Compounds with multiple acrylic radicals, compositions containing them, and uses thereof

• US 3,952,032 A
• Filed: 05/14/1974
• Issued: 04/20/1976
• Est. Priority Date: 05/15/1973
• Status: Expired due to Term

• Current Assignee: UCB Incorporated (UCB SA)
• Original Assignee: UCB Societe Anonyme
• Inventors: Dufour, Paul, Vrancken, August, Holderic, Jean, Noat, Jacques
• Primary Examiner(s): Douglas, Winston A.
• Assistant Examiner(s): Niebling, John F.
• Application Number:
  US05/469,891
• Time in Patent Office: 707 Days
• Field of Search: 260/404.8, 260/407, 260/410.6
• US Class Current: 560/127
• CPC Class Codes: C07C 69/54 Acrylic acid esters; Methacrylic acid esters
• CPC Class Codes: C08F 120/36 containing oxygen in addition to the carboxy oxygen , e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate
• CPC Class Codes: C08F 20/20 of polyhydric alcohols or polyhydric phenols , e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
• CPC Class Codes: C08G 18/67 Unsaturated compounds having active hydrogen
• CPC Class Codes: C08G 18/68 Unsaturated polyesters
• CPC Class Codes: C09D 11/101 Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing

Abstract

Compounds with multiple acrylic radicals, the average composition of which has the general formula:

X--y--(z)_m--p--1 ]_n

Wherein X is the radical derived by removing the OH groups from the carboxyl groups of an organic carboxylic acid containing n COOH groups and the number of carbon atoms of which is between 14 and 90,

Y is the radical derived by removing m-p hydrogen atoms from the hydroxyl groups of an organic compound containing m OH groups,

Z is the monovalent radical derived by removing the OH group from the carboxyl group of a monocarboxylic acid having at least one terminal CH₂ =CH--COO-- radical,

n is a whole number from 1 to 6,

m is a whole number from 2 to 8, and

p is a number of from 0 to 2.5

With the proviso that m-p-1 is a positive number different from zero and that n(m-p-1) is between 2 and 15, processes for the preparation thereof, polymers obtained by polymerization thereof and compositions of matter, in particular UV inks or varnishes, comprising said compounds.

Claims

1. Compounds with multiple acrylic radicals, the average composition of which has the general formula

X--y-(z)_m-p-l ]_n

wherein X is the radical derived by removing the OH groups from the carboxyl groups of an organic carboxylic acid containing n COOH groups and the number of carbon atoms of which is between 14 and 90,

Y is the radical derived by removing m-p hydrogen atoms from the hydroxyl groups of an organic compound containing m OH groups,

Z is the monovalent radical derived by removing the OH group from the carboxyl group of a monocarboxylic acid having at least one terminal CH₂ =CH-COO- radical,

n is a whole number from 1 to 6,

m is a whole number from 2 to 8,

p is a number of from 0 to 2.5, with the proviso that m-p-l is a positive number different from zero and that n(m-p-l) is between 2 and 15.

3. Compounds according to claim 1, in which X is the radical derived from an organic aliphatic monocarboxylic acid.

4. Compounds according to claim 1, in which X is the radical derived from an organic polycarboxylic acid.

5. Compounds according to claim 1, in which X is the radical derived from a mixture of at least 25 mole % of an organic carboxylic acid having from 14 to 90 carbon atoms and at most 75 mole % of at least one organic aliphatic, cycloaliphatic or aromatic carboxylic acid having less than 14 carbon atoms.

6. Compounds according to claim 1, in which Y is the radical derived from an organic compound selected from the group consisting of an aliphatic polyhydric alcohol, an oxyalkylated aliphatic polyhydric alcohol, a polyester-alcohol, a polyether-alcohol, an oxyalkylated polyester-alcohol and an alkoxylated polyether-alcohol.

