CN102807582A - Preparation methods of organic phosphate ester and organic phosphate nucleating agent - Google Patents
Preparation methods of organic phosphate ester and organic phosphate nucleating agent Download PDFInfo
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- CN102807582A CN102807582A CN2011101513877A CN201110151387A CN102807582A CN 102807582 A CN102807582 A CN 102807582A CN 2011101513877 A CN2011101513877 A CN 2011101513877A CN 201110151387 A CN201110151387 A CN 201110151387A CN 102807582 A CN102807582 A CN 102807582A
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Abstract
The invention discloses a method for preparing organic phosphate ester. The preparation method comprises the following steps of: (1) performing primary contact on a substituted diaryl phenol raw material shown as a formula (I) and a phosphorylation reagent under a phosphorylation reaction condition in the presence of a phosphorylation solvent and an acid-binding agent; and (2) performing secondary contact on a product obtained through the primary contact and water under a hydrolysis condition, wherein in the formula, R1, R2, R3 and R4 are the same as or different from each other, and represent substituted or unsubstituted direct chain or branch chain alkyl with 1-6 carbon atoms respectively. The method is characterized in that: the phosphorylation solvent is halogenated hydrocarbon. The invention further discloses a method for preparing an organic phosphate nucleating agent. The method comprises the following steps of: preparing the organic phosphate ester; and making the organic phosphate ester contact with a salt forming agent under a salt forming reaction condition and in the presence of a salt forming agent. In the method, the halogenated alkane is taken as a solvent, so that the toxicity is low, and environment friendliness is facilitated; and combustion is not performed, so that operation is safe, the solvent is easy to recycle, raw material cost is reduced, and higher yield can be achieved.
Description
Technical field
The present invention relates to a kind of preparation method of organophosphate and a kind of preparation method of organic phosphate nucleating agent.
Background technology
The substituted aryl organic phosphate nucleating agent is widely used as the nucleation improving agent of acrylic resin; Be applied to the modification of acrylic resin; Wherein substituted diaryl organic phosphate nucleating agent such as two (2,4-di-t-butyl phenoxy) sodium phosphate, 2,2 '-methylene radical-two (4; 6-di-t-butyl phenoxy) sodium phosphate etc. can improve the processing characteristics of these resins significantly.Above content can referring to scientific and technical literature " polyacrylic high performance-nucleator " (" chemical industry ", 1999 (8), p11), " nucleator is to the influence of Properties of Polypropylene " (" synthetic resins and plastics ", 2001,18 (4), 39-41).
At present, substituted aryl organic phosphate nucleating agent synthetic is by making the diaryl organic phosphate nucleating agent behind substituted aryl phenol and phosphorus esterification reagent reaction in benzene class organic solvent, hydrolysis, the salify." the synthetic and application of PP nucleator " (plastics industry, Vol.27, No.5,29-31; 1999) reported the synthetic of PP nucleator methylene bis (2,4-di-t-butyl phenoxy) phosphagel phosphaljel in, it is through 2; 2 '-methylene radical-two (4, the 6-DI-tert-butylphenol compounds) is a solvent with toluene, with phosphorus oxychloride reaction; The hydrolysis preparation 2 then, 2 '-methylene radical-two (4, the 6-DI-tert-butylphenol compounds) SULPHOSUCCINIC ACID ESTER.Products obtained therefrom is prepared methylene bis (2,4-di-t-butyl phenoxy) sodium phosphate with the aluminium reaction neutralization in solvent.The shortcoming of this technology is that the yield of substituted aryl organic phosphate nucleating agent is lower, and owing to uses toluene to produce environmental pollution as the phosphorylated solvent.
Summary of the invention
The objective of the invention is to, solve the lower problem of prior art nucleator yield, the preparation method of the high organophosphate of a kind of product yield and the preparation method of organic phosphate nucleating agent are provided.
The present invention provides a kind of preparation method of organophosphate; This method may further comprise the steps: (1) is under the phosphorus acylation reaction condition; In the presence of phosphorylated solvent and acid binding agent, will carry out first with phosphorus esterification reagent by the substituted aryl phenol raw material shown in the following formula (I) and contact; (2) under hydrolysising condition, the first contact products therefrom is carried out second with water contact;
In the formula, R
1, R
2, R
3And R
4Identical or inequality, represent C separately
1-C
6Replacement or unsubstituted straight or branched alkyl; It is characterized in that said phosphorylated solvent is a halogenated alkane.
