CN101328304A - Flame-retardant anti-dropping thermoplastic resin composition - Google Patents
Flame-retardant anti-dropping thermoplastic resin composition Download PDFInfo
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- CN101328304A CN101328304A CNA2007100238518A CN200710023851A CN101328304A CN 101328304 A CN101328304 A CN 101328304A CN A2007100238518 A CNA2007100238518 A CN A2007100238518A CN 200710023851 A CN200710023851 A CN 200710023851A CN 101328304 A CN101328304 A CN 101328304A
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- retardant
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Abstract
The invention discloses a thermoplastic resin composition with fire retardant anti-dripping performance. The composition comprises the following components: (a) thermoplastic resin; (b) silicon containing cross linker selected from polysiloxane and silicone resin; (c) phosphorus containing fire retardant selected from organic phosphate, phosphonate and phosphorus oxide; (d) nitrogen containing fire retardant with a ring structure selected from triazine, cyanuramide, cyanurate and isocyanurate. The composition of the invention does not contain halogen and also has extremely excellent fire retardant anti-dripping performance.
Description
Technical field:
The present invention relates to a kind of flame-retardant anti-dropping thermoplastic resin composition.
Background technology:
That thermoplastic material has is light, manufacture method simply, dye, be convenient to the advantage of scale operation easily, be widely used in various fields such as interior materials such as home textile product, automobile, aircraft, construction material.But thermoplastic resin has a very big shortcoming, that is easy firing when meeting fire, self is heated and softening transform takes place even drip to hang down.In order to overcome these shortcomings, normally add one or more fire retardants to improve its inflammableness in thermoplastic resin, these fire retardants comprise halogenated flame retardant, inorganic combustion inhibitor, organophosphorus system and phosphorus-halogenated flame retardant, expansion type flame retardant, silicon-series five-retardant or the like.Yet, these additives can bring extra problem again during burning, for example, if when containing halogenide such as bromine compounds in the fire retardant that is added, when burning and high temperature, easily discharge deleterious flue dust and gas, for example the aromatics of high bromine content is when burning and high temperature, can produce the bromination furans and the Xiuization dioxin compound of severe toxicity, badly influence people's health and environment, even it is not burned, a large amount of wastes that use these fire retardants, its recovery and handle environment and Yan Junhui throws into question.In addition,,, cause secondary combustion easily, cause any property loss and personnel's injury preventing that effect is limited aspect the melt drippage though some fire retardant can effectively suppress burning.
Therefore, for thermoplastic polyester, the utmost point need be developed a kind of not halogen-containing anti-drippage fire retardant.And in the present not halogen-containing flame retardant system of developing, what attract most attention is that phosphorus is and the nitrogen flame retardant.Phosphorus series compound is as the fire retardant of thermoplastic polyester, and known have No. 491,986, European patent and No. 685,518, European patent and a USP5, and 733,957, it discloses use aromatic phosphoric acid ester oligomer as fire retardant.Use aromatic phosphoric acid ester oligomer is disclosed for Japanese patent laid-open 10-60160 number as fire retardant and cooperate other fire retardant or flame retardant such as silicon compound.Japanese patent laid-open 10-251497 number and spy open flat 11-21458 and then disclose use red phosphorus and small molecules phosphate compound respectively as fire retardant.In addition, the phosphate compound that uses as phenolic aldehyde is then disclosed as fire retardant for Japanese kokai publication hei 7-292050 number.And USP4,278,591 and 5,618,865 items disclose and have used derived from the compound nitrogen series of the trimeric cyanamide fire retardant as thermoplastic polyester.In addition, the flame retardant system that more thermoplastic polyester is arranged then is in conjunction with phosphorus system and compound nitrogen series, so as to strengthening its flame retardant effect and improving thermal properties and melt-processed character, as USPS, 814,690, Japanese kokai publication hei 10-175,985 and the spy open flat 9-296120.
In order to reach the performance requriements of anti-drippage, some have the document that the high molecular polymer that is subjected to heat shrinkability characteristic is used to improve melt droplets report have been arranged.For example: Japanese Patent 3-190958 discloses the resin combination of silicon rubber as anti-dripping agent; The patent CN96195311 of Germany BASF AG has introduced a kind of aromatic ethenyl thing.Having the fluorine resin that is fine performance in recent years becomes the development main flow as Antidrip agent, and existing various trials use fluoropolymer to improve the fire-retardant anti-drippage performance of synthetic resins.
