CN102993650A - Polybutylene terephthalate-based thermoplastic elastomer composition, and preparation method and application thereof - Google Patents

Polybutylene terephthalate-based thermoplastic elastomer composition, and preparation method and application thereof Download PDF

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CN102993650A
CN102993650A CN201210367420.4A CN201210367420A CN102993650A CN 102993650 A CN102993650 A CN 102993650A CN 201210367420 A CN201210367420 A CN 201210367420A CN 102993650 A CN102993650 A CN 102993650A
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polybutylene terephthalate
thermoplastic elastomer
elastomer composition
styrene
terephthalate base
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CN102993650B (en
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陈国雄
李欣
孙刚
张春怀
李东
陶四平
宋晓东
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Tianjin Kingfa Advanced Materials Co Ltd
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Tianjin Kingfa Advanced Materials Co Ltd
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Abstract

The invention discloses a polybutylene terephthalate-based thermoplastic elastomer composition, and a preparation method and an application thereof. The polybutylene terephthalate-based thermoplastic elastomer composition comprises polybutylene terephthalate, styrene thermoplastic elastomer, an olefin polymer, a compatibilizer, a heat stabilizer and other processing agents. The preparation method comprises the following steps of: adding polybutylene terephthalate, styrene thermoplastic elastomer, olefin polymer, the compatibilizer, the heat stabilizer and other processing agents to an extruder in parts by weight; melting, mixing and dispersing the mixture in an extruder, wherein the temperature at each section of the extruder is 230 DEG C to 265 DEG C; and extruding and granulating the mixture to obtain the product. The product prepared by the preparation method disclosed by the invention is mainly applied to the automobile airbag cover plate.

