CN114907410A - Flame retardant, preparation thereof and application thereof in preparation of flame-retardant regenerated cellulose fiber - Google Patents
Flame retardant, preparation thereof and application thereof in preparation of flame-retardant regenerated cellulose fiber Download PDFInfo
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- 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 111
- 239000003063 flame retardant Substances 0.000 title claims abstract description 110
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- 238000002360 preparation method Methods 0.000 title claims abstract description 14
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- 239000000835 fiber Substances 0.000 claims description 33
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- 238000006243 chemical reaction Methods 0.000 description 20
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 9
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- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 7
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- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 5
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 5
- 238000001819 mass spectrum Methods 0.000 description 5
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 5
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 5
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 5
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 5
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- 241001330002 Bambuseae Species 0.000 description 4
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- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 4
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 239000011425 bamboo Substances 0.000 description 4
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
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- 239000000126 substance Substances 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- RAOZVFGTRXLBTA-UHFFFAOYSA-N 2-chloro-5,5-dimethyl-1,3,2-dioxaphosphinane Chemical compound CC1(C)COP(Cl)OC1 RAOZVFGTRXLBTA-UHFFFAOYSA-N 0.000 description 2
- 229920000433 Lyocell Polymers 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
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- 239000007810 chemical reaction solvent Substances 0.000 description 2
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- 235000021317 phosphate Nutrition 0.000 description 2
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
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- 238000012360 testing method Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 238000004383 yellowing Methods 0.000 description 2
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 2
- 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
- 244000025254 Cannabis sativa Species 0.000 description 1
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 1
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920002101 Chitin Polymers 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical class [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 241000219146 Gossypium Species 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- UMVBXBACMIOFDO-UHFFFAOYSA-N [N].[Si] Chemical class [N].[Si] UMVBXBACMIOFDO-UHFFFAOYSA-N 0.000 description 1
- HIVGXUNKSAJJDN-UHFFFAOYSA-N [Si].[P] Chemical class [Si].[P] HIVGXUNKSAJJDN-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 238000012658 bimolecular nucleophilic substitution Methods 0.000 description 1
- 235000009120 camo Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 235000005607 chanvre indien Nutrition 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
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- 238000002485 combustion reaction Methods 0.000 description 1
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- 239000013078 crystal Substances 0.000 description 1
- 239000011903 deuterated solvents Substances 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical compound CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 238000005935 nucleophilic addition reaction Methods 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 125000005624 silicic acid group Chemical group 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/6574—Esters of oxyacids of phosphorus
- C07F9/65742—Esters of oxyacids of phosphorus non-condensed with carbocyclic rings or heterocyclic rings or ring systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/6574—Esters of oxyacids of phosphorus
- C07F9/65746—Esters of oxyacids of phosphorus the molecule containing more than one cyclic phosphorus atom
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K21/00—Fireproofing materials
- C09K21/06—Organic materials
- C09K21/12—Organic materials containing phosphorus
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
- D01F2/06—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from viscose
- D01F2/08—Composition of the spinning solution or the bath
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Biochemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
Abstract
The invention provides a flame retardant, a preparation method thereof and application thereof in preparation of flame-retardant regenerated cellulose fibers, belonging to the field of flame retardants and flame-retardant textiles. The invention aims to prepare a flame retardant of a phosphorus-nitrogen compound with excellent flame retardant effect based on the research of a phosphorus-nitrogen (P-N) compound flame retardant, and realizes the flame retardant application on regenerated cellulose fibers by replacing a halogen-containing flame retardant with excellent flame retardant effect with a higher dosage of the phosphorus-nitrogen compound flame retardant.
Description
Technical Field
The invention relates to a flame retardant, a preparation method thereof and an application thereof in preparation of flame-retardant regenerated cellulose fibers, belonging to the field of flame retardants and flame-retardant textiles.
Background
Regenerated cellulose fibers are produced from natural cellulose (cotton, hemp, bamboo, trees, shrubs, etc.) by physical modification alone without changing the chemical structure of the cellulose. The regenerated cellulose fiber has the advantages of natural and renewable energy sources; meanwhile, compared with chemical fibers, the fabric has good hygroscopicity and air permeability, is more comfortable to wear after being made into clothes, is softer and smoother in handfeel, and is environment-friendly green fiber with excellent comprehensive performance. However, the LOI of the regenerated cellulose fiber is only 17%, which is more flammable than chemical fiber, so that the textile made of single regenerated cellulose is very easy to cause fire when being applied in life. Therefore, more and more practical applications of textiles put higher demands on the flame retardant grade of textiles, and research on flame retardant regenerated cellulose textiles is urgently needed.
