CN102337010B - Thermal aging resistant PET modified material and its preparation method - Google Patents
Thermal aging resistant PET modified material and its preparation method Download PDFInfo
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- CN102337010B CN102337010B CN 201110143980 CN201110143980A CN102337010B CN 102337010 B CN102337010 B CN 102337010B CN 201110143980 CN201110143980 CN 201110143980 CN 201110143980 A CN201110143980 A CN 201110143980A CN 102337010 B CN102337010 B CN 102337010B
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- 239000000463 material Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000003878 thermal aging Methods 0.000 title abstract 4
- 239000003063 flame retardant Substances 0.000 claims abstract description 19
- 239000000314 lubricant Substances 0.000 claims abstract description 15
- 239000003365 glass fiber Substances 0.000 claims abstract 2
- 230000032683 aging Effects 0.000 claims description 22
- 238000005303 weighing Methods 0.000 claims description 21
- 230000000979 retarding effect Effects 0.000 claims description 14
- 239000011521 glass Substances 0.000 claims description 13
- 239000003112 inhibitor Substances 0.000 claims description 13
- 230000003647 oxidation Effects 0.000 claims description 13
- 238000007254 oxidation reaction Methods 0.000 claims description 13
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 7
- -1 antimony peroxide Chemical class 0.000 claims description 6
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical group O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000005469 granulation Methods 0.000 claims description 6
- 230000003179 granulation Effects 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 238000006386 neutralization reaction Methods 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 239000005977 Ethylene Substances 0.000 claims description 2
- 238000013019 agitation Methods 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 2
- 229930195729 fatty acid Natural products 0.000 claims description 2
- 239000000194 fatty acid Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 claims description 2
- 150000001649 bromium compounds Chemical group 0.000 claims 1
- 238000007667 floating Methods 0.000 abstract description 5
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000835 fiber Substances 0.000 abstract description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract 2
- 241000519996 Teucrium chamaedrys Species 0.000 abstract 1
- 239000003963 antioxidant agent Substances 0.000 abstract 1
- 230000003078 antioxidant effect Effects 0.000 abstract 1
- 235000006708 antioxidants Nutrition 0.000 abstract 1
- 229910052742 iron Inorganic materials 0.000 abstract 1
- 239000002667 nucleating agent Substances 0.000 abstract 1
- 125000006850 spacer group Chemical group 0.000 abstract 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 42
- 229920000139 polyethylene terephthalate Polymers 0.000 description 42
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 239000002932 luster Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- DGZQEAKNZXNTNL-UHFFFAOYSA-N 1-bromo-4-butan-2-ylbenzene Chemical class CCC(C)C1=CC=C(Br)C=C1 DGZQEAKNZXNTNL-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 241000580063 Ipomopsis rubra Species 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 201000007094 prostatitis Diseases 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
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- 238000009987 spinning Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
Abstract
The invention discloses a thermal aging resistant PET modified material and its preparation method. The PET modified material provided by the invention comprises the following components of: by weight, 38-62% of PET, 0.3-0.1% of a nucleating agent, 5-10% of a flame retardant, 2-5% of a flame-retardant synergist, 0.1-1% of an anti-oxidant, 0.1-1.5% of a lubricant and 30-50% of glass fibre. The thermal aging resistant PET modified material prepared in the invention has advantages of high temperature resistance, thermal aging resistance, good physical comprehensive properties and good surface glossiness without no floating fibre, and can be widely applied in the field of electronic and electrical products such as coil winders, integrated circuit packages, timer packages, relays and the like, in the field of automobile spare and accessory parts such as automobile headlight decorative loops, heatproof automobile wheel covers, midget electric motor cover casing and the like, and in the field of household electrical appliances such as straight hair device shells, electric iron pedestals, straight hair device heat spacers and the like.
Description
[technical field]
The present invention relates to polymeric material field, it is material modified and preparation method thereof to relate in particular to a kind of heat-proof aging PET.
