CN103333492A - Halogen-free flame retardant nylon resin composition - Google Patents

Halogen-free flame retardant nylon resin composition Download PDF

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Publication number
CN103333492A
CN103333492A CN2013103074661A CN201310307466A CN103333492A CN 103333492 A CN103333492 A CN 103333492A CN 2013103074661 A CN2013103074661 A CN 2013103074661A CN 201310307466 A CN201310307466 A CN 201310307466A CN 103333492 A CN103333492 A CN 103333492A
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Prior art keywords
parts
halogen
resin composition
retardant
nylon resin
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CN2013103074661A
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Chinese (zh)
Inventor
许第修
段海斌
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SHENZHEN XINGSHENGDI NEW MATERIALS CO Ltd
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SHENZHEN XINGSHENGDI NEW MATERIALS CO Ltd
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Priority to CN2013103074661A priority Critical patent/CN103333492A/en
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Abstract

The invention relate to a halogen-free flame-retardant nylon resin composition, which comprises the following components in parts by weight: 58 parts of nylon 66 (PA66), 30 parts of glass fiber (GF), 1 to 10 parts of flame retardant, 1 to 10 parts of toughening agent, 0.1 to 5 parts of flowing agent, and 0.5 to 5 parts of light stabilizer, wherein the glass fiber is a non-alkali short glass fiber, and the flame retardant is at least one of component selected from triphenyl phosphate, triscresyl phosphate, bisphenol-A Bis(diphenyl phosphate) and melamine polyphosphate (MPP). The halogen-free flame-retardant nylon resin composition provided by the invention fully adopts a halogen-free flame retardant as a flame retardant material, but the overall performance achieves the performance index of a nylon resin composition using a halogen flame retardant.

