CN115612259A - Easily-sprayed and low-warpage PBT (polybutylene terephthalate) composition and preparation method thereof - Google Patents
Easily-sprayed and low-warpage PBT (polybutylene terephthalate) composition and preparation method thereof Download PDFInfo
- Publication number
- CN115612259A CN115612259A CN202211235709.0A CN202211235709A CN115612259A CN 115612259 A CN115612259 A CN 115612259A CN 202211235709 A CN202211235709 A CN 202211235709A CN 115612259 A CN115612259 A CN 115612259A
- Authority
- CN
- China
- Prior art keywords
- low
- pbt composition
- warpage
- thermoplastic elastomer
- pbt
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920001707 polybutylene terephthalate Polymers 0.000 title claims abstract description 92
- 239000000203 mixture Substances 0.000 title claims abstract description 71
- -1 polybutylene terephthalate Polymers 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title description 8
- 239000003365 glass fiber Substances 0.000 claims abstract description 29
- 229920002725 thermoplastic elastomer Polymers 0.000 claims abstract description 27
- 238000005507 spraying Methods 0.000 claims abstract description 21
- 239000000945 filler Substances 0.000 claims abstract description 19
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229920001400 block copolymer Polymers 0.000 claims abstract description 9
- 229920000578 graft copolymer Polymers 0.000 claims abstract description 8
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 3
- 239000007921 spray Substances 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 12
- 239000000835 fiber Substances 0.000 claims description 8
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 6
- 239000005357 flat glass Substances 0.000 claims description 6
- 239000004595 color masterbatch Substances 0.000 claims description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- 238000001125 extrusion Methods 0.000 claims description 4
- 238000005469 granulation Methods 0.000 claims description 4
- 230000003179 granulation Effects 0.000 claims description 4
- 239000006229 carbon black Substances 0.000 claims description 3
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 3
- 239000000049 pigment Substances 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 2
- CNJPFZOQZWIGIB-UHFFFAOYSA-N ethene;methyl prop-2-enoate;oxiran-2-ylmethyl 2-methylprop-2-enoate Chemical group C=C.COC(=O)C=C.CC(=C)C(=O)OCC1CO1 CNJPFZOQZWIGIB-UHFFFAOYSA-N 0.000 claims 1
- 239000000454 talc Substances 0.000 claims 1
- 229910052623 talc Inorganic materials 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 17
- 239000003963 antioxidant agent Substances 0.000 abstract description 16
- 230000003078 antioxidant effect Effects 0.000 abstract description 9
- 239000000314 lubricant Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 11
- 239000002131 composite material Substances 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 239000003973 paint Substances 0.000 description 6
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 238000007667 floating Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- XYXJKPCGSGVSBO-UHFFFAOYSA-N 1,3,5-tris[(4-tert-butyl-3-hydroxy-2,6-dimethylphenyl)methyl]-1,3,5-triazinane-2,4,6-trione Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C)=C1CN1C(=O)N(CC=2C(=C(O)C(=CC=2C)C(C)(C)C)C)C(=O)N(CC=2C(=C(O)C(=CC=2C)C(C)(C)C)C)C1=O XYXJKPCGSGVSBO-UHFFFAOYSA-N 0.000 description 1
- WPMYUUITDBHVQZ-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid Chemical compound CC(C)(C)C1=CC(CCC(O)=O)=CC(C(C)(C)C)=C1O WPMYUUITDBHVQZ-UHFFFAOYSA-N 0.000 description 1
- 229920001342 Bakelite® Polymers 0.000 description 1
- 229920003314 Elvaloy® Polymers 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 235000009827 Prunus armeniaca Nutrition 0.000 description 1
- 244000018633 Prunus armeniaca Species 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000000655 anti-hydrolysis Effects 0.000 description 1
- 239000004637 bakelite Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- 229920006225 ethylene-methyl acrylate Polymers 0.000 description 1
- 239000005043 ethylene-methyl acrylate Substances 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3045—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/04—Thermoplastic elastomer
Landscapes
- 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 an easily-sprayed and low-warpage PBT composition. The PBT composition comprises the following components in parts by weight: 35-55 parts of polybutylene terephthalate; 5-15 parts of a thermoplastic elastomer; 25-35 parts of glass fiber; 5-15 parts of a filling agent; 1-2 parts of black seeds; 1-2 parts of other auxiliary agents; 0.1 to 0.3 portion of antioxidant; the thermoplastic elastomer is a block copolymer or a graft copolymer containing glycidyl methacrylate, wherein the mass fraction of the glycidyl methacrylate is not less than 2%. The glycidyl methacrylate in the thermoplastic elastomer can react with the PBT molecular chain terminal group, the compatibility of the system is further improved, the dosage ratio of the thermoplastic elastomer and the filler is limited, and the thermoplastic elastomer and the filler are cooperated to adjust the modulus and the bonding capability of the system, so that the PBT composition has better spraying effect and warping degree and has good comprehensive performance.
