WO2019070208A1 - Antioxidant composition - Google Patents
Antioxidant composition Download PDFInfo
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- WO2019070208A1 WO2019070208A1 PCT/TH2018/000044 TH2018000044W WO2019070208A1 WO 2019070208 A1 WO2019070208 A1 WO 2019070208A1 TH 2018000044 W TH2018000044 W TH 2018000044W WO 2019070208 A1 WO2019070208 A1 WO 2019070208A1
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- Prior art keywords
- aqueous emulsion
- antioxidant composition
- compound
- composition according
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- PRRINTZNQPGZHB-UHFFFAOYSA-N CCc(cc1C)cc(C)c1O Chemical compound CCc(cc1C)cc(C)c1O PRRINTZNQPGZHB-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/20—Aqueous medium with the aid of macromolecular dispersing agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F114/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F114/02—Monomers containing chlorine
- C08F114/04—Monomers containing two carbon atoms
- C08F114/06—Vinyl chloride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/005—Stabilisers against oxidation, heat, light, ozone
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
Definitions
- an antioxidant is conventionally used to terminate polymerization reaction, and also prevent polymer from heat/UV degradation during drying process or processing or use.
- the antioxidant may be added during polymerization or polymer compounding.
- the most commonly used antioxidants are phenolic antioxidants, sulfur antioxidants, phosphite antioxidants and amine antioxidants. A selection of antioxidant depends on various factors, e.g. type of polymers, production processes and final products.
- emulsion polymerization or micro-suspension polymerization in aqueous medium e.g. a process for producing polyvinyl chloride (PVC) or acrylonitrile butadiene styrene (ABS)
- antioxidants can be added in a form of liquid or solution.
- the antioxidant in liquid form may not provide good antioxidant performance.
- the antioxidant in organic solution form has some disadvantages, i.e. wastewater problem caused by using organic solvents to dissolve the powdered antioxidant, residual organic solvents in polymer resin which may affect the mechanical and physical properties of the polymers.
- the emulsion or suspension antioxidant is used in emulsion or suspension polymerization due to its compatibility with the polymerization medium, good dispersion in polymer, and simply added to the polymerization process by pressurization.
- US 5011897 discloses a process for polymerizing polyvinyl chloride using an antioxidant dispersion which is consisting of an antioxidant having a melting point not lower than 30°C (i.e., solid form at room temperature), and a suspending agent in water.
- US 7327505 B2 discloses an emulsion of a solid phenolic antioxidant, which can be prepared by melting the solid phenolic antioxidant and then dispersing in water with polyvinyl alcohol as a dispersant.
- said antioxidants may recrystallize during storage at temperature below 40°C. This leads to larger antioxidant's particle size, and possibility of antioxidant's precipitation caused an inferior antioxidant performance.
- US 6433074 discloses a vinyl chloride polymer production process using a mixed antioxidant having good anti-initial-discoloration and thermal stability.
- the mixed antioxidant comprises a phenolic antioxidant which is liquid at 20°C, and an antioxidant which is powdery at 20°C.
- the mixed antioxidant is in a form of rather viscous oil providing poor dispersion of the mixed antioxidant in polymerization system, an inferior antioxidant performance, and also being wax once stored at temperatures below 20°C causing difficulty in applying.
- the objective of this invention is to develop an aqueous emulsion antioxidant composition which can be easily added to a suspension or an emulsion polymerization and well disperse in polymer where the obtained polymer still has good polymer properties, good thermal stability and no discoloration, particularly in a polyvinyl chloride production process.
- This invention relates to an aqueous emulsion antioxidant composition, comprising
- the Compound a. is present in a range of 0.1-45 wt% based on total weight of the antioxidant, and the Compound a. and b. are in a form of liquid droplets that are uniformly dispersed in water at a temperature ranging from 10-50°C.
- An emulsion means a colloidal system including at least two heterogeneous liquids mixed homogeneously with no phase separation by one liquid dispersed as small droplets in another one.
