CN111040170B - Antibacterial durable N-P-Si synergistic flame-retardant fabric finishing agent and preparation method thereof - Google Patents
Antibacterial durable N-P-Si synergistic flame-retardant fabric finishing agent and preparation method thereof Download PDFInfo
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 101
- 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 title claims abstract description 100
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 54
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 48
- 230000002195 synergetic effect Effects 0.000 title claims abstract description 43
- 239000000675 fabric finishing Substances 0.000 title claims abstract description 25
- 238000009962 finishing (textile) Methods 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title abstract description 5
- 229920000642 polymer Polymers 0.000 claims abstract description 43
- -1 secondary amine compound Chemical class 0.000 claims abstract description 24
- 239000004753 textile Substances 0.000 claims abstract description 20
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 15
- CMPQUABWPXYYSH-UHFFFAOYSA-N phenyl phosphate Chemical group OP(O)(=O)OC1=CC=CC=C1 CMPQUABWPXYYSH-UHFFFAOYSA-N 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
- 239000004593 Epoxy Substances 0.000 claims abstract description 9
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims abstract description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 57
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 48
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 26
- 229960000583 acetic acid Drugs 0.000 claims description 24
- 239000003995 emulsifying agent Substances 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 16
- 239000012362 glacial acetic acid Substances 0.000 claims description 15
- 239000003960 organic solvent Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 5
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 5
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 4
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 4
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000002736 nonionic surfactant Substances 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 3
- 239000004033 plastic Substances 0.000 claims description 3
- 229920003023 plastic Polymers 0.000 claims description 3
- 238000009988 textile finishing Methods 0.000 claims 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000004744 fabric Substances 0.000 abstract description 47
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 19
- 230000000694 effects Effects 0.000 abstract description 11
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 8
- 150000003242 quaternary ammonium salts Chemical group 0.000 abstract description 6
- 229910052710 silicon Inorganic materials 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 27
- 238000010521 absorption reaction Methods 0.000 description 14
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 14
- 229910019142 PO4 Inorganic materials 0.000 description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 10
- 239000010452 phosphate Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
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- 239000007787 solid Substances 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 5
- ONJQDTZCDSESIW-UHFFFAOYSA-N polidocanol Chemical compound CCCCCCCCCCCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO ONJQDTZCDSESIW-UHFFFAOYSA-N 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
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- 238000002329 infrared spectrum Methods 0.000 description 4
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- 239000000047 product Substances 0.000 description 4
- 229910002808 Si–O–Si Inorganic materials 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
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- 238000002390 rotary evaporation Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 2
- 229920003043 Cellulose fiber Polymers 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 241000191967 Staphylococcus aureus Species 0.000 description 2
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 2
- JQYOCVPEXWBLGO-UHFFFAOYSA-N [N].[Si].[P] Chemical compound [N].[Si].[P] JQYOCVPEXWBLGO-UHFFFAOYSA-N 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
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- 239000010703 silicon Substances 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
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- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 1
- 206010000369 Accident Diseases 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 239000002872 contrast media Substances 0.000 description 1
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- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000007730 finishing process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000003534 oscillatory effect Effects 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 1
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- 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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
- C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
- C08G77/385—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing halogens
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- 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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/452—Block-or graft-polymers containing polysiloxane sequences containing nitrogen-containing sequences
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- 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
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
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- 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
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/667—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing phosphorus in the main chain
- D06M15/673—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing phosphorus in the main chain containing phosphorus and nitrogen in the main chain
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- 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
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- 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
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- 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
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/32—Polyesters
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- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/30—Flame or heat resistance, fire retardancy properties
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Abstract
The invention discloses an antibacterial durable N-P-Si synergistic flame-retardant fabric finishing agent and a preparation method thereof, belonging to the technical field of textile functional finishing. The molecular chain of the flame-retardant component of the finishing agent simultaneously contains N, P, Si element units, quaternary ammonium salt groups and reactive C-Cl bonds, so that the finishing agent can form ternary synergistic flame retardance and has antibacterial property and durability. The synthesis route of the invention is that phenyl dichlorophosphate and a secondary amine compound are firstly utilized to generate tertiary aminated phenyl phosphate, then the tertiary aminated phenyl phosphate is reacted with epoxy terminated polysiloxane to obtain a block polymer, and the block polymer is reacted with epoxy chloropropane to obtain a quaternized modified block polymer, namely the target product. The invention has the advantages of good flame retardant effect, good antibacterial property and durability, and can improve the comfort of the finished fabric.
