CN113943479A - Modified thermoplastic reinforced fiber material and preparation method thereof - Google Patents
Modified thermoplastic reinforced fiber material and preparation method thereof Download PDFInfo
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- CN113943479A CN113943479A CN202111509167.7A CN202111509167A CN113943479A CN 113943479 A CN113943479 A CN 113943479A CN 202111509167 A CN202111509167 A CN 202111509167A CN 113943479 A CN113943479 A CN 113943479A
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- 229920001169 thermoplastic Polymers 0.000 title claims abstract description 38
- 239000004416 thermosoftening plastic Substances 0.000 title claims abstract description 38
- 239000002657 fibrous material Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 93
- 239000000835 fiber Substances 0.000 claims abstract description 49
- 239000000463 material Substances 0.000 claims abstract description 44
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 32
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 32
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 31
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims abstract description 31
- 229920000747 poly(lactic acid) Polymers 0.000 claims abstract description 31
- 239000004626 polylactic acid Substances 0.000 claims abstract description 31
- 229920000881 Modified starch Polymers 0.000 claims abstract description 27
- 239000004368 Modified starch Substances 0.000 claims abstract description 27
- 235000019426 modified starch Nutrition 0.000 claims abstract description 27
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 claims abstract description 23
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 23
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229940051841 polyoxyethylene ether Drugs 0.000 claims abstract description 23
- 229920000056 polyoxyethylene ether Polymers 0.000 claims abstract description 23
- 238000002156 mixing Methods 0.000 claims description 42
- 239000002245 particle Substances 0.000 claims description 32
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 239000002105 nanoparticle Substances 0.000 claims description 24
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 24
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 16
- 239000000839 emulsion Substances 0.000 claims description 16
- 238000002844 melting Methods 0.000 claims description 16
- 230000008018 melting Effects 0.000 claims description 16
- QUNKWBSQGVPICW-UHFFFAOYSA-N C(C)N.OC1=C(C=CC=C1)O Chemical compound C(C)N.OC1=C(C=CC=C1)O QUNKWBSQGVPICW-UHFFFAOYSA-N 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 14
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 13
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 12
- 229920002472 Starch Polymers 0.000 claims description 12
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 claims description 12
- 235000010265 sodium sulphite Nutrition 0.000 claims description 12
- 239000008107 starch Substances 0.000 claims description 12
- 235000019698 starch Nutrition 0.000 claims description 12
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 11
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 11
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 claims description 10
- 235000010262 sodium metabisulphite Nutrition 0.000 claims description 10
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 claims description 9
- 229930003836 cresol Natural products 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 238000009987 spinning Methods 0.000 claims description 9
- LKAPTZKZHMOIRE-KVTDHHQDSA-N (2s,3s,4s,5r)-3,4-dihydroxy-5-(hydroxymethyl)oxolane-2-carbaldehyde Chemical compound OC[C@H]1O[C@H](C=O)[C@@H](O)[C@@H]1O LKAPTZKZHMOIRE-KVTDHHQDSA-N 0.000 claims description 8
- 239000001856 Ethyl cellulose Substances 0.000 claims description 8
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims description 8
- 239000007983 Tris buffer Substances 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- LKAPTZKZHMOIRE-UHFFFAOYSA-N chitose Natural products OCC1OC(C=O)C(O)C1O LKAPTZKZHMOIRE-UHFFFAOYSA-N 0.000 claims description 8
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 claims description 8
- 239000003431 cross linking reagent Substances 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 229920001249 ethyl cellulose Polymers 0.000 claims description 8
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 8
- 230000014759 maintenance of location Effects 0.000 claims description 8
- 238000002074 melt spinning Methods 0.000 claims description 8
- 239000012528 membrane Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 229920000642 polymer Polymers 0.000 claims description 7