Summary of the invention:
The object of the present invention is to provide a kind of flame-retardant anti-dropping thermoplastic resin composition, it is not halogen-containing, can improve the flame-retardant nature of thermoplastic polyester, anti-drippage performance, has good especially flame-retardant anti-dropping and high heat resistance.
Technical solution of the present invention is:
A kind of flame-retardant anti-dropping thermoplastic resin composition is characterized in that: comprise following weight item:
(a) thermoplastic resin 100 weight parts;
(b) silicon class linking agent 2-10 weight part, and silicon class linking agent is at least a in polysiloxane-based linking agent, the silicone resin class linking agent;
(c) phosphonium flame retardant 15-35 weight part, and phosphonium flame retardant is at least a in phosphoric acid ester fire retardant, phosphonic acid ester fire retardant, the phosphorus oxide based flame retardant;
(d) contain nitrogen combustion inhibitor 10-20 weight part, and to contain nitrogen combustion inhibitor be that triazines, melamine class, cyanurate class, isocyanuric acid ester class have at least a in the fire retardant of ring texture.
Described thermoplastic resin is at least a in polyester, liquid crystal type polyester, Wholly aromatic polyester, polycarbonate, polymeric amide, fully aromatic polyamide, polyimide, polystyrene, polyphenylene oxide, Polyphenylene Sulfone, the polysulfones.
Described polyester is polyethylene terephthalate and/or polybutylene terephthalate.
Silicon class linking agent has following general structure:
R wherein
1And R
2Be identical or different-OH, H, siliceous biphenyl alkane or silylation, R
3Be siloxy or phenyl.
Phosphonium flame retardant is with to contain nitrogen combustion inhibitor consumption sum be the 25-45 weight part, and phosphonium flame retardant and the weight ratio that contains nitrogen combustion inhibitor are at least 1.2.
Phosphonium flame retardant has following general structure:
R wherein
4, R
5And R
6Be identical or different H, C
1-12Alkyl, stretch on phenyl, phenoxy group or the phenyl ring phenyl that replaces through hydroxyl.
Perhaps:
R wherein
10-R
13Be C independently of one another
1-C
6Alkyl, C
6-C
12Aryl, C
7-C
12Aralkyl or C
7-C
12Alkaryl, X are the diphenol compound H O-X-OH (for example dihydroxyphenyl propane) that has the group of at least two aryl units, and monohydroxy compound R that can be identical or different
4OH-R
7OH, for example phenol.
The following phosphonium flame retardant that comprises that other is suitable comprises the phosphamide of following general structure:
R wherein
14Can be amino, R
15And R
16Be C independently
1-C
12Alkoxyl group, C
6-C
12Aryloxy or C
6-C
12The aryloxy residue, it contains at least one alkyl or amino.Preferably phosphamide has at least about 0 ℃, preferably at least about 10 ℃, more preferably at least about 20 ℃ glass transition point.
Other phosphamides comprise those of following general structure:
Wherein each A is phenyl, 2 independently, 6-3,5-dimethylphenyl or 2,4,6-trimethylphenyl.Preferred phosphamide is four-xylyl piperazine, two phosphamides.
Phosphonium flame retardant can mix use with one or more nitrogenous fire retardants.The suitable nitrogen combustion inhibitor that contains comprises a kind of or its mixture in the nitrogen combustion inhibitor of containing such as triazines, cyanurate class and isocyanuric acid ester class.It is triazines that wherein preferred ring-type contains nitrogen combustion inhibitor, has following general structure:
R wherein
7, R
8And R
9Be C independently
1-C
12Alkyl, C
1-C
12Alkoxyl group, C
6-C
12Aryl, amino, C
1-C
12Amino or hydrogen that alkyl replaces.Preferred triazines comprises 2,4,6-triamine-1,3,5-triazines, melamine derivative, melam, melem, cyanogen urea acid amide, cyanurodiamide, cyanuramide, 2-urea groups melamine, acetylguanamine, benzoguanamine etc.Can use the salt/adducts of these compounds and boric acid or phosphoric acid in the composition.Example comprises melamine pyrophosphate salt and melamine polyphosphate.Preferred cyanurate/isocyanuric acid salt compound comprises the salt/adducts of triaizine compounds and the acid of cyanogen urea, for example melamine cyanurate.
