U.S. patent application number 10/054360 was filed with the patent office on 2002-10-03 for polymerizable compounds and compositions.
Invention is credited to Klee, Joachim E., Walz, Uwe.
Application Number | 20020143108 10/054360 |
Document ID | / |
Family ID | 27490659 |
Filed Date | 2002-10-03 |
United States Patent
Application |
20020143108 |
Kind Code |
A1 |
Klee, Joachim E. ; et
al. |
October 3, 2002 |
Polymerizable compounds and compositions
Abstract
An esterified macromonomer within the scope of the general
formula: 1 wherein Z is an organic moiety, R.sub.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 containing moiety and at
least one E is an ester containing 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.sub.3H.sub.2, --SO.sub.3H, --BO.sub.2H 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.
Inventors: |
Klee, Joachim E.;
(Radolfzell, DE) ; Walz, Uwe; (Konstanz,
DE) |
Correspondence
Address: |
DALE R. LOVERCHECK
DENTSPLY INTERNATIONAL INC.
570 West College Avenue
York
PA
17405-0872
US
|
Family ID: |
27490659 |
Appl. No.: |
10/054360 |
Filed: |
January 22, 2002 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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10054360 |
Jan 22, 2002 |
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08582235 |
Jan 3, 1996 |
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6369164 |
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08582235 |
Jan 3, 1996 |
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08359217 |
Dec 19, 1994 |
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08359217 |
Dec 19, 1994 |
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08231535 |
Apr 22, 1994 |
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08231535 |
Apr 22, 1994 |
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08217998 |
Mar 25, 1994 |
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5624976 |
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08217998 |
Mar 25, 1994 |
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08067774 |
May 26, 1993 |
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Current U.S.
Class: |
525/285 |
Current CPC
Class: |
A61K 6/20 20200101; C08F
290/064 20130101; Y10S 525/922 20130101; C08G 59/10 20130101; C08G
59/1466 20130101; A61K 6/30 20200101; A61K 6/893 20200101; A61K
6/887 20200101; A61K 6/20 20200101; C08G 59/12 20130101; A61K 6/30
20200101; C08G 18/835 20130101; A61K 6/30 20200101; A61K 6/893
20200101; C08L 67/07 20130101; A61K 6/20 20200101; C08F 283/02
20130101; C08F 290/06 20130101; C08G 63/52 20130101; C08L 63/00
20130101; C08L 43/02 20130101; C08L 75/16 20130101; C08L 75/16
20130101; C08L 43/02 20130101; C08L 33/00 20130101; C08L 75/16
20130101; C08L 43/02 20130101; C08L 43/02 20130101; C08L 43/02
20130101; C08L 75/16 20130101; C08L 33/00 20130101; C08L 33/00
20130101; C08L 63/00 20130101; C08L 43/02 20130101; C08L 33/00
20130101; C08L 63/00 20130101; C08L 75/16 20130101; A61K 6/20
20200101; C08L 75/16 20130101; A61K 6/887 20200101; C08L 33/00
20130101; C08L 33/00 20130101; C08L 63/00 20130101; C08L 63/00
20130101; C08L 63/00 20130101; A61K 6/20 20200101; A61K 6/30
20200101; C08G 59/1494 20130101; A61K 6/893 20200101; C08G 2270/00
20130101; C08F 290/061 20130101; A61K 6/30 20200101; A61K 6/20
20200101; A61K 6/20 20200101; A61K 6/30 20200101; A61K 6/891
20200101; A61K 6/30 20200101; A61K 6/30 20200101; A61K 6/30
20200101; C08G 59/4292 20130101; A61K 6/20 20200101; A61K 6/887
20200101; A61K 6/887 20200101; A61K 6/891 20200101; A61K 6/891
20200101; A61K 6/887 20200101; A61K 6/20 20200101 |
Class at
Publication: |
525/285 |
International
Class: |
C08F 267/04 |
Claims
What is claimed is:
1. An esterified macromonomer within the scope of the general
formula: 13wherein Z is an organic moiety, R.sub.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 or inorganic ester moiety and at least one E is an organic
or inorganic ester moiety, n and m each independently is an integer
from 2 to 12.
2. The esterified macromonomer of claim 1 wherein said esterified
macromonomer is within the scope at least one of formulas M-1 to
M-12: 14wherein each E independently is a hydroxyl group, an
organic or inorganic ester moiety and at least one E is an organic
ester moiety or inorganic ester moiety, R is a diether containing
moiety, or diester containing moiety or tertiary amine containing
moiety, R.sub.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.sub.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.sub.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.sub.4 is a substituted or unsubstituted aryl having
from 6 to 12 carbon atoms, and n is an integers of at least 1.
3. The esterified macromonomer of claim 2 wherein R is within the
scope of the general formula: 15wherein X is C(CH.sub.3).sub.2,
--CH.sub.2--, --O--, --S--, --CO--, or --SO.sub.2--.
4. The esterified macromonomer of claim 2 wherein R is 16
5. The esterified macromonomer of claim 2 wherein R.sub.4 is within
the scope of at least one of the general formulas: 17wherein X is
C(CH.sub.3).sub.2, --CH.sub.2--, --O--, --S--, --CO-- or
--SO.sub.2--.
6. The esterified macromonomer of claim 2 wherein at least one E
comprises a carboxyl group.
7. The esterified macromonomer of claim 1 wherein E is derived from
succinic acid anhydride, maleic acid anhydride, dichloro maleic
acid anhydride, dimethyl maleic acid anhydride, malonic acid
anhydride, aconit acid anhydride, adipic acid anhydride,
3,3-tetramethylen glutaric acid anhydride, cyclohexen-1,2 acid
anhydride, nadinic acid anhydride, phthalic acid anhydride,
trimellitic acid anhydride, 2-sulfobenzoic acid anhydride, 2-sulfo
succinic acid anhydride, phthalic acid anhydride p-(O-phosphate),
phthaloylchloride, succinic acid dimethyl ester, phosphorous penta
chloride, phosphorous trichloride, phosphorous oxychloride,
sulfuryl chloride, thionyl chloride, phosphor thionyl chloride,
boric acid anhydride and boron trichloride.
8. The epoxide macromonomer of claim 1 wherein at least one E is a
salt selected from the group consisting of ammonium, sulfonium,
sodium, potassium, strontium, calcium and magnesium salts.
9. The esterified macromonomer of claim 2 wherein said macromonomer
is esterified with a derivative of an inorganic or organic acid
whereby at least a portion of --OH groups is converted into groups
selected from the group consisting of --COOH, --PO.sub.3H.sub.2,
--SO.sub.3H, --BO.sub.2H and salt thereof.
10. The macromonomer of claim 9 wherein said esterification is
carried out in a solvent selected from the group consisting of THF,
triethylenglycol bismethacrylate, diethylenglycol bismethacrylate,
dioxolan bismethacrylate, vinyl-, vinylen- or vinyliden-, acrylate-
or methacrylate substituted spiro-orthoester, spiroorthocarbonate
or bicyloorthoester and
2,2-Bis[p-(acryloxyethoxy)phenyl]propane.
11. The macromonomer of claim 9 wherein said esterification is
carried out in the presence of a tertiary amine.
12. The macromonomer of claim 2 further comprising a filler, a
polymerizable monomer having at least one phosphorous ester group,
a polymerization initiator and a stabilizer.
13. The composition according to claim 12 further comprising a
polymerizable monomer selected from the group consisting of mono-
and polyfunctional (meth)-acrylate, a urethane di- and poly(meth)
acrylate, a vinyl-, vinylen- or vinyliden-, acrylate- or
methacrylate substituted spiro-orthoester, a spiroorthocarbonate or
a bicyloorthoester, and said monomer comprises from about 5 to
about 80 percent by weight.
14. The composition according to claim 12 wherein said
polymerization initiator is a thermal initiator, a redox-initiator
or a photoinitiator.
15. The composition according to claim 12 wherein said filler
comprises an inorganic filler and/or an organic filler.
16. The composition according to claim 15 wherein said filler is a
fluoride releasing inorganic filler.
