Acrylated or methacrylated urethane oligomer without isocyanate

Abstract

The invention relates to a monofunctional or multifunctional acrylated or methacrylated urethane oligomer where said urethane bond is obtained without use of isocyanate and by the carbonate-amine reaction between a cyclic carbonate and a monoamine or polyamine, with subsequently the conversion of the hydroxyls in the position with respect to the urethane bond into ester-acids by reaction with a cyclic anhydride, which reaction is followed by the conversion of said acid functional groups into acrylated or methacrylated end groups by reaction with a polyepoxide compound in the presence of acrylic or methacrylic acid. The invention also relates to a preparation process. Said oligomer is used as crosslinkable binder for a functionality of at least 2 in coating, molding, leaktightness agent or sealing compositions or, if monofunctional, as macromonomer in polymerizable compositions for the production of grafted polymers.

Claims

1. A linear or branched urethane oligomer having at least p acrylate or methacrylate end groups, wherein said urethane bond is obtained without isocyanate by carbonate-amine reaction between cyclic monocarbonate (carbonate) (III) and amine (II) of n primary amine functionality which is a monoamine or polyamine, with subsequently conversion of at least one of n hydroxyls formed in position with respect to each of the n urethane bonds, into ester-acids by reaction with cyclic anhydride compound (IV), which reaction is followed by conversion of said acid functional groups into p acrylate or methacrylate end groups by reaction with a polyepoxide compound (V) carrying m epoxide functional groups, with m equal at least to 2, m=m1 epoxide groups of which being converted into acrylate and/or methacrylate esters, and with the final functionality p being at least equal to m.

2. The oligomer of claim 1 wherein said conversion of said hydroxyls is complete and said overall functionality p is equal to m*n.

3. The oligomer of claim 2 comprising product of formula (I):
R.sub.1[NH(CO)OCH(R.sub.2)(CH.sub.2)r-CH(R.sub.2)O(OC)R.sub.3(CO)OR.sub.4R.sub.5(R.sub.4R.sub.6).sub.m].sub.n(I) with R.sub.1: hydrocarbyl of valence n in said amine compound (II), carrying n amine NH.sub.2groups, R.sub.2 or R.sub.2: substituents which are identical or different and interchangeable in their position, which are selected from the group consisting of: H, alkyl and hydroxyalkyl, said alkyl being a C.sub.1 to C.sub.3 alkyl, optionally with R.sub.2 and R.sub.2 to be located on adjacent carbons, if r=0, or on two carbons separated by a methylene, if r=1, optionally with combined radical CH(R.sub.2)(CH.sub.2)r-CH(R.sub.2) representing a C.sub.5 or C.sub.6 cycloalkylene radical forming before reaction, part of the ring of said cyclic carbonate compound (III), R.sub.3: selected from the group consisting of alkylene radical, cycloalkylene radical, and arylene radical which can be substituted, or unsubstituted, R.sub.3 forming before reaction, part of an anhydride ring of a cyclic anhydride compound (IV), R.sub.4R.sub.5(R.sub.4)m being hydrocarbyl residue of overall valence m (m=m1), corresponding to said epoxide compound (V) after reaction of the m epoxide groups, with R.sub.4 representing the CH.sub.2CH(OH) radical, the precursor of which is an epoxy (oxirane) group, and R.sub.5 being the hydrocarbyl radical of valence m in said epoxide compound (V) carrying, at the start, m precursor epoxide (oxirane) groups of said radical R.sub.4, optionally said compound (V) being a hydrocarbon chain epoxidized on the carbons forming said chain, R.sub.6: CH2=C(R.sub.7)(CO)O being acrylate when R.sub.7 is H or methacrylate when R.sub.7 is CH.sub.3 or a mixture of two groups, acrylate and methacrylate, for p>1, said oligomer being monofunctional having m*n equal to 1, or multifunctional having p=m*n equal to 2 or greater than 2.

