CN112252033B - 一种接枝改性抗菌植物纤维材料及其制备方法 - Google Patents
一种接枝改性抗菌植物纤维材料及其制备方法 Download PDFInfo
- Publication number
- CN112252033B CN112252033B CN202011167713.9A CN202011167713A CN112252033B CN 112252033 B CN112252033 B CN 112252033B CN 202011167713 A CN202011167713 A CN 202011167713A CN 112252033 B CN112252033 B CN 112252033B
- Authority
- CN
- China
- Prior art keywords
- plant fiber
- antibacterial
- plant
- fiber material
- diphenyl ether
- 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.)
- Active
Links
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 67
- 239000002657 fibrous material Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000000835 fiber Substances 0.000 claims abstract description 105
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000003242 anti bacterial agent Substances 0.000 claims abstract description 22
- -1 hydroxyl diphenyl ether Chemical compound 0.000 claims abstract description 21
- 150000001350 alkyl halides Chemical class 0.000 claims abstract description 11
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 11
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000004480 active ingredient Substances 0.000 claims abstract description 8
- 239000007800 oxidant agent Substances 0.000 claims abstract description 8
- 241000196324 Embryophyta Species 0.000 claims description 93
- 239000000243 solution Substances 0.000 claims description 36
- 238000002791 soaking Methods 0.000 claims description 19
- 238000005406 washing Methods 0.000 claims description 18
- 235000004431 Linum usitatissimum Nutrition 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 16
- 239000007864 aqueous solution Substances 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- 238000001914 filtration Methods 0.000 claims description 13
- 125000002887 hydroxy group Polymers [H]O* 0.000 claims description 12
- 239000003513 alkali Substances 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 11
- DUYCTCQXNHFCSJ-UHFFFAOYSA-N dtpmp Chemical compound OP(=O)(O)CN(CP(O)(O)=O)CCN(CP(O)(=O)O)CCN(CP(O)(O)=O)CP(O)(O)=O DUYCTCQXNHFCSJ-UHFFFAOYSA-N 0.000 claims description 10
