CN110156840B - Phosphorus-nitrogen flame retardant containing DOPO and preparation method thereof - Google Patents
Phosphorus-nitrogen flame retardant containing DOPO and preparation method thereof Download PDFInfo
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- CN110156840B CN110156840B CN201910406293.6A CN201910406293A CN110156840B CN 110156840 B CN110156840 B CN 110156840B CN 201910406293 A CN201910406293 A CN 201910406293A CN 110156840 B CN110156840 B CN 110156840B
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- dopo
- phosphaphenanthrene
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 69
- 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 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 title claims abstract description 17
- DWSWCPPGLRSPIT-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinin-6-ium 6-oxide Chemical compound C1=CC=C2[P+](=O)OC3=CC=CC=C3C2=C1 DWSWCPPGLRSPIT-UHFFFAOYSA-N 0.000 title abstract 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 48
- 238000003756 stirring Methods 0.000 claims description 29
- 239000000047 product Substances 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 21
- BSYJHYLAMMJNRC-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-ol Chemical compound CC(C)(C)CC(C)(C)O BSYJHYLAMMJNRC-UHFFFAOYSA-N 0.000 claims description 19
- 239000003377 acid catalyst Substances 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000006227 byproduct Substances 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 14
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims description 11
- 229940092714 benzenesulfonic acid Drugs 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 7
- ZEYUSQVGRCPBPG-UHFFFAOYSA-N 4,5-dihydroxy-1,3-bis(hydroxymethyl)imidazolidin-2-one Chemical compound OCN1C(O)C(O)N(CO)C1=O ZEYUSQVGRCPBPG-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- BNCADMBVWNPPIZ-UHFFFAOYSA-N 2-n,2-n,4-n,4-n,6-n,6-n-hexakis(methoxymethyl)-1,3,5-triazine-2,4,6-triamine Chemical compound COCN(COC)C1=NC(N(COC)COC)=NC(N(COC)COC)=N1 BNCADMBVWNPPIZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- USDJGQLNFPZEON-UHFFFAOYSA-N [[4,6-bis(hydroxymethylamino)-1,3,5-triazin-2-yl]amino]methanol Chemical compound OCNC1=NC(NCO)=NC(NCO)=N1 USDJGQLNFPZEON-UHFFFAOYSA-N 0.000 claims description 2
- YGCOKJWKWLYHTG-UHFFFAOYSA-N [[4,6-bis[bis(hydroxymethyl)amino]-1,3,5-triazin-2-yl]-(hydroxymethyl)amino]methanol Chemical compound OCN(CO)C1=NC(N(CO)CO)=NC(N(CO)CO)=N1 YGCOKJWKWLYHTG-UHFFFAOYSA-N 0.000 claims description 2
- 230000001476 alcoholic effect Effects 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- MVIOINXPSFUJEN-UHFFFAOYSA-N benzenesulfonic acid;hydrate Chemical compound O.OS(=O)(=O)C1=CC=CC=C1 MVIOINXPSFUJEN-UHFFFAOYSA-N 0.000 claims description 2
- AUQAUAIUNJIIEP-UHFFFAOYSA-N 3,4,5-trimethylphenyl methylcarbamate Chemical compound CNC(=O)OC1=CC(C)=C(C)C(C)=C1 AUQAUAIUNJIIEP-UHFFFAOYSA-N 0.000 claims 1
- AVKLPTSKTBCMGS-UHFFFAOYSA-N but-2-ene-1,2,3,4-tetrol urea Chemical class NC(=O)N.C(O)C(=C(O)CO)O AVKLPTSKTBCMGS-UHFFFAOYSA-N 0.000 claims 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 claims 1
- 239000000463 material Substances 0.000 abstract description 13
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 230000007062 hydrolysis Effects 0.000 abstract description 4
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 231100000053 low toxicity Toxicity 0.000 abstract description 3
- 239000000779 smoke Substances 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 238000012662 bulk polymerization Methods 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 description 11
- 238000002485 combustion reaction Methods 0.000 description 9
- 238000001125 extrusion Methods 0.000 description 9
- 230000009477 glass transition Effects 0.000 description 9
- 239000000155 melt Substances 0.000 description 9
- 125000003118 aryl group Chemical group 0.000 description 7
- 229920000742 Cotton Polymers 0.000 description 6
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical group OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 125000001072 heteroaryl group Chemical group 0.000 description 5
- 229920002292 Nylon 6 Polymers 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 4
- 239000003822 epoxy resin Substances 0.000 description 4
- 238000005469 granulation Methods 0.000 description 4
- 230000003179 granulation Effects 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 229920000647 polyepoxide Polymers 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- -1 polypropylene Polymers 0.000 description 3
- 125000006413 ring segment Chemical group 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 125000006702 (C1-C18) alkyl group Chemical group 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 125000004367 cycloalkylaryl group Chemical group 0.000 description 2
