CN112646332B - Low-haze high-gloss PBT (polybutylene terephthalate) composite material and preparation method thereof - Google Patents
Low-haze high-gloss PBT (polybutylene terephthalate) composite material and preparation method thereof Download PDFInfo
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
The invention relates to a low-haze high-gloss PBT composite material and a preparation method thereof, wherein the composite material comprises 73-89 parts of PBT resin by weight; 10-25 parts of thermoplastic polyester elastomer TPEE; 0.2-0.5 part of antioxidant; 0.5 to 1.5 portions of other additives. The PBT composite material disclosed by the invention has the characteristics of low haze and high gloss, and after a haze experiment at 160 ℃/24h, the material is low in haze and high in gloss retention rate, and meets the performance requirements for manufacturing parts such as automobile lamp decorative rings, connectors and the like.
Description
Technical Field
The invention belongs to the technical field of modified PBT composite materials, and particularly relates to a low-haze high-gloss PBT material and a production method thereof, in particular to a material for a decorative ring of an automobile lamp.
Background
The car light is used as a part of the car body, not only a functional part, but also an appearance part, and is increasingly becoming a part of the key of the car model and the whole appearance. Besides appearance requirements, the functional requirements of the automobile lamp are based on the inspection that the defects of deformation, cracking, fog lamp and the like of the assembled lamp in various lighting tests and sports tests are avoided, and the requirements on materials are intensively reflected in the aspects of fluidity, heat distortion temperature, condensable components and mechanical properties. Particularly, the material has higher melt index so as to meet the requirements of complex structure and integrated molding of the car lamp; the heat distortion temperature is higher to adapt to the working condition that the automobile headlamp generates heat after being used for a long time; the shock resistance has relatively high impact strength so as to meet the requirements of vehicle lamp assembly, running vibration and the like; haze which influences the lighting effect does not appear in the lamp when very low condensable components are used for guaranteeing long-time lighting of the vehicle lamp.
The automobile lamps can be roughly divided into illuminating lamps and signal lamps in terms of functions, wherein the illuminating lamps comprise a headlamp, a front fog lamp and a rear fog lamp; the signal lamp comprises a tail lamp, a high-order brake lamp, a steering lamp, a daytime new car lamp and the like, the requirement of the former headlight is the highest on the whole, and the material which can be generally used for manufacturing the headlight can generally meet the requirements of other car lamps from the viewpoint of material use. The parts of a common head lamp comprise a lens, a lamp decorative ring, a reflector and a shell material, wherein the lens mainly comprises a raw material PC, the lamp decorative ring material generally comprises HT-PC, PC/ABS, PBT and the like, the reflector is generally a BMC material due to high use temperature price, and the shell material is mainly filled with a PP material. There are many materials used as a lamp trim including PP, PC/ABS, PBT and PBT/PET alloy, etc., and with the widespread use of halogen light sources and xenon light sources, the heat resistance of the headlamp material is required to be higher, and the PC/ABS material that has been used in common before can not meet the requirement of heat resistance, while the heat-resistant PC can meet the requirement of heat resistance, but the use of the material is limited due to its high price, and the PBT material is favored by host factories and parts suppliers due to its excellent heat distortion temperature, surface gloss and relatively low cost.
CN10266010B discloses a PBT material with high fluidity, high finish and no prime coating and a preparation method thereof, wherein a silicon mesoporous material with a pore diameter of 2-50 nanometers is added to control the migration of small molecules in the PBT material to an aluminum layer in a high-temperature environment, so that the problems of surface glossiness reduction of the aluminum layer and the like are caused.
CN102719060B discloses a high temperature-resistant high-gloss PET/PBT composite material and a preparation method thereof, and the components of the composite material are PET 100, PBT 20-40, mineral filler 10-40, toughening agent 3-10, antioxidant 0.3-0.6, processing aid 0.2-0.6, heat-resistant agent 0.5-1.2 and nucleating agent 0.5-1. The composite material has the advantages of PET and PBT, excellent forming and processing properties and improved temperature resistance. The patent does not address the problem of surface fogging during high temperature use.
Disclosure of Invention
The invention aims to solve the technical problem of providing a low-haze high-gloss PBT composite material so as to overcome the phenomenon that the surface of a car lamp decorative ring is hazy in the long-term use process under the high-temperature environment condition in the prior art.
One purpose of the invention is to provide a PBT composite material, which comprises the following components in parts by weight: 73-89 parts of PBT resin; 10-25 parts of thermoplastic polyester elastomer TPEE; 0.2-0.5 part of antioxidant; 0.5 to 1.5 portions of other additives.
Preferably, in the composition, the concentration of the terminal carboxyl groups of the PBT resin is less than 30meq/kg.
Preferably, in the composition, the concentration of the terminal amino groups of the PBT resin is less than 20meq/kg.