17. The composition formed by polymerizating the composition of
claim 12 to form a polymeric product having an adhesion to dentine
of at least 2 MPa, a fluoride release of at least 1 .mu.g F.sup.-
per week and per cm.sup.2 of the exposed surface of the
composition, an opacity of at least C.sub.0.7=40% and a compressive
strength of at least 200 MPa.
18. The composition of claim 2 comprising from about 5 to about 20
percent by weight of said esterified macromonomer, from about 10 to
about 25 percent by weight of a di- or poly(meth)acrylate monomer
having at least one phosphorous acid ester group, from about 20 to
about 35 percent by weight of a polymerizable monomer, from about
50 to about 65 percent by weight of a filler and polymerization
initiator and stabilizers.
19. The composition of claim 2 comprising from about 3 to about 15
percent by weight of said esterified macromonomer, from about 5 to
about 25 percent by weight of di- or poly(meth)acrylate monomer
having at least one phosphorous acid ester group, from about 7 to
about 40 percent by weight of a polymerizable monomer, from about
50 to about 85 percent by weight of a filler and polymerization
initiator and stabilizers.
20. The composition of claim 2 comprising from about 5 to about 25
percent by weight of said esterified macromonomer, from about 10 to
about 30 percent by weight of di- or poly(meth)acrylate monomer
having at least one phosphorous acid ester group, from about 20 to
about 40 percent by weight of a polymerizable monomer, from about
10 to about 50 percent by weight of a filler and polymerization
initiator and stabilizers.
21. The composition of claim 2 comprising from about 5 to about 25
percent by weight of said esterified macromonomer, from about 5 to
about 30 percent by weight of di- or poly(meth)acrylate monomer
having at least one phosphorous acid ester group, from about 10 to
about 40 percent by weight of a polymerizable monomer, from about
30 to about 90 percent by weight of a diluent and polymerization
initiator and stabilizers.
22. The composition of claim 2 comprising from about 1 to about 25
percent by weight of said esterified macromonomer, di- or
poly(meth) acrylate monomer having at least one phosphous acid
ester group and a polymerizable monomer and polymerization
initiator from about 75 to about 99 percent by weight of an organic
solvent and polymerization co-initiator.
23. 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.sub.3H.sub.2, --SO.sub.3H, --BO.sub.2H
and salts thereof, whereby the number of said acid moieties is
chosen such that a polymer obtained by polymerizing said monomers
has an adhesive strength to dentine of at least 2 MPa.
Description
[0001] This is a continuation-in-part of U.S. patent application
Ser. No. 231,535 filed Apr. 22, 1994 (Case 1723) which is a
continuation-in-part of U.S. patent application Ser. No. 217,998
filed Mar. 25, 1994 (Case 1718), which is a continuation-in-part of
U.S. patent application Ser. No. 067,774 filed May 26, 1993 (Case
1710).
[0002] 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.
[0003] It is an object of the invention to provide an esterified
macromonomer within the scope of the general formula: 2
[0004] wherein Z is an organic moiety, R.sub.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.
[0005] 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.sub.3H.sub.2, --SO.sub.3H, --BO.sub.2H 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.
[0006] 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.
[0007] 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.
[0008] 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
[0009] An esterified macromonomer within the scope of the general
formula (I): 3
[0010] wherein Z is an organic moiety. R.sub.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.sub.3H.sub.2, --SO.sub.3H, --BO.sub.2H
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
[0011] 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.
[0012] Preperation of Epoxide-macromonomers
[0013] 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: 4
[0014] wherein
[0015] each E independently is a hydroxyl group, an organic ester
moiety or an inorganic ester moiety,
[0016] at least one E is an ester moiety,
[0017] R is a diether or a diester containing moiety or tertiary
amine,
[0018] R.sub.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,
[0019] R.sub.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,
[0020] R.sub.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,
[0021] R.sub.4 is a substituted or unsubstituted aryl having from 6
to 12 carbon atoms,
[0022] and n is an integer of at least 1.
[0023] Preferably R is a moiety within the scope of the general
formulas: 5
[0024] (according to R of the foreclosures)
[0025] wherein
[0026] X is C(CH.sub.3).sub.2, --CH.sub.2--, --O--, --S--, --CO--,
or --SO.sub.2--.
[0027] Preferably R.sub.4 is a moiety within the scope of the
general formulas: 6
[0028] wherein X is C(CH.sub.3).sub.2, --CH.sub.2--, --O--, --S--,
--CO--, --SO.sub.2--.
[0029] Preferably E is a hydroxyl group, an ester moiety, a boric
acid moiety, a sulfuric acid moiety or a phosphoric acid
moiety.
[0030] 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 .alpha.,.beta.-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 diepoxicle 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). 7
[0031] 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.
[0032] 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: 8
[0033] Consequently, macromonomers M-1, M-2, M-3 and M-6 wherein
each E is hydrogen contain both types of molecules having primary
and/or secondary alcohol units.
[0034] The resulting macromonomers are viscous liquids or solids
which are soluble in THF, CHCl.sub.3 and DMF. Their glass
transition temperatures are relatively low (between 0 and
50.degree. C.) depending on the nature of the comonomer and the
molecular mass of the macromonomers.
[0035] The degree of polymerisation P.sub.n and the macromonomer
value n depends on the mol ratio of the monomers, the diepoxide and
the comonomers and were calculated by 1 P n = 1 + r 1 - r and n = r
1 - r ,
[0036] respectively using r=z/x. That means each macromonomer M is
a definite mixture of a series of homologous oligomers
(n=1,2,3,4,5, . . . ) and contains a certain amount of the molecule
(n=0).
[0037] Macromonomers M-5 wherein each E is hydrogen are prepared by
one-step reaction of the diepoxides, disecondary diamines and
2,3-epoxypropyl-(meth)acrylate according to the following equation:
9
[0038] A second route to obtain macromonomers M-5 wherein each E is
hydrogen is a two-step reaction. In the first step the diepoxide is
reacted with the disecondary diamine to an
.alpha.,.omega.-terminated prepolymer. In the second step the
obtained prepolymer is reacted with 2,3-epoxypropyl-(meth) acrylate
(DD 277689, J. Klee, H.-H. Horhold, H. Schutz, Acta Polym. 42
(1991)17-20).
[0039] Instead of disecondary diamines in the second step also were
used primary monoamines react to macromonomers M-4, bisphenols
react to macromonomers M-7 or dicarboxylic acids react to
macromonomers M-8.
[0040] Macromonomers M-9 wherein each E is hydrogen are prepared by
reaction of diepoxides, dicarboxylic acids and aminoalkyl
(meth)acrylates according to the following equation: 10
[0041] M-9 (wherein E is hydrogen)
[0042] Instead of dicarboxylic acids, primary monoamines were used
to prepare macromonomers M-10, disecondary diamines were used to
prepare macromonomers M-11, bis-phenols were used to prepare
macromonomers M-12.
[0043] Specific macromonomers M-1 to M-12 representing molecules of
n=0, n=1 or n=2 may be isolated from the mixture by fractionated
precipitation or by chromatography and subjected to esterification
as described.
[0044] Esterification of Macromonomers
[0045] The reaction of epoxide macromonomers M-1 to M-12 with
organic acids or inorganic acids or derivatives thereof leads to
macromonomers having ester moieties.
[0046] As derivatives of organic acids preferably were used
succinic acid anhydride, maleic acid anhydride, dichloromaleic acid
anhydride, dimethyl maleic acid anhydride, malonic acid anhydride,
aconit acid anhydride, adipic acid anhydride, 3,3-tetramethylen
glutaric acid anhydride, cyclohexen-1,2 acid anhydride, nadinic
acid anhydride, phthalic acid anhydride, trimellitic acid
anhydride, 2-sulfo-benzoic acid anhydride, 2-sulfo succinic acid
anhydride, phthalic acid anhydride p-(O-phosphat),
phthaloylchloride, succinic acid dimethyl ester.
[0047] As derivatives of inorganic acids preferably were used
phosphorous penta chloride, phosphorous trichloride, phosphorous
oxychloride, sulfuryl chloride, thionyl chloride, phosphor thionyl
chloride, boric acid anhydride, boron trichloride.
