Monofunctional or multifunctional urethane acrylate oligomers without isocyanates

Abstract

An acrylated and/or methacrylated urethane oligomer obtained by reaction of a specific polyamine with a cyclic carbonate compound carrying m cyclic carbonate groups, giving an intermediate product carrying m formed urethane groups which carry residual reactive amine —NH— groups, and subsequently an addition reaction of each of the residual reactive amine groups of the intermediate product with an acrylate group of a compound carrying, in addition to the acrylate group, p additional acrylate and/or methacrylate groups, with each residual reactive amine —NH— group of the intermediate product being thus converted into a carbon-nitrogen bond carrying the acrylate and/or methacrylate groups, and thus production of the urethane oligomer, with the urethane oligomer carrying m urethane groups and m hydroxyl groups and having a functionality in acrylates and/or methacrylates ranging from m*p(n−1) to m*p(2n−2).

Claims

1. A urethane oligomer which is monofunctional or multifunctional in acrylates and/or methacrylates, which can be obtained from the reaction of a specific polyamine a) with a cyclic carbonate compound b) carrying m cyclic carbonate groups, the polyamine being in stoichiometric excess with respect to b) and the reaction giving an intermediate product c) carrying m formed urethane groups, which groups carry residual reactive amine —NH— groups, and subsequently by an addition reaction of each of the residual reactive amine groups of the product c) with an acrylate group of a compound d) carrying, in addition to the acrylate group, p additional acrylate and/or methacrylate groups, with each residual reactive amine —NH— group of the product c) being thus converted into a carbon-nitrogen bond carrying the acrylate and/or methacrylate groups, and thus production of the urethane oligomer, with: the polyamine a) being a secondary-primary diamine having a single primary amine group and a single secondary amine group according to formula a1):
R.sub.1—NH—R.sub.2—NH—R,  a1) with R being H, R.sub.1 being alkyl, the alkyl optionally being alkoxylated and a cycloalkyl, and R.sub.2 selected from the group consisting of alkylene and cycloalkylene comprising an aliphatic C6 ring or aralkylene of valency n ranging from 2 to 5, with it being possible for R.sub.2 to carry or comprise at least one tertiary amine group, the carbonate b) carrying m cyclic carbonate groups with m ranging from 1 to 2, the ring of the cyclic carbonate groups being a ring having 5 atoms, wherein carbonate b) is i) a complete or partial ester of a monomeric or oligomeric polyacid; ii) a complete or partial ether of a monomeric or oligomeric polyol with a hydroxylated carbonate; iii) a complete or partial ether of a phenolic derivative with a hydroxylated carbonate; iv) an ether of allyl or vinyl alcohol with a hydroxylated carbonate or a methacrylate of a hydroxylated carbonate; v) a carbonate obtained by addition of CO.sub.2 to a precursor monomeric or oligomeric epoxidized compound; or vi) is the product of the reaction of dimethyl carbonate with an aliphatic or cycloaliphatic polyol with a functionality of from 2 to 6, the intermediate product c) carrying m urethane groups and m OH groups in the alpha or beta position with respect to the urethane group and c) carrying from m*(n−1) to m*(2n−2) residual reactive amine —NH— groups, wherein n equals 2, the compound d) carrying p acrylate and/or methacrylate groups in addition to the acrylate group which reacts with one of the residual reactive amine —NH— groups, with p being from 1 to 11, and the number of the residual reactive amine —NH— groups of the product c) being less than or equal to the number of moles of the compound d), each carbon-nitrogen bond formed carrying p acrylate and/or methacrylate groups and the urethane oligomer carrying m urethane groups and m hydroxyl groups in the alpha or beta position with respect to the urethane and having a functionality in acrylates and/or methacrylates ranging from m*p(n−1) to m*p(2n−2) wherein n equals 2, wherein the urethane oligomer has a general formula (I):
[RCH.sub.2═C(R.sub.6)—CO.sub.2).sub.p—R.sub.5—O.sub.2C—CH.sub.2—CH.sub.2—N(R.sub.1)—R.sub.2—NH—CO.sub.2—C(R.sub.4).sub.2—CH(OH)—].sub.mR.sub.3  (I) with R1 being alkyl, the alkyl optionally being alkoxylated and a cycloalkyl, and R2 selected from the group consisting of alkylene and cycloalkylene comprising an aliphatic C6 ring or aralkylene of valency n ranging from 2 to 5, with it being possible for R2 to carry or comprise at least one tertiary amine group, R.sub.3 being a hydrocarbon radical of aliphatic, cycloaliphatic and aromatic structure and optionally hydroxylated or a simple hydrogen when m=1, R.sub.4 selected from the group consisting of H and an optionally hydroxylated hydrocarbon substituent of aliphatic, cycloaliphatic or aromatic structure identical to or different from that of R.sub.3 and it optionally being possible for R.sub.4 to form a ring attached to the carbonate ring by two common carbon atoms, R.sub.5 selected from the group consisting of: (i) a polyol residue chosen from optionally alkoxylated and/or substituted alkylene polyol, optionally substituted cycloalkylene polyol or aralkylene polyol optionally alkoxylated and/or substituted on the aromatic ring or polyether polyol or polyester polyol and (ii) a residue of a multifunctional epoxy acrylate compound carrying an acrylate group and p additional acrylate and/or methacrylate groups, R.sub.6 selected from the group consisting of H or methyl or H and methyl if p is other than 1.

