CN105524105A - Preparation method of phosphomonoester - Google Patents
Preparation method of phosphomonoester Download PDFInfo
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- CN105524105A CN105524105A CN201510943427.XA CN201510943427A CN105524105A CN 105524105 A CN105524105 A CN 105524105A CN 201510943427 A CN201510943427 A CN 201510943427A CN 105524105 A CN105524105 A CN 105524105A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000000463 material Substances 0.000 claims abstract description 7
- 150000002440 hydroxy compounds Chemical class 0.000 claims abstract description 6
- 238000009413 insulation Methods 0.000 claims abstract description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 39
- 239000010452 phosphate Substances 0.000 claims description 39
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 21
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 12
- 125000001931 aliphatic group Chemical group 0.000 claims description 8
- 239000003112 inhibitor Substances 0.000 claims description 7
- 230000003647 oxidation Effects 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- 125000001997 phenyl group Chemical class [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 5
- 229920001519 homopolymer Polymers 0.000 claims description 4
- 125000000217 alkyl group Chemical class 0.000 claims description 2
- 150000002191 fatty alcohols Chemical class 0.000 claims description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 claims description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 3
- 239000003054 catalyst Substances 0.000 abstract 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 abstract 2
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 abstract 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 abstract 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 abstract 1
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 26
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 22
- 239000000203 mixture Substances 0.000 description 21
- -1 phosphate diester Chemical class 0.000 description 20
- 238000000034 method Methods 0.000 description 19
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N tetradecan-1-ol Chemical compound CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 description 18
- 238000004448 titration Methods 0.000 description 18
- 239000002253 acid Substances 0.000 description 15
- 238000004458 analytical method Methods 0.000 description 14
- 150000002148 esters Chemical class 0.000 description 14
- 238000001914 filtration Methods 0.000 description 13
- 230000011218 segmentation Effects 0.000 description 13
- 238000003756 stirring Methods 0.000 description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 11
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 11
- 239000000243 solution Substances 0.000 description 9
- 150000003014 phosphoric acid esters Chemical class 0.000 description 6
- 102000004160 Phosphoric Monoester Hydrolases Human genes 0.000 description 5
- 108090000608 Phosphoric Monoester Hydrolases Proteins 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 206010040880 Skin irritation Diseases 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000008052 alkyl sulfonates Chemical class 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- WRKCIHRWQZQBOL-UHFFFAOYSA-N octyl dihydrogen phosphate Chemical compound CCCCCCCCOP(O)(O)=O WRKCIHRWQZQBOL-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000036556 skin irritation Effects 0.000 description 1
- 231100000475 skin irritation Toxicity 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- QAJSOWVLJWYKLV-UHFFFAOYSA-N tetracosyl dihydrogen phosphate Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCOP(O)(O)=O QAJSOWVLJWYKLV-UHFFFAOYSA-N 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/11—Esters of phosphoric acids with hydroxyalkyl compounds without further substituents on alkyl
-
- 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
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/091—Esters of phosphoric acids with hydroxyalkyl compounds with further substituents on alkyl
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a preparation method of phosphomonoester and mainly solves problems of complex preparation technology of phosphomonoester and low content of phosphomonoester existing in the prior art. The preparation method of the invention comprises the following steps: (1) adding a hydroxy compound and water into a reactor, and heating to 55-80 DEG C; (2) slowly pouring P2O5, controlling temperature of materials in the reactor to 55-95 DEG C, and controlling pouring time within 1-2 h; (3) carrying out thermal insulation at 75-95 DEG C for 3-6 h so as to obtain a material A; and (4) adding water and a catalyst X into the material A, controlling temperature to 70-90 DEG C, and carrying out thermal insulation at the temperature for 2-3 h so as to obtain phosphomonoester. The hydroxy compound accords with the following general formula: RO(EO)m(PO)nH. The catalyst X is at least one compound selected from SnCl4, MnO2 and CuSO4. The preparation method can be used in preparation of phosphomonoester.
Description
Technical field
The present invention relates to the preparation method of phosphate monoester.
