CN112080142A - Polytetramethylene adipamide composite material and preparation method thereof - Google Patents

Polytetramethylene adipamide composite material and preparation method thereof Download PDF

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CN112080142A
CN112080142A CN202010948063.5A CN202010948063A CN112080142A CN 112080142 A CN112080142 A CN 112080142A CN 202010948063 A CN202010948063 A CN 202010948063A CN 112080142 A CN112080142 A CN 112080142A
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hyperbranched polyester
gas
parts
composite material
antioxidant
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朱怀才
谢平
罗海威
杨建军
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Sinoplast New Material Ltd
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06Polyamides derived from polyamines and polycarboxylic acids
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06Polymers provided for in subclass C08G
    • C08F290/061Polyesters; Polycarbonates
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/06Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/91Polymers modified by chemical after-treatment
    • C08G63/912Polymers modified by chemical after-treatment derived from hydroxycarboxylic acids
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/03Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

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Abstract

The invention provides a polytetramethylene adipamide composite material and a preparation method thereof. The polytetramethyleneadipamide composite material is prepared from the following raw materials: 40-60 parts of polytetramethylene adipamide, 30-50 parts of reinforcing material, 5-12 parts of hyperbranched polyester copolymer, 0.3-1.5 parts of antioxidant and 0.5-1.5 parts of lubricant; 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 polytetramethyleneadipamide composite material has low dielectric constant and dielectric loss, excellent mechanical property and high heat resistance.

