Polymerizable compounds and compositions

Details Polymerizable compounds and compositions Polymerizable compounds and compositions

1996-01-03

2002-04-09

Moore, Margaret G. (Department: 1712)

Synthetic resins or natural rubbers -- part of the class 520 ser

Synthetic resins

Mixing of two or more solid polymers; mixing of solid...

C525S287000, C525S291000, C525S301000, C525S407000, C525S531000, C525S922000, C523S105000, C523S109000, C526S277000

Reexamination Certificate

active

06369164

ABSTRACT:

The invention relates to polymerizable macromonomers and dental and medical compositions containing polymerizable macromonomers. The invention provides macromonomers for dental compositions and a process for preparing them. Dental/medical compositions which include macromonomers of the invention have a high adhesion to hard dental tissue and low volumetric shrinkage.
It is an object of the invention to provide an esterified macromonomer within the scope of the general formula:
wherein Z is an organic moiety, R
1
is hydrogen or a substituted or unsubstituted alkyl having from 1 to 12 carbon atoms, oxyalkyl having from 1 to 12 carbon atoms, alkenyl having from 2 to 12 carbon atoms, cycloalkyl having from 5 to 12 carbon atoms, aryl having from 6 to 12 carbon atoms or aralkyl having from 7 to 12 carbon atoms. Each E independently is a hydroxyl group, an organic ester moiety or an inorganic ester moiety and at least one E is a ester containing moiety. n and m each independently is an integer from 2 to 12.
It is the object of the invention to provide an esterified macromonomer obtainable by esterification of at least a portion of the —OH groups of a macromonomer having at least one terminal double bond with at least one derivative of an inorganic or organic acid which introduces pendant groups exhibiting at least one acid moiety selected from the group of consisting of —COOH, —PO
3
H
2
, —SO
3
H, —BO
2
H and salts thereof. The number of the acid moieties is chosen such that a polymer obtained by polymerizing said monomers has an adhesive strength to dentine of at least 2 MPa.
Prior Art dental/medical compositions such as cements are either water-based ionic cements or resin based materials. The water-based cements have the advantage of a modest adhesion to hard tooth tissues and of a high fluoride ion release from inorganic filler material. They have the disadvantage of high water solubility, low abrasion resistance and an excessive opacity. The resin-based materials have the advantage of excellent mechanical properties, a suitable opacity and low water solubility. They have the disadvantage of a lack of adhesion, a very poor release of fluoride ions from an inorganic filler and a high volumetric shrinkage.
Engelbrecht et al in U.S. Pat. No. 4,806,381 discloses Polymerizable Compounds Containing Acid and Acid Derivatives, Mixtures Containing the Same, and Use Thereof. Blackwell et al in U.S. Pat. No. 4,816,495 discloses Biologically Compatible Adhesive Visible Light Curable Compositions.
These disadvantages of prior art dental compounds and compositions are overcome by the novel and nonobvious compounds and compositions of the invention.
BRIEF DESCRIPTION OF THE INVENTION
An esterified macromonomer within the scope of the general formula (I):
wherein Z is an organic moiety. R
1
is hydrogen or a substituted or unsubstituted alkyl having from 1 to 12 carbon atoms, oxyalkyl having from 1 to 12 carbon atoms, alkenyl having from 2 to 12 carbon atoms, cycloalkyl having from 5 to 12 carbon atoms, aryl having from 6 to 12 carbon atoms or aralkyl having from 7 to 12 carbon atoms. Each E independently is a hydroxyl group, an organic ester moiety, or an inorganic ester moiety. At least one E is an ester moiety. n and m each independently is an integer from 2 to 12. The esterified macromonomer is obtainable by esterification of at least a portion of the —OH groups of a macromonomer having at least one terminal double bond with at least one derivative of an inorganic or organic acid which introduces pendant groups exhibiting at least one acid moiety selected from the group of consisting of —COOH, —PO
3
H
2
, —SO
3
H, —BO
2
H or salts thereof. The number of the acid moieties is chosen such that a polymer obtained by polymerizing those monomers has an adhesive strength to dentine of at least 2 MPa.
