CN101899160A - Preparation method of oligomerization phosphate polyalcohol - Google Patents
Preparation method of oligomerization phosphate polyalcohol Download PDFInfo
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- CN101899160A CN101899160A CN 201010227072 CN201010227072A CN101899160A CN 101899160 A CN101899160 A CN 101899160A CN 201010227072 CN201010227072 CN 201010227072 CN 201010227072 A CN201010227072 A CN 201010227072A CN 101899160 A CN101899160 A CN 101899160A
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- oligomerization
- oligomerization phosphate
- polyalcohol
- phosphate polyalcohol
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- 229910019142 PO4 Inorganic materials 0.000 title claims abstract description 43
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title claims abstract description 42
- 239000010452 phosphate Substances 0.000 title claims abstract description 42
- 150000005846 sugar alcohols Polymers 0.000 title claims abstract description 42
- 238000006384 oligomerization reaction Methods 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000000203 mixture Substances 0.000 claims abstract description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000002253 acid Substances 0.000 claims abstract description 15
- 239000011230 binding agent Substances 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 67
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 27
- 239000007789 gas Substances 0.000 claims description 21
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 19
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 19
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 19
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 claims description 19
- 238000005406 washing Methods 0.000 claims description 16
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical group Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 14
- 239000000706 filtrate Substances 0.000 claims description 14
- -1 phosphoric acid ester alkane Chemical class 0.000 claims description 14
- 238000004821 distillation Methods 0.000 claims description 12
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 125000003963 dichloro group Chemical group Cl* 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000009413 insulation Methods 0.000 claims description 7
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 claims description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 3
- 229940051250 hexylene glycol Drugs 0.000 claims description 3
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 3
- 108091034117 Oligonucleotide Proteins 0.000 claims description 2
- JLCPHMBAVCMARE-UHFFFAOYSA-N [3-[[3-[[3-[[3-[[3-[[3-[[3-[[3-[[3-[[3-[[3-[[5-(2-amino-6-oxo-1H-purin-9-yl)-3-[[3-[[3-[[3-[[3-[[3-[[5-(2-amino-6-oxo-1H-purin-9-yl)-3-[[5-(2-amino-6-oxo-1H-purin-9-yl)-3-hydroxyoxolan-2-yl]methoxy-hydroxyphosphoryl]oxyoxolan-2-yl]methoxy-hydroxyphosphoryl]oxy-5-(5-methyl-2,4-dioxopyrimidin-1-yl)oxolan-2-yl]methoxy-hydroxyphosphoryl]oxy-5-(6-aminopurin-9-yl)oxolan-2-yl]methoxy-hydroxyphosphoryl]oxy-5-(6-aminopurin-9-yl)oxolan-2-yl]methoxy-hydroxyphosphoryl]oxy-5-(6-aminopurin-9-yl)oxolan-2-yl]methoxy-hydroxyphosphoryl]oxy-5-(6-aminopurin-9-yl)oxolan-2-yl]methoxy-hydroxyphosphoryl]oxyoxolan-2-yl]methoxy-hydroxyphosphoryl]oxy-5-(5-methyl-2,4-dioxopyrimidin-1-yl)oxolan-2-yl]methoxy-hydroxyphosphoryl]oxy-5-(4-amino-2-oxopyrimidin-1-yl)oxolan-2-yl]methoxy-hydroxyphosphoryl]oxy-5-(5-methyl-2,4-dioxopyrimidin-1-yl)oxolan-2-yl]methoxy-hydroxyphosphoryl]oxy-5-(5-methyl-2,4-dioxopyrimidin-1-yl)oxolan-2-yl]methoxy-hydroxyphosphoryl]oxy-5-(6-aminopurin-9-yl)oxolan-2-yl]methoxy-hydroxyphosphoryl]oxy-5-(6-aminopurin-9-yl)oxolan-2-yl]methoxy-hydroxyphosphoryl]oxy-5-(4-amino-2-oxopyrimidin-1-yl)oxolan-2-yl]methoxy-hydroxyphosphoryl]oxy-5-(4-amino-2-oxopyrimidin-1-yl)oxolan-2-yl]methoxy-hydroxyphosphoryl]oxy-5-(4-amino-2-oxopyrimidin-1-yl)oxolan-2-yl]methoxy-hydroxyphosphoryl]oxy-5-(6-aminopurin-9-yl)oxolan-2-yl]methoxy-hydroxyphosphoryl]oxy-5-(4-amino-2-oxopyrimidin-1-yl)oxolan-2-yl]methyl [5-(6-aminopurin-9-yl)-2-(hydroxymethyl)oxolan-3-yl] hydrogen phosphate Polymers Cc1cn(C2CC(OP(O)(=O)OCC3OC(CC3OP(O)(=O)OCC3OC(CC3O)n3cnc4c3nc(N)[nH]c4=O)n3cnc4c3nc(N)[nH]c4=O)C(COP(O)(=O)OC3CC(OC3COP(O)(=O)OC3CC(OC3COP(O)(=O)OC3CC(OC3COP(O)(=O)OC3CC(OC3COP(O)(=O)OC3CC(OC3COP(O)(=O)OC3CC(OC3COP(O)(=O)OC3CC(OC3COP(O)(=O)OC3CC(OC3COP(O)(=O)OC3CC(OC3COP(O)(=O)OC3CC(OC3COP(O)(=O)OC3CC(OC3COP(O)(=O)OC3CC(OC3COP(O)(=O)OC3CC(OC3COP(O)(=O)OC3CC(OC3COP(O)(=O)OC3CC(OC3COP(O)(=O)OC3CC(OC3COP(O)(=O)OC3CC(OC3CO)n3cnc4c(N)ncnc34)n3ccc(N)nc3=O)n3cnc4c(N)ncnc34)n3ccc(N)nc3=O)n3ccc(N)nc3=O)n3ccc(N)nc3=O)n3cnc4c(N)ncnc34)n3cnc4c(N)ncnc34)n3cc(C)c(=O)[nH]c3=O)n3cc(C)c(=O)[nH]c3=O)n3ccc(N)nc3=O)n3cc(C)c(=O)[nH]c3=O)n3cnc4c3nc(N)[nH]c4=O)n3cnc4c(N)ncnc34)n3cnc4c(N)ncnc34)n3cnc4c(N)ncnc34)n3cnc4c(N)ncnc34)O2)c(=O)[nH]c1=O JLCPHMBAVCMARE-UHFFFAOYSA-N 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- 239000003063 flame retardant Substances 0.000 abstract description 18
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 13
- 239000000463 material Substances 0.000 abstract description 12
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 abstract description 9
- 229920002635 polyurethane Polymers 0.000 abstract description 7
- 239000004814 polyurethane Substances 0.000 abstract description 7
- 229910052736 halogen Inorganic materials 0.000 abstract description 6
- 150000002367 halogens Chemical class 0.000 abstract description 5
- 239000004721 Polyphenylene oxide Substances 0.000 abstract description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 abstract description 2
- 239000012948 isocyanate Substances 0.000 abstract description 2
- 150000002513 isocyanates Chemical class 0.000 abstract description 2
- 229920005906 polyester polyol Polymers 0.000 abstract description 2
- 229920000570 polyether Polymers 0.000 abstract description 2
- 239000012295 chemical reaction liquid Substances 0.000 abstract 2
- 238000006757 chemical reactions by type Methods 0.000 abstract 1
- 238000004321 preservation Methods 0.000 abstract 1
- 239000003053 toxin Substances 0.000 abstract 1
- 231100000765 toxin Toxicity 0.000 abstract 1
- 235000021317 phosphate Nutrition 0.000 description 23
- 238000012360 testing method Methods 0.000 description 23
- 238000000034 method Methods 0.000 description 13
- 238000009835 boiling Methods 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 229920005830 Polyurethane Foam Polymers 0.000 description 10
- 239000011496 polyurethane foam Substances 0.000 description 10
- 230000008569 process Effects 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 239000012530 fluid Substances 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000003595 mist Substances 0.000 description 4
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 3
- 229920000388 Polyphosphate Polymers 0.000 description 3
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000001205 polyphosphate Substances 0.000 description 3
