CN116988180A - Graphene bio-based nylon functional fiber and preparation method thereof - Google Patents
Graphene bio-based nylon functional fiber and preparation method thereof Download PDFInfo
- Publication number
- CN116988180A CN116988180A CN202310992412.7A CN202310992412A CN116988180A CN 116988180 A CN116988180 A CN 116988180A CN 202310992412 A CN202310992412 A CN 202310992412A CN 116988180 A CN116988180 A CN 116988180A
- Authority
- CN
- China
- Prior art keywords
- graphene
- solution
- nylon
- pentanediamine
- bio
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 297
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 187
- 239000000835 fiber Substances 0.000 title claims abstract description 66
- 229920006118 nylon 56 Polymers 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 229920001778 nylon Polymers 0.000 claims abstract description 126
- KJOMYNHMBRNCNY-UHFFFAOYSA-N pentane-1,1-diamine Chemical compound CCCCC(N)N KJOMYNHMBRNCNY-UHFFFAOYSA-N 0.000 claims abstract description 77
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000003607 modifier Substances 0.000 claims abstract description 34
- 239000001361 adipic acid Substances 0.000 claims abstract description 27
- 235000011037 adipic acid Nutrition 0.000 claims abstract description 27
- 239000003999 initiator Substances 0.000 claims abstract description 27
- 239000007787 solid Substances 0.000 claims abstract description 26
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 24
- -1 polyoxypropylene glycerol Polymers 0.000 claims abstract description 22
- 239000002994 raw material Substances 0.000 claims abstract description 18
- 239000002518 antifoaming agent Substances 0.000 claims abstract description 17
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 17
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 16
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 claims abstract description 12
- 239000013530 defoamer Substances 0.000 claims abstract description 10
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims abstract description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 8
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims abstract description 8
- 150000001412 amines Chemical class 0.000 claims abstract description 8
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229940106681 chloroacetic acid Drugs 0.000 claims abstract description 8
- 239000006224 matting agent Substances 0.000 claims abstract description 8
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims abstract description 8
- RBNPOMFGQQGHHO-UHFFFAOYSA-N glyceric acid Chemical compound OCC(O)C(O)=O RBNPOMFGQQGHHO-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229920002545 silicone oil Polymers 0.000 claims abstract description 6
- 239000011276 wood tar Substances 0.000 claims abstract description 6
- XESZUVZBAMCAEJ-UHFFFAOYSA-N 4-tert-butylcatechol Chemical compound CC(C)(C)C1=CC=C(O)C(O)=C1 XESZUVZBAMCAEJ-UHFFFAOYSA-N 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 172
- 239000004677 Nylon Substances 0.000 claims description 98
- 239000002028 Biomass Substances 0.000 claims description 67
- 239000012266 salt solution Substances 0.000 claims description 48
- 238000001035 drying Methods 0.000 claims description 41
- 239000011259 mixed solution Substances 0.000 claims description 40
- 238000006116 polymerization reaction Methods 0.000 claims description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- 239000008367 deionised water Substances 0.000 claims description 32
- 229910021641 deionized water Inorganic materials 0.000 claims description 32
- 229920000642 polymer Polymers 0.000 claims description 24
- 239000000843 powder Substances 0.000 claims description 24
- KDXKERNSBIXSRK-YFKPBYRVSA-N L-lysine Chemical compound NCCCC[C@H](N)C(O)=O KDXKERNSBIXSRK-YFKPBYRVSA-N 0.000 claims description 21
- 238000009987 spinning Methods 0.000 claims description 20
- 238000000855 fermentation Methods 0.000 claims description 18
- 230000004151 fermentation Effects 0.000 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 16
- 238000002844 melting Methods 0.000 claims description 16
- 230000008018 melting Effects 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- 239000000376 reactant Substances 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- 239000000126 substance Substances 0.000 claims description 16
- 238000012360 testing method Methods 0.000 claims description 15
- 239000004472 Lysine Substances 0.000 claims description 12
- 241000588724 Escherichia coli Species 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 235000019766 L-Lysine Nutrition 0.000 claims description 9
- 238000006068 polycondensation reaction Methods 0.000 claims description 9
- 238000007664 blowing Methods 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 229910002804 graphite Inorganic materials 0.000 claims description 8
- 239000010439 graphite Substances 0.000 claims description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 238000010583 slow cooling Methods 0.000 claims description 8
- 238000005507 spraying Methods 0.000 claims description 8
- 238000009210 therapy by ultrasound Methods 0.000 claims description 8
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 4
- 229910052799 carbon Inorganic materials 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000004753 textile Substances 0.000 description 4
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 description 3
- 239000004952 Polyamide Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 229920006021 bio-based polyamide Polymers 0.000 description 3
- 235000018977 lysine Nutrition 0.000 description 3
- 229920002647 polyamide Polymers 0.000 description 3
- 239000000654 additive Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- NYUNHMRXBVASOA-UHFFFAOYSA-N 1,7-dioxacyclotridecane-8,13-dione Chemical compound O=C1CCCCC(=O)OCCCCCO1 NYUNHMRXBVASOA-UHFFFAOYSA-N 0.000 description 1
- BJEMXPVDXFSROA-UHFFFAOYSA-N 3-butylbenzene-1,2-diol Chemical group CCCCC1=CC=CC(O)=C1O BJEMXPVDXFSROA-UHFFFAOYSA-N 0.000 description 1
- JIGUICYYOYEXFS-UHFFFAOYSA-N 3-tert-butylbenzene-1,2-diol Chemical group CC(C)(C)C1=CC=CC(O)=C1O JIGUICYYOYEXFS-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 241000222122 Candida albicans Species 0.000 description 1
- 241000186226 Corynebacterium glutamicum Species 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 229940095731 candida albicans Drugs 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000011269 tar Chemical group 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/90—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyamides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
- D01F1/103—Agents inhibiting growth of microorganisms
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a graphene bio-based nylon functional fiber and a preparation method thereof, wherein the raw materials of the fiber comprise: graphene oxide solution, a surface modifier, an initiator, a molecular chain terminator, a defoaming agent, a delustering agent, a pentanediamine solution and solid adipic acid. The surface modifier is acetic acid and/or chloroacetic acid; the initiator is styrene and its derivative and/or methyl methacrylate; the molecular chain terminator is terminator bisphenol A, p-tert-butyl catechol, wood tar and the like; the defoamer is emulsified silicone oil, polyoxyethylene polyoxypropylene pentaerythritol ether, polyoxyethylene polyoxypropylene alcohol amine ether, polyoxypropylene glycerol ether and the like; the matting agent is anatase titanium dioxide and/or rutile titanium dioxide. The invention also provides a preparation method of the graphene bio-based nylon functional fiber. The fiber prepared by the invention has an antibacterial effect, and has a wider market prospect compared with the common nylon fiber, and the tensile strength and the wear resistance of the fiber are improved.
Description
Technical Field
The invention relates to a graphene bio-based nylon 56 composite fiber and a preparation method thereof, in particular to a graphene bio-based nylon functional fiber and a preparation method thereof.
