CN100532451C - High impact-resistant reinforced PET composition and method of making the same - Google Patents

High impact-resistant reinforced PET composition and method of making the same Download PDF

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CN100532451C
CN100532451C CNB2006100837045A CN200610083704A CN100532451C CN 100532451 C CN100532451 C CN 100532451C CN B2006100837045 A CNB2006100837045 A CN B2006100837045A CN 200610083704 A CN200610083704 A CN 200610083704A CN 100532451 C CN100532451 C CN 100532451C
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polyethylene terephthalate
weight
styrene
powdered rubber
vinyl pyridine
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CN101081924A (en
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尹华
张师军
张薇
邵静波
张丽英
吕明福
吕芸
刘涛
张�浩
李魁
陈力
段淑清
王小兰
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Abstract

The present invention relates to enhanced PET composition with high impact strength and its preparation process. The enhanced PET composition is PET engineering plastic modified comprehensively with toughening agent comprising nanometer styrene-butadiene-pyridine rubber powder and EXL2314. The enhanced PET composition has high mechanical strength, high impact strength, low processing mold temperature, short shaping period and good product look.

Description

A kind of high impact-resistant reinforced PET composition and preparation method thereof
Technical field
The present invention relates to a kind of REINFORCED PET engineering plastics of high impact property, it is to be raw material with PET (polyethylene terephthalate), adds that toughening material, reinforcing filler, processing aid etc. are prepared from, and belongs to the engineering plastics field.
Background technology
A series of good characteristic such as thermoplastic polyester polyethylene terephthalate (PET) has that density is light, intensity is high, electrical insulating property and thermal insulation are good, therefore having a wide range of applications in national economy and in national defense industry and the new high-tech industry, is a kind of indispensable type material.PET is the very large thermoplastic polyester plastic of a kind of output and consumption, and it also is being widely used in a plurality of fields such as electronic apparatus, machinery, instrument, automobile, medicine equipment, field work except being used for fiber and packing, hollow container etc. after strengthening.
But, because itself chemical structure and physicals, make that its low temperature crystallization speed is very slow, and toughness is relatively poor, can produce after hot-work and stick up district's metamorphism, molding processing is difficulty especially, generally speaking, PET is carried out injection moulding needs very high mould temperature (about 110~140 ℃), and this has limited the application of PET in other field to a great extent.In addition, after the fire-retardant enhancing of PET engineering plastics, though some strongthener such as glass improve to material impact intensity, can only improve part, strongthener can not unconfinedly add simultaneously.
Therefore, press for the method for preparing the PET engineering plastics that research and development make new advances, so that can improve the shortcoming that its crystallization velocity is improved product properties, Mo Wengao.
In the current method for preparing the PET engineering plastics, have and in polymerization process, in the presence of monomer, catalyzer, stablizer, carry out transesterify, polycondensation, layered silicate material is mixed into suspension adding polycondensation system obtains the PET resin, obtaining a PET matrix material, is 97122065.4 patent as application number.Patent 95104996.8 adopts and add nucleator nylon in PET, toughness reinforcing, chainextender Resins, epoxy, and then extrude with the glass fibre composite molten that water-soluble epoxy resin is handled.Patent 98102049.6 is to come direct toughened PET with self-control maleic anhydride graft POE, and not seeing has enhancing.In above-mentioned three patents, first is to use the polymeric method, needs layered silicate is carried out loaded down with trivial details processing; Second is to add chainextender, nylon nucleator etc., but the impact effect that obtains is lower than the present invention; The 3rd is that maleic anhydride has pungency with self-control maleic anhydride graft POE toughened PET, and easily pollution, and this patent does not in process of production have other strongthener, and property related to the present invention is little.
Summary of the invention
Technical problem to be solved by this invention provides a kind of high impact-resistant PET composition and method of making the same of enhancing modified.