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 6
- UGTZMIPZNRIWHX-UHFFFAOYSA-K sodium trimetaphosphate Chemical compound [Na+].[Na+].[Na+].[O-]P1(=O)OP([O-])(=O)OP([O-])(=O)O1 UGTZMIPZNRIWHX-UHFFFAOYSA-K 0.000 claims description 6
- OXIKLRTYAYRAOE-CMDGGOBGSA-N (e)-3-(1-benzyl-3-pyridin-3-ylpyrazol-4-yl)prop-2-enoic acid Chemical group N1=C(C=2C=NC=CC=2)C(/C=C/C(=O)O)=CN1CC1=CC=CC=C1 OXIKLRTYAYRAOE-CMDGGOBGSA-N 0.000 claims description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical class CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 5
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 238000004321 preservation Methods 0.000 claims description 3
- 230000003014 reinforcing effect Effects 0.000 claims 4
- 239000004133 Sodium thiosulphate Substances 0.000 claims 1
- 239000004296 sodium metabisulphite Substances 0.000 claims 1
- 239000012783 reinforcing fiber Substances 0.000 description 12
- 229940001584 sodium metabisulfite Drugs 0.000 description 9
- 238000001694 spray drying Methods 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 230000000007 visual effect Effects 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
- C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
-
- 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
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
-
- 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
- C08J2403/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
- C08J2403/04—Starch derivatives
-
- 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
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/26—Silicon- containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a modified thermoplastic reinforced fiber material, which comprises the following components, by weight, 15-30 parts of modified starch, 30-65 parts of polylactic acid, 10-25 parts of modified silica particles, 70-90 parts of fiber slices, 2-8 parts of sodium dodecyl sulfate, 3-8 parts of nonylphenol polyoxyethylene ether, 2-7 parts of maleic anhydride, 4-10 parts of an antioxidant and 10-20 parts of glycerol. The fiber material can be naturally degraded, and simultaneously the thermoplasticity of the fiber is increased by different modified materials, and the corresponding strength is increased.
Description
Technical Field
The invention relates to the technical field of fiber materials, in particular to a modified thermoplastic reinforced fiber material and a preparation method thereof.
Background
The polyester fiber is a synthetic fiber obtained by spinning polyester formed by polycondensation of organic dibasic acid and dihydric alcohol, is called PET fiber for short, belongs to a high molecular compound, and fiber composite materials can be divided into two types: thermoplastic carbon fiber composites and thermoset carbon fiber composites. After the thermosetting resin is processed and molded, an insoluble three-dimensional network structure is formed in polymer molecules, the structure endows the thermosetting resin with better strength, heat resistance and chemical corrosion resistance, simultaneously, the material presents larger brittleness, and part of composite material can not realize natural degradation while being incapable of being recycled, thereby causing great damage to the ecological environment and forming extremely obvious visual pollution.
In view of the above, the present application particularly provides a new reinforcing fiber to meet the needs of use.
Disclosure of Invention
The invention aims to provide a modified thermoplastic reinforced fiber material and a preparation method thereof, and the modified thermoplastic reinforced fiber material can be naturally degraded, and simultaneously increases the thermoplasticity of fibers increased by different modified materials and the corresponding strength.
The purpose of the invention is realized by the following technical scheme: the modified thermoplastic reinforced fiber material comprises, by weight, 15-30 parts of modified starch, 30-65 parts of polylactic acid, 10-25 parts of modified silica particles, 70-90 parts of fiber slices, 2-8 parts of sodium dodecyl sulfate, 3-8 parts of nonylphenol polyoxyethylene ether, 2-7 parts of maleic anhydride, 4-10 parts of an antioxidant and 10-20 parts of glycerol.
The modified thermoplastic reinforced fiber material comprises the following components, by weight, 15 parts of modified starch, 30 parts of polylactic acid, 10 parts of modified silica particles, 70 parts of fiber slices, 2 parts of sodium dodecyl sulfate, 3 parts of nonylphenol polyoxyethylene ether, 2 parts of maleic anhydride, 4 parts of an antioxidant and 10 parts of glycerol.
