CN116925375B - Graphene oxide grafted modified polyamide composite material, fabric and preparation method thereof - Google Patents
Graphene oxide grafted modified polyamide composite material, fabric and preparation method thereof Download PDFInfo
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- CN116925375B CN116925375B CN202310877157.1A CN202310877157A CN116925375B CN 116925375 B CN116925375 B CN 116925375B CN 202310877157 A CN202310877157 A CN 202310877157A CN 116925375 B CN116925375 B CN 116925375B
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- Prior art keywords
- graphene oxide
- modified polyamide
- grafted modified
- oxide grafted
- composite material
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- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 91
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 239000004952 Polyamide Substances 0.000 title claims abstract description 70
- 229920002647 polyamide Polymers 0.000 title claims abstract description 70
- 239000002131 composite material Substances 0.000 title claims abstract description 43
- 239000004744 fabric Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000004519 manufacturing process Methods 0.000 title description 4
- 239000006185 dispersion Substances 0.000 claims abstract description 37
- 239000007788 liquid Substances 0.000 claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 15
- 238000009987 spinning Methods 0.000 claims abstract description 12
- TXFOLHZMICYNRM-UHFFFAOYSA-N dichlorophosphoryloxybenzene Chemical compound ClP(Cl)(=O)OC1=CC=CC=C1 TXFOLHZMICYNRM-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000047 product Substances 0.000 claims abstract description 11
- 238000010992 reflux Methods 0.000 claims abstract description 11
- 239000013067 intermediate product Substances 0.000 claims abstract description 10
- 150000008064 anhydrides Chemical class 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 8
- 230000004224 protection Effects 0.000 claims abstract description 8
- 150000004985 diamines Chemical class 0.000 claims abstract description 7
- 150000007530 organic bases Chemical class 0.000 claims abstract description 7
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052786 argon Inorganic materials 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 46
- 238000003756 stirring Methods 0.000 claims description 19
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000000835 fiber Substances 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- 235000019441 ethanol Nutrition 0.000 claims description 13
- 238000002074 melt spinning Methods 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 10
- 239000003638 chemical reducing agent Substances 0.000 claims description 8
- JPSKCQCQZUGWNM-UHFFFAOYSA-N 2,7-Oxepanedione Chemical compound O=C1CCCCC(=O)O1 JPSKCQCQZUGWNM-UHFFFAOYSA-N 0.000 claims description 6
- CSJDCSCTVDEHRN-UHFFFAOYSA-N methane;molecular oxygen Chemical compound C.O=O CSJDCSCTVDEHRN-UHFFFAOYSA-N 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- 238000009941 weaving Methods 0.000 claims description 5
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 4
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000000155 melt Substances 0.000 claims description 4
- 239000012279 sodium borohydride Substances 0.000 claims description 4
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 4
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 3
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 2
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 229960005070 ascorbic acid Drugs 0.000 claims description 2
- 235000010323 ascorbic acid Nutrition 0.000 claims description 2
- 239000011668 ascorbic acid Substances 0.000 claims description 2
- QVYARBLCAHCSFJ-UHFFFAOYSA-N butane-1,1-diamine Chemical compound CCCC(N)N QVYARBLCAHCSFJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- VANNPISTIUFMLH-UHFFFAOYSA-N glutaric anhydride Chemical compound O=C1CCCC(=O)O1 VANNPISTIUFMLH-UHFFFAOYSA-N 0.000 claims description 2
- SYECJBOWSGTPLU-UHFFFAOYSA-N hexane-1,1-diamine Chemical compound CCCCCC(N)N SYECJBOWSGTPLU-UHFFFAOYSA-N 0.000 claims description 2
- KJOMYNHMBRNCNY-UHFFFAOYSA-N pentane-1,1-diamine Chemical compound CCCCC(N)N KJOMYNHMBRNCNY-UHFFFAOYSA-N 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 2
- 239000001509 sodium citrate Substances 0.000 claims description 2
- 229940014800 succinic anhydride Drugs 0.000 claims description 2
- 150000008065 acid anhydrides Chemical class 0.000 claims 1
- 239000003063 flame retardant Substances 0.000 abstract description 18
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 abstract description 12
- 238000009954 braiding Methods 0.000 abstract description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 24
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 18
- 229920001778 nylon Polymers 0.000 description 11
- 150000001412 amines Chemical class 0.000 description 9
- 125000003651 hexanedioyl group Chemical group C(CCCCC(=O)*)(=O)* 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- LFGREXWGYUGZLY-UHFFFAOYSA-N phosphoryl Chemical group [P]=O LFGREXWGYUGZLY-UHFFFAOYSA-N 0.000 description 9
- 229920006389 polyphenyl polymer Polymers 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 239000008041 oiling agent Substances 0.000 description 8