- An aqueous emulsion is meant to include an emulsion having water as an external or continuous phase.
- This invention relates to an aqueous emulsion antioxidant composition, comprising an antioxidant comprising
- the Compound a. is present in a range of 0.1-45 wt% based on total weight of the antioxidant, and the Compound a. and b. are in a form of liquid droplets that are uniformly dispersed in water at a temperature ranging from 10-50°C.
- Ri and R 2 are each independently selected from hydrogen or d-C 4 alkyl group; x is 0-3;
- R 3 is selected from C 5 -Ci 3 alkyl group.
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
This invention relates to an aqueous emulsion antioxidant composition, comprising an antioxidant comprising a. a sterically hindered phenolic ester compound or a thioether-ester compound, having a melting point higher than 25°C (Compound a.), b. a sterically hindered phenolic ester compound having a melting point lower than 25°C (Compound b.), and c. optionally, an epoxidized vegetable oil (Compound c); a dispersant; and water, wherein the Compound a. is present in a range of 0.1 -45 wt% based on total weight of the antioxidant, and the Compound a. and b. are in a form of liquid droplets that are uniformly dispersed in water at a temperature ranging from 10-50°C. In a preferred embodiment, said aqueous emulsion antioxidant composition used in a polyvinyl chloride production process disperse well in the polymer wherein the obtained polymer has good thermal stability and no discoloration.
Description
TITLE OF THE INVENTION
ANTIOXIDANT COMPOSITION
FIELD OF THE INVENTION
The present invention is in a chemical field relating to an antioxidant.
BACKGROUND OF THE INVENTION
In a process for producing polymer, an antioxidant is conventionally used to terminate polymerization reaction, and also prevent polymer from heat/UV degradation during drying process or processing or use. The antioxidant may be added during polymerization or polymer compounding. The most commonly used antioxidants are phenolic antioxidants, sulfur antioxidants, phosphite antioxidants and amine antioxidants. A selection of antioxidant depends on various factors, e.g. type of polymers, production processes and final products.
For a suspension polymerization, emulsion polymerization or micro-suspension polymerization in aqueous medium, e.g. a process for producing polyvinyl chloride (PVC) or acrylonitrile butadiene styrene (ABS), antioxidants can be added in a form of liquid or solution. However, the antioxidant in liquid form may not provide good antioxidant performance. In addition, the antioxidant in organic solution form has some disadvantages, i.e. wastewater problem caused by using organic solvents to dissolve the powdered antioxidant, residual organic solvents in polymer resin which may affect the mechanical and physical properties of the polymers. To address said problems, the emulsion or suspension antioxidant is used in emulsion or suspension polymerization due to its compatibility with the polymerization medium, good dispersion in polymer, and simply added to the polymerization process by pressurization.
Several attempts have been conducted to develop the suspension or aqueous emulsion antioxidant, which is able to disperse in the reaction medium, and has good antioxidant performance and excellent storage stability. For example, US 5011897 discloses a process for polymerizing polyvinyl chloride using an antioxidant dispersion which is consisting of an antioxidant having a melting point not lower than 30°C (i.e., solid form at room temperature), and a suspending agent in water. US 7327505 B2 discloses an emulsion of a solid phenolic antioxidant, which can be prepared by melting the solid phenolic antioxidant and then dispersing in water with polyvinyl alcohol as a dispersant. However, said antioxidants may recrystallize during storage at temperature below 40°C. This leads to larger antioxidant's
particle size, and possibility of antioxidant's precipitation caused an inferior antioxidant performance.
US 6433074 discloses a vinyl chloride polymer production process using a mixed antioxidant having good anti-initial-discoloration and thermal stability. The mixed antioxidant comprises a phenolic antioxidant which is liquid at 20°C, and an antioxidant which is powdery at 20°C. The mixed antioxidant is in a form of rather viscous oil providing poor dispersion of the mixed antioxidant in polymerization system, an inferior antioxidant performance, and also being wax once stored at temperatures below 20°C causing difficulty in applying.