The modified thermoplastic reinforced fiber material comprises, by weight, 30 parts of modified starch, 65 parts of polylactic acid, 25 parts of modified silica particles, 90 parts of fiber slices, 8 parts of sodium dodecyl sulfate, 8 parts of nonylphenol polyoxyethylene ether, 7 parts of maleic anhydride, 10 parts of an antioxidant and 20 parts of glycerol.
Further, the antioxidant is one or more of sodium sulfite, sodium metabisulfite, sodium thiosulfate, dibutyl cresol and citric acid.
Further, the modified starch method is as follows,
adding a cross-linking agent into starch, heating at high temperature to achieve a gelatinization state, and adjusting the pH value to be within the range of 12-15;
the cross-linking agent is one or two of epichlorohydrin and sodium trimetaphosphate.
Further, the modified silica particle method is as follows:
preparing an ethylamine pyrocatechol solution, wherein the ethylamine pyrocatechol solution contains 2.5-3.5g/L of ethylamine pyrocatechol, 1.4-2.2g/L of copper sulfate pentahydrate, 0.4-0.8mL/L of hydrogen peroxide, 2-2.5g/L of Tris and 10g/L of sodium hydroxide, adjusting the pH value to 8.0-9.0, adding porous nanoparticles, treating at 40 ℃ for 15-20r/s, stirring for 1.5-2.5h, after the reaction is finished, washing the modified porous nanoparticles for 5 minutes in ultrasonic by using deionized water, and drying for later use.
Further, the modified porous nano particles are synthesized by ethyl cellulose or chitose high molecular wall materials, and form a semipermeable membrane on the surface after spray drying.
A method of preparing a modified thermoplastic reinforcing fiber material, comprising the steps of:
uniformly mixing the dried modified starch with modified silica particles, an antioxidant, nonylphenol polyoxyethylene ether and maleic anhydride according to parts by weight, mixing at a high speed for 10-25min under the conditions of 110 ℃ for 100 plus materials and 400RPM for 250 plus materials, heating to 280 ℃ for heat preservation for 270 plus materials, mixing and melting for 30min, and granulating to obtain mixed particles;
mixing and melting the mixed particles, polylactic acid, fiber slices, sodium dodecyl sulfate and glycerol according to weight, and then extruding;
mixing the mixed particles with polylactic acid, fiber slices, sodium dodecyl sulfate and glycerol according to the weight part ratio of 30-50:20-30:70-90:1-2: 1-2;
during melt spinning, the rotating speed of a screw is 220-300 revolutions per minute, the retention time of materials in the screw is 1-3 minutes, the temperature is 190-200 ℃, and the spinning speed is 350-500 m/min;
further, the fiber slices are soaked in emulsion, and the emulsion is a mixed solution of two or more of modified 1-butene, 1-pentene, 1-hexene and 1-octene.
Compared with the prior art, the invention has the beneficial effects that: the fiber has better toughness and processability and better thermoplastic property by mixing and adding different modified materials, can be used for quickly processing a formed product, has low cost and can realize natural degradation.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, rather than all embodiments, and all other embodiments obtained by a person of ordinary skill in the art without any creative work based on the embodiments of the present invention belong to the protection scope of the present invention.
The modified thermoplastic reinforced fiber material comprises, by weight, 15-30 parts of modified starch, 30-65 parts of polylactic acid, 10-25 parts of modified silica particles, 70-90 parts of fiber slices, 2-8 parts of sodium dodecyl sulfate, 3-8 parts of nonylphenol polyoxyethylene ether, 2-7 parts of maleic anhydride, 4-10 parts of an antioxidant and 10-20 parts of glycerol.
The modified thermoplastic reinforced fiber material comprises the following components, by weight, 15 parts of modified starch, 30 parts of polylactic acid, 10 parts of modified silica particles, 70 parts of fiber slices, 2 parts of sodium dodecyl sulfate, 3 parts of nonylphenol polyoxyethylene ether, 2 parts of maleic anhydride, 4 parts of an antioxidant and 10 parts of glycerol.
