Patent US5872197A successfully refreshed from Google Patents.
US5872197A
Expired / Lapsed
US
⏱️ 0.0 years remaining
Initiator system and adhesive composition made therewith
Assignee: 3M Innovative Properties Co
•
Filing: 1997-06-23
•
Granted: 1999-02-16
•
Expires: 2017-06-23
Abstract
Abstract Systems for initiating the polymerization of acrylic monomers comprising (1) organoborane amine complexes and (2) bireactive decomplexers preferably comprising at least one free-radically polymerizable group and at least one amine-reactive group in the same molecule. The decomplexer is capable of forming a covalent bond with both the acrylic monomers and amine complex, resulting in a reduced level of mobile constituents. Furthermore, when the organoborane amine complex of the initiator system comprises a polyamine compound, polymerized acrylic compositions having improved solvent resistance are advantageously provided.
Inventors
- 👤 E. John Deviny
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-23 20:10
CPC Classifications
C; C08; C08F; C08F4/00; C08F4/42; C08F4/44; C08F4/52; C08F220/00; C08F220/02; C08F220/10; C09; C09J; C09J4/00
Claims Analysis
Total Claims: 57
Claim 1
Independent Claim
53 words
A polymerizable acrylic composition comprising: a) at least one acrylic monomer; b) an effective amount of an organoborane amine complex; and c) an effective amount of a bireactive decomplexer containing isocyanate functionality, said decomplexer being reactive with said amine to liberate the organoborane to initiate polymerization of the at least one acrylic monomer.
Claim 2
Dependent Claim
53 words
A polymerizable acrylic composition comprising: a) at least one acrylic monomer; b) an effective amount of an organoborane amine complex; and c) an effective amount of a bireactive decomplexer containing isocyanate functionality, said decomplexer being reactive with said amine to liberate the organoborane to initiate polymerization of the at least one acrylic monomer.
Claim 3
Dependent Claim
38 words
A polymerizable acrylic composition according to claim 1 wherein the at least one acrylic monomer is selected from the group consisting of monofunctional acrylate ester, monofunctional methacrylate ester, substituted derivatives of the foregoing, and blends of the foregoing.
Claim 4
Dependent Claim
30 words
A polymerizable acrylic composition according to claim 1 wherein said bireactive decomplexer comprises at least one free radically polymerizable group and at least one isocyanate group in the same molecule.
Claim 5
Dependent Claim
28 words
A polymerizable acrylic composition according to claim 1 wherein said bireactive decomplexer comprises at least one alkene group and at least one isocyanate group in the same molecule.
Claim 6
Dependent Claim
28 words
A polymerizable acrylic composition according to claim 1 wherein said bireactive decomplexer comprises at least one acrylic group and at least one isocyanate group in the same molecule.
Claim 7
Dependent Claim
35 words
A polymerizable acrylic composition according to claim 1 wherein said decomplexer comprises the reaction product of a polyisocyanate and a hydroxyl compound containing a group capable of forming a covalent bond with an acrylic monomer.
Claim 8
Dependent Claim
63 words
A polymerizable acrylic composition according to claim 6 wherein said hydroxyl compound has the structure: (A).sub.a --Q--OH wherein "A" is a group capable of forming a covalent bond with an acrylic monomer; "a" is an integer having a value of at least one; and Q is selected from the group consisting of alkyl, aryl, cycloalkyl, alkylene ether and carbonyl groups, and combinations thereof.
Claim 9
Dependent Claim
65 words
A polymerizable acrylic composition according to claim 6 wherein said hydroxyl compound has the structure: ##STR10## wherein R 1 is selected from the group consisting of hydrogen, methyl, ethyl and chlorine; R 2 is an alkyl group; and X is selected from the group consisting of oxygen and NR 3 , wherein R 3 is selected from the group consisting of hydrogen and alkyl groups.
Claim 10
Dependent Claim
37 words
A polymerizable acrylic composition according to claim 8 wherein R 1 is selected from the group consisting of hydrogen and methyl; R 2 is an alkyl group having 2 to 16 carbon atoms; and X is oxygen.