SUMMARY OF THE INVENTION
m light of the above mentioned, the objective of this invention is to develop an aqueous emulsion antioxidant composition which can be easily added to a suspension or an emulsion polymerization and well disperse in polymer where the obtained polymer still has good polymer properties, good thermal stability and no discoloration, particularly in a polyvinyl chloride production process.
This invention relates to an aqueous emulsion antioxidant composition, comprising
an antioxidant comprising
a. a sterically hindered phenolic ester compound or a thioether-ester compound, having a melting point higher than 25°C (Compound a.),
b. a sterically hindered phenolic ester compound having a melting point lower than 25°C (Compound b.), and
c. optionally, an epoxidized vegetable oil (Compound a);
a dispersant; and
water
wherein the Compound a. is present in a range of 0.1-45 wt% based on total weight of the antioxidant, and the Compound a. and b. are in a form of liquid droplets that are uniformly dispersed in water at a temperature ranging from 10-50°C.
The antioxidant composition of this invention is suitable for preventing polymer degradation caused by oxidization of polymers, such as polyvinyl chloride, acrylonitrile butadiene styrene, etc. Said antioxidant composition also has excellent anti-discoloration and thermal stability, good dispersion in polymer and good storage stability with no phase separation or crystallization on the wall of storage container.
DETAILED DESCRIPTION OF THE INVENTION
Definitions
Technical or scientific terms used herein have the meaning that are understood by a person ordinary skilled in the art, unless indicated otherwise.
Any instruments, devices, methods or chemicals mentioned herein shall mean instruments, devices, methods or chemicals commonly practiced or used by a person ordinary skilled in the art, unless indicated obviously as a special or specific instruments, devices, methods or chemicals to this invention.
Throughout this application, the term "about" used to indicate any value that is appeared or expressed herein may be varied or deviated, which the variation or deviation may occur from the errors of instruments, the methods or the person used the equipment or conducted according to said methods.
An emulsion means a colloidal system including at least two heterogeneous liquids mixed homogeneously with no phase separation by one liquid dispersed as small droplets in another one.
An aqueous emulsion is meant to include an emulsion having water as an external or continuous phase.
An emulsifier means a substance that enhances heterogeneous liquids to be coalescent or well dispersed with no phase separation.
A dispersant means a substance added to the system to enhance dispersion of solid particles and/or liquid in the medium, prevent precipitation and aggregation.
phr (parts per hundred) means a proportion of substance's parts compared to 100 parts of polymer calculated by weight, unless indicated otherwise.
Median diameter (D50) means a diameter where 50% by volume of the particles have diameters that are smaller or equivalent to the said median diameter.
The following shows a detail of the invention without any intention to limit the scope of the invention.
This invention relates to an aqueous emulsion antioxidant composition, comprising an antioxidant comprising
a. a sterically hindered phenolic ester compound or a thioether-ester compound, having a melting point higher than 25°C (Compound a.), b. a sterically hindered phenolic ester compound having a melting point lower than 25°C (Compound b.), and
c. optionally, an epoxidized vegetable oil (Compound c);
a dispersant; and
water
wherein the Compound a. is present in a range of 0.1-45 wt% based on total weight of the antioxidant, and the Compound a. and b. are in a form of liquid droplets that are uniformly dispersed in water at a temperature ranging from 10-50°C.
In a preferred embodiment of the invention, the Compound a. is present in a range of 10-40 wt% based on total weight of the antioxidant.
In an embodiment, the stencally hindered phenolic ester compound having the melting point higher than 25 °C is a co
Formula I
wherein
Ri and R2 are each independently selected from hydrogen or d-C4 alkyl group; x is 0-3;
is selected from CH-C20 alkyl group and/or a group having a structure of Formula A or Formula B
Formula A
Formula B
wherein
Ri' and R2' are each independent wherein one of which is selected from Ci-C4 alkyl group and the other is selected from C3-C4 alkyl group;
x is 0-3;
y is 1-6.
