CN111978491A - Hyperbranched polyester copolymer, spraying-free polycarbonate fiber-adding composite material and preparation method thereof - Google Patents

Hyperbranched polyester copolymer, spraying-free polycarbonate fiber-adding composite material and preparation method thereof Download PDF

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CN111978491A
CN111978491A CN202010871919.3A CN202010871919A CN111978491A CN 111978491 A CN111978491 A CN 111978491A CN 202010871919 A CN202010871919 A CN 202010871919A CN 111978491 A CN111978491 A CN 111978491A
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hyperbranched polyester
temperature
zone
composite material
polyester copolymer
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朱怀才
谢平
刘羽玲
梁振锋
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Guangdong Sinoplast Advanced Material Co ltd
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Guangdong Sinoplast Advanced Material Co ltd
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    • 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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular 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
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/061—Polyesters; Polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/91—Polymers modified by chemical after-treatment
    • C08G63/912—Polymers modified by chemical after-treatment derived from hydroxycarboxylic acids
    • 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
    • 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
    • C08J5/10—Reinforcing macromolecular compounds with loose or coherent fibrous material characterised by the additives used in the polymer mixture
    • 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
    • C08J2369/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
    • 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
    • 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 hyperbranched polyester copolymer, a spraying-free polycarbonate fiber-reinforced composite material and a preparation method thereof. The hyperbranched polyester copolymer is obtained by copolymerizing hyperbranched polyester acrylate containing carboxyl and glycidyl methacrylate; the carboxyl-containing hyperbranched polyester acrylate is obtained by modifying hyperbranched polyester with succinic anhydride, hexamethylene diisocyanate and hydroxyethyl acrylate. The spraying-free polycarbonate fiber-reinforced composite material is prepared from the following raw materials in percentage by weight: 57-80% of polycarbonate, 10-30% of glass fiber, 0.2-1% of hyperbranched polyester copolymer, 5-10% of toughening agent, 0.1-0.5% of antioxidant, 0.5-1.5% of lubricant and 0.1-0.5% of anti-UV agent. The spraying-free polycarbonate fiber-added composite material has the advantages of low surface floating fiber, high gloss and excellent scratch resistance, and also has excellent mechanical properties.

Description

Hyperbranched polyester copolymer, spraying-free polycarbonate fiber-adding composite material and preparation method thereof
Technical Field
The invention belongs to the technical field of polymer composite materials, and particularly relates to a hyperbranched polyester copolymer, a spraying-free polycarbonate fiber-added composite material and a preparation method thereof.
Background
The glass fiber reinforced polycarbonate composite material has good toughness, rigidity and chemical resistance, and is widely applied to electronic products such as mobile phones, flat plates, notebooks and the like. After the glass fiber reinforced polycarbonate composite material is injection molded, plastic on the surface of a product is sprayed or electroplated to make up for the defects of fiber floating and easy scratching on the surface of the product. With the push of the spraying-free material in recent years, compared with the traditional plastic material, the spraying-free material has the advantages of rich colors, good surface gloss, good chemical resistance, good surface scratch resistance, more environmental protection, lower comprehensive use cost and the like. Therefore, the research on the spraying-free PC fiber-reinforced composite material has important significance in the development of electronic and electrical and communication equipment and the like.
At present, some problems to be solved still exist in the field of spraying-free PC fiber-added composite materials, particularly the problem of fiber floating on the surface and the problem of poor surface scratch resistance. The prior art generally improves the above problems by two methods: 1. the addition of glass fibers is reduced, which results in a large compromise in the overall mechanical and temperature and chemical resistance properties of such products; 2. the compatibilizer is added and is mostly a graft of maleic anhydride, and because the surface activity of the compatibilizer is not high, if the addition amount is small, the compatibilization effect is limited, and the surface floating fiber cannot be improved; if the amount is large, a third phase in the polymer is formed, which not only largely affects the mechanical properties and surface hardness of the whole material, but also deteriorates the flowability and processability of the material.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a spraying-free polycarbonate fiber-reinforced composite material which has the advantages of low surface floating fiber, high gloss and excellent scratch resistance and also has excellent mechanical properties.