Description

Polytetramethylene adipamide composite material and preparation method thereof
Technical Field
The invention belongs to the technical field of polymer composite materials, and particularly relates to a polytetramethylene adipamide 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 the above, the present invention aims to provide a polytetramethyleneadipamide composite material (PA46 composite material), wherein the PA46 composite material has a relatively low dielectric constant and dielectric loss, and at the same time, has relatively high heat resistance and mechanical strength.
The specific technical scheme is as follows:
the polybutylene adipate composite material is prepared from the following raw materials in parts by weight:
Figure BDA0002675983110000031
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 polytetramethylene adipamide composite material is prepared from the following raw materials in parts by weight:
Figure BDA0002675983110000032
in some of these embodiments, the parts by weight of the polytetramethyleneadipamide in the polytetramethyleneadipamide composite can be 40 parts, 41 parts, 42 parts, 43 parts, 44 parts, 45 parts, 46 parts, 47 parts, 48 parts, 49 parts, 50 parts, 51 parts, 52 parts, 53 parts, 54 parts, 55 parts, 56 parts, 57 parts, 58 parts, 59 parts, or 60 parts.
In some of these embodiments, the reinforcing material in the polytetramethyleneadipamide composite may be 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, 45 parts, 46 parts, 47 parts, 48 parts, 49 parts, or 50 parts by weight.
In some of these embodiments, the weight parts of the hyperbranched polyester copolymer in the polytetramethyleneadipamide composite can be 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, or 12 parts.
In some of these embodiments, the weight parts of the antioxidant in the polytetramethyleneadipamide composite can be 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, 0.8 parts, 0.85 parts, 0.9 parts, 0.95 parts, 1.0 parts, 1.05 parts, 1.1 parts, 1.15 parts, 1.20 parts, 1.25 parts, 1.3 parts, 1.35 parts, 1.4 parts, 1.45 parts, or 1.5 parts.
In some of these embodiments, the weight parts of the lubricant in the polytetramethyleneadipamide composite may be 0.5 parts, 0.55 parts, 0.6 parts, 0.65 parts, 0.7 parts, 0.75 parts, 0.8 parts, 0.85 parts, 0.9 parts, 0.95 parts, 1.0 parts, 1.05 parts, 1.1 parts, 1.15 parts, 1.20 parts, 1.25 parts, 1.3 parts, 1.35 parts, 1.4 parts, 1.45 parts, or 1.5 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 relative density of the polytetramethylene adipamide is from 1.15 to 1.20g/cm3The melting point is 290 ℃ and 300 ℃.
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 is comprised of a hindered phenolic antioxidant and a phosphite antioxidant in a mass ratio of 1-2:1 (e.g., 1:1, 1.2:1, 1.3:1, 1.5:1, 1.6:1, 1.8:1, or 2:1, etc.).
In some of these embodiments, the hindered phenolic antioxidant is antioxidant 1098(N, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine).
In some of these examples, the phosphite antioxidant is the antioxidant S-9228 (bis (2, 4-dicumylphenyl) pentaerythritol diphosphite).
In some of these embodiments, the lubricant consists of a silicone-based lubricant and a montan wax-based lubricant in a mass ratio of 1:1 to 3.
In some of these embodiments, the silicone-based lubricant is ST-LS100 (polydimethylsiloxane).
In some of these embodiments, the montan wax-based lubricant is an OP wax (partially saponified montan ester wax).
On the other hand, the invention also provides a preparation method of the polytetramethyleneadiamide composite material.
The specific technical scheme is as follows:
a preparation method of polytetramethylene adipamide composite material comprises the following steps:
uniformly mixing the polytetramethylene adipamide, the reinforcing material, the hyperbranched polyester copolymer, the antioxidant and the lubricant, adding the obtained mixture into an extruder, carrying out melt blending, and extruding to obtain the polytetramethylene adipamide composite material.
In some of these embodiments, the extruder is a parallel co-rotating twin screw extruder.
In some embodiments, the temperature of the extrusion is 310-330 ℃, for example, 310 ℃, 315 ℃, 320 ℃, 325 ℃, or 330 ℃.
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 5-20rpm/min, for example 5, 8, 10, 12, 14, 16, 18 or 20 rpm/min.
Compared with the prior art, the invention has the following beneficial effects:
the invention uses carboxyl-containing hyperbranched polyester acrylate and glycidyl methacrylate to copolymerize to obtain a hyperbranched polyester copolymer, and then adds the hyperbranched polyester copolymer in a specific proportion into matrix resin PA46 (polytetramethylene adipamide), and under the coordination of a certain amount of reinforcing materials, a novel PA46 composite material which has lower dielectric constant and dielectric loss, excellent mechanical properties and higher heat resistance can be prepared. The hyperbranched polyester copolymer has a spherical and annular dendritic three-dimensional structure, and a large number of tiny 'hole' structures are formed in the hyperbranched polyester copolymer after the matrix resin PA46 is added, so that the dielectric constant and the dielectric loss of PA46 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 PA46 resin, and improves the compatibility of the reinforcing material (such as glass fiber) and PA46 resin, so that the mechanical strength of the obtained PA46 composite material is correspondingly enhanced, and the overall chemical resistance of the composite material is improved due to the addition of the reinforcing material (such as glass fiber). And the antioxidant is matched to delay or inhibit the oxidation of the polymer, the lubricant is used for improving the fluidity of the material, and the components are matched with each other according to a certain proportion, so that the obtained PA46 composite material has low dielectric constant and dielectric loss, excellent mechanical properties 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:
