalent of 0.18 to 0.4 (100 g / g).

[0023] Preferably, the impregnating agent for the impregnated glass fiber is an aqueous polyurethane emulsion and / or an ester-based silane coupling agent.

[0024] Preferably, in the impregnated glass fiber, the mass ratio of glass fiber to impregnating agent is 1:(0.05~0.1).

[0025] Preferably, the average diameter of the impregnated glass fiber is 7–40 μm.

[0026] More preferably, the average diameter of the impregnated glass fiber is 10–20 μm.

[0027] Preferably, the thermoplastic elastomer is one or more of hydrogenated polystyrene-butadiene-styrene block copolymer (SEBS), hydrogenated styrene-isoprene block copolymer (SEPS), or styrene-[ethylene-(ethylene / propylene)]-styrene block copolymer (SEEPS).

[0028] Preferably, the plasticizer is paraffin oil and / or naphthenic oil.

[0029] Preferably, the processing aid is one or more of antioxidants, light stabilizers, or lubricants; the antioxidant is a hindered phenolic antioxidant and / or a phosphite antioxidant; the light stabilizer is one or more of hindered amine light stabilizers, benzotriazole light stabilizers, or benzophenone light stabilizers; and the lubricant is one or more of organosilicon lubricants, amide lubricants, or stearic acid lubricants.

[0030] The present invention also protects the preparation method of the above-mentioned thermoplastic elastomer material, which includes the following steps: mixing the components evenly, melting and extruding them through a twin-screw extruder at 160-210°C, granulating them, and drying them to obtain the thermoplastic elastomer material.

[0031] The thermoplastic elastomer material prepared by this invention has excellent tensile strength, impact strength, heat resistance and low hardness, and can be widely used in the preparation of plastic products. This invention particularly protects the application of the thermoplastic elastomer material in the preparation of bench drill bases.

[0032] Compared with the prior art, the beneficial effects of the present invention are:

[0033] This invention discloses a thermoplastic elastomer material. By utilizing the synergistic effect of a compatibilizer and epoxy resin, the epoxy groups react with the terminal amino groups of the polyurethane and the ester groups on the surface of the impregnated glass fiber, respectively, improving the dispersion effect of the impregnated glass fiber in the system. This results in a better compatibility between the thermoplastic elastomer and the impregnated glass fiber, thereby significantly improving the tensile strength and impact strength of the material. Furthermore, the interface between the thermoplastic elastomer molecular chain and the impregnated glass fiber is a flexible connection, allowing the material to maintain good flexibility and reduce the magnitude of hardness increase.

[0034] Furthermore, since impregnated glass fibers can restrict the free movement volume of styrene segments in thermoplastic elastomers within the molecular chain, requiring the absorption of more heat to enable the molecular chain to move, the heat resistance of thermoplastic elastomer materials is significantly improved. Detailed Implementation

[0035] The present invention will be further described below with reference to specific embodiments, but the embodiments do not limit the present invention in any way. Unless otherwise stated, the raw materials and reagents used in the embodiments of the present invention are conventionally purchased raw materials and reagents.

[0036] Thermoplastic elastomer 1: Hydrogenated polystyrene-butadiene-styrene block copolymer, SEBS 1651, Kronen;

[0037] Thermoplastic elastomer 2: Hydrogenated styrene-isoprene block copolymer, SEPS YH-4053, manufactured by Yueyang Petrochemical;

[0038] Thermoplastic elastomer 3: Styrene-[ethylene-(ethylene / propylene)]-styrene block copolymer, SEEPS4055, manufactured by Kuraray;

[0039] Plasticizer: Paraffin oil, PW-90, Idemitsu, Japan;

[0040] Compatibilizer 1: Hydrogenated styrene-polyurethane block copolymer, TU-S5265, Kuraray;

[0041] Compatibilizer 2: Maleic anhydride-grafted hydrogenated styrene-butadiene-styrene block copolymer, SEBS FG1901GT, Kronen;

[0042] Epoxy Resin 1: Bisphenol A type epoxy resin; E-44, epoxy equivalent is 0.4 (100g / g), Wuxi Lanxing Petrochemical Co., Ltd.

[0043] Epoxy Resin 2: Bisphenol A type epoxy resin; E-20, epoxy equivalent is 0.18 (100g / g), Wuxi Lanxing Petrochemical Co., Ltd.

[0044] Epoxy Resin 3: Bisphenol S type epoxy resin; CW-1100, epoxy equivalent 0.5 (100g / g), Suizhou Jiake Bioengineering Co., Ltd.