Description
Technical Field
The invention relates to an antibacterial durable N-P-Si synergistic flame-retardant fabric finishing agent and a preparation method thereof, belonging to the technical field of textile functional finishing.
Background
With the development of society and the improvement of living standard, the application range and the consumption of textiles are continuously increased, and the textiles have been extended to a plurality of fields such as industry, transportation, military, fire control, aerospace and the like from the initial warm-keeping function. Meanwhile, the flame retardant property of the textile plays an important role in reducing the fire hazard and the life and property loss in the fire, and according to incomplete statistics, the fire caused by the fact that the textile does not have the flame retardant property accounts for more than 20% of fire accidents. The flame retardant is an auxiliary agent for improving the flame resistance of the material, namely preventing the material from being ignited and inhibiting flame propagation, and can reduce the flammability of the fabric and slow down the burning speed of the fabric by endowing the textile with a flame retardant function, thereby providing more time for people to escape and rescue disasters. The flame retardant comprises an additive type flame retardant and a post-finishing type flame retardant, and the post-finishing type flame retardant is used for flame-retardant finishing of the fabric, so that the fabric has flame retardant performance.
The existing flame retardant for textile mainly comprises halogen flame retardant, phosphorus flame retardant, nitrogen-phosphorus synergistic flame retardant and latest nitrogen-phosphorus-silicon synergistic flame retardant. The halogen flame retardant has good flame retardant effect, but can release a large amount of corrosive toxic gases such as dense smoke, dioxin, benzofuran and the like during combustion, has great influence on the environment and limits the application of the halogen flame retardant. The phosphorus flame retardant is an environment-friendly flame retardant material, but the flame retardant effect when used alone is not ideal, and the application requirements are difficult to meet. The nitrogen-phosphorus synergistic flame retardant only emits a small amount of smoke during combustion, flame retardance is realized through the synergistic effect of nitrogen and phosphorus, and antimony and halogen are avoided, so that the composite flame retardant is an important development direction of the halogen-free flame retardant. The nitrogen-phosphorus-silicon synergistic flame retardant has the advantages of high efficiency, low toxicity and environmental friendliness, however, most of mature synthetic techniques in the prior art are flame retardants for rubber, plastics and the like, products are solid or insoluble liquid and are not suitable for the after-finishing of fabrics, the fabrics need to be washed in the using process, the bonding fastness between the flame-retardant finishing agent and the fabrics is the bottleneck problem after the flame retardant for the fabrics is applied, namely the durability of the flame retardant on the fabrics is also the bottleneck problem after the flame retardant for the fabrics is applied. Meanwhile, as the hygienic requirements for textiles are increased, higher requirements are also placed on the antibacterial properties of the fabrics. Therefore, it is important to develop a flame retardant finishing agent for fabric with both durability and antibacterial property.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides an antibacterial durable N-P-Si synergistic flame-retardant fabric finishing agent and a preparation method thereof.
The purpose of the invention is realized by the following technical scheme: an antibacterial durable N-P-Si synergistic flame-retardant fabric finishing agent comprises flame-retardant components with the following chemical structural formula:
wherein R is1Is C2H5、C2H4OH or C3H7And m and n are positive integers satisfying 1. ltoreq. m.ltoreq.12 and 1. ltoreq. n.ltoreq.100.
