CN117264407A - Continuous fiber reinforced bio-based copolyamide pipe and preparation method and application thereof - Google Patents
Continuous fiber reinforced bio-based copolyamide pipe and preparation method and application thereof Download PDFInfo
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- 239000000835 fiber Substances 0.000 title claims abstract description 82
- 238000002360 preparation method Methods 0.000 title abstract description 31
- 239000011342 resin composition Substances 0.000 claims abstract description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000007822 coupling agent Substances 0.000 claims abstract description 29
- 229920005989 resin Polymers 0.000 claims abstract description 27
- 239000011347 resin Substances 0.000 claims abstract description 27
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 22
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 20
- 229920000098 polyolefin Polymers 0.000 claims abstract description 15
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 13
- 238000004804 winding Methods 0.000 claims description 80
- 239000003365 glass fiber Substances 0.000 claims description 40
- 238000010438 heat treatment Methods 0.000 claims description 33
- 238000005470 impregnation Methods 0.000 claims description 29
- 239000000155 melt Substances 0.000 claims description 29
- 238000001816 cooling Methods 0.000 claims description 28
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 22
- 239000004917 carbon fiber Substances 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 22
- -1 polyethylene Polymers 0.000 claims description 22
- 239000004698 Polyethylene Substances 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- 229920000573 polyethylene Polymers 0.000 claims description 10
- UAUDZVJPLUQNMU-UHFFFAOYSA-N Erucasaeureamid Natural products CCCCCCCCC=CCCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-UHFFFAOYSA-N 0.000 claims description 9
- 239000004743 Polypropylene Substances 0.000 claims description 9
- 238000005520 cutting process Methods 0.000 claims description 9
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 claims description 9
- 238000001125 extrusion Methods 0.000 claims description 9
- 229920001155 polypropylene Polymers 0.000 claims description 9
- 238000005096 rolling process Methods 0.000 claims description 9
- 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 8
- 238000002844 melting Methods 0.000 claims description 8
- 230000008018 melting Effects 0.000 claims description 8
- 238000003892 spreading Methods 0.000 claims description 8
- 230000007480 spreading Effects 0.000 claims description 8
- 238000009966 trimming Methods 0.000 claims description 8
- 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 7
- 229920001971 elastomer Polymers 0.000 claims description 6
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
- 238000000465 moulding Methods 0.000 claims description 4
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 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
- 150000001412 amines Chemical class 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 3
- 239000000806 elastomer Substances 0.000 claims description 3
- 239000005060 rubber Substances 0.000 claims description 3
- 229910000077 silane Inorganic materials 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
- 241000208202 Linaceae Species 0.000 claims description 2
- 235000004431 Linum usitatissimum Nutrition 0.000 claims description 2
- 150000004645 aluminates Chemical class 0.000 claims description 2
- 239000004760 aramid Substances 0.000 claims description 2
- 229920006231 aramid fiber Polymers 0.000 claims description 2
- 238000010276 construction Methods 0.000 claims description 2
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical group CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 claims description 2
- FATBGEAMYMYZAF-UHFFFAOYSA-N oleicacidamide-heptaglycolether Natural products CCCCCCCCC=CCCCCCCCC(N)=O FATBGEAMYMYZAF-UHFFFAOYSA-N 0.000 claims description 2
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 2
- 229920001748 polybutylene Polymers 0.000 claims description 2
- 229920006012 semi-aromatic polyamide Polymers 0.000 claims description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims 1
- 239000006087 Silane Coupling Agent Substances 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 abstract description 7
- 239000004952 Polyamide Substances 0.000 description 16
- 229920002647 polyamide Polymers 0.000 description 16
- 239000000463 material Substances 0.000 description 14
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 12
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 12
- KJOMYNHMBRNCNY-UHFFFAOYSA-N pentane-1,1-diamine Chemical compound CCCCC(N)N KJOMYNHMBRNCNY-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 238000006116 polymerization reaction Methods 0.000 description 11
- 150000003839 salts Chemical class 0.000 description 11
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 7
- 235000011037 adipic acid Nutrition 0.000 description 6
- 239000001361 adipic acid Substances 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 238000003825 pressing Methods 0.000 description 6
- 238000007493 shaping process Methods 0.000 description 6
- 229920006021 bio-based polyamide Polymers 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000004677 Nylon Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229920001778 nylon Polymers 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 238000005086 pumping Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229920001169 thermoplastic Polymers 0.000 description 3
- 239000004416 thermosoftening plastic Substances 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002530 phenolic antioxidant Substances 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 150000003504 terephthalic acids Chemical class 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910001018 Cast iron Inorganic materials 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000010883 coal ash Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 239000003733 fiber-reinforced composite Substances 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000011150 reinforced concrete Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000012815 thermoplastic material Substances 0.000 description 1
- 229920002397 thermoplastic olefin Polymers 0.000 description 1
Classifications
-
- 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
- C08J2423/06—Polyethene
-
- 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
- C08J2423/10—Homopolymers or copolymers of propene
- C08J2423/12—Polypropene
-
- 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
- C08J2451/06—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 homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
-
- 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
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Reinforced Plastic Materials (AREA)
Abstract
The invention discloses a continuous fiber reinforced bio-based copolyamide pipe and a preparation method and application thereof. The continuous fiber reinforced biobased copolyamide pipe comprises a biobased copolyamide resin composition and continuous fibers, wherein the mass fraction ratio of the biobased copolyamide resin composition to the continuous fibers is (10:90) - (50:50); wherein the bio-based copolyamide resin composition comprises: 60-90 parts of bio-based copolyamide resin, 8-25 parts of polyolefin, 3-12 parts of compatilizer, 0.1-1 part of antioxidant, 0.1-0.8 part of coupling agent and 0.1-1 part of release agent. The pipe prepared by the invention has the characteristics of low water absorption, good heat resistance, excellent mechanical property, high-temperature internal pressure resistance and the like, and has wider application fields.
Description
Technical Field
The invention relates to a continuous fiber reinforced bio-based copolyamide pipe and a preparation method and application thereof.
