CN111334007A - Reinforced polyethylene terephthalate composition and preparation method thereof - Google Patents
Reinforced polyethylene terephthalate composition and preparation method thereof Download PDFInfo
- Publication number
- CN111334007A CN111334007A CN202010317415.7A CN202010317415A CN111334007A CN 111334007 A CN111334007 A CN 111334007A CN 202010317415 A CN202010317415 A CN 202010317415A CN 111334007 A CN111334007 A CN 111334007A
- Authority
- CN
- China
- Prior art keywords
- polyethylene terephthalate
- temperature
- zone
- resin
- screw
- 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
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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 relates to a reinforced polyethylene terephthalate composition and a preparation method thereof, wherein the reinforced polyethylene terephthalate composition is prepared from the following raw materials: polyethylene terephthalate A resin, polyethylene terephthalate B resin, ethylene-octene copolymer grafted glycidyl methacrylate, hollow glass beads, polyhedral oligomeric silsesquioxane polymer, low dielectric constant glass fiber, titanate coupling agent, polytetrafluoroethylene resin, hyperbranched polyester polymer, erucamide, antioxidant CY and bis (2, 4-dicumylphenyl) pentaerythritol diphosphite. The reinforced polyethylene glycol terephthalate composition has excellent mechanical property, processability and low dielectric constant, and can be applied to shells, coating materials, protective materials and the like of 5G base stations, micro base station systems, data communication terminals, antennas and radio frequency modules.
Description
Technical Field
The invention relates to the field of materials, in particular to a reinforced polyethylene terephthalate composition and a preparation method thereof.
Background
Dielectric materials, also known as dielectrics, are electrically insulating materials. There are high dielectric materials and low dielectric materials, depending on the properties. With the rapid advance of electronic information technology, electronic products are being developed toward light weight, high performance and multiple functions, and development of low dielectric constant (D) having good performance is increasingly required for low dielectric materialsk<3) A material. Meanwhile, with the coming of the 5G era, the requirements on the transmission speed and the loss of electronic signals are higher than those of 4G products, generally, the dielectric constant of the 4G products for the resin material is only required to be less than 3.7(1GHz), and the dielectric constant of the 5G products for the resin material is required to be less than 3.2(1 GHz).
Generally, there are three methods for reducing the dielectric constant of a polymer, which are ① introducing fluorine atoms into a polymer molecular chain to reduce the stacking density of the molecular chain and increase the free movement space of the molecular chain, ② introducing a bulky structure (such as polyhedral oligomeric silsesquioxane polymer) or a microporous structure or introducing large molecular chain side groups (such as benzene rings) by a physical or chemical method, ③ reducing the dielectric constant of a blend by blending other materials with lower dielectric constant, such as blending with Polytetrafluoroethylene (PTFE) with a relative dielectric constant of 2.0(1GHz), or blending with materials such as polyhedral oligomeric silsesquioxane Polymer (POSS) which can increase the free volume, and the like.
Polyethylene terephthalate (PET) has excellent mechanical properties and dimensional stability, the long-term use temperature can reach 120 ℃, the electrical insulation property is excellent, but PET contains ester bonds, the PET can be decomposed under the action of strong acid, strong base and water vapor, and the crystallization rate is slow, the forming and processing are difficult, and the impact property is poor due to high density of benzene rings. Therefore, it is necessary to toughen and strengthen PET and reduce the dielectric constant of the composition to meet the increasing demands in the fields of electronics and electricians, integrated circuit packaging, electromagnetic wave shielding, etc.
Currently, some studies on PET dielectric systems are made in the prior art, such as: chinese patent CN 108973281a discloses a resin laminate capable of effectively suppressing the occurrence of appearance defects such as cracking, wrinkling, and white turbidity during bending. A resin laminate comprising a resin layer having a dielectric constant of 3.5 or more and a hard coat layer laminated on at least one surface of the resin layer, wherein the pencil hardness on the hard coat layer side is 4B or more and satisfies the following relationships (1) to (3): l is more than or equal to 20PET≤130(1)，0.4≤LHC/LPMMA≤1.5(2)，1≤THCLess than or equal to 30 (3). Chinese patent CN 110574205a discloses a packaging element comprising a polymer layer and having a thickness between 10 and 200 microns; wherein the encapsulation member is for providing a substantially sealed, void-free enclosure for an energy storage device, and wherein the polymer is selected from the group consisting of: parylene, poly (m-xylylene adipamide), a dielectric polymer, a silicon-based polymer, polyurethane, an acrylic polymer, a rigid gas impermeable polymer, a fluorinated polymer, an epoxy, a polyisocyanate, PET, silicone rubber, a silicone elastomer, a polyamide, and any combination thereof. Chinese patent CN109971139A discloses PBT-PET modified plastic for communication equipment, which comprises the following components in parts by weight: 25-55 parts of PBT, 30-75 parts of PET, 10-30 parts of vinylidene fluoride, 15-30 parts of tetrafluoroethylene, 1-5 parts of an ester exchange inhibitor, 20-30 parts of an inorganic filler and 0-5 parts of an auxiliary agent. Chinese patent CN 109679304A discloses a PBT/PCT composite material and a preparation method and application thereof. The PBT/PCT composite material comprises the following components in parts by weight: 30-45 parts of PBT, 78-20 parts of PCT4, (vinyl POSS, MAH) -g-PP 5-10 parts and 25-40 parts of reinforcing material.
Disclosure of Invention
Based on the above, the present invention aims to provide a reinforced polyethylene terephthalate composition with excellent mechanical properties and processability and a low dielectric constant, which can be applied to a 5G base station, a micro base station system, a data communication terminal, a housing and a coating of an antenna and a radio frequency module, a protective material, etc.
In order to achieve the purpose, the invention adopts the following scheme:
the reinforced polyethylene terephthalate composition is prepared from the following raw materials in parts by weight:
60-93 parts of polyethylene terephthalate A resin (PET-A),
5-20 parts of polyethylene terephthalate B resin (PET-B),
2-20 parts of ethylene-octene copolymer grafted glycidyl methacrylate (POE-g-GMA),
the total weight of the polyethylene terephthalate A resin, the polyethylene terephthalate B resin and the ethylene-octene copolymer grafted glycidyl methacrylate is 100 parts,
the intrinsic viscosity of the polyethylene terephthalate A resin is 0.62-0.67 dL/g; the intrinsic viscosity of the polyethylene terephthalate B resin is 1.0-1.1 dL/g; the compressive strength of the hollow glass beads is not lower than 53 MPa; the number average molecular weight of the polytetrafluoroethylene resin is 1-10 ten thousand; the dielectric constant of the low-dielectric-constant glass fiber at 1GHz is not higher than 4.5.
In some embodiments, the reinforced polyethylene terephthalate composition is prepared from the following raw materials in parts by weight:
68-85 parts of polyethylene terephthalate A resin (PET-A),
9-16 parts of polyethylene terephthalate B resin (PET-B),
6-16 parts of ethylene-octene copolymer grafted glycidyl methacrylate (POE-g-GMA),
the total weight of the polyethylene terephthalate A resin, the polyethylene terephthalate B resin and the ethylene-octene copolymer grafted glycidyl methacrylate is 100 parts,
in some embodiments, the reinforced polyethylene terephthalate composition is further preferably prepared from the following raw materials in parts by weight:
72-78 parts of polyethylene terephthalate A resin (PET-A),
12-14 parts of polyethylene terephthalate B resin (PET-B),
10-14 parts of ethylene-octene copolymer grafted glycidyl methacrylate (POE-g-GMA),
the total weight of the polyethylene terephthalate A resin, the polyethylene terephthalate B resin and the ethylene-octene copolymer grafted glycidyl methacrylate is 100 parts,
in some embodiments, the reinforced polyethylene terephthalate composition is further preferably prepared from the following raw materials in parts by weight:
74-76 parts of polyethylene terephthalate A resin (PET-A),
12-14 parts of polyethylene terephthalate B resin (PET-B),
11-13 parts of ethylene-octene copolymer grafted glycidyl methacrylate (POE-g-GMA),
the total weight of the polyethylene terephthalate A resin, the polyethylene terephthalate B resin and the ethylene-octene copolymer grafted glycidyl methacrylate is 100 parts,
in some embodiments, the ethylene-octene copolymer grafted with glycidyl methacrylate has a glycidyl methacrylate grafting ratio of 1.2-1.8%.
In some of these embodiments, the polytetrafluoroethylene resin has a number average molecular weight of from 2 to 8 million; further, 3 to 7 ten thousand; further, it is 4 to 6 ten thousand.
In some of the embodiments, the compressive strength of the hollow glass microspheres is 55-65 MPa.
In some of these embodiments, the terminal group of the polyhedral oligomeric silsesquioxane polymer is an epoxy group.
