CN104119557A - Organic phosphinate flame retardant and preparation method thereof - Google Patents
Organic phosphinate flame retardant and preparation method thereof Download PDFInfo
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 44
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 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 abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 10
- 229910052742 iron Inorganic materials 0.000 claims abstract description 7
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 7
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 7
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 48
- 230000007062 hydrolysis Effects 0.000 claims description 17
- 238000006460 hydrolysis reaction Methods 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 16
- 239000000047 product Substances 0.000 claims description 16
- 150000003839 salts Chemical class 0.000 claims description 13
- 238000010792 warming Methods 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- CZHYKKAKFWLGJO-UHFFFAOYSA-N dimethyl phosphite Chemical compound COP([O-])OC CZHYKKAKFWLGJO-UHFFFAOYSA-N 0.000 claims description 10
- 238000009413 insulation Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 150000001345 alkine derivatives Chemical class 0.000 claims description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 6
- 239000000413 hydrolysate Substances 0.000 claims description 6
- MJBPUQUGJNAPAZ-UHFFFAOYSA-N Butine Natural products O1C2=CC(O)=CC=C2C(=O)CC1C1=CC=C(O)C(O)=C1 MJBPUQUGJNAPAZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 4
- 239000011707 mineral Substances 0.000 claims description 4
- 150000007530 organic bases Chemical group 0.000 claims description 4
- MWWATHDPGQKSAR-UHFFFAOYSA-N propyne Chemical compound CC#C MWWATHDPGQKSAR-UHFFFAOYSA-N 0.000 claims description 4
- 238000004080 punching Methods 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 6
- 239000011574 phosphorus Substances 0.000 abstract description 6
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 3
- 229920006351 engineering plastic Polymers 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 10
- 238000007792 addition Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- 239000007818 Grignard reagent Substances 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- -1 alkyl phosphinate Chemical compound 0.000 description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000000498 cooling water Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000011152 fibreglass Substances 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 150000004795 grignard reagents Chemical class 0.000 description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 2
- XRBCRPZXSCBRTK-UHFFFAOYSA-N phosphonous acid Chemical compound OPO XRBCRPZXSCBRTK-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000007342 radical addition reaction Methods 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- IUZDCOWLGJCVHC-UHFFFAOYSA-N [Ca].P(O)O Chemical compound [Ca].P(O)O IUZDCOWLGJCVHC-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 159000000013 aluminium salts Chemical class 0.000 description 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- LXCYSACZTOKNNS-UHFFFAOYSA-N diethoxy(oxo)phosphanium Chemical compound CCO[P+](=O)OCC LXCYSACZTOKNNS-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 150000001457 metallic cations Chemical class 0.000 description 1
- 238000005649 metathesis reaction Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 229910001392 phosphorus oxide Inorganic materials 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention discloses an organic phosphinate flame retardant. The chemical formula of the organic phosphinate flame retardant is as shown in the specification, wherein M is selected from any one of metal ions such as Mg, Al, Fe, Zn, Ca, Sn and the like, and x is 2 to 4. The invention also discloses a preparation method of the organic phosphinate flame retardant. The preparation method is simple in process, low-cost and available in raw materials, mild in reaction conditions, easy to operate, small in equipment investment, safe and environment-friendly; the prepared organic phosphinate flame retardant is high in purity, high in product yield, good in product thermal stability of and high in content of phosphorus; when the organic phosphinate flame retardant is applied to engineering plastics, the organic phosphinate flame retardant is relatively good in flame retardant effect, mechanical property and electrical property.
Description
Technical field
The invention belongs to chemical field, be specifically related to a kind of organic phosphinate fire retardant and preparation method thereof.
Background technology
Bromide fire retardant has excellent cost performance, be widely used in various engineering plastics, but its harm to environment and HUMAN HEALTH bringing is very important, day by day by the fire retardant of various environment friendly non-halogens, replaced, organic phosphine flame retardant is considered to substitute one of the most promising fire retardant of bromide fire retardant.
