WO2024083096A1 - 一种可透射激光的无卤阻燃增强pbt组合物及其制备和应用 - Google Patents
一种可透射激光的无卤阻燃增强pbt组合物及其制备和应用 Download PDFInfo
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- pbt composition
- pbt
- halogen
- pa6t
- free flame
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 23
- 239000000203 mixture Substances 0.000 title claims abstract description 22
- 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 abstract description 14
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 239000000835 fiber Substances 0.000 claims abstract description 16
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 13
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 13
- 239000005357 flat glass Substances 0.000 claims abstract description 12
- 229920006131 poly(hexamethylene isophthalamide-co-terephthalamide) Polymers 0.000 claims abstract description 12
- 229920005989 resin Polymers 0.000 claims abstract description 11
- 239000011347 resin Substances 0.000 claims abstract description 11
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims abstract description 11
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 claims abstract description 9
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 8
- 239000000314 lubricant Substances 0.000 claims abstract description 8
- 239000002667 nucleating agent Substances 0.000 claims abstract description 8
- 229920006111 poly(hexamethylene terephthalamide) Polymers 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 6
- 239000004033 plastic Substances 0.000 claims description 6
- 229920003023 plastic Polymers 0.000 claims description 6
- -1 polyethylene Polymers 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 3
- 229910001377 aluminum hypophosphite Inorganic materials 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000005453 pelletization Methods 0.000 claims description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- INJVFBCDVXYHGQ-UHFFFAOYSA-N n'-(3-triethoxysilylpropyl)ethane-1,2-diamine Chemical compound CCO[Si](OCC)(OCC)CCCNCCN INJVFBCDVXYHGQ-UHFFFAOYSA-N 0.000 claims description 2
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 claims description 2
- UTOPWMOLSKOLTQ-UHFFFAOYSA-M octacosanoate Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCC([O-])=O UTOPWMOLSKOLTQ-UHFFFAOYSA-M 0.000 claims description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 claims description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 19
- 230000026030 halogenation Effects 0.000 abstract 1
- 238000005658 halogenation reaction Methods 0.000 abstract 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 38
- 238000002834 transmittance Methods 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 9
- 238000003466 welding Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920006123 polyhexamethylene isophthalamide Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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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
- 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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/10—Reinforcing macromolecular compounds with loose or coherent fibrous material characterised by the additives used in the polymer mixture
-
- 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
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
-
- 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
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- 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
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
Definitions
- the invention belongs to the field of plastic processing, and particularly relates to a laser-transmissive halogen-free flame-retardant reinforced PBT composition and a preparation method and application thereof.
- Laser welding technology is a technology that uses the heat generated by the laser beam to melt the plastic contact surface and bond the molded parts together.
- laser welding has high efficiency, low environmental pollution, and is particularly suitable for assembly line processing of automotive plastic parts.
- plastic parts are very precise electronic components or require a sterile environment, laser welding technology has obvious advantages.
- more and more electronic components such as electronic actuators and pipe joints, use laser welding technology.
- flame-retardant PBT materials are widely used, so higher requirements are placed on the light transmittance of halogen-free flame-retardant enhanced PBT materials.
- Polybutylene terephthalate is a polyester made from the condensation of terephthalic acid and 1,4-butanediol. It is a crystalline engineering material and the resin is translucent. After glass fiber and flame retardant are added to PBT resin, the transmittance of the composite material is greatly reduced.
- the halogen-free flame retardant reinforced PBT material faces the problem of insufficient transmittance as the light-transmitting layer material for laser welding.
- the technical problem to be solved by the present invention is to provide a halogen-free flame-retardant reinforced PBT composition capable of transmitting laser, and the preparation and application thereof.
- a PBT composition of the present invention comprises, by weight:
- the intrinsic viscosity of PBT resin is 0.8-1dL/g; the intrinsic viscosity test standard is GB/T 14190-2008.
- the weight content of PA6T in the PA6T/6I is not higher than 41%.
