CN104479353A - Novel halogen-free flame-retardant composition, halogen-free flame-retardant PBT engineering plastic composite material and preparation method thereof - Google Patents

Novel halogen-free flame-retardant composition, halogen-free flame-retardant PBT engineering plastic composite material and preparation method thereof Download PDF

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CN104479353A
CN104479353A CN201410799557.6A CN201410799557A CN104479353A CN 104479353 A CN104479353 A CN 104479353A CN 201410799557 A CN201410799557 A CN 201410799557A CN 104479353 A CN104479353 A CN 104479353A
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halogen
composite material
pbt
retardant
engineering plastic
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CN104479353B (en
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陈明军
钟柳
刘治国
林羿成
王小宁
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Xihua University
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • 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
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • 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
    • B29C2948/9258—Velocity
    • 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
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/003—Additives being defined by their diameter
    • C—CHEMISTRY; METALLURGY
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

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Abstract

The invention relates to the field of flame-retardant high polymer materials, and particularly relates to a novel halogen-free flame-retardant composition, a halogen-free flame-retardant PBT engineering plastic composite material and a preparation method thereof. The halogen-free flame retardant FRs is mainly obtained by mixing FR1, FR2, FR3, FR4 and FR5 according to a specific proportion, and the halogen-free flame retardant system has higher heat resistance stability and good flame retardant property by matching the substances. A kind of halogen-free inflaming retarding PBT engineering plastics composite material, this material is mainly made of PBT, alkali-free glass fibre, halogen-free flame retardant FRs, CTI synergist, anti-oxidant, lubricant, coupling agent, compatibilizer, flexibilizer, every component cooperates, the halogen-free inflaming retarding PBT engineering plastics composite material made is flame retardant, electrical property, heat resistance, mechanical property, colorability, etc. comprehensive performance superiority; the preparation method of the composite material is simple and feasible, and the prepared composite material has excellent comprehensive performance.

Description

A kind of novel halogen-free flame-retardant composition, fire retardant PBT with no halogen engineering plastic composite material and preparation method thereof
Technical field
The present invention relates to flame retarded polymeric material field, in particular to a kind of novel halogen-free flame-retardant composition, fire retardant PBT with no halogen engineering plastic composite material and preparation method thereof.
Background technology
Polybutylene terephthalate (PBT) is a kind of crystallinity line style saturated polyester, there is excellent processing characteristics, mechanical property, heat-resistant aging, solvent resistance, water stability, and electric property etc., be widely used in automobile, mechanical means, household electrical appliance, electric production, become a member important in engineering plastics.
Need to add fire retardant to improve its flame retardant properties in PBT engineering plastics.For a long time, flame-retardant PBT engineering plastic composite material selects bromide fire retardant usually.Bromide fire retardant has the features such as flame retarding efficiency is high, good flame retardation effect, but containing causing dysgenic hazardous substance to environment in bromide fire retardant.Along with promulgation, the execution of RoHS Directive and REACH regulation, the fire retardant material used in electric, the industry such as information, office household electrical appliances in European Union, North America market requires non-halogen, therefore a lot of modified PBT engineering plastics manufacturers active development fire retardant PBT with no halogen product
Fire retardant PBT with no halogen mainly adopts the fire retardants such as inorganics, red phosphorus flame-retardant system, phosphorus-nitrogen containing flame retardant and organic hypophosphite.Wherein, inorganics is magnesium hydroxide, aluminium hydroxide mainly, just can reach flame retardant effect, make poor compatibility between inorganics and PBT body material because needs add these two kinds of inorganicss in a large number, cause the physical and mechanical properties of the finished product to decline very large, be difficult to meet application request.Although adopt red phosphorus flame-retardant system partly to solve, addition is large, the problem of product performance decline, but due to red phosphorus combustion inhibitor color articles poor performance, particularly red phosphorus poor heat stability, with PBT hybrid process process in produce the comparatively large and poisonous gas of a large amount of smells, limit many purposes of red phosphorus flame-retardant PBT.For above-mentioned situation, phosphorus-nitrogen containing flame retardant or organic phosphonateflame retardant are one of good halogen-free flame retardantss of current fire retardant PBT with no halogen.But, domestic prior art still also exists certain defect compared with the high-end product of the international major company of minority, mainly phase ratio creepage tracking index (CTI), heat-resistant stability are lower, therefore, exploitation has the halogen free flame-retardant reinforced PBT composite material of independent intellectual property right, has major application and is worth and broad development space.
In view of this, special proposition the present invention.
