CN116262810B - Preparation method of reactive flame retardant containing phosphorus and nitrogen elements - Google Patents
Preparation method of reactive flame retardant containing phosphorus and nitrogen elements Download PDFInfo
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- CN116262810B CN116262810B CN202111530597.7A CN202111530597A CN116262810B CN 116262810 B CN116262810 B CN 116262810B CN 202111530597 A CN202111530597 A CN 202111530597A CN 116262810 B CN116262810 B CN 116262810B
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- phosphorus
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 55
- 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 54
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 19
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 239000011574 phosphorus Substances 0.000 title claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 49
- 150000002191 fatty alcohols Chemical class 0.000 claims abstract description 19
- 238000003756 stirring Methods 0.000 claims abstract description 17
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims abstract description 15
- MRVZORUPSXTRHD-UHFFFAOYSA-N bis(hydroxymethyl)phosphorylmethanol Chemical compound OCP(=O)(CO)CO MRVZORUPSXTRHD-UHFFFAOYSA-N 0.000 claims abstract description 13
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 8
- 239000012074 organic phase Substances 0.000 claims abstract description 7
- 239000003513 alkali Substances 0.000 claims abstract description 5
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229920005862 polyol Polymers 0.000 claims description 16
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 16
- 229920002635 polyurethane Polymers 0.000 claims description 15
- 239000004814 polyurethane Substances 0.000 claims description 15
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 14
- 229920000570 polyether Polymers 0.000 claims description 14
- 150000003077 polyols Chemical class 0.000 claims description 14
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 13
- 150000001299 aldehydes Chemical class 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 10
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 10
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 claims description 4
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 claims description 4
- ZWRUINPWMLAQRD-UHFFFAOYSA-N nonan-1-ol Chemical compound CCCCCCCCCO ZWRUINPWMLAQRD-UHFFFAOYSA-N 0.000 claims description 4
- RLOWWWKZYUNIDI-UHFFFAOYSA-N phosphinic chloride Chemical compound ClP=O RLOWWWKZYUNIDI-UHFFFAOYSA-N 0.000 claims description 3
- 150000002192 fatty aldehydes Chemical class 0.000 claims description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 229910052736 halogen Inorganic materials 0.000 abstract description 5
- 150000002367 halogens Chemical class 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 238000002485 combustion reaction Methods 0.000 abstract description 2
- SXXLKZCNJHJYFL-UHFFFAOYSA-N 4,5,6,7-tetrahydro-[1,2]oxazolo[4,5-c]pyridin-5-ium-3-olate Chemical compound C1CNCC2=C1ONC2=O SXXLKZCNJHJYFL-UHFFFAOYSA-N 0.000 abstract 1
- 101000799461 Homo sapiens Thrombopoietin Proteins 0.000 abstract 1
- 102100034195 Thrombopoietin Human genes 0.000 abstract 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 abstract 1
- 239000000047 product Substances 0.000 description 26
- 239000007788 liquid Substances 0.000 description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 12
- 239000001301 oxygen Substances 0.000 description 12
- 229910052760 oxygen Inorganic materials 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 8
- 239000008098 formaldehyde solution Substances 0.000 description 7
- 230000006835 compression Effects 0.000 description 6
- 238000007906 compression Methods 0.000 description 6
- -1 flame retardant polyol Chemical class 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000006757 chemical reactions by type Methods 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000012263 liquid product Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000002649 leather substitute Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229910001392 phosphorus oxide Inorganic materials 0.000 description 1
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- KVMPUXDNESXNOH-UHFFFAOYSA-N tris(1-chloropropan-2-yl) phosphate Chemical compound ClCC(C)OP(=O)(OC(C)CCl)OC(C)CCl KVMPUXDNESXNOH-UHFFFAOYSA-N 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3878—Low-molecular-weight compounds having heteroatoms other than oxygen having phosphorus
- C08G18/3889—Low-molecular-weight compounds having heteroatoms other than oxygen having phosphorus having nitrogen in addition to phosphorus
-
- 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