Organic phosphonate fire retardant has the hood that presses down of the fire retardation of phosphorus flame retardant gas phase and condensed phase and metallic cation concurrently, Heat stability is good, consumption is few, flame retarding efficiency is high, and color and luster is good, and smoke density is low, good mechanical property, the advantages such as CTI (phase ratio creepage tracking index) higher (600V) are had an application prospect in electrical industry very much, are specially adapted to thin-walled electronic devices and components, transparent film-making and film.
In prior art, Chinese patent CN201010217750 discloses a kind of preparation method of alkyl phosphinate polymer, the method generates alkyl phosphinate polymer by alkynes and alkene and Hypophosporous Acid, 50 (salt) by free radical addition method successively under initiator effect, there is replacement(metathesis)reaction with aluminium salt etc. again and generate polymerization alkyl phosphinic acid aluminium etc., this technique need to be reacted under higher temperature and pressure, higher to the security requirement of producing, energy consumption is also larger, 2 step Radical Additions are wayward, and product purity is lower; Patent CN201010613835 discloses a kind of preparation method of dialkylphosphinic salts, the method adopts Grignard reagent to react with diethyl phosphite and generates dialkyl group phosphorus oxide, obtain dialkylphosphinic salts again with after oxidant reaction acidifying, it is raw material that the method is used Grignard reagent, operational hazards, complex process, and can obtain the mixed systems such as monoalkyl-phosphinous acid, dialkyl phosphinic acid, Hypophosporous Acid, 50, by product is more, not easily separated, and productive rate and purity are all very low; Patent CN98811622, CN98811626, CN98811627, CN200410104692 etc. disclose Hypophosporous Acid, 50 (salt) solution in acidic medium, free radical causes the method for preparing dialkylphosphinic salts with ethylene reaction, there is following defect in the method: can generate monoalkyl phosphinates by product, the easy cancellation inactivation of free radical causes speed of response to reduce, reaction pressure is higher, higher to equipment and security requirement, recycled solvent difficulty, energy consumption is larger.
Summary of the invention
Goal of the invention: the object of the invention is to for the deficiencies in the prior art, a kind of organic phosphinate fire retardant is provided.
Another object of the present invention is to provide the preparation method of above-mentioned fire retardant.
Technical scheme: in order to reach foregoing invention object, the present invention is specifically achieved like this: a kind of organic phosphinate fire retardant, this fire retardant is a compounds as shown in the formula (I):
Wherein M be in the metal ions such as Mg, Al, Fe, Zn, Ca, Sn any, x=2～4.
Described organic phosphinate fire retardant, its preparation comprises the following steps:
(1) dimethylphosphite is dropped in dry reactor, open and stir, then to limit in reactor, drip catalyzer limit and pass into alkynes or diolefine gas, keep still internal pressure 0～0.6MPa, temperature of reaction is controlled at 0～100 ℃, when the gas volume passing into reaches a half of dimethylphosphite molar weight, close source of the gas, insulation reaction 1～2 hour;
(2) material of step (1) gained is transferred in hydrolysis kettle, adds the water of 1～10 times of weight of material, stir and be warming up to 100～110 ℃ of hydrolysis, insulation reaction 1～2 hour is collected the methyl alcohol in hydrolysate in addition after rectifying tower is purified;
(3) be hydrolyzed complete, by material be down to 20 ℃ following and be transferred in and in still, be warming up to 20～100 ℃, then drip aqueous metal salt, adularescent solid is separated out, after filtration, washing, dryly obtain organic phosphinate finished product.
In this fire retardant preparation process (1), described alkynes is acetylene, propine or butine, and described diolefine is 1,3-butadiene, and described catalyzer is organic bases or mineral alkali, is preferably triethylamine, sodium methylate, sodium hydroxide, sodium carbonate.
In this fire retardant preparation process (2), hydrolysis adopts steam punching to steam rectifying methyl alcohol method or backflow rectifying methyl alcohol method.
In this fire retardant preparation process (3), described aqueous metal salt is any aqueous solution in the metal ions such as Mg, Al, Fe, Zn, Ca, Sn.
