CN102807583A - Synthesis methods of organophosphate ester and organophosphate salt - Google Patents
Synthesis methods of organophosphate ester and organophosphate salt Download PDFInfo
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Abstract
The invention relates to synthesis methods of organophosphate ester and organophosphate salt. The synthesis method of organophosphate ester is characterized by comprising the following steps of: (1) carrying out first contact on organic solvent solution of substituted diaryl phenol shown in formula (I) with a phosphorylation reagent in the presence of an acid-binding agent under the phosphorylation reaction conditions; and (2) carrying out second contact on the product obtained after first contact with water under hydrolysis conditions, wherein the use amount of water is 17-70wt% of substituted diaryl phenol shown in the formula (I); and R1, R2, R4 and R4, the same or different, respectively represent C1-C6 straight-chain or branched alkyl. Therefore, the waste of water resources is avoided, the recovery efficiency of organic reagents in reaction is improved, the discharge amount of industrial wastewater is reduced, and the treatment difficulty of industrial wastewater is reduced, so that the synthesis method is beneficial to environmental protection and generates significant social benefits and economic benefits.
Description
Technical field
The present invention relates to a kind of compound method of organophosphate and the compound method of organophosphate.
Background technology
Diaryl organophosphorus acyl compound is widely used as the nucleation improving agent of acrylic resin, is applied to the modification of acrylic resin.Wherein substituted diaryl organic metal phosphate 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 acrylic resin significantly.
Existing organic phosphoric acid metal-salt nucleator production technique is generally made by the substituted diaryl organophosphate, so the preparation of substituted diaryl organophosphate is an important step of producing organic phosphoric acid metal-salt nucleator.
The substituted diaryl organophosphate generally generates substituted diaryl organic phosphoric acid acyl chlorides through corresponding substituted diaryl phenol through phosphorus acylation reaction; Again the hydrolysis of substituted diaryl organic phosphoric acid acyl chlorides is obtained the substituted diaryl organophosphate, last substituted diaryl organophosphate and salt forming agent are carried out to reactant salt and obtain organophosphate.At present in the production process of organic phosphate nucleating agent; The process water that adds in the hydrolysing step is quite big; Be generally 5-10 times of weight of substituted diaryl phenol, be equivalent to 5.5-11 times of weight of substituted diaryl organic phosphoric acid acyl chlorides, for full technical process expends the technology water yield more than 65%.Why a large amount of process waters is used in existing organic phosphate nucleating agent phosphorylated-hydrolysing step production; Be can heat release, carry out cooling protection so hope the excessive greatly process water of adding because consider in phosphoric acid acyl chlorides hydrolysis reaction and excessive phosphorus esterification reagent hydrolysis reaction all.Because process water is participated in reaction, can't recycle as washing water, so caused the serious waste to water resources.Use a large amount of process waters must produce a large amount of industrial sewage dischargings, also bring problems such as environmental pollution, increase environmental protection cost easily.
Simultaneously, owing in phosphorylated-hydrolysing step, need to add triethylamine as acid binding agent.Consider that the triethylamine price is higher, should reclaim it.But because triethylamine at normal temperatures, is slightly soluble in water, the triethylamine about every 100g water dissolvable 2g.So if exist the amount of process water big more, be dissolved in aqueous phase and discharge thereupon in the reaction system with regard to having more triethylamines, can't Separation and Recovery.Increase the difficulty of effluent sewerage environmental protection treatment on the one hand, also reduced the organic efficiency of triethylamine on the other hand.
Consider the problems referred to above; If can invent a kind of optimization method that reduces hydrolysis reaction amount of water in the organophosphate production; Not only can reduce the production cost of nucleator greatly, and to avoiding the waste of valuable water resources, reduce pollutant emission, the protection environment is significant; Cleaner production be can realize, remarkable economic efficiency and social benefit obtained.
Summary of the invention
The compound method that the objective of the invention is to solve organophosphate of the prior art exists because the process water amount causes the low problem of organic efficiency of the wasting of resources and triethylamine greatly, the compound method of the little and organophosphate that the triethylamine organic efficiency is high of a kind of process water amount is provided and comprises the compound method of organophosphate of the compound method of this organophosphate.