Preferably, the sterically hindered phenolic ester compound having the melting point higher than 25°C is octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate compound, pentaerythritol tetrakis (3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate compound or a mixture thereof.
In an embodiment, the sterically hindered phenolic ester compound having the melting point lower than 25°C ( of Formula I
Formula I
wherein
Ri and R2 are each independently selected from hydrogen or d-C4 alkyl group; x is 0-3;
R3 is selected from C5-Ci3 alkyl group.
Preferably, the sterically hindered phenolic ester compound having the melting point lower than 25°C (Compound b. ) is octyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate compound.
In an embodiment of the invention, the thioether-ester compound is a compound having a structure of Formula II or Formula III
Formula II
Formula III
wherein
R4 is selected from CM-CIS alkyl group;
R5 is selected from C12-C18 alkyl group;
X is 2-4;
Y is 2-methyl-l ,2,3-propane-triyl group or 1 ,2,3,4-methane-tetryl group.
Preferably, the thioether-Ester compound is a distearyl thiodipropionate compound, dimyristyl thiodipropionate compound, pentaeiythrityl tetrakis (3-laurylthiopropionate) compound or a mixture thereof.
In an embodiment of the invention, the antioxidant is present in a range of 20-60 wt% based on weight of the aqueous emulsion antioxidant composition, preferably in a range of 30- 50 wt% based on weight of the aqueous emulsion antioxidant composition.
In an embodiment of the invention, the dispersant is polyvinyl alcohol (PVA) or vinyl alcohol- vinyl acetate copolymer, having a viscosity in a range of 4- 120 mPa-s, and a degree of hydrolysis in a range of 70-99.9 mol%, preferably in a range of 80-90 mol%.
In an embodiment of the invention, the dispersant comprises a mixture of a dispersant having a viscosity in a range of 4-6 mPa-s and a dispersant having a viscosity in a range of 70-120 mPa-s, as measured in accordance with DIN 53015/JIS K6728 (4% aqueous solution at 20°C).
In an embodiment of the invention, the dispersant is present in a range of 0.5-5 wt% based on weight of the aqueous emulsion antioxidant composition, preferably in a range of 1-4 wt%, more preferably in a range of 2-3 wt% based on weight of the aqueous emulsion antioxidant composition.
In an embodiment of the invention, the epoxidized vegetable oil is present not greater than 20 wt% based on weight of the aqueous emulsion antioxidant composition, preferably in a range of 0-15 wt%, more preferably in a range of 0-10 wt% based on weight of the aqueous emulsion antioxidant composition.
An example of the epoxidized vegetable oil is epoxidized soybean oil.
In an embodiment of the invention, the aqueous emulsion antioxidant composition further comprises an emulsifier. The emulsifier is an ionic emulsifier, non-ionic emulsifier or a mixture thereof. The preferred emulsifier is a non-ionic emulsifier.
In an embodiment of the invention, the non-ionic emulsifier is sorbitan ester, sorbitan ester ethoxylate, ethoxylate fatty alcohol, polyethylene glycol fatty acid ester or a mixture thereof.
In another embodiment of the invention, the ionic emulsifier is ammonium or alkali metal salt of fatty acid, ammonium or alkali metal salt of alkyl sulfate, ammonium or alkali metal salt of alkyl ether sulfate, ammonium or alkali metal salt of alkyl or alkylaryl sulfonate, ammonium or alkali metal salt of alkyl sulfosuccinate, ammonium or alkali metal salt of alkylene glycol ether sulfate or a mixture thereof.
In an embodiment of the invention, the emulsifier is present in a range of 0.2-3 wt% based on weight of the aqueous emulsion antioxidant composition, preferably in a range of 1 -2 wt% based on weight of the aqueous emulsion antioxidant composition.