Background
With the continuous expansion of research space of mankind, pipeline engineering is one of basic construction engineering, and the consumption and performance of pipeline are increasing day by day, for example in the transportation of crude oil, coal ash in steam power plant and ore plant high abrasion ore pulp, the pipeline of super wear resistance, corrosion resistance and high pressure resistance is all required, and the pipeline of single material such as cast iron pipe, steel pipe, prestressed reinforced concrete pipe, polyethylene pipe, polypropylene pipe, hard polyvinyl chloride pipe can not satisfy the operation requirement of special harsh environment. Composite tubing is thus a research hotspot in recent years
The preparation of the composite pipe by using the fiber reinforced thermoplastic material is one direction of current attention, and the obtained pipe has a series of unique advantages of light weight, high strength, low cost, corrosion resistance, green environmental protection and the like, and has great application prospects in the fields of municipal administration, water conservancy, coal, chemistry, oil gas and the like.
The existing fiber reinforced thermoplastic winding pipes mostly use polyethylene, polypropylene and polyvinyl chloride as resin matrixes, and the performance of the fiber reinforced thermoplastic winding pipes is improved compared with that of the traditional pipes, but the fiber reinforced thermoplastic winding pipes can only be used for conveying liquid or gas at about 100 ℃. Nylon plastic is a general engineering plastic with long history and wide application, wherein the research and application of PA6 and PA66 are the most extensive, but the material is easy to absorb moisture, the mechanical property is reduced, and the service life and application field of the nylon material are limited. In addition, PA6 and PA66 materials with excellent properties are derived from import, which undoubtedly increases the production and processing costs.
Therefore, there is an urgent need in the art for a fiber reinforced polyamide tubing with low water absorption, good heat resistance, and good mechanical properties, and a method for preparing the same.
Disclosure of Invention
The invention aims to solve the problems of poor mechanical property and poor heat resistance of fiber reinforced thermoplastic polyolefin pipes and limited application fields caused by high preparation cost and high water absorption of nylon plastics in the prior art, thereby providing a continuous fiber reinforced bio-based copolyamide pipe and a preparation method and application thereof. The preparation method of the continuous fiber reinforced bio-based copolyamide pipe is simple and feasible, low in cost, high in production efficiency and good in impregnation effect, and the prepared continuous fiber reinforced bio-based copolyamide pipe is excellent in comprehensive performance, good in heat resistance, low in water absorption rate, good in mechanical performance and recyclable.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the invention provides a continuous fiber reinforced biobased copolyamide pipe, which comprises a biobased copolyamide resin composition and continuous fibers, wherein the mass fraction ratio of the biobased copolyamide resin composition to the continuous fibers is (10:90) - (50:50);
wherein the bio-based copolyamide resin composition comprises: 60-90 parts of bio-based copolyamide resin, 8-25 parts of polyolefin, 3-12 parts of compatilizer, 0.1-1 part of antioxidant, 0.1-0.8 part of coupling agent and 0.1-1 part of release agent.
In some embodiments, the biobased copolyamide resin contains the following structural units (I), (II) and (III)
The molar ratio of the structural unit (I) to the structural unit (II) is 1: (0.1-0.9);
the molar ratio of the structural unit (I) to the structural unit (III) is 1: (0.1-0.9);
the molar ratio of the structural unit (II) to the structural unit (III) is 1: (0.1-1.5);
the structural units (I), (II) and (III) are connected by amide bonds.
In some specific embodiments, the molar ratio of adipic acid to terephthalic acid may be 1: (0.35-0.55), e.g. 1:0.45; or 1: (0.55-0.85), e.g. 1:0.72; or 1: (0.85-1.2), e.g., 1:1.05.
In some specific embodiments, the biobased copolyamide resin has a relative viscosity of 2.0 to 3.2. The relative viscosity was determined by the Ubbelohde viscometer method with concentrated sulfuric acid (96% concentration).
In some specific embodiments, the bio-based copolyamide resin has a number average molecular weight of 2 to 7 ten thousand, and further 3 to 6 ten thousand.
In some specific embodiments, the biobased copolyamide resin has a water content of 500 to 2000ppm. The water content can be reduced by drying.
In some specific embodiments, the bio-based copolyamide resin has a melting point of 260-330 ℃, and further 270-300 ℃.
In some specific embodiments, the biobased copolyamide resin is formed from pentanediamine and dicarboxylic acid, wherein the molar ratio of the pentanediamine to dicarboxylic acid is (1-1.05): 1, for example 1.05:1.
in some specific embodiments, the method of preparing the bio-based copolyamide resin comprises the steps of: the preparation method comprises the steps of preparing a polyamide salt solution from pentanediamine, dicarboxylic acid and water, and heating and polymerizing the polyamide salt solution to obtain the bio-based copolyamide resin.
In some embodiments, the dicarboxylic acid comprises 40 to 90 mole% adipic acid and 10 to 60 mole% terephthalic acid or derivatives of terephthalic acid, the percentages being mole percent.
In some specific embodiments, the method of preparing the bio-based copolyamide resin comprises the steps of: (1) Mixing water, pentanediamine and terephthalic acid or derivatives of terephthalic acid and adipic acid under nitrogen or inert gas atmosphere to prepare polyamide salt water solution with the concentration of 30-75wt%; (2) Transferring the aqueous solution of the polyamide salt into a polymerization device (such as a polymerization kettle), heating under nitrogen or inert gas atmosphere, raising the temperature in a reaction system to 230-310 ℃, raising the pressure to 0.7-2.5MPa, and keeping for 60-180 minutes; then exhausting and reducing the pressure to normal pressure within 30-120 minutes, and simultaneously raising the temperature to 260-340 ℃; vacuumizing to reduce the pressure to- (0.02-0.08) MPa, and maintaining for 30-120 minutes to obtain a melt; (3) And (3) carrying out bracing and granulating on the melt to obtain the bio-based copolyamide resin PA56/5T.
In the present invention, the content of the bio-based copolyamide resin is preferably 68 to 83 parts, for example 68 parts, 70 parts, 71 parts, 75 parts, 78 parts, 80 parts, 83 parts.
In some specific embodiments, the polyolefin is selected from one or more of polyethylene, polypropylene, polybutylene; for example, polyethylene PE100S is available from Jilin petrochemical and polypropylene PP212E is available from Nordic chemical.
In the present invention, the polyolefin content is preferably 10 to 23 parts, for example, 10 parts, 14 parts, 16 parts, 20 parts, 23 parts.