The method of preparing above-mentioned organic phosphinate fire retardant, comprises the following steps:
(1) dimethylphosphite is dropped in dry reactor, open and stir, then to limit in reactor, drip catalyzer limit and pass into alkynes or diolefine gas, keep still internal pressure 0～0.6MPa, temperature of reaction is controlled at 0～100 ℃, when the gas volume passing into reaches a half of dimethylphosphite molar weight, close source of the gas, insulation reaction 1～2 hour;
(2) material of step (1) gained is transferred in hydrolysis kettle, adds the water of 1～10 times of weight of material, stir and be warming up to 100～110 ℃ of hydrolysis, insulation reaction 1～2 hour is collected the methyl alcohol in hydrolysate in addition after rectifying tower is purified;
(3) be hydrolyzed complete, by material be down to 20 ℃ following and be transferred in and in still, be warming up to 20～100 ℃, then drip aqueous metal salt, adularescent solid is separated out, after filtration, washing, dryly obtain organic phosphinate finished product.
Wherein, in step (1), described alkynes is acetylene, propine or butine, and described diolefine is 1,3-butadiene, and described catalyzer is organic bases or mineral alkali, is preferably triethylamine, sodium methylate, sodium hydroxide, sodium carbonate.
Wherein, in step (2), hydrolysis adopts steam punching to steam rectifying methyl alcohol method or backflow rectifying methyl alcohol method.
Wherein, the aqueous metal salt described in step (3) is any aqueous solution in the metal ions such as Mg, Al, Fe, Zn, Ca, Sn.
The reaction equation following (take 1,3-butadiene as example) the present invention relates to:
The finished product ultimate yield that the present invention produces is 95～99%, purity >=98%.
Beneficial effect: preparation method's technique of the present invention is simple, raw material is cheap and easy to get, reaction conditions is gentle, easy handling, and facility investment is few, safety and environmental protection, organic phosphinate purity of preparation is high, and the yield of product is high, product Heat stability is good, phosphorus content is high, and being applied to has better flame retardant effect, mechanical property and electric property in engineering plastics.
Embodiment
Embodiment 1:
3.3Kg dimethylphosphite is dropped in dry 5L reactor, open and stir, pass into acetylene gas, keeping still internal pressure is 0.3MPa, drip 30%(mass percentage concentration simultaneously) sodium methoxide solution 100g, in chuck, passing into cooling water control reactor temperature is 30～35 ℃, when acetylene gas intake reaches 390g, insulation reaction 1 hour, then closes source of the gas.
Material is transferred in hydrolysis kettle, add 2Kg deionized water, be warming up to 105 ℃, adopt the hydrolysis of backflow rectifying methyl alcohol method, hydrolysate methyl alcohol being reclaimed after rectifying tower is purified to it uses, be hydrolyzed complete, material is lowered the temperature and be transferred in and still in, be warming up to 75 ℃, then drip 40%(mass percentage concentration) aluminum sulfate aqueous solution 9.4Kg, adularescent solid is separated out, washing after filtration,, dry obtain organic phosphonous acid aluminium finished product 3230.1g, yield 97.0%, purity records 98.2%, phosphorus content 27.72%.
Structural formula is:
Embodiment 2:
3.3Kg dimethylphosphite is dropped in dry 5L reactor, open and stir, pass into 1,3-butadiene gas, keeping still internal pressure is 0.4MPa, drip 30%(mass percentage concentration simultaneously) sodium methoxide solution 100g, in chuck, passing into cooling water control reactor temperature is 35～40 ℃, when 1,3-butadiene gas intake reaches 810g, insulation reaction 1 hour, then closes source of the gas.Material is transferred in hydrolysis kettle, add 2Kg deionized water, be warming up to 108 ℃, adopt the hydrolysis of backflow rectifying methyl alcohol method, hydrolysate methyl alcohol being reclaimed after rectifying tower is purified to him uses, be hydrolyzed complete, material is lowered the temperature and be transferred in and still in, be warming up to 85 ℃, then drip 40%(mass percentage concentration) aluminum sulfate aqueous solution 9.4Kg, adularescent solid is separated out, washing after filtration,, dry obtain organic phosphonous acid aluminium finished product 3660.0g, yield 97.6%, purity records 98.6%, phosphorus content 24.68%.