In some of these embodiments, the titanate coupling agent is a monoalkoxy fatty acid titanate coupling agent.
In some of these embodiments, the polyhedral oligomeric silsesquioxane polymer is epoxycyclohexylethyl-POSS and/or glycidyl-POSS.
It is another object of the present invention to provide a process for the preparation of reinforced polyethylene terephthalate compositions.
The preparation method of the reinforced polyethylene terephthalate composition comprises the following steps:
(1) drying the polyethylene terephthalate A resin and the polyethylene terephthalate B resin, and mixing the dried polyethylene terephthalate A resin and the polyethylene terephthalate B resin with the ethylene-octene copolymer grafted glycidyl methacrylate, polytetrafluoroethylene resin, an antioxidant CY and bis (2, 4-dicumylphenyl) pentaerythritol diphosphite (in a stirrer);
(2) mixing the hollow glass beads, the polyhedral oligomeric silsesquioxane polymer, the titanate coupling agent, the hyperbranched polyester polymer and the erucamide (in another stirrer);
(3) and (2) adding the mixed material obtained in the step (1) into a parallel twin-screw extruder through a feeder, adding the mixed material obtained in the step (2) into the parallel twin-screw extruder in the lateral direction (for example, the fourth zone) of the parallel twin-screw extruder (total eight zones), and adding the low-dielectric-constant glass fiber into the parallel twin-screw extruder in the other lateral direction (for example, the third zone) of the parallel twin-screw extruder for melt extrusion and granulation.
In some of the embodiments, the polyethylene terephthalate A resin and the polyethylene terephthalate B resin are dried at a temperature of 90 to 120 ℃ for 4 to 8 hours in the step (1); preferably, the polyethylene terephthalate A resin and the polyethylene terephthalate B resin are dried at a temperature of 100-110 ℃ for 4-6 hours in the step (1).
In some of the embodiments, the process parameters of the parallel twin-screw extruder in step (3) include: the temperature of the first zone is 260-280 ℃, the temperature of the second zone is 265-285 ℃, the temperature of the third zone is 265-285 ℃, the temperature of the fourth zone is 270-290 ℃, the temperature of the fifth zone is 270-290 ℃, the temperature of the sixth zone is 265-285 ℃, the temperature of the seventh zone is 265-285 ℃, the temperature of the eighth zone is 265-285 ℃, the temperature of the die head is 265-285 ℃ and the rotation speed of the screw is 265-285 rpm. Preferably, the process parameters of the parallel twin-screw extruder in the step (3) comprise: the temperature of the first zone is 265-275 ℃, the temperature of the second zone is 270-280 ℃, the temperature of the third zone is 270-280 ℃, the temperature of the fourth zone is 275-285 ℃, the temperature of the fifth zone is 275-285 ℃, the temperature of the sixth zone is 270-280 ℃, the temperature of the seventh zone is 270-280 ℃, the temperature of the eighth zone is 270-280 ℃, the temperature of the die head is 270-280 ℃, and the rotating speed of the screw is 270-280 rpm.
In some of these embodiments, the screw shape of the parallel twin screw extruder is a single thread; the ratio L/D of the length L and the diameter D of the screw of the parallel double-screw extruder is 35-50; preferably, the ratio L/D of the length L of the screw to the diameter D of the screw is 35 to 45.
The screw of the parallel double-screw extruder is provided with more than 1 (including 1) meshing block area and more than 1 (including 1) reverse thread area. Preferably, the screw is provided with 2 meshing block areas and 1 reverse thread area.
In some embodiments, in step (1) and/or step (2), the mixing step is performed by using a stirrer, wherein the stirrer is a high-speed stirrer and the rotating speed is 500-1500 rpm.
The principle of the reinforced polyethylene terephthalate composition of the present invention is as follows:
in order to solve the defect of poor compatibility between PET and low dielectric filler hollow glass microspheres (HGS), polyhedral oligomeric silsesquioxane Polymers (POSS) and low dielectric constant glass fibers (D glass fibers) in a reinforced polyethylene glycol terephthalate composition, the invention improves the compatibility between the PET and the low dielectric filler by adding a compatilizer POE-g-GMA, improves the compatibility between the PET and the low dielectric filler by adding a titanate coupling agent, and improves the effect of coating the low dielectric filler by the titanate coupling agent and the processing performance of the PET composition by adding a lubricating dispersant hyperbranched polyester polymer and erucamide. According to the invention, the addition of the auxiliary agent improves the interface bonding force and compatibility between PET and the low dielectric filler, and simultaneously improves the mechanical property and processability of the PET composition, so that the reinforced polyethylene glycol terephthalate composition with excellent comprehensive properties is prepared.
The intrinsic viscosity of the polyethylene terephthalate A resin adopted by the invention is 0.62-0.67 dL/g, the processability is good, and the mechanical property is general, while the intrinsic viscosity of the polyethylene terephthalate B resin adopted by the invention is 1.0-1.1 dL/g, the mechanical property is good, but the processability is general, so the polyethylene terephthalate composition with excellent mechanical property and processability is obtained by compounding the two PET resins.
Epoxy groups in the compatilizer POE-g-GMA adopted by the invention can react with terminal hydroxyl groups of PET, terminal hydroxyl groups of hollow glass beads and a coupling agent coating the low dielectric filler, so that the compatibility between the PET and the low dielectric filler is improved, and the POE-g-GMA can also improve the impact property of the PET composition.
The hollow glass micro-beads (HGS) adopted by the invention are hollow spherical powdery inorganic nonmetallic materials, the main components of the hollow spherical powdery inorganic nonmetallic materials are soda lime borosilicate glass, and inert gases such as thin nitrogen, carbon dioxide and the like are filled in the cavity of the hollow spherical inorganic nonmetallic materials, so that the dielectric constant of the hollow glass micro-beads is only 1.2-1.5 (1 GHz).
The polyhedral oligomeric silsesquioxane Polymer (POSS) adopted by the invention has a highly symmetrical cubic cage type framework, the intrinsic nanopores of the POSS enable the POSS to have a very low dielectric constant which is 2.1-2.5 (1GHz), the dielectric constant of the blend can be effectively reduced, the mechanical property of the blend is not obviously influenced, the POSS has good compatibility with a base material resin, the particle agglomeration can be effectively reduced, meanwhile, inorganic cores composed of silicon and oxygen are contained in POSS molecules, the POSS has good thermal stability, the molecular size of the POSS is large, and the POSS has the effect of blocking the movement of polymer molecule chain segments, so that the addition of the POSS is beneficial to improving the thermal stability of the PET composition.
The effect of the titanate coupling agent used in the invention is attributed to the effect on the interface, i.e. it can form chemical bridge bonds between the filler of the inorganic blend and the organic polymer, and the coupling is carried out by the direct chemical action of the alkoxy groups of the titanate coupling agent and the trace hydroxyl groups adsorbed on the surface of the low-dielectric filler, and the compatibility of the organic phase of the titanate coupling agent and PET is good.
The polytetrafluoroethylene resin adopted by the invention is mainly used as a modifier and a release agent of the composition by utilizing the special lubricating property and non-stick property, and the dielectric constant of the polytetrafluoroethylene resin is lower and is only 2.0(1 GHz).
The hyperbranched polyester polymer adopted by the invention is a high temperature resistant dendritic structural additive with a polyester structural unit, which can obviously improve the processing fluidity of the PET composition and the coating effect of the coupling agent, improve the dispersion degree of the low dielectric filler in the PET composition product, effectively solve the surface defect of the product and simultaneously improve the surface glossiness of the product.
The erucamide adopted by the invention has higher melting point and good thermal stability, can obviously improve the processing fluidity of the PET composition and the coating effect of the coupling agent, improves the dispersion degree of the low dielectric filler in the PET composition system, and has little influence on the mechanical property of the PET composition.
The antioxidant CY (1,3, 5-tri (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) -1,3, 5-triazine-2, 4,6- (1H,3H,5H) -trione) adopted by the invention has excellent hydrolysis resistance, and can effectively inhibit thermal oxidation and degradation of the polymer in the processing and using processes at high temperature; the bis (2, 4-dicumylphenyl) pentaerythritol diphosphite adopted by the invention has the main characteristics of high molecular weight, high steric hindrance, low volatilization and high phosphorus content (7.3%), is the highest molecular weight in all current commercial phosphite antioxidant products, has excellent high-temperature stability and migration precipitation resistance, can effectively prevent the polymer from being easily yellowed or generating black spots in the high-temperature processing process, and provides effective high-temperature degradation protection.