- -1 phenylphosphoryl Chemical group 0.000 description 8
- 239000003921 oil Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 230000003068 static effect Effects 0.000 description 6
- 239000004677 Nylon Substances 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- 230000001276 controlling effect Effects 0.000 description 4
- 238000009940 knitting Methods 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- 238000001132 ultrasonic dispersion Methods 0.000 description 4
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 4
- 230000005611 electricity Effects 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 230000000670 limiting effect Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 239000002216 antistatic agent Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000005389 magnetism Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection 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
- 238000010998 test method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
-
- 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
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/001—Macromolecular compounds containing organic and inorganic sequences, e.g. organic polymers grafted onto silica
-
- 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
- D01F6/96—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from other synthetic polymers
-
- D—TEXTILES; PAPER
- D03—WEAVING
- D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
- D03D15/00—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
- D03D15/20—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the material of the fibres or filaments constituting the yarns or threads
- D03D15/283—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the material of the fibres or filaments constituting the yarns or threads synthetic polymer-based, e.g. polyamide or polyester fibres
-
- D—TEXTILES; PAPER
- D03—WEAVING
- D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
- D03D15/00—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
- D03D15/50—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the properties of the yarns or threads
- D03D15/513—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the properties of the yarns or threads heat-resistant or fireproof
-
- D—TEXTILES; PAPER
- D03—WEAVING
- D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
- D03D15/00—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
- D03D15/50—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the properties of the yarns or threads
- D03D15/533—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the properties of the yarns or threads antistatic; electrically conductive
-
- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2331/00—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
- D10B2331/30—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polycondensation products not covered by indexing codes D10B2331/02 - D10B2331/14
-
- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2401/00—Physical properties
- D10B2401/16—Physical properties antistatic; conductive
Abstract
The invention provides a graphene oxide grafted modified polyamide composite material, a fabric and a preparation method thereof, comprising the following steps: adding phenyl phosphoryl dichloride into a solvent, then adding diamine and organic base under the protection of nitrogen or argon, and carrying out reflux reaction to obtain an intermediate product 1 after the reaction is finished; heating the obtained intermediate product 1 and anhydride to react to obtain a polymerization product 2; taking graphene oxide dispersion liquid 1, and then adding the polymerization product 2 in the step S1 into the graphene oxide dispersion liquid 1 to obtain dispersion liquid 2; and adding a silane coupling agent into the dispersion liquid 2, heating for reaction, and obtaining the graphene oxide grafted modified polyamide composite material after the reaction is finished. The novel antistatic flame-retardant wear-resistant fabric can be obtained by spinning and braiding the composite material, and has the advantages of high char yield, good flame retardance, excellent antistatic performance, high breaking strength, good wear resistance and the like.
Description
Technical Field
The invention belongs to the technical field of preparation of composite materials and high polymer fabrics, and particularly relates to a graphene oxide grafted modified polyamide composite material, a fabric and a preparation method thereof.
Background
Polyamide fibers, also known as nylon, are the first synthetic fibers in the world and are widely used in the textile industry, and nylon fibers have the characteristics of soft hand feel, moisture absorption and perspiration, easy coloring and fastness, but also have the disadvantages of easy aging, easy static electricity generation, poor flame retardance, and the like. The development of the nylon industry is gradually changed from conventional production to functional modification, and a batch of functional composite nylon fibers are sequentially developed, for example, titanium dioxide is added into nylon to improve the ultraviolet resistance of the nylon, nano metal particles are added to improve the sterilization performance of the nylon, and nano graphite is added to produce dye-free black nylon fibers.