In some embodiments, the compatibilizing agent may be selected from one or more of a polyolefin grafted maleic anhydride-based compatibilizing agent, a polyolefin grafted methyl ester acrylic compatibilizing agent, and a rubber elastomer grafted maleic anhydride-based compatibilizing agent. Wherein the polyolefin grafted maleic anhydride-based compatibilizer may be conventional in the art, such as PP-g-MAH or POE-g-MAH. The polyolefin grafted methyl ester acrylic compatibilizer may be conventional in the art, such as POE-g-GMA. The rubber elastomer grafted maleic anhydride-based compatibilizer may be conventional in the art, such as EPDM-g-MAH.
Preferably, the compatibilizer is selected from one or more of PP-g-MAH, POE-g-GMA or EPDM-g-MAH.
In the present invention, the content of the compatibilizing agent is preferably 4 to 9 parts, for example, 5.8 parts, 7 parts, 7.6 parts, 8 parts, 8.2 parts.
In some specific embodiments, the antioxidant may be 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. 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.
In the present invention, the antioxidant content is preferably 0.2 to 1.0 parts, for example, 0.3 parts, 0.5 parts, 0.6 parts, 0.7 parts, 0.8 parts.
In some embodiments, the coupling agent may be selected from one or more of a silane-based coupling agent, a carbonate-based coupling agent, and an aluminate-based coupling agent; 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 and the melting point of the bio-based polyamide resin.
In the present invention, the coupling agent is preferably used in an amount of 0.3 to 0.8 parts, for example, 0.4 parts, 0.5 parts, 0.7 parts.
In some specific embodiments, the mold release agent is selected from oleamide and/or erucamide.
In the present invention, the content of the release agent is preferably 0.1 to 0.5 parts, for example, 0.2 parts, 0.3 parts, 0.4 parts.
In the present invention, the continuous fibers may be of a variety conventional in the art, such as one or more of carbon fibers, glass fibers, silicon carbide fibers, basalt fibers, natural flax fibers, aramid fibers, semi-aromatic polyamide fibers, or polyolefin fibers. Preferably, the continuous fibers may be continuous long fibers.
Preferably, the continuous fibers are continuous long glass fibers, and the monofilament diameter may be 8-15 μm, and further 8-10 μm. Preferably, the continuous long glass fibers have a linear density of 1200-4800Tex, e.g. 1200Tex, 2400Tex, 3600Tex. 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 continuous fibers are continuous long carbon fibers, such as polyacrylonitrile-based carbon fibers; the continuous long carbon fiber may have a filament number of 10K-60K, for example 12K,24K,36K. The continuous long carbon fibers may have a monofilament diameter of 5-10 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, the bio-based copolyamide resin composition may be prepared by a method conventional in the art, and generally comprises mixing the above components in a high-speed mixer.
The second aspect of the invention provides a method for preparing the continuous fiber reinforced bio-based copolyamide pipe, which comprises the following steps:
s1, extruding the bio-based copolyamide resin composition, and enabling a melt to enter an impregnation die head;
s2, introducing continuous fibers into the impregnation die head, wherein the melt and the fibers are impregnated;
s3, molding, cooling, drawing and winding the impregnated fiber to obtain a prepreg tape;
s4, winding the prepreg tape on a mandrel, rolling, cooling, demolding and cutting to obtain the finished product.
In the present invention, the mass fraction ratio of the bio-based copolyamide resin composition to the continuous fibers is controlled to be (10:90) - (50:50) by adjusting the speed of extrusion and the speed of winding.
Preferably, in step S1, the extrusion may be performed using a twin screw extruder or a single screw extruder, which are conventional in the art, preferably a twin screw extruder. Wherein the aspect ratio of the twin-screw extruder is preferably 36:1.
Preferably, in step S1, the extrusion temperature may be 170-340 ℃.
Preferably, the twin-screw extruder adopts an eight-zone heating mode, and the temperatures from one zone to eight zones are 205-260 ℃, 265-305 ℃, 275-325 ℃ and 275-325 ℃ in sequence.
Preferably, in step S1, the extrusion speed is 200-600rpm, e.g. 300rpm, 400rpm, expressed as screw speed.
Preferably, in step S1, the step of filtering is preferably further included after the extrusion. The filtration may be performed using melt filters conventional in the art. Preferably, when a twin screw extruder is used, the temperature of the melt filter is in the range of 0-15 ℃ above and below the eight zone temperature of the twin screw extruder, such as 275 ℃, 285 ℃, 315 ℃.
In step S1, the impregnation die may employ a die conventional in the art. The width of the impregnation die is preferably 100-650mm.
Preferably, in step S1, the temperature of the impregnation die is 240-330 ℃, preferably 290-330 ℃. Preferably, when a twin screw extruder is used, the temperature of the impregnation die is in the range of 0-15 ℃ above and below the eight zone temperature of the twin screw extruder, such as 290 ℃, 295 ℃, 315 ℃ or 330 ℃.
In step S2, when the fibers are continuous long fibers, the introducing generally includes the following processes: the continuous long fibers are unwound from the creel through the tension controller, enter the yarn spreading system through the yarn dividing frame, fully spread each filament bundle, enter the yarn drying device for preheating, and then enter the dipping die head; wherein when the fibers are continuous long glass fibers, the temperature of the yarn drying device is preferably 70-90 ℃, such as 80 ℃, 85 ℃; when the fibers are continuous long carbon fibers, the temperature of the yarn drying device is preferably 70-400 ℃, such as 80 ℃, 100 ℃, 200 ℃, 250 ℃, 300 ℃, 350 ℃.
In step S2, the continuous fibers are as described above.
In step S3, the molding and cooling may be performed by using a conventional press roll machine in the art, preferably a four-roll machine. The temperature of the internal circulation water of the four-roll machine may be 15-40 ℃, for example 20 ℃.
In step S3, the pulling may be performed using pulling means conventional in the art, in which further cooling and trimming are performed. The traction speed of the traction may be 5-20m/min, e.g. 8m/min, 5m/min.
In step S3, the winding may be performed by a winding device, preferably an automatic winder, which is conventional in the art. The speed of the winding may be 3-15m/min, for example 8m/min, 3m/min.
In the present invention, the prepreg tape preferably means a tape-like prepreg made by impregnating resin with continuous fibers parallel to each other.
In the present invention, the prepreg tape preferably has a thickness of 0.15 to 0.4mm, for example, 0.25mm,0.33mm.
In the present invention, preferably, in step S4, the winding temperature is 280-350 ℃, and the temperature is obtained by hot air heating or infrared heating.