The traditional flame retardant occupies a smaller and smaller position in the aspect of flame retardance of textiles, and is mainly applied to flame retardance of textiles because most of the traditional flame retardant is a halogen-containing flame retardant, can generate a large amount of smoke and corrosive toxic and harmful gas (such as dioxin) during combustion, and can cause certain damage to human bodies and the environment. At present, the use of halogen-containing flame retardants is gradually prohibited, and the appearance of halogen-free flame retardants such as phosphates, phosphorus-nitrogen compounds, phosphorus-silicon compounds, nitrogen-silicon compounds, etc. is beginning to gradually occupy the mainstream of flame retardants. Among them, the flame retardant effect of the phosphorus-nitrogen compound-based flame retardant is most effective for the flame retardant effect of regenerated cellulose fibers.
Part of phosphazene and phosphate flame retardants are in a liquid state, and can only prepare corresponding flame-retardant fibers with low yield, and the introduced liquid flame retardants have poor retention in the fibers and hardly have washability (US 4111701, US3455713, US 4193805).
The flame retardant containing the silicic acid structure has poor flame retardant effect, and the flame retardant requirement can be met only when the adding proportion is too high (EP 1918431), so that the fiber strength is rapidly reduced correspondingly.
Disclosure of Invention
The invention aims to solve the environmental protection problem of the application of halogen-containing flame retardant in the field of regenerated fiber in the market. The invention provides a P-N compound series flame retardant suitable for regenerated cellulose fiber, and the flame-retardant regenerated cellulose fiber prepared by using the flame retardant has better flame retardant property, and does not change the original wearability of the regenerated cellulose fiber.
The present invention provides a compound represented by the formula (II):
in the formula (II), R 1 、R 2 Each independently represents C 1-4 Alkyl (specifically, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and tert-butyl), R 3 、R 4 Each independently represents C 1-4 Alkylene (specifically, methylene, 1, 2-ethylene, n-propylene, isopropylene, n-butylene); r 21 、R 22 When not bonded, R 21 、R 22 Each independently represents a hydrogen atom or C 1-6 When R is alkyl (methyl or ethyl) 21 And R 22 When bound, the N atom is bonded to R 21 、R 22 Form C 3-8 The nitrogen-containing aliphatic heterocyclic structure of (a) may specifically be;
in the nitrogen-dioxy-phosphacycloalkane flame retardant represented by the formula (II), R is preferably used from the viewpoint of improving flame retardancy 1 And R 2 Is methyl, R 3 And R 4 Is the synthetic structure of methylene.
Specifically, the compound represented by the formula (II) is any one of the following compounds:
the present invention provides a compound represented by the formula (III):
in the formula (III), R 1 、R 2 、R 5 And R 6 Each is independentStanding to represent C 1-4 Alkyl (specifically, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and tert-butyl), R 3 、R 4 、R 7 And R 8 Each independently represents C 1-4 Alkylene (specifically, methylene, 1, 2-ethylene, n-propylene, isopropylene, n-butylene); r 11 And R 12 When not linked, R 11 And R 12 Each represents a hydrogen atom or C 1-4 Alkyl of R 11 And R 12 When linked, R 11 -R 12 and-N-R 13 -N-forms a five-eight membered aliphatic ring structure; r 11 And R 12 When not linked, R 13 Represents C 1-6 Alkylene (specifically, methylene, 1, 2-ethylene, n-hexylene), R 11 And R 12 When linked, R 13 And the left and right N and R 11 -R 12 Forming a five-eight membered aliphatic ring structure, which may specifically be:
specifically, the compound represented by the formula (III) is any one of the following:
r of the formula (III) 1 、R 2 、R 5 And R 6 Preferably C 1-4 Alkyl structure of (3), more preferably C 1-2 Methyl and ethyl radicals of carbon atoms. R 3 、R 4 、R 7 And R 8 Preference should also be given to C 1-4 Alkylene structure of (3), more preferably C 1-2 Short chain structure of methylene and 1, 2-ethylene.