Description
Technical Field
The invention relates to the technical field of engineering plastics, and particularly relates to an easily-sprayed and low-warpage PBT composition and a preparation method thereof.
Background
Polybutylene terephthalate (PBT), one of five general engineering plastics, has excellent mechanical properties, weather resistance, aging resistance, heat resistance and solvent resistance. In addition, PBT has the advantages of high crystallization speed, short molding period, low water absorption, good dimensional stability and the like, so that PBT can be widely applied to the fields of electronics and electrics, household appliances, motors, coil frames and the like. However, for the glass fiber reinforced PBT material, due to the characteristic of rapid crystallization, a manufactured part is often subjected to fiber floating and warping in the injection molding process; in addition, the glass fiber reinforced PBT has high modulus and floating fiber, so that the phenomena of uneven spraying surface, paint falling and the like are easily caused in the spraying process.
Currently, CN 104151789 discloses a low-warpage high-voltage-resistance PBT modified material and a preparation method thereof. According to the invention, by adding a proper amount of mica powder and nano particles, the warping characteristic of the PBT material is improved, and the special requirements of electronic and electrical products on dimensional stability and high voltage resistance are met; CN110452502 discloses a low-warpage good-appearance high-heat-resistance polyester composite material and a preparation method thereof, PET and PBT are compounded, a mixture consisting of LCP, modified montmorillonite, silicon dioxide and sodium polyacrylate is used as a nucleating agent, and the composite material has stable shrinkage and good injection molding processability, simultaneously has excellent heat resistance, good appearance and low warpage, and is mainly applied to precision structure appearance parts and heat-resistant parts in the industries of electronic appliances, automobiles and new energy.
CN110172235 discloses an anti-hydrolysis low-warpage PBT composite material, and a preparation method and application thereof. The hydrolysis resistance of the PBT composite material is improved by adopting the PBT resin with low carboxyl content and the hydrolysis resistant glass fiber, and the warpage of the PBT composite material is reduced by compounding the PBT resin with ABS. The composite material has excellent hydrolysis resistance and size stability, can be used in the field of automobile connectors with higher requirements on hydrolysis resistance and size stability, and has good market popularization prospect.
CN102040808 discloses a high-gloss low-warpage glass fiber reinforced PET/PBT alloy and a preparation method thereof, PET and PBT are fused to prepare the PET/PBT alloy, and the PET/PBT alloy has the advantages of high crystallization rate, good mechanical property, high thermal deformation temperature, high surface glossiness, low shrinkage rate, stable size, low warpage and low cost, and can completely replace bakelite powder with the PBT/PET alloy in certain occasions.
However, the prior art has little research on the easy spraying performance of the paint, and the background color of a common scene in spraying is black. Therefore, there is a need in the art to develop a new PBT composition having good spray properties and at the same time having good mechanical properties with low warpage.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide an easily-sprayed and low-warpage PBT composition, which has a good spraying effect and low warpage and comprehensive performance.
Still another object of the invention is to provide a process for preparing an easily sprayable, low warpage PBT composition.
The invention also aims to provide the application of the easily-sprayed and low-warpage PBT composition in electronic product shells and automobile product shells.
The above purpose of the invention is realized by the following technical scheme:
an easy-spraying and low-warpage PBT composition comprises the following components in parts by weight:
the thermoplastic elastomer is a block copolymer or a graft copolymer containing glycidyl methacrylate, wherein the mass fraction of the glycidyl methacrylate is not less than 2%.