Background
Bio-based nylon (Polyamide, PA) 56 is poly (pentylene adipate) polymerized from bio-based pentylene diamine and petroleum-based adipic acid. The bio-based pentylene diamine can be obtained by microbial fermentation, or lysine can be directly converted into pentylene diamine by constructing an escherichia coli system by a whole cell method.
L-lysine is a direct precursor of pentanediamine, and the traditional lysine production strain takes corynebacterium glutamicum and escherichia coli as starting bacteria to prepare the pentanediamine through lysine decarboxylation. Compared with the traditional process, the cost of preparing diamine by using the biological method is obviously reduced, the production efficiency is greatly improved, the greenhouse gas discharged in the process of producing bio-based pentanediamine is greatly reduced, and the environmental benefit is considerable.
The purity of the pentanediamine has great influence on the quality of the PA56 salt, so that the performance of the PA56 is further influenced, the purity of the pentanediamine superior product is required to be more than or equal to 99.9, and the purity is mainly analyzed by detection means such as GC-MS, LC-MS and the like.
The spinning grade PA56 slice can refer to the standards of spinning grade PA6 and PA66, and has requirements on relative viscosity, moisture, hue, amine end content, black particles and the like, for example, the relative viscosity M1 + -0.03, the amine end content < 30, and the moisture less than or equal to 0.09.
In the textile and clothing industry, the bio-based Polyamide (PA) 56 fiber can be widely applied to civil silk and industrial textiles. PA56 fibers currently come in the category of filaments, spun yarns, and textured air yarns (BCF), where filaments include textured stretch (DTY) and Fully Drawn (FDY) products.
Although the bio-based polyamide 56 fiber has certain advantages compared with the traditional nylon fiber, the functionality of the bio-based polyamide 56 fiber is still single, and along with the social development, the traditional nylon fiber can not meet the demands of people on the functional textile.
Disclosure of Invention
The invention aims to provide a graphene bio-based nylon 56 composite fiber and a preparation method thereof, which can solve the problems in the prior art, the production process is environment-friendly and efficient, the added value of a nylon material can be improved, and the application range of the nylon fiber is expanded.
In order to achieve the above purpose, the invention provides a graphene bio-based nylon functional fiber, wherein the raw materials of the fiber comprise the following components in percentage by mass: 5 to 8 percent of graphene oxide solution, 0.1 to 1 percent of surface modifier, 0.1 to 5 percent of initiator, 0.1 to 5 percent of molecular chain terminator, 1 to 5 percent of defoamer, 1 to 5 percent of flatting agent, 36 to 45 percent of pentanediamine solution and 36 to 45 percent of solid adipic acid.
The graphene bio-based nylon functional fiber, wherein the surface modifier is acetic acid and/or chloroacetic acid; the initiator is styrene and its derivative and/or methyl methacrylate; the molecular chain terminator is one or more of terminator bisphenol A, p-tert-butylcatechol and wood tar; the defoaming agent is any one or more of emulsified silicone oil, polyoxyethylene polyoxypropylene pentaerythritol ether, polyoxyethylene polyoxypropylene alcohol amine ether and polyoxypropylene glycerol ether; the matting agent is anatase titanium dioxide and/or rutile titanium dioxide.
The invention also provides a preparation method of the graphene bio-based nylon functional fiber, wherein the method comprises the following steps: step 1, preparing raw materials; step 2, preparing a modified graphene solution; step 3, preparing a pentanediamine solution through biological fermentation, purifying to obtain high-purity pentanediamine, and preparing a diluted pentanediamine solution; step 4, adding the modified graphene oxide solution, the diluted pentylene diamine solution and the solid adipic acid into a solution reactor, and reacting to obtain a graphene nylon salt solution; step 5, filtering the graphene nylon salt solution to obtain graphene nylon refined salt solution, and concentrating to obtain concentrated mixed solution; step 6, conveying the concentrated mixed solution to a preheater for preheating, simultaneously adding an initiator, a molecular chain terminator and a defoaming agent, continuously conveying to a pre-polycondensation reactor, and reacting to obtain a graphene nylon pre-polycondensate; step 7, conveying the pre-polymerized substance to a pre-polymerization reactor, and simultaneously adding a delustering agent for reaction to obtain a pre-polymerization reactant; step 8, continuously conveying reactants obtained by pre-polymerization to a post-polymerization reactor, and reacting to obtain graphene biomass nylon polymer melt; step 9, conveying the graphene biomass nylon polymer melt to a devolatilization reactor to remove substances with low molecular weight; step 10, extruding a polymer from a devolatilization reactor, extruding the polymer in a strip shape through a polymer melt filter, and cooling and granulating the strip to obtain graphene biomass nylon chips; step 11, placing the graphene biomass nylon slices into a dryer for drying treatment; step 12, testing the performance of the obtained graphene biomass nylon chips, and then feeding the chips which are qualified in the test into a spinning machine; step 13, enabling graphene biomass nylon slices to enter a spinning box, melting at high temperature, spraying out the graphene biomass nylon slices into filaments through a spinneret orifice, then cooling and forming the filaments through a slow cooling device by side blowing, oiling and primarily forming filament bundles; and 14, stretching the obtained molded tows by a tension roller to obtain graphene biomass nylon fibers.
The preparation method of the graphene bio-based nylon functional fiber comprises the following steps: step 2.1, adding graphene oxide powder into deionized water, and performing ultrasonic treatment on the obtained graphite oxide solution at normal temperature for 10-20 min, wherein the solution contains 5-10% of graphene oxide in percentage by mass; step 2.2, adding a surface modifier into the solution, and stirring for 10-20 min to obtain a mixed modified graphene solution; step 2.3, drying the obtained mixed solution at the temperature of 95-100 ℃ to obtain modified graphene powder; and 2.4, cleaning and drying the modified graphene powder again by using deionized water, removing redundant residual surface modifier, adding the modified graphene powder into the deionized water, and stirring and mixing uniformly to obtain a modified graphene solution, wherein the modified graphene solution contains 3-20% by mass percent of modified graphene.
In the step 3, adding escherichia coli cells expressing L-lysine decarboxylase into an L-Lai Ansu monohydrochloride solution, setting the pH value of the solution to be 7-8 and the temperature to be 35-40 ℃, and keeping the temperature for 3-6 days for continuous fermentation to convert L-Lai Ansu monohydrochloride into pentanediamine; and then distilling the obtained mixed solution through a distiller to obtain a pentanediamine solution, further purifying to obtain high-purity pentanediamine with the purity of more than or equal to 99.9, and finally adding deionized water to prepare a diluted pentanediamine solution with the mass concentration of 30 percent.
In the preparation method of the graphene bio-based nylon functional fiber, in the step 4, the ratio of the modified graphene oxide solution to the diluted pentanediamine solution to the solid adipic acid is (4% to 48%) to (10% to 45%) in percentage by mass.