- 125000005215 cycloalkylheteroaryl group Chemical group 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 150000005208 1,4-dihydroxybenzenes Chemical group 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- QBOCEXJDAKRLNK-UHFFFAOYSA-N ClP(OBr)Cl Chemical class ClP(OBr)Cl QBOCEXJDAKRLNK-UHFFFAOYSA-N 0.000 description 1
- 229940126062 Compound A Drugs 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000007014 Michaelis-Becker reaction Methods 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- VBQRUYIOTHNGOP-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinine 6-oxide Chemical class C1=CC=C2P(=O)OC3=CC=CC=C3C2=C1 VBQRUYIOTHNGOP-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229920006342 thermoplastic vulcanizate Polymers 0.000 description 1
- 125000004417 unsaturated alkyl group Chemical group 0.000 description 1
Classifications
-
- 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
- C07F9/657163—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 the ring phosphorus atom being bound to at least one carbon atom
- C07F9/657172—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 the ring phosphorus atom being bound to at least one carbon atom the ring phosphorus atom and one oxygen atom being part of a (thio)phosphinic acid ester: (X = O, S)
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Fireproofing Substances (AREA)
Abstract
The invention discloses a phosphorus-nitrogen flame retardant containing DOPO and a preparation method thereof. Book (I)The DOPO-containing phosphorus-nitrogen flame retardant has the chemical structural formula as follows:
Description
Technical Field
The invention belongs to the technical field of flame retardants, and particularly relates to a phosphorus-nitrogen flame retardant containing DOPO and a preparation method thereof.
Background
The high polymer material has the advantages of light weight, high specific strength, good processing property and the like, so the high polymer material is widely applied to various fields of national economy. However, the carbon-hydrogen composite material is extremely easy to burn due to the fact that the carbon-hydrogen composite material mainly comprises carbon and hydrogen elements, and great fire safety hidden dangers are hidden while convenience is brought to life of people.
Because the DOPO-based flame retardant has the advantages of good flame retardant property, no halogen, no toxicity, environmental friendliness and the like, the DOPO-based flame retardant is widely applied to epoxy resin (EP), polyester, polypropylene (PP) and other high polymer materials in recent years. DOPO is an organic phosphorus intermediate, wherein the P-H bond is active and can generate addition reaction with unsaturated bond, carbonyl and the like, and various types of DOPO-based flame retardants can be prepared by utilizing the capability of forming various derivatives.
WO2010135398 reports derivatives of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) containing 2 phosphorus centers (didoo) in one molecule, having good thermal stability and flame retardancy.
US8536256 discloses didoo with different bridges as flame retardants for epoxy resins, which does not include aryl substituted vinyl bridges.
DiDOPO derivatives are reported in JPH11-106619 and do not mention aromatic substituted vinyl bridges.
The DiDOPO flame retardants are prepared by the Michaelis-Becker reaction of DOPO and dihalogenated alkane under the action of strong alkali, expensive strong alkali is used as a raw material, the production cost is high, and the defects of low reaction yield are overcome.
CN1040865393A discloses that the bridge chain structure connecting two DOPO compounds is vinyl containing aryl, and the compound has rigidity and avoids plasticity greatly due to short bridge chain. The aryl on the vinyl increases the steric hindrance, not only greatly increases the chemical stability, but also reduces the volatility of the compound, and overcomes the defects of the known DiDOPO flame retardant.
CN1563152A discloses a method for preparing a polymer type phosphorus-containing flame retardant, which adopts DOPO modified hydroquinone or hydroquinone, phenyl or naphthyl substituted dichloro (bromo) oxyphosphorus as a reaction substrate to obtain the phosphorus-containing polymer type flame retardant, but a catalyst is required to be used in the preparation process of the flame retardant, and a precipitator with 5-10 times of solvent amount is required to be used in the separation process, so that the pollution to the environment is large.
