CN102796366B - Non-antimony flame-retardant polyamide composite material and preparation method and application thereof - Google Patents
Non-antimony flame-retardant polyamide composite material and preparation method and application thereof Download PDFInfo
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- CN102796366B CN102796366B CN201110407019.4A CN201110407019A CN102796366B CN 102796366 B CN102796366 B CN 102796366B CN 201110407019 A CN201110407019 A CN 201110407019A CN 102796366 B CN102796366 B CN 102796366B
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- retardant
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- 239000004952 Polyamide Substances 0.000 title claims abstract description 53
- 229920002647 polyamide Polymers 0.000 title claims abstract description 53
- 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 title claims abstract description 52
- 229910052787 antimony Inorganic materials 0.000 title claims abstract description 49
- 239000003063 flame retardant Substances 0.000 title claims abstract description 47
- 239000002131 composite material Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 48
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 16
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 12
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 239000000314 lubricant Substances 0.000 claims abstract description 10
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 8
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 8
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 8
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims description 17
- 239000003607 modifier Substances 0.000 claims description 17
- 230000000979 retarding effect Effects 0.000 claims description 14
- 150000001408 amides Chemical class 0.000 claims description 13
- 239000004793 Polystyrene Substances 0.000 claims description 8
- 229920002223 polystyrene Polymers 0.000 claims description 8
- 229920002292 Nylon 6 Polymers 0.000 claims description 7
- 229920002302 Nylon 6,6 Polymers 0.000 claims description 7
- 229960001866 silicon dioxide Drugs 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 239000010456 wollastonite Substances 0.000 claims description 5
- 229910052882 wollastonite Inorganic materials 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 4
- 239000003365 glass fiber Substances 0.000 claims description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 3
- ZJOLCKGSXLIVAA-UHFFFAOYSA-N ethene;octadecanamide Chemical compound C=C.CCCCCCCCCCCCCCCCCC(N)=O.CCCCCCCCCCCCCCCCCC(N)=O ZJOLCKGSXLIVAA-UHFFFAOYSA-N 0.000 claims description 3
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 3
- 238000012986 modification Methods 0.000 claims description 3
- 230000004048 modification Effects 0.000 claims description 3
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 3
- -1 polyethylene Polymers 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 229920001296 polysiloxane Polymers 0.000 claims description 3
- 239000005995 Aluminium silicate Substances 0.000 claims description 2
- 235000012211 aluminium silicate Nutrition 0.000 claims description 2
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 2
- 238000009826 distribution Methods 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000010445 mica Substances 0.000 claims description 2
- 229910052618 mica group Inorganic materials 0.000 claims description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 abstract description 19
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 abstract description 9
- 230000000052 comparative effect Effects 0.000 abstract description 6
- 229910052736 halogen Inorganic materials 0.000 abstract description 3
- 150000002367 halogens Chemical class 0.000 abstract description 3
- GHPGOEFPKIHBNM-UHFFFAOYSA-N antimony(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Sb+3].[Sb+3] GHPGOEFPKIHBNM-UHFFFAOYSA-N 0.000 abstract 1
- 238000007796 conventional method Methods 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 16
- 239000011159 matrix material Substances 0.000 description 7
- 238000001125 extrusion Methods 0.000 description 4
- 238000005453 pelletization Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- BZQKBFHEWDPQHD-UHFFFAOYSA-N 1,2,3,4,5-pentabromo-6-[2-(2,3,4,5,6-pentabromophenyl)ethyl]benzene Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1CCC1=C(Br)C(Br)=C(Br)C(Br)=C1Br BZQKBFHEWDPQHD-UHFFFAOYSA-N 0.000 description 1
- 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
- 229920000426 Microplastic Polymers 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
- B29C48/911—Cooling
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/001—Combinations of extrusion moulding with other shaping operations
- B29C48/0022—Combinations of extrusion moulding with other shaping operations combined with cutting
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/04—Particle-shaped
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/78—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling
- B29C48/875—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling for achieving a non-uniform temperature distribution, e.g. using barrels having both cooling and heating zones
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92895—Barrel or housing
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a non-antimony flame-retardant polyamide composite material, which comprises the following raw materials in percentage by weight: 20 to 90 percent of polyamide, 5 to 25 percent of halogen flame retardant, 2 to 10 percent of non-antimony flame-retardant synergist, 0.1 to 3 percent of lubricant, 0.1 to 1 percent of antioxidant, 0.3 to 3 percent of surface modifying agent and 1 to 40 percent of enhancement modifying agent, wherein the non-antimony flame-retardant synergist comprises magnesium oxide, silicon dioxide and tin dioxide in a molar ratio of (2-3):(1-2):1. The invention also provides a preparation method for the non-antimony flame-retardant polyamide composite material and application of the non-antimony flame-retardant polyamide composite material. According to the non-antimony flame-retardant polyamide composite material, a comparative tracking index (CTI) value is improved to more than 400 V under the condition of no antimony sesquioxide and zinc borate, the phenomenon of flow marks is avoided, and the production cost is reduced. The non-antimony flame-retardant polyamide composite material can be prepared by the conventional equipment and the conventional method, manufacturing equipment is not needed to be transformed, and industrial production is easy to realize.
Description
Technical field
The present invention relates to modified high-molecular field of new, be specifically related to a kind of non-antimony flame-retardant polyamide composite material and its preparation method and application.
Background technology
Polymeric amide is commonly called as nylon (PA), is an analog thermoplastic resin general name that contains recurring amide radical group (NHCO-) on molecular backbone chain.The polymeric amide flame retardant properties of non-modified is poor, in use initiation fire very easily.While therefore applying in fields such as electronic apparatuss, all need polymeric amide to carry out flame-retardant modified.Can be used for the flame-retardant modified fire retardant kind of polymeric amide and mainly contain halogen system, phosphorus system, nitrogen system etc.Halogen is that Flameproof polyamide use is the most extensive at present.And the halogenated flame retardant flame retardant properties that fire retarding synergist just can reach of conventionally need to arranging in pairs or groups, the most frequently used fire retarding synergist has antimonous oxide, zinc borate etc. at present.Ministry of Land and Resources's issuing control antimony ore exploitation total amount requirement in 2011, antimony is resource continuous in short supply, causes antimonous oxide price constantly to be ascended to heaven, and finds antimonous oxide substitute and brings into schedule.And adopt antimonous oxide lower as the phase ratio creepage tracking index (CTI) of fire retarding synergist, conventionally all lower than 300V.
In patent 200610053337.4 < < high fire resistance property Enhanced polyamide with high CT 1 value > >, use zinc borate as fire retarding synergist, improved CTI value.But actual in application, first zinc borate itself contains crystal water, and temperature tolerance is not high, under the hot conditions of preparing Flameproof polyamide, easily discharge crystal water extruding, thereby make the plastic pellet foaming of extruding, have hollow.Based on same reason, easily there is the undesirable appearance situations such as current mark in zinc borate Flameproof polyamide product surface when injection moulding.During as contactor product application, when accepting high frequency test, under voltage rating effect, this frequent energising can produce heat energy, and heat energy impels the inherent crystal water of zinc borate to discharge generation steam, just breakdown while causing longevity test number of times also not reach requirement.
Summary of the invention
Technical problem to be solved by this invention is to have overcome and in existing polyamide compoiste material, contains scarce resource antimonous oxide, and adopt the polyamide compoiste material CTI value of antimonous oxide not high, and zinc borate surface when injection moulding is prone to the defects such as current mark, a kind of non-antimony flame-retardant polyamide composite material is provided, in this matrix material, do not contain antimonous oxide and zinc borate, and the CTI value of this matrix material is greater than 400V, also there will not be the problems such as current mark.The present invention also provides the preparation method and application of described non-antimony flame-retardant polyamide composite material.
