WO2015032033A1

WO2015032033A1 - Composition providing heat stability for polymer and application thereof

Info

Publication number: WO2015032033A1
Application number: PCT/CN2013/082888
Authority: WO
Inventors: 李化毅; 张瑜; 王柯; 胡友良
Original assignee: 中国科学院化学研究所
Priority date: 2013-09-03
Filing date: 2013-09-03
Publication date: 2015-03-12

Abstract

Provided is an antioxidant composition comprising: (1) a hindered phenol, (2) a phosphite ester or thioester, (3) an acid scavenger, (4) a sulphite or hydrosulphite or sulphide, wherein the weight ratio of the raw materials is as follows: hindered phenol : phosphite ester or thioester : acid scavenger : sulphite or hydrosulphite or sulphide= 1 : 1-4 : 0.5-2 : 0.5-3. Provided is the use of the composition as an antioxidant in a polymer resin. The composition can lower the melt index of a polyolefin, eliminate the intermediate products of quinoid compounds, and decrease the yellow index of a polyolefin.

Description

Description A composition for providing thermal stability to a polymer and its application

The present invention relates to a composition, and in particular to a composition that provides thermal stability to a polymer. Background technique

During thermal processing and long-term use, the polymer is exposed to light and heat, and is oxidized by oxygen in the air. The mechanical properties of the polymer are lost and the appearance becomes unattractive. It is therefore necessary to add an antioxidant to increase the thermal stability of the polymer.

Hindered phenolic antioxidants are widely used in polymers to reduce thermal oxygen aging in polymer processing, reduce performance degradation in polymer use, and extend polymer life. Commonly used hindered phenolic antioxidants are: tetra-[p-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid] pentaerythritol (trade name Antioxidant 1010), 4-hydroxyphenylpropane Octadecyl alcohol ester (trade name Antioxidant 1076), 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene Antioxidant 1330).

Antioxidant 1010 has high molecular weight, good compatibility with plastic materials, and excellent anti-oxidation effect, and has become one of the most consumed products in plastic antioxidants. The antioxidant 1076 can be used as an antioxidant for polyethylene, polypropylene, polyvinyl chloride, fiber plastic, and various rubbers. It has good compatibility, high anti-oxidation performance, no coloring, no pollution, washing resistance, and low volatility. The intermediate (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate of antioxidant 1010 is also an excellent antioxidant. It has good anti-aging function for various plastics such as polyethylene, polypropylene and other plastics, animal and vegetable oils and rubber, and it is also an intermediate for producing high-grade antioxidants such as antioxidants 1076, 259, 1098, 3125. . Antioxidant 1010 and 1076 consumption accounts for about 40% of the total antioxidant consumption.

Therefore, there is a need for a safe composition which lowers the polyolefin melt index, eliminates the intermediate product of terpenoids, and lowers the yellowness index of the polyolefin. Summary of the invention

In order to solve the above problems, it is an object of the present invention to provide a composition capable of providing excellent thermal stability to a polymer.

The technical solution adopted by the present invention is as follows:

An antioxidant composition comprising:

(1) hindered phenol;

(2) a phosphite or a thioester;

(3) an acid scavenger;

(4) sulfite or bisulfite or sulfide;

Among them, the quality of each raw material is as follows: hindered phenol: phosphite or thioester: acid scavenger: sulfite (or hydrogen sulfite or stone ghost) = 1: 1-4: 0.5-2: 0.5-3.

According to the present invention, the mass ratio of the above four components is preferably 1: 1.5-3.5: 0.8-1.5: 1-2.75, more preferably the mass ratio of the above four components is 1: 2-3: 1- 1.2: 1.25-2.

The compositions of the present invention provide thermal stability to the polymer.

