CN116675957A - PBT/PC composite material and preparation method and application thereof - Google Patents
PBT/PC composite material and preparation method and application thereof Download PDFInfo
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- CN116675957A CN116675957A CN202310662356.0A CN202310662356A CN116675957A CN 116675957 A CN116675957 A CN 116675957A CN 202310662356 A CN202310662356 A CN 202310662356A CN 116675957 A CN116675957 A CN 116675957A
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- 239000002131 composite material Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 37
- 238000005809 transesterification reaction Methods 0.000 claims abstract description 37
- 229920005989 resin Polymers 0.000 claims abstract description 36
- 239000011347 resin Substances 0.000 claims abstract description 36
- 239000003112 inhibitor Substances 0.000 claims abstract description 35
- GHPGOEFPKIHBNM-UHFFFAOYSA-N antimony(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Sb+3].[Sb+3] GHPGOEFPKIHBNM-UHFFFAOYSA-N 0.000 claims abstract description 28
- 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 class 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 claims abstract description 16
- 239000003365 glass fiber Substances 0.000 claims abstract description 13
- 239000004593 Epoxy Substances 0.000 claims abstract description 11
- 229920001577 copolymer Polymers 0.000 claims abstract description 9
- 125000000524 functional group Chemical group 0.000 claims abstract description 3
- 239000004417 polycarbonate Substances 0.000 claims description 58
- 238000000034 method Methods 0.000 claims description 11
- 229920001897 terpolymer Polymers 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 9
- 239000003963 antioxidant agent Substances 0.000 claims description 8
- PFNROQCAJVOSIR-UHFFFAOYSA-N oxiran-2-ylmethyl 2-methylprop-2-enoate;5-phenylpenta-2,4-dienenitrile Chemical group CC(=C)C(=O)OCC1CO1.N#CC=CC=CC1=CC=CC=C1 PFNROQCAJVOSIR-UHFFFAOYSA-N 0.000 claims description 6
- 239000012745 toughening agent Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 235000019820 disodium diphosphate Nutrition 0.000 claims description 5
- GYQBBRRVRKFJRG-UHFFFAOYSA-L disodium pyrophosphate Chemical compound [Na+].[Na+].OP([O-])(=O)OP(O)([O-])=O GYQBBRRVRKFJRG-UHFFFAOYSA-L 0.000 claims description 5
- 239000000314 lubricant Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000006057 Non-nutritive feed additive Substances 0.000 claims description 4
- 239000004793 Polystyrene Substances 0.000 claims description 4
- 230000003078 antioxidant effect Effects 0.000 claims description 4
- 239000007822 coupling agent Substances 0.000 claims description 4
- 239000000155 melt Substances 0.000 claims description 4
- 229920002223 polystyrene Polymers 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- BZQKBFHEWDPQHD-UHFFFAOYSA-N 1,2,3,4,5-pentabromo-6-[2-(2,3,4,5,6-pentabromophenyl)ethyl]benzene Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1CCC1=C(Br)C(Br)=C(Br)C(Br)=C1Br BZQKBFHEWDPQHD-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- -1 pentabromobenzyl Chemical group 0.000 claims description 3
- 229920000515 polycarbonate Polymers 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- MFXMOUUKFMDYLM-UHFFFAOYSA-L zinc;dihydrogen phosphate Chemical compound [Zn+2].OP(O)([O-])=O.OP(O)([O-])=O MFXMOUUKFMDYLM-UHFFFAOYSA-L 0.000 claims description 3
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 claims description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 2
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 2
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 2
- 229920000058 polyacrylate Polymers 0.000 claims description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 2
- 150000003440 styrenes Chemical class 0.000 claims description 2
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 229920006351 engineering plastic Polymers 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 229920000642 polymer Polymers 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 12
- 230000014759 maintenance of location Effects 0.000 description 11
- 230000000694 effects Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000003063 flame retardant Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 230000002829 reductive effect Effects 0.000 description 5
- 125000003700 epoxy group Chemical group 0.000 description 4
- 239000000956 alloy Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 230000001603 reducing effect Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 230000032683 aging Effects 0.000 description 2