PET composition of the present invention comprises following component:
PET polyester 100 weight parts
Toughner EXL 2,314 1~20 weight parts
Nanometer butadiene-styrene-vinyl pyridine powdered rubber 1~20 weight part
Be 100 listed as parts by weight with the PET polyester wherein, toughner EXL2314 (Luo Men-Haars Co., Ltd, commercially available) is preferably 1~15 weight part; Problems such as adding too much can cause that mechanical strength declines to a great extent.
With the PET polyester is 100 listed as parts by weight, and the nanometer butadiene-styrene-vinyl pyridine powdered rubber is preferably 1~15 weight part; Add too much nanometer butadiene-styrene-vinyl pyridine powdered rubber and can cause mechanical strength decline problem.
Nanometer butadiene-styrene-vinyl pyridine powdered rubber of the present invention preferably has the butylbenzene pyrrole powdered rubber of crosslinking structure, and its rubber particles has equal phase structure, and its median size is 30~200nm, is preferably 50~150nm; Its gel content is at 60 weight % or higher, preferred 80 weight % or higher.
Described nanometer butadiene-styrene-vinyl pyridine powdered rubber can adopt the prepared full sulfuration butylbenzene pyrrole powdered rubber of method of the applicant's record in the International Application No. WO of submitting on September 18th, 2000 (priority date on December 3rd, 1999) 01/40356 (priority number 99125530.5).This kind butylbenzene pyrrole powdered rubber is to get by to vinylpyridiene-styrene-butadiene rubber latex cross-linking radiation the particle diameter of vinylpyridiene-styrene-butadiene rubber latex particle being fixed.The concrete scope of its median size is 30~200nm, more preferably 50~150nm.The gel content of full sulfuration butylbenzene pyrrole powdered rubber reaches 60 weight % or higher, is preferably 75 weight % or higher.Each particulate in this fully vulcanized powder rubber all is a homogeneous, and promptly single particulate all is a homogeneous on forming, and does not find layering in the particulate under the observation of existing microtechnique, divides the phenomenon that equates uneven phase.
The part by weight of preferred EXL2314 and nanometer butadiene-styrene-vinyl pyridine powdered rubber is 1:10~10:1, more preferably 3:7~7:3.
Can also comprise some auxiliary agents commonly used in an amount of polyester course of processing in the PET composition of the present invention, as toughener (glass etc.), fire retardant (Sb 2O 3, decabromodiphenyl oxide etc.) and/or nucleator etc., its consumption is conventional amount used, or adjusts according to practical requirements.Generalized case, glass is 100 listed as parts by weight with the PET polyester, is 10~55 weight parts, is preferably 20~50 weight parts; Other processing aid is 0.1~1.0 weight part.
PET preparation of compositions method of the present invention comprises: components such as above-described PET polyester, toughner EXL 2314, nanometer butadiene-styrene-vinyl pyridine powdered rubber are made described PET composition by the rubber and plastic melt-mixing method.
Specifically comprise: after PET polyester and the toughner that is composited by nanometer butadiene-styrene-vinyl pyridine powdered rubber and EXL2314, other processing aid etc. are measured by prescription, high-speed stirring is even, put into the main feeder of blending equipment, long strand glass adds from the glass charging opening of blending equipment, extrude through fusion plastification, cooling granulation is prepared into high tenacity REINFORCED PET polyester mixture material.
The employed blending equipment of present method is the general blending equipment in the rubber and plastic processing industry, can be twin screw extruder, single screw extrusion machine, mill or Banbury mixer etc.The preferred twin screw extruder that adopts with side direction feeding device, glass slave unit fiber charging opening adds, and the control by expressing technique parameter such as temperature, screw speed, feed rate, spiral shell piece array mode etc., obtain the PET material of high impact, satisfactory mechanical property.
In preparation process, the blending temperature of material is used blending temperature in the common PET processing, can decide according to the melt temperature of the concrete material of PET, should select not only guaranteeing the complete fusion of matrix PET material but also can not make in the scope of its decomposition.As the blending temperature of PET in 250~270 ℃ scope.