[0045] Epoxy Resin 4: Bisphenol A type epoxy resin; E-20, epoxy equivalent is 0.2 (100g / g), Wuxi Lanxing Petrochemical Co., Ltd.

[0046] Epoxy Resin 5: Bisphenol A type epoxy resin; E-14, epoxy equivalent is 0.1 (100g / g), Wuxi Lanxing Petrochemical Co., Ltd.

[0047] General Plastics 1: Polypropylene: PP HP500N, CNOOC Shell;

[0048] General Plastics 2: Polystyrene: PS 350K, Taiwan Guoheng;

[0049] General Plastics 3: ABS: ABS D-120A, Taiwan Kuo Chiao;

[0050] Impregnated glass fiber 1: Glass fiber 508S, Jushi glass fiber, alkali-free glass fiber, impregnating agent is Dow Corning Incorporated's ester-based silane coupling agent Z-603, the chemical name of the ester-based silane coupling agent is 3-(methacryloyloxy)propyltrimethoxysilane, the mass ratio of glass fiber to impregnating agent is 1:0.05, and the average diameter is 10 micrometers;

[0051] Impregnated glass fiber 2: Glass fiber CR15-10, Wuhu Baiyun Glass Fiber, medium alkali glass fiber, impregnating agent is Dow Corning Incorporated's ester-based silane coupling agent Z-603, the chemical name of the ester-based silane coupling agent is 3-(methacryloyloxy)propyltrimethoxysilane, the mass ratio of glass fiber to impregnating agent is 1:0.05, and the average diameter is 15 micrometers;

[0052] Impregnated glass fiber 3: Glass fiber E110, Jushi glass fiber, alkali-free glass fiber, impregnating agent is Dow Corning Incorporated's ester-based silane coupling agent Z-603, the chemical name of the ester-based silane coupling agent is 3-(methacryloyloxy)propyltrimethoxysilane, the mass ratio of glass fiber to impregnating agent is 1:0.05, and the average diameter is 7 micrometers;

[0053] Impregnated glass fiber 4: Glass fiber 362H, Jushi glass fiber, alkali-free glass fiber, impregnating agent is Dow Corning Incorporated's ester-based silane coupling agent Z-603, the chemical name of the ester-based silane coupling agent is 3-(methacryloyloxy)propyltrimethoxysilane, the mass ratio of glass fiber to impregnating agent is 1:0.05, and the average diameter is 20 micrometers;

[0054] Impregnated glass fiber 5: Glass fiber 508SY-1#, alkali-free glass fiber, impregnating agent is Dow Corning Incorporated's ester-based silane coupling agent Z-603, the chemical name of which is 3-(methacryloyloxy)propyltrimethoxysilane, customized by the supplier, the mass ratio of glass fiber to impregnating agent is 1:0.05, and the average diameter is 40 micrometers;

[0055] Impregnated glass fiber 6: Glass fiber 508SY-2#, alkali-free glass fiber, impregnating agent is Shenzhen Yoshida's water-based polyurethane emulsion F0400, self-made, the mass ratio of glass fiber to impregnating agent is 1:0.05, and the average diameter is 10 micrometers;

[0056] Impregnated glass fiber 7: Glass fiber 508SY-3#, alkali-free glass fiber, impregnating agent is polyvinyl acetate BRJ-3904 from Lianyungang Yinghui Adhesive Industry Co., Ltd., self-made, the mass ratio of glass fiber to impregnating agent is 1:0.05, and the average diameter is 10 micrometers;

[0057] Impregnated glass fiber 8: Glass fiber 508SY-4#, alkali-free glass fiber, impregnating agent is Korean SK polyester emulsion SKYBON EM-110, self-made, the mass ratio of glass fiber to impregnating agent is 1:0.05, and the average diameter is 10 micrometers;

[0058] Impregnated glass fiber 9: Glass fiber 508SY-5#, alkali-free glass fiber, impregnating agent is Dow Corning Incorporated's ester-based silane coupling agent Z-603, the chemical name of the ester-based silane coupling agent is 3-(methacryloyloxy)propyltrimethoxysilane, self-made, the mass ratio of glass fiber to impregnating agent is 1:0.03, and the average diameter is 10 micrometers;

[0059] Impregnated glass fiber 10: Glass fiber 508SY-6#, alkali-free glass fiber, impregnating agent is Dow Corning's ester-based silane coupling agent Z-603, the chemical name of the ester-based silane coupling agent is 3-(methacryloyloxy)propyltrimethoxysilane, self-made, the mass ratio of glass fiber to impregnating agent is 1:0.1, and the average diameter is 10 micrometers;

[0060] The above impregnated glass fibers 5, 6, 7, 8, 9 and 10 are all homemade. The method of making them is as follows: soak the glass fibers in the impregnating agent solution according to the proportion, place them at room temperature (23℃) / 50% humidity for 24 hours, and then take them out.

