CN111004364A - Preparation method of reactive halogen-free nitrogen-phosphorus flame retardant - Google Patents
Preparation method of reactive halogen-free nitrogen-phosphorus flame retardant Download PDFInfo
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- CN111004364A CN111004364A CN201911342730.9A CN201911342730A CN111004364A CN 111004364 A CN111004364 A CN 111004364A CN 201911342730 A CN201911342730 A CN 201911342730A CN 111004364 A CN111004364 A CN 111004364A
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 39
- 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 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 229930040373 Paraformaldehyde Natural products 0.000 claims abstract description 50
- 229920002866 paraformaldehyde Polymers 0.000 claims abstract description 50
- -1 alcohol amine Chemical class 0.000 claims abstract description 38
- 238000003756 stirring Methods 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 26
- 239000007788 liquid Substances 0.000 claims abstract description 24
- 238000001914 filtration Methods 0.000 claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 230000018044 dehydration Effects 0.000 claims abstract description 7
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 7
- 239000012467 final product Substances 0.000 claims abstract description 7
- 150000008301 phosphite esters Chemical class 0.000 claims abstract description 5
- 239000000843 powder Substances 0.000 claims abstract description 5
- 230000006837 decompression Effects 0.000 claims abstract description 3
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 23
- 238000005303 weighing Methods 0.000 claims description 18
- LXCYSACZTOKNNS-UHFFFAOYSA-N diethoxy(oxo)phosphanium Chemical compound CCO[P+](=O)OCC LXCYSACZTOKNNS-UHFFFAOYSA-N 0.000 claims description 14
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 claims description 7
- 229940043276 diisopropanolamine Drugs 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 6
- CZHYKKAKFWLGJO-UHFFFAOYSA-N dimethyl phosphite Chemical compound COP([O-])OC CZHYKKAKFWLGJO-UHFFFAOYSA-N 0.000 claims description 5
- NFORZJQPTUSMRL-UHFFFAOYSA-N dipropan-2-yl hydrogen phosphite Chemical compound CC(C)OP(O)OC(C)C NFORZJQPTUSMRL-UHFFFAOYSA-N 0.000 claims description 5
- BVXOPEOQUQWRHQ-UHFFFAOYSA-N dibutyl phosphite Chemical compound CCCCOP([O-])OCCCC BVXOPEOQUQWRHQ-UHFFFAOYSA-N 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 29
- 239000002253 acid Substances 0.000 abstract description 21
- 230000002411 adverse Effects 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 230000007062 hydrolysis Effects 0.000 abstract description 3
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 3
- 230000002401 inhibitory effect Effects 0.000 abstract description 2
- 239000000543 intermediate Substances 0.000 abstract 5
- 239000000243 solution Substances 0.000 description 27
- 230000002829 reductive effect Effects 0.000 description 26
- 238000006243 chemical reaction Methods 0.000 description 24
- 229940043237 diethanolamine Drugs 0.000 description 22
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 15
- 239000011575 calcium Substances 0.000 description 11
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 229920002635 polyurethane Polymers 0.000 description 9
- 239000004814 polyurethane Substances 0.000 description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 8
- 238000005187 foaming Methods 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000004448 titration Methods 0.000 description 5
- CCJKFLLIJCGHMO-UHFFFAOYSA-N 2-[diethoxyphosphorylmethyl(2-hydroxyethyl)amino]ethanol Chemical compound CCOP(=O)(OCC)CN(CCO)CCO CCJKFLLIJCGHMO-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 229910001415 sodium ion Inorganic materials 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 229920005830 Polyurethane Foam Polymers 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 239000008098 formaldehyde solution Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000011496 polyurethane foam Substances 0.000 description 3
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 229940095564 anhydrous calcium sulfate Drugs 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 239000011949 solid catalyst Substances 0.000 description 2
- 229920002994 synthetic fiber Polymers 0.000 description 2
- UZDJBTWIMFRARW-UHFFFAOYSA-N 2-[dimethoxyphosphorylmethyl(2-hydroxyethyl)amino]ethanol Chemical compound COP(=O)(OC)CN(CCO)CCO UZDJBTWIMFRARW-UHFFFAOYSA-N 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 238000010533 azeotropic distillation Methods 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 229940095672 calcium sulfate Drugs 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- OSPSWZSRKYCQPF-UHFFFAOYSA-N dibutoxy(oxo)phosphanium Chemical compound CCCCO[P+](=O)OCCCC OSPSWZSRKYCQPF-UHFFFAOYSA-N 0.000 description 1
- UIBCDEFKKLRXHR-UHFFFAOYSA-N diethoxyphosphorylmethanamine Chemical compound CCOP(=O)(CN)OCC UIBCDEFKKLRXHR-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
- C07F9/06—Phosphorus compounds without P—C bonds
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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)
Abstract
The invention provides a reactive halogen-free nitrogen-phosphorus flame retardant and a preparation method thereof, wherein the reactive halogen-free nitrogen-phosphorus flame retardant comprises the following steps: (1) adding paraformaldehyde ground into powder into molten alcohol amine, stirring at 40-50 ℃, and reacting for 1-2h to obtain an intermediate solution; (2) heating the intermediate obtained in the step (1) to 70-90 ℃, and performing vacuum pump decompression dehydration to obtain an intermediate; (3) heating the intermediate obtained in the step (2) to 50-70 ℃ again, dropwise adding phosphite ester while stirring, and reacting for 2-4 h after dropwise adding to obtain yellow transparent liquid; (4) adding Ca (OH) into the yellow transparent liquid obtained in the step (3)2Stirring for 2-4 h at normal temperature, and filtering to obtain the final product. The process eliminates the adverse effect of water on inhibiting the generation of intermediates and the hydrolysis of phosphonate ester, and the obtained product has low acid value, thereby optimizing the process flow and improving the yield and purity of the product.