- 229940090960 diethylenetriamine pentamethylene phosphonic acid Drugs 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 230000001590 oxidative effect Effects 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 235000013312 flour Nutrition 0.000 claims description 4
- 244000198134 Agave sisalana Species 0.000 claims description 3
- 240000000491 Corchorus aestuans Species 0.000 claims description 3
- 235000011777 Corchorus aestuans Nutrition 0.000 claims description 3
- 235000010862 Corchorus capsularis Nutrition 0.000 claims description 3
- 240000007594 Oryza sativa Species 0.000 claims description 3
- 235000007164 Oryza sativa Nutrition 0.000 claims description 3
- 230000003213 activating effect Effects 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 230000004048 modification Effects 0.000 claims description 3
- 238000012986 modification Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 235000009566 rice Nutrition 0.000 claims description 3
- 241000609240 Ambelania acida Species 0.000 claims description 2
- KGGZEVXYIAMNCG-UHFFFAOYSA-N OP(O)=O.N.N.N Chemical compound OP(O)=O.N.N.N KGGZEVXYIAMNCG-UHFFFAOYSA-N 0.000 claims description 2
- 239000010905 bagasse Substances 0.000 claims description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims description 2
- 239000010902 straw Substances 0.000 claims description 2
- 238000002604 ultrasonography Methods 0.000 claims description 2
- 239000002023 wood Substances 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 6
- 240000006240 Linum usitatissimum Species 0.000 claims 1
- 238000005956 quaternization reaction Methods 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 3
- 230000007246 mechanism Effects 0.000 abstract description 3
- 230000001954 sterilising effect Effects 0.000 abstract description 3
- 238000004659 sterilization and disinfection Methods 0.000 abstract description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 21
- 241000208202 Linaceae Species 0.000 description 17
- 244000025254 Cannabis sativa Species 0.000 description 13
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 13
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 13
- 235000009120 camo Nutrition 0.000 description 13
- 235000005607 chanvre indien Nutrition 0.000 description 13