In addition, the present invention also provides a kind of preparation method of organic phosphate nucleating agent, and this method comprises and adopt method for preparing organophosphate of the present invention, and said organophosphate is contacted with salt forming agent in the presence of salt-forming reaction condition and one-tenth salt solvent.
It is solvent that the present invention adopts halogenated alkane; Therefore can obtain higher organophosphate yield, thereby the yield of organophosphate is also higher, for example; 98.95%, the average yield of organic phosphate nucleating agent is 95.35% according to the organophosphate average yield of embodiments of the invention 1-3; And be respectively 85% and 80% according to the organophosphate of the prior art in the Comparative Examples 1 and the yield of organic phosphate nucleating agent.In addition, because halogenated alkane has uninflammability, so operational safety, and because the boiling point of halogenated alkane is lower usually, reclaim easily, help solvent recovery cycle and use, therefore can reduce raw materials cost.
Embodiment
According to the present invention, said phosphorylated solvent can be various halogenated alkanes, and preferable case is C
1-C
4Halogenated alkane; Preferably, said phosphorylated solvent is C
1-C
4Chloroparaffin and/or C
1-C
4Bromo alkane; More preferably; Said phosphorylated solvent is at least a in the following halogenated alkane: methylene dichloride, trichloromethane, tetracol phenixin, trichloroethane, tetrachloroethane, Ethylene Dichloride, tri chloropropene, propylene dichloride, chlorobutane, methylene bromide, methenyl bromide, monobromethane, glycol dibromide; Most preferably, at least a in the following halogenated alkane: methylene dichloride, methylene bromide, trichloromethane and propylene dichloride.
Use the benefit of above-mentioned most preferably halogenated alkane to be: halogen element and protium have bigger difference on electronegativity, after carbon links to each other, show stronger polarity; Therefore, make solvent molecule that very big moment of dipole arranged, its result not only makes this solvent that reactant is had excellent dissolving power; And under the effect of the halogen element of strong negative very, the positive charge density on the carbon of solvent molecule increases; Attraction and bonding force to the halogen element in the reactant phosphorus esterification reagent strengthen; Cause phosphorus esterification reagent in reaction is carried out, to lose halogen element more easily, expose the phosphoric of positive charge can be rapidly be that oxonium ion in the substituted phenol combines with another reactant, form phosphorus oxygen key; Generate corresponding SULPHOSUCCINIC ACID ESTER, reaction is thoroughly carried out fast.In the present invention, halogenated hydrocarbon solvent has played the effect of this reaction of catalysis, and the benzene series thing solvent that prior art is used has only played solvency action.
Because the present invention relates generally to the improvement that organophosphate is prepared phosphorylated solvent species in the process, thus organophosphate prepare the consumption of kind and consumption, phosphorus acylation reaction condition, hydrolysis reaction condition and the water of other processing condition such as phosphorylated solvent types and consumption in the process, acid binding agent can be for known in those skilled in the art.Under the preferable case, said phosphorus acylation reaction condition comprises that temperature is-25-80 ℃, is preferably 20-30 ℃; Time is 1-36 hour, preferred 10-16 hour.
Phosphorus esterification reagent is preferably at least a in the following material: phosphorus trichloride, POCl3; Preferably, POCl3.
The consumption of said phosphorus esterification reagent is preferably, and counts substituted diaryl phenol raw material: phosphorus esterification reagent=1: 1-3 in molar ratio; More preferably, substituted diaryl phenol raw material: phosphorus esterification reagent=1: 1.7-2.
Said acid binding agent can be the conventional various acid binding agents that use in this area, is preferably triethylamine.
The add-on of said acid binding agent is preferably, and counts phosphorus esterification reagent: acid binding agent (like triethylamine)=1: 1-3 in molar ratio; Further preferred, phosphorus esterification reagent: acid binding agent=1: 1-2; More preferably, phosphorus esterification reagent: acid binding agent=1: 1.5-1.6.