Compared with the prior art, the invention has the following beneficial effects:
aiming at the defect of poor compatibility of PET, low dielectric filler hollow glass microspheres (HGS), polyhedral oligomeric silsesquioxane Polymers (POSS) and low dielectric constant glass fibers (D glass fibers) in the existing reinforced polyethylene terephthalate composition, the compatibility between PET and the low dielectric filler is improved by adding compatilizer POE-g-GMA, titanate coupling agent, lubricating dispersant hyperbranched polyester polymer and erucamide, the processability of the composition is improved by adopting low molecular weight PTFE (polytetrafluoroethylene), the dielectric constant of the composition is reduced by compounding HGS, POSS and PTFE, the yellowing phenomenon and the thermal stability of the reinforced polyethylene terephthalate composition in the blending processing process are improved by compounding antioxidant CY and bis (2, 4-dicumylphenyl) pentaerythritol diphosphite, and the raw material components are mutually matched to ensure that the reinforced polyethylene terephthalate composition has excellent mechanical property and is added with bis (2, 4-dicumylphenyl) pentaerythritol diphosphite The material has the advantages of high work performance and low dielectric constant, and can be applied to shells, cladding, protective materials and the like of 5G base stations, micro base station systems, data communication terminals, antennas and radio frequency modules.
The preparation method of the reinforced polyethylene glycol terephthalate composition provided by the invention has the advantages of simple process, easiness in control and low requirement on equipment, and the used equipment is general polymer processing equipment, so that the investment is low, and the preparation method is favorable for industrial production.
Drawings
FIG. 1 is a flow diagram of a process for preparing a reinforced polyethylene terephthalate composition according to one embodiment of the present invention.
Detailed Description
Experimental procedures according to the invention, in which no particular conditions are specified in the following examples, are generally carried out under conventional conditions, or under conditions recommended by the manufacturer. The various chemicals used in the examples are commercially available.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
The terms "comprising" and "having," and any variations thereof, are intended to cover non-exclusive inclusions. For example, a process, method, apparatus, article, or device that comprises a list of steps is not limited to only those steps or modules listed, but may alternatively include other steps not listed or inherent to such process, method, article, or device.
The "plurality" referred to in the present invention means two or more. "and/or" describes the association relationship of the associated objects, meaning that there may be three relationships, e.g., a and/or B, which may mean: a exists alone, A and B exist simultaneously, and B exists alone. The character "/" generally indicates that the former and latter associated objects are in an "or" relationship.
The present invention will be described in further detail with reference to specific examples.
The reaction mechanism of the reinforced polyethylene terephthalate composition according to an embodiment of the present invention is as follows (see fig. 1 for a flow chart of the preparation process):
wherein R is1POE-g-GMA or POSS, R2PET, HGS or coupling agent; as can be seen from the above reaction formula, the epoxy groups of POE-g-GMA and POSS can react with the terminal hydroxyl groups of PET, HGS or coupling agent, thereby improving the compatibility between PET and low dielectric filler.
The examples of the invention and the comparative examples used the following raw materials:
polyethylene terephthalate A resin having an intrinsic viscosity of 0.64dL/g selected from DuPont, USA;
a polyethylene terephthalate B resin having an intrinsic viscosity of 1.05dL/g selected from DuPont, USA;
the ethylene-octene copolymer is grafted with glycidyl methacrylate, the grafting ratio of the glycidyl methacrylate is 1.5 percent, and the ethylene-octene copolymer is selected from new molecular material science and technology company of Nantong Ri;
the hollow glass microspheres have the compressive strength of 60MPa and are selected from New Material science and technology Limited company of Middling Steel group Maanshan Ministry;
the hollow glass microspheres have the compressive strength of 30MPa and are selected from New Material science and technology Limited company of Middling Steel group Maanshan Ministry;
epoxycyclohexylethyl-POSS selected from the American company Hybrid Plastics;
glycidyl-POSS selected from Hybrid Plastics, USA;
low dielectric constant glass fiber having a dielectric constant of 4.4 selected from the group consisting of Taishan glass fiber, Inc.;
common glass fiber with dielectric constant of 6.3 selected from Taishan glass fiber Co;
mono-alkoxy fatty acid titanate coupling agent (type is titanate coupling agent TC-130), selected from chemical auxiliary oil material factory of Tianchang city;
polytetrafluoroethylene resin having a number average molecular weight of 5 ten thousand selected from the large-scale fluoroplastics (China) Co., Ltd;
polytetrafluoroethylene resin having a number average molecular weight of 200 ten thousand selected from the large-scale fluoroplastics (China) Co., Ltd;
the hyperbranched polyester polymer (the type is CYD-C600), the thermal decomposition temperature is more than or equal to 350 ℃, and the hyperbranched polyester polymer is selected from Wehaichen molecular new materials GmbH;
erucamide, selected from the group consisting of Haimengteng New materials science and technology, Inc.;
antioxidant CY selected from Cyanote, USA;
bis (2, 4-dicumylphenyl) pentaerythritol diphosphite selected from Dover corporation, USA.
The present invention will be described in detail with reference to specific examples.
Example 1:
the embodiment provides a reinforced polyethylene terephthalate composition, which is prepared from the following raw materials in parts by weight:
60 parts of polyethylene terephthalate A resin,
20 parts of polyethylene terephthalate B resin,
20 parts of ethylene-octene copolymer grafted glycidyl methacrylate,
the total weight of the polyethylene terephthalate A resin, the polyethylene terephthalate B resin and the ethylene-octene copolymer grafted glycidyl methacrylate is 100 parts,
the preparation method of the reinforced polyethylene terephthalate composition comprises the following steps:
(1) drying the polyethylene terephthalate A resin and the polyethylene terephthalate B resin at the temperature of 90 ℃ for 8 hours, cooling, adding the cooled polyethylene terephthalate A resin, the cooled polyethylene terephthalate B resin, the ethylene-octene copolymer grafted glycidyl methacrylate, polytetrafluoroethylene resin, an antioxidant CY and bis (2, 4-dicumylphenyl) pentaerythritol diphosphite into a stirrer for mixing;
(2) adding the hollow glass beads, epoxy cyclohexyl ethyl-POSS, monoalkoxyl fatty acid titanate coupling agent, hyperbranched polyester polymer and erucamide into another stirrer for mixing;
(3) adding the mixed material obtained in the step (1) into a parallel twin-screw extruder through a feeder, adding the mixed material obtained in the step (2) into the parallel twin-screw extruder (totally eight zones) in a lateral direction (such as a fourth zone), and adding low-dielectric-constant glass fibers into the parallel twin-screw extruder in another lateral direction (such as a third zone) for melt extrusion and granulation, wherein the process parameters comprise: the temperature in the first zone was 260 ℃, the temperature in the second zone was 265 ℃, the temperature in the third zone was 265 ℃, the temperature in the fourth zone was 270 ℃, the temperature in the fifth zone was 270 ℃, the temperature in the sixth zone was 265 ℃, the temperature in the seventh zone was 265 ℃, the temperature in the eighth zone was 265 ℃, the temperature in the die head was 265 ℃ and the screw speed was 200 rpm.
The screw of the parallel double-screw extruder is in a single-thread shape, the ratio L/D of the length L and the diameter D of the screw is 35, and the screw is provided with 2 meshing block areas and 1 back-thread area; the stirrer in the step (1) and the step (2) is a high-speed stirrer, and the rotating speed is 1000 revolutions per minute.
Example 2:
the embodiment provides a reinforced polyethylene terephthalate composition, which is prepared from the following raw materials in parts by weight:
93 parts of polyethylene terephthalate A resin,
5 parts of polyethylene terephthalate B resin,
2 parts of ethylene-octene copolymer grafted glycidyl methacrylate,
the total weight of the polyethylene terephthalate A resin, the polyethylene terephthalate B resin and the ethylene-octene copolymer grafted glycidyl methacrylate is 100 parts,
the preparation method of the reinforced polyethylene terephthalate composition comprises the following steps:
(1) drying the polyethylene terephthalate A resin and the polyethylene terephthalate B resin at the temperature of 120 ℃ for 4 hours, cooling, adding the cooled polyethylene terephthalate A resin, the cooled polyethylene terephthalate B resin, the ethylene-octene copolymer grafted glycidyl methacrylate, polytetrafluoroethylene resin, an antioxidant CY and bis (2, 4-dicumylphenyl) pentaerythritol diphosphite into a stirrer for mixing;
(2) adding the hollow glass beads, glycidyl-POSS, monoalkoxyl fatty acid titanate coupling agent, hyperbranched polyester polymer and erucamide into another stirrer for mixing;
(3) adding the mixed material obtained in the step (1) into a parallel twin-screw extruder through a feeder, adding the mixed material obtained in the step (2) into the parallel twin-screw extruder (totally eight zones) in a lateral direction (such as a fourth zone), and adding low-dielectric-constant glass fibers into the parallel twin-screw extruder in another lateral direction (such as a third zone) for melt extrusion and granulation, wherein the process parameters comprise: the temperature of the first zone is 280 ℃, the temperature of the second zone is 285 ℃, the temperature of the third zone is 285 ℃, the temperature of the fourth zone is 290 ℃, the temperature of the fifth zone is 290 ℃, the temperature of the sixth zone is 285 ℃, the temperature of the seventh zone is 285 ℃, the temperature of the eighth zone is 285 ℃, the temperature of the die head is 285 ℃ and the rotating speed of the screw is 600 rpm.