Description
Technical Field
The invention belongs to the field of flame retardant materials, and particularly relates to a preparation method of a reactive halogen-free nitrogen-phosphorus flame retardant.
Background
Polyurethane is an important industrial synthetic polymer material, and is applied to various aspects of life, but the flammability of polyurethane also brings serious harm, and the fire retardant can reduce the fire hazard, so research on the flame retardant material is concerned by researchers. At present, the most commonly used flame retardant in the world is a halogen-containing flame retardant, the addition amount of the halogen-containing flame retardant is small, the flame retardant efficiency is high, but the halogen-containing flame retardant emits a large amount of toxic and corrosive gases during combustion, so that the environment pollution is caused, the body health is harmed, and the application range of the halogen-containing flame retardant is increasingly limited. Therefore, the halogen-free flame-retardant material with high flame-retardant efficiency, good safety performance, low toxicity, low smoke and no corrosive gas is important to research. The flame retardant disclosed by the invention is a halogen-free environment-friendly reactive flame retardant, not only accords with the future development trend of environmental protection and health of the flame retardant, but also can be compounded on a polymer molecular chain through a chemical reaction in the preparation process of a polymer, has small influence on the mechanical property of the material, has a good flame retardant effect, and is particularly suitable for preparing polyurethane foam plastic.
U.S. Pat. No. 4, 3076010 discloses a process for the preparation of diethyl N, N-bis (2-hydroxyethyl) aminomethylphosphonate by reacting (1) diethanolamine with formaldehyde (37% formaldehyde solution) to form an intermediate 3- (2-hydroxyethyl) -1, 3-oxaziridine solution; (2) reacting the intermediate 3- (2-hydroxyethyl) -1, 3-oxazepine solution with diethyl phosphite; (3) extracting with diethyl ether; (4) distilling and separating under reduced pressure to obtain N, N-bis (2-hydroxyethyl) aminomethyl diethyl phosphonate. The method has the problems that a large amount of water exists in the preparation process of the intermediate, the cyclization reaction of the diethanol amine and the formaldehyde is a reversible reaction, and the water is one of raw materials of the reverse reaction, so that the generation of the intermediate is not facilitated due to the existence of a large amount of water. In addition, diethyl phosphite is easy to hydrolyze in a large amount of water, so that the acid value of the product is high, side reactions are easy to generate, the purity of the product is low, and the separation is difficult. Therefore, the method has low product yield and low purity.
The patent CN 1583768A improves the preparation process of the US 3076010, and adopts a reduced pressure distillation method to remove water in a reaction system after the first step reaction is finished, thereby reducing the hydrolysis of diethyl phosphite to a certain extent; solid acid catalyst is added in the second step reaction, so that the yield and the purity of the product are improved. However, the process also uses formaldehyde solution containing a large amount of water, which is not beneficial to the generation of an intermediate, and the high-temperature dehydration efficiency after the first-step reaction is low, so that the water content is difficult to reduce to a reasonable range, the raw material diethyl phosphite for the next-step reaction is hydrolyzed, and the finally obtained product has a large acid value. In addition, the removal of a large amount of water at high temperature increases the process energy consumption, and is not beneficial to industrial production.