- 239000011487 hemp Substances 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 12
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 12
- 229940050176 methyl chloride Drugs 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- JQWHASGSAFIOCM-UHFFFAOYSA-M sodium periodate Chemical compound [Na+].[O-]I(=O)(=O)=O JQWHASGSAFIOCM-UHFFFAOYSA-M 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000004753 textile Substances 0.000 description 4
- 241000894006 Bacteria Species 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- XEFQLINVKFYRCS-UHFFFAOYSA-N Triclosan Chemical compound OC1=CC(Cl)=CC=C1OC1=CC=C(Cl)C=C1Cl XEFQLINVKFYRCS-UHFFFAOYSA-N 0.000 description 3
- 230000001580 bacterial effect Effects 0.000 description 3
- 239000001913 cellulose Substances 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 125000001453 quaternary ammonium group Chemical group 0.000 description 3
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical group NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 2
- 241000588724 Escherichia coli Species 0.000 description 2
- 229920002488 Hemicellulose Polymers 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 2
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000001963 growth medium Substances 0.000 description 2
- 229920005610 lignin Polymers 0.000 description 2
- 239000006916 nutrient agar Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000011112 process operation Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- VFKZECOCJCGZQK-UHFFFAOYSA-M 3-hydroxypropyl(trimethyl)azanium;chloride Chemical group [Cl-].C[N+](C)(C)CCCO VFKZECOCJCGZQK-UHFFFAOYSA-M 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- 244000062175 Fittonia argyroneura Species 0.000 description 1
- 240000000907 Musa textilis Species 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000003113 alkalizing effect Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229940102396 methyl bromide Drugs 0.000 description 1
- 210000001724 microfibril Anatomy 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- KHIWWQKSHDUIBK-UHFFFAOYSA-N periodic acid Chemical compound OI(=O)(=O)=O KHIWWQKSHDUIBK-UHFFFAOYSA-N 0.000 description 1