Description

A kind of halogen-free flame-retardant nylon resin composition
Technical field
The present invention relates to polymeric material field, relate in particular to a kind of halogen-free flame-retardant nylon resin composition.
Background technology
Nylon resin, it is polymeric amide, have excellent mechanical strength, wear resistance, self lubricity, erosion resistance and machine-shaping property preferably, at present oneself become output maximum in the five big general engineering plastic, kind at most, the base resin of the widest, the high comprehensive performance of purposes.The flame retardant type nylon resin composition of prior art is that ZL201110117041.5 is disclosed, and it is as follows that the disclosed flame retardant type nylon resin of ZL201110117041.5 composition is counted the component that comprises by weight:
Figure BDA00003543329700011
Its preferred version of the disclosed flame retardant type nylon resin of ZL201110117041.5 composition comprises that also parts by weight are 7~15 parts fire retarding synergist.
In the disclosed flame retardant type nylon resin of ZL201110117041.5 composition, described compatilizer is selected from least a in glycidyl acrylate, maleic anhydride graft polyolefine and vinylbenzene one copolymer-maleic anhydride.
In the disclosed flame retardant type nylon resin of ZL201110117041.5 composition, described glass fibre is alkali free glass fibre.
In the disclosed flame retardant type nylon resin of ZL201110117041.5 composition, described fire retardant is selected from least a in TDE, three-(tribromophenoxy)-triazine, brominated Polystyrene, brominated epoxy resin and the trimeric cyanamide urate; Fire retarding synergist is selected from least a in oxide compound, stibnate and the V family metallic element compound of antimony.
In the disclosed flame retardant type nylon resin of ZL201110117041.5 composition, described anti-dripping agent is selected from ptfe micropowder, polytetrafluoroethylene granule and is at least a in the tetrafluoroethylene master batch of carrier with acrylonitritrile-styrene resin, acrylonitrile-styrene-butadienecopolymer or polystyrene resin.
In the disclosed flame retardant type nylon resin of ZL201110117041.5 composition, described oxidation inhibitor is selected from 4,4'-thiobis (the 6-tertiary butyl-3-methylphenol), tris phosphite (2, the 4-di-tert-butyl-phenyl) and four [β-(3,5 di-tert-butyl-hydroxy phenyls) propionic acid] at least a in the pentaerythritol ester, described lubricant is selected from least a in ethylene bis stearamide, tetramethylolmethane stearate and the polyethylene wax.
The disclosed this flame retardant type nylon resin composition of ZL201110117041.5 can use any known plastic working method preparation, as by processing such as forcing machine, mixing machine, kneaders, can be periodical operation, also can be operate continuously.The method that provides among the embodiment is to use the preparation of twin screw extruder melt-blending process, and each component mixes back employing standard twin screw extruder and standard technology extruding pelletization, namely gets a kind of flame retardant type nylon resin composition.
The disclosed this flame retardant type nylon resin composition of ZL201110117041.5 by adding the fire retardant modification, makes the flame retardant properties excellence of whole resin combination; Simultaneously, the consistency of each component is better in the prescription, the synergy of lubricant and oxidation inhibitor, can improve the processing flowability of nylon resin, improve the dispersing property of fire retardant in composition, prepared flame retardant type nylon resin composition outdoor weatherability can be good, shock strength, bending strength and tensile strength height, fire-retardant degree well, mobile high.But from its prescription, be not difficult to find out, its fire-retardant employing be halogen containing flame-retardant, simultaneously be used as fire retarding synergist for the flame retardant effect that promotes halogen containing flame-retardant has also cooperated oxide compound, stibnate or the V family metallic element compound of antimony.Halogen containing flame-retardant refers to contain the fire retardant of elements such as Cl, Br, F, halogen containing flame-retardant is the maximum flame retardant products of fire-retardant application in the present plastic, rubber material, mainly be that it is organic fire-retardant, chemical property is inertia, relatively good with the consistency of plastics, good flame retardation effect, use cost are low, and many features all are that other fire retardant is irreplaceable, but the Halogen fire retardant material can produce a large amount of smog and poisonous corrosive hydrogen halides gas, causes secondary harm.Now forbid fully in some developed countries, obviously prior art has further improved necessity.
Summary of the invention
The object of the present invention is to provide a kind of halogen-free flame-retardant nylon resin composition, to overcome the problem that prior art exists.
A kind of halogen-free flame-retardant nylon resin composition of the present invention, count by weight that it is composed as follows:
Described glass fibre is the alkali-free short glass fiber;
Described fire retardant is selected from least a in triphenylphosphate, Tritolyl Phosphate, dihydroxyphenyl propane bis phosphoric acid diphenyl ester and the melamine polyphosphate (MPP);
Described toughner is selected from least a in terpolymer EP rubber (EPDM), methyl methacrylate-butadiene-styrene (MBS), maleic anhydride graft Low Density Polyethylene (LDPE-G-MAH) and the maleic anhydride graft styrene-ethylene-butylene-styrene segmented copolymer (SEBS-G-MAH);
Described photostabilizer is selected from Whitfield's ointment dihydroxyphenyl propane ester, 2-hydroxyl-4 n-octyloxies-benzophenone, 2,4 dihydroxyl benzophenone and 2-(2 '-dihydroxyl-3 '-tertiary butyl-5 '-aminomethyl phenyl)-at least a in the 5-chlorobenzotriazole;
Described flowing agent is selected from least a in ethylene bis stearamide (EBS), tetramethylolmethane stearic acid (PETS), PE wax and the PP wax.
This halogen-free flame-retardant nylon resin composition of the present invention can use any known plastic working method preparation, as by processing such as forcing machine, mixing machine, kneaders, can be periodical operation, also can be operate continuously.Recommend to use the preparation of twin screw extruder melt-blending process, each component mixes back employing standard twin screw extruder and standard technology extruding pelletization, namely gets halogen-free flame-retardant nylon resin composition product.
This case contriver surprising discovery, this halogen-free flame-retardant nylon resin composition of the present invention, adopt halogen-free flame retardants as fire retardant material fully, but its performance has reached the performance index that adopt the nylon resin composition of halogen fire retardant comprehensively, obvious purpose of the present invention is achieved.
Embodiment
The invention will be further described below with reference to a kind of halogen-free flame-retardant nylon resin composition that preferred embodiment of the present invention provides.
Embodiment: the prescription of each embodiment is shown in table 1, and the prescription of described each embodiment is meter by weight.Performance perameter title and the test condition of the halogen-free flame-retardant nylon resin composition product of each embodiment gained are shown in table 2, and the performance index representative value that the condition test that the halogen-free flame-retardant nylon resin composition product of each embodiment gained lists by table 2 obtains is shown in table 3.
Table 1: embodiment one to embodiment three prescription
Figure BDA00003543329700031
Performance perameter title and the test condition of the halogen-free flame-retardant nylon resin composition product of table 2: embodiment one to embodiment three gained:
The performance index of the flame retardant type nylon resin composition product of table 3:ZL201110117041.5 embodiment three and the halogen-free flame-retardant nylon resin composition product of the embodiment of the invention one to embodiment three gained.
Figure BDA00003543329700042
The halogen-free flame-retardant nylon resin composition of each embodiment mixes the side of extruding pelletization afterwards with each component, namely gets the halogen-free flame-retardant reinforced nylon resin combination.Use homogenizer to stir when suggestion mixes, adopt the 75# twin screw extruder when extruding, rotating speed is 450r/min, and the first district of forcing machine temperature is 260 ℃, and two district's temperature are 270 ℃, and three district's temperature are 270 ℃, and four district's temperature are 270 ℃, and five district's temperature are 265 ℃.