Summary of the invention
The first object of the present invention is to provide a kind of novel halogen-free flame-retardant agent FRs, described halogen-free flame retardants FRs is mixed to get according to specific ratio primarily of FR1, FR2, FR3, FR4 and FR5, wherein, FR1 is a kind of heat-resistant stability Halogen phosphorus flame retardant, containing the high heat stability phosphoric acid ester of four quaternary carbon structures, have good coking performance, phosphorus content reaches more than 20%; FR2 is a kind of melamine pyrophosphate, belongs to Halogen phosphorus-nitrogenated flame retardant; FR3 is a kind of dendritic bittern-free phosphorous-nitrogen flame retardant, belongs to hyperbranched phosphorus-nitrogenated flame retardant, has certain increasing tougheness, and three has good cooperative flame retardant efficiency; FR4 is a kind of polyetherimide improving material over-all properties, and FR5 is a kind of anti-molten drop and the additive improving processing characteristics, FR4 and FR5 adds the anti-dropping performance that can improve halogen-free flame-retardant system FRs flame-retardant PBT further and the over-all properties improving material; This several material has higher heat-resistant stability and good flame retardant properties with the use of making halogen-free flame-retardant system.
The second object of the present invention is to provide a kind of fire retardant PBT with no halogen engineering plastic composite material, and this material makes primarily of PBT, alkali free glass fibre, halogen-free flame retardants FRs, CTI synergist, oxidation inhibitor, lubricant, coupling agent, expanding material, toughner.Wherein, fine and close, the isolated material of the insulating layer structure porous generated when halogen-free flame retardants FRs is conducive to the burning of flame-retardant PBT engineering plastic composite material and transmission ofenergy, effectively raise the flame retardant properties of halogen-free flame-retardant system; Each composition coordinated, the over-all properties such as flame retardant properties, electric property, resistance toheat, mechanical property, tinctorial property of obtained fire retardant PBT with no halogen engineering plastic composite material is superior.
The third object of the present invention is the preparation method providing a kind of described fire retardant PBT with no halogen engineering plastic composite material, and the method is simple, and obtained fire retardant PBT with no halogen engineering plastic composite material over-all properties is superior.
In order to realize above-mentioned purpose of the present invention, spy by the following technical solutions:
A kind of novel halogen-free flame-retardant agent FRs, is mixed to get according to weight ratio 2.6-2.8:0.8-1.2:0.4-0.6:0.9-1.1:0.05-0.15 primarily of FR1, FR2, FR3, FR4 and FR5;
Wherein, FR1 structure is as follows:
FR2 structure is as follows:
FR3 structure is as follows:
FR4 structure is as follows:
FR5 structure is as follows:
Resistance toheat, anti-dropping performance, low CTI value and the painted problem such as undesirable that fire retardant PBT with no halogen engineering plastic composite material exists is prepared for existing halogen-free flame retardants, the invention provides a kind of novel halogen-free flame-retardant agent FRs, described FRs is mixed to get according to specific ratio primarily of FR1, FR2, FR3, FR4 and FR5, wherein, FR1 is a kind of heat-resistant stability Halogen phosphorus flame retardant, containing the high heat stability phosphoric acid ester of four quaternary carbon structures, have good coking performance, phosphorus content reaches more than 20%; FR2 is a kind of melamine pyrophosphate, belongs to Halogen phosphorus-nitrogenated flame retardant; FR3 is a kind of dendritic bittern-free phosphorous-nitrogen flame retardant, belongs to hyperbranched phosphorus-nitrogenated flame retardant, has certain increasing tougheness, and three forms efficient collaborative flame-retardant system; FR4 is a kind of polyetherimide improving material over-all properties, and FR5 is a kind of anti-molten drop and the additive improving processing characteristics, FR4 and FR5 adds the anti-dropping performance that can improve halogen-free flame-retardant system FRs flame-retardant PBT further and the over-all properties improving material; This several material has higher heat-resistant stability and good flame retardant properties with the use of making halogen-free flame-retardant system.
Wherein, FR1 is Caged bicyclic phosphate flame retardant disclosed in application number 200810147613.2; The universal models of FR2 is MPP, can buy from Jiangsu Su Li group, Su Li fine chemistry industry limited-liability company; FR3 is according to document (Han Huan, Zhong Liu, Liu Zhiguo.Hyperbranched phosphorus flame retardant preparation and fire retarding epoxide resin thereof, Chinese fire-retardant Annual Conference in 2010) synthesis; The model of FR4 is ULTEM 1000, and trade name is ULTEM HU1000, can manufacture purchase obtain from radical innovations plastics (U.S.); FR5 is Teflon powder, can buy from Dongguan City Ji Hong plastic cement company limited.