In the present invention, preferably, in step S4, the winding speed is 1-30m/min, preferably 5-20m/min.
In the present invention, preferably, in step S4, the winding angle is within a range of 30 ° to 75 °, preferably 40 ° to 60 °.
In the present invention, the mandrel is preferably circular. The rolling is performed by using steel rollers, the number and diameter of which are confirmed by those skilled in the art according to the actual situation. The cooling adopts a water cooling mode.
The third aspect of the invention provides application of the continuous fiber reinforced bio-based copolyamide pipe in the fields of facilities such as building water supply and drainage pipelines, heating pipelines, gas pipelines, electric wire pipes, industrial pipelines, submarine pipelines and the like.
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 bio-based copolyamide as a raw material:
(1) The monomer pentanediamine in the raw materials is prepared by biological fermentation, so that the content of biological base is high, and the use of fossil raw materials can be effectively reduced, thereby reducing carbon emission;
(2) The bio-based copolyamide material has low viscosity, good fluidity and good wettability to fibers in a molten state;
(3) The material selection range of the unidirectional tape is enlarged, and the cost is reduced.
2. The fiber content of the pipe is high and is in the range of 50-90%; and has the characteristics of low water absorption, good heat resistance, excellent mechanical property, high-temperature internal pressure resistance, recyclable materials and the like.
3. The preparation method is simple and quick, can realize continuous production of the pipe, and has low cost and high practicability.
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.
The following examples and comparative examples are commercially available as raw materials unless otherwise specified:
pentanediamine is available from Kaiser (Kingxiang) biological materials Co., ltd; polyethylene PE100S is purchased from Jilin petrochemical industry, and polypropylene PP212E is purchased from Nordic chemical industry; antioxidants were purchased from basf group, germany; the compatibilizing agent is available from Shanghai good compatible polymers limited; coupling agent was purchased from jercard chemical company, hangzhou; the release agent was purchased from Kaiyin chemical Co., ltd; 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.
Biobased copolyamide a: the preparation method comprises the following steps: (1) Mixing water, pentanediamine and dicarboxylic acid (adipic acid and terephthalic acid in a molar ratio of 1:1.05) under nitrogen atmosphere to obtain a polyamide salt aqueous solution with a concentration of 65 wt%; the molar ratio of the pentanediamine to the dicarboxylic acid is 1.05:1, a step of; (2) Transferring the aqueous solution of the polyamide salt into a polymerization kettle, heating the aqueous solution of the polyamide salt in a nitrogen atmosphere, raising the temperature in the kettle to 290 ℃, raising the pressure in a polymerization device to 1.6MPa, and keeping the temperature for 110 minutes; then exhausting and reducing the pressure to normal pressure within 85 minutes, and simultaneously raising the temperature in the polymerization device to 300 ℃; vacuum pumping to reduce the pressure to-0.05 MPa, maintaining for 60 min to obtain melt, and strand granulating to obtain bio-based polyamide resin PA56/5T-A (relative viscosity 2.24, number average molecular weight 3 ten thousand, melting point 300 deg.C, and water content 800ppm after drying).
Biobased copolyamide B: the preparation method comprises the following steps: (1) Mixing water, pentanediamine and dicarboxylic acid (adipic acid and terephthalic acid in a molar ratio of 1:0.72) under nitrogen atmosphere to obtain a polyamide salt aqueous solution with a concentration of 65 wt%; the molar ratio of the pentanediamine to the dicarboxylic acid is 1.05:1, a step of; (2) Transferring the aqueous solution of the polyamide salt into a polymerization kettle, heating the aqueous solution of the polyamide salt in a nitrogen atmosphere, raising the temperature in the kettle to 290 ℃, raising the pressure in a polymerization device to 1.6MPa, and keeping the temperature for 110 minutes; then exhausting and reducing the pressure to normal pressure within 85 minutes, and simultaneously raising the temperature in the polymerization device to 300 ℃; vacuum pumping to reduce the pressure to-0.05 MPa, maintaining for 60 min to obtain melt, and strand granulating to obtain bio-based polyamide resin PA56/5T-B (relative viscosity 2.31, number average molecular weight 4 ten thousand, melting point 290 ℃, and water content 800ppm after drying).
Biobased polyamide C: the preparation method comprises the following steps: (1) Mixing water, pentanediamine and dicarboxylic acid (adipic acid and terephthalic acid in a molar ratio of 1:0.45) under nitrogen atmosphere to obtain a polyamide salt aqueous solution with a concentration of 65 wt%; the molar ratio of the pentanediamine to the dicarboxylic acid is 1.05:1, a step of; (2) Transferring the aqueous solution of the polyamide salt into a polymerization kettle, heating the aqueous solution of the polyamide salt in a nitrogen atmosphere, raising the temperature in the kettle to 290 ℃, raising the pressure in a polymerization device to 1.6MPa, and keeping the temperature for 110 minutes; then exhausting and reducing the pressure to normal pressure within 85 minutes, and simultaneously raising the temperature in the polymerization device to 300 ℃; vacuum pumping to reduce the pressure to-0.05 MPa, maintaining for 60 min to obtain melt, and strand granulating to obtain bio-based polyamide resin PA56/5T-C (relative viscosity 2.45, number average molecular weight 6 ten thousand, melting point 270 ℃, and water content 800ppm after drying).
Example 1
1. Preparation of biobased copolyamide resin composition:
biobased copolyamide a:68 parts of polyethylene PE100S:23 parts of an antioxidant 1098:0.8 part of compatilizer PE-g-MAH:7.6 parts of coupling agent KH560:0.4 part of release agent erucamide: 0.2 parts. The components are added into a high-speed stirrer to be mixed, and the bio-based copolyamide resin composition is obtained.
2. Preparing a continuous fiber reinforced bio-based copolyamide pipe:
s1, extruding the obtained bio-based copolyamide resin composition by using a double-screw extruder, filtering an extruded melt by using a melt filter, and entering an impregnation die head; wherein: the twin-screw extruder is in an eight-zone heating mode, and the temperatures from one zone to eight zones (feeding to a machine head) are 250 ℃, 275 ℃, 300 ℃, 310 ℃ and 300 ℃ in sequence; the rotating speed of the screw is 400r/min; the length-diameter ratio of the twin-screw extruder is 36:1; the temperature of the melt filter was 300 ℃; the die temperature was 300 ℃.