The invention provides a kind of non-antimony flame-retardant polyamide composite material, its raw material comprises following component by weight percentage: polymeric amide 20%-90%, halogenated flame retardant 5%-25%, non-antimony fire retarding synergist 2%-10%, lubricant 0.1%-3%, antioxidant 0.1%-1%, surface-modifying agent 0.3%-3% and reinforced modifier 1%-40%; Wherein said non-antimony fire retarding synergist comprises magnesium oxide, silicon-dioxide and tindioxide, magnesium oxide: silicon-dioxide: tindioxide=mol ratio 2-3: 1-2: 1.
In the present invention one preferably in embodiment, the raw material of described non-antimony flame-retardant polyamide composite material comprises following component by weight percentage: kymene 5%-75%, halogenated flame retardant 10%-25%, non-antimony fire retarding synergist 4%-10%, lubricant 0.2%-0.8%, antioxidant 0.2%-0.8%, surface-modifying agent 0.8%-1.2% and reinforced modifier 5%-32%.
In the present invention, described polymeric amide can be the polymeric amide of various routines in this area, as nylon 66 and/or nylon 6.The relative viscosity of described polymeric amide is preferably 2.3-2.7.
In the present invention, described halogenated flame retardant can be the conventional various halogenated flame retardants that use in this area, is preferably one or more in brominated polystyrene, brominated Polystyrene and TDE.Wherein said brominated polystyrene can adopt the brominated polystyrene of all size model of using as fire retardant in this area.Described brominated Polystyrene can adopt the brominated Polystyrene of all size model of using as fire retardant in this area.
In the present invention, described lubricant can be the conventional various lubricants for polyamide compoiste material that use in this area, is preferably one or more in ethylene bis stearic acid amide (EBS), modification EBS, polyethylene wax and stearate.
In the present invention, described antioxidant can be the conventional various antioxidants for polyamide compoiste material that use in this area, is preferably one or more in antioxidant 1010,1098 and 168.
In the present invention, described surface-modifying agent can be the conventional various surface-modifying agents for polyamide compoiste material that use in this area, be preferably ethylene-vinyl acetate copolymer and/or silicone, wherein the weight content of vinyl acetate segment in this multipolymer is preferably 20%-30%.
In the present invention, described reinforced modifier can be the conventional various reinforced modifier for polyamide compoiste material of using in this area, be preferably one or more in alkali free glass fibre, glass microballon and inorganic mineral, described inorganic mineral is preferably one or more in talcum powder, wollastonite, kaolin, polynite and mica.
The present invention also provides the preparation method of described non-antimony flame-retardant polyamide composite material, it comprises the steps: to add described polymeric amide at the main spout of twin screw extruder, in the first side spout, add the mixture of following component: described halogenated flame retardant, described non-antimony fire retarding synergist, described lubricant, described antioxidant and described surface-modifying agent, in the second side spout, add described reinforced modifier, extrude, cooling.
Wherein, described mixture is preferably mixed to get by high-speed mixer.
Wherein, the temperature distribution of described twin screw extruder is: by feed zone, to head, be respectively: 210-240 ℃, 230-275 ℃, 245-280 ℃, 245-275 ℃, 240-270 ℃, 235-265 ℃, 230-265 ℃ and 230-260 ℃, die head temperature is 235-270 ℃.
The present invention also provides described non-antimony flame-retardant polyamide composite material in the application for the manufacture of in low-voltage circuit breaker housing, coil rack, car electrics, industrial electrical equipment housing, alternating current contactor shell and electronic connector.
In the present invention, above-mentioned optimum condition can arbitrary combination on the basis that meets this area general knowledge, obtains the each preferred embodiment of the present invention.
Raw material of the present invention and reagent is commercially available obtaining all.
