CN110483992B - Low-warpage reinforced semi-aromatic high-temperature nylon composite material and preparation method thereof - Google Patents
Low-warpage reinforced semi-aromatic high-temperature nylon composite material and preparation method thereof Download PDFInfo
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- CN110483992B CN110483992B CN201910833872.9A CN201910833872A CN110483992B CN 110483992 B CN110483992 B CN 110483992B CN 201910833872 A CN201910833872 A CN 201910833872A CN 110483992 B CN110483992 B CN 110483992B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
Abstract
The invention discloses a low-warpage reinforced semi-aromatic high-temperature nylon composite material which is mainly prepared from the following raw materials in percentage by weight: 20% -85% of semi-aromatic high-temperature nylon; 5-40% of polyarylate; 0.5 to 5 percent of compatilizer; 5% -60% of reinforcing fiber; 0.5 to 3 percent of auxiliary agent, wherein the compatilizer is polyepoxy compound modified poly-phenol-oxygen resin. The invention also discloses a preparation method of the composite material, which comprises the following steps: mixing and uniformly mixing the semi-aromatic high-temperature nylon, the polyarylate, the compatilizer and the auxiliary agent in a high-speed mixer, adding the reinforced fiber from a glass fiber port or a side feeding port of an extruder, and performing double-screw melt extrusion, cooling, granulating and drying to obtain the low-warpage reinforced high-temperature nylon composite material. The composite material of the invention adopts the polyepoxy compound modified polyphenoxy resin as the compatilizer, and can solve the compatibility problem of polyarylate and semi-aromatic high-temperature nylon.
Description
Technical Field
The invention belongs to the technical field of nylon materials, and particularly relates to a low-warpage reinforced semi-aromatic high-temperature nylon composite material and a preparation method thereof.
Background
The semi-aromatic polyamide resin is more excellent in heat resistance and mechanical properties than a common aliphatic polyamide resin, and is also more excellent in low water absorption, and thus is more and more widely applied to the automobile industry, rail transit industry and the electronic and electrical industry. Applications in these areas require resins with metal-like properties that are often only achievable with highly filled, reinforced materials, especially high glass fiber content reinforced molding materials. However, the high glass fiber content material inevitably causes severe fiber floating on the surface of the injection molding product, and the warping is obvious due to the orientation of the glass fiber and the internal crystallization stress of the polyamide.
CN102585491B discloses a reinforced polyamide composition with excellent fluidity and low warpage, a preparation method and application thereof, wherein the reinforced polyamide composition is prepared from 30-60% of polyamide, 40-70% of inorganic reinforcing filler and 0-20% of flame retardant, the polyamide is composed of semi-aromatic polyamide and aliphatic polyamide, and the mass ratio of the semi-aromatic polyamide to the aliphatic polyamide is 10: 1-3. According to the scheme, the aliphatic polyamide is added into the semi-aromatic polyamide in a certain proportion, so that the fluidity is greatly improved, the surface is relatively ideal, the warpage is obviously reduced, and the semi-aromatic polyamide has a considerable mechanical property. However, the aliphatic polyamide is added in the scheme, so that the water absorption rate of the material is improved, the strength of the material is greatly reduced after water absorption, the strength and modulus retention rate of the material at high temperature are lowered, and the use of the material under the high-temperature and high-humidity working condition is limited.
CN103756310A discloses a polyamide/polyarylate alloy, which is prepared from the following components in parts by mass: 40-60 parts of polyamide, 20-40 parts of bisphenol A polyarylate, 5-20 parts of compatilizer, 0.2-2 parts of antioxidant and 0.2-2 parts of lubricant. The polyamide/polyarylate alloy has small molding shrinkage rate, and the product is not easy to deform and warp; the water absorption of the alloy is obviously lower than that of polyamide resin, and the drying time before material molding is shortened. However, the scheme uses aliphatic polyamide without adding a reinforcing material, so that the mechanical property and the heat resistance of the material are poor, and the application range of the material is limited.
