CN109735100A - A kind of halogen flame-retardant polyamide composite material of no antimony and preparation method thereof - Google Patents
A kind of halogen flame-retardant polyamide composite material of no antimony and preparation method thereof Download PDFInfo
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Abstract
The invention discloses halogen flame-retardant polyamide composite materials of a kind of no antimony and preparation method thereof, include component: 20-80 parts of polyamide；1-30 parts of bromide fire retardant；0.01-15 parts of condensation of aluminum phosphate.The present invention is using condensation of aluminum phosphate as new flame retardant, under the premise of not introducing stibium trioxide, the flame retardant effect same with bromo- antimony flame-retardant system can be reached, it can assign bromine system Flameproof polyamide excellent electric property simultaneously, and harm of the mitigation to environment and human body, have than bromo- antimony flame-retardant polyamide composite material and is more widely applied range.
Description
Technical field
The invention belongs to engineering plastics technical field, in particular to the halogen Flameproof polyamide composite wood of a kind of no antimony
Material and preparation method thereof.
Background technique
Polyamide has good fire-retardant, belongs to self-extinguishing, electrical insulation capability is good (CTI 600), but still being can
More easy firing after the substances such as glass fibre is added, due to feelings such as electric leakage, short circuit, electric arc, sparks in live line work environment in combustion things
Condition causes the case where fire to still have, and therefore, polyamide material is for that must carry out fire-retardant change before producing electronics, electric component
Property, and the flame-retardant modified reduction that may result in its creepage trace index (CTI) to polyamide material, such as it is halogen fire-retardant
The CTI value of the fire-retardant polyamide material of agent can be down to 300 or so.
Bromine system fire-retardant polyamide material has flame retarding efficiency height, excellent in mechanical performance etc. advantage, widely answers at present
For fields such as electric industries.At this stage, in the formula design process of bromine system fire-retardant polyamide material, mainly pass through
The mode of bromo- antimony compounding realizes its excellent flame retardant property, but this formula design is also the application of fire-retardant polyamide material
Bring some problems: 1. bromo- antimony compound systems have excellent at carbon performance, this can be to bromine system fire-retardant polyamide material
CTI causes certain negative effect；2. fire retardant containing antimony can generate the device in Gas such as antimonous bromide in process, not only for
Instrument and equipment has certain corrosiveness, and larger harm can be also caused to environment and health of human body, and certain countries and area have gone out
The relevant laws and regulations of platform control the use of antimony.For these reasons, to need to find antimony class in engineering field fire-retardant
The substitute of agent can assign bromine system Flameproof polyamide excellent electric property, and mitigate on the basis of keeping flame retardant property
Harm to environment and human body.
2009/0069478 A1 of patent US discloses a kind of extremely low fire-retardant scheme of bromine system of antimony substance, which adopts
It uses brominated Polystyrene as main fire retardant, and using zinc salt or calcium salt as synergistic flame retardant, on this basis, need to only add
Add the antimony oxide of extremely low content to can reach preferable flame retardant effect.2007267607 A of patent US discloses a kind of no antimony
Change the fire-retardant scheme of bromine system, on the basis of adding bromide fire retardant, further adds zinc salt and suitable Antidrip agent, finally
Preferable flame retardant effect is obtained.8889770 B2 of patent US discloses a kind of fire-retardant scheme of bromine system of no antimony, using bromination
Polyphenylene ether and phenoxy group oligomer and polymer compounding mode can obtain preferable flame retardant effect.
At this stage, although having there are some low antimony or the bromine system Flameproof polyamide scheme without antimony to occur, these sides
The flame retarding efficiency of case still shows slightly insufficient compared to bromo- sb system, and less focuses on the CTI performance of material, so that these
There are potential risks for application of the no fire-retardant scheme of antimonyization in electronic and electrical field.
Summary of the invention
To overcome the problems of the above-mentioned prior art, the purpose of the present invention is to provide a kind of the halogen fire-retardant of no antimony
Polyamide compoiste material, which can not only reach the flame retardant effect same with bromo- antimony flame-retardant system, while can have
Effect promotes CTI.
The purpose of the present invention is realized by following proposal:
A kind of halogen flame-retardant polyamide composite material of no antimony includes according to parts by weight following components:
20-80 parts of polyamide；
1-30 parts of bromide fire retardant；
0.01-15 parts of condensation of aluminum phosphate.
The technical solution further preferred as the present invention, a kind of halogen Flameproof polyamide composite wood of no antimony
Material,
According to parts by weight, include following components:
25-55 parts of polyamide；
10-25 parts of bromide fire retardant；
1-12 parts of condensation of aluminum phosphate.