[background technology]
PET (polyethylene terephthalate, polyethylene terephthalate) resin is that price is the cheapest in the five big general engineering plastic matrix resins, and the PET resin price has only 50% of PA6 resin, and the PET section has only 40% of PA66 resin.In today that the prices of raw and semifnished materials skyrocket, the material that the selectivity price ratio is high is very crucial.The all industrialization of the PET domestic very great synthetic factory of section, the factory that PA6 and PA66 section are produced at home just seldom.But not slow through the PET resin crystallization velocity of modification, shaping cycle length, poor toughness, heat-resisting low, the easy warpage of being heated, there is floating fibre on the product surface under low mould temperature, and these defectives have a strong impact on its industriallization use.
Need carry out modification production to PET, du pont company, Japanese Japan spin offshore companies such as company, Polyplastics and realize all that in the eighties in 20th century suitability for industrialized production PET is material modified for this reason.Companies such as domestic precious Riamb, Ke Di are also walked in the prostatitis in the material modified industrialization of PET., present PET of the prior art is material modified exists heat-resisting low, the insufficient problem of heat-proof aging.
[summary of the invention]
It is material modified and preparation method thereof to the invention provides a kind of heat-proof aging PET, material modified high temperature resistant, the heat-proof aging of this PET, and physical synthesis is functional, surface luster property is good do not have floating fine.
Technical scheme of the present invention is:
A kind of heat-proof aging PET is material modified, and is by weight percentage, composed of the following components:
The material modified preparation method of a kind of heat-proof aging PET may further comprise the steps:
Step 1, take by weighing each component by above-mentioned described weight percent;
Step 2, the PET that takes by weighing, nucleator, fire retardant, fire retarding synergist, oxidation inhibitor, lubricant were mixed in moderate-speed mixers 3-7 minute;
Step 3, throw the mixed material of step 2 into take by weighing spun glass blending, through melt extruding granulation in twin screw extruder neutralization; Manufacturing condition is: twin screw extruder is respectively distinguished temperature and is controlled at 200-260 ℃ respectively, and the residence time is 50-90s.
Material modified, high temperature resistant, the heat-proof aging of heat-proof aging PET of the present invention's preparation, and physical synthesis is functional, and the good nothing of surface luster property is floating fine.Can be widely used in field of electronics such as coil-winding device, ic shell, timing register shell and rly. etc.; Auto-parts field such as automobile front case ring, heat-resisting automobile interior wheel cover, pony pump case etc., household appliance technical field is as doing heater of hair straightener shell, electriciron base, heater of hair straightener heat shield etc.
[embodiment]
Below in conjunction with specific embodiment the present invention is done a detailed elaboration.
In following each embodiment; The limiting viscosity of PET is 0.65-1.05Dl/g, and fusing point is 240-265 ℃, can select the Jiangsu Yizheng Fiber Optical plant to produce and have much light section SB-500; Also can select Foshan letter China to produce and have much light section FC-01-68; The section of low viscous spinning level PET is high because of fusing point, and easy and crystalline more is so preferentially select LV PET section; Fire retardant adopts bromide fire retardant, like brominated Polystyrene, brominated epoxy resin, TDE, preferentially selects sky, Shandong one to produce TDE; Fire retarding synergist adopts Antimony Trioxide: 99.5Min or antimony peroxide, preferred Antimony Trioxide: 99.5Min; Lubricant adopts the ethylene fatty acid amide, also can select the macromolecule wax of Clariant, like Clariant OP wax; Oxidation inhibitor adopts Shanghai Gaoqiao company product 1076 or 412S; The diameter of spun glass is the 4-17 micron, cuts the 534D fiber such as the weak point that megalith group produces.
