CN117820797A - Injection molding-grade high-transparency TPE material and preparation method thereof - Google Patents
Injection molding-grade high-transparency TPE material and preparation method thereof Download PDFInfo
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- CN117820797A CN117820797A CN202311851810.3A CN202311851810A CN117820797A CN 117820797 A CN117820797 A CN 117820797A CN 202311851810 A CN202311851810 A CN 202311851810A CN 117820797 A CN117820797 A CN 117820797A
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- 239000000463 material Substances 0.000 title claims abstract description 143
- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- 238000002347 injection Methods 0.000 title claims description 10
- 239000007924 injection Substances 0.000 title claims description 10
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 152
- 239000003365 glass fiber Substances 0.000 claims abstract description 91
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 76
- 238000001746 injection moulding Methods 0.000 claims abstract description 51
- 238000002156 mixing Methods 0.000 claims abstract description 46
- -1 polypropylene Polymers 0.000 claims abstract description 43
- 239000003921 oil Substances 0.000 claims abstract description 39
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 claims abstract description 39
- 238000003756 stirring Methods 0.000 claims abstract description 31
- 239000000203 mixture Substances 0.000 claims abstract description 29
- 239000003381 stabilizer Substances 0.000 claims abstract description 26
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- 239000011248 coating agent Substances 0.000 claims description 26
- 238000000576 coating method Methods 0.000 claims description 26
- 239000000243 solution Substances 0.000 claims description 20
- 239000002245 particle Substances 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 17
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 15
- 239000011521 glass Substances 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- XWXMGTIHBYFTIE-UHFFFAOYSA-N chembl203360 Chemical compound OC1=CC=CC=C1C1=NC2=CC=CC=C2N1 XWXMGTIHBYFTIE-UHFFFAOYSA-N 0.000 claims description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 239000006060 molten glass Substances 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 10
- 235000002906 tartaric acid Nutrition 0.000 claims description 10
- 239000011975 tartaric acid Substances 0.000 claims description 10
- 238000001291 vacuum drying Methods 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
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- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000002844 melting Methods 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 238000005554 pickling Methods 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
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- 238000005507 spraying Methods 0.000 claims description 5
- ACTRVOBWPAIOHC-UHFFFAOYSA-N succimer Chemical compound OC(=O)C(S)C(S)C(O)=O ACTRVOBWPAIOHC-UHFFFAOYSA-N 0.000 claims description 5
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000002861 polymer material Substances 0.000 abstract description 3
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- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 18
- OCKPCBLVNKHBMX-UHFFFAOYSA-N butylbenzene Chemical compound CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 description 10
- 238000005979 thermal decomposition reaction Methods 0.000 description 10
- 238000007254 oxidation reaction Methods 0.000 description 9
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- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 5
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 5
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- Injection Moulding Of Plastics Or The Like (AREA)
Abstract
The application relates to the field of polymer materials, and particularly discloses an injection molding-level high-transparency TPE material and a preparation method thereof. The injection molding high-transparency TPE material comprises SEBS, white oil, polypropylene, glass fiber, n-butylbenzene phthalic anhydride, stabilizer and antioxidant; the preparation method comprises the following steps: sequentially adding SEBS and white oil into a mixer at room temperature, and uniformly stirring and mixing to enable the SEBS to fully absorb the white oil; polypropylene, glass fiber, n-butylbenzene phthalic anhydride, stabilizer, antioxidant and modified nano calcium carbonate are put into a mixer to be mixed with SEBS which absorbs white oil, and the mixture is obtained after uniform stirring and mixing; and (3) putting the mixture into a feed inlet of a double-screw extruder, wherein the material extruded from a discharge outlet of the double-screw extruder is the injection molding high-transparency TPE material. The injection molding type high-transparency TPE material has the advantage of improving the thermal stability of the TPE material.
Description
Technical Field
The application relates to the field of polymer materials, in particular to an injection molding type high-transparency TPE material and a preparation method thereof.
Background
TPE (thermoplastic elastomer) is a polymer material, and integrates the advantages of thermoplastic plastics and elastic rubber. The traditional plastic materials often have the problems of high hardness, brittleness, fragility and the like, while the rubber materials have good elasticity and flexibility, but the processing difficulty is high. The appearance of TPE material fills the gap, and the perfect balance of strength and softness is realized by reasonably blending the proportion of thermoplastic resin and elastomer.
TPE materials have many advantages. Firstly, the plastic has excellent elastic recovery capability, can quickly recover after multiple stretching deformation, and avoids the problem that the traditional plastic is difficult to recover after deformation. And secondly, the TPE material has excellent low temperature resistance, keeps good flexibility even in extremely cold environments, and is not easy to become brittle and fracture. In addition, TPE materials also exhibit good chemical resistance and recyclable environmental protection properties.