Further under the preferable case, the consumption of said phosphorylated solvent is that the mass concentration that makes substituted aryl phenol in the gained solution is 10%-60%; Preferred 10%-30%; More preferably, 19-20%.When said solution is made up of substituted diaryl phenol raw material, phosphorus esterification reagent, phosphorylated solvent and acid binding agent shown in the formula (I); The feasible total amount with substituted diaryl phenol raw material, phosphorus esterification reagent, phosphorylated solvent and the acid binding agent shown in the formula (I) of the consumption of said phosphorylated solvent is a benchmark, and the mass concentration of the substituted aryl phenol shown in the formula (I) is 10%-60%; Preferred 10%-30%; More preferably, 19-20%.
According to the preparation method of organophosphate of the present invention, wherein, in the following formula (I), R
1, R
2, R
3And R
4For being selected from methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec.-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, tert-pentyl, neo-pentyl, n-hexyl, 2-methyl amyl, 3-methyl amyl, 2 respectively; 3-dimethylbutyl and 2, a kind of in 2 '-dimethylbutyl.
Preferably, said substituted aryl phenol raw material is for being selected from 2,2 '-methylene radical-two (4, the 6-xylenol), 2; 2 '-methylene radical-two (4, the 6-diethyl phenol), 2,2 '-methylene radical-two (4,6-di phenol), 2; 2 '-methylene radical-two (4, the 6-diisopropyl phenol), 2,2 '-methylene radical-two (4,6-di-n-butyl phenol), 2; 2 '-methylene radical-two (4, the 6-di sec-butylphenol), 2,2 '-methylene radical-two (4, the 6-diisobutyl phenol), 2; 2 '-methylene radical-two (4, the 6-DI-tert-butylphenol compounds), 2,2 '-methylene radical-two (4,6-two n-pentyl phenol), 2; 2 '-methylene radical-two (4,6-diisoamyl phenol), 2,2 '-methylene radical-two (4, the 6-di-tert-pentyl phenol), 2; 2 '-methylene radical-two (4,6-di neo-pentyl phenol), 2,2 '-methylene radical-two (4,6-di-n-hexyl phenol), 2.2 '-methylene radical-two [4; 6-two (2-methyl amyl) phenol], 2,2 '-methylene radical-two [4,6-two (3-methyl amyl) phenol], 2,2 '-methylene radical-two [4; 6-two (2, the 3-dimethylbutyl) phenol], 2, [4,6-two (2 for 2 '-methylene radical-two; 2 '-dimethylbutyl) phenol], 2,2 '-methylene radical-two (4-methyl-6-tert butyl phenol), 2,2 '-methylene radical-two (4-ethyl-6-tert.-butyl phenol), 2,2 '-methylene radical-two (4-normal-butyl-6-tert.-butyl phenol), 2; 2 '-methylene radical-two (4-sec.-butyl-6-tert.-butyl phenol), 2,2 '-methylene radical-two (4-isobutyl--6-tert.-butyl phenol), 2,2 '-methylene radical-two (4-n-pentyl-6-tert.-butyl phenol), 2,2 '-methylene radical-two (4-isopentyl-6-tert.-butyl phenol), 2; 2 '-methylene radical-two (4-tert-pentyl-6-tert.-butyl phenol), 2,2 '-methylene radical-two (4-neo-pentyl-6-tert.-butyl phenol), 2,2 '-methylene radical-two (4-normal hexane-6-tert.-butyl phenol), 2; 2 '-methylene radical-two [4-(2-methyl amyl)-6-tert.-butyl phenol], 2,2 '-methylene radical-two [4-(3-methyl amyl)-6-tert.-butyl phenol], 2, [4-(2 for 2 '-methylene radical-two; The 3-dimethylbutane)-the 6-tert.-butyl phenol], 2,2 '-methylene radical-two [4-(2,2 '-dimethylbutyl)-6-tert.-butyl phenol].
More preferably, said raw material is 2,2 '-methylene radical-two (4, the 6-DI-tert-butylphenol compounds) or 2,2 '-methylene radical-two (4-methyl-6-tert butyl phenol).
The win product of contact of step (1) can not separate or separate afterwards to contact with water and is hydrolyzed.