The graphene is the only two-dimensional free state atomic crystal found at present, is a two-dimensional monoatomic layer flaky crystal material formed by closely arranging sp2 hybridized carbon atom honeycomb hexagonal structures, has a structure with a large pi conjugated system and the thinnest monolayer atomic thickness, has unique physical properties and chemical properties such as light, electricity, magnetism, machinery and the like, has great attention since 2004, and has high development potential and application value in specific practical application in the fields such as electronics, optics, magnetism, biomedicine, catalysis, energy storage, sensors and the like.
The graphene particles are added into the nylon fiber, so that the nylon fiber has the performances of resisting bacteria, inhibiting bacteria, preventing static electricity and the like, the graphene composite nylon fiber is generally prepared by firstly preparing graphene powder into master batches, mixing the master batches with polyamide particles according to a certain proportion, and then carrying out melt spinning. In addition, in daily life and industrial production, fires or even explosion accidents, which inadvertently cause burning of textiles, occur. In the past, halogen-containing polymers or flame retardant materials combined with halogen-containing flame retardants have been widely used because of their good flame retardant properties. However, in the event of a fire, such halogen-containing flame retardant materials generate a large amount of smoke and toxic corrosive hydrogen halide gases, causing secondary harm to the human body and the environment.
To overcome these problems, halogen-free flame retardant materials are beginning to be widely used. The halogen-free flame retardant material is prepared by adding a halogen-free flame retardant into the material, and the material does not volatilize or generate corrosive gas when being burnt. The halogen-free flame retardant mainly comprises phosphorus compounds, metal hydroxides, silicon flame retardants, nitrogen flame retardants and the like. The main technical route adopted in the research of antistatic and flame-retardant fabrics is domestic and foreign in recent years: after finishing of the antistatic agent and the flame retardant is carried out on the fabric, however, due to the interaction between the organic antistatic agent and the organic flame retardant, the antistatic performance and the flame retardant performance of the fabric are often reduced, the strength of the fabric is greatly reduced, the hand feeling is rough and hard, and in addition, the washing resistance of the fabric is very poor, so that the actual use requirement is difficult to reach. Therefore, it is necessary to invent a novel graphene oxide grafted modified polyamide composite material, a novel graphene oxide grafted modified polyamide composite fabric and a novel graphene oxide grafted modified polyamide composite fabric preparation method.
Disclosure of Invention
In order to solve the technical problems, the invention provides a novel graphene oxide grafted modified polyamide composite material, a novel graphene oxide grafted modified polyamide fabric and a preparation method of the novel graphene oxide grafted modified polyamide composite material.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the invention relates to a preparation method of a novel graphene oxide grafted modified polyamide composite material, which specifically comprises the following steps:
s1: adding phenyl phosphoryl dichloride into a solvent, then adding diamine and organic base under the protection of nitrogen or argon, and carrying out reflux reaction to obtain an intermediate product 1 after the reaction is finished; heating the obtained intermediate product 1 and anhydride to react to obtain a polymerization product 2;
s2: taking graphene oxide dispersion liquid 1, and then adding the polymerization product 2 in the step S1 into the graphene oxide dispersion liquid 1 to obtain dispersion liquid 2;
s3: and (2) adding a silane coupling agent into the dispersion liquid 2 in the step (S2), and heating for reaction to obtain the graphene oxide grafted modified polyamide composite material after the reaction is finished.
Further, the diamine comprises one or more of butanediamine, pentanediamine, hexanediamine and p-phenylenediamine;
further, the organic base comprises one or more of trimethylamine, triethylamine, pyridine and 4-dimethylaminopyridine;
further, the solvent comprises one or more of 1, 2-dichloroethane, chloroform, chlorobenzene and tetrahydrofuran;
further, the anhydride comprises one or more of succinic anhydride, glutaric anhydride and adipic anhydride.