- 239000000419 plant extract Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 208000017520 skin disease Diseases 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229960001124 trientine Drugs 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/165—Ethers
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/07—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof
- D06M11/30—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof with oxides of halogens, oxyacids of halogens or their salts, e.g. with perchlorates
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
- D06M11/38—Oxides or hydroxides of elements of Groups 1 or 11 of the Periodic Table
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/08—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with halogenated hydrocarbons
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
- D06M13/282—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing phosphorus
- D06M13/288—Phosphonic or phosphonous acids or derivatives thereof
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/04—Vegetal fibres
- D06M2101/06—Vegetal fibres cellulosic
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Biochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Microbiology (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
一种接枝改性抗菌植物纤维材料及其制备方法,所述抗菌植物纤维材料上接枝有季铵盐抗菌活性成分和多卤羟基二苯醚抗菌活性成分。本发明将植物纤维与含膦酸三胺反应,用卤代烷进行季铵化来提高表面的荷电性和疏水性,然后用氧化剂氧化植物纤维,氧化的植物纤维再与多卤羟基二苯醚类抗菌剂,最后制备出同时具有季铵盐类抗菌剂和多卤羟基二苯醚类抗菌剂双重杀菌机理的抗菌植物纤维,两种抗菌剂彼此发挥写了协同作用,使接枝改性的抗菌植物纤维具有更强的杀菌能力,抗菌效果更持久、高效。本发明制备工艺绿色环保,简单且易控制,所制备的抗菌植物纤维材料对人体无害,适合工业化生产。
Description
技术领域
本发明属于抗菌材料及纤维改性技术领域,具体的本发明涉及一种接枝改性抗菌植物纤维材料及其制备方法。
背景技术
天然植物纤维是由植物的种子、果实、茎、叶等处理得到的纤维,从植物韧皮得到的纤维如亚麻、黄麻、罗布麻,从植物的叶上得到的纤维如剑麻、蕉麻。植物纤维的主要化学成分是纤维素,故也称纤维素纤维。植物纤维来源广泛、价格低廉,绿色环保可降解,是非常优秀的天然纺织原料。然而,纺织品疏松多孔,日常生活使用过程中极易成为众多细菌传播的载体,纺织品上滋生的细菌不仅能导致纤维制品发生变色、发霉、脆化降解,而且会对人体皮肤产生异常的刺激并可能诱发皮肤疾病,影响人体健康。随着科学进步及人类生活水平的提高,人们对纺织品的抗菌性能提出了更高的要求,纤维抗菌化变得越来越有必要。纤维抗菌化是采用物理或化学的方法将具有能够抑制细菌生长的物质引入纤维表面或内部而成的,抗菌剂不仅能在纤维上不易脱落而且能通过纤维内部平衡扩散,保持持久的抗菌效果。
如专利CN201910402270.8公开了一种纳米抗菌麻类纤维及其制备方法和应用,纳米抗菌麻类纤维由麻类纤维经银离子溶液浸泡后,与工业大麻花叶植物提取液反应后获得。该专利以银离子溶液为银源先驱体,采用植物提取液为生物还原剂,在麻类纤维吸附银离子后,利用工业大麻花叶植物提取液原位还原银离子并在纤维表面或内部生长出纳米银颗粒,这种抗菌纤维虽然具有快速的杀菌能力,但随着材料中银颗粒的消耗殆尽,最终材料丧失抗菌能力,不具有永久的抗菌性。专利CN201810820352.X公开一种汉麻抗菌纤维材料及其应用,汉麻纤维大分子链上接枝有季铵抗菌功能基团,所述季铵抗菌功能基团为共价连接有羟基丙基三甲基氯化铵基的三乙烯四胺基团,所述汉麻抗菌纤维材料中,C元素含量为40~50%,O元素含量为30~40%,H元素含量为5~10%,N元素含量为2~5%;专利CN201810820351.5公开了一种汉麻抗菌纤维材料制备方法,包括先将汉麻原纤维碱化、氧化;再将麻纤与三乙烯四胺反应,得到胺化麻纤;最后与环氧丙基三甲基卤化铵反应,得到含季铵抗菌功能基团的汉麻抗菌纤维材料,上述专利所得抗菌纤维不具有持久抗菌性,存在长久防止或者水冲洗后抗菌效果不理想的问题。