[0048] It is possible to synthesize the esterified macromonomers
without using any catalysts in the cases of M-2 to M-5, M-10, M11
(n>0). These macromonomers contain the catalytic active amine in
the backbone of the molecule. The use of catalysts such as tertiary
amines or quarterly ammonium salts is possible and in the case of
esterification of M-1, M-6, M-7, M-8, M-9 and M-12 necessary.
[0049] The esterification of the macromonomer hydroxyl groups is
carried out in pure substance or in diluted solutions. Preferably,
solvents such as tetrahydro furane, dioxane, or polymerizable
monomers such as triethylenglycol bismethacrylate, diethylenglycol
bismethacrylate, dioxolan bismethacrylate, vinyl-, vinylen- or
vinyliden-, acrylate- or methacrylate substituted spiroorthoesters
and 2,2-Bis[p-(acryloxyethoxy)p- henyl]propane are present during
esterification of the macromonomers. The temperature is in the
preferred range of 60.degree. C. to 120.degree. C.
[0050] Dental/medical Application
[0051] A dental/medical composite, a dental/medical sealant, a
dental/medical adhesive and a dental/medical primer have been
developed comprising a modified .alpha.,.omega.-(meth) acryloyl
terminated macromonomer notably a di- or poly(meth)acrylate monomer
having phosphorous ester groups or salts thereof, polymerizable
monomers, fillers, polymerization initiators and stabilizers.
[0052] As di- or poly(meth)acrylate monomer having phosphorous
ester groups and salts thereof are employed pentaerythrit
triacrylate monophosphate, dipentaerythrit penta-acrylate
monophosphate, glycerol di(meth)acrylate monophosphate,
triethylenglycol (meth)acrylate monophosphate.
[0053] As organic polymerizable monomers were used mono- and
polyfunctional (meth)acrylates, such as polyalylenoxide di- and
poly(meth)acrylates, urethane di- and poly(meth)acrylates, vinyl-,
vinylen- or vinyliden-, acrylate- or methacrylate substituted
spiroorthoesters, spiroorthocarbonates or bicyloorthoesters.
Preferably were used diethylenglycol dimethacrylate,
triethylenglycol dimethacrylate,
3,(4),8,(9)-dimethacryloyloxymethyltricyclodecane, dioxolan
bismethacrylate, glycerol trimethacrylate, furfuryl methacrylate in
a content of 5 to 80 wt-%.
[0054] As polymerization initiators are used thermal initiators,
redox initiators and/or photo initiators in a content of 0.001 to 3
wt-%.
[0055] Thermal initiators are initiators such as peroxides,
peresters, perketals, peroxy carbonates, hydroxyperoxides,
persulfates and azo compounds preferably dibenzoyl peroxide, cumol
hydroperoxide, diisopropyl peroxycarbonate, dipotassium persulfate,
azobisisobutylonitril.
[0056] Preferred redox initiator systems for use in compositions in
accordance with the invention are peroxide/amine systems, such as
peracid/amine, perester/amine, perketal/amine,
peroxycarbonate/amine and hydroxyperoxide/amine systems;
peroxide/metal ion salts, such as ascorbic acid/peroxide/metal ion
compounds, (thio)barbituric acid/peroxide/metal ion compounds,
metal ion compounds/sulfinates, metal ion
compounds/(thio)barbituric acid; transition metal carbonyl
compounds and halogenids of organic compounds; boralkyl compounds,
peroxysulfates and thiols. Most preferred redox-initiators are
benzoylperoxide/N,N-bis-(.bet- a.-hydroxyethyl)-p-toluidine,
benzoylperoxide/N,N-bis-(.beta.-hydroxyethyl- )-p-benzoic acid
ethylester, benzoylperoxide/tributylamine, cumol
hydroperoxide/N,N-bis-(.beta.-hydroxyethyl)-p-toluidine,
diisopropyl peroxycarbonate/dimethylbenzylamine.
[0057] Preferred photoinitiators for use in polymerizable
compositions in accordance with the invention which include
macromonomers with the scope of general formulas M-1 through M-12
are camphorquinone, benzophenone and 2,2-dimethylbenzylketal.
[0058] Preferred fillers for use in compositions in accordance with
the invention include inorganic compounds, such as La.sub.2O.sub.3,
ZrO.sub.2, BiPO.sub.4, CaWO.sub.4, BaWO.sub.4, SrF.sub.2,
Bi.sub.2O.sub.3, glasses and/or organic fillers, such as polymer
granulate. Dental/medical composite compositions of the invention
preferably include filler in an amount from about 50 to about 85
percent by weight. Dental/medical adhesive compositions of the
invention preferably include filler in an amount from about 50 to
about 65 percent by weight. Dental/medical sealant compositions of
the invention preferably include filler in an amount from about 10
to about 50 percent by weight.
[0059] Dental/medical composite compositions, adhesives and sealant
of the invention include one-component and two-component
paste/paste and powder/liquid-material which is to be mixed
immediately before use.
[0060] Shrinkage of composite compositions of the invention is
preferably less than 4.5 and more preferably less than 1.5 percent
by volume. Adhesive dental composite compositions of the invention
containing radio-opaque fillers preferably provide a radio-opacity
of at least 1.5 mm/mm Al, more preferably at least 3 to 7 mm/mm Al,
and most preferably at least 7 mm/mmAl.
[0061] The self-adhesive dental/medical composites compositions in
accordance with a preferred embodiment of the invention have a
fluoride release of at least 1 .mu.g/cm.sup.2, more preferably at
least 1-3 .mu.g/cm.sup.2, and most preferably at least 3-10
.mu.g/cm.sup.2.
[0062] Self-adhesive dental/medical composites compositions in
accordance with a preferred embodiment of the invention have an
opacity of at least 40%, more preferably at least 20-40%, and most
preferably at least 5-20%.
[0063] The setting time of the adhesive dental/medical adhesive
compositions in accordance with a preferred embodiment of the
invention at 37.degree. C. is between 1 minute and 60 minutes, more
preferably between 5 and 30 minutes and most preferably between 2
and 5 minutes. The setting time of adhesive compositions in
accordance with a preferred embodiment of the invention at
23.degree. C. is preferably between 10 minutes and 300 minutes
more, preferably between 5 and 100 minutes and most preferably
between 5 and 20 minutes.
[0064] Dental/medical composition in accordance with the invention
is characterised by having an adhesion to dentine of at least 2
MPa; a fluoride release of at least 1 .mu.g F.sup.- per week and
per cm.sup.2 of the exposed surface of the composition; an opacity
of at least C.sub.0.7=40%; and a compressive strength of at least
200 Mpa.
[0065] In the following examples bond strength to dentin is
measured using extracted human teeth. The teeth used for the shear
bond strength test are treated in 1% sodium hypochlorite for one
hour and then stored in distilled water in a refrigerator at about
4.degree. C. until needed. The teeth are washed with water,
mechanically sanded with 320 grit carborundum paper until a flat
dentin surface is exposed.
[0066] The teeth are then individually blown dry with compressed
dry air to ensure the dentin surface is free from noticeable
moisture. A small plastic straw with 5 mm inner diameter and 2 to 3
mm in length is filled with the polymerizable composition being
tested and seated on the dentin so as to form a post without
pressure. The upper open end of the straw is covered with a thin
film and cured. The specimens are then stored in distilled water at
37.degree. C. for 24 hours. The teeth are then vertically mounted
in a 7 cm ring using gypsum to provide a base for testing with the
post at right angles thereto. The mounted specimens are then loaded
in shear in an Zwick device model number 1455 manufactured by Zwick
GmbH for measurement of adhesion of the post to dentin at 1
mm/minute crosshead speed. The load is applied parallel to the
prepared tooth surface and at right angles to the post until
fracture occurred. The shear bond strength is then calculated.
[0067] In the examples Fluoride Release is measured by making three
1.times.20 mm (diameter) discs of each material. Each disc is
placed in 25 ml water stored for a week at 37.degree. C. Using an
ion selective electrode, the fluoride concentration in mg
F.sup.-/cm.sup.2 is determined for each disc. The average value of
the three discs is recorded.