[0061] Antioxidants: hindered phenolic antioxidants and phosphite antioxidants, with a mass ratio of hindered phenolic antioxidants to phosphite antioxidants of 1:1, commercially available and the same type used in all examples and comparative examples.

[0062] Light stabilizer: Hindered amine light stabilizer, commercially available and the same type used in all examples and comparative examples.

[0063] Examples 1-22

[0064] A thermoplastic elastomer material, comprising the following components by weight:

[0065] Thermoplastic elastomers; plasticizers; compatibilizers; epoxy resins; general-purpose plastics; impregnated glass fibers; processing aids, including antioxidants and light stabilizers.

[0066] Table 1. Thermoplastic elastomer material composition of each embodiment (parts by weight)

[0067]

[0068]

[0069] Continued from Table 1

[0070]

[0071]

[0072] The specific preparation method of the above-mentioned thermoplastic elastomer material is as follows:

[0073] The components are mixed evenly, melt-extruded and granulated at 160-210°C using a twin-screw extruder, and then dried to obtain the thermoplastic elastomer material.

[0074] S1. Add the thermoplastic elastomer to a low-speed mixer, add the plasticizer while stirring, and mix evenly;

[0075] S2. Add the material from S1 and all other materials into the high-speed mixer and mix thoroughly;

[0076] S3. The material mixed in S2 is fed into a twin-screw extruder via a loss-in-weight metering method. After extrusion at 160-210℃, it is granulated and dried to obtain a thermoplastic elastomer material. The twin-screw extruder used has an aspect ratio of (36-60) / 1, and the material residence time in the screw is 30-80s.

[0077] Comparative Examples 1-8

[0078] A thermoplastic elastomer material, comprising the following components by weight:

[0079] Thermoplastic elastomers; plasticizers; compatibilizers; epoxy resins; general-purpose plastics; impregnated glass fibers; processing aids, including antioxidants and light stabilizers.

[0080] The specific content of each component is shown in Table 2 below.

[0081] Table 2. Thermoplastic elastomer material composition for each comparative example (by weight parts)

[0082]

[0083]

[0084] The preparation method of the above thermoplastic elastomer material is the same as that in the examples.

[0085] Result detection

[0086] The thermoplastic elastomer materials of the above embodiments and comparative examples were tested using the following performance testing methods:

[0087] Tensile strength: determined according to the ISO 37-2012 standard method.

[0088] Impact strength: determined according to the ISO 180-2019 standard method.

[0089] Shore hardness: Measured according to the ISO 7619-2010 standard method, a hardness of 80A-95A is more suitable.

[0090] Vicat softening point: determined according to the standard method of ISO 306-2013.

[0091] The specific test results are shown in Table 3 below:

[0092]

[0093]

[0094] As can be seen from the above data, the thermoplastic elastomer material of the present invention has a tensile strength of 20.1-36.7 MPa, an impact strength of 20.4-38.9 MPa, a Shore hardness of 80-94 A, and a Vicat softening point of 110-120 °C.

[0095] As can be seen from Examples 1, 6, and 7, adding different types of thermoplastic elastomers can yield reinforced thermoplastic elastomer materials with good overall performance.

[0096] As can be seen from Examples 1, 8, 9, 10, and 11, the higher the epoxy equivalent, the greater the tensile strength, but the lower the impact strength, the higher the hardness, and the higher the Vicat softening point. When the epoxy resin has an epoxy equivalent of 0.18-0.4 (100g / g), it is more conducive to achieving a balance of comprehensive performance in terms of tensile strength, impact strength, Shore hardness, and Vicat softening point.

[0097] As can be seen from Examples 1, 12, 13, 14, and 15, when the surface treatment of the impregnated glass fibers is the same, the average diameter has an optimal effect on the material properties. The particle size is best when it is 10-20 μm. When the average diameter is too fine or too coarse, it is not conducive to dispersion, which leads to a certain decrease in performance.