综上,非常有必要开发一种具有长期抗菌性能,且抗菌效果理想的植物纤维材料。
发明内容
为了解决上述技术问题,本发明将植物纤维与含膦酸三胺反应,用卤代烷进行季铵化来提高表面的荷电性和疏水性,然后用氧化剂氧化植物纤维,利用氧化的植物纤维上的醛基再与多卤羟基二苯醚类抗菌剂上的酚羟基反应,最后制备出同时具有季铵盐类抗菌剂和多卤羟基二苯醚类抗菌剂特点的双重抗菌植物纤维,这种抗菌植物纤维具有持久、高效抗菌效果。
一种接枝改性抗菌植物纤维材料,所述抗菌植物纤维材料上接枝有季铵盐抗菌活性成分和多卤羟基二苯醚抗菌活性成分。
所述季铵盐抗菌活性成分是用膦酸三胺胺化后的植物纤维和卤代烷反应得到,所述多卤羟基二苯醚抗菌活性成分是氧化后的植物纤维和多卤羟基二苯醚类抗菌剂反应得到。
所述膦酸三胺选自二乙烯三胺五甲叉膦酸、二己烯三胺五甲叉膦酸中的至少一种。
所述多卤羟基二苯醚类抗菌剂选自4,4'-二氯-2-羟基二苯醚、2,4,4-三氯-2-羟基二苯醚、5-氯-2-(2,4-二氯苯氧基)苯酚中的至少一种。
所述接枝季铵盐抗菌活性成分是通过将植物纤维以重量比例5-20:100浸泡于浓度为20-50wt%的膦酸三胺水溶液中,所得胺化植物纤维再以重量比例5-20:100浸泡于浓度为60-80wt%的卤代胺溶液中反应获得。
所述接枝多卤羟基二苯醚抗菌活性成分是通过将氧化后的植物纤维以重量比5-20:100浸泡于浓度为30-70wt%的多卤羟基二苯醚类抗菌剂溶液中反应获得。
所述植物纤维包括黄麻、剑麻、亚麻、木粉、甘蔗渣、稻壳粉、稻草粉中的至少一种。
一种抗菌植物纤维材料的制备方法,包括如下步骤:
S1、活化植物纤维:对植物纤维进行碱处理,得预处理植物纤维;
S2、季铵化植物纤维:将预处理植物纤维浸泡在含膦酸三胺水溶液中,在超声、加热条件下反应,然后降温、过滤、洗涤、烘干得胺化植物纤维;将胺化植物纤维浸泡在卤代烷溶液中,升温在搅拌条件下反应,最后降温、过滤、洗涤、烘干得季铵化植物纤维;
S3、醚化植物纤维:将步骤S2所得植物纤维用氧化剂氧化,氧化后的植物纤维与多卤羟基二苯醚类抗菌剂反应得抗菌植物纤维材料。
步骤S1所述碱处理为本领域熟知的植物纤维处理方法:将植物纤维浸泡在碱溶液中,恒温反应一段时间,过滤、洗涤、烘干。植物纤维是一种以木质素和半纤维素为基体、纤维素微纤丝为增强体的复合材料,这些主要成分的表面上有大量的极性羟基和酚羟基官能团,但植物纤维在不经任何处理的情况下,官能团彼此包埋,羟基和酚羟基官能团不具有活性。碱处理过程是一个纤维素、半纤维素及木质素的溶解和降解的过程,经碱处理的植物纤维上的极性基团暴露于纤维表面,表现出很大的活性。
所述碱溶液溶质包括但不限于氢氧化钠、氢氧化钾中的至少一种;所述碱液的质量分数为15-30wt%,所述植物纤维与碱液的质量比为1:30-80,反应温度为20-40℃,反应时间为30-120min。
步骤S2所述季铵化植物纤维为以重量比例5-20:100将步骤S1所得预处理植物纤维浸泡于浓度为30-60wt%的含膦酸三胺水溶液中,超声功率为60-80Hz,加热温度为70-100℃,反应时间为2-4h,降温温度为20-30℃。所述卤代烷选自氯甲烷、溴甲烷、氯甲苯中的至少一种。其中,所述卤代烷溶液的溶剂为本领域常用即可,包括但不限于DMSO、乙醇、异丙醇中的至少一种。
步骤S3所述氧化植物纤维为本领域熟知工艺,具体为将植物纤维以重量比例1-5:100浸泡于浓度为10-40g/L的氧化剂水溶液中,升温至40-70℃反应1-5h,过滤、洗涤、烘干即得氧化植物纤维。步骤S3所述氧化剂为没有特别的限制,本领域常用的高碘酸盐溶液即可,包括但不限于高碘酸钠溶液。
步骤S3所醚化植物纤维具体的为将氧化后的植物纤维以比例5-20:100浸入浓度为30-70wt%的多卤羟基二苯醚类抗菌剂溶液中,升温至30-80℃并搅拌,向混合物中滴加1-5wt%的碱液,反应3-8h结束后降温至室温,过滤、洗涤、烘干即得所述抗菌植物纤维材料。其中,所述多卤羟基二苯醚类抗菌剂溶液的溶剂包括四氯化碳、苯中的至少一种;所述碱液没有特别限制,本领域常用即可,包括但不限于氢氧化钠、氢氧化钡、氢氧化钙水溶液中的至少一种。
与现有技术相比,本发明的有益效果是:
本发明将植物纤维与含膦酸三胺反应,用卤代烷进行季铵化来提高表面的荷电性和疏水性,然后用氧化剂氧化植物纤维,氧化的植物纤维再与多卤羟基二苯醚类抗菌剂,最后制备出同时具有季铵盐类抗菌剂和多卤羟基二苯醚类抗菌剂双重杀菌机理的抗菌植物纤维,两种抗菌剂彼此发挥写了协同作用,使接枝改性的抗菌植物纤维具有更强的杀菌能力,抗菌效果更持久、高效。
