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GB2124221A - Coated powder of ???,???- ethylenically unsaturated carboxylic acid metal salt and production thereof - Google Patents
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GB2124221A - Coated powder of ???,???- ethylenically unsaturated carboxylic acid metal salt and production thereof - Google Patents

Coated powder of ???,???- ethylenically unsaturated carboxylic acid metal salt and production thereof Download PDF

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Publication number
GB2124221A
GB2124221A GB08318294A GB8318294A GB2124221A GB 2124221 A GB2124221 A GB 2124221A GB 08318294 A GB08318294 A GB 08318294A GB 8318294 A GB8318294 A GB 8318294A GB 2124221 A GB2124221 A GB 2124221A
Authority
GB
United Kingdom
Prior art keywords
acid
unsaturated carboxylic
carboxylic acid
ethylenically unsaturated
fatty acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
GB08318294A
Other versions
GB2124221B (en
GB8318294D0 (en
Inventor
Ichiro Tominaga
Akihiro Nakahara
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sumitomo Rubber Industries Ltd
Original Assignee
Sumitomo Rubber Industries Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP11806982A external-priority patent/JPS5921640A/en
Priority claimed from JP9552083A external-priority patent/JPS59219250A/en
Application filed by Sumitomo Rubber Industries Ltd filed Critical Sumitomo Rubber Industries Ltd
Publication of GB8318294D0 publication Critical patent/GB8318294D0/en
Publication of GB2124221A publication Critical patent/GB2124221A/en
Application granted granted Critical
Publication of GB2124221B publication Critical patent/GB2124221B/en
Expired legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C57/00Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms
    • C07C57/02Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms with only carbon-to-carbon double bonds as unsaturation
    • C07C57/03Monocarboxylic acids
    • C07C57/04Acrylic acid; Methacrylic acid
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C53/00Saturated compounds having only one carboxyl group bound to an acyclic carbon atom or hydrogen
    • C07C53/126Acids containing more than four carbon atoms
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/04Oxygen-containing compounds
    • C08K5/09Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098Metal salts of carboxylic acids

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)

Abstract

Powder of ???,???-ethylenically unsaturated carboxylic acid metal salt is coated with a C10-C24 fatty acid having a melting point of at least 30 DEG C. A powder of ???,???-ethylenically unsaturated carboxylic acid metal salt, especially zinc acrylate, is useful as a component to make a solid golf ball, but is disadvantageously liable to coagulate in a rubber composition or to adhere to the roll or to the inner surface of a blender during the preparation of the rubber compound. In order to avoid such problems a powder of the metal salt is coated with the fatty acid mentioned above.