- C07F9/6515—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having three nitrogen atoms as the only ring hetero atoms
- C07F9/6521—Six-membered rings
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Polyurethanes Or Polyureas (AREA)
- Fireproofing Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a preparation method of a reactive flame retardant containing phosphorus and nitrogen elements, which comprises the following steps: step 1) reacting phosphorus chloride with fatty alcohol; step 2) reacting the product obtained in the step 1) with trimethylol phosphorus oxide, adding alkali for neutralization, standing for layering, and taking an organic phase product; step 3) mixing and stirring melamine and aldehyde solution, reacting at 50-70 ℃ until the solution is transparent, adding the organic phase product obtained in step 2), heating to 90-100 ℃ for continuous reaction, and drying the product after the reaction is completed to obtain the phosphorus-nitrogen element-containing reactive flame retardant. According to the method, phosphorus chloride reacts with THPO, and the synthesized reactive flame retardant at least contains 3P atoms, so that the P content of the flame retardant is improved, and the flame retardance is further improved. The synthesized reactive flame retardant does not contain halogen, and has little influence on environment after combustion. By introducing the melamine structure into the flame retardant chain segment, the flame retardant effect is further improved.
Description
Technical Field
The invention relates to the field of chemical engineering and technology, in particular to a preparation method of a reactive flame retardant containing phosphorus and nitrogen.
Background
Polyurethane is an artificially synthesized polymer material, and has very special mechanical property and physical and chemical properties. Different raw materials are selected, and different synthesis processes are adopted, so that polyurethane products with different performances can be prepared. Such as foam, elastomeric rubber, paint, high resilience synthetic fiber, artificial leather, adhesives, etc. However, polyurethane is very easy to burn, toxic gas is generated during burning, the personal and property safety is endangered, and flame retardant is required to be added into raw materials to improve the flame retardant property. The additive flame retardant is convenient to use and good in flame retardant property, but the use amount is large, so that the mechanical property of the material is seriously reduced. The reactive flame retardant is liquid or solid flame retardant polyol containing P, N or halogen. With the increasing environmental requirements, the use of halogen-containing flame retardants is limited. The preparation process of the common flame-retardant polyol containing P, N is complex, the P, N content is low, and the flame retardance is poor. In order to solve the problems in the prior art, there is an urgent need to find a new preparation method of a reactive flame retardant containing phosphorus and nitrogen.
Disclosure of Invention
The invention provides a preparation method of a reactive flame retardant containing phosphorus and nitrogen, which aims at the defects that the reactive flame retardant prepared by the preparation method of the reactive flame retardant containing phosphorus and nitrogen contains halogen, is not friendly to the environment and has poor flame retardance in the prior art.
The technical scheme provided by the invention is as follows:
A preparation method of a reactive flame retardant containing phosphorus and nitrogen elements comprises the following steps:
step 1) reacting phosphorus chloride with fatty alcohol;
Step 2) reacting the product obtained in the step 1) with trimethylol phosphorus oxide, adding alkali for neutralization, standing for layering, and taking an organic phase product;
step 3) mixing and stirring melamine and aldehyde solution, reacting at 50-70 ℃ until the solution is transparent, adding the organic phase product obtained in step 2), heating to 90-100 ℃ for continuous reaction, and drying the product after the reaction is completed to obtain the phosphorus-nitrogen element-containing reactive flame retardant.
The reaction equation of the preparation method in the invention is as follows:
In the preparation method of the invention, step 1) utilizes fatty alcohol to react with phosphorus chloride first, so that the average polymerization degree of the final product can be reduced. Preferably, in the present invention, the phosphorus chloride may be one or more selected from PCl 3、PCl5 and POCl 3. In the case of various phosphorus chlorides, the composition ratio may be any suitable ratio.
