CN109535666A - Inexpensive, high CTI, high GWIT fire-retardant reinforced PBT composite material and preparation method thereof - Google Patents
Inexpensive, high CTI, high GWIT fire-retardant reinforced PBT composite material and preparation method thereof Download PDFInfo
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- CN109535666A CN109535666A CN201811292846.1A CN201811292846A CN109535666A CN 109535666 A CN109535666 A CN 109535666A CN 201811292846 A CN201811292846 A CN 201811292846A CN 109535666 A CN109535666 A CN 109535666A
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 73
- 239000002131 composite material Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000003365 glass fiber Substances 0.000 claims abstract description 11
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 10
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 10
- 150000001875 compounds Chemical class 0.000 claims abstract description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 8
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 7
- 150000002367 halogens Chemical class 0.000 claims abstract description 7
- 229920005989 resin Polymers 0.000 claims abstract description 7
- 239000011347 resin Substances 0.000 claims abstract description 7
- 239000006057 Non-nutritive feed additive Substances 0.000 claims abstract description 6
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 6
- 229910001463 metal phosphate Inorganic materials 0.000 claims abstract description 6
- 239000010452 phosphate Substances 0.000 claims abstract description 6
- 238000012545 processing Methods 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 239000012745 toughening agent Substances 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims description 13
- 239000007822 coupling agent Substances 0.000 claims description 7
- 239000000347 magnesium hydroxide Substances 0.000 claims description 7
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 7
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 239000000314 lubricant Substances 0.000 claims description 4
- 239000002530 phenolic antioxidant Substances 0.000 claims description 4
- 229920000877 Melamine resin Polymers 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 238000013329 compounding Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 3
- 230000007613 environmental effect Effects 0.000 claims description 3
- 238000001125 extrusion Methods 0.000 claims description 3
- 230000004927 fusion Effects 0.000 claims description 3
- 238000004898 kneading Methods 0.000 claims description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical group NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000005453 pelletization Methods 0.000 claims description 3
- 150000008301 phosphite esters Chemical class 0.000 claims description 3
- 229920000388 Polyphosphate Polymers 0.000 claims description 2
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 2
- TXQVDVNAKHFQPP-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] octadecanoate Chemical group CCCCCCCCCCCCCCCCCC(=O)OCC(CO)(CO)CO TXQVDVNAKHFQPP-UHFFFAOYSA-N 0.000 claims description 2
- -1 magnesium hydroxide compound Chemical class 0.000 claims description 2
- 239000001205 polyphosphate Substances 0.000 claims description 2
- 235000011176 polyphosphates Nutrition 0.000 claims description 2
- 229920001897 terpolymer Polymers 0.000 claims description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical class OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 15
- 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 abstract description 11
- 238000000034 method Methods 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 3
- 230000008676 import Effects 0.000 abstract description 2
- 238000012986 modification Methods 0.000 abstract description 2
- 230000004048 modification Effects 0.000 abstract description 2
- 239000004033 plastic Substances 0.000 abstract description 2
- 229920003023 plastic Polymers 0.000 abstract description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 28
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000002708 enhancing effect Effects 0.000 description 3
- 238000004079 fireproofing Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- LXWPJAGZRHTAOO-UHFFFAOYSA-N [Sb].[Br] Chemical compound [Sb].[Br] LXWPJAGZRHTAOO-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 2
- FZZMTSNZRBFGGU-UHFFFAOYSA-N 2-chloro-7-fluoroquinazolin-4-amine Chemical compound FC1=CC=C2C(N)=NC(Cl)=NC2=C1 FZZMTSNZRBFGGU-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 230000000875 corresponding effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- TVHALOSDPLTTSR-UHFFFAOYSA-H hexasodium;[oxido-[oxido(phosphonatooxy)phosphoryl]oxyphosphoryl] phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O TVHALOSDPLTTSR-UHFFFAOYSA-H 0.000 description 1
- 238000005213 imbibition Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical class C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/08—Copolymers of ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/04—Ingredients characterised by their shape and organic or inorganic ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/2224—Magnesium hydroxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34928—Salts
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Reinforced Plastic Materials (AREA)
Abstract
The present invention relates to PBT plastic technical field of modification, in particular to a kind of low cost, high CTI, high GWIT fire-retardant reinforced PBT composite material and preparation method thereof, PBT composite is made of the raw material of following parts by weight: 40-52 parts of PBT resin；14-25 parts of Halogenless composite fire retardant；25-30 parts of glass fibre；1-5 parts of toughener；0.1-0.5 parts of antioxidant；0.5-1 parts of other processing aids；The Halogenless composite fire retardant selects metal phosphate fire retardant, organic phosphate fire retardant, inorganic fire retardants to compound.Halogen free flame-retardant reinforced PBT engineering material provided by the invention has good mechanical property and flame retardant property, high CTI (600V) and high GWIT (800 DEG C of whole process of glowing filament ignition temperature are nonflammable), and material is environmentally friendly, and processing performance is good；Particularly, the Halogenless composite fire retardant used is low in cost, 40%-50% lower than the fire retardant price of similar import, has the very big market competitiveness.