Although the hydrolysis reaction of the hydrolysis reaction of phosphoric acid acyl chlorides and excessive phosphorus esterification reagent all is thermopositive reaction; Yet contriver of the present invention finds through industrial amplification test; Even if reduce the input amount of process water greatly; Also can guarantee the temperature-stable of reaction system, existing common " temperature runaway " problem of worrying can not occur, accomplish the present invention thus.
The present invention provides a kind of compound method of organophosphate, and this method may further comprise the steps:
(1) under the phosphorus acylation reaction condition, the organic solvent solution of the substituted diaryl phenol shown in the formula (I) is carried out first with phosphorus esterification reagent contact in the presence of acid binding agent;
(2) under hydrolysising condition, the product after the win contact is carried out second with water contact, the consumption of said water is the 17-70 weight % of the substituted diaryl phenol shown in the formula (I),
Wherein, R
1, R
2, R
3And R
4Identical or inequality, represent C separately
1-C
6Replacement or unsubstituted straight or branched alkyl.
The present invention provides a kind of compound method of organophosphate, and this method comprises that the compound method through above-mentioned organophosphate prepares organophosphate, and said organophosphate is contacted with salt forming agent in the presence of the one-tenth salt solvent.
The water consumption of the compound method of organophosphate of the present invention is the 5-15 weight % of the water consumption of traditional technology; Therefore avoided waste on the one hand to valuable water resources; Reduce the quantity discharged of trade effluent simultaneously; Also improve the recovery of acid binding agent on the other hand, reduced the intractability of trade effluent, thereby can significantly reduce the production cost of organic phosphate nucleating agent.
Embodiment
According to the compound method of organophosphate of the present invention, further under the preferable case, the consumption of water described in the step (2) is the 20-60 weight % of the substituted diaryl phenol shown in the formula (I); More preferably 30-50 weight %.
Because water is used to make step (1) gained phosphorylated product to be hydrolyzed in the step (2); Therefore the consumption of said water also can be that benchmark is confirmed with the phosphorylated product that contacts with water in the step (2); Need only and satisfy the theoretical requirement that makes the whole hydrolysis of said phosphorylated product, and confirm that as benchmark meeting is more accurate.Therefore yet owing to behind step (1) phosphorus acylation reaction, can pass through separation and also can directly carry out the reaction of step (2) without separation, from angle easily, generally the amount with the substituted diaryl phenol shown in the raw material formula (I) is that benchmark is confirmed.
According to the present invention; In the total amount of substituted diaryl phenol, organic solvent, acid binding agent, phosphorus esterification reagent and the water shown in the formula (I) total amount of reaction raw materials (below be also referred to as) is 100 weight parts; The consumption of the substituted diaryl phenol shown in the formula (I) is the 25-35 weight part, and the consumption of organic solvent is the 23-57 weight part, and the consumption of acid binding agent is the 6-12 weight part; The consumption of phosphorus esterification reagent is the 6-12 weight part, and the consumption of water is the 6-18 weight part; Under the preferable case; Total amount in substituted diaryl phenol, organic solvent, acid binding agent, phosphorus esterification reagent and the water shown in the formula (I) is 100 weight parts; The consumption of the substituted diaryl phenol shown in the formula (I) is the 26-32 weight part, and the consumption of organic solvent is the 33-48 weight part, and the consumption of acid binding agent is the 8-10 weight part; The consumption of phosphorus esterification reagent is the 8-10 weight part, and the consumption of water is the 10-15 weight part.
Said phosphorus acylation reaction condition can comprise that temperature is 20-60 ℃, and the reaction times is 10-20 hour; Under the preferable case, temperature is 30-50 ℃, and the reaction times is 12-16 hour; More preferably under the situation, temperature of reaction is 35-40 ℃, and the reaction times is 14-15 hour.
Compound method according to organophosphate of the present invention; Above-mentioned temperature of reaction can be carried out in the jacketed reactor and in this chuck, feeds cold water or steam is realized through making to be reflected at; When temperature is higher than said temperature; In chuck, feed cold water, when temperature is lower than said temperature, in chuck, feed steam.
