CN110527100A - Poly- phosphamide fire retardant and its preparation method and application - Google Patents
Poly- phosphamide fire retardant and its preparation method and application Download PDFInfo
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- CN110527100A CN110527100A CN201910868126.3A CN201910868126A CN110527100A CN 110527100 A CN110527100 A CN 110527100A CN 201910868126 A CN201910868126 A CN 201910868126A CN 110527100 A CN110527100 A CN 110527100A
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- poly
- monomer
- fire retardant
- phosphamide
- phosphamide fire
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 70
- MCWXGJITAZMZEV-UHFFFAOYSA-N dimethoate Chemical compound CNC(=O)CSP(=S)(OC)OC MCWXGJITAZMZEV-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000000178 monomer Substances 0.000 claims description 46
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 239000002861 polymer material Substances 0.000 claims description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 11
- -1 Phenyl Ester Chemical class 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 229920000642 polymer Polymers 0.000 claims description 9
- 239000011347 resin Substances 0.000 claims description 9
- 229920005989 resin Polymers 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 6
- ZLSMCQSGRWNEGX-UHFFFAOYSA-N bis(4-aminophenyl)methanone Chemical compound C1=CC(N)=CC=C1C(=O)C1=CC=C(N)C=C1 ZLSMCQSGRWNEGX-UHFFFAOYSA-N 0.000 claims description 6
- 238000005360 mashing Methods 0.000 claims description 6
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 239000011159 matrix material Substances 0.000 claims description 5
- BZCGWAXQDLXLQM-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O.ClP(Cl)(Cl)=O BZCGWAXQDLXLQM-UHFFFAOYSA-N 0.000 claims description 5
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 239000004677 Nylon Substances 0.000 claims description 3
- 239000012752 auxiliary agent Substances 0.000 claims description 3
- 125000003963 dichloro group Chemical group Cl* 0.000 claims description 3
- 239000001177 diphosphate Substances 0.000 claims description 3
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 claims description 3
- 235000011180 diphosphates Nutrition 0.000 claims description 3
- 230000006872 improvement Effects 0.000 claims description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 3
- 229920001778 nylon Polymers 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 claims description 2
- WVPKAWVFTPWPDB-UHFFFAOYSA-N dichlorophosphinic acid Chemical compound OP(Cl)(Cl)=O WVPKAWVFTPWPDB-UHFFFAOYSA-N 0.000 claims description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims 2
- 230000008021 deposition Effects 0.000 claims 2
- 230000035484 reaction time Effects 0.000 claims 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims 1
- 235000017557 sodium bicarbonate Nutrition 0.000 claims 1
- DWSWCPPGLRSPIT-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinin-6-ium 6-oxide Chemical class C1=CC=C2[P+](=O)OC3=CC=CC=C3C2=C1 DWSWCPPGLRSPIT-UHFFFAOYSA-N 0.000 abstract description 14
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 abstract description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 12
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 10
- 230000008901 benefit Effects 0.000 abstract description 8
- 239000011574 phosphorus Substances 0.000 abstract description 8
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 8
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 6
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 14
- 239000000463 material Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 8
- 238000000354 decomposition reaction Methods 0.000 description 5
- 229920002647 polyamide Polymers 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 229910019142 PO4 Inorganic materials 0.000 description 4
- 239000004952 Polyamide Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000010452 phosphate Substances 0.000 description 4
- 229920000747 poly(lactic acid) Polymers 0.000 description 4
- 239000004626 polylactic acid Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 229920000388 Polyphosphate Polymers 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- DMSZORWOGDLWGN-UHFFFAOYSA-N ctk1a3526 Chemical compound NP(N)(N)=O DMSZORWOGDLWGN-UHFFFAOYSA-N 0.000 description 2
- 101150073654 dapB gene Proteins 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000003546 flue gas Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000001205 polyphosphate Substances 0.000 description 2
- 235000011176 polyphosphates Nutrition 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 101000931422 Photobacterium phosphoreum Methenyltetrahydrofolate cyclohydrolase Proteins 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 101000752546 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) Transaminated amino acid decarboxylase Proteins 0.000 description 1