7. Compounds according to claim 1, in which Z is the radical derived from a monocarboxylic acid selected from the group consisting of acrylic acid, an ester of one mole of a hydroxyalkyl acrylate with one mole of a dicarboxylic acid or anhydride, an ester of two moles of a hydroxyalkyl acrylate with one mole of a tricarboxylic acid and an ester of three moles of a hydroxylalkyl acrylate with one mole of a tetracarboxylic aicd, the alkyl radical of said hydroxyalkyl acrylates having from 2 to 12 carbon atoms.

12. A process for decreasing the viscosity of the compounds according to claim 1, wherein said compounds are partially transesterified with an organic hydroxy compound having a molecular weight lower than 200.

13. The process of claim 12, wherein the hydroxy compound is an aliphatic monohydric alcohol, an aliphatic polyhydric alcohol or a hydroxyalkyl acrylate.

14. A process for the preparation of a polymer of the compounds with multiple acrylic radicals according to claim 1, which comprises heating said compounds at a temperature of from 50°

C. to 250°

C., in the absence of oxygen.

15. The process of claim 14, in which the heating is carried out at a temperature of from 50°

to 150°

C.

2. Compounds according to claim l, in which X is the radical derived from an organic carboxylic acid having from 18 to 54 carbon atoms, n is a whole number of from 1 to 4 and m is a whole number of from 3 to 6.

8. A compound with multiple acrylic radicals selected from the group consisting of:

the reaction product of 1 mole of ricinoleic acid with 1 mole of trimethylolpropane and 3 moles of acrylic acid;

the reaction product of 1 mole of stearic acid with 1 mole of sorbitol and 5 moles of the ester of 1 mole of adipic acid with 1 mole of hydroxyethyl acrylate;

the reaction product of 1 mole of oleic acid with 1 mole of dipentaerythritol and 5 moles of the ester of 1 mole of maleic anhydride with 1 mole of hydroxyethyl acrylate;

the reaction product of 1 mole of linseed oil fatty acid with 1 mole of the addition product of about 12 moles of ethylene oxide with 1 mole of sorbitol and 5 moles of the ester of 1 mole of phthalic anhydride with 1 mole of hydroxyethyl acrylate;

the reaction product of 1 mole of C₃₆ dimer acid with 2 moles of pentaerythritol and 6 moles of acrylic acid;

the reaction product of 1 mole of C₃₆ dimer acid with 2 moles of the addition product of 3 moles of propylene oxide with 1 mole of glycerol and 4 moles of acrylic acid;

the reaction product of 1 mole of the addition product of maleic anhydride on 9,12-linoleic acid with 3 moles of ethylene glycol and 3 moles of the ester of 1 mole of maleic anhydride with 1 mole of 2-hydroxypropyl acrylate;

the reaction product of 1 mole of the ester of 1 mole of pyromellitic acid and 4 moles of ricinoleic acid, with 4 moles of trimethylolpropane and 8 moles of acrylic acid;

the reaction product of 1 mole of C₃₆ dimer acid with 2 moles of the addition product of 12 moles of ethylene oxide with 1 mole of glycerol and 4 moles of the ester of 1 mole of maleic anhydride with 1 mole of hydroxyethyl acrylate;

the reaction product of 1 mole of C₃₆ dimer acid chloride with 2 moles of pentaerythritol and 6 moles of acrylyl chloride;

the reaction product of 1 mole of the addition product of maleic anhydride on 9,12-linoleic acid with 3 moles of the addition product of 3 moles of propylene oxide with 1 mole of glycerol and 3 moles of acrylic anhydride;

the reaction product of 1 mole of the dimer of methyl linoleate with 2 moles of glycerol and 4 moles of ethyl acrylate;

the reaction product of 1 mole of oleic acid with 1 mole of the addition product of 12 moles of ethylene oxide with 1 mole of sorbitol and 5 moles of acrylic acid;

the reaction product of 1 mole of stearic acid with 1 mole of the addition product of 7 moles ethylene oxide with 1 mole pentaerythritol and 3 moles of the ester of 1 mole of maleic anhydride with 1 mole of hydroxyethyl acrylate;

