Disclosed herein is a composition and method of making a polymerizable antibacterial/antimicrobial resin and using such a bioactive resin in formulated dental compositions.

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Patent
   RE47512
Priority
Jun 22 2011
Filed
Jun 03 2016
Issued
Jul 16 2019
Expiry
Jun 22 2032
Inventors
Jin, Xiaom…
Assg.orig
DENTSPLY S…
Assg.curr
DENTSPLY S…
Entity
Large
Referenced by
0
References
13
Maint.:
currently ok
BRIEF DESCRIPTION OF…
DETAILED DESCRIPTION
EXAMPLES
Example 1
Example 2
Example 3a
Example 3b
Example 3c
Example 3d
Example 4
Example 5
Example 6
Example 7
Example 8
Example 9
Example 10
Example 11
Example 12
Example 13
Example 14-15
Example 16-17
Example 18-21
Example 22-25
Example 26-29
Example 30
Example 31
Example 32
Example 33
Comparative Example …
Comparative Example 3
0. 12. A curable antimicrobial composition comprising:
an imidazolium-based polymerizable resin comprising:
at least one polymerizable group, and
at least one imidazolium moiety comprising a linear long alkyl chain of from eight to fourteen carbon atoms.
0. 25. An imidazole-based precursor for forming an imidazolium-based polymerizable resin, comprising:
a polymerizable imidazole-based resin selected from a monoimidazole resin and a polyimidazole(meth)acrylate resin, the moniomidiazole resin having a formula selected from:
##STR00010##
the polyimidazole(meth)acrylate resin having a formula selected from:
##STR00011##
##STR00012##
0. 26. An imidazole-based polymerizable resin comprising: an imidazole moiety, the imidazole-based polymerizable resin selected from a isosorbide-based bisimidazole-dimethacrylate resin, a TCDC-based bisimidazole-dimethacrylate resin, a butanediol-based bisimidazole-dimethacrylate resin, a TCDC-based bisimidazole-dimethacrylate resin, a paraxylenediol-based bisimidazole-dimethacrylate resin, a HEMA-based monoimidazole-dimethacrylate resin, a AMAHP-based monoimidazole-monomethacrylate resin, and a EGAMA-based monoimidazole-monomethacrylate.
0. 5. A curable antimicrobial composition comprising: at least one ionic imidazolium moiety, and a polymerizable moiety, the imidazolium-based polymerizable resin selected from a HEMA-based monoimidazoliumbromide-dimethacrylate resin, a 3-dodecanylimidazoliumbromide-dimethacrylate resin, a bis(3-dodecanylimidazoliumbromide)-bisacrylate resin, a bis(3-butylimidazoliumbromide)-bisacrylate resin, a EGAMA-based monoimidazoliumbromide-monomethacrylate resin, a 3-dodecanylimidazoliumbromide-monomethacrylate resin, a AMAHP-based monoimidazolium-methacrylate resin, a isosorbide-based bisimidazoliumbromide-dimethacrylate resin, a isosorbide-based bis(3-butylimidazoliumbromide)-dimethacrylate resin, and a 1,6-hexane-bisimidazoliumbromide-dimethacrylate resin.
1. A dental curable antimicrobial composition comprising:
from about 0.1 weight percent to about 5.0 weight percent of an imidazolium-based polymerizable resin;
from about 5 weight percent to about 60 weight percent of a non-imidazolium-based polymerizable resin;
from about 0.005 weight percent to about 5 weight percent of at least one of a photoinitiator, a thermal/redox initiator or other additive;
from about 40 weight percent to about 90 weight percent of a glass filler having a particle size of from about 10 nm to about 100 microns; and
an optional inert solvent
wherein the imidazolium-based polymerizable resin has a formula of:

(A-X)n—Z—(Y—B—HRQR)m
wherein A is a polymerizable moiety selected from the group consisting of methacrylate, acrylate, epoxy and vinylether,
wherein B is an imidazole or a methyl imidazole imidazolium moiety,
wherein R is a hydrogen atom or an alky group having from 1 to 22 carbon atoms,
wherein H Q is a halogen atom, a chlorine atom, a bromine atom or an iodine atom an imidazolium counter ion,
wherein X and Y are the same or different and are an ether, ester, amide, imide, direct link, alkyl, or aromatic,
wherein Z is an alkyl or an aromatic, and
wherein n and m are integers of at least 1.
2. The dental curable antimicrobial composition according to claim 1, wherein the imidazolium-based polymerizable resin demonstrates antibacterial activity capable of killing at least 99 percent of S. mutans.
3. The dental curable antimicrobial composition according to claim 1, wherein the dental composition in its entirety is capable of an imidazolium-based polymerizable resin demonstrates antibacterial activity capable to of killing more than 99 percent of S. mutans and S. aureus.