The screw of the parallel double-screw extruder is in a single-thread shape, the ratio L/D of the length L and the diameter D of the screw is 50, and the screw is provided with 2 meshing block areas and 1 back-thread area; the stirrer in the step (1) and the step (2) is a high-speed stirrer, and the rotating speed is 1000 revolutions per minute.
Example 3:
the embodiment provides a reinforced polyethylene terephthalate composition, which is prepared from the following raw materials in parts by weight:
68 parts of polyethylene terephthalate A resin,
16 parts of polyethylene terephthalate B resin,
16 parts of ethylene-octene copolymer grafted glycidyl methacrylate,
the total weight of the polyethylene terephthalate A resin, the polyethylene terephthalate B resin and the ethylene-octene copolymer grafted glycidyl methacrylate is 100 parts,
the preparation method of the reinforced polyethylene terephthalate composition comprises the following steps:
(1) drying the polyethylene terephthalate A resin and the polyethylene terephthalate B resin at the temperature of 100 ℃ for 6 hours, cooling, adding the cooled polyethylene terephthalate A resin, the cooled polyethylene terephthalate B resin, the ethylene-octene copolymer grafted glycidyl methacrylate, polytetrafluoroethylene resin, an antioxidant CY and bis (2, 4-dicumylphenyl) pentaerythritol diphosphite into a stirrer for mixing;
(2) adding the hollow glass beads, glycidyl-POSS, monoalkoxyl fatty acid titanate coupling agent, hyperbranched polyester polymer and erucamide into another stirrer for mixing;
(3) adding the mixed material obtained in the step (1) into a parallel twin-screw extruder through a feeder, adding the mixed material obtained in the step (2) into the parallel twin-screw extruder (totally eight zones) in a lateral direction (such as a fourth zone), and adding low-dielectric-constant glass fibers into the parallel twin-screw extruder in another lateral direction (such as a third zone) for melt extrusion and granulation, wherein the process parameters comprise: the temperature in the first zone was 265 deg.C, the temperature in the second zone was 270 deg.C, the temperature in the third zone was 270 deg.C, the temperature in the fourth zone was 275 deg.C, the temperature in the fifth zone was 275 deg.C, the temperature in the sixth zone was 270 deg.C, the temperature in the seventh zone was 270 deg.C, the temperature in the eighth zone was 270 deg.C, the temperature in the die head was 270 deg.C, and.
The screw of the parallel double-screw extruder is in a single-thread shape, the ratio L/D of the length L and the diameter D of the screw is 35, and the screw is provided with 2 meshing block areas and 1 back-thread area; the stirrer in the step (1) and the step (2) is a high-speed stirrer, and the rotating speed is 1000 revolutions per minute.
Example 4:
the embodiment provides a reinforced polyethylene terephthalate composition, which is prepared from the following raw materials in parts by weight:
85 parts of polyethylene terephthalate A resin,
9 parts of polyethylene terephthalate B resin,
6 parts of ethylene-octene copolymer grafted glycidyl methacrylate,
the total weight of the polyethylene terephthalate A resin, the polyethylene terephthalate B resin and the ethylene-octene copolymer grafted glycidyl methacrylate is 100 parts,
the preparation method of the reinforced polyethylene terephthalate composition comprises the following steps:
(1) drying the polyethylene terephthalate A resin and the polyethylene terephthalate B resin at the temperature of 110 ℃ for 4 hours, cooling, adding the cooled polyethylene terephthalate A resin, the cooled polyethylene terephthalate B resin, the ethylene-octene copolymer grafted glycidyl methacrylate, polytetrafluoroethylene resin, an antioxidant CY and bis (2, 4-dicumylphenyl) pentaerythritol diphosphite into a stirrer for mixing;
(2) adding the hollow glass beads, glycidyl-POSS, monoalkoxyl fatty acid titanate coupling agent, hyperbranched polyester polymer and erucamide into another stirrer for mixing;
(3) adding the mixed material obtained in the step (1) into a parallel twin-screw extruder through a feeder, adding the mixed material obtained in the step (2) into the parallel twin-screw extruder (totally eight zones) in a lateral direction (such as a fourth zone), and adding low-dielectric-constant glass fibers into the parallel twin-screw extruder in another lateral direction (such as a third zone) for melt extrusion and granulation, wherein the process parameters comprise: the temperature of the first zone was 275 deg.C, the temperature of the second zone was 280 deg.C, the temperature of the third zone was 280 deg.C, the temperature of the fourth zone was 285 deg.C, the temperature of the fifth zone was 285 deg.C, the temperature of the sixth zone was 280 deg.C, the temperature of the seventh zone was 280 deg.C, the temperature of the eighth zone was 280 deg.C, the temperature of the die head was 280 deg.C, and.
The screw of the parallel double-screw extruder is in a single-thread shape, the ratio L/D of the length L and the diameter D of the screw is 45, and the screw is provided with 2 meshing block areas and 1 back-thread area; the stirrer in the step (1) and the step (2) is a high-speed stirrer, and the rotating speed is 1000 revolutions per minute.
Example 5:
the embodiment provides a reinforced polyethylene terephthalate composition, which is prepared from the following raw materials in parts by weight:
72 parts of polyethylene terephthalate A resin,
14 parts of polyethylene terephthalate B resin,
14 parts of ethylene-octene copolymer grafted glycidyl methacrylate,
the total weight of the polyethylene terephthalate A resin, the polyethylene terephthalate B resin and the ethylene-octene copolymer grafted glycidyl methacrylate is 100 parts,
the preparation method of the reinforced polyethylene terephthalate composition comprises the following steps:
(1) drying the polyethylene terephthalate A resin and the polyethylene terephthalate B resin at the temperature of 105 ℃ for 5 hours, cooling, adding the cooled polyethylene terephthalate A resin, the cooled polyethylene terephthalate B resin, the ethylene-octene copolymer grafted glycidyl methacrylate, polytetrafluoroethylene resin, an antioxidant CY and bis (2, 4-dicumylphenyl) pentaerythritol diphosphite into a stirrer for mixing;
(2) adding the hollow glass beads, glycidyl-POSS, monoalkoxyl fatty acid titanate coupling agent, hyperbranched polyester polymer and erucamide into another stirrer for mixing;
(3) adding the mixed material obtained in the step (1) into a parallel twin-screw extruder through a feeder, adding the mixed material obtained in the step (2) into the parallel twin-screw extruder (totally eight zones) in a lateral direction (such as a fourth zone), and adding low-dielectric-constant glass fibers into the parallel twin-screw extruder in another lateral direction (such as a third zone) for melt extrusion and granulation, wherein the process parameters comprise: the temperature in the first zone was 270 ℃, the temperature in the second zone was 275 ℃, the temperature in the third zone was 275 ℃, the temperature in the fourth zone was 280 ℃, the temperature in the fifth zone was 280 ℃, the temperature in the sixth zone was 275 ℃, the temperature in the seventh zone was 275 ℃, the temperature in the eighth zone was 275 ℃, the temperature in the die head was 275 ℃ and the screw speed was 400 rpm.
The screw of the parallel double-screw extruder is in a single-thread shape, the ratio L/D of the length L and the diameter D of the screw is 40, and the screw is provided with 2 meshing block areas and 1 back-thread area; the stirrer in the step (1) and the step (2) is a high-speed stirrer, and the rotating speed is 1000 revolutions per minute.