In order to achieve the purpose, the invention firstly prepares a hyperbranched polyester copolymer, and the hyperbranched polyester copolymer is added into the spraying-free polycarbonate fiber-added composite material, so that the spraying-free polycarbonate fiber-added composite material has low surface fiber floating, high luster, good scratch resistance and good mechanical property.
The specific technical scheme is as follows:
a hyperbranched polyester copolymer is obtained by copolymerization 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 hyperbranched polyester acrylate containing carboxyl groups and the glycidyl methacrylate are in a mass ratio of 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.
The preparation method of the hyperbranched polyester copolymer comprises the following steps:
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 organic solvent at a temperature of 85 to 95 ℃ for a time of 4 to 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.
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.
The spraying-free polycarbonate and fiber composite material is prepared from the following raw materials in percentage by weight:
Figure BDA0002651393490000041
the hyperbranched polyester copolymer is the hyperbranched polyester copolymer or the hyperbranched polyester copolymer prepared by the preparation method.
In some embodiments, the spraying-free polycarbonate fiber-reinforced composite material is prepared from the following raw materials in percentage by weight:
Figure BDA0002651393490000042
Figure BDA0002651393490000051
in some embodiments, the spraying-free polycarbonate fiber-reinforced composite material is prepared from the following raw materials in percentage by weight:
Figure BDA0002651393490000052
according to the invention, PC (polycarbonate) is used as a base material, and is matched with the glass fiber and the hyperbranched polyester copolymer in a proper proportion, so that the obtained composite material has a spraying-free effect, has the advantages of low surface floating fiber, high gloss and excellent scratch resistance, and simultaneously has excellent mechanical properties.
In some of these embodiments, the glass fiber has a length of 3-4mm, and preferably the glass fiber has a length of 3 mm.
In some of these embodiments, the diameter of the glass fiber is 10-13 μm, preferably, the diameter of the glass fiber is 10 μm. The smaller the diameter and the length of the glass fiber are, the better the fiber floating effect of the surface of the obtained composite material is.
In some of these embodiments, the toughening agent is selected from Mitsubishi SX-006 or S-2001; wherein S-2001 has higher cost performance.
In some of these embodiments, the antioxidant is selected from hindered phenolic antioxidants and/or phosphite antioxidants; preferably a compound B900 consisting of the antioxidant 1076 and the antioxidant 168 according to the mass ratio of 2-4: 1.
In some of these embodiments, the lubricant is selected from montan waxes, preferably OP waxes.
In some of these embodiments, the anti-UV agent is selected from benzotriazole-based ultraviolet absorbers, preferably UV-234.
The invention also provides a preparation method of the spraying-free polycarbonate fiber-reinforced composite material.
The specific technical scheme is as follows:
a preparation method of a spraying-free polycarbonate fiber-reinforced composite material comprises the following steps:
and mixing the polycarbonate, the hyperbranched polyester copolymer, the toughening agent, the antioxidant, the lubricant and the anti-UV agent, adding the mixed mixture into a double-screw extruder from a main feeding port, adding the glass fiber into a side feeding port of the double-screw extruder, melting and blending, and extruding to obtain the spraying-free polycarbonate fiber-added composite material.
In some of these embodiments, the process parameters of the twin screw extruder include: the temperature of the first zone is 195-205 ℃, the temperature of the second zone is 265-275 ℃, the temperature of the third zone is 275-285 ℃, 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 265-275 ℃, the temperature of the seventh zone is 265-275 ℃, the temperature of the eighth zone is 275-285 ℃, the temperature of the die head is 275-285 ℃, the rotating speed of the main machine is 200-500 rpm, and the rotating speed of the feeding machine is 8-15 rpm.