- 235000011176 polyphosphates Nutrition 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000002521 alkyl halide group Chemical group 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 230000002045 lasting effect Effects 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 229910004856 P—O—P Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004500 asepsis Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229960004756 ethanol Drugs 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000003500 flue dust Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- JISVIRFOSOKJIU-UHFFFAOYSA-N hexylidene Chemical group [CH2+]CCCC[CH-] JISVIRFOSOKJIU-UHFFFAOYSA-N 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- ASLWPAWFJZFCKF-UHFFFAOYSA-N tris(1,3-dichloropropan-2-yl) phosphate Chemical compound ClCC(CCl)OP(=O)(OC(CCl)CCl)OC(CCl)CCl ASLWPAWFJZFCKF-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to a preparation method of oligomerization phosphate polyalcohol. Dissolvent and phosphorus oxychloride are put into an agitated reactor; monohydric alcohol is dropwise added; after the monohydric alcohol is dropwise added, heat preservation and backflow are carried out to obtain reaction liquid; acid binding agent and catalyst are added into reaction liquid; dihydric alcohol is slowly dropwise added; after the dihydric alcohol is dropwise added, backflow reaction is carried out to obtain mixture; the mixture is filtered, heated and distilled to obtain solvent; oligomerization phosphate polyalcohol is obtained, and oligomerization phosphate polyalcohol containing hydroxy terminal is synthesized; the oligomerization phosphate polyalcohol contains no halogen, protects environment, has no toxin and belongs to reaction type fire retardant. Because of the contained hydroxy terminal, the oligomerization phosphate polyalcohol can replace parts of polyether glycol or polyester polyol and reacts with isocyanate to produce polyurethane, i.e. the oligomerization phosphate polyalcohol can be combined into polyurethane material; and when being heated, the oligomerization phosphate polyalcohol does not move and is not separated out, and so that the material has enduring flame retardant property.
Description
Technical field
The present invention relates to a kind of preparation method of phosphine flame retardant, specifically, relate to a kind of preparation method of oligomerization phosphate polyalcohol.
Background technology
Urethane foam is one of at present the most frequently used plastics variety, is widely used in industries such as furniture, automobile, cushion, petrochemical pipe and device fabrication.But polyurethane foamed material is very easily burning in air, and when burning produces a large amount of toxic gas and flue dust.Therefore, both at home and abroad given great concern to urethane foam fire-retardant.
Be applied to the Flame Retardancy of Polyurethane Foam agent at present and mainly be liquid halophosphate, for example tricresyl phosphate (2-chloro isopropyl) ester (TCPP), tricresyl phosphate (2,2 '-two chloro isopropyls) ester (TDCPP) tricresyl phosphate (2-chloroethyl) ester (TCEP) of containing.But these halogen containing flame-retardants are separated out from polyurethane material easily, reduce the flame retardant properties of material, easily produce hydrogen halide corrosion gas during burning.Along with the raising of environmental requirement, Halogen, environmental protection low toxicity become the fire retardant development trend, and halogenous phosphoric acid ester will be subjected to increasing restriction in the application of some industries.
The preparation of Chinese patent 200710022380.9 disclosed low polyphosphates, adopt the dichloro mono phosphoric acid ester alkane ester monomer and the dibasic alcohol polymerization of phosphorus oxychloride or phosphorus oxychloride and monohydroxy-alcohol reaction gained, at last by the monohydroxy-alcohol end-blocking, obtain low polyphosphate, substantially do not contain terminal hydroxy group, belong to additive flame retardant.Though this fire retardant is Halogen not, in body material, belong to the interpolation component, also migration precipitation easily reduces its flame retardant properties when being heated.