本发明制备工艺绿色环保,简单且易控制,所制备的抗菌植物纤维材料对人体无害,适合工业化生产。
具体实施方式
下面结合具体实施例对本发明作进一步的说明,但并不局限于说明书上的内容。若无特殊说明,本发明实施例中所述“份”均为重量份。所用试剂均为本领域可商购的试剂。
本发明实施例所用亚麻纤维采购自哈尔滨亚麻厂;
二乙烯三胺五甲叉膦酸、二己烯三胺五甲叉膦酸购自萨恩化学技术(上海)有限公司;
4,4'-二氯-2-羟基二苯醚购自上海山的实业有限公司;
5-氯-2-(2,4-二氯苯氧基)苯酚购自上海吉至生化科技有限公司。
实施例1
抗菌植物纤维材料的制备:
S1、活化亚麻纤维:将亚麻纤维以质量比1:30浸泡在20wt%的氢氧化钠溶液中,升温至40℃恒温反应90min,过滤,用去离子水洗涤3次、真空干燥箱60℃烘干即得预处理亚麻纤维。
S2、季铵化亚麻纤维:将步骤S1所得预处理亚麻纤维以重量比20:100浸泡在浓度为40wt%的二乙烯三胺五甲叉膦酸水溶液中,在超声功率为80Hz、70℃加热条件下反应3h,然后降温至23℃,经过滤、去离子水洗涤3次后,60℃烘干得胺化亚麻纤维;将胺化亚麻纤维以重量比为20:100浸泡在浓度为70wt%氯甲烷的DMSO溶液中,升温至60℃在转速为60rpm/min的搅拌下反应,最后降至23℃,经过滤、DMSO洗涤3次、烘干得季铵化亚麻纤维;
S3、醚化亚麻纤维:将步骤S2所得亚麻纤维以重量比例1.25:100浸泡于浓度为40g/L的高碘酸钠水溶液中,升温至50℃反应3h,过滤、去离子水洗涤3次、烘干即得氧化亚麻纤维;将氧化后的亚麻纤维以重量比例20:100浸入浓度为50wt%的4,4'-二氯-2-羟基二苯醚的四氯化碳溶液中,升温至70℃并搅拌,向混合物中滴加质量分数为2.5wt%的氢氧化钠溶液,反应5h结束后降温至室温,过滤、去离子水洗涤4次、烘干即得所述抗菌亚麻纤维材料。
实施例2
其余与实施例1相同,不同之处在于,步骤S2中二乙烯三胺五甲叉膦酸水溶液的浓度为20wt%,氯甲烷的DMSO溶液浓度为60wt%,4,4'-二氯-2-羟基二苯醚的四氯化碳溶液浓度为70wt%。
实施例3
其余与实施例1相同,不同之处在于,步骤S2中二乙烯三胺五甲叉膦酸水溶液的浓度为50wt%,氯甲烷的DMSO溶液浓度为80wt%,4,4'-二氯-2-羟基二苯醚的四氯化碳溶液浓度为30wt%。
实施例4
其余与实施例1相同,不同之处在于,步骤S2中二乙烯三胺五甲叉膦酸水溶液的浓度为40wt%,氯甲烷的DMSO溶液浓度为70wt%,4,4'-二氯-2-羟基二苯醚的四氯化碳溶液浓度为20wt%。
实施例5
其余与实施例1相同,不同之处在于,步骤S2中二乙烯三胺五甲叉膦酸水溶液的浓度为40wt%,氯甲烷的DMSO溶液浓度为70wt%,4,4'-二氯-2-羟基二苯醚的四氯化碳溶液浓度为80wt%。
实施例6
其余与实施例1相同,不同之处在于,步骤S2的二乙烯三胺五甲叉膦酸更换为二己烯三胺五甲叉膦酸。
实施例7
其余与实施例1相同,不同之处在于,步骤S3的4,4'-二氯-2-羟基二苯醚更换为5-氯-2-(2,4-二氯苯氧基)苯酚。
对比例1
其余与实施例1相同,不同之处在于,步骤S1之后,直接进行步骤S3,即省去了步骤S2的工艺操作。
对比例2
其余与实施例1相同,不同之处在于,没有步骤S3的工艺操作。
将上述实施例和对比例制备的纤维材料进行以下性能测试:
振荡烧瓶法抗菌实验:
菌种:大肠杆菌、金黄色葡萄球菌。
菌悬液:取1mL活化后的上述细菌菌液,12000rpm离心2min,并用无菌生理盐水清洗菌体2-3次,然后重悬于20mL的无菌生理盐水中。
抗菌实验:在无菌状态下,将菌悬液(培养6h后)用0.9%氯化钠溶液稀释至1.5×105-2.0×105cfu/mL,分别取1mL加入烧瓶内,轻摇至均匀。将抗菌植物纤维加入到烧瓶内并固定于37℃电热恒温振荡器上,以频率200r/min振荡24h后,取0.1mL振摇后的溶液,分别做1:10、1:1×102、1:1×103、1:1×104稀释后取0.1mL倾注于培养皿,再倒入营养琼脂培养基,轻摇使其混合均匀,待冷却凝固后,置于37℃恒温培养箱培养24h后计数,抑菌率计算公式如下所示,实验结果见下表1。
洗涤实验:
配制浓度为0.1wt%的立白洗衣粉水溶液,在常温下将植物纤维洗涤烘干42次后,重复上述抗菌实验,测试结果见表1。
表1
本发明将植物纤维与含膦酸三胺反应,用卤代烷进行季铵化来提高表面的荷电性和疏水性,然后用氧化剂氧化植物纤维,氧化的植物纤维再与多卤羟基二苯醚类抗菌剂,最后制备出同时具有季铵盐类抗菌剂和多卤羟基二苯醚类抗菌剂双重杀菌机理的抗菌植物纤维,这种抗菌植物纤维具有更强的杀菌能力,抗菌效果更持久、高效。再多次洗涤后,扔保持令人满意的抗菌效果。
由实施例和对比例可以看出植物纤维接枝的两种抗菌小分子具有协同提高对大肠杆菌的抗菌能力的作用。
本发明制备工艺绿色环保,简单且易控制,所制备的抗菌植物纤维材料对人体无害,适合工业化生产。
上述详细说明是针对本发明其中之一可行实施例的具体说明,该实施例并非用以限制本发明的专利范围,凡未脱离本发明所为的等效实施或变更,均应包含于本发明技术方案的范围内。
Claims (8)