Compared with the prior art, the invention has the following beneficial effects:
the hyperbranched polyester copolymer is obtained by copolymerizing hyperbranched polyester acrylate containing carboxyl and glycidyl methacrylate, and is applied to the polycarbonate fiber-added composite material, so that the spraying-free polycarbonate fiber-added composite material with the low-floating fiber on the surface can be prepared on the premise of not reducing the content of glass fiber and not using a compatibilizer. The polycarbonate is selected as a substrate, and the mechanical property, the temperature resistance, the chemical resistance and the scratch resistance of the composite material are further improved through the reinforcement of the glass fiber; the hyperbranched polyester copolymer prepared by the invention has high surface activity, can improve the processing performance of materials, can improve the interface layer of polycarbonate and glass fiber, increase the compatibility of the glass fiber and PC resin, improve the surface fiber floating effect and improve the surface glossiness, and can provide good enhancement effect on the rigidity, toughness, chemical resistance, processability and the like of composite materials; and then an antioxidant is matched to delay or inhibit the oxidation of the polymer, a lubricant is used for improving the fluidity of the material, a flexibilizer is used for improving the toughness of the material, an anti-UV agent is used for reducing the photodegradation and delaying the aging of the material, and the components are matched with each other according to a certain proportion, so that the spraying-free polycarbonate fiber-reinforced composite material has the advantages of low fiber floating on the surface, high gloss and excellent scratch resistance and has excellent mechanical properties.
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:
polycarbonate (C): japanese emperor 1250Y.
Glass fiber: japanese NEGT-511, 3mm in length and 10 μm in diameter.
B900: the antioxidant 1076 and the antioxidant 168 are a compound formed by 3:1 of antioxidant by mass ratio.
Hyperbranched polyester copolymer: the preparation method is self-made as follows:
(1) with Pentaerythritol (PE) as the core and dimethylolpropionic acid (DMPA) as AB2 monomer in a mixture of PE (4.5mmol,0.62g), DMPA (12.6mmol,1.68g) and N, N-dimethylacetamide (DMCA, 5mmol,1.406g),toluene sulfonic acid (p-TSA, 0.05g) was added as a catalyst, placed in a three-necked flask with a stirrer, and N was introduced thereinto2Continuously 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 spraying-free polycarbonate fiber-reinforced composite material which is prepared from the following components in percentage by weight:
Figure BDA0002651393490000091
the preparation method of the spraying-free polycarbonate fiber-added composite material comprises the following steps:
mixing the polycarbonate, the hyperbranched polyester copolymer, the toughening agent S-2001, the antioxidant B900, the lubricant OP wax and the anti-UV agent UV-234, adding the mixed mixture into a double-screw extruder from a main feeding port, adding the glass fiber into a side feeding port of the double-screw extruder, melting and blending, and extruding to obtain the spraying-free polycarbonate fiber-added composite material; the technological parameters of the double-screw extruder are as follows: the temperature of the first zone is 200 ℃, the temperature of the second zone is 270 ℃, the temperature of the third zone is 280 ℃, the temperature of the fourth zone is 280 ℃, the temperature of the fifth zone is 280 ℃, the temperature of the sixth zone is 270 ℃, the temperature of the seventh zone is 270 ℃, the temperature of the eighth zone is 280 ℃, the temperature of the die head is 280 ℃, the rotating speed of the main machine is 340rpm, and the feeding rotating speed is 12 rpm.
Example 2
The embodiment provides a spraying-free polycarbonate fiber-reinforced composite material which is prepared from the following components in percentage by weight:
Figure BDA0002651393490000101
the preparation method of the spraying-free polycarbonate fiber-added composite material comprises the following steps:
mixing the polycarbonate, the hyperbranched polyester copolymer, the toughening agent S-2001, the antioxidant B900, the lubricant OP wax and the anti-UV agent UV-234, adding the mixed mixture into a double-screw extruder from a main feeding port, adding the glass fiber into a side feeding port of the double-screw extruder, melting and blending, and extruding to obtain the spraying-free polycarbonate fiber-added composite material; the technological parameters of the double-screw extruder are as follows: the temperature of the first zone is 200 ℃, the temperature of the second zone is 270 ℃, the temperature of the third zone is 280 ℃, the temperature of the fourth zone is 280 ℃, the temperature of the fifth zone is 280 ℃, the temperature of the sixth zone is 270 ℃, the temperature of the seventh zone is 270 ℃, the temperature of the eighth zone is 280 ℃, the temperature of the die head is 280 ℃, the rotating speed of the main machine is 340rpm, and the feeding rotating speed is 12 rpm.
