CN112094485A - Polybutylene terephthalate composite material and preparation method thereof - Google Patents

Polybutylene terephthalate composite material and preparation method thereof Download PDF

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CN112094485A
CN112094485A CN202010934728.7A CN202010934728A CN112094485A CN 112094485 A CN112094485 A CN 112094485A CN 202010934728 A CN202010934728 A CN 202010934728A CN 112094485 A CN112094485 A CN 112094485A
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hyperbranched polyester
gas
composite material
polybutylene terephthalate
parts
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朱怀才
谢平
谭善兴
朱怀玉
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Jiangxi Zhongsu New Material Technology Co ltd
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Jiangxi Zhongsu New Material Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
    • C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/01—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to unsaturated polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2451/08—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/04—Ingredients characterised by their shape and organic or inorganic ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • C08K5/134—Phenols containing ester groups
    • C08K5/1345—Carboxylic esters of phenolcarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
    • C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass

Abstract

The invention provides a polybutylene terephthalate composite material and a preparation method thereof. The polybutylene terephthalate composite material is prepared from the following raw materials: 50-70 parts of polybutylene terephthalate, 25-45 parts of reinforcing material, 3-9 parts of hyperbranched polyester copolymer and 0.2-0.8 part of antioxidant; the total weight of all the raw materials is 100 parts; the hyperbranched polyester copolymer is a copolymer of carboxyl-containing hyperbranched polyester acrylate and glycidyl methacrylate; the carboxyl-containing hyperbranched polyester acrylate is obtained by modifying hyperbranched polyester with succinic anhydride, hexamethylene diisocyanate and hydroxyethyl acrylate. The polybutylene terephthalate composite material has low dielectric constant and dielectric loss, excellent mechanical property and processability and high heat resistance.

Description

Polybutylene terephthalate composite material and preparation method thereof
Technical Field
The invention belongs to the technical field of polymer composite materials, and particularly relates to a polybutylene terephthalate composite material and a preparation method thereof.
Background
The 5G era has come, and the polymer industry has also met a completely new era, especially in the field of electronic communications, as mobile communications will become faster, the requirements for the electromagnetic delay rate and the loss rate of mobile phone signals will become higher and higher under the condition of high frequency. Therefore, engineering plastics with low dielectric constant and low dielectric loss will become a new favorite in the 5G era.
Since the advent of the nanometer injection molding material, the nanometer injection molding material is widely used by various major mainstream brand manufacturers of mobile phones, flat panels and notebook computers. Along with the development of 5G electronic information technology, the requirement of electronic communication products on the transmittance of electromagnetic signals becomes higher and higher, so that the research and development of nano injection molding materials with low dielectric property have very important significance for the application of the nano injection molding materials in application ends of mobile phones, base stations, the internet, automobiles and the like.
At present, there are two main methods for reducing the dielectric constant and dielectric loss of polymer materials: firstly, the polarizability of the material is reduced through molecular design; and secondly, forming the nano microporous material containing the air gap. The first method mainly introduces low-polarity polymer materials and is realized by blending, but due to the difference of component composition, the low dielectric effect of the modified product is not obvious, and the modified product has the defect of poor compatibility. The second method mostly adopts a foaming mode, but the comprehensive mechanical property of the material is poor, and the normal use requirement cannot be met.