- PBT resin polybutylene terephthalate.
- PA6T/6I Polyhexamethylene terephthalamide/polyhexamethylene isophthalamide copolymer.
- the halogen-free flame retardant is at least one of organic zinc hypophosphite and organic aluminum hypophosphite.
- the amino-based silane coupling agent is one or more of ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, and N-(2-aminoethyl)-3-aminopropyltriethoxysilane.
- the antioxidant is one or more of hindered phenol antioxidants (such as antioxidants 1010, 1076, 1098) and phosphite antioxidants (antioxidant 168);
- the lubricant is one or more of esters (such as polyethylene glycol esters, polyol esters), montanate, ethylene bisstearamide, and polyethylene wax.
- the nucleating agent is at least one of Na 2 CO 3 and NaHCO 3 .
- the weight content of PA6T in the PA6T/6I is 30-40%.
- the components include:
- a method for preparing the PBT composition of the present invention comprises:
- the solution of the amino silane coupling agent and the flat glass fiber are stirred and mixed, and dried to obtain the flat glass fiber treated with the amino silane coupling agent;
- PBT resin, PA6T/6I, antioxidant, lubricant and nucleating agent are premixed according to a ratio, plasticized by a twin-screw extruder, flat glass fiber treated with an amino silane coupling agent and a halogen-free flame retardant are added in proportion from different side feed ports, and a PBT composition is obtained after traction, cooling, pelletizing and drying.
- the twin-screw extruder is set at a temperature of 220-250°C and a screw speed of 300-400 rpm.
- the drying temperature is 80-100° C. and the drying time is 10-12 hours.
- the PBT composition of the present invention is used in plastic electronic components or energy vehicles, such as electronic valve bodies, controllers, high-voltage connectors, electric control boxes, etc.
- PBT is a polymer material with a polyester structure
- PA material is a polymer material with an amide bond structure.
- Polyamide material containing PA6T structure has a certain compatibility with PBT and can improve the light transmittance of PBT.
- the compatibility with PBT is improved in theory.
- the rigidity of PA6T/6I material is relatively large, the mobility of molecular chain is relatively weak, and the mixing effect with PBT material during processing is very poor, which is not conducive to improving the light transmittance of the material.
- the proportion of PA6T is reduced, the mobility of molecular chain of the material is enhanced, and it can have a good mixing effect with PBT material at the molecular level, taking into account the mechanical properties and light transmittance of the material.
- the intrinsic viscosity of PBT When the intrinsic viscosity of PBT is lower than 0.8dL/g, the molecular weight of PBT is small, the molecular weight distribution is wide, and the mechanical properties of the prepared composite material are low; when the intrinsic viscosity of PBT is higher than 1.0, the molecular weight of PBT is too high, the viscosity is high, and the crystallinity is high, which is not conducive to the dispersion and compatibility of the material, and affects the mechanical and light transmittance properties of the material.
- the flame retardant reinforced PBT material of the present invention can simultaneously meet the requirements of laser weldability, high strength and halogen-free; the notched impact strength is ⁇ 9.8KJ/ m2 , the light transmittance is ⁇ 27%, and the flame retardancy reaches V-0 to V-1 level.
- PBT resin-1 intrinsic viscosity 0.8dL/g, GX112 Sinopec Yizheng Chemical Fiber;
- PBT resin-2 intrinsic viscosity 1dL/g, GX121 Sinopec Yizheng Chemical Fiber;
- PBT resin-3 intrinsic viscosity 0.7dL/g, GX111 Sinopec Yizheng Chemical Fiber;
- PBT resin-4 intrinsic viscosity 1.2dL/g, GL236 Sinopec Yizheng Chemical Fiber;
- the intrinsic viscosity test standard of PBT resin is GB/T 14190-2008.