Because of these advantages, TPE materials are widely used in many fields. In the automotive industry, TPE materials are used to manufacture automotive seals, suspension systems, interior trim, and the like, improving ride comfort and safety. In household products, TPE materials are used for manufacturing soft handles, anti-slip pads, protective sleeves and the like, so that humanized design and use experience of the products are improved. TPE materials are widely used in the medical device field to make flexible tubing, fittings and seals, ensuring the safety and reliability of medical devices.
However, the TPE material still has a disadvantage in terms of thermal stability, and because the TPE material generally contains thermoplastic resin and elastomer, the TPE material loses elasticity and flexibility due to high temperature, so that the TPE material cannot effectively bear external pressure and tensile force, thereby affecting the function and service life of the product, and the TPE material deforms and contracts due to high temperature, which causes the TPE material to fail to meet the requirements in certain application scenarios, especially in the fields requiring high temperature resistance.
Disclosure of Invention
In order to improve the thermal stability of the TPE material, the application provides an injection molding type high-transparency TPE material and a preparation method thereof.
In a first aspect, the injection molding high transparent TPE material provided in the present application adopts the following technical scheme:
an injection molding type high-transparency TPE material comprises the following SEBS in parts by weight: 120-180 parts of white oil: 100-150 parts of polypropylene: 20-40 parts of glass fiber: 40-60 parts of n-butylbenzene phthalic anhydride: 30-50 parts of stabilizer: 1-2 parts of an antioxidant: 1-5 parts.
By adopting the technical scheme, the glass fiber has high strength and rigidity, and can effectively enhance the mechanical properties of the TPE material. Under the high-temperature environment, the glass fiber can effectively inhibit the deformation and shrinkage of the TPE material, and improve the dimensional stability and heat resistance of the TPE material. The glass fiber has good heat conductivity, can effectively transfer heat from outside to inside, and reduces the temperature gradient in the material, so that the thermal stress generated by the material due to temperature change is reduced, and the heat stability of the TPE material is effectively improved through the mixing of the glass fiber and the TPE material. N-butylbenzene phthalic anhydride can effectively prevent thermal decomposition reaction of TPE material under high temperature condition. N-butylbenzene phthalic anhydride can be subjected to crosslinking reaction with polymer molecular chains in the TPE material to form a three-dimensional network structure. The cross-linked structure can improve the thermal stability and heat resistance of the material, so that the material can maintain good mechanical property and dimensional stability at high temperature.
Optionally, the glass fiber has a length of 2-4mm and a diameter of 5-15 μm.
By adopting the technical scheme, the shorter glass fiber length is beneficial to increasing the strength and rigidity of the material. This reinforcing effect allows the TPE material to withstand greater loads and stresses in application, improving its overall durability and service life. The selection of shorter glass fibers can effectively increase the thermal conductivity of the material. By rapidly transferring and dispersing heat, the formation of hot spots can be reduced and the risk of thermal decomposition of the material in a high temperature environment can be reduced. This further improves the thermal stability of the injection molded highly transparent TPE material, enabling it to maintain excellent performance under high temperature conditions.
Optionally, the preparation method of the glass fiber comprises the following steps:
a1, adding a glass raw material with silicon dioxide purity more than or equal to 99% into a glass melting furnace, heating to 1300-1500 ℃, and preserving heat to melt the glass raw material into molten glass;
a2, stretching the molten glass into a plurality of parallel glass fibers by using a spraying device, and rapidly cooling the pulled glass fibers;
a3, placing the glass fiber into a sufficient amount of 15% (w/v) dilute hydrochloric acid solution for pickling, and cleaning the pickled glass fiber for 1-3 times by adopting deionized water;
and A4, mixing titanium isopropoxide accounting for 20-30% of the mass of the glass fiber with isopropanol, stirring and heating to 40-60 ℃ to obtain a uniform coating solution, immersing the glass fiber in the coating solution, carrying out ultrasonic vibration on the coating solution for 5-10min, standing for 2-4h, taking out the glass fiber after standing, transferring the glass fiber to a drying box, drying at the temperature of 100-120 ℃, and cooling the glass fiber to room temperature after drying.
By adopting the technical scheme, the coating treatment can provide a uniform coating for the glass fiber, and the surface property of the glass fiber is improved. This enhances the interfacial adhesion between the glass fibers and the TPE matrix, allowing them to bond better together. Good interfacial adhesion is helpful for preventing the materials from peeling, cracking or debonding under high temperature conditions, and improving thermal stability and durability. The coating treatment has better stability in high-temperature environment by introducing the coating formed by the titanium isopropoxide. The titanium isopropoxide can resist high-temperature oxidation reaction, and reduces thermal decomposition and aging of the material. Therefore, the coating treatment can effectively improve the high temperature resistance of the TPE material and prolong the service life of the TPE material.
Optionally, the modified nano calcium carbonate comprises 10-30 parts by weight of modified nano calcium carbonate, wherein the particle size of the modified nano calcium carbonate is 50-200nm, and the purity of the modified nano calcium carbonate is more than or equal to 98%.
