CA2073159A1

CA2073159A1 - Unsaturated esters, a process for their preparation and their use for the production of moldings, coatings, grouts and sealants

Info

Publication number: CA2073159A1
Application number: CA 2073159
Authority: CA
Inventors: Juergen Meixner; Josef Pedain; Karl-Heinz Buechel; Hans-Joachim Traenckner
Original assignee: Individual
Current assignee: Bayer AG
Priority date: 1991-07-10
Filing date: 1992-07-06
Publication date: 1993-01-11
Also published as: EP0522400A2; DE4122765A1; EP0522400A3

Abstract

Mo-3755 LeA 28,481 UNSATURATED ESTERS, A PROCESS FOR THEIR
PREPARATION AND THEIR USE FOR THE PRODUCTION
OF MOLDINGS, COATINGS, GROUTS AND SEALANTS
ABSTRACT OF THE DISCLOSURE
The present invention relates to .alpha.,.beta.-ethylenically unsaturated polyesters having a molecular weight (Mn) of 300 to 10,000 and containing a) 5 to 70% by weight of octadienyl groups (calculated as C8H13) incorporated via ether bridges and b) 10 to 65% by weight of ester residues of unsaturated dicarboxylic acids (calculated as C4H2O4).
The present invention also relates to a process for the preparation of these unsaturated polyesters and to their use for the production of moldings, coatings, grouts and sealants.

Description

2~73:~9 Mo-3755 LeA 28,481 UNSATURATED ESTERS, A PROCESS FOR THEIR

OF MOLDINGS, COATINGS. GROUTS AND SEALANTS
BACKGROUND OF THE INVENTION
Field of the Inyention The present invention relates to monomer-free ethylenically unsaturated esters containing octadienyl ether groups, to a process for their preparation and to their use as binders for coating or grouting compositions and for the production of moldings.
Description of the Prior Art The usual binders based on unsaturated polyesters contain ~ ethylenically unsaturated polyesters and monomers which are copolymerizable therewith. The monomer used is almost always styrene, but styrene evaporates during processing, thereby necessitating expensive processes far the purification of the air in the factories and the exhaust air of the drying plants.
Unsaturated polyesters which are free from copolymerizable monomers and can be cured by UV irradiation are described e.g. in DE-PS 2,221,335. Monomer-free grouting compositions based on unsaturated polyesters which can be cured in the presence of peroxides are disclosed in DE-OS 3,409,271.
Both systems contain unsaturated polyesters with residues of allyl ethers of polyhydric alcohols. During the curing reaction volatile decomposition products are produced due to auto-oxidation of the allyl ether groups resulting in unpleasant odors.

2073:1~9 It is an object of the present invention to provlde unsaturated esters which would be suitable for the preparation of ~onomer-free coating or grouting compositions and moldings curable by free radical reactions, wherein the products would have technical properties at least equal to the previously mentioned prior art compositions without having their disadvantages.
It has now surprisingly been found that monomer-free ~ ethylenically unsaturated esters which contain octadienyl groups attached via ether bridges fulfil these requirements.
These esters can be cross-linked by ~eans of free radical formers such as peroxides as well as by radiation curing.
Although coating compositions based on unsaturated polyester resins containing octadienyl groups have previously been described in US-PS 4,378,251, the binders described in this prior publication are products which are free from ether groups obtained by the reaction of octadienol with unsaturated carboxylic acids or derivatives of unsaturated dicarboxylic acids~ and can only be cured at elevated temperatures. The 20 . prior publication contains no mention of incorporating the octadienyl groups in the resins via ether bridges in order thereby to obtain resins which can be cured much more rapidly, in particular at room temperature. Further, there is no indication that the coating compositions may also be cured by means of peroxides.
SUMMARY OF THE INVENTION
The present invention relates to ~ ethylenically unsaturated polyesters having a molecular weight (Mn) o~ 300 to 10,000 and containing a) 5 to 70% by weight of octadienyl groups tcalculated as C8H13) incorporated via ether bridges and b) 10 to 65% by weight of ester residues of unsaturated dicarboxylic acids (calculated as C4H204).
The invention also relates to a process for the preparation of these unsaturated polyesters by esterifying Mo-3755 20~3~59 A) a dicarboxylic acid component containing i) 50 to 100 carboxyl equivalents-% of one or more ethylenically unsaturated dicarboxylic acids and/or their anhydrides and ii) 0 to 50 carboxyl equivalents-% of one or more compounds selected from the group of aliphatic saturated dicarboxylic acids having 4 to 10 carbon atoms~ cycloaliphatic dicarboxylic acids having 8 to 10 carbon atoms, aromatic dicarboxylic acids having 8 o to 12 carbon atoms and the anhydrides of any of these dicarboxylic acids with B) an alcohol component containing i) 5 to 100 hydroxyl equivalents-% of one or more monohydric or polyhydric alcohols having a molecular we;ght of 170 to 1000 and containing octadienyl groups incorporated via ether bridges and ii~ O to 95 hydroxyl equivalents-% of monohydric or polyhydric alcohols having a molecular weight of from 32 to 200 other than those set forth in i), 20 while maintaining an equivalent ratio of carboxyl groups of component A) to hydroxyl groups o~ component B) of at most l:l.
The invention also relates to the use of the unsaturated polyesters for the production of moldings and as binders for coating compositions and grouting and sealing compositions.
DETAILED DESCRIPTION OF THE INVENTION
The acid component A) to be used in the process according to the invention has the composition indicated above.
Preferred ~ ethylenically unsaturated dicarboxylic acids or dicarboxylic acid anhydrides have 4 to 5 carbon atoms and 30 include maleic acid, fumaric acid, itaconic acid and maleic acid anhydride. Fumaric acid, maleic acid and/or maleic acid anhydride are particularly preferred for the process according to the invention as ~ ethylenically unsaturated dicarboxylic acid components.
Mo-3755 -.

2~73159 Suitable aliphatic saturated dicarboxylic acids haviny 4 to 10 carbon atoms are preferably succinic acid, adipic acid, sebacic acid and the anhydrides of such acids.
Examples of suitable cycloaliphatic dicarboxylic acids or dicarboxylic acid anhydrides having 8 to 10 carbon atoms include tetrahydrophthalic acid, hexahydrophthalic acid, norbornene dicarboxylic acid and the anhydrides of these acids.
Examples of suitable aromatic dicarboxylic acids or dicarboxylic acid anhydrides having 8 to 12 carbon atoms o include phthalic acid, phthalic acid anhydride, isophthalicacid and terephthalic acid. Phthalic acid and phthalic acid anhydride are preferred aromatic dicarboxylic acid companents.
The alcohol component B) has the composition indicated above. Alcohol component B) preferably contains 10 to 100 hydroxyl equivalents percent of monohydric and/or polyhydric alcohols having a molecular weight of 17Q to 800 and containing octadienyl groups and O to 90 hydroxyl equivalents-%
of other monohydric and/or polyhydric alcohols having a molecular weight of 62 to 200.
The octadienyl group-containing alcohols which are essential for this invention are obtained by the telomerkation of butadiene with polyhydric alcohols. Th;s reaction is known and described, for example, in DE-OS 2,148,156, DE-OS 2 011 163, GB-PS 2,114,974, J. Chem. Soc. D. t4), 193-4 (1971) and Izv. akad. Nauk SSSR, Ser. knim. t1981) (8), pages 1837-1842.
The octadienyl groups required for the invention are structural units having the overall formula C8H13 and preferably correspond to the structural formula -CH2-CH=CH-CH2-CH2-CH2-CH=CH2.

The octadienyl groups are incorporated into the alcohols via ether bridges, -O-, and the alcohols are then used to produce the polyesters according to the invention.

Mo-3755 . ~ ~ . ., ' .

- 2~731~9 The starter molecules used for the above-ment~oned telomerization may be polyhydric alcohols having a molecular weight of 62 to 400 such as ethylene glycol, propylene glycol, glycerol, trimethylolpropane, pentaerythritol~ sorbitol, saccharose and mixtures of these alcohols. The telomerization is preferably carried out in the presence of palladium catalysts such as pallad;um-phosphine complexes and frequently in the presence of solvents, e.g., isopropanol.
When carrying out the telomerization reaction it is, necessary to ensure by suitable choice of the amounts of the reactants that the telomerizat;on products contain free hydroxyl groups and are suitable for use as starting component B~ or as part of starting component B). Particularly preferred telomers have an average of at least one free hydroxyl group per molecule and are prepared from alcohols which are at least trihydric or alcohol mixtures which on statistical average are at least trifunctional. The telomerization products of glycerol and butadiene having a hydroxyl number of 182 to 561 and/or the telomerization products of trimethylolpropane and 20 . butadiene having a hydroxyl number of 160 to 464 are particularly suitable.
The monohydric and/or polyhydric alcohols which may optionally be used as a portion of component B) and differ from the unsaturated alcohols which are essential for this invention are known and include methanol, ethanol, n-butanol, isooctanol, benzyl alcohol, ethylene glycol, propylene glycol, diethylene glycol, tetramethylene diol, hexamethylene diol and mixtures of these monohydric and polyhydric alcohols.
In the esterification reaction according to the invention, the starting components A) and B) are used in quantities corresponding to an equivalent ratio of carboxyl groups to hydroxyl groups of at most l:l, preferably 1:1.5 to 1:1.
The esters according to the invention may be prepared by known methods, such as solvent-free or azeotropic Mo-3755 2073~9 ~sterification of the alcohols and acids or their esterifiable derivatives. See "Methoden der organischen Chemie"
(Houben-Weyl) 4th Edition, Volume 14/2, Georg Thieme Verlag, Stuttgart 1961, pages 1-5, 21-33, 40-44.
The process according to the invention is preferably carried out under an inert gas atmosphere at temperatures of 1~0 to 220C.
In order to prevent unwanted premature cross-linking of the esters according to the invention it is advisable to add 0.001 to 0.1% by weight of polymerization inhibitors or antioxidants during the preparation stage of the esters.
Suitable stabilizers are described in "Methoden der organischen Chemie" (Houben-Weyl), 4th Edition, Volume 14jl, pages 433 et seq, Georg Thieme Yerlag, Stuttgart 1961. For example, p-benzoquinone when used at a concentration of 0.01 to C.05% by weight, based on the ester according to the invent;on, is very su;table.
In the process according to the invention, the nature and proportions of the starting components are chosen such that the resulting polyesters accordiny to the invention have a ~olecular weight ~Mn~ determined by gel permeation chromatography using polystyrene as standard) of 300 to 10,000, preferably 400 to 5000; have acid numbers of 0 to 80, preferably 5 to 50; contain 5 to 70% by weight, preferably from 10 to 65% by weight, of octadienyl groups (calculated as C8H13) incorporated via ether bridges; and contain 10 to 65% by weight, preferably from 15 to 60% by weight, of unsaturated dicarboxylic ac;d ester residues corresponding to the formula O O
" "
-0-C-CH=CH-C-0-.

Mo-3755 2 ~

The polyesters according to the invention are generally clear, low viscosity or medium to high viscosity liquids.
Conversion of the unsaturated esters containing octadienyl groups, which are synthetic resin precursors, into cured synthetic resins is generally carried out after a molding process.
The term "molding process" is intended to denote, ~n the context of this invention, both the production of any three dimensional, cured moldings and cured putties or grouting compositions, and also coatings, in particular lacquer coatings. It is particularly preferred to use the products according to the invention as binders for the production of lacquer coatings on substrates such as paper, cardboard, leather, wood, synthetic resins, non-woven webs, textiles, ceramic materials, mineral materials, glass, metal or synthetic leather and as binders for grouting and sealing compositions.
The unsaturated esters containing octadienyl groups may be mixed with various types of auxiliary agents and additives before the molding process, depend;ng upon the purpose for which they are intended and upon the desired viscosity. These additives, which are used in known quantities, include fillers, pigments, dyes, thickeners~
glazing agents, matting agents and levelling agents.
The products according to the invention may also be used as solutions in known lacquer solvents or emulsions in ~ater, in particular for the production of lacquer coatings.
Acetone, butyl acetate and xylene are examples of suitable lacquer solvents. These solvents may be used in quantities of up to 70% by weight, preferably up to 60% by weight, based on the total weight of the mixture including the solvent.
The products according to the invention may also be mixed with copolymerizable monomers, although this is not essential. Examples of suitable copolymerizable monomers include organic compounds having at least one copolymerizable Mo-375s .

,.~

- 2a73l~s olefinic double bond per molecule and a viscosity at 23C of at most 500 mPa.s.
If the products according to the invention are to be worked up from an aqueous emulsion, suitable aqueous emulsions may be prepared~ for example, with the aid of emulsif~ers and optionally auxiliary agents conventionally used in emulsion technology. Suitable emulsifiers for this purpose are known an~ described, e.g., in Ullmanns Enzyklopadie der techn.
Chemie, Yolume 10, 4th Edition, pages 449 et seq.
o The aqueous emulsions generally contain from 10 to 70% by weight, preferably from 30 to 70% by weight, of the octadienyl group-containing unsaturated esters of the present invention. The emulsions may be prepared by stirring water into the mixture of the unsaturated esters according to the invention and emulsifier, e.g., by simple stirring or by means of a dissolver.
Addition of water in portions at temperatùres below 30C is advantageous for producing a finely divided emulsion, i.e., for more efficient introduction of shearing forces.
Oil-in-water emulsions are obtained under optimum shearing conditions.
Curing of the products used according to the invention, which is optionally preceded by evaporation of volatile auxiliary agents such as inert solvents or water, may be carried out by means of high energy radiation such as UV
light or electron or gamma rays, or by peroxide curing using (hydro)peroxides, optionally in combination with siccatives, at temperatures from room temperature to 250C. If rapid curing is not essential, a purely oxidative curing may be carried out by the addition of siccatives in the absence of (hydro)peroxides.
The optional siccatives include cobalt, lead or manganese salts of acids such as linseed oil fatty acid, napthenic acid, acetic acid and isooctanoic acid. They are preferably used, if at all, in an amount such that the metal Mo-3755 ' , .

2~73~ ~9 content, 0.001 to 1% by weight, based on the weight of the products according to the invention.
Examples of (hydro)peroxides lnclude dicumyl peroxide, di-tert.-butyl peroxide, benzoyl peroxide, cyclohexanone peroxide, methyl ethyl ketone peroxide, acetyl acetone peroxide, dinonyl peroxide, bis-(4-tert.-butylcyclo-hexyl)-peroxydicarbonate, tert.-butyl-hydroperoxide, 2,5-dimethylhexane-2,5-hydroperoxide, diisopropylbenzene-monohydroperoxide and hydrogen peroxide. These (hydro)peroxides are preferably used in quantities of 1 to 10%
by weight, based on the weight of the products according to the invention.
Other compounds which are capable of initiating a crosslinking reaction by the format;on of free radicals may also be added. In addition, cross-linking initiated by ~hydro)peroxides may be combined with cross-linking by means of high energy radiation, for example for obtaining a pigmented coating with good covering power according to DE-OS 3,612,422.
When Uv irradiation is used for cross-linking, it is necessary to add photoinitiators to the coating compositions.
The usual photoinitiator compounds may be used for this purpose, e.g., those described in Houben-Weyl, Methoden der organischen Chemie, Volume E 20, pages 80 et seq, Georg Thieme Verlag, Stuttgart 1987.
2~ Examples of suitable photoinitiators include benzoin ethers such as benzoin isopropyl ether, benzyl ketals such as benzyl dimethyl ketal and hydroxyalkylphenones such as 2-hydroxy-2-methyl-1-phenyl-1-propan-1-one. Depending upon the purpose for which the products are to be used, the photoinitiators are used in an amount of 0.1 to 10% by weight, preferably 0.1 to 5% by weight, based on the weight of the products according to the invention. They may be used individually or as mixtures to obtain advantageous synergistic effects.

Mo-3755 -` 2a73~5~

-lo-The following examples serve to illustrate the invention in more detail.
EXAMPLES
The starting components set forth in the following Table were subjected to solvent-free condensation at 160-180C
under a stream of nitrogen until the given acid numbers were obtained. The resulting polyesters were mixed with 2% by weight of a cobalt octoate solution (2.2% by weight C~) and 3%
by weight of methyl ethyl ketone peroxide and a coating 90 ~m in thickness was formed on glass plates and cured~ at 24'C. The time taken to reach a tack-free state is shown in the Table.
All the surfaces of lacquer films were scratch resistant after drying with the exception of Comparison Examples 7 and 8, which did not contain one of the two required components, i.e., either the octadienyl groups or the residual unsaturated dicarboxylic acid ester groups.
The octadienyl ethers were obtained by telomerization of butadiene with glycerol or trimethylolpropane.

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, 2~3~S9 Although the invention has been described in detail in the foregoing for the purpose of illustration, it ;s to be understood that such detail is solely for that purpose and that variat;ons can be made therein by those skilled in the art without departing from the sp;r~t and scope of the invention except as it may be limited by the claims.

Mo-3755

Claims

1. An .alpha.,.beta.,-ethylenically unsaturated polyester having a molecular weight (Mn) of 300 to 10,000 and containing a) 5 to 70% by weight of octadienyl groups (calculated as C8H13) incorporated via ether bridges and b) 10 to 65% by weight of ester residues of unsaturated dicarboxylic acids (calculated as C4H2O4).

2. A process for the preparation of an .alpha.,.beta.-ethylenically unsaturated polyester having a molecular weight (Mn) of 300 to 10,000 and containing a) 5 to 70% by weight of octadienyl groups (calculated as C8H13) incorporated via ether bridges and b) 10 to 65% by weight of ester residues of unsaturated dicarboxylic acids (calculated as C4H2O4), which comprises esterifying A) a dicarboxylic acid component containing i) 50 to 100 carboxyl equivalents-% of one or more .alpha.,.beta.-ethylenically unsaturated dicarboxylic acids and/or their anhydrides and ii) 0 to 50 carboxyl equivalents-% of one or more compounds selected from the group of aliphatic saturated dicarboxylic acids having 4 to 10 carbon atoms, cycloaliphatic dicarboxylic acids having 8 to 10 carbon atoms, aromatic dicarboxylic acids having 8 to 12 carbon atoms and the anhydrides of any of these dicarboxylic acids with B) an alcohol component containing i) 5 to 100 hydroxyl equivalents-% of one or more monohydric or polyhydric alcohols having a molecular weight of 170 to 1000 and containing octadienyl groups incorporated via ether bridges and ii) 0 to 95 hydroxyl equivalents-% of monohydric or polyhydric alcohols having a molecular weight of from 32 to 200 other than those set forth in i), Mo-3755 while maintaining an equivalent ratio of carboxyl groups of component A) to hydroxyl groups of component B) of at most 1:1.

3. The process of Claim 2 wherein component B) comprises i) 5 to 100 hydroxyl equivalents-% of glycerol octadienyl ethers having an OH number of 182 to 561 and/or trimethylolpropane octadienyl ethers having an OH number of 160 to 464 and ii) 0 to 95 hydroxyl equivalents-% of one or more saturated aliphatic, saturated cycloaliphatic or araliphatic monohydric or dihydric alcohols having a molecular weight of from 62 to 200 other than those set forth in i).

4. The process of Claim 2 wherein component A) comprises i) 50 to 100 carboxyl equivalents-% of fumaric acid, maleic acid and/or maleic acid anhydride and ii) 0 to 50 carboxyl equivalents-% of phthalic acid or phthalic acid anhydride.

5. The process of Claim 3 wherein component A) comprises i) 50 to 100 carboxyl equivalents-% of fumaric acid, maleic acid and/or maleic acid anhydride and ii) 0 to 50 carboxyl equivalents-% of phthalic acid or phthalic acid anhydride.

6. The process of Claim 2 which comprises maintaining components A) and B) at an equivalent ratio of carboxyl groups to hydroxyl groups of 1:1.5 to 1:1.

7. The process of Claim 3 which comprises maintaining components A) and B) at an equivalent ratio of carboxyl groups to hydroxyl groups of 1:1.5 to 1:1.

8. The process of Claim 4 which comprises maintaining components A) and B) at an equivalent ratio of carboxyl groups to hydroxyl groups of 1:1.5 to 1:1.

Mo-3755

9. The process of Claim 5 which comprises maintaining components A) and B) at an equivalent ratio of carboxyl groups to hydroxyl groups of 1:1.5 to 1:1.

10. A molding, coating, grout or sealant prepared from the .alpha.,.beta.-ethylenically unsaturated polyester of Claim 1.

Mo-3755