According to the invention, the hindered from 2,4-di-tert-butylphenol, 2,6-di-tert-butylphenol, 2,4,6-tri-tert-butylphenol, tetra[P-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid] pentaerythritol ester, P-(3,5-di-tert-butyl- 4-hydroxyphenyl)propionic acid n-octadecyl alcohol, or 1,3,5-trimethyl-2,4,6- =-(3,5-di-tert-butyl-4-hydroxybenzyl) Benzene, 2,6-di-tert-butylphenol, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanuric acid, triethylene glycol-bis(3-tert-butyl) 4-hydroxy-5-mercaptophenyl) propionate, 4,4,-thiobis(6-tert-butyl-3-nonylphenol), β-(3,5-di-tert-butyl) -4-hydroxyphenyl) isooctyl propionate, hydrazine, hydrazine, -bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl) hexamethylenediamine, 2,2 One or a combination of two or more of - thiodiethyl bis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)acrylic acid). Preferably, the hindered phenol is selected from the group consisting of 2,6-di-tert-butylphenol, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isoacid, triethylene glycol- Bis(3-tert-butyl-4-hydroxy-5-mercaptophenyl)propionate, 4,4,-thiobis(6-tert-butyl-3-nonylphenol), (3- (3) , 5-di-tert-butyl-4-hydroxyphenyl)propionic acid n-decyl alcohol ester or tetrakis[(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid] pentaerythritol ester, more preferably It is blocked by tetrakis[(3-(tert-butyl-4-hydroxyphenyl)propanoic acid] pentaerythritol ester.

According to the invention, the phosphite is selected from three [2.4-di-tert-butylphenyl] phosphites, or bis(2,4-di-tert-butylphenylhydrazine) pentaerythritol diphosphite, bis (2) - mercapto-4,6-bis(1,1'-diamidinoethyl)phenol)ethyl phosphate, tetrakis(2,4-di-tert-butylphenyl-4,4-biphenyl) double A mixture of one or both of phosphate, 2,2,-ethylenebis(4,6-di-tert-butylphenyl)fluorophosphite. Preferably, the phosphite is tris[2.4-di-tert-butylphenyl]phosphite or bis(2,4-di-tert-butylphenol)pentaerythritol diphosphite.

According to the present invention, the thioester is selected from the group consisting of didodecyl thiodipropionate, dioctadecyl thiodipropionate, ditetradecyl thiodipropionate, and thiodipropionic acid. Kind or two mixtures.

According to the present invention, the acid scavenger is selected from the group consisting of calcium stearate, zinc stearate, zinc oxide, and hard One or a mixture of two or more of magnesium oleate or hydrotalcite.

According to the present invention, the sulfite or bisulfite or sulfide is selected from the group consisting of sodium sulfite, magnesium sulfite, sulfite clock, calcium sulfite, sodium hydrogen sulfite, potassium hydrogen sulfite, potassium sulfide, sodium sulfide, One or a mixture of two or more of magnesium sulfide and calcium sulfide. Calcium sulfite or sodium sulfite is preferred. The present invention also provides a polymer composition comprising an antioxidant, wherein the antioxidant is as described above. According to the invention, the polymer refers to a polyolefin, a polyester, a polyfurfural, a polyurethane, a polyamide, a polycarbonate or a polyamide. Preferably, the polymer is a polyolefin, more preferably polyethylene or polypropylene.

According to the invention, the average particle size of said sulfite and bisulfite or sulfide

(D[4.3]) is in the range of 2-30 microns. According to the present invention, the composition further contains at least one selected from the group consisting of a plasticizer, an acid scavenger, a nucleating agent, an antibacterial agent, a flame retardant, a light stabilizer, an antistatic agent, a foaming agent or a coloring pigment. .

The present invention also provides a thermally stable polymer mixture, characterized in that the mixture comprises a polymer resin and the composition of any of the above.

According to the invention, the polymer is selected from the group consisting of polyolefins, polyesters, polyacetals, polyurethanes, polyamides, polycarbonates or polyamides.

According to the present invention, the amount of the composition added in the processing of the polymer mixture is

800-3000ppm. The invention also provides the use of the above composition, characterized in that it is used as an antioxidant.

According to the present invention, the composition is used as an antioxidant in a polymer resin.

According to the present invention, the composition as an antioxidant is added in the amount of 800 to 3000 ppm in the processing of the polymer. In particular, the composition is added to the polymer in an amount of from 800 to 2500 ppm. The compositions of the present invention can be added to the polymer in powder form. Can also be granulated The formed particles are added to the polyolefin.

The hindered phenol antioxidant acts primarily as a free radical scavenger. When reacting with a free radical, the hindered phenol transfers hydrogen onto the generated free radical to form a non-radical compound, and the phenol becomes a stable hindered phenoxide, which no longer takes hydrogen from the polymer. atom. That is, the hydrogen removed from the hindered phenol can prevent the initiation reaction occurring on the polymer backbone. However, the structure of the hindered phenol allows the oxy radical to rearrange to the carbon atom to form a ruthenium-like structure. The quinone compound has a chromophoric group which increases the yellowness index of the polyolefin and affects the appearance of the polyolefin product.