[0068] In the Examples compressive strength is measured according
to ISO 9917, EN 29917; flexural strength is measured according to
ISO 4049, EN 24049; elastic modulus is measured according to ISO
4049, EN 24049; opacity is measured according to ISO 9912, EN
29912; IR spectra are measured using a Fourier transformation Infra
Red spectrometer at 23.degree. C.
Reference Example 1
[0069] The macromonomer of formula M-1 wherein n is 1, R is
--OC.sub.6H.sub.4--C(CH.sub.3).sub.2--C.sub.6H.sub.4O--, R.sub.1 is
--CH.sub.3, R.sub.2 is --(CH.sub.2).sub.4-- is referred to
hereinafter as macromonomer M-1A and is prepared by reacting
150.000 g (0.441 mol) bisphenol-A diglycidyl ether, 32.200 g (0.220
mol) adipic acid and 2.000 g triethylbenzylammoniumchloride for
four hours at 80.degree. C. while stirring. To the obtained
glycidyl terminated prepolymer are added 37.900 g (0.441 mol)
methacrylic acid and 0.444 g 2.6-di-tert.-butyl-p-cresol and are
reacted for another four hours at 80.degree. C. The methacrylate
terminated macromonomer is soluble in organic solvents such as
chloroform, DMF and THF. In the IR-spectrum no absorption of
epoxide groups at .nu.=915 and 3050 cm.sup.-1 is observed.
Absorption of ester groups is seen at .nu.=1720 cm.sup.-1. In the
.sup.1H NMR spectrum are found signals of the olefinic double bond
at .delta..sub.(CH2=)=6,137/6,1- 19/6,115 ppm and at
.delta..sub.(CH2=)=5,587/5,582/5,555/5,548 ppm.
Reference Example 2
[0070] Preparation of the Macromonomer of Formula M-1B wherein E is
Hydroxyl, n is 1, R is --O(CH.sub.2).sub.4O--, R.sub.1 is
--CH.sub.3, R.sub.2 is --(CH.sub.2).sub.4--.
[0071] 200.00 g (0.99 mol) butanediol diglycidyl ether, 72.26 g
(0.49 mol) adipic acid, 85.13 g (0.99 mol) methacrylic acid, 4.72 g
triethylbenzylammoniumchloride and 0.60 g
2,6-di-tert.-butyl-p-cresol are stirred together and heated for
four hours at 90.degree. C. The obtained methacrylate terminated
macromonomer is soluble in organic solvents such as chloroform, DMF
and THF. In the IR-spectrum no absorption of epoxide groups at 915
and 3050 cm.sup.-1 is observed. Absorption of ester groups is seen
at 1720 cm.sup.-1. The viscosity measured with a Bohlin rheometer
is .eta..sub.dyn=3.3 Pas (25.degree. C.).
Reference Example 3
[0072] Preparation of the Macromonomer of Formula M-1F wherein E is
Hydroxyl, n is 1, R is
--OC.sub.6H.sub.4--CH.sub.2--C.sub.6H.sub.4O--, R.sub.1 is
--CH.sub.3, R.sub.2 is --(CH.sub.2).sub.4--.
[0073] 100.00 g (0,32 mol) bisphenol-F diglycidyl ether, 23.39 g
(0.16 mol) adipic acid, 27.56 g (0.32 mol) methacrylic acid, 65.47
g triethylenglycol dimethacrylate, 1.53 g
triethylbenzylammoniumchloride and 0.30 g
2,6-di-tert.-butyl-p-cresol are stirred together and heated for
four hours at 90.degree. C. The obtained methacrylate terminated
macromonomer is soluble in organic solvents such as chloroform, DMF
and THF. In the IR-spectrum no absorption of epoxide groups at 915
and 3050 cm.sup.-1 is observed. Absorption of ester groups is seen
at 1720 cm.sup.-1. The viscosity measured with a Bohlin rheometer
is .eta..sub.dyn=3.6 Pas (25.degree. C.).
Reference Example 4
[0074] Preparation of the Macromonomer of Formula M-3 wherein E is
Hydroxyl n is 1, R is
--OC.sub.6H.sub.4--C(CH.sub.3).sub.2--C.sub.6H.sub.- 4O--, R.sub.1
is --CH.sub.3, R.sub.2 is --CH.sub.3, R.sub.2 is
--(CH.sub.2).sub.4O(CH.sub.2).sub.4--, R.sub.3 is
C.sub.6H.sub.5CH.sub.2-- -.
[0075] 150.000 g (0.441 mol) bisphenol-A diglycidyl ether, 37.935 g
(0.441 mol) methacrylic acid, 2.000 g triethylbenzylammonium
chloride, 1.115 g 2,6-di-tert.-butyl-p-cresol (BHT) and 111.695 g
triethylenglycol dimethacrylate were homogeneously mixed while
heating. The mixture was kept for two hours at 90.degree. C. After
this time 75.020 g (0.221 mol) N,N'-dibenzyl-5-oxanonanediamine-1,9
were added to the mixture while stirring and kept for additional
two hours at 90.degree. C. The obtained methacrylate terminated
macromonomer is soluble in organic solvents such as chloroform, DMF
and THF. No absorption of epoxide groups at 915 and 3050 cm.sup.-1
is observed in the IR-spectrum. Absorption of ester groups were
found at 1720 cm.sup.-1.
Reference Example 5
[0076] Preparation of the Macromonomer of Formula M-5 wherein E is
Hydroxyl, n is 1, R is
--OC.sub.6H.sub.4--C(CH.sub.3).sub.2--C.sub.6H.sub- .4O--, R.sub.1
is --CH.sub.3, R.sub.2 is --(CH.sub.2).sub.4O(CH.sub.2).sub- .4--,
R.sub.3 is C.sub.6H.sub.5CH.sub.2--. 20.000 g (58.75 mmol)
bisphenol-A diglycidyl ether and 40.012 g (117.50 mmol)
N,N'-dibenzyl-5-oxanonanediamine-1,9 are homogeneously mixed while
heating. The mixture is kept for two hours at 90.degree. C. After
this time 16.704 g (117.50 mmol) 2,3-epoxypropyl methacrylate is
added to the mixture while stirring and the mixture is for another
two hours at 90.degree. C. The obtained methacrylate terminated
macromonomer is soluble in organic solvents such as chloroform, DMF
and THF. In the IR-spectrum no absorption of epoxide groups at 915
and 3050 cm.sup.-1 is observed.
Reference Example 6
[0077] Preparation of the Macromonomer of Formula M-5 wherein E is
Hydroxyl, n is 0, R.sub.1 is --CH.sub.3, R.sub.2 is
--(CH.sub.2).sub.4O(CH.sub.2).sub.4--, R.sub.3 is
C.sub.6H.sub.5CH.sub.2-- -.
[0078] 50.000 g (146.83 mmol)
N,N'-dibenzyl-5-oxanonianediamine-1.9, 41.750 g (293.67 mmol)
2,3-epoxypropyl methacrylate and 0.213 g BHT are homogeneously
mixed while heating. The mixture is kept for two hours at
90.degree. C. The obtained methacrylate terminated macromonomer is
soluble in organic solvents such as chloroform, DMF and THF. In the
IR-spectrum no absorption of epoxide groups at 915 and 3050
cm.sup.-1 are observed.
Reference Example 7
[0079] Preparation of the Macromonomer of Formula M-6 wherein E is
Hydroxyl, n is 1, R is
--OC.sub.6H.sub.4--C(CH.sub.3).sub.2--C.sub.6H.sub- .4O--, R.sub.1
is --CH.sub.3, R.sub.4 is --C.sub.6H.sub.4--C(CH.sub.3).sub-
.2--C.sub.6H.sub.4--.
[0080] 150.000 g (0.441 mol) bisphenol-A diglycidyl ether, 50.299 g
(0.220 mol) 2,2-bis-(4-hydroxy-phenyl)propane, 37.901 g (0.441 mol)
methacrylic acid, 102.086 g triethylenglycol dimethacrylate, 2.000
g triethylbenzylammoniumchloride and 0.959 g
2,6-di-tert.-butyl-p-cresol are heated for four hours at 80.degree.
