US4439291A
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Acrylate-containing compositions and their polymerization
Assignee: Seam Team Inc
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Filing: 1982-07-22
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Granted: 1984-03-27
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Expires: 2002-07-22
Abstract
Abstract Polymerizable compositions comprise (a) a compound containing both (i) at least one acryloyloxy or methacryloyloxy group, (ii) at least one allyl, methallyl, or 1-propenyl group attached directly to a carbon atom which forms part of an aromatic nucleus or to an oxygen atom or an oxycarbonyl group which are in turn directly attached to such a carbon atom, the total of the said groups (i) and (ii) being at least three, and (b) a compound containing at least two mercaptan groups directly attached to aliphatic carbon atoms, in a proportion as to supply at least 0.8 such mercaptan group per allyl, methallyl or 1-propenyl group in (a) but less than 1.0 such mercaptan group in (a) per acryloyl, methacryloyl, allyl, methallyl, or 1-propenyl group. Examples of (a) are 2,2-bis(3-allyl-4-(methacryloyloxy)phenyl)propane, bis(3-methallyl-4-(methacryloyloxy)phenyl)methane, 2,2-bis(3-allyl-4-(3-(methacryloyloxy)-2-hydroxypropoxy)phenyl)propane, 2,6-dimethallylphenyl acrylate, 1-(allyloxycarbonyl)-2,4- and 2,5-bis(3-(methacryloyloxy)-2-hydroxypropoxycarbonyl)benzene, and benzophenone-3,4,3',4'-tetracarboxylic acid X,X'-diallyl esters Y,Y'-bis(3-(methacryloyloxy)-2-hydroxypropyl) esters. Examples of (b) are pentaerythritol tetrathioglycollate, trimethylolpropane trithioglycollate, and 3,6-dioxa-1,8-dimercapto-octane. The compositions may be polymerized by means of actinic irradiation in the presence of an added or "built-in" photosensitizer or by the action of a free-radical catalyst. Compositions containing both a photosensitizing agent and a heat-activated free-radical catalyst may be subjected to a two-stage process, comprising brief exposure to actinic radiation followed by, when desired, heating. They are useful in the production of surface coatings, adhesive bonds, and of reinforced composites.
Inventors
- 👤 Edward Irving
- 👤 George E. Green
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-27 07:59
CPC Classifications
C; C09; C09D; C09D4/00; C08; C08F; C08F20/00; C08F20/02; C08F20/10; C08F20/40; C08F216/00; Y; Y10; Y10S; Y10S525/00; Y10S525/922
Claims Analysis
Total Claims: 15
Claim 1
Independent Claim
332 words
A polymerizable composition comprising (a) a compound containing in the molecule both (i) at least one group chosen from acryloyloxy and methacryloyloxy groups, said acryloyloxy or methacryloyloxy group in compound (a) being attached to a carbon atom of an aromatic nucleus, directly or through the (terminal) ether oxygen atom of a group of formula ##STR24## where R denotes a hydrogen atom or a methyl group and a is an integer of from 1 to 6, and (ii) at least one group chosen from allyl, methallyl, and 1-propenyl groups, which allyl, methallyl or 1-propenyl group is attached directly to a carbon atom which forms part of an aromatic nucleus, to an oxygen atom or to an oxycarbonyl group which oxygen or oxycarbonyl is in turn directly attached to such a carbon atom, the total of the said groups (i) and (ii) being at least three, or in which compound (a) is of the formula ##STR25## where each R 6 denotes a group of formula ##STR26## wherein R denotes a hydrogen atom or a methyl group and a is an integer of from 1 to 6, and each R 2 denotes an allyl, methallyl, or 1-propenyl group, or in which compound (a) is of the formula ##STR27## where one of R 7 and R 8 , and one of R 9 and R 10 , have the same meaning and each denotes an allyl or methallyl group, and each of the remaining symbols of R 7 and R 8 , and R 9 and R 10 , represent a group of formula ##STR28## where R and R 6 are defined as above, and (b) a compound containing, per molecule, at least two mercaptan groups directly attached to aliphatic carbon atoms, in a proportion such as to supply at least 0.8 such mercaptan group per group selected from allyl, methallyl, and 1-propenyl groups in (a) but less than 1.0 such mercaptan group per group selected from acryloyl, methacryloyl, allyl, methallyl, and 1-propenyl groups in (a).