the reaction product of 1 mole of the addition product of 2 moles of thioglycolic acid on 1 mole of linolenic acid with 3 moles of polyethylene glycol and 3 moles of acrylic acid;

the reaction product of 1 mole of the addition product of maleic anhydride on oleic acid with 3 moles of the addition product of 12 moles of ethylene oxide with 1 mole sorbitol and 15 moles of acrylic acid;

the reaction product of 1 mole of the addition product of maleic anhydride on linseed oil with 2 moles of the addition product of 12 moles of ethylene oxide with 1 mole of sorbitol and 10 moles of acrylic acid;

the reaction product of 1 mole of the addition product of maleic anhydride on beta-eleostearic acid with 3 moles of the addition product of 12 moles of ethylene oxide with 1 mole of sorbitol and 15 moles of acrylic acid;

the reaction product of 1 mole of C₃₆ dimer acid with 2 moles of the addition product of 12 moles of ethylene oxide with 1 mole of sorbitol and 10 moles of acrylic acid;

the reaction product of 1 mole of the addition product of maleic anhydride on castor oil with 2 moles of the addition product of 7 moles of ethylene oxide with 1 mole of pentaerythritol and 6 moles of acrylic acid;

the reaction product of 0.5 mole of C₃₆ dimer acid and 0.5 mole of adipic acid with 2 moles of pentaerythritol and 6 moles of acrylic acid;

the reaction product of 0.5 mole of C₃₆ dimer acid and 0.5 mole of 1,4,5,6,7,7-hexachlorobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid with 2 moles of pentaerythritol and 6 moles of acrylic acid;

the reaction product of 0.5 mole of C₃₆ dimer acid and 0.5 mole of tetrabromophthalic anhydride with 2 moles of pentaerythritol and 6 moles of acrylic acid; and

the reaction product of 0.5 mole of C₃₆ dimer acid and 0.5 mole of isophthalic acid with 2 moles of pentaerythritol and 6 moles of acrylic acid.

16. The compound of claim 8 which is the reaction product of 0.5 mol of C₃₆ dimer acid and 0.5 mol of adipic acid with 2 mols of pentaerythritol and 6 mols of acrylic acid.

9. A process for the preparation of compounds with multiple acrylic radicals, the average composition of which has the general formula

X--y-(z)_m-p-l m-p-l]_n

wherein X is the radical derived by removing the OH groups from the carboxyl groups of an organic carboxylic acid containing n COOH groups and the number of carbon atoms of which is between 14 and 90,

Y is the radical derived by removing m-p hydrogen atoms from the hydroxyl groups of an organic compound containing m OH groups,

Z is the monovalent radical derived by removing the OH group from the carboxyl group of a monocarboxylic acid having at least one terminal CH₂ =CH-COO- radical,

n is a whole number from 1 to 6,

m is a whole number from 2 to 8,

p is a number of from 0 to 2.5,

with the proviso that m-p-l is a positive number different from zero and that n(m-p-l) is between 2 and 15, which comprises reacting together 1 mole of an organic carboxylic acid of the formule X(OH)_n, n moles of an organic compound of the formula YH_m and n(m-l) moles of an organic monocarboxylic acid of the formula ZOH having at least one terminal CH₂ =CH-COO- radical, X, Y, Z, n and m having the meanings given above, the reaction being carried out in the presence of an esterification catalyst, at atmospheric pressure and at a temperature of from about 70°

C. to 140°

C., for a period of from 2 to 10 hours.

10. A two step embodiment of the process according to claim 9, which comprises esterifying, in a first step, the organic compound YH_m with the organic carboxylic acid X(OH)_n and then esterifying in a second step the obtained hydroxy ester X-YH_m-l)_n with the organic monocarboxylic acid ZOH.

11. A two step embodiment of the process according to claim 9, which comprises esterifying, in a first step, the organic compound YH_m with the organic monocarboxylic acid ZOH and subsequently esterifying in a second step the obtained hydroxy ester Y(H)-Z_m-l with the organic carboxylic acid X(OH)_n.