CN101955430B - Method for producing antioxygen 1076 through noncrystalline method - Google Patents

Abstract

The invention relates to a method for producing an antioxygen 1076 through a noncrystalline method, comprising the following steps of: sequentially adding beta (3,5 di-tertiary-butyl 4-hydroxy phenyl) methyl propionate, octodecyl alcohol and a catalyst to a reaction kettle; displacing nitrogen, and vacuumizing; keeping at air pressure less than -0.1 MPa; heating to 110 DEG C; starting a stirring paddle, and controlling the number of turns to 300 turns/minute; uniformly heating for 2 hours to reach 165 DEG C; then uniformly heating for 2 hours to reach 180 DEG C; reducing the temperature to about 120 DEG C; adding glacial acetic acid in vacuum to carry out neutralization; regulating a pH value to 7; keeping the vacuum at 0.5-1 mmHg, and simultaneously heating to 195 DEG C; controlling the number of turns to about 700 turns/minute; depriving excess beta (3,5 di-tertiary-butyl 4-hydroxy phenyl) methyl propionate for about 2 hours; carrying out heat filtration on a product molten solution; and shifting to a constant-temperature sheeting device to carry out uniform dripping sheeting. The invention has the advantages of simplified process, short production period and high productivity.

Description

Noncrystalline method is produced the antioxidant 1076 method

Technical field

The invention belongs to the field of chemical synthesis, relate to a kind of method that adopts noncrystalline method to produce antioxidant 1076 particularly.

Background technology

Antioxidant 1076, chemical name are β-(3,5 di-t-butyl 4-phenylor) propionic acid octadecanol ester.Be that a kind of consistency is good, antioxygen usefulness is high, does not pollute, and not painted, volatility is little, one of water-fast extractive good phenolic antioxidant.The good discoloration that light and heat causes that prevents is arranged, better heat-resisting and water-fast extraction ability are arranged.Thereby be a kind of oxidation inhibitor that is widely used in Vilaterm, Vestolen PP 7052, PS, ABS resin, SE, nylon, polyester, urethane, cellulosics and various rubber.

But, in the existing working method, mainly adopt crystallization process.Because the solvability of antioxidant 1076 in solvent is little, solubleness is on the low side, so required quantity of solvent increases, the recovered solvent amount also increases, and then energy consumption is increased greatly, and the use of a large amount of organic solvents, and environment is polluted.In addition, because the melting range of antioxidant 1076 between 49～54 ℃, so just makes in the production process, drying is difficulty relatively, and processing requirement is higher, and time of drying is longer, and energy consumption is big.

Summary of the invention

In order to address the above problem, the purpose of this invention is to provide a kind of method that adopts noncrystalline method to produce antioxidant 1076.This method has overcome the problems referred to above of ordinary method, use this kind method can produce at short notice have the purity height, antioxidant 1076 that productive rate is high.Compare crystallization processes, easy and simple to handle, technology is oversimplified, and is with short production cycle.

To achieve these goals, the technical scheme that the present invention adopts is: a kind of noncrystalline method is produced the method for antioxidant 1076, comprises the steps:

1) batching: 50～55 parts of methyl propionates of β (3,5 di-t-butyls, 4 monohydroxy phenyl), 40～50 parts of stearyl alcohol, 0.3～0.6 part of catalyzer, 0.2～0.8 part in Glacial acetic acid min. 99.5;

2) change material: in the reaction kettle of sealing, drop into β (3 successively; 5 di-t-butyls, 4 monohydroxy phenyl) methyl propionate, stearyl alcohol and catalyzer, with nitrogen replacement and vacuumize, make vacuum tightness remain on＜-0.1Mpa; Temperature increasing for melting materials; When temperature rises to 105～115 ℃, open stirring rake, the control revolution is at 300 rev/mins;

3) minimum living: continue to heat up, temperature is evenly risen to 163～167 ℃ with 2 hours;

4) high guarantor: continue to heat up, temperature is evenly risen to 178～182 ℃ with 2 hours;

5) neutralization: be cooled to about 118～122 ℃, the adding Glacial acetic acid min. 99.5 neutralizes under the vacuum state, closes vacuum pump after 5 minutes, closes stirring rake after 15 minutes, adjust pH to 6.5～7.5;

6) take off ester: the open vacuum pump, make vacuum tightness remain on 0.5～1mmHg, simultaneously temperature is risen to 190～200 ℃; And the unlatching stirring rake, improve revolution, be controlled at about 700 rev/mins; Remove excessive β (3; 5 di-t-butyls, 4 monohydroxy phenyl) methyl propionate, the time is about 2 hours, gets title product.

Described noncrystalline method is produced the method for antioxidant 1076, also comprises

7) knot sheet: with title product liquid heat filtering, drip and to be spread across on 5～10 ℃ of homothermic knot sheet devices, controlled filter drips 1～2 droplet/minute of the speed of spilling, and 3～7 meters/minute of the travelling speed of knot sheet device are evenly dripped and spilt the knot sheet.

Noncrystalline method is produced the method for antioxidant 1076, and described catalyzer is sodium methylate, zinc octoate, Lithamide or aluminum isopropylate.Certainly, other can directly or indirectly isolating transesterification catalyst can be as catalyzer from product.

The invention has the beneficial effects as follows: technology of the present invention is simple, and one pot reaction can obtain finished product, drips the speed of spilling and temperature and the travelling speed of tying the sheet device through controlled filter, makes the product rapid shaping.The main content of the antioxidant 1076 finished fluid of producing through method of the present invention reaches more than 99%; Purity is high, good colors, and transmittance is more than 98%, and melting range is between 52～54 ℃; Yield of product reaches more than 99%, and each item index all reaches foreign standard.