Nucleator adopts the self-control nucleator, and it prepares by following method:
Take by weighing 2500 purpose ultra-fine barium sulfate 90-110 parts, absolute ethyl alcohol 2-4 part, nano zine oxide 18-25 part by weight; The ultra-fine barium sulfate that takes by weighing (such as the inferior mineral products of Guizhou gold) is put into agitation vat with absolute ethyl alcohol stir, add the nano zine oxide (producing such as the Hua Derun of Jiangxi Province) that takes by weighing afterwards again, the middling speed stirring made in 5-8 minute.
Use ultra-fine barium sulfate and nano zine oxide to make nucleator; These two kinds of inorganicss own are with regard to high temperature resistant, heat-proof aging; And can effectively improve crystallization velocity and the percent crystallinity of PET, reduce material modified die temperature when the injection molding moulding, the high heat resistance ability of plastic component can be provided simultaneously.
Embodiment 1
The heat-proof aging PET of this embodiment is material modified, and is by weight percentage, composed of the following components:
PET 62%; Nucleator 0.3%; Fire retardant 5%; Fire retarding synergist 2%; Oxidation inhibitor 0.2%; Lubricant 0.5%; Spun glass 30%.
Its preparation method is following:
Step 1, take by weighing each component by above-mentioned described weight percent;
Step 2, the PET that takes by weighing, nucleator, fire retardant, fire retarding synergist, oxidation inhibitor, lubricant were mixed in moderate-speed mixers 3 minutes;
Step 3, throw the mixed material of step 2 into take by weighing spun glass blending, through melt extruding granulation in twin screw extruder neutralization; Manufacturing condition is: twin screw extruder is respectively distinguished temperature and is respectively: 200 ℃ of district's temperature, 240 ℃ of two district's temperature, 255 ℃ of three district's temperature, 260 ℃ of four district's temperature, 245 ℃ of five district's temperature, the residence time is 90s.
Embodiment 2
The heat-proof aging PET of this embodiment is material modified, and is by weight percentage, composed of the following components:
PET 55.1%; Nucleator 0.4%; Fire retardant 6.6%; Fire retarding synergist 2.6%; Oxidation inhibitor 0.2%; Lubricant 0.1%; Spun glass 35%.
Its preparation method is following:
Step 1, take by weighing each component by above-mentioned described weight percent;
Step 2, the PET that takes by weighing, nucleator, fire retardant, fire retarding synergist, oxidation inhibitor, lubricant were mixed in moderate-speed mixers 5 minutes;
Step 3, throw the mixed material of step 2 into take by weighing spun glass blending, through melt extruding granulation in twin screw extruder neutralization; Manufacturing condition is: twin screw extruder is respectively distinguished temperature and is respectively: 200 ℃ of district's temperature, 230 ℃ of two district's temperature, 245 ℃ of three district's temperature, 250 ℃ of four district's temperature, 255 ℃ of five district's temperature, the residence time is 50s.
Embodiment 3
The heat-proof aging PET of this embodiment is material modified, and is by weight percentage, composed of the following components:
PET 49.2%; Nucleator 0.5%; Fire retardant 6.4%; Fire retarding synergist 2.4%; Oxidation inhibitor 1%; Lubricant 1.5%; Spun glass 39%.
Its preparation method is following:
Step 1, take by weighing each component by above-mentioned described weight percent;
Step 2, the PET that takes by weighing, nucleator, fire retardant, fire retarding synergist, oxidation inhibitor, lubricant were mixed in moderate-speed mixers 7 minutes;
Step 3, throw the mixed material of step 2 into take by weighing spun glass blending, through melt extruding granulation in twin screw extruder neutralization; Manufacturing condition is: twin screw extruder is respectively distinguished temperature and is respectively: 205 ℃ of district's temperature, 240 ℃ of two district's temperature, 245 ℃ of three district's temperature, 250 ℃ of four district's temperature, 260 ℃ of five district's temperature, the residence time is 70s.
Embodiment 4
The heat-proof aging PET of this embodiment is material modified, and is by weight percentage, composed of the following components:
PET 43.5%; Nucleator 0.6%; Fire retardant 7.5%; Fire retarding synergist 2.5%; Oxidation inhibitor 0.2%; Lubricant 0.7%; Spun glass 45%.