For example, CN 107365480a discloses a NMT material with high heat resistance and low dielectric constant, which comprises PCT resin, glass fiber, toughening agent, antioxidant and lubricant, and the dielectric constant of the material under the 100MHz test condition is about 2.9. For another example, CN 108102311a discloses a low dielectric PBT/PETG alloy nano injection molding composite material, which comprises 30-50 parts by weight of PBT resin, 30-50 parts by weight of PETG resin, 30-40 parts by weight of glass fiber, 0.2-0.8 part by weight of antioxidant, 1-2 parts by weight of lubricant, 0.3-0.5 part by weight of anti-UV agent and 3-8 parts by weight of compatilizer, and the dielectric constant of the composite material under 100MHz test condition reaches 2.9-3.02. For another example, CN109679304A discloses a PBT/PCT composite material, a preparation method and application thereof. The material is prepared from 30-45 parts of PBT, 4-20 parts of PCT, (5-10 parts of vinyl POSS, MAH) -g-PP and 25-40 parts of a reinforcing material, wherein the dielectric constant of the material under the 100MHz test condition is 2.55-2.96. Although both CN 107365480A, CN 108102311a and CN109679304A disclose that the dielectric constant of the modified composite material is 3.0 or less, the test conditions are the result of the test under the low frequency transmission condition of 1GHz or less, and the signal frequency test of mobile phone communication is usually ≥ 2.5GHz, and at such high frequency, the dielectric constant of the material disclosed in the above patent document is actually much higher than that under the low frequency condition. In addition, although CN109679304A adopts a special space structure of POSS to realize the reduction of dielectric constant, octavinyl POSS-g- (EMA-co-GMA) is realized by extrusion and melt modification grafting, and the graft copolymer has the defects of low grafting rate, unstable grafting and low surface activity, so that the amount of octavinyl POSS-g- (EMA-co-GMA) required to be added is increased to realize lower dielectric constant, and further the integral mechanical and processing performance of the material is poor.
Therefore, there is a need to further develop a nano injection molding composite material having lower dielectric properties and excellent in all properties.
Disclosure of Invention
Based on this, the invention aims to provide a polybutylene terephthalate composite (PBT composite) which has high heat resistance and mechanical strength while having low dielectric constant and dielectric loss.
The specific technical scheme is as follows:
the polybutylene terephthalate composite material is prepared from the following raw materials in parts by weight:
Figure BDA0002671535360000031
the total weight of all the raw materials is 100 parts;
the hyperbranched polyester copolymer is a copolymer of carboxyl-containing hyperbranched polyester acrylate and glycidyl methacrylate;
the carboxyl-containing hyperbranched polyester acrylate is obtained by modifying hyperbranched polyester with succinic anhydride, hexamethylene diisocyanate and hydroxyethyl acrylate.
In some embodiments, the polybutylene terephthalate composite material is prepared from the following raw materials in parts by weight:
Figure BDA0002671535360000032
in some of these embodiments, the parts by weight of the polybutylene terephthalate in the polybutylene terephthalate composite can be 50 parts, 51 parts, 52 parts, 53 parts, 54 parts, 55 parts, 56 parts, 57 parts, 58 parts, 59 parts, 60 parts, 61 parts, 62 parts, 63 parts, 64 parts, 65 parts, 66 parts, 67 parts, 68 parts, 69 parts, or 70 parts.
In some of these embodiments, the weight fraction of the reinforcing material in the polybutylene terephthalate composite can be 25 parts, 26 parts, 27 parts, 28 parts, 29 parts, 30 parts, 31 parts, 32 parts, 33 parts, 34 parts, 35 parts, 36 parts, 37 parts, 38 parts, 39 parts, 40 parts, 41 parts, 42 parts, 43 parts, 44 parts, or 45 parts.
In some of these embodiments, the parts by weight of the hyperbranched polyester copolymer in the polybutylene terephthalate composite can be 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, 5.5 parts, 6 parts, 6.5 parts, 7 parts, 7.5 parts, 8 parts, 8.5 parts, 9 parts.
In some of these embodiments, the weight fraction of the antioxidant in the polybutylene terephthalate composite can be 0.2 parts, 0.25 parts, 0.3 parts, 0.35 parts, 0.4 parts, 0.45 parts, 0.5 parts, 0.55 parts, 0.6 parts, 0.65 parts, 0.7 parts, 0.75 parts, or 0.8 parts.
In some embodiments, the mass ratio of the hyperbranched polyester acrylate containing carboxyl groups to the glycidyl methacrylate is 2-4: 1-2.
In some of these embodiments, the mass ratio of succinic anhydride, hexamethylene diisocyanate, hydroxyethyl acrylate, and hyperbranched polyester is 4-5:7-8:5-6: 1.
In some of these embodiments, the hyperbranched polyester is polymerized from pentaerythritol and dimethylolpropionic acid.
In some of these embodiments, the molar ratio of pentaerythritol to dimethylolpropionic acid is 1:1 to 6.
In some of these embodiments, the molar ratio of pentaerythritol to dimethylolpropionic acid is 1:2 to 4.