4. The oligomer as claimed in claim 1 wherein said oligomer is monofunctional with p=m*n=1, m=1 and n=1.

5. The oligomer as claimed in claim 1 wherein said oligomer is multifunctional and of functionality p=m*n=2 or greater than 2 with m1and n2.

6. The oligomer as claimed in claim 1 wherein said oligomer is multifunctional and of functionality p=m*n=2 or greater than 2 with m2 and n1.

7. The oligomer as claimed in claim 5 wherein said oligomer is multifunctional and of functionality p=m*n from 2 to 32 .

8. The oligomer as claimed in claim 1 wherein said cyclic anhydride compound (IV) is selected from the group consisting of: succinic (R3: ethylene), maleic (R3: vinylene), phthalic (R3: 1,2 phenylene), itaconic, chlorendic, nadic, tetrahydrophthalic, hexahydrophthalic, methylhexahydrophthalic, methyltetra-hydrophthalic, naphthenic dicarboxylic, glutaric, trimellitic, adipic, sebacic dodecylsuccinic anhydride, tetrahydro-phthalic, hexahydrophthalic, and methyltetrahydrophthalic anhydrides.

9. The oligomer as claimed in claim 1 wherein said cyclic carbonate (III) is chosen from the group consisting of carbonates of ethylene glycol (R.sub.2=R.sub.2; H and r=0), of 1,3-propylene diol (R.sub.2=H, R.sub.2: CH.sub.3, r=0), of 1,2-propylene diol (R.sub.2=R.sub.2: H, r=1), of glycerol (R.sub.2: H, R.sub.2: CH.sub.2OH, r=0), of 1,2butanediol (R2: H and R.sub.2: CH.sub.2CH.sub.3), of 2,3 butanediol (R.sub.2 and R.sub.2: CH.sub.3) and of 1,3 butanediol (R.sub.2 or R.sub.2=CH.sub.3 and r=1) and the carbonate corresponding to a glycidyl ether of C.sub.1-C.sub.4 alcohol or of phenol, by addition of CO.sub.2 to the corresponding epoxide.

10. The oligomer as claimed in claim 1 wherein said epoxide Compound (V) is a diepoxide monomer selected from the group consisting of: ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, hexanediol diglycidyl ether, cyclohexanedimethanol diglycidyl ether, hydrogenated and nonhydrogenated bisphenol A diglycidyl ether (BADGE), hydrogenated and nonhydrogenated bisphenol F diglycidyl ether (BFDGE), optionally being alkoxylated, terephthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester and hexahydrophthalic acid diglycidyl ester.

11. The oligomer as claimed in claim 1 wherein said epoxide compound (V) is either a triepoxide selected from the group consisting of: trimethylolpropane triglycidyl ether, glycerol triglycidyl ether and triglycidyl isocyanurate, or a tetraepoxide selected from the group consisting of: pentaerythritol tetraglycidyl ether and ditrimethylolpropane tetraglycidyl ether, or dipentaerythritol hexaglycidyl ether, all of these optionally being alkoxyated.

12. The oligomer as claimed in claim 1 wherein said epoxy compound (V) is an epoxy resin with a number-average weight Mn<1000, chosen from the group consisting of: epoxidized, linear and branched, phenol-formaldehyde (novolac) resins, epoxidized oils, epoxidized polybutadiene and epoxidized condensation and addition prepolymer.

13. The oligomer as claimed in claim 1 wherein said amine R.sub.1(NH.sub.2)n (II) has monomer or oligomer structure.

14. The oligomer as claimed in claim 1 wherein said amine R.sub.1(NH.sub.2)n (II) is a monoamine monourethane or a diamine diurethane, which are the condensation products of a primary diamine with respectively a cyclic monocarbonate, which may be identical to or different from said cyclic carbonate compound (III), or a cyclic dicarbonate having two cyclic carbonate groups, and correspond to a ratio of primary amine groups to cyclic carbonates groups of 2.