Both phosphite and thioester antioxidants reduce the hydroperoxide to a stable alcohol, reducing the likelihood of ROOH homogenization. That is, both the phosphite and the thioester antioxidant can react with the radical initiator to prevent the generation of free radicals. Moreover, it can work synergistically with resistance.

Sulfite/bisulfite/sulfide are commonly used inorganic reducing agents which react directly with oxygen in the air. When applied to a polymer, the sulfite/bisulfite/sulfide acts directly on the oxygen to protect the polymer. At the same time, they also reduce the steroid intermediates of hindered phenols, thereby reducing the yellowness index of the polymer.

Sulfite/bisulfite is commonly used as a reducing agent, an antioxidant, an antibacterial agent, etc. in industries such as food and water treatment. For example, calcium sulfite antibacterial, anti-mildew, non-static, not only adsorbs organic matter, but also has strong adsorption to toxic and harmful metal ions and bacterial viruses. It is widely used in high-grade water treatment systems in Southeast Asian countries such as Japan, Korea, and Malaysia. . Sodium bisulfite is used in the pharmaceutical industry to produce intermediates of dipyridamole and aminopyrine, and its food grade products are used in food bleaches, preservatives and antioxidants.

Light metal sulfites, bisulfites or sulfides have certain reducing properties and are commonly used inorganic reducing agents, which are easily redoxed with oxygen in the air. In polyolefin These sulfur-containing inorganic salts react with oxygen during processing, which reduces the thermal aging of the polyolefin. At the same time, due to its reducibility, it can also reduce the intermediates of the hindered antimony compound, eliminate the chromophore, and reduce the yellow index of the polyolefin. Moreover, these sulfur-containing inorganic salts can greatly reduce the cost of the product. detailed description

The present invention will be described in detail below by way of specific embodiments, but those skilled in the art understand that the embodiments are not intended to limit the scope of the present invention, and any modifications and changes made on the basis of the present invention are within the scope of the present invention. within.

Twin-screw extrusion test: Extrusion in a twin-screw extruder with screw temperature set to

TS1: 195 °C, TS2: 205 °C, TS3-TS9: 210 °C, TS10: 200 ° (:.

The evaluation of the antioxidant effect was carried out by measurement of the melt index and the yellow index. When the melt index is low, the resin has good processing stability and less thermal oxygen degradation; when the yellow index is low, the resin has good anti-yellowing effect and good appearance. That is, the lower the melt index and the yellow index, the more obvious the antioxidant effect. Example 1

Tetrakis[P-(3,5-di-tert-butyl-4-hydroxyphenyl)propanoic acid] pentaerythritol ester, tris[2.4-di-tert-butylphenyl]phosphite, calcium stearate and calcium sulfite , made by the ratio of the shield ratio 1: 2: 1.5: 1.25.

This was uniformly mixed with a powder, added to polypropylene in an amount of 1,500 ppm, and after being extruded three times in a screw, the polypropylene had a melt index of 14.8 _g /10 min and a yellow index of 6.5. Example 2

P-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid n-octadecyl alcohol ester, three 〖2.4-di-tert-butylphenyl] phosphite, calcium stearate and sulfurous acid Calcium, made by a ratio of 1: 3: 1.5: 1.75.

This was uniformly mixed with a powder, added to polypropylene in an amount of 2000 ppm, and after being extruded three times in a screw, the polypropylene had a melt index of 11.8 _g /10 min and a yellow index of 4.9. Example 3

Tetrakis[P-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid] pentaerythritol ester, bis(2,4-di-tert-butylphenol) pentaerythritol diphosphite, calcium stearate and Magnesium sulphate is prepared by mixing in a mass ratio of 1:2.5: 1:2.5.

This was uniformly mixed with a powder, added to polypropylene in an amount of 1,500 ppm, and after being extruded three times in a screw, the polypropylene had a melt index of 10.7 _g /10 min and a yellow index of 4.8. Example 4

Tetrakis[P-(3,5-di-tert-butyl-4-hydroxyphenyl)propanoic acid] pentaerythritol ester, tris[2.4-di-tert-butylphenyl]phosphite, zinc stearate and calcium sulfite , made by mixing the mass ratio 1: 2: 0.5: 3.