Polyamide of the present invention is selected from the polyamide obtained by diamine and dicarboxylic acids polycondensation, passes through
Polyamide that the ring-opening polymerisation of lactams obtains, the polyamide self condensed by amino carboxylic acid, Yi Jitong
Polyamide copolymer obtained from the copolymerization for the unit that two kinds or more constitute these polyamides is crossed, in the present invention, is gathered
One of above-mentioned polyamide can be individually used only in amide resin, and two kinds or more, preferably polyamides can also be applied in combination
Amine 66 or polyamide 6.
Bromide fire retardant of the present invention is brominated polystyrene, poly- bromstyrol copolymer, brominated epoxy resin
Or the mixing of one or more of brominated polyphenylene oxide, preferred brominated polyphenyl second of the bromine content within the scope of 60-70 weight %
Alkene, higher bromine content allows lower fire retardant to load, and better flowing property.
Condensation of aluminum phosphate of the present invention is mainly the mixture of phosphorus pentoxide and aluminum oxide, wherein three oxidations
The weight content of two aluminium is 30-40%, and the weight content of phosphorus pentoxide is 50-60%, and partial size is 100-1000 mesh, is not had to environment
It is harmful, commercially available acquisition can be passed through.
The technical solution further preferred as the present invention, a kind of halogen Flameproof polyamide composite wood of no antimony
Material, further includes 10-50 parts of glass fibre according to parts by weight；The glass fibre is coming from using at least one type
The glass fibre of the following group: E glass, H glass, R, S glass, D glass, C glass and quartz glass are particularly preferably used by E
Glass fibre made of glass；The diameter of the glass fibre is 7-18 μm, preferably 9-15 μm.
According to actual performance needs, a kind of halogen flame-retardant polyamide composite material of no antimony of the present invention, by weight
Number meter is measured, further includes 0.01-5 parts of zinc borate, 0.1~1 part of antioxidant, 0.1~1 part of lubricant.
Zinc borate of the invention can melt at a higher temperature as synergistic flame retardant, and be formed in solid phase
Vitreum coating, blocked polymer surface play a part of to completely cut off air, to play the fire-retardant effect of synergistic.
As antioxidant, from the viewpoint of being easy to get, preferred hindered phenol anti-oxidants are not limited to following object
Matter can be enumerated for example: 3-(3 ', 5 '-and tert-butyl -4 '-hydroxy phenyl) n-octadecyl propionate, 3-(3 '-methyl -5-
Tert-butyl -4 '-hydroxy phenyl) n-octadecyl propionate, 3-(3 ', 5 '-di-t-butyls -4 '-hydroxy phenyl) propionic acid positive 14
Bis- (the 3-(3,5- and tert-butyl-hydroxy phenyl) propionic esters of Arrcostab, 1,6-HD), four (methylene -3-(3 ', 5 '-two
Tert-butyl -4 '-hydroxy phenyl) propionic ester) methane, bis- (2-(3-(3- tertiary butyl-4-hydroxy -5- aminomethyl phenyl) the propionyl oxygen of 3,9-
Base) -1,1- dimethyl ethyl) -2,4,8,10- four oxaspiro (5,5) hendecane etc..
As lubricant, it is not limited to following substance, can be enumerated for example: higher fatty acids, higher fatty acid metal salt, height
Grade aliphatic ester, higher fatty acid amides etc..
The higher fatty acids is not limited to following substance, can enumerate for example: stearic acid, palmitinic acid, behenic acid, erucic acid,
Saturated or unsaturated, linear chain or branched chain the aliphatic monocarboxylic acid of the carbon atom numbers such as oleic acid, lauric acid and montanic acid 8~40
Deng.In these substances, is generated from gas when inhibiting melt-processed, the viewpoint of mold deposit when processing and forming in mold is inhibited to examine
Consider, preferably stearic acid, montanic acid.
The higher fatty acid metal salt refers to the metal salt of higher fatty acids.As constitute metal salt metallic element,
The first, second, third race of preferred elements periodic table element, zinc and aluminium etc., more preferable calcium, sodium, potassium, magnesium etc..As described advanced
Fatty acid metal salts are not limited to following substance, can enumerate for example: calcium stearate, aluminum stearate, zinc stearate, magnesium stearate,
Montanic acid calcium, montanic acid sodium, calcium palmitate etc..In these substances, is generated from gas when inhibiting melt-processed, molding is inhibited to add
From the viewpoint of mold deposit in working hour mold, the preferably metal salt of montanic acid and stearic metal salt.