PA 46: TE300 for DSM; the relative density is 1.18/cm3The melting point is 295 ℃;
glass fiber: japanese NEGT-511, 3mm in length and 10 μm in diameter.
Hyperbranched polyester copolymer: the preparation method is self-made as follows:
(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 1.406g of N, N-Dimethylacetamide (DMCA), toluenesulfonic acid (p-TSA, 0.05g) was added as a catalyst, 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 PA46 composite material, which is prepared from the following components in parts by weight:
Figure BDA0002675983110000101
the preparation method of the PA46 composite material comprises the following steps:
uniformly mixing the hyperbranched polyester copolymer with PA46, glass fiber, an antioxidant and a lubricant, adding the obtained mixture into a parallel co-rotating twin-screw extruder (the feeding rotating speed of the extruder is 15rpm/min), carrying out melt blending, setting the extrusion temperature to be 320 ℃, and the rotating speed of a screw (the main machine rotating speed of the extruder) to be 350r/min, and extruding to obtain the PA46 composite material.
Example 2
The embodiment provides a PA46 composite material, which is prepared from the following components in parts by weight:
Figure BDA0002675983110000102
Figure BDA0002675983110000111
the preparation method of the PA46 composite material comprises the following steps:
uniformly mixing the hyperbranched polyester copolymer with PA46, glass fiber, an antioxidant and a lubricant, adding the obtained mixture into a parallel co-rotating twin-screw extruder (the feeding rotating speed of the extruder is 15rpm/min), carrying out melt blending, setting the extrusion temperature to be 320 ℃, and the rotating speed of a screw (the main machine rotating speed of the extruder) to be 350r/min, and extruding to obtain the PA46 composite material.
Example 3
The embodiment provides a PA46 composite material, which is prepared from the following components in parts by weight:
Figure BDA0002675983110000112
the preparation method of the PA46 composite material comprises the following steps:
uniformly mixing the hyperbranched polyester copolymer with PA46, glass fiber, an antioxidant and a lubricant, adding the obtained mixture into a parallel co-rotating twin-screw extruder (the feeding rotating speed of the extruder is 15rpm/min), carrying out melt blending, setting the extrusion temperature to be 320 ℃, and the rotating speed of a screw (the main machine rotating speed of the extruder) to be 350r/min, and extruding to obtain the PA46 composite material.
Example 4
The embodiment provides a PA46 composite material, which is prepared from the following components in parts by weight:
Figure BDA0002675983110000121
the preparation method of the PA46 composite material comprises the following steps:
uniformly mixing the hyperbranched polyester copolymer with PA46, glass fiber, an antioxidant and a lubricant, adding the obtained mixture into a parallel co-rotating twin-screw extruder (the feeding rotating speed of the extruder is 15rpm/min), carrying out melt blending, setting the extrusion temperature to be 320 ℃, and the rotating speed of a screw (the main machine rotating speed of the extruder) to be 350r/min, and extruding to obtain the PA46 composite material.
Example 5
The embodiment provides a PA46 composite material, which is prepared from the following components in parts by weight:
Figure BDA0002675983110000122
Figure BDA0002675983110000131
the preparation method of the PA46 composite material comprises the following steps:
uniformly mixing the hyperbranched polyester copolymer with PA46, glass fiber, an antioxidant and a lubricant, adding the obtained mixture into a parallel co-rotating twin-screw extruder (the feeding rotating speed of the extruder is 15rpm/min), carrying out melt blending, setting the extrusion temperature to be 320 ℃, and the rotating speed of a screw (the main machine rotating speed of the extruder) to be 350r/min, and extruding to obtain the PA46 composite material.
Example 6
The embodiment provides a PA46 composite material, which is prepared from the following components in parts by weight:
Figure BDA0002675983110000132
the preparation method of the PA46 composite material comprises the following steps:
uniformly mixing the hyperbranched polyester copolymer with PA46, glass fiber, an antioxidant and a lubricant, adding the obtained mixture into a parallel co-rotating twin-screw extruder (the feeding rotating speed of the extruder is 15rpm/min), carrying out melt blending, setting the extrusion temperature to be 320 ℃, and the rotating speed of a screw (the main machine rotating speed of the extruder) to be 350r/min, and extruding to obtain the PA46 composite material.
Comparative example 1
The difference from example 6 is that the same amount of PA46 was used instead of the hyperbranched polyester copolymer, and the other components, amounts and preparation steps were the same as in 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:
pentaerythritol (PE) as a core and dimethylolpropionic acid (DMPA) asAB2 monomer, in 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 with a stirrer, and N was passed through2Continuously 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 weight portion of the hyperbranched polyester copolymer is 15 parts, and other components, the using amount and the preparation steps are the same as those of the example 6.
The PA46 composites provided in examples 1-6 and comparative examples 1-5 above were tested for their performance, with the test criteria and results shown in table 1 below:
TABLE 1
Figure BDA0002675983110000161
According to the data in table 1, the PA46 composite material provided by the invention has the advantages of low dielectric constant and dielectric loss, excellent mechanical properties and good heat resistance, and can be used as a nano injection molding material for electronic communication products.