Patent CN 102276645A replaces above-mentioned preparation technology formaldehyde solution with paraformaldehyde, and paraformaldehyde uses the alcoholic solution as the solvent, makes the paraformaldehyde solid completely dissolve under certain temperature and pH value (pH 9 ~ 11) condition, and this has just eliminated the adverse effect of moisture, has improved the quality of product. However, the acid value of the product prepared by the method is large, and the shrinkage and the closed cell of the polyurethane foam product are easily caused by the large acid value. In addition, the pH value of the paraformaldehyde depolymerization process is adjusted by using a NaOH solution, and two adverse factors are provided, namely water is introduced into the system, and sodium ions are introduced into the system and are used as catalysts for polyurethane foaming, so that the subsequent polyurethane foaming reaction is very adverse.
Disclosure of Invention
The invention aims to provide a reactive halogen-free nitrogen-phosphorus flame retardant and a preparation method thereof, wherein the preparation process does not introduce external moisture and sodium ions, so that the moisture in a reaction system is reduced to the minimum, the adverse effect of water on inhibiting the generation of an intermediate and promoting the hydrolysis of phosphonate is eliminated to the maximum extent, the acid value of the obtained product is low, the yield and the purity of the product are improved, the process flow is optimized, and the product quality is improved.
The purpose of the invention is realized by the following technical scheme:
a reaction type halogen-free nitrogen phosphorus flame retardant has the following structure:
wherein R is1is-CH2CH2-、-CH(CH3)CH2Any one of-R, R2is-CH3、-CH2CH3、-CH(CH3)2、-CH2CH2CH2CH3Any one of them.
A preparation method of a reactive halogen-free nitrogen phosphorus flame retardant comprises the following specific steps:
(1) weighing paraformaldehyde solid, grinding into powder, weighing alcohol amine and melting, adding the powder-ground paraformaldehyde into the molten alcohol amine, stirring at 40-50 ℃, and continuously reacting for 1-2 hours after the solid is completely dissolved to obtain an intermediate solution;
(2) heating the intermediate solution obtained in the step (1) to 70-90 ℃, and performing vacuum dehydration by using a vacuum pump to obtain an intermediate;
(3) controlling the temperature of the intermediate obtained in the step (2) at 50-70 ℃, dropwise adding phosphite ester while stirring, and reacting for 2-4 h after dropwise adding to obtain yellow transparent liquid;
(4) adding Ca (OH) into the yellow transparent liquid obtained in the step (3)2Stirring for 2-4 h at normal temperature, and filtering to obtain the final product.
Further, in the step (1), the paraformaldehyde, namely the alcohol amine, is calculated according to molar mass, and the (1-3) is obtained.
Further, the alcohol amine is any one of diethanolamine or diisopropanolamine.
Further, in the step (2), the decompression pressure of the vacuum pump is-0.097 to-0.1 MPa, and the dehydration time is 1-2 h.
Further, in the step (3), the phosphite ester, namely the alcohol amine (1.05-1.85) and 1 are calculated according to parts by weight.
Further, in the step (3), the phosphite is any one of dimethyl phosphite, diethyl phosphite, diisopropyl phosphite and dibutyl phosphite.
Further, in the step (4), the Ca (OH)2The adding amount is 1-2% of the mass of the yellow transparent liquid.
Has the advantages that:
(1) the paraformaldehyde is used for replacing a formaldehyde aqueous solution, and the powdery paraformaldehyde directly reacts with the alcohol amine, so that new moisture is prevented from being introduced into a reaction system. Therefore, only water generated in the reaction of preparing the intermediate in the first step needs to be removed, so that the reduced pressure distillation time is short, the energy consumption is reduced, and the intermediate decomposition caused by long-time distillation and dehydration is avoided. The water content in the final product is reduced to a reasonable level, the water content of the final product is less than 0.1 percent through the Karl-Fischer method, and the requirement of polyurethane foaming on the water content of the flame retardant is met.
(2) The paraformaldehyde is directly reacted with the alcohol amine, so that the step of depolymerization under the conditions of solvent and alkalinity in the patent is omitted, and on one hand, the solvent is not used and recovered, so that the energy consumption is reduced, and the process flow is simplified. On the other hand, NaOH solution is not introduced in the reaction process, the obtained final product does not contain sodium ions, and the sodium ions are a catalyst for polyurethane foaming and can cause abnormal reaction speed in the foaming process, so that the flame retardant prepared by the method has good performance when applied to the foamed plastic obtained in the polyurethane foaming process.
