CN114806191B - Styrene elastomer TPS material composition and preparation and application thereof - Google Patents
Styrene elastomer TPS material composition and preparation and application thereof Download PDFInfo
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- CN114806191B CN114806191B CN202210238343.6A CN202210238343A CN114806191B CN 114806191 B CN114806191 B CN 114806191B CN 202210238343 A CN202210238343 A CN 202210238343A CN 114806191 B CN114806191 B CN 114806191B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
- C08L91/06—Waxes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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Abstract
The invention relates to a styrene elastomer TPS material composition, and preparation and application thereof, and the composition comprises the following components: high melt index PP resin, ultra-high melt index PP resin, low molecular weight linear SEBS, high molecular weight linear SEBS, paraffin oil, antioxidant, light stabilizer, handfeel agent and filler. The TPS material with high fluidity and low glossiness is prepared by the mutual matching and synergistic effect of the high melt index PP resin, the non-melt-blown ultra-high melt index PP resin, the low-component linear SEBS and the high-component linear SEBS and the components such as the lubricant, the filler and the like.
Description
Technical Field
The invention belongs to the technical field of thermoplastic elastomers, and particularly relates to a styrene elastomer TPS material composition, and preparation and application thereof.
Background
Compared with thermosetting rubber, the thermoplastic elastomer has the excellent elasticity of the thermosetting rubber and the thermoplastic processability of plastics, has the advantages of simple and convenient processing, continuous production, low comprehensive cost, environmental protection, recycling and the like, and is widely used in the fields of automobiles, electronic and electric parts, industrial parts, daily necessities and the like.
Thermoplastic elastomers are of a wide variety, and common thermoplastic elastomer varieties include polyvinyl chloride (PVC) elastomers, block styrene elastomers (TPS), dynamic fully vulcanized thermoplastic elastomers (TPV), polyurethane elastomers (TPU), and the like. PVC, TPV and TPS are widely applied in thermoplastic elastomer materials of automobile interiors, wherein PVC elastomers are gradually replaced by other elastomers due to poor high and low temperature resistance, high specific gravity and halogen-containing non-environment-friendly materials; TPV (EPDM/PP) products have excellent high and low temperature resistance, lower compression set and lower gloss, but because of the material involved in dynamic vulcanization, the product preparation process is more complex, the product cost is higher and the smell is larger; TPS has excellent low temperature resistance, low odor, excellent resilience and good processability. However, for larger part products, not only is the material required to have good flowability, but the product is also required to maintain a lower gloss. After injection molding of TPS material, the appearance defects of tiger skin lines, molding lacked glue and the like may be brought due to the poor flowability of the material, and the TPS product with high flowability is difficult to have both high flowability and very low glossiness.
Disclosure of Invention
Based on the defects existing in the prior art, the technical problem to be solved by the invention is to provide a styrene elastomer TPS material composition and preparation and application thereof, and the TPS material has ultrahigh fluidity, heat resistance and lower glossiness.
The invention provides a TPS material composition, which comprises the following components in parts by weight:
wherein the melt index of the high melt index PP resin is between 45 and 60g/10min under the condition of 230 ℃ and 2.16kg,
the melt index of the ultra-high melt index PP resin is 230 ℃ and 80-130g/10min under the condition of 2.16kg,
the weight average molecular weight of the low molecular weight SEBS is 40000-70000 g/mol,
the weight average molecular weight of the high molecular weight SEBS is 200000 ～ 250000g/mol.
The weight average molecular weight test was performed by gel chromatography, specifically by calibration with styrene markings.
Preferably, the open flash point of the paraffinic oil is greater than or equal to 250 ℃.
The flash point of the opening is tested according to the GB/T267-1988 standard method, and the temperature rising speed is 1 ℃/min.
Further, preferably, the paraffinic oil is a high flash point paraffinic oil free of polycyclic aromatic hydrocarbons.
The paraffin oil does not contain polycyclic aromatic hydrocarbon, and is more environment-friendly. The open flash point is higher, and the TPV product prepared by the method has better heat resistance and lower haze.
Preferably, the antioxidant is one or more of antioxidant 1010, antioxidant 1076, antioxidant 1790, antioxidant 168 and antioxidant DLTP.
Preferably, the light stabilizer is a compound of a hindered amine light stabilizer and a triazine light stabilizer; wherein preferably, the hindered amine light stabilizer is one or more of a light stabilizer 622, a light stabilizer 944, a light stabilizer 3853 and a light stabilizer 123; the triazine light stabilizer is one or more of UV-234, UV-236 and UV-237.
More preferably, the light stabilizer is a mixture of hindered amine light stabilizer and triazine light stabilizer compounded in a weight ratio of 3:2.
Preferably, the handfeel agent is one or more of vinyl bis-stearamide, erucamide, zinc stearate, magnesium stearate and organic silicone.
Preferably, the filler is white carbon black.