1.一种接枝改性抗菌植物纤维材料,其特征在于,所述抗菌植物纤维材料上接枝有季铵盐抗菌活性成分和多卤羟基二苯醚抗菌活性成分;所述季铵盐抗菌活性成分是用膦酸三胺胺化后的植物纤维和卤代烷反应得到,所述多卤羟基二苯醚抗菌活性成分是氧化后的植物纤维和多卤羟基二苯醚类抗菌剂反应得到;所述膦酸三胺选自二乙烯三胺五甲叉膦酸、二己烯三胺五甲叉膦酸中的至少一种。
2.如权利要求1所述植物纤维材料,其特征在于,所述多卤羟基二苯醚类抗菌剂选自4,4'-二氯-2-羟基二苯醚、2,4,4-三氯-2-羟基二苯醚中的至少一种。
3.如权利要求1所述植物纤维材料,其特征在于,所述接枝季铵盐抗菌活性成分是通过将植物纤维以重量比例5-20:100浸泡于浓度为20-50wt%的膦酸三胺水溶液中,所得胺化植物纤维再以重量比例5-20:100浸泡于浓度为60-80wt%的卤代烷溶液中反应获得。
4.如权利要求1所述植物纤维材料,其特征在于,所述接枝多卤羟基二苯醚抗菌活性成分是通过将氧化后的植物纤维以重量比5-20:100浸泡于浓度为30-70wt%的多卤羟基二苯醚类抗菌剂溶液中反应获得。
5.如权利要求1所述植物纤维材料,其特征在于,所述植物纤维包括黄麻、剑麻、亚麻、木粉、甘蔗渣、稻壳粉、稻草粉中的至少一种。
6.一种如权利要求1-5任一项所述抗菌植物纤维材料的制备方法,包括如下步骤:
S1、活化植物纤维:对植物纤维进行碱处理,得预处理植物纤维;
S2、季铵化植物纤维:将预处理植物纤维浸泡在含膦酸三胺水溶液中,在超声、加热条件下反应,然后降温、过滤、洗涤、烘干得胺化植物纤维;将胺化植物纤维浸泡在卤代烷溶液中,升温在搅拌条件下反应,最后降温、过滤、洗涤、烘干得季铵化植物纤维;
S3、醚化植物纤维:将步骤S2所得植物纤维用氧化剂氧化,氧化后的植物纤维与多卤羟基二苯醚类抗菌剂反应得抗菌植物纤维材料。
7.如权利要求6所述植物纤维材料的制备方法,其特征在于,步骤S2所述季铵化植物纤维为以重量比例5-20:100将步骤S1所得预处理植物纤维浸泡于浓度为30-60wt%的含膦酸三胺水溶液中,超声功率为60-80Hz,加热温度为70-100℃,反应时间为2-4h,降温温度为20-30℃。
8.如权利要求6所述植物纤维材料的制备方法,其特征在于,步骤S3所述醚化植物纤维具体的为将氧化后的植物纤维以比例5-20:100浸入浓度为30-70wt%的多卤羟基二苯醚类抗菌剂溶液中,升温至30-80℃并搅拌,向混合物中滴加1-5wt%的碱液,反应3-8h结束后降温至室温,过滤、洗涤、烘干即得所述抗菌植物纤维材料。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202011167713.9A CN112252033B (zh) | 2020-10-27 | 2020-10-27 | 一种接枝改性抗菌植物纤维材料及其制备方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202011167713.9A CN112252033B (zh) | 2020-10-27 | 2020-10-27 | 一种接枝改性抗菌植物纤维材料及其制备方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN112252033A CN112252033A (zh) | 2021-01-22 |
CN112252033B true CN112252033B (zh) | 2021-05-11 |
Family
ID=74262589
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202011167713.9A Active CN112252033B (zh) | 2020-10-27 | 2020-10-27 | 一种接枝改性抗菌植物纤维材料及其制备方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN112252033B (zh) |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20030055263A (ko) * | 2000-09-14 | 2003-07-02 | 시바 스페셜티 케미칼스 홀딩 인크. | 섬유 물질의 항균 처리 방법 |
CN1328957C (zh) * | 2003-12-05 | 2007-08-01 | 洪麟 | 多元体协同增效多功能广谱消毒剂及其应用 |
CN103526319A (zh) * | 2013-09-26 | 2014-01-22 | 江苏金太阳纺织科技有限公司 | 非溶出型耐久抗菌性再生纤维素纤维的制备方法 |
CN104437394B (zh) * | 2014-10-27 | 2017-02-08 | 中山大学 | 一种双层高氨基密度植物纤维基吸附材料及其制备方法和应用 |
CN108823963B (zh) * | 2018-07-24 | 2019-07-09 | 中国农业科学院麻类研究所 | 一种汉麻抗菌纤维材料制备方法 |