In the step 5, the graphene nylon salt solution is filtered through activated carbon, the mesh number of the activated carbon is 1000-2000 meshes, the graphene nylon refined salt solution is obtained, and then the graphene nylon refined salt solution is conveyed to a concentration kettle and concentrated to obtain the mixed solution with the mass concentration of 70-75%.
In the preparation method of the graphene bio-based nylon functional fiber, in the step 11, the drying temperature is 60-80 ℃ and the drying time is 12-24 hours.
In the preparation method of the graphene bio-based nylon functional fiber, in the step 13, the high-temperature melting temperature is 240-260 ℃.
In the preparation method of the graphene bio-based nylon functional fiber, in the step 14, the stretching elongation range is 20% -40%, and the breaking strength of the finished fiber after stretching is 4.5-5.5.
The graphene bio-based nylon functional fiber and the preparation method thereof provided by the invention have the following advantages:
the preparation method mainly comprises the steps of preparing biomass pentanediamine by a fermentation method, adding modified graphene in a polymerization process, and finally preparing the graphene bio-based nylon 56 functional fiber. The method has simple and easy production process, high production efficiency of finished products and is beneficial to the environment. The graphene bio-based nylon 56 fiber has an antibacterial effect, and has a wider market prospect compared with the common nylon 56 fiber, and the tensile strength and the wear resistance of the fiber are improved.
Detailed Description
The following describes the present invention in more detail.
The graphene bio-based nylon functional fiber provided by the invention comprises the following raw materials in percentage by mass: 5 to 8 percent of graphene oxide solution, 0.1 to 1 percent of surface modifier, 0.1 to 5 percent of initiator, 0.1 to 5 percent of molecular chain terminator, 1 to 5 percent of defoamer, 1 to 5 percent of flatting agent, 36 to 45 percent of pentanediamine solution and 36 to 45 percent of solid adipic acid. 1% -5% of additives with different functions can be added according to the requirements.
Preferably, the raw materials of the fiber comprise 5% -8% of graphene oxide solution, 0.1% -1% of surface modifier, 0.1% -5% of initiator, 0.1% -5% of molecular chain terminator, 1% -5% of defoamer, 1% -5% of flatting agent, 36% -45% of pentanediamine solution and 36% -45% of solid adipic acid. 1% -5% of additives with different functions can be added according to the requirements.
The concentration of the pentanediamine solution is about 30 percent by mass percent, and the graphene oxide solution contains 5 to 10 percent of graphene oxide.
The surface modifier is acetic acid and/or chloroacetic acid; the initiator is styrene and its derivative and/or methyl methacrylate; the molecular chain terminator is one or more of terminator bisphenol A, para-tertiary butyl catechol, tar and the like; the defoaming agent is any one or more of emulsified silicone oil, polyoxyethylene polyoxypropylene pentaerythritol ether, polyoxyethylene polyoxypropylene alcohol amine ether, polyoxypropylene glycerol ether and the like; the matting agent is anatase titanium dioxide and/or rutile titanium dioxide.
The invention also provides a preparation method of the graphene bio-based nylon functional fiber, which comprises the following steps: step 1, preparing raw materials; step 2, preparing a modified graphene solution; step 3, preparing a pentanediamine solution through biological fermentation, purifying to obtain high-purity pentanediamine, and preparing a diluted pentanediamine solution; step 4, adding the modified graphene oxide solution, the diluted pentylene diamine solution and the solid adipic acid into a solution reactor, and reacting to obtain a graphene nylon salt solution; step 5, filtering the graphene nylon salt solution through a filter to obtain graphene nylon refined salt solution, and concentrating to obtain a concentrated mixed solution; step 6, conveying the concentrated mixed solution to a preheater for preheating, simultaneously adding an initiator, a molecular chain terminator and a defoaming agent, continuously conveying to a pre-polycondensation reactor, and reacting to obtain a graphene nylon pre-polycondensate; step 7, conveying the pre-polymerized substance to a pre-polymerization reactor, setting the air pressure and the temperature according to the requirement, setting the air pressure to be preferably 0.2-0.5MPa, adding a matting agent at the same time, and performing pre-polymerization reaction to obtain a pre-polymerization reactant; step 8, continuously conveying reactants obtained by pre-polymerization to a post-polymerization reactor for reaction, and further volatilizing moisture generated by polycondensation in the post-polymerization reactor to obtain graphene biomass nylon polymer melt; step 9, conveying the graphene biomass nylon polymer melt to a devolatilization reactor to remove substances with low molecular weight; the air pressure of the devolatilization generator is in a vacuum state; step 10, extruding a polymer from a devolatilization reactor, extruding the polymer from a casting belt head in the form of a strip through a polymer melt filter, cooling the strip in a water tank of an underwater pelletizer, and then granulating the strip in a pelleting head to obtain graphene biomass nylon chips; step 11, placing the graphene biomass nylon slices into a dryer, setting the temperature and the drying time of the dryer, and performing drying treatment; step 12, testing the relevant performance of the obtained graphene biomass nylon chips, then feeding the qualified chips into a feeding bin of a spinning machine, and setting the temperature and feeding speed of the spinning machine; step 13, enabling graphene biomass nylon slices to enter a spinning box through a feeding hopper of a spinning machine, melting at high temperature, spraying out the graphene biomass nylon slices into filaments through a spinneret orifice, then cooling and forming the filaments through a slow cooling device by side blowing air, oiling, and primarily forming filament bundles; and 14, stretching the obtained molded tows by a tension roller to obtain graphene biomass nylon fibers.
Preferably, step 2 comprises: step 2.1, adding graphene oxide powder into deionized water, and performing ultrasonic treatment on the obtained graphite oxide solution at normal temperature for 10-20 min, wherein the solution contains 5-10% of graphene oxide in percentage by mass; step 2.2, adding a surface modifier into the solution, and stirring for 10-20 min to obtain a mixed modified graphene solution; step 2.3, drying the obtained mixed solution at the temperature of 95-100 ℃ to obtain modified graphene powder; and 2.4, cleaning and drying the modified graphene powder again by using deionized water, removing redundant residual surface modifier, adding the modified graphene powder into the deionized water, and stirring and mixing uniformly to obtain a modified graphene solution, wherein the modified graphene solution contains 3-20% by mass percent of modified graphene.
In the step 3, adding escherichia coli cells expressing L-lysine decarboxylase into high-concentration L-Lai Ansu monohydrochloride solution, setting the pH value of the solution to be 7-8 and the temperature to be 35-40 ℃, and keeping the solution for 3-6 days while continuously fermenting to convert L-Lai Ansu monohydrochloride into pentanediamine; and then distilling the obtained mixed solution through a distiller to obtain a pentanediamine solution, further purifying to obtain high-purity pentanediamine with the purity of more than or equal to 99.9, and finally adding deionized water to prepare a diluted pentanediamine solution with the mass concentration of 30 percent.
In the step 4, the ratio of the modified graphene oxide solution to the diluted pentanediamine solution to the solid adipic acid is (4 percent: 48 percent) to (10 percent: 45 percent) in percentage by mass; the parameters of the solution reactor are set according to the needs, and the pH and the temperature are kept in a certain range for reaction.