The modified thermoplastic reinforced fiber material comprises, by weight, 30 parts of modified starch, 65 parts of polylactic acid, 25 parts of modified silica particles, 90 parts of fiber slices, 8 parts of sodium dodecyl sulfate, 8 parts of nonylphenol polyoxyethylene ether, 7 parts of maleic anhydride, 10 parts of an antioxidant and 20 parts of glycerol.
The antioxidant is one or more of sodium sulfite, sodium metabisulfite, sodium thiosulfate, dibutyl cresol and citric acid.
A modified thermoplastic reinforcing fiber material, the modified starch being obtained by a process comprising,
adding a cross-linking agent into starch, heating at high temperature to achieve a gelatinization state, and adjusting the pH value to be within the range of 12-15;
the cross-linking agent is one or two of epichlorohydrin and sodium trimetaphosphate.
A modified thermoplastic reinforcing fiber material, said modified silica particles being prepared by the following process:
preparing an ethylamine pyrocatechol solution, wherein the ethylamine pyrocatechol solution contains 2.5-3.5g/L of ethylamine pyrocatechol, 1.4-2.2g/L of copper sulfate pentahydrate, 0.4-0.8mL/L of hydrogen peroxide, 2-2.5g/L of Tris and 10g/L of sodium hydroxide, adjusting the pH value to 8.0-9.0, adding porous nanoparticles, treating at 40 ℃ for 15-20r/s, stirring for 1.5-2.5h, after the reaction is finished, washing the modified porous nanoparticles for 5 minutes in ultrasonic by using deionized water, and drying for later use.
As a preferable example, the modified porous nano-particles are synthesized by ethyl cellulose or chitose macromolecule wall materials and then spray-dried to form a semi-permeable membrane on the surface.
A method of preparing a modified thermoplastic reinforcing fiber material, comprising the steps of:
uniformly mixing the dried modified starch with modified silica particles, an antioxidant, nonylphenol polyoxyethylene ether and maleic anhydride according to parts by weight, mixing at a high speed for 10-25min under the conditions of 110 ℃ for 100 plus materials and 400RPM for 250 plus materials, heating to 280 ℃ for heat preservation for 270 plus materials, mixing and melting for 30min, and granulating to obtain mixed particles;
mixing and melting the mixed particles, polylactic acid, fiber slices, sodium dodecyl sulfate and glycerol according to weight, and then extruding;
mixing the mixed particles with polylactic acid, fiber slices, sodium dodecyl sulfate and glycerol according to the weight part ratio of 30-50:20-30:70-90:1-2: 1-2;
during melt spinning, the rotating speed of a screw is 220-300 revolutions per minute, the retention time of materials in the screw is 1-3 minutes, the temperature is 190-200 ℃, and the spinning speed is 350-500 m/min;
in a preferred embodiment, the fiber slices are soaked in an emulsion, wherein the emulsion is a mixture of two or more of modified 1-butene, 1-pentene, 1-hexene and 1-octene.
The first embodiment is as follows:
the modified thermoplastic reinforced fiber material comprises, by weight, 30 parts of modified starch, 65 parts of polylactic acid, 25 parts of modified silica particles, 90 parts of fiber slices, 8 parts of sodium dodecyl sulfate, 8 parts of nonylphenol polyoxyethylene ether, 7 parts of maleic anhydride, 10 parts of an antioxidant and 20 parts of glycerol.
A modified thermoplastic reinforcing fiber material, the modified starch being obtained by a process comprising,
mixing epichlorohydrin and sodium trimetaphosphate, adding into starch, heating at high temperature to obtain a gelatinized state, and adjusting pH to 12-15;
the modified silica particle method is as follows:
preparing an o-dihydroxyethylamine solution, containing 2.5g/L o-dihydroxyethylamine, 1.4g/L copper sulfate pentahydrate, 0.4mL/L hydrogen peroxide, 2-2.5g/L Tris and 10g/L sodium hydroxide, adjusting the pH to 8.0, adding porous nanoparticles, treating at 40 ℃ for 15r/s, stirring for 1.5h, after the reaction is finished, cleaning the modified porous nanoparticles for 5 minutes in ultrasound by using deionized water, and drying for later use.