- AFCIMSXHQSIHQW-UHFFFAOYSA-N [O].[P] Chemical compound [O].[P] AFCIMSXHQSIHQW-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000001793 charged compounds Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000013461 intermediate chemical Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- CMPQUABWPXYYSH-UHFFFAOYSA-N phenyl phosphate Chemical compound OP(O)(=O)OC1=CC=CC=C1 CMPQUABWPXYYSH-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 150000003141 primary amines Chemical group 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- AYEKOFBPNLCAJY-UHFFFAOYSA-O thiamine pyrophosphate Chemical compound CC1=C(CCOP(O)(=O)OP(O)(O)=O)SC=[N+]1CC1=CN=C(C)N=C1N AYEKOFBPNLCAJY-UHFFFAOYSA-O 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
- C08G79/02—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing phosphorus
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyamides (AREA)
- Fireproofing Substances (AREA)
Abstract
The present invention provides a kind of poly- phosphamide fire retardants and its preparation method and application.The poly- phosphamide fire retardant of the present invention has the general formula structure as shown in formula (I).Poly- phosphamide fire retardant provided by the invention is the new flame retardant for combining poly- phosphamide and double DOPO derivatives, combine the fire-retardant and DOPO fire-retardant advantage of the phosphorus nitrogen of poly- phosphamide, so that fire retardant of the present invention has high content of phosphorus, nitrogen content, high-fire resistance, the advantages of high charring rate and high residue amount, excellent fireproof performance.
Description
Technical field
The present invention relates to flame retardant areas, in particular to a kind of poly- phosphamide fire retardant and preparation method thereof and answer
With.
Background technique
Although traditional halogenated flame retardant shows excellent flame retardant effect, but can be generated in combustion process it is a large amount of it is toxic,
Mordant hydrogen halide etc. increases raw smoke and flue gas toxity, therefore the trend of Fire Retardant Industry circle is exactly to seek now
It looks for high thermal stability, chemical stability, the halogen-free flame retardants of electrical property and high flame resistance.Phosphorus flame retardant is nothing at present
The first major class of halogen fire retardant, including be mostly inorganic matter such as red phosphorus or small organic molecule such as TPP etc., these fire retardants have or
Have concurrently: thermal stability is poor, volatility is larger, easy to migrate and polymer compatibility is poor, influences on polymer machinery physical property
The disadvantages of larger, limits its application.
In recent years, the polyphosphate of high relative molecular mass and poly- phosphamide are achieved at the flame-retardant modified aspect of polymer
Preferable effect.
The derivative of the miscellaneous -10- phospho hetero phenanthrene -10- oxide (DOPO) of 9,10- dihydro-9-oxy is also the more one kind of research
Phosphorus flame retardant.DOPO has rigid structure and stable phosphorus structure, so that the environmental protection with higher of the fire retardant containing DOPO
The advantages that discharging less flue gas in property, thermal stability and combustion process.DOPO because in structure contain P-H key, thus to double bond,
The great activity such as epoxy group and carbonyl can react and generate many DOPO derivatives, these derivatives have than general not cyclic
Machine phosphate has higher thermal stability and anti-flammability.Compared to phosphate, phosphoramide types fire-retardant composite material is burning
During can form bigger crossover network structure, make it there are more residual layer of charcoal to enhance solid phase flame retardant effect.Also,
Most of phosphate compound is not still able to satisfy the processing request of the higher polymer of processing temperature such as polyamide.
In view of this, the present invention is specifically proposed.
Summary of the invention
The first object of the present invention is to provide a kind of poly- phosphamide fire retardant.Flame retardance of polymer provided by the present invention
Agent, be using poly- phosphamide as molecular skeleton, and side chain introduce DOPO structure, molecular weight with higher can be effectively
The compatibility for improving fire retardant and basis material, and disperses fire retardant more uniformly in basis material, obtain compared with
While high fire-retardance efficiency, basis material can also maintain preferable mechanical property.
The second object of the present invention is to provide the preparation method of poly- phosphamide fire retardant described in one kind.
The third object of the present invention is to provide poly- phosphamide fire retardant described in one kind in the improvement of polymer flame resistance
Application.
The fourth object of the present invention is to provide a kind of polymer material that flame resistance improves.