Structural formula is:
Embodiment 3:
In being transferred to the solution obtaining after embodiment 1 hydrolysis and in still, be warming up to 75 ℃, then drip 40%(mass percentage concentration) calcium chloride water 9.15Kg, adularescent solid is separated out, washing after filtration,, dry obtain organic phosphonous acid calcium finished product 3918.2g, yield 98.2%, purity records 98.8%, phosphorus content 23.17%.
Product structure formula is:
Embodiment 4:
The finished product of embodiment 1 gained is applied in to (addition 12.5%) in 30% fiber glass reinforced PBT, obtains following data:
| Tensile strength | Flexural strength | Modulus in flexure | Notched Izod impact strength | Elongation at break | Flame retardant resistance |
| 120MPa | 185MPa | 11000MPa | 120J/M | 2.3% | V-0 |
Embodiment 5:
The finished product of embodiment 1 gained is applied in to (addition 12.5%) in 30% glass fiber reinforced PA66, obtain as
Lower data:
| Tensile strength | Flexural strength | Notched Izod impact strength | Elongation at break | Heat-drawn wire | Flame retardant resistance |
| 190MPa | 220MPa | 170J/M | 2.0% | 260℃ | V-0 |
Embodiment 6:
The finished product of embodiment 2 gained is applied in to (addition 15%) in 30% fiber glass reinforced PBT, obtains following data:
| Tensile strength | Flexural strength | Modulus in flexure | Notched Izod impact strength | Elongation at break | Flame retardant resistance |
| 110MPa | 175MPa | 11000MPa | 110J/M | 2.8% | V-0 |
Embodiment 7:
The finished product of embodiment 2 gained is applied in to (addition 15%) in 30% glass fiber reinforced PA66, obtains following data:
| Tensile strength | Flexural strength | Notched Izod impact strength | Elongation at break | Heat-drawn wire | Flame retardant resistance |
| 180MPa | 210MPa | 160J/M | 2.2% | 255℃ | V-0 |
Claims (9)
1. an organic phosphinate fire retardant, is characterized in that: this fire retardant is a compounds as shown in the formula (I):
Wherein M be in the metal ions such as Mg, Al, Fe, Zn, Ca, Sn any, x=2～4.
2. organic phosphinate fire retardant according to claim 1, is characterized in that, its preparation comprises the following steps:
(1) dimethylphosphite is dropped in dry reactor, open and stir, then to limit in reactor, drip catalyzer limit and pass into alkynes or diolefine gas, keep still internal pressure 0～0.6MPa, temperature of reaction is controlled at 0～100 ℃, when the gas volume passing into reaches a half of dimethylphosphite molar weight, close source of the gas, insulation reaction 1～2 hour;
(2) material of step (1) gained is transferred in hydrolysis kettle, adds the water of 1～10 times of weight of material, stir and be warming up to 100～110 ℃ of hydrolysis, insulation reaction 1～2 hour is collected the methyl alcohol in hydrolysate in addition after rectifying tower is purified;
(3) be hydrolyzed complete, by material be down to 20 ℃ following and be transferred in and in still, be warming up to 20～100 ℃, then drip aqueous metal salt, adularescent solid is separated out, after filtration, washing, dryly obtain organic phosphinate finished product.
3. organic phosphinate fire retardant according to claim 2, it is characterized in that, in this fire retardant preparation process (1), described alkynes is acetylene, propine or butine, described diolefine is 1,3-divinyl, described catalyzer is organic bases or mineral alkali, is preferably triethylamine, sodium methylate, sodium hydroxide, sodium carbonate.
4. organic phosphinate fire retardant according to claim 2, is characterized in that, in this fire retardant preparation process (2), hydrolysis adopts steam punching to steam rectifying methyl alcohol method or backflow rectifying methyl alcohol method.
5. organic phosphinate fire retardant according to claim 2, is characterized in that, in this fire retardant preparation process (3), described aqueous metal salt is any aqueous solution in the metal ions such as Mg, Al, Fe, Zn, Ca, Sn.