- PA6T/6I-1 PA6T weight content 30%, glass transition temperature Tg ⁇ 130°C, Shandong Dongchen Ruisen;
- PA6T/6I-2 PA6T weight content 40%, glass transition temperature Tg ⁇ 135°C Shandong Dongchen Ruisen;
- PA6T/6I-3 PA6T weight content 20%, glass transition temperature Tg ⁇ 125°C Shandong Dongchen Ruisen;
- PA6T/6I-4 PA6T weight content 60%, melting point Tm ⁇ 310°C Shandong Dongchen Ruisen;
- PA612 Type II, Shandong Dongchen Ruisen
- PA6I TM01 Shandong Dongchen Ruisen
- Halogen-free flame retardant (organic aluminum hypophosphite): brand OP1230 Clariant Chemicals (China) Co., Ltd.
- Amino silane coupling agent ⁇ -aminopropyltrimethoxysilane, brand KH-550, Shin-Etsu Chemical Co., Ltd., Japan;
- Antioxidant 1010 is commercially available;
- the antioxidant, lubricant and nucleating agent in the parallel examples and comparative examples are all the same commercially available product.
- Preparation method of amino silane coupling agent treated flat glass fiber take water and adjust it with glacial acetic acid to an aqueous solution with a pH value of 3.5-5.5, dilute the silane coupling agent KH-550 with the aqueous solution at a ratio of 1:9 to prepare a coupling agent solution, then spray the coupling agent solution evenly on the surface of the flat glass fiber, and stir it evenly, and place the treated flat glass fiber in a blast oven at 80°C for 12 hours;
- the components are weighed according to weight proportions, PBT resin, PA6T/6I, antioxidant, lubricant and nucleating agent are premixed and plasticized by a twin-screw extruder, flat glass fiber treated with amino silane coupling agent and halogen-free flame retardant are added in proportion from different side feed ports, and a PBT composition is obtained after traction, cooling, pelletizing and drying; the twin-screw extruder is set at a temperature of 220-250°C and a screw speed of 300-400 rpm.
- Light transmittance test The prepared materials were injected into 60mm ⁇ 60mm ⁇ 2mm samples (thickness 2mm) using an injection molding machine, with a barrel temperature of 260°C and a mold temperature of 100°C. The light transmittance of the samples was tested using a near-infrared spectrometer (wavelength 900-1700nm, Ocean Optics NIRQuest spectrometer), and the transmittance at a wavelength of 750nm was measured.
- a near-infrared spectrometer wavelength 900-1700nm, Ocean Optics NIRQuest spectrometer
- Flame retardant performance test The sample is injection molded into a 127mm*12.7mm*1.6mm strip, tested according to the UL94-2016 method, the burning time is recorded, and the flame retardant grade is determined based on the burning time;
- Notched impact strength Simply supported beam notched impact strength: The sample was injection molded into 80mm*10mm*4mm strips with 8mm thickness at the notch. It was tested according to ISO 179/1eA-2010 method with pendulum energy of 4J.
- Comparative Example 5 It can be seen from Comparative Example 5 that after adding halogen-free flame retardant and glass fiber to PBT resin, the transmittance is low, only 12%. It can be seen from Comparative Examples 3-4 that after adding PA612 or PA6T/6I-4 (PA6T weight ratio 60%) to the system, the transmittance is improved, but it cannot meet the requirements. It can be seen from Examples 1, 3 and 8 that the use of PA6T/6I with a PA6T weight ratio of no more than 40% greatly improves the light transmittance. In Comparative Example 7, the number of PA6T/6I is relatively high, which can theoretically increase the light transmittance, but the processability is poor, extrusion is difficult, and the material impact performance is low. The transparent nylon used in Comparative Example 9 has poor compatibility with PBT and does not have the structure of PA6T. The two are incompatible and have poor light transmittance.
- Example 1 It can be seen from Example 1 and Comparative Examples 1-2 that if the viscosity of PBT is too large or too small, the light transmittance and impact performance will be poor.
- the halogen-free flame-retardant reinforced PBT composition of the present invention has flame retardancy and good notched impact strength, and at the same time, the light transmittance is above 27% and can meet the requirements of laser weldability.