- 229920006127 amorphous resin Polymers 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- 239000002981 blocking agent Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 229920001038 ethylene copolymer Polymers 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 230000000670 limiting effect Effects 0.000 description 2
- 239000012994 photoredox catalyst Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- NSBGJRFJIJFMGW-UHFFFAOYSA-N trisodium;stiborate Chemical compound [Na+].[Na+].[Na+].[O-][Sb]([O-])([O-])=O NSBGJRFJIJFMGW-UHFFFAOYSA-N 0.000 description 2
- UAUDZVJPLUQNMU-UHFFFAOYSA-N Erucasaeureamid Natural products CCCCCCCCC=CCCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- JQCXWCOOWVGKMT-UHFFFAOYSA-N diheptyl phthalate Chemical compound CCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC JQCXWCOOWVGKMT-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 229920006225 ethylene-methyl acrylate Polymers 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002431 foraging effect Effects 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 description 1
- 125000001741 organic sulfur group Chemical group 0.000 description 1
- 235000013873 oxidized polyethylene wax Nutrition 0.000 description 1
- 239000004209 oxidized polyethylene wax Substances 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- AYEKOFBPNLCAJY-UHFFFAOYSA-O thiamine pyrophosphate Chemical compound CC1=C(CCOP(O)(=O)OP(O)(O)=O)SC=[N+]1CC1=CN=C(C)N=C1N AYEKOFBPNLCAJY-UHFFFAOYSA-O 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- 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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a PBT/PC composite material, a preparation method and application thereof, belonging to the technical field of high polymer engineering plastics; the PBT/PC composite material provided by the invention comprises the following components in parts by mass: 30-50 parts of PBT resin, 10-20 parts of PC resin, 25-40 parts of glass fiber, 8-20 parts of brominated flame retardant, 0.4-1 part of antimony white, 1-3 parts of end capping agent and 0.2-0.5 part of transesterification inhibitor; the end capping agent is a copolymer containing epoxy functional groups; the mass ratio of the end capping agent to the antimony white to the transesterification inhibitor is as follows: antimony white: transesterification inhibitor= (4-12): (1.8-4): 1. the PBT/PC composite material provided by the invention has excellent low warpage and high heat resistance; the preparation method provided by the invention is simple and is beneficial to actual production.
Description
Technical Field
The invention belongs to the technical field of high molecular engineering plastics, and particularly relates to a PBT/PC composite material, and a preparation method and application thereof.
Background
PBT resin is a crystalline thermoplastic plastic, has the advantages of high crystallization speed, chemical resistance, good melt fluidity and the like, but has the defects of low glass transition temperature, large molding shrinkage, low notch impact strength, insufficient rigidity at high temperature and the like. After flame retardation and reinforcing modification are carried out on the PBT, the strength is obviously improved, the PBT is widely applied to the fields of OA, household appliances and the like, but the reinforced PBT still has the defect of large shrinkage, and the glass fiber is introduced to further increase the anisotropy of the material, so that the warping of the thin-wall part is obvious, and the flame retardation reinforced PBT obviously cannot cope with the fields with requirements on precise assembly.
The method for reducing the warping property of the flame-retardant reinforced PBT material has a plurality of methods, the sheet-shaped filler is added to reduce the anisotropy, the cost is lower, but the filler has limited warping property reducing effect and obvious influence on mechanical properties, and the method cannot be used in partial fields, and the method has obvious effects on reducing the crystallization trend of the PBT by adding amorphous resin, and ABS, PC, ASA and other materials, but in many amorphous resins, PC is definitely the most ideal choice, and PC is used as an amorphous engineering plastic, and has excellent comprehensive properties, particularly high impact strength, high glass transition temperature and good heat resistance, and the compatibility of PBT and PC is excellent.