The emulsifier consists of hydrophilic and lipophilic parts. Selection of a suitable emulsifier assists to prevent a coalescence of oil droplets of the antioxidant, maintain the stability of the antioxidant's equilibrium in the aqueous emulsion system, and also provide suitable droplet diameter. However, the selection of emulsifier also depends on other factors such as an adverse effect on the polymer conductivity, e.g. polyvinyl chloride for forming insulated wire, etc.
In an embodiment of the invention, the aqueous emulsion antioxidant composition has a median diameter (D50) in a range of 0.1-10 microns, preferably in a range of 1-5 microns.
Droplet diameter in the aqueous emulsion antioxidant composition depends on not only chemical properties of the emulsifier but also the emulsion preparation process e.g. greater shear force in the emulsion preparation process provides smaller droplet diameter than the low shear one.
The aqueous emulsion antioxidant composition according to this invention has small droplet diameter, great storage stability owing to adding suitable dispersant and/or emulsifier. Moreover, due to low viscosity, it can be simply added to a suspension polymerization process or emulsion polymerization process or micro-suspension polymerization process, and also has a good dispersion in polymers.
According to this invention, the above-mentioned aqueous emulsion antioxidant composition is used for preventing degradation from polymer oxidization in the suspension polymerization process or emulsion polymerization process or micro-suspension polymerization process, for example, in the polymerization process of polyvinyl chloride, acrylonitrile butadiene styrene (ABS), methyl methacrylate butadiene styrene (MBS), nitrile- butadiene rubber or styrene-butadiene rubber, etc.
The following illustrates features of this invention, which is not intended to limit the scope of the invention.
A preparation of the aqueous emulsion antioxidant composition according to the invention comprises the following steps:
(1) homogeneously mixing antioxidants with the type and amount as shown in Tables 1 and 2 at 50-90°C,
(2) adding 5% w/w polyvinyl alcohol in deionized water and emulsifier with the type and amount as shown in Tables 1 and 2 into a mixture from (1),
(3) stirring a mixture from (2) vigorously with a high-speed homogenizer for about 10 minutes at a controlled temperature not higher than 50°C.
Following is an example of various properties testing of sample prepared from the aqueous emulsion antioxidant composition according to this invention. The methods and instruments used are the ones that are commonly used. It is also not intended to limit the scope of the invention.
A droplet diameter in the antioxidant composition was determined using a particle size analyzer with the laser diffraction technique, the Malvern Mastersizer 2000 and reported as a median diameter (D50) in microns.
A storage stability was determined by storing the antioxidant composition at 40°C to observe any changes, e.g. precipitation, phase separation or formation of oil droplets at the liquid's surface, and then reporting as 3 levels:
"A" means no change found as stored for more than 3 months,
"B" means change found as stored for 1-3 months,
"C" means change found as stored for less than 1 month.
The preparation of polyvinyl chloride having the antioxidant composition comprises the following steps:
(1) mixing 7,900 g of deionized water, 1.1 g of cumyl peroxynedecanoate, 2.3 g of di-2 -ethylhexyl peroxydicarbonate, 4 g of polyvinyl alcohol having degree of hydrolysis of
72 mol% and 4 g of polyvinyl alcohol having degree of hydrolysis of 80 mol%, respectively, in a 20 litters polymerization reactor,
(2) vacuumizing inside the reactor, then adding 4,500 g of vinyl chloride monomer together with stirring a mixture and increasing temperature to 58°C, internal pressure of the reactor to 9 kg/cm2 for polymerization,
(3) adding the antioxidant composition when an internal pressure of the reactor decreased to 6 kg/cm2, i.e. at the end of polymerization,
(4) removing the remaining monomers from the obtained polymer slurry then dehydrating and drying the polymer slurry to obtain polyvinyl chloride resin.