If FR1 is by preparing with under type: with Resorcinol, phosphorus oxychloride, tetramethylolmethane for raw material, reaction process is: by tetramethylolmethane, 1,4-dioxane adds reactor, heat to interior temperature 80 DEG C, phosphorus oxychloride is added first quick and back slow in 1h, finish and continue back flow reaction 2h, leave standstill cool to room temperature, filter to obtain white powdery solids tetramethylolmethane phosphonic acid ester PEPA.Phosphorus oxychloride and Resorcinol (mol ratio 1:2) and catalyzer are added in reaction vessel, reacts 3h under heating, then add the PEPA of above-mentioned synthesis, under acid binding agent effect, obtain fire retardant FR 1.
As FR3 is prepared according to above-mentioned document; specific as follows: dimethylbenzene, mphenylenediamine and triethylamine are added in reactor; under nitrogen protection and mechanical stirring, mixing of materials is evenly heated to 50 DEG C simultaneously, slowly drips phosphorus oxychloride and control rate of addition and make temperature of reaction be no more than 80 DEG C.Dropwise in 100 DEG C of reaction 4h, infrared spectra judges reaction end, and reaction mixture is cooled to room temperature, separates cured article, pulverizes after vacuum-drying, is washed with distilled water to till not having chlorion, obtains hyperbranched mphenylenediamine phosphamide product F R3.
Preferably, described halogen-free flame retardants FRs is mixed to get according to weight ratio 2.7:1:0.5:1:0.1 by FR1, FR2, FR3, FR4 and FR5;
Wherein, the fusing point of FR1 is 294-301 DEG C, P% is 20.24;
The melt temperature of FR3 is 101-103 DEG C.
FR1, FR2, FR3, FR4 and FR5 mixing of this weight ratio, has better collaborative reinforced effects; And the fusing point of the specific FR1 of selecting is 294-301 DEG C, P% be the melt temperature of 20.24, FR3 is 101-103 DEG C, and the halogen-free flame retardants FRs over-all properties made is more superior.Wherein, P% is the mass percentage of phosphorus.
FR1, FR2, FR3, FR4 and FR5 mixing obtains by halogen-free flame retardants FRs.As FR1, FR2, FR3, FR4 and FR5 put into mixing roll, mix with the rotating speed of 60-200r/min; After total material puts into, be difficult to stir, lower speed therefore can be selected to stir for some time, then increase stirring velocity and stir again, to accelerate the mixing of each composition.
Present invention also offers fire retardant PBT with no halogen engineering plastic composite material, make primarily of following composition, by weight,
For the defect of PBT process plastics composite in the market, the present invention adopts heat-resistant stability good and has the halogen-free flame retardants FRs of high coking performance, this halogen-free flame retardants FRs has alkali free glass fibre enhancing and effect PBT being carried out to halogen-free flameproof modification, fine and close, the isolated material of the insulating layer structure porous that halogen-free flame retardants FRs generates when being conducive to the burning of flame-retardant PBT engineering plastic composite material and transmission ofenergy, effectively raise the flame retardant properties of halogen-free flame-retardant system; And a kind of high thermal stability of the preparation such as composite CTI synergistic agent, anti-dropping, high CTI and be easy to painted fire retardant PBT with no halogen engineering plastic composite material.
In order to make PBT and other compositions better merge, it is more homogeneous that each material composition disperses, and the performance of obtained fire retardant PBT with no halogen engineering plastic composite material is better, and further, the limiting viscosity of described PBT is 0.85-1.20dlg -1, relative density is 1.30-1.33, and melting range is 220 ~ 235 DEG C, and content of carboxyl end group≤30mol/t in described PBT resin.
In order to make alkali free glass fibre better merge with other compositions, the insulativity of the fire retardant PBT with no halogen engineering plastic composite material that enhancing obtains, thermotolerance, erosion resistance and physical strength are high, and preferably, described alkali free glass fibre diameter is 4-17 μm;
Between CTI synergist and organophosphorous fire retardant, there is antagonistic effect, mechanical property and the flame retardant properties of PBT composite can be reduced, in order to the mechanical property and the flame retardant properties that make CTI synergist neither affect PBT composite, the CTI of material can be improved again, the specific CTI synergist selecting 0.1 ~ 0.5 part of the present invention.Further, described CTI synergist is calcium oxide.CTI synergist is calcium oxide, has better trade-off effect.