However, with the continuous development of material technology and the increasingly strict use environment, higher requirements are put on the heat resistance of the PBT/PC alloy, and in some higher-temperature use conditions, the performance of the PBT/PC alloy decays too fast, based on the fact, systematic research shows that the flame-retardant reinforced PBT/PC alloy with high heat resistance and low warpage can be obtained by controlling the PC content, inhibiting the transesterification of the material and other means, and the new scheme has great application value because the temperature resistance and the long-term service performance at high temperature are greatly improved on the premise of keeping low warpage.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a PBT/PC composite material which has lower warpage and better heat resistance on the basis of flame retardance, and a preparation method and application thereof.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows: the PBT/PC composite material comprises the following components in parts by mass: 30-50 parts of PBT resin, 10-20 parts of PC resin, 25-40 parts of glass fiber, 8-20 parts of brominated flame retardant, 0.4-1 part of antimony white, 1-3 parts of end capping agent and 0.2-0.5 part of transesterification inhibitor; the end capping agent is a copolymer containing epoxy functional groups; the mass ratio of the end capping agent to the antimony white to the transesterification inhibitor is as follows: antimony white: transesterification inhibitor= (4-12): (1.8-4): 1.
according to the PBT/PC composite material, by adding proper mass parts of PC resin, the end capping agent, the antimony white and the transesterification inhibitor and limiting the mass ratio of the end capping agent to the antimony white to the transesterification inhibitor and the type of the end capping agent, the low warpage and high heat resistance of a product can be realized; on one hand, the added transesterification inhibitor can deactivate the residual titanium catalyst in the PBT resin, but because the transesterification inhibitor has acidity, too high addition of the transesterification inhibitor can bring negative influence to a system, and on the other hand, antimony white can promote the degradation of the PC resin while assisting in flame retardance, so that the content can be improved to obtain a product with better flame retardance effect, but the transesterification reaction is more severe in the process of promoting the degradation of the PC resin; in the mass parts and mass ratio range of the end-capping agent, the antimony white and the transesterification inhibitor, the three components can play an excellent synergistic balance role, so that the comprehensive effects of flame retardance, low warpage and high heat resistance can be optimal.
As a preferred embodiment of the PBT/PC composite material, the mass ratio of the end-capping agent to the antimony white to the transesterification inhibitor is as follows: antimony white: transesterification inhibitor= (6-8): 2:1.
the inventors have found that when the mass ratio of the capping agent, antimony white and the transesterification inhibitor is further preferable to be within the above range, the resultant product is more excellent in combination properties.
Preferably, the content of the end-capping agent in the composite is 1wt% to 3wt%; the antimony white content is less than or equal to 1wt percent, and the transesterification inhibitor is less than or equal to 0.5 wt percent.
Preferably, the PC resin is contained in the composite material in an amount of 10wt% to 20wt%.
As a preferred embodiment of the PBT/PC composite material, the end-capping agent is a styrene-acrylonitrile-glycidyl methacrylate terpolymer or an ethylene-acrylate-glycidyl methacrylate terpolymer.
Preferably, the capping agent has an epoxy equivalent weight of 400 to 850g/mol.
Preferably, the capping agent is a styrene-acrylonitrile-glycidyl methacrylate terpolymer.
When the selected end-capping agent is a styrene-acrylonitrile-glycidyl methacrylate terpolymer, the heat resistance of the obtained product is more excellent, and the retention rate of the tensile property is higher.
As a preferred embodiment of the PBT/PC composite material of the present invention, the transesterification inhibitor is at least one of disodium dihydrogen pyrophosphate, sodium dihydrogen phosphate, and zinc dihydrogen phosphate.
Preferably, the transesterification inhibitor is disodium dihydrogen pyrophosphate. When the transesterification inhibitor is disodium dihydrogen pyrophosphate, the heat resistance of the resulting product is more excellent and the warpage is lower.
As a preferred embodiment of the PBT/PC composite material, the brominated flame retardant is at least one of brominated epoxy, brominated polystyrene, polybrominated styrene, brominated polycarbonate, decabromodiphenylethane and pentabromobenzyl polyacrylate.
Preferably, the brominated flame retardant is brominated epoxy or brominated polystyrene; when both of the above are preferable, the resulting product is lower in warpage and is more excellent in heat resistance.