CN101643650A discloses the formation of flame retardant by reacting hydroquinone or hydroquinone containing DOPO with an olefin bearing reactive functional groups, but has poor compatibility with polymers and leaching problems.
In a word, the DOPO-based flame retardant in the prior art has the problems of poor compatibility, easy leaching, low hydrolysis resistance, high preparation cost, low yield, great environmental pollution and the like. Therefore, the invention develops the phosphorus-nitrogen flame retardant containing DOPO and the preparation method thereof, the flame retardant is the organic intumescent flame retardant and is prepared by bulk polymerization, and the preparation method is simple, high in yield, free from environmental pollution and green and environment-friendly.
Disclosure of Invention
The invention aims to provide a phosphorus-nitrogen flame retardant containing DOPO and a preparation method thereof. The phosphorus-nitrogen flame retardant containing DOPO has excellent flame retardant effect, good compatibility with a base material, no exudation in the base material, excellent hydrolysis resistance, low smoke and low toxicity, simple preparation process, high yield and environmental protection.
In order to achieve the purpose, the invention adopts the following technical scheme:
a phosphorus-nitrogen type flame retardant containing DOPO has the following structure:
wherein,
R1、R2one or two selected from H, C1-C18 alkyl, C6-C18 aryl, C3-C18 heteroaryl, fused cycloalkylaryl, fused cycloalkylheteroaryl, fused heterocyclylaryl, fused heterocyclylheteroaryl, and silicon-, oxygen-, sulfur-, carbonyl-, or sulfonyl-substituted C1-C18 alkyl;
or,
R1、R2linked through a saturated/unsaturated alkyl group, or with the N atom, to form a heteroaryl, fused cycloalkylaryl, fused cycloalkylheteroaryl, fused heterocyclylaryl or fused heterocyclylheteroaryl group.
Further, the heteroaryl group is a monocyclic or polycyclic aromatic group, the N atom is attached to an aromatic ring, the heteroaryl group contains one, two or three heterocyclic atoms selected from N, O and S, and the remaining ring atoms are C.
Further, one or more carbon atoms of said heteroaryl group are replaced by a carbonyl group.
Further, said heterocyclyl is a non-aromatic mono-or polycyclic group wherein one or more ring atoms is selected from N, O or S (O)nWherein n is an integer from 0 to 2 and the remaining ring atoms are C.
Further, the alkyl group includes a linear, branched or aromatic ring-containing alkyl group.
For example, the flame retardant may have the structure shown below:
the above is an example of the structure of the DOPO-containing phosphorus-nitrogen type flame retardant of the present invention, and is not limited to the above structure.
The invention also provides a preparation method of the DOPO-containing phosphorus-nitrogen flame retardant, which comprises the following steps:
(1) heating 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) to melt the 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide completely;
(2) adding a compound A with the following structure into molten 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide:
stirring and reacting for a period of time, then raising the temperature and continuing stirring until the reaction is finished, and cooling to obtain the phosphorus-nitrogen flame retardant containing DOPO.
Further, in the above preparation method, a strong acid catalyst is further added in the step (2). The strong acid catalyst can accelerate the reaction speed and improve the production efficiency.
Preferably, the strong acid catalyst is selected from one or more of p-benzenesulfonic acid, p-benzenesulfonic acid hydrate or alcoholic solution thereof, phosphoric acid, hydrochloric acid or sulfuric acid.
Furthermore, the addition amount of the strong acid catalyst is 0.01-5% of the mass of the raw materials.
Further, in the preparation method, the heating temperature in the step (1) is 215-221 ℃.
The temperature is heated to melt the molten metal, and too high a temperature increases energy consumption and increases the process cost.
Further, in the above preparation method, after the step (2) of stirring the reaction for 30-40 minutes, the temperature is raised to 225-230 ℃. According to the preparation method, the viscosity of the system is increased in the later reaction stage, and the reaction can be promoted by effectively stirring by increasing the reaction temperature.
The invention has the following technical characteristics:
1) the phosphorus-nitrogen flame retardant containing DOPO has excellent flame retardant effect and wide application range, and is effective in high polymer flame retardance such as epoxy resin, ABS, PMMA, TPV, nylon, polyester, polyolefin, polyurethane, polycarbonate and the like.
2) The flame retardant belongs to organic macromolecules, so that the flame retardant has good substrate compatibility, cannot seep out of a substrate, and has excellent hydrolysis resistance.