By adopting the flame-retardant components, chemical bonds are formed between nitrogen and phosphorus, and the electronegativity of nitrogen is large, so that the electrophilicity of phosphorus is enhanced, namely the electron cloud density around phosphorus atoms is reduced, the bond energy is low, and the carbon is degraded into acid after being heated, thereby being beneficial to promoting the dehydration of fabrics to form a carbon layer. Meanwhile, silicon in molecules is degraded, and the silicon migrates to the surface of the material due to small surface tension, so that a carbon layer formed by dewatering the fabric is polymerized with silicon oxide, the density of the carbon layer is increased, the stability of the carbon layer is improved, and the carbon layer has better heat insulation and air insulation. The nitrogen in the molecule is degraded to generate the flame-retardant gas, the concentration of the thermally degraded free radicals is diluted, the chain reaction of the free radicals is disturbed, and the area of the carbon layer is promoted to be increased. The flame-retardant component has the characteristics of good flame-retardant property due to the N-P-Si ternary synergistic flame-retardant effect formed in combustion. In addition, the molecular structure of the flame retardant component also contains antibacterial quaternary ammonium salt groups and reactive C-Cl bonds, and when the fabric is finished, the reactive C-Cl bonds can react with-OH on the cellulose fibers to form a firm chemical bonding effect, so that the fabric has good durability and is endowed with antibacterial property.
Further, the flame-retardant plastic composite material further comprises glacial acetic acid, an emulsifier and deionized water, wherein the addition amount of the glacial acetic acid is 2 wt% of the flame-retardant component, and the addition amount of the emulsifier is 0.1-20 wt% of the flame-retardant component. Preferably, the emulsifier is a nonionic surfactant.
The finishing agent consists of a flame-retardant component, glacial acetic acid, an emulsifier and deionized water, and when the finishing agent is applied, the using amount of the finishing agent is determined according to the solid content of the finishing agent, wherein the solid content of the finishing agent can be 10-40 wt%. The emulsifier is a nonionic surfactant, and may be commercially available emulsifiers, such as AEO-9, AEO-6, 1309 and 1306.
The invention also provides a method for preparing the antibacterial durable N-P-Si synergistic flame-retardant fabric finishing agent, which comprises the following steps:
s1, in an organic solvent, carrying out ice-bath reaction on phenyl dichlorophosphate and a secondary amine compound for 6-24 hours in the presence of an acid-binding agent to generate tertiary aminated phenyl phosphate. Preferably, the organic solvent is any one of dichloromethane, diethyl ether or n-hexane.
S2, in an organic solvent, mixing and stirring the tertiary aminated phenyl phosphate obtained in the step S1 and acetic acid for 10-30 min, and then adding epoxy terminated polysiloxane to react for 4-20 h at the temperature of 75-85 ℃ to generate a block polymer solution. Preferably, the organic solvent is isopropanol.
And S3, adding epoxy chloropropane into the block polymer solution obtained in the step S2, and reacting for 3-8 h at the temperature of 50-70 ℃ to generate a quaternized modified block polymer, namely the flame retardant component.
And S4, adding glacial acetic acid and an emulsifier into the quaternized modified block polymer obtained in the step S3, wherein the adding amount of the glacial acetic acid is 2 wt% of the quaternized modified block polymer, the adding amount of the emulsifier is 0.1-20 wt% of the quaternized modified block polymer, and after uniform mixing, adding deionized water to obtain the antibacterial durable N-P-Si synergistic flame-retardant fabric finishing agent.
The secondary amine compound is any one of diethylamine, diethanolamine or dipropylamine.
The molar ratio of phenyl dichlorophosphate to the secondary amine compound in S1 is 1: 2.
The chemical structural formula of the terminal epoxy polysiloxane is as follows:
wherein m is a positive integer satisfying 1-12; the molar ratio of the tertiary aminated phenyl phosphate to the epoxy-terminated polysiloxane is n +1: n, wherein n is a positive integer which satisfies the condition that n is more than or equal to 1 and less than or equal to 100.
The molar ratio of the block polymer to the epichlorohydrin in S3 is 1: 2.
The invention has the beneficial effects that:
1) the molecular chain of the flame-retardant component of the finishing agent contains N, P, Si element units, so that the N-P-Si ternary synergistic flame-retardant effect can be formed, and the finishing agent is favorable for endowing the finished fabric with good flame retardance.
2) The molecular chain of the flame-retardant component of the finishing agent also contains reactive C-Cl bonds, and the reactive C-Cl bonds react with-OH on fabric fibers in the finishing process to form firm chemical bonding effect, thereby being beneficial to improving the durability of the flame-retardant property of the finished fabric.