Said hydrolysising condition comprises that preferred temperature is 15 ℃-75 ℃, and the time is 0.1 hour-6 hours; More preferably, temperature 35-40 ℃, the time is 1-2 hour.
The consumption of the water that uses in the said hydrolysis reaction is preferably, substituted aryl phenol: the quality ratio is 1: 1-40; More preferably, substituted aryl phenol: the quality ratio is 1: 1-10; Further preferred, substituted aryl phenol: the quality ratio is 1: 3-4.
According to the preparation method of organophosphate provided by the invention, under the preferable case, this method removes solvent, filtration after also comprising hydrolysis, and the solids washing that leaches is extremely neutral; And the drying solid thing, promptly obtain the substituted diaryl organophosphate.
Under the preferable case, said salt-forming reaction condition comprises: temperature is 16 ℃-100 ℃, is preferably 15-40 ℃, and the time is 0.1-5 hour, is preferably 0.5-1.5 hour.
Salt forming agent is preferably a kind of in the following material: calcium hydroxide, Marinco H, white lake, zinc hydroxide, hydrated barta, verditer, aluminum chloride, magnesium chloride, zinc chloride; Preferably, a kind of in white lake, the aluminum chloride; Most preferably, aluminum chloride.
The add-on of said salt forming agent is to count substituted diaryl organophosphate: salt forming agent=3-5: 1 in molar ratio; Preferably, substituted diaryl organophosphate: salt forming agent=3-4: 1.
Said one-tenth salt solvent is preferably water and is selected from mixture at least a in the following material: acetone, ethanol, propyl alcohol, methyl alcohol, ETHYLE ACETATE, benzene, THF, hexanaphthene, normal hexane, butanols; More preferably, at least a mixture in water and the following material: acetone, ethanol, propyl alcohol, methyl alcohol; Most preferably, the mixture of water and acetone.
The content of water 10-90 weight % preferably in the said one-tenth salt solvent; More preferably, 30-50 weight %.
The add-on of said one-tenth salt solvent is that preferred, the substituted diaryl organophosphate: salify solvent quality ratio is 1: 20-50; More preferably, substituted diaryl organophosphate: salify weight of solvent ratio is 1: 20-40; Most preferably, substituted diaryl organophosphate: become salt solvent=1: 25-35.
Under the preferable case, said organophosphate is added the described salt solvent that becomes with described substituted diaryl organophosphate and salt forming agent successively becoming the mode that contacts with salt forming agent in the presence of the salt solvent to comprise.
Products therefrom preferably further process distillation, filtration, washing obtains described substituted diaryl organic phosphate nucleating agent product to neutrality, drying.
Compare with the nonpolar benzene class organic solvent that prior art adopts, the present invention adopts halogenated alkane series solvent, and its advantage is to obtain higher substituted diaryl organophosphate yield, thereby obtains higher organic phosphate nucleating agent yield.
Below with embodiment and application examples the present invention is described in more detail.But the present invention does not receive any restriction of following examples.
Embodiment 1
This embodiment is used for explaining the preparation method of organophosphate provided by the invention and the preparation method of organic phosphate nucleating agent.
The preparation of organophosphate: in reaction flask, add 2; 2 '-methylene radical-two (4; The 6-DI-tert-butylphenol compounds) (Shanghai Taurus chemical industry ltd produces, and the trade mark is 2246) 42.4g, methylene dichloride 140ml and triethylamine 50ml are stirred to solid and fully dissolve; Slowly add POCl3 20ml at ambient temperature, at room temperature reacted after dropwising 10 hours; Add water 150ml then and stir 1.5hr, steam solvent then, get solid product after the filtration washing; Solid product is purified with ethyl alcohol recrystallization, remove liquid phase, get white solid 48.5g after the drying; Be intermediate product 2; 2 '-methylene radical-two (4,6-di-t-butyl phenoxy) SULPHOSUCCINIC ACID ESTER, the yield of this intermediate product is 99.8%.