In the step 5, the graphene nylon salt solution is filtered through an active carbon filter, the mesh number of the active carbon is 1000-2000 meshes, the graphene nylon refined salt solution is obtained, and then the graphene nylon refined salt solution is conveyed to a concentration kettle and concentrated to obtain the mixed solution with the mass concentration of 70-75%.
In the step 11, the drying temperature is 60-80 ℃ and the drying time is 12-24 hours.
In step 13, the high temperature melting temperature is 240-260 ℃.
In the step 14, the elongation range of the stretching is 20% -40%, and the breaking strength of the finished fiber after the stretching is 4.5-5.5 cN/dtex.
The equipment and other processes, reaction conditions, parameter ranges, reagent types, etc. employed in the present invention are all suitable choices known to those skilled in the art.
The graphene bio-based nylon functional fiber and the preparation method thereof provided by the invention are further described below with reference to examples.
Example 1
The graphene bio-based nylon functional fiber comprises the following raw materials in percentage by mass: 5% of graphene oxide solution, 0.1% of surface modifier, 1.4% of initiator, 1.1% of molecular chain terminator, 1.2% of defoamer, 1.2% of flatting agent, 45% of pentanediamine solution and 45% of solid adipic acid.
Preferably, the surface modifier is acetic acid; the initiator is styrene and derivatives thereof; the molecular chain terminator is a terminator bisphenol A; the defoaming agent is emulsified silicone oil; the delustrant is anatase titanium dioxide.
The embodiment also provides a preparation method of the graphene bio-based nylon functional fiber, which comprises the following steps:
step 1, preparing each raw material.
And 2, preparing a modified graphene solution.
Preferably, step 2 comprises:
and 2.1, adding graphene oxide powder into deionized water, and performing ultrasonic treatment on the obtained graphite oxide solution at normal temperature for 10min, wherein the solution contains 5% of graphene oxide in percentage by mass.
And 2.2, adding the surface modifier into the solution, and stirring for 10min to obtain the mixed modified graphene solution.
And 2.3, drying the obtained mixed solution at the temperature of 95 ℃ to obtain modified graphene powder.
And 2.4, cleaning and drying the modified graphene powder again by using deionized water, removing redundant residual surface modifier, adding the modified graphene powder into the deionized water, and stirring and mixing uniformly to obtain a modified graphene solution, wherein the modified graphene solution contains 3% by mass percent of modified graphene.
And 3, preparing a pentanediamine solution through biological fermentation, purifying to obtain high-purity pentanediamine, and preparing a diluted pentanediamine solution.
Preferably, adding the escherichia coli cells expressing the L-lysine decarboxylase into the L-Lai Ansu monohydrochloride solution, setting the pH value of the solution to 7-8 and the temperature to 35 ℃, and keeping the solution for 3 days for continuous fermentation to convert the L-Lai Ansu monohydrochloride into the pentanediamine; and then distilling the obtained mixed solution through a distiller to obtain a pentanediamine solution, further purifying to obtain high-purity pentanediamine with the purity of more than or equal to 99.9, and finally adding deionized water to prepare a diluted pentanediamine solution with the mass concentration of 30 percent.
And step 4, adding the modified graphene oxide solution, the diluted pentylene diamine solution and the solid adipic acid into a solution reactor, and reacting to obtain a graphene nylon salt solution.
Preferably, the ratio of the modified graphene oxide solution, the diluted pentylene diamine solution and the solid adipic acid is 10% by mass percent: 45%:45%.
And 5, filtering the graphene nylon salt solution to obtain graphene nylon refined salt solution, and concentrating to obtain concentrated mixed solution.
Preferably, the graphene nylon salt solution is filtered through activated carbon, the mesh number of the activated carbon is 1000 meshes, the graphene nylon refined salt solution is obtained, and then the graphene nylon refined salt solution is conveyed to a concentration kettle and concentrated to obtain the mixed solution with the mass concentration of 70%.
And step 6, conveying the concentrated mixed solution to a preheater for preheating, simultaneously adding an initiator, a molecular chain terminator and a defoaming agent, continuously conveying to a pre-polycondensation reactor, and reacting to obtain the graphene nylon pre-polycondensate.
And 7, conveying the pre-polymerized substance to a pre-polymerization reactor, and simultaneously adding a delustering agent for reaction to obtain a pre-polymerization reactant.
And 8, continuously conveying reactants obtained by pre-polymerization to a post-polymerization reactor, and reacting to obtain graphene biomass nylon polymer melt.
And 9, conveying the graphene biomass nylon polymer melt to a devolatilization reactor to remove substances with low molecular weight.
And 10, extruding the polymer from a devolatilization reactor, extruding the polymer in the form of a strip through a polymer melt filter, and cooling and granulating the strip to obtain graphene biomass nylon chips.
And 11, placing the graphene biomass nylon slices into a dryer for drying treatment.
Preferably, the drying temperature is 60 ℃ and the drying time is 12 hours.
And step 12, testing the performance of the obtained graphene biomass nylon chips, and then feeding the chips which are qualified in the test into a spinning machine.
And 13, enabling the graphene biomass nylon slices to enter a spinning box, melting at high temperature, spraying out the graphene biomass nylon slices into filaments through a spinneret orifice, then cooling and forming the filaments through a slow cooling device by side blowing, oiling, and primarily forming the filament bundles.
Preferably, the high temperature melting temperature is 240 ℃.
And 14, stretching the obtained molded tows by a tension roller to obtain graphene biomass nylon fibers.
Preferably, the elongation range of the stretching is 20%, and the breaking strength of the finished fiber after the stretching is between 4.5 and 5.5.
Example 2
The graphene bio-based nylon functional fiber comprises the following raw materials in percentage by mass: 8% of graphene oxide solution, 0.2% of surface modifier, 5% of initiator, 5% of molecular chain terminator, 5% of defoamer, 4.8% of flatting agent, 36% of pentanediamine solution and 36% of solid adipic acid.
Preferably, the surface modifier is chloroacetic acid; the initiator is methyl methacrylate; the molecular chain terminator is tert-butyl catechol; the defoaming agent is polyoxyethylene polyoxypropylene pentaerythritol ether; the delustring agent is rutile titanium dioxide.
The embodiment also provides a preparation method of the graphene bio-based nylon functional fiber, which comprises the following steps:
step 1, preparing each raw material.
And 2, preparing a modified graphene solution.
Preferably, step 2 comprises:
and 2.1, adding graphene oxide powder into deionized water, and performing ultrasonic treatment on the obtained graphite oxide solution at normal temperature for 20min, wherein the solution contains 6% of graphene oxide in percentage by mass.
And 2.2, adding the surface modifier into the solution, and stirring for 20min to obtain the mixed modified graphene solution.
And 2.3, drying the obtained mixed solution at 100 ℃ to obtain modified graphene powder.
And 2.4, cleaning and drying the modified graphene powder again by using deionized water, removing redundant residual surface modifier, adding the modified graphene powder into the deionized water, and stirring and mixing uniformly to obtain a modified graphene solution, wherein the modified graphene solution contains 20% by mass percent of modified graphene.
