CN114230985B - High-flame-retardance precipitation-resistant halogen-free flame-retardant reinforced PBT material and preparation method thereof - Google Patents
High-flame-retardance precipitation-resistant halogen-free flame-retardant reinforced PBT material and preparation method thereof Download PDFInfo
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 102
- 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 80
- 238000001556 precipitation Methods 0.000 title claims abstract description 33
- 239000000463 material Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 239000002131 composite material Substances 0.000 claims abstract description 35
- 239000003365 glass fiber Substances 0.000 claims abstract description 25
- 239000002994 raw material Substances 0.000 claims abstract description 22
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 8
- 239000011574 phosphorus Substances 0.000 claims abstract description 8
- 229920005989 resin Polymers 0.000 claims abstract description 7
- 239000011347 resin Substances 0.000 claims abstract description 7
- 239000012745 toughening agent Substances 0.000 claims abstract description 5
- 239000003963 antioxidant agent Substances 0.000 claims abstract 2
- 230000003078 antioxidant effect Effects 0.000 claims abstract 2
- 239000000314 lubricant Substances 0.000 claims abstract 2
- 238000000034 method Methods 0.000 claims description 12
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 238000001125 extrusion Methods 0.000 claims description 8
- 238000005469 granulation Methods 0.000 claims description 8
- 230000003179 granulation Effects 0.000 claims description 8
- 239000004114 Ammonium polyphosphate Substances 0.000 claims description 6
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims description 6
- 229920001276 ammonium polyphosphate Polymers 0.000 claims description 6
- COAPBYURHXLGMG-UHFFFAOYSA-N azane;1,3,5-triazine-2,4,6-triamine Chemical compound N.NC1=NC(N)=NC(N)=N1 COAPBYURHXLGMG-UHFFFAOYSA-N 0.000 claims description 6
- 238000012360 testing method Methods 0.000 claims description 6
- 229910001377 aluminum hypophosphite Inorganic materials 0.000 claims description 4
- 230000005251 gamma ray Effects 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 2
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 2
- WWNGFHNQODFIEX-UHFFFAOYSA-N buta-1,3-diene;methyl 2-methylprop-2-enoate;styrene Chemical compound C=CC=C.COC(=O)C(C)=C.C=CC1=CC=CC=C1 WWNGFHNQODFIEX-UHFFFAOYSA-N 0.000 claims description 2
- 238000007580 dry-mixing Methods 0.000 claims description 2
- 239000000155 melt Substances 0.000 claims description 2
- 238000004381 surface treatment Methods 0.000 claims description 2
- 229920001897 terpolymer Polymers 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 238000013329 compounding Methods 0.000 claims 1
- 239000011159 matrix material Substances 0.000 abstract description 7
- 239000006185 dispersion Substances 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 125000000524 functional group Chemical group 0.000 abstract description 2
- 230000001678 irradiating effect Effects 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 229920000728 polyester Polymers 0.000 abstract 3
- 238000002156 mixing Methods 0.000 abstract 1
- 229920001169 thermoplastic Polymers 0.000 abstract 1
- 239000004416 thermosoftening plastic Substances 0.000 abstract 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 31
- 230000000052 comparative effect Effects 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 4
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- -1 Polybutylene terephthalate Polymers 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 2
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910001382 calcium hypophosphite Inorganic materials 0.000 description 1
- 229940064002 calcium hypophosphite Drugs 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000005338 heat storage Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- SEQVSYFEKVIYCP-UHFFFAOYSA-L magnesium hypophosphite Chemical compound [Mg+2].[O-]P=O.[O-]P=O SEQVSYFEKVIYCP-UHFFFAOYSA-L 0.000 description 1
- 229910001381 magnesium hypophosphite Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- CNALVHVMBXLLIY-IUCAKERBSA-N tert-butyl n-[(3s,5s)-5-methylpiperidin-3-yl]carbamate Chemical compound C[C@@H]1CNC[C@@H](NC(=O)OC(C)(C)C)C1 CNALVHVMBXLLIY-IUCAKERBSA-N 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
-
- 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
- C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
- C08J5/08—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials 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
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- 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
- C08J2423/10—Homopolymers or copolymers of propene
- C08J2423/12—Polypropene
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- 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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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- 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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/004—Additives being defined by their length
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
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Abstract
The invention discloses a high-flame-retardance and precipitation-resistant halogen-free flame-retardant reinforced PBT material and a preparation method thereof, belonging to the technical field of high polymer flame retardance, and specifically comprising the following raw materials in parts by weight: 40-70 parts of PBT resin, 5-20 parts of composite phosphorus flame retardant, 10-30 parts of glass fiber, 0-8 parts of toughening agent, 0.3-1 part of lubricant and 0.2-1 part of antioxidant. The invention also discloses a preparation method of the high-flame-retardance and precipitation-resistant halogen-free flame-retardant reinforced PBT material, which comprises the steps of firstly irradiating the composite phosphorus flame retardant by gamma rays to ensure that the surface of the flame retardant is rich in active functional groups capable of reacting with thermoplastic polyester, so that chemical bonding can be formed with the polyester, and the dispersion effect of the flame retardant in a polyester matrix and the bonding capability of the flame retardant with the matrix can be effectively improved; then blending and extruding with other components, the prepared halogen-free flame-retardant reinforced PBT material not only can reach UL94 V0 of 0.8mm, but also has good precipitation resistance under the conditions of high temperature and high humidity.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a halogen-free flame-retardant reinforced PBT material with high flame retardance and precipitation resistance and a preparation method thereof.