In some of these embodiments, the method of making the hyperbranched polyester copolymer comprises the steps of:
reacting the hexamethylene diisocyanate with hydroxyethyl acrylate to obtain an HDI-HEA product;
reacting the hyperbranched polyester with succinic anhydride in a first organic solvent, and then adding the HDI-HEA product into the obtained reaction mixture for reaction to obtain the carboxyl-containing hyperbranched polyester acrylate;
and reacting the carboxyl-containing hyperbranched polyester acrylate, glycidyl methacrylate and a proper amount of polymerization inhibitor to obtain the hyperbranched polyester copolymer.
In some of these examples, the hexamethylene diisocyanate and hydroxyethyl acrylate are reacted at a temperature of 35-45 ℃ for a period of 10-15 hours.
In some of these embodiments, the hyperbranched polyester and succinic anhydride are reacted in the first organic solvent at a temperature of 85-95 ℃ for a time of 4-8 hours.
In some of these examples, the HDI-HEA product is added to the resulting reaction mixture at a temperature of 50 to 60 ℃ for a period of 4 to 8 hours.
In some embodiments, the temperature for reacting the carboxyl-containing hyperbranched polyester acrylate, the glycidyl methacrylate and a proper amount of polymerization inhibitor is 65-75 ℃, and the reaction is carried out until the acid value is stable.
In some of these embodiments, the first organic solvent is acetone.
In some of these embodiments, the polymerization inhibitor is p-hydroxyanisole.
In some of these embodiments, the method of preparing the hyperbranched polyester comprises the steps of: and mixing the pentaerythritol, the dimethylolpropionic acid and a second organic solvent, adding a catalyst, and reacting to obtain the hyperbranched polyester.
In some of these embodiments, the pentaerythritol may be used in an amount of (2.25mol,0.31g), (2.7mol,0.38g), (3.15mol,0.44g), (3.6mol,0.5g), (4.05mol,0.56g), or (4.5mol,0.62g), etc.; the dimethylolpropionic acid may be used in an amount of (6.3mol,0.84g), (7.56mol,1.01g), (8.82mol,1.18g), (10.08mol,1.35g), (11.34mol,1.52g) or (12.6mol,1.68g), etc.
In some embodiments, the temperature of the reaction is 130-150 ℃ and the time is 3-7 hours in the preparation step of the hyperbranched polyester.
In some of these embodiments, the second organic solvent is N, N-dimethylacetamide.
In some of these embodiments, the catalyst is toluene sulfonic acid, which may be used in an amount of 0.01g, 0.02g, 0.03g, 0.04g, or 0.05g, etc.
In some of these embodiments, the polybutylene terephthalate has a viscosity at 25 ℃ of 0.9 to 1.1gL/gr, phaseHas a density of 1.29-1.33g/cm3The melting point is 223-.
In some of these embodiments, the reinforcing material is glass fiber.
In some of these embodiments, the glass fibers have a length of 3-4 mm; for example, it may be 3mm, 3.1mm, 3..2mm, 3.3mm, 3.4mm, 3.5mm, 3.6mm, 3.7mm, 3.8mm, 3.9mm, 4mm, or the like.
In some of these embodiments, the glass fibers have a diameter of 10-13 μm; for example, it may be 10 μm, 10.5 μm, 11 μm, 11.5 μm, 12 μm, 12.5 μm or 13 μm.
In some of these embodiments, the antioxidant consists of a hindered phenolic antioxidant and a phosphite antioxidant in a mass ratio of 2-4:1 (e.g., 2:1, 2.2:1, 2.3:1, 2.5:1, 2.6:1, 2.8:1, 3:1 or 3:1, 3.2:1, 3.3:1, 3.5:1, 3.6:1, 3.8:1, or 4:1, etc.).
In some of these embodiments, the hindered phenolic antioxidant is antioxidant 1010 (pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate) ].
In some of these examples, the phosphite antioxidant is antioxidant 168 (tris [ 2.4-di-tert-butylphenyl ] phosphite).
On the other hand, the invention also provides a preparation method of the polybutylene terephthalate composite material.
The specific technical scheme is as follows:
a preparation method of a polybutylene terephthalate composite material comprises the following steps:
and uniformly mixing the polybutylene terephthalate, the reinforcing material, the hyperbranched polyester copolymer and the antioxidant, adding the obtained mixture into an extruder, carrying out melt blending, and extruding to obtain the polybutylene terephthalate composite material.