3) The flame retardant of the invention belongs to intumescent flame retardants and has the performance of low smoke and low toxicity.
4) The preparation method has the advantages of simple process, few byproducts, short reaction time, high yield, no use of solvent harmful to the environment, and environmental friendliness.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the described embodiments of the invention without any inventive step, are within the scope of protection of the invention.
Unless defined otherwise, technical or scientific terms used herein shall have the ordinary meaning as understood by one of ordinary skill in the art to which this invention belongs.
Example 1: preparation of flame retardants
490 g of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (dopo) are added into a 1000 ml three-neck flask with a stirrer, the flask is heated to 170 ℃, 210 g of hexamethylol melamine hexa-methyl ether is added after the mixture is completely melted, 0.1% of benzenesulfonic acid serving as a strong acid catalyst can be added for accelerating the reaction, strong stirring is continued, the melt viscosity rises violently, and a byproduct methanol is generated at the same time. After 30 minutes, the temperature was then increased further to 230 ℃ and stirring was continued until almost no methanol was produced. After cooling, the product was a pale yellow solid in 84% yield, which was found to have a glass transition temperature of 140 ℃ by DSC.
The reaction equation is as follows:
example 2: preparation of flame retardants
525 g of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (dopo) are added into a 1000 ml three-neck flask with a stirrer, heated to 170 ℃, and after the mixture is completely melted, 175 g of hexamethylol melamine hexa methyl ether is added, 0.1% of benzenesulfonic acid serving as a strong acid catalyst can be added for accelerating the reaction, the strong stirring is continued, the melt viscosity is increased violently, and a byproduct methanol is generated at the same time. After 35 minutes, the temperature was then increased further to 235 ℃ and stirring was continued until almost no methanol was produced. After cooling, the product was a colorless transparent solid in 89% yield, and the glass transition temperature of this product was 121 ℃ as determined by DSC.
Example 3: preparation of flame retardants
520 g of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (dopo) are added into a 1000 ml three-neck flask with a stirrer, the flask is heated to 165 ℃, after the mixture is completely melted, 140 g of hexamethylolmelamine is added, 0.1% of benzenesulfonic acid serving as a strong acid catalyst can be added for accelerating the reaction, the strong stirring is continued, the melt viscosity rises sharply, and water as a byproduct is generated. After 40 minutes, the temperature was then increased to 240 ℃ and stirring was continued until almost no water was produced. After cooling, the product was a pale yellow transparent solid in 89% yield, which was determined by DSC to have a glass transition temperature of 147 ℃.
The reaction equation is as follows:
example 4: preparation of flame retardants
520.0 g of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (dopo) is added into a 1000 ml three-neck flask with a stirrer, heated to 170 ℃, and after the mixture is completely melted, 160.0 g of trimethylolmelamine monomethyl ether is added, in order to accelerate the reaction, 0.1% of benzenesulfonic acid can be added as a strong acid catalyst, the strong stirring is continued, the melt viscosity is increased violently, and meanwhile, methanol and water as byproducts are generated. After 30 minutes, the temperature was then increased further to 230 ℃ and stirring was continued until almost no methanol and water were produced. And cooling to obtain the flame retardant product. The product was a pale yellow transparent solid in 86% yield, and the glass transition temperature of this product was 145 ℃ as determined by DSC.
The reaction equation is as follows:
example 5: preparation of flame retardants
448.0 g of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (dopo) are added into a 1000 ml three-neck flask with a stirrer, the flask is heated to 165 ℃ and the like, 252.0 g of dimethylol dihydroxyethylene urea is added after the mixture is completely melted, in order to accelerate the reaction, a small amount of strong acid 0.1% benzenesulfonic acid catalyst (the catalyst can be not added) can be added, the strong stirring is continued, the melt viscosity is increased violently, and water as a by-product is generated at the same time. After 40 minutes, the temperature was then increased further to 220 ℃ and stirring was continued until almost no water vapor was generated. After cooling, the product was a dark red solid in 83% yield, which was measured by DSC to have a glass transition temperature of 105 ℃.
Example 6: preparation of flame retardants
580.3 g of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (dopo) are added into a 1000 ml three-neck flask with a stirrer, the flask is heated to 165 ℃ and after the mixture is completely melted, 119.7 g of dimethylol dihydroxyethylene urea is added, in order to accelerate the reaction, a small amount of strong acid 0.1% benzenesulfonic acid catalyst (the catalyst can be omitted) can be added, the mixture is stirred strongly continuously, the melt viscosity rises sharply, and water as a by-product is generated at the same time. After 40 minutes, the temperature was then increased further to 200 ℃ and stirring was continued until almost no water vapor was generated. After cooling, the product was a dark red solid in 80% yield and had a glass transition temperature of 60 ℃ as determined by DSC.