Example 6:
the embodiment provides a reinforced polyethylene terephthalate composition, which is prepared from the following raw materials in parts by weight:
78 parts of polyethylene terephthalate A resin,
12 parts of polyethylene terephthalate B resin,
10 parts of ethylene-octene copolymer grafted glycidyl methacrylate,
the total weight of the polyethylene terephthalate A resin, the polyethylene terephthalate B resin and the ethylene-octene copolymer grafted glycidyl methacrylate is 100 parts,
the preparation method of the reinforced polyethylene terephthalate composition comprises the following steps:
(1) drying the polyethylene terephthalate A resin and the polyethylene terephthalate B resin at the temperature of 105 ℃ for 5 hours, cooling, adding the cooled polyethylene terephthalate A resin, the cooled polyethylene terephthalate B resin, the ethylene-octene copolymer grafted glycidyl methacrylate, polytetrafluoroethylene resin, an antioxidant CY and bis (2, 4-dicumylphenyl) pentaerythritol diphosphite into a stirrer for mixing;
(2) adding the hollow glass beads, glycidyl-POSS, monoalkoxyl fatty acid titanate coupling agent, hyperbranched polyester polymer and erucamide into another stirrer for mixing;
(3) adding the mixed material obtained in the step (1) into a parallel twin-screw extruder through a feeder, adding the mixed material obtained in the step (2) into the parallel twin-screw extruder (totally eight zones) in a lateral direction (such as a fourth zone), and adding low-dielectric-constant glass fibers into the parallel twin-screw extruder in another lateral direction (such as a third zone) for melt extrusion and granulation, wherein the process parameters comprise: the temperature in the first zone was 270 ℃, the temperature in the second zone was 275 ℃, the temperature in the third zone was 275 ℃, the temperature in the fourth zone was 280 ℃, the temperature in the fifth zone was 280 ℃, the temperature in the sixth zone was 275 ℃, the temperature in the seventh zone was 275 ℃, the temperature in the eighth zone was 275 ℃, the temperature in the die head was 275 ℃ and the screw speed was 400 rpm.
The screw of the parallel double-screw extruder is in a single-thread shape, the ratio L/D of the length L and the diameter D of the screw is 40, and the screw is provided with 2 meshing block areas and 1 back-thread area; the stirrer in the step (1) and the step (2) is a high-speed stirrer, and the rotating speed is 1000 revolutions per minute.
Example 7:
the embodiment provides a reinforced polyethylene terephthalate composition, which is prepared from the following raw materials in parts by weight:
75 parts of polyethylene terephthalate A resin,
13 parts of polyethylene terephthalate B resin,
12 parts of ethylene-octene copolymer grafted glycidyl methacrylate,
the total weight of the polyethylene terephthalate A resin, the polyethylene terephthalate B resin and the ethylene-octene copolymer grafted glycidyl methacrylate is 100 parts,
the preparation method of the reinforced polyethylene terephthalate composition comprises the following steps:
(1) drying the polyethylene terephthalate A resin and the polyethylene terephthalate B resin at the temperature of 105 ℃ for 5 hours, cooling, adding the cooled polyethylene terephthalate A resin, the cooled polyethylene terephthalate B resin, the ethylene-octene copolymer grafted glycidyl methacrylate, polytetrafluoroethylene resin, an antioxidant CY and bis (2, 4-dicumylphenyl) pentaerythritol diphosphite into a stirrer for mixing;
(2) adding the hollow glass beads, glycidyl-POSS, monoalkoxyl fatty acid titanate coupling agent, hyperbranched polyester polymer and erucamide into another stirrer for mixing;
(3) adding the mixed material obtained in the step (1) into a parallel twin-screw extruder through a feeder, adding the mixed material obtained in the step (2) into the parallel twin-screw extruder (totally eight zones) in a lateral direction (such as a fourth zone), and adding low-dielectric-constant glass fibers into the parallel twin-screw extruder in another lateral direction (such as a third zone) for melt extrusion and granulation, wherein the process parameters comprise: the temperature in the first zone was 270 ℃, the temperature in the second zone was 275 ℃, the temperature in the third zone was 275 ℃, the temperature in the fourth zone was 280 ℃, the temperature in the fifth zone was 280 ℃, the temperature in the sixth zone was 275 ℃, the temperature in the seventh zone was 275 ℃, the temperature in the eighth zone was 275 ℃, the temperature in the die head was 275 ℃ and the screw speed was 400 rpm.
The screw of the parallel double-screw extruder is in a single-thread shape, the ratio L/D of the length L and the diameter D of the screw is 40, and the screw is provided with 2 meshing block areas and 1 back-thread area; the stirrer in the step (1) and the step (2) is a high-speed stirrer, and the rotating speed is 1000 revolutions per minute.
Example 8:
the embodiment provides a reinforced polyethylene terephthalate composition, which is prepared from the following raw materials in parts by weight:
75 parts of polyethylene terephthalate A resin,
13 parts of polyethylene terephthalate B resin,
12 parts of ethylene-octene copolymer grafted glycidyl methacrylate,
the total weight of the polyethylene terephthalate A resin, the polyethylene terephthalate B resin and the ethylene-octene copolymer grafted glycidyl methacrylate is 100 parts,
the preparation method of the reinforced polyethylene terephthalate composition comprises the following steps:
(1) drying the polyethylene terephthalate A resin and the polyethylene terephthalate B resin at the temperature of 105 ℃ for 5 hours, cooling, adding the cooled polyethylene terephthalate A resin, the cooled polyethylene terephthalate B resin, the ethylene-octene copolymer grafted glycidyl methacrylate, polytetrafluoroethylene resin, an antioxidant CY and bis (2, 4-dicumylphenyl) pentaerythritol diphosphite into a stirrer for mixing;
(2) adding the hollow glass beads, glycidyl-POSS, monoalkoxyl fatty acid titanate coupling agent, hyperbranched polyester polymer and erucamide into another stirrer for mixing;
(3) adding the mixed material obtained in the step (1) into a parallel twin-screw extruder through a feeder, adding the mixed material obtained in the step (2) into the parallel twin-screw extruder (totally eight zones) in a lateral direction (such as a fourth zone), and adding low-dielectric-constant glass fibers into the parallel twin-screw extruder in another lateral direction (such as a third zone) for melt extrusion and granulation, wherein the process parameters comprise: the temperature in the first zone was 270 ℃, the temperature in the second zone was 275 ℃, the temperature in the third zone was 275 ℃, the temperature in the fourth zone was 280 ℃, the temperature in the fifth zone was 280 ℃, the temperature in the sixth zone was 275 ℃, the temperature in the seventh zone was 275 ℃, the temperature in the eighth zone was 275 ℃, the temperature in the die head was 275 ℃ and the screw speed was 400 rpm.
The shape of a screw of the parallel double-screw extruder is double-thread, the ratio L/D of the length L and the diameter D of the screw is 40, and the screw is provided with 2 meshing block areas and 1 back-thread area; the stirrer in the step (1) and the step (2) is a high-speed stirrer, and the rotating speed is 1000 revolutions per minute.
Comparative example 1:
the comparative example provides a reinforced polyethylene terephthalate composition prepared from the following raw materials in parts by weight:
88 parts of polyethylene terephthalate A resin,
12 parts of ethylene-octene copolymer grafted glycidyl methacrylate,
the total weight of the polyethylene terephthalate A resin and the ethylene-octene copolymer grafted glycidyl methacrylate is 100 parts,
the preparation method of the reinforced polyethylene terephthalate composition comprises the following steps:
(1) drying the polyethylene terephthalate A resin at the temperature of 105 ℃ for 5 hours, cooling, and adding the cooled polyethylene terephthalate A resin, the ethylene-octene copolymer grafted glycidyl methacrylate, polytetrafluoroethylene resin, an antioxidant CY and bis (2, 4-dicumylphenyl) pentaerythritol diphosphite into a stirrer for mixing;
(2) adding the hollow glass beads, glycidyl-POSS, monoalkoxyl fatty acid titanate coupling agent, hyperbranched polyester polymer and erucamide into another stirrer for mixing;
(3) adding the mixed material obtained in the step (1) into a parallel twin-screw extruder through a feeder, adding the mixed material obtained in the step (2) into the parallel twin-screw extruder (totally eight zones) in a lateral direction (such as a fourth zone), and adding low-dielectric-constant glass fibers into the parallel twin-screw extruder in another lateral direction (such as a third zone) for melt extrusion and granulation, wherein the process parameters comprise: the temperature in the first zone was 270 ℃, the temperature in the second zone was 275 ℃, the temperature in the third zone was 275 ℃, the temperature in the fourth zone was 280 ℃, the temperature in the fifth zone was 280 ℃, the temperature in the sixth zone was 275 ℃, the temperature in the seventh zone was 275 ℃, the temperature in the eighth zone was 275 ℃, the temperature in the die head was 275 ℃ and the screw speed was 400 rpm.
The screw of the parallel double-screw extruder is in a single-thread shape, the ratio L/D of the length L and the diameter D of the screw is 40, and the screw is provided with 2 meshing block areas and 1 back-thread area; the stirrer in the step (1) and the step (2) is a high-speed stirrer, and the rotating speed is 1000 revolutions per minute.