In order to realize above-mentioned purpose of the invention, the following technical scheme is adopted:
A kind of poly- phosphamide fire retardant, the poly- phosphamide fire retardant have following general formula structure:
Wherein, in formula (I), wherein in formula (I), R1、R2、R'1、R'2It is independently the alkyl of C1-C12, C3-C6
Naphthenic base, the aryl of C5-C12, the alkylidene aryl of C6-C12 or the arlydene alkyl of C6-C12；A, b, a', b' distinguish
It is independently the integer of 0-4；
R3ForOrAny one of structure.
Meanwhile present invention provides a kind of preparation methods of poly- phosphamide fire retardant, comprising:
(a) willIt is reacted with 4,4'- diaminobenzophenone, obtains list
Body 1；
(b) monomer 1 is reacted with monomer 2, obtains phosphamide fire retardant；Wherein, monomer 2 is benzene phosphinylidyne dichloro, dichloride
Any one of two phosphoryl chloride phosphorus oxychloride of phenyl phosphate or pentaerythrite diphosphate rouge.
Further, the answering in the improvement of polymer flame resistance the present invention also provides the poly- phosphamide fire retardant of the present invention
With.
Likewise, present invention provides a kind of improved polymer material of flame resistance, the polymer material includes: poly-
Object material matrix is closed, and is doped in the poly- phosphamide fire retardant of the present invention of polymer material matrix.
Compared with prior art, the invention has the benefit that
(1) poly- phosphamide fire retardant provided by the invention is the novel resistance for combining poly- phosphamide and double DOPO derivatives
Agent is fired, the fire-retardant and DOPO fire-retardant advantage of the phosphorus nitrogen of poly- phosphamide is combined, so that fire retardant of the present invention contains with high phosphorus
The advantages of amount, nitrogen content, high-fire resistance, high charring rate and high residue amount, excellent fireproof performance.
(2) the poly- phosphamide flame retardant molecule amount of the present invention is higher, good with basis material compatibility, disperses in basis material
Property is good, so that basis material mechanical property is preferable.
(3) the poly- phosphamide fire retardant preparation method of the present invention is simple, and condition is easily controllable, and yield is relatively high and stable, product
Purity is high.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described.
Fig. 1 is the mass spectrogram of monomer 1 in embodiment 1；
Fig. 2 is the infrared spectrum of monomer 1 and target product in embodiment 1；
Fig. 3 is the thermogravimetric analysis figure of monomer 1 and target product in embodiment 1.
Specific embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
Understand, the following example is merely to illustrate the present invention, and is not construed as limiting the scope of the invention.It is not specified in embodiment specific
Condition person carries out according to conventional conditions or manufacturer's recommended conditions.Reagents or instruments used without specified manufacturer is
The conventional products that can be obtained by commercially available purchase.
In view of existing phosphorus flame retardant, the fire retardant of polyphosphate especially containing DOPO structure is in anti-flammability and polymerization
Deficiency present in object modification etc., the present invention provides a kind of poly- phosphoramide types fire retardants.
Specifically, polyamide flame retardant mechanism provided by the present invention is as follows:
In certain embodiments of the present invention, in polyamide flame retardant compound shown in formula (I), R1、R2、R3、R4Respectively
It is independently the alkyl of C1-C12, the naphthenic base of C3-C6, the aryl of C5-C12, the alkylidene aryl or C6-C12 of C6-C12
Arlydene alkyl；
Preferably, R1、R2、R'1、R'2It is independently the alkyl of C1-C6, such as R1、R2、R'1、R'2Independently
It can be methyl, ethyl, propyl, isopropyl, butyl, isobutyl group, amyl, neopentyl, octyl, one of iso-octyl etc..
A, b, a', b' are independently the integer of 0-4, for example, a, b, c, d independently can be 0,1,2,3, or
Person 4.
R3 is(PPDC yl),(PDCP yl), or
Any one of (SPDPC yl) structure.
N is the integer of 3-20, for example, n can be 3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19
Or 20 etc..