The modified porous nano particles are synthesized by ethyl cellulose or chitose polymer wall materials, and form a semipermeable membrane on the surface after spray drying.
A method of preparing a modified thermoplastic reinforcing fiber material, comprising the steps of:
uniformly mixing the dried modified starch with modified silicon dioxide particles, an antioxidant (a composition of sodium sulfite, sodium metabisulfite, dibutyl cresol and citric acid serving as the antioxidant), nonylphenol polyoxyethylene ether and maleic anhydride according to parts by weight, mixing at a high speed for 10min under the conditions of 100 ℃ and 250RPM, heating to 270 ℃ and 280 ℃, preserving heat, mixing and melting for 30min, and granulating to obtain mixed particles;
mixing and melting the mixed particles, polylactic acid, fiber slices, sodium dodecyl sulfate and glycerol according to weight, and then extruding;
mixing the mixed particles with polylactic acid, fiber slices, sodium dodecyl sulfate and glycerol according to the weight part ratio of 30:20:70:1: 1;
during melt spinning, the rotating speed of a screw is 220 rpm, the retention time of materials in the screw is 1-3 minutes, the temperature is 200 ℃, and the spinning speed is 3500 m/min;
the fiber slices are soaked in emulsion, and the emulsion is a mixed solution of modified 1-butene and 1-pentene.
Detailed description of the invention
The modified thermoplastic reinforced fiber material comprises, by weight, 30 parts of modified starch, 65 parts of polylactic acid, 10 parts of modified silica particles, 70 parts of fiber slices, 2 parts of sodium dodecyl sulfate, 3 parts of nonylphenol polyoxyethylene ether, 2 parts of maleic anhydride, 4 parts of an antioxidant and 10 parts of glycerol.
The antioxidant is one or more of sodium sulfite, sodium metabisulfite, sodium thiosulfate, dibutyl cresol and citric acid.
The method for modifying the starch is as follows,
adding a cross-linking agent into starch, heating at high temperature to achieve a gelatinization state, and adjusting the pH range to 15;
the cross-linking agent is one or two of epichlorohydrin and sodium trimetaphosphate.
The modified silica particle method is as follows:
preparing an o-phenylethanamine solution which contains 3.5g/L o-phenylethanamine, 2.2g/L copper sulfate pentahydrate, 0.8mL/L hydrogen peroxide, 2.5g/L Tris and 10g/L sodium hydroxide, adjusting the pH to 9.0, adding porous nanoparticles, treating at 40 ℃ for 20r/s, stirring for 1.5h, after the reaction is finished, cleaning the modified porous nanoparticles for 5 minutes in ultrasonic by using deionized water, and drying for later use.
The modified porous nano particles are synthesized by ethyl cellulose or chitose polymer wall materials, and form a semipermeable membrane on the surface after spray drying.
A method of preparing a modified thermoplastic reinforcing fiber material, comprising the steps of:
uniformly mixing the dried modified starch with modified silicon dioxide particles, an antioxidant (a composition of sodium sulfite, sodium metabisulfite, sodium thiosulfate and dibutyl cresol is used as the antioxidant), nonylphenol polyoxyethylene ether and maleic anhydride according to parts by weight, mixing at a high speed for 10-25min under the conditions of 110 ℃ for increasing temperature to 270 ℃ for increasing temperature to 280 ℃, mixing and melting for 30min, and granulating to obtain mixed particles;
mixing and melting the mixed particles, polylactic acid, fiber slices, sodium dodecyl sulfate and glycerol according to weight, and then extruding;
mixing the mixed particles with polylactic acid, fiber slices, sodium dodecyl sulfate and glycerol according to the weight part ratio of 30:25: 90:2: 1;
during melt spinning, the rotating speed of a screw is 300 revolutions per minute, the retention time of materials in the screw is 1-3 minutes, the temperature is 200 ℃, and the spinning speed is 500 meters per minute;
the fiber slices are soaked in emulsion, and the emulsion is a mixed solution of modified 1-butene, 1-pentene and 1-hexene.