The invention provides an easily-sprayed and low-warpage PBT composition, wherein a block copolymer or a graft copolymer containing glycidyl methacrylate is selected as a thermoplastic elastomer in the easily-sprayed and low-warpage PBT composition, the mass fraction of the glycidyl methacrylate is limited, the glycidyl methacrylate can react with terminal groups of PBT molecular chains, the compatibility of a system is further improved, and a large number of bonding points or riveting points can be provided for the PBT composition by the specific thermoplastic elastomer, so that the bonding strength of the PBT composition is improved; the appearance and the warping performance of the PBT composition can be improved by adding the filler, and the filler and the thermoplastic elastomer are mutually cooperated to adjust the modulus and the bonding capability of a system, so that the PBT composition has better spraying effect and warping degree and has good comprehensive performance.
Preferably, the mass ratio of the thermoplastic elastomer to the filler is 1:2 to 2:1.
Preferably, the intrinsic viscosity of the polybutylene terephthalate is 0.70 to 0.85dL/g. The polybutylene terephthalate with low intrinsic viscosity can further improve the mechanical property and the processing property of the PBT composition.
Preferably, the intrinsic viscosity of the polybutylene terephthalate is measured according to ISO 1628-5-2015 standard method.
Preferably, the thermoplastic elastomer is an ethylene-methyl acrylate-glycidyl methacrylate block copolymer or an ethylene octene-glycidyl methacrylate graft copolymer.
Preferably, the filler is one or more of barium sulfate, montmorillonite, calcium carbonate or talcum powder.
The glass fiber may be a glass fiber commonly used in the art, and preferably, the glass fiber is a flat glass fiber or a cylindrical glass fiber.
More preferably, the glass fibers are flat glass fibers having a flatness ratio of 1:3-1:4.
More preferably, the glass fibers are modified with a coupling agent.
Specifically, the coupling agent is a mixture of gamma-methacryloxypropyltrimethoxysilane and isopropyl di (methacryloyl) isostearyl titanate in a mass ratio of 1:1 to 2:1.
preferably, the black seeds are black color master batches taking PE as a carrier.
More preferably, the black seed is a black color master batch taking PE as a carrier and carbon black as a pigment. Preferably, the other auxiliaries are antioxidants and lubricants.
In the present invention, conventional antioxidants may be selected, including hindered phenol antioxidants, phosphite antioxidants, diphenylamine antioxidants, copper salt antioxidants or thioether antioxidants. Preferably, the antioxidant is a hindered phenol antioxidant.
Specifically, the hindered phenol antioxidant is one or more of beta (3,5 di-tert-butyl-4-hydroxyphenyl) propionic acid octadecyl ester, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, tetra [ beta (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester or diethylene glycol bis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionic acid methyl ester ].
In the present invention, conventional lubricants including ester grease, amide lubricant, polyethylene lubricant or stearic acid lubricant may be selected according to the prior art. Preferably, the lubricant is an ester lubricant.
Specifically, the ester lubricant is one or more of lower alcohol ester of fatty acid, higher alcohol ester of fatty acid, polyol ester or polyethylene glycol ester.
The invention protects a preparation method of the PBT composition with easy spraying and low warping, which comprises the following steps:
s1, mixing a filling agent and other auxiliary agents to obtain a first mixture;
s2, mixing the polybutylene terephthalate, the thermoplastic elastomer and the black seeds to obtain a second mixture;
and S3, carrying out melt blending, extrusion and granulation on the first mixture, the second mixture and the glass fiber to obtain the PBT composition.
Preferably, in the step S1, the rotation speed of the mixing is 700-900 rpm, and the mixing time is 2-4 minutes.
Preferably, in the step S2, the rotation speed of the mixing is 600-800 rpm, and the mixing time is 2-4 minutes.
Preferably, the extrusion granulation is performed in a twin screw extruder.
Preferably, the temperature of the first zone of the double-screw extruder is 200-230 ℃, the temperature of the second zone is 240-260 ℃, the temperature of the third zone is 235-255 ℃, the temperature of the fourth zone is 235-255 ℃, the temperature of the fifth zone is 235-255 ℃, the temperature of the sixth zone is 240-260 ℃, the temperature of the seventh zone is 240-260 ℃, the temperature of the eighth zone is 220-240 ℃, the temperature of the ninth zone is 220-240 ℃, the temperature of the tenth zone is 240-260 ℃, and the screw rotating speed of the double-screw extruder is 200-450 revolutions per minute.