15. The oligomer as claimed in claim 14, wherein n.sub.1=n hydroxyls per amine compound (II) are present in the position with respect to the urethane bond formed by carbonate-amine reaction in said monoamine urethane or in said diamine diurethane and that these n.sub.1=n hydroxyls are also converted, for at least one group among them, by successive reactions with said cyclic anhydride (IV), into ester-acid groups, followed by the conversion of said acid functional groups into at least m additional acrylated or methacrylated end groups by reaction with said polyepoxide compound (V) with an additional acrylate or methacrylate group functionality of said oligomer equal to at least m.

16. The oligomer as claimed in claim 14 wherein said amine R.sub.1(NH.sub.2)n comprises, in said radical R.sub.1, at least n.sub.2 hydroxyl different from the hydroxyls formed in the position with respect to a urethane bond by amine-carbonate reaction and that said n.sub.2 hydroxyls are converted by successive reactions with said cyclic anhydride (IV) into as many ester-acid groups, followed by conversion of said acid functional groups into m*n2 additional acrylated or methacrylated end groups by reaction with said polyepoxide compound (V), with the overall acrylate or methacrylate group functionality being increased by m*n2.

17. The oligomer as claimed in claim 14 wherein at least one of said n.sub.1 hydroxyls or n.sub.2 hydroxyls are converted to said acrylates or methacrylates with the respective additional functionality being at least m.

18. The oligomer as claimed in claim 13, wherein said amine R.sub.1(NH.sub.2)n (II) is an oligomer having a number-average weight Mn of less than 1500, of linear or branched or hyperbranched or dendrimer structure.

19. The oligomer as claimed in claim 17, wherein said amine R.sub.1(NH.sub.2)n (II) is an oligomer based on polyalkyleneimine, with said alkylene being ethylene, propylene or butylene (tetramethylene), or a polyether amine or a polyamine amine or a polyesteramide amine or an amine-epoxide addition prepolymer or an amine having as R.sub.1 radical, a fatty chain corresponding to fatty acid dimer or of trimer.

20. The oligomer as claimed in claim 14 wherein said oligomer carries, in addition to the acrylate and/or methacrylate groups, free hydroxyl groups.

21. The urethane oligomer as claimed in claim 3 which is the product of the following successive reactions: i) carbonate-amine reaction between a cyclic carbonate (III) including, in its ring, the CH(R.sub.2)CH.sub.2)r-CH(R.sub.2) radical and an amine R1(NH.sub.2).sub.n (II) with formation of n urethane groups carried by the R.sub.1 radical, each urethane group having an hydroxyl in theft position, ii) esterification of at least one of the hydroxyl groups generated in the position with respect to said bond, by a cyclic anhydride compound (IV) including, in its ring, a divalent organic radical R.sub.3, with formation in place of said hydroxyl of an ester-acid group, iii) reaction of the acid groups of said ester-acid group with an epoxide compound (V) carrying m epoxide groups which are precursors of the R.sub.4 radical and which are carried by an organic radical R.sub.5 of valence m, with m being at least 2, and with formation in place of each acid group of said ester-acid of an ester carrying m=m1 epoxide groups, said reaction iii) being followed by iv) reaction with acrylic and/or methacrylic acid of said m1 epoxide groups of said ester-epoxide groups, or, optionally, in said reaction iii), said epoxide compound (V) is replaced by the acrylated and/or methacrylated compound (VI) having m1 acrylated and/or methacrylated epoxide groups (mixture if m=m1>1) before said reaction iii) or simultaneously with said reaction iii) and, in the latter case, by simultaneous reaction between said epoxide compound (V) and acrylic and/or methacrylic acid in a molar ratio of m=m1mol of acrylic and/or methacrylic acid per mol of said epoxide compound (V), in which case (simultaneous reaction) said subsequent reaction according to iv) does not take place, with R.sub.1, R.sub.2, R.sub.2, R.sub.3, R.sub.4, R.sub.5, n, r and m being defined according to claim 3.