Claim 2
Dependent Claim
332 words
A polymerizable composition comprising (a) a compound containing in the molecule both (i) at least one group chosen from acryloyloxy and methacryloyloxy groups, said acryloyloxy or methacryloyloxy group in compound (a) being attached to a carbon atom of an aromatic nucleus, directly or through the (terminal) ether oxygen atom of a group of formula ##STR24## where R denotes a hydrogen atom or a methyl group and a is an integer of from 1 to 6, and (ii) at least one group chosen from allyl, methallyl, and 1-propenyl groups, which allyl, methallyl or 1-propenyl group is attached directly to a carbon atom which forms part of an aromatic nucleus, to an oxygen atom or to an oxycarbonyl group which oxygen or oxycarbonyl is in turn directly attached to such a carbon atom, the total of the said groups (i) and (ii) being at least three, or in which compound (a) is of the formula ##STR25## where each R 6 denotes a group of formula ##STR26## wherein R denotes a hydrogen atom or a methyl group and a is an integer of from 1 to 6, and each R 2 denotes an allyl, methallyl, or 1-propenyl group, or in which compound (a) is of the formula ##STR27## where one of R 7 and R 8 , and one of R 9 and R 10 , have the same meaning and each denotes an allyl or methallyl group, and each of the remaining symbols of R 7 and R 8 , and R 9 and R 10 , represent a group of formula ##STR28## where R and R 6 are defined as above, and (b) a compound containing, per molecule, at least two mercaptan groups directly attached to aliphatic carbon atoms, in a proportion such as to supply at least 0.8 such mercaptan group per group selected from allyl, methallyl, and 1-propenyl groups in (a) but less than 1.0 such mercaptan group per group selected from acryloyl, methacryloyl, allyl, methallyl, and 1-propenyl groups in (a).
Claim 3
Dependent Claim
27 words
A composition according to claim 1, in which component (a) contains at least two and at most six groups chosen from acryloyloxy and methacryloyloxy groups per molecule.
Claim 4
Dependent Claim
28 words
A composition according to claim 1, in which component (a) contains at least two and at most fifteen groups chosen from allyl, methallyl, and 1-propenyl groups per molecule.
Claim 5
Dependent Claim
121 words
A composition according to claim 1, in which component (a) is a polyhydric phenol, at least two phenolic hydroxyl groups of which are esterified with groups chosen from acryloyl and methacryloyl groups, either directly or through the (terminal) ether oxygen atom of a group of formula ##STR29## where R denotes a hydrogen atom or a methyl group and a is an integer of from 1 to 6, and either at least two phenolic hydroxyl groups of which are directly etherified with groups chosen from allyl, methallyl, and 1-propenyl groups, or the said polyhydric phenol is substituted directly on carbon atoms in a benzene or naphthalene nucleus or nuclei thereof by at least two groups selected from allyl, methallyl and 1-propenyl groups.
Claim 6
Dependent Claim
200 words
A composition according to claim 1, in which component (a) is selected from the compounds of formula ##STR30## where R denotes a hydrogen atom or a methyl group, a is an integer of from 1 to 6, each R 1 denotes an oxygen-carbon bond or a group of formula ##STR31## each R 2 denotes an allyl, methallyl, or 1-propenyl group, R 3 denotes a carbon-carbon bond, an alkylene or alkylidene group of up to 5 carbon atoms, an ether oxygen atom, a sulfur atom, or a group of formula --CO--, --SS--, --SO--, or --SO 2 --, each R 4 denotes a hydrogen, chlorine, or bromine atom, or an alkyl group of 1 to 4 carbon atoms, and each R 5 denotes a group of formula CH 2 ═C(R)COOR 1 -- or an allyloxy, methallyloxy, or 1-propenyloxy group, such that at least one denotes a said group of formula CH 2 ═C(R)COOR 1 -- and at least two each denote an allyloxy, methallyloxy, or 1-propenyloxy group, with the proviso that, in formulae XII and XIII, each --CH 2 -- and R 2 -group shown is ortho or para to an indicated group CH 2 ═C(R)COOR 1 -- and R 5 --.
Claim 7
Dependent Claim
56 words
A composition according to claim 1, in which component (a) is of the formula ##STR32## where each R 6 denotes a group of formula ##STR33## wherein R denotes a hydrogen atom or a methyl group and a is an integer of from 1 to 6, and each R 2 denotes an allyl, methallyl, or 1-propenyl group.