The present invention provides a compound represented by the formula (IV):
in the formula (IV), R 1 、R 2 、R 5 And R 6 Each independently represents C 1-4 Alkyl (specifically, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and tert-butyl), R 3 、R 4 、R 7 And R 8 Each independently represents C 1-4 Alkylene (specifically, methylene, 1, 2-ethylene, n-propylene, isopropylene, n-butylene); r 11 And R 12 When not linked, R 11 And R 12 Each represents a hydrogen atom or C 1-4 Alkyl of R 11 And R 12 When linked, R 11 -R 12 and-N-R 13 -N-forms a five-eight membered aliphatic ring structure; r 11 And R 12 When not linked, R 13 Represents C 1-6 Alkylene (specifically, methylene, 1, 2-ethylene, n-hexylene), R 11 And R 12 When linked, R 13 And the left and right N and R 11 -R 12 Form a five-to eight-membered aliphatic ring structure, which may be specifically
Specifically, the compound represented by the formula (IV) is any one of the following compounds:
the present invention provides a compound represented by the formula (V):
in the formula (V), R 1 、R 2 、R 5 And R 6 Each independently represents C 1-4 Alkyl (specifically, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and tert-butyl), R 3 、R 4 、R 7 And R 8 Each independently represents C 1-4 Alkylene (specifically, methylene, 1, 2-ethylene, n-propylene, isopropylene, n-butylene); r 11 And R 12 When not linked, R 11 And R 12 Each represents a hydrogen atom or C 1-4 Alkyl of R 11 And R 12 When linked, R 11 -R 12 and-N-R 13 -N-forms a five-eight membered aliphatic ring structure; r 11 And R 12 When not linked, R 13 Represents C 1-6 Alkylene (specifically, methyl, 1, 2-ethylene, n-hexylene), R 11 And R 12 When linked, R 13 And the left and right N and R 11 -R 12 Form a five-to eight-membered aliphatic ring structure, which may be specifically
Specifically, the compound represented by the formula (V) is any one of the following:
r of the general formulae (IV) and (V) from the viewpoint of improving flame retardancy 1 、R 2 、R 5 And R 6 Preferably C 1-4 Alkyl structure of (3), more preferably C 1-2 Carbon atomMethyl and ethyl. R 3 、R 4 、R 7 And R 8 Preference should also be given to C 1-4 Alkylene structure of (2), more preferably C 1-2 A short chain structure of methylene group and 1, 2-ethylene group.
Among the compounds of the general formulae (II) to (V), flame retardants having flame retardant structures of (II-8), (III-1), (III-7), (IV-5) and (V-5) are preferred.
The compound shown in the formula (II) is prepared by taking the compound shown in the formula (I) as a precursor through a reaction flow chart shown in the attached figure 1, and the preparation method comprises the following steps: reacting a compound shown in a formula (I) with amine shown in a formula 2,
in the formula (I), R 1 、R 2 、R 3 、R 4 Respectively in the same formula (II) as R 1 、R 2 、R 3 、R 4 ，
In the formula 2, R 21 、R 22 In the same formula (II) R 21 、R 22 ，
In the method, the molar ratio of the compound shown in the formula (I) to the amine shown in the formula 2 can be 1: 1;
the compound shown in the formula (III) is prepared by taking the compound shown in the formula (I) as a precursor through a reaction flow chart shown in the attached figure 2, and the preparation method comprises the following steps: reacting a compound of formula (I), a compound of formula (I'), with an amine of formula 3:
in the formula (I), R 1 、R 2 、R 3 、R 4 Respectively in the same formula (III) as R 1 、R 2 、R 3 、R 4 ，
In the formula (I'), R 5 、R 6 、R 7 、R 8 Respectively in the same formula (III) as R 5 、R 6 、R 7 、R 8 ，
In the formula 3, R 11 、R 12 、R 13 Respectively in the same formula (III) as R 11 、R 12 、R 13 ，
In the method, the molar ratio of the compound shown as the formula (I), the compound shown as the formula (I') and the amine shown as the formula 3 can be 1:1:1 in sequence;
the compound shown in the formula (IV) is obtained by oxidizing the compound shown in the formula (III),
the oxidation can be carried out in ethyl acetate solvent under the action of hydrogen peroxide;
a compound of formula (V) is prepared by reacting a compound of formula (III) with S in toluene 8 And (3) reacting to obtain the product.