The invention protects the application of the PBT composition which is easy to spray and has low warpage in electronic product shells and automobile product shells.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides an easily-sprayed and low-warpage PBT composition, wherein a block copolymer or a graft copolymer of glycidyl methacrylate is used as a thermoplastic elastomer in the composition, the content of glycidyl methacrylate is limited, the glycidyl methacrylate can react with PBT molecular chain terminal groups, the compatibility of a system is further improved, the dosage ratio of the thermoplastic elastomer and a filler is limited, and the modulus and the bonding capability of the system are synergistically regulated by the glycidyl methacrylate and the filler, so that the PBT composition has good spraying effect and warping degree and good comprehensive performance.
Detailed Description
The present invention will be further described with reference to specific embodiments, but the examples are not intended to limit the present invention in any way. The starting reagents employed in the examples of the present invention are, unless otherwise specified, those that are conventionally purchased.
The raw materials used in the respective examples and comparative examples:
PBT resin 1: PBT 1200-211M, intrinsic viscosity 0.83dL/g, changchun chemical industry (Jiangsu) Co., ltd;
PBT resin 2: PBT GX111, intrinsic viscosity 0.70dL/g, changchun chemical industry (Jiangsu) Co., ltd;
PBT resin 3: PBT 1100-211X, intrinsic viscosity 1.30dL/g, changchun chemical industry (Jiangsu) Co., ltd;
thermoplastic elastomer 1: ethylene-methyl acrylate-glycidyl methacrylate block copolymer, dupont PTW, glycidyl methacrylate mass fraction of 5%, jejuri Plant (Pune);
thermoplastic elastomer 2: ethylene octene-glycidyl methacrylate graft copolymer, preferably easy to dissolve SOG-03, with glycidyl methacrylate mass fraction of 2%, preferably easy to dissolve polymer (shanghai) ltd;
thermoplastic elastomer 3: ethylene-methyl acrylate block copolymer, elvaloy AC resin 1125, glycidyl methacrylate mass fraction of 0%, dupont trade (shanghai) ltd;
glass fiber 1: flat glass fiber, TFG-3.0-T436, flatness ratio 1:4; taishan fiberglass Limited;
glass fiber 2: flat glass fibers, glass fibers ECS301HP-3-M3, flatness ratio 1:3; chongqing International composite materials, inc.;
glass fiber 3: cylindrical glass fiber, glass fiber ECS11-4.5-534A, flatness ratio 1:1; taishan glass fibers Ltd;
glass fiber 4: cylindrical glass fiber, glass fiber ECS11-3.0-T436CP, the aspect ratio is 1:1; taishan glass fibers ltd;
the glass fibers 1-3 are modified by adopting a mixture of gamma-methacryloxypropyltrimethoxysilane and isopropyl di (methacryloyl) isostearyl titanate, wherein the mass ratio of the gamma-methacryloxypropyltrimethoxysilane to the isopropyl di (methacryloyl) isostearyl titanate is 3:2; the glass fibers 4 have been modified with a mixture of gamma-methacryloxypropyltrimethoxysilane and isopropyldi (methacryloyl) isostearyl titanate in a mass ratio of 3:1.
filling agent: barium sulfate, AB-3000N1, cambodia lightness, inc., guangzhou, cambodia;
black seeds: PE is used as a carrier, carbon black is used as a black color master batch of pigment, PE2718, and limited trade of apricot Hui in Guangzhou city;
lubricant: a lipid lubricant; antioxidant: hindered phenol antioxidant beta (3,5 di-tert-butyl-4-hydroxyphenyl) propionic acid octadecyl ester; both the lubricant and the antioxidant were commercially available, and the same lubricant and antioxidant were used in examples 1 to 13 and comparative examples 1 to 3.