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
本发明涉及一种可透射激光的无卤阻燃增强PBT组合物及其制备和应用,组分包括:PBT树脂、PA6T/6I、无卤阻燃剂、扁平玻纤、氨基类硅烷偶联剂、抗氧剂、润滑剂、成核剂。本发明的阻燃增强PBT材料可同时满足可激光焊接性、高强度、无卤化的要求。
Description
本发明属于加工塑料领域,特别涉及一种可透射激光的无卤阻燃增强PBT组合物及其制备和应用。
激光焊接技术是借助激光束产生的热量使塑料接触面熔化,将模塑零部件粘结在一起的技术。与传统的热板焊接、振动摩擦焊接、超声波焊接相比,激光焊接效率高、环境污染小、特别适用于汽车塑料零部件的流水线加工,尤其是塑料零部件是非常精密的电子元件或要求无菌环境时,激光焊接技术具备明显的优势。近年来,随着新能源汽车的发展,越来越多的电子元件,如电子执行器、管路接头采用激光焊接的工艺,在该领域内,阻燃PBT材料应用广泛,因此对无卤阻燃增强PBT材料的透光率提出了更高的要求。
聚对苯二甲酸丁二醇酯(英文名polybutylene terephthalate,简称PBT),是由对苯二甲酸和1,4-丁二醇缩聚制成的聚酯,为结晶性工程材料,树脂呈半透明状态,玻璃纤维和阻燃剂加入到PBT树脂后,复合材料的透光度极大的降低,无卤阻燃增强PBT材料作为激光焊接的透光层材料面临透光度不足的问题。
发明内容
针对现有技术的缺陷,本发明所要解决的技术问题是提供一种可透射激光的无卤阻燃增强PBT组合物及其制备和应用。
本发明的一种PBT组合物,按重量份数,组分包括:
其中PBT树脂为特性粘度0.8-1dL/g;特性粘度测试标准GB/T 14190-2008。
所述PA6T/6I中PA6T重量含量不高于41%。
PBT树脂:聚对苯二甲酸丁二醇酯。
PA6T/6I:聚对苯二甲酰己二胺/聚间苯二甲酰己二胺共聚物。
优选地,所述无卤阻燃剂为有机次磷酸锌、有机次磷酸铝中的至少一种。
优选地,所述氨基类硅烷偶联剂为γ-氨丙基三甲氧基硅烷、γ-氨丙基三乙氧基硅烷、N-(2-氨乙基)-3-氨丙基三乙氧基硅烷中的一种或几种。
优选地,所述抗氧剂为受阻酚类抗氧剂(如抗氧剂1010、1076、1098)、亚磷酸酯类抗氧剂(抗氧剂168)中的一种或几种;所述润滑剂为酯类(如聚乙二醇酯、多元醇酯)、褐煤酸盐、乙撑双硬脂酸酰胺、聚乙烯蜡中的一种或几种。
优选地,所述成核剂为Na2CO3、NaHCO3中的至少一种。
优选地,所述PA6T/6I中PA6T的重量含量为30-40%。
优选地,按重量份数,组分包括:
本发明的一种所述PBT组合物的制备方法,包括:
氨基类硅烷偶联剂的溶液和扁平玻纤搅拌混匀,烘干,得到氨基类硅烷偶联剂处理后的扁平玻纤;
将PBT树脂、PA6T/6I、抗氧剂、润滑剂和成核剂按配比预混后,由双螺杆塑化,将氨基类硅烷偶联剂处理后的扁平玻纤、无卤阻燃剂分别按比例由不同的侧喂口加入,经过牵引、冷却、切粒、干燥后,得到PBT组合物;双螺杆挤出机设置温度为220~250℃,螺杆转速为300~400转/分。
所述烘干温度为80-100℃,时间为10-12h。
本发明的一种所述PBT组合物在塑料电子元件或能源汽车中的应用,如电子阀体、控制器、高压连接器、电控盒等。