In the formula (I), R 1 、R 2 Each independently represents C 1-4 Alkyl (specifically, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and tert-butyl), R 3 、R 4 Each independently represents C 1-4 The alkylene group (may specifically be a methylene group, a 1, 2-ethylene group, an n-propylene group, an isopropylene group or an n-butylene group).
The synthetic method of formula (I) is not particularly limited, and the synthetic procedures are described in various references [ Byard, Benjamin, et al. "New polyethylene diols as flame retardants for polyurethanes: Derivatives of epoxy-functionalized phosphors and phosphors." Fire and Materials 42.1(2018):3-17.] [ Ma, Xiao, et al. "Synthesis and Solubility of 5,5-Dimethyl-2- (phenyl) methyl) -1,3, 2-dioxaphospholine 2-oxide in Selected phosphors 278.15K and 347.15K." Journal of Data & Engineers 62.12(2017): 4196.4204 ]. The synthesis of formula (I) can be carried out according to known synthetic routes.
The application of the compounds shown in the formulas (II) to (V) as flame retardants in the preparation of regenerated cellulose flame-retardant fibers also belongs to the protection scope of the invention.
The invention also provides a regenerated cellulose flame-retardant fiber which adopts the compounds shown in the formulas (II) - (V) as flame retardants.
The flame retardant conforming to the general formulas (II) - (V) can be directly used without modification, and can also meet the requirements of special applications after being modified according to the actual using mode of the flame retardant.
The flame retardants contained in the formulas (II) - (V) can be used singly or in a composite way, and can also be used in a composite way with other halogen-free flame retardants to prepare the regenerated cellulose flame-retardant fiber with better flame-retardant property.
The flame retardant synthesized by the formulas (II) - (V) is preferably in a flame retardant structure with a small particle size, and the particle size of the flame retardant is preferably in a structure with a particle size of less than 5 microns, more preferably in a structure with a small particle size of 500nm-5 microns, so that good dispersion of the flame retardant in the flame retardant fiber can be realized later.
The flame retardant synthesized by the formulas (II) - (V) can not meet the basic flame-retardant requirement of the flame-retardant fiber when the dosage is smaller, and the mechanical strength of the flame-retardant fiber can be reduced when the dosage is too large. Therefore, in the process of preparing the flame-retardant fiber, the addition amount is preferably in the range of 5-50%, and more preferably in the range of 8% -30%, based on the mass of the regenerated fiber.
0.5-3% of thickening agent can be added to be used together in the using process of the flame retardant synthesized by the general formulas (II) - (V), so that the stability of the spinning solution is improved.
0.3-6% of dispersant can be added to be used in the process of using the flame retardant synthesized by the general formulas (II) - (V).
The flame retardant synthesized by the general formulas (II) - (V) can be used together with various additives in the using process, and comprises dyes, antistatic agents, antioxidants, antibacterial agents and the like.
The flame retardant synthesized according to the general formulas (II) - (V) prepared by the invention needs to be optimally ground to 100nm-10 mu m by adopting grinding equipment to obtain flame retardant particles with small particle size, so that the flame retardant is well dispersed in the preparation process of flame retardant fibers.
The regenerated cellulose fibers suitable for the synthetic flame retardants of the general formulae (II) to (V) of the present invention include bamboo fibers, chitin fibers, cuprammonium fibers, Tencel (Lyocell) fibers, Modal fibers, and the like.
The invention relates to a research based on a phosphorus-nitrogen (P-N) compound flame retardant, aiming at preparing a flame retardant of a phosphorus-nitrogen compound with excellent flame retardant effect, and replacing a halogen-containing flame retardant with excellent flame retardant effect by a phosphorus-nitrogen compound flame retardant with higher dosage to realize the flame retardant application on regenerated cellulose fiber.
Drawings
FIG. 1 is a reaction scheme for preparing a compound represented by formula (II) in the present invention.
FIG. 2 is a scheme showing the preparation of compounds of formula (III), (IV) and (V) in the present invention.
FIG. 3 shows the mass spectrum (M + H) of the product II-8 obtained in example 2 of the present invention.
FIG. 4 shows the product II-8 obtained in example 2 of the present invention 1 HNMR picture (deuterated DMSO-d6 is used as deuterated solvent, the same is applied below).
FIG. 5 shows the mass spectrum (M + H) of the product III-1 obtained in example 3 according to the invention.
FIG. 6 shows the product III-1 obtained in example 3 of the present invention 1 HNMR map.
