CN104562705A - Macromolecule functionalized fiber material and synthesis method thereof - Google Patents
Macromolecule functionalized fiber material and synthesis method thereof Download PDFInfo
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- CN104562705A CN104562705A CN201410770371.8A CN201410770371A CN104562705A CN 104562705 A CN104562705 A CN 104562705A CN 201410770371 A CN201410770371 A CN 201410770371A CN 104562705 A CN104562705 A CN 104562705A
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- 229920002521 macromolecule Polymers 0.000 title claims abstract description 26
- 239000002657 fibrous material Substances 0.000 title claims abstract description 13
- 238000001308 synthesis method Methods 0.000 title abstract 4
- 229920002972 Acrylic fiber Polymers 0.000 claims abstract description 30
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 13
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 12
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 7
- 239000000835 fiber Substances 0.000 claims description 42
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 claims description 17
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 16
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 12
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 11
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 claims description 11
- 150000007529 inorganic bases Chemical class 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- -1 polyhexamethylene Polymers 0.000 claims description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- UCMIRNVEIXFBKS-UHFFFAOYSA-N beta-alanine Chemical compound NCCC(O)=O UCMIRNVEIXFBKS-UHFFFAOYSA-N 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 150000001413 amino acids Chemical class 0.000 claims description 7
- 150000002605 large molecules Chemical class 0.000 claims description 7
- 239000011159 matrix material Substances 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- 239000002801 charged material Substances 0.000 claims description 6
- 229960000583 acetic acid Drugs 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 229940000635 beta-alanine Drugs 0.000 claims description 4
- 229960003692 gamma aminobutyric acid Drugs 0.000 claims description 4
- BTCSSZJGUNDROE-UHFFFAOYSA-N gamma-aminobutyric acid Chemical compound NCCCC(O)=O BTCSSZJGUNDROE-UHFFFAOYSA-N 0.000 claims description 4
- 229940072033 potash Drugs 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 235000015320 potassium carbonate Nutrition 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- VAZJLPXFVQHDFB-UHFFFAOYSA-N 1-(diaminomethylidene)-2-hexylguanidine Polymers CCCCCCN=C(N)N=C(N)N VAZJLPXFVQHDFB-UHFFFAOYSA-N 0.000 claims description 3
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical group C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 3
- 229920002413 Polyhexanide Polymers 0.000 claims description 3
- 108010039918 Polylysine Proteins 0.000 claims description 3
- 229920000656 polylysine Polymers 0.000 claims description 3
- 229960001124 trientine Drugs 0.000 claims description 3
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 claims description 2
- 229920000768 polyamine Polymers 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 4
- 238000005342 ion exchange Methods 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 241000894006 Bacteria Species 0.000 abstract 1
- 230000004071 biological effect Effects 0.000 abstract 1
- 230000009920 chelation Effects 0.000 abstract 1
- 230000007613 environmental effect Effects 0.000 abstract 1
- 238000010189 synthetic method Methods 0.000 description 10
- 239000000047 product Substances 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 5
- 230000000844 anti-bacterial effect Effects 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- BPYKTIZUTYGOLE-IFADSCNNSA-N Bilirubin Chemical compound N1C(=O)C(C)=C(C=C)\C1=C\C1=C(C)C(CCC(O)=O)=C(CC2=C(C(C)=C(\C=C/3C(=C(C=C)C(=O)N\3)C)N2)CCC(O)=O)N1 BPYKTIZUTYGOLE-IFADSCNNSA-N 0.000 description 4
- 229920002472 Starch Polymers 0.000 description 4
- 230000003115 biocidal effect Effects 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 235000019698 starch Nutrition 0.000 description 4
- 239000008107 starch Substances 0.000 description 4
- 239000004753 textile Substances 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 229920002873 Polyethylenimine Polymers 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 229910001385 heavy metal Inorganic materials 0.000 description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- KDXKERNSBIXSRK-RXMQYKEDSA-N D-lysine Chemical compound NCCCC[C@@H](N)C(O)=O KDXKERNSBIXSRK-RXMQYKEDSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000009940 knitting Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000012552 review Methods 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 229940123208 Biguanide Drugs 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- 108700005077 Viral Genes Proteins 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000005349 anion exchange Methods 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 150000004283 biguanides Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- SFZULDYEOVSIKM-UHFFFAOYSA-N chembl321317 Chemical group C1=CC(C(=N)NO)=CC=C1C1=CC=C(C=2C=CC(=CC=2)C(=N)NO)O1 SFZULDYEOVSIKM-UHFFFAOYSA-N 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 230000003013 cytotoxicity Effects 0.000 description 1