Comparative example 2:
the comparative example provides a reinforced polyethylene terephthalate composition prepared from the following raw materials in parts by weight:
75 parts of polyethylene terephthalate A resin,
13 parts of polyethylene terephthalate B resin,
12 parts of ethylene-octene copolymer grafted glycidyl methacrylate,
the total weight of the polyethylene terephthalate A resin, the polyethylene terephthalate B resin and the ethylene-octene copolymer grafted glycidyl methacrylate is 100 parts,
the preparation method of the reinforced polyethylene terephthalate composition comprises the following steps:
(1) drying the polyethylene terephthalate A resin and the polyethylene terephthalate B resin at the temperature of 105 ℃ for 5 hours, cooling, adding the cooled polyethylene terephthalate A resin, the cooled polyethylene terephthalate B resin, the ethylene-octene copolymer grafted glycidyl methacrylate, polytetrafluoroethylene resin, an antioxidant CY and bis (2, 4-dicumylphenyl) pentaerythritol diphosphite into a stirrer for mixing;
(2) adding the hollow glass beads, glycidyl-POSS, monoalkoxyl fatty acid titanate coupling agent, hyperbranched polyester polymer and erucamide into another stirrer for mixing;
(3) adding the mixed material obtained in the step (1) into a parallel twin-screw extruder through a feeder, adding the mixed material obtained in the step (2) into the parallel twin-screw extruder (totally eight zones) in a lateral direction (such as a fourth zone), and adding low-dielectric-constant glass fibers into the parallel twin-screw extruder in another lateral direction (such as a third zone) for melt extrusion and granulation, wherein the process parameters comprise: the temperature in the first zone was 270 ℃, the temperature in the second zone was 275 ℃, the temperature in the third zone was 275 ℃, the temperature in the fourth zone was 280 ℃, the temperature in the fifth zone was 280 ℃, the temperature in the sixth zone was 275 ℃, the temperature in the seventh zone was 275 ℃, the temperature in the eighth zone was 275 ℃, the temperature in the die head was 275 ℃ and the screw speed was 400 rpm.
The screw of the parallel double-screw extruder is in a single-thread shape, the ratio L/D of the length L and the diameter D of the screw is 40, and the screw is provided with 2 meshing block areas and 1 back-thread area; the stirrer in the step (1) and the step (2) is a high-speed stirrer, and the rotating speed is 1000 revolutions per minute.
Comparative example 3:
the comparative example provides a reinforced polyethylene terephthalate composition prepared from the following raw materials in parts by weight:
75 parts of polyethylene terephthalate A resin,
13 parts of polyethylene terephthalate B resin,
12 parts of ethylene-octene copolymer grafted glycidyl methacrylate,
the total weight of the polyethylene terephthalate A resin, the polyethylene terephthalate B resin and the ethylene-octene copolymer grafted glycidyl methacrylate is 100 parts,
the preparation method of the reinforced polyethylene terephthalate composition comprises the following steps:
(1) drying the polyethylene terephthalate A resin and the polyethylene terephthalate B resin at the temperature of 105 ℃ for 5 hours, cooling, adding the cooled polyethylene terephthalate A resin, the cooled polyethylene terephthalate B resin, the ethylene-octene copolymer grafted glycidyl methacrylate, polytetrafluoroethylene resin, an antioxidant CY and bis (2, 4-dicumylphenyl) pentaerythritol diphosphite into a stirrer for mixing;
(2) adding the monoalkoxy fatty acid titanate coupling agent, the hyperbranched polyester polymer and the erucamide into another stirrer for mixing;
(3) adding the mixed material obtained in the step (1) into a parallel twin-screw extruder through a feeder, adding the mixed material obtained in the step (2) into the parallel twin-screw extruder (totally eight zones) in a lateral direction (such as a fourth zone), and adding low-dielectric-constant glass fibers into the parallel twin-screw extruder in another lateral direction (such as a third zone) for melt extrusion and granulation, wherein the process parameters comprise: the temperature in the first zone was 270 ℃, the temperature in the second zone was 275 ℃, the temperature in the third zone was 275 ℃, the temperature in the fourth zone was 280 ℃, the temperature in the fifth zone was 280 ℃, the temperature in the sixth zone was 275 ℃, the temperature in the seventh zone was 275 ℃, the temperature in the eighth zone was 275 ℃, the temperature in the die head was 275 ℃ and the screw speed was 400 rpm.
The screw of the parallel double-screw extruder is in a single-thread shape, the ratio L/D of the length L and the diameter D of the screw is 40, and the screw is provided with 2 meshing block areas and 1 back-thread area; the stirrer in the step (1) and the step (2) is a high-speed stirrer, and the rotating speed is 1000 revolutions per minute.
Comparative example 4:
the comparative example provides a reinforced polyethylene terephthalate composition prepared from the following raw materials in parts by weight:
75 parts of polyethylene terephthalate A resin,
13 parts of polyethylene terephthalate B resin,
12 parts of ethylene-octene copolymer grafted glycidyl methacrylate,
the total weight of the polyethylene terephthalate A resin, the polyethylene terephthalate B resin and the ethylene-octene copolymer grafted glycidyl methacrylate is 100 parts,
the preparation method of the reinforced polyethylene terephthalate composition comprises the following steps:
(1) drying the polyethylene terephthalate A resin and the polyethylene terephthalate B resin at the temperature of 105 ℃ for 5 hours, cooling, adding the cooled polyethylene terephthalate A resin, the cooled polyethylene terephthalate B resin, the ethylene-octene copolymer grafted glycidyl methacrylate, polytetrafluoroethylene resin, an antioxidant CY and bis (2, 4-dicumylphenyl) pentaerythritol diphosphite into a stirrer for mixing;
(2) adding the hollow glass beads, glycidyl-POSS, monoalkoxyl fatty acid titanate coupling agent, hyperbranched polyester polymer and erucamide into another stirrer for mixing;
(3) adding the mixed material obtained in the step (1) into a parallel twin-screw extruder through a feeder, adding the mixed material obtained in the step (2) into the parallel twin-screw extruder (totally eight zones) in a lateral direction (such as a fourth zone), and adding low-dielectric-constant glass fibers into the parallel twin-screw extruder in another lateral direction (such as a third zone) for melt extrusion and granulation, wherein the process parameters comprise: the temperature in the first zone was 270 ℃, the temperature in the second zone was 275 ℃, the temperature in the third zone was 275 ℃, the temperature in the fourth zone was 280 ℃, the temperature in the fifth zone was 280 ℃, the temperature in the sixth zone was 275 ℃, the temperature in the seventh zone was 275 ℃, the temperature in the eighth zone was 275 ℃, the temperature in the die head was 275 ℃ and the screw speed was 400 rpm.
The screw of the parallel double-screw extruder is in a single-thread shape, the ratio L/D of the length L and the diameter D of the screw is 40, and the screw is provided with 2 meshing block areas and 1 back-thread area; the stirrer in the step (1) and the step (2) is a high-speed stirrer, and the rotating speed is 1000 revolutions per minute.
Comparative example 5:
the comparative example provides a reinforced polyethylene terephthalate composition prepared from the following raw materials in parts by weight:
75 parts of polyethylene terephthalate A resin,
13 parts of polyethylene terephthalate B resin,
12 parts of ethylene-octene copolymer grafted glycidyl methacrylate,
the total weight of the polyethylene terephthalate A resin, the polyethylene terephthalate B resin and the ethylene-octene copolymer grafted glycidyl methacrylate is 100 parts,
the preparation method of the reinforced polyethylene terephthalate composition comprises the following steps:
(1) drying the polyethylene terephthalate A resin and the polyethylene terephthalate B resin at the temperature of 105 ℃ for 5 hours, cooling, adding the cooled polyethylene terephthalate A resin, the cooled polyethylene terephthalate B resin, the ethylene-octene copolymer grafted glycidyl methacrylate, polytetrafluoroethylene resin, an antioxidant CY and bis (2, 4-dicumylphenyl) pentaerythritol diphosphite into a stirrer for mixing;
(2) adding the hollow glass beads, glycidyl-POSS and monoalkoxyl fatty acid titanate coupling agent into another stirrer for mixing;
(3) adding the mixed material obtained in the step (1) into a parallel twin-screw extruder through a feeder, adding the mixed material obtained in the step (2) into the parallel twin-screw extruder (totally eight zones) in a lateral direction (such as a fourth zone), and adding low-dielectric-constant glass fibers into the parallel twin-screw extruder in another lateral direction (such as a third zone) for melt extrusion and granulation, wherein the process parameters comprise: the temperature in the first zone was 270 ℃, the temperature in the second zone was 275 ℃, the temperature in the third zone was 275 ℃, the temperature in the fourth zone was 280 ℃, the temperature in the fifth zone was 280 ℃, the temperature in the sixth zone was 275 ℃, the temperature in the seventh zone was 275 ℃, the temperature in the eighth zone was 275 ℃, the temperature in the die head was 275 ℃ and the screw speed was 400 rpm.