And 3, preparing a pentanediamine solution through biological fermentation, purifying to obtain high-purity pentanediamine, and preparing a diluted pentanediamine solution.
Preferably, adding the escherichia coli cells expressing the L-lysine decarboxylase into the L-Lai Ansu monohydrochloride solution, setting the pH value of the solution to 7-8 and the temperature to 40 ℃, and keeping the solution for 6 days for continuous fermentation to convert the L-Lai Ansu monohydrochloride into the pentanediamine; and then distilling the obtained mixed solution through a distiller to obtain a pentanediamine solution, further purifying to obtain high-purity pentanediamine with the purity of more than or equal to 99.9, and finally adding deionized water to prepare a diluted pentanediamine solution with the mass concentration of 30 percent.
And step 4, adding the modified graphene oxide solution, the diluted pentylene diamine solution and the solid adipic acid into a solution reactor, and reacting to obtain a graphene nylon salt solution.
Preferably, the ratio of the modified graphene oxide solution, the diluted pentylene diamine solution and the solid adipic acid is 4% by mass percent: 48%:48%.
And 5, filtering the graphene nylon salt solution to obtain graphene nylon refined salt solution, and concentrating to obtain concentrated mixed solution.
Preferably, the graphene nylon salt solution is filtered through active carbon, the mesh number of the active carbon is 2000 meshes, the graphene nylon refined salt solution is obtained, and then the graphene nylon refined salt solution is conveyed to a concentration kettle and concentrated to obtain the mixed solution with the mass concentration of 75%.
And step 6, conveying the concentrated mixed solution to a preheater for preheating, simultaneously adding an initiator, a molecular chain terminator and a defoaming agent, continuously conveying to a pre-polycondensation reactor, and reacting to obtain the graphene nylon pre-polycondensate.
And 7, conveying the pre-polymerized substance to a pre-polymerization reactor, and simultaneously adding a delustering agent for reaction to obtain a pre-polymerization reactant.
And 8, continuously conveying reactants obtained by pre-polymerization to a post-polymerization reactor, and reacting to obtain graphene biomass nylon polymer melt.
And 9, conveying the graphene biomass nylon polymer melt to a devolatilization reactor to remove substances with low molecular weight.
And 10, extruding the polymer from a devolatilization reactor, extruding the polymer in the form of a strip through a polymer melt filter, and cooling and granulating the strip to obtain graphene biomass nylon chips.
And 11, placing the graphene biomass nylon slices into a dryer for drying treatment.
Preferably, the drying temperature is 80 ℃ and the drying time is 24 hours.
And step 12, testing the performance of the obtained graphene biomass nylon chips, and then feeding the chips which are qualified in the test into a spinning machine.
And 13, enabling the graphene biomass nylon slices to enter a spinning box, melting at high temperature, spraying out the graphene biomass nylon slices into filaments through a spinneret orifice, then cooling and forming the filaments through a slow cooling device by side blowing, oiling, and primarily forming the filament bundles.
Preferably, the high temperature melting temperature is 260 ℃.
And 14, stretching the obtained molded tows by a tension roller to obtain graphene biomass nylon fibers.
Preferably, the elongation range of the stretching is 40%, and the breaking strength of the finished fiber after the stretching is between 4.5 and 5.5.
Example 3
The graphene bio-based nylon functional fiber comprises the following raw materials in percentage by mass: 7% of graphene oxide solution, 1% of surface modifier, 1% of initiator, 1% of molecular chain terminator, 1% of defoamer, 1% of flatting agent, 44% of pentanediamine solution and 44% of solid adipic acid.
Preferably, the surface modifier is acetic acid or chloroacetic acid; the initiator is styrene and derivatives or methyl methacrylate thereof; the molecular chain terminator is wood tar; the defoaming agent is polyoxyethylene polyoxypropylene amine ether; the delustrant is anatase titanium dioxide or rutile titanium dioxide.
The embodiment also provides a preparation method of the graphene bio-based nylon functional fiber, which comprises the following steps:
step 1, preparing each raw material.
And 2, preparing a modified graphene solution.
Preferably, step 2 comprises:
and 2.1, adding graphene oxide powder into deionized water, and performing ultrasonic treatment on the obtained graphite oxide solution at normal temperature for 15min, wherein the solution contains 10% of graphene oxide in percentage by mass.
And 2.2, adding the surface modifier into the solution, and stirring for 15min to obtain the mixed modified graphene solution.
And 2.3, drying the obtained mixed solution at 96 ℃ to obtain modified graphene powder.
And 2.4, cleaning and drying the modified graphene powder again by using deionized water, removing redundant residual surface modifier, adding the modified graphene powder into the deionized water, and stirring and mixing uniformly to obtain a modified graphene solution, wherein the modified graphene solution contains 15% by mass percent.
And 3, preparing a pentanediamine solution through biological fermentation, purifying to obtain high-purity pentanediamine, and preparing a diluted pentanediamine solution.
Preferably, adding the escherichia coli cells expressing the L-lysine decarboxylase into the L-Lai Ansu monohydrochloride solution, setting the pH value of the solution to be 7-8 and the temperature to be 36 ℃, and keeping the solution for 4 days for continuous fermentation to convert the L-Lai Ansu monohydrochloride into the pentanediamine; and then distilling the obtained mixed solution through a distiller to obtain a pentanediamine solution, further purifying to obtain high-purity pentanediamine with the purity of more than or equal to 99.9, and finally adding deionized water to prepare a diluted pentanediamine solution with the mass concentration of 30 percent.
And step 4, adding the modified graphene oxide solution, the diluted pentylene diamine solution and the solid adipic acid into a solution reactor, and reacting to obtain a graphene nylon salt solution.
Preferably, the ratio of the modified graphene oxide solution, the diluted pentylene diamine solution and the solid adipic acid is 8% in mass percent: 46%:46%.
And 5, filtering the graphene nylon salt solution to obtain graphene nylon refined salt solution, and concentrating to obtain concentrated mixed solution.
Preferably, the graphene nylon salt solution is filtered through active carbon, the mesh number of the active carbon is 1500 meshes, the graphene nylon refined salt solution is obtained, and then the graphene nylon refined salt solution is conveyed to a concentration kettle and concentrated to obtain the mixed solution with the mass concentration of 72%.
And step 6, conveying the concentrated mixed solution to a preheater for preheating, simultaneously adding an initiator, a molecular chain terminator and a defoaming agent, continuously conveying to a pre-polycondensation reactor, and reacting to obtain the graphene nylon pre-polycondensate.
And 7, conveying the pre-polymerized substance to a pre-polymerization reactor, and simultaneously adding a delustering agent for reaction to obtain a pre-polymerization reactant.
And 8, continuously conveying reactants obtained by pre-polymerization to a post-polymerization reactor, and reacting to obtain graphene biomass nylon polymer melt.
And 9, conveying the graphene biomass nylon polymer melt to a devolatilization reactor to remove substances with low molecular weight.
