CN110452502B - Low-warpage good-appearance high-heat-resistance polyester composite material and preparation method thereof - Google Patents

Low-warpage good-appearance high-heat-resistance polyester composite material and preparation method thereof Download PDF

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CN110452502B
CN110452502B CN201910654886.4A CN201910654886A CN110452502B CN 110452502 B CN110452502 B CN 110452502B CN 201910654886 A CN201910654886 A CN 201910654886A CN 110452502 B CN110452502 B CN 110452502B
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CN110452502A (en
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苏健新
苏志军
周乾桃
廖乾明
郭丽
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Shenzhen Gk Plastics Co ltd
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/30Sulfur-, selenium- or tellurium-containing compounds
    • C08K2003/3045Sulfates
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/02Flame or fire retardant/resistant
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/08Stabilised against heat, light or radiation or oxydation
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/02Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/03Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/24Crystallisation aids

Abstract

The invention relates to the technical field of modification of high polymer materials, in particular to a low-warpage good-appearance high-heat-resistance polyester composite material and a preparation method thereof, wherein the polyester composite material is prepared from the following raw materials: PET resin, PBT resin, glass fiber, toughening agent, heat stabilizer, lubricant, nucleating agent, flame retardant and filler; the nucleating agent is a mixture consisting of LCP, modified montmorillonite, silicon dioxide and sodium polyacrylate. The low-warpage good-appearance high-heat-resistance polyester composite material disclosed by the invention has stable shrinkage rate and good injection molding processability, has lower water absorption rate and heat aging resistance than nylon, has toughness equivalent to PA66, has chemical corrosion resistance equivalent to PPS, can replace PA66 or PPS with high price, has better heat resistance, good appearance and low warpage than PBT and PA6, and is mainly applied to precise structural appearance parts and heat-resistant parts in the industries of electronic appliances, automobiles and new energy.

Description

Low-warpage good-appearance high-heat-resistance polyester composite material and preparation method thereof
Technical Field
The invention relates to the technical field of modification of high polymer materials, and particularly relates to a low-warpage good-appearance high-heat-resistance polyester composite material and a preparation method thereof.
Background
Polyester is one of five engineering plastics, including PBT, PET, PCT, PTT, PEN and the like, the PET and the PBT occupy the main market at present, and other types of polyester have high price, small market share and limited domestic technical level due to the synthesis of monomers and route processes. PET is a crystalline high polymer having a high melting temperature (Tm) and glass transition temperature (Tg), can maintain excellent physical and mechanical properties over a wide temperature range, and has excellent fatigue resistance, abrasion resistance, aging resistance, outstanding electrical insulation, stability to most organic solvents and inorganic acids, low production energy consumption, and good processability, and thus it is widely used in the fields of synthetic fibers, films, engineering plastics, etc., but its crystallization speed is slow due to its rigidity, it is easy to warp, and its appearance is poor, so its application in the field of engineering plastics is limited. And the PBT molecular chain segment has better flexibility than PET, good mechanical property, low thermal deformation temperature and higher crystallization rate.
At present, many patent documents mention flat glass fibers to solve the problem of low warpage of materials, and the polyester modification also mentions low-crystalline PET and flat glass fibers to solve the problem of low warpage, but the price of the flat glass fibers is too high, and the production cost is high. The invention achieves the effect of low warpage and improves the heat resistance and the glossiness from completely different directions.
Disclosure of Invention
In order to overcome the defects and shortcomings in the prior art, the invention aims to provide a low-warpage good-appearance high-heat-resistance polyester composite material which has stable shrinkage rate and good injection molding processability, has lower water absorption rate and heat aging resistance than nylon, toughness equivalent to PA66 and chemical corrosion resistance equivalent to PPS, can completely replace expensive PA66 or PPS under a specific occasion, and has better heat resistance, good appearance and low warpage than PBT and PA 6.
The invention also aims to provide a preparation method of the low-warpage good-appearance high-heat-resistance polyester composite material, which has the advantages of simple and controllable production process and convenient production operation.