In some of these embodiments, the extruder is a parallel co-rotating twin screw extruder.
In some of these embodiments, the temperature of the extrusion is 240-260 ℃, and may be, for example, 240 ℃, 245 ℃, 250 ℃, 255 ℃, or 260 ℃.
In some embodiments, the main machine rotation speed of the extruder is 300-400rpm/min, such as 300rpm/min, 320rpm/min, 340rpm/min, 360rpm/min, 380rpm/min or 400 rpm/min; the extruder may have a feed speed of 10-30rpm/min, for example 10, 13, 15, 18, 20, 23, 25, 28 or 30 rpm/min.
Compared with the prior art, the invention has the following beneficial effects:
the invention uses hyperbranched polyester acrylate containing carboxyl and glycidyl methacrylate to carry out copolymerization to obtain hyperbranched polyester copolymer, then adds the hyperbranched polyester copolymer with a specific proportion into matrix resin PBT (polybutylene terephthalate resin), and can prepare a novel PBT composite material with lower dielectric constant and dielectric loss, excellent mechanical property and processability and higher heat resistance under the coordination of a certain amount of reinforcing materials. The hyperbranched polyester copolymer has a spherical and annular dendritic three-dimensional structure, and a large number of tiny 'hole' structures can be formed in the hyperbranched polyester copolymer after the matrix resin PBT is added, so that the dielectric constant and the dielectric loss of the PBT are greatly changed and are lower. The modified hyperbranched polyester copolymer has a large number of carboxyl groups on the surface and also has reactive epoxy groups, so that the modified hyperbranched polyester copolymer has high surface activity, can improve the contact interface layer of a reinforcing material (such as glass fiber) and PBT resin, and improves the compatibility of the reinforcing material (such as glass fiber) and PBT resin, so that the mechanical strength of the obtained PBT composite material is correspondingly enhanced, and simultaneously, the chemical resistance of the whole composite material is improved due to the addition of the reinforcing material (such as glass fiber). In addition, since the hyperbranched polyester copolymer has less intermolecular chain entanglement, the interaction between molecules is mainly derived from the interaction between terminal functional groups. Therefore, compared with linear polyester, the hyperbranched polyester copolymer has lower melt viscosity, so that the PBT composite material has good processability. And the antioxidant is matched to delay or inhibit the oxidation of the polymer, and the components are matched with each other according to a certain proportion, so that the PBT composite material has low dielectric constant and dielectric loss, excellent mechanical property, processability and high heat resistance.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
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 examples of the invention and the comparative examples used the following raw materials:
PBT: 1100-; it has a viscosity of 1.00 + -0.02 dL/gr at 25 deg.C and a relative density of 1.30-1.32g/cm3The melting point is 223-.
Glass fiber: japanese NEG T-511, 3mm in length and 10 μm in diameter.
Hyperbranched polyester copolymer: the preparation method is self-made as follows:
(1) using herba seu radix Tetrastigmatis HypoglauciTetraol (PE) as a core, dimethylolpropionic acid (DMPA) as AB2 monomer, to a mixture of PE (4.5mmol,0.62g), DMPA (12.6mmol,1.68g) and 1.406g of N, N-Dimethylacetamide (DMCA), toluenesulfonic acid (p-TSA, 0.05g) as a catalyst was added, placed in a three-necked flask with a stirrer, and N was introduced2Continuously stirring, heating to 140 ℃, reacting for 5 hours, and cooling to room temperature to obtain a hyperbranched polyester crude product; dissolving the crude product in acetone, precipitating in diethyl ether for multiple times, and vacuum drying at 70 deg.C to obtain 2.53g of hyperbranched polyester (HBPE);
(2) modifying hyperbranched polyester by succinic anhydride, Hexamethylene Diisocyanate (HDI) and hydroxyethyl acrylate (HEA) by two steps: firstly, HDI (0.11mol, 18.72g) and HEA (0.11mol, 12.87g) are added into a single-neck flask and react for 12 hours at the constant temperature of 40 ℃ to obtain an HDI-HEA product; adding 2.53g of HBPE, succinic anhydride (0.11mol, 11.09g) and 6.34g of acetone into a round-bottom flask, heating to 90 ℃ under the action of a magnetic stirrer, reacting for 6 hours, cooling to 55 ℃, finally adding an HDI-HEA product, reacting for 6 hours, and cooling to room temperature to obtain a crude modified product; precipitating the crude product by diethyl ether, and finally performing vacuum drying at 45 ℃ to obtain 38.24g of carboxyl-containing hyperbranched polyester acrylate;
(3) and (3) placing the hyperbranched polyester acrylate obtained in the step (2), Glycidyl Methacrylate (GMA) (0.11mol, 18.95g) and 0.8g of p-hydroxyanisole (polymerization inhibitor) into a three-neck bottle, and stirring at constant temperature of 70 ℃ until the acid value is stable to obtain a copolymer of carboxyl-containing hyperbranched polyester acrylate and glycidyl methacrylate, namely the hyperbranched polyester copolymer.