The present invention does not have special qualification to the substituted diaryl phenol shown in the formula (I) and the way of contact of phosphorus esterification reagent; Under the preferable case; Phosphorus esterification reagent is slowly joined in the substituted diaryl phenol shown in the formula (I), and also can come control reaction temperature through the adding speed of control phosphorus esterification reagent this moment.Under the preferable case, the substituted diaryl phenol with respect to 1 mole, the adding speed of phosphorus esterification reagent is 0.5-2mL/ minute.
In order to improve the rate of utilization of phosphorus esterification reagent, under the preferable case, said phosphorus acylation reaction carries out under nitrogen protection.
According to organophosphate compound method of the present invention, in formula (I), R
1, R
2, R
3And R
4Respectively can be for 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; 3-dimethylbutyl and 2, a kind of in 2 '-dimethylbutyl; Preferably, R
1, R
2, R
3And R
4Be respectively and be selected from a kind of in n-propyl, sec.-propyl, normal-butyl, sec.-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, tert-pentyl or the neo-pentyl; More preferably, R
1, R
2, R
3And R
4Represent identical alkyl, and be selected from a kind of in normal-butyl, sec.-butyl, isobutyl-, the tertiary butyl.
In the step (1); Said organic solvent can be the solvent that is used for phosphorus acylation reaction of various routines; Be preferably selected from acetone, ethanol, methyl alcohol, propyl alcohol, Virahol, butanols, sherwood oil, THF, ETHYLE ACETATE, toluene, ethylbenzene, N; Dinethylformamide or 1, at least a in the 4-dioxane; More preferably, toluene or 1,4-dioxane.
The consumption of said organic solvent does, by mass ratio, and said substituted diaryl phenol: organic solvent=1: 0.5-2.5; Preferably, said substituted diaryl phenol: organic solvent=1: 1-2.
Said acid binding agent can be a various acid binding agent well known in the art, preferred triethylamine.
The consumption of said acid binding agent is to count said substituted diaryl phenol: acid binding agent=1: 1-1.5 in molar ratio; Preferably, said substituted diaryl phenol: acid binding agent=1: 1.2-1.4.
Said phosphorus esterification reagent can be selected from phosphorus trichloride and/or POCl3; Preferably, POCl3.
Consumption with said phosphorus esterification reagent is as the criterion, and counts said substituted diaryl phenol: phosphorus esterification reagent=1: 0.5-1.2 in molar ratio; Preferably, said substituted diaryl phenol: phosphorus esterification reagent=1: 0.8-0.9.
Said hydrolysis reaction condition comprises that temperature is 40-80 ℃, and the time is 2-5 hour; Preferably, temperature is 55-75 ℃, and the time is 2-4 hour; More preferably, temperature is 60-70 ℃, and the time is 2.5-3 hour.
The temperature of said hydrolyzed reaction also can be carried out in the jacketed reactor and in this chuck, feeds cold water or steam is realized through being reflected at; When temperature is higher than said temperature; In chuck, feed cold water, when temperature is lower than said temperature, in chuck, feed steam.
Above-mentioned phosphorus acylation reaction and hydrolysis reaction can carry out in identical or different reactor drum.And as stated, the product of above-mentioned phosphorus acylation reaction can pass through promptly corresponding with formula (I) the substituted diaryl organic phosphoric acid acyl chlorides of phosphorylated product that after the separation separation is obtained and contact the reaction that is hydrolyzed with water, and reaction also can directly be hydrolyzed without separation.
According to the compound method of organophosphate of the present invention, after said hydrolysis reaction finishes, can also comprise the step that steams organic solvent, desciccate.
The said step that steams organic solvent and desciccate has no particular limits, and this area method commonly used can be used.
Compound method according to organophosphate of the present invention; Because this method relates generally to the improvement of the compound method of organophosphate; Therefore said organophosphate is becoming in the presence of the salt solvent; Contact with salt forming agent and can adopt method well known in the art to carry out, becoming salt solvent and salt forming agent kind and consumption has been conventionally known to one of skill in the art, and the present invention repeats no more at this.
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 aluminum chloride, magnesium chloride and the sodium hydroxide.