By adopting the technical scheme, the modified nano calcium carbonate has smaller particle size and larger specific surface area, so that more effective enhanced contact points can be provided. The strength, the rigidity and the durability of the injection molding high-transparency TPE material can be enhanced by adding the modified nano calcium carbonate, so that the injection molding high-transparency TPE material has better load capacity in application. Because the modified nano calcium carbonate has higher purity and good heat conduction performance, the heat can be effectively dispersed and absorbed by adding the modified nano calcium carbonate, and the hot spot temperature of the material is reduced. The thermal stability of the injection molding-level high-transparency TPE material is further improved, the risks of thermal decomposition and oxidation reaction are reduced, and the service life of the injection molding-level high-transparency TPE material is prolonged.
Optionally, the preparation method of the modified nano calcium carbonate comprises the following steps:
b1, mixing and uniformly stirring nano calcium carbonate particles and tartaric acid, wherein the mass ratio of the nano calcium carbonate particles to the tartaric acid is 5 (2-3), and carrying out vacuum drying at 80-120 ℃ to obtain modified nano calcium carbonate;
and B2, washing the modified nano calcium carbonate for 1-3 times by using absolute ethyl alcohol, and then carrying out vacuum drying.
By adopting the technical scheme, the modified nano calcium carbonate can realize surface modification through mixing and stirring treatment with tartaric acid. Tartaric acid is used as a surface modifier, and a thin and uniform coating can be formed on the surface of the nano calcium carbonate particles. The coating can enhance the interfacial adhesion between the nano calcium carbonate and the TPE matrix and improve the compatibility and the bonding strength of the nano calcium carbonate and the TPE matrix. The modified nano calcium carbonate has better dispersibility after being stirred. The modified nano calcium carbonate added into the injection molding high-transparency TPE material can be better dispersed in the matrix, and particle aggregation and agglomeration phenomena are reduced. Good dispersion properties help to improve the uniformity and performance stability of the material.
Optionally, the stabilizer comprises 20% -40% 2-hydroxyphenyl benzimidazole and 60% -80% methyltri (2-ethylhexyl) stannoic acid.
By adopting the technical scheme, the 2-hydroxyphenyl benzimidazole and the methyltris (2-ethylhexyl) stannoic acid can effectively prevent the TPE material from thermal decomposition reaction in the processing process and the use. By adding the two stabilizers, the degradation and oxidation phenomena of the material under the high temperature condition can be reduced, and the thermal stability and durability of the TPE material are improved. Methyltri (2-ethylhexyl) stannoic acid can also stabilize the material by reacting with free radicals in the TPE material, reducing degradation reactions due to the free radicals.
Optionally, the antioxidant comprises one or more of bisphenol a or dimercaptosuccinic acid.
By adopting the technical scheme, bisphenol A and dimercaptosuccinic acid are common antioxidants, and the antioxidant performance of the injection molding-grade high-transparency TPE material can be effectively improved by adding the bisphenol A and dimercaptosuccinic acid into the material. These antioxidants are capable of capturing and neutralizing free radicals, slowing or preventing the occurrence of oxidation reactions. By adding these antioxidants, the TPE material can be protected from degradation, discoloration and loss of performance due to oxidation.
In a second aspect, the present application provides a method for preparing an injection molding high transparent TPE material, which adopts the following technical scheme:
a preparation method of an injection molding type high-transparency TPE material comprises the following steps:
s1, sequentially adding SEBS and white oil into a mixer at room temperature, and uniformly stirring and mixing to ensure that the SEBS fully absorbs the white oil;
s2, adding polypropylene, glass fiber, n-butylbenzene phthalic anhydride, a stabilizer, an antioxidant and modified nano calcium carbonate into a mixer, mixing with SEBS absorbing white oil, and uniformly stirring and mixing to obtain a mixture;
s3, throwing the mixture into a feed inlet of a double-screw extruder, and extruding the mixture from a discharge outlet of the double-screw extruder to obtain the injection molding high-transparency TPE material.
By adopting the technical scheme, through the uniform mixing of the SEBS and the white oil, other components added later can be ensured to be fully dissolved with the SEBS/white oil system, and the uniformity of materials is ensured. The reinforcing agents such as polypropylene, glass fiber, n-butylbenzene phthalic anhydride, stabilizing agent, antioxidant, modified nano calcium carbonate and the like are added into the SEBS which is absorbed with white oil, so that the strength, rigidity and durability of the material can be improved, the mechanical property of the injection molding high-transparency TPE material is enhanced, and meanwhile, the thermal stability and barrier property are improved.