原理:PBT是一种具备聚酯结构的高分子材料,PA材料是一种具有酰胺键结构的高分子材料,含有PA6T结构的聚酰胺材料与PBT有一定的相容性,能提高PBT的透光性,
当PA6T的含量较高时,理论上与PBT的相容性提高,但此时PA6T/6I材料的刚性较大,分子链运动能力较弱,与PBT材料加工时的混合效果很差,不利于材料透光性的提高;当PA6T的比例降低时,材料的分子链运动能力增强,能够与PBT材料在分子层面有很好的混合效果,兼顾材料的力学性能和透光性。
PBT的特性粘度低于0.8dL/g时,PBT的分子量较小,分子量分布较宽,制备的复合材料力学性能偏低;当PBT的特性粘度高于1.0时,PBT的分子量太高,粘度大,结晶度高,不利于材料的分散和相容,影响材料的力学和透光性能。
本发明的阻燃增强PBT材料可同时满足可激光焊接性、高强度、无卤化的要求;缺口冲击强度≥9.8KJ/m2以上,透光率≥27%,阻燃达到V-0~V-1等级。
下面结合具体实施例,进一步阐述本发明。应理解,这些实施例仅用于说明本发明而不用于限制本发明的范围。此外应理解,在阅读了本发明讲授的内容之后,本领域技术人员可以对本发明作各种改动或修改,这些等价形式同样落于本申请所附权利要求书所限定的范围。
一、原料来源
PBT树脂-1:特性粘度0.8dL/g,GX112中国石化仪征化纤;
PBT树脂-2:特性粘度1dL/g,GX121中国石化仪征化纤;
PBT树脂-3:特性粘度0.7dL/g,GX111中国石化仪征化纤;
PBT树脂-4:特性粘度1.2dL/g,GL236中国石化仪征化纤;
PBT树脂的特性粘度测试标准GB/T 14190-2008。
PA6T/6I-1:PA6T重量含量30%,玻璃化转变温度Tg≈130℃,山东东辰瑞森;
PA6T/6I-2:PA6T重量含量40%,玻璃化转变温度Tg≈135℃山东东辰瑞森;
PA6T/6I-3:PA6T重量含量20%,玻璃化转变温度Tg≈125℃山东东辰瑞森;
PA6T/6I-4:PA6T重量含量60%,熔点Tm≈310℃山东东辰瑞森;
PA612:TypeII,山东东辰瑞森;
PA6I:TM01山东东辰瑞森;
透明尼龙:TR90瑞士EMS;
无卤阻燃剂(有机次磷酸铝):牌号为OP1230科莱恩化工(中国)有限公司;
氨基类硅烷偶联剂:γ-氨丙基三甲氧基硅烷,牌号为KH-550日本信越化学工业株式会社;
扁平玻纤:典型牌号为TFG-3.0-T436泰山玻纤;
抗氧剂:抗氧剂1010市售;
润滑剂:PETS市售;
成核剂:Na2CO3市售;
平行实施例和对比例中抗氧剂、润滑剂和成核剂均为同一市售产品。
二、实施例和对比例的制备方法
氨基类硅烷偶联剂处理扁平玻纤的制备方法:取水用冰乙酸调节成PH值为3.5—5.5的水溶液,将硅烷偶联剂KH-550按1:9的比例用上述水溶液稀释配成偶联剂溶液,然后按将偶联剂溶液均匀的喷涂到扁平玻纤表面,并充分搅拌均匀,将处理过的扁平玻纤置于80℃的鼓风烘箱中12h;
按重量份数称取各组分,PBT树脂、PA6T/6I、抗氧剂、润滑剂和成核剂预混后,由双螺杆塑化,将氨基类硅烷偶联剂处理扁平玻纤、无卤阻燃剂分别按比例由不同的侧喂口加入,经过牵引、冷却、切粒、干燥后,得到PBT组合物;双螺杆挤出机设置温度为220~250℃,螺杆转速为300~400转/分。
三、测试标准和方法