Example 3
The embodiment provides a spraying-free polycarbonate fiber-reinforced composite material which is prepared from the following components in percentage by weight:
Figure BDA0002651393490000102
Figure BDA0002651393490000111
the preparation method of the spraying-free polycarbonate fiber-added composite material comprises the following steps:
mixing the polycarbonate, the hyperbranched polyester copolymer, the toughening agent S-2001, the antioxidant B900, the lubricant OP wax and the anti-UV agent UV-234, adding the mixed mixture into a double-screw extruder from a main feeding port, adding the glass fiber into a side feeding port of the double-screw extruder, melting and blending, and extruding to obtain the spraying-free polycarbonate fiber-added composite material; the technological parameters of the double-screw extruder are as follows: the temperature of the first zone is 200 ℃, the temperature of the second zone is 270 ℃, the temperature of the third zone is 280 ℃, the temperature of the fourth zone is 280 ℃, the temperature of the fifth zone is 280 ℃, the temperature of the sixth zone is 270 ℃, the temperature of the seventh zone is 270 ℃, the temperature of the eighth zone is 280 ℃, the temperature of the die head is 280 ℃, the rotating speed of the main machine is 340rpm, and the feeding rotating speed is 12 rpm.
Example 4
The embodiment provides a spraying-free polycarbonate fiber-reinforced composite material which is prepared from the following components in percentage by weight:
Figure BDA0002651393490000112
the preparation method of the spraying-free polycarbonate fiber-added composite material comprises the following steps:
mixing the polycarbonate, the hyperbranched polyester copolymer, the toughening agent S-2001, the antioxidant B900, the lubricant OP wax and the anti-UV agent UV-234, adding the mixed mixture into a double-screw extruder from a main feeding port, adding the glass fiber into a side feeding port of the double-screw extruder, melting and blending, and extruding to obtain the spraying-free polycarbonate fiber-added composite material; the technological parameters of the double-screw extruder are as follows: the temperature of the first zone is 200 ℃, the temperature of the second zone is 270 ℃, the temperature of the third zone is 280 ℃, the temperature of the fourth zone is 280 ℃, the temperature of the fifth zone is 280 ℃, the temperature of the sixth zone is 270 ℃, the temperature of the seventh zone is 270 ℃, the temperature of the eighth zone is 280 ℃, the temperature of the die head is 280 ℃, the rotating speed of the main machine is 340rpm, and the feeding rotating speed is 12 rpm.
Example 5
The embodiment provides a spraying-free polycarbonate fiber-reinforced composite material which is prepared from the following components in percentage by weight:
Figure BDA0002651393490000121
the preparation method of the spraying-free polycarbonate fiber-added composite material comprises the following steps:
mixing the polycarbonate, the hyperbranched polyester copolymer, the toughening agent S-2001, the antioxidant B900, the lubricant OP wax and the anti-UV agent UV-234, adding the mixed mixture into a double-screw extruder from a main feeding port, adding the glass fiber into a side feeding port of the double-screw extruder, melting and blending, and extruding to obtain the spraying-free polycarbonate fiber-added composite material; the technological parameters of the double-screw extruder are as follows: the temperature of the first zone is 200 ℃, the temperature of the second zone is 270 ℃, the temperature of the third zone is 280 ℃, the temperature of the fourth zone is 280 ℃, the temperature of the fifth zone is 280 ℃, the temperature of the sixth zone is 270 ℃, the temperature of the seventh zone is 270 ℃, the temperature of the eighth zone is 280 ℃, the temperature of the die head is 280 ℃, the rotating speed of the main machine is 340rpm, and the feeding rotating speed is 12 rpm.
Example 6
The embodiment provides a spraying-free polycarbonate fiber-reinforced composite material which is prepared from the following components in percentage by weight:
Figure BDA0002651393490000131
the preparation method of the spraying-free polycarbonate fiber-added composite material comprises the following steps:
mixing the polycarbonate, the hyperbranched polyester copolymer, the toughening agent S-2001, the antioxidant B900, the lubricant OP wax and the anti-UV agent UV-234, adding the mixed mixture into a double-screw extruder from a main feeding port, adding the glass fiber into a side feeding port of the double-screw extruder, melting and blending, and extruding to obtain the spraying-free polycarbonate fiber-added composite material; the technological parameters of the double-screw extruder are as follows: the temperature of the first zone is 200 ℃, the temperature of the second zone is 270 ℃, the temperature of the third zone is 280 ℃, the temperature of the fourth zone is 280 ℃, the temperature of the fifth zone is 280 ℃, the temperature of the sixth zone is 270 ℃, the temperature of the seventh zone is 270 ℃, the temperature of the eighth zone is 280 ℃, the temperature of the die head is 280 ℃, the rotating speed of the main machine is 340rpm, and the feeding rotating speed is 12 rpm.