In order to suppress the carrying out of oxidising process in fire retardant PBT with no halogen engineering plastic composite material, thus stop the aging of material, preferably, described oxidation inhibitor is four [3-(3, 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, β-(3, 5-di-tert-butyl-hydroxy phenyl) the positive octadecanol ester of propionic acid, N, N-pair-[3-(3, 5-di-tert-butyl-hydroxy phenyl) propionyl] hexanediamine, tricresyl phosphite (2, 4-6-di-tert-butyl phenyl ester), at least one in two [3-(3-di-t-butyl-4-hydroxy-5-methyl base the phenyl)] vinyl cyanide of triglycol.
Empirical tests, described oxidation inhibitor is preferably by four [3-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester and tricresyl phosphite (2,4-6-di-tert-butyl phenyl ester) form by weight for 1:1.5-2.5, and this oxidation inhibitor has more superior antioxidant property.
In order to make each composition better merge, each composition profiles of the mixture obtained more homogeneous, preferably, described lubricant is at least one in ethylene bis-fatty acid amides and pentaerythritol stearate; Further, described lubricant is for being made up of by weight for 1:1.2-1.5 pentaerythritol stearate and ethylene bis-fatty acid amides.
In order to reduce the viscosity of mixture melt, increase the dispersity of each composition to improve processing characteristics, and then improve the interface performance of material, preferably, described coupling agent is at least one in γ-glycidyl ether oxygen propyl trimethoxy silicane, γ-aminopropyl triethoxysilane; Further, described coupling agent is preferably γ-glycidyl ether oxygen propyl trimethoxy silicane; In order to make each composition better compatible, described expanding material is preferably ABS-g-MAH.
In order to increase the toughness of obtained fire retardant PBT with no halogen engineering plastic composite material, improve loading strength, preferably, described toughner is at least one in ethylene methyl methacrylate-glycidyl acrylate multipolymer, methyl methacrylate-butyl acrylate copolymer, Ethylene-butyl Acrylate-methacrylic Acid Glycerin Ester Copolymer, Phthalic acid, diallyl ester-vinyl chloride copolymer.
Present invention also offers the preparation method of above-mentioned fire retardant PBT with no halogen engineering plastic composite material, comprise the following steps:
(a), by except alkali free glass fibre composition stir 10-20min mixing, mixing speed is 100-500r/min;
(b), the composition mixed is melt extruded granulation through Bitruder, processing conditions is: twin screw extruder one district temperature 200-210 DEG C, two district temperature 210-230 DEG C, three district temperature 210-230 DEG C, four district temperature 210-230 DEG C, five district temperature 200-220 DEG C, six district temperature 200-220 DEG C, seven district temperature 200-220 DEG C, eight district temperature 210-230 DEG C;
Wherein, add alkali free glass fibre in the stage casing of Bitruder, described alkali free glass fibre is through silane coupling agent immersion treatment;
Screw speed is 350-500r/min.
The preparation method of fire retardant PBT with no halogen engineering plastic composite material provided by the invention, first by the composition mixing except alkali free glass fibre, then granulation is melt extruded through Bitruder, simultaneously, stage casing at Bitruder is added alkali free glass fibre, prevents alkali free glass fibre of degrading during high temperature process; In addition, because alkali free glass fibre surface polarity is comparatively large, with the poor compatibility of other compositions, alkali free glass fibre is through silane coupling agent immersion treatment, silicon is coupled to glass surface and carries out modification, increase alkali free glass fibre and macromolecular material consistency and dispersing property; Bitruder is adopted to melt extrude granulation each composition, heat through multiple high temp, enhance the consistency between each composition and homogeneity, the good fire retardant PBT with no halogen engineering plastic composite materials of over-all properties such as obtained a kind of flame retardant properties, electric property, resistance toheat, mechanical property, tinctorial property.
Compared with prior art, beneficial effect of the present invention is:
(1) halogen-free flame retardants FRs is mixed to get according to specific ratio by FR1, FR2, FR3, FR4 and FR5, and obtained halogen-free flame retardants FRs has extraordinary cooperative flame retardant performance, anti-dropping performance and improves the over-all properties of material; And this several material is with the use of making halogen-free flame-retardant system have higher heat-resistant stability and having coking performance;
(2) halogen-free flame retardants FRs is for the preparation of fire retardant PBT with no halogen engineering plastic composite material, fine and close, the isolated material of the insulating layer structure porous generated when being conducive to the burning of flame-retardant PBT engineering plastic composite material and transmission ofenergy, effectively raise the flame retardant properties of halogen-free flame-retardant system; And with other each composition coordinated, the over-all properties such as flame retardant properties, electric property, resistance toheat, mechanical property, tinctorial property of obtained fire retardant PBT with no halogen engineering plastic composite material is superior;
(3) preparation method of fire retardant PBT with no halogen engineering plastic composite material is simple, obtained fire retardant PBT with no halogen engineering plastic composite material excellent combination property.