Preferably, the components comprise, by weight:
the invention provides a preparation method of the TPS material composition, which comprises the following steps:
(1) Firstly, mixing and standing low molecular weight linear SEBS, high molecular weight linear SEBS and paraffin oil for more than 3 days to obtain pre-filled oil SEBS;
(2) And mixing the pre-filled oil SEBS, the filler, the high-melt-index PP resin, the ultra-high-melt-index PP material, the antioxidant, the light stabilizer and the handfeel agent, and performing melt extrusion granulation to obtain the TPS material.
Preferably, the equipment adopted in the step (1) is oil-filling equipment, wherein the screw speed of the oil-filling equipment is 40-80 r/min, and the mixing temperature is 40-80 ℃;
preferably, in the step (2), a double-screw extruder is adopted for melt extrusion, wherein the screw rotating speed is 300-450 r/min, and the melt mixing temperature is 140-190 ℃;
the TPS material composition is applied to automotive interiors.
According to the invention, through the synergistic combination of the high melt index PP resin and the ultra-high melt index PP resin, the melt viscosity of the high melt index PP resin is similar to the low molecular weight linear SEBS viscosity, so that the blending dispersion effect is facilitated; the ultra-high melt index PP resin can provide higher fluidity; the low molecular weight linear SEBS and the high melt index PP resin have good melt viscosity matching, have better blending effect, and the high molecular weight linear SBES has larger molecular weight, better oil locking capability and heat resistance, and the high molecular weight linear SEBS has serious molecular entanglement due to high molecular weight, relatively poorer dispersibility when the viscosity difference is larger, and forms a coarser surface, thereby improving the heat resistance of the material and reducing the glossiness of the material. Therefore, the heat resistance, the dispersion property and the glossiness of the TPS material can be optimized by combining the high melt index PP resin and the ultra high melt index PP resin and combining the low molecular weight linear SEBS and the high molecular weight linear SEBS.
The addition of the white carbon black has the advantages of reducing the initial glossiness of the material, enhancing the SEBS (styrene-ethylene-butylene-styrene) due to the extinction effect of the porous structure of the white carbon black, improving the oil locking capability of the material, improving the heat resistance of the TPS material and reducing the change of glossiness after aging.
Advantageous effects
The TPS material with high fluidity, low glossiness and aging resistance is prepared by the mutual matching and synergistic effect of the high melt index PP resin, the ultrahigh melt index PP resin, the low-component linear SEBS and the high-component linear SEBS.
Detailed Description
The invention will be further illustrated with reference to specific examples. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. Further, it is understood that various changes and modifications may be made by those skilled in the art after reading the teachings of the present invention, and such equivalents are intended to fall within the scope of the claims appended hereto.
1. Table 1 the components involved in the examples and comparative examples
The hand feeling agent, the filler, the antioxidant and the light stabilizer adopted in the parallel experiment are all the same commercial products.
2. Examples and comparative examples the prepared TPS materials were tested for performance by the following specific methods:
melt index:
the test is carried out according to ISO 1133-1-2011 standard method, and the temperature is 230 ℃ and the condition is 2.16 kg.
Gloss level:
the test conditions were 60℃angular gloss as measured according to ISO 2813-2014 standard.
Gloss after aging:
TPS is firstly subjected to heat aging according to an ISO 188-2011 standard method, the aging condition is 125 ℃ for 24 hours, taken out and cooled to room temperature, and then the glossiness is detected according to an ISO 2813-2014 standard method, and the testing condition is 60 degrees.
Shore A hardness: the test conditions were 23℃and the test pressure was 1kg,15 seconds readings, measured according to ISO 868-2003 standard.
Examples 1 to 6
The TPS material comprises the following components in parts by weight as shown in Table 2.
The preparation method comprises the following steps:
(1) The low molecular weight linear SEBS, the high molecular weight linear SEBS and the paraffin oil are fully mixed in the oil filling machine equipment in advance to prepare the pre-filled oil SEBS, and the pre-filled oil SEBS powder needs to be parked for more than 3 days so that the paraffin oil fully enters the SEBS molecular chain. Wherein the screw speed of the oil filling machine is 40-80 r/min, and the mixing temperature is 40-80 ℃. Oil filling machine rotation speed influence: the low oil charge efficiency of rotational speed, the rotational speed is too fast, and the material generates heat soon, and the caking adhesion of material can be made to the too high temperature, influences the production processability of follow-up material.
(2) And mixing the pre-filled oil SEBS, the filler, the high-melt-index PP resin, the ultra-high-melt-index PP resin, the antioxidant, the light stabilizer and the handfeel agent, adding the mixture into a double-screw extruder, and carrying out melt extrusion granulation to obtain the TPS material. Wherein the screw rotating speed of the double screw extruder is 300-450 r/min, and the melting mixing temperature is 140-190 ℃.
TABLE 2 component content (parts by weight) of TPS materials of examples 1 to 6
Examples 7 to 12
The components of TPS materials in parts by weight are shown in Table 3, and the preparation method is the same as that of example 1.
TABLE 3 component content (parts by weight) of TPS materials of examples 7-12
Implement 13-17
The components of TPS materials in parts by weight are shown in Table 4, and the preparation method is the same as that of example 1.