Claim 11
Dependent Claim
81 words
A polymerizable acrylic composition according to claim 6 wherein said hydroxyl compound has the structure: ##STR11## wherein R 1 is selected from the group consisting of hydrogen, methyl, ethyl and chlorine; R 2 is an alkyl group; X is selected from the group consisting of oxygen and NR 3 , wherein R 3 is selected from the group consisting of hydrogen and alkyl groups; R 4 is an alkyl group; and m is an integer greater than or equal to 1.
Claim 12
Dependent Claim
49 words
A polymerizable acrylic composition according to claim 10 wherein R 1 is selected from the group consisting of hydrogen and methyl; R 2 is an alkyl group having 2 to 16 carbon atoms; X is oxygen; and R 4 is an alkyl group having 2 to 11 carbon atoms.
Claim 13
Dependent Claim
38 words
A polymerizable acrylic composition according to claim 6 wherein said hydroxyl compound is selected from the group consisting of hydroxyethylmethacrylate, hydroxyethylacrylate, and hydroxybutylacrylate; and said polyisocyanate is selected from the group consisting of isophorone diisocyanate and toluene diisocyanate.
Claim 14
Dependent Claim
87 words
A polymerizable acrylic composition according to claim 1 wherein said organoborane amine complex has the structure: ##STR12## wherein R 6 is an alkyl group having 1 to 10 carbon atoms; R 7 and R 8 are independently selected from the group consisting of alkyl groups having 1 to 10 carbon atoms and phenyl-containing groups; the value of v is selected so as to provide a 0.5:1 to 4:1 ratio of primary or secondary amine nitrogen atoms to boron atoms in the complex; and Am is an amine.
Claim 15
Dependent Claim
81 words
A polymerizable acrylic composition according to claim 13 wherein Am has the structure: ##STR13## where R 9 and R 10 are independently selected from the group consisting of hydrogen, alkyl groups having 1 to 10 carbon atoms, ethanol and ##STR14## wherein R 11 and R 12 are independently selected from the group consisting of hydrogen and alkyl groups having 1 to 10 carbon atoms; m is an integer from 2 to 10; and n is an integer from 1 to 6.
Claim 16
Dependent Claim
87 words
A polymerizable acrylic composition according to claim 13 wherein Am is a polyoxyalkylenepolyamine having a structure selected from the group consisting of: H.sub.2 NR.sub.13 O--(R.sub.14 O).sub.w --(R.sub.15 O).sub.x --(R.sub.14 O).sub.y --R.sub.13 NH.sub.2 and H.sub.2 NR.sub.13 O--(R.sub.14 O).sub.w !.sub.z --R.sub.17 wherein R 13 , R 14 and R 15 are independently selected from the group consisting of alkylene and alkyl groups; R 17 is a polyol residue; the value of w is ≧1; the value of x and y are ≧0; and the value of z is >2.
Claim 17
Dependent Claim
51 words
A polymerizable acrylic composition according to claim 13 wherein Am has the structure E--(L--E) q --L--E wherein each E group is independently the residue of a diprimary amine-terminated material; each L is independently the residue of a material having at least two groups reactive with primary armine; and q is ≧0.
Claim 18
Independent Claim
99 words
A method of initiating the polymerization of at least one acrylic monomer, the method comprising the steps of: a) providing at least one acrylic monomer; b) blending the at least one acrylic monomer with the components of a polymerization initiator system, said system comprising: i) an organoborane amine complex; ii) an effective amount of a decomplexer comprising at least one acrylic group and at least one isocyanate group, said decomplexer being reactive with amine for liberating the organoborane to initiate polymerization of the at least one acrylic monomer; and c) initiating polymerization of the at least one acrylic monomer.
Claim 19
Independent Claim
99 words
A method of initiating the polymerization of at least one acrylic monomer, the method comprising the steps of: a) providing at least one acrylic monomer; b) blending the at least one acrylic monomer with the components of a polymerization initiator system, said system comprising: i) an organoborane amine complex; ii) an effective amount of a decomplexer comprising at least one acrylic group and at least one isocyanate group, said decomplexer being reactive with amine for liberating the organoborane to initiate polymerization of the at least one acrylic monomer; and c) initiating polymerization of the at least one acrylic monomer.
