ADDITION-FRAGMENTATION AGENTS

• US 20120208965A1
• Filed: 06/27/2011
• Published: 08/16/2012
• Est. Priority Date: 02/15/2011
• Status: Abandoned Application

• Current Assignee: 3M Innovative Properties Company (3M Company)
• Original Assignee: 3M Innovative Properties Company (3M Company)
• Inventors: Joly, Guy D., Krepski, Larry R., Gaddam, Babu N., Abuelyaman, Ahmed S., Fornof, Ann R., Yurt, Serkan
• Application Number:
  US13/169,306
• Publication Number:
  US 20120208965A1
• Time in Patent Office: Days
• US Class Current: 525/386
• CPC Class Codes: A61K 6/887 Compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
• CPC Class Codes: C07C 271/16 to carbon atoms of hydrocarbon radicals substituted by singly-bound oxygen atoms
• CPC Class Codes: C07C 67/14 from carboxylic acid halides
• CPC Class Codes: C07C 67/26 with an oxirane ring
• CPC Class Codes: C07C 69/593 Dicarboxylic acid esters having only one carbon-to-carbon double bond
• CPC Class Codes: C08K 3/22 of metals
• CPC Class Codes: C08K 3/36 Silica
• CPC Class Codes: C08K 5/11 of acyclic polycarboxylic acids
• CPC Class Codes: C08K 5/12 of cyclic polycarboxylic acids
• CPC Class Codes: C08K 5/205 Compounds containing groups, e.g. carbamates
• CPC Class Codes: C08L 33/08 Homopolymers or copolymers of acrylic acid esters
• CPC Class Codes: C08L 33/10 Homopolymers or copolymers of methacrylic acid esters
• CPC Class Codes: C09D 133/08 Homopolymers or copolymers of acrylic acid esters

Abstract

Addition-fragmentation agents of the formula are disclosed:

wherein

• R¹, R² and R³ are each independently Z-Q-, a (hetero)alkyl group or a (hetero)aryl group with the proviso that at least one of R¹, R² and R³ is Z_m-Q-,
• Q is a linking group have a valence of m+1;
• Z is an ethylenically unsaturated polymerizable group,
• m is 1 to 6;
• each X¹ is independently —O— or —NR⁴—, where R⁴ is H or C₁-C₄ alkyl, and
• n is 0 or 1.

Claims

1. An addition-fragmentation agent of the formula:

2. The addition-fragmentation agent of claim 1 where Z comprises a vinyl, vinyloxy, (meth)acryloxy, (meth)acrylamido, styrenic and acetylenic functional groups.

3. The crosslinking agent of claim 1 where Z is selected from:

4. The addition-fragmentation agent of claim 1 wherein Q is selected from from —

O—

. —

S—

, —

NR⁴—

, —

SO₂—

, —

PO₂—

, —

CO—

, —

OCO—

, —

R⁶—

, —

NR⁴—

CO—

NR⁴—

, NR⁴—

CO—

O—

, NR⁴—

CO—

NR⁴—

CO—

O—

R⁶—

, —

CO—

NR⁴—

R⁶—

, —

R⁶—

CO—

O—

R⁶—

, —

O—

R⁶—

. —

S—

R⁶—

, —

NR⁴—

R⁶—

, —

SO₂—

R⁶—

, —

PO₂—

R⁶—

, —

CO—

R⁶—

, —

OCO—

R⁶—

, —

NR⁴—

CO—

R⁶—

, NR⁴—

R⁶—

CO—

O—

, and NR⁴—

CO—

NR⁴—

, wherein each R⁴ is hydrogen, a C₁ to C₄ alkyl group, or aryl group, each R⁶ is an alkylene group having 1 to 6 carbon atoms, a 5- or 6-membered cycloalkylene group having 5 to 10 carbon atoms, or a divalent arylene group having 6 to 16 carbon atoms, with the proviso that Q-Z does not contain peroxidic linkages.

5. The addition-fragmentation agent of claim 1 where Q is an alkylene.

6. The addition-fragmentation agent of claim 5 wherein Q is an alkylene of the formula —

C_rH_2r—

, where r is 1 to 10.

