CN116925530A - Transparent bio-based polyamide resin composition and continuous fiber reinforced transparent bio-based polyamide composite material - Google Patents
Transparent bio-based polyamide resin composition and continuous fiber reinforced transparent bio-based polyamide composite material Download PDFInfo
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- 229920006021 bio-based polyamide Polymers 0.000 title claims abstract description 149
- 239000000835 fiber Substances 0.000 title claims abstract description 120
- 239000011342 resin composition Substances 0.000 title claims abstract description 78
- 239000002131 composite material Substances 0.000 title claims abstract description 66
- 229920005989 resin Polymers 0.000 claims abstract description 34
- 239000011347 resin Substances 0.000 claims abstract description 34
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 27
- 239000007822 coupling agent Substances 0.000 claims abstract description 26
- 239000000463 material Substances 0.000 claims abstract description 25
- 239000000314 lubricant Substances 0.000 claims abstract description 18
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 16
- -1 sports equipment Substances 0.000 claims abstract description 6
- 239000000843 powder Substances 0.000 claims description 43
- 239000002002 slurry Substances 0.000 claims description 40
- 239000003365 glass fiber Substances 0.000 claims description 32
- 238000002360 preparation method Methods 0.000 claims description 28
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 25
- 239000004917 carbon fiber Substances 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000004952 Polyamide Substances 0.000 claims description 23
- 229920002647 polyamide Polymers 0.000 claims description 23
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 20
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 19
- OKOBUGCCXMIKDM-UHFFFAOYSA-N Irganox 1098 Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NCCCCCCNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 OKOBUGCCXMIKDM-UHFFFAOYSA-N 0.000 claims description 13
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 13
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 10
- 235000019437 butane-1,3-diol Nutrition 0.000 claims description 10
- 239000004359 castor oil Substances 0.000 claims description 10
- 235000019438 castor oil Nutrition 0.000 claims description 10
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 10
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 claims description 10
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 claims description 10
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 claims description 10
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 claims description 10
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical group C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 9
- 229920001971 elastomer Polymers 0.000 claims description 8
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 8
- 229920003169 water-soluble polymer Polymers 0.000 claims description 7
- 239000003638 chemical reducing agent Substances 0.000 claims description 6
- 238000003892 spreading Methods 0.000 claims description 6
- 239000004094 surface-active agent Substances 0.000 claims description 6
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 5
- 150000001412 amines Chemical class 0.000 claims description 4
- 238000005452 bending Methods 0.000 claims description 4
- 239000000806 elastomer Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 229920000098 polyolefin Polymers 0.000 claims description 4
- 239000005060 rubber Substances 0.000 claims description 4
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 3
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 3
- 229920006231 aramid fiber Polymers 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 230000009477 glass transition Effects 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 229920002748 Basalt fiber Polymers 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical class OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 2
- 150000004645 aluminates Chemical class 0.000 claims description 2
- 229920002678 cellulose Polymers 0.000 claims description 2
- 239000001913 cellulose Substances 0.000 claims description 2
- 239000004035 construction material Substances 0.000 claims description 2
- 239000002530 phenolic antioxidant Substances 0.000 claims description 2
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 229910000077 silane Inorganic materials 0.000 claims description 2
- SFVFIFLLYFPGHH-UHFFFAOYSA-M stearalkonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 SFVFIFLLYFPGHH-UHFFFAOYSA-M 0.000 claims description 2
- 238000002834 transmittance Methods 0.000 claims description 2
- 125000001153 fluoro group Chemical group F* 0.000 claims 1
- 239000004566 building material Substances 0.000 abstract 1
- 239000012815 thermoplastic material Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 9
- 239000011199 continuous fiber reinforced thermoplastic Substances 0.000 description 7
- 239000004605 External Lubricant Substances 0.000 description 6
- 239000004610 Internal Lubricant Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 229920002430 Fibre-reinforced plastic Polymers 0.000 description 4
- 229920006025 bioresin Polymers 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000003733 fiber-reinforced composite Substances 0.000 description 4
- 239000011151 fibre-reinforced plastic Substances 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000855 fermentation Methods 0.000 description 2
- 230000004151 fermentation Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229920006122 polyamide resin Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229920001431 Long-fiber-reinforced thermoplastic Polymers 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- KJOMYNHMBRNCNY-UHFFFAOYSA-N pentane-1,1-diamine Chemical compound CCCCC(N)N KJOMYNHMBRNCNY-UHFFFAOYSA-N 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
Classifications
-
- 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
-
- 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
- C08J5/042—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with carbon 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
- C08J5/0405—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
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
-
- 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
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/08—Copolymers of ethene
-
- 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
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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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
Abstract
The invention discloses a transparent bio-based polyamide resin composition and a continuous fiber reinforced transparent bio-based polyamide composite material. The transparent bio-based polyamide resin composition comprises the following components in parts by weight: 80-99 parts of transparent bio-based polyamide resin, 0.2-1.2 parts of antioxidant, 0-1 part of lubricant, 0-15 parts of compatilizer and 0-1 part of coupling agent. The continuous fiber reinforced transparent bio-based polyamide composite material comprises a transparent bio-based polyamide resin composition and fibers, wherein the fibers account for 35-75% of the continuous fiber reinforced transparent bio-based polyamide composite material by mass. The continuous fiber reinforced transparent bio-based polyamide composite material has high fiber content, good mechanical property and recoverability, and can be applied to the fields of aerospace, military, automobile materials, sports equipment, building materials or electronic appliances.
Description
Technical Field
The invention relates to a transparent bio-based polyamide resin composition, a continuous fiber reinforced transparent bio-based polyamide composite material, a preparation method and application thereof.
