Hyperbranched macromolecule from epoxide nucleus and hydroxy-functional carboxylic acid chain extenders

• US 5,663,247 A
• Filed: 10/24/1995
• Issued: 09/02/1997
• Est. Priority Date: 10/24/1994
• Status: Expired due to Term

• Current Assignee: Perstorp AB
• Original Assignee: Perstorp AB
• Inventors: Pettersson, Bo, Sorensen, Kent
• Primary Examiner(s): Sellers, Robert E.
• Application Number:
  US08/547,447
• Time in Patent Office: 679 Days
• Field of Search: 424/DIG. 16, 525/533, 525/403, 525/404, 525/408, 525/409, 525/502, 525/504, 525/507, 525/508, 525/528, 525/529, 525/530, 525/531, 525/532
• US Class Current: 525/533
• CPC Class Codes: C08G 63/20 Polyesters having been prepared in the presence of compounds having one reactive group or more than two reactive groups
• CPC Class Codes: C08G 63/42 Cyclic ethers C08G59/00 takes precedence; Cyclic carbonates; Cyclic sulfites; Cyclic orthoesters
• CPC Class Codes: C08G 63/48 by unsaturated higher fatty oils or their acids; by resin acids
• CPC Class Codes: C08G 83/005 Hyperbranched macromolecules
• CPC Class Codes: Y10S 424/16 Dendrimers and dendritic polymers

Abstract

A hyperbranched macromolecule of polyester type comprising a central monomeric or polymeric nucleus and at least one generation of a branching chain extender having at least three reactive sites of which at least one is a hydroxyl or hydroxyalkyl substituted hydroxyl group and at least one is a carboxyl or terminal epoxide group. The nucleus is an epoxide compound having at least one reactive epoxide group. Optionally, the macromolecule comprises at least one generation consisting of at least one spacing chain extender having two reactive sites of which one is a hydroxyl or hydroxyalkyl substituted hydroxyl group and one is a carboxyl or terminal epoxide group. The macromolecule may be terminated by means of at least one chain stopper.

Claims

1. A hyperbranched macromolecule of the polyester type comprising a central nucleus and at least one generation of a branching chain extender, said macromolecule comprising

a) a monomeric or polymeric nucleus selected from the group consisting of

i) an epoxide compound having at least one reactive epoxide group and

ii) a reaction product of an epoxide compound, which reaction product has at least one reactive epoxide group;

b) at least one generation comprising a branching monomeric or polymeric chain extender having at least three reactive sites, of which reactive sites

i) at least one is a hydroxyl group or a hydroxyalkyl substituted hydroxyl group and at least one is a carboxyl group or

ii) at least one is a hydroxyl group or a hydroxyalkyl substituted hydroxyl group and at least one is a terminal epoxide group; and

, optionally,

c) at least one generation comprising a spacing monomeric or polymeric chain extender having two reactive sites, one being a hydroxyl group or a hydroxyalkyl substituted hydroxyl group and one being a carboxyl group or terminal epoxide group;

said macromolecule optionally terminated by at least one chain stopper, by epoxide or allyl functionalization, or by a combination of at least one chain stopper and epoxide or allyl functionalization.

2. The hyperbranched macromolecule according to claim 1 wherein the nucleus is selected from the group consisting of

i) a glycidyl ester of a saturated monofunctional carboxylic acid having 1-24 carbon atoms;

ii) a glycidyl ester of an unsaturated monofunctional carboxylic acid having 3-24 carbon atoms;

iii) a glycidyl ester of a saturated or unsaturated di, tri or polyfunctional carboxylic acid having 3-24 carbon atoms;

iv) a glycidyl ether of a saturated monofunctional alcohol having 1-24 carbon atoms;

v) a glycidyl ether of an unsaturated monofunctional alcohol having 2-24 carbon atoms;

vi) a glycidyl ether of a saturated or unsaturated di, tri or polyfunctional alcohol having 3-24 carbon atoms;

vii) a glycidyl ether of a phenol or a reaction product thereof;

viii) a mono, di or triglycidyl substituted isocyanurate;

ix) an epoxide of an unsaturated monocarboxylic acid, a fatty acid or corresponding triglyceride, which acid has 3-24 carbon atoms;

x) a reaction product between a glycidyl or epoxide ester or ether having x epoxide groups and a saturated or unsaturated aliphatic or cycloaliphatic carboxylic acid having y carboxylic groups, wherein x is an integer of between 2 and 20, y is an integer of between 1 and 10 and x-y≧

