CN1687201A - Method for preparing superfine nucleator in organic phosphate class - Google Patents

Abstract

The present invention discloses an ultrafine organic phosphate nucleating agent and its preparation method. Said method includes the following steps: dissolving organic phosphate nucleating agent in organic solvent, adding surfactant, under the action of stirring adding water to the above-mentioned solution, then collecting the described ultrafine organic phosphate nucleating agent from the reaction product. Its average particle size is less than 0.3 micrometer.

Description

A kind of preparation method of superfine organic phosphate nucleating agent

technical field

The invention relates to a preparation method of an ultrafine organophosphate nucleating agent.

Background technique

Organophosphate nucleating agents have been widely used in the modification of polypropylene due to their advantages of non-toxic, odorless, and high heat resistance. However, due to the high melting point of this type of nucleating agent, it is insoluble and infusible at the processing temperature of polypropylene, resulting in poor dispersion in polypropylene, which affects the nucleation efficiency, resulting in an increase in usage and a large increase in cost. , thus limiting its wide application. And reducing the particle size of the nucleating agent can improve its dispersion in polypropylene, thereby increasing the nucleating efficiency.

Usually, the preparation of superfine organophosphate nucleating agent is by mechanical pulverization. Zhu Weiping, Wang Yaming and others reported in Chinese patent (CN1432594) that an alkyl metal phosphate nucleating agent with an average particle size of 0.5-100 um was prepared by ordinary pulverization. However, the nucleating agent prepared by a single crushing method has a large particle size and a wide particle size distribution. Takahashi Masayuki and Haruna Tohru of Japan Asahi Denka Co., Ltd. reported in the European patent (EP1209190) that a method combining ball milling and jet milling was used to prepare organophosphate nucleating agents. They first ground the crude nucleating agent in a jet mill for 0.5 hours, and then ground it in a ball mill for 2.5 hours, and finally obtained an organophosphate nucleating agent with an average particle size of 0.3um. Since this method needs to grind the raw materials in two different equipments, and the grinding time is long, the equipment investment is large, the energy consumption is high, and the output is not high.

Contents of the invention

The technical problem to be solved in the present invention is to disclose a preparation method of an ultrafine organophosphate nucleating agent, so as to overcome the above-mentioned defects in the prior art.

Technical concept of the present invention is such:

Dissolve the crude product of the organophosphate nucleating agent in an organic solvent, add a surfactant, and then add water under the action of stirring to precipitate it. Due to the existence of the surfactant, the particle size of the nucleating agent precipitated can be effectively controlled, thereby An ultrafine organic phosphate nucleating agent is obtained.

Technology of the present invention comprises the steps:

(1) the crude product of organophosphate nucleating agent is dissolved in organic solvent, adds tensio-active agent; The general structural formula of said organophosphate nucleating agent crude product is as follows:

Among them: R ₁ and R ₂ represent C ₁ -C ₁₂ alkyl, nitro, halogen, aryl;

R ₃ represents C ₁ -C ₄ alkyl, oxygen or sulfur;

M is an alkali metal or an alkaline earth metal, the preferred alkali metal is lithium, sodium or potassium, and the preferred alkaline earth metal is calcium, magnesium or barium;

n is 1 or 2;

The crude organophosphate nucleating agent can be prepared by the method disclosed in CN1358728, or a commercially available product;

Preferred organophosphate nucleating agents include 2,2'-methylene-bis(4,6-di-tert-butylphenyl)sodium phosphate, 2,2'-methylene-bis(4,6- Di-tert-butylphenyl) lithium phosphate, 2,2'-methylene-bis(4,6-di-tert-butylphenyl)potassium phosphate, 2,2'-methylene-bis(4,-di Calcium tert-butylphenyl)phosphate, magnesium 2,2'-methylene-bis(4,6-di-tert-butylphenyl)phosphate.

Said organic solvent is selected from one or a mixture of methanol, ethanol, propanol, petroleum ether, butanol, tetrahydrofuran, dimethylformamide or acetone;

Said surfactant is selected from sodium dodecylsulfate, sodium dodecylsulfonate, sodium dodecylbenzenesulfonate, octadecyltrimethylammonium chloride, octadecyltrimethyl One or a mixture of ammonium bromide, cetyltrimethylammonium chloride, cetyltrimethylammonium bromide, polyethylene glycol or fatty polyoxyethylene ether;

Said fatty polyoxyethylene ether is preferably polyoxyethylene octylphenyl ether or polyoxyethylene nonylphenyl ether;

The amount of surfactant is 0.01% to 5% of the total weight of the system, preferably 0.1% to 3%;

(2) Under the action of stirring, water is added to the solution obtained in step (1), so that the organophosphate nucleating agent is precipitated, and then the superfine powder is collected from the product of step (2) by conventional methods. Organic phosphate nucleating agent, the longitudinal average particle size is 0.1-0.3um;

The volume ratio of water and organic solvent is 1:2～10:1, preferably 1:1～4:1;

The precipitation temperature is 0°C to 80°C, preferably 10°C to 40°C;

The precipitation time is 5min~120min, preferably 10min~60min;

Compared with the prior art, the process of the present invention has the advantages of high output, low equipment investment and energy saving. Since the equipment required in this process can utilize the complete set of equipment for synthesizing organophosphate nucleating agents, there is basically no need to add new equipment. At the same time, compared with the mechanical crushing equipment, the motor power of the reactor is much smaller than that of the mechanical crushing equipment, so energy can be greatly saved. The invention can obtain superfine organophosphate nucleating agent easily and easily, and has industrial application prospect.