(3) The flame retardant product prepared by the method disclosed in the patent has high acid value, is easy to cause shrinkage, closing and even collapse of a polyurethane foam product, and can only be applied to a high polymer synthetic material without strict requirements on the acid value. The method adopts Ca (OH)2The acid value of the product is reduced, and the acid value of the final product is less than 1mgKOH/g, so that the requirement of polyurethane foaming on the acid value of the flame retardant is met, and the polyurethane foaming flame retardant can be widely applied to other polymer synthetic materials.
Description of the drawings:
FIG. 1: structure of flame retardant of the invention
FIG. 2: preparation principle of flame retardant
Detailed Description
The paraformaldehyde, diethanolamine, diisopropanolamine, dimethyl phosphite, diethyl phosphite, diisopropyl phosphite, di-n-butyl phosphite and calcium hydroxide used in the examples of the invention are all common industrial products.
The present invention is further illustrated by the following examples, which should not be construed as limiting the scope of the invention as claimed.
Comparative example 1 (see method CN 1583768A)
(1) Adding 82 parts of 37% formaldehyde aqueous solution into a three-neck flask, heating to 30 ℃, magnetically stirring, weighing 105 parts of diethanolamine in a constant-pressure titration funnel, slowly adding the diethanolamine under stirring to react to obtain an exothermic reaction, controlling the reaction temperature to be 30 ℃, keeping the temperature at 30 ℃ after the diethanolamine is completely added, and continuing to react for 2 hours to obtain an intermediate 3- (2-hydroxyethyl) -1, 3-oxaziclopentane solution.
(2) Changing the reaction device into a pressure reducing device, heating to 50 ℃, distilling out water under reduced pressure under the condition that the gauge pressure is less than-0.095 MPa, and continuously distilling for 2h at 80 ℃ to obtain the intermediate 3- (2-hydroxyethyl) -1, 3-oxaziclopentane.
(3) Changing the pressure reducing device back to the reaction device, cooling to 40 ℃, adding 2 parts of anhydrous aluminum trichloride as a catalyst, weighing 138 parts of diethyl phosphite in a constant pressure titration funnel, slowly adding the diethyl phosphite into the three-neck flask under stirring, controlling the reaction temperature to be 40 ℃, heating to 60 ℃ after the dropwise addition is finished, and continuing to react for 4 hours.
(4) The temperature was lowered to room temperature, and the solid catalyst was recovered by filtration to obtain 261 parts of a yellow transparent product diethyl N, N-bis (2-hydroxyethyl) aminomethylphosphonate having an acid value of 11.24mgKOH/g, a hydroxyl value of 423mgKOH/g and a water content of 5.85%.
Comparative example 2 (see method CN 102276645A)
(1) Weighing 60 parts of isopropanol, putting the isopropanol into a 500ml three-neck flask with a magnetic stirrer, a constant pressure titration funnel and a thermometer, heating to 60 ℃, adding 30 parts of paraformaldehyde solid, adjusting the pH of the paraformaldehyde solution to 9-11 with a sodium hydroxide solution until the paraformaldehyde is completely dissolved, and cooling to 30 ℃.
(2) Weighing 20 parts of anhydrous calcium sulfate, adding the anhydrous calcium sulfate into a three-neck flask, weighing 105 parts of diethanolamine in a constant-pressure titration funnel, slowly adding the diethanolamine under stirring to react for an exothermic reaction, controlling the reaction temperature at 30 ℃, keeping the temperature at 30 ℃ after the diethanolamine is dropwise added, continuing to react for 2 hours, and filtering to remove the calcium sulfate after adsorbing water.
(3) Heating to 50 ℃, distilling under reduced pressure to remove the solvent isopropanol under the condition that the gauge pressure is-0.095 MPa, removing water generated by the reaction by utilizing the azeotropic distillation of the isopropanol and the water, and distilling under reduced pressure for 2h to obtain an intermediate 3- (2-hydroxyethyl) -1, 3-oxaziclopentane.
(4) Changing the pressure reducing device back to the reaction device, cooling to 60 ℃, adding 2 parts of anhydrous aluminum trichloride as a catalyst, weighing 138 parts of diethyl phosphite in a constant pressure titration funnel, slowly adding the diethyl phosphite into the three-neck flask under stirring, controlling the reaction temperature to be 60 ℃, preserving the heat for 60 ℃ after the dropwise addition is finished, and continuing the reaction for 4 hours.
(5) The temperature was lowered to room temperature, and the solid catalyst was recovered by filtration to obtain 258 parts of a yellow transparent product diethyl N, N-bis (2-hydroxyethyl) aminomethylphosphonate having an acid value of 9.75mgKOH/g, a hydroxyl value of 441mgKOH/g and a water content of 0.25%.