S2, unwinding the continuous long glass fiber from a creel through a tension controller, entering a yarn spreading system through a yarn dividing frame to fully spread each filament bundle, then entering a yarn drying device for preheating, setting the temperature of the yarn drying device to be 85 ℃, and then entering an impregnation die head, wherein the continuous long glass fiber and a melt are impregnated in the impregnation die head.
S3, carrying out mould pressing and cooling shaping on the immersed continuous long glass fiber by a four-roller machine, wherein the temperature of circulating water in the four-roller machine is set to be 20 ℃; then the mixture enters a traction device for further cooling and trimming, and the traction speed is 15m/min; and finally, winding the material into a roll in an automatic winding machine at a winding speed of 15m/min to obtain the unidirectional prepreg tape with the thickness of 0.22 mm. In the preparation process, the screw rotating speed of the double-screw extruder and the winding speed of the automatic winding machine are controlled, so that the mass fraction ratio of the bio-based copolyamide resin composition to the continuous long glass fiber is 35:65.
s4, winding the unidirectional prepreg tape on a circular winding mandrel at a winding angle of 60 DEG, wherein the winding temperature is 320 ℃ (obtained by adopting hot air heating or infrared heating), the winding speed is 13m/min, and the unidirectional prepreg tape is obtained by rolling, water cooling, demoulding and cutting.
Example 2
1. Preparation of biobased copolyamide resin composition:
biobased copolyamide B:83 parts of polypropylene PP212E:10 parts of an antioxidant 168:0.5 part of compatilizer PP-g-MAH:5.8 parts of coupling agent KH560:0.5 part of release agent erucamide: 0.2 parts. The components are added into a high-speed stirrer to be mixed, and the bio-based copolyamide resin composition is obtained.
2. Preparing a continuous fiber reinforced bio-based copolyamide pipe:
s1, extruding the obtained bio-based copolyamide resin composition by using a double-screw extruder, filtering an extruded melt by using a melt filter, and entering an impregnation die head; wherein: the twin-screw extruder is in an eight-zone heating mode, and the temperatures from one zone to eight zones (feeding to a machine head) are 250 ℃, 275 ℃, 300 ℃, 310 ℃ and 300 ℃ in sequence; the rotating speed of the screw is 450r/min; the length-diameter ratio of the twin-screw extruder is 36:1; the temperature of the melt filter was 300 ℃; the die temperature was 300 ℃.
S2, unwinding the continuous long glass fiber from a creel through a tension controller, entering a yarn spreading system through a yarn dividing frame to fully spread each filament bundle, then entering a yarn drying device for preheating, setting the temperature of the yarn drying device to be 85 ℃, and then entering an impregnation die head, wherein the continuous long glass fiber and a melt are impregnated in the impregnation die head.
S3, carrying out mould pressing and cooling shaping on the immersed continuous long glass fiber by a four-roller machine, wherein the temperature of circulating water in the four-roller machine is set to be 20 ℃; then the mixture enters a traction device for further cooling and trimming, and the traction speed is 9m/min; and finally, winding the material into a roll in an automatic winding machine at a winding speed of 9m/min to obtain the unidirectional prepreg tape with the thickness of 0.20 mm. In the preparation process, the screw rotating speed of the double-screw extruder and the winding speed of the automatic winding machine are controlled, so that the mass fraction ratio of the bio-based copolyamide resin composition to the continuous long glass fiber is 25:75.
s4, winding the unidirectional prepreg tape on a circular winding mandrel at a winding angle of 50 DEG, wherein the winding temperature is 305 ℃ (obtained by adopting hot air heating or infrared heating), the winding speed is 12m/min, and the unidirectional prepreg tape is obtained by rolling, water cooling, demoulding and cutting.
Example 3
1. Preparation of biobased copolyamide resin composition:
biobased copolyamide C:71 parts of polyethylene PE100S:20 parts of an antioxidant 1098:0.5 part of compatilizer POE-g-MAH:8 parts of coupling agent KH550:0.5 part of release agent erucamide: 0.2 parts. The components are added into a high-speed stirrer to be mixed, and the bio-based copolyamide resin composition is obtained.
2. Preparing a continuous fiber reinforced bio-based copolyamide pipe:
s1, extruding the obtained bio-based copolyamide resin composition by using a double-screw extruder, filtering an extruded melt by using a melt filter, and entering an impregnation die head; wherein: the twin-screw extruder is in an eight-zone heating mode, and the temperatures from one zone to eight zones (feeding to a machine head) are 250 ℃, 275 ℃, 300 ℃, 310 ℃ and 300 ℃ in sequence; the rotating speed of the screw is 350r/min; the aspect ratio of the twin screw extruder was 36:1, a step of; the temperature of the melt filter was 310 ℃; the die temperature was 310 ℃.
S2, unwinding the continuous long glass fiber from a creel through a tension controller, entering a yarn spreading system through a yarn dividing frame to fully spread each filament bundle, then entering a yarn drying device for preheating, setting the temperature of the yarn drying device to be 85 ℃, and then entering an impregnation die head, wherein the continuous long glass fiber and a melt are impregnated in the impregnation die head.
S3, carrying out mould pressing and cooling shaping on the immersed continuous long glass fiber by a four-roller machine, wherein the temperature of circulating water in the four-roller machine is set to be 20 ℃; then the mixture enters a traction device for further cooling and trimming, and the traction speed is 15m/min; and finally, winding the material into a roll in an automatic winding machine at a winding speed of 15m/min to obtain the unidirectional prepreg tape with the thickness of 0.20 mm. In the preparation process, the screw rotating speed of the double-screw extruder and the winding speed of the automatic winding machine are controlled, so that the mass fraction ratio of the bio-based copolyamide resin composition to the continuous long glass fiber is 30:70.
s4, winding the unidirectional prepreg tape on a circular winding mandrel at a winding angle of 45 DEG, wherein the winding temperature is 300 ℃ (obtained by adopting hot air heating or infrared heating), the winding speed is 15m/min, and the unidirectional prepreg tape is obtained by rolling, water cooling, demoulding and cutting.
Example 4
1. Preparation of biobased copolyamide resin composition:
biobased copolyamide a:70 parts of polypropylene PP212E:20 parts of an antioxidant 168:0.7 part of compatilizer POE-g-MAH:8.2 parts of coupling agent KH550:0.7 part of release agent erucamide: 0.2 parts. The components are added into a high-speed stirrer to be mixed, and the bio-based copolyamide resin composition is obtained.