C.
[0081] The obtained methacrylate terminated macromonomer is soluble
in organic solvents such as chloroform, DMF and THF. In the
IR-spectrum no absorption of epoxide groups at 915 and 3050
cm.sup.-1 is observed. Absorption of ester groups is found at 1720
cm.sup.-1.
Reference Example 8
[0082] Preparation of the Macromonomer of Formula M-7 wherein E is
Hydroxyl, n is 1, R is
--OC.sub.6H.sub.4--C(CH.sub.3).sub.2--C.sub.6H.sub- .4O--, R.sub.1
is --CH.sub.3, R.sub.4 is --C.sub.6H.sub.4--C(CH.sub.3).sub-
.2--C.sub.6H.sub.4--.
[0083] 100.000 g (0.294 mol) bisphenol-A diglycidyl ether, 134.235
g (0.588 mol) 2,2-bis-(4-hydroxy-phenyl)propane, 83.520 g (0.588
mmol) 2,3-epoxypropylmethacrylate, 2.000 g triethylbenzylammonium
chloride, 0.794 g 2,6-di-tert.-butyl-p-cresol (BHT) and 79.439 g
triethylenglycol dimethacrylate are homogeneously mixed while
heating. The mixture is kept for two hours at 80.degree. C. The
obtained methacrylate terminated macromonomer is soluble in organic
solvents such as chloroform, DMF and THF. No absorption of epoxide
groups at 915 and 3050 cm.sup.-1 is observed in the IR-spectrum.
Absorption of ester groups is found at 1720 cm.sup.-1.
EXAMPLE 1
[0084] The hydroxyl groups of macromonomer M-1A made by following
the procedure of reference example 1 are esterified by adding
16.023 g (160.13 mmol) succinic anhydride to 56.900 g of a
macromonomer-triethylen- glycol dimethacrylate mixture containing
40.000 g (40.03 mmol) macromonomer M-1A and 16.9 g of
triethylenglycol dimenthacrylate) while stirring for two hours at
90.degree. C. In the IR-spectrum the esterified macromonomer
containing dicarboxylic half ester units shows no absorption of
hydroxyl groups at 3400 cm.sup.-1.
EXAMPLE 2
[0085] The hydroxyl groups of macromonomer M-1B made by following
the procedure of reference example 2 are esterified by adding
197.93 g (1.98 mol) succinic anhydride and 0.56 g triethylamine to
362.71 g macromonomer M-1B while stirring for four hours at
90.degree. C. In the IR-spectrum the esterified macromonomer
containing dicarboxylic half ester units shows no absorption of
hydroxyl groups at 3400 cm.sup.-1. The viscosity measured with a
Bohlin rheometer is .theta..sub.dyn=245 Pas (25.degree. C.).
EXAMPLE 3
[0086] The hydroxyl groups of macromonomer M-1F made by following
the procedure of reference example 3 are esterified by adding 31.58
g (0.32 mol) succinic anhydride, 0.11 g triethylamine and 13.58 g
triethyleneglycol dimethacrylate to 107.57 g of a
macromonomer-triethylen- glycol dimethacrylate mixture (containing
74.40 g, 0.08 mol macromonomer M-1F) while stirring for two hours
at 90.degree. C. In the IR-spectrum the esterified macromonomer
containing dicarboxylic half ester units shows no absorption of
hydroxyl groups at 3400 cm.sup.-1. .theta..sub.dyn=55.2 Pas
(25.degree. C.).
EXAMPLE 4
[0087] The hydroxyl groups of macromonomer M-3 wherein each E is
hydroxyl made by following the procedure of reference example 4 are
esterified by adding to 40.000 g of a
macromonomer-triethyleneglycol dimethacrylate mixture (containing
27.844 g, 23.32 mmol macromonomer M-3 wherein each E is a hydroxy
moiety), 9.338 g (93.32 mmol) succinic anhydride and 12.156 g
triethylenglycol dimethacrylate while stirring for two hours at
90.degree. C. The IR-spectrum does not show any absorption of
hydroxyl groups at 3400 cm.sup.-1 of the newly modified
macromonomer containing dicarboxylic half ester units.
EXAMPLE 5
[0088] The hydroxyl groups of macromonomer M-5 wherein each E is
hydroxyl made by following the procedure of reference example 5 are
esterified by adding 23.516 g (235.00 mmol) succinic anhydride to a
macromonomer M-5 wherein each E is hydroxyl for four hours at
90.degree. C. In the IR-spectrum the esterified macromonomer
containing dicarboxylic half ester units show no absorption of
hydroxyl groups at 3400 cm.sup.-1. The macromonomer is
characterised by the following analytical data:
[0089] Melting point: Fp.=46.6.degree. C.
[0090] Elemental analysis: (C.sub.93H.sub.120N.sub.4O.sub.24)
1678,01
1 calc. C 66.57 H 7.24 N 3.34 found C 66.60 H 6.80 N 2.73
EXAMPLE 6
[0091] The hydroxyl groups of macromonomer M-5 wherein each E is
hydroxyl made by following the procedure of reference example 5 are
esterified by adding 8.239 g (42.88 mmol) trimellitic anhydride,
0.2 g N,N-bis(.beta.-hydroxyethyl)-p-toluidin, 140 ml dioxane and
9.247 g triethylenglycol dimethacrylate to 40.008 g of a
macromonomer-triethyleng- lycol dimethacrylate-mixture (containing
28.000 g, 21.44 mmol macromonomer M-5 wherein each E is hydroxyl)
and kept for eight hours at 90.degree. C. After evaporation of the
dioxane, the macromonomer was washed with petrol ether and dried at
40.degree. C. within six hours. In the IR-spectrum the newly
modified macromonomer containing two dicarboxylic half ester units
and two hydroxylic groups per average molecule show absorption of
hydroxyl groups at 3400 cm.sup.-1 and of the ester unit at 1720
cm.sup.-1.
EXAMPLE 7
[0092] The hydroxyl groups of macromonomer M-5 wherein each E is
hydroxyl made by following the procedure of reference example 6 are
esterified by adding 29.384 g (293.67 mmol) succinic anhydride to a
macromonomer and kept for four hours at 90.degree. C. In the
IR-spectrum the esterified macromonomer M-5 wherein each E is
hydrogen (n=0) containing dicarboxylic half ester units shows no
absorption of hydroxyl groups at 3400 cm.sup.-1.
EXAMPLE 8
[0093] The hydroxyl groups of macromonomer M-6 wherein each E is
hydroxyl made by following the procedure of reference example 7 are
esterified by adding 12.966 g (0.130 mol) succinic anhydride and
0.2 g N,N-bis(.beta.-hydroxyethyl)-p-toluidin to 50.000 g of a
macromonomer-triethylenglycol dimethacrylate mixture (containing
35.000 g, 0.032 mol macromonomer M-6 wherein each E is hydroxyl)
while stirring and were kept for eight hours at 50.degree. C.
[0094] In the IR-spectrum the esterified macromonomer containing
dicarboxylic half ester units shows no absorption of hydroxyl
groups at 3400 cm.sup.-1.
EXAMPLE 9
[0095] The hydroxyl groups of macromonomer M-7 wherein each E is
hydroxyl made by following the procedure of reference example 8 are
esterified by adding 12.966 g (0.130 mol) succinic anhydride and
0.2 g N,N-bis(.beta.-hydroxyethyl)-p-toluidin to 50.000 g of a
macromonomer-triethylenglycol dimethacrylate mixture (containing
35.000 g, 0.032 mol macromonomer M-7 wherein each E is hydroxyl)
while stirring and kept for two hours at 80.degree. C. The
IR-spectrum does not show any absorption of hydroxyl groups at 3400
cm.sup.-1 of the esterified macromonomer containing dicarboxylic
half ester units.
EXAMPLE 10
[0096] The hydroxyl groups of macromonomer M-6 wherein each E is
hydroxyl made by following the procedure of reference example 7 are
esterified by adding 29.760 g (0.297 mol) succinic anhydride and
0.2 g N,N-bis(.beta.-hydroxyethyl)-p-toluidin to a macromonomer M-6
wherein each E is hydroxyl while stirring and were kept for eight
hours at 50.degree. C. In the IR-spectrum the newly modified
macromonomer containing dicarboxylic half ester units shows no
absorption of hydroxyl groups at 3400 cm.sup.-1.