Further, the molar ratio of the phenyl phosphoryl dichloride to the diamine is 1:2-2.2;
further, the molar ratio of the phenyl phosphoryl dichloride to the organic base is 1:2-2.2;
further, in the step S1: the conditions of the reflux reaction are as follows: reflux reaction is carried out for 1.5 to 2.5 hours at the temperature of 85 to 95 ℃;
further, in the step S1, the molar ratio of the intermediate product 1 to the anhydride is 1:2-2.2;
further, the reaction conditions of the heating reaction of the obtained intermediate product 1 and the anhydride are as follows: stirring and reacting for 7-9h at 65-75 ℃ to obtain a polymerization product 1;
further, in the step S2: the solvent in the graphene oxide dispersion liquid 1 consists of deionized water and ethanol, wherein the volume ratio of the deionized water to the ethanol is 1:1, the size of the graphene oxide is 10-15um, and the carbon-oxygen ratio is 3-5;
further, in the step S3, the silane coupling agent includes one or more of KH550, KH560, KH570, KH792, DL 602;
further, the silane coupling agent is added to the dispersion liquid 2 in the step S2, and further includes: adding a silane coupling agent into absolute ethyl alcohol, and then adding the silane coupling agent into the dispersion liquid 2 in the step S2;
further, the adding mode of the silane coupling agent to the dispersion liquid 2 in the step S2 is dripping, stirring is kept at a constant speed in the dripping process, the temperature is controlled at 45-55 ℃, and after the dripping is finished, the temperature is adjusted to 65-75 ℃ to continue to react for 2-4 hours, so that the graphene oxide grafted modified polyamide composite material is obtained.
The invention also provides a graphene oxide grafted modified polyamide composite material, which is prepared by the preparation method.
In addition, the application also provides a preparation method of the graphene oxide grafted modified polyamide fabric, which comprises the steps of placing the graphene oxide grafted modified polyamide composite material prepared by the preparation method in a double-screw melt machine for melt spinning after vacuum drying, and obtaining the graphene grafted modified polyamide fiber by selecting the melt spinning temperature of 250-300 ℃ and the continuous spinning speed of 3000 m/min and the draft multiple of 3 times; braiding the graphene grafted modified polyamide fiber to obtain a graphene oxide grafted modified polyamide fabric;
further, after the melt comes out from the spinneret, oiling is carried out through a nozzle, then a hot roller with the temperature of 100-140 ℃ is used for hot drawing to obtain graphene-graphene oxide grafted modified polyamide fiber, and then the obtained graphene-graphene oxide grafted modified polyamide fiber is woven to obtain the graphene-graphene oxide grafted modified polyamide fabric;
wherein the oil in the oil tank is a white oil aqueous solution with the mass fraction of 10-20%, a reducing agent is added in the oil, and the mass fraction of the reducing agent in the oil is 8-12%; the reducing agent comprises one or more of sodium borohydride, sodium citrate and ascorbic acid.
The invention also provides a graphene oxide grafted modified polyamide fiber, and/or a graphene oxide grafted modified polyamide fabric, and/or a graphene-graphene oxide grafted modified polyamide fiber, and/or a graphene-graphene oxide grafted modified polyamide fabric.
Compared with the prior art, the invention has the following beneficial effects:
1. the preparation process is simple, the sources of raw materials are wide, the required production equipment is simple, and the preparation method can be used for large-scale production.
2. The graphene oxide grafted modified polyamide composite material contains a phenylphosphamide flame-retardant structure, and forms an intumescent flame-retardant system together with graphene oxide, so that the progress of a combustion chain reaction can be cooperatively restrained during combustion, and an excellent flame-retardant effect is achieved. In addition, the polyamide and the graphene oxide are connected together through the silane coupling agent, so that the graphene oxide can be effectively prevented from being aggregated to form particles with larger particle sizes, and can be firmly fixed on the surface of the polyamide, the antistatic capacity of the composite material is enhanced, and the flame retardant property of the composite material is improved.
3. The modified polyamide is subjected to high-speed continuous spinning, and the woven and blended product has high char yield, good flame retardance, excellent antistatic performance and higher breaking strength; meanwhile, the fabric has better morphological structure and mechanical property, and can still keep high performance after repeated washing, insolation and rubbing, and has good durability. In addition, the reduction treatment is carried out on the spinning, and the antistatic capacity of the fabric can be further improved while other performances of the fabric are not obviously reduced.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments, and all other embodiments obtained by those skilled in the art without making any inventive effort based on the embodiments of the present invention are within the scope of protection of the present invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs, and the terms used herein in this description of the invention are for the purpose of describing particular embodiments only and are not intended to be limiting of the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items. In the description of the present application, it should be understood that "and/or" describing the association relationship of the association object means that there may be three relationships, for example, a and/or B may mean: a alone, a and B together, and B alone. Wherein A, B may be singular or plural. In this application, "at least one" means one or more, and "a plurality" means two or more. "at least one", "at least one" or the like refer to any combination of these items, including any combination of single item(s) or plural items(s). For example, "at least one (individual) of a, b, or c," or "at least one (individual) of a, b, and c," may each represent: a, b, c, a-b (i.e., a and b), a-c, b-c, or a-b-c, wherein a, b, c may be single or multiple, respectively.