The add-on of said salt forming agent is as the criterion can make the whole as far as possible salifies of said organophosphate; For different salt forming agents; Make the amount of the required salt forming agent of the organophosphate salify of same amount different, the concrete valence state that depends on metals ion in the salt forming agent, usually; Count organophosphate: salt forming agent=1-5: 1 in molar ratio; Preferably, organophosphate: salt forming agent=1-4: 1, be the salt forming agent such as the above-mentioned sodium salt of lower valency for metals ion, fully to react in order to make organophosphate and salt forming agent, the usefulness of organophosphate is measured the smaller value of above-mentioned scope; For metals ion is salt forming agent such as the above-mentioned aluminium salt or the calcium salt of high valence state, fully reacts in order to make organophosphate and salt forming agent, and the usefulness of organophosphate is measured the higher value of above-mentioned scope.
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 %.
Because the reaction mechanism that the compound method of organophosphate of the present invention and each step of compound method of organophosphate relate to is very clear and definite; The Direction of Reaction is also very clear and definite; Bonding mechanism and reaction raw materials can be confirmed the reaction product of each step of the present invention, so the present invention does not carry out special structural characterization to the reaction product that each step relates to.
Below with embodiment and Comparative Examples the present invention is described in more detail.But the present invention does not receive any restriction of following examples.
Embodiment 1
The preparation of organophosphate: the charging opening in the jacketed type reaction kettle adds 2,2 '-methylene radical-two (4, the 6-di-t-butyl) phenol (Shanghai Taurus chemical industry ltd produces, and the trade mark is 2246) 26kg, toluene 48kg, triethylamine 8kg.The intake valve of opening device feeds nitrogen protection.In chuck, feed cold water and steam, between 35-40 ℃, react with controlled temperature.At the uniform velocity drip POCl3 8kg in charging opening with 0.8mL/ minute speed again after 1 hour.React after 14 hours, add the reaction that is hydrolyzed of 10kg water, come control reaction temperature to 60-70 ℃ through feeding cold water and steam in chuck in charging opening.React after 3 hours, reaction finishes.Steam toluene, filter and obtain product 2,2 '-methylene radical-two (4,6-di-t-butyl phenoxy) SULPHOSUCCINIC ACID ESTER filter cake, dry back is 29.3kg, with 2, the charging capacity meter of 2 '-methylene radical-two (4, the 6-di-t-butyl) phenol, yield is 98%.Collect filtrating and distillation recovery triethylamine, obtain the 7.78kg triethylamine, the triethylamine recovery is 97.2%.
The preparation of organic phosphoric acid metal-salt: will obtain 2,2 '-methylene radical-two (4,6-di-t-butyl phenoxy) SULPHOSUCCINIC ACID ESTER 29.3kg 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 2: 1, drips 10 weight % sodium hydrate regulator solution pH values to neutral; The distillation of products therefrom process, filtration, washing obtain solid product to neutrality, drying; 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
The preparation of organophosphate: add 2 in the reaction kettle charging opening, 2 '-methylene radical-two (4, the 6-di-t-butyl) phenol (Shanghai Taurus chemical industry ltd produces, and the trade mark is 2246) 31kg, 1,4-dioxane 34kg, triethylamine 10kg.The intake valve of opening device feeds nitrogen protection.In chuck, feed cold water and steam, controlled temperature reacts between 35-40 ℃.At the uniform velocity drip POCl3 10kg in charging opening with 0.65mL/ minute speed again after one hour.React after 15 hours, add the reaction that is hydrolyzed of 15kg water in charging opening, control reaction temperature is to 60-70 ℃.Reacted 2.5 hours, to the reaction end.Steam toluene, filter and obtain product 2,2 '-methylene radical-two (4,6-di-t-butyl phenoxy) SULPHOSUCCINIC ACID ESTER filter cake, dry back is 34.5kg, with 2, the charging capacity meter of 2 '-methylene radical-two (4, the 6-di-t-butyl) phenol, yield is 97%.Collect filtrating and reclaim triethylamine, obtain 9.5kg, the triethylamine recovery is 95%.