Examples 1 to 13 and comparative examples 1 to 3
According to the formulation in table 1, a spray-on, low warpage PBT composition was prepared as follows:
s1, putting a filler, an antioxidant and a lubricant into a high-speed mixer to be mixed for 2-4 minutes at the rotating speed of 700-900 rpm to obtain a first mixture;
s2, putting the polybutylene terephthalate, the thermoplastic elastomer and the black seeds into a high-speed mixer, and mixing for 2-4 minutes at a rotating speed of 600-800 rpm to obtain a second mixture;
s3, putting the first mixture, the second mixture and the glass fiber into a double-screw extruder, and carrying out melt blending, extrusion and granulation to obtain the PBT composition; the temperature of the first zone of the double-screw extruder is 200-230 ℃, the temperature of the second zone is 240-260 ℃, the temperature of the third zone is 235-255 ℃, the temperature of the fourth zone is 235-255 ℃, the temperature of the fifth zone is 235-255 ℃, the temperature of the sixth zone is 240-260 ℃, the temperature of the seventh zone is 240-260 ℃, the temperature of the eighth zone is 220-240 ℃, the temperature of the ninth zone is 220-240 ℃, the temperature of the tenth zone is 240-260 ℃, and the screw rotating speed of the double-screw extruder is 200-450 revolutions per minute.
TABLE 1 amounts (parts by weight) of components in the easy-to-spray, low-warpage PBT compositions of examples 1-9
TABLE 2 amount of each component (parts by weight) in the easy-to-spray, low-warpage PBT compositions of examples 10 to 13 and comparative examples 1 to 3
Performance testing
1. Test method
The PBT composition which is easy to spray and low in warpage and prepared in the above way is subjected to a performance test:
(1) Tensile strength: the PBT composition which is easy to spray and has low warpage and prepared in the above way is tested according to the standard ISO 527;
(2) Bending strength: the PBT composition which is easy to spray and has low warpage and is prepared in the above way is tested according to the standard ISO 178;
(3) Notched izod impact strength: the PBT composition which is easy to spray and has low warpage and is prepared in the above way is tested according to the standard ISO 180;
(4) Warping degree: injection molding the prepared easy-to-spray PBT composition into a square plate with the thickness of 100mm multiplied by 1.0mm, fixing one end of the square plate and keeping the square plate in a horizontal state, and measuring the distance of the other end deviating from the horizontal position;
(5) And (3) spraying effect: the spraying effect of the surface of the product is visually observed, and the product is divided into 4 grades from good to bad according to the spraying effect: excellent, good, passing and bad; the excellent characteristic is that the surface of the sprayed workpiece is basically free of flaws, and the paint cannot fall off; the good representation of the trace flaws on the surface of the sprayed workpiece can not cause the paint to fall off, and the good representation of the macroscopic flaws on the surface of the sprayed workpiece can not cause the paint to fall off; poor representation of a large number of flaws on the surface of the part and easy shedding of paint.
2. Test results
The results of the performance tests on the easy spray, low warpage PBT compositions prepared above are shown in Table 3.
Table 3 results of performance test of each example and comparative example
| Tensile strength/MPa | Flexural Strength/MPa | Notched izod impact strength/(kJ/m) 2 ) | Warp/mm | Effect of spray coating | |
| Example 1 | 118 | 178 | 12 | 3 | Good effect |
| Example 2 | 113 | 165 | 11 | 1 | Is excellent in |
| Example 3 | 108 | 159 | 10 | 0 | Is excellent in |
| Example 4 | 97 | 142 | 15 | 1 | Is excellent in |
| Example 5 | 109 | 161 | 13 | 2 | Is excellent in |
| Example 6 | 118 | 179 | 8 | 4 | It is excellent in |
| Example 7 | 104 | 158 | 13 | 2 | Is excellent in |
| Example 8 | 110 | 165 | 11 | 4 | Good effect |
| Example 9 | 104 | 152 | 9 | 4 | Good effect |
| Example 10 | 115 | 171 | 9 | 1 | Good effect |
| Example 11 | 112 | 165 | 12 | 1 | Is excellent in |
| Example 12 | 115 | 167 | 11 | 9 | Passing and lattice |
| Example 13 | 110 | 162 | 10 | 9 | Passing and lattice |
| Comparative example 1 | 78 | 117 | 6 | 12 | Difference (D) |
| Comparative example 2 | 65 | 98 | 11 | 3 | Is good |
| Comparative example 3 | 106 | 159 | 6 | 6 | Difference (D) |
As can be seen from Table 3, the PBT composition which is easy to spray and has low warpage and is prepared in the examples of the application has the performance of easy spraying, and has low warpage and good mechanical properties.
As can be seen from examples 1 to 3, the warpage of the PBT composition gradually decreased with the increase of the amount of the filler, and the spraying effect gradually became excellent.
As can be seen from examples 1 and 4 to 5, the PBT composition has a significantly improved spraying effect and a somewhat improved toughness with an increased amount of the thermoplastic elastomer, but has a slightly reduced tensile strength and flexural strength.
As can be seen from examples 2 and 8-9, when the intrinsic viscosity of the PBT resin is 0.70-0.85 dL/g, the tensile strength and flexural strength of the PBT composition are increased, and the combination properties are better.
As can be seen from the embodiment 2 and the embodiments 11 to 13, when the glass fiber is flat glass fiber and the flat ratio is 1:3-1:4, the prepared PBT composition has good spraying effect, obviously reduced warping degree and best comprehensive performance.
Comparing example 1 with comparative example 1, it can be seen that when the amount of filler is large and the weight ratio of thermoplastic elastomer to filler is 1:4, the PBT composition produced has warpage of 12mm and tensile strength is reduced.
Comparing example 1 with comparative example 2, it can be seen that when the amount of the thermoplastic elastomer is large and the weight ratio of the thermoplastic elastomer to the filler is 4:1, the obtained PBT composition has good spraying effect, but the mechanical properties of the PBT composition are reduced.
Comparing example 2 with comparative example 3, it can be seen that when the selected thermoplastic elastomer does not contain glycidyl methacrylate, the spraying effect of the prepared PBT composition is deteriorated and the comprehensive mechanical properties are reduced.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (10)
1. The easy-spraying and low-warpage PBT composition is characterized by comprising the following components in parts by weight:
the thermoplastic elastomer is a block copolymer or a graft copolymer containing glycidyl methacrylate, wherein the mass fraction of the glycidyl methacrylate is not less than 2 percent.
2. The easy-to-spray, low-warpage PBT composition of claim 1, wherein the mass ratio of the thermoplastic elastomer to the filler is 1:2-2:1.
3. The easy-to-spray, low-warpage PBT composition of claim 1, wherein the polybutylene terephthalate has an intrinsic viscosity of 0.70 to 0.85dL/g.
4. The sprayable, low warpage PBT composition of claim 1, wherein the thermoplastic elastomer is an ethylene methyl acrylate glycidyl methacrylate block copolymer or an ethylene octene glycidyl methacrylate graft copolymer.
5. The easily sprayable, low warpage PBT composition of claim 1 wherein the filler is one or more of barium sulfate, montmorillonite, calcium carbonate, or talc.
6. The easy-to-spray, low-warpage PBT composition of claim 1, wherein the glass fiber is a flat glass fiber with a flatness ratio of 1:3-1:4.
7. The easy-to-spray, low-warpage PBT composition of claim 1, wherein the black seed is a PE-supported black color masterbatch.
8. The easy-to-spray, low-warpage PBT composition of claim 1, wherein the black seed is a black color masterbatch with PE as a carrier and carbon black as a pigment.
9. The process for preparing an easily sprayable, low warpage PBT composition according to any one of claims 1 to 8, comprising the steps of:
s1, mixing a filling agent and other auxiliary agents to obtain a first mixture;
s2, mixing the polybutylene terephthalate, the thermoplastic elastomer and the black seeds to obtain a second mixture;
and S3, carrying out melt blending, extrusion and granulation on the first mixture, the second mixture and the glass fiber to obtain the PBT composition.
10. Use of the easy-to-spray, low-warpage PBT composition of any one of claims 1-8 in electronic product housings, automotive product housings.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211235709.0A CN115612259A (en) | 2022-10-10 | 2022-10-10 | Easily-sprayed and low-warpage PBT (polybutylene terephthalate) composition and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211235709.0A CN115612259A (en) | 2022-10-10 | 2022-10-10 | Easily-sprayed and low-warpage PBT (polybutylene terephthalate) composition and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115612259A true CN115612259A (en) | 2023-01-17 |
Family
ID=84862501
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211235709.0A Pending CN115612259A (en) | 2022-10-10 | 2022-10-10 | Easily-sprayed and low-warpage PBT (polybutylene terephthalate) composition and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115612259A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08253664A (en) * | 1995-03-16 | 1996-10-01 | Kanebo Ltd | Polyester resin composition |
| CN106280320A (en) * | 2016-08-31 | 2017-01-04 | 广东顺德顺炎新材料股份有限公司 | A kind of low warpage highlight antiflaming polybutylene terephthalate (PBT) and preparation method thereof |
| CN111154241A (en) * | 2020-02-14 | 2020-05-15 | 中广核瑞胜发（厦门）新材料有限公司 | Reinforced flame-retardant low-warpage PBT (polybutylene terephthalate) composite material and preparation method thereof |
| CN111995843A (en) * | 2020-08-24 | 2020-11-27 | 广东圆融新材料有限公司 | Low-linear expansion coefficient polybutylene terephthalate composite material and preparation method thereof |
| CN112552658A (en) * | 2020-12-11 | 2021-03-26 | 天津金发新材料有限公司 | Polybutylene terephthalate composition for encapsulating TPE (thermoplastic elastomer) and preparation method thereof |
-
2022
- 2022-10-10 CN CN202211235709.0A patent/CN115612259A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08253664A (en) * | 1995-03-16 | 1996-10-01 | Kanebo Ltd | Polyester resin composition |
| CN106280320A (en) * | 2016-08-31 | 2017-01-04 | 广东顺德顺炎新材料股份有限公司 | A kind of low warpage highlight antiflaming polybutylene terephthalate (PBT) and preparation method thereof |
| CN111154241A (en) * | 2020-02-14 | 2020-05-15 | 中广核瑞胜发（厦门）新材料有限公司 | Reinforced flame-retardant low-warpage PBT (polybutylene terephthalate) composite material and preparation method thereof |
| CN111995843A (en) * | 2020-08-24 | 2020-11-27 | 广东圆融新材料有限公司 | Low-linear expansion coefficient polybutylene terephthalate composite material and preparation method thereof |
| CN112552658A (en) * | 2020-12-11 | 2021-03-26 | 天津金发新材料有限公司 | Polybutylene terephthalate composition for encapsulating TPE (thermoplastic elastomer) and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110804282B (en) | Modified flat glass fiber reinforced PBT (polybutylene terephthalate) composite material and preparation method thereof | |
| CN108624006B (en) | High-fluidity glass fiber reinforced flame-retardant PC/PBT alloy material and preparation method thereof | |
| WO2006120184A1 (en) | Hydrolysis-resistant composition | |
| CN114292510B (en) | PC-ABS alloy material and preparation method thereof | |
| CN112625406B (en) | Cold-heat shock resistant polybutylene terephthalate composition | |
| EP3323854B1 (en) | Polybutylene terephthalate resin composition | |
| CN105419253A (en) | Polybutylene terephthalate composition and preparation method thereof | |
| CN111621123A (en) | Low-warpage PET/PBT composite material and preparation method thereof | |
| CN111500042A (en) | Matte PC/ABS alloy material and preparation method thereof | |
| CN110964322A (en) | Polyphenylene sulfide composite material and preparation method and application thereof | |
| EP0468673B1 (en) | Polybutylene Terephthalate resin composition | |
| KR100622710B1 (en) | Polyester resin composition excellent in heat resistance and surface smoothness | |
| CN115612259A (en) | Easily-sprayed and low-warpage PBT (polybutylene terephthalate) composition and preparation method thereof | |
| CN111004476B (en) | Engineering plastic composition and preparation method thereof | |
| CN119403879A (en) | Polyalkylene terephthalate resin composition and resin molded product | |
| CN117511142A (en) | A halogen-free flame retardant reinforced PBT composition that is resistant to moisture and heat aging and its preparation method and application | |
| CN115536971B (en) | Heat aging-resistant ASA/PBT composition and preparation method thereof | |
| KR101622807B1 (en) | PBT resin composition, injection molding product and method for preparing them | |
| CN111592755B (en) | Enhanced bio-based polyamide 56 composition and preparation method thereof | |
| KR20190017569A (en) | Polybutylene terephthalate resin composition | |
| CN116554650A (en) | Polyethylene terephthalate mixture and preparation method and application thereof | |
| JP3633199B2 (en) | Polyester resin composition | |
| KR100582338B1 (en) | Polyester resin composition excellent in heat resistance and surface smoothness | |
| JP2000038497A (en) | Black polyester resin composition and its molded product | |
| CN112646331A (en) | Polybutylene terephthalate mixture and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20230117 |