Example 7
The embodiment provides a spraying-free polycarbonate fiber-reinforced composite material which is prepared from the following components in percentage by weight:
Figure BDA0002651393490000141
the preparation method of the spraying-free polycarbonate fiber-added composite material comprises the following steps:
mixing the polycarbonate, the hyperbranched polyester copolymer, the toughening agent S-2001, the antioxidant B900, the lubricant OP wax and the anti-UV agent UV-234, adding the mixed mixture into a double-screw extruder from a main feeding port, adding the glass fiber into a side feeding port of the double-screw extruder, melting and blending, and extruding to obtain the spraying-free polycarbonate fiber-added composite material; the technological parameters of the double-screw extruder are as follows: the temperature of the first zone is 200 ℃, the temperature of the second zone is 270 ℃, the temperature of the third zone is 280 ℃, the temperature of the fourth zone is 280 ℃, the temperature of the fifth zone is 280 ℃, the temperature of the sixth zone is 270 ℃, the temperature of the seventh zone is 270 ℃, the temperature of the eighth zone is 280 ℃, the temperature of the die head is 280 ℃, the rotating speed of the main machine is 340rpm, and the feeding rotating speed is 12 rpm.
Comparative example 1
The comparative example provides a spraying-free polycarbonate fiber-reinforced composite material which is prepared from the following components in percentage by weight:
Figure BDA0002651393490000142
Figure BDA0002651393490000151
the preparation method of the spraying-free polycarbonate fiber-added composite material comprises the following steps:
mixing the polycarbonate, the toughening agent S-2001, the antioxidant B900, the lubricant OP wax and the anti-UV agent UV-234, adding the mixed mixture into a double-screw extruder from a main feeding port, adding the glass fiber into a side feeding port of the double-screw extruder, melting and blending, and extruding to obtain the spraying-free polycarbonate fiber-added composite material; the technological parameters of the double-screw extruder are as follows: the temperature of the first zone is 200 ℃, the temperature of the second zone is 270 ℃, the temperature of the third zone is 280 ℃, the temperature of the fourth zone is 280 ℃, the temperature of the fifth zone is 280 ℃, the temperature of the sixth zone is 270 ℃, the temperature of the seventh zone is 270 ℃, the temperature of the eighth zone is 280 ℃, the temperature of the die head is 280 ℃, the rotating speed of the main machine is 340rpm, and the feeding rotating speed is 12 rpm.
Comparative example 2
The comparative example provides a spraying-free polycarbonate fiber-reinforced composite material which is prepared from the following components in percentage by weight:
Figure BDA0002651393490000152
Figure BDA0002651393490000161
the preparation method of the spraying-free polycarbonate fiber-added composite material comprises the following steps:
mixing the polycarbonate, the compatibilizer SAG-02, the toughening agent S-2001, the antioxidant B900, the lubricant OP wax and the anti-UV agent UV-234, adding the mixed mixture into a double-screw extruder from a main feeding port, adding the glass fiber into a side feeding port of the double-screw extruder, melting and blending, and extruding to obtain the spraying-free polycarbonate fiber-added composite material; the technological parameters of the double-screw extruder are as follows: the temperature of the first zone is 200 ℃, the temperature of the second zone is 270 ℃, the temperature of the third zone is 280 ℃, the temperature of the fourth zone is 280 ℃, the temperature of the fifth zone is 280 ℃, the temperature of the sixth zone is 270 ℃, the temperature of the seventh zone is 270 ℃, the temperature of the eighth zone is 280 ℃, the temperature of the die head is 280 ℃, the rotating speed of the main machine is 340rpm, and the feeding rotating speed is 12 rpm.