PET preparation of compositions method concrete operations step of the present invention comprises:
(1) step of preparation mixing raw material
In material-compound tank, PET polyester, nanometer butadiene-styrene-vinyl pyridine powdered rubber, toughner EXL2314, other processing aid etc. by after the prescription metering, are added homogenizer, continuous high speed stirs 3~5min at normal temperatures, makes each component thorough mixing.
(2) extruding pelletization
Mixing raw material material with step (1) preparation, under 250~270 ℃ of temperature, melt extrude, the glass that adds long thigh in the extrusion at forcing machine glass mouth, with the rotating speed of 200~350r.p.m and suitable spiral shell piece combination, through melt blending, make the abundant melting mixing of each component even, extrude the postcooling pelletizing.
(3) injection molding step
The pellet that step (2) is made is 80~100 ℃ a baking oven inner drying 8~10 hours in temperature, then at 260~275 ℃, and 60~80 ℃ of following injection moldings of mould temperature.
The toughner comprehensively modifying PET engineering plastics that the present invention adopts nanometer butadiene-styrene-vinyl pyridine powdered rubber and EXL2314 to be composited.Use separately the EXL2314 can be so that toughness of material improves a lot, a lot of but performances such as its stretching, bending reduce.Behind the toughner that uses nanometer butadiene-styrene-vinyl pyridine powdered rubber and EXL2314 to be composited, enhanced PET engineering plastics such as the glass that makes do not lose or lose under the very little situation in physical strength, impact property is greatly improved, tensile strength, flexural strength are constant substantially or reduce very little, reduce the mould temperature that adds man-hour, make it have short shaping cycle and good products appearance.The toughner that adds has played certain nucleation promoter action, the crystallization velocity of PET also is improved, and processing characteristics improves, easier injection moulding, have good using value, solved the weak point of existing PET engineering plastics aspect exterior quality, impact property and processing.
PET preparation of compositions method of the present invention, technology is simple.
Embodiment
Further describe the present invention below in conjunction with embodiment.
Comparative Examples 1,3,5,7:
With polyethylene terephtalate (Yizheng Fiber Optical plant production) and full sulfuration butylbenzene pyrrole powdered rubber (in the butylbenzene pyrrole emulsion [trade mark 55555] of the prosperous extra large latex company limited of Zhejiang Cixi City, after pressing 3% adding crosslinking coagent Viscoat 295 of the dried glue weight of butylbenzene pyrrole emulsion, carry out radiation vulcanization, irradiation dose is 2.5Mrad, obtains after spray-dried.The inlet temperature of spray-dryer is 140 ℃-160 ℃, and temperature out is 40 ℃-60 ℃, and dried powder is collected in cyclonic separator, and vulcanizing butylbenzene pyrrole powdered rubber median size entirely is 100nm, gel content 87%), fire retardant (Sb 2O 3, brominated epoxy resin, commercially available) and calcium stearate (CaSt2, chemical plant, long positive farm, Beijing), phosphoric acid ester nucleator (9930T, East China University of Science) etc., put into high-speed mixer and stir 3~5min, make each component thorough mixing even.Be 100 parts by weight wherein in polyethylene terephthalate, Sb 2O 3Be that 4 parts, brominated epoxy resin are 0.5 part of 12 part, calcium stearate, 0.5 part of nucleator.Then with in the twin screw of said mixture material under 250~270 ℃ (ZSK 25, German WP company), with the rotating speed melt blending extruding pelletization of 200~350r.p.m.Roving glass fiber GF in the extrusion (Tong County, Beijing glass factory, alkali-free glass fiber) is by material blend in glass charging opening and the screw rod on the twin screw.The pellet of extruding is dried 9hr in 90 ℃ of constant temperature ovens, under 260~275 ℃ of injection temperatures, be injected into the standard batten then, carry out various Mechanics Performance Testings.Concrete prescription sees Table 1, and wherein each component concentration is all in parts by weight (the PET resin is 100 parts by weight).Testing standard and results of property are as shown in table 1.