CN110172741B (zh) * | 2019-02-26 | 2020-09-15 | 东华大学 | 一种功能性纤维素类纤维的制备方法 |
CN111234383B (zh) * | 2020-03-21 | 2023-02-24 | 贵州省材料技术创新基地 | 一种抗菌植物纤维增强复合材料及其制备方法和用途 |
-
2020
- 2020-10-27 CN CN202011167713.9A patent/CN112252033B/zh active Active
Also Published As
Publication number | Publication date |
---|---|
CN112252033A (zh) | 2021-01-22 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN107312315B (zh) | 一种木质素/银复合抗菌剂及其制备方法和应用 | |
CN106905438B (zh) | 一种壳聚糖季铵盐抗菌纤维素及其制备方法 | |
CN103159972A (zh) | 一种生物偶联纳米银的壳聚糖/纤维素抗菌敷膜的制备方法 | |
CN102373620B (zh) | 一种羟丙基三甲基氯化铵甲壳胺纤维的制备方法 | |
CN106344954A (zh) | 一种生物抗菌细菌纤维素敷料及其制备方法 | |
CN112252033B (zh) | 一种接枝改性抗菌植物纤维材料及其制备方法 | |
CN113943377B (zh) | 一种具有赖氨酸接枝n-卤胺型席夫碱结构的纤维素抗菌材料及其制备方法 | |
CN113445315A (zh) | 一种双酚酸抗菌棉织物的制备方法 | |
CN104784739A (zh) | 一种载磺胺嘧啶银复合抗菌敷料的制备方法 | |
CN104606710B (zh) | 一种高抗菌性藻酸盐敷料的制备方法 | |
CN102454105B (zh) | 一种高吸水性抗菌纤维的制备方法 | |
CN113265878A (zh) | 抗菌抗病毒聚丙烯非织造布及其制备方法 | |
CN108424467A (zh) | 一种纤维素基复合抗菌材料的制备方法 | |
CN105384957B (zh) | 一种基于细菌纤维素的有序纳米纤维膜的制备方法 | |
CN110791829B (zh) | 一种纳米抗菌纤维的制备方法及其应用 | |
CN109721757A (zh) | 一种医用硅橡胶及其制备方法与应用、硅橡胶产品 | |
CN116082666A (zh) | 一种菠萝叶纤维水凝胶及其制备方法 | |
CN109097418A (zh) | 原位制备抗菌性细菌纤维素膜的方法 | |
KR100277165B1 (ko) | 방사선 조사된 키토산을 이용한 생체친화성항균기능 의료용 섬유 제조 | |
MX2012002711A (es) | Composiciones y productos antimicrobianos. | |
US8771571B2 (en) | Method for preparing high water-absorption and anti-bacterial gamma polyglutamic acid fibers | |
CN104358123B (zh) | 一种丙酰氧基乙基三甲基氯化铵壳聚糖纤维的制备方法 | |
RU2525545C2 (ru) | Способ получения антимикробного серебросодержащего целлюлозного материала | |
CN112569405A (zh) | 一种壳聚糖季铵盐型脱细胞真皮基质材料的制备方法 | |
CN112431022A (zh) | 一种服装用抗菌材料及其制备方法 |
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 | ||
TA01 | Transfer of patent application right |
Effective date of registration: 20210419 Address after: No.167 Minsheng Road, Lanhe village, Lanhe Town, Nansha District, Guangzhou City, Guangdong Province Applicant after: GUANGZHOU TAIDA FIBER PRODUCTS Co.,Ltd. Address before: 100020 building 13, 145 Chaoyang North Road, Chaoyang District, Beijing Applicant before: Beijing Shenhe Intelligent Technology Co.,Ltd. |
|
TA01 | Transfer of patent application right | ||
GR01 | Patent grant | ||
GR01 | Patent grant |