CN112029271A - Spraying-free polycaprolactam composite material and preparation method thereof - Google Patents

Spraying-free polycaprolactam composite material and preparation method thereof Download PDF

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CN112029271A
CN112029271A CN202010899347.XA CN202010899347A CN112029271A CN 112029271 A CN112029271 A CN 112029271A CN 202010899347 A CN202010899347 A CN 202010899347A CN 112029271 A CN112029271 A CN 112029271A
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hyperbranched polyester
gas
free
composite material
polycaprolactam
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朱怀才
谢平
梁振锋
刘羽玲
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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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
    • C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/01—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to unsaturated polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • C08J2377/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2483/04—Polysiloxanes
    • 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
    • C08J2491/00—Characterised by the use of oils, fats or waxes; Derivatives thereof
    • C08J2491/06—Waxes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/04—Ingredients characterised by their shape and organic or inorganic ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/20—Carboxylic acid amides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
    • C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass

Abstract

The invention provides a spraying-free polycaprolactam (PA6) composite material and a preparation method thereof. The polycaprolactam composite material is prepared from the following raw materials: 55-80 parts of polycaprolactam, 20-42 parts of glass fiber, 0.2-1 part of hyperbranched polyester copolymer, 0.2-0.8 part of antioxidant and 0.5-2.0 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 spraying-free polycaprolactam composite material has high surface gloss and surface hardness, and also has excellent mechanical properties and high heat resistance.