2. The oligomer of claim 1 wherein the compound d) has a formula of R.sub.5—(O.sub.2CCH═CH.sub.2)(—O.sub.2CC(R.sub.6)═CH.sub.2).sub.p with R.sub.5 being a hydrocarbon residue of valency p+1.

3. The oligomer of claim 1, wherein the secondary-primary diamine is selected from the group consisting of N-methyl-1,3-propanediamine, N-methylethane diamine, N-methyl-1,4-butanediamine and N-methyl-1,5-pentanediamine.

4. The oligomer of claim 1, wherein the compound d) is a multifunctional acrylic monomer having a functionality of at least 2 and ranging up to p+1 equal to 6 and selected from the group consisting of: d1) acrylate esters of alkoxylated or nonalkoxylated polyols, with polyols chosen from the group: trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, diethylene glycol, dipropylene glycol, tripropylene glycol, glycerol, propylene glycol, butanediol and hexanediol, d2) epoxy acrylates, and d3) aminoacrylates.

5. The oligomer of claim 1, wherein the compound d) is a multifunctional acrylic oligomer having a functionality of at least 2 and ranging up to p+1 equal to 12 and selected from: d4) acrylated acrylic oligomer which is an acrylated glycidyl methacrylate copolymer or acrylated styrene oligomer which is a copolymer of styrene with maleic anhydride or acrylic acid which is acrylated by hydroxyethyl acrylate, d5) acrylated hydroxylated oligomer, from acrylated hydroxylated polydienes, d6) acrylated epoxidized oil, d7) acrylated epoxidized oligodiene, d8) oligoether acrylates, d9) oligoester acrylates, d10) oligoaminoacrylates.

6. The oligomer of claim 1, wherein the functionality in acrylate and/or methacrylate groups varies from 1 to 30.

7. The oligomer of claim 1, wherein m=2 and p varies from 2 to 11.

8. The oligomer of claim 1, wherein the compound d) is in molar excess with respect to the amine —NH— groups of the intermediate product c) and with the residual compound d) being present in the oligomer as reactive diluent.

9. A crosslinkable composition comprising, as binder, at least one oligomer according to claim 1.

10. The crosslinkable composition of claim 9, wherein the crosslinkable composition can be crosslinked by the radiation route and/or by the thermal or low-temperature peroxide route and/or by the Michael-type addition route, in the case of oligomers carrying at least two acrylate functional groups, and/or by another dual route involving at least two of the routes mentioned and/or involving all or a portion of the m residual hydroxyl groups of the oligomer, by reaction of these residual hydroxyl groups with a crosslinking agent which reacts with the hydroxyls.

11. The crosslinkable composition of claim 9, wherein the crosslinkable composition is a coating composition, chosen from paints, varnishes and inks or a moulding composition, a leaktightness agent or chemical sealing composition, an adhesive composition, a composition for systems for the layer-by-layer manufacture of 3D objects, a composition for 3D printing systems, a concrete composition or a composite composition.