As a preferred embodiment of the PBT/PC composite material, the PBT/PC composite material further comprises the following components in parts by mass: 0.01-5 parts of toughening agent and 0.01-1 part of processing aid.
As a preferred embodiment of the PBT/PC composite material of the present invention, at least one of the following (a) - (e):
(a) The intrinsic viscosity of the PBT resin is 0.7-1.3dL/g at 25 ℃;
(b) The melt index of the PC resin at 300 ℃ and 1.2Kg is 3-22g/10min;
(c) The glass fiber is alkali-free glass fiber treated by a coupling agent;
(d) The toughening agent is at least one of ethylene-acrylic ester-glycidyl methacrylate terpolymer, ethylene-acrylic ester binary copolymer, ethylene-vinyl acetate and glycidyl methacrylate grafted ethylene-octene copolymer;
(e) The processing aid is at least one of a lubricant and an antioxidant.
The PBT resin with the intrinsic viscosity and the PC resin with the melt index are selected, so that the stability of an injection molding process can be facilitated.
The test of the intrinsic viscosity of the PBT resin is referred to GB/T14190-2017; the melt index of the PC resin is tested according to GB/T3682-2000; the intrinsic viscosity of the PBT and PC resin is not particularly required, and the intrinsic viscosity of the PBT resin is preferably 0.7-1.3dL/g at 25 ℃, such as 0.7dL/g, 0.8dL/g, 0.9dL/g, 1.0dL/g, 1.1dL/g, 1.2dL/g and 1.3dL/g, which can realize the invention; preferably, the intrinsic viscosity of the PC resin is 3-22g/10min at 25 ℃, such as 3g/10min, 5g/10min, 7g/10min, 9g/10min, 11g/10min, 13g/10min, 15g/10min, 17g/10min, 19g/10min, 21g/10min, and the invention can be realized.
The invention has no special requirement on the glass fiber, preferably alkali-free glass fiber treated by a coupling agent, and the diameter is preferably 8-15 μm, such as 8 μm, 9 μm, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm and 15 μm, which can realize the invention; the coupling agent used is a silane coupling agent.
Preferably, the lubricant is at least one of aliphatic carboxylic acid ester, erucamide, ethylene bis-stearamide, montan ester, polyethylene wax and oxidized polyethylene wax; the antioxidant is at least one of hindered phenol antioxidants, phosphite antioxidants and organic sulfur antioxidants.
In addition, the invention also provides a preparation method of the PBT/PC composite material, which comprises the following steps: and weighing and mixing the dried raw materials, feeding the mixture into a double-screw extruder, and extruding, bracing, cooling, granulating and drying the mixture to obtain the polyester composite material.
As a preferred embodiment of the preparation method of the present invention, the drying process of the PBT resin and the PC resin is as follows: the PBT resin and the PC resin are dried for 4 to 6 hours at 115 to 125 ℃.
As a preferred embodiment of the preparation method of the present invention, the parameters of the twin-screw extruder are: the feeding speed is 450-800 kg/hour; the temperature from the feed inlet to the head of each section of screw is 220-230 ℃, 230-240 ℃, 240-250 ℃, 250-260 ℃, 240-250 ℃, 230-240 ℃ and 220-230 ℃ respectively; the screw speed was 250-400rpm.
In addition, the invention also provides application of the PBT/PC composite material in the field of household appliances. Illustratively, the PBT/PC composite material is used in the manufacture of integrated circuits, capacitors, switches, relays, connectors, transformer backbones, cables, cooling fans, low voltage appliances.
Compared with the prior art, the invention has the beneficial effects that:
according to the PBT/PC composite material, by adding proper mass parts of PC resin, the end capping agent, the antimony white and the transesterification inhibitor and limiting the mass ratio of the end capping agent to the antimony white to the transesterification inhibitor and the type of the end capping agent, low warpage and high heat resistance of a product can be realized, wherein the warpage of the obtained product is less than 3mm, and the retention rate of tensile property of the obtained product after being aged in an oven at 170 ℃ for 1000 hours is more than 84%; the preparation method provided by the invention is simple and is beneficial to actual production.