In summary, the present application has the following beneficial effects:
1. because the glass fiber adopted by the TPE material has high strength and rigidity, the mechanical property of the TPE material can be effectively enhanced. Under the high-temperature environment, the glass fiber can effectively inhibit the deformation and shrinkage of the TPE material, and improve the dimensional stability and heat resistance of the TPE material. The glass fiber has good heat conductivity, can effectively transfer heat from outside to inside, and reduces the temperature gradient in the material, so that the thermal stress generated by the material due to temperature change is reduced, and the heat stability of the TPE material is effectively improved through the mixing of the glass fiber and the TPE material. N-butylbenzene phthalic anhydride is a heat stabilizer, and can effectively prevent thermal decomposition reaction of TPE materials under high temperature conditions. N-butylbenzene phthalic anhydride can be subjected to crosslinking reaction with polymer molecular chains in the TPE material to form a three-dimensional network structure. The cross-linked structure can improve the thermal stability and heat resistance of the material, so that the material can maintain good mechanical property and dimensional stability at high temperature.
2. The modified nano calcium carbonate is preferably adopted in the application, has smaller particle size and larger specific surface area, and can provide more effective enhanced contact points. The strength, the rigidity and the durability of the injection molding high-transparency TPE material can be enhanced by adding the modified nano calcium carbonate, so that the injection molding high-transparency TPE material has better load capacity in application. Because the modified nano calcium carbonate has higher purity and good heat conduction performance, the heat can be effectively dispersed and absorbed by adding the modified nano calcium carbonate, and the hot spot temperature of the material is reduced. The thermal stability of the injection molding-level high-transparency TPE material is further improved, the risks of thermal decomposition and oxidation reaction are reduced, and the service life of the injection molding-level high-transparency TPE material is prolonged.
3. According to the method, through uniform mixing of the SEBS and the white oil, other components added later can be fully dissolved with the SEBS/white oil system, and uniformity of materials is guaranteed. The reinforcing agents such as polypropylene, glass fiber, n-butylbenzene phthalic anhydride, stabilizing agent, antioxidant, modified nano calcium carbonate and the like are added into the SEBS which is absorbed with white oil, so that the strength, rigidity and durability of the material can be improved, the mechanical property of the injection molding high-transparency TPE material is enhanced, and meanwhile, the thermal stability and barrier property are improved.
Detailed Description
The present application is described in further detail below with reference to examples.
Preparation example of glass fiber
Preparation example 1
A1, adding 10kg of glass raw materials with silicon dioxide purity more than or equal to 99% into a glass melting furnace, heating to 1400 ℃, and preserving heat to enable the glass raw materials to be melted into molten glass;
a2, stretching the molten glass into a plurality of parallel glass fibers with the diameter of 5-15 mu m by using a spraying device, and rapidly cooling the pulled glass fibers;
a3, placing the glass fiber into 5kg of a dilute hydrochloric acid solution with the concentration of 13% (w/v) for pickling, and cleaning the pickled glass fiber for 2 times by adopting deionized water;
a4, mixing 2.5kg of titanium isopropoxide with isopropanol, stirring and heating to 50 ℃ to obtain a uniform coating solution, immersing glass fibers in the coating solution, carrying out ultrasonic vibration on the coating solution for 8min, standing for 3h, taking out the glass fibers after standing, transferring the glass fibers to a drying box, drying at 110 ℃, cooling to room temperature after drying is finished, and cutting the glass fibers into glass fibers with the length of 2-4 mm.
Preparation example 2
A1, adding 10kg of glass raw materials with silicon dioxide purity more than or equal to 99% into a glass melting furnace, heating to 1400 ℃, and preserving heat to enable the glass raw materials to be melted into molten glass;
a2, stretching the molten glass into a plurality of parallel glass fibers with the diameter of 5-15 mu m by using a spraying device, and rapidly cooling the pulled glass fibers;
a3, placing the glass fiber into 5kg of a dilute hydrochloric acid solution with the concentration of 13% (w/v) for pickling, and cleaning the pickled glass fiber for 2 times by adopting deionized water;
a4, mixing 2kg of titanium isopropoxide with isopropanol, stirring and heating to 50 ℃ to obtain a uniform coating solution, immersing glass fibers in the coating solution, carrying out ultrasonic vibration on the coating solution for 8min, standing for 3h, taking out the glass fibers after standing, transferring the glass fibers to a drying box, drying at 110 ℃, cooling to room temperature after drying is finished, and cutting the glass fibers into glass fibers with the length of 2-4 mm.
Preparation example 3
A1, adding 10kg of glass raw materials with silicon dioxide purity more than or equal to 99% into a glass melting furnace, heating to 1400 ℃, and preserving heat to enable the glass raw materials to be melted into molten glass;
a2, stretching the molten glass into a plurality of parallel glass fibers with the diameter of 5-15 mu m by using a spraying device, and rapidly cooling the pulled glass fibers;
a3, placing the glass fiber into 5kg of a dilute hydrochloric acid solution with the concentration of 13% (w/v) for pickling, and cleaning the pickled glass fiber for 2 times by adopting deionized water;
and A4, mixing 3kg of titanium isopropoxide with isopropanol, stirring and heating to 50 ℃ to obtain a uniform coating solution, immersing glass fibers in the coating solution, carrying out ultrasonic vibration on the coating solution for 8min, standing for 3h, taking out the glass fibers after standing, transferring the glass fibers to a drying box, drying at 110 ℃, cooling to room temperature after drying is finished, and cutting the glass fibers into glass fibers with the length of 2-4 mm.
