CN102796366A - 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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- CN102796366A CN102796366A CN2011104070194A CN201110407019A CN102796366A CN 102796366 A CN102796366 A CN 102796366A CN 2011104070194 A CN2011104070194 A CN 2011104070194A CN 201110407019 A CN201110407019 A CN 201110407019A CN 102796366 A CN102796366 A CN 102796366A
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- antimony
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- polyamide matrix
- flameproof polyamide
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- 239000004952 Polyamide Substances 0.000 title claims abstract description 53
- 229920002647 polyamide Polymers 0.000 title claims abstract description 53
- 229910052787 antimony Inorganic materials 0.000 title claims abstract description 49
- 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 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000003063 flame retardant Substances 0.000 title abstract description 17
- 239000002131 composite material Substances 0.000 title abstract description 10
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 47
- 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
- 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
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 8
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 8
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 3
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 3
- 239000011159 matrix material Substances 0.000 claims description 33
- 239000000203 mixture Substances 0.000 claims description 19
- 239000003607 modifier Substances 0.000 claims description 17
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 14
- 230000000979 retarding effect Effects 0.000 claims description 14
- 150000001408 amides Chemical class 0.000 claims description 13
- 239000003112 inhibitor Substances 0.000 claims description 9
- 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
- DGZQEAKNZXNTNL-UHFFFAOYSA-N 1-bromo-4-butan-2-ylbenzene Chemical class CCC(C)C1=CC=C(Br)C=C1 DGZQEAKNZXNTNL-UHFFFAOYSA-N 0.000 claims description 2
- 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
- 239000012467 final product Substances 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
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 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
- 239000000395 magnesium oxide Substances 0.000 abstract 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 abstract 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 abstract 1
- 239000000463 material Substances 0.000 description 16
- 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
- 239000000047 product Substances 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
- 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
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 240000005373 Panax quinquefolius Species 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
- 230000002950 deficient 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
- 238000002156 mixing 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
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- 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 the modified high-molecular field of new, be specifically related to a kind of non-antimony Flameproof polyamide matrix material.
Background technology
Polymeric amide is commonly called as nylon (PA), is to contain recurring amide radical group (analog thermoplastic resin general name NHCO-) on the molecular backbone chain.The polymeric amide flame retardant properties of non-modified is relatively poor, in use initiation fire very easily.All need carry out flame-retardant modified when therefore using to polymeric amide in fields such as electronic apparatuss.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 the Flameproof polyamide use is the most extensive at present.And the halogenated flame retardant fire retarding synergist of need arranging in pairs or groups usually just can reach good flame retardant properties, and the most frequently used fire retarding synergist has Antimony Trioxide: 99.5Min, zinc borate etc. at present.Ministry of Land and Resources's issue control antimony ore exploitation total amount requirement in 2011, antimony is resource continuous in short supply, causes the Antimony Trioxide: 99.5Min price constantly to be ascended to heaven, and seeks the Antimony Trioxide: 99.5Min substitute and brings into schedule.And adopt Antimony Trioxide: 99.5Min lower as the phase ratio creepage tracking index (CTI) of fire retarding synergist, all be lower than 300V usually.
Use zinc borate as fire retarding synergist in the patent 200610053337.4 " high fire resistance property Enhanced polyamide with high CT 1 value ", improved the CTI value.But actual at first zinc borate itself contains crystal water, and temperature tolerance is not high in application, under the hot conditions of extruding the preparation Flameproof polyamide, discharges crystal water easily, thereby makes the plastic pellet foaming of extruding, and has hollow.Based on same reason, undesirable appearance situations such as current mark appear in zinc borate Flameproof polyamide product surface when injection moulding easily.During as the contactor product application, under the voltage rating effect, this frequent energising can produce heat energy when accepting the high frequency test, and heat energy impels the inherent crystal water of zinc borate to discharge generation steam, and is just breakdown when causing the 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 contains the scarce resource Antimony Trioxide: 99.5Min in the existing polyamide compoiste material; And adopt the polyamide compoiste material CTI value of Antimony Trioxide: 99.5Min not high; And zinc borate surface when injection moulding is prone to defectives such as current mark, and a kind of non-antimony Flameproof polyamide matrix material is provided, and does not contain Antimony Trioxide: 99.5Min and zinc borate in this matrix material; And the CTI value of this matrix material problems such as current mark also can not occur greater than 400V.The present invention also provides the preparation method and the application of said non-antimony Flameproof polyamide matrix material.
The invention provides a kind of non-antimony Flameproof polyamide matrix 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%; Inhibitor 0.1%-1%, surface-modifying agent 0.3%-3% and reinforced modifier 1%-40%; Wherein said non-antimony fire retarding synergist comprises Natural manganese dioxide, silicon-dioxide and tindioxide, Natural manganese dioxide: silicon-dioxide: tindioxide=mol ratio 2-3: 1-2: 1.
In the present invention's one preferred implementation; The raw material of said non-antimony Flameproof polyamide matrix 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%; Inhibitor 0.2%-0.8%, surface-modifying agent 0.8%-1.2% and reinforced modifier 5%-32%.
