阅读说明：本技术 一种双酚磷酸酯羟基铝盐成核剂的一锅式制备方法 (One-pot preparation method of bisphenol phosphate hydroxyl aluminum salt nucleating agent ) 是由 王克智 张建军 毛晨曦 李向阳 林福华 李训刚 王晶 王冉 刘凤玉 王晨 王凯 于 2019-10-16 设计创作，主要内容包括：本发明涉及聚合物的成核剂领域,是有关双酚磷酸酯羟基铝盐成核剂的制备方法,该双酚磷酸酯羟基铝盐按下述制备方法得到：首先,2,4-二叔丁基苯酚(单酚)、多聚甲醛、催化剂和乳化剂在有机溶剂和水的混合溶剂中反应制备双酚,反应结束后静置分层除水,然后加热回流溶解双酚的有机溶剂,经分水器除去有机溶剂中残留的水；其次,在双酚的有机溶剂中加入醇铝加热反应,蒸馏出副产物醇；最后,加水蒸馏副产物醇和有机溶剂,蒸完溶剂后冷却、过滤并干燥后的到产品双酚磷酸酯羟基铝盐。本发明制备方法简化了生产工艺,提高了生产效率,缩短了反应时间,提高了产品质量,并且大大降低了双酚生产过程中的废水量,而且双酚生产中的废水不经处理直接可以回用,生产工艺比较环保。(The invention relates to the field of nucleating agents of polymers, in particular to a preparation method of a bisphenol phosphate hydroxyl aluminum salt nucleating agent, wherein the bisphenol phosphate hydroxyl aluminum salt is prepared by the following preparation method: firstly, reacting 2, 4-di-tert-butylphenol (monophenol), paraformaldehyde, a catalyst and an emulsifier in a mixed solvent of an organic solvent and water to prepare bisphenol, standing for layering and dewatering after the reaction is finished, heating and refluxing the organic solvent for dissolving the bisphenol, and removing residual water in the organic solvent through a water separator; secondly, adding aluminum alkoxide into an organic solvent of bisphenol, heating for reaction, and distilling out a byproduct alcohol; and finally, adding water to distill the byproduct alcohol and the organic solvent, cooling, filtering and drying after the solvent is distilled off to obtain the product bisphenol phosphate hydroxyl aluminum salt. The preparation method of the invention simplifies the production process, improves the production efficiency, shortens the reaction time, improves the product quality, greatly reduces the wastewater amount in the bisphenol production process, can directly recycle the wastewater in the bisphenol production without treatment, and has more environment-friendly production process.)

1. A one-pot preparation method of a bisphenol phosphate hydroxyl aluminum salt nucleating agent is characterized by comprising the following steps:

(1) reacting 2, 4-di-tert-butylphenol (monophenol), paraformaldehyde, a catalyst and an emulsifier in a mixed solvent of an organic solvent and water to prepare bisphenol, standing for layering and dewatering after the reaction is finished, and heating to flow back to a water separator to remove residual water in the organic solvent;

(2) adding an acid-attaching agent into an organic solvent containing bisphenol, dropwise adding phosphorus oxychloride, heating for reaction to obtain an intermediate 1, washing with water to remove a byproduct, namely organic hydrochloride, heating, flowing back through a water separator to remove residual water in the organic solvent;

(3) adding aluminum alkoxide into an organic solvent containing bisphenol, heating for reaction, and distilling out a byproduct alcohol to obtain an intermediate 2;

(4) adding water to hydrolyze the intermediate 2, distilling by-product alcohol and organic solvent, cooling, filtering and drying after the solvent is distilled off to obtain the product bisphenol phosphate hydroxyl aluminum salt.

2. The method of claim 1 wherein said bisphenol phosphate hydroxy aluminum salt nucleating agent is [ bis [2, 2' -methylenebis (4, 6-di-t-butylphenoxy) phosphate ] hydroxy aluminum salt) ].

3. The method of claim 1, wherein the reaction is completed and the bisphenol product is dissolved in organic solvent and separated from water, and the water containing the catalyst and the emulsifier is recovered and reused for bisphenol production.

4. The process of claim 1 wherein intermediate 1 is 2, 2' -methylenebis (4, 6-di-tert-butylphenoxy) phosphate.

5. The method according to claim 1, wherein said aluminum alkoxide [ AL (OR)₃]Is low-carbon aluminum alkoxide consisting of 1-4 carbon atoms.

6. The method of claim 5, wherein said byproduct alcohol is a lower alcohol having 1 to 4 carbon atoms corresponding to said aluminum alkoxide.

7. The method of claim 1, wherein the intermediate 2 is bis [2, 2' -methylenebis (4, 6-di-tert-butylphenoxy) phosphate ] alcanoyl aluminum salt.

8. The method according to claim 1, wherein the alcohol group is a corresponding aluminum alkoxide [ AL (OR)₃]A lower alcohol having 1 to 4 carbon atoms.

9. A process for producing 2, 2' -methylenebis (4, 6-di-t-butylphenoxy) phosphate, which comprises the steps (1) to (2) of claim 1.

10. A process for producing an aluminum bis [2, 2' -methylenebis (4, 6-di-t-butylphenoxy) phosphate ] alcoholate salt, characterized by carrying out the production by the steps (1) to (3) in claim 1.

Technical Field

The invention relates to the technical field of polymer nucleating agents, in particular to a one-pot preparation method of a bisphenol phosphate hydroxyl aluminum salt nucleating agent.

Background

Compared with the traditional alpha crystal form nucleating agent, the aryl phosphate polypropylene alpha crystal form nucleating agent can endow polypropylene resin with good rigidity, transparency, surface gloss and heat distortion resistance under relatively low concentration. Chinese patents CN201610873241.6, CN201110151387.7 and CN20111051413.6 disclose processes for synthesizing aryl phosphate salts.