Background technology
Phosphate monoester refers to that monoester content is the product of more than 80.0%.Phosphate monoester has the biomembranous structure of class, its static resistance, foaminess, water-soluble, emulsifying property are all better than phosphate diester, and the anion surfactant such as alkylsulfonate and alkyl-sulphate is less than to skin irritation, be applicable to very much the aspects such as skin is cleaned, makeup emulsification.Phosphate monoester is strong relative to phosphate diester dispersive ability, there is higher whipability and more moderate froth stability, trapping agent flotation separation ink particle can be made in floatation and ink removing technique, be a kind of be applicable to simultaneously wash and floatation and ink removing technique, excellent property environmentally-friendly surfactant.Therefore, the content improving phosphate monoester meets the needs of its performance, becomes the target that numerous producer is pursued.
The relevant both at home and abroad research of phosphate monoester has just had more report since the 1950's.As German Henkel company, a large amount of research work has been done for alkyl phosphate monoester by Japanese Kao company, has promoted the development of its synthesis technique and application.Domesticly develop phosphate monoester from the 1950's, so far existing more than 60 years.The Tianjin light industry institute at the people places such as Fu Mingquan just assume responsibility for country " eight or five " key scientific and technological projects " monoalkyl phosphoric acid esters synthesising process research " from 1991, checked and accepted in 1996 by state verification, quality product reaches same kind of products at abroad quality.The producer of current domestic production phosphate monoester is also few, and quality is uneven, and highly purified phosphate monoester (more than 90%) is dependence on import mostly.
CN101450953A discloses the preparation method of a kind of monoalkyl phosphoric acid esters and salt thereof, describe a kind of thick monoalkyl phosphoric acid esters is carried out in and purification by liquid extraction obtain the method for high-content monoalkyl phosphoric acid esters, need thick monoalkyl phosphoric acid esters as raw material, and complex treatment process; CN103012469A discloses a kind of preparation method of alkyl phosphate, need to add solvent as water entrainer to remove the water in reaction system in synthetic phosphoric acid ester process, therefore also need to carry out to wash, distill, the multiple tracks postprocessing working procedures such as rectifying, complex process, energy consumption is high, and solvent is benzene, toluene etc., has detrimentally affect to operator's health and environment.
Summary of the invention
Technical problem to be solved by this invention exists in prior art, phosphate monoester complicated process of preparation, the problems such as phosphate monoester content is lower, provide a kind of preparation method of new phosphate monoester, and the method has the advantage that technique is simple, phosphate monoester content is high.
For solving the problems of the technologies described above, technical scheme of the present invention is as follows:
The preparation method of phosphate monoester, comprises the steps:
(1) add oxy-compound, water in the reactor, be warming up to 55 ~ 80 DEG C;
(2) slowly P is dropped into
2o
5, make temperature of charge in reactor control at 55 ~ 95 DEG C, charging time controls 1 ~ 2 hour;
(3) at 75 ~ 95 DEG C, insulation obtains material A in 3 ~ 6 hours;
(4) in material A, add water and catalyzer X, control temperature is 70 ~ 90 DEG C, and is incubated 2 ~ 3 hours at this temperature and obtains phosphate monoester;
Wherein said oxy-compound meets following general formula:
RO(EO)m(PO)nH；
R represents C
5 ~ 18aliphatic group, alkyl-substituted phenyl; Alkyl in alkyl-substituted phenyl is C
6 ~ 10alkyl; M=0 ~ 5; N=0 ~ 3;
The water added in step (1) and oxy-compound, P
2o
5mol ratio be 0.8: 1:(0.506 ~ 0.518);
The water that step (4) adds and the water weight ratio that step (1) adds are 0.3 ~ 0.5;
Described catalyzer X is selected from SnCl
4, MnO
2and CuSO
4in at least one.
In such scheme, step (1) and/or step (2) preferably add oxidation inhibitor, and the colourity now obtaining product is good.
In such scheme, described oxidation inhibitor is selected from least one in phosphorous acid, phosphite, ortho phosphorous acid and hypophosphite.
In such scheme, the add-on of oxidation inhibitor is preferably 0.10 ~ 0.50% of hydroxy compound amount.
In such scheme, the consumption of catalyzer is preferably 0.25 ~ 0.65% of hydroxy compound amount.