Embodiment
Below in conjunction with embodiment, embodiment of the present invention are described in detail, but it will be understood to those of skill in the art that the following example only for illustration of the present invention, and should not be considered as limiting the scope of the invention.Unreceipted actual conditions person in embodiment, the condition of conveniently conditioned disjunction manufacturers suggestion is carried out.Agents useful for same or the unreceipted production firm person of instrument, being can by the conventional products of commercially available acquisition.
Embodiment 1
In mixing roll, add 5.4kg FR1,2.0kg FR2,1.0kg FR3,2.0kg FR4 and 0.2kg FR5, respectively stir 5 minutes with 60rpm, 100rpm, 160rpm, 200rpm respectively, obtain novel halogen-free flame-retardant agent FRs;
Select the alkali free glass fibre of 11-15 μm to immerse in silane coupling agent after immersion, take out dry for standby;
PBT resin is cured 5.5 hours at 120-130 DEG C, 45kgPBT resin, 10kg halogen-free flame retardants FRs, 0.1kg calcium oxide, 0.6kg oxidation inhibitor, 0.3kg lubricant, 0.4kg coupling agent, 1kg expanding material and 5kg toughner after curing are added in mixing roll successively, then respectively stir 5 minutes with 100rpm, 200rpm, obtain halogen-free flame retardants FRs anti-flaming PBT composite pre-composition;
Wherein, oxidation inhibitor is made up of by weight for 1:1.5 four [3-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters and tricresyl phosphite (2,4-6-di-tert-butyl phenyl ester); Lubricant is for being made up of by weight for 1:1.2 pentaerythritol stearate and ethylene bis-fatty acid amides; Coupling agent is γ-glycidyl ether oxygen propyl trimethoxy silicane; Expanding material is ABS-g-MAH; Toughner is ethylene methyl methacrylate-glycidyl acrylate multipolymer;
Pre-composition is joined in twin screw extruder loading hopper, respectively with 200-210 DEG C, 210-230 DEG C, 210-230 DEG C, 210-230 DEG C, 200-220 DEG C, 200-220 DEG C, 200-220 DEG C, 210-230 DEG C temperature control machine barrel and the head temperature of forcing machine, in the loading hopper of twin screw mid-way, add 20kg alkali free glass fibre simultaneously, and with screw speed be that PBT composite is extruded through forcing machine by 350r/min, pelletizing, drying, obtain fire retardant PBT with no halogen engineering plastic composite material.
Embodiment 2
In mixing roll, add 7.8kg FR1,3.6kg FR2,1.2kg FR3,3.3kg FR4 and 0.15kg FR5, respectively stir 5 minutes with 80rpm, 120rpm, 140rpm, 180rpm respectively, obtain novel halogen-free flame-retardant agent FRs;
Select the alkali free glass fibre of 4-8 μm to immerse in silane coupling agent after immersion, take out dry for standby;
60kg PBT resin, 16kg halogen-free flame retardants FRs, 0.3kg calcium oxide, 0.3kg oxidation inhibitor, 0.5kg lubricant, 0.2kg coupling agent, 3kg expanding material and 1kg toughner are added in mixing roll successively, then respectively stir 5 minutes with 100rpm, 140rpm, 180rpm, 220rpm respectively, obtain halogen-free flame retardants FRs anti-flaming PBT composite pre-composition;
Wherein, oxidation inhibitor is 1:2.5 by four [3-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters and tricresyl phosphite (2,4-6-di-tert-butyl phenyl ester) by weight; Lubricant is for being made up of by weight for 1:1.5 pentaerythritol stearate and ethylene bis-fatty acid amides; Coupling agent is the mixture of γ-glycidyl ether oxygen propyl trimethoxy silicane and γ-aminopropyl triethoxysilane, wherein, and γ-glycidyl ether oxygen propyl trimethoxy silicane 0.1kg, γ-aminopropyl triethoxysilane 0.1kg; Expanding material is ABS-g-MAH; Toughner is the mixture of methyl methacrylate-butyl acrylate copolymer and Ethylene-butyl Acrylate-methacrylic Acid Glycerin Ester Copolymer, wherein, methyl methacrylate-butyl acrylate copolymer 0.3kg, Ethylene-butyl Acrylate-methacrylic Acid Glycerin Ester Copolymer 0.7kg;
Pre-composition is joined in twin screw extruder loading hopper, respectively with 200-210 DEG C, 210-230 DEG C, 210-230 DEG C, 210-230 DEG C, 200-220 DEG C, 200-220 DEG C, 200-220 DEG C, 210-230 DEG C temperature control machine barrel and the head temperature of forcing machine, in the loading hopper of twin screw mid-way, add 25kg alkali free glass fibre simultaneously, and with screw speed be that PBT composite is extruded through forcing machine by 450r/min, pelletizing, drying, obtain fire retardant PBT with no halogen engineering plastic composite material.