Preferably, in the above composition, the thermoplastic polyester elastomer TPEE is a linear block copolymer consisting of a high melting point, high hardness clean polyester hard segment and an amorphous polyether or polyester soft segment with a lower glass transition temperature. Preferably, the hard segment is an aromatic polyester. For example, a common aromatic polyester is PBT (polybutylene terephthalate), PET (polyethylene terephthalate), PTT (polytrimethylene terephthalate), or the like. Preferably, the soft segment (continuous phase) is an aliphatic polyester or polyether. For example, the aliphatic polyester is PGA (polyglycolide), PLLA (polylactide), PCL (polycaprolactone) or the like, and the polyether is PEG (polyethylene glycol), PPG (polypropylene glycol ether), PTMG (polytetrahydrofuran) or the like. Further, the hardness range is 30-82D Shore by adjusting the proportion of the soft segment to the soft segment.
Preferably, in the composition, the antioxidant comprises a primary antioxidant and a secondary antioxidant in a mass ratio of 1:1-2:1. Preferably, the primary antioxidant is hindered phenol, and the secondary antioxidant is thiodipropionate or phosphite.
Preferably, in the composition, the other additive is one or more of a light stabilizer, a lubricant, a mold release agent, an antistatic agent, a dye and a pigment.
The invention also aims to provide a preparation method of the PBT composite material, which comprises the following steps:
the first step is as follows: weighing the raw materials according to the weight ratio;
the second step: mixing the PBT resin, the thermoplastic polyester elastomer TPEE, the antioxidant and other additives which are respectively dried in advance at a high speed for later use;
the third step: feeding the mixed raw materials into a double-screw extruder provided with two vacuum devolatilization devices, wherein the vacuum degree is-0.08 MPa to-0.1 MPa, and extruding and granulating at the temperature of 230-260 ℃ to obtain the PBT composite material.
Preferably, the preparation method further comprises the following steps: respectively premixing two or more of the components, and feeding the premixed product into an extruder through one feed inlet or a plurality of feed inlets of a double-screw extruder; and two vacuum devolatilization devices are arranged on a screw cylinder of the extruder so as to remove small molecular substances generated in the process of melting and blending the materials in time and obtain a target product.
The invention also aims to provide application of the PBT composite material in the field of automobile industry. In particular to a material for a decorative ring of an automobile lamp.
Advantageous effects
The PBT composite material produced by adopting the low-end carboxyl resin PBT resin and the thermoplastic polyester elastic TPEE and adopting the two vacuum devolatilization devices has the characteristics of low haze and high gloss, and after a 160 ℃/24h haze experiment, the material has low haze and high gloss retention rate, and meets the performance requirements for manufacturing parts such as automobile lamp decorative rings, connectors and the like.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
(1) The types and sources of raw materials used in the examples and comparative examples:
low carboxyl PBT: PBT GX122J, characterization chemical fiber
Conventional PBT resin: PBT GX121, ceremony chemical fiber;
thermoplastic polyester elastomer TPEE: h40DMG, characterization of chemical fibers;
antioxidant: a main antioxidant and an auxiliary antioxidant in a mass ratio of 1:1;
main antioxidant: CYANOX 1790, solvay;
auxiliary antioxidant: RIANOX 412S, tianjin Li Anlong;
lubricant: GLYCOLUBE-P, LONZA.
(2) The test method comprises the following steps:
and (3) testing tensile strength: the samples were injection molded into 150mm by 10mm by 4mm dumbbell specimens, which were subjected to tensile strength testing according to ISO 527 at a tensile speed of 50mm/min;
and (3) testing the bending strength: performing a bending modulus test according to ISO 178, wherein the bending speed is 2mm/min;
notched impact strength test: performing impact strength test according to ISO 179/1eA, wherein the test temperature is 23 ℃;
fogging-gloss retention test: heating a standard wafer with the thickness of 2mm and the diameter of 80mm at 160 ℃ for 24h, condensing volatile matters on the aluminum foil paper cooled at 21 ℃, drying, comparing the weight change of the aluminum foil paper before and after the test with the original weight ratio of the test sample by using a balance, and calculating the haze of the tested substance. The calculation formula is as follows: f = (G1-G0)/G, where F represents haze, G is the original weight of the test sample, G1 is the weight of the aluminum foil paper with coagulum, and G0 is the weight of the aluminum foil paper without coagulum, the volatility of the material is characterized by this method.
TABLE 1 examples and comparative example formulations and procedures
Table 2 results of performance test of examples and comparative examples
As can be seen from Table 2, comparative example 1, which employs a conventional PBT resin, has a low gloss retention after the fogging test. Comparative example 2 the gloss retention is improved by adding part of PET on the basis of the conventional PBT resin, but the retention is still relatively lower. Comparative example 3 a portion of TPEE was added over the conventional PBT resin, but gloss retention was still relatively low with only 1 vacuum port.
From the performance test results of the embodiments 1 to 4, it can be seen that the material has higher impact strength by adopting the compounding of the low-end carboxyl PBT resin and the thermoplastic polyester elastic TPEE and adopting the double vacuum process, and after the atomization experiment, the material has higher gloss retention rate and has the characteristics of low haze and high gloss.