Preparation example of modified nano calcium carbonate
Preparation example 4
B1, mixing and uniformly stirring 10kg of nano calcium carbonate particles with 5kg of tartaric acid, and carrying out vacuum drying at 100 ℃ to obtain modified nano calcium carbonate;
and B2, washing the modified nano calcium carbonate for 2 times by adopting absolute ethyl alcohol, and then carrying out vacuum drying.
Preparation example 5
B1, mixing and uniformly stirring 10kg of nano calcium carbonate particles with 4kg of tartaric acid, and carrying out vacuum drying at 100 ℃ to obtain modified nano calcium carbonate;
and B2, washing the modified nano calcium carbonate for 2 times by adopting absolute ethyl alcohol, and then carrying out vacuum drying.
Preparation example 6
B1, mixing 10kg of nano calcium carbonate particles with 6kg of tartaric acid, uniformly stirring, and carrying out vacuum drying at 100 ℃ to obtain modified nano calcium carbonate;
and B2, washing the modified nano calcium carbonate for 2 times by adopting absolute ethyl alcohol, and then carrying out vacuum drying.
Examples
Example 1
A preparation method of an injection molding type high-transparency TPE material comprises the following steps:
s1, sequentially adding 12kg of SEBS and 10kg of white oil into a mixer at room temperature, and uniformly stirring and mixing to ensure that the SEBS fully absorbs the white oil;
s2, adding 2kg of polypropylene, 4kg of glass fiber, 3kg of n-butylbenzene phthalic anhydride, 0.1kg of stabilizer and 0.1kg of bisphenol A into a mixer, mixing with SEBS absorbed with white oil, heating to 180 ℃, preserving heat, and stirring and mixing uniformly to obtain a mixture;
s3, throwing the mixture into a feed inlet of a double-screw extruder, and extruding the mixture from a discharge outlet of the double-screw extruder to obtain the injection molding high-transparency TPE material.
Wherein, the glass fiber is prepared by preparation example 1, and the stabilizer is 30 percent of 2-hydroxy phenyl benzimidazole and 70 percent of methyl tri (2-ethylhexyl) stannoic acid.
Example 2
A preparation method of an injection molding type high-transparency TPE material comprises the following steps:
s1, sequentially adding 18kg of SEBS and 15kg of white oil into a mixer at room temperature, and uniformly stirring and mixing to ensure that the SEBS fully absorbs the white oil;
s2, adding 4kg of polypropylene, 6kg of glass fiber, 5kg of n-butylbenzene phthalic anhydride, 0.2kg of stabilizer and 0.5kg of bisphenol A into a mixer, mixing with SEBS absorbed with white oil, heating to 180 ℃, preserving heat, and stirring and mixing uniformly to obtain a mixture;
s3, throwing the mixture into a feed inlet of a double-screw extruder, and extruding the mixture from a discharge outlet of the double-screw extruder to obtain the injection molding high-transparency TPE material.
Wherein, the glass fiber is prepared by preparation example 1, and the stabilizer is 30 percent of 2-hydroxy phenyl benzimidazole and 70 percent of methyl tri (2-ethylhexyl) stannoic acid.
Example 3
A preparation method of an injection molding type high-transparency TPE material comprises the following steps:
s1, sequentially adding 15kg of SEBS and 13kg of white oil into a mixer at room temperature, and uniformly stirring and mixing to ensure that the SEBS fully absorbs the white oil;
s2, adding 3kg of polypropylene, 5kg of glass fiber, 4kg of n-butylbenzene phthalic anhydride, 1.15kg of stabilizer and 0.3kg of bisphenol A into a mixer, mixing with SEBS absorbed with white oil, heating to 180 ℃, preserving heat, and stirring and mixing uniformly to obtain a mixture;
s3, throwing the mixture into a feed inlet of a double-screw extruder, and extruding the mixture from a discharge outlet of the double-screw extruder to obtain the injection molding high-transparency TPE material.
Wherein, the glass fiber is prepared by preparation example 1, and the stabilizer is 30 percent of 2-hydroxy phenyl benzimidazole and 70 percent of methyl tri (2-ethylhexyl) stannoic acid.
Example 4
A preparation method of an injection molding type high-transparency TPE material comprises the following steps:
s1, sequentially adding 15kg of SEBS and 13kg of white oil into a mixer at room temperature, and uniformly stirring and mixing to ensure that the SEBS fully absorbs the white oil;
s2, adding 3kg of polypropylene, 5kg of glass fiber, 4kg of n-butylbenzene phthalic anhydride, 0.15kg of stabilizer, 0.3kg of bisphenol A and 2kg of modified nano calcium carbonate into a mixer, mixing with SEBS absorbing white oil, heating to 180 ℃, preserving heat, and stirring and mixing uniformly to obtain a mixture;
s3, throwing the mixture into a feed inlet of a double-screw extruder, and extruding the mixture from a discharge outlet of the double-screw extruder to obtain the injection molding high-transparency TPE material.