Comparative Examples 2,4,6,8:
With PET (with Comparative Examples 1), toughner EXL2314 (Rhom and Hass's production), calcium stearate (with Comparative Examples 1), fire retardant (Sb 2O 3, brominated epoxy resin, commercially available) and phosphoric acid ester nucleator (with Comparative Examples 1), put into high-speed mixer and stir 3~5min, make each component thorough mixing even.Be 100 parts by weight wherein in polyethylene terephthalate, Sb 2O 3Be that 4 parts, brominated epoxy resin are 0.5 part of 12 part, calcium stearate, 0.5 part of nucleator.Then with in the twin screw of said mixture material under 250~270 ℃ (ZSK 25, German WP company), with the rotating speed melt blending extruding pelletization of 200~350r.p.m.Roving glass fiber in the extrusion (with Comparative Examples 1) is by material blend in glass charging opening and the screw rod on the twin screw.The pellet of extruding is dried 9hr in 90 ℃ of constant temperature ovens, under 260~275 ℃ of injection temperatures, be injected into the standard batten then, carry out various Mechanics Performance Testings.Concrete prescription sees Table 1, and wherein each component concentration is all in parts by weight.Testing standard and results of property are as shown in table 1.
Embodiment 1~6:
With PET (with Comparative Examples 1) and full sulfuration butylbenzene pyrrole powdered rubber (with Comparative Examples 1), toughner EXL2314 (with Comparative Examples 2), calcium stearate (with Comparative Examples 1), fire retardant (Sb 2O 3, brominated epoxy resin, commercially available) and phosphoric acid ester nucleator (with Comparative Examples 1), put into high-speed mixer and stir 3~5min, make each component thorough mixing even.Be 100 parts by weight wherein in polyethylene terephthalate, Sb 2O 3Be 4 parts, 12 parts of brominated epoxy resins, 0.5 part of calcium stearate, 0.5 part of nucleator.Then with in the twin screw of said mixture material under 250~270 ℃ (ZSK 25, German WP company), with the rotating speed melt blending extruding pelletization of 200~350r.p.m.Roving glass fiber in the extrusion (with Comparative Examples 1) is by material blend in glass charging opening and the screw rod on the twin screw.The pellet of extruding is dried 9hr in 90 ℃ of constant temperature ovens, under 260~275 ℃ of injection temperatures, be injected into the standard batten then, carry out various Mechanics Performance Testings.Concrete prescription sees Table 1, and wherein each component concentration is all in parts by weight.Testing standard and results of property are as shown in table 1.
The modifying material of the PET that the above embodiment 1~6 obtains when common injection molding, its mould temperature between 60~80 ℃, and under the similarity condition mould temperature of comparative example 1~8 between 70~90 ℃.
Table 1
PET GF The nanometer butadiene-styrene-vinyl pyridine powdered rubber EXL 2314 CaSt 2 Nucleator Tensile strength Elongation at break Flexural strength Modulus in flexure The Izod notch shock
Unit - - - - - - MPa MPa GPa J/m
Testing standard ASTM D638 ASTM D638 ASTM D790 ASTM D790 ASTM D256
Comparative Examples 1 100 15 2 0.5 0.5 91 24 143.1 6.1 72
Comparative Examples 2 100 15 2 0.5 0.5 85 41 130 5.1 97
Embodiment 1 100 15 1 1 0.5 0.5 89 57 137 5.4 106
Comparative Examples 3 100 20 20 0.5 0.5 83 25 110 6.1 101
Comparative Examples 4 100 20 20 0.5 0.5 79 40 97 2.9 151
Embodiment 2 100 20 10 10 0.5 0.5 106.1 36 140.7 5.4 159
Comparative Examples 5 100 35 10 0.5 0.5 135.3 27 179 9.8 128
Comparative Examples 6 100 35 10 0.5 0.5 130 24 154 6.1 141
Embodiment 3 100 35 5 5 0.5 0.5 136 20 163 8.2 148
Embodiment 4 100 35 7 3 0.5 0.5 136.4 18 160.2 7.8 144
Embodiment 5 100 35 3 7 0.5 0.5 132.5 21 154 7.7 156
Comparative Examples 7 100 40 30 0.5 0.5 130.7 8.4 141 6.2 147
Comparative Examples 8 100 40 30 0.5 0.5 127 10 158 7.1 162
Embodiment 6 100 40 15 15 0.5 0.5 140 11 178 8.0 171
From above data as seen, polyethylene terephthalate composition toughness of the present invention is all better than independent use Nano powder rubber or EXL2314, also obtains certain raising in the two shared back in increase flexible other mechanical property of while; The mould temperature that adds man-hour has also reduced, and shaping cycle shortens, and products appearance is good.