The purpose of the invention is realized by the following technical scheme: a low-warpage good-appearance high-heat-resistance polyester composite material is composed of the following raw materials in parts by weight:
wherein the nucleating agent is LCP, modified montmorillonite, silicon dioxide and sodium polyacrylate in a weight ratio of 2-4: 1-3: 2-4: 1-3. LCP is a liquid crystal polymer, is a high molecular material, generally presents liquid crystallinity in a molten state, and has excellent heat resistance and molding processability; LCP micropowder is preferred, the crystallization of PET can be accelerated by the special crystal form of the LCP micropowder, the modified montmorillonite and the silicon dioxide are inorganic materials and are the key of PET nucleation, the nucleation crystal form of the PET can be more uniform and smaller, the nucleation termination caused by the formation of large crystal nucleus can be prevented, the nucleation is more sufficient, and the powder can be fully mixed by the dispersion powder of sodium polyacrylate and the moisture absorption effect; the LCP is preferably a Japanese executive LCPT 130. According to the invention, LCP, modified montmorillonite, silicon dioxide and sodium polyacrylate are adopted as nucleating agents for compounding, so that the crystallization rate and the nucleation rate of PET can be improved. More preferably, the nucleating agent is LCP, modified montmorillonite, silicon dioxide and sodium polyacrylate in a weight ratio of 3: 2: 3: 2, and (b) a mixture of the components.
The modified polyester composite material has stable shrinkage rate, good injection molding processability, lower water absorption rate than nylon, heat aging resistance, toughness equivalent to PA66 and chemical corrosion resistance equivalent to PPS, can completely replace PA66 or PPS with high price in a specific occasion, and has better heat resistance, good appearance and low warpage than PBT and PA 6.
Preferably, the feed consists of the following raw materials in parts by weight:
10-50 parts of PET resin, and any value of 10, 15, 20, 25, 30, 35, 40, 45 and 50 parts or 10-50 parts can be selected; the intrinsic viscosity of the PET resin is 0.67-0.80 dl/g. The PET resin with the viscosity has excellent physical properties and mechanical properties. More preferably, the PET resin is produced by the Dainichner chemical fiber company and is of the brand FG 600.
10-50 parts of PBT resin, which can be selected from 10, 15, 20, 25, 30, 35, 40, 45 and 50 parts, or any value between 10-50 parts; the PBT resin has the intrinsic viscosity of 0.8-1.0 dl/g. By adopting the PBT resin with the viscosity, the invention has the advantages of good mechanical property, low thermal deformation temperature and high crystallization rate. More preferably, the PBT resin is any one of hectorite 2083 and nantong 1100.
10-50 parts of the glass fiber, and any value of 10, 15, 20, 25, 30, 35, 40, 45 and 50 parts or 10-50 parts of the glass fiber can be selected; the glass fiber is glass fiber with diameter of 11-15 μm, such as 11 μm, 12 μm, 13 μm, 14 μm, and 15 μm. By adopting the glass fiber, the heat resistance and the mechanical property of the composite material can be improved. More preferably, the glass fiber is any one of 534A short fiber of boulder group and taishan T635B long fiber.
1-5 parts of toughening agent, which can be selected from 1, 3, 5 parts, or any value between 1-5 parts; the toughening agent is an ethylene-methyl acrylate copolymer. The invention can improve the impact strength of the composite material by adopting the ethylene-methyl acrylate copolymer as the toughening agent. More preferably, the toughening agent is any one of commercially available akoma AX8900 and japanese sumitomo BF-7M.
The lubricant is 0.1-2 parts, and can be selected from 0.1, 0.5, 1, 1.5 and 2 parts, or any value between 0.1-2 parts; the lubricant is PETS and silicone powder in a weight ratio of 0.5-1.5:1, in a mixture of the components. The invention adopts PETS (pentaerythritol stearate) and silicone powder as lubricant to be compounded, so that the frictional heat in the extrusion and processing processes of the material can be reduced, and the mold release performance in injection molding can be improved. More preferably, the lubricant is PETS and silicone powder which are mixed in a weight ratio of 1:1, in a mixture of the components. The PETS is any one of LG PETS and Italy hair base PETS; the silicone powder is any one of Dow Corning 4-7081 and Sichuan fine chemical CM 100A.