Background
Compared with the thermosetting material, the thermoplastic material can be processed and molded for multiple times without being crosslinked and cured, and the molding process is more convenient and efficient, so that the thermoplastic material has been steadily and continuously developed in recent years, and particularly the fiber reinforced thermoplastic material. The matrix resin of the fiber reinforced thermoplastic material can be thermoplastic materials such as polypropylene, polyamide, polyester and the like, and the fiber can be glass fiber, carbon fiber, aramid fiber and the like, wherein the glass fiber is more commonly used.
The fiber reinforced thermoplastic materials are mainly divided into short fiber (2-4 mm) reinforced thermoplastic materials, long fiber (12-24 mm) reinforced thermoplastic materials, fiber felt reinforced thermoplastic materials, continuous fiber reinforced thermoplastic materials and thermoplastic composite material core plates. The short fiber reinforced thermoplastic material cannot meet the performance requirement of the structural material because of poor strength, so that the long fiber reinforced thermoplastic material is developed; the reinforcing effect of the continuous fiber on the thermoplastic material is better than that of the short fiber and the long fiber, and the mechanical property and the fatigue resistance are greatly improved, so that the research is active in recent years. Continuous fiber reinforced thermoplastic materials have been mainly focused on aerospace and military applications, and have been gradually applied to the industries of automobile materials, sports equipment, construction and the like since 2003. With the development of industries such as automobiles, electronic appliances and the like, the demand of the continuous fiber reinforced thermoplastic material is also increased, so that the development and popularization of the continuous fiber reinforced thermoplastic material are accelerated.
The continuous fiber reinforced thermoplastic material can be stored for a long time, has excellent comprehensive performance, wide molding adaptability and high production efficiency, and the product can be repeatedly processed and recycled, so that the research is very active after the product is developed in the early 70 th century of 20 th century. Continuous fiber reinforced thermoplastic materials have also been studied in China from the late 80 s of the 20 th century. The production process of the continuous fiber reinforced thermoplastic material mainly comprises a melting method, a solution process method, a powder method, a calendaring method and the like, but the methods are characterized in that high-cost molding equipment is required to be used, and resin can not well impregnate and disperse fibers in the molding process, so that the fiber content of the continuous fiber reinforced composite material is low, the mechanical property is poor, and the application of matrix resin in the continuous fiber reinforced composite material is limited.
Disclosure of Invention
The invention provides a transparent bio-based polyamide resin composition, a continuous fiber reinforced transparent bio-based polyamide composite material, a preparation method and application thereof, and aims to overcome the defects of low fiber content, poor mechanical property and high cost of the continuous fiber reinforced composite material in the prior art. The transparent bio-based polyamide resin composition has good fiber wettability; the continuous fiber reinforced composite material prepared based on the transparent bio-based polyamide resin composition has high fiber content, good mechanical property and recoverability.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
one of the technical proposal is as follows: a transparent bio-based polyamide resin composition comprising the following components in parts by weight: 80-99 parts of transparent bio-based polyamide resin, 0.2-1.2 parts of antioxidant, 0-1 part of lubricant, 0-15 parts of compatilizer and 0-1 part of coupling agent.
In one embodiment of the present invention, the transparent bio-based polyamide resin has a relative viscosity of 1.5 to 3.5, and more preferably 2.3 to 2.7; the water content is not more than 5000ppm, preferably not more than 1500ppm.
In one embodiment of the invention, the transparent bio-based polyamide resin has a bio-based content of 21-41%, for example 31%.
In one embodiment of the present invention, the transparent bio-based polyamide resin has a glass transition temperature of 130 to 170 ℃, preferably 140 to 160 ℃.
In one embodiment of the present invention, the heat distortion temperature (1.8 MPa) of the transparent bio-based polyamide resin is 130-160 ℃, preferably 145-155 ℃.
In one embodiment of the present invention, 90% or more, preferably 90 to 98% of the transparent bio-based polyamide resin; the haze is 3.0% or less, and more preferably 1.6 to 2.0%.
In one embodiment of the present invention, the tensile strength of the transparent bio-based polyamide resin is 80MPa or more, and more preferably 80 to 95MPa; the tensile modulus is 2000MPa or more, and more preferably 2000 to 2400MPa; the bending strength is 100MPa or more, and more preferably 100 to 130MPa; the flexural modulus is 2500MPa or more, preferably 2500-3500MPa; notched impact strength of 10KJ/m 2 The above is more preferably 10 to 13KJ/m 2 。
In some specific embodiments, the transparent biobased polyamide resin is commercially available as transparent polyamide E-5000, available from Kaiser (Kingxiang) biological materials Co.
In the invention, the raw material monomer of the transparent bio-based polyamide resin, namely the pentylene diamine, is prepared by biological fermentation.
In the present invention, the transparent bio-based polyamide resin is preferably contained in an amount of 90 to 95 parts, for example 94.5, 93.5, 92.5 or 94.0 parts.
In the invention, the antioxidant is selected from one or more of hindered phenol antioxidants, hindered amine antioxidants and phosphite antioxidants; preferably a combination of hindered amine antioxidants and phosphite antioxidants. Wherein the hindered phenolic antioxidant may be conventional in the art, such as antioxidant 1010. The hindered amine antioxidant may be conventional in the art, such as antioxidant 1098 (CAS 23128-74-7). The phosphite antioxidants may be conventional in the art, such as antioxidant 168 (CAS 31570-04-4), antioxidant S9228.
Preferably, the antioxidant is selected from one or more of antioxidant 168, antioxidant 1098, antioxidant 1010 and antioxidant S9228. More preferably, the antioxidant is a combination of antioxidant 168 and antioxidant 1098; wherein the mass ratio of the antioxidant 168 to the antioxidant 1098 is preferably 1:1.