1;

xi) a reaction product between a glycidyl or epoxide ester or ether having x epoxide groups and an aromatic carboxylic acid having y carboxylic groups, wherein x is an integer of between 2 and 20, y is an integer of between 1 and 10 and x-y≧

1;

xii a reaction product between a glycidyl or epoxide ester or ether having x epoxide groups and an aliphatic, cycloaliphatic or aromatic hydroxyfunctional saturated or unsaturated carboxylic acid having y carboxyl groups, wherein x is an integer of between 2 and 20, y is an integer of between 1 and 10 and x-y≧

1; and

xiii an epoxidized polyolefin.

3. The hyperbranched macromolecule according to claim 1, wherein the nucleus is 1,2-epoxy-3-allyloxypropane, 1-allyloxy-2,3-epoxypropane, 1,2-epoxy-3-phenoxypropane, 1-glycidyloxy-2-ethylhexane, bisphenol A-diglycidyl ether or a reaction product thereof, diglycidyl terephthalate, epoxidized soybean fatty acid, epoxidized soybean oil, epoxidized polyvinyl alcohol or 3,4-epoxy-cyclohexyl methyl-3,4-epoxy cyclohexane carboxylate.

4. The hyperbranched macromolecule according to claim 1, wherein the hydroxyalkyl substituted hydroxyl groups in the branching or spacing chain extender has the general formula

5. The hyperbranched macromolecule according to claim 4, wherein n is an integer between 1 and 30.

6. The hyperbranched macromolecule according to claim 1, wherein the branching chain extender is selected from the group consisting of:

i) an aliphatic di, tri or polyhydroxyfunctional saturated or unsaturated monocarboxylic acid;

ii) a cycloaliphatic di, tri or polyhydroxyfunctional saturated or unsaturated monocarboxylic acid;

iii) an aromatic di, tri or polyhydroxyfunctional monocarboxylic acid;

iv) an aliphatic monohydroxyfunctional saturated or unsaturated di, tri or polycarboxylic acid;

v) a cycloaliphatic monohydroxyfunctional saturated or unsaturated di, tri or polycarboxylic acid;

vi) an aromatic monohydroxyfunctional di, tri or polycarboxylic acid; and

vii) an ester comprising two or more of the hydroxyfunctional carboxylic acids of i) through vi).

7. The hyperbranched macromolecule according to claim 6, wherein the branching chain extender is 2,2-dimethylolpropionic acid, α

,α

-bis-(hydroxymethyl)butyric acid, α

,α

,α

-tris(hydroxymethyl)acetic acid, α

,α

-bis-(hydroxymethyl)valeric acid, α

,α

-bis(hydroxy)propionic acid, 3,5-dihydroxybenzoic acid, α

,β

-dihydroxypropionic acid, heptonic acid, citric acid, d-or 1-tartaric acid, dihydroxymaloic acid or d-gluconic acid.

8. The hyperbranched macromolecule according to claim 1 wherein the hyperbranched macromolecule comprises at least one generation including at least one spacing monomeric or polymeric chain extender selected from the group consisting of:

i) an aliphatic monohydroxyfunctional saturated or unsaturated monocarboxylic acid;

ii) a cycloaliphatic monohydroxyfunctional saturated or unsaturated monocarboxylic acid;

iii) an aromatic monohydroxyfunctional monocarboxylic acid;

iv) an ester formed of two or more hydroxyfunctional carboxylic acids selected from the group consisting of (i), (ii) and (iii); and

v) a lactone.