Color of polyvinyl chloride was analyzed by mixing 10 g of vinyl chloride with 5 g of dioctyl phthalate for 5 mins, then determined color using a colorimetric spectrophotometer and reported a yellowness index (YI). The higher yellowness index represents the higher the yellowness of the obtained polyvinyl chloride.
An anti-initial discoloration property was determined by kneading a mixture of polyvinyl chloride, 5 phr of dioctyl phthalate, 1.5 phr of lead stabilizer, 5 phr of filler and 2 phr of titanium dioxide at 160°C for 5 mins using a two-roll mill; then pressed the kneaded mixture using a compression molding to obtain a sample sheet with 1 mm thickness. The sample sheet was analyzed using a colorimetric spectrophotometer and reported a* color value where a positive a* value indicated that a specimen has red color shade. A greater value exhibited intense red shade, thereby, the obtained polyvinyl chloride has low anti-initial discoloration.
A thermal stability of the samples was determined by kneading a mixture of polyvinyl chloride, 60 phr of dioctyl phthalate, 0.8 phr of tin stabilizer, and 0.2 phr of lubricant at 150°C for 3 mins using a two-roll mill with 1 mm gap between rolls. The specimens were cut to 1.5 cm x 30 cm, then placed in an oven at 200°C. The burnt time, i.e. time once the specimen started to burn, was reported. The longer burnt time indicated better thermal stability.
Effect of type and proportion of antioxidants on polyvinyl chloride properties
Table 1 shows that the proportion of antioxidants significantly affected the yellowness index and a* color value. When adding the antioxidants with the melting point higher than 25 °C alone (Comparative sample 2) or when adding the antioxidants with the melting point lower than 25°C alone (Comparative sample 3), it cannot resist the discoloration of the polyvinyl chloride resin. It is noticeable that said polyvinyl chloride resin has higher yellowness index and a* color value when compared with the polyvinyl chloride resin obtained by adding the antioxidant compositions according to this invention (Samples 1-4), which
contained both the antioxidant having the melting point higher than 25°C together with the antioxidant having the melting point lower than 25°C.
From the Comparative sample 4 , it is found that an addition of 50 wt% based on total weight of the antioxidant having a melting point higher than 25°C, solid particles dispersed in liquid is formed. When left, the solid stains formed on the surface/edge were found because the solid molecules try to find somewhere to adhere, so they adhered to the surface/edge of the container. This results in a reduction of antioxidant content in the liquid thereby, lowering the antioxidant performance. A suitable content of the antioxidant having the melting point higher than 25 °C for still obtaining the oil-in-water emulsion form of the antioxidant composition is less than 50 wt% based on total weight of the antioxidant (Samples 1-4).
Moreover, it is found that polyvinyl chloride resin obtained by adding the antioxidant composition in a form of liquid oil (Comparative sample 1) which consisting of the antioxidants with a melting point of both higher and lower than 25°C shows more intense yellow color and lower anti-initial discoloration than polyvinyl chloride resin added the antioxidant composition according to this invention (Samples 1-4) which presented in a form of oil-in-water emulsion.
Sample 4 shows that an addition of epoxidized soybean oil as another antioxidant together with the antioxidants having a melting point of both higher and lower than 25 °C provides polyvinyl chloride resin having low a* color value, good anti-initial discoloration and thermal stability, whereas replacing the antioxidant having the melting point lower than 25°C with epoxidized soybean oil (Comparative sample 5) provides worse performance of polyvinyl chloride resin.
Effect of dispersant and emulsifier on the antioxidant composition properties
Table 2 shows that the antioxidant compositions of this invention (Samples 5-12), comprising polyvinyl alcohols with various viscosities for both with or without emulsifiers provide good storage stability, i.e. no precipitation or phase separation. Moreover, it reveals better storage stability, smaller droplet diameter when using a combination of polyvinyl alcohol having low and high viscosity and emulsifiers.