For the improvement of the material warpage, the literature reports that inorganic fillers such as whiskers, mica, talc, glass flakes, glass beads and the like with a certain length-diameter ratio can be added for improvement, but the methods have a certain effect on improving the warpage unilaterally, but the addition ratio is higher, so that the mechanical property of the material is obviously reduced.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects and defects in the background technology and providing a low-warpage reinforced semi-aromatic high-temperature nylon composite material and a preparation method thereof.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
a low-warpage reinforced semi-aromatic high-temperature nylon composite material is mainly prepared from the following raw materials in percentage by weight:
20% -85% of semi-aromatic high-temperature nylon;
5-40% of polyarylate;
0.5 to 5 percent of compatilizer;
5% -60% of reinforcing fiber;
0.5 to 3 percent of auxiliary agent.
In the semi-aromatic high-temperature nylon composite material, the compatilizer is preferably polyepoxy compound modified polyphenoxy resin (the molecular weight of the polyphenoxy resin is 10000-; the polyepoxy compound is a compound containing more than two epoxy functional groups in a molecule, and comprises glycidyl type, ester ring type or mixed polyepoxy compounds; the glycidyl type polyepoxy compound is one or more of tetraphenylethane tetraglycidyl ether, trimesic acid triglycidyl ether, o (or m) phthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, trimesic acid triglycidyl ester, p-aminophenol triglycidyl epoxy resin, 4' -diaminodiphenylmethane tetraglycidyl epoxy resin and bisphenol A epoxy resin; the ester ring-type polyepoxy compound is one or more of 3, 4-epoxy group cyclohexane carboxylic acid 3 ', 4 ' -epoxy group cyclohexane methyl ester, 3, 4-epoxy group 6-methyl cyclohexane carboxylic acid 3 ', 4 ' -epoxy group 6 ' -methyl cyclohexane methyl ester and bis- (2, 3-epoxy group cyclopentyl) ether; the mixed polyepoxy compound is preferably vinyl cyclohexene diepoxy.
Further preferably, the polyepoxy compound is one or more of diglycidyl ortho (or meta) phthalate and diglycidyl tetrahydrophthalate.
The phenoxy resin is a thermoplastic resin with strong molecular polarity, has good compatibility with polar polyarylate and semi-aromatic high-temperature nylon, has a plurality of repeated hydroxyl groups on the side chain, can react with terminal carboxyl of the polyarylate and the semi-aromatic high-temperature nylon, improves the compatibility of the polyarylate and the semi-aromatic high-temperature nylon, but has lower reaction activity and limited action; the epoxy group in the polyepoxy compound has stronger reactivity with hydroxyl and carboxyl, the epoxy group in the polyepoxy compound reacts with the hydroxyl group on the side chain of the phenoxy resin to prepare the polyphenoxy resin modified by the polyepoxy compound, and the epoxy group introduced into the polyphenoxy resin modified by the polyepoxy compound has higher reactivity with the end groups of the polyarylate and the semi-aromatic high-temperature nylon, so that the compatibility of the polyarylate and the semi-aromatic high-temperature nylon can be further improved.
The semi-aromatic high-temperature nylon composite material is preferably one or more of polyhexamethylene terephthalamide-co-hexamethylene adipamide copolymer (PA6T/66), polyhexamethylene terephthalamide-co-caprolactam copolymer (PA6T/6), poly-nonane terephthalamide (PA9T), poly-decanediamide (PA10T), poly-tridecyl-terephthalamide (PA11T), tridecyl-diamine terephthalamide (PA12T) and tridecyl-diamine terephthalamide (PA13T) with a melting point of 285-330 ℃.
In the above semi-aromatic high-temperature nylon composite material, preferably, the repeating unit structure in the polyarylate is:
In the above semi-aromatic high-temperature nylon composite material, preferably, the reinforcing fibers are glass fibers and/or carbon fibers.