Wherein, the glass fiber is prepared by preparation example 1, the modified nano calcium carbonate is prepared by preparation example 4, the particle size of the modified nano calcium carbonate is 50-200nm, and the purity of the modified nano calcium carbonate is more than or equal to 98%; the stabilizer was 30% 2-hydroxyphenyl benzimidazole and 70% methyltris (2-ethylhexyl) stannoic acid.
Example 5
A method for preparing injection molding high-transparency TPE material, which is different from example 4 in that: the antioxidant is dimercaptosuccinic acid.
Example 6
A method for preparing injection molding high-transparency TPE material, which is different from example 4 in that: glass fibers were prepared from preparation 2.
Example 7
A method for preparing injection molding high-transparency TPE material, which is different from example 4 in that: glass fibers were prepared from preparation 3.
Example 8
A method for preparing injection molding high-transparency TPE material, which is different from example 4 in that: modified nano calcium carbonate was prepared from preparation example 5.
Example 9
A method for preparing injection molding high-transparency TPE material, which is different from example 4 in that: modified nano calcium carbonate was prepared from preparation example 6.
Example 10
A method for preparing injection molding high-transparency TPE material, which is different from example 4 in that: glass fibers are commercially available without special treatment.
Comparative example
Comparative example 1
A preparation method of an injection molding type high-transparency TPE material comprises the following steps:
s1, sequentially adding 15kg of SEBS and 13kg of white oil into a mixer at room temperature, and uniformly stirring and mixing to ensure that the SEBS fully absorbs the white oil;
s2, adding 3kg of polypropylene, 4kg of n-butylbenzene phthalic anhydride, 0.15kg of stabilizer, 0.3kg of bisphenol A and 2kg of modified nano calcium carbonate into a mixer, mixing with SEBS absorbed with white oil, heating to 180 ℃, preserving heat, stirring and mixing uniformly to obtain a mixture;
s3, throwing the mixture into a feed inlet of a double-screw extruder, and extruding the mixture from a discharge outlet of the double-screw extruder to obtain the injection molding high-transparency TPE material.
Wherein, the modified nano calcium carbonate is prepared by preparation example 4, the particle diameter of the modified nano calcium carbonate is 50-200nm, and the purity of the modified nano calcium carbonate is more than or equal to 98%; the stabilizer was 30% 2-hydroxyphenyl benzimidazole and 70% methyltris (2-ethylhexyl) stannoic acid.
Comparative example 2
A preparation method of an injection molding type high-transparency TPE material comprises the following steps:
s1, sequentially adding 15kg of SEBS and 13kg of white oil into a mixer at room temperature, and uniformly stirring and mixing to ensure that the SEBS fully absorbs the white oil;
s2, adding 3kg of polypropylene, 5kg of glass fiber, 0.15kg of stabilizer, 0.3kg of bisphenol A and 2kg of modified nano calcium carbonate into a mixer, mixing with SEBS absorbed with white oil, heating to 180 ℃, preserving heat, and stirring and mixing uniformly to obtain a mixture; s3, throwing the mixture into a feed inlet of a double-screw extruder, and extruding the mixture from a discharge outlet of the double-screw extruder to obtain the injection molding high-transparency TPE material.
Wherein, the glass fiber is prepared by preparation example 1, the modified nano calcium carbonate is prepared by preparation example 4, the particle size of the modified nano calcium carbonate is 50-200nm, and the purity of the modified nano calcium carbonate is more than or equal to 98%; the stabilizer was 30% 2-hydroxyphenyl benzimidazole and 70% methyltris (2-ethylhexyl) stannoic acid.
Comparative example 3
A preparation method of an injection molding type high-transparency TPE material comprises the following steps:
s1, sequentially adding 15kg of SEBS and 13kg of white oil into a mixer at room temperature, and uniformly stirring and mixing to ensure that the SEBS fully absorbs the white oil;
s2, adding 3kg of polypropylene, 5kg of glass fiber, 4kg of n-butylbenzene phthalic anhydride, 0.15kg of stabilizer, 0.3kg of bisphenol A and 2kg of nano calcium carbonate into a mixer, mixing with SEBS absorbing white oil, heating to 180 ℃, preserving heat, stirring and mixing uniformly to obtain a mixture;
s3, throwing the mixture into a feed inlet of a double-screw extruder, and extruding the mixture from a discharge outlet of the double-screw extruder to obtain the injection molding high-transparency TPE material.
Wherein, the glass fiber is prepared by preparation example 1, the grain diameter of the nano calcium carbonate is 50-200nm, and the purity of the nano calcium carbonate is more than or equal to 98%; the stabilizer was 30% 2-hydroxyphenyl benzimidazole and 70% methyltris (2-ethylhexyl) stannoic acid.