7. The addition-fragmentation agent of claim 1 where Q is a hydroxyl-substituted alkylene.

8. The addition-fragmentation agent of claim 1 where Q is —

CH₂—

CH(OH)—

CH₂—

9. The addition-fragmentation agent of claim 1 where Q is an aryloxy-substituted alkylene.

10. The addition-fragmentation agent of claim 1 where R⁵ is an alkoxy-substituted alkylene.

11. The addition-fragmentation agent of claim 1 wherein R¹—

X¹—

groups (and optionally R²—

X²—

groups) is selected from H₂C═

C(CH₃)C(O)—

O—

CH₂—

CH(OH)—

CH₂—

O—

, H₂C═

C(CH₃)C(O)—

O—

CH₂—

CH(O—

(O)C(CH₃)═

CH₂)—

CH₂—

O—

, H₂C═

C(CH₃)C(O)—

O—

CH(CH₂OPh)-CH₂—

O—

, H₂C═

C(CH₃)C(O)—

O—

CH₂CH₂—

N(H)—

C(O)—

O—

CH(CH₂OPh)-CH₂—

O—

, H₂C═

C(CH₃)C(O)—

O—

CH₂—

CH(O—

(O)C—

N(H)—

CH₂CH₂—

O—

(O)C(CH₃)C═

CH₂)—

CH—

O—

, H₂C═

C(H)C(O)—

O—

(CH₂)₄—

O—

CH₂—

CH(OH)—

CH₂—

O—

, H₂C═

C(CH₃)C(O)—

O—

CH₂—

CH(O—

(O)C—

N(H)—

CH₂CH₂—

O—

(O)C(CH₃)C═

CH₂)—

CH₂—

O—

, CH₃—

(CH₂)₇—

CH(O—

(O)C—

N(H)—

CH₂CH₂—

O—

(O)C(CH₃)C═

CH₂)—

CH₂—

O—

, H₂C═

C(H)C(O)—

O—

(CH₂)₄—

O—

CH₂—

CH(—

O—

(O)C(H)═

CH₂)—

CH₂—

O— and

H₂C═

C(H)C(O)—

O—

CH₂—

CH(OH)—

CH₂—

O—

. H₂C═

C(H)C(O)—

O—

(CH₂)₄—

O—

CH₂—

CH(—

O—

(O)C(H)═

CH₂)—

CH₂—

O—

, and CH₃—

(CH₂)₇—

CH(O—

(O)C—

N(H)—

CH₂CH₂—

O—

(O)C(CH₃)C═

CH₂)—

CH₂—

O—

.

12. A polymerizable composition comprising the addition-fragmentation agent of claim 1, at least one free-radically polymerizable monomer, and an initiator.

13. The polymerizable composition of claim 12 comprising:

a) 85 to 100 parts by weight of an (meth)acrylic acid ester of non-tertiary alcohol;

b) 0 to 15 parts by weight of an acid functional ethylenically unsaturated monomer;

c) 0 to 10 parts by weight of a non-acid functional, ethylenically unsaturated polar monomer;

d) 0 to 5 parts vinyl monomer; and

e) 0 to 5 parts of a multifunctional (meth)acrylate;

based on 100 parts by weight total monomer, and

f) 0.1 to 10 parts by weight of the addition-fragmentation agent, based on 100 parts by weight of a) to e).

14. The polymerizable composition of claim 13 further comprising 0.01 to 5 parts of a multifunctional (meth)acrylate.

15. The polymerizable composition of claim 12 further comprising a free radical initiator.

16. The polymerizable composition of claim 15 wherein the initiator is a thermal initiator.

17. A method of making the addition-fragmentation agent of claim 1 comprising the step of reacting a compound of the formula:

18. The method of claim 17 wherein R⁵ is selected from a single bond or a divalent linking group that joins an ethylenically unsaturated group to co-reactive functional group A.

19. The method of claim 17 wherein R⁵ is selected from —

O—

. —

S—

, —

NR⁴—

, —

SO₂—

, —

PO₂—

, —

CO—

, —

OCO—

, —

NR⁴—

CO—

, NR⁴—

CO—

O—

, NR⁴—

CO—

NR⁴—

, —

R⁶— and

combinations thereof, where R⁶ is an alkylene group having 1 to 6 carbon atoms, a 5- or 6-membered cycloalkylene group having 5 to 10 carbon atoms, or a divalent arylene group having 6 to 16 carbon atoms.

20. The method of claim 17 wherein the co-reactive functional group A is selected from hydroxyl, amino, oxazolinyl, oxazolonyl, acetyl, acetonyl, carboxyl, isocyanato, epoxy, aziridinyl, acyl halide, vinyloxy, and cyclic anhydride groups.

21. The method of claim 17,

where the reactive functional group X² is isocyanato functional group, the co-reactive functional group A comprises a secondary amino or hydroxyl group;

where the reactive functional group X² comprises a hydroxyl group, the co-reactive functional group comprises a carboxyl, ester, acyl halide, isocyanato, epoxy, anhydride, azlactonyl or oxazolinyl group;

where the reactive functional group X² comprises a carboxyl group, the co-reactive functional group A comprises a hydroxyl, amino, epoxy, isocyanate, or oxazolinyl group.