The preparation of organic phosphate nucleating agent: intermediate product substituted diaryl organophosphate is dissolved in the mixed solution of salify solvent acetone and water; The mass ratio of acetone and water is 4: 6 in the one-tenth salt solvent, and organophosphate is 1: 30 with the mass ratio that becomes salt solvent, 30 weight % aluminum chloride aqueous solutions is added described substituted diaryl organophosphate carry out salify; 2; The mol ratio of 2 '-methylene radical-two (4,6-di-t-butyl phenoxy) SULPHOSUCCINIC ACID ESTER and aluminum chloride is 3.5: 1, drips 10% sodium hydrate regulator solution pH value to neutral; Obtain solid product 48.16 grams after the distillation of products therefrom process, filtration, washing to neutrality, the drying; With initial feed 2, the charging capacity of 2 '-methylene radical-two (4-methyl-6-tert butyl phenol) is meter, yield 95%; Confirm as two [2,2 '-methylene radical-two (4,6-di-t-butyl phenoxy) phosphoric acid] oxyaluminum through mass spectrum and infrared analysis.
Embodiment 2
This embodiment is used for explaining the preparation method of organophosphate provided by the invention and the preparation method of organic phosphate nucleating agent.
The preparation of organophosphate: in reaction flask, add 2; 2 '-methylene radical-two (4, the 6-DI-tert-butylphenol compounds) (Shanghai Taurus chemical industry ltd produces, and the trade mark is 2246) 42.4g; Methylene bromide 150ml and triethylamine 45ml; Be stirred to solid and fully dissolve, slowly add POCl3 20ml at ambient temperature, at room temperature reacted after dropwising 16 hours; Add water 150ml then and stir 1.5hr, steam solvent then, get solid product after the filtration washing; Solid product is purified with ethyl alcohol recrystallization, remove liquid phase, get white solid 48.3g after the drying; Be intermediate product 2; 2 '-methylene radical-two (4,6-di-t-butyl phenoxy) SULPHOSUCCINIC ACID ESTER, the yield of this intermediate product is 99.4%.
The preparation of organic phosphate nucleating agent: intermediate product substituted diaryl organophosphate is dissolved in the mixed solution of salify solvent methanol and water, and becoming the mass ratio of first alcohol and water in the salt solvent is 3: 7, and organophosphate is 1: 25 with the mass ratio ratio that becomes salt solvent; 2; The mass ratio of 2 '-methylene radical-two (4,6-di-t-butyl phenoxy) SULPHOSUCCINIC ACID ESTER and aluminum chloride is 3.5: 1,30 weight % aluminum chloride aqueous solutions is added described substituted diaryl organophosphate carry out salify; Drip 10% sodium hydrate regulator solution pH value to neutral; The products therefrom process is distilled, filters, is washed extremely and gets solid product 48.97g after neutrality, the drying, and with initial feed 2, the charging capacity of 2 '-methylene radical-two (4-methyl-6-tert butyl phenol) is for counting; Yield 96.6%; Confirm as two [2,2 '-methylene radical-two (4, the 6-DI-tert-butylphenol compounds) phosphoric acid] oxyaluminum through mass spectrum and infrared analysis.
Embodiment 3
This embodiment is used for explaining the preparation method of organophosphate provided by the invention and the preparation method of organic phosphate nucleating agent.
The preparation of organophosphate: in reaction flask, add 2; (Shanghai Taurus chemical industry ltd produces 2 '-methylene radical-two (4-methyl-6-tert butyl phenol); The trade mark is 2246) 34.0g, trichloromethane 170ml and triethylamine 52ml; Be stirred to solid and fully dissolve, slowly add POCl3 22ml at ambient temperature, at room temperature reacted after dropwising 14 hours; Add water 150ml then and stir 1.5hr, steam solvent then, get solid product after the filtration washing; Solid product is purified with ethyl alcohol recrystallization; Remove liquid phase, get white solid 39.4g after the drying, be intermediate product 2; 2 '-methylene radical-two (4-methyl-6-di-t-butyl phenoxy) SULPHOSUCCINIC ACID ESTER, the yield of this intermediate product is 98%.