Description

Polybutylene terephthalate base thermoplastic elastomer composition, preparation method and application thereof
Technical field
This area relates to the polymeric composition field, particularly a kind of polybutylene terephthalate base thermoplastic elastomer composition, preparation method and application thereof.
Background technology
The automobile safe airbag lid plate is the automotive upholstery that integrates ornamental and functional, and during accident, the air bag emergency opening also penetrates airbag cover.Therefore, airbag cover not only need to ensure enough toughness when extreme low temperature, does not allow air bag to penetrate to have fragment to fly out when tearing cover plate to hurt sb.'s feelings; Simultaneously also need to when thermal extremes, ensure certain rigidity, not allow to be out of shape owing to high temperature rigid is not enough or to cause tearing excessively owing to the high temperature tear strength is too low, cause a serious accident.
Polybutylene terephthalate, (polybutylene terephthalate, PBT) because its excellent performance is widely used in the automotive field, but because it is torn excessive the distortion easily at high temperature and low temperature flies out, when being applied to automotive field, be subject to certain obstruction.Therefore, study a kind of both had excellent high temperature and low temperature blasting performance, can satisfy that automobile safe airbag lid plate hight warm spot quick-fried (85 ℃) is indeformable to fly out and tear excessively, and low warm spot quick-fried (35 ℃) do not produce the polybutylene terephthalate sill of the requirement of fragment, is the problem that those skilled in the art need solve.
Summary of the invention
In sum, for solving the problems of the technologies described above, the present invention is necessary to provide a kind of polybutylene terephthalate base thermoplastic elastomer composition.
Further, also be necessary to provide a kind of preparation method of above-mentioned polybutylene terephthalate base thermoplastic elastomer composition.
Further, also be necessary to provide a kind of application of above-mentioned polybutylene terephthalate base thermoplastic elastomer composition.
A kind of polybutylene terephthalate base thermoplastic elastomer composition, its main component is for comprising by weight:
Polybutylene terephthalate 21-48 part;
Styrene analog thermoplastic elastomer 10-40 part;
Olefin polymer 10-50 part;
Compatilizer 2-15 part;
Thermo-stabilizer 0-2 part;
Other processing aid 0-2 part.
A kind of polybutylene terephthalate base thermoplastic elastomer composition is made of by weight following one-tenth:
Polybutylene terephthalate 21-48 part;
Styrene analog thermoplastic elastomer 10-40 part;
Olefin polymer 10-50 part;
Compatilizer 2-15 part;
Thermo-stabilizer 0-2 part;
Other processing aid 0-2 part.
Wherein, the prescription of above-mentioned polybutylene terephthalate base thermoplastic elastomer composition may further be by weight:
Polybutylene terephthalate is 30-40 part or 32-38 part; Styrene analog thermoplastic elastomer is 20-30 part or 22-28 part; Olefin polymer 20-40 part or 25-35 part; Compatilizer 4-13 part or 6-10 part; Thermo-stabilizer 0.2-1.8 part or 1-1.5 part; Other processing aid 0.2-1.6 part or 0.8-1.2 part.
Wherein, the molecular weight of described polybutylene terephthalate is 19000 ~ 40000, and the limiting viscosity scope is 0.8-1.23dl/g.
Wherein, described styrene analog thermoplastic elastomer is one or several the mixture in styrene-butadiene-styrene ternary block polymer, hydrogenated styrene-butadiene-styrene ternary block polymer, styrene isoprene-polystyrene ternary segmented copolymer, the hydrogenated styrene-isoprene-polystyrene ternary segmented copolymer.
Wherein, described olefin polymer is a kind of or its mixture in Low Density Polyethylene, linear low density polyethylene, ethylene-butene copolymer, ethylene-propylene copolymer, the POE.
Wherein, described thermo-stabilizer is the mixture class of phenols, amine, phosphorous acid esters, acryl functional group and monothioester and any one or a few the mixture in the calixarene, and further, described thermo-stabilizer comprises half Hinered phenols.The effect of thermo-stabilizer is the degraded that produces in the inhibition course of processing.
Wherein, described compatilizer is selected from binary or terpolymer or its mixture of ethene/acrylic ester class/vinylformic acid glyceride type monomer.The effect of compatilizer is to make PBT and olefin polymer and styrene analog thermoplastic elastomer well compatible, and it is toughness reinforcing that olefin polymer and styrene analog thermoplastic elastomer play a part synergistic.
Wherein, described processing aid is selected from a kind of or its mixture in metal soap, stearic acid complex ester class, the amides.The effect of processing aid is in order to promote the dispersion of each component in the mixture.
A kind of preparation method of aforesaid polybutylene terephthalate base thermoplastic elastomer composition:
Polybutylene terephthalate, styrene analog thermoplastic elastomer, olefin polymer, compatilizer, thermo-stabilizer, other processing aid are disperseed than joining in the forcing machine melting mixing by weight, each section of forcing machine temperature is arranged on 230-265 ℃, extruding pelletization finally obtains product.
A kind of aforesaid polybutylene terephthalate base thermoplastic elastomer composition application in automotive field, the particularly application in the automobile safe airbag lid plate.
Compare prior art, the invention provides polybutylene terephthalate base thermoplastic elastomer composition and both had excellent high temperature and low temperature blasting performance, can satisfy that automobile safe airbag lid plate hight warm spot quick-fried (85 ℃) is indeformable to fly out and tear excessively, and low warm spot quick-fried (35 ℃) requirement that do not produce fragment.
After testing, the invention provides 35 ℃ of notched Izod impact strength 〉=60KJ/m of polybutylene terephthalate base thermoplastic elastomer composition 2, 85 ℃ of tear strength 〉=120KN/m, the mechanical property of its low temperature and high temperature is good than Comparative Examples products obtained therefrom all.