In such scheme, the numerical value of m and n is selected from the one in following three kinds of situations:
I (), m and n are not all 0, now, in described oxy-compound, EO and PO sequential structure is selected from random or block;
(ii), m × n=0, but be 0 when m with n is different, now described oxy-compound is EO homopolymer or PO homopolymer;
(iii), m and n be 0, and now described oxy-compound is fatty alcohol.
In such scheme, described block to be selected from after first EO segment EO segment after EO segment after PO segment or first PO segment, the random segment of first EO/PO.
In such scheme, described aliphatic group can be saturated or undersaturated aliphatic group.
In such scheme, described aliphatic group can be the aliphatic group of straight or branched.
In technique scheme, the preferred SnCl of catalyzer X
4, MnO
2and CuSO
4in at least two kinds, preferably comprise SnCl further simultaneously
4, MnO
2and CuSO
4, between the said components now forming catalyzer, in raising product, in phosphate monoester content, there is synergy.When catalyzer X comprises SnCl simultaneously
4, MnO
2and CuSO
4time, SnCl
4, MnO
2and CuSO
4can be such as (0.3 ~ 1.2) as non limiting example in mass ratio: 1: (0.1 ~ 0.6).
In such scheme, when described catalyzer is two or more described compound composition, first can mixes and be used further to the inventive method afterwards, also can simultaneously or successively add for the inventive method, all effect of the present invention significantly not affected.For ease of strictly on year-on-year basis, when the catalyzer in the specific embodiment of the invention is made up of two or more compound, re-use after being mixing.
Monoester content in the specific embodiment of the present invention is adopted and is obtained by double indicator titration analysis, according to phosphorus dissociation constants of acids difference (pK
1=2.1, pK
2=7.1, pK
3=12.3) double indicator titration is adopted, due to pK
3be worth very little, can not direct titration, therefore add CaCl
2, make it to generate calcium phosphate precipitation, separate out H
+, with the titration of KOH standardized solution.K
1hop point adopts tetrabromo-mcresolsulfonphthalein to make indicator (pH=3.8-5.4) K
2hop point adopts phenolphthalein indicator (pH=8-10).Concrete operation method is as follows:
Take about 0.20 gram of sample in 250ml Erlenmeyer flask, add 40ml dehydrated alcohol to be dissolved, add 3 0.1% tetrabromo-mcresolsulfonphthalein indicator, with the titration of 0.1NKOH standardized solution, when solution colour is terminal by xanthochromia blue-greenish colour, write down exhausted KOH solution milliliter number (a); Add 3 phenolphthalein indicators again, continue to be titrated to solution colour paleness purple, write down consumed KOH solution milliliter number (b).Add the CaCl that weight concentration is 10%
2aqueous solution 6ml, solution colour again in blue, then is titrated to livid purple look with 0.1NKOH standardized solution, write down consume the KOH solution (c) of getting.The weight percentage of phosphate diester, monoesters and phosphoric acid is defined as follows:
Dibasic acid esters %=[(a-b)/a] * 100%;
Monoesters %=[(b-c)/a] * 100%;
Phosphoric acid %=(c/a) * 100%.
Adopt the content of phosphate monoester in the inventive method product to be more than 80.0%, up to more than 95.0%, achieve good technique effect.
Below by embodiment and embodiment, the present invention is described in detail.
Embodiment
[embodiment 1]
The preparation of ten tetracosyl phosphate monoesters: add 12 alcohol mixtures (lauryl alcohol and tetradecyl alcohol mass ratio are 70: 30) 200.00g, ortho phosphorous acid 0.42g and pure water 14.80g in round-bottomed flask, opens and stirs and heat up; Start segmentation when temperature rises 70 DEG C and drop into Vanadium Pentoxide in FLAKES 74.28g, temperature controls at 75 ± 5 DEG C, and it is 1.5 hours that charging time controls; At 85 DEG C, be incubated 4.5 hours after adding, (described catalyzer is SnCl then to add pure water 5.18g and catalyzer
4, MnO
2and CuSO
4mass ratio is the mixture of 0.9: 1: 0.3) 0.88g, control temperature is 85 DEG C, and is incubated at this temperature and is cooled to 75 DEG C of filtrations after 2 hours and obtains phosphate ester product.Obtained by double indicator titration analysis: monoesters 90.6%, dibasic acid esters: 6.9%, phosphoric acid 2.5%.