Positive progressive effect of the present invention is:
1, non-antimony flame-retardant polyamide composite material of the present invention is in the situation that containing antimonous oxide and zinc borate, can realize more than CTI brings up to 400V, there will not be current mark problem simultaneously, and can also reduce production costs.
2, non-antimony flame-retardant polyamide composite material of the present invention can adopt conventional equipment and method to prepare, and does not need producing apparatus to transform, and is easy to carry out suitability for industrialized production.
Embodiment
For understanding better the present invention, below in conjunction with specific embodiment, the present invention will be further described, but the present invention is not limited.
The PA66 using in embodiment is purchased from the first promise of the U.S., and model is 21ZLV, and relative viscosity is 2.4.
PA6 is purchased from Taiwan collection and contains, and model is TP-4208, and relative viscosity is 2.4.
Brominated polystyrene is purchased from U.S. Chemtura Corporation, and model is PBS-64HW.
Brominated Polystyrene is purchased from U.S. Albemarle Corporation, and model is SAYTEX HP-5010P.
TDE is purchased from U.S. Albemarle Corporation, and model is SAYTEX 8010.
EBS is purchased from Shanxi one chemical science and technology (Wuxi) company limited, and model is EBA-60.
Modification EBS is purchased from Suzhou Xingtai state photochemistry auxiliary agent company limited, and model is TAF.
Polyethylene wax is purchased from U.S. Honeywell, and model is AC-540a.
Ethylene-vinyl acetate copolymer is purchased from Thailand's petrochemical industry, and model is SV1055, and vinyl acetate segment content is 28wt%.
Silicone is purchased from Dow corning, and model is MB50-011.
The composition that non-antimony fire retarding synergist in embodiment 1 and 2 is magnesium oxide, silicon-dioxide and tindioxide, wherein magnesium oxide: silicon-dioxide: the mol ratio of tindioxide is 2: 1: 1.
The composition that non-antimony fire retarding synergist in embodiment 3 and 4 is magnesium oxide, silicon-dioxide and tindioxide, wherein magnesium oxide: silicon-dioxide: the mol ratio of tindioxide is 3: 2: 1.
Embodiment 1-3:
The performance perameter of the composition of raw materials of non-antimony flame-retardant polyamide composite material and gained matrix material is in Table 1.
The preparation method of non-antimony flame-retardant polyamide composite material is: other all components during table 1 is filled a prescription except PA66 and reinforced modifier (alkali free glass fibre and wollastonite) adds and in high-speed mixer, mixes to obtain mixture, takes out.From the main spout of twin screw extruder, add PA66, at the first side spout, add described mixture, then add reinforced modifier at the second side spout, all materials are mixed in twin screw extruder, extrude, cooling, pelletizing, obtains non-antimony flame-retardant polyamide composite material.
The extrusion temperature of embodiment 1-3 is respectively to head by feed zone: 240 ℃, 275 ℃, 280 ℃, 275 ℃, 270 ℃, 265 ℃, 265 ℃ and 260 ℃, and 270 ℃ of die head temperatures.
Table 1
Embodiment 4
The performance perameter of the composition of raw materials of non-antimony flame-retardant polyamide composite material and gained matrix material is in Table 1.
The preparation method of non-antimony flame-retardant polyamide composite material is: other all components during table 1 is filled a prescription except PA6 and reinforced modifier (wollastonite) adds and in high-speed mixer, mixes to obtain mixture, takes out.From the main spout of twin screw extruder, add PA6, at the first side spout, add described mixture, then add reinforced modifier at the second side spout, all materials are mixed in twin screw extruder, extrude, cooling, pelletizing, obtains non-antimony flame-retardant polyamide composite material.
The extrusion temperature of embodiment 4 is respectively to head by feed zone: 210 ℃, 230 ℃, 245 ℃, 245 ℃, 240 ℃, 235 ℃, 230 ℃ and 230 ℃, and 235 ℃ of die head temperatures.