Embodiment 3
In mixing roll, add 14kg FR1,4kg FR2,3kg FR3,4.5kg FR4 and 0.25kg FR5, respectively stir 5 minutes with 80rpm, 140rpm, 200rpm respectively, obtain novel halogen-free flame-retardant agent FRs;
Select the alkali free glass fibre of 10-13 μm to immerse in silane coupling agent after immersion, take out dry for standby;
70kg PBT resin, 23kg halogen-free flame retardants FRs, 0.5kg calcium oxide, 0.4kg oxidation inhibitor, 0.8kg lubricant, 0.6kg coupling agent, 6kg expanding material and 12kg toughner are added in mixing roll successively, then respectively with 100rpm, 160rpm, 200rpm, each to stir 5 minutes, obtain halogen-free flame retardants FRs anti-flaming PBT composite pre-composition;
Wherein, oxidation inhibitor is β-positive octadecanol ester of (3,5-di-tert-butyl-hydroxy phenyl) propionic acid, lubricant is pentaerythritol stearate, coupling agent is γ-glycidyl ether oxygen propyl trimethoxy silicane, expanding material is ABS-g-MAH, toughner is ethylene methyl methacrylate-glycidyl acrylate multipolymer, methyl methacrylate-butyl acrylate copolymer, the mixture of Ethylene-butyl Acrylate-methacrylic Acid Glycerin Ester Copolymer and Phthalic acid, diallyl ester-vinyl chloride copolymer, wherein, methyl methacrylate-butyl acrylate copolymer 2kg, Ethylene-butyl Acrylate-methacrylic Acid Glycerin Ester Copolymer 3kg, Ethylene-butyl Acrylate-methacrylic Acid Glycerin Ester Copolymer 5kg, Phthalic acid, diallyl ester-vinyl chloride copolymer 2kg,
Pre-composition is joined in twin screw extruder loading hopper, respectively with 200-210 DEG C, 210-230 DEG C, 210-230 DEG C, 210-230 DEG C, 200-220 DEG C, 200-220 DEG C, 200-220 DEG C, 210-230 DEG C temperature control machine barrel and the head temperature of forcing machine, in the loading hopper of twin screw mid-way, add 32kg alkali free glass fibre simultaneously, and with screw speed be that PBT composite is extruded through forcing machine by 500r/min, pelletizing, drying, obtain fire retardant PBT with no halogen engineering plastic composite material.
Embodiment 4
In mixing roll, add 8.0kg FR1,3.0kg FR2,1.5kg FR3,3.0kg FR4 and 0.3kg FR5, respectively stir 10 minutes with 80rpm, 150rpm respectively, obtain novel halogen-free flame-retardant agent FRs;
Select the alkali free glass fibre of 15-17 μm to immerse in silane coupling agent after immersion, take out dry for standby;
50kg PBT resin, 14kg halogen-free flame retardants FRs, 0.3kg calcium oxide, 0.5kg oxidation inhibitor, 0.6kg lubricant, 0.4kg coupling agent, 2kg expanding material and 8kg toughner are added in mixing roll successively, then respectively stir 5 minutes with 120rpm, 160rpm, 200rpm respectively, obtain halogen-free flame retardants FRs anti-flaming PBT composite pre-composition;
Wherein, oxidation inhibitor is four [3-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester 0.1kg, β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid positive octadecanol ester 0.1kg, N, N-pair-[3-(3,5-di-tert-butyl-hydroxy phenyl) propionyl] mixture of two [3-(3-di-t-butyl-4-hydroxy-5-methyl base phenyl)] the vinyl cyanide 0.2kg of hexanediamine, tricresyl phosphite (2,4-6-di-tert-butyl phenyl ester) 0.1kg and triglycol; Lubricant is ethylene bis-fatty acid amides; Coupling agent is γ-glycidyl ether oxygen propyl trimethoxy silicane; Expanding material is ABS-g-MAH; Toughner is Phthalic acid, diallyl ester-vinyl chloride copolymer;
Pre-composition is joined in twin screw extruder loading hopper, in the loading hopper of twin screw mid-way, add 12.00Kg alkali free glass fibre simultaneously, respectively with 200-210 DEG C, 210-230 DEG C, 210-230 DEG C, 210-230 DEG C, 200-220 DEG C, 200-220 DEG C, 200-220 DEG C, 210-230 DEG C temperature control machine barrel and the head temperature of forcing machine, and with screw speed be that PBT composite is extruded through forcing machine by 400r/min, pelletizing, drying, obtain fire retardant PBT with no halogen engineering plastic composite material.