In the present invention, the antioxidant content is preferably 0.4 to 0.8 parts, for example 0.4, 0.5, 0.6 or 0.8 parts.
In the present invention, the lubricant may include an outer lubricant and an inner lubricant; wherein the mass ratio of the outer lubricant to the inner lubricant is preferably 1:1.
Wherein the external lubricant may be conventional in the art, such as WAXC available from Corview, germany. The internal lubricant may be conventional in the art, for example, WAXE available from Clariant, germany.
In the present invention, the content of the lubricant is preferably 0.1 to 0.8 parts, for example, 0.3, 0.4, 0.5 or 0.6 parts.
In the invention, the compatilizer can be one or more selected from polyolefin grafted maleic anhydride compatilizer and rubber elastomer grafted maleic anhydride compatilizer. Wherein the polyolefin grafted maleic anhydride-based compatibilizer may be conventional in the art, such as PP-g-MAH or POE-g-MAH. The rubber elastomer grafted maleic anhydride-based compatibilizer may be conventional in the art, such as EPDM-g-MAH.
In the present invention, the content of the compatibilizing agent is preferably 3 to 15 parts, and further 6 to 8 parts, for example, 4, 5, 6, 8, 10 or 12 parts.
In the invention, the coupling agent can be selected from one or more of silane coupling agents, carbonate coupling agents and aluminate coupling agents; preferably a silane-based coupling agent, such as coupling agent KH550, coupling agent KH560 or coupling agent KH570. The coupling agent is generally selected according to the composition and surface structure of the fibers used.
In the present invention, the coupling agent is preferably used in an amount of 0.1 to 0.8 parts, for example, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7 or 0.8 parts.
In certain preferred embodiments, the transparent biobased polyamide resin composition comprises the following components in parts by weight: 90-95 parts of transparent bio-based polyamide resin, 0.4-0.8 part of antioxidant, 0.1-0.8 part of lubricant, 3-15 parts of compatilizer and 0.1-0.8 part of coupling agent.
In a preferred embodiment, the transparent bio-based polyamide resin composition comprises the following components in parts by weight: 92-94 parts of transparent bio-based polyamide resin, 0.2-0.4 part of antioxidant 1098, 0.2-0.4 part of antioxidant 168, 0.2-0.3 part of internal lubricant WAXE, 0.2-0.3 part of external lubricant WAXC, 6-8 parts of compatilizer and 0.2-0.6 part of silane coupling agent.
In the invention, the transparent bio-based polyamide resin composition can be prepared by a method conventional in the art, and the components are generally uniformly mixed. Wherein the mixing may be performed using mixing equipment conventional in the art, such as a high speed mixer.
The second technical scheme is as follows: a continuous fiber reinforced transparent biobased polyamide composite material comprising a transparent biobased polyamide resin composition as described above and fibers, wherein the fibers comprise 35-75% by mass of the continuous fiber reinforced transparent biobased polyamide composite material.
In the present invention, the fibers preferably comprise 50 to 70%, such as 60%, 65% or 70% by mass of the continuous fiber reinforced transparent bio-based polyamide composite material.
In the present invention, the types of the fibers may be conventional in the art, such as carbon fibers, glass fibers, basalt fibers, or aramid fibers. The fibers are preferably continuous long fibers, preferably, the fibers are continuous long glass fibers. The continuous long glass fibers may have a filament diameter of 8-15 μm, preferably 8-10 μm. The continuous long glass fibers have a linear density of 1000-3600Tex, preferably 1200Tex, 2400Tex. The continuous long glass fibers are, for example, 1200Tex continuous long glass fibers from eulerian (OC) and 2400Tex continuous long glass fibers from boulder.
Preferably, the fibers are continuous long carbon fibers; the continuous long carbon fibers are preferably polyacrylonitrile-based carbon fibers; the number of monofilaments of the continuous long carbon fiber can be 20000-30000, preferably 12000 (12K) and 24000 (24K); the continuous long carbon fibers may have a filament diameter of 5 to 10 μm, preferably 6 to 8 μm. The continuous long carbon fiber is, for example, dongli T700 with the specification of 24K, or Guangwei composite continuous long carbon fiber 700S with the specification of 12K or 24K.
In the present invention, preferably, the continuous fiber-reinforced transparent bio-based polyamide composite material is in the form of a unidirectional prepreg tape. The unidirectional prepreg tape refers to a tape-like prepreg made by impregnating resin with continuous fibers parallel to each other.
In the present invention, preferably, the thickness of the continuous fiber reinforced transparent bio-based polyamide composite material is 0.15-0.5mm.
In the invention, when the fiber is continuous long glass fiber, the tensile strength of the continuous fiber reinforced transparent bio-based polyamide composite material is 500-1500MPa, and further 800-1500MPa; the tensile modulus is 20-60GPa, and further 30-60GPa; the elongation at break is 1.5-4.0%, and further 2.8-4.0%.
In the invention, when the fiber is continuous long carbon fiber, the tensile strength of the continuous fiber reinforced transparent bio-based polyamide composite material is 1300-2000MPa; the tensile modulus is 80-140GPa; the elongation at break is 1.5-4.0%, and further 2.5-4.0%.
And the third technical scheme is as follows: a method of preparing a continuous fiber reinforced transparent bio-based polyamide composite material as hereinbefore described comprising the steps of:
s1, preparing slurry containing transparent bio-based polyamide resin composition powder;
s2, pulling the fiber through slurry to enable the transparent bio-based polyamide resin composition powder to be soaked and dispersed into the fiber, heating to enable the fiber to be fully soaked, and extruding the fiber through a pultrusion die to obtain the transparent bio-based polyamide resin composition;
wherein the mass percentage of the fiber in the continuous fiber reinforced polyamide composite material is controlled to be 35-75% by adjusting the proportion of the transparent bio-based polyamide resin composition powder in the slurry and the traction speed.