- 231100000135 cytotoxicity Toxicity 0.000 description 1
- 230000001877 deodorizing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 231100000584 environmental toxicity Toxicity 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 235000019796 monopotassium phosphate Nutrition 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000000505 pernicious effect Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
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- 230000001681 protective effect Effects 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
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- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000003578 releasing effect Effects 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000001890 transfection Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
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Landscapes
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The invention discloses a macromolecule functionalized fiber material and a synthesis method thereof, and belongs to the technical field of macromolecule materials. According to the synthesis method, a macromolecular compound with amino is bonded to modified acrylic fiber with carboxyl through chemical bonding of carboxyl and amino, and a novel material with functions such as ion exchange, chelation and bacterium resistance is prepared. The synthesis method disclosed by the invention is environmental friendly, simple and convenient to operate, gentle in condition, beneficial to maintain chemical activity and biological activity of macromolecules, good in morphology and strength in product, remarkable in grafting amount and high in practical value.
Description
Technical field
The present invention relates to a kind of fibrous material and synthetic method thereof, particularly relate to a kind of fibrous material and synthetic method thereof of large molecules functionalize, belong to technical field of polymer materials.
Background technology
Functional fibre material has many-sided important purposes, as ion-exchange, chelating, reaction, catalysis, slowly-releasing, antibacterial and deodorizing, fire-retardant, antistatic, radiation proof etc.Acrylic fiber is the important matrix material of complex functionality fiber, it forms primarily of acrylonitrile polymerization, can be there is the reactions such as hydration, hydrolysis, addition, reduction in a large amount of cyano group contained in structure, the carboxyl being formed or introduce, amidoxime group, amino etc. can carry out chemical graft again and introduce new group and structure.
The macromolecular compounds such as polyvinylamine, polymine, PAH, shitosan, polylysine, polyhexamethylene list guanidine, poly hexamethylene biguanide are with functional groups such as amino, guanidine radicals, there is special chemism and biologically active, and physiological-toxicity and environmental toxicity little, there is important research and practical value.With this type of large molecule, functional modification is carried out to macromolecular material etc., significant effect can be played, such as: document " synthesis of starch-grafted polyvinylamine trapping agent and absorption property " (investigation of materials and application, 4th phase in 2012) copolymer of first synthetic starch and acrylamide, again through the copolymer of Hofmann degraded synthetic starch grafted polyethylene amine, heavy metal ion demonstrates good trapping ability.Chinese patent CN200710056397.6 " a kind of heavy metal ion adsorbed film and preparation method " introduces amine based polymer (polyvinylamine, PAH or branched polyethylene imine) in polyvinyl alcohol water solution, by being cross-linked to form Space network of polymer, the adsorption capacity of heavy metal ion improves a lot.Chinese patent CN02129051.2 " a kind of chelating function fiber and synthetic method " through acrylic fibers hydrolysis, introducing metal ion " bridge ", coating polymine, chemical crosslinking and transition, obtains the chelate fibre with good adsorption function successively.Document " application of shitosan in finishing functions of textile fabrics " (weaving Leader, o. 11th in 2005) review shitosan in antibacterial textile, wrinkle resistant, the antistatic and application that improves in dyeability, and to the bonding mechanism of shitosan and each kind fabric and after arranging fabric there is functional reason analyze.(Chinese science B collects document " development of poly-D-lysine starch nanometer granule genophore and application "; 6th phase in 2004) with poly-D-lysine, crosslinked starch nano particle is modified; as non-viral gene vector, have that gene useful load is large, transfection efficiency is high, cytotoxicity is low and the advantage such as biodegradable.Document " guanidine compound application on the textile " (dyeing and finishing technique, the 8th phase in 2007) reviews the application of guanidine compound on textile fabric arranges, and wherein polyhexamethylene list guanidine/biguanides etc. have the advantages such as toxicity is low, antibacterial effect is remarkable.Document " containing the synthesis of guanidine radicals cross-linking polyvinyl alcohol and to Adsorption of The Bilirubin research " (SCI; 6th phase in 1999) by immobilized for guanidine radicals on Cross-linked Polyvinylalcohol Gel, the adsorbent obtained has good absorption property to bilirubin.