The present application is specifically illustrated by the following examples, which are only some of the examples of the present application and are not limiting of the present application.
Example 1
S1: adding 0.1mol of phenylphosphoryl dichloride into 1, 2-dichloroethane, then dropwise adding a 1, 2-dichloroethane solution containing 0.22mol of hexamethylenediamine and 0.22mol of triethylamine under the protection of nitrogen, and then carrying out reflux reaction for 2 hours at 90 ℃ to obtain phenylphosphoryl di (hexamethylenediamine); adding the obtained phenyl phosphoryl di (hexamethylenediamine) and 0.22mol of adipic anhydride into tetrahydrofuran, and then stirring and reacting for 8 hours at 70 ℃ to obtain polyphenyl phosphoryl di (adipoyl amine caproic acid);
s2: adding 5g of graphene oxide into a mixed solvent of deionized water and ethanol, wherein the volume ratio of the deionized water to the ethanol is 1:1, and then performing ultrasonic dispersion for 2 hours to form uniform dispersion liquid 1, wherein the size of the graphene oxide is 10-15 micrometers, and the carbon-oxygen ratio is 3.5; then adding the polyphenyl phosphoryl di (adipoyl amine caproic acid) obtained in the step S1 into the dispersion liquid 1, and uniformly stirring to obtain a dispersion liquid 2;
s3: adding 6g of KH550 (gamma-aminopropyl triethoxysilane) into absolute ethyl alcohol, uniformly stirring, dripping into a dispersion liquid 2, keeping uniform stirring in the dripping process, controlling the temperature at 50 ℃, and after the dripping is finished, regulating the temperature to 70 ℃ for continuous reaction for 3 hours to obtain a graphene oxide grafted modified polyamide composite material;
s4: vacuum drying the graphene oxide grafted and modified polyamide composite material, and placing the dried graphene oxide grafted and modified polyamide composite material into a double-screw melt machine for melt spinning, wherein the melt spinning temperature is selected to be 280 ℃, the continuous spinning speed is 3000 m/min, and the draft multiple is 3 times, so that filaments are obtained; and weaving the obtained filaments by an HDR5DPLM/30 and E16 double needle bar warp knitting machine, and adjusting the gauge of the needle bar to obtain the graphene oxide grafted modified polyamide fabric with high flame retardance and static resistance.
Example 2
S1: adding 0.1mol of phenylphosphoryl dichloride into 1, 2-dichloroethane, then dropwise adding a 1, 2-dichloroethane solution containing 0.22mol of hexamethylenediamine and 0.22mol of triethylamine under the protection of nitrogen, and then carrying out reflux reaction for 2 hours at 90 ℃ to obtain phenylphosphoryl di (hexamethylenediamine); adding the obtained phenyl phosphoryl di (hexamethylenediamine) and 0.22mol of adipic anhydride into tetrahydrofuran, and then stirring and reacting for 8 hours at 70 ℃ to obtain polyphenyl phosphoryl di (adipoyl amine caproic acid);
s2: adding 5g of graphene oxide into a mixed solvent of deionized water and ethanol, wherein the volume ratio of the deionized water to the ethanol is 1:1, and then performing ultrasonic dispersion for 2 hours to form uniform dispersion liquid 1, wherein the size of the graphene oxide is 10-15 micrometers, and the carbon-oxygen ratio is 3.5; then adding the polyphenyl phosphoryl di (adipoyl amine caproic acid) obtained in the step S1 into the dispersion liquid 1, and uniformly stirring to obtain a dispersion liquid 2;
s3: adding 6g of KH550 (gamma-aminopropyl triethoxysilane) into absolute ethyl alcohol, uniformly stirring, dripping into a dispersion liquid 2, keeping uniform stirring in the dripping process, controlling the temperature at 50 ℃, and after the dripping is finished, regulating the temperature to 70 ℃ for continuous reaction for 3 hours to obtain a graphene oxide grafted modified polyamide composite material;
s4: vacuum drying the graphene oxide grafted and modified polyamide composite material, placing the material in a double-screw melt machine for melt spinning, enabling the melt to enter a nozzle after coming out of a spinneret for oiling, wherein the oiling agent in an oiling agent box is a white oil water solution with the mass fraction of 15%, sodium borohydride is added in the oiling agent, the mass fraction of the reducing agent in the oiling agent is 10%, wherein the melt spinning temperature is 280 ℃, the continuous spinning speed is 3000 m/min, and the draft multiple is 3 times, so that filaments are obtained; and weaving the obtained filaments by an HDR5DPLM/30 and E16 double needle bar warp knitting machine, and adjusting the gauge of the needle bar to obtain the graphene oxide grafted modified polyamide fabric with high flame retardance and static resistance.