Example 7: preparation of flame retardants
495.6 g of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (dopo) are added into a 1000 ml three-neck flask with a stirrer, the flask is heated to 165 ℃ and then melted completely, 204.4 g of dimethylol dihydroxyethylene urea is added, in order to accelerate the reaction, a small amount of strong acid 0.1% benzenesulfonic acid catalyst (the catalyst can be not added) can be added, the strong stirring is continued, the melt viscosity is increased violently, and water as a byproduct is generated. After 40 minutes, the temperature was then increased to 230 ℃ and stirring was continued until almost no steam was generated, and the reaction was stopped after about 50 minutes. After cooling, the product was a dark red solid in 80% yield and had a glass transition temperature of 85 ℃ as determined by DSC.
Example 8: preparation of flame retardants
420.0 g of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (dopo) is added into a 1000 ml three-neck flask with a stirrer, the flask is heated to 200 ℃, 280.0 g of methylated dimethyloldihydroxyethyleneurea is added after the mixture is completely melted, in order to accelerate the reaction, a small amount of strong acid 0.1% benzenesulfonic acid catalyst (the catalyst can be not added) can be added, the mixture is stirred strongly continuously, the melt viscosity is increased violently, and a byproduct methanol is generated at the same time. After 40 minutes, the temperature was then increased to 240 ℃ and stirring was continued until almost no methanol vapor was generated. After cooling, the product was a dark red solid in 80% yield and the glass transition temperature of this product was 100 ℃ as determined by DSC.
Example 9: preparation of flame retardants
473.9 g of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (dopo) are added into a 1000 ml three-neck flask with a stirrer, the flask is heated to 180 ℃, after the mixture is completely melted, 226.1 g of methylated dimethyloldihydroxyethyleneurea is added, in order to accelerate the reaction, a small amount of strong acid 0.1% benzenesulfonic acid catalyst (the catalyst can be omitted) can be added, the mixture is continuously and intensively stirred, the melt viscosity is increased, and a byproduct methanol is generated at the same time. After 40 minutes, the temperature was then increased further to 220 ℃ and stirring was continued until almost no methanol vapor was produced. After cooling, the product was a dark red solid in 83% yield, which was found to have a glass transition temperature of 85 ℃ by DSC.
Example 10: flame retardant performance
Polyether urethane TPU 5182 (Shanghai Yishou New materials Co., Ltd.) and the product obtained in example 2 were mixed in a weight ratio of 85:15 and strand-extruded and water-cooled pelletized in a 40 mm diameter twin-screw extruder (Nanjing Cotton sub mechanical manufacturing Co., Ltd.). The extrusion temperature was 180 ℃ and the screw speed was 300 rpm. The material was dried and placed in a mold of 1.7 mm thickness, preheated at 180 ℃ for 5 minutes in a press vulcanizer, then hot-pressed at 5MPa for 3 minutes to prepare a sheet of 1.7 mm thickness, which was then cut into test specimens. The flame retardant grade is 1.7 mm UL-94V0 according to the test of national combustion test standard GB/T2408-2008.
Example 11: flame retardant performance
Nylon 6 YH800 (Yueyangba Baling petrochemical) and the product obtained in example 1 were mixed in a weight ratio of 85:15, and strand-extruded and water-cooled for granulation in a 40 mm diameter twin-screw extruder (Nanjing cotton sub-mechanical manufacturing Co., Ltd.). The extrusion temperature was 200 ℃ and the screw speed was 300 revolutions per minute. The material was dried and placed in a mold of 1.7 mm thickness, preheated at 230 ℃ for 5 minutes in a press vulcanizer, then hot-pressed at 5MPa for 3 minutes to prepare a sheet of 1.7 mm thickness, which was then cut into test specimens. The flame retardant grade is 1.7 mm UL-94V0 according to the test of national combustion test standard GB/T2408-2008.