6. the method for preparing organic phosphinate fire retardant described in claim 1, is characterized in that, comprises the following steps:
(1) dimethylphosphite is dropped in dry reactor, open and stir, then to limit in reactor, drip catalyzer limit and pass into alkynes or diolefine gas, keep still internal pressure 0～0.6MPa, temperature of reaction is controlled at 0～100 ℃, when the gas volume passing into reaches a half of dimethylphosphite molar weight, close source of the gas, insulation reaction 1～2 hour;
(2) material of step (1) gained is transferred in hydrolysis kettle, adds the water of 1～10 times of weight of material, stir and be warming up to 100～110 ℃ of hydrolysis, insulation reaction 1～2 hour is collected the methyl alcohol in hydrolysate in addition after rectifying tower is purified;
(3) be hydrolyzed complete, by material be down to 20 ℃ following and be transferred in and in still, be warming up to 20～100 ℃, then drip aqueous metal salt, adularescent solid is separated out, after filtration, washing, dryly obtain organic phosphinate finished product.
7. prepare according to claim 6 the method for organic phosphinate fire retardant, it is characterized in that, in step (1), described alkynes is acetylene, propine or butine, described diolefine is 1,3-divinyl, described catalyzer is organic bases or mineral alkali, is preferably triethylamine, sodium methylate, sodium hydroxide, sodium carbonate.
8. prepare according to claim 6 the method for organic phosphinate fire retardant, it is characterized in that, in step (2), hydrolysis adopts steam punching to steam rectifying methyl alcohol method or backflow rectifying methyl alcohol method.
9. prepare according to claim 6 the method for organic phosphinate fire retardant, it is characterized in that, the aqueous metal salt described in step (3) is any aqueous solution in the metal ions such as Mg, Al, Fe, Zn, Ca, Sn.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106632468A (en) * | 2016-11-22 | 2017-05-10 | 同济大学 | A preparing method of an aminotris(methylenephosphonic acid) metal salt flame retardant |
| CN110066293A (en) * | 2018-01-24 | 2019-07-30 | 金发科技股份有限公司 | A kind of aminotrimethylenephosphonic acid aluminium and its preparation method and application |
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| CN1280584A (en) * | 1997-11-28 | 2001-01-17 | 科莱恩有限公司 | Method for producing dialkylphosphinic acids |
| CN101906117A (en) * | 2010-07-01 | 2010-12-08 | 叶金标 | Alkyl phosphinate polymer and preparation method and application thereof |
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2014
- 2014-04-15 CN CN201410151308.6A patent/CN104119557A/en active Pending
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|---|---|---|---|---|
| CN1280584A (en) * | 1997-11-28 | 2001-01-17 | 科莱恩有限公司 | Method for producing dialkylphosphinic acids |
| CN101906117A (en) * | 2010-07-01 | 2010-12-08 | 叶金标 | Alkyl phosphinate polymer and preparation method and application thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106632468A (en) * | 2016-11-22 | 2017-05-10 | 同济大学 | A preparing method of an aminotris(methylenephosphonic acid) metal salt flame retardant |
| CN106632468B (en) * | 2016-11-22 | 2019-08-06 | 同济大学 | Preparation method of amino trimethylene phosphonic acid metal salt flame retardant |
| CN110066293A (en) * | 2018-01-24 | 2019-07-30 | 金发科技股份有限公司 | A kind of aminotrimethylenephosphonic acid aluminium and its preparation method and application |
| WO2019144331A1 (en) * | 2018-01-24 | 2019-08-01 | 金发科技股份有限公司 | Aluminum amino trimethylene phosphonate, preparation method therefor and use thereof |
| JP2020518594A (en) * | 2018-01-24 | 2020-06-25 | キングファ サイエンス アンド テクノロジー カンパニーリミテッドＫｉｎｇｆａ Ｓｃｉ． ＆ Ｔｅｃｈ． Ｃｏ．，Ｌｔｄ． | Aluminum aminotrimethylene phosphonate, its preparation method and application |
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