Claims (4)

1. halogen-free flame-retardant nylon resin composition, it is composed as follows to it is characterized in that counting it by weight:
Nylon 66(PA66) 58 part
30 parts in glass fibre (GF)
1 ~ 10 part of fire retardant
1 ~ 10 part of toughner
0.1 ~ 5 part of flowing agent
0.5 ~ 5 part of photostabilizer
Described glass fibre is the alkali-free short glass fiber;
Described fire retardant is selected from least a in triphenylphosphate, Tritolyl Phosphate, dihydroxyphenyl propane bis phosphoric acid diphenyl ester and the melamine polyphosphate (MPP);
Described toughner is selected from least a in terpolymer EP rubber (EPDM), methyl methacrylate-butadiene-styrene (MBS), maleic anhydride graft Low Density Polyethylene (LDPE-G-MAH) and the maleic anhydride graft styrene-ethylene-butylene-styrene segmented copolymer (SEBS-G-MAH);
Described photostabilizer is selected from Whitfield's ointment dihydroxyphenyl propane ester, 2-hydroxyl-4 n-octyloxies-benzophenone, 2,4 dihydroxyl benzophenone and 2-(2 '-dihydroxyl-3 '-tertiary butyl-5 '-aminomethyl phenyl)-at least a in the 5-chlorobenzotriazole;
Described flowing agent is selected from least a in ethylene bis stearamide (EBS), tetramethylolmethane stearic acid (PETS), PE wax and the PP wax.
2. a kind of halogen-free flame-retardant nylon resin composition according to claim 1, it is composed as follows to it is characterized in that counting it by weight: nylon 66(PA66) 58 parts, 30 parts in glass fibre (GF), 5 parts of melamine polyphosphates, 5 parts of methyl methacrylate-butadiene-styrenes, 1.5 parts of 2,4 dihydroxyl benzophenones, 0.5 part of tetramethylolmethane stearic acid (PETS).
3. a kind of halogen-free flame-retardant nylon resin composition according to claim 1, it is composed as follows to it is characterized in that counting it by weight: nylon 66(PA66) 58 parts, 30 parts in glass fibre (GF), 2 parts of melamine polyphosphates, 5 parts of methyl methacrylate-butadiene-styrenes, 1.5 parts of 2,4 dihydroxyl benzophenones, 0.5 part of tetramethylolmethane stearic acid (PETS).
4. a kind of halogen-free flame-retardant nylon resin composition according to claim 1, it is composed as follows to it is characterized in that counting it by weight: nylon 66(PA66) 58 parts, 30 parts in glass fibre (GF), 5 parts of melamine polyphosphates, 2 parts of methyl methacrylate-butadiene-styrenes, 1.5 parts of 2,4 dihydroxyl benzophenones, 0.5 part of tetramethylolmethane stearic acid (PETS).
CN2013103074661A 2013-07-22 2013-07-22 Halogen-free flame retardant nylon resin composition Pending CN103333492A (en)

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104559174A (en) * 2015-01-29 2015-04-29 北京科方创业科技企业孵化器有限公司 Preparation method of unenhanced halogen-free flame retardant nylon 66
CN104861647A (en) * 2015-05-07 2015-08-26 贵州航天凯宏科技有限责任公司 Anti-corrosion material for automobile radiator intake chambers
CN105385155A (en) * 2015-12-31 2016-03-09 祥兴(福建)箱包集团有限公司 Nylon plastic bearing retainer for draw-bar box and preparation method of nylon plastic bearing retainer
CN105602244A (en) * 2016-02-04 2016-05-25 南通瑞隆新材料有限公司 Preparation method of glass fiber reinforced nylon
CN105778495A (en) * 2016-04-06 2016-07-20 广东泰昊新材料科技有限公司 Reinforced nylon plastic for water pump impeller by high-frequency welding and preparation method thereof
CN106497038A (en) * 2016-11-02 2017-03-15 安徽隆宇塑业有限公司 A kind of nylon 66 composite material
CN106854359A (en) * 2016-11-24 2017-06-16 广东美塑塑料科技有限公司 Inexpensive high heat-resistant halogen-free flame-retardant reinforced plastic PA66 composition and preparation method thereof
CN106867249A (en) * 2017-02-24 2017-06-20 上海凯赛生物技术研发中心有限公司 One kind enhancing static resistant polyamide composite and preparation method thereof
CN106883603A (en) * 2017-02-24 2017-06-23 上海凯赛生物技术研发中心有限公司 A kind of antistatic enhancing flame-retardant polyamide composite material and preparation method thereof
CN107987524A (en) * 2017-12-11 2018-05-04 青岛科技大学 A kind of preparation of low-cost and high-performance halogen-free flame-retardant nylon material