Comparative example 3
The comparative example provides a spraying-free polycarbonate fiber-reinforced composite material which is prepared from the following components in percentage by weight:
Figure BDA0002651393490000162
the preparation method of the spraying-free polycarbonate fiber-added composite material comprises the following steps:
mixing the polycarbonate, the hyperbranched polymer C100, the toughening agent S-2001, the antioxidant B900, the lubricant OP wax and the anti-UV agent UV-234, adding the mixed mixture into a double-screw extruder from a main feeding port, adding the glass fiber into a side feeding port of the double-screw extruder, melting and blending, and extruding to obtain the spraying-free polycarbonate fiber-added composite material; the technological parameters of the double-screw extruder are as follows: the temperature of the first zone is 200 ℃, the temperature of the second zone is 270 ℃, the temperature of the third zone is 280 ℃, the temperature of the fourth zone is 280 ℃, the temperature of the fifth zone is 280 ℃, the temperature of the sixth zone is 270 ℃, the temperature of the seventh zone is 270 ℃, the temperature of the eighth zone is 280 ℃, the temperature of the die head is 280 ℃, the rotating speed of the main machine is 340rpm, and the feeding rotating speed is 12 rpm.
Comparative example 4
The embodiment provides a spraying-free polycarbonate fiber-reinforced composite material which is prepared from the following components in percentage by weight:
Figure BDA0002651393490000171
the preparation method of the hyperbranched polyester comprises the following steps:
pentaerythritol (PE) as a core and dimethylolpropionic acid (DMPA) as an AB2 monomerTo a mixture of PE (4.5mmol,0.62g), DMPA (12.6mmol,1.68g) and N, N-dimethylacetamide (DMCA, 5mmol,1.406g), toluenesulfonic acid (p-TSA, 0.05g) was added as a catalyst, placed in a three-necked flask with a stirrer, and N was bubbled 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).
The preparation method of the spraying-free polycarbonate fiber-added composite material comprises the following steps:
mixing the polycarbonate, the hyperbranched polyester, the toughening agent S-2001, the antioxidant B900, the lubricant OP wax and the anti-UV agent UV-234, adding the mixed mixture into a double-screw extruder from a main feeding port, adding the glass fiber into a side feeding port of the double-screw extruder, melting and blending, and extruding to obtain the spraying-free polycarbonate fiber-added composite material; the technological parameters of the double-screw extruder are as follows: the temperature of the first zone is 200 ℃, the temperature of the second zone is 270 ℃, the temperature of the third zone is 280 ℃, the temperature of the fourth zone is 280 ℃, the temperature of the fifth zone is 280 ℃, the temperature of the sixth zone is 270 ℃, the temperature of the seventh zone is 270 ℃, the temperature of the eighth zone is 280 ℃, the temperature of the die head is 280 ℃, the rotating speed of the main machine is 340rpm, and the feeding rotating speed is 12 rpm.
Comparative example 5
The embodiment provides a spraying-free polycarbonate fiber-reinforced composite material which is prepared from the following components in percentage by weight:
Figure BDA0002651393490000181
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 N, N-dimethylacetamide (DMCA, 5mmol,1.406g) was added toluenesulfonic acid (p-TSA, 0.05g) as a catalyst, and the mixture was placed in a three-necked flask equipped with a stirrerIntroduction of N2Continuously 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.
The preparation method of the spraying-free polycarbonate fiber-added composite material comprises the following steps:
mixing the polycarbonate, the carboxyl-containing hyperbranched polyester acrylate, the flexibilizer S-2001, the antioxidant B900, the lubricant OP wax and the anti-UV agent UV-234, adding the mixed mixture into a double-screw extruder from a main feeding port, adding the glass fiber into a side feeding port of the double-screw extruder, and carrying out melt blending to obtain the spraying-free polycarbonate fiber-added composite material after extrusion; the technological parameters of the double-screw extruder are as follows: the temperature of the first zone is 200 ℃, the temperature of the second zone is 270 ℃, the temperature of the third zone is 280 ℃, the temperature of the fourth zone is 280 ℃, the temperature of the fifth zone is 280 ℃, the temperature of the sixth zone is 270 ℃, the temperature of the seventh zone is 270 ℃, the temperature of the eighth zone is 280 ℃, the temperature of the die head is 280 ℃, the rotating speed of the main machine is 340rpm, and the feeding rotating speed is 12 rpm.
