Multifunctional acrylic oligomers of branched structure, by polyaddition between multifunctional amines and acrylates

Patent metadata

Field	Value
Publication number	US-10125223-B2
Application number	US-201515321023-A
Country	US
Kind code	B2
Filing date	Jun 15, 2015
Priority date	Jun 23, 2014
Publication date	Nov 13, 2018
Grant date	Nov 13, 2018

Abstract

An acrylated oligomer, having a number-average acrylate functionality f o >2, of branched structure results from the polyaddition reaction of at least one amine A) having a functionality f A of N—H groups of at least 2, to at least one multifunctional acrylate B) having a functionality f B of acrylate groups of at least 2, with an average functionality per mole of all of the components A)+B) of greater than 2 and with the oligomer comprising in its repeating unit structure at least one —O 2 C—CH 2 —CH 2 —N═ aminoacrylate group resulting from the polyaddition and with a content of nitrogen resulting from the amine A) of greater than or equal to 0.35 mEq/g and an initial ratio r=acrylate/N—H of between r inf and 1.1 r sup with r inf =0.90*(f A −1)*(f B −1) and r sup =2*f A +2*f B −6 and the average number n av of repeating units per oligomer n av =1/[(r*f A /f B )+1−f A ].

First claim

The invention claimed is:

1. An acrylated oligomer, wherein the oligomer has a number-average acrylate functionality f o of greater than 2 acrylates per mole, has a branched structure and results from the polyaddition reaction of at least one amine A) having a functionality f A of N—H groups of at least 2, with said N—H functionality meaning a number-average functionality if it is a mixture of amines, said amine A) bearing primary and/or secondary amine functions, with said amine A) bearing at least one tertiary amine function (without N—H) and of at least one multifunctional acrylate B) having a functionality f B of acrylate groups of at least 2, with said acrylate functionality meaning a number-average functionality if it is a mixture of acrylates, with a number-average functionality per mole of all of the components A) and B) of greater than 2 and with said oligomer comprising in its repeating unit structure at least one —O 2 C—CH 2 —CH 2 —N═ aminoacrylate group resulting from said polyaddition and with a content of nitrogen t A , resulting from said amine A), of greater than or equal to 0.35 mEq/g and an initial ratio r=acrylate/N—H of between r inf and 1.1 r sup with the values r inf and r sup being defined according to equations (1) and (2) below:
r inf =0.90*( f A −1)*( f B −1)  (1)

r sup =2* f A +2* f B −6  (2)

and with an average number n av of repeating units per oligomer defined according to equation (3) below:
n av =1/[( r*f A /f B )+1− f A ]  (3).

2. The oligomer of claim 1 , wherein said amine A) bears in addition, at least one tertiary amine function and is selected from: dimethylaminopropylamine (DMAPA), dimethylaminopropylaminopropylamine (DMAPAPA) and 1,4-bis(3-aminopropyl)piperazine (1,4-BAPP) and with a content of nitrogen t A resulting from the amine of greater than or equal to 0.35 mEq/g.

3. The oligomer of claim 1 , wherein the viscosity of said acrylate B) measured according to the ISO 2555 method at 23° C. is less than 200 mPa·s under a shear rate of 100 s −1 .

4. The oligomer of claim 1 , wherein said acrylate B) is selected from the group consisting of: b1) optionally alkoxylated aliphatic or cycloaliphatic polyol acrylates, b2) oligoether acrylates, b3) alkoxylated phenolic acrylates and b4) acrylated aminoacrylates and mixtures thereof.

5. The oligomer of claim 1 , wherein said amine A) is selected from the group consisting of: a1) an aliphatic amine, a2) a cycloaliphatic amine and a3) an aralkylene amine with the amine function at a position other than the alpha or beta position of the aromatic ring, and mixtures thereof.

6. The oligomer of claim 1 , wherein said functionalities f A and f B are selected so that the sum f A +f B does not exceed 8.

7. The oligomer of claim 1 , wherein the oligomer has a content of acrylate groups t acr of greater than 2.3 mmol/g or milliequivalents/g.

8. The oligomer of claim 1 , wherein the oligomer has a number-average molecular mass Mn defined according to equation (4) below, ranging from 275 to 5000:
M n =M B +( n av *M u )  (4)

with M u being the molar mass of the repeating unit defined according to equation (5) below:
M u =M A +( f A2 +2* f A1 −1)* M B   (5)

n av being the average number of repeating units as defined in claim 1 ,
M B being the molar mass of the acrylate B),
M A being the molar mass of the amine A),
f A1 being the number of primary amine —NH 2 functions, per amine A) and
f A2 being the number of secondary amine —NH— functions, per amine A).