The present invention adopts specific modified acrylic fibres to be matrix material, by comparatively simply reacting the grafting amount making large molecule reach considerable on fiber, having significant functionalization effect, not yet having identical report at present.
Summary of the invention
The fibrous material of the large molecules functionalize that the object of the present invention is to provide a class novel; Be again to provide a kind of raw material to be easy to get, the synthetic method of this kind of easy and simple to handle, environmentally friendly fibrous material.
For realizing object of the present invention, technical scheme is: with the modified acrylic fibres with carboxyl for matrix material, utilize the chemical bonding between carboxyl and amino, macromolecular compound with amino (primary amino radical, secondary amino group or guanidine radicals) is grafted to fiber surface, grafting weight gaining rate is 5-20%, forms a kind of fibrous material of novel large molecules functionalize.
The chemical reaction (fragment) that macromolecular compound is bonded to fiber surface illustrates that route is as follows:
Synthetic method detailed process provided by the invention is: be immersed in by modified acrylic fibres in the solution of macromolecular compound, and in 70-130 DEG C of reaction 0.5-5h, product fiber washed with de-ionized water, dries at 40-70 DEG C; Charged material weight compares: fiber: macromolecular compound: solvent=1:0.1-1:10-50; The macromolecular compound adopted is selected from polyvinylamine, polymine, PAH, shitosan, polylysine, polyhexamethylene list guanidine and poly hexamethylene biguanide, and molecular weight is 0.1-10 ten thousand; The solvent adopted is selected from water, ethanol, isopropyl alcohol, ethylene glycol, propylene glycol and glycerol.
The matrix material adopted in above-mentioned synthetic method is namely with the modified acrylic fibres of carboxyl, take acrylic fiber as raw material, the method synthesis of reference literature 1-" acrylic fiber Complex Function research in aqueous " (Annual Conference proceeding-Green Chemistry branch of Chinese Chemical Society 2014) or document 2-" amino acid functionalised fibrous material and synthetic method thereof " (Chinese patent CN201110229789.4) obtains, concrete synthetic method is: the method for (1) reference literature 1, acrylic fiber is immersed in the aqueous solution being dissolved with amino-compound and inorganic base, in 80-100 DEG C of reaction 1-4h, product fiber washed with de-ionized water, dry at 40-70 DEG C, charged material weight compares: acrylic fiber: amino-compound: inorganic base: water=1:0.1-1:0.1-1:10-50, amino-compound is selected from amion acetic acid, Beta-alanine, GABA, diethylenetriamine, triethylene tetramine or polyethylene polyamine, inorganic base is selected from NaOH, potassium hydroxide, sodium carbonate or potash, (2) method of reference literature 2, is immersed in acrylic fiber and is dissolved with in amino acid and inorganic alkali alcosol, and in 90 DEG C-140 DEG C reaction 1-10h, product fiber washed with de-ionized water, dries at 40-70 DEG C, charged material weight compares: acrylic fiber: amino acid: inorganic base: solvent=1:1-10:0.5-10:10-50, amino acid is selected from amion acetic acid, Beta-alanine, GABA or iminodiacetic acid, inorganic base is selected from NaOH, potassium hydroxide, sodium carbonate or potash, solvent is selected from ethylene glycol, glycerol or propylene glycol.The above-mentioned raw material acrylic fiber for the synthesis of matrix material is that length is 2 ~ 10cm, fiber number is the commodity acrylic fiber containing more than 90% acrylonitrile unit in 1 ~ 5dtex, fibrous molecular structure.