Another nitrogen combustion inhibitor that contains that preferably has ring texture is the isocyanuric acid ester class, has following general structure:
Wherein R ' is C independently
1-C
12Alkyl, C
1-C
12Alkoxyl group, C
6-C
12Aryl, amino, C
1-C
12Amino or hydrogen that alkyl replaces.
The preferred nitrogen combustion inhibitor that contains is above two kinds of mixtures that contain nitrogen combustion inhibitor.
Thermoplastic polyester among the present invention is meant the polyester that has flowability and machine-shaping according to this after the heating.The specific examples of thermoplastic polyester of the present invention comprises: polyester, as poly-to (ethylene glycol terephthalate) (PET), poly-(mutual-phenenyl two acid bromide two alcohol ester) (PBT); Wholly aromatic polyester; Polycarbonate; Fully aromatic polyamide; Polyimide; Polystyrene; Polyphenylene oxide; Polyethersulfone; Polysulfones; Acrylonitrile-butadiene-styrene (ABS) (ABS) multipolymer etc.This polyester can be separately or is used with two or more the form of mixture.
Can contain in the composition based on the thermoplastic resin gross weight is the phosphonium flame retardant of 15-35.In this scope, preferably use and be at least 15, more preferably at least about 25 phosphonium flame retardant.
Can contain in the composition based on the thermoplastic resin gross weight is the nitrogen combustion inhibitor that contains of 1-30 weight part.In this scope, preferably use at least about 10 weight parts the preferred nitrogen combustion inhibitor that contains at least about 12 weight parts.Equally in this scope, preferably use about 25 weight parts at most, preferred about 20 weight parts at most contain nitrogen combustion inhibitor.
In fire-retardant thermoplastic resin composite of the present invention, also can add metal oxide or metal hydroxides, so as to its flame-retarding characteristic of further raising.The example comprises for example magnesium oxide, magnesium hydroxide, aluminum oxide, aluminium hydroxide etc.
The usage quantity of this metal oxide or metal hydroxides with respect in 100 weight part thermoplastic resins, is used 0 to 100 weight part, is preferably 0.5 to 80 weight part, more preferably 2 to 60 weight parts.
In flame-retardant anti-dropping thermoplastic resin composition of the present invention, also can add the known additive that is customarily used among the thermoplastic resin composition, only otherwise halogen-containing getting final product.These additives comprise for example thermo-stabilizer, antioxidant, UV light absorber, plasticizer, releasing agent, dyestuff, pigment and tinting material etc.
Be the physical strength of strengthening flame-retardant anti-dropping thermoplastic resin composition of the present invention and rigidity etc., can in composition of the present invention, add fibrous or granulous inorganic filling material, for example glass fibre, sheet glass, granulated glass sphere, carbon fiber, steel fiber, fragrant adoption phthalein amine fiber, barium sulfate, mica, talcum powder etc.
As from the foregoing, flame-retardant anti-dropping thermoplastic resin composition of the present invention is because not halogen-containing and antimonous oxide, and has good especially anti-drippage, flame retardant resistance and high heat resistance; Fire-retardant thermoplastic resin composite of the present invention in addition has the hanging low property of resin and the fire retardant of improvement separates out, and has kept the workability of thermoplastic resin and good physical property; Thereby can be in order to make e-machine articles for use, electric product articles for use, automobile spare part articles for use etc.
Below the invention will be further described by specific embodiment and comparative example, but the embodiment of the invention and comparative example are only in order to explanation the present invention but not in order to limit the scope of the invention.
Embodiment:
In the following example and comparative example, used following commercially available prod:
Thermoplastic polyester gathers (ethylene glycol terephthalate), is produced by Dong Li company, is half delustring section, and its IV value is 0.66.
Siliceous linking agent A: provided by Dong Li company, its structural formula is as follows:
P contained compound B: produced by Jiangsu Province Ru Dong fine chemistry industry company, structural formula is as follows:
P contained compound C: company limited is provided by the anti-chemical industry of Shanghai ancient cooking vessel, and structural formula is as follows:
P contained compound D: company limited is provided by the anti-chemical industry of Shanghai ancient cooking vessel, and structural formula is as follows:
Nitrogenous compound E: fire-retardant Science and Technology Ltd. provides by Lianyun Harbour legend, and its structural formula is as follows:
After composition as shown in table 1 below mixed with listed amount, mix 275 ℃ of fusions with the twin screw extruder of 18 millimeters of diameters, resulting composition after measured and observe its flame retardant resistance, anti-drippage property, dispersiveness and surface effect, its result is as shown in table 1.