In the step S1 of the present invention, the slurry containing the transparent bio-based polyamide resin composition powder comprises the following components in mass percent: transparent biobased polyamide resin composition powder: 10-50%, water: 50-90%, water-soluble polymer: 0.1-5%, surfactant: 0.1-5%, viscosity reducer: 0.1-5%.
In one embodiment, the transparent bio-based polyamide resin composition powder has a density of 1.0 to 1.5.
In one embodiment, the transparent bio-based polyamide resin composition powder has a particle size D50 of less than 50 microns, preferably less than or equal to 5 microns. The smaller the particle size of the powder, the easier it is to impregnate the fiber.
In one embodiment, the water-soluble polymer is selected from one or more of nonionic water-soluble cellulose, nonionic water-soluble hydroxypropyl methylcellulose and polyvinyl alcohol.
In one embodiment, the surfactant is selected from one or more of fluoroad 431, octadecyl benzyl dimethyl ammonium chloride, castor oil polyethylene oxide ether.
In one embodiment, the viscosity reducer is selected from one or more of 1, 3-butanediol and ethylene glycol series.
In one embodiment, the slurry has a viscosity of 0.1 to 100cps, preferably 2 to 30cps.
In the present invention, the method for preparing a slurry containing a transparent bio-based polyamide resin composition powder comprises: taking materials according to the proportion of each component in the slurry, firstly mixing and stirring a proper amount of water, a surfactant and a viscosity reducer to obtain a solution; dissolving water-soluble polymer with water (40-100deg.C water), adding into the above solution, and stirring; slowly adding the transparent bio-based polyamide resin composition powder into the solution in batches, and stirring to obtain the transparent bio-based polyamide resin composition powder. The ratio of the two water amounts is not particularly limited in the present invention, so long as the dissolution effect is achieved, and those skilled in the art can select the ratio according to the actual situation. In the invention, the stirring rotation speed is 500-1000r/min.
In the present invention, the fibers preferably account for 50 to 70% by mass, for example 60% by mass, 65% by mass, of the continuous fiber-reinforced transparent bio-based polyamide composite material.
In step S2, before pulling the fiber through the slurry, the fiber further comprises the following operations: the fiber is unreeled from the creel through the tension controller, enters the yarn spreading system through the yarn dividing frame, fully spreads each filament bundle, and then passes through slurry through traction, so that the transparent bio-based polyamide resin composition powder is uniformly soaked and dispersed into the fiber bundles. In step S2, the fibers are as described above.
In step S2, the traction is performed by using a traction device, and the traction speed of the traction may be 3-12m/min, for example 6m/min.
In step S2, the heating temperature is 290-310 ℃. The present invention causes the impregnated fibres to lose moisture on the one hand and the resin to melt on the other hand by heating.
In the present invention, the continuous fiber-reinforced transparent bio-based polyamide composite material prepared by the preparation method of the continuous fiber-reinforced transparent bio-based polyamide composite material is preferably in the form of a unidirectional prepreg tape.
In the present invention, preferably, the thickness of the continuous fiber reinforced transparent bio-based polyamide composite material prepared by the preparation method of the continuous fiber reinforced transparent bio-based polyamide composite material is 0.15-0.5mm.
The fourth technical scheme is as follows: a shaped article comprising a continuous fiber reinforced transparent bio-based polyamide composite as described above.
Fifth technical scheme: the use of a continuous fiber reinforced transparent bio-based polyamide composite material as described above in the aerospace field, the military field, automotive materials, sports equipment, construction materials or electronic appliances.
On the basis of conforming to the common knowledge in the field, the above preferred conditions can be arbitrarily combined to obtain the preferred examples of the invention.
The reagents and materials used in the present invention are commercially available.
The invention has the positive progress effects that:
1. the invention adopts transparent bio-based polyamide resin as raw material:
(1) The monomer pentanediamine in the raw materials is prepared by biological fermentation, the content of the biological base is between 21 and 41 percent, and the idea of sustainable development of material sources is met;
(2) The transparent bio-based polyamide resin composition prepared by adopting the transparent bio-based polyamide as a raw material has good fiber wettability;
(3) In the production process, a double-screw extruder, a resin melt extrusion impregnating roller and the like are not needed, so that the equipment investment is low, and the cost is reduced.
2. The continuous fiber reinforced transparent bio-based polyamide composite material comprises the following components:
(1) The fiber content is high and is in the range of 35-75%;
(2) Has excellent mechanical properties;
(3) The fibers are uniformly distributed, no fibers are exposed, and the processing is easy;
(4) The thickness of the composite material can be set between 0.15 and 0.5mm according to the requirement, so that more design freedom degrees can be provided for the product;
(5) The final molded product containing the continuous fiber reinforced transparent bio-based polyamide composite material provided by the invention can be recycled and reused, and the resource utilization rate is high.
3. The preparation method of the continuous fiber reinforced transparent bio-based polyamide composite material is simple and feasible, uses water as a dispersion medium, has relatively low boiling point, is easy to remove from slurry, and has wide sources and no pollution to the environment. In addition, the fiber content can be adjusted by adjusting the ratio of the transparent bio-based polyamide resin in the slurry or the thickness of the unidirectional tape, so that the fiber content can be adjusted more conveniently.