3) The molecular chain of the flame-retardant component of the finishing agent contains quaternary ammonium salt groups with antibacterial function, so that the finished fabric can have good antibacterial property, and the sanitation of the finished fabric is improved.
4) The molecular chain of the flame-retardant component of the finishing agent contains Si-O-Si chain links with excellent flexibility, so that the finished fabric has good hand feeling, and the comfort of the finished fabric is improved.
Drawings
FIG. 1 is an infrared spectrum of phenyl bis (N, N-diethyl) phosphate synthesized at S1 in example one of the present invention.
FIG. 2 is an infrared spectrum of a quaternized modified block polymer synthesized at S3 in example one of the present invention.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without inventive effort based on the embodiments of the present invention, are within the scope of the present invention.
The invention provides a method for preparing an antibacterial durable N-P-Si synergistic flame-retardant fabric finishing agent, which comprises the following steps:
s1, respectively dissolving phenyl dichlorophosphate and a secondary amine compound in an organic solvent, adding an acid-binding agent into the solvent in which the phenyl dichlorophosphate is dissolved, dropwise adding the solvent in which a secondary amine compound is dissolved under an ice bath condition, reacting at room temperature for 6-24 hours after dropwise adding, filtering, and evaporating the solvent to obtain tertiary aminated phenyl phosphate (I). The organic solvent can be dichloromethane, diethyl ether or n-hexane, the acid-binding agent can be triethylamine or pyridine, and the secondary amine compound can be diethylamine, diethanolamine or dipropylamine. Wherein, the replacement of the organic solvent and the acid-binding agent has no substantial influence on the reaction result and the performance of the product. Taking dichloromethane and triethylamine as examples, the reaction is shown as follows:
s2, in an organic solvent, mixing and stirring tertiary aminated phenyl phosphate (I) obtained in S1 and acetic acid for 10-30 min, and then adding epoxy terminated polysiloxane to react for 4-20 h at 75-85 ℃ to generate a block polymer (II) solution. By terminating organopolysiloxanes with
The organic solvent is isopropanol, and the reaction is as follows:
s3, adding epoxy chloropropane into the block polymer (II) solution obtained in the step S2, and reacting for 3-8 h at the temperature of 50-70 ℃ to generate a quaternized modified block polymer (III), namely a flame retardant component, wherein the reaction is as follows:
and S4, adding glacial acetic acid and an emulsifier into the quaternized modified block polymer obtained in the step S3, wherein the adding amount of the glacial acetic acid is 2 wt% of the quaternized modified block polymer, the adding amount of the emulsifier is 0.1-20 wt% of the quaternized modified block polymer, the emulsifier can be a common commercial product of a nonionic surfactant, the specific types of the emulsifiers have no substantial influence on the performance of a final finishing agent product, and the N-P-Si synergistic flame-retardant fabric finishing agent with antibacterial and durable effects is obtained by adding deionized water after uniform mixing.
Example one
The embodiment provides a method for preparing an antibacterial and durable N-P-Si synergistic flame-retardant fabric finishing agent, which comprises the following steps:
s1, under the ice bath condition, adding 0.1mol of phenyl dichlorophosphate, 0.4mol of triethylamine and 200mL of dichloromethane into 500mL of three-necked bottle with a mechanical stirring and constant-pressure funnel, stirring for 10min, slowly dropwise adding diethylamine dissolved in 50mL of dichloromethane, continuing to react for 8h at room temperature after dropwise adding, filtering, and removing dichloromethane and excessive tris-tert-butyl ether by rotary evaporationEthylamine to give phenyl bis (N, N-diethyl) phosphate. As shown in FIG. 1, FIG. 1 is an infrared spectrum of the product of this step, 3066.8cm-1Is the C-H stretching vibration absorption peak in the benzene ring, 2976.2 and 2837.6cm-1is-CH3and-CH2Peak of stretching vibration of 1593.2, 1491.0 and 1458.2cm-1Is the stretching vibration absorption peak of C ═ C bond in benzene ring, 1278.8cm-1Characteristic absorption peak of P ═ O, 1165.0cm-1Bending vibration peaks for P-N bond, 1039.6 and 968.3cm-1Characteristic absorption peaks for P-O-C, which indicate the successful synthesis of phenyl bis (N, N-diethyl) phosphate.