The preparation process of bisphenol phosphate hydroxyl aluminum salt in the prior art comprises the following steps: firstly, reacting 2, 4-di-tert-butylphenol (monophenol), paraformaldehyde, a catalyst and an emulsifier in water to prepare bisphenol; secondly, reacting bisphenol, phosphorus oxychloride and an acid-adding agent in a solvent such as toluene to prepare bisphenol phosphate; thirdly, adding bisphenol phosphate into a solvent for neutralization to prepare bisphenol phosphate sodium salt; and fourthly, the bisphenol phosphate sodium salt and aluminum salt undergo double decomposition reaction in the aqueous solution to prepare the bisphenol phosphate hydroxyl aluminum salt product.

Disclosure of Invention

The invention provides a preparation method of a bisphenol phosphate hydroxyl aluminum salt nucleating agent, which overcomes the defects of the prior art, and bisphenol phosphate can be prepared from monophenol, bisphenol phosphate can be prepared from bisphenol, and bisphenol phosphate hydroxyl aluminum salt can be prepared from bisphenol phosphate by a one-pot method for continuous reaction.

A one-pot preparation method of a bisphenol phosphate hydroxyl aluminum salt nucleating agent comprises the following steps:

(1) reacting 2, 4-di-tert-butylphenol (monophenol), paraformaldehyde, a catalyst and an emulsifier in a mixed solvent of an organic solvent and water to prepare bisphenol, standing for layering and dewatering after the reaction is finished, and heating to flow back to a water separator to remove residual water in the organic solvent;

(2) adding an acid-attaching agent into an organic solvent containing bisphenol, dropwise adding phosphorus oxychloride, heating for reaction to obtain an intermediate 1, washing with water to remove a byproduct, namely organic hydrochloride, heating, flowing back through a water separator to remove residual water in the organic solvent;

(3) adding aluminum alkoxide into an organic solvent containing bisphenol, heating for reaction, and distilling out a byproduct alcohol to obtain an intermediate 2;

(4) adding water to hydrolyze the intermediate 2, distilling by-product alcohol and organic solvent, cooling, filtering and drying after the solvent is distilled off to obtain the product bisphenol phosphate hydroxyl aluminum salt.

The bisphenol phosphate hydroxyl aluminum salt nucleating agent is [ bis [2, 2' -methylene bis (4, 6-di-tert-butyl phenoxy) phosphate ] hydroxyl aluminum salt) ].

And after the reaction is finished, standing, layering and dewatering, namely dissolving the bisphenol product in an organic solvent and layering with water after the reaction is finished, and recovering water containing the catalyst and the emulsifier for preparing the bisphenol.

The water remaining in the organic solvent is removed by the water separator, namely the water which can not be completely removed by simple layering is heated and distilled in the water separator and the solvent is layered and then recycled.

The intermediate 1 is 2, 2' -methylene bis (4, 6-di-tert-butyl phenoxy) phosphate.

The aluminum alkoxide [ AL (OR)₃]Is low-carbon aluminum alkoxide consisting of 1-4 carbon atoms.

The byproduct alcohol refers to a low-carbon alcohol consisting of 1-4 carbon atoms corresponding to the aluminum alkoxide.

The intermediate 2 is bis [2, 2' -methylene bis (4, 6-di-tert-butyl phenoxy) phosphate ] alcohol-based aluminum salt.

The alcohol group is corresponding aluminium alkoxide [ AL (OR)₃]A lower alcohol having 1 to 4 carbon atoms.

Said intermediates 1 and 2 are prepared according to the process of the invention.

Has the advantages that:

the preparation method of the invention simplifies the production process, improves the production efficiency, shortens the reaction time, improves the product quality, greatly reduces the wastewater amount in the bisphenol production process, can directly recycle the wastewater in the bisphenol production without treatment, and has more environment-friendly production process.

Drawings

FIG. 1 shows the infrared detection spectra of the products prepared by the two methods of the present invention.

Detailed Description

Comparative example:

(1) 32 g of 2, 4-di-tert-butylphenol, 2.75 g of paraformaldehyde, 0.14 g of emulsifier, 0.65 g of catalyst and 85 ml of water are put into a reaction kettle to be heated and refluxed for reaction for 3 hours. The temperature is reduced and the bisphenol is filtered to obtain 32.0 g.

(2) Adding the 32.0 g of bisphenol, 31.2 g of acid-attaching agent and 110 ml of toluene into a reaction bottle, stirring at room temperature, dropwise adding 20.8 g of phosphorus oxychloride, heating for reflux reaction for 6 hours after dropwise adding, cooling, adding water to wash the organic hydrochloride, adding water to distill and recover toluene, cooling after distilling, and performing suction filtration to obtain 36 g of bisphenol phosphate.

(3) Adding 3.34 g of sodium hydroxide and 100 ml of water into a reaction bottle, adding 36 g of bisphenol phosphate while stirring, heating to 80 ℃, keeping reacting for two hours, filtering, and drying to obtain bisphenol phosphate sodium salt.

(4) Adding the sodium salt into 170 ml of alcohol-water mixed solution, heating to about 60 ℃, dropwise adding 8.4 g of aluminum trichloride and 10 ml of water mixed solution into a reaction kettle after the sodium salt is completely dissolved, reacting for two hours, then adding 1.56 g of caustic soda flakes into the kettle, reacting for half an hour, discharging, filtering, and drying to obtain the bisphenol phosphate hydroxyl aluminum salt.

The product is as follows: white powder, 34.58 g, yield: 92.10 percent