Example 12: flame retardant performance
Nylon 6,6101F (DuPont, USA) and the product obtained in example 1 were mixed in a weight ratio of 90:10, and extruded into strands in a 40 mm diameter twin-screw extruder (Nanjing Cotton machinery manufacturing Co., Ltd.) and granulated by water cooling. The extrusion temperature was 255 ℃ and the screw speed was 300 revolutions per minute. The material was dried and placed in a mold of 1.7 mm thickness, preheated at 260 ℃ for 5 minutes in a press vulcanizer, then hot-pressed at 5MPa for 3 minutes to prepare a sheet of 1.7 mm thickness, which was then cut into test specimens. The flame retardant grade is 1.7 mm UL-94V0 according to the test of national combustion test standard GB/T2408-2008.
Example 13: flame retardant performance
Polyester PET FG600 (intrinsic viscosity: 0.675) (China petrochemical company, chemical fiber, Inc.) and the product obtained in example 1 were mixed at a weight ratio of 90:10, and strand-extruded and water-cooled and pelletized in a 40 mm diameter twin-screw extruder (Nanjing cotton, Sudoku Kogyo Co., Ltd.). The extrusion temperature was 255 ℃ and the screw speed was 300 revolutions per minute. The material was dried and placed in a mold having a thickness of 3 mm, preheated at 260 ℃ for 5 minutes in a press vulcanizer, then hot-pressed at 5MPa for 3 minutes to prepare a sheet having a thickness of 3 mm, and then cut into test specimens. And the flame retardant grade is 3 mm UL-94V0 according to the test of the national combustion test standard GB/T2408-2008.
Example 14: flame retardant performance
Polypropylene PP MR700 (Shanghai Kingshan petrochemical Co.) was mixed with the product obtained in example 1 at a ratio of 75:25 by weight, and strand-extruded and water-cooled for pelletization in a 40 mm diameter twin-screw extruder (Nanjing cotton sub mechanical manufacturing Co., Ltd.). The extrusion temperature was 220 ℃ and the screw speed was 300 revolutions per minute. The material was dried and placed in a mold of 3 mm thickness, preheated in a press vulcanizer at 220 ℃ for 5 minutes, then hot-pressed at 5MPa for 3 minutes to prepare a sheet of 3 mm thickness, which was then cut into test specimens. And the flame retardant grade is 3 mm UL-94V0 according to the test of the national combustion test standard GB/T2408-2008.
Example 15: flame retardant performance
Polyether urethane TPU 5182 (Shanghai Yishou New Material Co., Ltd.) and the product from example 5 were mixed in a ratio by weight of 90:10 and strand-extruded and water-cooled pelletized in a 40 mm diameter twin-screw extruder (Nanjing Cotton sub mechanical manufacturing Co., Ltd.). The extrusion temperature was 180 ℃ and the screw speed was 300 rpm. The material was dried and placed in a 0.8 mm thick mold, preheated at 180 ℃ for 5 minutes in a press vulcanizer, then hot-pressed at 5MPa for 3 minutes to prepare a 0.8 mm thick sheet, which was then cut into test specimens. The flame retardant grade is 0.8 mm UL-94V0 according to the test of national combustion test standard GB/T2408-2008.
Example 16: flame retardant performance
Nylon 6 YH800 (Yueyangba Baling petrochemical) and the product obtained in example 5 were mixed in a weight ratio of 85:15, and strand-extruded and water-cooled for granulation in a 40 mm diameter twin-screw extruder (Nanjing cotton sub-mechanical manufacturing Co., Ltd.). The extrusion temperature was 200 ℃ and the screw speed was 300 revolutions per minute. The material was dried and placed in a mold of 1.7 mm thickness, preheated at 230 ℃ for 5 minutes in a press vulcanizer, then hot-pressed at 5MPa for 3 minutes to prepare a sheet of 1.7 mm thickness, which was then cut into test specimens. The flame retardant grade is 1.7 mm UL-94V0 according to the test of national combustion test standard GB/T2408-2008.
Example 17: flame retardant performance
Nylon 6 YH800 (Yueyangba Baling petrochemical) and the product obtained in example 8 were mixed in a weight ratio of 85:15, and strand-extruded and water-cooled for granulation in a 40 mm diameter twin-screw extruder (Nanjing cotton sub-mechanical manufacturing Co., Ltd.). The extrusion temperature was 200 ℃ and the screw speed was 300 revolutions per minute. The material was dried and placed in a mold of 1.7 mm thickness, preheated at 230 ℃ for 5 minutes in a press vulcanizer, then hot-pressed at 5MPa for 3 minutes to prepare a sheet of 1.7 mm thickness, which was then cut into test specimens. The flame retardant grade is 1.7 mm UL-94V0 according to the test of national combustion test standard GB/T2408-2008.