More preferably, in one embodiment of the present invention, the phosphorus chloride described in step 1) is POCl 3.
In order to make the reaction proceed better, in one embodiment of the present invention, the reaction in step 1) may be performed under nitrogen protection and ice bath conditions, and the fatty alcohol is slowly added dropwise to the above phosphorus chloride. The rate of addition may be 0.5g/min. In the present invention, the fatty alcohol is a liquid fatty alcohol.
Preferably, in one embodiment of the present invention, the above fatty alcohol may be one or more selected from ethanol, n-propanol, n-butanol, n-heptanol, n-octanol, n-nonanol, or n-decanol; in the case of a plurality of fatty alcohols, the composition ratio may be any suitable ratio.
More preferably, in one embodiment of the present invention, the above fatty alcohol may be ethanol, n-propanol or n-butanol.
In each step of the preparation method of the present invention, the criterion for judging the end of the reaction may be that the reaction is complete or that the product reaches a desired amount, etc., which can be determined by a method conventional in the art.
In the various steps of the preparation process of the present invention, the reaction may be carried out in any suitable reactor. In an embodiment of the present invention, the reactor is a reaction vessel.
Preferably, the liquid product is obtained by continuing the reaction for 15 to 30 minutes after the completion of the dropping of the fatty alcohol in the step 1). Preferably, in one embodiment of the present invention, the reaction of the step 1) is performed at normal temperature.
In order to make the reaction proceed better, in one embodiment of the present invention, the reaction in step 2) may be performed under nitrogen protection and ice bath conditions, and the liquid product obtained in step 1) is slowly added dropwise to trimethylol phosphorus oxide (THPO). The rate of addition may be 1g/min. Preferably, after the completion of the above-mentioned dropwise addition, the reaction is continued for 15 to 30 minutes. Preferably, in one embodiment of the present invention, the reaction is carried out under normal temperature conditions with a vacuum of-0.02 Mpa.
After the reaction of the step 2), adding alkali, stirring and neutralizing to pH 7-9. Preferably, in one embodiment of the present invention, the alkali is a 10% NaOH solution.
In an embodiment of the present invention, the organic phase product obtained in step 2) is dried and used as a starting material for the next reaction.
In the preparation method of the present invention, the step of adjusting the pH of the aldehyde solution to 8 to 9 may be further included before the mixing and stirring in the step 3). The pH may be adjusted using any suitable material, but preferably, in one embodiment of the invention, the pH of the aldehyde solution is adjusted using triethanolamine.
Preferably, in an embodiment of the present invention, the aldehyde may be a fatty aldehyde. Namely, the aldehyde compound in which an aldehyde group is bonded to an aliphatic hydrocarbon group (or a hydrogen atom) has the general formula R-CHO. Such as formaldehyde, acetaldehyde, propionaldehyde. More preferably, in one embodiment of the present invention, the aldehyde is formaldehyde. The aldehyde solution is formaldehyde solution, and the mass fraction of the formaldehyde solution can be 37%.
Preferably, in the embodiment of the invention, after the pH value of the formaldehyde solution is regulated, melamine with a certain mass is added, and the mixture is stirred and heated to 50-70 ℃, and the solution is continuously reacted for 30min after being transparent. And (3) adding the dried product obtained in the step (2), heating to 90-100 ℃, and reacting for 12-24h.
Preferably, in the embodiment of the invention, after the reaction is finished, the product is dried in vacuum under the condition of vacuum degree of-0.10 MPa and temperature of 110 ℃ to obtain the reactive flame retardant containing phosphorus and nitrogen.
Preferably, in one embodiment of the present invention, the molar ratio of each reactant in the above preparation method is n (phosphorus chloride): n (fatty alcohol): n (trimethylol phosphorus oxide): n (aldehyde): n (melamine) =1: 1:2: (1-2): (1-2).