This was uniformly mixed with a powder, added to polypropylene in an amount of 3000 ppm, and after being extruded three times in a screw, the polypropylene had a melt index of 9.8 _g /10 min and a yellow index of 3.9. Four [P-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid] pentaerythritol ester, tris[2.4-di-tert-butylphenyl]phosphite, hydrotalcite and sodium sulfite, according to the shield Ratio 1:4: 1: 0.5 mixed evenly.

This was uniformly mixed with a powder, added to polypropylene in an amount of 2000 ppm, and after being extruded three times in a screw, the polypropylene had a melt index of 6.3 _g /10 min and a yellow index of 4.0. Example 6

Tetrakis[P-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid] pentaerythritol ester, bis(2,4-di-tert-butylphenol) pentaerythritol diphosphite, calcium stearate and Sodium sulfite is prepared by mixing in a mass ratio of 1:2.5:1.5:1.25.

This was uniformly mixed with a powder, added to polypropylene in an amount of 1,500 ppm, and after being extruded three times in a screw, the polypropylene had a melt index of 7.2 _g /10 min and a yellow index of 7.9. Example 7

P-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid n-octadecyl alcohol ester, three 〖2.4-di-tert-butylphenyl] phosphite, calcium stearate and sodium sulfite, Made by mass ratio 1: 2: 2: 1.75.

This was uniformly mixed with a powder, added to polypropylene in an amount of 2500 ppm, and after being extruded three times in a screw, the polypropylene had a melt index of 8.6 _g /10 min and a yellow index of 9.6. Example 8

Will tetra[P-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid] pentaerythritol ester, three [2.4- Di-tert-butylphenyl]phosphite, calcium stearate and sodium sulfite, according to the ratio of 1: 2: 1.5:

2.5 mixed and made.

This was uniformly mixed with a powder, added to polypropylene in an amount of 1,500 ppm, and after being extruded three times in a screw, the polypropylene had a melt index of 11.8 _g /10 min and a yellow index of 17.8. Example 9

2,4-di-tert-butylphenol, tris[2.4-di-tert-butylphenyl]phosphite, dioctadecyl thiodipropionate, hydrotalcite and sodium sulfite, by mass ratio 1: 2:2 : 0.5: 3 mixed and made.

This was uniformly mixed with a powder, added to polypropylene in an amount of 800 ppm, and after being extruded three times in a screw, the polypropylene had a melt index of 8.5 _g /10 min and a yellow index of 7.1. Example 10

1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanuric acid, tetrakis(2,4-di-tert-butylphenyl-4,4-biphenyl) Phosphate, hydrotalcite and sodium sulfite are prepared by mixing in a mass ratio of 1: 2: 1: 2.75.

This was uniformly mixed with a powder, added to polypropylene in an amount of 1800 ppm, and after being extruded three times in a screw, the polypropylene had a melt index of 8.0 _g /10 min and a yellow index of 9.3. Example 11

Triethylene glycol-bis(3-tert-butyl-4-hydroxy-5-mercaptophenyl)propionate, 2,2,-ethylenebis(4,6-di-tert-butylphenyl) fluoride Hypophosphite, dodecyl thiodipropionate, calcium stearate And the stone is made by mixing the mass ratio 1: 1: 1: 2: 2.75.

This was uniformly mixed with a powder and added to polypropylene in an amount of 1,500 ppm. After three times of extrusion in a screw, the polypropylene melt index was 7.7 _g /10 min and the yellow index was 7.9. Example 12

4,4,-thiobis(6-tert-butyl-3-nonylphenol), tetrakis(2,4-di-tert-butylphenyl-4,4-biphenyl)bisphosphate, stearic acid Zinc acid: Potassium sulfide is prepared by mixing in a mass ratio of 1: 1.5: 1.5: 2. 5 .

This was uniformly mixed with a powder, added to polyethylene in an amount of 2500 ppm, and after being extruded three times in a screw, the polypropylene had a melt index of 6.5 _g /10 min and a yellow index of 7.3. Example 13

2,2,-thiodiethylbis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)acrylic acid), bis(2,4-di-tert-butylphenol) pentaerythritol diphosphoric acid The ester, magnesium stearate and sodium hydrogen sulfite are uniformly mixed in a mass ratio of 1:4:1.5:2.