Claims (9)
1. The low-haze high-gloss PBT composite material is characterized by comprising the following components in parts by weight: 73-89 parts of PBT resin; 10-25 parts of thermoplastic polyester elastomer TPEE; 0.2-0.5 part of antioxidant; 0.5 to 1.5 portions of other additives; the PBT resin is PBT GX122J; the preparation method comprises the following steps:
the first step is as follows: weighing the raw materials according to the weight ratio;
the second step is that: mixing the PBT resin, the thermoplastic polyester elastomer TPEE, the antioxidant and other additives which are respectively dried in advance at a high speed for later use;
the third step: feeding the mixed raw materials into a double-screw extruder provided with two vacuum devolatilization devices, wherein the vacuum degree is-0.08 MPa to-0.1 MPa, and extruding and granulating at the temperature of 230-260 ℃ to obtain the PBT composite material.
2. The PBT composite material according to claim 1, wherein the concentration of the terminal amino groups of the PBT resin is < 20meq/kg.
3. The PBT composite material according to claim 1, wherein the thermoplastic polyester elastomer TPEE is a linear block copolymer consisting of a high melting point, high hardness, clean polyester hard segment and an amorphous polyether or polyester soft segment with a lower glass transition temperature.
4. The PBT composite material of claim 3, wherein the hard segment is an aromatic polyester; the soft segment is aliphatic polyester or polyether; and the hardness range is 30-82D Shore by adjusting the proportion of the soft segment and the hard segment.
5. The PBT composite material of claim 1, wherein the antioxidant comprises a primary antioxidant and a secondary antioxidant in a mass ratio of 1:1-2:1; the main antioxidant is hindered phenol antioxidant, and the auxiliary antioxidant is thiodipropionate or phosphite antioxidant.
6. The PBT composite material according to claim 1, wherein the other additive is one or more of a light stabilizer, a lubricant, a mold release agent, an antistatic agent, a dye and a pigment.
7. A method for preparing the PBT composite material of claim 1, comprising the steps of:
the first step is as follows: weighing the raw materials according to the weight ratio;
the second step: mixing the PBT resin, the thermoplastic polyester elastomer TPEE, the antioxidant and other additives which are respectively dried in advance at a high speed for later use;
the third step: feeding the mixed raw materials into a double-screw extruder provided with two vacuum devolatilization devices, wherein the vacuum degree is-0.08 MPa to-0.1 MPa, and extruding and granulating at the temperature of 230-260 ℃ to obtain the PBT composite material.
8. The method according to claim 7, further comprising the steps of: respectively premixing two or more of the components, and feeding the premixed product into an extruder through one feed inlet or a plurality of feed inlets of a double-screw extruder; and two vacuum devolatilization devices are arranged on a screw cylinder of the extruder.
9. Use of the PBT composite material of claim 1 in the automotive industry.
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| CN115260710A (en) * | 2022-08-03 | 2022-11-01 | 湖北合聚新材料有限公司 | Refrigerant-resistant low-precipitation PBT (polybutylene terephthalate) material and preparation method thereof |
| CN115232449B (en) * | 2022-08-08 | 2023-08-25 | 湖北合聚高分子材料有限公司 | Double-85-resistant PBT material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106867211A (en) * | 2017-03-20 | 2017-06-20 | 四川中物材料股份有限公司 | A kind of low haze is high heat-resisting to exempt from PBT composite of primary coat and preparation method thereof |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH09108557A (en) * | 1995-10-16 | 1997-04-28 | Sumitomo Heavy Ind Ltd | Agitation treatment method |
| CN102002220B (en) * | 2010-12-10 | 2012-08-08 | 上海金发科技发展有限公司 | Polyester alloy composite material for decorative ring of vehicle lamp and preparation method thereof |
| CN102719060B (en) * | 2012-03-19 | 2014-06-18 | 深圳市科聚新材料有限公司 | High-temperature resistant and high-gloss PET / PBT composite material and preparation method thereof |
| KR101484390B1 (en) * | 2012-04-24 | 2015-01-19 | 주식회사 엘지화학 | Thermoplastic polyester elastomer resin composition and molding articles comprising the same |
| CN103804859B (en) * | 2014-01-23 | 2016-04-27 | 金发科技股份有限公司 | A kind of high light low volatilization polybutylene terephthalate composition and method of making the same and application |
| KR20180102326A (en) * | 2017-03-07 | 2018-09-17 | 이충진 | Styrene TPR and PBT resin compounded composition |
| KR101974747B1 (en) * | 2017-10-24 | 2019-05-02 | (주)제이월드텍 | Vacuum mixer |
| CN108034204B (en) * | 2017-12-28 | 2020-01-31 | 广东聚石化学股份有限公司 | low-temperature impact resistant polyester composition and preparation method thereof |
| ES2944078T3 (en) * | 2019-04-11 | 2023-06-19 | Basf Se | Polybutylene terephthalate thermoforming process |
| CN111117197B (en) * | 2020-01-06 | 2022-04-26 | 公牛集团股份有限公司 | High-gloss long-acting solvent-resistant polycarbonate material and preparation method thereof |
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