In another aspect of the present invention, there is provided a reactive flame retardant prepared by the above preparation method.
In another aspect of the invention, there is provided the use of the reactive flame retardant described above in the preparation of polyurethane products.
In another aspect of the invention, a method of using the reactive flame retardant in the preparation of polyurethane products is provided. The polyurethane product comprises a component A: 50-100 parts by weight of polyether polyol, 0-50 parts by weight of reactive flame retardant and 0.5 parts by weight of catalyst; component B: polymeric MDI. Wherein the parts by weight are based on the mass of component A.
Preferably, in one embodiment of the present invention, the polyether polyol has a functionality of 3; more preferably, in one embodiment of the present invention, the polyether polyol described above is polyether polyol 305.
Preferably, in one embodiment of the present invention, the catalyst is a mixture of T12 and triethylenediamine.
Preferably, in one embodiment of the present invention, the volume ratio of the component a to the component B is 1:1.
The beneficial effects of the invention are as follows:
According to the preparation method, phosphorus chloride reacts with THPO, and the synthesized reactive flame retardant at least contains 3P atoms, so that the P content of the flame retardant is improved, and the flame retardance is further improved. The synthesized reactive flame retardant does not contain halogen, and has little influence on environment after combustion. Meanwhile, the melamine structure is introduced into the flame retardant chain segment, so that the flame retardant effect is further improved.
Detailed Description
The invention discloses a preparation method of a reactive flame retardant containing phosphorus and nitrogen elements, and a person skilled in the art can refer to the content of the reactive flame retardant and properly improve the technological parameters. It is to be particularly pointed out that all similar substitutes and modifications apparent to those skilled in the art are deemed to be included in the invention and that the relevant person can make modifications and appropriate alterations and combinations of what is described herein to make and use the technology without departing from the spirit and scope of the invention.
In the present invention, unless otherwise indicated, scientific and technical terms used herein have the meanings commonly understood by one of ordinary skill in the art. Throughout the specification and claims, unless explicitly stated otherwise, the term "comprise" or variations thereof such as "comprises" or "comprising", etc. will be understood to include the stated element or component without excluding other elements or components. The terms "such as," "for example," and the like are intended to refer to exemplary embodiments and are not intended to limit the scope of the present disclosure.
The following is a description of some of the terms appearing in the present invention.
The term "reactive flame retardant" refers to a small molecule flame retardant containing flame retardant elements (such as phosphorus, chlorine, bromine, nitrogen) and reactive groups (carboxyl, hydroxyl, anhydride, etc.) in the molecule. The reactive flame retardant is directly combined into polyester molecules, the flame retardant effect is uniform, the flame retardance is durable, the flame retardant can not separate out fibers in the process of flame-retarding fibers, and the fibers can have good flame retardant effect by adding the flame retardant with lower content (3% -8%).
The term "Fatty alcohol" refers to an alcohol in which a hydroxyl group is linked to a Fatty hydrocarbon group. Generally referred to as lower aliphatic or lower alcohols containing 1 to 2 carbon atoms; 3-5 carbon atoms are medium carbon number fatty alcohol or medium alcohol; higher aliphatic alcohols or higher alcohols having 6 or more carbon atoms.
The term "trimethylol phosphorus oxide" (TPHO) has the formula C 3H9O4 P, a molecular weight of 140.07, and a chemical formula: The density is 1.5+/-0.1 g/cm 3, the boiling point is 504.9 +/-45.0 ℃ at 760mmHg, and the CAS number is 1067-12-5.
The term "polymeric MDI", MDI is 4,4' diphenylmethane diisocyanate, and a mixture containing a proportion of pure MDI and polyphenyl polymethylene polyisocyanate is polymeric MDI, which is the most important raw material for producing polyurethane.
In order to enable those skilled in the art to better understand the technical solution of the present invention, the present invention will be further described in detail with reference to specific embodiments.