Example 1
The embodiment provides a PBT composite material, which is prepared from the following components in parts by weight:
Figure BDA0002671535360000101
the preparation method of the PBT composite material comprises the following steps:
and (2) uniformly mixing the hyperbranched polyester copolymer with PBT, glass fiber and an antioxidant, adding the obtained mixture into a parallel co-rotating twin-screw extruder (the feeding rotating speed of the extruder is 20rpm/min), melting and blending, setting the extrusion temperature to be 250 ℃ and the rotating speed of a screw (the rotating speed of a main machine of the extruder) to be 350r/min, and extruding to obtain the PBT composite material.
Example 2
The embodiment provides a PBT composite material, which is prepared from the following components in parts by weight:
Figure BDA0002671535360000102
the preparation method of the PBT composite material comprises the following steps:
and (2) uniformly mixing the hyperbranched polyester copolymer with PBT, glass fiber and an antioxidant, adding the obtained mixture into a parallel co-rotating twin-screw extruder (the feeding rotating speed of the extruder is 20rpm/min), melting and blending, setting the extrusion temperature to be 250 ℃ and the rotating speed of a screw (the rotating speed of a main machine of the extruder) to be 350r/min, and extruding to obtain the PBT composite material.
Example 3
The embodiment provides a PBT composite material, which is prepared from the following components in parts by weight:
Figure BDA0002671535360000111
the preparation method of the PBT composite material comprises the following steps:
and (2) uniformly mixing the hyperbranched polyester copolymer with PBT, glass fiber and an antioxidant, adding the obtained mixture into a parallel co-rotating twin-screw extruder (the feeding rotating speed of the extruder is 20rpm/min), melting and blending, setting the extrusion temperature to be 250 ℃ and the rotating speed of a screw (the rotating speed of a main machine of the extruder) to be 350r/min, and extruding to obtain the PBT composite material.
Example 4
The embodiment provides a PBT composite material, which is prepared from the following components in parts by weight:
Figure BDA0002671535360000112
the preparation method of the PBT composite material comprises the following steps:
and (2) uniformly mixing the hyperbranched polyester copolymer with PBT, glass fiber and an antioxidant, adding the obtained mixture into a parallel co-rotating twin-screw extruder (the feeding rotating speed of the extruder is 20rpm/min), melting and blending, setting the extrusion temperature to be 250 ℃ and the rotating speed of a screw (the rotating speed of a main machine of the extruder) to be 350r/min, and extruding to obtain the PBT composite material.
Example 5
The embodiment provides a PBT composite material, which is prepared from the following components in parts by weight:
Figure BDA0002671535360000121
the preparation method of the PBT composite material comprises the following steps:
and (2) uniformly mixing the hyperbranched polyester copolymer with PBT, glass fiber and an antioxidant, adding the obtained mixture into a parallel co-rotating twin-screw extruder (the feeding rotating speed of the extruder is 20rpm/min), melting and blending, setting the extrusion temperature to be 250 ℃ and the rotating speed of a screw (the rotating speed of a main machine of the extruder) to be 350r/min, and extruding to obtain the PBT composite material.
Example 6
The embodiment provides a PBT composite material, which is prepared from the following components in parts by weight:
Figure BDA0002671535360000122
Figure BDA0002671535360000131
the preparation method of the PBT composite material comprises the following steps:
and (2) uniformly mixing the hyperbranched polyester copolymer with PBT, glass fiber and an antioxidant, adding the obtained mixture into a parallel co-rotating twin-screw extruder (the feeding rotating speed of the extruder is 20rpm/min), melting and blending, setting the extrusion temperature to be 250 ℃ and the rotating speed of a screw (the rotating speed of a main machine of the extruder) to be 350r/min, and extruding to obtain the PBT composite material.