Detailed Description
For a better description of the objects, technical solutions and advantages of the present invention, the present invention will be further described with reference to the following specific examples.
The reagents, methods and apparatus employed in the present invention are those conventional in the art unless otherwise indicated.
PBT resin: the intrinsic viscosity is 0.8dL/g, the PBT is 1200-211M, and the Taiwan vinpockels are adopted;
PC resin: melt index of 12g/10min, PC 1300-22NP, korean LG;
brominated flame retardant 1: brominated polystyrene, SAYTEX 621, yabao in united states;
brominated flame retardant 2: brominated epoxy, F-2100, israel CL;
brominated flame retardant 3: brominated polycarbonate, FG8500, japan emperor;
brominated flame retardant 4: decabromodiphenylethane, SAYTEX 4010, yabao in the united states;
antimony white: S-05N, chenzhou antimony industry;
sodium antimonate: SA-F, chenzhou antimony industry;
blocking agent 1: styrene-acrylonitrile-glycidyl methacrylate terpolymer with an epoxy equivalent of 400-850g/mol, SAG-002, shanghai day liter;
blocking agent 2: ethylene-acrylate-glycidyl methacrylate terpolymers having an epoxy equivalent weight of 400-500g/mol, PTW, duPont U.S.;
end capping agent 3: anhydride modified ethylene copolymer, N493, dupont, usa;
end capping agent 4: styrene-acrylonitrile-glycidyl methacrylate terpolymer with an epoxy equivalent of 920-1200g/mol, SAG-008, shanghai day liter;
transesterification inhibitor 1: disodium dihydrogen pyrophosphate, DHPP, japan taiping chemistry;
transesterification inhibitor 2: zinc dihydrogen phosphate, BUDIT T21, bourdon sea m, germany;
transesterification inhibitor 3: triphenyl phosphate, TPP, zhejiang wansheng;
toughening agent: ethylene-methyl acrylate copolymers, commercially available;
glass fiber: glass fiber diameter 10 μm, ECS10-4.5-T436H, taishan glass fiber Co., ltd;
an antioxidant: the product is commercially available in the form of a powder,
and (3) a lubricant: are commercially available;
the toughening agents, glass fibers, antioxidants and lubricants used in the parallel experiments of the examples and comparative examples remained identical.
Examples 1 to 13 and comparative examples 1 to 10
The contents (parts by weight) of the components of inventive examples 1 to 13 and comparative examples 1 to 10 are shown in tables 1 and 2;
TABLE 1
TABLE 2
The preparation methods of examples 1-13 and comparative examples 1-10 were:
weighing the dried raw materials, adding the raw materials into a mixer, uniformly mixing, then feeding the mixture into a double-screw extruder, adjusting the feeding amount of the double-screw extruder to 600 kg/hour, extruding, bracing, cooling, granulating, and drying to obtain a polyester composite material; the drying process of the PBT resin and the PC resin comprises the following steps: drying the PBT resin and the PC resin at 120 ℃ for 5 hours; the parameters of the double-screw extruder are as follows: the temperature of each section of screw from the feed inlet to the machine head is 230 ℃, 240 ℃, 250 ℃, 260 ℃, 250 ℃, 240 ℃, 230 ℃ and 220 ℃ respectively; the screw speed was 400rpm.
Effect example
The effect examples of the present invention verify the properties of the products prepared in examples 1 to 13 and comparative examples 1 to 10;
the flame retardant performance test method comprises the following steps:
drying the product obtained by extrusion and granulating at 125 ℃ for 3.5 hours; then according to the combustion standard of UL94-2013, the standard strip-shaped sample is injection molded, the size is 125+/-5 mm long, the width is 13.0+/-0.5 mm, and the thickness is 1.5+/-0.15 mm; pretreatment before testing: two groups of samples with humidity of 50+/-5% at 23+/-2 ℃ are treated for 48 hours; after adjusting each of the other two groups of 5 specimens in an oven at 70.+ -. 1 ℃ for 168 hours, the specimens were placed in a dryer and cooled to room temperature, and the test was conducted in accordance with the combustion standard of UL 94-2013.