[comparative example 1]
Be not add catalyzer with the difference of embodiment 1.
In round-bottomed flask, add 12 alcohol mixtures (lauryl alcohol and tetradecyl alcohol mass ratio are 70: 30) 200.00g, ortho phosphorous acid 0.42g and pure water 14.80g, open and stir and heat up; Start segmentation when temperature rises 70 DEG C and drop into Vanadium Pentoxide in FLAKES 74.28g, temperature controls at 75 ± 5 DEG C, and it is 1.5 hours that charging time controls; At 85 DEG C, be incubated 4.5 hours after adding, then add pure water 5.18g, control temperature is 85 DEG C, and is incubated at this temperature and is cooled to 75 DEG C of filtrations after 2 hours and obtains phosphate ester product.Obtained by double indicator titration and high-efficient liquid phase chromatogram technique analysis: monoesters 72.3%, dibasic acid esters: 19.0%, phosphoric acid 8.7%.
[comparative example 2]
Pure water is not added when being to add catalyzer with the difference of embodiment 1.
In round-bottomed flask, add 12 alcohol mixtures (lauryl alcohol and tetradecyl alcohol mass ratio are 70: 30) 200.00g, ortho phosphorous acid 0.42g and pure water 14.80g, open and stir and heat up; Start segmentation when temperature rises 70 DEG C and drop into Vanadium Pentoxide in FLAKES 74.28g, temperature controls at 75 ± 5 DEG C, and it is 1.5 hours that charging time controls; At 85 DEG C, be incubated 4.5 hours after adding, (described catalyzer is SnCl then to add catalyzer
4, MnO
2and CuSO
4mass ratio is the mixture of 0.9: 1: 0.3) 0.88g, control temperature is 85 ± 2 DEG C, and is incubated at this temperature and is cooled to 75 DEG C of filtrations after 2 hours and obtains phosphate ester product.Obtained by double indicator titration analysis: monoesters 75.6%, dibasic acid esters: 19.9%, phosphatase 24 .5%.
[embodiment 2]
Be that catalyzer is SnCl with the difference of embodiment 1
4.
In round-bottomed flask, add 12 alcohol mixtures (lauryl alcohol and tetradecyl alcohol mass ratio are 70: 30) 200.00g, ortho phosphorous acid 0.42g and pure water 14.80g, open and stir and heat up; Start segmentation when temperature rises 70 DEG C and drop into Vanadium Pentoxide in FLAKES 74.28g, temperature controls at 75 ± 5 DEG C, and it is 1.5 hours that charging time controls; At 85 DEG C, be incubated 4.5 hours after adding, then add pure water 5.18g and SnCl
40.88g, control temperature is 85 ± 2 DEG C, and is incubated at this temperature and is cooled to 75 DEG C of filtrations after 2 hours and obtains phosphate ester product.Obtained by double indicator titration analysis: monoesters 79.6%, dibasic acid esters: 16.9%, phosphoric acid 3.5%.
[embodiment 3]
Be that catalyzer is MnO with the difference of embodiment 1
2.
In round-bottomed flask, add 12 alcohol mixtures (lauryl alcohol and tetradecyl alcohol mass ratio are 70: 30) 200.00g, ortho phosphorous acid 0.42g and pure water 14.80g, open and stir and heat up; Start segmentation when temperature rises 70 DEG C and drop into Vanadium Pentoxide in FLAKES 74.28g, temperature controls at 75 ± 5 DEG C, and it is 1.5 hours that charging time controls; At 85 DEG C, be incubated 4.5 hours after adding, then add pure water 5.18g and MnO20.88g, control temperature is 85 ± 2 DEG C, and is incubated at this temperature and is cooled to 75 DEG C of filtrations after 2 hours and obtains phosphate ester product.Obtained by double indicator titration analysis: monoesters 80.6%, dibasic acid esters: 13.9%, phosphoric acid 5.5%.
[embodiment 4]
Be that catalyzer is CuSO with the difference of embodiment 1
4.