The heat stabilizer is 0.1-1 part, and can be selected from 0.1, 0.5 and 1 part, or any value between 0.1 and 1 part; the heat stabilizer is a mixture of an antioxidant 1098 and an antioxidant 168 in a weight ratio of 0.5-1.5: 1. According to the invention, the antioxidant 1098 and the antioxidant 168 are used as heat stabilizers in a compounding manner, so that overheating and yellowing in the extrusion and injection molding processes can be prevented. More preferably, the heat stabilizer is a mixture of antioxidant 1098 and antioxidant 168 in a weight ratio of 1: 1. The antioxidant 1098 and the antioxidant 168 are produced by Ningbo Jinhaiyabao.
1-10 parts of filler, which can be selected from 1, 3, 5, 7, 9 and 10 parts, or any value between 1-10 parts; the filler is talcum powder with the grain diameter of 8000-12000 meshes and barium sulfate with the grain diameter of 4000-6000 meshes in a weight ratio of 0.5-1.5:1, in a mixture of the components. The invention adds the fillers with different meshes, so that the low warpage of the crystalline material is more stable. More preferably, the filler is talcum powder with the grain diameter of 10000 meshes and barium sulfate with the grain diameter of 5000 meshes in a weight ratio of 1:1, in a mixture of the components.
5-25 parts of flame retardant, wherein 5, 10, 15, 20 and 25 parts of flame retardant can be selected, or any value between 5-25 parts of flame retardant can be selected; the flame retardant is epoxy resin and sodium antimonate in a weight ratio of 2-4: 1, in a mixture of the components. According to the invention, the epoxy resin and the sodium antimonate are adopted as the flame retardant for compounding, so that the flame retardant effect is good, and the product has a good color. More preferably, the flame retardant is epoxy resin and sodium antimonate in a weight ratio of 3: 1, in a mixture of the components. The epoxy resin is any one of the open-beauty science K2025 and K2015; sodium antimonate is produced by Changsha and other industries.
A low-warpage good-appearance high-heat-resistance polyester composite material comprises the following steps:
(1) mixing PET resin, PBT resin, a toughening agent and a nucleating agent for 2-5 min;
(2) adding a flame retardant, a filler, a heat stabilizer and a lubricant after the step (1), and continuously mixing for 2-5 min;
(3) melting and extruding the mixed raw materials obtained in the step (2) through a double-screw extruder, and granulating, wherein glass fibers are added into a glass fiber opening of the double-screw extruder; the process conditions of the double-screw extruder are as follows: the temperature of the first zone is 230-plus-250 ℃, the temperature of the second zone is 250-plus-270 ℃, the temperature of the third zone is 270-plus-290 ℃, the temperature of the fourth zone is 270-plus-290 ℃, the temperature of the fifth zone is 250-plus-270 ℃, the temperature of the sixth zone is 250-plus-270 ℃, the temperature of the seventh zone is 240-plus-260 ℃, the temperature of the eighth zone is 230-plus-250 ℃, the temperature of the ninth zone is 230-plus-250 ℃, the temperature of the tenth zone is 230-plus-250 ℃, the temperature of the head is 290-plus-310 ℃ and the retention time of the raw materials is 25-35 seconds.
The invention has the beneficial effects that: the low-warpage good-appearance high-heat-resistance polyester composite material disclosed by the invention has stable shrinkage rate and good injection molding processability, and simultaneously has lower water absorption rate and heat aging resistance than nylon, toughness equivalent to PA66 and chemical corrosion resistance equivalent to PPS, can completely replace PA66 or PPS with high price in a specific occasion, has better heat resistance, good appearance and low warpage than PBT and PA6, and is mainly applied to precise structure appearance parts and heat-resistant parts in the industries of electronic appliances, automobiles and new energy.
Aiming at the problem that the existing PBT and PET modified products in the market are difficult to simultaneously meet the three requirements of low warpage, high gloss, high heat resistance and the like and influence the use occasions of the modified products, the invention improves the production formula and the process of PET/PBT modification, mainly improves the crystallization of PET, prepares alloy with PBT, and when the crystallization rate and the nucleation rate of PET and PBT are close, the blending composite material achieves stability on shrinkage, can prepare the polyester modified composite material with low warpage, high gloss and high heat resistance, can basically cover the use fields of PET and PBT, can replace PA6, PA66 and PPS with higher cost in many occasions, and has very high application prospects.