Among the present invention, described polymeric amide can be the polymeric amide of various routines in this area, like nylon 66 and/or nylon 6.The relative viscosity of said polymeric amide preferably is 2.3-2.7.
Among the present invention, described halogenated flame retardant can be the conventional various halogenated flame retardants that use in this area, preferably is in brominated polystyrene, brominated Polystyrene and the TDE one or more.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.
Among the present invention, described lubricant can be the conventional various lubricants that are used for polyamide compoiste material that use in this area, preferably is in ethylene bis stearic acid amide (EBS), modification EBS, polyethylene wax and the stearate one or more.
Among the present invention, described inhibitor can be the conventional various inhibitors that are used for polyamide compoiste material that use in this area, preferably is in the antioxidant 1010,1098 and 168 one or more.
Among the present invention; Described surface-modifying agent can be the conventional various surface-modifying agents that are used for polyamide compoiste material that use in this area; Preferably be ethylene-vinyl acetate copolymer and/or silicone, wherein the weight content of vinyl acetate segment in this multipolymer preferably is 20%-30%.
Among the present invention; Described reinforced modifier can be the conventional various reinforced modifier of using that are used for polyamide compoiste material in this area; Preferably be in alkali free glass fibre, glass microballon and the inorganic mineral one or more, described inorganic mineral preferably is one or more in talcum powder, wollastonite, kaolin, polynite and the mica.
The present invention also provides the preparation method of said non-antimony Flameproof polyamide matrix material; It comprises the steps: to add said polymeric amide at the main spout of twin screw extruder; The mixture that in the first side spout, adds following component: said halogenated flame retardant, said non-antimony fire retarding synergist, said lubricant, said inhibitor and said surface-modifying agent; In the second side spout, add said reinforced modifier, extrude, cooling gets final product.
Wherein, described mixture preferably obtains through the high-speed mixer mixing.
Wherein, The temperature distribution of said twin screw extruder is: be respectively to head by feed zone: 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 said non-antimony Flameproof polyamide matrix material in the application that is used for making low-voltage circuit breaker housing, coil rack, car electrics, industrial electrical equipment housing, alternating current contactor shell and electronic connector.
Among the present invention, but above-mentioned optimum condition arbitrary combination on the basis that meets this area general knowledge promptly gets each preferred embodiment of the present invention.
Raw material of the present invention and reagent are all commercially available to be got.
Positive progressive effect of the present invention is:
1, non-antimony Flameproof polyamide matrix material of the present invention can realize that CTI brings up to more than the 400V under the situation that does not contain Antimony Trioxide: 99.5Min and zinc borate, the current mark problem can not occur simultaneously, and can also reduce production costs.
2, non-antimony Flameproof polyamide matrix material of the present invention can adopt conventional equipment and method to prepare, and need not transform producing apparatus, is easy to carry out suitability for industrialized production.
Embodiment
For understanding the present invention better, below in conjunction with specific embodiment the present invention is further specified, but the present invention is not limited.
Employed PA66 purchases the first promise in the U.S. among the embodiment, and model is 21ZLV, and relative viscosity is 2.4.
PA6 purchases the collection Sheng in Taiwan, and model is TP-4208, and relative viscosity is 2.4.
Brominated polystyrene is purchased the Chemtura Corporation in the U.S., and model is PBS-64HW.
Brominated Polystyrene is purchased the Albemarle Corporation in the U.S., and model is SAYTEX HP-5010P.
TDE is purchased the Albemarle Corporation in the U.S., and model is SAYTEX 8010.
EBS purchases one chemical science and technology (Wuxi) ltd in the Shanxi, and model is EBA-60.
Modification EBS purchases the Xingtai state photochemistry auxiliary agent ltd in Suzhou, and model is TAF.
Polyethylene wax is purchased in U.S. Honeywell, and model is AC-540a.
Ethylene-vinyl acetate copolymer is purchased the petrochemical industry in Thailand, and model is SV1055, and vinyl acetate segment content is 28wt%.
Silicone is purchased in Dow corning, and model is MB50-011.
The compsn that non-antimony fire retarding synergist among the embodiment 1 and 2 is Natural manganese dioxide, silicon-dioxide and tindioxide, wherein Natural manganese dioxide: silicon-dioxide: the mol ratio of tindioxide is 2: 1: 1.
The compsn that non-antimony fire retarding synergist among the embodiment 3 and 4 is Natural manganese dioxide, silicon-dioxide and tindioxide, wherein Natural manganese dioxide: silicon-dioxide: the mol ratio of tindioxide is 3: 2: 1.
Embodiment 1-3:
The composition of raw materials of non-antimony Flameproof polyamide matrix material and gained performance of composites parameter are seen table 1.
The preparation method of non-antimony Flameproof polyamide matrix material is: with mix in other all components adding high-speed mixer except that PA66 and reinforced modifier (alkali free glass fibre and wollastonite) in table 1 prescription mixture, taking-up.Add PA66 from the main spout of twin screw extruder, add said mixture, add reinforced modifier at the second side spout again at the first side spout; All materials are mixed in twin screw extruder, extrude, cooling; Pelletizing obtains non-antimony Flameproof polyamide matrix 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 composition of raw materials of non-antimony Flameproof polyamide matrix material and gained performance of composites parameter are seen table 1.