The warp test method is as follows:
drying the product obtained by extrusion and granulating at 120-130 ℃ for 3-4 hours; and (3) carrying out injection molding on the dried granules to obtain 5 square plates with the size of 100 x 1.5mm, cooling the square plates for 24 hours, pressing one of four corners of the square plates on a table top, measuring the highest height of other corners of the square plates away from the table top, and taking an average value of 5 blocks for each sample.
The heat resistance evaluation method was as follows:
drying the product obtained by extrusion and granulating at 120-130 ℃ for 3-4 hours; preparing a test national standard tensile spline by injection molding according to ISO 527-1A-2012 standard, placing the spline in a high temperature oven at 170 ℃ for aging, testing the mechanical property after aging for 1000 hours, and testing the tensile strength according to ISO 527 standard; the method for calculating the tensile property retention rate comprises the following steps: tensile property retention = (tensile strength after aging/initial tensile strength) 100%.
The results obtained from the test are shown in Table 3;
TABLE 3 Table 3
As can be seen from Table 3, when the technical scheme of the invention is adopted, the obtained product has excellent low warpage performance and heat resistance on the basis of flame retardance, the flame retardance of the obtained product is V-0, the warpage is below 3mm, and the tensile property retention rate is above 84%;
as can be seen from examples 1-4 and comparative examples 1-2, the mass ratio of the capping agent, antimony white and the transesterification inhibitor has a significant effect on the warpage properties and heat resistance properties of the product, when the mass ratio of the capping agent, antimony white and the transesterification inhibitor is in the range of (4-12): (1.8-4): when the range of 1 is within, the obtained warp is below 3mm, and the tensile strength retention is above 87%; especially when the mass ratio of the end-capping agent, antimony white and the transesterification inhibitor is (6-8): 2: when the tensile strength is within the range of 1, the obtained product has more excellent comprehensive performance, specifically, the warpage is less than 2mm, the tensile strength retention rate is more than 93%, and the heat resistance is better;
as can be seen from example 1 and comparative examples 3 to 5, the heat resistance of the product is affected whenever the addition of any one of the capping agent, antimony white and the transesterification inhibitor is out of the range of the present invention, and the tensile property retention obtained in comparative examples 3 to 5 is between 68 and 88%, particularly when the antimony white or the transesterification inhibitor is excessively added, the decrease in the heat resistance is more remarkable, and the obtained tensile property retention is only 66%, which is 28.42% as compared with that in example 1; when the addition amount of the end-capping agent is too large, although the heat resistance is not greatly reduced compared with comparative examples 4 to 5, the flame retardant property is reduced, and the flame retardant grade is only V-1 grade;
as can be seen from example 1 and comparative example 6, when the amount of the added PC resin is too small, the heat resistance of the obtained product is excellent, but the warpage is remarkably increased to 6mm, and the flame retardant property of the product is reduced to V-1 grade only; as can be seen from example 1 and comparative example 7, when the amount of the added PC resin was excessive, the heat resistance of the obtained product was significantly lowered, and the tensile property retention was lowered by 36.84% as compared with example 1;
it can be seen from examples 1, 5 and 13 that the content of the epoxy group of the end-capping agent also affects the performance of the product, and that when the content of the epoxy group of the end-capping agent is more preferably within the scope of the present invention, the resultant product is more excellent in combination effect; meanwhile, as can be seen from examples 1, 5 and 8, the type of the end-capping agent also affects the properties of the product, when the epoxy group-containing copolymer of the present invention is selected as the end-capping agent, the resulting product has excellent heat resistance and low warpage properties, and when the selected end-capping agent is not an epoxy group-containing copolymer but an anhydride-modified ethylene copolymer, the resulting product has significantly reduced heat resistance, a tensile property retention of only 62%, and the resulting product also exhibits a reduced tendency in initial tensile strength; as can be seen from example 1 and comparative example 9, when antimony white is not used but sodium antimonate is used, the flame retardancy of the obtained product is lowered, only V-1 grade.