Description
Technical field
The present invention relates to PBT plastic technical field of modification, in particular to low cost, high CTI, high GWIT flame-retardant reinforced PBT
Composite material and preparation method.
Background technique
Polybutylene terephthalate (PBT) (PBT) is a kind of crystalline thermoplastic polyester.It has high temperature resistant, weatherability,
The advantages that chemical-resistant, electrical insulating property are good, water imbibition is small, dimensional stability is high, processability is good is that a kind of comprehensive performance is excellent
Good engineering plastics are widely used in the industries such as electric, automobile, household electrical appliance.
It is stepped up with the development of science and technology with living standards of the people, home intelligence will be realized gradually, uncared for
Electrical equipment also gradually popularize, glowing filament ignition temperature (GWIT) to material and relative discharge tracking index (CTI) propose
Higher requirement.Traditional PBT enhancing flame resistant method is the fire-retardant mode with fiberglass reinforced of bromine antimony, good flame retardation effect, sexual valence
Than high, but the CTI of this fire-retardant reinforcing material only has 175-200V, limits answering in high-end field under severe conditions
With.Although the PBT material of the fire-retardant enhancing of bromine antimony has part of the manufacturer that can reach 800 DEG C of nonflammable requirements, but need to add a large amount of
Fire retardant can be only achieved, and with high costs, poor mechanical property.In addition, issuing with RoHS Directive and REACH regulation
Cloth, execution, the non-halogen of fire proofing become a kind of trend.
Although the halogen-free flame retardants that offshore company develops can be able to satisfy the high CTI and height of PBT enhancing fire proofing simultaneously
The requirement of GWIT, but cost is sufficiently expensive, to limit its application and develop.
In conclusion main problem existing for halogen free flame-retardant reinforced PBT material is at present: (1) halogen-free flame retardants cost is high
It is expensive；(2) it is difficult to meet high CTI and the big harsh conditions of high GWIT two simultaneously, and the poor mechanical property of material；(3) processing technology
It is difficult.
Summary of the invention
To solve the problems in above-mentioned background technique, low cost provided by the invention, high CTI, high GWIT flame-retardant reinforced PBT
Composite material has the advantages that low cost, high CTI, high GWIT (800 DEG C of whole process of glowing filament ignition temperature are nonflammable), and simultaneously
It is able to maintain excellent mechanical property and processing performance.
Specifically, low cost provided by the invention, high CTI, high GWIT fire-retardant reinforced PBT composite material are by following parts by weight
Raw material composition:
The Halogenless composite fire retardant selects metal phosphate fire retardant, organic phosphate fire retardant, inorganic fire retardants multiple
With forming.
Further, the PBT viscosity is 0.8-1.0dl/g.
Further, the metal phosphate fire retardant is hypo-aluminum orthophosphate HT-202A；
The organic phosphate fire retardant is melamine polyphosphate MPP；
The inorganic fire retardants magnesium hydroxide；
In the Halogenless composite fire retardant, HT-202A:MPP: magnesium hydroxide is (0.5-5): 1:(1-3 again).
Further, the glass fibre selects continuous long glass fiber, preferably megalith 988A
Further, the toughener is ethylene-methyl acrylate-glyceryl methacrylate terpolymer,
It is preferred that AX8900 or PTW.
Further, the antioxidant is the compound of phenolic antioxidant and phosphite ester antioxidant, and the phenols is anti-
The compounding weight ratio of oxygen agent and phosphite ester antioxidant is 1:1-1:2.5, and phenolic antioxidant antioxidant/phosphorous acid esters are anti-
Oxygen agent preferably 1010/168.