Description

Spraying-free polycaprolactam composite material and preparation method thereof
Technical Field
The invention belongs to the technical field of polymer composite materials, and particularly relates to a spraying-free polycaprolactam composite material and a preparation method thereof.
Background
The glass fiber reinforced polycaprolactam composite material has better mechanical property, temperature resistance and chemical resistance, and is widely applied to the fields of electronics, electrics, automobiles, communication, mechanical engineering, sports equipment and the like. After the glass fiber reinforced polycaprolactam composite material is injection molded, plastic on the surface of a workpiece is sprayed to make up for the defects of fiber floating on the surface of the product and low surface hardness. With the introduction of the spraying-free material in recent years, compared with the traditional plastic material, the spraying-free material has the advantages of rich color, good surface gloss, good surface hardness, environmental protection, lower comprehensive use cost and the like. Therefore, the research on the spraying-free polycaprolactam composite material has important significance on the development of electronics and electricity.
At present, some problems to be solved still exist in the field of spraying-free polycaprolactam composite materials, particularly the problem of fiber floating on the surface and the problem of poor surface glossiness. 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 and the surface hardness cannot be improved; if the addition amount is large, the whole mechanical property and temperature resistance of the composite material are damaged, and the processing property of the material is also poor.
Disclosure of Invention
Based on the defects in the prior art, the invention aims to provide the spraying-free polycaprolactam composite material, which has the advantages of low fiber floating on the surface, high gloss and high hardness, and also has excellent mechanical property and temperature resistance.
In order to achieve the purpose, the specific technical scheme is as follows:
the spraying-free polycaprolactam composite material is prepared from the following raw materials in parts by weight:
Figure BDA0002659303910000021
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 spray-free polycaprolactam composite material is prepared from the following raw materials in parts by weight:
Figure BDA0002659303910000022
in some embodiments, the spray-free polycaprolactam composite material is prepared from the following raw materials in parts by weight:
Figure BDA0002659303910000031
the invention takes PA6 (Chinese name is polycaprolactam or polyamide-6) as a base material, and the PA6 is matched with the glass fiber and the hyperbranched polyester copolymer in proper proportion, so that the obtained composite material has the spraying-free effect, has the advantages of low surface floating fiber, high gloss and high hardness, and simultaneously has excellent mechanical property and temperature resistance.
In some embodiments, the weight parts of the polycaprolactam in the spray-free polycaprolactam composite may be 55 parts, 56 parts, 57 parts, 58 parts, 59 parts, 60 parts, 61 parts, 62 parts, 63 parts, 64 parts, 65 parts, 66 parts, 67 parts, 68 parts, 69 parts, 70 parts, 71 parts, 72 parts, 73 parts, 74 parts, 75 parts, 76 parts, 77 parts, 78 parts, 79 parts, or 80 parts.
In some embodiments, the weight parts of the glass fibers in the spray-free polycaprolactam composite may be 20 parts, 21 parts, 22 parts, 23 parts, 24 parts, 25 parts, 26 parts, 27 parts, 28 parts, 29 parts, 30 parts, 31 parts, 32 parts, 33 parts, 34 parts, 35 parts, 36 parts, 37 parts, 38 parts, 39 parts, 40 parts, 41 parts, or 42 parts.
In some of these embodiments, the weight part of the hyperbranched polyester copolymer in the spray-free polycaprolactam composite may be 0.2 part, 0.3 part, 0.4 part, 0.5 part, 0.6 part, 0.7 part, 0.8 part, 0.9 part, or 1 part.
In some embodiments, the weight part of the antioxidant in the spray-free polycaprolactam composite material may be 0.2 part, 0.25 part, 0.3 part, 0.35 part, 0.4 part, 0.45 part, 0.5 part, 0.55 part, 0.6 part, 0.65 part, 0.7 part, 0.75 part or 0.8 part.
In some of these embodiments, the weight parts of the lubricant in the spray-free polycaprolactam composite may be 0.5 parts, 0.6 parts, 0.7 parts, 0.8 parts, 0.9 parts, 1.0 parts, 1.1 parts, 1.2 parts, 1.3 parts, 1.4 parts, 1.5 parts, 1.6 parts, 1.7 parts, 1.8 parts, 1.9 parts, or 2.0 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 polycaprolactam has a relative density of 1.13 to 1.15g/cm3The melting point is 210-230 ℃.
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-LS 100.
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 spraying-free polycaprolactam composite material.
The specific technical scheme is as follows:
a preparation method of a spray-free polycaprolactam composite material comprises the following steps:
and uniformly mixing the polycaprolactam, the glass fiber, the hyperbranched polyester copolymer, the antioxidant and the lubricant, adding the obtained mixture into an extruder, melting and blending, and extruding to obtain the spray-free polycaprolactam composite material.
In some of these embodiments, the extruder is a parallel co-rotating twin screw extruder.
In some of these embodiments, the temperature of the extrusion is 250-270 ℃, and may be, for example, 250 ℃, 255 ℃, 260 ℃, 265 ℃ or 270 ℃.
In some embodiments, the rotation speed of the main machine of the extruder is 300-400rpm, for example, 300rpm, 320rpm, 340rpm, 360rpm, 380rpm or 400 rpm; the feeding speed of the extruder is 5-20rpm, and may be, for example, 5rpm, 8rpm, 10rpm, 12rpm, 14rpm, 16rpm, 18rpm or 20 rpm.
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 with a specific proportion into matrix resin PA6 (polycaprolactam resin), and under the coordination of a certain amount of glass fiber, a novel PA6 composite material with high surface gloss and surface hardness, excellent mechanical properties and high heat resistance can be prepared. The hyperbranched polyester copolymer has a spherical and annular dendritic three-dimensional structure, and particularly a large number of polar carboxyl groups and reactive polar epoxy groups exist on the surface of the modified hyperbranched polyester copolymer, so that the modified hyperbranched polyester copolymer has high surface activity, a contact interface layer of glass fibers and PA6 resin can be improved, the compatibility of the glass fibers and the PA6 resin is improved, surface floating fibers of the PA6 composite material are improved, the surface gloss and the surface hardness of the composite material are improved, and good reinforcing effects on the rigidity, toughness, chemical resistance, processability and the like of the composite material can be provided; 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 spray-free polycaprolactam composite material has the advantages of low fiber floating on the surface, high gloss, high hardness and the like, and has excellent mechanical property and temperature 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:
polycaprolactam (PA 6): BL3280H, Chinese petrochemical; the relative density was 1.13g/cm3The melting point is 220 ℃;
glass fiber: erwining 983, 3mm in length, 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 spraying-free polycaprolactam composite material which is prepared from the following components in parts by weight:
Figure BDA0002659303910000091
the preparation method of the spraying-free polycaprolactam composite material comprises the following steps:
uniformly mixing the hyperbranched polyester copolymer with polycaprolactam, 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), melting and blending, setting the extrusion temperature to be 260 ℃ and the rotating speed of a screw (the main machine rotating speed of the extruder) to be 400rpm, and extruding to obtain the spray-free polycaprolactam composite material.
Example 2
The embodiment provides a spraying-free polycaprolactam composite material which is prepared from the following components in parts by weight:
Figure BDA0002659303910000101
the preparation method of the spraying-free polycaprolactam composite material comprises the following steps:
uniformly mixing the hyperbranched polyester copolymer with polycaprolactam, 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), melting and blending, setting the extrusion temperature to be 260 ℃ and the rotating speed of a screw (the main machine rotating speed of the extruder) to be 350rpm, and extruding to obtain the spray-free polycaprolactam composite material.
Example 3
The embodiment provides a spraying-free polycaprolactam composite material which is prepared from the following components in parts by weight:
Figure BDA0002659303910000111
the preparation method of the spraying-free polycaprolactam composite material comprises the following steps:
uniformly mixing the hyperbranched polyester copolymer with polycaprolactam, 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), melting and blending, setting the extrusion temperature to be 260 ℃ and the rotating speed of a screw (the main machine rotating speed of the extruder) to be 350rpm, and extruding to obtain the spray-free polycaprolactam composite material.
Example 4
The embodiment provides a spraying-free polycaprolactam composite material which is prepared from the following components in parts by weight:
Figure BDA0002659303910000112
Figure BDA0002659303910000121
the preparation method of the spraying-free polycaprolactam composite material comprises the following steps:
uniformly mixing the hyperbranched polyester copolymer with polycaprolactam, 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), melting and blending, setting the extrusion temperature to be 260 ℃ and the rotating speed of a screw (the main machine rotating speed of the extruder) to be 350rpm, and extruding to obtain the spray-free polycaprolactam composite material.
Example 5
The embodiment provides a spraying-free polycaprolactam composite material which is prepared from the following components in parts by weight:
Figure BDA0002659303910000122
the preparation method of the spraying-free polycaprolactam composite material comprises the following steps:
uniformly mixing the hyperbranched polyester copolymer with polycaprolactam, 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), melting and blending, setting the extrusion temperature to be 260 ℃ and the rotating speed of a screw (the main machine rotating speed of the extruder) to be 350rpm, and extruding to obtain the spray-free polycaprolactam composite material.
Example 6
The embodiment provides a spraying-free polycaprolactam composite material which is prepared from the following components in parts by weight:
Figure BDA0002659303910000131
the preparation method of the spraying-free polycaprolactam composite material comprises the following steps:
uniformly mixing the hyperbranched polyester copolymer with polycaprolactam, 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), melting and blending, setting the extrusion temperature to be 260 ℃ and the rotating speed of a screw (the main machine rotating speed of the extruder) to be 350rpm, and extruding to obtain the spray-free polycaprolactam composite material.
Example 7
The embodiment provides a spraying-free polycaprolactam composite material which is prepared from the following components in parts by weight:
Figure BDA0002659303910000132
Figure BDA0002659303910000141
the preparation method of the spraying-free polycaprolactam composite material comprises the following steps:
uniformly mixing the hyperbranched polyester copolymer with polycaprolactam, 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), melting and blending, setting the extrusion temperature to be 260 ℃ and the rotating speed of a screw (the main machine rotating speed of the extruder) to be 350rpm, and extruding to obtain the spray-free polycaprolactam composite material.
Comparative example 1
The difference from example 1 is that the same amount of polycaprolactam is used instead of the hyperbranched polyester copolymer, and the other components, the amounts and the preparation steps are the same as those of example 1.
Comparative example 2
The difference from the example 1 is that the same amount of the maleic anhydride grafted polypropylene compatilizer KT-1 is used for replacing the hyperbranched polyester copolymer, and other components, the using amount and the preparation steps are the same as those of the example 1.
Comparative example 3
The difference from example 1 is that the same amount of hyperbranched polymer C100 was used instead of the hyperbranched polyester copolymer, and the other components, amounts and preparation steps were the same as in example 1.
Comparative example 4
The difference from example 1 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 1.
The preparation method of the hyperbranched polyester comprises the following steps:
with Pentaerythritol (PE) as a core and dimethylolpropionic acid (DMPA) as AB2 monomer, to a mixture of PE (4.5mmol,0.62g), DMPA (12.6mmol,1.68g) and 5mmol,1.406g 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; 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 5
The difference from example 1 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 1.
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.
The spray-free polycaprolactam composites provided in examples 1-7 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 BDA0002659303910000161
Figure BDA0002659303910000171
From the experimental data in table 1, it can be seen that: the spraying-free polycaprolactam composite material provided by the invention has the advantages of low surface floating fiber, high gloss, high hardness and the like, and has excellent mechanical properties and heat resistance.
1. In examples 1-5, with the increase of the addition amount of the hyperbranched polyester copolymer, the surface gloss and Rockwell hardness of the obtained spray-free polycaprolactam composite material are improved, and when the addition amount reaches 0.8%, various performances, the surface gloss and the Rockwell hardness reach the optimal state; the dosage of the hyperbranched polyester copolymer is further increased, the mechanical property, the surface gloss and the Rockwell hardness of the obtained spraying-free polycaprolactam 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 Rockwell hardness is reduced, and the tensile strength, the bending modulus, the impact strength and the heat distortion temperature are all reduced; example 7 compared with example 1, the addition amount of the glass fiber is increased, although the tensile strength, the bending modulus, the impact strength and the heat distortion temperature are improved, the glossiness is lower, and the melt index is lower, so that the processability of the material is reduced; the glass fiber in example 1 is added in a better amount in combination with various properties.
3. Compared with the example 1, the prepared spraying-free polycaprolactam composite material has poor surface gloss, surface hardness and mechanical property compared with the example 1 without adding the hyperbranched polyester copolymer; compared with the embodiment 1, the spraying-free polycaprolactam composite material prepared by using the traditional maleic anhydride grafted polypropylene compatibilizer KT-1 to replace the hyperbranched polyester copolymer has the advantages that although the mechanical property, the surface gloss and the surface hardness are improved compared with the comparative example 1 without adding the hyperbranched polyester copolymer, the performances are poorer than those of the embodiment 1; comparative example 3 compared with example 1, hyperbranched polymer C100 was used in place of the hyperbranched polyester copolymer of the present invention, and the surface gloss, hardness and mechanical properties of the prepared spray-free polycaprolactam composite material were inferior to those of example 1, indicating that the effect of C100 on improving the surface gloss and surface hardness of the spray-free polycaprolactam composite material was inferior to that of the hyperbranched polyester copolymer of the present invention; comparative example 4 compared with example 1, the spraying-free polycaprolactam composite material prepared by replacing the hyperbranched polyester copolymer with the hyperbranched polyester has poorer surface gloss, surface hardness and mechanical properties than example 1; comparative example 5 compared with example 1, the surface gloss, the surface hardness and the mechanical properties of the spray-free polycaprolactam 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 surface hardness and the mechanical properties of the spray-free polycaprolactam 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 (10)