The mensuration of flame retardant resistance and anti-drippage behavior: flat strips is made combustion test with flame according to UL-4294.When satisfying following criterion, fire-retardant thermoplastic resin can carry out classification by burning grade UL-94V0:
Select for use a cover to have five samples that are of a size of 127 * 12.7 * 1.6mm,, do not have sample can burn away above 10 seconds by after 10 seconds of twice usefulness naked light (flame height 19mm) sustained combustion.Under with 5 samples of 10 flame ignition burning, the summation of its time that burns away was no more than for 50 seconds.Drippage, perfect combustion or the development burning of particle of must not catching fire surpassed for 30 seconds.Classification in burning grade UL94VI requires to be no more than for 30 seconds and to be no more than for 250 seconds with the summation of time that burns away of 5 samples of 10 flame ignition for time of burning away respectively.The development burning must be no more than for 60 seconds.Other criterion is same as described above.When the criterion outside satisfying burning grade UL94V1 and the drippage of the particle that catches fire, suit with burning grade UL94V2 classification.
Dispersed: adopt appearance method that the dispersiveness of gained blend is carried out classification, when the blend blend evenly and extrude easily, judge that then it is better dispersed; Be bonded on the extrusion screw rod when blend and extrude more at need, its dispersiveness is then relatively poor.
Surface effect: adopt appearance method to carry out classification to extruding section, slice surface feels that very smooth smooth then to be considered as surface effect fine; A foreign matter is arranged a little then be considered as more smooth if feel; Foreign matter is bigger, and just looking at up is not that the very smooth crystalline substance that then is considered as is put coarse.
The main composition and the character thereof of thermoplastic shaping material are listed in table 1.
Table 1:
Claims (8)
1, a kind of flame-retardant anti-dropping thermoplastic resin composition is characterized in that: comprise following weight item:
(a) thermoplastic resin 100 weight parts;
(b) silicon class linking agent 2-10 weight part, and silicon class linking agent is at least a in polysiloxane-based linking agent, the silicone resin class linking agent;
(c) phosphonium flame retardant 15-35 weight part, and phosphonium flame retardant is at least a in phosphoric acid ester fire retardant, phosphonic acid ester fire retardant, the phosphorus oxide based flame retardant;
(d) contain nitrogen combustion inhibitor 10-20 weight part, and to contain nitrogen combustion inhibitor be that triazines, melamine class, cyanurate class, isocyanuric acid ester class have at least a in the fire retardant of ring texture.
2, flame-retardant anti-dropping thermoplastic resin composition according to claim 1 is characterized in that: described thermoplastic resin is at least a in polyester, liquid crystal type polyester, Wholly aromatic polyester, polycarbonate, polymeric amide, fully aromatic polyamide, polyimide, polystyrene, polyphenylene oxide, Polyphenylene Sulfone, the polysulfones.
3, flame-retardant anti-dropping thermoplastic resin composition according to claim 2 is characterized in that: described polyester is polyethylene terephthalate and/or polybutylene terephthalate.
4, according to claim 1,2 or 3 described flame-retardant anti-dropping thermoplastic resin compositions, it is characterized in that: silicon class linking agent has following general structure:
R wherein
1And R
2Be identical or different-OH, H, siliceous biphenyl alkane or silylation, R
3Be siloxy or phenyl.
5, according to claim 1,2 or 3 described flame-retardant anti-dropping thermoplastic resin compositions, it is characterized in that: phosphonium flame retardant is with to contain nitrogen combustion inhibitor consumption sum be the 25-45 weight part, and phosphonium flame retardant and the weight ratio that contains nitrogen combustion inhibitor are at least 1.2.
6, according to claim 1,2 or 3 described flame-retardant anti-dropping thermoplastic resin compositions, it is characterized in that: phosphonium flame retardant has following general structure:
R wherein
4, R
5And R
6For identical or different and represent H, C
1-12Alkyl, stretch on phenyl, phenoxy group or the phenyl ring phenyl that replaces through hydroxyl.