Claims (11)

1. polyethylene terephthalate composition comprises following component:
Polyethylene terephthalate 100 weight parts
Toughner EXL 2,314 1~20 weight parts
Nanometer butadiene-styrene-vinyl pyridine powdered rubber 1~20 weight part;
The part by weight of wherein said toughner EXL2314 and described nanometer butadiene-styrene-vinyl pyridine powdered rubber is 1:10~10:1; Described nanometer butadiene-styrene-vinyl pyridine powdered rubber median size is 30~200nm, has crosslinking structure, and gel content is at 60 weight % or higher, and its rubber particles has equal phase structure.
2. polyethylene terephthalate composition as claimed in claim 1 is characterized in that: with polyethylene terephthalate is 100 listed as parts by weight, and described toughner EXL2314 is 1~15 weight part.
3. polyethylene terephthalate composition as claimed in claim 1 or 2 is characterized in that: with polyethylene terephthalate is 100 listed as parts by weight, and described nanometer butadiene-styrene-vinyl pyridine powdered rubber is 1~15 weight part.
4. polyethylene terephthalate composition as claimed in claim 1 is characterized in that: the part by weight of described toughner EXL2314 and described nanometer butadiene-styrene-vinyl pyridine powdered rubber is 3:7~7:3.
5. polyethylene terephthalate composition as claimed in claim 1 is characterized in that: described nanometer butadiene-styrene-vinyl pyridine powdered rubber with crosslinking structure is full sulfuration butylbenzene pyrrole powdered rubber.
6. polyethylene terephthalate composition as claimed in claim 1 is characterized in that: the median size of described nanometer butadiene-styrene-vinyl pyridine powdered rubber is 50~150nm.
7. polyethylene terephthalate composition as claimed in claim 1 is characterized in that: the gel content of described nanometer butadiene-styrene-vinyl pyridine powdered rubber is at 80 weight % or higher.
8. polyethylene terephthalate composition as claimed in claim 1 is characterized in that: comprise toughener, fire retardant and/or nucleator in the described composition, its consumption is conventional amount used.
9. polyethylene terephthalate composition as claimed in claim 8 is characterized in that: described toughener is a glass, is 100 listed as parts by weight with polyethylene terephthalate, is 10~55 weight parts.
10. polyethylene terephthalate composition as claimed in claim 9 is characterized in that: the toughener glass is 100 listed as parts by weight with polyethylene terephthalate, is 20~50 weight parts.
11. as each described polyethylene terephthalate preparation of compositions method among the claim 1-10, it is characterized in that comprising: described each component melts blend is made described polyethylene terephthalate composition.
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CN102543316A (en) * 2012-02-17 2012-07-04 杭州电缆股份有限公司 Processing method for insulation process of 500kV cross-linked cable
CN105670242A (en) * 2016-04-11 2016-06-15 广州煌垅生物科技有限公司 Polyethylene glycol terephthalate composite material and preparation method thereof
CN106751577A (en) * 2016-12-26 2017-05-31 东莞市佳乾新材料科技有限公司 A kind of PET resin component and preparation method

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