United States Patent (USP) 5608100 discloses a kind of preparation method of oligomerization phosphate polyalcohol, by trialkyl phosphates and Vanadium Pentoxide in FLAKES reaction, obtains containing the polymer of P-O-P bond structure, with reacting ethylene oxide, obtains oligomerization phosphate polyalcohol again.The low polyphosphate that this method makes, distribution of polymerization degree is wide, does not contain the alkyl phosplate content height of terminal hydroxy group.The disadvantageous effect that this alkyl phosplate brings is owing to do not contain terminal hydroxy group, can not with the polyurethane material Chemical bond, separate out easily, promptly influence environment for use, reduce fire-retardant timeliness again; And the oxyethane that this method adopts, unstable chemcial property, under certain condition, easily a large amount of heats is emitted in decomposition or polymerization, forms blast.Its boiling point is low, and normal temperature is gas, and is very wide with the air mixed explosive range; Vanadium Pentoxide in FLAKES is the moisture absorption very easily, emits a large amount of heat, the danger of burning of contact skin, poor stability.
Summary of the invention
The technical problem to be solved in the present invention is at above deficiency, a kind of preparation method of response type oligomerization phosphate polyalcohol is provided, oligomerization phosphate polyalcohol with this method preparation, has terminal hydroxy group, Halogen not, can be attached in the polyurethane material, make material have lasting flame retardant properties, and safe.
For overcoming the above problems, technical scheme of the present invention is as follows: a kind of preparation method of oligomerization phosphate polyalcohol, and the structure of oligomerization phosphate polyalcohol is shown in (I):
Wherein, R is C
1-C
4No alkylhalide group;
R
1Be hydroxyethyl, hydroxypropyl or hydroxyl hexyl;
R
2Be ethylidene, propylidene or hexylidene;
N represents the polymerization degree of this polymkeric substance, is the natural number between the 1-20;
It is characterized in that: described preparation method may further comprise the steps:
(1) synthetic dichloro mono phosphoric acid ester alkane fat
Solvent and phosphorus oxychloride are placed reactor, and temperature is controlled at 30 ± 5 ℃, splashes into monohydroxy-alcohol, drip monohydroxy-alcohol after, insulation is back to the effusion of no hydrogen chloride gas, obtains reaction solution, reaction formula is:
(2) synthesis of oligonucleotides phosphate polyalcohol
Acid binding agent triethylamine and catalyzer are placed reaction solution, and temperature is controlled at 20 ± 5 ℃, splashes into dibasic alcohol, drip dibasic alcohol after, back flow reaction is overflowed to there being hydrogen chloride gas, obtains mixture, reaction equation is:
Wherein, R is C
1-C
6No alkylhalide group;
R
1Be C
1-C
6Alkylidene group;
N represents the polymerization degree of this polymkeric substance, is the natural number between the 1-20.
(3) mixture is carried out filtration treatment, obtain filtrate and triethylamine hydrochloride, use the solvent washing triethylamine hydrochloride, obtain washings, after filtrate and washings merging, the distillation of heating obtains oligomerization phosphate polyalcohol.
As further improvement in the technical proposal:
In the step (1), the mol ratio of monohydroxy-alcohol and phosphorus oxychloride is 1: 1.
In the step (1), monohydroxy-alcohol is a kind of in methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol or the isopropylcarbinol.
In the step (2), the mol ratio of dibasic alcohol and phosphorus oxychloride is 1.1～1.9: 1.
In the step (2), dibasic alcohol is an ethylene glycol, 1, ammediol or 1, a kind of in the 6-hexylene glycol.
Described solvent is a kind of in methylene dichloride, the ethylene dichloride.
Described solvent is the mixture of methylene dichloride, ethylene dichloride, and the volume ratio of methylene dichloride and ethylene dichloride is 1～2: 3～4.
In the step (2), catalyzer is an aluminum chloride.
To add catalyst consumption be 1.5 of phosphorus oxychloride quality～2 ‰.
The mol ratio of described acid binding agent triethylamine and phosphorus oxychloride is 2: 1.