Detailed Description
The invention is further illustrated by means of the following examples, which are not intended to limit the scope of the invention. The experimental methods, in which specific conditions are not noted in the following examples, were selected according to conventional methods and conditions, or according to the commercial specifications. In the following examples and comparative examples, the sources of the respective raw materials are described as follows:
transparent biobased polyamide resin E-5000: the relative viscosity is 2.35; the water content is 900ppm; the biobased content is 31%; the glass transition temperature is 150 ℃; the heat distortion temperature (1.8 MPa) is 145 ℃; the light transmittance is 90.2% and the haze is 1.91%; tensile strength 90MPa, tensile modulus 2300MPa, bending strength 110MPa, bending modulus 2600MPa and notch impact strength 11KJ/m 2 Purchased from kesai (jinxiang) biomaterial limited;
antioxidants were purchased from basf group, germany; WAXE and WAXC are available from Clariant, germany; the compatibilizing agent is available from Shanghai good compatible polymers limited; coupling agent was purchased from jercard chemical company, hangzhou; continuous long glass fibers were purchased from eurvescening (OC) in a specification of 1200Tex; the continuous long carbon fiber is Toli T700 with the specification of 24K.
Example 1
1. Preparation of transparent biobased Polyamide resin composition
The transparent bio-based resin composition used in this example comprises the following components in parts by weight:
transparent biobased polyamide resin E-5000:94.5 parts of an antioxidant 1098:0.2 parts of an antioxidant 168:0.2 parts of internal lubricant WAXE:0.3 parts of external lubricant WAXC:0.3 part of compatilizer POE-g-MAH:4 parts of coupling agent KH550:0.5 part. The above components are added into a high-speed stirrer to be mixed, and the transparent bio-based polyamide resin composition is obtained.
2. Preparation of continuous fiber reinforced polyamide composite material
S1, preparing slurry containing transparent bio-based polyamide resin composition powder; wherein, the mud comprises the following components in percentage by mass: transparent biobased polyamide resin composition powder (density 1.12, d50=10 microns): 10%, water: 88%, nonionic water-soluble hydroxypropyl methylcellulose: 0.5%, castor oil polyethylene oxide ether: 0.5%,1, 3-butanediol: 1.0%.
The specific preparation method comprises the following steps: taking materials according to the proportion of each component in the slurry, firstly stirring a proper amount of water, castor oil polyethylene oxide ether and 1, 3-butanediol at a stirring speed of 800r/min to obtain a solution; using deionized water with the temperature of 80 ℃ to independently dissolve nonionic water-soluble hydroxypropyl methyl cellulose, adding the solution into the solution, and stirring for at least half an hour; the transparent bio-based polyamide resin composition powder was slowly added to the above solution in batches, stirred at a high speed for at least 6 hours, and the resulting slurry had a viscosity of 15cps.
S2, unwinding continuous long glass fibers from a creel through a tension controller, entering a yarn spreading system through a yarn dividing frame to fully spread each filament bundle, uniformly soaking and dispersing transparent bio-based polyamide superfine powder into the fiber bundles through slurry through a traction device, wherein the traction speed is 6m/min, heating to fully soak the fiber bundles, the heating temperature is 300 ℃, and extruding the fiber bundles through a pultrusion die to obtain the fiber reinforced plastic composite material.
In the preparation process, the weight fraction ratio of the continuous long glass fiber to the transparent bio-based polyamide resin composition is 65 by adjusting the ratio of the transparent bio-based polyamide resin composition powder in the slurry and the traction speed: 35. the continuous long glass fiber reinforced polyamide composite material prepared by the method is a unidirectional prepreg tape, and the performance parameters are shown in table 1.
Example 2
1. Preparation of transparent biobased Polyamide resin composition
The transparent bio-based resin composition used in this example comprises the following components in parts by weight:
transparent biobased polyamide resin E-5000:93.5 parts of an antioxidant 1098:0.3 parts of an antioxidant 168:0.3 parts of internal lubricant WAXE:0.2 parts of external lubricant WAXC:0.2 part of compatilizer POE-g-MAH:5 parts of coupling agent KH550:0.5 part. The above components are added into a high-speed stirrer to be mixed, and the transparent bio-based polyamide resin composition is obtained.
2. Preparation of continuous fiber reinforced polyamide composite material
S1, preparing slurry containing transparent bio-based polyamide resin composition powder; wherein, the mud comprises the following components in percentage by mass: transparent biobased polyamide resin composition powder (density 1.15, d50=10 microns): 10%, water: 87%, nonionic water-soluble hydroxypropyl methylcellulose: 1.0%, castor oil polyethylene oxide ether: 1.0%,1, 3-butanediol: 1.0%.
The specific preparation method comprises the following steps: taking materials according to the proportion of each component in the slurry, firstly stirring a proper amount of water, castor oil polyethylene oxide ether and 1, 3-butanediol at a stirring speed of 800r/min to obtain a solution; using deionized water with the temperature of 80 ℃ to independently dissolve nonionic water-soluble hydroxypropyl methyl cellulose, adding the solution into the solution, and stirring for at least half an hour; the transparent bio-based polyamide resin composition powder was slowly added to the above solution in batches, stirred at a high speed for at least 6 hours, and the resulting slurry had a viscosity of 18cps.
S2, unwinding continuous long glass fibers from a creel through a tension controller, entering a yarn spreading system through a yarn dividing frame to fully spread each filament bundle, uniformly soaking and dispersing transparent bio-based polyamide superfine powder into the fiber bundles through slurry through a traction device, wherein the traction speed is 6m/min, heating to fully soak the fiber bundles, the heating temperature is 300 ℃, and extruding the fiber bundles through a pultrusion die to obtain the fiber reinforced plastic composite material.