Finally, it should be noted that the above-mentioned embodiments illustrate rather than limit the scope of the invention, and that those skilled in the art will understand that changes can be made to the technical solutions of the invention or equivalents thereof without departing from the spirit and scope of the technical solutions of the invention.
Claims (10)
1. The PBT/PC composite material is characterized by comprising the following components in parts by mass: 30-50 parts of PBT resin, 10-20 parts of PC resin, 25-40 parts of glass fiber, 8-20 parts of brominated flame retardant, 0.4-1 part of antimony white, 1-3 parts of end capping agent and 0.2-0.5 part of transesterification inhibitor;
the end capping agent is a copolymer containing epoxy functional groups;
the mass ratio of the end capping agent to the antimony white to the transesterification inhibitor is as follows: antimony white: transesterification inhibitor= (4-12): (1.8-4): 1.
2. the PBT/PC composite material according to claim 1, wherein the mass ratio of the capping agent, antimony white and transesterification inhibitor is: antimony white: transesterification inhibitor= (6-8): 2:1.
3. the PBT/PC composite material according to claim 1, characterized in that the end-capping agent is a styrene-acrylonitrile-glycidyl methacrylate terpolymer or an ethylene-acrylate-glycidyl methacrylate terpolymer.
4. The PBT/PC composite material according to claim 1, wherein the transesterification inhibitor is at least one of disodium dihydrogen pyrophosphate, sodium dihydrogen phosphate and zinc dihydrogen phosphate.
5. The PBT/PC composite of claim 1, wherein the brominated flame retardant is at least one of brominated epoxy, brominated polystyrene, polybrominated styrene, brominated polycarbonate, decabromodiphenylethane, and pentabromobenzyl polyacrylate.
6. The PBT/PC composite material according to claim 1, further comprising the following components in parts by mass: 0.01-5 parts of toughening agent and 0.01-1 part of processing aid.
7. The PBT/PC composite material according to claim 6, wherein at least one of the following (a) - (e):
(a) The intrinsic viscosity of the PBT resin is 0.7-1.3dL/g at 25 ℃;
(b) The melt index of the PC resin at 300 ℃ and 1.2kg is 3-22g/10min;
(c) The glass fiber is alkali-free glass fiber treated by a coupling agent;
(d) The toughening agent is at least one of ethylene-acrylic ester-glycidyl methacrylate terpolymer, ethylene-acrylic ester binary copolymer, ethylene-vinyl acetate and glycidyl methacrylate grafted ethylene-octene copolymer;
(e) The processing aid is at least one of a lubricant and an antioxidant.
8. The method of preparing a PBT/PC composite material according to claim 7, wherein the method of preparing comprises the steps of: and weighing and mixing the dried raw materials, feeding the mixture into a double-screw extruder, and extruding, bracing, cooling, granulating and drying the mixture to obtain the PBT/PC composite material.
9. The method of claim 8, wherein the twin screw extruder parameters are: the feeding speed is 450-800 kg/hour; the temperature from the feed inlet to the head of each section of screw is 220-230 ℃, 230-240 ℃, 240-250 ℃, 250-260 ℃, 240-250 ℃, 230-240 ℃ and 220-230 ℃ respectively; the screw speed was 250-400rpm.
10. Use of the PBT/PC composite material according to any of claims 1 to 7 in the field of household appliances.
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| CN115627063A (en) * | 2022-11-07 | 2023-01-20 | 金发科技股份有限公司 | Flame-retardant PBT/PC alloy material and preparation method and application thereof |
| WO2023055099A1 (en) * | 2021-09-30 | 2023-04-06 | (주) 엘지화학 | Thermoplastic resin and molded article made thereof |
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| WO2022110674A1 (en) * | 2020-11-25 | 2022-06-02 | 金发科技股份有限公司 | Glass fiber reinforced pbt/pc alloy with high strength, low warpage and high thermal deformation temperature, preparation method therefor and use thereof |
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| WO2023055099A1 (en) * | 2021-09-30 | 2023-04-06 | (주) 엘지화학 | Thermoplastic resin and molded article made thereof |
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