Further, other processing aids include inside and outside lubricant agent and coupling agent；
The lubricant is pentaerythritol stearate, and the coupling agent is silane coupling agent, as KH560 silanes is even
Join agent.
The present invention also provides a kind of basis any low costs as above, high CTI, high GWIT flame-retardant reinforced PBT composite wood
The preparation method of material, including following preparation step:
Step a, PBT resin is dried 2-4 hours at 120 DEG C, controls 0.05% or less moisture <；
Step b, the various raw materials in addition to glass fibre are weighed by weight percentage, by the PBT resin weighed up elder generation and coupling
Agent premixes 1 minute in high mixer, obtains mixture M 1；
Step c, each component in Halogenless composite fire retardant is premixed in high mixer according to compound proportion, it is compound obtains Halogen
Fire retardant；Until being uniformly mixed；
Step d, mixture M 1 and toughener, antioxidant and other processing aid components are added in high mixed pot, then 2 points mixed
Double screw extruder is sent into Zhong Hou, discharging, is carried out fusion plastification, kneading mixing, is obtained mixture M 2；
Step e, Halogenless composite fire retardant is claimed to be added in mixture M 2 by side feed through weightlessness, glass fibre is passed through into side
Feeding warp adds fine mouth to be added, most afterwards through head extrusion, tie rod, cooling, pelletizing, dry CTI inexpensive, high to get environmental protection, high GWIT
Fire-retardant reinforced PBT composite material.
Further, the draw ratio of the double screw extruder is 40:1；
The extruder temperature range is 200-235 DEG C；
The screw speed is 350-400rpm；
The processing temperature of each section of the double screw extruder is respectively as follows: T1=190~200 DEG C, T2=200~210 DEG C, T3
=205~220 DEG C, T4=215~230 DEG C, T5=215~230 DEG C, T6=210~220 DEG C, T7=205~215 DEG C, T8=
200~215 DEG C, T9=205~215 DEG C, mould=220~235 DEG C T.
The present invention provides low cost, high CTI, high GWIT fire-retardant reinforced PBT composite material compared with prior art, has
Effect below:
(1) present invention by adopting the above technical scheme, by metal phosphate and organic phosphate in burning to PBT material
It carries out being dehydrated into carbon, while forming porosity carbon-coating performance flame-retarded efficiency with the incombustibility gas generated is decomposed, in addition, price
Cheap inorganic fire retardants magnesium hydroxide burning time-division heat of desorption, release combine water, reduce material surface temperature, therefore prepare
Material can meet high CTI (600V) and high GWIT (800 DEG C of whole process of glowing filament ignition temperature are nonflammable) two big harsh conditions simultaneously,
Better than conventional inexpensive, high CTI, high GWIT fire-retardant reinforced PBT composite material；
(2) flame-retardant enhanced PBT material provided by the present invention also has well while with good flame retardant property
Mechanical property；
(3) Halogenless composite fire retardant i.e. HT-202A, MPP and magnesium hydroxide that the present invention selects, three's compounding can not only
The CTI and GWIT of PBT fire proofing are effectively improved, and cost is 40%-50% lower than the fire retardant price of similar import, had
There is the very strong market competitiveness；In addition, the Halogenless composite fire retardant also has, processability is good, no pollution to the environment, to mold corruption
Lose the advantages that small.
Specific embodiment
In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below in conjunction with the embodiment of the present invention
In technical solution be clearly and completely described, it is clear that described embodiments are some of the embodiments of the present invention, without
It is whole embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art are not before making creative work
Every other embodiment obtained is put, shall fall within the protection scope of the present invention.
The present invention also provides embodiments as shown in the table:
Table 1
Specifically, according in above table being embodiment and comparative example formula, the present invention also provides following preparation implementations
The scheme of example:
Step a, PBT resin is dried 2-4 hours at 120 DEG C, controls 0.05% or less moisture <；
Step b, the various raw materials in addition to glass fibre are weighed by weight percentage, by the PBT resin weighed up elder generation and coupling
Agent premixes 1 minute in high mixer, obtains mixture M 1；
Step c, each component in Halogenless composite fire retardant is premixed in high mixer according to compound proportion, it is compound obtains Halogen
Fire retardant；Until being uniformly mixed；
Step d, mixture M 1 and toughener, antioxidant and other processing aid components are added in high mixed pot, then 2 points mixed
Double screw extruder is sent into Zhong Hou, discharging, is carried out fusion plastification, kneading mixing, is obtained mixture M 2；
Step e, Halogenless composite fire retardant is claimed to be added in mixture M 2 by side feed through weightlessness, glass fibre is passed through into side
Feeding warp adds fine mouth to be added, most afterwards through head extrusion, tie rod, cooling, pelletizing, dry CTI inexpensive, high to get environmental protection, high GWIT
Fire-retardant reinforced PBT composite material.