S2. adding 0.1mol of phenyl bis (N, N-diethyl) phosphate prepared by S1, 0.2mol of acetic acid and 100mL of isopropanol, stirring at room temperature for 0.5h, then adding 0.05mol of epoxy terminated polysiloxane (m ═ 12), heating to 80 ℃ and continuing the reaction for 6h to obtain a block polymer solution.
S3, adding 0.1mol of epoxy chloropropane into the block polymer solution obtained in the step S2, continuously reacting for 6h at the temperature of 60 ℃, and removing isopropanol under reduced pressure to obtain the quaternized modified block polymer. FIG. 2 shows the infrared spectrum of the resulting quaternized modified block polymer, 3431.4cm-1A stretching vibration absorption peak of-OH, 3047.5cm-1Is the C-H stretching vibration absorption peak in the benzene ring, 2962.7 and 2877.8cm-1is-CH3and-CH2Has a stretching vibration absorption peak of 1593.0cm-1Is the stretching vibration absorption peak of C ═ C bond in benzene ring, 1384.9cm-1Is a stretching vibration absorption peak of a C-N bond on a quaternary ammonium salt group, 1278.8cm-1Characteristic absorption peak of P ═ O, 1259.2cm-1Is Si-CH3Has a stretching vibration absorption peak of 1163.1cm-1Bending vibration peaks for P-N bond, 1089.8 and 1028.1cm-1Is a characteristic absorption peak of Si-O-Si, 968.3cm-1Is a characteristic absorption peak of P-O-C, 613.4cm-1Is the expansion vibration absorption peak of the C-Cl bond, which shows that the flame retardant component containing the active group C-Cl bond and the antibacterial quaternary ammonium salt group and simultaneously containing N-P-Si on the molecular chain is successfully synthesized.
S4, adding 2 wt% of glacial acetic acid and 20 wt% of emulsifier AEO-9 into the quaternized modified block polymer obtained in S3, uniformly stirring, slowly adding deionized water, and quickly stirring and emulsifying to obtain the antibacterial durable N-P-Si synergistic flame-retardant fabric finishing agent with the solid content of 20 wt%.
Example two
The embodiment provides a method for preparing an antibacterial and durable N-P-Si synergistic flame-retardant fabric finishing agent, which comprises the following steps:
s1, under the ice bath condition, adding 0.1mol of phenyl dichlorophosphate, 0.4mol of triethylamine and 200mL of dichloromethane into 500mL of three-necked bottle with a mechanical stirring and constant-pressure funnel, stirring for 10min, slowly dropwise adding diethanolamine dissolved in 50mL of dichloromethane, continuing to react for 8h at room temperature after dropwise adding, filtering, and removing dichloromethane and excessive triethylamine through rotary evaporation to obtain bis (N, N-dihydroxyethyl) phenyl phosphate.
S2. adding 0.1mol of phenyl bis (N, N-dihydroxyethyl) phosphate prepared by S1, 0.2mol of acetic acid and 100mL of isopropanol, stirring at room temperature for 0.5h, subsequently adding 0.099mol of epoxy-terminated polysiloxane (m ═ 1), heating to 80 ℃ and continuing the reaction for 6h to obtain a block polymer solution.
S3, adding 0.002mol of epoxy chloropropane into the block polymer solution obtained in the step S2, continuously reacting for 6h at the temperature of 60 ℃, and removing isopropanol under reduced pressure to obtain the quaternized modified block polymer.
S4, adding 2 wt% of glacial acetic acid and 0.1 wt% of emulsifier AEO-9 into the quaternized modified block polymer obtained in S3, uniformly stirring, slowly adding deionized water, and quickly stirring and emulsifying to obtain the antibacterial durable N-P-Si synergistic flame-retardant fabric finishing agent with the solid content of 20 wt%.