1. The spraying-free polycaprolactam composite material is characterized by being prepared from the following raw materials in parts by weight:
Figure FDA0002659303900000011
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 spray-free polycaprolactam composite material of claim 1, prepared from the following raw materials in parts by weight:
Figure FDA0002659303900000012
3. the spray-free polycaprolactam composite material of claim 1, wherein the mass ratio of the carboxyl-containing hyperbranched polyester acrylate 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. The spray-free polycaprolactam composite of claim 1, wherein the hyperbranched polyester is obtained from the polymerization of pentaerythritol and dimethylolpropionic acid; preferably, the molar ratio of pentaerythritol to dimethylolpropionic acid is 1: 1-6; more preferably, the molar ratio of pentaerythritol to dimethylolpropionic acid is from 1:2 to 4.
5. The spray-free polycaprolactam composite material of any one of claims 1-4, wherein the hyperbranched polyester copolymer is prepared by a method comprising the steps of:
reacting the hexamethylene diisocyanate with hydroxyethyl acrylate to obtain an HDI-HEA product;
reacting the hyperbranched polyester with succinic anhydride in a first organic solvent, and then adding the HDI-HEA product into the obtained reaction mixture for reaction to obtain the carboxyl-containing hyperbranched polyester acrylate;
and reacting the carboxyl-containing hyperbranched polyester acrylate, glycidyl methacrylate and a proper amount of polymerization inhibitor to obtain the hyperbranched polyester copolymer.
6. The spray-free polycaprolactam composite of claim 5, wherein the hexamethylene diisocyanate and the hydroxyethyl acrylate are reacted at a temperature of 35-45 ℃ for 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. The spray-free polycaprolactam composite material according to any one of claims 1 to 4, wherein the hyperbranched polyester is prepared by a method comprising 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 spray-free polycaprolactam composite material of 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. Spray-free polycaprolactam composite according to any of claims 1 to 4, wherein the polycaprolactam has a relative density of 1.13 to 1.15g/cm3The melting point is 210-230 ℃; and/or the presence of a gas in the gas,
the length of the glass fiber is 3-4mm, and the diameter of the glass fiber is 10-13 mm; 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 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 process for preparing spray-free polycaprolactam composite material according to any one of claims 1 to 9, comprising the steps of:
uniformly mixing the polycaprolactam, the glass fiber, the hyperbranched polyester copolymer, the antioxidant and the lubricant, adding the obtained mixture into an extruder, melting and blending, and extruding to obtain the spray-free polycaprolactam composite material;
preferably, the extruder is a parallel co-rotating twin screw extruder;
the extrusion temperature is 250-270 ℃;
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.
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