Detailed description of the preferred embodiment
The modified thermoplastic reinforced fiber material comprises the following components, by weight, 15 parts of modified starch, 30 parts of polylactic acid, 10 parts of modified silica particles, 70 parts of fiber slices, 2 parts of sodium dodecyl sulfate, 3 parts of nonylphenol polyoxyethylene ether, 2 parts of maleic anhydride, 4 parts of an antioxidant and 10 parts of glycerol.
The antioxidant is one or more of sodium sulfite, sodium metabisulfite, sodium thiosulfate, dibutyl cresol and citric acid.
The method for modifying the starch is as follows,
adding sodium trimetaphosphate into starch, heating at high temperature to achieve a gelatinization state, and adjusting the pH value range to 13;
a modified thermoplastic reinforcing fiber material, said modified silica particles being prepared by the following process:
preparing an o-phenylethanamine solution which contains 3.5g/L o-phenylethanamine, 1.4g/L copper sulfate pentahydrate, 0.8mL/L hydrogen peroxide, 2.5g/L Tris and 10g/L sodium hydroxide, adjusting the pH to 9.0, adding porous nanoparticles, treating at 40 ℃ for 20r/s, stirring for 2.5h, after the reaction is finished, cleaning the modified porous nanoparticles for 5 minutes in ultrasonic by using deionized water, and drying for later use.
The modified porous nano particles are synthesized by ethyl cellulose or chitose polymer wall materials, and form a semipermeable membrane on the surface after spray drying.
A method of preparing a modified thermoplastic reinforcing fiber material, comprising the steps of:
uniformly mixing the dried modified starch with modified silica particles, an antioxidant (a composition of sodium sulfite, sodium metabisulfite and sodium thiosulfate), nonylphenol polyoxyethylene ether and maleic anhydride in parts by weight, mixing at high speed for 15min at 110 ℃ and 300RPM, heating to 280 ℃, keeping the temperature, mixing and melting for 30min, and granulating to obtain mixed particles;
mixing and melting the mixed particles, polylactic acid, fiber slices, sodium dodecyl sulfate and glycerol according to weight, and then extruding;
mixing the mixed particles with polylactic acid, fiber slices, sodium dodecyl sulfate and glycerol according to the weight part ratio of 40:25:90:1: 2;
during melt spinning, the rotating speed of a screw is 280 revolutions per minute, the retention time of materials in the screw is 3 minutes, the temperature is 190 ℃, and the spinning speed is 450 meters per minute;
the fiber slices are soaked in emulsion, and the emulsion is a mixed solution of modified 1-hexene and 1-octene.
Detailed description of the invention
The modified thermoplastic reinforced fiber material comprises, by weight, 30 parts of modified starch, 65 parts of polylactic acid, 25 parts of modified silica particles, 90 parts of fiber slices, 8 parts of sodium dodecyl sulfate, 8 parts of nonylphenol polyoxyethylene ether, 7 parts of maleic anhydride, 10 parts of an antioxidant and 20 parts of glycerol.
The antioxidant is one or more of sodium sulfite, sodium metabisulfite, sodium thiosulfate, dibutyl cresol and citric acid.
The method for modifying the starch is as follows,
adding epoxy chloropropane into starch, heating at high temperature to achieve a gelatinization state, and adjusting the pH value range to 15;
the modified silica particle method is as follows:
preparing an ethylamine pyrocatechol solution, wherein the ethylamine pyrocatechol solution contains 2.5-3.5g/L of ethylamine pyrocatechol, 1.4-2.2g/L of copper sulfate pentahydrate, 0.4-0.8mL/L of hydrogen peroxide, 2-2.5g/L of Tris and 10g/L of sodium hydroxide, adjusting the pH value to 8.0-9.0, adding porous nanoparticles, treating at 40 ℃ for 15-20r/s, stirring for 1.5-2.5h, after the reaction is finished, washing the modified porous nanoparticles for 5 minutes in ultrasonic by using deionized water, and drying for later use.