Table 1 : Effect of types and proportions of the antioxidants on polyvinyl chloride properties
Table 2: Effect of dispersants and emulsifiers on the antioxidant composition properties
Sample
5 6 7 8 9 10 11 12
Composition (wt% compared with weight of the aqueous emulsion antioxidant composition)
Octadecyl-3-(3,5-di-tert-butyl-4-
8 8 8 8 8 8 8 8 hydroxyphenyl) propionate compound
Pentaerythritol tetrakis (3-(3,5-di-tert-butyl-
8 8 8 8 8 8 8 8 4-hydroxyphenyl) propionate) compound
Octyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)
24 24 24 24 24 24 24 24 propionate compound
Polyvinyl alcohol having viscosity in a
- - 2 2 1.25 1.5 2 1.5 range of 80-110 mPa-s*
Polyvinyl alcohol having viscosity in a
- 2 - - - - - - range of 45-52 mPa-s*
Polyvinyl alcohol having viscosity in a
2 - - - - - - - range of 32-38 mPa-s*
Polyvinyl alcohol having viscosity in a
- - - 1 0.75 0.5 - 1.5 range of 4.6-5.4 mPa-s*
Sorbitan monolaurate - - - - 1.35 1.35 1.35 1.35
Polyethylene glycol monolaurate having
- - - - 0.15 0.15 0.15 0.15 molecular weight about 200
Water 58 58 58 57 56.5 56.5 56.5 55.5
Properties of the antioxidant composition
Median diameter (D50) 4.9 3.5 3.5 2.4 1.5 1.2 1.2 1.1
Storage stability B A A A A A A A
*in accordance with DIN 53015/JIS K6728 (4% aqueous solution at 20°C) BEST MODE OF THE INVENTION
Best mode of the invention is as disclosed in the detailed description.
Claims
An aqueous emulsion antioxidant composition, comprising
- an antioxidant comprising
a. a sterically hindered phenolic ester compound or a thioether-ester compound, having a melting point higher than 25°C (Compound a.), b. a sterically hindered phenolic ester compound having a melting point lower than 25°C (Compound b.), and
c. optionally, an epoxidized vegetable oil (Compound a);
- a dispersant; and
- water
wherein the Compound a. is present in a range of 0.1-45 wt% based on total weight of the antioxidant, and the Compound a. and b. are in a form of liquid droplets that are uniformly dispersed in water at a temperature ranging from 10-50°C.
The aqueous emulsion antioxidant composition according to claim 1, wherein the sterically hindered phenolic ester compound, having the melting point higher than 25°C, is a compound having a structure of Formula I
Formula I
wherein
Ri and R2 are each independently selected from hydrogen or 0-C4 alkyl group; x is 0-3;
Rs is selected from Ci4-C2o alkyl group and/or a group having a structure of Formula A or Formula B
o
<H2x C 0- (CH2) -C (CH2) -
Formula A
Formula B
wherein
Ri' and R2' are each independent wherein one of which is selected from d-C4 alkyl group and the other is selected from C3-C4 alkyl group;
x is 0-3;
y is 1-6.
The aqueous emulsion antioxidant composition according to claim 1 or 2, wherein the sterically hindered phenolic ester compound, having the melting point higher than 25°C, is octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate compound, pentaerythritol tetrakis (3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate compound or a mixture thereof.
The aqueous emulsion antioxidant composition according to any one of claims 1 to 3, wherein the Compound b. is a compound having a structure of Formula I
Formula I
wherein
Ri and R2 are each independently selected from hydrogen or C1-C4 alkyl group; x is 0-3;
R3 is selected from C5-C13 alkyl group.
The aqueous emulsion antioxidant composition according to any one of claims 1 to 4, wherein the Compound b. is octyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate compound.
The aqueous emulsion antioxidant composition according to any one of claims 1 to 5, wherein the thioether-ester compound is a compound having a structure of Formula II or Formula III
Formula II
Formula III
wherein
R4 is selected from C14-C18 alkyl group;
R5 is selected from C12-C18 alkyl group;
X is 2-4;
Y is 2-methyl-l,2,3-propane-triyl group or 1,2,3,4-methane-tetryl group.