The invention has the beneficial effects that: the PET/PBT is modified by adopting PET resin, PBT resin and glass fiber and adding auxiliary agents such as a flexibilizer, a nucleating agent, a filling agent, a heat stabilizer, a filling agent, a flame retardant, a lubricant and the like; the glass fiber greatly increases the mechanical property and heat resistance of the PET material, and the toughening agent can enable the composite material to have excellent toughness; the heat stabilizer can inhibit yellowing and degradation of the product in the processing process in the using process to a certain extent; the lubricant has the functions of dispersing powder and reducing thermal shear; the brominated epoxy resin and the sodium antimonate are used as the flame retardant of the composite material, the color and the flame retardant effect of the product are both optimal, meanwhile, the compound nucleating agent is adopted, the crystallization temperature of the PET composite material is obviously improved, the crystallization rate of the PET composite material is accelerated, the shrinkage rate is stably reduced, the PET composite material is made into an alloy with the PBT, two obvious crystallization peaks exist, DSC tests show that as shown in figure 1, the two crystallization peak areas (representing the crystallization rates) are close, the peak widths (representing the crystallization rates) are close, the PET crystallization rate is close to that of the PBT, the two crystallization peaks do not have obvious overlapping areas, the integral crystallization time is longer, and the crystallization temperature span is large. In the injection molding process, the size and deformation of a product are influenced by the crystallization speed and degree of the material in the molding cooling process of the product, the deformation is mainly caused by different shrinkage rates of a crystallization area of the product during crystallization, a best method is to introduce a non-crystallization material, prolong the crystallization time or reduce the crystallization area, and the introduction of the non-crystallization material can damage the heat resistance and the mechanical property. The fillers with different meshes are added, so that the low warpage of the crystalline material is more stable.
The preparation method of the invention has simple and controllable production process and convenient production operation.
Drawings
FIG. 1 is a DSC chart of a low warpage good appearance high heat resistant polyester composite material obtained in example 2 of the present invention.
FIG. 2 is a DSC chart of the low warpage good appearance high heat resistant polyester composite material of comparative example 1 of the present invention.
Detailed Description
For the understanding of those skilled in the art, the present invention will be further described with reference to the following examples and accompanying fig. 1-2, which are not intended to limit the present invention.
Comparative example 1
The following raw materials in parts by weight are selected: 25 parts of PET resin, 25 parts of PBT resin (KH2083), 2 parts of toughening agent AX8900, 13 parts of flame retardant, 0.4 part of antioxidant, 0.6 part of lubricant, 3 parts of filler and 1 part of commercially available PET resin nucleating agent (Bluggeman P250) are mixed in a medium-speed mixer for 5min, and 30 parts of glass fiber T635B 30 (added through a glass fiber port) are extruded by a double-screw extruder with the melting temperature of 240 plus 270 ℃ and are granulated. Wherein the temperature of each section of the double-screw extruder is set as follows: the temperature of the first zone is 240 ℃, the temperature of the second zone is 260 ℃, the temperature of the third zone is 270 ℃, the temperature of the fourth zone is 270 ℃, the temperature of the fifth zone is 260 ℃, the temperature of the sixth zone is 260 ℃, the temperature of the seventh zone is 250 ℃, the temperature of the eighth zone is 240 ℃, the temperature of the ninth zone is 240 ℃, the temperature of the tenth zone is 240 ℃, the temperature of the machine head is 270 ℃ and the retention time is 30 s.
Comparative example 2
The following raw materials in parts by weight are selected: 51 parts of PBT resin (KH2083), 2 parts of toughening agent AX8900, 13 parts of flame retardant, 0.4 part of antioxidant and 0.6 part of lubricant, 3 parts of filler are mixed in a medium-speed stirrer for 5min, and 30 parts of glass fiber T635B 30 (added through a glass fiber port) are extruded by a double-screw extruder with the melting temperature of 240-DEG C and 270-DEG C, and then are granulated. Wherein the temperature of each section of the double-screw extruder is set as follows: the temperature of the first zone is 240 ℃, the temperature of the second zone is 260 ℃, the temperature of the third zone is 270 ℃, the temperature of the fourth zone is 270 ℃, the temperature of the fifth zone is 260 ℃, the temperature of the sixth zone is 260 ℃, the temperature of the seventh zone is 250 ℃, the temperature of the eighth zone is 240 ℃, the temperature of the ninth zone is 240 ℃, the temperature of the tenth zone is 240 ℃, the temperature of the machine head is 270 ℃ and the retention time is 30 s.