Comparative example 1
The difference from example 6 is that the same amount of PBT resin is used instead of the hyperbranched polyester copolymer, and the other components, the amounts and the preparation steps are the same as example 6.
Comparative example 2
The difference from example 6 is that the same amount of (octavinyl POSS, MAH) -g-PP was used instead of the hyperbranched polyester copolymer, and the other components, amounts and preparation steps were the same as in example 6.
Among them, (octavinyl POSS, MAH) -g-PP was prepared with reference to CN 109679304A.
Comparative example 3
The difference from example 6 is that the same amount of hyperbranched polyester is used instead of the hyperbranched polyester copolymer, and the other components, the amount and the preparation steps are the same as those of example 6.
The preparation method of the hyperbranched polyester comprises the following steps:
with Pentaerythritol (PE) as a core and dimethylolpropionic acid (DMPA) as AB2 monomer, to a mixture of PE (4.5mmol,0.62g), DMPA (12.6mmol,1.68g) and 5mmol,1.406g of N, N-Dimethylacetamide (DMCA), toluenesulfonic acid (p-TSA, 0.05g) was added as a catalyst, placed in a three-necked flask equipped with a stirrer, and N was introduced2Continuously stirring, heating to 140 ℃, reacting for 5 hours, and cooling to room temperature to obtain a hyperbranched polyester crude product; and dissolving the crude product in acetone, carrying out multiple times of precipitation in diethyl ether, and finally carrying out vacuum drying at 70 ℃ to obtain 2.53g of hyperbranched polyester (HBPE).
Comparative example 4
The difference from example 6 is that the same amount of carboxyl group-containing hyperbranched polyester acrylate is used instead of the hyperbranched polyester copolymer, and the other components, the amounts and the preparation steps are the same as example 6.
The preparation method of the carboxyl-containing hyperbranched polyester acrylate comprises the following steps:
(1) with Pentaerythritol (PE) as a core and dimethylolpropionic acid (DMPA) as AB2 monomer, to a mixture of PE (4.5mmol,0.62g), DMPA (12.6mmol,1.68g) and 5mmol,1.406g of N, N-Dimethylacetamide (DMCA), toluenesulfonic acid (p-TSA, 0.05g) was added as a catalyst, placed in a three-necked flask equipped with a stirrer, and N was introduced2Continuously stirring, heating to 140 ℃, reacting for 5 hours, and cooling to room temperature to obtain a hyperbranched polyester crude product; and dissolving the crude product in acetone, carrying out multiple times of precipitation in diethyl ether, and finally carrying out vacuum drying at 70 ℃ to obtain 2.53g of hyperbranched polyester (HBPE).
(2) Modifying hyperbranched polyester by succinic anhydride, Hexamethylene Diisocyanate (HDI) and hydroxyethyl acrylate (HEA) by two steps: firstly, HDI (0.11mol, 18.72g) and HEA (0.11mol, 12.87g) are added into a single-neck flask and react for 12 hours at the constant temperature of 40 ℃ to obtain an HDI-HEA product; adding 2.53g of HBPE, succinic anhydride (0.11mol, 11.09g) and 6.34g of acetone into a round-bottom flask, heating to 90 ℃ under the action of a magnetic stirrer, reacting for 6 hours, cooling to 55 ℃, finally adding an HDI-HEA product, reacting for 6 hours, and cooling to room temperature to obtain a crude modified product; and precipitating the crude product by diethyl ether, and finally performing vacuum drying at 45 ℃ to obtain 38.24g of carboxyl-containing hyperbranched polyester acrylate.
Comparative example 5
The difference from the example 6 is that the hyperbranched polyester copolymer has the weight part of 10 parts, and other components, the using amount and the preparation steps are the same as those of the example 6.
The properties of the PBT composites provided in examples 1-6 and comparative examples 1-5 above were tested, and the test criteria and results are shown in Table 1 below:
TABLE 1
Figure BDA0002671535360000151
According to the data in table 1, the PBT composite material provided by the invention has low dielectric constant and dielectric loss, good fluidity, easy processing, high heat resistance and mechanical strength, and can be used as a nano injection material for electronic communication products.