DETAILED DESCRIPTION OF THE INVENTION
The invention provides macromonomers esterfied, with organic acids or inorganic acids or derivatives thereof. The esterified macromonomers are useful in composition with or without water, such as water free self-adhesive dental/medical composite. The dental/medical composite comprises a modified macromonomer, and/or di- or poly(methacrylates) containing phosphoric acid ester groups or salts thereof, polymerizable monomers, acid-reactive and/or reactive and/or non-reactive fillers, diluents, polymerization initiators and stabilizers. Composition in accordance with the invention include polymerization initiators, such as thermal initiators, redox initiators and/or photoinitiators. The new adhesive dental composite develops adhesion to dentine of about 4 MPa. Fillers of high X-ray absorbence provide radio-opacity values greater than that of the same thickness of aluminium.
Preparation of Epoxide-macromonomers
Macromonomers in accordance with the invention are produced by chemical modification of macromonomers containing hydroxyl groups. Macromonomer containing hydroxyl groups useful for making esterified macromonomer in accordance with the invention are described for example in Polym. Bull. 27 (1992) 511-517, Acta Polym. 42 (1991) 17-20 and DE 4217761.8 incorporated herein by reference. Preferred polymerizable compounds for use in compositions in accordance with the invention are within the scope of general formulas M1-M12 as follows:
wherein
each E independently is a hydroxyl group, an organic ester moiety or an inorganic ester moiety,
at least one E is an ester moiety,
R is a diether or a diester containing moiety or tertiary amine,
R
1
is hydrogen or a substituted or unsubstituted alkyl having from 1 to 12 carbon atoms, oxyalkyl having from 1 to 12 carbon atoms, alkenyl having from 2 to 12 carbon atoms, cycloalkyl having from 5 to 12 carbon atoms, aryl having from 6 to 12 carbon atoms or aralkyl having from 7 to 12 carbon atoms,
R
2
is a difunctional substituted or unsubstituted alkyl group having from 1 to 12 carbon atoms, alkenyl group having from 2 to 12 carbon atoms, cycloalkyl having from 5 to 12 carbon atoms, aryl having from 6 to 12 carbon atoms or aralkyl having from 7 to 12 carbon atoms,
R
3
is hydrogen or a substituted or unsubstituted alkyl group having from 1 to 12 carbon atoms, alkenyl group having from 2 to 12 carbon atoms, cycloalkyl having from 5 to 12 carbon atoms, aryl having from 6 to 12 carbon atoms or aralkyl having from 7 to 12 carbon atoms,
R
4
is a substituted or unsubstituted aryl having from 6 to 12 carbon atoms,
and n is an integer of at least 1.
Preferably R is a moiety within the scope of the general formulas:
(according to R of the foreclosures)
wherein X is C(CH
3
)
2
, —CH
2
—, —O—, —S—, —CO—, or —SO
2
—.
Preferably R4 is a moiety within the scope of the general formulas:
wherein X is C(CH
3
)
2
, —CH
2
—, —O—, —S—, —CO—, —SO
2
—.
Preferably E is a hydroxyl group, an ester moiety, a boric acid moiety, a sulfuric acid moiety or a phosphoric acid moiety.
Macromonomers within the scope of general formula M-1 are synthesized in two steps. At first an oligomer mixture is obtained by reaction of an &agr;,&bgr;-unsaturated acids with excessive amounts of a diepoxide, such as bisphenol-A diglycidyl ether (DGEBA), bisphenol-F diglycidyl ether (DGEBF), butanediol diglycidyl ether (BDODGE), tetrahydro terephtalic acid diglycidyl ether or diglycidyl aniline. This mixture contains the bis-ester of the diepoxide along with the mono-ester and unreacted diepoxide as governed by the ratio of the diepoxide and the unsaturated acid. The formation of macromonomers follows in a second reaction of the previous reacted oligomers with dicarboxylic acids to M-1 (DE 4217761.8).
Instead of dicarboxylic acids in the second step also primary monoamines were used which react to macromonomers M-2, disecondary diamines which react to macromonomers M-3, (J. Klee et. al. Polym. Bull. 27 (1992) 511-517, DD 279667) and bisphenols which react to macromonomers M-6.
During the epoxide ring cleavage by carboxylic acids an amount equal to approximately 20 percent by weight of the epoxide groups is opened to the corresponding primary alcohols:
Consequently, macr

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