In the above semi-aromatic high-temperature nylon composite material, preferably, the glass fibers include continuous long glass fibers and short glass fibers; the length of the short glass fiber is 2-50 mm. Further preferably, the short glass fibers are selected from fibers having a non-circular cross section and a size ratio of a major axis of the cross section to a minor axis of the cross section of more than 2 (further preferably 2 to 8, particularly 2 to 5), and the glass fibers are favorable for reducing warpage.
Preferably, the auxiliary agent comprises a conventional heat stabilizer and a lubricant.
As a general inventive concept, the present invention also provides a preparation method of the above semi-aromatic high temperature nylon composite material, comprising the following steps:
(1) preparing a compatilizer;
(2) drying the semi-aromatic high-temperature nylon for later use;
(3) uniformly mixing the dried semi-aromatic high-temperature nylon, the polyarylate, the compatilizer and the auxiliary agent in a high-speed mixer, adding the reinforcing fiber from a glass fiber port or a side feeding port of an extruder, and performing double-screw melt extrusion, cooling, granulating and drying to obtain the low-warpage reinforced high-temperature nylon composite material.
In the preparation method, preferably, in the step (1), the specific process for preparing the compatibilizer is as follows: uniformly mixing the phenoxy resin and the polyepoxy compound, and carrying out high-temperature melting and blending in a Haake torque rheometer to obtain the polyepoxy compound modified polyphenoxy resin compatilizer; wherein the mass addition amount of the polyepoxy compound is not more than 5% of the mass of the phenolic resin, and the processing conditions of the torque rheometer are as follows: the working temperature is 160 ℃ and 200 ℃, the rotating speed is 40-100rpm, and the blending time is 6-12 min.
In the preparation method, preferably, in the step (2), the drying refers to drying in an oven at 130 ℃ and 100 ℃ for 3-6 h;
in the step (3), the melt extrusion temperature is 290-335 ℃, and the rotation speed of the screw is 200r/min-500 r/min.
Compared with the prior art, the invention has the advantages that:
(1) the composite material of the invention adopts the polyepoxy compound modified polyphenoxy resin as the compatilizer, and can solve the compatibility problem of polyarylate and semi-aromatic high-temperature nylon.
(2) The raw material resin of the invention adopts semi-aromatic high-temperature nylon, which can ensure the advantages of low mechanical property, heat resistance and water absorption of the material; meanwhile, the poly epoxy compound modified poly phenolic oxygen resin is introduced, so that the appearance of the material is improved, and the warpage and water absorption are reduced on the premise of not reducing the mechanical property and heat resistance of the material.
Detailed Description
In order to facilitate an understanding of the present invention, the present invention will be described more fully and in detail with reference to the preferred embodiments, but the scope of the present invention is not limited to the specific embodiments below.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
The specific raw materials used in the following examples and comparative examples are as follows:
semi-aromatic polyamide: PA13T, relative viscosity 2.1, available from Junhenwushui group Biotech Limited, Henan province;
polyarylate: u-100, available from Unico, U.S.A.;
glass fiber: ECS301HP, 1:4 flat fiber, Chongqing international composite limited;
a compatilizer: 1. polyphenoxy resin (PKHH), molecular weight 52000, available from invem Corp;
2. modified poly (phenol-oxygen) resin: after a polyoxyphenol resin (PKHH) (having a molecular weight of 52000, available from incom Corp) and 3% diglycidyl tetrahydrophthalate (based on the mass of the polyoxyphenol resin) were mixed, a modified polyoxyphenol resin was prepared by high-temperature melt blending in a haake torque rheometer, under the processing conditions of the torque rheometer: the working temperature is 180 ℃, the rotating speed is 60rpm, and the mixture is mixed for 10 min;
3. POE-g-MAH, brand: FUSABOND N416, available from DuPont.
The processing aid comprises a heat stabilizer and a lubricant; the heat stabilizer is copper salt stabilizer H3336 which is purchased from Bluggeman company; the lubricant was a montan wax licomax OP available from clariant corporation.