22. A process for the preparation of an oligomer according to claim 1 comprising the following reaction steps: i) carbonate-amine reaction between a cyclic monocarbonate (carbonate) (III) and a monoamine or polyamine (II) of primary amine functionality n with formation of n urethane groups and, per urethane group, of an hydroxyl in the position with respect to said bond, ii) esterification of at least one of said hydroxyl groups generated in the position with respect to said urethane bond, by a cyclic anhydride compound (IV) with formation, in place of said hydroxyl in the position, of an ester-acid group, iii) reaction of the acid group of said ester-acid group with an epoxide-group of a polyepoxide compound (V) carrying m epoxide groups with m equal to at least 2, with each new ester formed carrying m=m1 epoxide groups, iv) reaction, with acrylic acid and/or methacrylic acid, or said m=m1 epoxide groups in order to form m acrylate and/or methacrylate groups, with as optional alternative for said iii), iiia) said polyepoxide (epoxide) compound (V) is replaced with its acrylated and/or methacrylated equivalent (VI) having m=m1 epoxide groups preacrylated and/or premethacrylated, or iiib) said acrylated or methacrylated compound (VI) is formed simultaneously with said reaction and by reaction, simultaneously with that of stage iii), between said epoxide compound (V) and acrylic or methacrylic acid and in a molar ratio of m1 mol of acrylic or methacrylic acid per mol of said epoxide compound (V), in which case, according to options iiia) or iiib), said iv) has no reason to exist.

23. A polymerizable composition comprising at least one oligomer according to claim 1.

24. The composition of claim 23 which is crosslinkable and is a paint, varnish, ink, an adhesive, or a sealant.

25. The composition of claim 23 which is a polymerizable composition for the preparation of a grafted polymer comprising at least one comonomer which can be copolymerized by the radical route.

Description

EXPERIMENTAL PART

(1) 1) Preparation of Oligomers According to the Invention

Example 1

(2) 341.02 g of Priamine 1075 (Croda, equivalent weight M.sub.f of 275 g per amine functional group, a C.sub.36 fatty diamine from fatty acid dimer) and 0.06 g of triphenyl phosphite are introduced into a 1 l reactor. 122.69 g of propylene carbonate (Huntsman, Mw 102 g/mol) are added over one hour at an unvarying flow rate, with stirring at ambient temperature. An exothermicity of approximately 15 C. is observed. At the end of the addition, the temperature of the mixture is brought to 60 C. After reacting at 60 C. for 1 hour, 13.41 g of acrylic acid, 1.23 g of 2,4,6-trimethyl-p-cresol, 1.23 g of HQME (hydroquinone methyl ether) and 124.13 g of succinic anhydride are added to the mixture. The temperature of the medium is increased to 90 C. The progress of the reaction is monitored by measuring the total acid number. When the total acid number is less than 181 mg KOH/g, 316 g of butanediol diglycidyl ether (of EMSM.sub.f=127.5 g/mol of epoxide functional groups), 67.0 g of acrylic acid and 2.1 g of tetraethylammonium chloride are added to the mixture and the temperature is brought to 120 C. The progress of the reaction is monitored by measuring the acid and epoxy numbers. Additions of acrylic acid and/or of trimethylolpropane triglycidyl ether are carried out in order to keep a difference of 3 points between the acid number and the epoxy number EN (AN+3=EN). The reaction is halted when the acid number AN is less than 2 mg KOH/g and the epoxy number EN is less than 5 mg KOH/g.

(3) TABLE-US-00001 Starting Materials Parts by weight Tetraethylammonium chloride 4.0 Propylene carbonate 122.69 Acrylic acid 89.41 Priamine 1075 341.02 Triphenyl phosphite 0.06 Butanediol diglycidyl ether 316.22 2,4,6-Trimethyl-p-cresol 1.23 HQME 1.23 Succinic anhydride 124.13