Example 1:
15.3g of phosphorus oxychloride is added into a reaction kettle, nitrogen is introduced under the ice bath condition for protection, and 4.6g of ethanol is slowly added dropwise under the stirring condition. After the completion of the dropwise addition, the reaction was continued for 15min to obtain liquid A. 30.4g of trimethylol phosphorus oxide (THPO, weight 92%) is added into a reaction kettle, nitrogen is introduced under the ice bath condition for protection, liquid A is slowly added dropwise, and the reaction is continued for 15min under the vacuum degree of-0.02 MPa after the dropwise addition is completed. Adding 10% NaOH aqueous solution, stirring for neutralization until the pH is 7, standing for liquid separation, taking out the lower layer liquid, and drying to obtain a product B. 8.1g of formaldehyde solution (weight 37%) is added into a reaction kettle, triethanolamine is added to adjust the pH of the liquid to 8-9, 12.6g of melamine is added, stirring and heating are carried out to 50 ℃, and the reaction is continued for 30min after the solution is transparent. Product B was added and the reaction was carried out for 12h with warming to 90 ℃. And after the reaction is finished, vacuum drying is carried out on the product at the temperature of 110 ℃ and the vacuum degree of-0.10 MPa, and the reaction type flame retardant containing P, N elements is obtained after drying.
50 Parts of polyether polyol 305, 50 parts of reactive flame retardant, 0.1 part of T12 and 0.4 part of triethylene diamine are uniformly mixed to prepare a component A, and the polymeric MDI is a component B. The polyurethane is prepared by mixing the components A and B in a volume ratio of 1:1. The compressive strength was measured with reference to GB/T8813-2008 standard, the sample size was 50 mm. Times.50 mm, and the compression rate was 5mm/min. Limiting oxygen index was measured using a limiting oxygen index analyzer, with reference to GB/T2406-1993 standard. The compressive strength was 40MPa and the LOI was 31%.
Example 2:
30.6g of phosphorus oxychloride is added into a reaction kettle, nitrogen is introduced under the ice bath condition for protection, and 12.0g of n-propanol is slowly added dropwise under the stirring condition. After the completion of the dropwise addition, the reaction was continued for 25min to obtain liquid A. 60.8g of trimethylol phosphorus oxide (THPO, weight 92%) is added into a reaction kettle, nitrogen is introduced under the ice bath condition for protection, liquid A is slowly added dropwise, and the reaction is continued for 25min under the vacuum degree of-0.02 MPa after the dropwise addition is completed. Adding 10% NaOH aqueous solution, stirring for neutralization until the pH is 8, standing for liquid separation, taking out the lower layer liquid, and drying to obtain a product B. 24.3g of formaldehyde solution (weight 37%) is added into a reaction kettle, triethanolamine is added to adjust the pH of the liquid to 8-9, 37.8g of melamine is added, stirring and heating are carried out to 60 ℃, and the reaction is continued for 30min after the solution is transparent. Product B was added and the temperature was raised to 100 ℃ and reacted for 16h. And after the reaction is finished, vacuum drying is carried out on the product at the temperature of 110 ℃ and the vacuum degree of-0.10 MPa, and the reaction type flame retardant containing P, N elements is obtained after drying.
70 Parts of polyether polyol 305, 30 parts of reactive flame retardant, 0.1 part of T12 and 0.4 part of triethylene diamine are uniformly mixed to prepare a component A, and the polymeric MDI is a component B. The polyurethane is prepared by mixing the components A and B in a volume ratio of 1:1. The compressive strength was measured with reference to GB/T8813-2008 standard, the sample size was 50 mm. Times.50 mm, and the compression rate was 5mm/min. Limiting oxygen index was measured using a limiting oxygen index analyzer, with reference to GB/T2406-1993 standard. The compressive strength was measured to be 45MPa and the LOI 29%.