The high-grade aliphatic ester refers to the carboxylate of higher fatty acids and alcohol.Wherein, from gas when inhibiting melt-processed
Body generates, when inhibiting processing and forming from the viewpoint of mold deposit in a mold, preferably the aliphatic carboxylic acid of carbon atom number 8~40 with
The ester of the aliphatic alcohol of carbon atom number 8~40.Here, above-mentioned fatty acid can be used as higher fatty acids.As aliphatic
Alcohol is not limited to following substance, can enumerate for example: stearyl alcohol, behenyl alcohol, laruyl alcohol etc..As high-grade aliphatic ester, it is not limited to
Following substance can be enumerated for example: stearyl stearate, behenic acid Shan Yu ester etc..
The higher fatty acid amides refer to the amide compound of higher fatty acids.It is unlimited as higher fatty acid amides
It in following substance, can enumerate for example: stearmide, oleamide, erucic amide, ethylenebisstearamide, ethylenebis oleoyl
Amine, N- stearyl stearamide, N- stearyl erucic amide etc..In these substances, generated from gas when inhibiting melt-processed, suppression
From the viewpoint of mold deposit when processing and forming processed in mold, preferably stearmide, erucic amide, ethylenebisstearamide, N- are hard
Aliphatic radical erucic amide, more preferable ethylenebisstearamide, N- stearyl erucic amide.
These higher fatty acids, higher fatty acid metal salt, high-grade aliphatic ester and high fatty acid amide, respectively can be single
One kind is solely used only, can also be used in combination.
The invention also discloses the preparation methods of the halogen flame-retardant polyamide composite material of above-mentioned no antimony, including walk as follows
It is rapid:
Each raw material is proportionally weighed, is pre-mixed to obtain pre-composition in high mixer, pre-composition is then put into twin-screw
Melting mixing, and extruding pelletization are carried out in extruder, obtain the halogen flame-retardant polyamide composite material of no antimony；Wherein,
The screw slenderness ratio of double screw extruder is 40 ~ 48:1, and barrel temperature is 270 ~ 300 DEG C, and screw speed is 200 ~ 550rpm.
The present invention also provides condensation of aluminum phosphate to improve the application in polyamide compoiste material electric property, with polyamide
Composite material total weight, the weight content of condensation of aluminum phosphate are 0.01-15%, preferably 1-12%.
The present invention compared with the existing technology, have the following advantages and the utility model has the advantages that
The present invention, as new flame retardant, under the premise of not introducing stibium trioxide, can be reached and be hindered with bromo- antimony using condensation of aluminum phosphate
The same flame retardant effect of combustion system, while can assign bromine system Flameproof polyamide excellent electric property, and mitigate to environment and
The harm of human body has than bromo- antimony flame-retardant polyamide composite material and is more widely applied range.
Specific embodiment
Further illustrate that the present invention, following specific embodiments are this with comparative example combined with specific embodiments below
Preferable embodiment is invented, but embodiments of the present invention are not limited by following embodiments, are especially not limited to down
State the model of each component raw material used in specific embodiment.
Each component raw material used in the present invention are as follows:
A1:66 type polyamide, the trade mark PA66 EP-158, viscosity number 180(ISO 307, using the concentrated sulfuric acid of 0.01g/mL as molten
Liquid), 263 DEG C of fusing point；
A2:6 type polyamide, the trade mark PA6 HY2800A, viscosity number 150(ISO 307, using the concentrated sulfuric acid of 0.01g/mL as molten
Liquid), 221 DEG C of fusing point；
B: bromide fire retardant, trade mark SAYTEX 621, bromine content 60% or so, the refined treasured in the U.S.；
C1: antimony oxide synergistic flame retardant, trade mark S-05N, 1-2 μm of partial size, Hunan Chen Zhou mining company；
C2: zinc borate synergistic flame retardant, trade mark ZB-500, Australian Rio Tinto PLC；
D: condensation of aluminum phosphate, partial size are 100-1000 mesh, the prosperous Sheng Huagong in Shijiazhuang；
E1: Hinered phenols antioxidant IRGANOX 1098, Tianjin Li Anlong；
E2: lipid lubricant L OXIOL G 32, German HENKEL company；
F: short glass fiber, ECS11-4.5-560A, Chongqing Polycomp International Co., Ltd；
Performance test standard or method:
Flame retardant property: according to the relevant criterion of UL 94 to batten carry out flame retardant property test, thickness of sample be 0.8mm and
1.5mm；
CTI performance: material surface is able to take 50 drop electrolyte (0.1% aqueous ammonium chloride solution) without forming tracking
Maximum voltage value, unit V.CTI performance test is carried out according to the relevant regulations in standard IEC -60112, thickness of sample must not
Less than 3mm.