In the preparation process, the weight fraction ratio of the continuous long glass fiber to the transparent bio-based polyamide resin composition is ensured to be 60 by adjusting the ratio of the transparent bio-based polyamide resin composition powder in the slurry and the traction speed: 40. the continuous long glass fiber reinforced polyamide composite material prepared by the method is a unidirectional prepreg tape, and the performance parameters are shown in table 1.
Example 3
1. Preparation of transparent biobased Polyamide resin composition
The transparent bio-based resin composition used in this example comprises the following components in parts by weight:
transparent biobased polyamide resin E-5000:94.0 parts of an antioxidant 1098:0.3 parts of an antioxidant 168:0.3 parts of internal lubricant WAXE:0.3 parts of external lubricant WAXC:0.3 part of compatilizer POE-g-MAH:4 parts of coupling agent KH550:0.8 parts. The above components are added into a high-speed stirrer to be mixed, and the transparent bio-based polyamide resin composition is obtained.
2. Preparation of continuous fiber reinforced polyamide composite material
S1, preparing slurry containing transparent bio-based polyamide resin composition powder; wherein, the mud comprises the following components in percentage by mass: transparent biobased polyamide resin composition powder (density 1.2, d50=10 microns): 12%, water: 86%, nonionic water-soluble hydroxypropyl methylcellulose: 0.5%, castor oil polyethylene oxide ether: 0.5%,1, 3-butanediol: 1.0%.
The specific preparation method comprises the following steps: taking materials according to the proportion of each component in the slurry, firstly stirring a proper amount of water, castor oil polyethylene oxide ether and 1, 3-butanediol at a stirring speed of 800r/min to obtain a solution; using deionized water with the temperature of 80 ℃ to independently dissolve nonionic water-soluble hydroxypropyl methyl cellulose, adding the solution into the solution, and stirring for at least half an hour; the transparent bio-based polyamide resin composition powder was slowly added to the above solution in portions, stirred at a high speed for at least 6 hours, and the resulting slurry had a viscosity of 26cps.
S2, unwinding continuous long glass fibers from a creel through a tension controller, entering a yarn spreading system through a yarn dividing frame to fully spread each filament bundle, uniformly soaking and dispersing transparent bio-based polyamide superfine powder into the fiber bundles through slurry through a traction device, wherein the traction speed is 7m/min, heating to fully soak the fiber bundles, the heating temperature is 300 ℃, and extruding the fiber bundles through a pultrusion die to obtain the fiber reinforced plastic composite material.
In the preparation process, the weight fraction ratio of the continuous long glass fiber to the transparent bio-based polyamide resin composition is ensured to be 70 by adjusting the proportion and the traction speed of the transparent bio-based polyamide resin composition powder in the slurry: 30. the continuous long glass fiber reinforced polyamide composite material prepared by the method is a unidirectional prepreg tape, and the performance parameters are shown in table 1.
Example 4
1. Preparation of transparent biobased Polyamide resin composition
The transparent bio-based resin composition used in this example comprises the following components in parts by weight:
transparent biobased polyamide resin E-5000:92.5 parts of an antioxidant 1098:0.2 parts of an antioxidant 168:0.2 parts of internal lubricant WAXE:0.2 parts of external lubricant WAXC:0.2 part of compatilizer POE-g-MAH:6 parts of coupling agent KH550:0.7 parts. The above components are added into a high-speed stirrer to be mixed, and the transparent bio-based polyamide resin composition is obtained.
2. Preparation of continuous fiber reinforced polyamide composite material
S1, preparing slurry containing transparent bio-based polyamide resin composition powder; wherein, the mud comprises the following components in percentage by mass: transparent biobased polyamide resin composition powder (density 1.12, d50=5 microns): 10%, water: 88%, nonionic water-soluble hydroxypropyl methylcellulose: 0.6%, castor oil polyethylene oxide ether: 0.6%,1, 3-butanediol: 0.8%.
The specific preparation method comprises the following steps: taking materials according to the proportion of each component in the slurry, firstly stirring a proper amount of water, castor oil polyethylene oxide ether and 1, 3-butanediol at a stirring speed of 800r/min to obtain a solution; using deionized water with the temperature of 80 ℃ to independently dissolve nonionic water-soluble hydroxypropyl methyl cellulose, adding the solution into the solution, and stirring for at least half an hour; the transparent bio-based polyamide resin composition powder was slowly added to the above solution in batches, stirred at a high speed for at least 6 hours, and the resulting slurry had a viscosity of 23cps.
S2, unwinding continuous long glass fibers from a creel through a tension controller, entering a yarn spreading system through a yarn dividing frame to fully spread each filament bundle, uniformly soaking and dispersing transparent bio-based polyamide superfine powder into the fiber bundles through slurry through a traction device, wherein the traction speed is 6m/min, heating to fully soak the fiber bundles, the heating temperature is 300 ℃, and extruding the fiber bundles through a pultrusion die to obtain the fiber reinforced plastic composite material.
In the preparation process, the weight fraction ratio of the continuous long glass fiber to the transparent bio-based polyamide resin composition is 68 by adjusting the ratio of the transparent bio-based polyamide resin composition powder in the slurry and the traction speed: 32. the continuous long glass fiber reinforced polyamide composite material prepared by the method is a unidirectional prepreg tape, and the performance parameters are shown in table 1.
Example 5
The same procedure as in example 1 was followed except that continuous long carbon fibers were used in the preparation of the continuous fiber-reinforced polyamide composite material.
Example 6
The same procedure as in example 2 was followed except that continuous long carbon fibers were used in the preparation of the continuous fiber-reinforced polyamide composite material.
Example 7
The same procedure as in example 3 was followed except that continuous long carbon fibers were used in the preparation of the continuous fiber-reinforced polyamide composite material.