Example 3:
30.6g of phosphorus oxychloride is added into a reaction kettle, nitrogen is introduced under the ice bath condition for protection, and 16.8g of n-butanol is slowly added dropwise under the stirring condition. And after the dripping is finished, the reaction is continued for 30min to obtain liquid A. 60.8g of trimethylol phosphorus oxide (THPO, weight 92%) is added into a reaction kettle, nitrogen is introduced under the ice bath condition for protection, liquid A is slowly added dropwise, and the reaction is continued for 305min under the vacuum degree of-0.02 MPa after the dropwise addition is completed. Adding 10% NaOH aqueous solution, stirring for neutralization until the pH is 8, standing for liquid separation, taking out the lower layer liquid, and drying to obtain a product B. 32.4g of formaldehyde solution (weight 37%) is added into the reaction kettle, triethanolamine is added to adjust the pH of the liquid to 9, 50.4g of melamine is added, stirring and heating are carried out to 70 ℃, and the reaction is continued for 30min after the solution is transparent. Product B was added and the temperature was raised to 100 ℃ and reacted for 24h. And after the reaction is finished, vacuum drying is carried out on the product at the temperature of 110 ℃ and the vacuum degree of-0.10 MPa, and the reaction type flame retardant containing P, N elements is obtained after drying.
80 Parts of polyether polyol 305, 20 parts of reactive flame retardant, 0.1 part of T12 and 0.4 part of triethylene diamine are uniformly mixed to prepare a component A, and the polymeric MDI is a component B. The polyurethane is prepared by mixing the components A and B in a volume ratio of 1:1. The compressive strength was measured with reference to GB/T8813-2008 standard, the sample size was 50 mm. Times.50 mm, and the compression rate was 5mm/min. Limiting oxygen index was measured using a limiting oxygen index analyzer, with reference to GB/T2406-1993 standard. The compressive strength was 49MPa and the LOI was 28%.
Comparative example 1:
100 parts of polyether polyol 305,0.1 parts of T12 and 0.4 part of triethylene diamine are uniformly mixed to prepare a component A, and the polymeric MDI is a component B. The polyurethane is prepared by mixing the components A and B in a volume ratio of 1:1. The compressive strength was measured with reference to GB/T8813-2008 standard, the sample size was 50 mm. Times.50 mm, and the compression rate was 5mm/min. Limiting oxygen index was measured using a limiting oxygen index analyzer, with reference to GB/T2406-1993 standard. The compressive strength was measured to be 51MPa and the LOI was measured to be 18%.
Comparative example 2:
50 parts of polyether polyol 305, 50 parts of additive flame retardant TCPP,0.1 part of T12 and 0.4 part of triethylene diamine are uniformly mixed to prepare a component A, and the polymeric MDI is a component B. The polyurethane is prepared by mixing the components A and B in a volume ratio of 1:1. The compressive strength was measured with reference to GB/T8813-2008 standard, the sample size was 50 mm. Times.50 mm, and the compression rate was 5mm/min. Limiting oxygen index was measured using a limiting oxygen index analyzer, with reference to GB/T2406-1993 standard. The compressive strength was measured to be 31MPa and the LOI was measured to be 32%.
Comparative example 3:
60.8g of trimethylol phosphorus oxide (THPO, weight 92%) is added into a reaction kettle, nitrogen is introduced under the ice bath condition for protection, 30.6g of phosphorus oxychloride is slowly added dropwise, and the reaction is continued for 25min under the vacuum degree of-0.02 MPa after the dropwise addition is completed. Adding 10% NaOH aqueous solution, stirring for neutralization until the pH is 8, standing for separating liquid, dividing the product into three layers, wherein the lower layer is solid, the middle layer is viscous oily substance, the upper layer is water phase, and the middle layer product is dried to obtain the product B. 24.3g of formaldehyde solution (weight 37%) is added into a reaction kettle, triethanolamine is added to adjust the pH of the liquid to 8-9, 37.8g of melamine is added, stirring and heating are carried out to 60 ℃, and the reaction is continued for 30min after the solution is transparent. Product B was added and the temperature was raised to 100 ℃ and reacted for 16h. And after the reaction is finished, vacuum drying is carried out on the product at the temperature of 110 ℃ and the vacuum degree of-0.10 MPa, and the reaction type flame retardant containing P, N elements is obtained after drying.