In round-bottomed flask, add 12 alcohol mixtures (lauryl alcohol and tetradecyl alcohol mass ratio are 70: 30) 200.00g, ortho phosphorous acid 0.42g and pure water 14.80g, open and stir and heat up; Start segmentation when temperature rises 70 DEG C and drop into Vanadium Pentoxide in FLAKES 74.28g, temperature controls at 75 ± 5 DEG C, and it is 1.5 hours that charging time controls; At 85 DEG C, be incubated 4.5 hours after adding, then add pure water 5.18g and CuSO
40.88g, control temperature is 85 ± 2 DEG C, and is incubated at this temperature and is cooled to 75 DEG C of filtrations after 2 hours and obtains phosphate ester product.Obtained by double indicator titration analysis: monoesters 78.3%, dibasic acid esters: 15.8%, phosphoric acid 5.9%.
[embodiment 5]
Be that catalyzer is SnCl with the difference of embodiment 1
4and MnO
2.
In round-bottomed flask, add 12 alcohol mixtures (lauryl alcohol and tetradecyl alcohol mass ratio are 70: 30) 200.00g, ortho phosphorous acid 0.42g and pure water 14.80g, open and stir and heat up; Start segmentation when temperature rises 70 DEG C and drop into Vanadium Pentoxide in FLAKES 74.28g, temperature controls at 75 ± 5 DEG C, and it is 1.5 hours that charging time controls; At 85 DEG C, be incubated 4.5 hours after adding, then add pure water 5.18g, (described catalyzer is SnCl to catalyzer
4, MnO
2mass ratio is the mixture of 0.9: 1) 0.88g, control temperature is 85 ± 2 DEG C, and is incubated at this temperature and is cooled to 75 DEG C of filtrations after 2 hours and obtains phosphate ester product.Obtained by double indicator titration analysis: monoesters 81.4%, dibasic acid esters: 14.1%, phosphatase 24 .5%.
[embodiment 6]
Be that catalyzer is SnCl with the difference of embodiment 1
4and CuSO
4.
In round-bottomed flask, add 12 alcohol mixtures (lauryl alcohol and tetradecyl alcohol mass ratio are 70: 30) 200.00g, ortho phosphorous acid 0.42g and pure water 14.80g, open and stir and heat up; Start segmentation when temperature rises 70 DEG C and drop into Vanadium Pentoxide in FLAKES 74.28g, temperature controls at 75 ± 5 DEG C, and it is 1.5 hours that charging time controls; At 85 DEG C, be incubated 4.5 hours after adding, then add pure water 5.18g, (described catalyzer is SnCl to catalyzer
4and CuSO
4mass ratio is the mixture of 0.9: 0.3) 0.88g, control temperature is 85 ± 2 DEG C, and is incubated at this temperature and is cooled to 75 DEG C of filtrations after 2 hours and obtains phosphate ester product.Obtained by double indicator titration analysis: monoesters 80.8%, dibasic acid esters: 15.5%, phosphoric acid 3.7%.
[embodiment 7]
Be that catalyzer is MnO with the difference of embodiment 1
2and CuSO
4.
In round-bottomed flask, add 12 alcohol mixtures (lauryl alcohol and tetradecyl alcohol mass ratio are 70: 30) 200.00g, ortho phosphorous acid 0.42g and pure water 14.80g, open and stir and heat up; Start segmentation when temperature rises 70 DEG C and drop into Vanadium Pentoxide in FLAKES 74.28g, temperature controls at 75 ± 5 DEG C, and it is 1.5 hours that charging time controls; At 85 DEG C, be incubated 4.5 hours after adding, then add pure water 5.18g, (described catalyzer is MnO to catalyzer
2and CuSO
4mass ratio is the mixture of 1: 0.3) 0.88g, control temperature is 85 ± 2 DEG C, and is incubated at this temperature and is cooled to 75 DEG C of filtrations after 2 hours and obtains phosphate ester product.Obtained by double indicator titration analysis: monoesters 83.5%, dibasic acid esters: 13.2%, phosphoric acid 3.3%.