Example 1:
(1) weighing paraformaldehyde and alcohol amine in a ratio of 1:1 by molar mass, converting into parts by mass, namely 30 parts of paraformaldehyde and 105 parts of diethanolamine, grinding into powder, adding the powder of paraformaldehyde into a flask filled with the diethanolamine, stirring, controlling the temperature at 40 ℃, and continuing to react for 1h after the paraformaldehyde is completely dissolved to obtain an intermediate 3- (2-hydroxyethyl) -1, 3-oxaziridine solution.
(2) And (2) dehydrating the intermediate 3- (2-hydroxyethyl) -1, 3-oxazepine solution obtained in the step (1) for 1h at the temperature of 80 ℃ by using an oil pump under reduced pressure (gauge pressure of-0.097 Mpa), so as to obtain the intermediate 3- (2-hydroxyethyl) -1, 3-oxazepine.
(3) And (3) controlling the temperature of the intermediate 3- (2-hydroxyethyl) -1, 3-oxazacyclopentane obtained in the step (2) at 60 ℃, dropwise adding 110 parts of dimethyl phosphite while stirring, and reacting for 2 hours after the dropwise adding is finished to obtain 231 parts by weight of yellow transparent liquid.
(4) Cooling to room temperature, 2.31 parts by weight Ca (OH)2Adding the obtained product into the yellow transparent liquid obtained in the step (3), stirring for 3h at normal temperature, and filtering to obtain 231 parts of a yellow transparent product, namely N, N-bis (2-hydroxyethyl) aminomethylphosphonic acid dimethyl ester, wherein the hydroxyl value is 462mgKOH/g of a sample, the water content is 0.062%, and the acid value is 0.26mgKOH/g of the sample.
Example 2:
(1) weighing paraformaldehyde and alcohol amine in a ratio of 2:1 by molar mass, converting into parts by mass, 60 parts of paraformaldehyde and 105 parts of diethanolamine, adding the powdered paraformaldehyde into a flask of the diethanolamine, stirring, controlling the temperature at 45 ℃, and continuing to react for 1.5 hours after the paraformaldehyde is completely dissolved to obtain an intermediate 3- (2-hydroxyethyl) -1, 3-oxazacyclopentane solution.
(2) And (2) dehydrating the 3- (2-hydroxyethyl) -1, 3-oxazepine intermediate solution obtained in the step (1) for 1h at the temperature of 70 ℃ by using an oil pump under reduced pressure (gauge pressure of-0.097 Mpa), so as to obtain an intermediate 3- (2-hydroxyethyl) -1, 3-oxazepine.
(3) And (3) controlling the temperature of the intermediate 3- (2-hydroxyethyl) -1, 3-oxazacyclopentane obtained in the step (2) at 60 ℃, dropwise adding 138 parts of diethyl phosphite while stirring, and reacting for 2 hours after the dropwise adding is finished to obtain 261 parts by weight of yellow transparent liquid.
(4) The temperature is reduced to room temperature, 5.22 weight method Ca (OH)2Adding the obtained product into the yellow transparent liquid obtained in the step (3), stirring for 2h at normal temperature, and filtering to obtain 261 parts of yellow transparent product diethyl N, N-bis (2-hydroxyethyl) aminomethylphosphonate with a hydroxyl value of 446mgKOH/g, water content of 0.058% and an acid value of 0.23 mgKOH/g.
Example 3:
(1) weighing paraformaldehyde and alcohol amine 2:3 according to molar mass, converting into mass parts of 30 parts of paraformaldehyde and 157.5 parts of diethanolamine, adding the powdered paraformaldehyde into a flask of the diethanolamine, stirring, controlling the temperature at 50 ℃, and continuing to react for 2 hours after the paraformaldehyde is completely dissolved to obtain an intermediate 3- (2-hydroxyethyl) -1, 3-oxaziclopentane solution.
(2) And (2) dehydrating the intermediate 3- (2-hydroxyethyl) -1, 3-oxazepine solution obtained in the step (1) for 1h at the temperature of 90 ℃ by using an oil pump under reduced pressure (gauge pressure of-0.098 Mpa) to obtain the intermediate 3- (2-hydroxyethyl) -1, 3-oxazepine.