Claim 20
Independent Claim
120 words
A method of increasing the solvent resistance of a polymerized acrylic adhesive composition obtained by organoborane-initiated polymerization of acrylic monomer, said method comprising the steps of: a) providing at least one acrylic monomer; b) providing a bireactive decomplexer; c) blending the bireactive decomplexer with the at least one acrylic monomer; d) providing and blending an organoborane polyamine complex to the blend formed in step c) whereby the polyamine portion of the complex reacts with and covalently bonds to the bireactive decomplexer, thereby liberating the organoborane portion of the complex; and e) initiating polymerization of the at least one acrylic monomer with the liberated organoborane portion of the complex and continuing polymerization until a solvent resistant acrylic adhesive composition is obtained.
Claim 21
Independent Claim
120 words
A method of increasing the solvent resistance of a polymerized acrylic adhesive composition obtained by organoborane-initiated polymerization of acrylic monomer, said method comprising the steps of: a) providing at least one acrylic monomer; b) providing a bireactive decomplexer; c) blending the bireactive decomplexer with the at least one acrylic monomer; d) providing and blending an organoborane polyamine complex to the blend formed in step c) whereby the polyamine portion of the complex reacts with and covalently bonds to the bireactive decomplexer, thereby liberating the organoborane portion of the complex; and e) initiating polymerization of the at least one acrylic monomer with the liberated organoborane portion of the complex and continuing polymerization until a solvent resistant acrylic adhesive composition is obtained.
Claim 22
Dependent Claim
9 words
A polymerizable acrylic adhesive composition according to claim 1.
Claim 23
Dependent Claim
39 words
A polymerizable acrylic adhesive composition according to claim 19 wherein the at least one acrylic monomer is selected from the group consisting of monofunctional acrylate ester, monofunctional methacrylate ester, substituted derivatives of the foregoing, and blends of the foregoing.
Claim 24
Dependent Claim
17 words
A polymerizable acrylic adhesive composition according to claim 19 having about 0.03 to 1.5 weight % boron.
Claim 25
Dependent Claim
64 words
A polymerizable acrylic composition comprising: a) at least one acrylic monomer; b) an effective amount of an organoborane amine complex; and c) an effective amount of a decomplexer that is reactive with amine to liberate the organoborane from the complex; wherein the decomplexer is selected such that the resulting polymerized material is essentially free from amine-decomplexer reaction product that has not been polymerized therein.
Claim 26
Dependent Claim
64 words
A polymerizable acrylic composition comprising: a) at least one acrylic monomer; b) an effective amount of an organoborane amine complex; and c) an effective amount of a decomplexer that is reactive with amine to liberate the organoborane from the complex; wherein the decomplexer is selected such that the resulting polymerized material is essentially free from amine-decomplexer reaction product that has not been polymerized therein.
Claim 27
Dependent Claim
14 words
A polymerizable composition according to claim 22 wherein said decomplexer is a bireactive decomplexer.
Claim 28
Dependent Claim
28 words
A polymerizable composition according to claim 22 wherein said decomplexer comprises at least one free radically polymerizable group and at least one amine-reactive group in the same molecule.
Claim 29
Dependent Claim
13 words
A polymerizable composition according to claim 23 wherein said decomplexer contains isocyanate functionality.
Claim 30
Dependent Claim
26 words
A polymerizable composition according to claim 25 wherein said decomplexer comprises at least one acrylic group and at least one isocyanate group in the same molecule.
Claim 31
Dependent Claim
34 words
A polymerizable composition according to claim 23 wherein said decomplexer comprises the reaction product of a polyisocyanate and a hydroxyl compound containing a group capable of forming a covalent bond with an acrylic monomer.
Claim 32
Dependent Claim
37 words
A polymerizable composition according to claim 27 wherein said hydroxyl compound is selected from the group consisting of hydroxyethylmethacrylate, hydroxyethylacrylate, and hydroxybutylacrylate; and said polyisocyanate is selected from the group consisting of isophorone diisocyanate and toluene diisocyanate.
Claim 33
Dependent Claim
87 words
A polymerizable acrylic composition according to claim 22 wherein said organoborane amine complex has the structure: ##STR15## wherein R 6 is an alkyl group having 1 to 10 carbon atoms; R 7 and R 8 are independently selected from the group consisting of alkyl groups having 1 to 10 carbon atoms and phenyl-containing groups; the value of v is selected so as to provide a 0.5:1 to 4:1 ratio of primary or secondary amine nitrogen atoms to boron atoms in the complex; and Am is an amine.