Example 8
The same procedure as in example 4 was followed except that continuous long carbon fibers were used in the preparation of the continuous fiber-reinforced polyamide composite material.
Comparative example 1
The same procedure as in example 1 was followed except that a commercially available EMS TR90 transparent polyamide was used in preparing the transparent polyamide resin composition.
Comparative example 2
The same procedure as in example 5 was followed except that a commercially available EMS TR90 transparent polyamide was used in preparing the transparent polyamide resin composition.
Comparative example 3
The same procedure as in example 1 was followed except that a commercially available Akema G850 transparent polyamide was used in the preparation of the transparent bio-based polyamide resin composition.
Comparative example 4
The same procedure as in example 5 was followed except that a commercially available Akema G850 transparent polyamide was used in the preparation of the transparent bio-based polyamide resin composition.
The continuous fiber reinforced polyamide composite unidirectional prepreg tapes of examples 1-8 and comparative examples 1-4 were subjected to performance testing according to the following test method: (1) fiber content: ASTM D5630; (2) tensile Strength: ASTM D3039; (3) tensile modulus: ASTM D3039; (4) elongation at break: ASTM D3039. The results are shown in Table 1.
TABLE 1
As can be seen from Table 1, examples 1-4 are different transparent biobased polyamides comprising continuous long glass fibers as can be seen from Table 1, examples 1-4 are different transparent biobased polyamide composites comprising continuous long glass fibers, each having a tensile strength of 800MPa or more, a tensile modulus of 30GPa or more, and an elongation at break of 2.8% or more. Examples 5-8 are different transparent biobased polyamide composites containing continuous long carbon fibers, all with tensile strengths above 1300MPa, tensile moduli above 80GPa, and elongations at break of 1.5-4.0%. The commercial EMS TR90 transparent polyamide composites of comparative example 1 and comparative example 2, which were composed of continuous long glass fibers and continuous long carbon fibers, respectively, were inferior in mechanical properties to the corresponding examples having similar fiber contents. Similarly, comparative examples 3 and 4 are commercially available Akema G850 transparent polyamide composites of continuous long glass fibers and continuous long carbon fibers, respectively, which are also inferior in mechanical properties to the corresponding examples having similar fiber contents. In the comprehensive view, the embodiment of the invention has excellent mechanical properties, and the transparent bio-based polyamide of the invention uses bio-based pentylene diamine, has high carbon content, and effectively reduces the use of fossil raw materials, thereby reducing carbon emission.
Claims (10)
1. The transparent bio-based polyamide resin composition is characterized by comprising the following components in parts by weight: 80-99 parts of transparent bio-based polyamide resin, 0.2-1.2 parts of antioxidant, 0-1 part of lubricant, 0-15 parts of compatilizer and 0-1 part of coupling agent.
2. The transparent bio-based polyamide resin composition according to claim 1, wherein the relative viscosity of the transparent bio-based polyamide resin is 1.5 to 3.5, and more preferably 2.3 to 2.7; the water content is less than or equal to 5000ppm, and more preferably less than or equal to 1500ppm;
and/or the transparent bio-based polyamide resin has a bio-based content of 21-41%, for example 31%;
and/or the glass transition temperature of the transparent bio-based polyamide resin is 130-170 ℃, preferably 140-160 ℃;
and/or the heat distortion temperature (1.8 MPa) of the transparent bio-based polyamide resin is 130-160 ℃, preferably 145-155 ℃;
and/or the transparent bio-based polyamide resin has a light transmittance of 90% or more, preferably 90 to 98%; the haze is 3.0% or less, and more preferably 1.6 to 2.0%;
and/or the tensile strength of the transparent bio-based polyamide resin is 80MPa or more, and more preferably 80 to 95MPa; the tensile modulus is 2000MPa or more, and more preferably 2000 to 2400MPa; the bending strength is 100MPa or more, and more preferably 100 to 130MPa; the flexural modulus is 2500MPa or more, preferably 2500-3500MPa; notched impact strength of 10KJ/m 2 The above is more preferably 10 to 13KJ/m 2 ；
And/or the transparent bio-based polyamide resin is preferably contained in an amount of 90 to 95 parts, for example 94.5, 93.5, 92.5 or 94.0 parts.
3. The transparent biobased polyamide resin composition of claim 1, wherein said antioxidant is selected from one or more of hindered phenolic antioxidants, hindered aminic antioxidants, and phosphite antioxidants; preferably a combination of hindered amine antioxidants and phosphite antioxidants;
preferably, the antioxidant is selected from one or more of antioxidant 168, antioxidant 1098, antioxidant 1010 and antioxidant S9228, more preferably, the antioxidant is a combination of antioxidant 168 and antioxidant 1098; wherein the mass ratio of the antioxidant 168 to the antioxidant 1098 is preferably 1:1;
and/or the antioxidant content is preferably 0.4-0.8 parts, for example 0.4, 0.5, 0.6 or 0.8 parts;
and/or the lubricant may include an outer lubricant and an inner lubricant; wherein the mass ratio of the outer lubricant to the inner lubricant is preferably 1:1; wherein the outer lubricant is, for example, WAXC and the inner lubricant is, for example, WAXE;
and/or the lubricant is preferably present in an amount of 0.1 to 0.8 parts, for example 0.3, 0.4, 0.5 or 0.6 parts;
and/or the compatilizer can be selected from one or more of polyolefin grafted maleic anhydride compatilizer and rubber elastomer grafted maleic anhydride compatilizer; wherein, the polyolefin grafted maleic anhydride compatilizer is preferably PP-g-MAH or POE-g-MAH; the rubber elastomer grafted maleic anhydride type compatibilizer is preferably EPDM-g-MAH;
and/or the content of the compatibilizing agent is preferably 3 to 15 parts, and further 6 to 8 parts, for example 4, 5, 6, 8, 10 or 12 parts;
and/or the coupling agent is selected from one or more of silane coupling agents, carbonate coupling agents and aluminate coupling agents; preferably a silane-based coupling agent, such as coupling agent KH550, coupling agent KH560 or coupling agent KH570;
and/or the coupling agent is used in an amount of 0.1 to 0.8 parts, for example 0.2, 0.3, 0.4, 0.5, 0.6, 0.7 or 0.8 parts.