Example 3
S1: adding 0.1mol of phenylphosphoryl dichloride into 1, 2-dichloroethane, then dropwise adding a 1, 2-dichloroethane solution containing 0.22mol of hexamethylenediamine and 0.22mol of triethylamine under the protection of nitrogen, and then carrying out reflux reaction for 2 hours at 90 ℃ to obtain phenylphosphoryl di (hexamethylenediamine); adding the obtained phenyl phosphoryl di (hexamethylenediamine) and 0.22mol of adipic anhydride into tetrahydrofuran, and then stirring and reacting for 8 hours at 70 ℃ to obtain polyphenyl phosphoryl di (adipoyl amine caproic acid);
s2: adding 5g of graphene oxide into a mixed solvent of deionized water and ethanol, wherein the volume ratio of the deionized water to the ethanol is 1:1, and then performing ultrasonic dispersion for 2 hours to form uniform dispersion liquid 1, wherein the size of the graphene oxide is 10-15 micrometers, and the carbon-oxygen ratio is 3.5; then adding the polyphenyl phosphoryl di (adipoyl amine caproic acid) obtained in the step S1 into the dispersion liquid 1, and uniformly stirring to obtain a dispersion liquid 2;
s3: adding 6g of KH570 (gamma- (methacryloyloxy) propyl trimethoxy silane) into absolute ethyl alcohol, uniformly stirring, dripping into a dispersion liquid 2, keeping constant stirring in the dripping process, controlling the temperature at 50 ℃, and after the dripping is finished, regulating the temperature to 70 ℃ for continuous reaction for 3 hours to obtain a graphene oxide grafted modified polyamide composite material;
s4: vacuum drying the graphene oxide grafted and modified polyamide composite material, placing the material in a double-screw melt machine for melt spinning, enabling the melt to enter a nozzle after coming out of a spinneret for oiling, wherein the oiling agent in an oiling agent box is a white oil water solution with the mass fraction of 15%, sodium borohydride is added in the oiling agent, the mass fraction of the reducing agent in the oiling agent is 10%, wherein the melt spinning temperature is 280 ℃, the continuous spinning speed is 3000 m/min, and the draft multiple is 3 times, so that filaments are obtained; and weaving the obtained filaments by an HDR5DPLM/30 and E16 double needle bar warp knitting machine, and adjusting the gauge of the needle bar to obtain the graphene oxide grafted modified polyamide fabric with high flame retardance and static resistance.