The preparation of organophosphate: with intermediate product 2,2 '-methylene radical-two (4,6-di-t-butyl phenoxy) SULPHOSUCCINIC ACID ESTER is dissolved in the mixed solution of salify solvent acetone and water, and the mass ratio of acetone and water is 4: 6; Organophosphate is 1: 30 with the ratio that becomes salt solvent, 30 weight % magnesium chloride brines is added described 2, and 2 '-methylene radical-two (4,6-di-t-butyl phenoxy) SULPHOSUCCINIC ACID ESTER carries out salify; Magnesium chloride and 2, the mol ratio of 2 '-methylene radical-two (4,6-di-t-butyl phenoxy) SULPHOSUCCINIC ACID ESTER is 2: 1; Drip 10 weight % sodium hydrate regulator solution pH values to neutral, steam acetone, obtain white solid product; After the filtration, to pH=7-8, get product behind the heat drying with deionized water wash; Confirm as two [2,2 '-methylene radical-two (4,6-di-t-butyl phenoxy) phosphoric acid] magnesium through mass spectrum and infrared analysis.
Embodiment 3
The preparation of organophosphate: add 2 in the reaction kettle charging opening, 2 '-methylene radical-two (4, the 6-di-t-butyl) phenol (Shanghai Taurus chemical industry ltd produces, and the trade mark is 2246) 28kg, toluene 22kg, 1,4-dioxane 20kg, triethylamine 8.5kg.The intake valve of opening device feeds nitrogen protection.In chuck, feed cold water and steam, controlled temperature reacts between 35-40 ℃.At the uniform velocity drip POCl3 9kg in charging opening with 0.75mL/ minute speed again after one hour.React after 14 hours, add the reaction that is hydrolyzed of 12.5kg water in charging opening, control reaction temperature is to 60-70 ℃.Reacted 3 hours, to the reaction end.Steam toluene, filter and obtain product 2,2 '-methylene radical-two (4,6-di-t-butyl phenoxy) SULPHOSUCCINIC ACID ESTER filter cake, dry back is 31.2kg, with 2, the charging capacity meter of 2 '-methylene radical-two (4, the 6-di-t-butyl) phenol, yield is 97%.。Collect filtrating and reclaim triethylamine, obtain 8.14kg, the triethylamine recovery is 95.8%.
The preparation of organophosphate: with intermediate product 2,2 '-methylene radical-two (4,6-di-t-butyl phenoxy) SULPHOSUCCINIC ACID ESTER is dissolved in the mixed solution of salify solvent acetone and water, and the mass ratio of acetone and water is 4: 6; Organophosphate is 1: 30 with the ratio that becomes salt solvent, 30 weight % aqueous sodium hydroxide solutions are added described 2,2 '-methylene radical-two (4; 6-di-t-butyl phenoxy) SULPHOSUCCINIC ACID ESTER carries out salify neutralization, sodium hydroxide and 2,2 '-methylene radical-two (4; 6-di-t-butyl phenoxy) mol ratio of SULPHOSUCCINIC ACID ESTER is 1: 1, steams acetone, obtains white solid product; After the filtration, to pH=7-8, get product behind the heat drying with deionized water wash; Confirm as 2 through mass spectrum and infrared analysis, 2 '-methylene radical-two (4,6-di-t-butyl phenoxy) sodium phosphate.
Comparative Examples 1
Through preparing organophosphate with embodiment 3 identical methods, but the amount 12.5kg of employed water replaces with 180kg in hydrolysis reaction.Obtain product 2,2 '-methylene radical-two (4,6-di-t-butyl phenoxy) SULPHOSUCCINIC ACID ESTER 32.0kg.Collect filtrating and reclaim triethylamine, obtain 7.41kg, the triethylamine recovery is 87.2%.With intermediate product 2,2 '-methylene radical-two (4,6-di-t-butyl phenoxy) SULPHOSUCCINIC ACID ESTER continues to synthesize according to the preparation method of the organophosphate of embodiment 3, obtains 2,2 '-methylene radical-two (4,6-di-t-butyl phenoxy) sodium phosphate.
Table 1
From table 1, can find out, under the condition of the productive rate that does not influence organophosphate, according to the usage quantity of the process water of the embodiment of the invention, only be the 5%-10% of traditional technology amount of water.Improved the organic efficiency of acid binding agent, when acid binding agent is triethylamine, used the compound method after improving, organic efficiency can improve about 7-10%.Reduced the synthesizer discharged waste water.
Application examples
This application examples is used for explaining the application of nucleator in polymer processing.