The modified porous nano particles are synthesized by ethyl cellulose or chitose polymer wall materials, and form a semipermeable membrane on the surface after spray drying.
A method of preparing a modified thermoplastic reinforcing fiber material, comprising the steps of:
uniformly mixing the dried modified starch with modified silica particles, an antioxidant (sodium sulfite, sodium thiosulfate and a citric acid composition), nonylphenol polyoxyethylene ether and maleic anhydride according to parts by weight, mixing at a high speed of 110 ℃ and 400RPM for 25min, heating to 280 ℃, preserving heat, mixing and melting for 30min, and granulating to obtain mixed particles;
mixing and melting the mixed particles, polylactic acid, fiber slices, sodium dodecyl sulfate and glycerol according to weight, and then extruding;
mixing the mixed particles with polylactic acid, fiber slices, sodium dodecyl sulfate and glycerol according to the weight part ratio of 50:30:90:2: 2;
during melt spinning, the rotating speed of a screw is 300 revolutions per minute, the retention time of materials in the screw is 3 minutes, the temperature is 200 ℃, and the spinning speed is 350 meters per minute;
the fiber slices are soaked in emulsion, and the emulsion is a mixture of two or more of modified 1-pentene, 1-hexene and 1-octene.
Detailed description of the preferred embodiment
The preparation method of the modified thermoplastic reinforced fiber material comprises 25 parts of modified starch, 55 parts of polylactic acid, 20 parts of modified silicon dioxide particles, 80 parts of fiber slices, 2 parts of sodium dodecyl sulfate, 3 parts of nonylphenol polyoxyethylene ether, 7 parts of maleic anhydride, 4 parts of antioxidant and 20 parts of glycerol.
The antioxidant is one or more of sodium sulfite, sodium metabisulfite, sodium thiosulfate, dibutyl cresol and citric acid.
The method for modifying the starch is as follows,
adding epoxy chloropropane into starch, heating at high temperature to achieve a gelatinization state, and adjusting the pH value range to 15;
the modified silica particle method is as follows:
preparing an ethylamine pyrocatechol solution, wherein the ethylamine pyrocatechol solution contains 2.5-3.5g/L of ethylamine pyrocatechol, 1.4-2.2g/L of copper sulfate pentahydrate, 0.4-0.8mL/L of hydrogen peroxide, 2-2.5g/L of Tris and 10g/L of sodium hydroxide, adjusting the pH value to 8.0-9.0, adding porous nanoparticles, treating at 40 ℃ for 15-20r/s, stirring for 1.5-2.5h, after the reaction is finished, washing the modified porous nanoparticles for 5 minutes in ultrasonic by using deionized water, and drying for later use.
The modified porous nano particles are synthesized by ethyl cellulose or chitose polymer wall materials, and form a semipermeable membrane on the surface after spray drying.
A method of preparing a modified thermoplastic reinforcing fiber material, comprising the steps of:
uniformly mixing the dried modified starch with modified silica particles, an antioxidant (sodium sulfite, sodium thiosulfate and a citric acid composition), nonylphenol polyoxyethylene ether and maleic anhydride according to parts by weight, mixing at a high speed of 110 ℃ and 400RPM for 25min, heating to 280 ℃, preserving heat, mixing and melting for 30min, and granulating to obtain mixed particles;
mixing and melting the mixed particles, polylactic acid, fiber slices, sodium dodecyl sulfate and glycerol according to weight, and then extruding;
mixing the mixed particles with polylactic acid, fiber slices, sodium dodecyl sulfate and glycerol according to the weight part ratio of 50:30:90:2: 2;
during melt spinning, the rotating speed of a screw is 300 revolutions per minute, the retention time of materials in the screw is 3 minutes, the temperature is 200 ℃, and the spinning speed is 350 meters per minute;
the fiber slices are soaked in emulsion, and the emulsion is a mixture of two or more of modified 1-pentene, 1-hexene and 1-octene.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (9)
1. The modified thermoplastic reinforced fiber material is characterized by comprising the following components, by weight, 15-30 parts of modified starch, 30-65 parts of polylactic acid, 10-25 parts of modified silica particles, 70-90 parts of fiber slices, 2-8 parts of sodium dodecyl sulfate, 3-8 parts of nonylphenol polyoxyethylene ether, 2-7 parts of maleic anhydride, 4-10 parts of an antioxidant and 10-20 parts of glycerol.