Comparative example 1
The contrast composition of raw materials of polyamide compoiste material and the performance perameter of gained matrix material are in Table 1.
The preparation method of contrast polyamide compoiste material is: other all components during table 1 is filled a prescription except PA66 and reinforced modifier (alkali free glass fibre) adds and in high-speed mixer, mixes to obtain mixture, taking-up.From the main spout of twin screw extruder, add PA66, at the first side spout, add described mixture, then add reinforced modifier at the second side spout, all materials are mixed in twin screw extruder, extrude, cooling, pelletizing, obtains polyamide compoiste material.
Comparative example 1 extrusion temperature is respectively to head by feed zone: 240 ℃, 275 ℃, 280 ℃, 275 ℃, 270 ℃, 265 ℃, 265 ℃ and 260 ℃, and 270 ℃ of die head temperatures.
Comparative example 2
The contrast composition of raw materials of polyamide compoiste material and the performance perameter of gained matrix material are in Table 1.
The preparation method of contrast polyamide compoiste material is: other all components during table 1 is filled a prescription except PA6 and reinforced modifier (wollastonite) adds and in high-speed mixer, mixes to obtain mixture, taking-up.From the main spout of twin screw extruder, add PA6, at the first side spout, add described mixture, then add reinforced modifier at the second side spout, all materials are mixed in twin screw extruder, extrude, cooling, pelletizing, obtains polyamide compoiste material.
Comparative example 2 extrusion temperature is respectively to head by feed zone: 210 ℃, 230 ℃, 245 ℃, 245 ℃, 240 ℃, 235 ℃, 230 ℃ and 230 ℃, and 235 ℃ of die head temperatures.
Effect embodiment 1
According to the standard testing described in table 1, the matrix material of embodiment 1-4 and comparative example 1-2 is carried out to performance test, the results are shown in Table 1.
The non-antimony flame-retardant polyamide composite material of embodiment 1-4 there will not be current mark in surface when injection moulding.
As can be seen from Table 1, the phase ratio creepage tracking index (CTI) of non-antimony flame-retardant polyamide composite material of the present invention is higher than 400V, and use the CTI value of antimonous oxide flame-retardant polyamide composite material to be less than 300V, prove that its CTI value of non-antimony flame-retardant polyamide composite material of the present invention is significantly improved.
Claims (10)
1. a non-antimony flame-retardant polyamide composite material, it is characterized in that: its raw material comprises following component by weight percentage: polymeric amide 20%-90%, halogenated flame retardant 5%-25%, non-antimony fire retarding synergist 2%-10%, lubricant 0.1%-3%, antioxidant 0.1%-1%, surface-modifying agent 0.3%-3% and reinforced modifier 1%-40%, per-cent is the weight percent of each component with respect to described raw material; Wherein said non-antimony fire retarding synergist comprises magnesium oxide, silicon-dioxide and tindioxide, and three's mol ratio is 2-3:1-2:1.
2. non-antimony flame-retardant polyamide composite material as claimed in claim 1, it is characterized in that: its raw material comprises following component by weight percentage: kymene 5%-75%, halogenated flame retardant 10%-25%, non-antimony fire retarding synergist 4%-10%, lubricant 0.2%-0.8%, antioxidant 0.2%-0.8%, surface-modifying agent 0.8%-1.2% and reinforced modifier 5%-32%.
3. non-antimony flame-retardant polyamide composite material as claimed in claim 1 or 2, is characterized in that: described polymeric amide is nylon 66 and/or nylon 6, and the relative viscosity of described polymeric amide is 2.3-2.7.
4. non-antimony flame-retardant polyamide composite material as claimed in claim 1 or 2, is characterized in that: described halogenated flame retardant is brominated Polystyrene and/or TDE.