And 10, extruding the polymer from a devolatilization reactor, extruding the polymer in the form of a strip through a polymer melt filter, and cooling and granulating the strip to obtain graphene biomass nylon chips.
And 11, placing the graphene biomass nylon slices into a dryer for drying treatment.
Preferably, the drying temperature is 70℃and the drying time is 18 hours.
And step 12, testing the performance of the obtained graphene biomass nylon chips, and then feeding the chips which are qualified in the test into a spinning machine.
And 13, enabling the graphene biomass nylon slices to enter a spinning box, melting at high temperature, spraying out the graphene biomass nylon slices into filaments through a spinneret orifice, then cooling and forming the filaments through a slow cooling device by side blowing, oiling, and primarily forming the filament bundles.
Preferably, the high temperature melting temperature is 250 ℃.
And 14, stretching the obtained molded tows by a tension roller to obtain graphene biomass nylon fibers.
Preferably, the elongation range of the stretching is 30%, and the breaking strength of the finished fiber after the stretching is between 4.5 and 5.5.
Example 4
The graphene bio-based nylon functional fiber comprises the following raw materials in percentage by mass: 6% of graphene oxide solution, 0.4% of surface modifier, 1.5% of initiator, 1.6% of molecular chain terminator, 1.5% of defoamer, 5% of matting agent, 42% of pentanediamine solution and 42% of solid adipic acid.
Preferably, the surface modifying agent is acetic acid and chloroacetic acid; the initiator is styrene, derivatives thereof and methyl methacrylate; the molecular chain terminator is any one of terminator bisphenol A, p-tert-butyl catechol and wood tar; the defoaming agent is polyoxypropylene glycerol ether; the matting agent is anatase titanium dioxide and rutile titanium dioxide.
The embodiment also provides a preparation method of the graphene bio-based nylon functional fiber, which comprises the following steps:
step 1, preparing each raw material.
And 2, preparing a modified graphene solution.
Preferably, step 2 comprises:
and 2.1, adding graphene oxide powder into deionized water, and performing ultrasonic treatment on the obtained graphite oxide solution at normal temperature for 10min, wherein the solution contains 8% of graphene oxide in percentage by mass.
And 2.2, adding the surface modifier into the solution, and stirring for 10min to obtain the mixed modified graphene solution.
And 2.3, drying the obtained mixed solution at the temperature of 95 ℃ to obtain modified graphene powder.
And 2.4, cleaning and drying the modified graphene powder again by using deionized water, removing redundant residual surface modifier, adding the modified graphene powder into the deionized water, and stirring and mixing uniformly to obtain a modified graphene solution, wherein the modified graphene solution contains 12% by mass percent of modified graphene.
And 3, preparing a pentanediamine solution through biological fermentation, purifying to obtain high-purity pentanediamine, and preparing a diluted pentanediamine solution.
Preferably, adding the escherichia coli cells expressing the L-lysine decarboxylase into the L-Lai Ansu monohydrochloride solution, setting the pH value of the solution to 7-8 and the temperature to 35 ℃, and keeping the solution for 5 days for continuous fermentation to convert the L-Lai Ansu monohydrochloride into the pentanediamine; and then distilling the obtained mixed solution through a distiller to obtain a pentanediamine solution, further purifying to obtain high-purity pentanediamine with the purity of more than or equal to 99.9, and finally adding deionized water to prepare a diluted pentanediamine solution with the mass concentration of 30 percent.
And step 4, adding the modified graphene oxide solution, the diluted pentylene diamine solution and the solid adipic acid into a solution reactor, and reacting to obtain a graphene nylon salt solution.
Preferably, the ratio of the modified graphene oxide solution, the diluted pentylene diamine solution and the solid adipic acid is 6% by mass percent: 47%:47%.
And 5, filtering the graphene nylon salt solution to obtain graphene nylon refined salt solution, and concentrating to obtain concentrated mixed solution.
Preferably, the graphene nylon salt solution is filtered through active carbon, the mesh number of the active carbon is 1200, the graphene nylon refined salt solution is obtained, and then the graphene nylon refined salt solution is conveyed to a concentration kettle and concentrated to obtain the mixed solution with the mass concentration of 74%.
And step 6, conveying the concentrated mixed solution to a preheater for preheating, simultaneously adding an initiator, a molecular chain terminator and a defoaming agent, continuously conveying to a pre-polycondensation reactor, and reacting to obtain the graphene nylon pre-polycondensate.
And 7, conveying the pre-polymerized substance to a pre-polymerization reactor, and simultaneously adding a delustering agent for reaction to obtain a pre-polymerization reactant.
And 8, continuously conveying reactants obtained by pre-polymerization to a post-polymerization reactor, and reacting to obtain graphene biomass nylon polymer melt.
And 9, conveying the graphene biomass nylon polymer melt to a devolatilization reactor to remove substances with low molecular weight.
And 10, extruding the polymer from a devolatilization reactor, extruding the polymer in the form of a strip through a polymer melt filter, and cooling and granulating the strip to obtain graphene biomass nylon chips.
And 11, placing the graphene biomass nylon slices into a dryer for drying treatment.
Preferably, the drying temperature is 60℃and the drying time is 16 hours.
And step 12, testing the performance of the obtained graphene biomass nylon chips, and then feeding the chips which are qualified in the test into a spinning machine.
And 13, enabling the graphene biomass nylon slices to enter a spinning box, melting at high temperature, spraying out the graphene biomass nylon slices into filaments through a spinneret orifice, then cooling and forming the filaments through a slow cooling device by side blowing, oiling, and primarily forming the filament bundles.
Preferably, the high temperature melting temperature is 240 ℃.
And 14, stretching the obtained molded tows by a tension roller to obtain graphene biomass nylon fibers.
Preferably, the elongation range of the stretching is 20%, and the breaking strength of the finished fiber after the stretching is between 4.5 and 5.5.
Example 5
The graphene bio-based nylon functional fiber comprises the following raw materials in percentage by mass: 5.5% of graphene oxide solution, 0.5% of surface modifier, 2% of initiator, 2% of molecular chain terminator, 2% of defoamer, 2% of matting agent, 43% of pentanediamine solution and 43% of solid adipic acid.
Preferably, the surface modifier is acetic acid or chloroacetic acid; the initiator is styrene and derivatives or methyl methacrylate thereof; the molecular chain terminator is any multiple of terminator bisphenol A, p-tert-butyl catechol and wood tar; the defoaming agent is any multiple of emulsified silicone oil, polyoxyethylene polyoxypropylene pentaerythritol ether, polyoxyethylene polyoxypropylene alcohol amine ether and polyoxypropylene glycerol ether; the delustrant is anatase titanium dioxide or rutile titanium dioxide.
The embodiment also provides a preparation method of the graphene bio-based nylon functional fiber, which comprises the following steps:
step 1, preparing each raw material.
And 2, preparing a modified graphene solution.