Its preparation method is identical with embodiment 1.
Embodiment 5
The heat-proof aging PET of this embodiment is material modified, and is by weight percentage, composed of the following components:
PET 38%; Nucleator 0.7%; Fire retardant 10%; Fire retarding synergist 2.5%; Oxidation inhibitor 0.5%; Lubricant 0.8%; Spun glass 47.5%.
Its preparation method is identical with embodiment 2.
Embodiment 6
The heat-proof aging PET of this embodiment is material modified, and is by weight percentage, composed of the following components:
PET 53.8%; Nucleator 0.5%; Fire retardant 7.5%; Fire retarding synergist 2.5%; Oxidation inhibitor 0.2%; Lubricant 0.5%; Spun glass 35%.
Its preparation method is identical with embodiment 3.
Embodiment 7
The heat-proof aging PET of this embodiment is material modified, and is by weight percentage, composed of the following components:
PET 37.8%; Nucleator 1.0%; Fire retardant 6%; Fire retarding synergist 5%; Oxidation inhibitor 0.2%; Lubricant 1.0%; Spun glass 50%.
Its preparation method is identical with embodiment 1.
Performance test:
The particle material that above-mentioned 7 embodiment are accomplished granulation in 130-150 ℃ convection oven dry 4-6 hour again with the injection moulding sample preparation on the 80T injection moulding machine of exsiccant particle material, keeps the mould temperature at 70-100 ℃ in the sample making course.
Tensile strength is tested by GB/T 1040 standards., specimen types is the I type, batten size (mm): 170 (length) * (20 ± 0.2) (end width) * (4 ± 0.2) (thickness), and draw speed is 50mm/min; Flexural strength and modulus in flexure are tested by GB 9341/T standard.Specimen types is specimen size (mm): (80 ± 2) * (10 ± 0.2) * (4 ± 0.2), rate of bending are 20mm/min; Notched Izod impact strength is tested by the GB/T1043 standard.Specimen types is the I type, specimen size (mm): (80 ± 2) * (10 ± 0.2) * (4 ± 0.2); The breach type is a category-A, and the breach residual thickness is 3.2mm; Heat-drawn wire is tested by GB/T 1634.2 standards, load for the 1.80MPa. span be 100mm. flame retardant properties bar according to the UL-94 standard, thickness is 1.6 millimeters.
The performance test data of embodiment 1-7 is as shown in table 1 below:
Table 1
Through finding out to last table 1; Used the composite nucleator that makes of ultra-fine barium sulfate and nano zine oxide, the particle of processing becomes white, and the heat resisting temperature of PET is further improved from 60-120 ℃; Heat-drawn wire reaches more than 200 ℃; The heat-proof aging PET that the present invention's preparation is described is material modified, high temperature resistant, not yielding; Heat resisting temperature has reached 225 ℃ for the highest when nucleator is 0.5% (weight percent), and can wear out 172 hours at 250 ℃, and color is flavescence a little, and the heat-proof aging xanthochromia is relatively good; And physical synthesis such as shock strength, flexural strength, modulus in flexure are functional and the product surface glossiness good do not have floating fine.When nucleator increases (0.5% to 1.0%), the impact strength decreased amplitude is bigger, and heat resisting temperature increases not obvious, so the most preferred embodiment for this reason invented of embodiment 6.
Above-described embodiment of the present invention does not constitute the qualification to protection domain of the present invention.Any modification of within spirit of the present invention and principle, being done, be equal to replacement and improvement etc., all should be included within the claim protection domain of the present invention.