The screw of the parallel double-screw extruder is in a single-thread shape, the ratio L/D of the length L and the diameter D of the screw is 40, and the screw is provided with 2 meshing block areas and 1 back-thread area; the stirrer in the step (1) and the step (2) is a high-speed stirrer, and the rotating speed is 1000 revolutions per minute.
Comparative example 6:
the comparative example provides a reinforced polyethylene terephthalate composition prepared from the following raw materials in parts by weight:
75 parts of polyethylene terephthalate A resin,
13 parts of polyethylene terephthalate B resin,
12 parts of ethylene-octene copolymer grafted glycidyl methacrylate,
the total weight of the polyethylene terephthalate A resin, the polyethylene terephthalate B resin and the ethylene-octene copolymer grafted glycidyl methacrylate is 100 parts,
the preparation method of the reinforced polyethylene terephthalate composition comprises the following steps:
(1) drying the polyethylene terephthalate A resin and the polyethylene terephthalate B resin at the temperature of 105 ℃ for 5 hours, cooling, adding the cooled polyethylene terephthalate A resin, the cooled polyethylene terephthalate B resin, the ethylene-octene copolymer grafted glycidyl methacrylate, polytetrafluoroethylene resin, an antioxidant CY and bis (2, 4-dicumylphenyl) pentaerythritol diphosphite into a stirrer for mixing;
(2) adding the hollow glass beads, glycidyl-POSS, monoalkoxyl fatty acid titanate coupling agent, hyperbranched polyester polymer and erucamide into another stirrer for mixing;
(3) adding the mixed material obtained in the step (1) into a parallel double-screw extruder through a feeder, adding the mixed material obtained in the step (2) into the parallel double-screw extruder (totally eight zones) (for example, a fourth zone), and adding common glass fiber into the parallel double-screw extruder (totally eight zones) (for example, a third zone) in the other side direction (for example, the third zone) for melt extrusion and granulation, wherein the process parameters comprise: the temperature in the first zone was 270 ℃, the temperature in the second zone was 275 ℃, the temperature in the third zone was 275 ℃, the temperature in the fourth zone was 280 ℃, the temperature in the fifth zone was 280 ℃, the temperature in the sixth zone was 275 ℃, the temperature in the seventh zone was 275 ℃, the temperature in the eighth zone was 275 ℃, the temperature in the die head was 275 ℃ and the screw speed was 400 rpm.
The screw of the parallel double-screw extruder is in a single-thread shape, the ratio L/D of the length L and the diameter D of the screw is 40, and the screw is provided with 2 meshing block areas and 1 back-thread area; the stirrer in the step (1) and the step (2) is a high-speed stirrer, and the rotating speed is 1000 revolutions per minute.
The following is a list of raw material compositions of examples and comparative examples (table 1).
TABLE 1 summary of the composition parts by weight of the raw materials of the examples and comparative examples
Remarking: a, changing a screw structure; b, the compressive strength of the hollow glass beads is 30 MPa; c, the number average molecular weight of the polytetrafluoroethylene resin is 200 ten thousand; d, the D glass fiber is changed into the common glass fiber, and the dielectric constant of the glass fiber is 6.3.
Wherein, the antioxidant CY and the bis (2, 4-dicumylphenyl) pentaerythritol diphosphite of the above examples and comparative examples are added in an amount of 0.2 part.
The reinforced polyethylene terephthalate compositions prepared in the above examples and comparative examples were subjected to the following performance tests:
tensile property: testing according to GB/T1040-2006 standard, wherein the stretching speed is 50 mm/min;
impact properties: according to the test of GB/T1843-2008 standard, the thickness of the sample strip is 4 mm;
melt index: testing according to GB/T3682-2000 standard, wherein the testing temperature is 285 ℃, and the load is 2.16 kg;
dielectric constant: the test frequency is 1GHz according to the test of GB/T5597-1999 standard. For the present composition, the lower the dielectric constant, the better.
The results of the performance tests are shown in table 2.
TABLE 2 Properties of reinforced polyethylene terephthalate compositions of examples and comparative examples
In examples 1 to 7, the addition amounts of PET-A, PET-B, POE-g-GMA, HGS, POSS, D glass fiber, titanate coupling agent, PTFE, hyperbranched polyester polymer, and erucamide were adjusted, and it can be seen from the table that as the addition amount of PET increases (or the addition amount of POE-g-GMA decreases), the tensile strength of the PET tends to increase, while the impact strength and melt index tend to decrease, mainly because the tensile strength of the PET substrate is higher; the POE-g-GMA has lower tensile strength and better processing fluidity and plays a toughening role; meanwhile, as the addition amounts of HGS and POSS are reduced, the dielectric constant thereof shows a tendency to increase. By comparison, the overall performance of example 7 is best.
Example 7 in comparison to example 8, the screw shape of the parallel twin screw extruder of example 8 was a twin screw flight and the screw shape of the parallel twin screw extruder of example 7 was a single screw flight, and by comparison it was found that the reinforced polyethylene terephthalate composition prepared using the screw parameters of the parallel twin screw extruder described in example 7 had better tensile strength, notched impact strength and melt index, and lower dielectric constant.
Example 7 comparative example 1 compared to comparative example 1, comparative example 1 did not use a higher intrinsic viscosity polyethylene terephthalate B resin, and therefore both the tensile strength and notched impact strength of comparative example 1 were lower than those of example 7; example 7 compared with comparative example 2, the compressive strength of the hollow glass bead used in comparative example 2 was 30MPa, while the compressive strength of the hollow glass bead used in example 7 was 60MPa, and since the compressive strength of the hollow glass bead used in comparative example 2 was low, the hollow glass bead was easily broken during the parallel twin-screw extruder processing, and lost the characteristics of reinforcement and low dielectric constant, resulting in a great decrease in mechanical properties and an increase in dielectric constant; example 7 compared to comparative example 3, the dielectric constant of the composition was higher than that of example 7 since comparative example 3 did not add HGS and POSS having low dielectric constants; example 7 compared with comparative example 4, the polytetrafluoroethylene resin used in comparative example 4 has a number average molecular weight of 200 ten thousand, is poor in processing fluidity during processing by a parallel twin-screw extruder, and is prone to extrusion swelling to cause composition breaking, and the prepared composition is poorer in tensile strength, notch impact strength and melt index, and higher in dielectric constant; example 7 compared to comparative example 5, since comparative example 5 does not add the hyperbranched polyester polymer and erucamide, and the two lubricating dispersants can function as the titanate coupling agent for dispersing, the monoalkoxy fatty acid titanate coupling agent has a poor effect of coating the hollow glass microspheres and the glycidyl-POSS, the interfacial bonding force and compatibility of the PET composition with the low dielectric filler are reduced, and the processability of the composition is deteriorated, so that the composition prepared in comparative example 5 has poorer tensile strength, notched impact strength and melt index, and higher dielectric constant; example 7 in comparison with comparative example 6, comparative example 6 uses a common glass fiber having a dielectric constant of 6.3, so that the dielectric constant of the prepared composition is much higher than that of example 7.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. The reinforced polyethylene terephthalate composition is characterized by being prepared from the following raw materials in parts by weight:
the intrinsic viscosity of the polyethylene terephthalate A resin is 0.62-0.67 dL/g; the intrinsic viscosity of the polyethylene terephthalate B resin is 1.0-1.1 dL/g; the compressive strength of the hollow glass beads is not lower than 53 MPa; the number average molecular weight of the polytetrafluoroethylene resin is 1-10 ten thousand; the dielectric constant of the low-dielectric-constant glass fiber at 1GHz is not higher than 4.5.
2. The reinforced polyethylene terephthalate composition of claim 1, prepared from the following raw materials in parts by weight:
3. the reinforced polyethylene terephthalate composition of claim 2, which is prepared from the following raw materials in parts by weight:
4. the reinforced polyethylene terephthalate composition according to any one of claims 1 to 3, wherein the ethylene-octene copolymer has a glycidyl methacrylate graft ratio of 1.2 to 1.8% to the glycidyl methacrylate; and/or the terminal group of the polyhedral oligomeric silsesquioxane polymer is an epoxy group.
5. The reinforced polyethylene terephthalate composition of any of claims 1-3, wherein the titanate coupling agent is a monoalkoxy fatty acid titanate coupling agent.
6. A process for the preparation of the reinforced polyethylene terephthalate composition according to any of claims 1 to 5, characterized in that it comprises the following steps:
(1) drying the polyethylene terephthalate A resin and the polyethylene terephthalate B resin, and mixing the dried polyethylene terephthalate A resin and the polyethylene terephthalate B resin with the ethylene-octene copolymer grafted glycidyl methacrylate, polytetrafluoroethylene resin, an antioxidant CY and bis (2, 4-dicumylphenyl) pentaerythritol diphosphite;
(2) mixing the hollow glass beads, the polyhedral oligomeric silsesquioxane polymer, the titanate coupling agent, the hyperbranched polyester polymer and the erucamide;
(3) and (3) adding the mixed material obtained in the step (1) into a parallel double-screw extruder through a feeder, adding the mixed material obtained in the step (2) into the parallel double-screw extruder in the lateral direction, adding the low-dielectric-constant glass fiber into the parallel double-screw extruder in the other lateral direction, performing melt extrusion, and granulating.