4. A continuous fiber-reinforced transparent bio-based polyamide composite material, characterized in that it comprises the transparent bio-based polyamide resin composition according to any one of claims 1 to 3 and fibers, wherein the fibers account for 35 to 75% by mass of the continuous fiber-reinforced transparent bio-based polyamide composite material.
5. The continuous fiber reinforced transparent biobased polyamide composite material according to claim 4, wherein said fibers comprise preferably 50-70%, such as 60%, 65% or 70% by mass of said continuous fiber reinforced transparent biobased polyamide composite material;
and/or the type of the fiber is carbon fiber, glass fiber, basalt fiber or aramid fiber;
and/or the fibers are continuous long fibers;
preferably, the fibers are continuous long glass fibers; the continuous long glass fiber may have a monofilament diameter of 8-15 μm; the linear density of the continuous long glass fiber is 1000-3600Tex;
preferably, the fibers are continuous long carbon fibers; the continuous long carbon fibers are preferably polyacrylonitrile-based carbon fibers; the number of the monofilaments of the continuous long carbon fiber can be 20000 to 30000; the monofilament diameter of the continuous long carbon fiber may be 5-10 μm;
and/or, the continuous fiber reinforced transparent bio-based polyamide composite material is in the form of a unidirectional prepreg tape;
and/or the thickness of the continuous fiber reinforced transparent bio-based polyamide composite material is 0.15-0.5mm;
and/or, when the fibers are continuous long glass fibers, the continuous fiber reinforced transparent bio-based polyamide composite material has a tensile strength of 500-1500MPa; the tensile modulus is 20-60GPa; the elongation at break is 1.5-4.0%;
and/or, when the fibers are continuous long carbon fibers, the continuous fiber reinforced transparent bio-based polyamide composite material has a tensile strength of 1300-2000MPa; the tensile modulus is 80-140GPa; the elongation at break is 1.5-4.0%.
6. A method of preparing the continuous fiber reinforced transparent bio-based polyamide composite material of claim 4 or 5, comprising the steps of:
s1, preparing slurry containing transparent bio-based polyamide resin composition powder;
s2, pulling the fiber through slurry to enable the transparent bio-based polyamide resin composition powder to be soaked and dispersed into the fiber, heating to enable the fiber to be fully soaked, and extruding the fiber through a pultrusion die to obtain the transparent bio-based polyamide resin composition;
wherein the mass percentage of the fiber in the continuous fiber reinforced polyamide composite material is controlled to be 35-75% by adjusting the proportion of the transparent bio-based polyamide resin composition powder in the slurry and the traction speed.
7. The method for producing a continuous fiber-reinforced transparent bio-based polyamide composite material according to claim 6, wherein in step S1, the slurry containing the transparent bio-based polyamide resin composition powder comprises, in mass percent: transparent biobased polyamide resin composition powder: 10-50%, water: 50-90%, water-soluble polymer: 0.1-5%, surfactant: 0.1-5%, viscosity reducer: 0.1-5%;
wherein the transparent bio-based polyamide resin composition powder has a density of 1.0 to 1.5;
and/or the transparent bio-based polyamide resin composition powder has a particle diameter D50 of less than 50 microns, preferably less than or equal to 5 microns;
and/or the water-soluble polymer is selected from one or more of nonionic water-soluble cellulose, nonionic water-soluble hydroxypropyl methyl cellulose and polyvinyl alcohol;
and/or the surfactant is selected from one or more of fluoro 431, octadecyl benzyl dimethyl ammonium chloride and castor oil polyethylene oxide ether;
and/or the viscosity reducer is selected from one or more of 1, 3-butanediol and ethylene glycol series;
and/or, the preparation method of the slurry containing the transparent bio-based polyamide resin composition powder comprises the following steps: taking materials according to the proportion of each component in the slurry, firstly mixing and stirring a proper amount of water, a surfactant and a viscosity reducer to obtain a solution; using water to independently dissolve water-soluble polymer, then adding the water-soluble polymer into the above-mentioned solution and stirring; slowly adding the transparent bio-based polyamide resin composition powder into the solution in batches, and stirring to obtain the transparent bio-based polyamide resin composition powder;
and/or the slurry has a viscosity of 0.1 to 100cps, preferably 2 to 30cps.
8. The method of producing a continuous fiber-reinforced transparent bio-based polyamide composite material according to claim 6, wherein the fiber is preferably 50-70% by mass of the continuous fiber-reinforced transparent bio-based polyamide composite material;
and/or, in step S2, before pulling the fiber through the slurry, the fiber further comprises the following operations: the fiber is unreeled from the creel through the tension controller, enters the yarn spreading system through the yarn dividing frame, fully spreads each tow, and then passes through slurry through traction;
and/or the traction is performed using a traction device, the traction speed of the traction may be 3-12m/min, such as 6m/min;
and/or, the heating temperature is 290-310 ℃.
9. A molded article comprising the continuous fiber-reinforced transparent bio-based polyamide composite material according to claim 4 or 5.
10. Use of the continuous fiber reinforced transparent bio-based polyamide composite material of claim 4 or 5 in the aerospace field, military field, automotive material, sports equipment, construction material or electronic appliances.
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