This was uniformly mixed with a powder, added to polypropylene in an amount of 1000 ppm, and after being extruded three times in a screw, the polypropylene had a melt index of 6.9 _g /10 min and a yellow index of 8.5. Example 14

N, N,-bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hexamethylenediamine, tetrakis(2,4-di-tert-octadecyloxy-4, 4-biphenyl)phosphate, thiodipropionic acid, zinc stearate, and sodium sulfide are uniformly mixed at a mass ratio of 1: 1:0.5: 1:0.5. This was uniformly mixed with a powder, added to polypropylene in an amount of 2000 ppm, and after being extruded three times in a screw, the polypropylene melt index was 7.3 _g /10 min, and the yellow index was 6.9.

Comparative Example 1 Calcium stearate powder was added to polypropylene in an amount of 300 ppm, and after extruding three times in a screw, the polypropylene melt index was 31.5 g/10 min, and the yellow index was 1.28.

Comparative Example 2 Tetrakis[P-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid] pentaerythritol ester, tris[2.4-di-tert-butylphenyl]phosphite, calcium stearate It is made by mixing the shield ratio 1:2:1.5.

This was uniformly mixed with a powder and added to polypropylene in an amount of 1,500 ppm. After three times of extrusion in a screw, the polypropylene melt index was 12.9 _g /10 min and the yellow index was 7.3.

Claims

Rights request

An antioxidant composition, characterized in that: the composition comprises:

(1) hindered phenol;

(2) a phosphite or a thioester;

(3) an acid scavenger;

(4) sulfite or bisulfite or sulfide;

The composition according to claim 1, wherein: the hindered face is selected from the group consisting of 2,4-di-tert-butylphenol, 2,6-di-tert-butylphenol, 2,4,6-three Tert-Butylphenol, tetrakis(卩-(3,5-di-tert-butyl-4-hydroxyphenyl)propanoic acid] pentaerythritol ester, P-(3,5-di-tert-butyl-4-hydroxyphenyl)propane Acid n-alcohol ester, or 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 2,6-di-tert-butyl Indophenol, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isoacid, triethylene glycol-bis(3-tert-butyl-4-hydroxy-5-fluorenyl) Phenyl) propionate, 4,4,-thiobis(6-tert-butyl-3-nonylphenol), (3,5-di-tert-butyl-4-hydroxyphenyl)propanoic acid isooctanol Ester, N, N,-bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl) hexamethylenediamine, 2,2,-thiodiethyl bis(3- One or a combination of two or more of 3,5-di-tert-butyl-4-hydroxyphenyl)acrylic acid.

The composition according to claim 1 or 2, wherein the phosphite is selected from the group consisting of tris[2.4-di-tert-butylphenyl]phosphite, or bis(2,4-di-tertiary). Butylphenol) pentaerythritol diphosphite, bis(2-mercapto-4,6-bis(1,1,-didecylethyl)phenyl face)ethyl phosphate, tetra (2,4-di-tert Butylphenyl-4,4-biphenyl)bisphosphate, 2,2,-ethylene bis (4,6-di-tert Mixture of one or both of butylphenyl) fluorophosphites.

The composition according to any one of claims 1 to 3, wherein the thioester is selected from the group consisting of didodecyl thiodipropionate, bis-octadecyl thiodipropionate, One or a mixture of ditetradecyl thiodipropionate, thiodipropionic acid.

The composition according to any one of claims 1 to 4, wherein the metal portion of the sulfite, bisulfite and sulfide salt is a light metal, including lithium metal (Li), sodium. (Na), magnesium (Mg), potassium (K), calcium (Ca).

The composition according to any one of claims 1 to 5, wherein the composition further contains at least one selected from the group consisting of a plasticizer, an acid scavenger, a nucleating agent, an antibacterial agent, and a flame retardant. , light stabilizer, antistatic agent, foaming agent or coloring pigment.

7. A thermally stable polymer mixture, characterized in that the mixture comprises a polymer resin and the composition of any of claims 1-6.

8. Polymer mixture according to claim 7, characterized in that the polymer refers to a polyolefin, a polyester, a polyfurfural, a polyurethane, a polyamide, a polycarbonate or a polyamide.

9. Polymer mixture according to claim 8, characterized in that the composition according to any one of claims 1-6 is added in the polymer processing in an amount of from 800 to 3000 ppm.

The use of the composition according to any one of claims 1 to 6, characterized in that the composition is used as an antioxidant in a polymer resin.