(3) And (3) controlling the temperature of the intermediate 3- (2-hydroxyethyl) -1, 3-oxaziclopentane obtained in the step (2) at 70 ℃, dropwise adding 166 parts of diisopropyl phosphite while stirring, and reacting for 4 hours after the dropwise adding is finished to obtain 292 parts by weight of yellow transparent liquid.
(4) The temperature is reduced to room temperature, 4.38 parts by weight of Ca (OH)2Adding the obtained mixture into the yellow transparent liquid prepared in the step (3), stirring for 3 hours at normal temperature, and filtering to obtain 292 parts of yellow transparent product N, N-bis (2-hydroxyethyl) aminomethyl diisopropyl phosphonate with a hydroxyl value of 423mgKOH/g sample, 0.066 percent of water and 0.16mgKOH/g sample.
Example 4:
(1) weighing paraformaldehyde and alcohol amine in a ratio of 1:1 by molar mass, converting into parts by mass, namely 30 parts of paraformaldehyde and 105 parts of diethanolamine, adding the powdered paraformaldehyde into a flask of the diethanolamine, stirring, controlling the temperature at 40 ℃, and continuously reacting for 1h after the paraformaldehyde is completely dissolved to obtain an intermediate 3- (2-hydroxyethyl) -1, 3-oxaziclopentane solution.
(2) And (2) dehydrating the intermediate 3- (2-hydroxyethyl) -1, 3-oxazepine solution obtained in the step (1) for 1.5h at the temperature of 70 ℃ by using an oil pump under reduced pressure (gauge pressure of-0.097 Mpa), so as to obtain the intermediate 3- (2-hydroxyethyl) -1, 3-oxazepine.
(3) And (3) controlling the temperature of the intermediate 3- (2-hydroxyethyl) -1, 3-oxaziclocyclopentane obtained in the step (2) at 50 ℃, dropwise adding 194 parts of dibutyl phosphite while stirring, and reacting for 2.5 hours after the dropwise adding is completed to obtain 317 parts of yellow transparent liquid.
(4) The temperature is reduced to room temperature, 4.76 parts of Ca (OH)2Adding the mixture into the yellow transparent liquid prepared in the step (3), stirring for 2.5h at normal temperature, and filtering to obtain 317 parts of yellow transparent product N, N-bis (2-hydroxyethyl) aminomethyl dibutyl phosphonate, wherein the hydroxyl value is 406mgKOH/g of sample, the water content is 0.052%, and the acid value is 0.13mgKOH/g of sample.
Example 5:
(1) weighing paraformaldehyde and alcohol amine in a ratio of 1:1 by molar mass, converting into parts by mass, namely 30 parts of paraformaldehyde and 105 parts of diethanolamine, adding the powdered paraformaldehyde into a flask containing diisopropanolamine, stirring, controlling the temperature at 50 ℃, and continuously reacting for 1h after the paraformaldehyde is completely dissolved to obtain an intermediate 3- (2-hydroxyisopropyl) -5-methyloxazole solution.
(2) And (2) dehydrating the intermediate 3- (2-hydroxyisopropyl) -5-methyloxazole solution obtained in the step (1) for 2h at the temperature of 85 ℃ by using an oil pump under reduced pressure (gauge pressure-0.098 Mpa) to obtain an intermediate 3- (2-hydroxyisopropyl) -5-methyloxazole.
(3) Controlling the temperature of the intermediate 3- (2-hydroxyisopropyl) -5-methyloxazole obtained in the step (2) at 60 ℃, dropwise adding 110 parts of dimethyl phosphite while stirring, and reacting for 2 hours after the dropwise adding is completed to obtain 259 parts of yellow transparent liquid.
(4) The temperature is reduced to room temperature, 5.18 parts of Ca (OH)2Adding the obtained product into the yellow transparent liquid obtained in the step (3), stirring for 2h at normal temperature, and filtering to obtain 259 parts of a yellow transparent product, namely N, N-bis (2-hydroxyisopropyl) aminomethyl dimethyl phosphonate, wherein the hydroxyl value is 458mgKOH/g of a sample, the water content is 0.073%, and the acid value is 0.24mgKOH/g of the sample.
Example 6:
(1) weighing paraformaldehyde and alcohol amine in a ratio of 2:1 by molar mass, converting into parts by mass, 60 parts of paraformaldehyde and 105 parts of diethanolamine, adding the powdered paraformaldehyde into a flask containing diisopropanolamine, stirring, controlling the temperature at 50 ℃, and continuing to react for 1h after the paraformaldehyde is completely dissolved to obtain an intermediate 3- (2-hydroxyisopropyl) -5-methyloxazole solution.