The present invention adopts above technical scheme, compared with prior art, has the following advantages: the present invention adopts the synthetic oligomerization phosphate polyalcohol that contains terminal hydroxy group of conventional raw material, Halogen not, and environment-protecting asepsis belongs to reactive flame retardant.Oligomerization phosphate polyalcohol is because of containing terminal hydroxy group, alternative part polyether glycol or polyester polyol, produce urethane with isocyanate reaction, be that it can be attached in the polyurethane material and goes, not migration precipitation when being heated makes material have lasting flame retardant properties, and compares with United States Patent (USP) 5608100 described technologies, the present invention does not use oxyethane and Vanadium Pentoxide in FLAKES, and is safe.
The present invention will be further described below in conjunction with embodiment.
Specific embodiment
The present invention is described in detail below by experiment.
Embodiment 1, is that the phosphorus oxychloride of 153.5g is dissolved in the 200mL methylene dichloride with 1mol, quality, joins then in the four-hole boiling flask that stirring, thermometer, reflux exchanger and fluid drips feeder apparatus are housed.Open and stir, slowly adding 1mol, quality are the methyl alcohol of 32g, dropping process water-bath cooling, temperature of reaction is controlled at 30 ± 5 ℃, the hydrogen chloride gas water that produces in the dropping process absorbs, after dropping finishes, and insulation backflow 4h, do not overflow to there being hydrogen chloride gas, obtain containing the reaction solution of dichloro mono phosphoric acid ester alkane fat.In this reaction solution, add 2mol then, quality is acid binding agent triethylamine and the 0.31g catalyzer aluminum chloride of 202g, control reaction temperature is at 20 ± 5 ℃, slowly add 1.1mol, quality is the ethylene glycol of 68.3g, add back back flow reaction 10h, do not overflow to there being hydrogen chloride gas, obtain oligomerization phosphate polyalcohol, the mixture of triethylamine hydrochloride and methylene dichloride, mixture is carried out filtration treatment, obtain filtrate and solid triethylamine hydrochloride, twice of 200mL washed with dichloromethane of solid triethylamine hydrochloride, obtain washings, filtrate and washings are merged the distillation of heating under the normal pressure of back, steam methylene dichloride, when temperature at the bottom of the still rises to 90 ℃, underpressure distillation boils off residual dichloromethane and gets faint yellow thick oligomerization phosphate polyalcohol liquid 162.9g.After testing, the viscosity under 25 ℃ of the products is 2400mPa.s, and acid number is 0.34mgKOH/g, and phosphorus content is 16.81%, and hydroxyl value is 160mgKOH/g.
Embodiment 2, are that the phosphorus oxychloride of 153.5g is dissolved in the 200mL methylene dichloride with 1mol, quality, join then in the four-hole boiling flask that stirring, thermometer, reflux exchanger and fluid drips feeder apparatus are housed.Open and stir, slowly adding 1mol, quality are the dehydrated alcohol of 46g, dropping process water-bath cooling, temperature of reaction is controlled at 30 ± 5 ℃, the hydrogen chloride gas water that produces in the dropping process absorbs, after dropping finishes, and insulation backflow 4h, do not overflow to there being hydrogen chloride gas, obtain containing the reaction solution of dichloro mono phosphoric acid ester alkane fat.In reaction solution, add 2mol, quality is acid binding agent triethylamine and the 0.23g catalyzer aluminum chloride of 202g, control reaction temperature is at 20 ± 5 ℃, slowly add 1.5mol, quality is the ethylene glycol of 93.1g, add back back flow reaction 16h, do not overflow to there being hydrogen chloride gas, obtain oligomerization phosphate polyalcohol, the mixture of triethylamine hydrochloride and methylene dichloride, mixture is carried out filtration treatment, obtain filtrate and solid triethylamine hydrochloride, twice of 200mL washed with dichloromethane of solid triethylamine hydrochloride, obtain washings, filtrate and washings are merged the distillation of heating under the normal pressure of back, steam methylene dichloride, when temperature at the bottom of the still rises to 90 ℃, underpressure distillation boils off residual dichloromethane and gets faint yellow thick oligomerization phosphate polyalcohol liquid 170.1g.After testing, the viscosity under 25 ℃ of the products is 500mPa.s, and acid number is 0.29mgKOH/g, and phosphorus content is 17.2%, and hydroxyl value is 182mgKOH/g.