The aqueous emulsion antioxidant composition according to any one of claims 1 to 6, wherein the Compound a. is present in a range of 10-40 wt% based on total weight of the antioxidant.
8. The aqueous emulsion antioxidant composition according to any one of claims 1 to 7, wherein the antioxidant is present in a range of 20-60 wt% based on weight of the aqueous emulsion antioxidant composition.
9. The aqueous emulsion antioxidant composition according to any one of claims 1 to 8, wherein the antioxidant is present in a range of 30-50 wt% based on weight of the aqueous emulsion antioxidant composition.
10. The aqueous emulsion antioxidant composition according to any one of claims 1 to 9, wherein the dispersant is polyvinyl alcohol (PVA) or vinyl alcohol-vinyl acetate copolymer, having a viscosity in a range of 4-120 mPa.s and a degree of hydrolysis in a range of 70-99.9 mol%.
11. The aqueous emulsion antioxidant composition according to any one of claims 1 to 10, wherein the dispersant comprises a mixture of a dispersant having a viscosity in a range of 4-6 mPa.s and a dispersant having a viscosity in a range of 70-120 mPa.s.
12. The aqueous emulsion antioxidant composition according to any one of claims 1 to 11, wherein the dispersant is present in a range of 0.5-5 wt% based on weight of the aqueous emulsion antioxidant composition.
13. The aqueous emulsion antioxidant composition according to any one of claims 1 to 12, wherein the dispersant is present in a range of 1-4 wt% based on weight of the aqueous emulsion antioxidant composition.
14. The aqueous emulsion antioxidant composition according to any one of claims 1 to 13, further comprising an emulsifier.
15. The aqueous emulsion antioxidant composition according to any one of claims 1 to 14, wherein the emulsifier is an ionic emulsifier, non-ionic emulsifier or a mixture thereof.
16. The aqueous emulsion antioxidant composition according to any one of claims 1 to 15, wherein the non-ionic emulsifier is a compound in a group of sorbitan ester, sorbitan ester ethoxylate, ethoxylate fatty alcohol, polyethylene glycol fatty acid ester or a mixture thereof.
17. The aqueous emulsion antioxidant composition according to any one of claims 1 to 16, wherein the emulsifier is present in a range of 0.2-3 wt% based on weight of the aqueous emulsion antioxidant composition.
18. The aqueous emulsion antioxidant composition according to any one of claims 1 to 17, wherein the emulsifier is present in a range of 1-2 wt% based on weight of the aqueous emulsion antioxidant composition.
19. The aqueous emulsion antioxidant composition according to any one of claims 1 to 18, having a median diameter (D50) in a range of 0.1-10 microns.
20. The aqueous emulsion antioxidant composition according to any one of claims 1 to 19 having a median diameter (D50) in a range of 1-5 microns.
21. Use of the aqueous emulsion antioxidant composition according to any one of claims 1 to 20 in a suspension polymerization process, emulsion polymerization process or micro-suspension polymerization process.
22. Use of the aqueous emulsion antioxidant composition according to any one of claims 1 to 20 in a polymerization process of polyvinyl chloride, acrylonitrile butadiene styrene (ABS), methyl methacrylate butadiene styrene (MBS), nitrile-butadiene rubber or styrene-butadiene rubber.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TH1701006008 | 2017-10-06 | ||
| TH1701006008A TH179039A (en) | 2017-10-06 | Antioxidant composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2019070208A1 true WO2019070208A1 (en) | 2019-04-11 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/TH2018/000044 WO2019070208A1 (en) | 2017-10-06 | 2018-10-05 | Antioxidant composition |
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| Country | Link |
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| WO (1) | WO2019070208A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113667182A (en) * | 2021-08-24 | 2021-11-19 | 长春工业大学 | Method for continuously producing aqueous antioxidant emulsion |
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