2. Preparing a continuous fiber reinforced bio-based copolyamide pipe:
s1, extruding the obtained bio-based copolyamide resin composition by using a double-screw extruder, filtering an extruded melt by using a melt filter, and entering an impregnation die head; wherein: the twin-screw extruder is in an eight-zone heating mode, and the temperatures from one zone to eight zones (feeding to a machine head) are 250 ℃, 275 ℃, 300 ℃, 310 ℃ and 300 ℃ in sequence; the rotating speed of the screw is 450r/min; the length-diameter ratio of the twin-screw extruder is 36:1; the temperature of the melt filter was 300 ℃; the die temperature was 300 ℃.
S2, unwinding the continuous long glass fiber from a creel through a tension controller, entering a yarn spreading system through a yarn dividing frame to fully spread each filament bundle, then entering a yarn drying device for preheating, setting the temperature of the yarn drying device to be 85 ℃, and then entering an impregnation die head, wherein the continuous long glass fiber and a melt are impregnated in the impregnation die head.
S3, carrying out mould pressing and cooling shaping on the immersed continuous long glass fiber by a four-roller machine, wherein the temperature of circulating water in the four-roller machine is set to be 20 ℃; then the mixture enters a traction device for further cooling and trimming, and the traction speed is 12m/min; and finally, winding the material into a roll in an automatic winding machine at a winding speed of 12m/min to obtain the unidirectional prepreg tape with the thickness of 0.24 mm. In the preparation process, the screw rotating speed of the double-screw extruder and the winding speed of the automatic winding machine are controlled, so that the mass fraction ratio of the bio-based copolyamide resin composition to the continuous long glass fiber is 25:75.
s4, winding the unidirectional prepreg tape on a circular winding mandrel at a winding angle of 50 DEG, wherein the winding temperature is 320 ℃ (obtained by adopting hot air heating or infrared heating), the winding speed is 10m/min, and the unidirectional prepreg tape is obtained by rolling, water cooling, demoulding and cutting.
Example 5
1. Preparation of biobased copolyamide resin composition:
biobased copolyamide B:75 parts of polyethylene PE100S:16 parts of an antioxidant 1098:0.6 part of compatilizer POE-g-MAH:8 parts of coupling agent KH550:0.4 part of release agent erucamide: 0.3 parts. The components are added into a high-speed stirrer to be mixed, and the bio-based copolyamide resin composition is obtained.
2. Preparing a continuous fiber reinforced bio-based copolyamide pipe:
s1, extruding the obtained bio-based copolyamide resin composition by using a double-screw extruder, filtering an extruded melt by using a melt filter, and entering an impregnation die head; wherein: the twin-screw extruder is in an eight-zone heating mode, and the temperatures from one zone to eight zones (feeding to a machine head) are 250 ℃, 275 ℃, 300 ℃, 310 ℃ and 300 ℃ in sequence; the rotating speed of the screw is 400r/min; the length-diameter ratio of the twin-screw extruder is 36:1; the temperature of the melt filter was 300 ℃; the die temperature was 300 ℃.
S2, unwinding the continuous long glass fiber from a creel through a tension controller, entering a yarn spreading system through a yarn dividing frame to fully spread each filament bundle, then entering a yarn drying device for preheating, setting the temperature of the yarn drying device to be 85 ℃, and then entering an impregnation die head, wherein the continuous long glass fiber and a melt are impregnated in the impregnation die head.
S3, carrying out mould pressing and cooling shaping on the immersed continuous long glass fiber by a four-roller machine, wherein the temperature of circulating water in the four-roller machine is set to be 20 ℃; then the mixture enters a traction device for further cooling and trimming, and the traction speed is 15m/min; and finally, winding the material into a roll in an automatic winding machine at a winding speed of 15m/min to obtain the unidirectional prepreg tape with the thickness of 0.23 mm. In the preparation process, the screw rotating speed of the double-screw extruder and the winding speed of the automatic winding machine are controlled, so that the mass fraction ratio of the bio-based copolyamide resin composition to the continuous long glass fiber is 35:65.
s4, winding the unidirectional prepreg tape on a circular winding mandrel at a winding angle of 45 DEG, wherein the winding temperature is 305 ℃ (obtained by adopting hot air heating or infrared heating), the winding speed is 15m/min, and the unidirectional prepreg tape is obtained by rolling, water cooling, demoulding and cutting.
Example 6
1. Preparation of biobased copolyamide resin composition:
biobased copolyamide C:78 parts of polypropylene PP212E:14 parts of an antioxidant 168:0.3 part of compatilizer PE-g-MAH:7 parts of coupling agent KH560:0.5 part of release agent erucamide: 0.2 parts. The components are added into a high-speed stirrer to be mixed, and the bio-based copolyamide resin composition is obtained.
2. Preparing a continuous fiber reinforced bio-based copolyamide pipe:
s1, extruding the obtained bio-based copolyamide resin composition by using a double-screw extruder, filtering an extruded melt by using a melt filter, and entering an impregnation die head; wherein: the twin-screw extruder is in an eight-zone heating mode, and the temperatures from one zone to eight zones (feeding to a machine head) are 250 ℃, 275 ℃, 300 ℃, 310 ℃ and 300 ℃ in sequence; the rotating speed of the screw is 400r/min; the length-diameter ratio of the twin-screw extruder is 36:1; the temperature of the melt filter was 300 ℃; the die temperature was 300 ℃.
S2, unwinding the continuous long glass fiber from a creel through a tension controller, entering a yarn spreading system through a yarn dividing frame to fully spread each filament bundle, then entering a yarn drying device for preheating, setting the temperature of the yarn drying device to be 85 ℃, and then entering an impregnation die head, wherein the continuous long glass fiber and a melt are impregnated in the impregnation die head.