The compositions in the examples and comparative examples of the invention were dried at 120 ℃ for 4 hours and then tested after standard injection molding, and the specific test methods for the relevant performance indicators were as follows:
tensile strength: measured according to ISO 527-2, the test conditions are 23 ℃ and 10 mm/min;
bending strength: measured according to ISO 178, the test conditions are 23 ℃ and 2 mm/min;
flexural modulus: measured according to ISO 178, the test conditions are 23 ℃ and 2 mm/min;
IZOD notched impact strength: the test conditions were 23 ℃ determined according to ISO 180;
water absorption: the test condition is 23 ℃ and 24 hours in water according to ISO 62;
warping: the sample was injection-molded into a square plate of 100mm X100 m X1 mm, and the test piece was left for one day and night at 25 ℃ with a humidity of 65%. The gate is placed on a horizontal plane, and the height of the end surface on the opposite side of the gate is set as a "warping height" (warping) based on the gate side;
injection molding surface: the samples were injection molded into 100mm by 1mm square plaques, and the surface injection molding was visually evaluated and classified into four grades, good, medium and poor.
The raw materials of the low warpage reinforced semi-aromatic high temperature nylon composite materials of examples 1-3 and comparative examples 1-4 are shown in table 1, and the preparation methods are the same: the raw materials (excluding glass fiber) are uniformly mixed in a homogenizing pot, and then the mixture and the glass fiber are put into a double-screw extruder to be melted and mixed, and the glass fiber is fed laterally. The rotating speed of the extruder is 350rpm, the temperatures of the screw barrel in the 1-9 areas are respectively 280 ℃, 310, 320, 315, 320 ℃, and the head is 320 ℃. The molten polymer is quenched with water after being extruded from the extruder, and then pelletized.
The performance test results of the low warpage reinforced semi-aromatic high temperature nylon composite materials obtained in examples 1-3 and comparative examples 1-4 are shown in table 1.
TABLE 1 formulation and Properties of Low warpage reinforced semi-aromatic high temperature nylon composites prepared in examples 1-3 and comparative examples 1-4
As can be seen from example 1 and comparative examples 1 to 4, the composition using the semi-aromatic polyamide resin alone has an undesirable injection molding surface and a large warpage in a high glass fiber reinforced material system (50% glass fiber); the polyarylate with the concentration of 10% is added into the semi-aromatic polyamide, the warpage and the injection molding surface are not obviously improved due to poor compatibility, but the mechanical property is obviously reduced, and the compatibility is improved to a certain extent after the phenol-oxygen resin serving as the compatilizer is added; after 3% of modified poly (phenoxy) resin is added, the mechanical property of the material is obviously improved, the warpage is reduced by 73%, and the water absorption is reduced by 41%, which shows that the compatilizer modified poly (phenoxy) resin can promote the compatibility of semi-aromatic nylon and polyarylate to be very good, and the compatibilization effect is obviously better than that of the conventional compatilizer POE-g-MAH.
Claims (9)
1. The low-warpage reinforced semi-aromatic high-temperature nylon composite material is characterized by being mainly prepared from the following raw materials in percentage by weight:
20% -85% of semi-aromatic high-temperature nylon;
5-40% of polyarylate;
0.5 to 5 percent of compatilizer;
5% -60% of reinforcing fiber;
0.5 to 3 percent of auxiliary agent;
the compatilizer is polyepoxy compound modified polyphenoxy resin.
2. The semi-aromatic high temperature nylon composite material according to claim 1, wherein the polyepoxy compound is a compound having two or more epoxy functional groups in a molecule.
3. The semi-aromatic high temperature nylon composite material of claim 1, wherein the polyepoxy compound comprises one or more of glycidyl type, ester ring type and mixed type polyepoxy compound; wherein the content of the first and second substances,
the glycidyl type polyepoxy compound is one or more of tetraphenylethane tetraglycidyl ether, trimesic acid triglycidyl ether, phthalic acid diglycidyl ester, isophthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, trimesic acid triglycidyl ester, p-aminophenol triglycidyl epoxy resin, 4' -diaminodiphenylmethane tetraglycidyl epoxy resin and bisphenol A epoxy resin;
the ester ring-shaped polyepoxy compound is one or more of 3, 4-epoxy group cyclohexane carboxylic acid 3 ', 4 ' -epoxy group cyclohexane methyl ester and 3, 4-epoxy group 6-methyl cyclohexane carboxylic acid 3 ', 4 ' -epoxy group 6 ' -methyl cyclohexane methyl ester;
the mixed polyepoxy compound is vinyl cyclohexene diepoxy.