Background
Polybutylene terephthalate (PBT) is a thermoplastic resin with high crystallization speed, has excellent electrical insulation property, mechanical property and heat resistance, is the widest one of the modified applications of the polybutylene terephthalate (PBT), and is widely applied to the fields of electronic plug-ins, lighting systems, household appliances and the like.
With the development of new energy automobile industry, the flame-retardant reinforced PBT gradually becomes the main choice of the core power battery connector of the new energy automobile due to low water absorption, good dimensional stability and high cost performance. The new energy automobile industry has strict requirements on combustion and battery safety, the traditional flame-retardant PBT mainly comprises bromine and antimony for flame retardance, and the brominated flame retardant has good universality and high flame retardance efficiency, but generates a large amount of toxic gas during combustion, and is gradually limited by WEEE and RoHS instructions of European Union. In order to meet the trend of the international market on the development and application of flame-retardant polymers, the use of halogen-free flame-retardant PBT is advocated in more and more fields at present, and particularly, a power battery part of a new energy automobile not only provides higher requirements on CTI of the flame-retardant PBT, but also has higher and higher requirements on thin-wall flame retardance and special environmental stability. The filling amount of the halogen-free flame retardant is large, so that the mechanical property of the material is greatly and negatively affected; the halogen-free flame retardant has low molecular weight and poor temperature resistance, and in the severe application environment of the power battery, the phenomenon of flame retardant precipitation often occurs, so that the appearance and flame retardant performance of a finished product are affected, and even the safety of a power battery system is affected. Therefore, for the sensitivity and the specificity of the application field of the power battery, the stability of the halogen-free flame-retardant PBT material is required to be higher and higher in the future.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a high-flame-retardant precipitation-resistant halogen-free flame-retardant reinforced PBT material.
The aim of the invention is realized by the following technical scheme:
the high-flame-retardant precipitation-resistant halogen-free flame-retardant reinforced PBT material comprises the following raw materials in parts by weight:
the composite phosphorus flame retardant is prepared by the following steps of 60 Co gamma rays are irradiated in an oxidizing atmosphere, the irradiation dosage rate is 0.01-10kGy/h, the irradiation time is 1-10min, and the irradiation dosage is 0.1-2kGy.
The halogen-free flame retardant reinforced PBT material with high flame retardance and precipitation resistance comprises the following components:
the viscosity of the PBT resin is 0.85-1.0dl/g, the tensile strength is 55MPa, and the melt index is 15-65 g/10min under the test condition of 250 ℃ and 2.16 kg.
The composite phosphorus flame retardant is a compound of organic hypophosphite and melamine ammonium polyphosphate, and the proportion of the organic hypophosphite to the melamine ammonium polyphosphate is (2-4): 1. preferably, the organic hypophosphite flame retardant is one or more of organic aluminum hypophosphite, organic magnesium hypophosphite, organic calcium hypophosphite and organic zinc hypophosphite.
The glass fiber is alkali-free glass fiber subjected to surface treatment by a silane coupling agent.
The toughening agent is more than one of terpolymer of methyl methacrylate-butadiene-styrene and ethylene-methyl acrylate-glycidyl methacrylate.