The preparation method of non-antimony Flameproof polyamide matrix material is: with mix in other all components adding high-speed mixer except that PA6 and reinforced modifier (wollastonite) in table 1 prescription mixture, taking-up.Add PA6 from the main spout of twin screw extruder, add said mixture, add reinforced modifier at the second side spout again at the first side spout; All materials are mixed in twin screw extruder, extrude, cooling; Pelletizing obtains non-antimony Flameproof polyamide matrix 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.
The comparative example 1
The composition of raw materials and the gained performance of composites parameter of contrast polyamide compoiste material are seen table 1.
The preparation method of contrast polyamide compoiste material is: with mix in other all components adding high-speed mixer except that PA66 and reinforced modifier (alkali free glass fibre) in table 1 prescription mixture, taking-up.Add PA66 from the main spout of twin screw extruder, add said mixture, add reinforced modifier at the second side spout again at the first 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.
The comparative example 2
The composition of raw materials and the gained performance of composites parameter of contrast polyamide compoiste material are seen table 1.
The preparation method of contrast polyamide compoiste material is: with mix in other all components adding high-speed mixer except that PA6 and reinforced modifier (wollastonite) in table 1 prescription mixture, taking-up.Add PA6 from the main spout of twin screw extruder, add said mixture, add reinforced modifier at the second side spout again at the first 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 described standard testing of table 1 matrix material of embodiment 1-4 and comparative example 1-2 is carried out performance test, the result sees table 1.
Non-antimony Flameproof polyamide matrix material surface when injection moulding of embodiment 1-4 current mark can not occur.
Can find out from table 1; The phase ratio creepage tracking index (CTI) of non-antimony Flameproof polyamide matrix material of the present invention is higher than 400V; And the CTI value of using Antimony Trioxide: 99.5Min Flameproof polyamide matrix material proves that less than 300V non-its CTI value of antimony Flameproof polyamide matrix material of the present invention is significantly improved.
Claims (10)
1. non-antimony Flameproof polyamide matrix 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%; Inhibitor 0.1%-1%, surface-modifying agent 0.3%-3% and reinforced modifier 1%-40%, per-cent are the weight percent of each component with respect to said raw material; Wherein said non-antimony fire retarding synergist comprises Natural manganese dioxide, silicon-dioxide and tindioxide, and three's mol ratio is 2-3: 1-2: 1.
2. non-antimony Flameproof polyamide matrix 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%; Inhibitor 0.2%-0.8%, surface-modifying agent 0.8%-1.2% and reinforced modifier 5%-32%.
3. according to claim 1 or claim 2 non-antimony Flameproof polyamide matrix material, it is characterized in that: described polymeric amide is nylon 66 and/or nylon 6, and the relative viscosity of said polymeric amide is 2.3-2.7.
4. according to claim 1 or claim 2 non-antimony Flameproof polyamide matrix material, it is characterized in that: described halogenated flame retardant is one or more in brominated polystyrene, brominated Polystyrene and the TDE.
5. according to claim 1 or claim 2 non-antimony Flameproof polyamide matrix material, it 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 the stearate.
6. according to claim 1 or claim 2 non-antimony Flameproof polyamide matrix material, it is characterized in that: described inhibitor is one or more in the antioxidant 1010,1098 and 168.
7. according to claim 1 or claim 2 non-antimony Flameproof polyamide matrix material; It is characterized in that: described surface-modifying agent is ethylene-vinyl acetate copolymer and/or silicone, and wherein the weight content of vinyl acetate segment in this multipolymer preferably is 20%-30%; And/or described reinforced modifier is one or more in alkali free glass fibre, glass microballon and the inorganic mineral, and described inorganic mineral preferably is one or more in talcum powder, wollastonite, kaolin, polynite and the mica.
8. preparation method like each described non-antimony Flameproof polyamide matrix material in the claim 1～7; It comprises the steps: to add said polymeric amide at the main spout of twin screw extruder; The mixture that in the first side spout, adds following component: said halogenated flame retardant, said non-antimony fire retarding synergist, said lubricant, said inhibitor and said surface-modifying agent; In the second side spout, add said reinforced modifier, extrude, cooling gets final product.
9. the preparation method of non-antimony Flameproof polyamide matrix material as claimed in claim 8; It is characterized in that: the temperature distribution of said twin screw extruder is: be respectively to head by feed zone: 210-240 ℃, 230-275 ℃, 245-280 ℃, 245-275 ℃, 240-270 ℃, 235-265 ℃, 230-265 ℃ and 230-260 ℃, die head temperature is 235-270 ℃.
In the claim 1～7 each described non-antimony Flameproof polyamide matrix material in the application that is used for making low-voltage circuit breaker housing, coil rack, car electrics, industrial electrical equipment housing, alternating current contactor shell and electronic connector.
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| CN114213838A (en) * | 2021-12-03 | 2022-03-22 | 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 |
| 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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