Claim 34
Dependent Claim
81 words
A polymerizable acrylic composition according to claim 29 wherein Am has the structure: ##STR16## where R 9 and R 10 are independently selected from the group consisting of hydrogen, alkyl groups having 1 to 10 carbon atoms, ethanol and ##STR17## wherein R 11 and R 12 are independently selected from the group consisting of hydrogen and alkyl groups having 1 to 10 carbon atoms; m is an integer from 2 to 10; and n is an integer from 1 to 6.
Claim 35
Dependent Claim
88 words
A polymerizable acrylic composition according to claim 29 wherein Am is a polyoxyalkylenepolyamine having a structure selected from the group consisting of: H.sub.2 NR.sub.13 --O--(R.sub.14 O).sub.w --(R.sub.14 O).sub.w --(R.sub.15 O).sub.x --(R.sub.14 O).sub.y --R.sub.13 NH.sub.2 and H.sub.2 NR.sub.13 O--(R.sub.14 O).sub.w!.sub.z --R.sub.17 wherein R 13 , R 14 and R 15 are independently selected from the group consisting of alkylene and alkyl groups; R 17 is a polyol residue; the value of w is ≧1; the value of x and y are ≧0; and the value of z is >2.
Claim 36
Dependent Claim
51 words
A polymerizable acrylic composition according to claim 29 wherein Am has the structure E--(L--E) q L--E wherein each E group is independently the residue of a diprimary amine-terminated material; each L is independently the residues of a material having at least two groups reactive with primary amine, and q is ≧0.
Claim 37
Dependent Claim
9 words
A polymerizable acrylic adhesive composition according to claim 22.
Claim 38
Dependent Claim
39 words
A polymerizable acrylic adhesive composition according to claim 33 wherein the at least one acrylic monomer is selected from the group consisting of monofunctional acrylate ester, monofunctional methacrylate ester, substituted derivatives of the foregoing, and blends of the foregoing.
Claim 39
Dependent Claim
17 words
A polymerizable acrylic adhesive composition according to claim 33 having about 0.03 to 1.5 weight % boron.
Claim 40
Dependent Claim
34 words
A two-part curable acrylic adhesive composition comprising: (a) a first part comprising at least one acrylic monomer and a bireactive decomplexer having isocyanate functionality; and (b) a second part comprising an organoborane amine complex.
Claim 41
Dependent Claim
34 words
A two-part curable acrylic adhesive composition comprising: (a) a first part comprising at least one acrylic monomer and a bireactive decomplexer having isocyanate functionality; and (b) a second part comprising an organoborane amine complex.
Claim 42
Dependent Claim
33 words
A two part curable acrylic adhesive composition according to claim 36 wherein said bireactive decomplexer comprises at least one free radically polymerizable group and at least one isocyanate group in the same molecule.
Claim 43
Dependent Claim
38 words
A two part curable acrylic adhesive composition according to claim 37 wherein said decomplexer comprises the reaction product of a polyisocyanate and a hydroxyl compound containing a group capable of forming a covalent bond with an acrylic monomer.
Claim 44
Dependent Claim
31 words
A two part curable acrylic adhesive composition according to claim 37 wherein said bireactive decomplexer comprises at least one acrylic group and at least one isocyanate group in the same molecule.
Claim 45
Dependent Claim
31 words
A two part curable acrylic adhesive composition according to claim 37 wherein said at least one acrylic monomer comprises a blend of an alkyl acrylate monomer and an alkyl methacrylate monomer.
Claim 46
Dependent Claim
88 words
A two part curable acrylic adhesive composition according to claim 39 wherein said organoborane amine complex has the structure: ##STR18## wherein R 6 is an alkyl group having 1 to 10 carbon atoms; R 7 and R 8 are independently selected from the group consisting of alkyl groups having 1 to 10 carbon atoms and phenyl-containing groups; the value of v is selected so as to provide an effective ratio of primary or secondary amine nitrogen atoms to boron atoms in the complex; and Am is an amine.