Example 4
S1: adding 0.1mol of phenylphosphoryl dichloride into 1, 2-dichloroethane, then dropwise adding a 1, 2-dichloroethane solution containing 0.22mol of hexamethylenediamine and 0.22mol of triethylamine under the protection of nitrogen, and then carrying out reflux reaction for 2 hours at 90 ℃ to obtain phenylphosphoryl di (hexamethylenediamine); adding the obtained phenyl phosphoryl di (hexamethylenediamine) and 0.22mol of adipic anhydride into tetrahydrofuran, and then stirring and reacting for 8 hours at 70 ℃ to obtain polyphenyl phosphoryl di (adipoyl amine caproic acid);
s2: adding 5g of graphene oxide into a mixed solvent of deionized water and ethanol, wherein the volume ratio of the deionized water to the ethanol is 1:1, and then performing ultrasonic dispersion for 2 hours to form uniform dispersion liquid 1, wherein the size of the graphene oxide is 10-15 micrometers, and the carbon-oxygen ratio is 3.5; then adding the polyphenyl phosphoryl di (adipoyl amine caproic acid) obtained in the step S1 into the dispersion liquid 1, and uniformly stirring to obtain a dispersion liquid 2;
s3: adding 6g of KH560 (gamma-glycidoxypropyl trimethoxysilane) into absolute ethyl alcohol, uniformly stirring, dripping into a dispersion liquid 2, keeping uniform stirring in the dripping process, controlling the temperature at 50 ℃, and after the dripping is finished, regulating the temperature to 70 ℃ for continuous reaction for 3 hours to obtain a graphene oxide grafted modified polyamide composite material;
s4: vacuum drying the graphene oxide grafted and modified polyamide composite material, and placing the dried graphene oxide grafted and modified polyamide composite material into a double-screw melt machine for melt spinning, wherein the melt spinning temperature is selected to be 280 ℃, the continuous spinning speed is 3000 m/min, and the draft multiple is 3 times, so that filaments are obtained; and weaving the obtained filaments by an HDR5DPLM/30 and E16 double needle bar warp knitting machine, and adjusting the gauge of the needle bar to obtain the graphene oxide grafted modified polyamide fabric with high flame retardance and static resistance.
Comparative example 1
Comparative example 1 differs from example 1 in that: the product obtained in the step S1 is directly sent into the step S4 for spinning instead of the step S2 and the step S3, and the corresponding fabric is obtained.
Comparative example 2
Comparative example 1 differs from example 1 in that: and (3) not performing the step (S3), namely, not adding a silane coupling agent in the reaction process, but directly feeding the product obtained by drying the dispersion liquid 2 obtained in the step (S2) into the step (S4) for spinning to obtain the corresponding fabric.
Comparative example 3
Comparative example 2 differs from example 1 in that: step S2 is not carried out, namely graphene oxide is not added in the reaction process, but the polyphenyl phosphoryl di (adipoyl amine caproic acid) obtained in step S1 is uniformly dispersed in deionized water and ethanol, then absolute ethanol of KH560 is directly added, and the dried product is sent to step S4 for spinning, so that the corresponding fabric is obtained.
Performance test:
(1) Oxygen Index (LOI) test the flame retardancy of the samples was tested with a digital oxygen display index meter.
(2) Vertical burn test (UL-94) samples were tested using a CZF-2 vertical burn test instrument. The test standard is based on ASTM D380.TPU sample size: 130X 3mm 3 。
(3) Carbon residue rate the carbon residue rate at 480 ℃ was obtained from thermal weight loss (TG) test data and tested using an differential thermal scanner.
(4) Volume surface resistivity test the test was performed according to GB/T1410-2006 test method for volume resistivity and surface resistivity of solid insulation material.
(5) Breaking strength test the breaking strength of the samples was tested by an electronic single fiber strength tester.
Table 1 experimental test results
The principles and embodiments of the present application are described herein with specific examples, the above examples being provided only to assist in understanding the methods of the present application and their core ideas; meanwhile, as for those skilled in the art, there are various changes in the specific embodiments and application scope according to the idea of the present application, and in summary, the present disclosure should not be construed as limiting the present application, and the scope of the present disclosure should be defined by the claims. It will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the spirit and scope of the invention, and such modifications and adaptations are intended to be comprehended within the scope of the invention.
Claims (10)
1. The preparation method of the graphene oxide grafted modified polyamide composite material is characterized by comprising the following steps of:
s1: adding phenyl phosphoryl dichloride into a solvent, then adding diamine and organic base under the protection of nitrogen or argon, and carrying out reflux reaction to obtain an intermediate product 1 after the reaction is finished; heating the obtained intermediate product 1 and anhydride to react to obtain a polymerization product 2;
s2: taking graphene oxide dispersion liquid 1, and then adding the polymerization product 2 in the step S1 into the graphene oxide dispersion liquid 1 to obtain dispersion liquid 2;
s3: adding a silane coupling agent into the dispersion liquid 2 in the step S2, and heating for reaction to obtain a graphene oxide grafted modified polyamide composite material after the reaction is finished;
in the step S1, the molar ratio of the phenyl phosphoryl dichloride to the diamine is 1:2-2.2; the molar ratio of the phenyl phosphoryl dichloride to the organic base is 1:2-2.2; the molar ratio of the intermediate product 1 to the anhydride is 1:2-2.2; the diamine comprises one or more of butanediamine, pentanediamine, hexanediamine and p-phenylenediamine; the organic base comprises one or more of trimethylamine, triethylamine, pyridine and 4-dimethylaminopyridine; the anhydride comprises one or more of succinic anhydride, glutaric anhydride and adipic anhydride.