Embodiment

Embodiment 1

1) batching: β (3,5 di-t-butyls, 4 monohydroxy phenyl) methyl propionate 53.9g

Stearyl alcohol 45g

Sodium methylate 0.45g

Glacial acetic acid min. 99.5 0.5g

2) change material: in the reaction kettle of sealing, drop into β (3,5 di-t-butyls, 4 monohydroxy phenyl) methyl propionate, stearyl alcohol and sodium methylate successively, with nitrogen replacement 3 times; And vacuumize; Make vacuum tightness remain on＜-0.1Mpa, temperature increasing for melting materials is when temperature rises to 100 ℃ of left and right sides; Material wholeization is most, and small bubbles occur; When temperature rose to 110 ℃ of left and right sides, great amount of bubbles appearred.Open stirring rake this moment, revolution is controlled at 300 to be changeed;

3) minimum living: continue to heat up, temperature is evenly risen to about 165 ℃ with 2 hours;

4) high guarantor: continue to heat up, with 2 hours temperature is evenly risen to about 180 ℃, reaction finishes;

5) neutralization: when being cooled to about 120 ℃ of left and right sides, suction Glacial acetic acid min. 99.5 under the vacuum state (forbidding in the operating process in the air admission reaction kettle) neutralizes; Close vacuum pump after 5 minutes; Continue neutralization, close stirring rake after 15 minutes, dip in the reaction solution that takes a morsel with glass stick; Drop on the pH test paper, be about 7 to the pH value.Stop neutralization, get an amount of reaction solution and carry out liquid-phase chromatographic analysis, measure the transformation efficiency of 1076 reaction solutions.

6) take off ester: the open vacuum pump, make vacuum tightness remain on 0.5～1mmHg, simultaneously temperature is risen to about 195 ℃; And the unlatching stirring rake, improve revolution, be controlled at about 700 rev/mins; Begin to remove excessive β (3,5 di-t-butyls, 4 monohydroxy phenyl) methyl propionate, the time is about 2 hours; Get title product, make the content of β in the title product (3,5 di-t-butyls, 4 monohydroxy phenyl) methyl propionate low as much as possible.

7) knot sheet: will take off β (3; 5 di-t-butyls, 4 monohydroxy phenyl) title product of methyl propionate, the liquid heat filtering drips and to be spread across on about 5 ℃ of homothermic knot sheet device; Controlled filter drips 1～2 droplet/minute of the speed of spilling; 5 meters/minute of the travelling speed of knot sheet device are evenly dripped and are spilt the knot sheet, get antioxidant 1076 knot sheet.

The result: the main content that the knot sheet is measured the antioxidant 1076 finished product is 99.5%, and fusing point is 53.2 ℃, and transmittance is 98.6%.Productive rate is 99.2%.The product National standard.

Embodiment 2

Method is with embodiment 1, and the ratio of different just batchings is different.

Batching: β (3,5 di-t-butyls, 4 monohydroxy phenyl) methyl propionate 50.6g

Stearyl alcohol 40.6g

Zinc octoate 0.32g

Glacial acetic acid min. 99.5 0.22g

The result: the main content that the knot sheet is measured the antioxidant 1076 finished product is 99.3%, and fusing point is 52.4 ℃, and transmittance is 98.4%.Productive rate is 99.1%.The product National standard.

Embodiment 3

Method is with embodiment 1, and different is the ratio of batching

Batching: β (3,5 di-t-butyls, 4 monohydroxy phenyl) methyl propionate 54.8g

Stearyl alcohol 48.7g

Aluminum isopropylate 0.55g

Glacial acetic acid min. 99.5 0.76g

The result: the main content that the knot sheet is measured the antioxidant 1076 finished product is 99.5%, and fusing point is 53.7 ℃, and transmittance is 98.6%.Productive rate is 99.4%.The product National standard.

Claims (1)

1. the method that noncrystalline method is produced antioxidant 1076 is characterized in that comprising the steps:

1) batching: β-(3, the 5-di-tert-butyl-hydroxy phenyl) 50～55 parts of methyl propionates, 40～50 parts of stearyl alcohol, 0.3～0.6 part of the catalyzer that is selected from sodium methylate, zinc octoate, Lithamide or aluminum isopropylate, 0.2～0.8 part in Glacial acetic acid min. 99.5;

2) change material: in the reaction kettle of sealing, drop into β-(3 successively; The 5-di-tert-butyl-hydroxy phenyl) methyl propionate, stearyl alcohol and catalyzer, with nitrogen replacement and vacuumize, make vacuum tightness remain on＜-0.1Mpa; Temperature increasing for melting materials; When temperature rises to 105～115 ℃, open stirring rake, the control revolution is at 300 rev/mins;

3) minimum living: continue to heat up, temperature is evenly risen to 163～167 ℃ with 2 hours;

4) high guarantor: continue to heat up, temperature is evenly risen to 178～182 ℃ with 2 hours;

5) neutralization: be cooled to 118～122 ℃, the adding Glacial acetic acid min. 99.5 neutralizes under the vacuum state, closes vacuum pump after 5 minutes, closes stirring rake after 15 minutes, adjust pH to 6.5～7.5;

6) take off ester: the open vacuum pump, make vacuum tightness remain on 0.5～1mmHg, simultaneously temperature is risen to 190～200 ℃; And the unlatching stirring rake, improve revolution, be controlled at about 700 rev/mins; Remove excessive β-(3; The 5-di-tert-butyl-hydroxy phenyl) methyl propionate, the time is about 2 hours, gets title product;

7) knot sheet: with title product liquid heat filtering, drip and to be spread across on 5～10 ℃ of homothermic knot sheet devices, controlled filter drips 1～2 droplet/minute of the speed of spilling, and 3～7 meters/minute of the travelling speed of knot sheet device are evenly dripped and spilt the knot sheet.