FIG. 7 shows a mass spectrum (M + H) of the product III-7 obtained in example 4 of the present invention.
FIG. 8 shows the product III-7 obtained in example 4 of the present invention 1 HNMR map.
FIG. 9 shows a mass spectrum (M + H) of the product IV-5 obtained in example 5 of the present invention.
FIG. 10 shows the product IV-5 obtained in example 5 of the present invention 1 HNMR map.
FIG. 11 shows a mass spectrum (M + H) of the product V-5 obtained in example 6 of the present invention.
FIG. 12 shows the product V-5 obtained in example 6 of the present invention 1 HNMR picture (M + H).
Detailed Description
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
Example 1
The above synthesis steps are nucleophilic addition reaction. According to the principle of selecting solvent in the reaction, an aprotic solvent such as chloroform, benzene, tetrahydrofuran and 1, 4-dioxane is generally adopted as the reaction solvent in the step, and tetrahydrofuran is selected as the solvent in the reaction process in the step of synthesizing.
104.15g of neopentyl glycol (1.00mol) was charged in a 500mL three-necked flask, 72.1g of tetrahydrofuran (1.00mol) was added, the temperature was maintained at 0 to 5 ℃ in an ice-water bath, and N was introduced during the whole reaction 2 Protecting and maintaining the condition of condensation reflux. 137.32g of phosphorus trichloride (1.00mol) is controlled within 2h, and the reaction is continued for 3h after the phosphorus trichloride is added. Finally 205.5g of white product are obtained.
Example 2
168.56g of the product 5, 5-dimethyl-2-chloro-1, 3, 2-dioxaphosphorinane (1.00mol) obtained by the synthesis are added into a 500mL three-neck flask, dissolved in 72.1g of tetrahydrofuran (1.00mol), the initial dropping temperature is controlled to be 15 ℃, 45g of ethylamine is dropped into the 500mL three-neck flask under the condition of stirring for 2h, and after the dropping of the ethylamine is finished, the temperature is kept at 30 ℃ for continuous reaction for 4 h. The white solid obtained above was filtered and separated. And continuously washing and filtering the obtained white solid for multiple times by using acetone and deionized water until the pH value of the filtrate of the deionized water is close to neutral. The white solid obtained by final filtration was dried in a vacuum oven at 70 ℃ for 12 hours to give 147.63g of the flame retardant of the structure (II-8). (yield: 83.2%)
Example 3
The above-mentioned synthesis step is nucleophilic substitution reaction, belonging to SN 2 The bimolecular nucleophilic substitution reaction process also adopts the aprotic solvent as the solventThe reaction solvent in the step, such as chloroform, carbon tetrachloride, 1, 4-dioxane and acetonitrile, can be chloroform.
168.56g of the product 5, 5-dimethyl-2-chloro-1, 3, 2-dioxaphosphorinane (1.00mol) obtained in example 1 is added into a 500mL three-neck flask, 238.4g of chloroform (2.0mol) is added to be completely dissolved, 30.05 ethylene diamine (0.50mol) is dropwise added at about 0 ℃ at the beginning, the dropwise addition is controlled to be finished within 2h, the temperature is raised to 40 ℃ for continuous reaction for 3h after the reaction is finished, all white feed liquid is poured into ice acetone to be cooled and separated out after the reaction is finished, the mixture is filtered and separated, acetone and deionized water are used for cleaning for multiple times until the pH of the reaction product is close to neutral, and the finally filtered white solid is placed in a vacuum oven at 70 ℃ for drying for 12h to obtain 153.72g of the flame retardant product with the structure (III-1). (yield: 94.8%)
Example 4
168.56g of the product of the above synthesis, 5-dimethyl-2-chloro-1, 3, 2-dioxaphosphorinane (1.00mol), was taken and placed in a 500mL three-necked flask, and dissolved in 72.1g of tetrahydrofuran (1.00mol) under control of N 2 Under the protected reaction conditions, the initial dropping temperature was controlled to be 5 ℃, 43.07g of piperazine (0.50mol) was added dropwise to the 500ml three-neck flask over 2 hours under stirring, and after the addition of piperazine was completed, the temperature was kept at 30 ℃ to continue the reaction for 4 hours. The white solid solution obtained above was filtered and separated. And continuously washing and filtering the obtained white solid for multiple times by using acetone and deionized water until the pH value of the filtrate of the deionized water is close to neutral. The white solid obtained by final filtration was dried in a vacuum oven at 70 ℃ for 12 hours to give 157.23g of the flame retardant of the structure (III-7). (yield: 89.7%)