Beneficial effect of the present invention is: (1) the present invention utilizes carboxyl and amino chemical bonding, by better simply single step reaction, macromolecular compound is grafted on fiber, building-up process is easy, mild condition, be conducive to keeping macromolecular chemism and biologically active; (2) fibrous material has that mechanical strength is good, groups density is high, specific area is processed into the advantages such as multi-form greatly, easily, is conducive to realizing applying widely; (3) the present invention adopts the specific modified acrylic fibres with carboxyl as matrix material, compared with the general fiber without special treatment, bonding is firm not only and between macromolecular compound, and grafting amount is large, has significant ion-exchange, chelating, the function such as antibacterial; (4) new material synthesized by the present invention has a good application prospect: the ion-exchange and the chelating function that utilize the groups such as amino, guanidine radicals, can purify or metal ion, acid ion and organic molecule etc. in enrichment water; Utilize the acid of group, alkalescence and reactivity can purify the pernicious gas such as hydrogen chloride, hydrogen sulfide, ammonia, formaldehyde eliminated in air; Utilize the macromolecular antibacterial activity of institute's grafting, can be used for manufacturing medical supplies and protective articles etc.; (5) raw material acrylic fiber of the present invention itself has good mechanical strength, and the reaction condition that adopts is gentle, be easy to control, to fibre structure and strength failure little, product can keep good form and intensity; (6) chemical raw material of the present invention is nontoxic or low toxicity raw material, and course of reaction Raw consumption is less, and does not have harmful by-products to generate, and is a kind of environmentally friendly synthetic method.
Detailed description of the invention
For the present invention is described in detail better, as follows for embodiment:
Embodiment 1:
Take 10g acrylic fiber, be immersed in the solution be made into by 5g triethylene tetramine, 1.5g NaOH and 150g deionized water, 90 DEG C add thermal response 2h, be hydrolyzed/grafting is composite modified, product fiber washed with de-ionized water, 50 DEG C of oven dry, obtain lurid modified acrylic fibres (F-1) 11.53g.
Take the F-1 fiber 2g of above-mentioned synthesis, be immersed in the solution be made into by 3g polymine (mean molecule quantity is 3000) and 50g ethylene glycol, 120 DEG C add thermal response 2h, product fiber washed with de-ionized water, 50 DEG C of oven dry, obtain fiber (F-2) 2.26g of lurid grafting polyethylene imine, grafting weight gaining rate is 13%.
, embodiment 2:
Take the F-1 fiber 2g that embodiment 1 is synthesized, be immersed in the solution that 5g polyhexamethylene list guanidine (mean molecule quantity is 2000) and 100g deionized water be made into, 80 DEG C add thermal response 1.5h, product fiber washed with de-ionized water, 50 DEG C of oven dry, obtain fiber (F-2) 2.30g of lurid grafting polyhexamethylene list guanidine, grafting weight gaining rate is 15%.
Application examples 1:
Take the F-2 fiber 0.1g that embodiment 1 is synthesized, dropping into 25mL copper ion concentration is in the copper chloride solution of 200ppm, constant temperature 25 DEG C fully vibrates absorption, recording F-2 fiber to the adsorbance of copper ion is 37.6mg/g fiber, fiber becomes blueness from light yellow, shows that this fiber has good chelating adsorption function.