Example 2

(4) 256.20 g of Priamine 1075 (CrodaM.sub.f=275 g/mol of amine functional group) and 0.05 g of triphenyl phosphite are introduced into a 1 l reactor. 92.18 g of propylene carbonate (Huntsman, Mw 102 g/mol) are added over one hour at an unvarying flow rate, with stirring at ambient temperature. An exothermicity of approximately 15 C. is observed. At the end of the addition, the temperature of the mixture is brought to 60 C. After reacting at 60 C. for 1 hour, 20.15 g of acrylic acid, 0.92 g of 2,4,6-trimethyl-p-cresol, 0.93 g of HQME and 93.26 g of succinic anhydride are added to the mixture. The temperature of the medium is increased to 90 C. The progress of the reaction is monitored by measuring the total acid number. When the total acid number is less than 152 mg KOH/g, 169.75 g of trimethylolpropane triglycidyl ether (EMSM.sub.f=149.6 g/mol of epoxide functional group), 100.76 g of acrylic acid and 2.1 g of tetraethylammonium chloride are added to the mixture and the temperature is brought to 120 C. The progress of the reaction is monitored by measuring the acid and epoxy numbers. Additions of acrylic acid and/or of trimethylolpropane triglycidyl ether are carried out in order to keep a difference of 3 points between the acid number and the epoxy number (AN+3=EN). The reaction is halted when the acid number is less than 2 mg KOH/g and the epoxy number is less than 5 mg KOH/g.

(5) TABLE-US-00002 Starting Materials Parts by weight Tetraethylammonium chloride 4.0 Propylene carbonate 92.18 Acrylic acid 134.34 Priamine 1075 256.20 Triphenyl phosphite 0.05 Trimethylolpropane triglycidyl ether 418.13 2,4,6-Trimethyl-p-cresol 0.92 HQME 0.93 Succinic anhydride 93.26
2) Characteristics of the Products Prepared

(6) TABLE-US-00003 Characteristics Unit Example 1 Example 2 Functionality p 2 4 (calculated) Noury viscosity Pa .Math. s 6.7 (50 C.) 16 (60 C.) Rate of crosslinking m/min <1 25 under UV lamp Persoz hardness Number of 37 44 oscillations Pencil hardness 6B 4B according to ASTM D3363 Flexibility mm 3 3 Resistance to s 6 57 acetone

(7) The applicative properties are measured on a film crosslinked under a 120 W/cm fusion UV lamp starting from a mixture of urethane acrylate according to the invention and Darocur 1173 photoinitiator in the proportions of 96/4 w/w.

(8) Methods Used

(9) Determination of the reactivity (crosslinking rate): The mixture is applied as a 12 m film to a contrast chart (Penoparc charts form 1B, Leneta) and is then crosslinked using a 120 W/cm Hg Fusion lamp. The minimum rate of passage (in m/min) necessary in order to obtain a film dry to the touch is measured.

(10) For the following tests of hardness, flexibility and resistance to acetone, the photocrosslinked films are left in a climate-controlled room (T=23 C.) for 24 hours after crosslinking and before the measurements. Determination of the Persoz hardness: The mixture to be examined is applied as a 100 m film to a sheet of glass and crosslinked by a 120 W/cm Hg Fusion lamp at a rate of 8 m/min. The number of oscillations, before the oscillations die out (change from 12 to 4 in amplitude), of a pendulum in contact with the coated sheet of glass is measured according to the standard ISO 1522. Determination of the flexibility: The mixture is applied as a 100 m film to a smooth sheet of steel of 25/10 mm in thickness (D-46 Q-Panel) and is then crosslinked by a 120 W/cm Hg Fusion lamp at a rate of 8 m/min.

(11) The coated sheet is curved over cylindrical mandrels according to the standard ISO 1519. The result is expressed by the value (in mm) of the lowest radius of curvature which can be inflicted on the coating without it cracking or detaching from the support. Determination of the resistance to acetone: The mixture is applied as a 12 m film to a sheet of glass and then crosslinked by a 120 W/cm Hg Fusion lamp at a rate of 8 m/min. The coating is rubbed with a rag impregnated with acetone. The result is the time (expressed in seconds) beyond which the film detaches and/or disintegrates.