Chemical reagent used in embodiment 1-4 is bought or self-control, specific as follows:
Prepared by FR1 mode disclosed in application number 200810147613.2, specific as follows: with Resorcinol, phosphorus oxychloride, tetramethylolmethane for raw material, reaction process is: by tetramethylolmethane, 1,4-dioxane adds reactor, heat to interior temperature 80 DEG C, in 1h, add phosphorus oxychloride first quick and back slow, finish and continue back flow reaction 2h, leave standstill cool to room temperature, filter to obtain white powdery solids tetramethylolmethane phosphonic acid ester PEPA.Phosphorus oxychloride and Resorcinol (mol ratio 1:2) and catalyzer are added in reaction vessel, reacts 3h under heating, then add the PEPA of above-mentioned synthesis, under acid binding agent effect, obtain fire retardant FR 1; Obtained FR1 fusing point is 294-301 DEG C, P% is 20.24.
FR3 is according to document (hyperbranched phosphorus flame retardant preparation and fire retarding epoxide resin thereof; Chinese fire-retardant Annual Conference in 2010) be prepared; specific as follows: dimethylbenzene, mphenylenediamine and triethylamine are added in reactor; under nitrogen protection and mechanical stirring, mixing of materials is evenly heated to 50 DEG C simultaneously, slowly drips phosphorus oxychloride and control rate of addition and make temperature of reaction be no more than 80 DEG C.Dropwise in 100 DEG C of reaction 4h, infrared spectra judges reaction end, and reaction mixture is cooled to room temperature, separates cured article, pulverizes after vacuum-drying, is washed with distilled water to till not having chlorion, obtains hyperbranched mphenylenediamine phosphamide product F R3.The melt temperature of FR3 is 101-103 DEG C.
FR2 buys from Su Li fine chemistry industry limited-liability company; The model of FR4 is ULTEM1000, and trade name is ULTEM HU1000, manufactures purchase obtain from radical innovations plastics (U.S.); FR5 is Teflon powder, buys from Dongguan City Ji Hong plastic cement company limited.
In addition, the limiting viscosity of PBT is 0.85-1.20dlg-1, and relative density is 1.30-1.33, and melting range is 220 ~ 235 DEG C, and content of carboxyl end group≤30mol/t in described PBT resin.
The fire retardant PBT with no halogen engineering plastic composite material that embodiment 1-4 is obtained measures tensile strength, breaking tenacity, flexural strength, modulus in flexure, Izod notched impact strength, the non-notched Izod impact strength of socle girder, thermal change temperature, flame retardant properties, molding shrinkage, CTI value etc. according to national standard, and specific standards is as shown in table 1.What record the results are shown in Table 2.
The testing standard of each performance perameter of table 1
The numerical value of each performance of table 2 fire retardant PBT with no halogen engineering plastic composite material
As can be seen from Table 2, fire retardant PBT with no halogen engineering plastic composite material provided by the invention has good comprehensive mechanical property, thermal property and flame retardant properties, particularly has excellent CTI value.
Although illustrate and describe the present invention with specific embodiment, however it will be appreciated that can to make when not deviating from the spirit and scope of the present invention many other change and amendment.Therefore, this means to comprise all such changes and modifications belonged in the scope of the invention in the following claims.

Claims (10)

1. a novel halogen-free flame-retardant agent FRs, is characterized in that, is mixed to get according to weight ratio 2.6-2.8:0.8-1.2:0.4-0.6:0.9-1.1:0.05-0.15 primarily of FR1, FR2, FR3, FR4 and FR5;
Wherein, FR1 structure is as follows:
FR2 structure is as follows:
FR3 structure is as follows:
FR4 structure is as follows:
FR5 structure is as follows:
2. novel halogen-free flame-retardant agent FRs according to claim 1, is characterized in that, described halogen-free flame retardants FRs is mixed to get according to weight ratio 2.7:1:0.5:1:0.1 by FR1, FR2, FR3, FR4 and FR5;
Wherein, the fusing point of FR1 is 294-301 DEG C, P% is 20.24;
The melt temperature of FR3 is 101-103 DEG C.