Polyamide-based fire retardant has thermal stability high, and volatility is low, and due to hydrogen bond action and viscosity is higher, P-N association
Same-action can promote the formation of the crossover network in burning.These features can increase the density of whole system, make poly- phosphamide
It is polymer-modified to be more retained in the base in burning, generate more more stable layer of charcoal.It is provided by the present invention poly-
In amide fire retardant, DOPO and poly- phosphamide are organically combined, both comprehensive advantage, so that fire retardant has high content of phosphorus, nitrogen
The advantages of content, high-fire resistance, high charring rate and high residue amount, has good compatibility with high molecular polymer, in matrix
There is good dispersibility in material, can effectively improve the firing resistance of polymer material.
In currently preferred some embodiments, in the polyamide flame retardant compound as shown in above formula (I), R3For
SPDPC base.It is i.e. currently preferred to provide the flame retardant compound as shown in following formula (II):
In formula (II) compound, R1、R2、R'1、R'2It is independently the alkyl of C1-C12, the naphthenic base of C3-C6, C5-
The aryl of C12, the alkylidene aryl of C6-C12 or the arlydene alkyl of C6-C12；
Preferably, R1、R2、R3、R4It is independently the alkyl of C1-C6, such as R1、R2、R3、R4Independently can be with
For methyl, ethyl, propyl, isopropyl, butyl, isobutyl group, amyl, neopentyl, octyl, one of iso-octyl etc..
A, b, a', b' are independently the integer of 0-4, for example, a, b, a', b' independently can be 0,1,2,3,
Or 4.
N is the integer of 3-20, for example, n can be 3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19
Or 20 etc..
In preferred some embodiments of the invention, provided poly- phosphamide flame retardant mechanism is as follows:
Wherein, in poly- phosphamide compound shown in formula (III), n is the integer of 3-20, for example, n can be 3,4,5,6,7,
8,9,10,11,12,13,14,15,16,17,18,19 or 20 etc..
Meanwhile the present invention also provides the preparation methods of the poly- phosphamide fire retardant of arbitrary structures as above, main includes such as
Lower step:
(a) willIt is reacted with 4,4'- diaminobenzophenone (DAPB),
Obtain monomer 1；
Specific reaction equation can refer to as follows:
Specific steps condition can refer to as follows:
In gas shield (nitrogen or the inert gas shielding such as helium, argon gas) and solvent-free presence (that is, this step
Reaction is without being added solvent) under the conditions of, after compound (i) is mixed with DAPB, 3-5h is reacted under the conditions of 180-200 DEG C；
Then, after completion of the reaction, solvent is added, so that product is precipitated, after product purification, obtains monomer 1.
In some embodiments of the present invention, the molar ratio of compound (i) and 4,4'- diaminobenzophenone is 6:1.
In some embodiments of the present invention, solvent for use is toluene.
In some embodiments of the present invention, the purifying has to carry out mashing washing for the crude product of Precipitation
Body includes successively carrying out mashing washing to crude product with tetrahydrofuran, methylene chloride and methanol.
(b) after dissolving monomer 1 and monomer 2 in a solvent, acid binding agent is added, is heated to 80-100 DEG C of reaction 6-8h；So
Afterwards, after product be precipitated precipitating being separated by filtration, product is washed and is purified, the poly- phosphamide fire retardant of target product is obtained.
In some embodiments of the present invention, monomer 2 is benzene phosphinylidyne dichloro, PhosphorodichloridicAcid Acid Phenyl Ester or pentaerythrite
Any one of two phosphoryl chloride phosphorus oxychloride of biphosphonate；
Preferably, monomer 2 is two phosphoryl chloride phosphorus oxychloride of pentaerythrite diphosphate rouge.
In some embodiments of the present invention, acid binding agent used is triethylamine, diethylamine, diisopropylethylamine and carbon
At least one of sour hydrogen sodium.
In some embodiments of the present invention, the molar ratio of monomer 1, monomer 2 and acid binding agent is 1:1:2.
In some embodiments of the present invention, solvent for use is the mixed solvent of one or both of DMF or DMAC.
In some embodiments of the present invention, the washing purifying be successively with methylene chloride, water and methanol to product into
Row washing purifying.
Further, the flame resistance that the poly- phosphamide fire retardant of the present invention can be further used for polymer material is improved,
Therefore, the present invention can also provide a kind of improved resin combination of flame resistance and a kind of polymerization with preferable flame resistance
Object material.