S3, carrying out mould pressing and cooling shaping on the immersed continuous long glass fiber by a four-roller machine, wherein the temperature of circulating water in the four-roller machine is set to be 20 ℃; then the mixture enters a traction device for further cooling and trimming, and the traction speed is 10m/min; and finally, winding the material into a roll in an automatic winding machine at a winding speed of 10m/min to obtain the unidirectional prepreg tape with the thickness of 0.18 mm. In the preparation process, the screw rotating speed of the double-screw extruder and the winding speed of the automatic winding machine are controlled, so that the mass fraction ratio of the bio-based copolyamide resin composition to the continuous long glass fiber is 22:78.
s4, winding the unidirectional prepreg tape on a circular winding mandrel at a winding angle of 45 DEG, wherein the winding temperature is 300 ℃ (obtained by adopting hot air heating or infrared heating), the winding speed is 10m/min, and the unidirectional prepreg tape is obtained by rolling, water cooling, demoulding and cutting.
Example 7
The procedure was carried out in the same manner as in example 1, except that: using the biobased copolyamide B, the other conditions were the same as in example 1.
Example 8
The procedure was carried out in the same manner as in example 1, except that: using the biobased copolyamide C, the other conditions were the same as in example 1.
Example 9
The procedure was carried out in the same manner as in example 1, except that: continuous long carbon fibers are used in the preparation of continuous fiber reinforced bio-based copolyamide tubing.
Example 10
The procedure was carried out in the same manner as in example 2, except that: continuous long carbon fibers are used in the preparation of continuous fiber reinforced bio-based copolyamide tubing.
Example 11
The procedure was carried out in the same manner as in example 3, except that: continuous long carbon fibers are used in the preparation of continuous fiber reinforced bio-based copolyamide tubing.
Comparative example 1
The procedure was carried out in the same manner as in example 1, except that:
1. preparation of biobased copolyamide resin composition:
biobased copolyamide a:45 parts of polyethylene PE100S:46 parts of an antioxidant 1098:0.5 part of compatilizer PE-g-MAH:8 parts of coupling agent KH560:0.5 part of release agent erucamide: 0.2 parts. Other conditions were the same as in example 1.
Comparative example 2
The procedure was carried out in the same manner as in comparative example 1, except that:
2. preparing a continuous fiber reinforced bio-based copolyamide pipe:
in S2, the continuous long glass fiber is replaced with a continuous long carbon fiber. Other conditions were the same as in example 1.
Comparative example 3
The procedure was carried out in the same manner as in example 1, except that:
1. preparation of biobased copolyamide resin composition:
the biobased copolyamide A was replaced with polyamide PA6 (available from New Conmeida, having a viscosity of 2.3 and a melting point of 223 ℃).
2. Preparing a continuous fiber reinforced bio-based copolyamide pipe:
the twin-screw extruder is in an eight-zone heating mode, and the temperatures from one zone to eight zones (feeding to a machine head) are 230 ℃, 250 ℃, 270 ℃, 275 ℃ and 260 ℃ in sequence; the rotating speed of the screw is 300r/min; the temperature of the melt filter was 250 ℃; the die temperature was 250 ℃. Other conditions were the same as in example 1.
Comparative example 4
The procedure was carried out in the same manner as in comparative example 3, except that: the continuous long glass fibers are replaced with continuous long carbon fibers.
Comparative example 5
The procedure was carried out in the same manner as in example 1, except that:
1. preparation of biobased copolyamide resin composition:
the biobased copolyamide A was replaced with polyamide PA66 (available from DuPont with a viscosity of 2.6 and a melting point of 255 ℃).
2. Preparing a continuous fiber reinforced bio-based copolyamide pipe:
the twin-screw extruder is in an eight-zone heating mode, and the temperatures from one zone to eight zones (fed to a machine head) are 240 ℃, 270 ℃, 280 ℃, 285 ℃, 280 ℃ in sequence; the rotating speed of the screw is 400r/min; the temperature of the melt filter was 270 ℃; the die temperature was 270 ℃. Other conditions were the same as in example 1.
Comparative example 6
The same procedure as in comparative example 5 was carried out except that: the continuous long glass fibers are replaced with continuous long carbon fibers.
The continuous fiber reinforced biobased copolyamide tubing of examples 1-11 and comparative examples 1-6 was subjected to performance testing according to the following test method:
(1) Cutting according to ISO-178-2010 standard to obtain sample bars with sample size of 80mm long, 10mm wide and 4mm thick, which are used for bending experiments;
(2) Referring to national standard GB/T1634.2-2004, firstly preparing a spline with the sample size of 80mm long, 10mm wide and 4mm thick, and applying a bending stress of 1.8MPa for HDT experiments;
(3) Firstly preparing a water absorbing plate with the length of 60mm, the width of 60mm and the thickness of 2mm according to the standard ASTM-D570-2005, and testing according to a test method of the water absorption rate of plastics, wherein the test time is 24 hours;
(4) Intercepting a 200mm pipe section according to the GB/T6671-2001 standard requirement for measuring the longitudinal retraction rate;
(5) The high temperature internal pressure resistance was measured according to GB/T6111-2018 standard, and the results are shown in Table 1.
TABLE 1
As can be seen from Table 1, the mechanical property, heat resistance, water absorption and high-temperature internal pressure resistance of the fiber reinforced bio-based copolyamide pipe prepared by the bio-based copolyamide resin are obviously improved compared with the corresponding performance of the fiber reinforced composite pipe based on PA6 or PA66, and the application field is wider.
Claims (10)
1. The continuous fiber reinforced bio-based copolyamide pipe is characterized by comprising a bio-based copolyamide resin composition and continuous fibers, wherein the mass fraction ratio of the bio-based copolyamide resin composition to the continuous fibers is (10:90) - (50:50);
wherein the bio-based copolyamide resin composition comprises: 60-90 parts of bio-based copolyamide resin, 8-25 parts of polyolefin, 3-12 parts of compatilizer, 0.1-1 part of antioxidant, 0.1-0.8 part of coupling agent and 0.1-1 part of release agent.
2. The continuous fiber-reinforced biobased copolyamide pipe according to claim 1, wherein the biobased copolyamide resin contains the following structural units (i), (ii) and (iii)
The molar ratio of the structural unit (I) to the structural unit (II) is 1: (0.1-0.9);
the molar ratio of the structural unit (I) to the structural unit (III) is 1: (0.1-0.9);
the molar ratio of the structural unit (II) to the structural unit (III) is 1: (0.1-1.5);
the structural units (I), (II) and (III) are connected by amide bonds.