Embodiment 3, are that the phosphorus oxychloride of 153.5g is dissolved in the 200mL methylene dichloride with 1mol, quality, join then in the four-hole boiling flask that stirring, thermometer, reflux exchanger and fluid drips feeder apparatus are housed.Open and stir, slowly add 1mol, quality is the n-propyl alcohol of 60.1g, dropping process water-bath cooling, temperature of reaction is controlled at 30 ± 5 ℃, the hydrogen chloride gas water that produces in the dropping process absorbs, after dripping end, insulation backflow 5h, do not overflow to there being hydrogen chloride gas, obtain containing the reaction solution of dichloro mono phosphoric acid ester alkane fat. in reaction solution, add 2mol, quality is acid binding agent triethylamine and the 0.28g catalyzer aluminum chloride of 202g, 20 ± 5 ℃ of control reaction temperature, slowly add 1.9mol, quality is the ethylene glycol of 117.9g, add back back flow reaction 20h, do not overflow to there being hydrogen chloride gas, obtain oligomerization phosphate polyalcohol, the mixture of triethylamine hydrochloride and methylene dichloride, mixture is carried out filtration treatment, obtain filtrate and solid triethylamine hydrochloride, twice of 200mL washed with dichloromethane of solid triethylamine hydrochloride, obtain washings, filtrate and washings are merged the distillation of heating under the normal pressure of back, steam the lower boiling methylene dichloride, when temperature at the bottom of the still rises to 90 ℃, underpressure distillation boils off residual dichloromethane and gets faint yellow thick oligomerization phosphate polyalcohol liquid 208.7g.After testing, the viscosity under 25 ℃ of the products is 900mPa.s, and acid number is 0.25mgKOH/g, and phosphorus content is 14.15%, and hydroxyl value is 170mgKOH/g.
Embodiment 4, are that the phosphorus oxychloride of 153.5g is dissolved in the 200mL ethylene dichloride with 1mol, quality, join then in the four-hole boiling flask that stirring, thermometer, reflux exchanger and fluid drips feeder apparatus are housed.Open and stir, slowly add 1mol, quality is the propyl carbinol of 74.1g, dropping process water-bath cooling, temperature of reaction is controlled at 30 ± 5 ℃, the hydrogen chloride gas water that produces in the dropping process absorbs, after dripping end, insulation backflow 5h, do not overflow to there being hydrogen chloride gas, obtain containing the reaction solution of dichloro mono phosphoric acid ester alkane fat. in reaction solution, add 2mol, quality is acid binding agent triethylamine and the 0.25g catalyzer aluminum chloride of 202g, 20 ± 5 ℃ of control reaction temperature, slowly add 1.3mol, quality is 1 of 98.9g, ammediol, add back back flow reaction 20h, do not overflow to there being hydrogen chloride gas, obtain oligomerization phosphate polyalcohol, the mixture of triethylamine hydrochloride and ethylene dichloride, mixture is carried out filtration treatment, obtain filtrate and solid triethylamine hydrochloride, the solid triethylamine hydrochloride obtains washings with 200mL ethylene dichloride washed twice, and filtrate and washings are merged the distillation of heating under the normal pressure of back, steam the lower boiling ethylene dichloride, when temperature at the bottom of the still rose to 90 ℃, underpressure distillation boiled off remaining ethylene dichloride and gets faint yellow thick oligomerization phosphate polyalcohol liquid 201.8g.After testing, the viscosity under 25 ℃ of the products is 1400mPa.s, and acid number is 0.27mgKOH/g, and phosphorus content is 11.8%, and hydroxyl value is 14.4mgKOH/g.