4. The semi-aromatic high temperature nylon composite material of claim 1, wherein the semi-aromatic high temperature nylon is one or more blends of polyhexamethylene terephthalamide-co-hexamethylene adipamide copolymer (PA6T/66), polyhexamethylene terephthalamide-co-caprolactam copolymer (PA6T/6), poly-nonane terephthalamide (PA9T), poly-decamethylene terephthalamide (PA10T), poly-undecamethylene terephthalamide (PA11T), poly-dodecamethylene terephthalamide (PA12T) and poly-tridecyl terephthalamide (PA13T) with melting point of 285-330 ℃.
5. The semi-aromatic high temperature nylon composite according to claim 1, wherein the repeating unit structure in the polyarylate is:
6. The semi-aromatic high temperature nylon composite of claim 1, wherein the reinforcing fiber is a glass fiber and/or a carbon fiber;
the glass fibers comprise continuous long glass fibers and short glass fibers; the length of the short glass fiber is 2-50 mm;
the auxiliary agent comprises a heat stabilizer and a lubricant.
7. The preparation method of the semi-aromatic high temperature nylon composite material according to any one of claims 1 to 6, comprising the following steps:
(1) preparing a compatilizer;
(2) drying the semi-aromatic high-temperature nylon for later use;
(3) and (2) uniformly mixing the dried semi-aromatic high-temperature nylon, the polyarylate, the compatilizer and the auxiliary agent in a high-speed mixer, adding the reinforcing fiber from a glass fiber port or a side feeding port of an extruder, and performing double-screw melt extrusion, cooling, granulating and drying to obtain the low-warpage reinforced high-temperature nylon composite material.
8. The preparation method according to claim 7, wherein in the step (1), the specific process for preparing the compatibilizer is: uniformly mixing the phenoxy resin and the polyepoxy compound, and carrying out high-temperature melting and blending in a Haake torque rheometer to obtain the polyepoxy compound modified polyphenoxy resin compatilizer; wherein the mass addition amount of the polyepoxy compound is not more than 5% of the mass of the phenolic resin, and the processing conditions of the torque rheometer are as follows: the working temperature is 160 ℃ and 200 ℃, the rotating speed is 40-100rpm, and the blending time is 6-12 min.
9. The method as claimed in claim 7, wherein in the step (2), the drying is performed in an oven at 130 ℃ and 100 ℃ for 3-6 h;
in the step (3), the melt extrusion temperature is 290-335 ℃, and the rotation speed of the screw is 200r/min-500 r/min.
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| CN107446346A (en) * | 2017-09-27 | 2017-12-08 | 株洲时代新材料科技股份有限公司 | A kind of wear-resisting high-temperature nylon composite of fibre reinforced and preparation method thereof |
| JP2018083872A (en) * | 2016-11-22 | 2018-05-31 | フドー株式会社 | Production method of fiber reinforced plastic product |
| CN109535704A (en) * | 2017-09-22 | 2019-03-29 | 上海杰事杰新材料(集团)股份有限公司 | A kind of nylon composite materials and preparation method thereof |
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| CN103756310A (en) * | 2014-01-08 | 2014-04-30 | 合肥杰事杰新材料股份有限公司 | Polyamide/polyarylate alloy and preparation method thereof |
| CN106147221A (en) * | 2015-04-28 | 2016-11-23 | 株洲时代新材料科技股份有限公司 | Fiberglass reinforced fire retardant heat conduction semiaromatic copolymer nylon composite and preparation method thereof |
| JP2018083872A (en) * | 2016-11-22 | 2018-05-31 | フドー株式会社 | Production method of fiber reinforced plastic product |
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