Application examples 2:
Take the F-2 fiber 0.1g that embodiment 1 is synthesized, after 0.1M HCl treatment, cleaning, drying, dropping into 25mL phosphate concentration is in the potassium dihydrogen phosphate aqueous solution of 500ppm, constant temperature 25 DEG C fully vibrates absorption, recording F-2 fiber to the adsorbance of phosphate radical is 75.3mg/g fiber, shows that this fiber has good anion exchange function.
Application examples 3:
Take the F-2 fiber 0.1g that embodiment 1 is synthesized, after 0.1M HCl treatment, cleaning, drying, dropping into 25mL fluorinion concentration is in the sodium fluoride aqueous solution of 10ppm, constant temperature 25 DEG C fully vibrates absorption, recording F-2 fiber to the adsorbance of fluorine ion is 1.27mg/g fiber, shows that this fiber also has obvious adsorption effect to the fluorine ion of more difficult removal.
Application examples 4:
Take the F-2 fiber 0.1g that embodiment 1 is synthesized, according in " FZT 73023-2006 antibiosis knitting product " " D.8 antibiosis knitting thing method of testing: succusion ", record and 99.9% is reached to the antibiotic rate of staphylococcus aureus, show that this fiber has the application prospect as anti-biotic material.
Claims (3)
1. the fibrous material of large molecules functionalize, it is characterized in that, with the modified acrylic fibres with carboxyl for matrix material, being surface-functionalized layer with the macromolecular compound of amino, by the chemical bonding between carboxyl and amino, macromolecular compound is grafted on fiber surface securely, and grafting weight gaining rate is 5-20%; Macromolecular compound is selected from polyvinylamine, polymine, PAH, shitosan, polylysine, polyhexamethylene list guanidine or the poly hexamethylene biguanide that molecular weight is 0.1-10 ten thousand.
2. synthesize the method for fibrous material as claimed in claim 1, it is characterized in that, the modified acrylic fibres with carboxyl is immersed in the solution with the macromolecular compound of amino, in 70-130 DEG C of reaction 0.5-5h, product fiber washed with de-ionized water, dries at 40-70 DEG C; Reactant charged material weight ratio is: modified acrylic fibres: macromolecular compound: solvent=1:0.1-1:10-50; Solvent is selected from water, ethanol, isopropyl alcohol, ethylene glycol, propylene glycol and glycerol.
3. the method for synthetic macromolecule functional fiber material as claimed in claim 2, it is characterized in that, the described modified acrylic fibres with carboxyl synthesizes by the following method: take acrylic fiber as raw material, be immersed in the aqueous solution being dissolved with amino-compound and inorganic base, in 80-100 DEG C of reaction 1-4h, product fiber washed with de-ionized water, dries at 40-70 DEG C; Charged material weight compares: acrylic fiber: amino-compound: inorganic base: water=1:0.1-1:0.1-1:10-50; Amino-compound is selected from amion acetic acid, Beta-alanine, GABA, diethylenetriamine, triethylene tetramine or polyethylene polyamine; Inorganic base is selected from NaOH, potassium hydroxide, sodium carbonate or potash;
Or the described modified acrylic fibres with carboxyl synthesizes by the following method: take acrylic fiber as raw material, be immersed in and be dissolved with in amino acid and inorganic alkali alcosol, in 90 DEG C-140 DEG C reaction 1-10h, product fiber washed with de-ionized water, dries at 40-70 DEG C; Charged material weight compares: acrylic fiber: amino acid: inorganic base: solvent=1:1-10:0.5-10:10-50; Amino acid is selected from amion acetic acid, Beta-alanine, GABA or iminodiacetic acid; Inorganic base is selected from NaOH, potassium hydroxide, sodium carbonate or potash; Solvent is selected from ethylene glycol, glycerol or propylene glycol;
The described acrylic fiber as raw material is length is 2 ~ 10cm, fiber number is the commodity acrylic fiber containing more than 90% acrylonitrile unit in 1 ~ 5dtex, structure.
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