Detailed ways

Example 1

Add 20ml of methanol, 5g of 2,2'-methylene-bis(4,6-di-tert-butylphenyl)sodium phosphate, 0.6 g polyoxyethylene octylphenyl ether, stirred, the flask was placed in a constant temperature water bath at 20°C, then 40ml of water was added dropwise, stirred for 30min, suction filtered, and the filter cake was dried at 80°C for 24hr to obtain 4.6g of white powder. The melting point is higher than 400°C, the yield is 92%, and the longitudinal average diameter is 0.15um.

Example 2

Add 20ml of methanol, 5g of 2,2'-methylene-bis(4,6-di-tert-butylphenyl)sodium phosphate, 0.6 g sodium lauryl sulfate, stirred, the flask was placed in a constant temperature water bath at 20°C, then 40ml of water was added dropwise, stirred for 30min, filtered with suction, and the filter cake was dried at 80°C for 24hr to obtain 4.6g of white powder. The melting point is higher than 400°C, the yield is 92%, and the longitudinal average diameter is 0.25um.

Example 3

Add 20ml of methanol, 5g of 2,2'-methylene-bis(4,6-di-tert-butylphenyl) calcium phosphate, 0.6 g polyoxyethylene octylphenyl ether, stirred, the flask was placed in a constant temperature water bath at 20°C, then 40ml of water was added dropwise, stirred for 30min, suction filtered, and the filter cake was dried at 80°C for 24hr to obtain 4.6g of white powder. The melting point is greater than 400°C, the yield is 92%, and the longitudinal average diameter is 0.28um.

Claims (8)

1. the preparation method of a superfine nucleator in organic phosphate class is characterized in that, comprises the steps:

(1) with the dissolving crude product of nucleator in organic phosphate class in organic solvent, add tensio-active agent; The general structure of said nucleator in organic phosphate class crude product is as follows:

Wherein: R ₁, R ₂Represent C ₁-C ₁₂Alkyl, nitro, halogen, aryl;

R ₃Represent C ₁-C ₄Alkyl, oxygen or sulphur;

M is basic metal or alkaline-earth metal, and n is 1 or 2;

(2) under the effect of stirring, water is joined in the solution of step (1) gained, machine phosphoric acid salt nucleator is separated out, adopt ordinary method from the product of step (2), to collect said superfine nucleator in organic phosphate class then.

2. method according to claim 1 is characterized in that, basic metal is lithium, sodium or potassium, and alkaline-earth metal is calcium, magnesium or barium.

3. method according to claim 1 is characterized in that, said organic solvent is selected from a kind of or mixture in methyl alcohol, ethanol, propyl alcohol, sherwood oil, butanols, tetrahydrofuran (THF), dimethyl formamide or the acetone.

4. method according to claim 1, it is characterized in that said tensio-active agent is selected from a kind of or mixture in sodium lauryl sulphate, sodium laurylsulfonate, Sodium dodecylbenzene sulfonate, octadecyl trimethyl ammonium chloride, octadecyl trimethylammonium bromide, palmityl trimethyl ammonium chloride, cetyl trimethylammonium bromide, polyoxyethylene glycol or the fats Soxylat A 25-7;

Said fats Soxylat A 25-7 is selected from polyoxyethylene octyl phenyl ether or polyoxyethylene nonylplenyl ether.

5. method according to claim 1 is characterized in that, the consumption of tensio-active agent is 0.01%～5% of a system gross weight.

6. method according to claim 1 is characterized in that, water is 1: 2～10: 1 with the volume of organic solvent ratio, and separating out temperature is 0 ℃～80 ℃, and the time of separating out is 5min～120min.

7. according to each described method of claim 1～5, it is characterized in that preferred nucleator in organic phosphate class comprises 2,2 '-methylene radical-two (4, the 6-di-tert-butyl-phenyl) sodium phosphate, 2,2 '-methylene radical-two (4, the 6-di-tert-butyl-phenyl) Trilithium phosphate, 2,2 '-methylene radical-two (4, the 6-di-tert-butyl-phenyl) potassiumphosphate, 2,2 '-methylene radical-two (4 ,-di-tert-butyl-phenyl) calcium phosphate, 2,2 '-methylene radical-two (4, the 6-di-tert-butyl-phenyl) trimagnesium phosphate.

8. method according to claim 7 is characterized in that, vertical median size of superfine nucleator in organic phosphate class is 0.1～0.3um.