Wherein, the draw ratio of the double screw extruder is 40:1；The extruder temperature range is 200-235 DEG C；Institute
Stating screw speed is 350-400rpm；The processing temperature of each section of the double screw extruder is respectively as follows: T1=190~200 DEG C, T2
=200~210 DEG C, T3=205~220 DEG C, T4=215~230 DEG C, T5=215~230 DEG C, T6=210~220 DEG C, T7=
205~215 DEG C, T8=200~215 DEG C, T9=205~215 DEG C, mould=220~235 DEG C T.
It is adopted according to inexpensive, high CTI, high GWIT fire-retardant reinforced PBT composite material prepared by above-described embodiment and comparative example
It is molded into standard sample with injection molding machine, in addition, patent CN 101497738A discloses a kind of fire retardant PBT with no halogen, however the patent
In not in terms of CTI, GWIT of cost and high request further screening is made to the classification and ratio of flame-retardant system, by the patent
In embodiment 4 in material (as the comparative example 4 in this patent) carry out correlated performance test, concrete outcome is referring to table 2.With
Known patent is compared, the phosphonium flame retardant in this patent can be effectively formed in PBT material combustion process porous carbon layer every
From heat source, and the combination water that magnesium hydroxide decomposition generates quickly reduces material surface temperature, and collective effect between three can
Reach the requirement of material high CTI, high GWIT with lower cost approach.Simple organic phosphoric acid aluminium and melamine in comparative example 4
Amine Quadrafos compound flame retardant can satisfy fire-retardant and CTI and require, but higher cost, and GWIT can only achieve 725 DEG C
It is nonflammable.
Table 2
Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent
Pipe present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: its according to
So be possible to modify the technical solutions described in the foregoing embodiments, or to some or all of the technical features into
Row equivalent replacement；And these are modified or replaceed, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution
The range of scheme.
Claims (9)
1. low cost, high CTI, high GWIT fire-retardant reinforced PBT composite material, which is characterized in that by the raw material group of following parts by weight
At:
The Halogenless composite fire retardant select metal phosphate fire retardant, organic phosphate fire retardant, three kinds of inorganic fire retardants it is multiple
With forming.
2. low cost according to claim 1, high CTI, high GWIT fire-retardant reinforced PBT composite material, it is characterised in that: institute
Stating PBT viscosity is 0.8-1.0dl/g.
3. low cost according to claim 1, high CTI, high GWIT fire-retardant reinforced PBT composite material, it is characterised in that: institute
Stating metal phosphate fire retardant is hypo-aluminum orthophosphate HT-202A；
The organic phosphate fire retardant is melamine polyphosphate MPP；
The inorganic fire retardants is magnesium hydroxide；
In the Halogenless composite fire retardant, HT-202A:MPP: magnesium hydroxide compound proportion is (0.5-5): 1:(1-3).
4. low cost according to claim 1, high CTI, high GWIT fire-retardant reinforced PBT composite material, it is characterised in that: institute
The glass fibre stated selects continuous long glass fiber.
5. low cost according to claim 1, high CTI, high GWIT fire-retardant reinforced PBT composite material, it is characterised in that: institute
Stating toughener is ethylene-methyl acrylate-glyceryl methacrylate terpolymer.
6. low cost according to claim 1, high CTI, high GWIT fire-retardant reinforced PBT composite material, it is characterised in that: institute
State the compound that antioxidant is phenolic antioxidant and phosphite ester antioxidant, the phenolic antioxidant and phosphorous acid esters antioxygen
The compounding weight ratio of agent is 1:1-1:2.5.
7. low cost according to claim 1, high CTI, high GWIT fire-retardant reinforced PBT composite material, it is characterised in that: institute
Stating other processing aids includes inside and outside lubricant agent and coupling agent；
The lubricant is pentaerythritol stearate, and the coupling agent is silane coupling agent.