EXAMPLE III
The embodiment provides a method for preparing an antibacterial and durable N-P-Si synergistic flame-retardant fabric finishing agent, which comprises the following steps:
s1, under the ice bath condition, adding 0.1mol of phenyl dichlorophosphate, 0.4mol of triethylamine and 200mL of dichloromethane into 500mL of three-necked bottle with a mechanical stirring and constant-pressure funnel, stirring for 10min, slowly dropwise adding dipropylamine dissolved in 50mL of dichloromethane, continuing to react for 8h at room temperature after dropwise adding, filtering, and removing the dichloromethane and excessive triethylamine through rotary evaporation to obtain the phenyl di (N, N-dipropyl) phosphate.
S2. adding 0.1mol of phenyl bis (N, N-dipropyl) phosphate prepared in S1, 0.2mol of acetic acid and 100mL of isopropanol, stirring at room temperature for 0.5h, subsequently adding 0.09mol of epoxy-terminated polysiloxane (m ═ 6), heating to 80 ℃ and continuing the reaction for 6h to obtain a block polymer solution.
S3, adding 0.02mol of epoxy chloropropane into the block polymer solution obtained in the step S2, continuously reacting for 6h at the temperature of 60 ℃, and removing isopropanol under reduced pressure to obtain the quaternized modified block polymer.
S4, adding 2 wt% of glacial acetic acid and 10 wt% of emulsifier AEO-9 into the quaternized modified block polymer obtained in S3, uniformly stirring, slowly adding deionized water, and quickly stirring and emulsifying to obtain the antibacterial durable N-P-Si synergistic flame-retardant fabric finishing agent with the solid content of 20 wt%.
Example four
The embodiment provides a method for preparing an antibacterial and durable N-P-Si synergistic flame-retardant fabric finishing agent, which comprises the following steps:
s1, under the ice bath condition, adding 0.1mol of phenyl dichlorophosphate, 0.4mol of triethylamine and 200mL of dichloromethane into 500mL of three-necked bottle with a mechanical stirring and constant-pressure funnel, stirring for 10min, slowly dropwise adding diethanolamine dissolved in 50mL of dichloromethane, continuing to react for 8h at room temperature after dropwise adding, filtering, and removing dichloromethane and excessive triethylamine through rotary evaporation to obtain bis (N, N-dihydroxyethyl) phenyl phosphate.
S2. adding 0.1mol of phenyl bis (N, N-dihydroxyethyl) phosphate prepared by S1, 0.2mol of acetic acid and 100mL of isopropanol, stirring at room temperature for 0.5h, subsequently adding 0.098mol of epoxy-terminated polysiloxane (m ═ 6), heating to 80 ℃ and continuing the reaction for 6h to obtain a block polymer solution.
S3, adding 0.004mol of epoxy chloropropane into the block polymer solution obtained in the step S2, continuously reacting for 6h at the temperature of 60 ℃, and removing isopropanol under reduced pressure to obtain the quaternized modified block polymer.
S4, adding 2 wt% of glacial acetic acid and 1 wt% of emulsifier AEO-9 into the quaternized modified block polymer obtained in S3, uniformly stirring, slowly adding deionized water, and quickly stirring and emulsifying to obtain the antibacterial durable N-P-Si synergistic flame-retardant fabric finishing agent with the solid content of 20 wt%.
EXAMPLE five
The difference between the present embodiment and the second embodiment is mainly as follows: in this example, diethyl ether was used as the organic solvent in S1, and the reaction time was 6 hours; mixing phenyl bis (N, N-dihydroxyethyl) phosphate with acetic acid and isopropanol in S2, stirring for 10min, adding epoxy terminated polysiloxane (m is 6), heating to 85 ℃, and continuing to react for 4 h; continuously reacting the block polymer solution in the S3 with epichlorohydrin for 8h at the temperature of 50 ℃; the emulsifier used in S4 was AEO-6.
EXAMPLE six
The difference between the present embodiment and the second embodiment is mainly as follows: in this embodiment, n-hexane is used as the organic solvent in S1, and the reaction time is 24 hours; mixing phenyl bis (N, N-dihydroxyethyl) phosphate with acetic acid and isopropanol in S2, stirring for 20min, adding epoxy terminated polysiloxane (m is 6), heating to 75 ℃, and continuing to react for 20 h; continuously reacting the block polymer solution in the S3 with epichlorohydrin for 3h at 70 ℃; the emulsifier used in S4 was 1309.