1. From examples 1 to 6, with the increasing of the addition amount of the hyperbranched polyester copolymer, the dielectric constant and the dielectric loss of the composite material show a tendency of decreasing, when the addition amount reaches 8 parts, the dielectric constant is less than 3.0, and the dielectric loss factor is also decreased to 0.007, because the hyperbranched polyester copolymer has a unique three-dimensional structure similar to a spherical shape and a ring-shaped dendritic shape, when the PBT resin is added, a large amount of tiny 'hole' structures are formed in the PBT resin, and the larger the amount of the hyperbranched polyester copolymer is, the more holes are formed in the resin, so that the dielectric constant and the dielectric loss of the PBT composite material are both decreased. And for the fluidity of the PBT composite material, when the addition amount of the hyperbranched polyester copolymer is gradually increased, the tendency of rising starts to appear, which is because the hyperbranched polyester copolymer has less molecular entanglement, low viscosity and good fluidity.
2. Compared with the embodiment 6, the PBT composite material has high dielectric constant and dielectric loss factor test values under the condition of not adding the hyperbranched polyester copolymer, and can not meet the requirement of low dielectric at all; and the mechanical strength was also lower than that of example 6.
3. Comparative example 2 compared with example 6, through the comparative tests of the hyperbranched polyester copolymer and the (octavinyl POSS, MAH) -g-PP, although the dielectric properties of the composite material are changed through the molecular structure, the effect is substantially different due to different polymerization modes; wherein (octavinyl POSS, MAH) -g-PP adopts an extrusion melting and mixing grafting method, so that the obtained polymer has low grafting rate of effective groups, is unstable and has no practicability of mass production; the hyperbranched polyester copolymer adopts a three-step synthesis method, so that the grafting rate of effective groups is high, the stability is high, and the method is suitable for mass production popularization and application; the dielectric constant and the dielectric loss factor of the PBT composite material added with the hyperbranched polyester copolymer are far lower than those of the PBT composite material added with (octavinyl POSS, MAH) -g-PP, and the mechanical property of the PBT composite material added with the hyperbranched polyester copolymer is also better than that of the PBT composite material added with (octavinyl POSS, MAH) -g-PP.
4. Compared with the example 6, the hyperbranched polyester and the hyperbranched polyester acrylate containing carboxyl are respectively used for replacing the hyperbranched polyester copolymer, the mechanical property and the dielectric property of the obtained PBT composite material are poorer than those of the example 6, and the comparison result shows that the copolymer of the glycidyl methacrylate and the hyperbranched polyester acrylate containing carboxyl can effectively improve the mechanical property and the dielectric property of the PBT composite material compared with the hyperbranched polyester and the hyperbranched polyester acrylate containing carboxyl.
5. In comparison with example 6, when the amount of the hyperbranched polyester copolymer added is 10 parts, the dielectric constant and the dielectric dissipation factor of the PBT composite material are further reduced, but the mechanical properties of the PBT composite material are deteriorated, and the PBT composite material has no practical application value.
The technical features of the above embodiments can be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the above embodiments are not described, however, as long as there is no contradiction between the combinations of the technical features, the scope of the present description should be considered as being described in the present specification.
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 present 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 polybutylene terephthalate composite material is characterized by being prepared from the following raw materials in parts by weight:
Figure FDA0002671535350000011
the total weight of all the raw materials is 100 parts;
the hyperbranched polyester copolymer is a copolymer of carboxyl-containing hyperbranched polyester acrylate and glycidyl methacrylate;
the carboxyl-containing hyperbranched polyester acrylate is obtained by modifying hyperbranched polyester with succinic anhydride, hexamethylene diisocyanate and hydroxyethyl acrylate.
2. The polybutylene terephthalate composite material according to claim 1, which is prepared from the following raw materials in parts by weight:
Figure FDA0002671535350000012
3. the polybutylene terephthalate composite material according to claim 1, wherein the mass ratio of the carboxyl group-containing hyperbranched polyester acrylate to glycidyl methacrylate is 2-4: 1-2; and/or the presence of a gas in the gas,
the mass ratio of the succinic anhydride, the hexamethylene diisocyanate, the hydroxyethyl acrylate and the hyperbranched polyester is 4-5:7-8:5-6: 1.