Claim 8
Dependent Claim
122 words
A composition according to claim 1, in which component (a) is of the formula ##STR34## where each R 1 5 denotes a group of formula CH 2 ═C(R)COOR 1 -- or an allyloxy, methallyloxy, or 1-propenyloxy group such that at least two denote a said group of formula CH 2 ═C(R)COOR 1 -- and one denotes an allyloxy, methallyloxy, or 1-propenyloxy group, the --CH 2 -- groups being ortho or para to a group R 1 5 , wherein R denotes a hydrogen atom or a methyl group, and R 1 denotes an oxygen-carbon bond or a group of formula ##STR35## and each R 4 denotes a hydrogen, chlorine, or bromine atom, or an alkyl group of 1 to 4 carbon atoms.
Claim 9
Dependent Claim
91 words
A composition according to claim 1, in which component (a) is of the formula ##STR36## where one of R 7 and R 8 , and one of R 9 and R 10 , have the same meaning and each denotes an allyl or methallyl group, and each of the remaining symbols of R 7 and R 8 , and of R 9 and R 10 , denotes the residue of an alcohol after removal of the hydrogen atom or an alcoholic hydroxyl group, said residue containing an acryloyloxy or methacryloyloxy group.
Claim 10
Dependent Claim
61 words
A composition according to claim 8, wherein each of the remaining symbols of R 7 and R 8 , and R 9 and R 10 , represent a group of formula ##STR37## where R denotes a hydrogen atom or a methyl group, and R 6 denotes a group of formula ##STR38## wherein a is an integer of from 1 to 6.
Claim 11
Dependent Claim
30 words
A composition according to claim 1, wherein component (b) is an ester of a monomercaptanalkylenecarboxylic acid with a polyhydric alcohol or of an aliphatic monomercaptanmonohydric alcohol with a polycarboxylic acid.
Claim 12
Dependent Claim
377 words
A composition according to claim 1, wherein component (b) is of one of the formulae ##STR39## where a and f are each independently an integer of from 1 to 6, d and e each represent zero but are not the same, g is a positive integer, h is zero or 1, j is zero or a positive integer such that (j+k) is at most 6, k is an integer of from 2 to 6, n is an integer which has an average value of at least 1, either p is zero, in which case q and r are each also zero, or p is 1, in which case q is zero and r is 1, s is an integer of more than one, t is an integer of at least one, and u is zero or a positive integer, each R denotes a hydrogen atom or a methyl group, R 14 denotes --CH 2 --, --(CH 2 ) 2 , or --CH(CH 3 )--, R 15 represents a divalent organic radical, linked through a carbon atom or carbon atoms thereof to the indicated --O-- or --CO-- units, R 16 represents a divalent organic radical, linked through a carbon atom or carbon atoms thereof to the indicated --SH group and --O-- or --CO-- unit, R 17 represents an organic radical, which must contain at least one aliphatic --SH group when f is 1, linked through a carbon atom or carbon atoms thereof to the indicated --O-- or --CO-- unit or units, R 18 represents the radical of a polyhydric alcohol after removal of (j+k) alcoholic hydroxyl groups, each R 19 denotes an alkylene group containing a chain of at least 2 and at most 6 carbon atoms between the indicated consecutive oxygen atoms, R 20 represents an aliphatic radical of 1 to 6 carbon atoms, each R 21 denotes an alkylene hydrocarbon group containing from 2 to 4 carbon atoms, R 22 denotes a hydrogen atom or a methyl or ethyl group, R 23 represents --CN, --COOH, --CONH 2 , --COOR 24 , --C 6 H 5 , or COOR 24 , where R 24 is an alkyl group of one to eight carbon atoms, and R 25 denotes a group --OCR 14 SH or a hydrogen atom.
Claim 13
Dependent Claim
28 words
A process for the polymerisation of a composition as claimed in claim 1 which comprises exposing it, in the presence of a photoinitiator if required, to actinic radiation.
Claim 14
Dependent Claim
24 words
A process for polymerisation of a composition as claimed in claim 1 which comprises exposing, it to the effect of a heat-activated free-radical catalyst.
Claim 15
Dependent Claim
47 words
A process for the polymerisation of a composition as claimed in claim 1, which contains, if required, a photoinitiator, and which also contains a heat-activated free-radical catalyst, comprising partially polymerising it by exposing it to actinic radiation and then heating it to activate the heat-activated free-radical catalyst.
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USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1987-03-27 | 1987-09-26 | 1988-03-27 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1991-03-27 | 1991-09-26 | 1992-03-27 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1995-03-27 | 1995-09-26 | 1996-03-27 | $7700.00 | Window Closed / Lapsed |