The antibacterial durable N-P-Si synergistic flame-retardant fabric finishing agent prepared in the first to fourth embodiments is used for finishing polyester-cotton fabrics, the using amount of the finishing agent is 30g/L, and the finishing fabrics of the embodiments are obtained by two-time soaking and two-time rolling, drying at 100 ℃ and baking at 130 ℃. Meanwhile, a commercially available flame-retardant finishing agent is used as a contrast agent, the polyester-cotton fabric is finished to obtain a contrast finishing fabric, and the partially finished fabrics of the examples and the contrast finishing fabric are respectively washed for 12 times and 50 times. According to the content of the national standard oxygen index method for testing the burning performance of textiles (GB/T5454-1997), the Limit Oxygen Index (LOI) of the finished textile is determined by using a LLY-07A type textile flame retardant performance tester. The antibacterial property of the finished fabric against staphylococcus aureus is measured according to the content of the national standard, evaluation of antibacterial properties of textiles, part 3 of the oscillatory law (GB/T20944.3-2008). The results of the measurements are shown in the following table:
TABLE 1 determination of the finished fabrics and the finished fabrics after multiple washings of the examples
A higher Limiting Oxygen Index (LOI) indicates that the material is not readily combustible, and a low LOI indicates that the material is readily combustible. It is generally believed that LOI < 22% is a flammable material, LOI between 22% and 27% is a flammable material, and LOI > 27% is a nonflammable material. As can be seen from Table 1, the fabric finished by the antibacterial durable N-P-Si synergistic flame-retardant fabric finishing agent has good flame-retardant performance and antibacterial performance before washing, and the flame-retardant effect of the fabric finished by the antibacterial durable N-P-Si synergistic flame-retardant fabric finishing agent reaches or is superior to the flame-retardant performance of the fabric finished by the current commercially available flame-retardant finishing agent. Meanwhile, the flame-retardant antibacterial finishing agent can endow the finished fabric with a good antibacterial effect, the antibacterial property to staphylococcus aureus is more than 99.0%, and the commercial flame retardant cannot provide the antibacterial effect. After being washed for many times, the fabric finished by the finishing agent still has very good flame retardance and antibacterial property, and the flame retardance of the fabric finished by the commercial flame retardant is greatly reduced. In addition, the finishing agent can also endow the fabric with good hand feeling after finishing.
The results show that the antibacterial durable N-P-Si synergistic flame-retardant fabric finishing agent can endow the fabric with excellent flame-retardant effect and durability, and simultaneously endow the fabric with good antibacterial performance, thereby being beneficial to improving the safety and the sanitation of the fabric. The improvement of the performances is essentially the unique chemical structure in the durable N-P-Si ternary synergistic flame-retardant fabric finishing agent with the antibacterial function: (1) the molecular chain simultaneously contains N, P, Si element units, so that N-P-Si ternary synergistic flame retardance can be formed, and good flame retardance is achieved; (2) the molecular chain contains reactive C-Cl bonds, can react with-OH on the cellulose fiber to form firm chemical bonding effect, and has good durability; (3) the molecular chain contains quaternary ammonium salt groups with antibacterial function, so that the finished fabric can be endowed with good antibacterial property, and the sanitation of the finished fabric is improved; (4) the molecular chain contains Si-O-Si chain links with excellent flexibility, so that the finished fabric can have good hand feeling, and the comfort of the finished fabric is improved.
The foregoing is illustrative of the preferred embodiments of this invention, and it is to be understood that the invention is not limited to the precise form disclosed herein and that various other combinations, modifications, and environments may be resorted to, falling within the scope of the concept as disclosed herein, either as described above or as apparent to those skilled in the relevant art. And that modifications and variations may be effected by those skilled in the art without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. The antibacterial durable N-P-Si synergistic flame-retardant fabric finishing agent is characterized in that: comprises flame retardant components with the following chemical structural formula:
wherein R is1Is C2H5、C2H4OH or C3H7And m and n are positive integers satisfying 1. ltoreq. m.ltoreq.12 and 1. ltoreq. n.ltoreq.100.