Embodiment 5, with 1mol, quality is the mixture that the phosphorus oxychloride of 153.5g is dissolved in 200mL methylene dichloride and ethylene dichloride, the volume ratio of methylene dichloride and ethylene dichloride is 1: 4 in the mixture, joins then in the four-hole boiling flask that stirring, thermometer, reflux exchanger and fluid drips feeder apparatus are housed.Open and stir, slowly add 1mol, quality is the isopropylcarbinol of 74.1g, dropping process water-bath cooling, temperature of reaction is controlled at 30 ± 5 ℃, the hydrogen chloride gas water that produces in the dropping process absorbs, after dripping end, insulation backflow 5h, do not overflow to there being hydrogen chloride gas, obtain containing the reaction solution of dichloro mono phosphoric acid ester alkane fat. in reaction solution, add 2mol, quality is acid binding agent triethylamine and the 0.29g catalyzer aluminum chloride of 202g, 20 ± 5 ℃ of control reaction temperature, slowly add 1.7mol, quality is 1 of 200.9g, the 6-hexylene glycol, add back back flow reaction 20h, do not overflow to there being hydrogen chloride gas, obtain oligomerization phosphate polyalcohol, triethylamine hydrochloride, the mixture of methylene dichloride and ethylene dichloride, mixture is carried out filtration treatment, obtain filtrate and solid triethylamine hydrochloride, the solid triethylamine hydrochloride obtains washings with the mixture washed twice of 200mL methylene dichloride and ethylene dichloride, and filtrate and washings are merged the distillation of heating under the normal pressure of back, steam the mixture of lower boiling methylene dichloride and ethylene dichloride, when temperature at the bottom of the still rose to 90 ℃, underpressure distillation boiled off residual dichloromethane and gets faint yellow thick oligomerization phosphate polyalcohol liquid 303g.After testing, the viscosity under 25 ℃ of the products is 1100mPa.s, and acid number is 0.31mgKOH/g, and phosphorus content is 10.1%, and hydroxyl value is 165mgKOH/g.
Among the above embodiment, monohydroxy-alcohol can also be Virahol.
As the methylene dichloride of solvent and the mixture of ethylene dichloride, the volume ratio of methylene dichloride and ethylene dichloride can also be 1～2: other ratio in 3～4 except that 1: 4, the boiling point that can make mixture is between the boiling point of the boiling point of methylene dichloride and ethylene dichloride.
Simultaneous test, if 6 polyurethane foam test examples, the polyurethane foam of test example 1 is added the prepared product of embodiment 1, the polyurethane foam of test example 2 is added the prepared product of embodiment 2, the polyurethane foam of test example 3 is added the prepared product of embodiment, the polyurethane foam of test example 4 is added the prepared product of embodiment 4, the polyurethane foam of test example 5 is added the prepared product of embodiment 5, another one test example as a comparative example, the polyurethane foam of comparative example is not added fire-retardant thing, tests 6 polyurethane foams and tests routine foamy combustionproperty and " mist value ".
The composition such as the following table of 6 polyurethane foam test examples:
Test-results such as following table:
Can obtain from above result:
(1) the test example foaming that adds fire retardant is tested, and compares with barren comparative example foaming experiment, does not have the closed pore of contraction phenomenon.
(2) combustion experiment, according to GB 8410-2006, " combustioncharacteristics of automotive interior material " carries out.Test example 1, test example 4 reach the A level, and test example 2, test example 3 and test example 5 reach the B level.
(3) " the mist value " of additive flame retardant is generally 1.5, and " mist value "≤0.6 behind above 3 test example interpolation fire retardants.The product of present embodiment is without adding thermomaturation, and the product after the slaking " mist value " can further reduce.
Claims (10)
1. the preparation method of an oligomerization phosphate polyalcohol, it is characterized in that: described preparation method may further comprise the steps:
(1) synthetic dichloro mono phosphoric acid ester alkane fat
Solvent and phosphorus oxychloride are placed reactor, and temperature is controlled at 30 ± 5 ℃, splashes into monohydroxy-alcohol, drip monohydroxy-alcohol after, insulation is back to the effusion of no hydrogen chloride gas, obtains reaction solution;
(2) synthesis of oligonucleotides phosphate polyalcohol
Acid binding agent triethylamine and catalyzer are placed reaction solution, and temperature is controlled at 20 ± 5 ℃, splashes into dibasic alcohol, drip dibasic alcohol after, back flow reaction is overflowed to there being hydrogen chloride gas, obtains mixture;
(3) mixture is carried out filtration treatment, obtain filtrate and triethylamine hydrochloride, use the solvent washing triethylamine hydrochloride, obtain washings, after filtrate and washings merging, the distillation of heating obtains oligomerization phosphate polyalcohol.