The raw material of the resin combination includes: the poly- phosphamide fire retardant of resin and the present invention to be modified, and optionally
Auxiliary agent；
In certain embodiments of the present invention, resin to be modified includes: PET, PLA, PP, ABS and nylon etc.；
In certain embodiments of the present invention, the auxiliary agent includes: synergist (graphite etc.), carbon forming agent (pentaerythrite
One or more of Deng) etc..
The improved method of polymer material flame resistance be referred to following steps progress: by poly- phosphamide fire retardant with polymerize
Object material is uniformly mixed, and then melting extrusion is granulated, so that poly- phosphamide fire retardant is doped into polymer material matrix, is realized
The flame resistance of polymer material is improved.
In certain embodiments of the present invention, can be used for modified polymer material includes: PET, PLA, PP, ABS, with
And nylon.
Embodiment 1
(1) in 500ml single necked round bottom flask, DOPO 64g (0.296mol), 4,4'- diaminobenzophenone is added
(DABP) 10.5g (0.049mol), bottleneck load onto constant pressure funnel, built-in 250mL deaerated toluene.
After replacing nitrogen, 180 DEG C are heated to, so that DOPO reacts 5 hours under solvent-free conditions with DABP.Reaction terminates
Afterwards, 120 DEG C are cooled to, toluene is added into system from constant pressure funnel, a large amount of yellow solids are precipitated.After filtering, by yellow
Solid successively with tetrahydrofuran, methylene chloride, methanol mashing washing, obtains white powder product monomer 1, yield 80%.
Reaction process is shown below:
1 Mass Spectrometer Method result of monomer is as shown in Figure 1, by Fig. 1 testing result it is found that 1 molecular weight detection result of gained monomer
Close with notional result, it is correct that the molecular ion peak at 627.15 demonstrates product.Thus it is able to verify that title intermediate chemical combination
The acquisition of object.
(2) in 2L single necked round bottom flask, 62.66g (0.1mol) monomer 1 is added, 32.3g (0.1mol) pentaerythrite is double
Two phosphoryl chloride phosphorus oxychloride of phosphate ester, triethylamine 20.2g (0.2mol, 27.7mL), dry DMF950mL are heated to 80 DEG C after replacing nitrogen
Reaction 5 hours, is precipitated a large amount of white solid products, after filtering, is successively washed with methylene chloride, methanol, obtain final product, produces
Rate 95%.
Reaction process is shown below:
The infrared spectrum control test result of gained target polymerization product and monomer 1 is as shown in Fig. 2, as shown in Figure 2: In
3200cm-1To 3500cm-1The variation of peak type illustrates-NH in monomer 12Group has occurred and that reaction；In 1700cm-1And 1300cm-1Place, it can be seen that monomer 1 respectively has more after polymerization reaction obtains polymerizate carrys out an absorption peak, respectively phosphorus in monomer 2
The stretching vibration peak of oxygen double bond and phosphorus oxygen singly-bound illustrates monomer 1 and monomer 2 successful polymerization.
Meanwhile the thermogravimetric control test result of polymerizate and monomer 1 is as shown in figure 3, from the figure 3, it may be seen that polymerizate
Decomposition temperature is 304 DEG C, and 700 DEG C of residual quantities are 32%, and the decomposition temperature of monomer 1 is 321 DEG C, and 700 DEG C of residual quantities are 18.3%.
Monomer 1 before fast decoupled, there is certain weightlessness because there is primary amine groups.Monomer 2 compared with monomer 1, thermal stability it is poor but
Phosphorus content is higher.So polymerizate is after introducing monomer 2, relative to monomer 1, decomposition temperature is lower, and residual quantity is higher.
Experimental example 1
By 50g product and 950g polylactic acid (PLA, row number: 4032d) after twin-screw extrusion, it is molded obtained fire retardant and contains
The test batten of amount 5%.Flame retardant test is measured through oxygen index instrument, and batten limit oxygen index is 31.7.It is surveyed through Vertical combustion instrument
Fixed, batten burning rank is V-0 grades.Mechanics Performance Testing is measured through pendulum impact test, and batten toughness is 2.15kj/m2。
It is measured through omnipotent test machine, batten tensile strength is 54.25MPa, tensile modulus of elasticity 587.56MPa.Batten bending strength
For 82.02Mpa, bending modulus 3213MPa.Thermodynamic property test, measures, batten temperature of initial decomposition through thermogravimetric analyzer
It is 346.8 DEG C, residual mass score is 1.6% when maximum decomposition temperature is 417.3 DEG C, 700 DEG C.
Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent
Pipe present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: its according to
So be possible to modify the technical solutions described in the foregoing embodiments, or to some or all of the technical features into
Row equivalent replacement；And these are modified or replaceed, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution
The range of scheme.
Claims (10)
1. a kind of poly- phosphamide fire retardant, which is characterized in that the poly- phosphamide fire retardant has following general formula structure:
Wherein, in formula (I), R1、R2、R'1、R'2It is independently the alkyl of C1-C12, the naphthenic base of C3-C6, the virtue of C5-C12
Base, the alkylidene aryl of C6-C12 or the arlydene alkyl of C6-C12；
A, b, a', b' are independently the integer of 0-4；
R3ForOrAny one of structure；
N is the integer of 3-20.
2. poly- phosphamide fire retardant according to claim 1, which is characterized in that the poly- phosphamide fire retardant has as follows
General formula structure:
3. poly- phosphamide fire retardant according to claim 2, which is characterized in that the structure of the poly- phosphamide fire retardant is such as
Under:
4. the preparation method of poly- phosphamide fire retardant of any of claims 1-3 characterized by comprising
(a) willIt is reacted with 4,4'- diaminobenzophenone, obtains monomer 1；
(b) monomer 1 is reacted with monomer 2, obtains phosphamide fire retardant；
Wherein, monomer 2 is benzene phosphinylidyne dichloro, appointing in two phosphoryl chloride phosphorus oxychloride of PhosphorodichloridicAcid Acid Phenyl Ester or pentaerythrite diphosphate rouge
It is a kind of.
5. the preparation method according to claim 4, which is characterized in that step (a) includes the following steps:
By compound (i) and 4, reaction is heated after the mixing of 4'- diaminobenzophenone, obtains monomer 1；Then solvent is added, it will
After deposition and purification be precipitated, monomer 1 is obtained；
Preferably, the molar ratio of compound (i) and 4,4'- diaminobenzophenone is 6:1；
Preferably, reaction temperature is 180-200 DEG C, reaction time 3-5h；
It preferably, further include that solvent is added into system after heating reaction in the method, it then will be after deposition and purification be precipitated
The step of obtaining monomer 1；
It is furthermore preferred that the solvent includes toluene, at least one of dimethylbenzene and Isosorbide-5-Nitrae-dioxane；
It is furthermore preferred that purifying includes mashing washing；
It is furthermore preferred that mashing washing includes: successively to carry out mashing washing with tetrahydrofuran, methylene chloride and methanol.
6. the preparation method according to claim 4, which is characterized in that step (b) includes the following steps:
To dissolved with acid binding agent heating reaction in the solution of monomer 1 and monomer 2, is added, poly- phosphamide fire retardant is obtained；
Preferably, the molar ratio of monomer 1 and monomer 2 is 1:1；
Preferably, it includes: at least one of DMF and DMAC that monomer 1 and monomer 2, which dissolve solvent for use,；
Preferably, acid binding agent includes: at least one of triethylamine, diethylamine, diisopropylethylamine and sodium bicarbonate；
Preferably, acid binding agent and monomer 1, the molar ratio of monomer 2 are 1:1:2；
Preferably, the temperature for heating reaction is 80-100 DEG C, time 6-8h.
7. application of the poly- phosphamide fire retardant of any of claims 1-3 in the improvement of polymer flame resistance.
8. a kind of improved polymer material of flame resistance, which is characterized in that the polymer material includes: polymer material base
Body, and it is doped in the poly- phosphamide fire retardant of any of claims 1-3 of polymer material matrix.
9. a kind of improved resin combination of flame resistance, which is characterized in that the raw material of the resin combination includes:
Resin, poly- phosphamide fire retardant of any of claims 1-3 and optional auxiliary agent.
10. resin combination according to claim 9, which is characterized in that the resin includes: PET, PLA, PP, ABS,
And one or more of nylon.
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