The properties of the spray-free polycarbonate fiber-reinforced composites provided in examples 1-7 and comparative examples 1-5 above were tested, and the test criteria and results are shown in table 1 below:
TABLE 1
Figure BDA0002651393490000201
Note: the pencil hardness is a method for testing the surface hardness of a material, pencils with different hardness are scratched on the surface of a sample under a certain load, then the surface of the sample is wiped off by using an eraser, the hardness grade is judged by observing whether scratches are left on the surface of the sample, and the hardness is gradually increased from 1-6B, HB, F and 1-5H; the higher the pencil hardness, the more scratch resistant the sample surface.
From the experimental data in table 1, it can be seen that: the spraying-free polycarbonate fiber-reinforced composite material provided by the invention has the advantages of low surface floating fiber, high gloss and excellent scratch resistance, and also has excellent mechanical properties.
1. In examples 1-5, with the increase of the addition amount of the hyperbranched polyester copolymer, the surface gloss and the pencil hardness of the obtained spraying-free polycarbonate fiber-reinforced composite material are improved, and when the addition amount reaches 0.8%, various performances, the surface gloss and the pencil hardness reach the optimal state; the dosage of the hyperbranched polyester copolymer is further increased, the mechanical property, the surface gloss and the pencil hardness of the obtained spraying-free polycarbonate fiber-reinforced composite material are not obviously changed, the melt index is very low, and the processability of the material is poor.
2. Example 6 compared with example 1, the addition amount of the glass fiber is reduced, the surface gloss is slightly improved, the pencil hardness is reduced, the tensile strength, the bending modulus and the heat distortion temperature are reduced, and the impact strength is improved; example 7 compared with example 1, the addition amount of the glass fiber is increased, although the tensile strength, the bending modulus and the heat distortion temperature are improved, the glossiness is lower, and the melt index is reduced, so that the processability of the material is reduced; the glass fiber in example 1 was added in an even greater amount, combining the properties.
3. Compared with the example 1, the prepared spraying-free polycarbonate fiber-added composite material has poor surface gloss and poor scratch resistance and mechanical property compared with the example 1 without adding the hyperbranched polyester copolymer; compared with the example 1, the spraying-free polycarbonate fiber-added composite material prepared by replacing the hyperbranched polyester copolymer with the traditional compatibilizer SAG-02 has improved mechanical properties compared with the comparative example 1 without the hyperbranched polyester copolymer, but the surface gloss and the pencil hardness are not improved, and the properties are poorer than those of the example 1; comparative example 3 compared with example 1, hyperbranched polyesteramide C100 is used to replace the hyperbranched polyester copolymer of the invention, and the surface gloss, scratch resistance and mechanical properties of the prepared spraying-free polycarbonate fiber-reinforced composite material are all worse than those of example 1, which shows that the effect of C100 on improving the surface gloss and scratch resistance of the spraying-free polycarbonate fiber-reinforced composite material is not as good as that of the hyperbranched polyester copolymer of the invention; comparative example 4 compared with example 1, the surface gloss, scratch resistance and mechanical properties of the spray-free polycarbonate fiber-reinforced composite material prepared by replacing the hyperbranched polyester copolymer with hyperbranched polyester are poorer than those of example 1; comparative example 5 compared with example 1, the surface gloss, the scratch resistance and the mechanical properties of the spray-free polycarbonate fiber-reinforced composite material prepared by replacing the hyperbranched polyester copolymer with the hyperbranched polyester acrylate containing carboxyl are poorer than those of example 1, which shows that after the hyperbranched polyester acrylate containing carboxyl is subjected to grafting modification treatment by glycidyl methacrylate, the surface gloss, the scratch resistance and the mechanical properties of the spray-free polycarbonate fiber-reinforced composite material can be more effectively improved compared with unmodified hyperbranched polyester and the hyperbranched polyester acrylate containing carboxyl.
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 (17)

1. The hyperbranched polyester copolymer is characterized by being obtained by copolymerizing 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 hyperbranched polyester copolymer of claim 1, wherein the mass ratio of the carboxyl-containing hyperbranched polyester acrylate to the glycidyl methacrylate is 2-4: 1-2.
3. The hyperbranched polyester copolymer of claim 1, wherein the mass ratio of succinic anhydride, hexamethylene diisocyanate, hydroxyethyl acrylate to hyperbranched polyester is 4-5:7-8:5-6: 1.
4. Hyperbranched polyester copolymer according to any of claims 1 to 3, wherein the hyperbranched polyester is obtained by polymerizing pentaerythritol and dimethylolpropionic acid.