7, according to claim 1,2 or 3 described flame-retardant anti-dropping thermoplastic resin compositions, it is characterized in that: the nitrogen combustion inhibitor that contains of ring texture is a triazines, has following general structure:
R wherein
7, R
8And R
9Be C independently
1-C
12Alkyl, C
1-C
12Alkoxyl group, C
6-C
12Aryl, amino, C
1-C
12Amino or hydrogen that alkyl replaces.
8, according to claim 1,2 or 3 described flame-retardant anti-dropping thermoplastic resin compositions, it is characterized in that: it is the isocyanuric acid ester class that cyclic contains nitrogen combustion inhibitor, has following general structure:
Wherein R ' is C independently
1-C
12Alkyl, C
1-C
12Alkoxyl group, C
6-C
12Aryl, amino, C
1-C
12Amino or hydrogen that alkyl replaces.
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| CNA2007100238518A CN101328304A (en) | 2007-06-22 | 2007-06-22 | Flame-retardant anti-dropping thermoplastic resin composition |
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|---|---|---|---|
| CNA2007100238518A CN101328304A (en) | 2007-06-22 | 2007-06-22 | Flame-retardant anti-dropping thermoplastic resin composition |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101942189A (en) * | 2010-10-25 | 2011-01-12 | 江苏技术师范学院 | Halogen-free flame-retardant PC/PBT alloy material and preparation method thereof |
| CN102382448A (en) * | 2011-09-07 | 2012-03-21 | 上海日之升新技术发展有限公司 | Halogen free inflaming retardant polyphenylene oxide alloy and preparation method thereof |
| JP2014185293A (en) * | 2013-03-25 | 2014-10-02 | Mitsubishi Chemicals Corp | Curable silicone resin |
| CN104387571A (en) * | 2014-11-10 | 2015-03-04 | 杭州湘隽纺织阻燃科技有限公司 | Phosphorous-nitrogen-containing polyethylene glycol terephthalate flame retardant copolyester and application of flame retardant copolyester |
| US20150313012A1 (en) * | 2012-11-27 | 2015-10-29 | Shengyi Technology Co., Ltd. | Resin composition and its use |
| CN109705341A (en) * | 2019-01-10 | 2019-05-03 | 军事科学院系统工程研究院军需工程技术研究所 | A kind of P-N-Si synergistic fire-resistant copolyesters polyamide 66 and preparation method thereof |
-
2007
- 2007-06-22 CN CNA2007100238518A patent/CN101328304A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101942189A (en) * | 2010-10-25 | 2011-01-12 | 江苏技术师范学院 | Halogen-free flame-retardant PC/PBT alloy material and preparation method thereof |
| CN102382448A (en) * | 2011-09-07 | 2012-03-21 | 上海日之升新技术发展有限公司 | Halogen free inflaming retardant polyphenylene oxide alloy and preparation method thereof |
| CN102382448B (en) * | 2011-09-07 | 2013-05-29 | 上海日之升新技术发展有限公司 | Halogen free inflaming retardant polyphenylene oxide alloy and preparation method thereof |
| US20150313012A1 (en) * | 2012-11-27 | 2015-10-29 | Shengyi Technology Co., Ltd. | Resin composition and its use |
| US10149380B2 (en) * | 2012-11-27 | 2018-12-04 | Shengyi Technology Co., Ltd. | Resin composition and its use |
| JP2014185293A (en) * | 2013-03-25 | 2014-10-02 | Mitsubishi Chemicals Corp | Curable silicone resin |
| CN104387571A (en) * | 2014-11-10 | 2015-03-04 | 杭州湘隽纺织阻燃科技有限公司 | Phosphorous-nitrogen-containing polyethylene glycol terephthalate flame retardant copolyester and application of flame retardant copolyester |
| CN104387571B (en) * | 2014-11-10 | 2015-10-28 | 杭州湘隽纺织阻燃科技有限公司 | Phosphorus-nitrogen containing polyethylene terephthalate flame-proof copolyester and application thereof |
| CN109705341A (en) * | 2019-01-10 | 2019-05-03 | 军事科学院系统工程研究院军需工程技术研究所 | A kind of P-N-Si synergistic fire-resistant copolyesters polyamide 66 and preparation method thereof |
| CN109705341B (en) * | 2019-01-10 | 2021-04-16 | 军事科学院系统工程研究院军需工程技术研究所 | P-N-Si synergistic flame-retardant copolymerized polyamide 66 and preparation method thereof |
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Open date: 20081224 |