2. The modified thermoplastic reinforced fiber material of claim 1, which comprises 15 parts of modified starch, 30 parts of polylactic acid, 10 parts of modified silica particles, 70 parts of fiber slices, 2 parts of sodium dodecyl sulfate, 3 parts of nonylphenol polyoxyethylene ether, 2 parts of maleic anhydride, 4 parts of antioxidant and 10 parts of glycerol.
3. The modified thermoplastic reinforced fiber material of claim 1, which comprises, by weight, 30 parts of modified starch, 65 parts of polylactic acid, 25 parts of modified silica particles, 90 parts of fiber slices, 8 parts of sodium dodecyl sulfate, 8 parts of nonylphenol polyoxyethylene ether, 7 parts of maleic anhydride, 10 parts of an antioxidant, and 20 parts of glycerol.
4. A modified thermoplastic reinforcing fibre material according to claim 1, wherein the antioxidant is one or a combination of sodium sulphite, sodium metabisulphite, sodium thiosulphate, dibutyl cresol, citric acid.
5. A modified thermoplastic reinforcing fibre material according to claim 1, characterized in that the modified starch is prepared by a process,
adding a cross-linking agent into starch, heating at high temperature to achieve a gelatinization state, and adjusting the pH value to be within the range of 12-15;
the cross-linking agent is one or two of epichlorohydrin and sodium trimetaphosphate.
6. A modified thermoplastic reinforcing fibre material according to claim 1, characterized in that the modified silica particles are prepared by the following process:
preparing an ethylamine pyrocatechol solution, wherein the ethylamine pyrocatechol solution contains 2.5-3.5g/L of ethylamine pyrocatechol, 1.4-2.2g/L of copper sulfate pentahydrate, 0.4-0.8mL/L of hydrogen peroxide, 2-2.5g/L of Tris and 10g/L of sodium hydroxide, adjusting the pH value to 8.0-9.0, adding porous nanoparticles, treating at 40 ℃ for 15-20r/s, stirring for 1.5-2.5h, after the reaction is finished, washing the modified porous nanoparticles for 5 minutes in ultrasonic by using deionized water, and drying for later use.
7. The modified thermoplastic reinforced fiber material of claim 6, wherein the modified porous nanoparticles are synthesized from ethyl cellulose or chitose polymer wall material and spray-dried to form a semi-permeable membrane on the surface.
8. A method for preparing a modified thermoplastic reinforcing fibre material according to any one of claims 1 to 6, characterised in that it comprises the following steps:
uniformly mixing the dried modified starch with modified silica particles, an antioxidant, nonylphenol polyoxyethylene ether and maleic anhydride according to parts by weight, mixing at a high speed for 10-25min under the conditions of 110 ℃ for 100 plus materials and 400RPM for 250 plus materials, heating to 280 ℃ for heat preservation for 270 plus materials, mixing and melting for 30min, and granulating to obtain mixed particles;
mixing and melting the mixed particles, polylactic acid, fiber slices, sodium dodecyl sulfate and glycerol according to weight, and then extruding;
mixing the mixed particles with polylactic acid, fiber slices, sodium dodecyl sulfate and glycerol according to the weight part ratio of 30-50:20-30:70-90:1-2: 1-2;
during melt spinning, the rotating speed of the screw is 220-300 revolutions per minute, the retention time of materials in the screw is 1-3 minutes, the temperature is 190-200 ℃, and the spinning speed is 350-500 m/min.
9. The method of claim 8, wherein the fiber slices are soaked in an emulsion, wherein the emulsion is a mixture of two or more of modified 1-butene, 1-pentene, 1-hexene, and 1-octene.
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