Example 18: flame retardant performance
Nylon 6 YH800 (Yueyangba Baling petrochemical) and the product obtained in example 8 were mixed in a weight ratio of 90:10, and strand-extruded and water-cooled for granulation in a 40 mm diameter twin-screw extruder (Nanjing cotton sub-mechanical manufacturing Co., Ltd.). The extrusion temperature was 200 ℃ and the screw speed was 300 revolutions per minute. The material was dried and placed in a mold of 1.7 mm thickness, preheated at 230 ℃ for 5 minutes in a press vulcanizer, then hot-pressed at 5MPa for 3 minutes to prepare a sheet of 1.7 mm thickness, which was then cut into test specimens. The flame retardant grade is 1.7 mm UL-94V2 according to the test of national combustion test standard GB/T2408-2008.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core ideas. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
Claims (4)
1. A preparation method of a phosphorus-nitrogen flame retardant containing DOPO is characterized by comprising the following steps,
(1) heating 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) to melt the 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide completely;
(2) adding hexamethylol melamine hexa methyl ether into molten 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, continuously and intensely stirring, increasing the viscosity of a solution, and simultaneously generating a byproduct methanol; raising the temperature and continuing stirring until no methanol is generated, and cooling to obtain a light yellow solid;
or
Adding hexamethylol melamine into molten 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, continuously and intensely stirring to increase the viscosity of a solution and generate water as a by-product; raising the temperature and continuing stirring until no water is generated, and cooling to obtain a light yellow transparent solid;
or
Adding trimethylolmelamine trimethacarb into molten 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, continuously and intensely stirring, increasing the viscosity of a solution, and simultaneously generating by-products of methanol and water; raising the temperature and continuing stirring until no methanol or water is produced, and cooling to obtain a light yellow transparent solid;
or
Adding dimethylol dihydroxyethylene urea into molten 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and continuously stirring strongly to increase the viscosity of a solution and generate water as a byproduct; raising the temperature and continuing stirring until no water is generated, and cooling to obtain a dark red solid;
or
Adding methylated dimethylol dihydroxyethylene urea into molten 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, continuously and intensely stirring, increasing the solution viscosity, and simultaneously generating a byproduct methanol; stirring was continued with increasing temperature until no methanol was produced and the product was a dark red solid after cooling.
2. The method for preparing a phosphorus-nitrogen type flame retardant containing DOPO according to claim 1, wherein a strong acid catalyst is further added in the step (2); the strong acid catalyst is selected from one or more of benzene sulfonic acid, benzene sulfonic acid hydrate or alcoholic solution thereof, phosphoric acid, hydrochloric acid or sulfuric acid.
3. The method for preparing a phosphorus-nitrogen flame retardant containing DOPO according to claim 2, wherein the amount of the strong acid catalyst added is 0.01 to 5% by mass of the raw material.
4. The method for preparing DOPO-containing phosphazene flame retardant as claimed in claim 1, wherein the temperature is raised to 225 ℃ and 230 ℃ after the step (2) is continued to the strongly stirred reaction for 30 to 40 minutes.
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| US4086206A (en) * | 1976-07-05 | 1978-04-25 | Sanko Kaihatsu Kagaku Kenkyosho | Organophosphorus compounds and process for the production thereof |
| US4742088A (en) * | 1986-09-12 | 1988-05-03 | Kolon Industries, Inc. | Phosphorus-containing nitrogen compounds as flame retardants and synthetic resins containing them |
| CN108640949A (en) * | 2018-03-21 | 2018-10-12 | 中国科学院宁波材料技术与工程研究所 | A kind of DOPO- phthalimides analog derivative, preparation method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US4086206A (en) * | 1976-07-05 | 1978-04-25 | Sanko Kaihatsu Kagaku Kenkyosho | Organophosphorus compounds and process for the production thereof |
| US4742088A (en) * | 1986-09-12 | 1988-05-03 | Kolon Industries, Inc. | Phosphorus-containing nitrogen compounds as flame retardants and synthetic resins containing them |
| CN108640949A (en) * | 2018-03-21 | 2018-10-12 | 中国科学院宁波材料技术与工程研究所 | A kind of DOPO- phthalimides analog derivative, preparation method and application |
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