The preparation of organic phosphate nucleating agent: intermediate product substituted diaryl organophosphate is dissolved in the mixed solution of salify etoh solvent and water; Becoming the mass ratio of second alcohol and water in the salt solvent is 5: 5, and organophosphate is 1: 35 with the mass ratio that becomes salt solvent, 30 weight % aluminum chloride aqueous solutions is added described substituted diaryl organophosphate carry out salify; 2; The mass ratio of 2 '-methylene radical-two (4,6-di-t-butyl phenoxy) SULPHOSUCCINIC ACID ESTER and aluminum chloride is 3.5: 1, drips 10% sodium hydrate regulator solution pH value to neutral; The products therefrom process is distilled, filters, is washed extremely and gets solid product 40.2 grams after neutrality, the drying; With initial feed 2, the charging capacity of 2 '-methylene radical-two (4-methyl-6-tert butyl phenol) is meter, and yield is 95.1%; Confirm as two [2,2 '-methylene radical-two (4-methyl-6-tert butyl phenoxy) phosphoric acid] oxyaluminum through mass spectrum and infrared analysis.
Comparative Examples 1
This Comparative Examples is used to explain the preparation method of existing organophosphate and the preparation method of organic phosphate nucleating agent.
Method according to embodiment 3 prepares organophosphate and organic phosphate nucleating agent; Different is; Preparation during organophosphate used organic solvent trichloromethane replace by the toluene of identical weight, intermediate product 2 as a result, the yield of 2 '-methylene radical-two (4-methyl-6-di-t-butyl phenoxy) SULPHOSUCCINIC ACID ESTER is 85%; Two [2,2 '-methylene radical-two (4-methyl-6-tert butyl phenoxy) phosphoric acid] oxyaluminum yield is 80%.
Table 1
| The embodiment numbering | The yield % of organophosphate | The yield % of organic phosphate nucleating agent |
| Embodiment 1 | 99.8％ | 95％ |
| Embodiment 2 | 99.4％ | 96.6％ |
| Embodiment 3 | 98％ | 95.1％ |
| Comparative Examples 1 | 85％ | 80％ |
Can find out that from table 1 therefore method provided by the invention compared with prior art can obviously improve the yield of organophosphate, thereby obviously improve the yield of organic phosphate nucleating agent owing to use halogenated alkane as the phosphorylated solvent.
Application examples
This application examples is used for explaining the application of nucleator in polymer processing.
Get Vestolen PP 7052 (raising sub-petrochemical iy produced F401) 100 weight parts; Get nucleator 0.1 weight part that embodiment 1-3 makes respectively; In super mixer, extrude in TE-34 type twin screw extruder behind the mixing; 220 ℃ of extrusion temperatures become sample standard batten through injector (ST125 type) injection moulding (230 ℃ of injection temperatures) then; The Vestolen PP 7052 that does not add nucleator is handled through same, as check sample.
The batten that obtains is carried out modulus in flexure test (pressing the ASTMD790 testing standard), and the result that mist degree (by the ASTMD1003-07 testing standard) and heat-drawn wire test (by the ASTMD648 testing standard) obtain lists in table 2.
Table 2
| The nucleator that uses | Sample modulus in flexure/GPa | Mist degree | Heat-drawn wire/℃ |
| Embodiment 1 | 1.622 | 17.32 | 125.8 |
| Embodiment 2 | 1.618 | 19.36 | 125.4 |
| Embodiment 3 | 1.596 | 23.92 | 119.60 |
| Comparative Examples 1 | 1.594 | 27.37 | 117.8 |
| Not with nucleator | 1.270 | 42.07 | 100.1 |
Can clearly be seen that from table 2 data; Use the nucleator of the Comparative Examples 1 that the method for nucleator and the prior art of the embodiment 1-3 that preparation method of the present invention makes makes all can significantly improve the multiple processing characteristics of polymkeric substance; And when improving mist degree, modulus in flexure also is significantly increased.The effect of the substituted aryl organophosphate that makes all is significantly improved.Can satisfy polymkeric substance fully and improve performance demands in Application Areas.
Claims (13)
1. the preparation method of an organophosphate, this method may further comprise the steps: (1) in the presence of phosphorylated solvent and acid binding agent, will carry out first with phosphorus esterification reagent by the substituted diaryl phenol raw material shown in the following formula (I) and contact under the phosphorus acylation reaction condition; (2) under hydrolysising condition; The first contact products therefrom is carried out second with water contact
In the formula, R
1, R
2, R
3And R
4Identical or inequality, represent C separately
1-C
6The straight or branched alkyl;
It is characterized in that said phosphorylated solvent is a halogenated alkane.