The irradiation dose rate is 5kGy/h, the irradiation time is 5min, and the irradiation dose is 0.4kGy.
The irradiation oxidizing atmosphere is more than one of air, oxygen, nitrogen dioxide, chlorine, sulfur dioxide and sulfur trioxide. Preferably, the irradiation oxidizing atmosphere is air.
The preparation method of the high-flame-retardance precipitation-resistant halogen-free flame-retardant reinforced PBT material comprises the following steps of:
(1) Weighing the components according to the weight percentage;
(2) Dry mixing the components except the flame retardant and the glass fiber in a high-speed mixer for 3-5min to uniformly mix the components;
(3) And (3) feeding the mixed components in the step (2) into a double-screw extruder through a main feed, respectively feeding the composite flame retardant and glass fiber into the double-screw extruder through side feeds, and performing a series of procedures such as melt extrusion, granulation, drying treatment and the like to obtain the high-flame-retardant and precipitation-resistant halogen-free flame-retardant reinforced PBT composite material, wherein the screw diameter of the extruder is 35mm, the length-diameter ratio L/D is 40, the screw rotating speed is 200-400rpm/min, and the temperatures of all sections of the extruder are 220-250 ℃.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention is realized by 60 Co gamma-ray pair organic phosphorusThe composite flame retardant of the acid salt and the melamine ammonium polyphosphate is subjected to irradiation treatment in an air atmosphere, and methylene and hydroxyl in the flame retardant are oxidized into carboxyl which can be bonded with a resin matrix, so that the active functional group on the surface of the flame retardant is increased, the bonding capability of the flame retardant and the PBT matrix can be improved, the dispersion of the flame retardant in the matrix is facilitated, the migration resistance of the flame retardant in the matrix is increased, and the precipitation of the flame retardant in a special environment can be reduced.
(2) The halogen-free flame retardant reinforced PBT material with high flame retardance and precipitation resistance prepared by the method ensures that the high flame retardance reaching UL94 of 0.8mm V0 is ensured, meanwhile, the retention rate of the conventional mechanical properties of the material, such as tensile strength, notch impact strength and the like, is still above 85% after the material is subjected to a high-temperature high-humidity long-term storage experiment, the surface condition is good, and the precipitation condition of the flame retardant component is obviously improved.
(3) In addition, after long-period high-temperature and high-humidity storage, the flame retardant property of the high-flame-retardant and precipitation-resistant halogen-free flame-retardant reinforced PBT material prepared by the method can still be kept at a high flame retardant level.
Detailed Description
The invention is further illustrated by the following specific embodiments, which are intended to be illustrative of the invention and not limiting.
The raw materials used in the embodiment of the invention are as follows:
PBT: xinjiang blue mountain river TH6100, viscosity 1.0dl/g, melt index MFR 30g/10min (250 ℃, 2.16 Kg).
Toughening agent: PTW, dow chemical.
Organic aluminum hypophosphite: t310, zhejiang Xuesen non-halogen smoke abatement flame retardant Co., ltd, and the effective phosphorus content is more than or equal to 23%.
Melamine ammonium polyphosphate: MPP, xuesen, zhejiang, non-halogen smoke abatement flame retardant Co., ltd.
The organic aluminum hypophosphite and the melamine ammonium polyphosphate are compounded into the composite organic phosphorus flame retardant according to the proportion of 4:1, and then gamma-ray irradiation is carried out in air atmosphere, wherein the irradiation dosage rate is 5kGy, and the irradiation time is 5min.
Glass fiber: ECS-303H glass fiber, the chopped length of the fiber is 3mm, and the diameter is 10 mu m. Chongqing glass fiber CPIC.
Product performance test:
tensile properties: the test was performed according to ISO527-2, at a rate of 5mm/min.
Notched impact properties: the test was carried out on a simple beam impact tester according to ISO179-1 standard, with the notch of the spline being A, at normal temperature (23 ℃).
Vertical combustion: test according to the standard method of UL94, 127X 12.7X10.8 mm and 127X 12.7X11.6 mm samples were used.
Example 1
The raw materials were weighed according to the weight percentage of example 1 described in table 1, stirred in a high-speed mixer for 3 to 5 minutes, and dried by an oven to obtain a mixed raw material.