Comparative example 3
The following raw materials in parts by weight are selected: 10 parts of PET resin, 41 parts of PBT resin (KH2083), 2 parts of toughening agent AX8900, 13 parts of flame retardant, 0.4 part of antioxidant and 0.6 part of lubricant, 3 parts of filler are mixed in a medium-speed mixer for 5min, and 30 parts of flat glass fiber (Mount Taishan T435TM with the flat ratio of 3.5 and the length of 5mm, added by side feeding) is extruded by a double-screw extruder with the melting temperature of 240 and 270 ℃ and is pelletized. Wherein the temperature of each section of the double-screw extruder is set as follows: the temperature of the first zone is 240 ℃, the temperature of the second zone is 260 ℃, the temperature of the third zone is 270 ℃, the temperature of the fourth zone is 270 ℃, the temperature of the fifth zone is 260 ℃, the temperature of the sixth zone is 260 ℃, the temperature of the seventh zone is 250 ℃, the temperature of the eighth zone is 240 ℃, the temperature of the ninth zone is 240 ℃, the temperature of the tenth zone is 240 ℃, the temperature of the machine head is 270 ℃ and the retention time is 30 s.
Example 1
The following raw materials in parts by weight are selected: 30 parts of PET resin, 20 parts of PBT resin (KH2083), 2 parts of toughening agent AX8900, 13 parts of flame retardant, 0.4 part of antioxidant, 0.6 part of lubricant, 3 parts of filler and 1 part of nucleating agent, mixing for 5min in a medium-speed stirrer, extruding 30 parts of glass fiber T635B 30 (added through a glass fiber port) by a double-screw extruder with the melting temperature of 240-270 ℃, and granulating. Wherein the temperature of each section of the double-screw extruder is set as follows: the temperature of the first zone is 240 ℃, the temperature of the second zone is 260 ℃, the temperature of the third zone is 270 ℃, the temperature of the fourth zone is 270 ℃, the temperature of the fifth zone is 260 ℃, the temperature of the sixth zone is 260 ℃, the temperature of the seventh zone is 250 ℃, the temperature of the eighth zone is 240 ℃, the temperature of the ninth zone is 240 ℃, the temperature of the tenth zone is 240 ℃, the temperature of the machine head is 270 ℃ and the retention time is 30 s.
Example 2
The following raw materials in parts by weight are selected: 25 parts of PET resin, 25 parts of PBT resin (KH2083), 2 parts of toughening agent AX8900, 13 parts of flame retardant, 0.4 part of antioxidant, 0.6 part of lubricant, 3 parts of filler and 1 part of nucleating agent, mixing for 5min in a medium-speed stirrer, extruding the glass fiber T635B 30 parts (added through a glass fiber port) by a double-screw extruder with the melting temperature of 240-270 ℃, and granulating. Wherein the temperature of each section of the double-screw extruder is set as follows: the temperature of the first zone is 240 ℃, the temperature of the second zone is 260 ℃, the temperature of the third zone is 270 ℃, the temperature of the fourth zone is 270 ℃, the temperature of the fifth zone is 260 ℃, the temperature of the sixth zone is 260 ℃, the temperature of the seventh zone is 250 ℃, the temperature of the eighth zone is 240 ℃, the temperature of the ninth zone is 240 ℃, the temperature of the tenth zone is 240 ℃, the temperature of the machine head is 270 ℃ and the retention time is 30 s.