(2) And (2) dehydrating the intermediate 3- (2-hydroxyisopropyl) -5-methyloxazole solution obtained in the step (1) for 1h at the temperature of 75 ℃ by using an oil pump under reduced pressure (gauge pressure-0.01 Mpa) to obtain an intermediate 3- (2-hydroxyisopropyl) -5-methyloxazole.
(3) And (3) controlling the temperature of the intermediate 3- (2-hydroxyisopropyl) -5-methyloxazole prepared in the step (2) to be 60 ℃, dropwise adding 138 parts of diethyl phosphite while stirring, and reacting for 3 hours after the dropwise adding is finished to obtain 288 parts of yellow transparent liquid.
(4) The temperature is reduced to room temperature, 5.76 parts of Ca (OH)2Adding the mixture into the yellow transparent liquid prepared in the step (3), stirring for 3 hours at normal temperature, and filtering to obtain 288 parts of yellow transparent product N, N-bis (2)Hydroxyethyl) aminomethylphosphonic acid diethyl ester, hydroxyl value of 445mgKOH/g sample, water content of 0.061%, acid value of 0.21mgKOH/g sample.
Example 7:
(1) weighing paraformaldehyde and alcohol amine of 2:3 by molar mass, converting into parts by mass, namely 30 parts of paraformaldehyde and 157.5 parts of diethanolamine, adding the powdered paraformaldehyde into a flask containing diisopropanolamine, stirring, controlling the temperature at 50 ℃, and continuously reacting for 1.5 hours after the paraformaldehyde is completely dissolved to obtain an intermediate 3- (2-hydroxyisopropyl) -5-methyloxazole solution.
(2) And (2) dehydrating the intermediate 3- (2-hydroxyisopropyl) -5-methyloxazole solution obtained in the step (1) for 1h at the temperature of 70 ℃ by using an oil pump under reduced pressure (gauge pressure-0.097 Mpa) to obtain an intermediate 3- (2-hydroxyisopropyl) -5-methyloxazole.
(3) And (3) controlling the temperature of the intermediate 3- (2-hydroxyisopropyl) -5-methyloxazole obtained in the step (2) to be 50 ℃, dropwise adding 166 parts of diisopropyl phosphite while stirring, and reacting for 3 hours after the dropwise adding is completed to obtain 318 parts of yellow transparent liquid.
(4) The temperature is reduced to room temperature, 4.77 parts of Ca (OH)2Adding the obtained product into the yellow transparent liquid obtained in the step (3), stirring for 3h at normal temperature, and filtering to obtain 318 parts of a yellow transparent product, namely N, N-bis (2-hydroxyisopropyl) aminomethyl diisopropyl phosphonate, wherein the hydroxyl value is 421mgKOH/g of a sample, the water content is 0.049%, and the acid value is 0.15mgKOH/g of the sample.
Example 8:
(1) weighing paraformaldehyde and alcohol amine in a ratio of 2:3 by molar mass, converting into parts by mass, namely 30 parts of paraformaldehyde and 157.5 parts of diethanolamine, adding the powdered paraformaldehyde into a flask containing diisopropanolamine, stirring, controlling the temperature at 45 ℃, and continuously reacting for 1h after the paraformaldehyde is completely dissolved to obtain an intermediate 3- (2-hydroxyisopropyl) -5-methyloxazole solution.
(2) And (2) dehydrating the intermediate 3- (2-hydroxyisopropyl) -5-methyloxazole solution obtained in the step (1) for 1h at the temperature of 90 ℃ by using an oil pump under reduced pressure (gauge pressure-0.098 Mpa) to obtain an intermediate 3- (2-hydroxyisopropyl) -5-methyloxazole.
(3) And (3) controlling the temperature of the intermediate 3- (2-hydroxyisopropyl) -5-methyloxazole obtained in the step (2) to be 70 ℃, adding 194 parts of dibutyl phosphite dropwise while stirring, and reacting for 3 hours after the dropwise addition is completed to obtain 345 parts of yellow transparent liquid.
(4) The temperature is reduced to room temperature, 4.21 parts of Ca (OH)2And (3) adding the yellow transparent liquid obtained in the step (3), stirring for 3 hours at normal temperature, and filtering to obtain 345 parts of yellow transparent product N, N-bis (2-hydroxyethyl) aminomethyl dibutyl phosphonate, wherein the hydroxyl value of the sample is 398mgKOH/g, the water content is 0.056%, and the acid value of the sample is 0.14 mgKOH/g.