透光率测试:将制备的材料使用注塑机分别注塑成60mm×60mm×2mm的样板(厚度2mm),料筒温度260℃,模具温度100℃。采用近红外光谱仪(波长为900‐1700nm,海洋光学公司NIRQuest光谱仪)对样板分别测试材料的透光率,测定波长为750nm处的透过率。
阻燃性能测试:样品注塑成127mm*12.7mm*1.6mm样条,按照UL94-2016的方法测试,记录燃烧时间,根据燃烧时间判定阻燃等级;
缺口冲击强度:简支梁缺口冲击强度:样品注塑成80mm*10mm*4mm样条,缺口处8mm厚,按照ISO 179/1eA-2010方法测试,摆锤能量4J。
表1实施例的配比(重量份)
表2对比例的配比(重量份)
表3实施例的性能效果数据
表4对比例的性能效果数据
由对比例5可知,在PBT树脂中加入无卤阻燃剂和玻纤后透光度较低,仅仅为12%。从对比例3-4可知,体系中加入PA612或PA6T/6I-4(PA6T重量比例60%)后,透光率有提高,但是不能满足要求,实施例1,3和8可知,采用PA6T重量比不高于40%的PA6T/6I,极大的提高了透光性能。对比例7中PA6T/6I份数较高,理论上能增加透光性,但加工性较差,挤出困难,材料冲击性能低。对比例9中采用的透明尼龙与PBT相容性差,不具备PA6T的结构,两者不相容,透光率差。
实施例1和对比例1-2可知,PBT粘度过大或过小,透光性能差、冲击也差。
本发明中无卤阻燃增强PBT组合物具有阻燃性、较好的缺口冲击强度的同时,透光率为27%以上能够满足可激光焊接性。
Claims (9)
- 一种PBT组合物,其特征在于,按重量份数,组分包括:
其中PBT树脂的特性粘度为0.8-1dL/g;所述PA6T/6I中PA6T重量含量不高于41%。 - 根据权利要求1所述PBT组合物,其特征在于,所述无卤阻燃剂为有机次磷酸锌、有机次磷酸铝中的至少一种。
- 根据权利要求1所述PBT组合物,其特征在于,所述氨基类硅烷偶联剂为γ-氨丙基三甲氧基硅烷、γ-氨丙基三乙氧基硅烷、N-(2-氨乙基)-3-氨丙基三乙氧基硅烷中的一种或几种。
- 根据权利要求1所述PBT组合物,其特征在于,所述抗氧剂为受阻酚类抗氧剂、亚磷酸酯类抗氧剂中的一种或几种;所述润滑剂为酯类、褐煤酸盐、乙撑双硬脂酸酰胺、聚乙烯蜡中的一种或几种。
- 根据权利要求1所述PBT组合物,其特征在于,所述成核剂为Na2CO3、NaHCO3中的至少一种。
- 根据权利要求1所述PBT组合物,其特征在于,所述PA6T/6I中PA6T的重量含量为30-40%。
- 根据权利要求1所述PBT组合物,其特征在于,按重量份数,组分包括:
- 一种权利要求1-7任一所述PBT组合物的制备方法,包括:将氨基类硅烷偶联剂的溶液和扁平玻纤搅拌混匀,烘干,得到氨基类硅烷偶联剂处理后的扁平玻纤;将PBT树脂、PA6T/6I、抗氧剂、润滑剂和成核剂按配比预混后,由双螺杆塑化,将氨基类硅烷偶联剂处理后的扁平玻纤、无卤阻燃剂分别按比例由不同的侧喂口加入,经过牵引、冷却、切粒、干燥后,得到PBT组合物;双螺杆挤出机设置温度为220~250℃,螺杆转速为300~400转/分。
- 一种权利要求1-7任一所述PBT组合物在塑料电子元件或新能源汽车中的应用。
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