Get Vestolen PP 7052 (trade mark K8303 that Yanshan Mountain branch office of China Petrochemical Industry produces) 100 weight parts; Get nucleator 0.1 weight part that embodiment 1-3 and Comparative Examples 1 make 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 1.
Table 2
| The nucleator that uses | Sample modulus in flexure GPa | Mist degree | Heat-drawn wire ℃ |
| Embodiment 1 | ?1.597 | 18.46 | 124.75 |
| Embodiment 2 | ?1.599 | 19.67 | 123.67 |
| Embodiment 3 | ?1.595 | 20.84 | 121.40 |
| Comparative Examples 1 | ?1.591 | 22.76 | 125.21 |
| Not with nucleator | ?1.324 | 38.87 | 104.50 |
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.
Hence one can see that; Optimization method disclosed by the invention is in the production of substituted diaryl phosphoric acid salt nucleator; Can avoid the waste of water resources, improve the organic efficiency of organic reagent in the reaction, reduce the quantity discharged of trade effluent; Reduce the intractability of trade effluent, be of value to environmental protection and produce remarkable social benefit and economic benefit; And 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 (10)
1. the compound method of an organophosphate is characterized in that, this method may further comprise the steps:
(1) under the phosphorus acylation reaction condition, the organic solvent solution of the substituted diaryl phenol shown in the formula (I) is carried out first with phosphorus esterification reagent contact in the presence of acid binding agent;
(2) under hydrolysising condition, the product after the win contact is carried out second with water contact, the consumption of said water is the 17-70 weight % of the substituted diaryl phenol shown in the formula (I),
Wherein, R
1, R
2, R
3And R
4Identical or inequality, represent C separately
1-C
6The straight or branched alkyl.
2. compound method according to claim 1, wherein, the consumption of said water is the 20-60 weight % of the substituted diaryl phenol shown in the formula (I).
3. compound method according to claim 1; Wherein, be 100 weight parts in the total amount of substituted diaryl phenol, organic solvent, acid binding agent, phosphorus esterification reagent and the water shown in the formula (I), the consumption of the substituted diaryl phenol shown in the formula (I) is the 25-35 weight part; The consumption of organic solvent is the 23-57 weight part; The consumption of acid binding agent is the 6-12 weight part, and the consumption of phosphorus esterification reagent is the 6-12 weight part, and the consumption of water is the 6-18 weight part.
4. compound method according to claim 1, wherein, R
1, R
2, R
3And R
4A kind of in n-propyl, sec.-propyl, normal-butyl, sec.-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, tert-pentyl or the neo-pentyl respectively does for oneself.
5. compound method according to claim 1, wherein, said organic solvent is selected from toluene or 1, at least a in the 4-dioxane.
6. compound method according to claim 1, wherein, said phosphorus esterification reagent is selected from one or more in phosphorus trichloride, the POCl3.
7. compound method according to claim 1, wherein, said phosphorus acylation reaction condition comprises that temperature of reaction is 30-50 ℃, the reaction times is 12-16 hour.
8. compound method according to claim 1, wherein, said hydrolysising condition comprises that temperature of reaction is 55-75 ℃, the reaction times is 2-4 hour.
9. the compound method of an organophosphate; This method comprises synthetic organophosphate, again with said organophosphate becoming in the presence of the salt solvent, contact with salt forming agent; It is characterized in that the method for synthetic said organophosphate is any described compound method among the claim 1-8.
10. compound method according to claim 9; Wherein, Said salt forming agent is a kind of in aluminum chloride, magnesium chloride, white lake and the sodium hydroxide, and said one-tenth salt solvent is an at least a mixture in water and the following material: acetone, ethanol, propyl alcohol, methyl alcohol.
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| CN110684049A (en) * | 2019-10-16 | 2020-01-14 | 山西省化工研究所（有限公司） | One-pot preparation method of bisphenol phosphate hydroxyl aluminum salt nucleating agent |
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| CN101302234A (en) * | 2008-06-27 | 2008-11-12 | 洛阳市中达化工有限公司 | Synthetic method of 2,2'-methano-bis (4,6-ditertbutyl phenol) phosphate |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110684049A (en) * | 2019-10-16 | 2020-01-14 | 山西省化工研究所（有限公司） | One-pot preparation method of bisphenol phosphate hydroxyl aluminum salt nucleating agent |
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