9. The oligomer of claim 1 , wherein the oligomer has a content of nitrogen t A resulting from the amine expressed in mEq/g ranging from 0.4 to 5 with t A being defined according to equation (6) below:
t A =1000* n av *( f A1 +f A2 +f A3 )/ Mn   (6)

with Mn being the number-average molecular mass as defined as claimed in claim 8 ,
f A1 being the number of primary amine —NH 2 functions, per amine A) and
f A2 being the number of secondary amine —NH— functions, per amine A)
f A3 being the number of tertiary amine —N=functions, per amine A).

10. The oligomer of claim 1 , wherein said amine A) has a functionality f A greater than or equal to 2 and said acrylate B) has a functionality f B greater than or equal to 3 or conversely said amine A) has a functionality f A greater than or equal to 3 and that said acrylate B) has a functionality f B greater than or equal to 2.

11. The oligomer of claim 1 , wherein:
said amine A) is of general formula (NH 2 ) fA1 R2(NHR3) fA2 , with R2=R′(NR″R′″) fA3 , R3, R′, R″ and R′″ being identical or different C 1 to C 3 alkyls with f A1 being equal to 0 and being the number of primary amine functions per mole, f A2 being greater than or equal to 2 and being the number of secondary amine functions per mole and f A3 being greater than 0 and being the number of tertiary amine functions per mole and with f A =f A2
said acrylate B) is of general formula R1(X) fB with X being a CH 2 ═CH—CO 2 — acrylate group and R1 being the residue of said acrylate B) bearing f B acrylates per mole
said oligomer comprises the product of the general formula (I) below:
X (fB-1) R1[O 2 CCH 2 CH 2 NR3R2Y (fA2-2) NR3CH 2 CH 2 CO 2 R1X (fB-2) ] n X  (I)

with Y=—(NR3CH 2 CH 2 COOR1X (fB-1) ).

12. The oligomer of claim 1 , wherein:
said amine A) is of general formula (NH 2 ) fA1 R2(NHR3) fA2 , with R2=R′(NR″R′″) fA3 , R3, R′, R″ and R′″ being identical or different C 1 to C 3 alkyls with f A1 being greater than or equal to 1 and being the number of primary amine functions per mole, f A2 being greater than or equal to 0 and being the number of secondary amine functions per mole and f A3 being greater than 0 and being the number of tertiary amine functions per mole and with
f A =2* f A1 +f A2

said acrylate B) is of general formula R1(X) fB with X being a CH 2 ═CH—CO 2 — acrylate group and R1 being the residue of said acrylate B) bearing f B acrylates per mole
said oligomer comprises the product of the general formula (II) below:
X (fB-1) R1[O 2 CCH 2 CH 2 NR2Y fA2 Z (fA1-1) CH 2 CH 2 CO 2 R1X (fB-2) ] n X  (II)

with Y=—(NR3CH 2 CH 2 CO 2 R1X (fB-1) and
Z=—(N(CH 2 CH 2 COOR1X (fB-1) ) 2 ).

13. The oligomer of claim 10 , wherein said functionality f A is equal to 3 and said amine A) is selected from a diamine bearing a primary amine function and a secondary amine function or a triamine bearing 3 secondary amine functions.

14. The oligomer of claim 10 , wherein said amine A) has a functionality f A equal to 2 and is a primary amine or a diamine bearing 2 secondary amine functions and that said acrylate B) is an optionally alkoxylated triacrylate with, in the case where said triacrylate is alkoxylated, a number of alkoxy units per acrylate that does not exceed 3 if said alkoxy is ethoxy and a number of alkoxy units per acrylate that does not exceed 1 if said alkoxy is propoxy.

15. The oligomer of claim 10 , wherein said amine A) has a functionality f A equal to 3, which is a primary-secondary diamine or a triamine bearing 3 secondary amine functions and said acrylate B) is an optionally alkoxylated diacrylate with, in the case where said diacrylate is alkoxylated, a number of alkoxy units per acrylate that does not exceed 2 if said alkoxy is ethoxy and a number of alkoxy units per acrylate that does not exceed 1 if said alkoxy is propoxy.

16. The oligomer of claim 10 , wherein said functionality f A is equal to 4 and said amine A) is selected from a diamine bearing 2 primary amine functio

Assignees

• Arkema France

Inventors

• Ciceron Philippe
• Bourrousse Charles
• Leroy Catherine M

Classifications

• C08G73/02

  Polyamines · CPC title

• C08J3/24

  Crosslinking, e.g. vulcanising, of macromolecules (mechanical aspects B29C35/00; crosslinking agents C08K) · CPC title

• C09D11/101

  Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing · CPC title

• C09J4/00

  Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond {; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16} · CPC title

• C09D4/00

  Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond {; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16} · CPC title