2. The antibacterial durable N-P-Si synergistic flame retardant textile finishing agent according to claim 1, characterized in that: the flame-retardant plastic composite material further comprises glacial acetic acid, an emulsifier and deionized water, wherein the addition amount of the glacial acetic acid is 2 wt% of the flame-retardant component, and the addition amount of the emulsifier is 0.1-20 wt% of the flame-retardant component.
3. The antibacterial durable N-P-Si synergistic flame retardant textile finishing agent according to claim 2, characterized in that: the emulsifier is a nonionic surfactant.
4. A process for preparing the antibacterial durable N-P-Si synergistic flame retardant textile finish according to any one of claims 1 to 3, characterized in that: the method comprises the following steps:
s1, in an organic solvent, carrying out ice-bath reaction on phenyl dichlorophosphate and a secondary amine compound for 6-24 hours in the presence of an acid-binding agent to generate tert-aminated phenyl phosphate;
s2, in an organic solvent, mixing and stirring tertiary aminated phenyl phosphate obtained in the step S1 and acetic acid for 10-30 min, and then adding epoxy terminated polysiloxane to react for 4-20 h at the temperature of 75-85 ℃ to generate a block polymer solution;
s3, adding epoxy chloropropane into the block polymer solution obtained in the step S2, and reacting at the temperature of 50-70 ℃ for 3-8 h to generate a quaternized modified block polymer, namely a flame retardant component;
and S4, adding glacial acetic acid and an emulsifier into the quaternized modified block polymer obtained in the step S3, wherein the adding amount of the glacial acetic acid is 2 wt% of the quaternized modified block polymer, the adding amount of the emulsifier is 0.1-20 wt% of the quaternized modified block polymer, and after uniform mixing, adding deionized water to obtain the antibacterial durable N-P-Si synergistic flame-retardant fabric finishing agent.
5. The method of preparing an antibacterial durable N-P-Si synergistic flame retardant textile finish according to claim 4, characterized in that: the organic solvent adopted in S1 is any one of dichloromethane, diethyl ether or n-hexane.
6. The method of preparing an antibacterial durable N-P-Si synergistic flame retardant textile finish according to claim 4, characterized in that: the organic solvent used in S2 is isopropanol.
7. The method of preparing an antibacterial durable N-P-Si synergistic flame retardant textile finish according to claim 4, characterized in that: the secondary amine compound is any one of diethylamine, diethanolamine or dipropylamine.
8. The method of preparing an antibacterial durable N-P-Si synergistic flame retardant textile finish according to claim 4, characterized in that: the molar ratio of phenyl dichlorophosphate to the secondary amine compound in S1 is 1: 2.
9. The method of preparing an antibacterial durable N-P-Si synergistic flame retardant textile finish according to claim 4, characterized in that: the chemical structural formula of the terminal epoxy polysiloxane is as follows:
wherein m is a positive integer satisfying 1-12; the molar ratio of the tertiary aminated phenyl phosphate to the epoxy-terminated polysiloxane is n +1: n, wherein n is a positive integer which satisfies the condition that n is more than or equal to 1 and less than or equal to 100.
10. The method of preparing an antibacterial durable N-P-Si synergistic flame retardant textile finish according to claim 4, characterized in that: the molar ratio of the block polymer to the epichlorohydrin in S3 is 1: 2.
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Address after: 610000 No. 1166, Tianlong Avenue, Jinniu high tech Industrial Park, Chengdu, Sichuan Patentee after: Sichuan Textile Research Institute Co.,Ltd. Patentee after: SICHUAN YIXIN TECHNOLOGY Co.,Ltd. Patentee after: Sichuan Yilong Kefang Group Co.,Ltd. Address before: No.2, Shierqiao Road, Qingyang District, Chengdu, Sichuan 610000 Patentee before: Sichuan Textile Research Institute Co.,Ltd. Patentee before: SICHUAN YIXIN TECHNOLOGY Co.,Ltd. Patentee before: Sichuan Yilong Kefang Group Co.,Ltd. |