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CN1314898A (en) * 1998-07-08 2001-09-26 Dsm有限公司 Polyphosphate salt of 1,3,5-triazine compound with high degree of condensation and its use as flame retardent in polymer compositions
CN101280105A (en) * 2008-04-11 2008-10-08 卢文生 Preparation of halogen-free flame-proof nylon 66 having high-mechanical property and composite material
CN101307147A (en) * 2007-09-18 2008-11-19 佛山市南海易乐工程塑料有限公司 Glass fibre reinforced nylon colorful heat insulation stripe for al-alloy door & window and method for preparing same
CN101440210A (en) * 2007-11-19 2009-05-27 上海日之升新技术发展有限公司 Environment-protecting flame-retardant composite filling reinforced nylon 6 resin composition
CN101659787A (en) * 2009-09-14 2010-03-03 浙江工业大学 Special material of high-strength flame-retardant reinforced nylon 6 and preparation method thereof
CN102643541A (en) * 2012-04-27 2012-08-22 常熟市发东塑业有限公司 Antibacterial halogen-free flame retardant nylon alloy material
CN103131175A (en) * 2011-11-25 2013-06-05 上海日之升新技术发展有限公司 Low smoke halogen-free flame retardant reinforced nylon composite material and manufacture method

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Publication number Priority date Publication date Assignee Title
US6008349A (en) * 1996-05-22 1999-12-28 Nissan Chemical Industries, Ltd. Melamine polymetaphosphate and process for its production
CN1314898A (en) * 1998-07-08 2001-09-26 Dsm有限公司 Polyphosphate salt of 1,3,5-triazine compound with high degree of condensation and its use as flame retardent in polymer compositions
CN101307147A (en) * 2007-09-18 2008-11-19 佛山市南海易乐工程塑料有限公司 Glass fibre reinforced nylon colorful heat insulation stripe for al-alloy door & window and method for preparing same
CN101440210A (en) * 2007-11-19 2009-05-27 上海日之升新技术发展有限公司 Environment-protecting flame-retardant composite filling reinforced nylon 6 resin composition
CN101280105A (en) * 2008-04-11 2008-10-08 卢文生 Preparation of halogen-free flame-proof nylon 66 having high-mechanical property and composite material
CN101659787A (en) * 2009-09-14 2010-03-03 浙江工业大学 Special material of high-strength flame-retardant reinforced nylon 6 and preparation method thereof
CN103131175A (en) * 2011-11-25 2013-06-05 上海日之升新技术发展有限公司 Low smoke halogen-free flame retardant reinforced nylon composite material and manufacture method
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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104559174A (en) * 2015-01-29 2015-04-29 北京科方创业科技企业孵化器有限公司 Preparation method of unenhanced halogen-free flame retardant nylon 66
CN104861647A (en) * 2015-05-07 2015-08-26 贵州航天凯宏科技有限责任公司 Anti-corrosion material for automobile radiator intake chambers
CN105385155A (en) * 2015-12-31 2016-03-09 祥兴(福建)箱包集团有限公司 Nylon plastic bearing retainer for draw-bar box and preparation method of nylon plastic bearing retainer
CN105602244A (en) * 2016-02-04 2016-05-25 南通瑞隆新材料有限公司 Preparation method of glass fiber reinforced nylon
CN105778495A (en) * 2016-04-06 2016-07-20 广东泰昊新材料科技有限公司 Reinforced nylon plastic for water pump impeller by high-frequency welding and preparation method thereof
CN106497038A (en) * 2016-11-02 2017-03-15 安徽隆宇塑业有限公司 A kind of nylon 66 composite material
CN106854359A (en) * 2016-11-24 2017-06-16 广东美塑塑料科技有限公司 Inexpensive high heat-resistant halogen-free flame-retardant reinforced plastic PA66 composition and preparation method thereof
CN106867249A (en) * 2017-02-24 2017-06-20 上海凯赛生物技术研发中心有限公司 One kind enhancing static resistant polyamide composite and preparation method thereof
CN106883603A (en) * 2017-02-24 2017-06-23 上海凯赛生物技术研发中心有限公司 A kind of antistatic enhancing flame-retardant polyamide composite material and preparation method thereof
CN106867249B (en) * 2017-02-24 2019-11-29 上海凯赛生物技术股份有限公司 A kind of enhancing static resistant polyamide composite material and preparation method
CN106883603B (en) * 2017-02-24 2021-09-07 上海凯赛生物技术股份有限公司 Antistatic reinforced flame-retardant polyamide composite material and preparation method thereof
CN107987524A (en) * 2017-12-11 2018-05-04 青岛科技大学 A kind of preparation of low-cost and high-performance halogen-free flame-retardant nylon material

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Application publication date: 20131002