70 Parts of polyether polyol 305, 30 parts of reactive flame retardant, 0.1 part of T12 and 0.4 part of triethylene diamine are uniformly mixed to prepare a component A, and the polymeric MDI is a component B. The polyurethane is prepared by mixing the components A and B in a volume ratio of 1:1. The compressive strength was measured with reference to GB/T8813-2008 standard, the sample size was 50 mm. Times.50 mm, and the compression rate was 5mm/min. Limiting oxygen index was measured using a limiting oxygen index analyzer, with reference to GB/T2406-1993 standard. The compressive strength was measured to be 32MPa and the LOI was 35%.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (16)
1. The preparation method of the reactive flame retardant containing phosphorus and nitrogen elements is characterized by comprising the following steps:
step 1) reacting phosphorus chloride with fatty alcohol;
Step 2) reacting the product obtained in the step 1) with trimethylol phosphorus oxide, adding alkali for neutralization, standing for layering, and taking an organic phase product;
step 3) mixing and stirring melamine and aldehyde solution, reacting at 50-70 ℃ until the solution is transparent, adding the organic phase product obtained in the step 2), heating to 90-100 ℃ for continuous reaction, and drying the product after the reaction is completed to obtain the phosphorus-nitrogen element-containing reactive flame retardant;
wherein, the phosphorus chloride in the step 1) is POCl 3;
The mole ratio of the phosphorus chloride, the fatty alcohol and the trimethylol phosphorus oxide is n (phosphorus chloride): n (fatty alcohol): n (trimethylol phosphorus oxide) =1: 1:2.
2. The method according to claim 1, wherein the fatty alcohol in step 1) is one or more selected from ethanol, n-propanol, n-butanol, n-heptanol, n-octanol, n-nonanol and n-decanol.
3. The method according to claim 2, wherein the fatty alcohol in step 1) is ethanol, n-propanol or n-butanol.
4. The process according to claim 1, wherein the neutralization in step 2) is to a pH of 7 to 9.
5. The method of claim 1, wherein the aldehyde in step 3) is a fatty aldehyde.
6. The process according to claim 5, wherein the aldehyde in step 3) is formaldehyde.
7. The method according to claim 1, wherein the step 3) further comprises the step of adjusting the pH of the aldehyde solution to 8 to 9 before the mixing and stirring.
8. The method of claim 7, wherein the pH of the aldehyde solution is adjusted using triethanolamine.
9. The preparation method according to claim 1, wherein the molar ratio of each reactant in the preparation method is n (phosphorus chloride): n (fatty alcohol): n (trimethylol phosphorus oxide): n (aldehyde): n (melamine) =1: 1:2: (1-2): (1-2).
10. A reactive flame retardant, characterized in that it is produced by the production method as claimed in any one of claims 1 to 7.
11. Use of the reactive flame retardant according to claim 10 for the preparation of polyurethane products.
12. Use according to claim 11, characterized in that the polyurethane product comprises component a: 50-100 parts by weight of polyether polyol, 0-50 parts by weight of reactive flame retardant and 0.5 parts by weight of catalyst; component B: polymeric MDI.
13. Use according to claim 12, characterized in that the polyether polyol has a functionality of 3.
14. Use according to claim 13, characterized in that the polyether polyol is polyether polyol 305.
15. Use according to claim 12, characterized in that the catalyst is a mixture of T12 and triethylenediamine.
16. The use according to claim 12, characterized in that the volume ratio of component a and component B is 1:1.
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