TABLE 4 component content (parts by weight) of TPS materials of examples 13 to 17
Comparative examples 1 to 8
The TPS material is prepared by the same method as in example 1, wherein the contents of the components in the TPS material are shown in Table 5 in parts by weight.
TABLE 5 component content (parts by weight) of TPS materials of comparative examples 1 to 8
TABLE 6 TPS Material test results for examples 1-6
Table 7 shows the TPS material test results for examples 7-17
TABLE 8 TPS Material test results for comparative examples 1-8
As can be seen from the embodiment 1 and the comparative examples 1-4, the high melt index PP resin and the ultra-high melt index PP resin are compounded cooperatively, the low-component linear SEBS and the high-component linear SEBS are compounded cooperatively, so that the TPS material obtained finally has ultra-high fluidity, low glossiness and ageing resistance and good comprehensive performance.
Claims (10)
1. TPS material composition comprises the following components in parts by weight:
wherein the melt index of the high melt index PP resin is between 45 and 50g/10min under the condition of 2.16kg at 230 ℃,
the melt index of the ultra-high melt index PP resin is 100-120g/10min under the condition of 230 ℃ and 2.16kg,
the weight average molecular weight of the low molecular weight SEBS is 50000-70000 g/mol,
the weight average molecular weight of the high molecular weight SEBS is 200000 ～ 220000g/mol.
2. The composition of claim 1, wherein the paraffinic oil has an open flash point of greater than or equal to 250 ℃.
3. The composition of claim 1, wherein the antioxidant is one or more of antioxidant 1010, antioxidant 1076, antioxidant 1790, antioxidant 168, antioxidant DLTP.
4. The composition of claim 1, wherein the light stabilizer is a complex of a hindered amine light stabilizer and a triazine light stabilizer; wherein the hindered amine light stabilizer is one or more of a light stabilizer 622, a light stabilizer 944, a light stabilizer 3853 and a light stabilizer 123; the triazine light stabilizer is one or more of UV-234, UV-236 and UV-237.
5. The composition of claim 1, wherein the hand feeling agent is one or more of vinyl bis-stearamide, erucamide, zinc stearate, magnesium stearate, and organic silicone.
6. The composition of claim 1 wherein the filler is white carbon black.
7. The composition of claim 1, wherein the composition comprises, in parts by weight:
8. a method of preparing the TPS material composition of claim 1 comprising:
(1) Firstly, mixing and standing low molecular weight linear SEBS, high molecular weight linear SEBS and paraffin oil for more than 3 days to obtain pre-filled oil SEBS;
(2) And mixing the pre-filled oil SEBS, the filler, the high-melt-index PP resin, the ultra-high-melt-index PP material, the antioxidant, the light stabilizer and the handfeel agent, and performing melt extrusion granulation to obtain the TPS material.
9. The composition of claim 8, wherein the equipment used in the mixing in step (1) is an oil filler equipment, wherein the screw speed of the oil filler is 40-80 r/min, and the mixing temperature is 40-80 ℃; and (2) adopting a double-screw extruder for melt extrusion, wherein the screw rotating speed is 300-450 r/min, and the melt mixing temperature is 140-190 ℃.
10. Use of the TPS material composition of claim 1 in automotive interiors.
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| CN102372893B (en) * | 2010-08-13 | 2013-01-02 | 上海锦湖日丽塑料有限公司 | Styrenic thermoplastic elastomer composition and preparation method thereof |
| CN105255202A (en) * | 2015-11-18 | 2016-01-20 | 南通普力马弹性体技术有限公司 | Wear-resistant and high-resilience-rate TPE trundle material used for adhering to PP and preparation method |
| CN105482239B (en) * | 2016-01-12 | 2017-11-17 | 盛嘉伦橡塑(深圳）股份有限公司 | Signal transmssion line thermoplastic elastic material and preparation method thereof |
| CN106543750A (en) * | 2016-11-18 | 2017-03-29 | 武汉理工大学 | A kind of TPE material of chemical blowing and preparation method thereof |
| KR20190140577A (en) * | 2018-06-12 | 2019-12-20 | 대일소재(주) | Olefinic thermoplastic silicon elastomer composite and molding article formed from the same |
| CN110452549B (en) * | 2019-08-12 | 2021-12-21 | 上海晨光文具股份有限公司 | Thermoplastic elastomer-silicone resin composite material and preparation method thereof |
| CN112745681B (en) * | 2020-12-30 | 2022-05-20 | 金发科技股份有限公司 | TPV material capable of being foamed by injection molding and preparation method and application thereof |
| CN112795105B (en) * | 2020-12-30 | 2022-04-19 | 金发科技股份有限公司 | High-fluidity scratch-resistant TPV material and preparation method and application thereof |
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| CN103740031A (en) * | 2013-12-23 | 2014-04-23 | 深圳市普特美橡塑原料有限公司 | Styrene-ethylene-butylene-styrene (SEBS) rubber composition and preparation method thereof |
| CN111607236A (en) * | 2020-05-28 | 2020-09-01 | 宁波泰甬汽车零部件有限公司 | High-fluidity low-gloss styrene-based thermoplastic elastomer material and preparation method thereof |
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