Performance test
Detection method
Tensile Properties
The test was performed using an electronic universal tensile tester, and injection-molded highly transparent TPE materials were prepared as samples according to the specification of type 1BA in ISO 527-2-2012 "plastic tensile testing method", respectively, in examples 1-9 and comparative examples 1-3. The test was carried out at room temperature at a tensile speed of 200mm/min, 5 bars were tested for each sample, and the median value was taken from the test data.
Thermal stability properties:
at N 2 Under the environment, 10mg of samples are respectively weighed from examples 1-9 and comparative examples 1-3, placed in a crucible, and tested by adopting a thermogravimetric analyzer, wherein the temperature range is 20-400 ℃ and the temperature rising rate is 20K/min.
TABLE 1 Experimental data for examples 1-9 and comparative examples 1-3
| Tensile Strength/MPa | Heat loss/% | |
| Example 1 | 14.1 | 20.7 |
| Example 2 | 14.6 | 19.8 |
| Example 3 | 14.8 | 19.2 |
| Example 4 | 16.2 | 17.3 |
| Example 5 | 15.3 | 18.1 |
| Example 6 | 16.0 | 17.9 |
| Example 7 | 15.7 | 17.5 |
| Example 8 | 15.6 | 17.4 |
| Example 9 | 15.9 | 17.7 |
| Example 10 | 14.5 | 22.3 |
| Comparative example 1 | 7.1 | 42.6 |
| Comparative example 2 | 12.8 | 31.8 |
| Comparative example 3 | 9.3 | 37.5 |
As can be seen from the combination of example 4 and comparative example 1 and the combination of table 1, comparative example 1 differs from example 4 in that no glass fiber is added, and from the test results, it can be seen that since glass fiber obtained in preparation example 1 is added in example 4, example 4 is significantly higher in both tensile strength and thermal stability than comparative example 1, thereby demonstrating that glass fiber can effectively inhibit deformation and shrinkage of TPE material under high temperature environment, improving dimensional stability and heat resistance thereof. The glass fiber has good heat conductivity, can effectively transfer heat from outside to inside, and reduces the temperature gradient in the material, so that the thermal stress generated by the material due to temperature change is reduced, and the heat stability of the TPE material is effectively improved through the mixing of the glass fiber and the TPE material.
As can be seen from the combination of example 4 and comparative example 2 and the combination of table 1, comparative example 2 has no n-butylbenzene phthalic anhydride added thereto, and thus comparative example 2 has significantly lower thermal stability than example 4, thereby indicating that n-butylbenzene phthalic anhydride can effectively prevent thermal decomposition reaction of TPE materials under high temperature conditions. N-butylbenzene phthalic anhydride can be subjected to crosslinking reaction with polymer molecular chains in the TPE material to form a three-dimensional network structure. The cross-linked structure can improve the thermal stability and heat resistance of the material, so that the material can maintain good mechanical property and dimensional stability at high temperature.
It can be seen from the combination of example 4 and comparative example 3 and the table 1 that the nano calcium carbonate which is not modified is used in comparative example 3, and the tensile strength and thermal stability of comparative example 3 are much lower than those of example 4, thus demonstrating that tartaric acid as a surface modifier can form a thin and uniform coating on the surface of nano calcium carbonate particles. The coating can enhance the interfacial adhesion between the nano calcium carbonate and the TPE matrix and improve the compatibility and the bonding strength of the nano calcium carbonate and the TPE matrix. The modified nano calcium carbonate has better dispersibility after being stirred. The modified nano calcium carbonate added into the injection molding high-transparency TPE material can be better dispersed in the matrix, and particle aggregation and agglomeration phenomena are reduced. Good dispersion properties help to improve the uniformity and performance stability of the material.
It can be seen in combination with examples 1-3 and with Table 1 that by adjusting the amounts of the components, the thermal stability of the TPE material can be further improved.
It can be seen in combination with examples 3-4 and with table 1 that the modified nano calcium carbonate has a smaller particle size and a larger specific surface area, and thus can provide more effective enhanced contact points. The strength, the rigidity and the durability of the injection molding high-transparency TPE material can be enhanced by adding the modified nano calcium carbonate, so that the injection molding high-transparency TPE material has better load capacity in application. Because the modified nano calcium carbonate has higher purity and good heat conduction performance, the heat can be effectively dispersed and absorbed by adding the modified nano calcium carbonate, and the hot spot temperature of the material is reduced. The thermal stability of the injection molding-level high-transparency TPE material is further improved, the risks of thermal decomposition and oxidation reaction are reduced, and the service life of the injection molding-level high-transparency TPE material is prolonged.