Embodiment
Be described further below in conjunction with the application of some embodiments to polybutylene terephthalate base thermoplastic elastomer composition of the present invention, preparation method and described matrix material.Specific embodiment is for further describing the present invention, non-limiting protection scope of the present invention.
In the embodiment of the invention there be used material:
PBT-1, polybutylene terephthalate, Dong Li company, weight-average molecular weight 40000, limiting viscosity are 1.23dl/g, trade mark 1200M;
PBT-2, polybutylene terephthalate, Changchun, Taiwan company, weight-average molecular weight 19000, limiting viscosity are 0.8dl/g, trade mark 1100L;
PBT-3, polybutylene terephthalate, Yizheng Fiber Optical plant company, weight-average molecular weight 30000, limiting viscosity are 1.0dl/g, the trade mark 2100;
SBS, styrene-butadiene-styrene ternary block polymer, Baling Petrochemical Co., Ltd., SINOPEC, trade mark YH-792;
SEBS, hydrogenated styrene-butadiene-styrene ternary block polymer, Baling Petrochemical Co., Ltd., SINOPEC, trade mark YH-561;
LDPE, Low Density Polyethylene, CSPC, melting index 1.9g/10min(190 ℃, 2.16KG), trade mark 2420H.
Ethylene-butene copolymer, Mitsui, melting index 1.2g/10min(190 ℃, 2.16KG), trade mark DF610;
PTW, DuPont, trade mark ElvaloyPTW;
EBS, Korea S cell KCC, trade mark 500P;
1010, thermo-stabilizer, chemical name 2,6--di-tert-butyl-4-methy phenol;
168, thermo-stabilizer, chemical name tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester;
The detection method of using in the embodiment of the invention has:
(1) three-point bending modulus by standard ISO 178 test, is tested under probe temperature is the condition of 23 ℃ and 85 ℃ respectively;
(2) tensile break strength by standard ISO 527-2/5A/500 test, is tested under the condition of probe temperature for-35 ℃, 23 ℃ and 85 ℃ respectively;
(3) elongation at break by standard ISO 527-2/5A/500 test, is tested under the condition of probe temperature for-35 ℃, 23 ℃ and 85 ℃ respectively;
(4) tear strength by standard ISO 34 test, is tested under the condition of probe temperature for-35 ℃, 23 ℃ and 85 ℃ respectively;
(5) shore hardness is by standard ISO 868 tests;
(6) density is by standard ISO 1183 tests;
(7) notched Izod impact strength, by standard ISO 180 test, A type breach, test environment temperature-35 ℃.
Embodiment 1-8
Polybutylene terephthalate PBT, styrene analog thermoplastic elastomer SBS and/or SEBS, olefin polymer, compatilizer, thermo-stabilizer, other processing aid are joined in the forcing machine melting mixing by the weight part shown in the table 1 to be disperseed, each section of forcing machine temperature is arranged on 230-265 ℃, extruding pelletization finally obtains product.The properties of test products obtained therefrom is listed in the table 1.
Comparative Examples 1-8
Polybutylene terephthalate PBT, styrene analog thermoplastic elastomer SBS and/or SEBS, olefin polymer, compatilizer, thermo-stabilizer, other processing aid are joined in the forcing machine melting mixing by the weight part shown in the table 2 to be disperseed, each section of forcing machine temperature is arranged on 230-265 ℃, extruding pelletization finally obtains product.The properties of test products obtained therefrom is listed in the table 2.
Table 1
Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5 Embodiment 6
PBT-1 21 32 38 20
PBT-2 48 18
PBT-3 30
SBS 10 20 20 28 30
SEBS 20 22
LDPE 10 10 35 40
Ethylene-butene copolymer 50 20 15
PTW 2 4 6 13 10 15
EBS 0.2 0.8 1.2 1.6 2
1010 0.2 1 1 1 2
168 0.5 0.8
Shore hardness (Shore D) 43 42 46 45 45 41
Density (g/cm 3 0.96 0.95 0.96 0.97 0.96 0.96
23 ℃ of three-point bending modulus (MPa) 1020 1015 980 955 920 930
23 ℃ of tensile break strengths (MPa) 20 22 20 18 18 17
23 ℃ of elongation at breaks (%) 200 240 230 235 260 240
23 ℃ of tear strengths (KN/m) 215 245 255 275 260 250
-35 ℃ of tensile break strengths (MPa) 40 42 41 38 42 43
-35 ℃ of elongation at breaks (%) 90 110 130 120 115 140
-35 ℃ of notched Izod impact strength (KJ/m 2 70 73 74 77 82 74
-35 ℃ of tear strengths (KN/m) 310 330 315 350 335 330
85 ℃ of three-point bending modulus (MPa) 330 335 345 350 340 335
85 ℃ of tensile break strengths (MPa) 10.8 11.4 11.2 12.3 11.6 10.9
85 ℃ of elongation at breaks (%) 550 700 800 650 900 700
85 ℃ of tear strengths (KN/m) 135 140 175 120 165 130
Table 2
Comparative Examples 1 Comparative Examples 2 Comparative Examples 3 Comparative Examples 4 Comparative Examples 5 Comparative Examples 6
PBT-1 21 32 38 20
PBT-2 48 18
PBT-3 30
SBS 20 28 30
SEBS 22
LDPE 10
Ethylene-butene copolymer 50
PTW 2 4 6 13 10 15
EBS 0.2 0.8 1.2 1.6 2
1010 0.2 1 1 1 2
168 0.5 0.8
Density (g/cm 3) 0.95 0.96 0.96 0.97 0.96 0.96
23 ℃ of three-point bending modulus (MPa) 1050 1000 960 950 900 900
23 ℃ of elongation at breaks (%) 105 80 70 90 110 120
23 ℃ of tear strengths (KN/m) 115 128 109 131 122 118
-35 ℃ of elongation at breaks (%) 25 20 30 29 35 33
-35 ℃ of notched Izod impact strength (KJ/m 2) 24 37 31 29 33 34
-35 ℃ of tear strengths (KN/m) 198 202 210 185 194 190
85 ℃ of three-point bending modulus (MPa) 330 330 365 360 370 370
85 ℃ of elongation at breaks (%) 150 200 190 220 240 200
85 ℃ of tear strengths (KN/m) 65 73 81 59 62 68
Test result by table 1 and table 2 can be found, the invention provides-35 ℃ of notched Izod impact strength 〉=60KJ/m of polybutylene terephthalate base thermoplastic elastomer composition among the embodiment 2, 85 ℃ of tear strength 〉=120KN/m, the mechanical property of its low temperature and high temperature is good than Comparative Examples products obtained therefrom all.
The above instrument is embodiments of the invention; be not so limit claim of the present invention; every equivalent structure or equivalent flow process conversion that utilizes description of the present invention to do; or directly or indirectly be used in other relevant technical fields, all in like manner be included in the scope of patent protection of the present invention.