Example 5
175.17g of N, N '-bis (5, 5-dimethyl-1, 3-dioxo-2-phosphocyclohexylphosphoramido) -3, 3' -piperazine (obtained in example 4) were weighed out, dissolved in 132.17g of ethyl acetate (1.50mol), and N was introduced during the reaction 2 And (3) protecting, controlling the dropping temperature to be 20 ℃, dropping 68.02.g of hydrogen peroxide (2.00mol) within 2h, and subsequently raising the reaction temperature to 60 ℃ for reacting for 6 h. After the reaction is finished, pouring the reaction liquid into the ice methanol for precipitation, and continuously washing and filtering the obtained white solid for 3 times by using acetone and deionized water. The white solid obtained by the final filtration was dried in a vacuum oven at 80 ℃ for 12 hours to obtain 139.82g of the flame retardant having the structure (IV-5). (yield: 73.1%)
Example 6
175.17g of N, N '-bis (5, 5-dimethyl-1, 3-dioxo-2-phosphocyclamate) -3, 3' -piperazine obtained in example 4 were weighed out (0.50mol), dissolved in 138.12g of toluene (1.50mol), and charged with N during the reaction 2 Protecting, controlling the dropping temperature at 60 ℃, and adding 64.13g of S in batches in 2 hours 8 (2.00mol) of crystal powder, and then raising the reaction temperature to 100 ℃ for 6 hours. After the reaction is finished, pouring the reaction liquid into the ice methanol for precipitation, and continuously washing and filtering the obtained white solid for 3 times by using acetone and deionized water. The white solid obtained by final filtration was dried in a vacuum oven at 80 ℃ for 12 hours to give 138.64g of a flame retardant having the structure (V-5). (yield: 66.9%)
The following examples illustrate specific applications of the present invention
Example 7
Selecting viscose fibers in regenerated cellulose to prepare viscose flame-retardant fibers;
bamboo fiber pulp is used as a raw material, and the alkali cellulose is prepared by the working procedures of dipping, squeezing, crushing, ageing, cooling, yellowing and the like;
mixing and dissolving a flame retardant with the mass fraction of 20% relative to viscose fibers and the yellowed alkali cellulose into flame-retardant cellulose viscose, adding polyethylene glycol with the mass fraction of 3% relative to the flame retardant in the dissolving process to realize good dispersion of a dispersing agent in the dissolved viscose, filtering, ripening, defoaming and filtering to obtain viscose spinning dope, spinning, and preparing the flame-retardant viscose by controlling the temperature of the spinning dope to be 50 ℃ through the working procedures of drafting, cutting, washing, desulfurizing, oiling, drying and the like, wherein the content of sulfuric acid in the spinning dope is 100g/L, the content of zinc sulfate is 9g/L, the content of sodium sulfate is 300g/L and the content of aluminum sulfate is 10 g/L.
Comparative example 1
Selecting viscose fibers in regenerated cellulose to prepare viscose flame-retardant fibers;
bamboo fiber pulp is used as a raw material, and the alkali cellulose is prepared by the working procedures of dipping, squeezing, crushing, ageing, cooling, yellowing and the like;
mixing and dissolving a commercial flame retardant NLD-02, 2,2 '-dioxo [ 5.5-dimethyl-1, 3, 2-dioxaphosphorinane ]2,2' -disulfide with the mass fraction of the viscose fiber being 20% with sulfonated alkali cellulose to obtain flame-retardant cellulose viscose, adding polyethylene glycol with the mass fraction being 3% relative to the mass fraction of the flame retardant during the dissolving process, filtering, ripening, defoaming and filtering to obtain viscose fiber spinning dope, spinning, controlling the temperature of the spinning dope to be 50 ℃, and preparing the flame-retardant viscose fiber through the working procedures of drafting, cutting, washing, desulfurizing, oiling, drying and the like.