Preferably, step 2 comprises:
and 2.1, adding graphene oxide powder into deionized water, and performing ultrasonic treatment on the obtained graphite oxide solution at normal temperature for 20min, wherein the solution contains 9% of graphene oxide in percentage by mass.
And 2.2, adding the surface modifier into the solution, and stirring for 20min to obtain the mixed modified graphene solution.
And 2.3, drying the obtained mixed solution at 100 ℃ to obtain modified graphene powder.
And 2.4, cleaning and drying the modified graphene powder again by using deionized water, removing redundant residual surface modifier, adding the modified graphene powder into the deionized water, and stirring and mixing uniformly to obtain a modified graphene solution, wherein the modified graphene solution contains 10% by mass percent.
And 3, preparing a pentanediamine solution through biological fermentation, purifying to obtain high-purity pentanediamine, and preparing a diluted pentanediamine solution.
Preferably, adding the escherichia coli cells expressing the L-lysine decarboxylase into the L-Lai Ansu monohydrochloride solution, setting the pH value of the solution to 7-8 and the temperature to 40 ℃, and keeping the solution for 4 days for continuous fermentation to convert the L-Lai Ansu monohydrochloride into the pentanediamine; and then distilling the obtained mixed solution through a distiller to obtain a pentanediamine solution, further purifying to obtain high-purity pentanediamine with the purity of more than or equal to 99.9, and finally adding deionized water to prepare a diluted pentanediamine solution with the mass concentration of 30 percent.
And step 4, adding the modified graphene oxide solution, the diluted pentylene diamine solution and the solid adipic acid into a solution reactor, and reacting to obtain a graphene nylon salt solution.
Preferably, the ratio of the modified graphene oxide solution, the diluted pentylene diamine solution and the solid adipic acid is 7% by mass percent: 46.5%:46.5%.
And 5, filtering the graphene nylon salt solution to obtain graphene nylon refined salt solution, and concentrating to obtain concentrated mixed solution.
Preferably, the graphene nylon salt solution is filtered through active carbon, the mesh number of the active carbon is 1600 meshes, the graphene nylon refined salt solution is obtained, and then the graphene nylon refined salt solution is conveyed to a concentration kettle and concentrated to obtain the mixed solution with the mass concentration of 75%.
And step 6, conveying the concentrated mixed solution to a preheater for preheating, simultaneously adding an initiator, a molecular chain terminator and a defoaming agent, continuously conveying to a pre-polycondensation reactor, and reacting to obtain the graphene nylon pre-polycondensate.
And 7, conveying the pre-polymerized substance to a pre-polymerization reactor, and simultaneously adding a delustering agent for reaction to obtain a pre-polymerization reactant.
And 8, continuously conveying reactants obtained by pre-polymerization to a post-polymerization reactor, and reacting to obtain graphene biomass nylon polymer melt.
And 9, conveying the graphene biomass nylon polymer melt to a devolatilization reactor to remove substances with low molecular weight.
And 10, extruding the polymer from a devolatilization reactor, extruding the polymer in the form of a strip through a polymer melt filter, and cooling and granulating the strip to obtain graphene biomass nylon chips.
And 11, placing the graphene biomass nylon slices into a dryer for drying treatment.
Preferably, the drying temperature is 80 ℃ and the drying time is 20 hours.
And step 12, testing the performance of the obtained graphene biomass nylon chips, and then feeding the chips which are qualified in the test into a spinning machine.
And 13, enabling the graphene biomass nylon slices to enter a spinning box, melting at high temperature, spraying out the graphene biomass nylon slices into filaments through a spinneret orifice, then cooling and forming the filaments through a slow cooling device by side blowing, oiling, and primarily forming the filament bundles.
Preferably, the high temperature melting temperature is 260 ℃.
And 14, stretching the obtained molded tows by a tension roller to obtain graphene biomass nylon fibers.
Preferably, the elongation range of the stretching is 40%, and the breaking strength of the finished fiber after the stretching is between 4.5 and 5.5.
The graphene bio-based nylon 56 functional fibers prepared by the embodiments of the invention are respectively tested, and the results prove that the graphene bio-based nylon 56 functional fibers have improved tensile strength and wear resistance compared with common nylon 56 fibers, and have excellent antibacterial effect, wherein the antibacterial rate on escherichia coli, staphylococcus aureus and candida albicans reaches more than 99%.
The invention provides a graphene bio-based nylon functional fiber and a preparation method thereof, and aims to provide a preparation method of graphene bio-based nylon 56 functional fiber, which is characterized in that biomass pentanediamine is prepared mainly through a fermentation method, then a continuous polymerization technology is adopted, modified graphene is added in the polymerization process to prepare graphene biomass nylon 56 master batch, and then the graphene bio-based nylon 56 functional fiber is spun. The method expands the application range of the traditional nylon material, improves the added value of the product, and well meets the requirements of people on healthy and environment-friendly functional textiles.
While the present invention has been described in detail through the foregoing description of the preferred embodiment, it should be understood that the foregoing description is not to be considered as limiting the invention. Many modifications and substitutions of the present invention will become apparent to those of ordinary skill in the art upon reading the foregoing. Accordingly, the scope of the invention should be limited only by the attached claims.
Claims (10)
1. The graphene bio-based nylon functional fiber is characterized by comprising the following raw materials in percentage by mass: 5 to 8 percent of graphene oxide solution, 0.1 to 1 percent of surface modifier, 0.1 to 5 percent of initiator, 0.1 to 5 percent of molecular chain terminator, 1 to 5 percent of defoamer, 1 to 5 percent of flatting agent, 36 to 45 percent of pentanediamine solution and 36 to 45 percent of solid adipic acid.
2. The graphene bio-based nylon functional fiber of claim 1, wherein the surface modifier is acetic acid and/or chloroacetic acid; the initiator is styrene and its derivative and/or methyl methacrylate; the molecular chain terminator is one or more of terminator bisphenol A, p-tert-butylcatechol and wood tar; the defoaming agent is any one or more of emulsified silicone oil, polyoxyethylene polyoxypropylene pentaerythritol ether, polyoxyethylene polyoxypropylene alcohol amine ether and polyoxypropylene glycerol ether; the matting agent is anatase titanium dioxide and/or rutile titanium dioxide.