The mixed raw materials except the composite flame retardant and the glass fiber are uniformly added into a meshing homodromous double-screw extruder from a main feed, meanwhile, the composite flame retardant and the glass fiber are respectively fed into the extruder from side feeds, and a series of processes such as melt extrusion, granulation and drying treatment are carried out, so that the high-flame-retardant and precipitation-resistant halogen-free flame-retardant reinforced PBT composite material is obtained, wherein the diameter of a screw of the extruder is 35mm, the length-diameter ratio L/D is 40, the rotating speed of the screw is 200-400rpm/min, and the temperature of each section of the extruder is 220-250 ℃.
Table 1A formulation table (unit:%) of a high flame retardant, precipitation resistant halogen free flame retardant reinforced PBT material
Example 2
The raw materials were weighed according to the weight percentage of example 2 described in table 1, stirred in a high-speed mixer for 3 to 5 minutes, and dried in an oven to obtain a mixed raw material.
The mixed raw materials except the composite flame retardant and the glass fiber are uniformly added into a meshing homodromous double-screw extruder from a main feed, meanwhile, the composite flame retardant and the glass fiber are respectively fed into the extruder from side feeds, and a series of processes such as melt extrusion, granulation and drying treatment are carried out, so that the high-flame-retardant and precipitation-resistant halogen-free flame-retardant reinforced PBT composite material is obtained, wherein the diameter of a screw of the extruder is 35mm, the length-diameter ratio L/D is 40, the rotating speed of the screw is 200-400rpm/min, and the temperature of each section of the extruder is 220-250 ℃.
Example 3
The raw materials were weighed according to the weight percentage of example 3 described in table 1, stirred in a high-speed mixer for 3 to 5 minutes, and dried in an oven to obtain a mixed raw material.
The mixed raw materials except the composite flame retardant and the glass fiber are uniformly added into a meshing homodromous double-screw extruder from a main feed, meanwhile, the composite flame retardant and the glass fiber are respectively fed into the extruder from side feeds, and a series of processes such as melt extrusion, granulation and drying treatment are carried out, so that the high-flame-retardant and precipitation-resistant halogen-free flame-retardant reinforced PBT composite material is obtained, wherein the diameter of a screw of the extruder is 35mm, the length-diameter ratio L/D is 40, the rotating speed of the screw is 200-400rpm/min, and the temperature of each section of the extruder is 220-250 ℃.
Example 4
The raw materials were weighed according to the weight percentage of example 4 described in table 1, stirred in a high-speed mixer for 3 to 5 minutes, and dried by an oven to obtain a mixed raw material.
The mixed raw materials except the composite flame retardant and the glass fiber are uniformly added into a meshing homodromous double-screw extruder from a main feed, meanwhile, the composite flame retardant and the glass fiber are respectively fed into the extruder from side feeds, and a series of processes such as melt extrusion, granulation and drying treatment are carried out, so that the high-flame-retardant and precipitation-resistant halogen-free flame-retardant reinforced PBT composite material is obtained, wherein the diameter of a screw of the extruder is 35mm, the length-diameter ratio L/D is 40, the rotating speed of the screw is 200-400rpm/min, and the temperature of each section of the extruder is 220-250 ℃.
Comparative example 1
The raw materials were weighed according to the weight percentage of comparative example 1 shown in table 1, stirred in a high-speed mixer for 3-5min, and dried in an oven to obtain a mixed raw material.
The mixed raw materials except the composite flame retardant and the glass fiber are uniformly added into a meshing homodromous double-screw extruder from a main feed, meanwhile, the composite flame retardant and the glass fiber are respectively fed into the extruder from side feeds, and a series of processes such as melt extrusion, granulation and drying treatment are carried out, so that the high-flame-retardant and precipitation-resistant halogen-free flame-retardant reinforced PBT composite material is obtained, wherein the diameter of a screw of the extruder is 35mm, the length-diameter ratio L/D is 40, the rotating speed of the screw is 200-400rpm/min, and the temperature of each section of the extruder is 220-250 ℃.
Comparative example 2
The raw materials were weighed according to the weight percentage of comparative example 2 shown in table 1, stirred in a high-speed mixer for 3-5min, and dried in an oven to obtain a mixed raw material.
The mixed raw materials except the composite flame retardant and the glass fiber are uniformly added into a meshing homodromous double-screw extruder from a main feed, meanwhile, the composite flame retardant and the glass fiber are respectively fed into the extruder from side feeds, and a series of processes such as melt extrusion, granulation and drying treatment are carried out, so that the high-flame-retardant and precipitation-resistant halogen-free flame-retardant reinforced PBT composite material is obtained, wherein the diameter of a screw of the extruder is 35mm, the length-diameter ratio L/D is 40, the rotating speed of the screw is 200-400rpm/min, and the temperature of each section of the extruder is 220-250 ℃.
Table 2 test results of a high flame retardant, precipitation resistant halogen free flame retardant reinforced PBT Material
As can be seen from tables 1 and 2, the composite material modified by the composite flame retardant (examples 1-4) subjected to irradiation treatment has good mechanical properties and high flame retardance, and after being subjected to 85 ℃ and 85% RH for 1000 hours of wet heat storage, the tensile strength and notch impact strength of the composite material can still be kept at higher levels above 85%, meanwhile, the surface of the composite material is free from the phenomenon of precipitation of the flame retardant, and the high flame retardance can still be maintained. The methylene and hydroxyl in the flame retardant can be oxidized into carboxyl by irradiating the composite flame retardant in an oxidizing atmosphere, so that the combination capability of the flame retardant and a PBT resin matrix can be improved, and the problem of precipitation of the flame retardant is solved. In flame retardant modification, different flame retardants are often compounded to achieve the effect of coordinating flame retardance, and as can be seen from comparative example 5, the use of a single flame retardant has larger performance degradation amplitude after thin-wall flame retardance and long-period wet heat aging. Therefore, the halogen-free flame-retardant reinforced PBT material with high flame retardance and precipitation resistance prepared by the method has excellent comprehensive performance, meets the performance requirements of products such as an electrode base, an electric control box shell, a battery shell and the like required in the current new energy automobile battery system, and has wide development and application prospects.
Claims (5)
1. A high-flame-retardant precipitation-resistant halogen-free flame-retardant reinforced PBT material is characterized in that: the material comprises the following raw materials in parts by weight:
40-70 parts of PBT resin;
15 parts of composite phosphorus flame retardant;
10-30 parts of glass fiber;
0-8 parts of a toughening agent;
0.3-1 part of lubricant;
0.1-1 part of antioxidant;
the composite phosphorus flame retardant is prepared by compounding organic aluminum hypophosphite and melamine ammonium polyphosphate according to the proportion of 4:1, and then gamma-ray irradiation is carried out in an air atmosphere, wherein the irradiation dose rate is 5kGy/h, the irradiation time is 5min, and the irradiation dose is 0.4kGy.
2. The high flame retardant, precipitation resistant halogen free flame retardant reinforced PBT material of claim 1, wherein: the viscosity of the PBT resin is 0.85-1.0dl/g, the tensile strength is 55MPa, and the melt index of the PBT resin is 15-65 g/10min under the test condition of 250 ℃ and 2.16 kg.
3. The high flame retardant, precipitation resistant halogen free flame retardant reinforced PBT material of claim 1, wherein: the glass fiber is alkali-free glass fiber subjected to surface treatment by a silane coupling agent.
4. The high flame retardant, precipitation resistant halogen free flame retardant reinforced PBT material of claim 1, wherein: the toughening agent is more than one of terpolymer of methyl methacrylate-butadiene-styrene and ethylene-methyl acrylate-glycidyl methacrylate.
5. The method for preparing the high-flame-retardant precipitation-resistant halogen-free flame-retardant reinforced PBT material according to any one of claims 1 to 4, which is characterized by comprising the following steps:
(1) Weighing the components according to the weight percentage;
(2) Dry mixing the components except the flame retardant and the glass fiber in a high-speed mixer for 3-5min to uniformly mix the components;
(3) And (3) feeding the mixed components in the step (2) into a double-screw extruder through a main feed, respectively feeding the composite flame retardant and glass fiber into the double-screw extruder through side feeds, and performing a series of procedures such as melt extrusion, granulation, drying treatment and the like to obtain the high-flame-retardant and precipitation-resistant halogen-free flame-retardant reinforced PBT composite material, wherein the screw diameter of the extruder is 35mm, the length-diameter ratio L/D is 40, the screw rotating speed is 200-400rpm/min, and the temperatures of all sections of the extruder are 220-250 ℃.
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