Example 7 is the same except for the difference in flame retardant
Performance testing
The results of the flame retardant effect and mechanical property tests of the five synthetic flame retardants of comparative examples 7 to 11 with commercially available flame retardants are shown in Table 1 below
TABLE 1
| Example 7 | Example 8 | Example 9 | Example 10 | Example 11 | Comparative example 1 | |
| Flame retardant | (II-8) | (III-1) | (III-7) | (IV-5) | (V-5) | NLD-02 |
| Tensile strength (CN/dtex) | 3.47 | 3.59 | 3.63 | 3.67 | 3.65 | 2.60 |
| LOI(％) | 26 | 31 | 30 | 29 | 31 | 22 |
As is clear from the data in Table 1, the flame retardant effect of the commercially available flame retardants is inferior to that of the flame retardant of the present invention, and the commercially available flame retardants cause a decrease in tensile strength.
The flame retardant (II) - (V) synthesized by the invention has good flame retardant property and mechanical property in the application of flame-retardant regenerated fiber, and has wide prospect in the field of internal addition type flame retardants of regenerated fiber.
The particular embodiments chosen above are illustrative of the preferred forms of the invention and are not limiting of the application, as numerous modifications and variations will readily occur to those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the principle of the present application shall be included in the protection scope of the present application.
Claims (10)
1. A compound of formula (II):
in the formula (II), R 1 、R 2 Each independently represents C 1-4 Alkyl of R 3 、R 4 Each independently represents C 1-4 An alkylene group of (a); r 21 、R 22 When not bonded, R 21 、R 22 Each independently represents a hydrogen atom or C 1-6 Alkyl of R 21 And R 22 When bound, the N atom is bonded to R 21 、R 22 Form C 3-8 The nitrogen-containing aliphatic heterocyclic structure of (1).
2. The compound of claim 1, wherein: the compound shown in the formula (II) is any one of the following compounds:
3. a compound represented by the formula (III):
in the formula (III), R 1 、R 2 、R 5 And R 6 Each independently represents C 1-4 Alkyl of R 3 、R 4 、R 7 And R 8 Each independently represents C 1-4 An alkylene group of (a); r 11 And R 12 When not linked R 11 And R 12 Each represents a hydrogen atom or C 1-4 Alkyl of R 11 And R 12 When linked, R 11 -R 12 and-N-R 13 -N-forms a five-eight membered aliphatic ring structure; r is 11 And R 12 When not linked, R 13 Represents C 1-6 Alkylene of (A), R 11 And R 12 When linked, R 13 And the left and right N and R 11 -R 12 Forming a five-eight membered aliphatic ring structure.
4. The compound of claim wherein:
the compound shown in the formula (III) is any one of the following compounds:
5. a compound of formula (IV):
in the formula (IV), R 1 、R 2 、R 5 And R 6 Each independently represents C 1-4 Alkyl of R 3 、R 4 、R 7 And R 8 Each independently represents C 1-4 An alkylene group of (a); r 11 And R 12 When not linked R 11 And R 12 Each represents a hydrogen atom or C 1-4 Alkyl of R 11 And R 12 When linked, R 11 -R 12 and-N-R 13 -N-forms a five-eight membered aliphatic ring structure; r 11 And R 12 When not linked, R 13 Represents C 1-6 Alkylene of (A), R 11 And R 12 When linked, R 13 And the left and right N and R 11 -R 12 Forming a five-to eight-membered aliphatic ring structure.
6. The compound of claim 5, wherein: the compound shown in the formula (IV) is any one of the following compounds:
7. a compound of formula (V):
in the formula (V), R 1 、R 2 、R 5 And R 6 Each independently represents C 1-4 Alkyl of R 3 、R 4 、R 7 And R 8 Each independently represents C 1-4 An alkylene group of (a); r 11 And R 12 When not linked, R 11 And R 12 Each represents a hydrogen atom or C 1-4 Alkyl of R 11 And R 12 When linked, R 11 -R 12 and-N-R 13 -N-forms a five-to eight-membered aliphatic ring structure; r is 11 And R 12 When not linked, R 13 Represents C 1-6 Alkylene of (A), R 11 And R 12 When linked, R 13 And the left and right two of N and R 11 -R 12 Forming a five-to eight-membered aliphatic ring structure.
8. The compound of formula (V) according to claim 7, characterized in that: the compound represented by the formula (V) is any one of the following compounds:
9. use of a compound according to any one of claims 1 to 8 as a flame retardant in the preparation of regenerated cellulose flame retardant fibres.
10. A regenerated cellulose flame-retardant fiber using the compound of any one of claims 1 to 9 as a flame retardant.
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