Claims (10)

1. polybutylene terephthalate base thermoplastic elastomer composition, its main component is for comprising by weight:
Polybutylene terephthalate 21-48 part;
Styrene analog thermoplastic elastomer 10-40 part;
Olefin polymer 10-50 part;
Compatilizer 2-15 part;
Thermo-stabilizer 0-2 part;
Other processing aid 0-2 part.
2. polybutylene terephthalate base thermoplastic elastomer composition is made of by weight following one-tenth:
Polybutylene terephthalate 21-48 part;
Styrene analog thermoplastic elastomer 10-40 part;
Olefin polymer 10-50 part;
Compatilizer 2-15 part;
Thermo-stabilizer 0-2 part;
Other processing aid 0-2 part.
3. polybutylene terephthalate base thermoplastic elastomer composition according to claim 1 and 2 is characterized in that:
The molecular weight of described polybutylene terephthalate is 19000 ~ 40000, and the limiting viscosity scope is 0.8-1.23dl/g.
4. polybutylene terephthalate base thermoplastic elastomer composition according to claim 1 and 2 is characterized in that:
Described styrene analog thermoplastic elastomer is one or several the mixture in styrene-butadiene-styrene ternary block polymer, hydrogenated styrene-butadiene-styrene ternary block polymer, styrene-isoprene-phenylethene ternary block polymer, the hydrogenated styrene-isoprene-polystyrene ternary segmented copolymer.
5. polybutylene terephthalate base thermoplastic elastomer composition according to claim 1 and 2 is characterized in that:
Described olefin polymer is a kind of or its mixture in Low Density Polyethylene, linear low density polyethylene, ethylene-butene copolymer, ethylene-propylene copolymer, the ethylene-octene copolymer.
6. polybutylene terephthalate base thermoplastic elastomer composition according to claim 1 and 2 is characterized in that:
Described thermo-stabilizer is the mixture class of phenols, amine, phosphorous acid esters, acryl functional group and monothioester and any one or a few the mixture in the calixarene.
7. polybutylene terephthalate base thermoplastic elastomer composition according to claim 1 and 2 is characterized in that:
Described compatilizer is selected from binary or terpolymer or its mixture of ethene/acrylic ester class/vinylformic acid glyceride type monomer.
8. polybutylene terephthalate base thermoplastic elastomer composition according to claim 1 and 2 is characterized in that:
Described processing aid is selected from a kind of or its mixture in metal soap, stearic acid complex ester class, the amides.
9. the preparation method of each described polybutylene terephthalate base thermoplastic elastomer composition of claim 1-8 is characterized in that:
Polybutylene terephthalate, styrene analog thermoplastic elastomer, olefin polymer, compatilizer, thermo-stabilizer, other processing aid are disperseed than joining in the forcing machine melting mixing by weight, each section of forcing machine temperature is arranged on 230-265 ℃, extruding pelletization finally obtains product.
10. each described polybutylene terephthalate base thermoplastic elastomer composition application in automotive field of claim 1-8.
CN201210367420.4A 2012-09-27 2012-09-27 Polybutylene terephthalate-based thermoplastic elastomer composition, and preparation method and application thereof Active CN102993650B (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104151784A (en) * 2013-05-14 2014-11-19 常熟市沈氏塑业有限公司 Nano carbon fiber reinforced polybutylene terephthalate alloy composite material
CN104151783A (en) * 2013-05-14 2014-11-19 常熟市沈氏塑业有限公司 Preparation method of carbon nanofiber reinforced polybutylene terephthalate alloy composite material
CN105440594A (en) * 2015-10-23 2016-03-30 华晨汽车集团控股有限公司 Polymer synthetic material for vehicle sunroof flow board
CN105754306A (en) * 2016-03-24 2016-07-13 叶青 PBT (polybutylene terephthalate) plastic alloy
CN112812491A (en) * 2020-12-30 2021-05-18 江西博硕电子有限公司 External coating material and preparation method and application thereof