EXAMPLE 11
[0097] The hydroxyl groups of macromonomer M-1A made by following
the procedure of reference example 1 are esterified by adding
40.000 g (40.03 mmol) of a macromonomer M-1A dissolved in 100 ml
THF 16.204 g triethylamine in 50 ml THF. After adding 24.553 g
POCl.sub.3 (153.33 mmol) drops by drops while stirring at 0.degree.
to 5.degree. C. the solution is stirred for further two hours at
room temperature. Than the triethylamine hydrochloride is filtered
off and the mixture is hydrolysed with 20 ml water. The organic
solution is extracted three times with Na.sub.2CO.sub.3 solution
and is separated from water. From the solution, dried over
MgSO.sub.4, the solvent is evaporated and the macromonomer is
dried.
[0098] In the IR-spectrum the esterified macromonomer containing
phosphoric ester units shows no absorption of hydroxyl groups at
.nu.=3400 cm.sup.-1. New absorptions were found at .nu.=1007
cm.sup.-1, .nu.=2362 cm.sup.-1 and as shoulder at .nu.=3302
cm.sup.-1. In the .sup.1H NMR spectrum signals of the olefinic
double bonds at .delta..sub.(CH2=)=6.06/6.12 ppm and at
.delta..sub.(CH2=)=5.58/5.59 ppm were found. The signals of the
methine protons (CH--OP) appears at .delta..sub.(CH)=5.22 and 5.88
ppm. Those of unreacted macromonomer (CH--OH) appears at
.delta..sub.(CH)=4.34/4.35 ppm.
[0099] The HPLC analysis of the modified macromonomer shows the
same distribution of oligomers as those of unreacted M-1.
Consequently, only the oligomer analogous reaction takes place
which does not change the distribution, and no side reaction or
crosslinking was observed.
EXAMPLE 12
[0100] The hydroxyl groups of macromonomer with M-3 wherein each E
is hydroxyl made by following the procedure of reference example 4
are esterified by adding 60.000 g (50.26 mmol) of a macromonomer
M-3 wherein each E is hydroxyl dissolved in 150 ml THF to 20.346 g
triethylamine in 50 ml THF. After adding 30.829 g (201.06 mmol)
POCl.sub.3 drops by drops while stirring at 0.degree. to 5.degree.
C. the solution is stirred for further two hours at room
temperature. Than the triethylamine hydrochloride is filtered off
and the mixture is hydrolysed with 20 ml water. The organic
solution is extracted three times with Na.sub.2CO.sub.3 solution
and is separated from water. From the solution, dried over
MgSO.sub.4, the solvent is evaporated and the macromonomer is
dried. In the IR-spectrum the esterified macromonomer containing
phosphoric ester units shows no absorption of hydroxyl groups at
.nu.=3400 cm.sup.-1. New absorptions are found at .nu.=1007
cm.sup.-1, .nu.=2362 cm.sup.-1 and as shoulder at .nu.=3302
cm.sup.-1 and an broad absorption at .nu.=2600 to 2800 cm.sup.-1 of
the ammonium salt.
EXAMPLE 13
[0101] The hydroxyl groups of macromonomer M-6 wherein each E is
hydroxyl made by following the procedure of reference example 7 are
esterified by adding 40.000 g (37.83 mmol) of a macromonomer M-6
wherein each E is hydroxyl dissolved in 100 ml THF to 15.312 g
triethylamine in 50 ml THF. After adding 23.200 g (151.31 mmol)
POC.sub.3 drops by drops while stirring at 0.degree. to 5.degree.
C. the solution is stirred for further two hours at room
temperature. Than the triethylamine hydrochloride is filtered off
and the mixture is hydrolysed with 20 ml water. The organic
solution is extracted three times with Na.sub.2CO.sub.3 solution
and is separated from water. From the solution, dried over
MgSO.sub.4, the solvent is evaporated and the macromonomer is
dried. In the IR-spectrum the esterified macromonomer containing
phosphoric ester units shows no absorption of hydroxyl groups at
.nu.=3400 cm.sup.-1. New absorptions are found at .nu.=1007
cm.sup.-1, .nu.=2362 cm.sup.-1 and as shoulder at .nu.=3302
cm.sup.-1.
EXAMPLE 14
[0102] 1) 75% of hydroxyl groups of the macromonomer M-1A made by
following procedure of reference example 1 are esterified with
succinic acid anhydride by adding 148.387 g (0.116 mol) of a
macromonomer M-1A to 34.890 g (0.349 mol) succinic anhydride and
0.183 g triethylamine and reacted for two hours at 80.degree. C.
while stirring. The macromonomer is dissolved in 250 ml THF and
stirred for a further hour. The esterified macromonomer M-1A
containing (n+2)-carboxylic half ester groups show in the
IR-spectrum an absorption of .nu..sub.CO=1720 cm.sup.-1.
[0103] 2) Esterification of the residual unreacted hydroxy groups
of the macromonomer with POCl.sub.3.
[0104] To 183.460 g (0.141 mol) of the obtained macromonomer M-1A
dissolved in 250 ml THF were added 14.287 g triethylamine in 50 ml
THF. After adding 21.659 g (0.141 mol) POCl.sub.3 drops by drops
while stirring at 0.degree. to 5.degree. C. the solution is stirred
for further two hours at room temperature. Than the triethylamine
hydrochloride is filtered off and the mixture is hydrolysed with 50
ml water. The organic solution is extracted three times with
Na.sub.2CO.sub.3 solution and is separated from water. From the
solution, dried over MgSO.sub.4, the solvent is evaporated and the
macromonomer is dried. In the IR-spectrum the esterified
macromonomer containing phosphoric ester units shows no absorption
of hydroxyl groups at .nu.=3400 cm.sup.-1. New absorptions are
found at .nu.=1007 cm.sup.-1, .nu.=2362 cm.sup.-1 and as shoulder
at .nu.=3302 cm.sup.-1. In the .sup.1H NMR spectrum signals of the
olefinic double bonds at .delta..sub.(CH2=)=6.,06/6.12 ppm and at
.delta..sub.(CH2=)=5.58/5.59 ppm were found. The signals of the
methine protons (CH-O-P) appear at .delta..sub.(CH)=5,22 and 5,88
ppm. Those containing succinic half ester units appear at
.delta..sub.(CH)=5,38 ppm. The esterified macromonomer M-1
containing (n+2)-carboxylic half ester groups and n-phosphoric acid
groups is described by the following formula (n=1,
R=--OC.sub.6H.sub.4--C(CH.sub.3).sub.2--C.sub.6H.sub.4O--,R.sub.2=--
-(CH.sub.2).sub.4--, R.sub.5=--CH.sub.2CH.sub.2--): 11
EXAMPLE 15
[0105] 100.00 g (161.29 mmol) of a monophosphate ester of
pentaerythrit pentmethacrylate and 27.29 g (161.29 mmol)
dimethylaminoethyl methacylate are dissolved in 84.86 g
triethyleneglycol dimethacrylate and reacted for two hours at
50.degree. C. In the IR spectrum at 2600 to 2850 cm.sup.-1 an
absorption of the ammonium salt is found. At 3400 cm.sup.-1 no
absorption of OH-groups is observed. The pH of the salt is 3.9.
Application Example 1
[0106] (Dental Adhesive)
[0107] 1.242 g of the esterified macromonomer M-5 wherein each E is
succinic acid half ester made by following the procedure of example
5, 0.411 g triethyleneglycol dimethacrylate, 0.008 g
N,N-bis(.beta.-hydroxye- thyl)-p-toluidine and 0.006 g
camphorquinone were homogeneously mixed. This mixture was applied
in a ring (2 mm high, 5 mm i.d.) on the surface of teeth and
exposed with visible light (irradiation lamp Prismetics Lite De
Trey Dentsply) for 40 seconds. Immediately after fixation, the
teeth are transferred for 24 hours to a chamber at 37.+-.2.degree.