2. preparation method according to claim 1, wherein, the consumption of said phosphorus esterification reagent is to count substituted diaryl phenol raw material: phosphorus esterification reagent=1: 1.7-2 in molar ratio; The add-on of acid binding agent is to count phosphorus esterification reagent: acid binding agent=1: 1-2 in molar ratio; The feasible total amount with substituted diaryl phenol raw material, phosphorus esterification reagent, phosphorylated solvent and the acid binding agent shown in the formula (I) of the consumption of said phosphorylated solvent is a benchmark, and the mass concentration of the substituted aryl phenol shown in the formula (I) is 10%-30%.
3. preparation method according to claim 1 and 2, wherein, said phosphorylated solvent is C
1-C
4Halogenated alkane.
4. preparation method according to claim 3, wherein, said phosphorylated solvent is C
1-C
3Chloroparaffin and/or C
1-C
3Bromo alkane.
5. preparation method according to claim 4, wherein, said phosphorylated solvent is at least a in methylene bromide, methylene dichloride, the trichloromethane.
6. preparation method according to claim 1, wherein, the consumption of water does in the hydrolysis reaction, by weight, substituted diaryl phenol: water=1: 1-10.
7. according to claim 1 or 6 described preparing methods, wherein, said substituted diaryl phenol raw material is for being selected from 2,2 '-methylene radical-two (4,6-di-t-butyl phenoxy) and 2, a kind of in 2 '-methylene radical-two (4-methyl-6-tert butyl phenol); Said phosphorus esterification reagent is at least a in phosphorus trichloride, the POCl3; Said acid binding agent is a triethylamine.
8. preparation method according to claim 1, wherein, said phosphorus acylation reaction condition comprises that temperature is 20-30 ℃, the time is 10-16 hour.
9. preparation method according to claim 1, wherein, said hydrolysising condition comprises that temperature is 35-40 ℃, the time is 1-2 hour.
10. the preparation method of an organic phosphate nucleating agent; This method comprises the preparation organophosphate; And with said organophosphate the salt-forming reaction condition with become salt solvent in the presence of contact with salt forming agent; It is characterized in that the method for preparing said organophosphate is any described method among the claim 1-9.
11. preparation method according to claim 10, wherein, said substituted diaryl organophosphate: becoming the mass ratio of salt solvent is 1: 20-50; Said substituted diaryl organophosphate: the mol ratio of salt forming agent is 3-4: 1.
12. according to claim 10 or 11 described preparing methods, wherein, said salt forming agent is white lake or aluminum chloride, said one-tenth salt solvent is an at least a mixture in water and the following material: acetone, ethanol, propyl alcohol, methyl alcohol.
13. preparation method according to claim 12, wherein, the content of water is 30-50 weight % in the said one-tenth salt solvent.
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Cited By (2)
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| WO2021196332A1 (en) * | 2020-04-01 | 2021-10-07 | 山西省化工研究所（有限公司） | Substituted bisphenol phosphate ester aluminum salt nucleating agent, manufacturing method therefor, and application thereof |
| CN113896745A (en) * | 2020-07-06 | 2022-01-07 | 华东理工大学 | Continuous preparation method of substituted diaryl phosphate compound |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101367833A (en) * | 2007-08-17 | 2009-02-18 | 中国石油化工股份有限公司 | Preparation method for organic phosphate nucleating agent |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101367833A (en) * | 2007-08-17 | 2009-02-18 | 中国石油化工股份有限公司 | Preparation method for organic phosphate nucleating agent |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021196332A1 (en) * | 2020-04-01 | 2021-10-07 | 山西省化工研究所（有限公司） | Substituted bisphenol phosphate ester aluminum salt nucleating agent, manufacturing method therefor, and application thereof |
| CN113896745A (en) * | 2020-07-06 | 2022-01-07 | 华东理工大学 | Continuous preparation method of substituted diaryl phosphate compound |
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Application publication date: 20121205 |