It can be seen in combination with examples 4-10 and with Table 1 that the coating treatment of the coating formed by incorporating titanium isopropoxide has better stability in high temperature environments. The strength, the rigidity and the durability of the injection molding high-transparency TPE material can be enhanced by adding the modified nano calcium carbonate, and the thermal conductivity is good, so that the heat can be effectively dispersed and absorbed by adding the modified nano calcium carbonate, and the hot spot temperature of the material is reduced. By adding these antioxidants, the TPE material can be protected from degradation, discoloration and loss of performance due to oxidation. 2-hydroxy phenylbenzimidazole and methyl tris (2-ethylhexyl) stannoic acid are effective in preventing thermal decomposition of TPE materials during processing and use. By adding the two stabilizers, the degradation and oxidation phenomena of the material under the high temperature condition can be reduced, and the thermal stability and durability of the TPE material are improved.
The present embodiment is merely illustrative of the present application and is not intended to be limiting, and those skilled in the art, after having read the present specification, may make modifications to the present embodiment without creative contribution as required, but is protected by patent laws within the scope of the claims of the present application.
Claims (8)
1. An injection molding type high-transparency TPE material is characterized by comprising the following SEBS in parts by weight: 120-180 parts of white oil: 100-150 parts of polypropylene: 20-40 parts of glass fiber: 40-60 parts of n-butylbenzene phthalic anhydride: 30-50 parts of stabilizer: 1-2 parts of an antioxidant: 1-5 parts.
2. The injection molded highly transparent TPE material according to claim 1, wherein: the glass fiber has a length of 2-4mm and a diameter of 5-15 μm.
3. The injection molded highly transparent TPE material according to claim 1, wherein: the preparation method of the glass fiber comprises the following steps:
a1, adding a glass raw material with silicon dioxide purity more than or equal to 99% into a glass melting furnace, heating to 1300-1500 ℃, and preserving heat to melt the glass raw material into molten glass;
a2, stretching the molten glass into a plurality of parallel glass fibers by using a spraying device, and rapidly cooling the pulled glass fibers;
a3, placing the glass fiber into a sufficient amount of 10-15% (w/v) dilute hydrochloric acid solution for pickling, and cleaning the pickled glass fiber for 1-3 times by adopting deionized water;
and A4, mixing titanium isopropoxide accounting for 20-30% of the mass of the glass fiber with isopropanol, stirring and heating to 40-60 ℃ to obtain a uniform coating solution, immersing the glass fiber in the coating solution, carrying out ultrasonic vibration on the coating solution for 5-10min, standing for 2-4h, taking out the glass fiber after standing, transferring the glass fiber to a drying box, drying at the temperature of 100-120 ℃, and cooling the glass fiber to room temperature after drying.
4. The injection molded highly transparent TPE material according to claim 1, wherein: the modified nano calcium carbonate comprises, by weight, 10-30 parts of modified nano calcium carbonate, wherein the particle size of the modified nano calcium carbonate is 50-200nm, and the purity of the modified nano calcium carbonate is more than or equal to 98%.
5. The injection molded highly transparent TPE material according to claim 4, wherein: the preparation method of the modified nano calcium carbonate comprises the following steps:
b1, mixing and uniformly stirring nano calcium carbonate particles and tartaric acid, wherein the mass ratio of the nano calcium carbonate particles to the tartaric acid is 5 (2-3), and carrying out vacuum drying at 80-120 ℃ to obtain modified nano calcium carbonate;
and B2, washing the modified nano calcium carbonate for 1-3 times by using absolute ethyl alcohol, and then carrying out vacuum drying.
6. The injection molded highly transparent TPE material according to claim 1, wherein: the stabilizer comprises 20% -40% of 2-hydroxy phenyl benzimidazole and 60% -80% of methyl tri (2-ethylhexyl) stannoic acid.
7. The injection molded highly transparent TPE material according to claim 1, wherein: the antioxidant includes one or more of bisphenol a or dimercaptosuccinic acid.
8. A method for preparing the injection molding-level high-transparency TPE material according to any one of claims 1-7, characterized by: the method comprises the following steps:
s1, sequentially adding SEBS and white oil into a mixer at room temperature, and uniformly stirring and mixing to ensure that the SEBS fully absorbs the white oil;
s2, adding polypropylene, glass fiber, n-butylbenzene phthalic anhydride, a stabilizer, an antioxidant and modified nano calcium carbonate into a mixer, mixing with SEBS absorbing white oil, and uniformly stirring and mixing to obtain a mixture;
s3, throwing the mixture into a feed inlet of a double-screw extruder, and extruding the mixture from a discharge outlet of the double-screw extruder to obtain the injection molding high-transparency TPE material.
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Non-Patent Citations (2)
| Title |
|---|
| 上海市化轻公司第二化工供应部编: "《化工产品应用手册 合成材料助剂•食品添加剂》", 31 May 1989, 上海科学技术出版社出版, pages: 140 * |
| 熊方武，余传隆，白秋江，修成娟主编: "《中国临床药物大辞典 化学药卷 上》", vol. 1, 31 August 2018, 中国医药科技出版社, pages: 1717 * |
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