7. The method according to claim 6, wherein the polyethylene terephthalate A resin and the polyethylene terephthalate B resin are dried at a temperature of 90 to 120 ℃ for 4 to 8 hours in the step (1); preferably, the polyethylene terephthalate A resin and the polyethylene terephthalate B resin are dried for 4 to 6 hours at the temperature of 100 to 110 ℃ in the step (1);
and/or the process parameters of the parallel twin-screw extruder in the step (3) comprise: the temperature of the first zone is 260-280 ℃, the temperature of the second zone is 265-285 ℃, the temperature of the third zone is 265-285 ℃, the temperature of the fourth zone is 270-290 ℃, the temperature of the fifth zone is 270-290 ℃, the temperature of the sixth zone is 265-285 ℃, the temperature of the seventh zone is 265-285 ℃, the temperature of the eighth zone is 265-285 ℃, the temperature of the die head is 265-285 ℃, and the rotation speed of the screw is 265-285 rpm; preferably, the process parameters of the parallel twin-screw extruder in the step (3) comprise: the temperature of the first zone is 265-275 ℃, the temperature of the second zone is 270-280 ℃, the temperature of the third zone is 270-280 ℃, the temperature of the fourth zone is 275-285 ℃, the temperature of the fifth zone is 275-285 ℃, the temperature of the sixth zone is 270-280 ℃, the temperature of the seventh zone is 270-280 ℃, the temperature of the eighth zone is 270-280 ℃, the temperature of the die head is 270-280 ℃, and the rotating speed of the screw is 270-280 rpm.
8. The production method according to claim 6 or 7, wherein the screw shape of the parallel twin-screw extruder is a single-screw thread; and/or the ratio L/D of the length L and the diameter D of the screw of the parallel double-screw extruder is 35-50; and/or more than 1 meshing block area and more than 1 reverse thread area are arranged on the screw of the parallel double-screw extruder.
9. The method according to claim 8, wherein the ratio L/D of the screw length L to the diameter D is 35 to 45; and 2 meshing block areas and 1 reverse thread area are arranged on the screw rod.
10. The method according to claim 6 or 7, wherein in step (1) and/or step (2), the mixing step is performed by using a stirrer with a rotation speed of 500 and 1500 rpm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010317415.7A CN111334007A (en) | 2020-04-21 | 2020-04-21 | Reinforced polyethylene terephthalate composition and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010317415.7A CN111334007A (en) | 2020-04-21 | 2020-04-21 | Reinforced polyethylene terephthalate composition and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111334007A true CN111334007A (en) | 2020-06-26 |
Family
ID=71179285
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010317415.7A Pending CN111334007A (en) | 2020-04-21 | 2020-04-21 | Reinforced polyethylene terephthalate composition and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111334007A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112920555A (en) * | 2021-03-01 | 2021-06-08 | 宁波市青湖弹性体科技有限公司 | TPEE composite material suitable for high-speed extrusion and preparation method thereof |
| US20230000083A1 (en) * | 2021-06-30 | 2023-01-05 | Nan Ya Plastics Corporation | Antibacterial and antifungal polyester laminated structure |
| CN116478513A (en) * | 2023-05-04 | 2023-07-25 | 深圳市英泰格瑞科技有限公司 | Engineering plastic with good dielectric property and processing technology thereof |
| CN117565526A (en) * | 2023-11-15 | 2024-02-20 | 江苏欧西建材科技发展有限公司 | High-strength TPO waterproof coiled material and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104845369A (en) * | 2015-05-11 | 2015-08-19 | 深圳华力兴新材料股份有限公司 | Hyperbranched resin-toughened PPS (polyphenylene sulfite) engineering plastic and preparation method thereof |
| CN105153654A (en) * | 2015-09-14 | 2015-12-16 | 余姚市海盛新材料科技有限公司 | Fiber-reinforced polyester composition and preparation method thereof |
| CN108329692A (en) * | 2018-02-07 | 2018-07-27 | 深圳华力兴新材料股份有限公司 | A kind of polyphenyl thioether resin composition and preparation method of low-k |
-
2020
- 2020-04-21 CN CN202010317415.7A patent/CN111334007A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104845369A (en) * | 2015-05-11 | 2015-08-19 | 深圳华力兴新材料股份有限公司 | Hyperbranched resin-toughened PPS (polyphenylene sulfite) engineering plastic and preparation method thereof |
| CN105153654A (en) * | 2015-09-14 | 2015-12-16 | 余姚市海盛新材料科技有限公司 | Fiber-reinforced polyester composition and preparation method thereof |
| CN108329692A (en) * | 2018-02-07 | 2018-07-27 | 深圳华力兴新材料股份有限公司 | A kind of polyphenyl thioether resin composition and preparation method of low-k |
Non-Patent Citations (2)
| Title |
|---|
| 张成德: ""低分子量聚四氟乙烯的制备"", 《有机氟工业》 * |
| 王文广等: "《聚合物改性原理》", 31 March 2018, 中国轻工业出版 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112920555A (en) * | 2021-03-01 | 2021-06-08 | 宁波市青湖弹性体科技有限公司 | TPEE composite material suitable for high-speed extrusion and preparation method thereof |
| US20230000083A1 (en) * | 2021-06-30 | 2023-01-05 | Nan Ya Plastics Corporation | Antibacterial and antifungal polyester laminated structure |
| CN116478513A (en) * | 2023-05-04 | 2023-07-25 | 深圳市英泰格瑞科技有限公司 | Engineering plastic with good dielectric property and processing technology thereof |
| CN117565526A (en) * | 2023-11-15 | 2024-02-20 | 江苏欧西建材科技发展有限公司 | High-strength TPO waterproof coiled material and preparation method thereof |
| CN117565526B (en) * | 2023-11-15 | 2024-06-07 | 江苏欧西建材科技发展有限公司 | High-strength TPO waterproof coiled material and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111410823A (en) | Reinforced polybutylene terephthalate composition and preparation method thereof | |
| CN111334007A (en) | Reinforced polyethylene terephthalate composition and preparation method thereof | |
| CN111286176A (en) | Liquid crystal polymer composition and preparation method thereof | |
| CN111334039A (en) | Reinforced polyamide 66 composition and method for making same | |
| CN111320848A (en) | Low dielectric constant liquid crystal polymer composition and preparation method thereof | |
| CN111303611A (en) | Reinforced polyphenylene ether composition for 5G and method for preparing same | |
| CN111286166A (en) | Polybutylene terephthalate composition and preparation method thereof | |
| EP3026083B1 (en) | Thermoplastic resin composition, and molded article thereof | |
| CN103044802A (en) | Waterproof and antiflaming PVC (polyvinyl chloride) cable material and preparation technology thereof | |
| CN111423723A (en) | Reinforced polyphenylene sulfide composition for 5G and preparation method thereof | |
| CN111349335A (en) | Reinforced polyamide 6 composition and preparation method thereof | |
| CN111484735A (en) | Polyamide 6 composition and preparation method thereof | |
| CN111320846A (en) | Polyethylene terephthalate composition and preparation method thereof | |
| CN110698839B (en) | High dielectric constant polyphenyl ether/high impact polystyrene composition and preparation method thereof | |
| CN111363351A (en) | Polyamide 66 composition and preparation method thereof | |
| CN111393828A (en) | Low dielectric constant polyphenyl ether composition and preparation method thereof | |
| CN103013101B (en) | Flame-retardant glass fiber-reinforced PA6/PA66 alloy material with high CTI value and high GWIT value | |
| CN113372733A (en) | Low-dielectric-constant liquid crystal composite material and preparation method thereof | |
| CN114213846A (en) | Polyphenylene sulfide resin-based high-frequency low-loss composite material and preparation method and application thereof | |
| CN111793335A (en) | Low-dielectric nano injection molding material | |
| CN109929245B (en) | High-air-tightness PPA composite material and preparation method thereof | |
| CN1204184C (en) | Polyethylene foam insulation composition for telecommunication cable and process for preparing the same | |
| CN111334042A (en) | Low-dielectric-constant polyphenylene sulfide composition and preparation method thereof | |
| CN111040448A (en) | Thermoplastic polyimide cable material for nuclear power aviation | |
| CN114181518B (en) | Nylon composite material with low dielectric constant 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 | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20200626 |