9. The hyperbranched macromolecule according to claim 8, wherein the spacing chain extender is hydroxyvaleric acid, hydroxypropionic acid, hydroxypivalic acid, glycolide, δ

-valerolactone, β

-propiolactone or ε

-caprolactone.

10. The hyperbranched macromolecule according to claim 1 wherein said macromolecule is terminated with at least one monomeric or polymeric chain stopper selected from the group consisting of:

i) an aliphatic or cycloaliphatic saturated or unsaturated monofunctional carboxylic acid or, where applicable, an anhydride thereof;

ii) an aromatic monofunctional carboxylic acid;

iii) a diisocyanate, an oligomer or an adduct thereof;

iv) an epihalohydrin;

v) a glycidyl ester of a monofunctional carboxylic acid having 1-24 carbon atoms;

vi) a glycidyl ester of a monofunctional alcohol having 1-24 carbon atoms;

ix) an adduct of an aromatic mono, di, tri or polyfunctional carboxylic acid or, where applicable, an anhydride thereof;

vii) an epoxide of an unsaturated monocarboxylic acid or corresponding triglyceride, which acid has 3-24 carbon atoms;

viii) an aliphatic or cycloaliphatic saturated or unsaturated monofunctional alcohol;

ix) an aromatic monofunctional alcohol; and

x) an adduct of a carboxylic acid and an alcohol.

11. The hyperbranched macromolecule according to claim 1 wherein the macromolecule is terminated with a chain stopper selected from the group consisting of lauric acid, linseed fatty acid, soybean fatty acid, tall oil fatty acid, dehydrated castor fatty acid, crotonic acid, capric acid, caprylic acid, acrylic acid, methacrylic acid, benzoic acid, para-tert-butylbenzoic acid, abietic acid, sorbinic acid, 1-chloro-2,3-epoxypropane, 1,4-dichloro-2,3-epoxybutane, epoxidized soybean fatty acid, trimethylolpropane diallyl ether maleate, 5-methyl-1,3-dioxane-5-methanol, 5-ethyl-1,3-dioxane-5-methanol, trimethylolpropane diallyl ether, pentaerythritol triallyl ether, pentaerythritol triacrylate, pentaerythritol triethoxylate triacrylate, toluene-2,4-diisocyanate, toluene-2,6-diisocyanate, hexamethylene diisocyanate and isophorone diisocyanate.

12. The hyperbranched macromolecule according to claim 1, wherein at least one generation includes at least one compound equal to a nucleus, the generation being followed by a generation consisting of at least one branching or spacing chain extender and optionally being further extended or terminated by a generation consisting of at least one branching or spacing chain extender or of at least one chain stopper.

13. The hyperbranched macromolecule according to claim 1, said macromolecule holding 1-100 branching, spacing or terminating generations, whereby at least one generation is a branching generation.

14. The hyperbranched macromolecule according to claim 1, said macromolecule holding 1-20 branching, spacing or terminating generations, whereby at least one generation is a branching generation.

15. The hyperbranched macromolecule according to claim 1, the macromolecule being epoxide functional, obtained through epoxidation of unsaturation within the macromolecule.

16. The hyperbranched macromolecule according to claim 1, the macromolecule being allyl functional, obtained through allylation of the macromolecule by means of an allylhalide.

17. The hyperbranched macromolecule according to claim 16, wherein the allylhalide is allylchloride or allylbromide.

18. The hyperbranched macromolecule according to claim 1 wherein the nucleus is a glycidyl ether of a condensation product between at least one phenol and at least one aldehyde or an oligomer thereof.

19. The hyperbranched macromolecule according to claim 1 wherein said macromolecule is terminated with at least one adduct between a carboxylic acid and an acrylate selected from the group consisting of hydroxyethyl acrylate, hydroxypropyl acrylate, trimethylolpropane diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, hydroxy-functional acrylates of alkoxylated trimethylolpropane and hydroxy-functional acrylates of alkoxylated pentaerythritol.

20. The hyperbranched macromolecule according to claim 1 wherein said macromolecule is terminated with at least one adduct between a carboxylic acid and a hydroxy-substituted allyl ether.