12. A urethane oligomer which is monofunctional or multifunctional in acrylates, which can be obtained from the reaction of a specific polyamine a) with a cyclic carbonate compound b) carrying m cyclic carbonate groups, the polyamine being in stoichiometric excess with respect to b) and the reaction giving an intermediate product c) carrying m formed urethane groups, which groups carry residual reactive amine —NH— groups, and subsequently by an addition reaction of each of the residual reactive amine groups of the product c) with a first acrylate group of a compound d) carrying, in addition to the first acrylate group, p additional acrylate groups, with each residual reactive amine —NH— group of the product c) being thus converted into a carbon-nitrogen bond carrying the acrylate groups, and thus production of the urethane oligomer, with: the polyamine a) being a secondary-primary diamine having a single primary amine group and a single secondary amine group according to formula a1):
R.sub.1—NH—R.sub.2—NH—R,  a1) with R being H, R.sub.1 being alkyl, the alkyl optionally being alkoxylated or a cycloalkyl, and R.sub.2 being alkylene or cycloalkylene comprising an aliphatic C6 ring or aralkylene of valency n ranging from 2 to 5, with it being possible for R.sub.2 to carry or comprise at least one tertiary amine group, the carbonate b) carrying m cyclic carbonate groups with m ranging from 1 to 2, the ring of the cyclic carbonate groups being a ring having 5 atoms, wherein carbonate b) is i) a complete or partial ester of a monomeric or oligomeric polyacid; ii) a complete or partial ether of a monomeric or oligomeric polyol with a hydroxylated carbonate; iii) a complete or partial ether of a phenolic derivative with a hydroxylated carbonate; iv) an ether of allyl or vinyl alcohol with a hydroxylated carbonate or a methacrylate of a hydroxylated carbonate; v) a carbonate obtained by addition of CO.sub.2 to a precursor monomeric or oligomeric epoxidized compound; or vi) is the product of the reaction of dimethyl carbonate with an aliphatic or cycloaliphatic polyol with a functionality of from 2 to 6, the intermediate product c) carrying m urethane groups and m OH groups in the alpha or beta position with respect to the urethane group and c) carrying from m*(n−1) to m*(2n−2) residual reactive amine —NH— groups, wherein n equals 2, the compound d) carrying p acrylate groups in addition to the first acrylate group which reacts with one of the residual reactive amine —NH— groups, with p being from 1 to 11, and the number of the residual reactive amine —NH— groups of the product c) being less than or equal to the number of moles of the compound d), each carbon-nitrogen bond formed carrying p acrylate groups and the urethane oligomer carrying m urethane groups and m hydroxyl groups in the alpha or beta position with respect to the urethane and having a functionality in acrylates ranging from m*p(n−1) to m*p(2n−2) wherein n equals 2, wherein the urethane oligomer has a general formula (I):
[RCH.sub.2═C(R.sub.6)—CO.sub.2).sub.p—R.sub.5—O.sub.2C—CH.sub.2—CH.sub.2—N(R.sub.1)—R.sub.2—NH—CO.sub.2—C(R.sub.4).sub.2—CH(OH)—].sub.mR.sub.3  (I) with R1 being alkyl, the alkyl optionally being alkoxylated and a cycloalkyl, and R2 selected from the group consisting of alkylene and cycloalkylene comprising an aliphatic C6 ring or aralkylene of valency n ranging from 2 to 5, with it being possible for R2 to carry or comprise at least one tertiary amine group, R.sub.3 being a hydrocarbon radical of aliphatic, cycloaliphatic or aromatic structure and optionally hydroxylated or a simple hydrogen when m=1, R.sub.4 selected from the group consisting of H and an optionally hydroxylated hydrocarbon substituent of aliphatic, cycloaliphatic or aromatic structure identical to or different from that of R.sub.3 and it optionally being possible for R.sub.4 to form a ring attached to the carbonate ring by two common carbon atoms, R.sub.5 selected from the group consisting of: (i) a polyol residue chosen from optionally alkoxylated and/or substituted alkylene polyol, optionally substituted cycloalkylene polyol or aralkylene polyol optionally alkoxylated and/or substituted on the aromatic ring or polyether polyol or polyester polyol and (ii) a residue of a multifunctional epoxy acrylate compound carrying an acrylate group and p additional acrylate groups, R.sub.6 being H or methyl or H and methyl if p is other than 1.