Claims (3)
1. a heat-proof aging PET is material modified, it is characterized in that: by weight percentage, composed of the following components:
The limiting viscosity of said PET is 0.65-1.05dl/g, and fusing point is 240-265 ℃;
Said nucleator prepares by following method:
Take by weighing 2500 purpose ultra-fine barium sulfate 90-110 parts, absolute ethyl alcohol 2-4 part, nano zine oxide 18-25 part by weight; The ultra-fine barium sulfate that takes by weighing and absolute ethyl alcohol are put into agitation vat stir, add the nano zine oxide that takes by weighing afterwards again, middling speed stirs and made in 5-8 minute;
Said fire retardant is a bromide fire retardant;
Said fire retarding synergist is Antimony Trioxide: 99.5Min or antimony peroxide;
Said lubricant is the ethylene fatty acid amide.
2. heat-proof aging PET according to claim 1 is material modified, it is characterized in that: said glass fiber diameter is the 4-17 micron.
3. the preparation method that heat-proof aging PET is material modified is characterized in that, may further comprise the steps: step 1, take by weighing each component by the described weight percent of claim 1;
Step 2, the PET that takes by weighing, nucleator, fire retardant, fire retarding synergist, oxidation inhibitor, lubricant were mixed in moderate-speed mixers 3-7 minute;
Step 3, throw the mixed material of step 2 into take by weighing spun glass blending, through melt extruding granulation in twin screw extruder neutralization; Manufacturing condition is: twin screw extruder is respectively distinguished temperature and is controlled at 200-260 ℃ respectively, and the residence time is 50-90s.
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| CN 201110143980 CN102337010B (en) | 2011-05-31 | 2011-05-31 | Thermal aging resistant PET modified material and its preparation method |
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| CN 201110143980 CN102337010B (en) | 2011-05-31 | 2011-05-31 | Thermal aging resistant PET modified material and its preparation method |
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| CN102337010B true CN102337010B (en) | 2012-12-19 |
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| CN103304965B (en) * | 2012-03-13 | 2016-12-14 | 合肥杰事杰新材料股份有限公司 | A kind of polybutylene terephthalate compositions and preparation method thereof |
| CN103044869B (en) * | 2013-01-25 | 2015-08-19 | 本松工程塑料（杭州）有限公司 | Fire-retardant enhancing pet material of high crystallization rate and preparation method thereof |
| CN106065165B (en) * | 2016-04-29 | 2018-04-06 | 合复新材料科技(无锡)有限公司 | A kind of high environment resistant aging high temperature resistant type polyester resin based composites |
| CN107163521A (en) * | 2017-07-14 | 2017-09-15 | 南通瑞隆新材料有限公司 | It is a kind of to strengthen the preparation method of Flame-Retarded PET Engineering Plastics |
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| CN100432127C (en) * | 2000-03-17 | 2008-11-12 | 陶氏环球技术公司 | Prepn. of macrocellular acoustic foam |
| JP2005521753A (en) * | 2001-09-21 | 2005-07-21 | バイエル アクチェンゲゼルシャフト | Impact resistant modified polycarbonate composition |
| CN101255268A (en) * | 2008-01-30 | 2008-09-03 | 深圳市科聚新材料有限公司 | Poly(ethylene terephthalate) flame-retardant modified material and preparation method thereof |
| CN101787181B (en) * | 2009-02-12 | 2012-05-23 | 深圳市科聚新材料有限公司 | Composite material special for heat-resistant hair iron heat baffle and preparation method thereof |
| CN101875761B (en) * | 2010-07-14 | 2012-11-14 | 深圳市科聚新材料有限公司 | Flame-retardant strengthening polythylene terephthalate (PET) material and preparation method thereof |
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Denomination of invention: Thermal aging resistant PET modified material and its preparation method Effective date of registration: 20181119 Granted publication date: 20121219 Pledgee: Bank of Shizuishan Limited by Share Ltd Yinchuan branch Pledgor: Shenzhen Keju New Material Co., Ltd.|Polymer Science (Anhui) New Material Co., Ltd. Registration number: 2018440020071 |
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| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20121219 Termination date: 20190531 |