[embodiment 8]
The preparation of lauryl alcohol polyoxyethylene (3) ether phosphoric acid monoesters: add lauryl alcohol polyoxyethylene (3) ether 200.00g, ortho phosphorous acid 0.56g and pure water 9.06g in round-bottomed flask, opens and stirs and heat up; Start segmentation when temperature rises 80 DEG C and drop into Vanadium Pentoxide in FLAKES 45.82g, temperature controls at 85 ± 5 DEG C, and it is 1.0 hours that charging time controls; At 90 DEG C, be incubated 6 hours after adding, (described catalyzer is SnCl then to add water 3.62g and catalyzer
4, MnO
2and CuSO
4mixture than being 0.5: 1: 0.4) 1.2g, control temperature is 90 ± 2 DEG C, and is incubated at this temperature and is cooled to 80 DEG C of filtrations after 3 hours and obtains phosphate ester product.Obtained by double indicator titration analysis: monoesters 89.3%, dibasic acid esters 6.8%, phosphatase 24 .9%.
[embodiment 9]
The preparation of 16 Inverse suspensions: add 16 alcohol mixtures (hexadecanol and stearyl alcohol mass ratio are 70: 30) 200.00g, phosphorous acid 0.54g and pure water 11.52g in round-bottomed flask, opens and stirs and heat up; Start segmentation when temperature rises 75 DEG C and drop into Vanadium Pentoxide in FLAKES 58.16g, temperature controls at 80 ± 5 DEG C, and it is 1.0 hours that charging time controls; At 90 DEG C, be incubated 5 hours after adding, (described catalyzer is SnCl then to add water 5.10g and catalyzer
4, MnO
2and CuSO
4mass ratio is the mixture of 0.7: 1: 0.3) 1.0g, control temperature is 90 ± 2 DEG C, and is incubated at this temperature and is cooled to 80 DEG C of filtrations after 2 hours and obtains phosphate ester product.Obtained by double indicator titration analysis: monoesters 89.1%, dibasic acid esters: 7.2%, phosphoric acid 3.7%.
[embodiment 10]
The preparation of isooctyl alcohol phosphate monoester: add isooctyl alcohol 200.00g, phosphorous acid 0.80g and pure water 22.15g in round-bottomed flask, opens and stirs and heat up; Start segmentation when temperature rises 55 DEG C and drop into Vanadium Pentoxide in FLAKES 110.54g, temperature controls at 60 ± 5 DEG C, and it is 2.0 hours that charging time controls; At 75 DEG C, be incubated 3 hours after adding, (described catalyzer is SnCl then to add water 8.84g and catalyzer
4, MnO
2and CuSO
4mass ratio is the mixture of 0.6: 1: 0.5) 0.70g, control temperature is 75 ± 2 DEG C, and is incubated at this temperature and is cooled to 70 DEG C of filtrations after 3 hours and obtains phosphate ester product.Obtained by double indicator titration analysis: monoesters 93.1%, dibasic acid esters: 5.4%, phosphatase 11 .5%.
[embodiment 11]
The preparation of octanol phosphate monoester: add octanol 200.00g, phosphorous acid 0.76g and pure water 22.15g in round-bottomed flask, opens and stirs and heat up; Start segmentation when temperature rises 60 DEG C and drop into Vanadium Pentoxide in FLAKES 110.54g, temperature controls at 65 ± 5 DEG C, and it is 1.5 hours that charging time controls; At 75 DEG C, be incubated 3 hours after adding, (described catalyzer is SnCl then to add water 8.20g and catalyzer
4, MnO
2and CuSO
4mass ratio is the mixture of 0.6: 1: 0.5) 0.68g, control temperature is 75 ± 2 DEG C, and is incubated at this temperature and is cooled to 70 DEG C of filtrations after 2 hours and obtains phosphate ester product.Obtained by double indicator titration analysis: monoesters 95.0%, dibasic acid esters: 3.9%, phosphatase 11 .1%.
For ease of comparing, by the principal reaction condition of embodiment and comparative example and the results are shown in table 1.
Table 1
Note: * comparative example 2 does not add water adding catalyzer while, adds-quantitative pure water reaction while that other not having * target example to be all and to add catalyzer; The add-on of oxidation inhibitor and catalyzer X all calculates with the mass percent accounting for oxy-compound; Catalyzer composition is SnCl
4, MnO
2, CuSO
4calculate in mass ratio successively.