Example 3
The following raw materials in parts by weight are selected: 20 parts of PET resin, 30 parts of PBT resin (KH2083), 2 parts of toughening agent AX8900, 13 parts of flame retardant, 0.4 part of antioxidant, 0.6 part of lubricant, 3 parts of filler and 1 part of nucleating agent, mixing for 5min in a medium-speed stirrer, extruding 30 parts of glass fiber T635B 30 (added through a glass fiber port) by a double-screw extruder with the melting temperature of 240-270 ℃, and granulating. Wherein the temperature of each section of the double-screw extruder is set as follows: the temperature of the first zone is 240 ℃, the temperature of the second zone is 260 ℃, the temperature of the third zone is 270 ℃, the temperature of the fourth zone is 270 ℃, the temperature of the fifth zone is 260 ℃, the temperature of the sixth zone is 260 ℃, the temperature of the seventh zone is 250 ℃, the temperature of the eighth zone is 240 ℃, the temperature of the ninth zone is 240 ℃, the temperature of the tenth zone is 240 ℃, the temperature of the machine head is 270 ℃ and the retention time is 30 s.
Example 4
The following raw materials in parts by weight are selected: 25 parts of PET resin, 24.5 parts of PBT resin (KH2083), 2 parts of toughening agent AX8900, 13 parts of flame retardant, 0.4 part of antioxidant, 0.6 part of lubricant, 3 parts of filler and 1.5 parts of nucleating agent, mixing for 5min in a medium-speed mixer, extruding and granulating glass fiber T635B 30 parts (added through a glass fiber port) by a double-screw extruder with the melting temperature of 240-270 ℃. Wherein the temperature of each section of the double-screw extruder is set as follows: the temperature of the first zone is 240 ℃, the temperature of the second zone is 260 ℃, the temperature of the third zone is 270 ℃, the temperature of the fourth zone is 270 ℃, the temperature of the fifth zone is 260 ℃, the temperature of the sixth zone is 260 ℃, the temperature of the seventh zone is 250 ℃, the temperature of the eighth zone is 240 ℃, the temperature of the ninth zone is 240 ℃, the temperature of the tenth zone is 240 ℃, the temperature of the machine head is 270 ℃ and the retention time is 30 s.
Example 5
The following raw materials in parts by weight are selected: 25 parts of PET resin, 25.5 parts of PBT resin (KH2083), 2 parts of toughening agent AX8900, 13 parts of flame retardant, 0.4 part of antioxidant, 0.6 part of lubricant, 3 parts of filler and 0.5 part of nucleating agent, mixing for 5min in a medium-speed mixer, extruding and granulating glass fiber T635B 30 parts (added through a glass fiber port) by a double-screw extruder with the melting temperature of 240-270 ℃. Wherein the temperature of each section of the double-screw extruder is set as follows: the temperature of the first zone is 240 ℃, the temperature of the second zone is 260 ℃, the temperature of the third zone is 270 ℃, the temperature of the fourth zone is 270 ℃, the temperature of the fifth zone is 260 ℃, the temperature of the sixth zone is 260 ℃, the temperature of the seventh zone is 250 ℃, the temperature of the eighth zone is 240 ℃, the temperature of the ninth zone is 240 ℃, the temperature of the tenth zone is 240 ℃, the temperature of the machine head is 270 ℃ and the retention time is 30 s.
Example 6
The following raw materials in parts by weight are selected: 26 parts of PET resin, 26 parts of PBT resin (KH2083), 2 parts of toughening agent AX8900, 13 parts of flame retardant, 0.4 part of antioxidant, 0.6 part of lubricant, 1 part of filler and 0.5 part of nucleating agent, mixing for 5min in a medium-speed stirrer, extruding and granulating glass fiber T635B 30 parts (added through a glass fiber port) by a double-screw extruder with the melting temperature of 240-270 ℃. Wherein the temperature of each section of the double-screw extruder is set as follows: the temperature of the first zone is 240 ℃, the temperature of the second zone is 260 ℃, the temperature of the third zone is 270 ℃, the temperature of the fourth zone is 270 ℃, the temperature of the fifth zone is 260 ℃, the temperature of the sixth zone is 260 ℃, the temperature of the seventh zone is 250 ℃, the temperature of the eighth zone is 240 ℃, the temperature of the ninth zone is 240 ℃, the temperature of the tenth zone is 240 ℃, the temperature of the machine head is 270 ℃ and the retention time is 30 s.