3. A method for preparing the graphene bio-based nylon functional fiber according to claim 1 or 2, wherein the method comprises:
step 1, preparing raw materials;
step 2, preparing a modified graphene solution;
step 3, preparing a pentanediamine solution through biological fermentation, purifying to obtain high-purity pentanediamine, and preparing a diluted pentanediamine solution;
step 4, adding the modified graphene oxide solution, the diluted pentylene diamine solution and the solid adipic acid into a solution reactor, and reacting to obtain a graphene nylon salt solution;
step 5, filtering the graphene nylon salt solution to obtain graphene nylon refined salt solution, and concentrating to obtain concentrated mixed solution;
step 6, conveying the concentrated mixed solution to a preheater for preheating, simultaneously adding an initiator, a molecular chain terminator and a defoaming agent, continuously conveying to a pre-polycondensation reactor, and reacting to obtain a graphene nylon pre-polycondensate;
step 7, conveying the pre-polymerized substance to a pre-polymerization reactor, and simultaneously adding a delustering agent for reaction to obtain a pre-polymerization reactant;
step 8, continuously conveying reactants obtained by pre-polymerization to a post-polymerization reactor, and reacting to obtain graphene biomass nylon polymer melt;
Step 9, conveying the graphene biomass nylon polymer melt to a devolatilization reactor to remove substances with low molecular weight;
step 10, extruding a polymer from a devolatilization reactor, extruding the polymer in a strip shape through a polymer melt filter, and cooling and granulating the strip to obtain graphene biomass nylon chips;
step 11, placing the graphene biomass nylon slices into a dryer for drying treatment;
step 12, testing the performance of the obtained graphene biomass nylon chips, and then feeding the chips which are qualified in the test into a spinning machine;
step 13, enabling graphene biomass nylon slices to enter a spinning box, melting at high temperature, spraying out the graphene biomass nylon slices into filaments through a spinneret orifice, then cooling and forming the filaments through a slow cooling device by side blowing, oiling and primarily forming filament bundles;
and 14, stretching the obtained molded tows by a tension roller to obtain graphene biomass nylon fibers.
4. The method for preparing graphene bio-based nylon functional fiber according to claim 3, wherein the step 2 comprises:
step 2.1, adding graphene oxide powder into deionized water, and performing ultrasonic treatment on the obtained graphite oxide solution at normal temperature for 10-20 min, wherein the solution contains 5-10% of graphene oxide in percentage by mass;
Step 2.2, adding a surface modifier into the solution, and stirring for 10-20 min to obtain a mixed modified graphene solution;
step 2.3, drying the obtained mixed solution at the temperature of 95-100 ℃ to obtain modified graphene powder;
and 2.4, cleaning and drying the modified graphene powder again by using deionized water, removing redundant residual surface modifier, adding the modified graphene powder into the deionized water, and stirring and mixing uniformly to obtain a modified graphene solution, wherein the modified graphene solution contains 3-20% by mass percent of modified graphene.
5. The method for preparing graphene bio-based nylon functional fiber according to claim 3, wherein in the step 3, escherichia coli cells expressing L-lysine decarboxylase are added into an L-Lai Ansu monohydrochloride solution, the pH value of the solution is set to be 7-8, the temperature is 35-40 ℃, and the solution is kept for 3-6 days for continuous fermentation, so that L-Lai Ansu monohydrochloride is converted into pentanediamine; and then distilling the obtained mixed solution through a distiller to obtain a pentanediamine solution, further purifying to obtain high-purity pentanediamine with the purity of more than or equal to 99.9, and finally adding deionized water to prepare a diluted pentanediamine solution with the mass concentration of 30 percent.
6. The preparation method of the graphene bio-based nylon functional fiber according to claim 3, wherein in the step 4, the ratio of the modified graphene oxide solution, the diluted pentanediamine solution and the solid adipic acid is (4%: 48%: 48%) to (10%: 45%: 45%) in percentage by mass.
7. The preparation method of the graphene bio-based nylon functional fiber according to claim 3, wherein in the step 5, the graphene nylon salt solution is filtered through activated carbon, the mesh number of the activated carbon is 1000-2000 meshes, the graphene nylon refined salt solution is obtained, and then the graphene nylon refined salt solution is conveyed to a concentration kettle and concentrated to obtain the mixed solution with the mass concentration of 70% -75%.
8. The method for preparing graphene bio-based nylon functional fibers according to claim 3, wherein in the step 11, the drying temperature is 60-80 ℃ and the drying time is 12-24 hours.
9. The method for preparing graphene bio-based nylon functional fibers according to claim 3, wherein in the step 13, the high-temperature melting temperature is 240-260 ℃.
10. The method for preparing graphene bio-based nylon functional fibers according to claim 3, wherein in the step 14, the stretching elongation range is 20% -40%, and the breaking strength of the finished fiber after stretching is 4.5-5.5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310992412.7A CN116988180A (en) | 2023-08-08 | 2023-08-08 | Graphene bio-based nylon functional fiber and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310992412.7A CN116988180A (en) | 2023-08-08 | 2023-08-08 | Graphene bio-based nylon functional fiber and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116988180A true CN116988180A (en) | 2023-11-03 |
Family
ID=88529910
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310992412.7A Pending CN116988180A (en) | 2023-08-08 | 2023-08-08 | Graphene bio-based nylon functional fiber and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116988180A (en) |
-
2023
- 2023-08-08 CN CN202310992412.7A patent/CN116988180A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101956240B (en) | Method for producing terylen fibers from polyester waste | |
| CN112779612B (en) | Efficient production and manufacturing method and equipment for lyocell fibers | |
| CN111005076A (en) | Spinning method of regenerated polyester full-dull FDY filament | |
| CN110938877A (en) | Method for spinning regenerated polyester filament yarn by using polyester waste | |
| CN111349253A (en) | Modified lignin/PBS (Poly Butylene succinate) bioplastic film and preparation method thereof | |
| CN111235688A (en) | Biodegradable polyester fiber and preparation method thereof | |
| CN116988180A (en) | Graphene bio-based nylon functional fiber and preparation method thereof | |
| CN111648039B (en) | Production process of green environment-friendly polypropylene melt-blown fabric | |
| CN112608514A (en) | Method for preparing antibacterial regenerated polyester by using waste polyester alcoholysis method | |
| CN101134815A (en) | Method for preparing ultraviolet-resistant polyphenylene sulfide resin by in situ Polymerization | |
| CN112111803B (en) | Preparation method of bio-based chinlon 5X fiber material | |
| CN114045562B (en) | High-stability bio-based polyamide 56 fiber and preparation process thereof | |
| CN109627495A (en) | The preparation method of the full Preen nono composite material of nano-cellulose-polylactic acid | |
| CN214529355U (en) | Novel polylactic acid fiber | |
| CN109608844A (en) | The preparation method of the full Preen nono composite material of acetic acid esterified nano-cellulose-polylactic acid | |
| CN111269412B (en) | Method for recycling caprolactam | |
| CN109666986B (en) | Easy-to-dye polyester FDY fiber and preparation method thereof | |
| CN110699861A (en) | Production method of high-strength regenerated nano-cellulose mixed membrane | |
| CN115506050B (en) | Preparation method of 48k carbon fiber precursor, 48k carbon fiber precursor and 48k carbon fiber | |
| CN117166079A (en) | Preparation method of furan-based monomer modified polyamide industrial yarn | |
| CN112341553B (en) | Preparation method of low ash content fiber-grade polyvinyl alcohol | |
| CN115074868B (en) | Preparation method of pre-oxidized fiber and pre-oxidized fiber | |
| US20220243364A1 (en) | Integrated and improved process for the production of acrylic fibers | |
| CN116837487A (en) | Polyester preparation method based on liquid phase tackifying technology | |
| CN116078185A (en) | Method for preparing membrane filaments of hollow fiber deamination membrane |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |