SE521020C2 - Acrylic modified polyester, for UV curable materials e.g. printing inks, comprises polyol core with fumaric and acrylic groups bonded onto it - Google Patents

Abstract

An acrylic modified polyester (P), comprises at least one fumaric group (B)and at least one acrylic group (C) are bonded to the polyol core (A), derived from a diol, triol or polyol. (B) is derived from fumaric acid and/or maleic anhydride, and (C) is derived from (meth)acrylic acid or crotonic acid. Independent claims are also included for: (a) a multi-step process for the preparation of (P); (b) the use of (P) for the preparation of aqueous dispersions or emulsions; (c) the use of (P) in radiation-curable systems or thixotropic coatings; and (d) the use of (P) in fibre-reinforced molding or casting materials.

Description

521,020 tetrahydrophthalic anhydride and derivatives thereof such as endoethylenetetrahydrophthalic acids and anhydride in possible side reactions, such as addition of the hydroxyl group to the unsaturated double bond, reduces the unsaturation of the resin and thus the mechanical and chemical properties, thermal cis / trans isomerization such as glycol does not exceed 10%. -butanediol, 1,6-hexanediol and ethylene glycols are used.

Catalysts for cis / trans isomerization, such as ZnCl 2, TiCl 4, secondary amines and tertiary amines, tend to favor side reactions, such as etherification and epoxidation, which later interfere with the curing process, and to result in severe discoloration of the product obtained.

Film-forming compositions, for example wood coatings, usually include raw materials, for example polyacrylic derivatives such as tripropylene glycol diacylate, pentaerythritol trialoylate, dipentaerythritol penta- and hexacrylate and triisocyanurate triacylate, all of which have the disadvantage of being unpleasant and allergenic.

The use of unsaturated polyesters, in applications such as castings, moldings, thixotropic coatings, UV-curing putty and the like, usually involves a certain amount of vinyl monomers, such as styrene, 11-tert-butylstyrene and methylnietacrylate. The present invention reduces up to complete replacement the amount of free vinyl monomer, including acrylate monomers, in the polyester delivery form. It appears on new curing resin types with low content or free from vinyl monomers. The acrylic iodinated unsaturated polyester of the present invention acts simultaneously as unsaturated polyester and monomer diluent.

The acrylic modified fumar residue of the present invention reduces or eliminates the problems shown above quite unexpectedly. The present invention discloses a novel unsaturated polyester having a designed degree of unsaturation derived from maleic or fumaric acid and having an acrylic modification derived from acrylic, methacrylic and / or crotonic acid. The ratio of acrylic groups to fumar / maleine groups is between 1: 1 and 6: 1. An oligoester comprising unsaturated trans double bonds, derived from ärimaric acid or preferably maleic anhydride, wherein the cis double bond isomerized, is obtained by preference wherein said acid or acidic acids, optionally in combination with one or more dicarboxylic acids or esters, anhydrides and anhydrides linear or branched di-, tri- or polyalcohol in a molar ratio resulting in an oligopolyester resin having a hydroxyl group to ester group ratio of between 1: 1 and 6: 1. The hydroxyl-functional unsaturated polyester thus obtained is then acrylated with acrylic, methacrylic and / or crotonic acid at a molar ratio of acrylic groups to transdubble bonds of between 1: 1 and 6: 1. Preferred embodiments of the present invention include acrylic-modified fumar esters wherein the di-, tri- or polyalcohol is from the group L 2 -ethanediol, 1,2-propanediol, 1β-propanediol, 1,3-butanediol, 1,4-butanediol, 1,6 11-Exanediol, 2,2-Oxydiethanol, 1,4-cyclohexanedimethanol, 2,2,4-trimethyl-1β-pentanediol, glycerol, 2,2-propylidene-bis- -p-phenylene oxide-diethanol or -dipropanol-2-alkyl-substituted β-propanediols such as Z-methyl-β-propanediol, 2,2-dialkyl-substituted β-propanediols such as neopentyl glycol and 2-butyl-2-ethyl-β-propanediol, glycerol, trimethylolpropane, trimethylolethane, di-trimethylolpropane, di-trimethylolethane, pentaerythrolithane , polyethoxylated and / or polypropoxylated neopentyl glycol, trimethylolpropane, trimethylolethane and pentaerythritol with for example 2-50, such as 2-20, alkoxy groups, diethoxylated and dipropoxylated bisphenol A.

Further preferred embodiments of the present invention include variants of aloyl-modified fumar esters in which said fumaric acid and / or maleic anhydride are esterified in combination with one or more dicarboxylic acids, anhydrides and / or esters from the group of phthalic anhydride, isophthalethydyrethoethydriethaldehyde, anhydride), dimethyl terephthalate, dimethyl adipate, dimethyl succinate and / or dimethyl glutarate.

In a further aspect, the present invention relates to a two or more process process for the preparation of an acrylic-modified unsaturated polyester obtained from a di-, thi- or poly-alcohol and to the alcohol with ester bonds attached fumar and acrylic groups, optionally in combination with further acyl groups . The process comprises the steps of i) adding maleic anhydride, optionally in combination with one or more dicarboxylic acids, anhydrides or esters, to a linear or branched di-, tri- or polyalcohol at a reaction temperature of 150-250 ° C, preferably 160-195 ° C, during which addition at least 80% of the maleicis double bonds are isomerized to fumar trans double bonds, said step being performed at an inole ratio acid to alcohol resulting in an oligoester having a hydroxyl group to ester bond ratio of between 1: 1 and 6: 1 and wherein said step is optionally performed in presence of at least one catalyst which catalyzes said addition and / or said isomerization, and ii) esterification of said hydroxyl groups of said oligoester with acrylic acid, inethacrylic acid and / or crotonic acid at a molar ratio of acrylic unsaturation to fumar double bonds of between 1: 1 and 6: 1, preferably between 1,511 and 2: 1.

The first step involves the synthesis of an oligoester containing unsaturated trans double bonds derived from maleic anhydride whereby cis double bonds are isomerized. Maleic anhydride, and optionally one or more carboxylic acids, anhydrides or esters, is esterified with a branched or linear di-, tri- or polyalcohol, optionally in the presence of at least one sulfur, nitrogen and / or phosphorus-containing catalyst such as elemental sulfur, 2,4-morpholinylmercaptobenstiasol, 4,4'-dimorpholinyl disulfur, Z-mercaptobenstiasol, 3,3'-disulfonyl disulfur, piperidine, pyridine, diphenylguanidine, urotropin, piperazine, triphenylphosphate, phosphoric acid, dinonylphenylphosphine. Linear alcohols normally require the presence of said catalyst during esterification. The esterification is carried out at a molar ratio resulting in an oily goester with a hydroxyl group ratio to transdubble bonds of between 1: 1 and 6: 1.

The second step involves acylation of the hydroxyl-functional oligomer obtained in step 1 wherein acrylic acid, methacrylic acid and / or crotonic acid are used at a zero ratio of acrylic groups to transdubble bonds of between 1: 1 and 6: 1. The acrylic modification is preferably carried out in the presence of an azeotropic solvent such as toluene and at a temperature of suitably 90-130 ° C such as 105-115 ° C.

The products obtained according to the present invention are active in, for example, radical polymerization initiated by UV initiators or by redox initiation, an accelerator such as cobalt octoate, dimethylaniline and peroxides selected from, for example, methyl ethyl peroxide, cyclohexanone peroxide and / or benzoyl peroxide being included.

Unsaturated monomers such as styrene and / or p-tert-butylstyrene are used in amounts reduced by as much as 30% or more relative to the nominal amount required when unsaturated polyesters are used in formulations intended for applications such as castings, moldings, thixotropic coatings and impregnations. The volume concentration is also reduced when the polyester of the present invention is used, as a result of the crosslinking process between the built-in unsaturation in the polyester chain and the terminal unsaturated groups obtained by aclyl modification.

Acrylic-functionalized fumar esters obtained by the present invention can be successfully used in applications such as waterborne polymerization to obtain water-borne dispersions and emulsions, for example in combination with vinyl monomers such as styrene, α-methylstyrene, α n-butyl acrylate, isobutyl acrylate and / or vinyl acetate. Additional application areas include, for example, radiation curing systems, thixotropic coatings and fiber-reinforced moldings and moldings compositions.

It is understood that those skilled in the art without further explanation, by using the description above, may take full advantage of the present invention. The following preferred specific embodiments are, therefore, to be construed as merely illustrative, and not in any way restrictive of the foregoing description. The following Examples 1-10 relate to the preparation and evaluation of embodiments of the polyether of the present invention.

Example 11113.6 g of 2-methyl-1,3-propanediol were charged to a laboratory autoclave equipped with a heating system, stirrer, Dean-Stark separator, condenser and nitrogen inlet.

The propanediol was heated to 100 ° C and 626.4 g of maleic anhydride was added with stirring.

An exotene peak was observed and the temperature was limited to 165 ° C and was maintained for one hour. The temperature was now raised to 205 ° C, gradient 10 ° C / hour. The reaction mixture was kept at 205 ° C for 1 hour. A toluene drop was introduced after said hour and the acid number was determined at intervals of one hour until free acidity was less than 1 ing KOH / g. Toluene was removed in vacuo and an unsaturated oligoester having a hydroxyl functionality and a fumar group content of at least 75% was obtained.

Properties obtained Dry content,%:> 99.1 Viscosity at 25 ° C, MPase: 450 Acid number, mg KOH / g: <1 Hydroxyl number, mg KOH / g: 430 Example 2 318.0 g trimethylolpropane and 90.0 g toluene were charged in a laboratory aitoclave equipped as in Example 1. The temperature was raised to 80 ° C and 464.7 g of maleic anhydride was added. the temperature was further raised to 100 ° C and 350.0 g of phthalic anhydride was added. the temperature of the reaction mixture was raised to 120 ° C and the subsequent exotic peak was limited to 160 ° C. The acid number was checked and found to be 340-360 mg KOH / g. 667.0 g of 2-methyl-1,3-propanediol were added with stirring and the temperature was raised to 165-170 ° C and maintained for one hour. The temperature was raised for 4 hours, after said hour at 65-70 ° C, to 205 ° C. Toluene residues were discarded and the acid number was determined at one hour intervals until free acidity was less than 1 mg KOH / g. Toluene was finally removed in vacuo to give an unsaturated oily goester having the following properties.

Properties obtained 521 020 6 Dry content,%:> 99.1 Viscosity at 25 ° C, MPase: 100 Acid number, mg KOH / g: <10 Hydroxyl number, mg KOH / g: 220 Example 3,737.5 g 2-methyl-1 , 3-propanediol and 90 g of toluene were charged to a laboratory autoclave equipped as in Example 1. 224.4 g of maleic anhydride and 628.5 g of phthalic anhydride were added in that order with stirring and heating. the reaction mixture was turned to 135 ° C and an exotene reaction elevated the temperature to 160-165 ° C. The temperature was raised for 4 hours to 205 ° C and maintained at said temperature for one hour. Toluene solution was inserted until one of less than 10 mg KOH / g was obtained. Toluene was finally removed in vacuo and an unsaturated oligoester having a hydroxyl functionality and a fumar cleavage content of at least 75% was obtained.

Properties obtained Dry content,%:> 99.1 Viscosity at 25 ° C, MPase: 90 Acid number, mg KOH / g: <10 Hydroxyl number, mg KOH / g: 140 Example 4 291.3 g trimethylolpropane, 638.1 g maleic anhydride and 90 g of toluene were charged to a laboratory autoclave equipped as in Example 1. The reaction mixture was turned to 135 DEG C. and an exothermic reaction raised the temperature to 160-165 ° C. The temperature was limited to 160-165 ° C by water cooling of the autoclave. 770.6 g of 1,6-hexanediol and 0.3 g of phosphoric acid were added with stirring. The temperature was raised for 4 hours to 205 ° C and maintained at said temperature for 1 hour. Toluene residues were now inserted until one of less than 10 mg KOH / g was obtained. Toluene was finally removed in vacuo and an unsaturated oligoester having a hydroxyl functionality and a fumar group content of at least 75% was obtained.

Properties Dry content,%:> 99.1 521 020 Viscosity at 25 ° C, MPase: 40 Acid number, mg KOH / g: <10 Hydroxyl number, mg KOH / g: 230 Example 5 1201.7 g 1,6-hexanediol, 498.3 g of maleic anhydride and 90 g of toluene were charged to a laboratory autoclave equipped as in Example 1. The reaction mixture was heated to 135 ° C and an exothermic reaction raised the temperature to 160-165 ° C. The temperature was limited to 160-165 ° C by toluene reflux and if necessary Water cooling of the autoclave. 0.05 g of 2,4-morpholinylmercaptobenstiasol was now added with stirring. The temperature was raised for 4 hours to 205 ° C and maintained at said temperature for 1 hour. Toluene solution was inserted until one of less than 10 mg KOH / g was obtained. Toluene was finally removed in vacuo and an unsaturated oligoester having a hydroxyl functionality and a fumar group content of at least 75% was obtained.

Properties obtained Dry content,%:> 99.1 Viscosity at 25 ° C, MPase: 5 Acid number, mg KOH / g: <10 Hydroxyl number, mg KOH / g: 430 Example 6 1013.1 g castor oil, 294.0 g maleic anhydride and 302.2 g of trimethylolpropane were charged to a laboratory autoclave equipped as in Example 1. The reaction mixture was heated to 135 ° C and an exothermic reaction raised the temperature to 160-165 ° C. The temperature was limited to 160-165 ° C by water cooling of the autoclave. 312.9 g of neopentyl glycol was now added with stirring. The temperature was raised for 4 hours to 205 ° C and maintained at this temperature for one hour. Toluene solution was inserted until one of less than 10 mg KOH / g was obtained.

Toluene was finally removed in vacuo and an unsaturated oligoester having a hydroxyl functionality and a fumar group content of at least 75% was obtained.

Properties obtained 521 020 8 Dry content,%:> 99.1 Viscosity at 25 ° C, MPase: 1,000 Acid number, mg KOH / g: <10 Hydroxyl number, mg KOH / g: 102 Example 7 Unsaturated oligoesters obtained in Example 1-6 was acrylated by the following procedure: Acrylic acid and polyester according to Examples 1-6 were charged in an ratio of acyl acid to hydroxyl groups in said polyester of 1.7 to 1. ø Acrylation was performed in the presence of toluene in a weight ratio of toluene to said polyester of 2 to 1.

The inhibition system consisted of 0.15% by weight of 4-methoxyphenol and 0.02% by weight of nitrobenzene based on said polyester. Methanesulfonic acid in an amount of 1.1% by weight, based on said polyester, was used as catalyst.

Acrylic acid, polyester, toluene, inhibitors and catalyst were charged into a laboratory autoclave equipped as in Example 1. The temperature was raised to 100-110 ° C with vigorous stirring and continuous supply of air (15 m 3 / min). The residue was maintained for 10 hours, after which the reaction mixture was cooled to 20-25 ° C and neutralized to pH 6.5 with a solution of 5-10% by weight of sodium hydroxide in water. The aqueous phase was separated after neutralization and the product phase was washed with water until a pH of 7 was obtained. Water was now separated and completely removed by partial distillation of toluene. The resulting product solution was filtered, the acrylated unsaturated polyester was dried by evaporation of toluene in vacuo.

Characterization of the obtained acrylated fumar esters Oligoester according to example: 1 2 3 4 5 6 Acrylic acid / maleic anhydride ratio: 1/2 1.62 / 1 1.44 / 1 1/12 1/2 1/1 Viscosity at 23 ° C, MPase 450 37,000 19,500 3,700 120 6,800 Example 8 UV-curing coatings were prepared from the acrylic iodinated polyurethane polyesters obtained in Example 7 and based on oligoesters prepared in Examples 1-6. 521 020 9 Formulations Acrylic modified fumar polyester acc. ex. 1-6, g: 95.5 Wetting agent, g: 0.4 Leaching agent, g: 0.1 Photoinitiator (benzophenone), g: 4.0 The respective aldyl-nosed fumar polyester was turned to 50 ° C and wetting agent saint leaching agent was added over 30 minutes. The photoinitiator was then added and dissolved.

Stirring of said components continued for 1 hour while observing that the temperature did not exceed 50 ° C.

Example 9 Coatings obtained in Example 8 were applied, with a film thickness of 100 μm wet film, to glass plates and UV cured at four different radiant energies, 200, 400, 800 and 1600 mJ / cm 2, an 80W / cm UV lamp having a radiant energy of 240 at 15 mJ / cm 2 at a belt speed of 20 m / min was used. The result, measured with a König pendulum, of said curing is shown in diagram 1, wherein examples 1, 2, 3, 4, 5 and 6 refer to the respective oligoester acylated in example 8.

Example 10 Water and ethanol resistance at 24 and 6 hours exposure and MEK double iubs (according to ASTM D4752-87) were determined for films obtained at 200mJ / cm 2 in Example 9. Examples 1, 2, 3, 4, 5 and 6 refer to respectively oligoester acrylated in Example 7.

Result Example 1 2 3 4 5 6. None None None None None None None None Water ”24 nmmar change change change change change change None None None None None None Ethanol” 6 hours: change change change change change change change MEK Double rubs:> 200> 200> 200> 200> 200 100-150 521 020 10 Diagram 1 Könighhardhet mot strållningsene ngi 4 120 É lw; 7¿¿í: m 1 / * // Tj; 4: / J .. 60 _ - 'Könighårdllet, svängninga m, ---_:' * "'=': -I -__ '. _ _ Fl - _; 20; + _ _; 4¿_ _; 0. 1 1, 200 mI / cmz 400 rrLI / cnlz 800 mI / crr? 1600 n fl / cn fi z UV-strålxüngsene rgi, mJ / cm *: __._ Exerrpel 1 Exemgšeïïn "'_ _ .. ¶.V.' .. __Exer'ñpe1'3 _ _ .. _ Example-lf * _ _ .. _ Example 5 _ -¿. Example 6

Claims (2)

521 020 ll CLAIMS Acrylic modified unsaturated polyester characterized in that at least one fuinar group and at least one acrylic group are bonded by ester bond to at least one di-, tri- or polyalcohol, said fumar group being derived from fumaric acid and / or maleic anhydride and said acrylic anhydride , methacrylic acid and / or crotonic acid. Acrylic modified unsaturated polyester according to claim 1, characterized in that said at least one di-, tri- or polyalcohol is 1,2-ethanediol, L 2 -propanediol, 1β-propanediol, 1β-butanediol, 1,4-butanediol, 10-hexanediol, 2,2 ° -oxydietanol, 1A-cyclohexamide dimethanol, 2,2,4-trimethyl-1β-pentanediol, glycerol, 2,2-propylidene-bis-p-phenylene oxide ditanol, 2,2-propylidene-bis-p-phenylene oxide dipropanol, acrylic modified Unsaturated polyester according to claim 1, characterized in that said at least one di-, tri- or polyalcohol is at least one 2-alkyl-substituted β-propanediol or at least one 2,2-dialkyl-substituted β-propanediol. Acrylic modified unsaturated polyester according to claim 1, wherein said at least one d1-, tri- or polyalcohol is 2-methyl-1β-propanediol, 2-butyl-2-ethyl-1β-propanediol, neopentyl glycol, glycerol, trimethylolpropane, trimethylolethane, di-trimethylolpropane, di-trimethylolethane, pentaerythritol or di-pentaerythritol. Acrylic-modified unsaturated polyester according to claim 1, characterized in that said at least one di-, tri- or polyalcohol is at least one ethoxylated and / or propoxylated neopentyl glycol, trimethylolpropane, trimethylolethane or pentaerythritol. Acrylic modified unsaturated polyester according to claim 5, characterized in that said at least one ethoxylated and / or propoxylated di-, tri- or polyalcohol comprises 2-50, preferably 2-20, alkoxy groups. Acrylic-modified unsaturated polyester according to claim 1, characterized in that at least one di-, tri- or polyalcohol is diethoxylated or dipropoxylated bisphenol A. Acrylic-modified unsaturated polyester according to any one of claims 1-7, characterized in that said fumaric group is derived from inhalic acid maleincisd double bonds are at least 80% isomerized to fumar trans double bonds. 10. 11. 12. 13. 14. 15. 16. 521 020 12 Acrylic modified unsaturated polyester according to any one of claims 1-8, characterized in that said polyester in addition to said fumar group and said acrylic group comprises at least one other acyl group. Acrylic modified unsaturated polyester according to claim 9, characterized in that the acyl group is derived from at least one dicarboxylic acid or at least one anhydride or ester thereof. Acrylic-modified unsaturated polyester according to Claim 9 or 10, characterized in that the acyl group is derived from phthalic anhydride, isophthalic acid, tetrahydrophthalic anhydride, 3,6-endomethylenetetrahydrophthalic anhydride, hexachloreridomethylenetetrahydrophthalethateethyl anethimethethyl anthimethyl anthimethyl anhydride. Process in two or more steps for the production of an acrylic-modified unsaturated polyester according to one of the claims 1. -11 characterized in that the process comprises the steps of i) adding maleic anhydride to a linear or branched di-, tri- or polyalcohol at a reaction temperature of 150-250 ° C, preferably 160-195 ° C, said addition being carried out in a molar ratio of said anhydride to said alcohol ester resin a ratio of ester bonds of between 1: 1 and 6: 1, and ii) destruction of the hydroxyl groups of the polyester resin with acrylic, methacrylic and / or crotonic acid at a molar ratio of acrylic unsaturation to fumar double bonds of between 1: 1 and 6: 1, preferably between 1.521 and 2: 1. resulting in a hydroxyl group to Process according to claim 12, characterized in that step (i) is carried out in the presence of at least one catalyst which catalyzes said isomerization of maleicis double bonds to fumaric transbound bonds. addition and / or catalyzing Process according to claim 13, characterized in that at least one catalyst is at least one sulfur, nitrogen and / or phosphorus-containing catalyst. Process according to claim 13 or 14, characterized in that said at least one elemental sulfur, 2,4-1-norpholinylmercaptobenzothiazole, 2.-mercaptobenstiasol catalyst is 4,4'-dimorpholinyl disulfur 3,3 "-disulfonyl disulfur, piperidine, pyridine, diphenylguanidine, urotropin, piperazine, triferylphosphate, phosphoric acid and / or dinonylphenylphosphate. A process according to any one of claims 12 to 15, characterized in that maleicis double bonds in step (i) are at least 80% isomerized to fumaric transbound bonds. 17. 18. 19. 521 020 13 Use of an acrylic-modified unsaturated polyester according to any one of claims 1-11 in Waterborne polymerization. Use of an acrylic-modified unsaturated polyester according to any one of claims 1 to 11 in waterborne dispersions and emulsions. Use of an acrylic-modified unsaturated polyester according to one of Claims 1 to 11 in radiation-curing systems.