C. and 100% relative humidity. The adhesion measured with a
Zwick-apparatus is 3.74.+-.1.29 MPa.
Comparative Example 1
[0108] 12
[0109] 2.420 g of
2,2-Bis-[p-(2-hydroxy-3-methacryloyloxypropoxy)-phenyl]-- propan
(Bis-GMA) which is modified with succinic anhydride at the hydroxyl
groups, 0.821 g triethylenglycol dimethacrylate, 0,016 g
N,N-bis(.beta.-hydroxyethyl)-p-toluidine and 0.012 g camphorquinone
were homogeneously mixed. This mixture is applied in a ring (2 mm
high, 5 mm i.d.) on the surface of teeth and exposed with visible
light (irradiation lamp Prismetics Lite De Trey Dentsply) for 40
seconds. Immediately after fixation, the teeth are transferred for
24 hours to a chamber at 37.+-.2.degree. C. and 100% relative
humidity. The adhesion is 0.45.+-.,20 Mpa, when measured with a
Zwick-apparatus model number 1455, manufactured by Zwick GmbH &
Co.
Application Example 2
[0110] (Dental Adhesive)
[0111] 1.276 g of the esterified macromonomer M-5 wherein each E is
succinic acid half ester made by following the procedure of example
5, 2.126 g triethylenglycol dimethacry-late, 6.5 g
Strontium-alumo-silicate glass, 0.036 g camphorquinone and 0.045 g
N,N-bis(.beta.-hydroxyethyl)-p-- toluidine are homogeneously mixed
and polymerized photochemical. The product has the following
properties: adhesin to dentine of 3.7.+-.1.1 MPa, compressive
strength 177.+-.3.5 MPa, Elastic Modulus of 2383.+-.71 MPa.
Application Example 3
[0112] (Dental Adhesive)
[0113] 1.755 g of macromonomer M-5 wherein each E is succinic acid
half ester of example 5, 0.752 g methylmethacrylate, 4.652 g
Strontium-alumo-silicate glass, 0.010 g camphorquinone and 0.012 g
N,N-bis(.beta.-hydroxyethyl)-p-toluidine are homogeneously mixed
and polymerized photochemically. The product obtained has the
following properties: adhesion to dentine: 3.9.+-.1.2 MPa,
compressive strength 134.+-.9.7 MPa, Elastic Modulus 2528.+-.158
MPa.
Application Example 4
[0114] (Dental Adhesive)
[0115] Paste A:
[0116] 3.0404 g of macromonomer M-5 wherein each E is succinic acid
half ester of example 5, 2.2512 g triethylenglycol dimethacrylate,
6.0 g CaWO.sub.4/ZrO.sub.2 (80/20) and 0.3135 g
Strontium-alumo-silicate glass containing 10% lithium-sulfinate are
homogeneously mixed.
[0117] Paste B):
[0118] 3.0404 g of macromonomer M-5 wherein each E is succinic acid
half ester of example 5, 2.2512 g triethylenglycol dimethacrylate,
6.0 g CaWO.sub.4/ZrO.sub.2 (80/20), 0.0057 g octophen and 0.0668 g
Strontium-alumo-silicate glass containing 1% Cu-(I)-thiourea
complex are homogeneously mixed.
[0119] Immediately before use paste A and paste B were mixed in the
wt.-ratio 1:1 homogeneously. The gel time at 23.degree. C. is
estimated to be 32 min. and the gel time at 23.degree. C. is 7
minutes. The radio-opacity (RO) of the obtained material is 6.5
mm/mm Al.
Application Example 5
[0120] (Dental Adhesive)
[0121] Paste A:
[0122] 8.001 g of macromonomer M-1A of example 1, 5.334 g
triethylenglycol dimethacrylate, 14.467 g CaWO.sub.4/ZrO2 (80/20),
0.014 g 2.6-di-tert.-butyl-p-cresol and 0.533 g
Strontium-alumo-silicate glass containing 10% lithium-sulfinate are
homogeneously mixed.
[0123] Paste B:
[0124] 8.001 g of macromonomer M-1A of example 1, 5.334 g
triethylenglycol dimethacrylate, 14.467 g CaWO.sub.4/ZrO.sub.2
(80/20), 0.014 g 2.6-di-tert.-butyl-p-cresol, 0.065 g octophen and
0.0533 g Strontium-alumo-silicate glass containing 1%
Cu-(I)-thiourea complex are homogeneously mixed.
[0125] Immediately before use paste A and paste B were mixed in the
wt.-ratio 1:1 homogeneously. The gel time at 23.degree. C. is about
96 minutes, and the gel time at 32.degree. C. is 19 min. The
radioopacity of the obtained material is about about 6.7 mm/mm
Al.
Application Example 6
[0126] (Dental Adhesive)
[0127] Powder:
[0128] 15.000 g silylated Strontium-alumo-silicate glass and 2.000
g silylated Strontium-alumo-silicate glass containing 10%
dibenzoylperoxide were mixed homogeneously.
[0129] Liquid:
[0130] 14.000 g of a macromonomer M-5 wherein each E is succinic
acid half ester of example 5, 6.000 g
tetrahydrofurfuryl-methacrylate, 0.405 g
N,N-bis(.beta.-hydroxyethyl)-p-toluidine, 0.0130 g
2,6-di-tert.-butyl-p-cresol are mixed homogeneously.
[0131] Immediately before use powder and liquid were mixed in the
wt.-ratio 1.73:1.00 homogeneously. The working time is 3.50 minutes
and the setting time is 3.25 minutes. The adhesion to dentine is
measured to be 2.2.+-.0.7 MPa. The composite shows the following
mechanical properties: compressive strength: 152.+-.15 MPa, and
elastic modulus of 1788.+-.81 MPa.
Application Example 7
[0132] (Dental Adhesive)
[0133] Paste A:
[0134] 3.000 g of an ammonium salt of dipenta erthrytrol
pentamethacrylate monophosphate and 2-(dimetyl)aminoethyl
methacrylate (AP-1), 2.000 g macromonomer M-1A of example 1, 5.000
g triethylenglycol dimethacrylate, 15.000 g
Strontium-alumo-silicate glass, 0.005 g 2,6-di-tert.-butyl-p-cre-
sol and 0.200 g cumenhydroperoxide are mixed homogeneously.
[0135] Paste B:
[0136] 3.000 g of AP-1, 2.000 g macromonomer M-1A of example 1,
5.000 g triethylenglycol dimethacrylate, 15.000 g
Strontium-alumo-silicate glass, 0.005 g
2,6-di-tert.-butyl-p-cresol, 0.4081 g of a 0.1% solution of cupric
acetylacetonate in 2-hydroxy propylmethacrylate and 0.041 g
ascorbic acid palmitate are mixed homogeneously.
[0137] The following values are measured: gel time (gt) at
23.degree. C. is 3:55 minutes, gel time is 37.degree. C. is 2.10
minutes, adhesion to dentine 5.12 MPa, shrinkage (reduction in
volume) is 4.33%.
[0138] Application Example 8
[0139] (Dental adhesive)
[0140] Paste A:
[0141] 3.000 g of AP-1, 2.000 g of macromonomer M-1,A of example 1,
5.000 g triethylenglycol dimethacrylate, 15.000 g
Strontium-alumo-silicate glass, 0.005 g 2,6-di-tert.-butyl-p-cresol
and 0.200 g tert.-butyl peroxy benzoate are mixed
homogeneously.
[0142] Paste B:
[0143] 3.000 g of AP-1, 2.000 g macromonomer M-1A of example 1,
5.000 g triethylenglycol dimethacrylate, 15.000 g
Strontium-alumo-silicate glass, 0.005 g
2,6-di-tert.-butyl-p-cresol, 0.6186 g of a 0.1% solution of cupric
acetyacetonate in 2-hydroxy-propylmethacrylate and 0.051 g ascorbic
acid palmitate are mixed homogeneously.
[0144] The following values were measured: gel time (gt) at
23.degree. C. is 6.10 minutes, (gt) at 37.degree. C. is 3.20
minutes, adhesion to dentine 4.02 MPa, shrinkage (or reduction in
volume) is 4.33%.