4. The polybutylene terephthalate composite material according to claim 1, wherein the hyperbranched polyester is obtained by polymerizing pentaerythritol and dimethylolpropionic acid; preferably, the molar ratio of pentaerythritol to dimethylolpropionic acid is 1: 1-6; more preferably, the molar ratio of pentaerythritol to dimethylolpropionic acid is from 1:2 to 4.
5. The polybutylene terephthalate composite material according to any one of claims 1 to 4, wherein the hyperbranched polyester copolymer is prepared by a method comprising the steps of:
reacting the hexamethylene diisocyanate with hydroxyethyl acrylate to obtain an HDI-HEA product;
reacting the hyperbranched polyester with succinic anhydride in a first organic solvent, and then adding the HDI-HEA product into the obtained reaction mixture for reaction to obtain the carboxyl-containing hyperbranched polyester acrylate;
and reacting the carboxyl-containing hyperbranched polyester acrylate, glycidyl methacrylate and a proper amount of polymerization inhibitor to obtain the hyperbranched polyester copolymer.
6. The polybutylene terephthalate composite material according to claim 5, wherein the reaction temperature of hexamethylene diisocyanate and hydroxyethyl acrylate is 35 to 45 ℃ and the reaction time is 10 to 15 hours; and/or the presence of a gas in the gas,
reacting the hyperbranched polyester and succinic anhydride in a first organic solvent at the temperature of 85-95 ℃ for 4-8 hours; and/or the presence of a gas in the gas,
adding the HDI-HEA product into the obtained reaction mixture to react at the temperature of 50-60 ℃ for 4-8 hours; and/or the presence of a gas in the gas,
reacting the carboxyl-containing hyperbranched polyester acrylate, glycidyl methacrylate and a proper amount of polymerization inhibitor at the temperature of 65-75 ℃ until the acid value is stable; and/or the presence of a gas in the gas,
the first organic solvent is acetone; and/or the presence of a gas in the gas,
the polymerization inhibitor is p-hydroxyanisole.
7. The polybutylene terephthalate composite material according to any one of claims 1 to 4, wherein the hyperbranched polyester is prepared by a method comprising the steps of: and mixing the pentaerythritol, the dimethylolpropionic acid and a second organic solvent, adding a catalyst, and reacting to obtain the hyperbranched polyester.
8. The polybutylene terephthalate composite material according to claim 7, wherein in the preparation step of the hyperbranched polyester, the reaction temperature is 130-150 ℃ and the reaction time is 3-7 hours; and/or the presence of a gas in the gas,
the second organic solvent is N, N-dimethylacetamide; and/or the presence of a gas in the gas,
the catalyst is toluenesulfonic acid.
9. The polybutylene terephthalate composite material according to any one of claims 1 to 4, wherein the polybutylene terephthalate has a viscosity of 0.9 to 1.1dL/gr at 25 ℃ and a relative density of 1.29 to 1.33g/cm3The melting point is 223-; and/or the presence of a gas in the gas,
the reinforcing material is glass fiber; and/or the presence of a gas in the gas,
the antioxidant consists of hindered phenol antioxidant and phosphite antioxidant according to the mass ratio of 2-4: 1; and/or the presence of a gas in the gas,
preferably, the length of the glass fiber is 3-4 mm; the diameter of the glass fiber is 10-13 μm;
the hindered phenol antioxidant is antioxidant 1010;
the phosphite antioxidant is antioxidant 168.
10. A method for preparing a polybutylene terephthalate composite material according to any one of claims 1 to 9, comprising the steps of:
uniformly mixing the polybutylene terephthalate, the reinforcing material, the hyperbranched polyester copolymer and the antioxidant, adding the obtained mixture into an extruder, carrying out melt blending, and extruding to obtain the polybutylene terephthalate composite material;
preferably, the extruder is a parallel co-rotating twin screw extruder;
the temperature of the extrusion is 240-260 ℃;
the rotating speed of the main machine of the extruder is 300-400 rpm/min;
the feeding speed of the extruder is 10-30 rpm/min.
CN202010934728.7A 2020-09-08 2020-09-08 Polybutylene terephthalate composite material and preparation method thereof Pending CN112094485A (en)

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