Description

SPECIFICATION Coated powder of a ethylenically unsaturated carboxylic acid metal salt and production thereof The present invention relates to a coated powder of a,P, ethylenically unsaturated carboxylic acid metal salt and production thereof.
It has been known that properties of a golf ball or a tyre can be improved by blending an ethylenically unsaturated carboxylic acid metal salt into rubber composition thereof. Especially, the improvement in core hardness, impact resistance and durability of solid golf ball is achieved by the addition of the metal salt.
On the contrary, the cg, -ethylenically unsaturated carboxylic acid metal salt is liable to adhere to blender and to coagulate in rubber at the formation, which causes a crack and a distortion and deteriorates the workability.
Additionally, the a,-ethylenically unsaturated carboxylic acid metal salt, which is prepared by the mixing of the acid and metal compound in a solvent, adheres to reaction vessel or stirrer during the reaction, and is contaminated into recovered solvent by bumping at the removement of the solvent, so that the recovery of the solvent as well as the yield of the reaction product reduces, which makes remarkable economical loss.
The present invention relates to a powder of an cu,P-ethylenically unsaturated carboxylic acid metal salt free from coagulation and the production thereof improved in such problems.
According to the present invention, powder of a,$ethylenically unsaturated carboxylic acid metal salt coated with a C,0424 fatty acid having a melting point of at least 300C is provided.
The cr,P-ethylenically unsaturated carboxylic acid of the present invention is preferably selected from aliphatic or arylaliphatic, alkaryl carboxylic acid having carbon atoms of from 3 to 9 such as acrylic acid, methacrylic acid, crotonic acid, sorbic acid, isocrotonic acid, cinnamic acid, isocinnamic acid, itaconic acid and the like. Particularly preferable cg,-ethylenically unsaturated carboxylic acid is acrylic acid or methacrylic acid, especially acrylic acid.
Metal compound used for forming the acid salt of the present invention includes oxides, carbonates, hydroxides or others polyvalent metal such as zinc, magnesium, cadmium, calcium, aluminum, barium, strontium, copper(ic), cobalt(ic), tin and the like. Most preferable one is zinc compound, particularly zinc oxide. Zinc salt of the acrylic or the methacrylic acid is the most useful compound for the improvement of the properties of solid gold ball and liable to cause to aforementioned problems such as coagulation, adhesion and loss during the production.
Preferable fatty acid in accordance with the present invention has carbon atoms of from ten to twenty-four and a melting point of at least 300C.
A fatty acid of less than ten carbon atoms may replace the metal salt with the a,-ethylenically unsaturated carboxylic acid, and a fatty acid having carbon atoms of more than 24 is economically unsuitable. Preferable fatty acid of the present invention includes capric acid, lauric acid, myristic acid, palmitic acid, margaric acid, stearic acid, arachic acid, behenic acid, lignoceric acid, and the like. Most preferable fatty acid is stearic acid and palmitic acid.The fatty acid may have a branch or an unsaturated group provided that the melting point thereof is at least 300C. In case of the melting point being less than 300C the coated film of the fatty acid melts at room temperature, and on the contrary being more than 850C of the melting point, an uneven coated film may be formed so as to cause coagulation or adhesion at the intermixture of the salt into rubber or plastics. Preferable melting point is from 40 to 750C.
The amount of the fatty acid is preferably about 5 to 20 parts of weight based on 100 parts by weight of o',-ethylenically unsaturated carboxylic acid. The fatty acid of less than about 5 parts by weight is insufficient to coat the metal salt, whereas the fatty acid of more than 20 parts by weight may ionically decompose peroxide incorporated into rubber or plastic compound as a radical initiator for polymerization of a ethylenically unsaturated carboxylic acid metal salt, so that the physical properties of an obtained cured rubber or plastics deteriorate in some cases.
Further aspect of the present invention is a production of the coated powder of a,P- ethylenically unsaturated carboxylic acid metal salt which comprises reacting the unsaturated carbocylic acid with metallic compound in the presence of solvent, adding a C1OC24 fatty acid having a melting point of at least 300C to the reaction product with stirring and then drying the resultant.
According to the present invention, the reaction of the cr"ss-ethylenically unsaturated carboxylic acid and the metalic compound is preferably carried out in the presence of an organic solvent, preferably hydrocarbon solvent such as benzene, toluene, xylene, n-heptane, nhexane and the like and alcohols such as methanol, ethanol and the like, which may contain a small amount of water.
A preferable temperature of the reaction is about 20 to 700C but not restricted. After the reaction of the unsaturated carboxylic acid with metalic compound, C1OC24 fatty acid having a melting point of at least 30"C is added to the reaction product in the amount of 5 to 20 parts by weight based on 100 parts by weight of the unsaturated carboxylic acid. The fatty acid may be added to the solution or dispersion of the reaction product in the form of a powder, a solution or a melt at or to about 40--90"C. After mixing, the solution is dried by a conventional method such as evaporation of the solvent under a reduced pressure to give a coated fine powder of a.,B- ethylenically unsaturated carboxylic acid metal salt free from coagulation in a high yield.
In the present invention, the unsaturated carboxylic acid may contain polymerizationinhibitor such as hydroquinone and hydroquinone monomethyl ether, which does not affect on curing of the rubber or plastics at all.