Claims (9)
1. the preparation method of phosphate monoester, comprises the steps:
(1) add oxy-compound, water in the reactor, be warming up to 55 ~ 80 DEG C;
(2) slowly P is dropped into
2o
5, make temperature of charge in reactor control at 55 ~ 95 DEG C, charging time controls 1 ~ 2 hour;
(3) at 75 ~ 95 DEG C, insulation obtains material A in 3 ~ 6 hours;
(4) in material A, add water and catalyzer X, control temperature is 70 ~ 90 DEG C, and is incubated 2 ~ 3 hours at this temperature and obtains phosphate monoester;
Wherein said oxy-compound meets following general formula:
RO(EO)m(PO)nH；
R represents C
5 ~ 18aliphatic group, alkyl-substituted phenyl; Alkyl in alkyl-substituted phenyl is C
6 ~ 10alkyl; M=0 ~ 5; N=0 ~ 3;
The water added in step (1) and oxy-compound, P
2o
5mol ratio be 0.8: 1: (0.506 ~ 0.518);
The water that step (4) adds and the water weight ratio that step (1) adds are 0.3 ~ 0.5;
Described catalyzer X is selected from SnCl
4, MnO
2and CuSO
4in at least one.
2. preparation method according to claim 1, is characterized in that step (1) and/or step (2) add oxidation inhibitor.
3. preparation method according to claim 2, is characterized in that described oxidation inhibitor is selected from least one in phosphorous acid, phosphite, ortho phosphorous acid and hypophosphite.
4. preparation method according to claim 2, is characterized in that the add-on of oxidation inhibitor is 0.10 ~ 0.50% of hydroxy compound amount.
5. preparation method according to claim 1, is characterized in that the consumption of catalyzer is 0.25 ~ 0.65% of hydroxy compound amount.
6. preparation method according to claim 1, is characterized in that the numerical value of m and n is selected from the one in following three kinds of situations:
I (), m and n are not all 0, now, in described oxy-compound, EO and PO sequential structure is selected from random or block;
(ii), m × n=0, but be 0 when m with n is different, now described oxy-compound is EO homopolymer or PO homopolymer;
(iii), m and n be 0, and now described oxy-compound is fatty alcohol.
7. preparation method according to claim 6, is characterized in that described block to be selected from after first EO segment EO segment after EO segment after PO segment or first PO segment, the random segment of first EO/PO.
8. preparation method according to claim 1, is characterized in that described aliphatic group is saturated or undersaturated aliphatic group.
9. preparation method according to claim 1, is characterized in that described aliphatic group is the aliphatic group of straight or branched.
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| CN107722050A (en) * | 2017-11-05 | 2018-02-23 | 上海多纶化工有限公司 | The preparation method of phosphate |
| CN109879906A (en) * | 2019-04-02 | 2019-06-14 | 上海多纶化工有限公司 | The preparation method of phosphate |
| US11572455B2 (en) | 2017-10-12 | 2023-02-07 | Si Group, Inc. | Antidegradant blend |
| US11879050B2 (en) | 2018-05-03 | 2024-01-23 | Si Group, Inc. | Antidegradant blend |
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| CN105713036A (en) * | 2016-04-28 | 2016-06-29 | 上海多纶化工有限公司 | Preparation method of phosphomonoester |
| US11572455B2 (en) | 2017-10-12 | 2023-02-07 | Si Group, Inc. | Antidegradant blend |
| CN107722050A (en) * | 2017-11-05 | 2018-02-23 | 上海多纶化工有限公司 | The preparation method of phosphate |
| CN107722050B (en) * | 2017-11-05 | 2019-11-19 | 上海多纶化工有限公司 | The preparation method of phosphate |
| US11879050B2 (en) | 2018-05-03 | 2024-01-23 | Si Group, Inc. | Antidegradant blend |
| CN109879906A (en) * | 2019-04-02 | 2019-06-14 | 上海多纶化工有限公司 | The preparation method of phosphate |
| CN109879906B (en) * | 2019-04-02 | 2021-05-07 | 上海多纶化工有限公司 | Process for the preparation of phosphoric esters |
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