Embodiment 1-8 and comparative example 1-2:
Each component is weighed respectively according to comparative example 1 ~ 2 described in table 1 and 1 ~ 8 formulation dosage of specific embodiment, and will be above-mentioned each
Mixing is carried out until uniformly, obtaining pre-composition in component investment mixing machine；Then gained pre-composition is put into double screw extruder
Middle carry out melting mixing, and extruding pelletization, obtain PA66/PPS alloy material；Wherein the screw slenderness ratio of double screw extruder is
40 ~ 48:1, barrel temperature are 270 ~ 300 DEG C, and screw speed is 300 ~ 450rpm.It will be obtained by the various embodiments described above and comparative example
Composite material the standard batten of test is first molded by standard size, then carry out each performance test according to testing standard；
The performance test data of each example sample is shown in Table 2:
1 comparative example 1 ~ 2 of table and 1 ~ 8 dosage of each component of embodiment (parts by weight)
From embodiment 1 and comparative example 1 as can be seen that although preferable flame retardant effect can be obtained using bromo- antimony flame-retardant system,
Its CTI value is lower, and the present invention replaces antimony based flame retardant using condensation of aluminum phosphate, can reach same with bromo- antimony flame-retardant system
Flame retardant effect, while can effectively promote the CTI performance of material.
Claims (10)
1. a kind of halogen flame-retardant polyamide composite material of no antimony, it is characterised in that: according to parts by weight, comprising with the following group
Point:
20-80 parts of polyamide；
1-30 parts of bromide fire retardant；
0.01-15 parts of condensation of aluminum phosphate.
2. a kind of halogen flame-retardant polyamide composite material of no antimony according to claim 1, it is characterised in that: by weight
Number meter includes following components:
25-55 parts of polyamide；
10-25 parts of bromide fire retardant；
1-12 parts of condensation of aluminum phosphate.
3. a kind of halogen flame-retardant polyamide composite material of no antimony according to claim 1 or 2, the polyamide
Selected from the polyamide obtained by diamine and dicarboxylic acids polycondensation, the polyamide obtained by the ring-opening polymerisation of lactams
Resin, the polyamide self condensed by amino carboxylic acid, and these polyamide resins are constituted by two kinds or more
Polyamide copolymer obtained from the copolymerization of the unit of rouge, preferably polyamide 66 or polyamide 6.
4. a kind of halogen flame-retardant polyamide composite material of no antimony according to claim 1 or 2, it is characterised in that: institute
Stating bromide fire retardant is in brominated polystyrene, poly- bromstyrol copolymer, brominated epoxy resin or brominated polyphenylene oxide
One or more of mixing, preferred brominated polystyrene of the bromine content within the scope of 60-70 weight %.
5. a kind of halogen flame-retardant polyamide composite material of no antimony according to claim 1 or 2, it is characterised in that: institute
The mixture that condensation of aluminum phosphate is mainly phosphorus pentoxide and aluminum oxide is stated, wherein the weight content of aluminum oxide is
30-40%, the weight content of phosphorus pentoxide are 50-60%, and partial size is 100-1000 mesh.
6. a kind of halogen flame-retardant polyamide composite material of no antimony according to claim 1 or 2, it is characterised in that: press
Parts by weight meter, further includes 10-50 parts of glass fibre, and the glass fibre is using at least one type from the following group
Glass fibre: E glass, H glass, R, S glass, D glass, C glass and quartz glass are particularly preferably used by E glass system
At glass fibre；The diameter of the glass fibre is 7-18 μm, preferably 9-15 μm.
7. a kind of halogen flame-retardant polyamide composite material of no antimony according to claim 1 or 2, it is characterised in that: press
Parts by weight meter further includes 0.01-5 parts of zinc borate, 0.1~1 part of antioxidant, 0.1~1 part of lubricant.
8. a kind of preparation side of the halogen flame-retardant polyamide composite material of no antimony described in any one of -7 according to claim 1
Method, characterized by the following steps:
Each raw material is proportionally weighed, is pre-mixed to obtain pre-composition in high mixer, pre-composition is then put into twin-screw
Melting mixing, and extruding pelletization are carried out in extruder, obtain the halogen flame-retardant polyamide composite material of no antimony；Wherein, double spiral shells
The screw slenderness ratio of bar extruder is 40 ~ 48:1, and barrel temperature is 270 ~ 300 DEG C, and screw speed is 200 ~ 550rpm.
9. condensation of aluminum phosphate is improving the application in polyamide compoiste material electric property.
10. application according to claim 8, which is characterized in that with polyamide compoiste material total weight, condensation of aluminum phosphate
Weight content be 0.01-15%, preferably 1-12%.
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| CN112745571A (en) * | 2020-12-16 | 2021-05-04 | 金发科技股份有限公司 | Antimony-free flame-retardant ceramic polyolefin composition and preparation method and application thereof |
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| CN112745571A (en) * | 2020-12-16 | 2021-05-04 | 金发科技股份有限公司 | Antimony-free flame-retardant ceramic polyolefin composition and preparation method and application thereof |
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