According to the present invention, the yield of the unsaturated carboxylic acid salt powder increases remarkably, and the coagulation of the salt in rubber or plastics and adhesion on rolls are not formed during the formulation of the rubber or plastics. In addition, a golf ball made from the rubber containing the coated ez,-ethylenically unsaturated carboxylic acid metal salt of the present invention is remarkably improved in physical properties such as core hardness, durability and so in comparison to a golf ball produced using a non-coated unsaturated carboxylic acid.This is unexpected from a common sense that a free carboxylic acid acts as an organic acid to decompose radical catalyst such as peroxides and ionic degradation of peroxide catalyst due to free carboxylic acid, that is, free fatty acid used as coatings in the present invention, would have been expected to cause a deterioration of the physical properties of the golf ball.
Example 1 Zinc oxide (600 g) and toluene (200 ml) are charged into a jacket type vertical mixer (5 litre) and suspended by stirring. To the resultant mixture, acrylic acid (1060 g) is added dropwise with stirring over 30 minutes to react at room temperature for 60 minutes to give zinc acrylate.
After the reaction, a solution prepared by dissolving stearic acid (130 g) into toluene (100 ml) at 45 to 500C is added to the zinc acrylate solution, followed by the stirring of the mixture for 30 minutes to form a slurry of zinc acrylate coated with stearic acid. The slurry is heated at 500C for 3 hours under 20 to 60 mmHg to evaporate the toluene and water to be dried without substantial amount of scattering and adhesion of the zinc salt. The dried coated zinc acrylate is a fine powder free from coagulation. The yield is 1620 g, heating loss of which is about 0.3 percent.
Comparative Example 1 Zinc acrylate is prepared by the same manner as described in Example 1 excepting coating with stearic acid. Yield of the zinc acrylate is 1120 g.
In the above process, the zinc acrylate is remarkably scattered during the removal of the solvent so as to mix into the removed solvent. It is difficult to collect the scattered and zinc acrylate contaminant during the removed solvent and to clean the internal surface of the reaction vessel, on which the zinc acrylate adheres. In addition to the loss of the zinc acrylate, a partial lump of the zinc acrylate is formed, which is difficult to be crushed to fine powder.
Comparative Example 2 Zinc acrylate as obtained in Comparative Example 1 is crushed to a powder of 10 to 1 7 by grinder. The grinded zinc acrylate (30 parts by weight) is blended into polybutadiene (100 parts by weight) using 6 inch roll. The resultant rubber compound contains many coagulations of larger than 0.5 mm and adheres remarkably on the roll.
Example 2 In the manner of Example 1, palmitic acid (130 g) is used replacing the stearic acid to give a fine powder of zinc acrylate coated with palmitic acid free from coagulation, the yield of which is 1620 g and heating loss is 0.3 percent.
During the removal of the solvent, the scattering and adhesion of zinc acrylate are not observed.
Example 3 Zinc oxide (1400 g) and toluene (1960 ml) are charged into a jacket type kneader (10 litter) and homogenized by kneading. While kneading, acrylic acid (2477 g) is added dropwise to the mixture over 60 minutes and reacts for one hour at 40 to 500C. After the reaction, stearic acid (376 g) is added to the reaction mixture with the continuation of kneading, heated to 750C and stirred for 30 minutes to coat the resultant zinc acrylate with the stearic acid. The toluene and water are removed by heating for two hours under 300 to 200 mmHg to give a dried fine powder of the zinc acrylate free from coagulation. The yield of the salt is 3720 g, heating loss of which is about 0.25 percent. In the above process a substantial amount of scattering and adhesion of the zinc salt are not observed.
Example 4 In the manner of Example 3, palmitic acid (376 g) is used replacing the stearic acid to give a fine powder of zinc acrylate coated with palmitic acid free from coagulation, the yield of which is 3720 g, and the heating loss is 0.25 percent.
During the removal of the solvent, the scattering and adhesion of zinc acrylate are not observed.
Example 5 Zinc oxide (2260 g) and methanol (2000 ml) are charged into a jacket type kneader (101itter) to make a slurry by kneading, followed by the dropwise addition of acrylic acid (4000 g) over 30 minutes. After the addition, the reaction is continued for about one hour, and then stearic acid (820 g) is added to the reaction mixture at 40 to 500C with stirring to coat zinc acrylate in the reaction mixture. The methanol is removed at 700C by the passing of vapor through the jacket, and the residue is taken out from the kneader to be dried at a low temperature, i.e. 400C to give zinc acrylate (6290 g), the heating loss of which is 0.25 percent.
In the above process, a substantial amount of scattering and adhesion of the zinc salt are not observed.
Example 6 In the manner of Example 5, palmitic acid (820 g) is used replacing the stearic acid to give a fine powder of zinc acrylate coated with palmitic acid free from coagulation, the yield of which is 620 g and heating loss is 0.25 percent.
During the removal of the solvent, the scattering and adhesion of zinc acrylate are not observed.
Example 7 Zinc oxide (900 g) and benzene (3000 ml) are charged into a jacket type vertical mixer (5 litter) and stirred to form a suspension. After acrylic acid (1590 g) is added dropwise to the suspension over 30 minutes with stirring, the reaction is continued for 60 minutes at a room temperature.
To the reaction mixture, a solution of stearic acid (80 g) in benzene (500 ml), which is prepared by heating the mixture thereof at 45 to 50"C, is added with stirring for 30 minutes to form a slurry, which is then heated at 500C under 275 to 100 mmHg for two hours to remove the solvent and water to give zinc acrylate coated with stearic acid (492 g), the heating loss of which is 0.25 percent.
In the above process, a substantial amount of scattering and adhesion of the zinc salt are not observed.
Example 8 In the manner of Example 7, palmitic acid (80 g) is used replacing the stearic acid to give a fine powder of zinc acrylate coated with palmitic acid free from coagulation, the yield of which is 492 g, and heating loss is 0.25 percent.
At the removal of the solvent, the scattering and adhesion of zinc acrylate are not observed.