5. non-antimony flame-retardant polyamide composite material as claimed in claim 1 or 2, is characterized in that: described lubricant is one or more in ethylene bis stearic acid amide, modification ethylene bis stearic acid amide, polyethylene wax and stearate.
6. non-antimony flame-retardant polyamide composite material as claimed in claim 1 or 2, is characterized in that: described antioxidant is one or more in antioxidant 1010,1098 and 168.
7. non-antimony flame-retardant polyamide composite material as claimed in claim 1 or 2, it is characterized in that: described surface-modifying agent is ethylene-vinyl acetate copolymer and/or silicone, wherein the weight content of vinyl acetate segment in this multipolymer is preferably 20%-30%; And/or described reinforced modifier is one or more in alkali free glass fibre, glass microballon and inorganic mineral, described inorganic mineral is preferably one or more in talcum powder, wollastonite, kaolin, polynite and mica.
8. the preparation method of the non-antimony flame-retardant polyamide composite material as described in any one in claim 1～7, it comprises the steps: to add described polymeric amide at the main spout of twin screw extruder, in the first side spout, add the mixture of following component: described halogenated flame retardant, described non-antimony fire retarding synergist, described lubricant, described antioxidant and described surface-modifying agent, in the second side spout, add described reinforced modifier, extrude, cooling.
9. the preparation method of non-antimony flame-retardant polyamide composite material as claimed in claim 8, it is characterized in that: the temperature distribution of described twin screw extruder is: by feed zone, to head, be respectively: 210-240 ℃, 230-275 ℃, 245-280 ℃, 245-275 ℃, 240-270 ℃, 235-265 ℃, 230-265 ℃ and 230-260 ℃, die head temperature is 235-270 ℃.
In claim 1～7 the non-antimony flame-retardant polyamide composite material described in any one in the application for the manufacture of in low-voltage circuit breaker housing, coil rack, car electrics, industrial electrical equipment housing, alternating current contactor shell and electronic connector.
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| CN103642233A (en) * | 2013-11-18 | 2014-03-19 | 安徽宜万丰电器有限公司 | Silica modified nylon 66 material for automobile plastic members |
| CN104693792B (en) * | 2013-12-10 | 2017-12-15 | 合肥杰事杰新材料股份有限公司 | A kind of fire-retardant polyamide material and preparation method thereof |
| CN105647179B (en) * | 2016-03-08 | 2018-12-07 | 绍兴金创意塑化电器有限公司 | A kind of carbon fiber-nylon composite materials and its manufacturing method |
| CN106497042B (en) * | 2016-10-28 | 2018-02-09 | 上海耐特复合材料制品有限公司 | Environment-friendly type bromine system fire-retardant nylon composite and preparation method thereof |
| CN110229514A (en) * | 2019-06-28 | 2019-09-13 | 江苏晋伦塑料科技有限公司 | A kind of color inhibition fire-resistant polyamide composite and preparation method thereof |
| CN114213838B (en) * | 2021-12-03 | 2024-03-15 | 上海金发科技发展有限公司 | Flame-retardant nylon composite material with low pungent smell and preparation method and application thereof |
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| EP1070745A1 (en) * | 1999-07-23 | 2001-01-24 | Albemarle Corporation | Flame retardant compositions |
| CN101928409A (en) * | 2009-06-25 | 2010-12-29 | 上海化工研究院 | A kind of halogen-free intumescent flame retardant for polyethylene and preparation method thereof |
| CN102174247A (en) * | 2011-03-02 | 2011-09-07 | 中国科学技术大学苏州研究院 | Halogen-free flame retardant glass fiber reinforced polyester composite and preparation method thereof |
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| EP1070745A1 (en) * | 1999-07-23 | 2001-01-24 | Albemarle Corporation | Flame retardant compositions |
| CN101928409A (en) * | 2009-06-25 | 2010-12-29 | 上海化工研究院 | A kind of halogen-free intumescent flame retardant for polyethylene and preparation method thereof |
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