1. From examples 1 to 6, with the increasing of the added amount of the hyperbranched polyester copolymer, the dielectric constant and the dielectric loss of the composite material show a tendency of decreasing, when the added amount reaches 9 parts, the dielectric constant is less than 3.3, and the dielectric loss factor is also reduced to 0.038, because the hyperbranched polyester copolymer has a unique three-dimensional structure similar to a spherical shape and a ring-shaped dendritic shape, when the PA46 resin is added, a large amount of tiny 'hole' structures are formed in the hyperbranched polyester copolymer, and the larger the amount of the added hyperbranched polyester copolymer is, the more holes are formed in the resin, so that the dielectric constant and the dielectric loss of the PA46 composite material are both reduced.
2. Compared with the example 6, in the case of not adding the hyperbranched polyester copolymer, the PA46 composite material has very high dielectric constant and dielectric loss factor test values, 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 PA46 composite material added with the hyperbranched polyester copolymer are far lower than those of the PA46 composite material added with (octavinyl POSS, MAH) -g-PP, and the mechanical property of the PA46 composite material added with the hyperbranched polyester copolymer is also better than that of the PA46 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 PA46 composite material are poorer than those of the example 6, and the comparison of the copolymer of the glycidyl methacrylate and the hyperbranched polyester acrylate containing carboxyl with the hyperbranched polyester acrylate containing carboxyl can effectively improve the mechanical property and the dielectric property of the PA46 composite material.
5. Compared with example 6, when the addition amount of the hyperbranched polyester copolymer reaches 15 parts, the dielectric constant and the dielectric loss factor of the PA46 composite material are reduced, but the mechanical property of the PA46 composite material is poor, and the PA46 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 polytetramethylene adipamide composite material is characterized by being prepared from the following raw materials in parts by weight:
Figure FDA0002675983100000011
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 polytetramethyleneadipamide composite material according to claim 1, which is prepared from the following raw materials in parts by weight:
Figure FDA0002675983100000012
3. the polytetramethyleneadipamide composite material according to claim 1, wherein the mass ratio of the hyperbranched polyester acrylate containing carboxyl groups to the 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. A composite material of polytetramethylene adipamide according to claim 1, characterized in that 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. A polytetramethyleneadipamide composite according to any one of claims 1 to 4, wherein the method for preparing 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.
6. A polytetramethylene adipamide composite according to claim 5, wherein the reaction temperature of the hexamethylene diisocyanate and the hydroxyethyl acrylate is 35-45 ℃ and the reaction time is 10-15 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. A polytetramethyleneadipamide composite according to any one of claims 1 to 4, characterized in that the method for the preparation of the hyperbranched polyester comprises the following steps: and mixing the pentaerythritol, the dimethylolpropionic acid and a second organic solvent, adding a catalyst, and reacting to obtain the hyperbranched polyester.
8. The polytetramethyleneadipamide 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. A polytetramethylene adipamide composite according to any of claims 1-4, characterized in that the relative density of the polytetramethylene adipamide is between 1.15 and 1.20g/cm3The melting point is 290-300 ℃; 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 1-2: 1; and/or the presence of a gas in the gas,
the lubricant consists of a silicone lubricant and a montan wax lubricant according to the mass ratio of 1: 1-3;
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 an antioxidant 1098;
the phosphite ester antioxidant is antioxidant S-9228;
the silicone lubricant is ST-LS 100;
the montan wax type lubricant is OP wax.
10. A method of preparing a polytetramethyleneadipamide composite according to any one of claims 1 to 9, comprising the steps of:
uniformly mixing the polytetramethylene adipamide, the reinforcing material, the hyperbranched polyester copolymer, the antioxidant and the lubricant, adding the obtained mixture into an extruder, carrying out melt blending, and extruding to obtain the polytetramethylene adipamide composite material;
preferably, the extruder is a parallel co-rotating twin screw extruder;
the temperature of the extrusion is 310-330 ℃;
the rotating speed of the main machine of the extruder is 300-400 rpm/min;
the feeding speed of the extruder is 5-20 rpm/min.
CN202010948063.5A 2020-09-10 2020-09-10 Polytetramethylene adipamide composite material and preparation method thereof Pending CN112080142A (en)

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CN108676355A (en) * 2018-05-23 2018-10-19 江苏金发科技新材料有限公司 Low floating fine high glaze fiber glass reinforced polyamide composition
CN108727810A (en) * 2018-05-23 2018-11-02 江苏金发科技新材料有限公司 Long glass fiber reinforced daiamid composition and preparation method thereof
CN110437612A (en) * 2019-08-29 2019-11-12 深圳海源恒业高新材料科技研发有限公司 Door and window heat insulating strip biology base nylon composite materials and preparation method thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105419319A (en) * 2015-12-30 2016-03-23 上海金发科技发展有限公司 Glass fiber enhanced nylon 6 material with high UV resistant performance and preparation method thereof
CN106995606A (en) * 2016-01-26 2017-08-01 合肥杰事杰新材料股份有限公司 A kind of dissaving polymer modified polyamide composite and preparation method thereof
CN108676355A (en) * 2018-05-23 2018-10-19 江苏金发科技新材料有限公司 Low floating fine high glaze fiber glass reinforced polyamide composition
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