Claims (14)

Claims
1. Powder of a,gethylenically unsaturated carboxylic acid metal salt, which is coated with a C10-C24 fatty acid having a melting point of at least 30"C.
2. The powder according to Claim 1, in which the ,p,ethylenically unsaturated carboxylic acid is acrylic acid or methacrylic acid.
3. The powder according to Claim 1, in which metal is one selected from the group consisting of zinc, magnesium, cadmium, calcium, aluminum, barium, strontium, copper(ic), cobalt(ic) and tin.
4. The powder according to Claim 3, in which metal is zinc.
5. The powder according to Claim 1, in which the cr,P-ethylenically unsaturated carboxylic acid metal salt is zinc acrylate.
6. The powder according to Claim 1, in which the melting point of the fatty acid is 40 to 750C.
7. The powder according to Claim 1, in which the fatty acid is palmitic acid or stearic acid.
8. A process for a production of a,/3-ethyleni- cally unsaturated carboxylic acid metal salt coated with a C10-C24 fatty acid, which comprises reacting the a,/3-ethylenically unsaturated carboxylic acid with a metallic compound in organic solvent, adding a C10-C24 fatty acid having a melting point of at least 300C to the reaction product with stirring and then drying the resultant.
9. The process according to Claim 8, in which the ,-ethylenically unsaturated carboxylic acid is acrylic acid of methacrylic acid.
1 0. The process according to Claim 8, in which the metalic compound is oxides, carbonates or hydroxides of polyvalent metal.
11. The process according to Claim 8, in which the metal compound is zinc oxide, zinc hydroxide or zinc carbonate.
12. the process according to Claim 8, in which the melting point of the fatty acid is from 40 to 750C.
13. The process according to Claim 8, in which the fatty acid is palmitic acid or stearic acid.
14. The process according to Claim 8, in which the fatty acid is used in an amount from 5 to 20 parts by weight based on 100 parts by weight of ,-ethylenically unsaturated carboxylic acid.
1 5. The process according to Claim 8, in which the solvent is hydrocarbon or alcohol.
GB08318294A 1982-07-07 1983-07-06 Coated powder of a,b-ethylenically unsaturated carboxylic acid metal salt and production thereof Expired GB2124221B (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP11806982A JPS5921640A (en) 1982-07-07 1982-07-07 Preparation of zinc acrylate
JP9552083A JPS59219250A (en) 1983-05-30 1983-05-30 Production of unsaturated carboxylic acid metal salt

Publications (3)

Publication Number Publication Date
GB8318294D0 GB8318294D0 (en) 1983-08-10
GB2124221A true GB2124221A (en) 1984-02-15
GB2124221B GB2124221B (en) 1985-11-13

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GB08318294A Expired GB2124221B (en) 1982-07-07 1983-07-06 Coated powder of a,b-ethylenically unsaturated carboxylic acid metal salt and production thereof

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7217829B2 (en) 2002-11-11 2007-05-15 Nippon Shokubai Co., Ltd. Zinc acrylate and method for production thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7217829B2 (en) 2002-11-11 2007-05-15 Nippon Shokubai Co., Ltd. Zinc acrylate and method for production thereof

Also Published As

Publication number Publication date
GB2124221B (en) 1985-11-13
GB8318294D0 (en) 1983-08-10

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PE20 Patent expired after termination of 20 years