2. The method for preparing a graphene oxide grafted modified polyamide composite material according to claim 1, wherein in the step S1, the solvent comprises one or more of 1, 2-dichloroethane, chloroform, chlorobenzene, and tetrahydrofuran.
3. The method for preparing a graphene oxide grafted modified polyamide composite material according to claim 1, wherein in the step S1, the condition of the reflux reaction is: reflux reaction is carried out for 1.5-2.5h at 85-95 ℃.
4. The method for preparing a graphene oxide grafted modified polyamide composite material according to claim 1, wherein in the step S1, the reaction conditions of the heating reaction of the obtained intermediate product 1 and the acid anhydride are as follows: the reaction was stirred at 65-75℃for 7-9h to give polymer 2.
5. The method for preparing the graphene oxide grafted modified polyamide composite material according to claim 1, wherein in the step S2: the solvent in the graphene oxide dispersion liquid 1 consists of deionized water and ethanol, wherein the volume ratio of the deionized water to the ethanol is 1:1, the size of the graphene oxide is 10-15um, and the carbon-oxygen ratio is 3-5.
6. The method for preparing a graphene oxide grafted modified polyamide composite material according to claim 1, wherein in the step S3, the silane coupling agent comprises one or more of KH550, KH560, KH570, KH792, DL 602;
and/or, before the silane coupling agent is added to the dispersion liquid 2 in the step S2, the method further comprises: adding a silane coupling agent into absolute ethyl alcohol, and then adding the silane coupling agent into the dispersion liquid 2 in the step S2;
and/or adding the silane coupling agent into the dispersion liquid 2 in the step S2 in a dropwise adding mode, keeping constant stirring in the dropwise adding process, controlling the temperature at 45-55 ℃, and after the dropwise adding is finished, adjusting the temperature to 65-75 ℃ to continue to react for 2-4 hours to obtain the graphene oxide grafted modified polyamide composite material.
7. The graphene oxide grafted modified polyamide composite material prepared by the preparation method according to any one of claims 1 to 6.
8. The preparation method of the graphene oxide grafted modified polyamide fabric is characterized by comprising the steps of drying a graphene oxide grafted modified polyamide composite material prepared by the preparation method according to any one of claims 1 to 6 in vacuum, placing the dried graphene oxide grafted modified polyamide composite material in a double-screw melt machine for melt spinning, and obtaining graphene oxide grafted modified polyamide fibers, wherein the melt spinning temperature is selected to be 250-300 ℃, the continuous spinning speed is 3000 m/min, and the draft multiple is 3 times; and weaving the graphene oxide grafted modified polyamide fiber to obtain the graphene oxide grafted modified polyamide fabric.
9. The preparation method of the graphene oxide grafted modified polyamide fabric according to claim 8, wherein after the melt is discharged from a spinneret, oiling is performed through an oil nozzle, and then thermal drafting is performed through a hot roller with the temperature of 100-140 ℃ to obtain graphene oxide grafted modified polyamide fiber, and then the obtained graphene oxide grafted modified polyamide fiber is woven to obtain the graphene oxide grafted modified polyamide fabric; wherein the oil in the oil tank is a white oil aqueous solution with the mass fraction of 10-20%, a reducing agent is added in the oil, and the mass fraction of the reducing agent in the oil is 8-12%; the reducing agent comprises one or more of sodium borohydride, sodium citrate and ascorbic acid.
10. The graphene oxide grafted modified polyamide fiber and/or the graphene oxide grafted modified polyamide fabric and/or the graphene-graphene oxide grafted modified polyamide fiber and/or the graphene-graphene oxide grafted modified polyamide fabric prepared by the preparation method according to any one of claims 8 to 9.
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