Example 7
The following raw materials in parts by weight are selected: 24 parts of PET resin, 24 parts of PBT resin (KH2083), 2 parts of toughening agent AX8900, 13 parts of flame retardant, 0.4 part of antioxidant, 0.6 part of lubricant, 5 parts of filler and 0.5 part of nucleating agent, mixing for 5min in a medium-speed stirrer, extruding and granulating glass fiber T635B 30 parts (added through a glass fiber port) by a double-screw extruder with the melting temperature of 240-270 ℃. Wherein the temperature of each section of the double-screw extruder is set as follows: the temperature of the first zone is 240 ℃, the temperature of the second zone is 260 ℃, the temperature of the third zone is 270 ℃, the temperature of the fourth zone is 270 ℃, the temperature of the fifth zone is 260 ℃, the temperature of the sixth zone is 260 ℃, the temperature of the seventh zone is 250 ℃, the temperature of the eighth zone is 240 ℃, the temperature of the ninth zone is 240 ℃, the temperature of the tenth zone is 240 ℃, the temperature of the machine head is 270 ℃ and the retention time is 30 s.
Example 8
The following raw materials in parts by weight are selected: 20 parts of PET resin, 20 parts of PBT resin (KH2083), 2 parts of toughening agent AX8900, 13 parts of flame retardant, 0.4 part of antioxidant, 0.6 part of lubricant, 3 parts of filler and 1 part of nucleating agent, mixing for 5min in a medium-speed stirrer, and extruding and granulating glass fiber T635B 40 parts (added through a glass fiber port) by a double-screw extruder with the melting temperature of 240-270 ℃. Wherein the temperature of each section of the double-screw extruder is set as follows: the temperature of the first zone is 240 ℃, the temperature of the second zone is 260 ℃, the temperature of the third zone is 270 ℃, the temperature of the fourth zone is 270 ℃, the temperature of the fifth zone is 260 ℃, the temperature of the sixth zone is 260 ℃, the temperature of the seventh zone is 250 ℃, the temperature of the eighth zone is 240 ℃, the temperature of the ninth zone is 240 ℃, the temperature of the tenth zone is 240 ℃, the temperature of the machine head is 270 ℃ and the retention time is 30 s.
Performance evaluation method and performance standard
The granules granulated in the 8 examples and the 3 comparative examples are dried in a blast oven at the temperature of 120 ℃ and 130 ℃ for 3-4h, and then the dried granules are subjected to injection molding on an 80T injection molding machine to prepare samples, wherein the mold temperature is set at 75 ℃ (water cooling constant temperature). The test sample strip and the test method are carried out according to the method specified by the national standard ISO.
The weight parts of the raw materials of examples 1 to 8 and comparative examples 1 to 3 and the formulations of the resulting composites are shown in the following table.
The performance data for the formulations of examples 1-8 and comparative examples 1-3 are shown in the following table.
As can be seen from the above two tables, comparative examples 1 to 3 show that comparative example 2, to which no PET resin is added, is the worst in appearance and warpage and performance, while comparative example 1 is not ideal, and comparative example 3 is PBT resin + a small amount of PET resin + flat glass fiber, which is improved in appearance and warpage, but the price of the flat glass fiber is too high; examples 1-8 all have the nucleating agent of the present invention added thereto, examples 2 and comparative examples 1 have significant effects and differences, which are illustrated by the DSC graphs of figures 1-2 (PET flame retardant-2 is example 2, PET flame retardant-1 is comparative example 1), examples 2 are better than comparative example 1 in terms of peak width (crystallization rate) and peak area (crystallization rate), the appearance and warpage of PET resin are improved apparently, and the PET resin nucleating agent actually improves the crystallization starting and ending temperatures and crystallization rate of PET resin, so that the injection molding processability (sticking, long cycle) is improved, the shrinkage after the product is stable, the flowability of the system is improved by adding the PET resin and the nucleating agent, and the proper amount of the nucleating agent has certain influence on the performances due to too little or too much, as in examples 2, 3, 4, the nucleating agent can obviously improve the MFI (melt index) of the composite material, which also shows that the appearance of the composite material is improved by adding the nucleating agent, but the impact and the mechanical property are reduced too much, mainly because the viscosity of the material is reduced by the nucleating agent at the same time, the corresponding mechanical property is reduced (the relationship between the molecular weight and the property), which is identical with the MFI increase of the material, the warping can be slightly improved by adding the filler, because the two powder bodies with different grain diameters fill the gap between the glass fiber and the resin, but the impact strength of the material is reduced by increasing the weight, because the powder bodies are easy to agglomerate in the extrusion processing process, and the possibility of stress cracking is increased; the data of the embodiment 2 and the embodiment 8 are best, and the mixture ratio of the embodiments 1 to 8 can be applied to products with corresponding requirements as the core data of the invention.