2. the preparation method of a kind of oligomerization phosphate polyalcohol as claimed in claim 1, it is characterized in that: in the step (1), the mol ratio of monohydroxy-alcohol and phosphorus oxychloride is 1: 1.
3. the preparation method of a kind of oligomerization phosphate polyalcohol as claimed in claim 1 or 2 is characterized in that: in the step (1), monohydroxy-alcohol is a kind of in methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol or the isopropylcarbinol.
4. the preparation method of a kind of oligomerization phosphate polyalcohol as claimed in claim 1, it is characterized in that: in the step (2), the mol ratio of dibasic alcohol and phosphorus oxychloride is 1.1～1.9: 1.
5. as the preparation method of claim 1 or 4 described a kind of oligomerization phosphate polyalcohols, it is characterized in that: in the step (2), dibasic alcohol is an ethylene glycol, 1, ammediol or 1, a kind of in the 6-hexylene glycol.
6. the preparation method of a kind of oligomerization phosphate polyalcohol as claimed in claim 1 is characterized in that: described solvent is a kind of in methylene dichloride, the ethylene dichloride.
7. the preparation method of a kind of oligomerization phosphate polyalcohol as claimed in claim 1, it is characterized in that: described solvent is the mixture of methylene dichloride, ethylene dichloride, the volume ratio of methylene dichloride and ethylene dichloride is 1～2: 3～4.
8. the preparation method of a kind of oligomerization phosphate polyalcohol as claimed in claim 1, it is characterized in that: in the step (2), catalyzer is an aluminum chloride.
9. as the preparation method of claim 1 or 8 described a kind of oligomerization phosphate polyalcohols, it is characterized in that: to add catalyst consumption be 1.5 of phosphorus oxychloride quality～2 ‰.
10. the preparation method of a kind of oligomerization phosphate polyalcohol as claimed in claim 1, it is characterized in that: the mol ratio of described acid binding agent triethylamine and phosphorus oxychloride is 2: 1.
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Application publication date: 20101201 Assignee: New Mstar Technology Ltd in Shandong Assignor: Shandong Brother Sci. & Tech. Co., Ltd. Contract record no.: 2018370000019 Denomination of invention: Preparation method of oligomerization phosphate polyalcohol Granted publication date: 20111207 License type: Common License Record date: 20180620 Application publication date: 20101201 Assignee: Shandong brotherhood flame retardant new materials Co., Ltd. Assignor: Shandong Brother Sci. & Tech. Co., Ltd. Contract record no.: 2018370000020 Denomination of invention: Preparation method of oligomerization phosphate polyalcohol Granted publication date: 20111207 License type: Common License Record date: 20180620 Application publication date: 20101201 Assignee: New Mstar Technology Ltd in Shandong Assignor: Shandong Brother Sci. & Tech. Co., Ltd. Contract record no.: 2018370000019 Denomination of invention: Preparation method of oligomerization phosphate polyalcohol Granted publication date: 20111207 License type: Common License Record date: 20180620 Application publication date: 20101201 Assignee: Shandong brotherhood flame retardant new materials Co., Ltd. Assignor: Shandong Brother Sci. & Tech. Co., Ltd. Contract record no.: 2018370000020 Denomination of invention: Preparation method of oligomerization phosphate polyalcohol Granted publication date: 20111207 License type: Common License Record date: 20180620 |
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Assignee: Shandong brotherhood flame retardant new materials Co., Ltd. Assignor: SHANDONG BROTHER SCI.&TECH. Co.,Ltd. Contract record no.: 2018370000020 Date of cancellation: 20200424 |