5. The hyperbranched polyester copolymer of claim 4, wherein 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.
6. A method for preparing the hyperbranched polyester copolymer of any one of claims 1 to 5, 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.
7. The method for preparing hyperbranched polyester copolymer as defined in claim 6, wherein the temperature for reacting hexamethylene diisocyanate with hydroxyethyl acrylate is 35-45 ℃ for 10-15 hours; and/or the presence of a gas in the gas,
the reaction temperature of the hyperbranched polyester and succinic anhydride in an organic solvent is 85-95 ℃, and the reaction time is 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,
the temperature for reacting the carboxyl-containing hyperbranched polyester acrylate, glycidyl methacrylate and a proper amount of polymerization inhibitor is 65-75 ℃, and the reaction is carried out until the acid value is stable.
8. The method of preparing a hyperbranched polyester copolymer according to claim 6 or the method of preparing a hyperbranched polyester copolymer, wherein the first organic solvent is acetone; and/or the polymerization inhibitor is p-hydroxyanisole.
9. The method for preparing hyperbranched polyester copolymer according to any one of claims 6 to 8, wherein the method for preparing 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.
10. The method for preparing hyperbranched polyester copolymer as claimed in claim 9, wherein the temperature of the reaction in the step of preparing hyperbranched polyester is 130-150 ℃ and the time is 3-7 hours.
11. The method of preparing a hyperbranched polyester copolymer as defined in claim 9 wherein the second organic solvent is N, N-dimethylacetamide; and/or the catalyst is toluenesulfonic acid.
12. The spraying-free polycarbonate fiber-reinforced composite material is characterized by being prepared from the following raw materials in percentage by weight:
Figure FDA0002651393480000021
Figure FDA0002651393480000031
the hyperbranched polyester copolymer is the hyperbranched polyester copolymer described in any one of claims 1 to 5, or the hyperbranched polyester copolymer prepared by the preparation method described in any one of claims 6 to 11.
13. The spray-free polycarbonate fiber-reinforced composite material of claim 12, which is prepared from the following raw materials in percentage by weight:
Figure FDA0002651393480000032
14. the spray-free polycarbonate fiber-reinforced composite material as claimed in claim 13, which is prepared from the following raw materials in percentage by weight:
Figure FDA0002651393480000033
15. the spray-free polycarbonate-fiber composite material of any one of claims 12-14, wherein the glass fibers have a length of 3-4 mm; and/or the presence of a gas in the gas,
the diameter of the glass fiber is 10-13 mm; and/or the presence of a gas in the gas,
the toughening agent is selected from Mitsubishi SX-006 or S-2001; and/or the presence of a catalyst in the reaction mixture,
the antioxidant is selected from hindered phenol antioxidants and/or phosphite antioxidants, preferably a compound B900 consisting of an antioxidant 1076 and an antioxidant 168 according to the mass ratio of 2-4: 1; and/or the presence of a catalyst in the reaction mixture,
the lubricant is selected from montan wax; and/or the presence of a catalyst in the reaction mixture,
the UV resistant agent is selected from benzotriazole ultraviolet absorbers, and is preferably UV-234.
16. A method for preparing a spray-free polycarbonate fiber composite material according to any one of claims 12 to 15, comprising the following steps:
and mixing the polycarbonate, the hyperbranched polyester copolymer, the toughening agent, the antioxidant, the lubricant and the anti-UV agent, adding the mixed mixture into a double-screw extruder from a main feeding port, adding the glass fiber into a side feeding port of the double-screw extruder, melting and blending, and extruding to obtain the spraying-free polycarbonate fiber-added composite material.
17. The method for preparing a spray-free polycarbonate fiber-reinforced composite material as claimed in claim 16, wherein the process parameters of the twin-screw extruder comprise: the temperature of the first zone is 195-205 ℃, the temperature of the second zone is 265-275 ℃, the temperature of the third zone is 275-285 ℃, 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 265-275 ℃, the temperature of the seventh zone is 265-275 ℃, the temperature of the eighth zone is 275-285 ℃, the temperature of the die head is 275-285 ℃, the rotating speed of the main machine is 200-500 rpm, and the rotating speed of the feeding machine is 8-15 rpm.
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