The above-described embodiments are preferred implementations of the present invention, and the present invention may be implemented in other ways without departing from the spirit of the present invention.

Claims (9)

1. A low-warpage good-appearance high-heat-resistance polyester composite material is characterized in that: the composition is characterized by comprising the following raw materials in parts by weight:
wherein the nucleating agent is LCP micro powder, modified montmorillonite, silicon dioxide and sodium polyacrylate in a weight ratio of 2-4: 1-3: 2-4: 1-3;
the filler is talcum powder with the grain diameter of 8000-12000 meshes and barium sulfate with the grain diameter of 4000-6000 meshes in a weight ratio of 0.5-1.5:1, in a mixture of the components.
2. The polyester composite material with low warpage, good appearance and high heat resistance as claimed in claim 1, wherein: the composition is characterized by comprising the following raw materials in parts by weight:
3. the polyester composite material with low warpage and good appearance and high heat resistance as claimed in claim 1 or 2, wherein: the intrinsic viscosity of the PET resin is 0.67-0.80 dl/g; the PBT resin has the intrinsic viscosity of 0.8-1.0 dl/g.
4. The polyester composite material with low warpage and good appearance and high heat resistance as claimed in claim 1 or 2, wherein: the glass fiber is glass fiber with the diameter of 11-15 μm.
5. The polyester composite material with low warpage and good appearance and high heat resistance as claimed in claim 1 or 2, wherein: the toughening agent is an ethylene-methyl acrylate copolymer.
6. The polyester composite material with low warpage and good appearance and high heat resistance as claimed in claim 1 or 2, wherein: the lubricant is PETS and silicone powder in a weight ratio of 0.5-1.5:1, in a mixture of the components.
7. The polyester composite material with low warpage and good appearance and high heat resistance as claimed in claim 1 or 2, wherein: the heat stabilizer is a mixture of an antioxidant 1098 and an antioxidant 168 in a weight ratio of 0.5-1.5: 1.
8. The polyester composite material with low warpage and good appearance and high heat resistance as claimed in claim 1 or 2, wherein: the flame retardant is epoxy resin and sodium antimonate in a weight ratio of 2-4: 1, in a mixture of the components.
9. The process for preparing a low warpage good appearance high heat resistant polyester composite as claimed in any one of claims 1 to 8, wherein: the method comprises the following steps:
(1) mixing PET resin, PBT resin, a toughening agent and a nucleating agent for 2-5 min;
(2) adding a flame retardant, a filler, a heat stabilizer and a lubricant after the step (1), and continuously mixing for 2-5 min;
(3) melting and extruding the raw materials mixed in the step (2) by a double-screw extruder, and granulating, wherein glass fibers are added at a glass fiber opening of the double-screw extruder; the process conditions of the double-screw extruder are as follows: the temperature of the first zone is 230-plus-250 ℃, the temperature of the second zone is 250-plus-270 ℃, the temperature of the third zone is 270-plus-290 ℃, the temperature of the fourth zone is 270-plus-290 ℃, the temperature of the fifth zone is 250-plus-270 ℃, the temperature of the sixth zone is 250-plus-270 ℃, the temperature of the seventh zone is 240-plus-260 ℃, the temperature of the eighth zone is 230-plus-250 ℃, the temperature of the ninth zone is 230-plus-250 ℃, the temperature of the tenth zone is 230-plus-250 ℃, the temperature of the head is 290-plus-310 ℃ and the retention time of the raw materials is 25-35 seconds.
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