[0098] As can be seen from Examples 1, 16, 17, and 18, several different surface treatment reagents can more effectively wet the dispersion of glass fibers, thereby obtaining better performance.

[0099] As can be seen from Examples 1, 19, and 20, when the amount of sizing agent used to impregnate the glass fiber is appropriately increased, its tensile strength is appropriately increased, and its hardness is significantly increased due to the increased reaction between the ester group and the epoxy resin.

[0100] Examples 1, 21, and 22 show the influence of different general-purpose plastics on material properties. Among them, polyolefin PP has the best compatibility with SEBS, and therefore the resulting material has the best overall performance.

[0101] As can be seen from Example 1 and Comparative Examples 1 and 2, without the addition of epoxy resin or compatibilizer, it is impossible to achieve the effect of enhancing and improving heat resistance.

[0102] As can be seen from Example 1 and Comparative Example 3, when the amount of SEBS added is too high, the dispersion is poor, resulting in a decrease in strength, a decrease in hardness, and a significant decrease in softening point.

[0103] As can be seen from Example 1 and Comparative Example 4, when the amount of plasticizer added is too high, the tensile strength and impact strength are low, and the softening point decreases significantly.

[0104] As can be seen from Example 1 and Comparative Example 5, when the amount of glass fiber added is too high, the hardness is too high and the impact is significantly reduced. Therefore, when used as a base for a bench drill press of an electric tool, it cannot play a shock absorption role.

[0105] As can be seen from Example 1 and Comparative Example 6, when the amount of compatibilizer added is too high, the tensile strength decreases significantly and the softening point decreases significantly.

[0106] As can be seen from Example 1 and Comparative Example 7, when the amount of epoxy resin added is too high, the hardness is significantly higher and the impact strength is significantly lower.

[0107] As can be seen from Example 1 and Comparative Example 8, adding other compatibilizers cannot achieve the effect of enhancing and improving heat resistance.

[0108] Obviously, the above embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the implementation of the present invention. Those skilled in the art can make other variations or modifications based on the above description. It is neither necessary nor possible to exhaustively describe all embodiments here. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention should be included within the scope of protection of the claims of the present invention.

Claims

1. A thermoplastic elastomer material, characterized in that, By weight parts, including the following components: Thermoplastic elastomer 5-30 parts; Plasticizer 5-40 parts; Compatibilizer 1-10 parts; Epoxy resin 0.1-10 parts; General plastic 0-20 parts; Glass fiber 10-50 parts; Processing aid 0-5 parts; The compatibilizer is hydrogenated styrene-polyurethane block copolymer; The glass fiber is impregnated with one or more of water-based polyurethane emulsion, polyvinyl acetate emulsion, ester silane coupling agent or polyester emulsion; The thermoplastic elastomer is one or more of hydrogenated polystyrene-butadiene-styrene block copolymer, hydrogenated styrene-isoprene block copolymer SEPS or styrene-[ethylene-(ethylene / propylene)]-styrene block copolymer SEEPS; The general plastic is polypropylene.

2. The thermoplastic elastomer material according to claim 1, wherein By weight parts, including the following components: Thermoplastic elastomer 10-20 parts; Plasticizer 10-30 parts; Compatibilizer 3-8 parts; Epoxy resin 1-5 parts; General plastic 5-15 parts; Glass fiber 20-40 parts; Processing aid 0-5 parts.

3. The thermoplastic elastomer material according to claim 1, wherein The epoxy resin has an epoxy equivalent weight of 0.1-0.5 (100g / g) and is tested according to GB / T 1677-2008 hydrochloric acid-acetone method.

4. The thermoplastic elastomer material according to claim 1, wherein The glass fiber is impregnated with water-based polyurethane emulsion and / or ester silane coupling agent.

5. The thermoplastic elastomer material as described in claim 1, characterized in that, In the glass fiber, the mass ratio of glass fiber to impregnant is 1:(0.05~0.1).

6. The thermoplastic elastomer material as described in claim 1, characterized in that, The average diameter of the glass fiber is 10~20μm.

7. The thermoplastic elastomer material as described in claim 1, characterized in that, The plasticizer is paraffin oil and / or naphthenic oil.

8. The method of preparing a thermoplastic elastomer material according to any one of claims 1 to 7, wherein Including the following steps: Mixing each component uniformly, melting and extruding through a double screw extruder at 160~210 ℃, granulating, drying, and then obtaining the thermoplastic elastomer material.

9. Use of the thermoplastic elastomer material of any one of claims 1-7 in the preparation of a bench drill base.

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