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Publication number Priority date Publication date Assignee Title
US5891943A (en) * 1996-06-28 1999-04-06 Polyplastics Co., Ltd. Thermoplastic resin composition and a method of producing the same
CN101412841A (en) * 2008-12-02 2009-04-22 上海金发科技发展有限公司 Heat resisting super ductibility polybutylene terephthalate complex and preparation thereof
CN101928447A (en) * 2009-06-24 2010-12-29 上海金发科技发展有限公司 Halogen-free antiflaming enhanced polybutylene terephthalate composite and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5891943A (en) * 1996-06-28 1999-04-06 Polyplastics Co., Ltd. Thermoplastic resin composition and a method of producing the same
CN101412841A (en) * 2008-12-02 2009-04-22 上海金发科技发展有限公司 Heat resisting super ductibility polybutylene terephthalate complex and preparation thereof
CN101928447A (en) * 2009-06-24 2010-12-29 上海金发科技发展有限公司 Halogen-free antiflaming enhanced polybutylene terephthalate composite and preparation method thereof

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104151784A (en) * 2013-05-14 2014-11-19 常熟市沈氏塑业有限公司 Nano carbon fiber reinforced polybutylene terephthalate alloy composite material
CN104151783A (en) * 2013-05-14 2014-11-19 常熟市沈氏塑业有限公司 Preparation method of carbon nanofiber reinforced polybutylene terephthalate alloy composite material
CN105440594A (en) * 2015-10-23 2016-03-30 华晨汽车集团控股有限公司 Polymer synthetic material for vehicle sunroof flow board
CN105754306A (en) * 2016-03-24 2016-07-13 叶青 PBT (polybutylene terephthalate) plastic alloy
CN112812491A (en) * 2020-12-30 2021-05-18 江西博硕电子有限公司 External coating material and preparation method and application thereof
CN112812491B (en) * 2020-12-30 2022-09-23 江西博硕电子有限公司 External coating material and preparation method and application thereof

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