Description

EXPERIMENTAL PART

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

Example 1

(2) 161.55 g of propylene carbonate (Huntsman Jeffsol, Mw of 102 g/mol), 0.81 g of tris(nonylphenyl) phosphite and 1 g of 2,6-di(tert-butyl)-4-methylphenol (BHT) are introduced into a 1 l reactor. 146.80 g of N-methyl-1,3-propanediamine (Aldrich, Mw of 88.15 g/mol) are added over one hour at a constant flow rate with stirring and bubbling with nitrogen. An exothermicity of approximately 30° C. is observed. At the end of the addition, the temperature of the mixture is brought to 60° C. After one hour at 60° C., while bubbling with air, 689.85 g of tripropylene glycol diacrylate (TPGDA, Sartomer SR306, Mw of 300 g/mol) are added to the mixture in fifteen minutes at a constant flow rate. At the end of the addition, the temperature of the mixture is brought to 85-90° C.

(3) The progress of the reaction is monitored by a measurement of the total amine and tertiary amine numbers. The reaction is halted when the tertiary amine number=total amine number.

Example 2

(4) 162.93 g of propylene carbonate (Huntsman Jeffsol, Mw of 102 g/mol), 0.81 g of tris(nonylphenyl) phosphite and 1 g of 2,6-di(tert-butyl)-4-methylphenol (BHT) are introduced into a 1 l reactor. 147.81 g of N-methyl-1,3-propanediamine (Aldrich, Mw of 88.15 g/mol) are added over one hour at a constant flow rate with stirring and bubbling with nitrogen. An exothermicity of approximately 30° C. is observed. At the end of the addition, the temperature of the mixture is brought to 60° C. After one hour at 60° C., while bubbling with air, 687.44 g of trimethylolpropane triacrylate (TMPTA, Sartomer SR351, Mw of 296 g/mol) are added to the mixture in fifteen minutes at a constant flow rate. At the end of the addition, the temperature of the mixture is brought to 85-90° C.

(5) The progress of the reaction is monitored by a measurement of the total amine and tertiary amine numbers. The reaction is halted when the tertiary amine number=total amine number.

Example 3

(6) 336.04 g of polyethylene oxide dicarbonate (Specific Polymers, Mw of 632.5 g/mol), 1.68 g of tris(nonylphenyl) phosphite and 2.07 g of 2,6-di(tert-butyl)-4-methylphenol (BHT) are introduced into a 1 l reactor. 95.38 g of N-methyl-1,3-propanediamine (Aldrich, Mw of 88.15 g/mol) are added over one hour at a constant flow rate with stirring and bubbling with nitrogen. An exothermicity of approximately 30° C. is observed. At the end of the addition, the temperature of the mixture is brought to 60° C. After one hour at 60° C., while bubbling with air, 564.84 g of trimethylolpropane triacrylate (TMPTA, Sartomer SR351, Mw of 296 g/mol) are added to the mixture in fifteen minutes at a constant flow rate. At the end of the addition, the temperature of the mixture is brought to 85-90° C.

(7) The progress of the reaction is monitored by a measurement of the total amine and tertiary amine numbers. The reaction is halted when the tertiary amine number=total amine number.

(8) 2) Characteristics of the Products Prepared

(9) TABLE-US-00001 Characteristics Unit Example 1 Example 2 Example 3 Noury viscosity Pa .Math. s 2.0 (25° C.) 24 (50° C.) 12.3 (50° C.) Rate of m/min <10 50 >80 crosslinking under UV lamp Persoz hardness Number of 60 75 103 oscillations Flexibility mm N/DA 20 Resistance to s 10 >300 >300 acetone

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

(11) Methods Used

(12) Determination of the Reactivity (Crosslinking Rate):

(13) The mixture is applied as a 12 μm 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.

(14) 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.

(15) Determination of the Persoz Hardness:

(16) The mixture is applied as a 100 μm 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 40 in amplitude), of a pendulum in contact with the coated sheet of glass is measured according to Standard ISO 1522.

(17) Determination of the Flexibility:

(18) The mixture is applied as a 100 μm film to a smooth sheet of 25/100 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. The coated sheet is curved over cylindrical mandrels according to 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.

(19) Determination of the Resistance to Acetone:

(20) The mixture is applied as a 12 μm 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.