Application Example 9
[0145] (Dental Adhesive)
[0146] Powder:
[0147] 41.842 g silylated Strontium-alumo-silicate glass and 0.423
g dibenzoyl peroxide are mixed homogeneously.
[0148] Liquid:
[0149] 18.000 g of AP-1, 12.000 g triethylenglycoldimethacrylate,
0.180 g N,N-dimethyl-3,5-dimethyl aniline and 0.009 g
2,6-di-tert.-butyl-p-cresol were mixed homogeneously. Immediately
before use powder and liquid were mixed in the weight ratio
1.40:1.00 homogeneously. The working time is 1:30 minutes and the
setting time is 2:30 minutes.
[0150] The following properties are measured:
2 adhesion to dentine: 7.68 .+-. 1.5 MPa compressive strength: 261
.+-. 14 MPa Elastic modules: 2917 .+-. 76 MPa shrinkage: 2.30%
(percent reduction in volume) expansion: 1.17% (after storage for
(expansion in length) 14 weeks in water at 37.degree. C.) fluoride
release: 5.33 .mu.g/cm.sup.2 (after storage for 9 weeks in water at
37.degree. C.).
Application Example 10
[0151] (Dental Adhesive)
[0152] Powder:
[0153] 47.0 g silylated Strontium-alumo-silicate glass, 07544 g
dibenzoyl peroxide and 2.52 g SrF.sub.2 are mixed
homogeneously.
[0154] Liquid:
[0155] 28.570 g of an ammonium salt of
dipentaerthrytrolpentamethacrylate monophosphate and
2-(dimetyl)aminoethyl methacrylate (ALP-1) containing 8.570 9
triethylenglycol dimethacrylate, 7.140 g macromonomer M-1A of
example 1 containing 2.140 g triethylenglycol dimethacrylate,
13.990 g triethylenglycol dimethacrylate 0.250 g
N,N-bis(.beta.-hydroxyethyl)-p-to- luidine and 0.05 g
2,6-di-tert.-butyl-p-cresol are mixed homogeneously.
[0156] Immediately before use powder and liquid are mixed in the
weight ratio 1.40:1.00 homogeneously. The working time is 5:50
minutes and the setting time is 4:15 minutes.
[0157] The following properties are measured:
3 adhesion to dentine: 7.7 .+-. 0.8 MPa compressive strength: 295
.+-. 9 MPa (ISO 9917, EN 29917) flexural strength: 77.1 .+-. 7.1
MPa (ISO 4049, EN 24049) Elastic modulus: 4482 .+-. 147 MPa (ISO
4049, EN 24049) Opacity: 90.6% (ISO 9912, EN 29912) shrinkage
.DELTA.V: 5.8 .+-. 0.5% expansion .DELTA.L: 1.52% (after storage
for 28 weeks in water at 37.degree. C.) fluoride release: 64.01
.mu.g/cm.sup.2 (after storage for 27 weeks in water at 37.degree.
C.).
Application Example 11
[0158] (Dental Adhesive)
[0159] Powder:
[0160] 46.2480 g silylated Strontium-alumo-silicate glass, 0.6937 g
dibenzoyl peroxide and 2.3124 g SrF.sub.2 are mixed
homogeneously.
[0161] Liquid:
[0162] 20.0000 g of AP-1 containing 14.0000 g triethylenglycol
dimethacrylate, 5.0000 g macromonomer M-1A of example 1 containing
1.5000 g triethylenglycol dimethacrylate, 1.323 g demineralised
water, 4.0000 g UDMA, 4.7000 g triethylenglycol dimethacrylate,
0.1485 g N,N-bis(.beta.-hydroxyethyl)-p-toluidine and 0.0098 g
2,6-di-tert.-butyl-p-cresol are mixed homogeneously. The viscosity
measured with a Bohlin rheometer is .theta..sub.dyn=1.086.+-.0.005
Pas (23.degree. C.).
[0163] Immediately before use powder and liquid are mixed in the
weight ratio 1.40:1.00 homogeneously. The working time is 4:00
minutes and the setting time is 4:00 minutes. The following
properties were measured:
4 adhesion to dentine: 5.86 .+-. 1.53 MPa compressive strength: 301
.+-. 11 MPa flexural strength: 74.8 .+-. 4.8 MPa Elastic modulus:
5320 .+-. 271 MPa expansion .DELTA.L: 1.10% (after storage for 5
weeks in water at 37.degree. C.) fluoride release: 114.05
.mu.g/cm.sup.2 (after storage for 28 weeks in water at 37.degree.
C.).
[0164] Application Example 12
[0165] (Dental Sealant)
[0166] 20.00 g macromonomer M-1A of example 1, 19.63 g
triethylenglycol dimethacrylate, 0.18 g
N,N-bis(.beta.-hydroxyethyl)-p-toluidine, 0.12 g camphorquinone,
0.07 g 2,6-di-tert.-butyl-p-cresol and 60.00 g
Strontium-alumo-silicate glass are mixed homogeneously. Results are
given in table 1.
Application Example 13
[0167] (Dental Sealant)
[0168] 20.00 g macromonomer M-1A of example 14, 19.63 g
triethylenglycol dimethacrylate, 0.18 g
N,N-bis(.beta.-hydroxyethyl)-p-toluidine, 0.12 g camphoro quinone,
0.07 g 2,6-di-tert.-butyl-p-cresol and 60.00 g
Strontium-alumo-silicate glass are mixed homogeneously. Results are
given in table 1.
Comparative Example 2
[0169] 20.00 g of
2,2-Bis-[p-(2-hydroxy-3-methacryloyloxypropoxy)-phenyl]-- propan
(Bis-GMA) which is modified with succinic anhydride at the hydroxyl
groups, 19.63 g triethylenglycol dimethacrylate, 0.18 g
N,N-bis(.beta.-hydroxyethyl)-p-toluidine, 0.12 g camphorquinone,
0.07 g 2,6di-tert.-butyl-p-cresol and 60.00 g
Strontium-alumo-silicate glass are mixed homogeneously. Results are
given in table 1.
5TABLE 1 Bis-GMA Macromonomer Macromonomer according M-1A according
M-1A according comparative example 12 example 13 example 2 Adhesion
to dentin 2.35 2.42 1.04 MPa Standard deviation .+-.0.79 .+-.1.06
.+-.0.34 MPa Molecular weight of 1399.4 1379.3 712.3 modified
Macromo- nomer Molecular weight 349.9 344.8 356.2 per ester
unit
Application Example 14
[0170] (Dental Sealant)
[0171] 10.00 g of AP-1 containing 3.00 g triethylenglycol
dimethacrylate, 2.50 g macromonomer M-1A of example 1 containing
0.75 g triethylenglycol dimethacrylate, 1.25 g triethylenglycol
dimethacrylate, 0.0875 g N,N-bis(.beta.-hydroxyethyl)-p-toluidine,
0.0875 g camphor quinone, 11.49 g Strontium-alumo-silicate glass,
0.30 g Aerosil and 0.0088 g 2,6-di-tert.-butyl-p-cresol are mixed
homogeneously. The viscosity measured with a Bohlin rheometer is
.theta..sub.dyn=1.086.+-.0.005 Pas (23.degree. C.).
Application Example 15
[0172] (Dental/medical Composite)
[0173] 2.000 g macromonomer M-6 of example 8 containing 0.400 g
triethylenglycol dimethacrylate, 5.273 g Strontium-alumo-silicate
glass, 0.010 g champhorquinon and 0.012 g
N,N-bis(.beta.-hydroxyethyl)-p-toluidi- n are homogeneously mixed
and polymerized photochemical. The composite shows the following
mechanical properties:
6 flexural strength: 76.6 .+-. 4.5 MPa flexural modules: 5074.0
.+-. 321 MPa compressive strength: 215.0 .+-. 6.0 MPa Elastic
modules: 3180.0 .+-. 88 Mpa
[0174] It should be understood that while the present invention has
been described in considerable detail with respect to certain
specific embodiments thereof, it should not be considered limited
to such embodiments but may be used in other ways without departure
from the spirit of the invention and the scope of the appended
claims.
* * * * *