8. a kind of according to low cost, high CTI, high GWIT fire-retardant reinforced PBT composite material as described in claim any one of 1-7
Preparation method, which is characterized in that including following preparation step:
Step a, PBT resin is dried 2-4 hours at 120 DEG C, controls 0.05% or less moisture <；
Step b, the various raw materials in addition to glass fibre are weighed by weight percentage, and the PBT resin elder generation weighed up and coupling agent are existed
It is premixed 1 minute in high mixer, obtains mixture M 1；
Step c, each component in Halogenless composite fire retardant is premixed in high mixer according to compound proportion, obtains Halogen composite flame-proof
Agent；Until being uniformly mixed；
Step d, mixture M 1 and toughener, antioxidant and other processing aid components are added in high mixed pot, then 2 minutes mixed
Afterwards, double screw extruder is sent into discharging, is carried out fusion plastification, kneading mixing, is obtained mixture M 2；
Step e, Halogenless composite fire retardant is claimed to be added in mixture M 2 by side feed through weightlessness, glass fibre is passed through by side feed
Fine mouth is added to be added, it is most fire-retardant through head extrusion, tie rod, cooling, pelletizing, dry CTI inexpensive, high to get environmental protection, high GWIT afterwards
Enhance PBT composite.
9. low cost according to claim 8, the preparation method of high CTI, high GWIT fire-retardant reinforced PBT composite material,
It is characterized in that:
The draw ratio of the double screw extruder is 40:1；
The extruder temperature range is 200-235 DEG C；
The screw speed is 350-400rpm；
The processing temperature of each section of the double screw extruder is respectively as follows: T1=190~200 DEG C, T2=200~210 DEG C, T3=
205~220 DEG C, T4=215~230 DEG C, T5=215~230 DEG C, T6=210~220 DEG C, T7=205~215 DEG C, T8=
200~215 DEG C, T9=205~215 DEG C, mould=220~235 DEG C T.
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| CN114230985A (en) * | 2021-12-28 | 2022-03-25 | 上海普利特复合材料股份有限公司 | High-flame-retardancy precipitation-resistant halogen-free flame-retardant reinforced PBT (polybutylene terephthalate) material and preparation method thereof |
| CN114891326A (en) * | 2022-05-30 | 2022-08-12 | 东莞市百思特塑胶有限公司 | Short glass fiber reinforced flame-retardant high-CTI high-glow-wire environment-friendly PBT (polybutylene terephthalate) |
| CN115505243A (en) * | 2022-09-22 | 2022-12-23 | 上海锦湖日丽塑料有限公司 | Preparation method of high-CTI high-glowing filament ignition temperature halogen-free flame-retardant reinforced PBT (polybutylene terephthalate) composite material |
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| CN111621125A (en) * | 2020-06-17 | 2020-09-04 | 宁波华腾首研新材料有限公司 | High-performance enhanced halogen-free red-phosphorus-free flame-retardant PBT (polybutylene terephthalate) engineering plastic material and preparation method thereof |
| CN111621125B (en) * | 2020-06-17 | 2022-02-01 | 宁波华腾首研新材料有限公司 | High-performance enhanced halogen-free red-phosphorus-free flame-retardant PBT (polybutylene terephthalate) engineering plastic material and preparation method thereof |
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| CN114230985A (en) * | 2021-12-28 | 2022-03-25 | 上海普利特复合材料股份有限公司 | High-flame-retardancy precipitation-resistant halogen-free flame-retardant reinforced PBT (polybutylene terephthalate) material and preparation method thereof |
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| CN114891326A (en) * | 2022-05-30 | 2022-08-12 | 东莞市百思特塑胶有限公司 | Short glass fiber reinforced flame-retardant high-CTI high-glow-wire environment-friendly PBT (polybutylene terephthalate) |
| CN115505243A (en) * | 2022-09-22 | 2022-12-23 | 上海锦湖日丽塑料有限公司 | Preparation method of high-CTI high-glowing filament ignition temperature halogen-free flame-retardant reinforced PBT (polybutylene terephthalate) composite material |
| CN115505243B (en) * | 2022-09-22 | 2023-10-27 | 上海锦湖日丽塑料有限公司 | Preparation method of halogen-free flame-retardant reinforced PBT composite material with high CTI (comparative tracking index) and high glow wire ignition temperature |
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Application publication date: 20190329 |