Table 1 examples product parameters
As can be seen from the experimental procedures and product data of the above examples and comparative examples, the process flow of the method of the present invention is simpler than that of the comparative example, and the acid value of the obtained reactive flame retardant is less than 1mgKOH/g of sample, and the moisture is less than 0.1%, which is much less than that of the comparative example.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the equivalent replacement or change according to the technical solution and the inventive concept should be covered by the scope of the present invention.
Claims (8)
1. The reactive halogen-free nitrogen-phosphorus flame retardant is characterized by having the following structure:
wherein R is1is-CH2CH2-、-CH(CH3)CH2Any one of-R, R2is-CH3、-CH2CH3、-CH(CH3)2、-CH2CH2CH2CH3Any one of them.
2. The preparation method of the reactive halogen-free nitrogen-phosphorus flame retardant of claim 1, which comprises the following steps:
(1) weighing paraformaldehyde solid, grinding into powder, weighing alcohol amine and melting, adding the powder-ground paraformaldehyde into the molten alcohol amine, stirring at 40-50 ℃, and continuously reacting for 1-2 hours after the solid is completely dissolved to obtain an intermediate solution;
(2) heating the intermediate solution obtained in the step (1) to 70-90 ℃, and performing vacuum dehydration by using a vacuum pump to obtain an intermediate;
(3) controlling the temperature of the intermediate obtained in the step (2) at 50-70 ℃, dropwise adding phosphite ester while stirring, and reacting for 2-4 h after dropwise adding to obtain yellow transparent liquid;
(4) adding Ca (OH) into the yellow transparent liquid obtained in the step (3)2Stirring for 2-4 h at normal temperature, and filtering to obtain the final product.
3. The preparation method of the reactive halogen-free nitrogen-phosphorus flame retardant according to claim 2, wherein in the step (1), the paraformaldehyde, namely the alcohol amine, is calculated by molar mass as 2 (1-3).
4. The method for preparing the reactive halogen-free nitrogen-phosphorus flame retardant according to claim 3, wherein the alcohol amine is one of diethanolamine and diisopropanolamine.
5. The preparation method of the reactive halogen-free nitrogen phosphorus flame retardant of claim 2, wherein in the step (2), the decompression pressure of the vacuum pump is-0.097 MPa to-0.1 MPa, and the dehydration time is 1-2 h.
6. The preparation method of the reactive halogen-free nitrogen-phosphorus flame retardant according to claim 2, wherein in the step (3), the phosphite ester is alkanolamine (1.05-1.85) 1 by weight.
7. The method for preparing the reactive halogen-free nitrogen phosphorus flame retardant according to claim 2, wherein in the step (3), the phosphite is any one of dimethyl phosphite, diethyl phosphite, diisopropyl phosphite and dibutyl phosphite.
8. The method for preparing the reactive nitrogen phosphorus free flame retardant according to claim 2, wherein in the step (4), the Ca (OH)2The adding amount is 1-2% of the mass of the yellow transparent liquid.
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| CN113512170A (en) * | 2021-08-06 | 2021-10-19 | 宁波长阳科技股份有限公司 | Flame-retardant thermoplastic polyurethane elastomer film and preparation method thereof |
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| JPS57163388A (en) * | 1981-04-01 | 1982-10-07 | Asahi Denka Kogyo Kk | Production of aminoalkylphosphonic acid derivative |
| CN102276645A (en) * | 2011-05-18 | 2011-12-14 | 烟台万华聚氨酯股份有限公司 | Preparation method of diethyl N,N-bis(2- hydroxyethyl) aminomethylphosphonate |
| CN108864184A (en) * | 2018-06-09 | 2018-11-23 | 河北晟凯新材料科技有限公司 | A kind of synthesis N, N- bis-（2- ethoxy）The method of aminomethyl phosphonic acid diethylester |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57163388A (en) * | 1981-04-01 | 1982-10-07 | Asahi Denka Kogyo Kk | Production of aminoalkylphosphonic acid derivative |
| CN102276645A (en) * | 2011-05-18 | 2011-12-14 | 烟台万华聚氨酯股份有限公司 | Preparation method of diethyl N,N-bis(2- hydroxyethyl) aminomethylphosphonate |
| CN108864184A (en) * | 2018-06-09 | 2018-11-23 | 河北晟凯新材料科技有限公司 | A kind of synthesis N, N- bis-（2- ethoxy）The method of aminomethyl phosphonic acid diethylester |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113512170A (en) * | 2021-08-06 | 2021-10-19 | 宁波长阳科技股份有限公司 | Flame-retardant thermoplastic polyurethane elastomer film and preparation method thereof |
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