3. comprise the fire retardant PBT with no halogen engineering plastic composite material of FRs described in any one of right 1-2, it is characterized in that, make primarily of following composition, by weight,
4. fire retardant PBT with no halogen engineering plastic composite material according to claim 3, is characterized in that, the limiting viscosity of described PBT is 0.85-1.20dlg -1, relative density is 1.30-1.33, and melting range is 220 ~ 235 DEG C, and content of carboxyl end group≤30mol/t in described PBT resin.
5. fire retardant PBT with no halogen engineering plastic composite material according to claim 3, is characterized in that, described alkali free glass fibre diameter is 4-17 μm;
Described CTI synergist is preferably calcium oxide.
6. fire retardant PBT with no halogen engineering plastic composite material according to claim 3, it is characterized in that, described oxidation inhibitor is four [3-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, β-(3,5-di-tert-butyl-hydroxy phenyl) the positive octadecanol ester of propionic acid, N, N-pair-[3-(3,5-di-tert-butyl-hydroxy phenyl) propionyl] hexanediamine, tricresyl phosphite (2,4-6-di-tert-butyl phenyl ester), at least one in two [3-(3-di-t-butyl-4-hydroxy-5-methyl base the phenyl)] vinyl cyanide of triglycol; Described oxidation inhibitor is preferably and is made up of by weight for 1:1.5-2.5 four [3-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters and tricresyl phosphite (2,4-6-di-tert-butyl phenyl ester).
7. fire retardant PBT with no halogen engineering plastic composite material according to claim 3, is characterized in that, described lubricant is at least one in ethylene bis-fatty acid amides and pentaerythritol stearate; Described lubricant is preferably and is made up of by weight for 1:1.2-1.5 pentaerythritol stearate and ethylene bis-fatty acid amides.
8. fire retardant PBT with no halogen engineering plastic composite material according to claim 3, is characterized in that, described coupling agent is at least one in γ-glycidyl ether oxygen propyl trimethoxy silicane, γ-aminopropyl triethoxysilane; Described coupling agent is preferably γ-glycidyl ether oxygen propyl trimethoxy silicane; Described expanding material is preferably ABS-g-MAH.
9. fire retardant PBT with no halogen engineering plastic composite material according to claim 3, it is characterized in that, described toughner is at least one in ethylene methyl methacrylate-glycidyl acrylate multipolymer, methyl methacrylate-butyl acrylate copolymer, Ethylene-butyl Acrylate-methacrylic Acid Glycerin Ester Copolymer, Phthalic acid, diallyl ester-vinyl chloride copolymer.
10. the preparation method of the fire retardant PBT with no halogen engineering plastic composite material described in any one of claim 3-9, is characterized in that, comprise the following steps:
(a), by except alkali free glass fibre composition stir 10-20min mixing, mixing speed is 100-500r/min;
(b), the composition mixed is melt extruded granulation through Bitruder, processing conditions is: twin screw extruder one district temperature 200-210 DEG C, two district temperature 210-230 DEG C, three district temperature 210-230 DEG C, four district temperature 210-230 DEG C, five district temperature 200-220 DEG C, six district temperature 200-220 DEG C, seven district temperature 200-220 DEG C, eight district temperature 210-230 DEG C;
Wherein, add alkali free glass fibre in the stage casing of Bitruder, described alkali free glass fibre is through silane coupling agent immersion treatment;
Screw speed is 350-500r/min.
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CN108102359A (en) * 2017-12-27 2018-06-01 重庆普利特新材料有限公司 A kind of environmentally protective, high-performance, high CTI flame-retardant reinforced nylon materials and preparation method thereof
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CN112144204A (en) * 2020-10-09 2020-12-29 北京深核智能科技有限公司 Preparation process of flame-retardant functional garment fabric
CN113683730A (en) * 2021-08-27 2021-11-23 西华大学 Corn straw cellulose-based water-absorbent resin composite material and preparation method thereof
CN115449207A (en) * 2022-09-21 2022-12-09 中车青岛四方机车车辆股份有限公司 Halogen-free flame-retardant reinforced PC composite material and preparation method and application thereof
CN115449207B (en) * 2022-09-21 2024-02-23 中车青岛四方机车车辆股份有限公司 Halogen-free flame-retardant reinforced PC composite material and preparation method and application thereof
CN118126384A (en) * 2024-05-10 2024-06-04 江苏恒力化纤股份有限公司 Preparation method of flame-retardant smoke-suppressing polyester film

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