Claim 47
Dependent Claim
84 words
A two part curable acrylic adhesive composition according to claim 41 wherein Am has the structure: ##STR19## where R 9 and R 10 are independently selected from the group consisting of hydrogen, alkyl groups having 1 to 10 carbon atoms, ethanol and ##STR20## wherein R 11 and R 12 are independently selected from the group consisting of hydrogen and alkyl groups having 1 to 10 carbon atoms; m is an integer from 2 to 10; and n is an integer from 1 to 6.
Claim 48
Dependent Claim
89 words
A two part curable acrylic adhesive composition according to claim 41 wherein Am is a polyoxyalkylenepolyamine having a structure selected from the group consisting of: H.sub.2 NR.sub.--O--(R.sub.14 O).sub.w --(R.sub.15 O).sub.x --(R.sub.14 O).sub.y --R.sub.13 NH.sub.2 and H.sub.2 NR.sub.13 O--(R.sub.14 O).sub.w !.sub.z --R.sub.17 wherein R 13 , R 14 and R 15 are independently selected from the group consisting of alkylene and alkyl groups; R 17 is a polyol residue; the value of w is ≧1; the value of x and y are >0; and the value of z is >2.
Claim 49
Dependent Claim
55 words
A two part curable acrylic adhesive composition according to claim 41 wherein Am has the structure E--(L--E) q --L--E wherein each E group is independently the residue of a diprimary amine-terminated material; each L is independently selected the residue of a material having at least two groups reactive with primary amine; and q is ≧0.
Claim 50
Dependent Claim
19 words
A two part curable acrylic adhesive composition according to claim 41 having about 0.03 to 1.5 weight % boron.
Claim 51
Dependent Claim
16 words
A two part curable acrylic adhesive composition according to claim 45 further comprising an elastomeric material.
Claim 52
Dependent Claim
9 words
A polymerized acrylic adhesive composition according to claim 46.
Claim 53
Dependent Claim
29 words
A bonded composite comprising a first substrate, a second substrate, and a polymerized acrylic adhesive composition according to claim 47 that adhesively bonds the first and second substrates together.
Claim 54
Dependent Claim
19 words
A bonded composite according to claim 48 wherein at least one of said substrates has a low energy surface.
Claim 55
Dependent Claim
9 words
A polymerized acrylic adhesive composition according to claim 1.
Claim 56
Dependent Claim
29 words
A bonded composite comprising a first substrate, a second substrate and a polymerized acrylic adhesive composition according to claim 50 that adhesively bonds the first and second substrates together.
Claim 57
Dependent Claim
19 words
A bonded composite according to claim 51 wherein at least one of said substrates has a low energy surface.
References Cited (Backward Citations)
CA664459A
Cited
US2985633A
Cited
US3275611A
Cited
US3340193A
Cited
US3141862A
Cited
GB904403A
Cited
US3451952A
Cited
GB988632A
Cited
GB1113722A
Cited
GB1132261A
Cited
US3425988A
Cited
JPS4214318Y1
Cited
US3476727A
Cited
US3418260A
Cited
JPS4529195Y1
Cited
US3527737A
Cited
JPS4616888Y1
Cited
JPS4818928B1
Cited
US3829973A
Cited
JPS53102394A
Cited
US4167616A
Cited
EP0051796A1
Cited
US4638092A
Cited
US4639498A
Cited
US4379728A
Cited
US4676858A
Cited
US4515724A
Cited
US4524181A
Cited
US4485229A
Cited
US4731416A
Cited
US4921921A
Cited
US4874814A
Cited
US4985516A
Cited
US4656229A
Cited
US4684538A
Cited
US5021507A
Cited
JPS62288675A
Cited
US4904360A
Cited
US4721751A
Cited
US4920188A
Cited
US4775734A
Cited
JPH03177470A
Cited
JPH03264509A
Cited
EP0511464A1
Cited
US5143884A
Cited
CA2061021A1
Cited
US5106928A
Cited
JPH05235089A
Cited
AU649582B2
Cited
US5286821A
Cited
US5376746A
Cited
US5401805A
Cited
US5310835A
Cited
WO1995022567A1
Cited
US5539070A
Cited
US5616796A
Cited
US5621143A
Cited
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 2002-02-15 | 2002-08-17 | 2003-02-16 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 2006-02-15 | 2006-08-17 | 2007-02-16 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 2010-02-15 | 2010-08-17 | 2011-02-16 | $7700.00 | Window Closed / Lapsed |