3. The continuous fiber reinforced biobased copolyamide pipe of claim 1, wherein the biobased copolyamide resin has a relative viscosity of 2.0 to 3.2;
and/or the number average molecular weight of the bio-based copolyamide resin is 2 to 7 ten thousand;
and/or the water content of the bio-based copolyamide resin is 500-2000 ppm;
and/or, the melting point of the bio-based copolyamide resin is 260-330 ℃;
and/or the content of the bio-based copolyamide resin is 68-83 parts, for example 68 parts, 70 parts, 71 parts, 75 parts, 78 parts, 80 parts, 83 parts.
4. The continuous fiber reinforced biobased copolyamide pipe according to claim 1, wherein the polyolefin is selected from one or more of polyethylene, polypropylene, polybutylene; and/or the polyolefin is present in an amount of 10-23 parts, for example 10 parts, 14 parts, 16 parts, 20 parts, 23 parts;
and/or the compatilizer is selected from one or more of polyolefin grafted maleic anhydride compatilizer, polyolefin grafted methyl ester acrylic compatilizer and rubber elastomer grafted maleic anhydride compatilizer; preferably, the compatilizer is selected from one or more of PP-g-MAH, POE-g-GMA or EPDM-g-MAH; and/or the content of the compatilizer is 4-9 parts, such as 5.8 parts, 7 parts, 7.6 parts, 8 parts, 8.2 parts;
and/or the antioxidant is selected from one or more of hindered phenol antioxidants, 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; and/or the antioxidant is present in an amount of 0.2-1.0 parts, for example 0.3 parts, 0.5 parts, 0.6 parts, 0.7 parts, 0.8 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 present in an amount of 0.3 to 0.8 parts, for example 0.4 parts, 0.5 parts, 0.7 parts;
and/or the release agent is selected from oleamide and/or erucamide; and/or the release agent is contained in an amount of 0.1 to 0.5 parts, for example, 0.2 parts, 0.3 parts, 0.4 parts.
5. The continuous fiber reinforced biobased copolyamide pipe of claim 1, wherein the continuous fibers comprise one or more of carbon fibers, glass fibers, silicon carbide fibers, basalt fibers, natural flax fibers, aramid fibers, semi-aromatic polyamide fibers, or polyolefin fibers; preferably, the continuous fibers are continuous long fibers;
preferably, the continuous fibers are continuous long glass fibers; the monofilament diameter of the continuous long glass fiber is 8-15 mu m; the linear density of the continuous long glass fiber is 1200-4800Tex;
preferably, the continuous 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 10K-60K; the continuous long carbon fibers may have a monofilament diameter of 5-10 μm.
6. A method of producing the continuous fiber reinforced biobased copolyamide pipe according to any one of claims 1-5, comprising the steps of:
s1, extruding the bio-based copolyamide resin composition, and enabling a melt to enter an impregnation die head;
s2, introducing continuous fibers into the impregnation die head, wherein the melt and the fibers are impregnated;
s3, molding, cooling, drawing and winding the impregnated fiber to obtain a prepreg tape;
s4, winding the prepreg tape on a mandrel, rolling, cooling, demolding and cutting to obtain the finished product.
7. The method according to claim 6, wherein in step S1, the extrusion is performed using a twin screw extruder or a single screw extruder, preferably a twin screw extruder; wherein the twin screw extruder preferably has an aspect ratio of 36:1, a step of;
and/or, in step S1, the extrusion temperature may be 170-340 ℃;
preferably, the twin-screw extruder adopts an eight-zone heating mode, and the temperatures from one zone to eight zones are 205-260 ℃, 265-305 ℃, 275-325 ℃ and 275-325 ℃ in sequence;
and/or, in step S1, the extrusion speed is 200-600rpm, for example 300rpm, 400rpm, expressed as screw speed;
and/or, in step S1, the extrusion further includes a step of filtering, where the filtering is performed by using a melt filter; preferably, when a twin-screw extruder is used, the temperature of the melt filter is in the range of 0-15 ℃ above and below the temperature of the eight zones of the twin-screw extruder;
and/or, in the step S1, the width of the dipping die head is 100-650mm;
and/or, in step S1, the temperature of the impregnation die head is 240-330 ℃, preferably 290-330 ℃; preferably, when a twin screw extruder is used, the temperature of the impregnation die is in the range of 0-15 ℃ above and below the eight zone temperature of the twin screw extruder.
8. The method according to claim 6, wherein in step S2, when the fiber is a continuous filament, the introducing comprises the following steps: the fiber is unwound from the creel through the tension controller, enters the yarn spreading system through the yarn dividing frame, fully spreads each silk bundle, enters the yarn drying device for preheating, and then enters the dipping die head; wherein when the fibers are continuous long glass fibers, the temperature of the yarn drying device is preferably 70-90 ℃, such as 80 ℃, 85 ℃; when the fibers are continuous long carbon fibers, the temperature of the yarn drying device is preferably 70-400 ℃, such as 80 ℃, 100 ℃, 250 ℃, 300 ℃, 350 ℃;
and/or, in step S3, the molding and cooling are performed by using a press roll machine, preferably a four-roll machine; the temperature of the internal circulating water of the four-roller machine is preferably 15-40 ℃;
and/or, in step S3, the traction is performed by adopting a traction device, and further cooling and trimming are performed in the traction device; the traction speed of the traction is preferably 5-20m/min;
and/or, in step S3, the winding is performed by a winding device, preferably an automatic winding machine;
and/or, in the step S3, the thickness of the obtained prepreg tape is 0.15-0.4mm.
9. The method according to claim 6, wherein in step S4, the winding temperature is 280 to 350 ℃, and the temperature is obtained by heating with hot air or infrared heating;
and/or, in step S4, the winding speed is 1-30m/min, preferably 5-20m/min;
and/or, in step S4, the winding angle is in the range of 30 ° -75 °, preferably 40 ° -60 °.
10. Use of the continuous fiber reinforced biobased copolyamide pipe according to any one of claims 1-5 in the field of construction of water supply and drainage pipelines, heating pipelines, gas pipelines, electric conduits, industrial pipelines, subsea pipelines and the like.
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| CN202210666201.XA CN117264407A (en) | 2022-06-13 | 2022-06-13 | Continuous fiber reinforced bio-based copolyamide pipe and preparation method and application thereof |
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| CN202210666201.XA CN117264407A (en) | 2022-06-13 | 2022-06-13 | Continuous fiber reinforced bio-based copolyamide pipe and preparation method and application thereof |
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