0. 4. A curable antimicrobial composition according to claim 1, wherein the imidazolium-based polymerizable resin is an alkylimidazoliumbromide-dimethacrylate resin having a formula selected from:
##STR00001##
0. 6. A curable antimicrobial composition according to claim 5, wherein the imidazolium-based polymerizable resin having a formula selected from:
(a) a bisimidazolium-dimethacrylate resin that has a formula selected from one of a:
an isosorbide-based bisimidazoliumbromide-dimethacrylate resin
e####
##STR00002##
a bis(3-dodecanylimidazoliumbromide)-bisacrylate resin
##STR00003##
a bis(3-butylimidazoliumbromide)-bisacrylate resin
##STR00004##
A 1,6-hexane-bisimidazoliumbromide-dimethacrylate resin
##STR00005##
(b) a monoimidazolium-dimethacrylate resin that has a formula of a HEMA-based monoimidazoliumbromide-dimethacrylate resin
##STR00006##
(c) a monoimidazolium-dimethacrylate resin that has a formula of a EGAMA-based monoimidazoliumbromide-monomethacrylate resin
##STR00007##
0. 7. A curable antimicrobial composition according to claim 5, wherein the imidazolium-based polymerizable resin is present from about 0.1 weight percent to about 20.0 weight percent, based on the total weight of the composition.
0. 8. A curable antimicrobial composition according to claim 7, comprising: one or more acidic resins or polymers, or reactive acidic glass powders complexed with the imidazolium-based polymerizable resin to form one of a soluble liquid resin, soft gel, hard gel and highly-crosslinked solid.
0. 9. A curable antimicrobial composition according to claim 8, comprising:
about 5 weight percent to about 99 weight percent of a non-imidazolium based polymerizable resin;
from about 0.001 weight percent to about 5 weight percent initiators and other additives;
from about 40 weight percent to about 90 weight percent of filler particles having a size of from about 10 nm to about 100 micron,
an optional inert solvent,
wherein all weight percents are based on the total weight of the curable antimicrobial composition.
0. 10. A curable antimicrobial composition according to claim 8, comprising:
from about 5 weight percent to about 60 weight percent of a non-imidazolium-based polymerizable resin;
from about 0.005 weight percent to about 5 weight percent of at least one of a photoinitiator, a thermal/redox initiator or other additive;
wherein the imidazolium-based polymerizable resin is present from about 0.1 weight percent to about 5.0 weight percent, and
wherein all weight percents are based on the total weight of the curable antimicrobial composition.
0. 11. A curable antimicrobial composition according to claim 10, comprising
about 80 weight percent of a glass filler having a particle size of from about 10 nm to about 100 microns; and
wherein the imidazolium-based polymerizable resin is present from about 0.9 weight percent to about 1.8 weight percent, and
wherein all weight percents are based on the total weight of the curable antimicrobial composition.
0. 13. A curable antimicrobial composition according to claim 12, the at least one polymerizable group selected from methacrylate, acrylate, epoxy and vinylether.
0. 14. A curable antimicrobial composition according to claim 12, the at least one polymerizable group selected from acrylate, methacrylate and polyacrylate.
0. 15. A curable antimicrobial composition according to claim 14, the at least one polymerizable group comprising two methacrylate groups, and the at least one imidazolium moiety comprising a linear alkyl chain of twelve carbon atoms.
0. 16. A curable antimicrobial composition according to claim 12 having a formula selected from:
a HEMA-based monoimidazoliumbromide-dimethacrylate resin
##STR00008##
a EGAMA-based monoimidazoliumbromide-monomethacrylate resin
##STR00009##
0. 17. A curable antimicrobial composition according to claim 12, wherein the imidazolium-based polymerizable resin is present from about 0.1 weight percent to about 20.0 weight percent based on the total weight of the composition.
0. 18. A curable antimicrobial composition according to claim 17, comprising: one or more acidic resins or polymers, or reactive acidic glass powders complexed with the imidazolium-based polymerizable resin to form one of a soluble liquid resin, a gel, and a crosslinked solid.
0. 19. A curable antimicrobial composition according to claim 18, comprising:
about 5 weight percent to about 99 weight percent of a non-imidazolium based polymerizable resin;
from about 0.001 weight percent to about 5 weight percent initiators and other additives;
from about 40 weight percent to about 90 weight percent of filler particles having a size of from about 10 nm to about 100 micron,
an optional inert solvent,
wherein all weight percents are based on the total weight of the curable antimicrobial composition.
0. 20. A curable antimicrobial composition according to claim 18, comprising:
from about 5 weight percent to about 60 weight percent of a non-imidazolium-based polymerizable resin;
from about 0.005 weight percent to about 5 weight percent of at least one of a photoinitiator, a thermal/redox initiator or other additive;
wherein the imidazolium-based polymerizable resin is present from about 0.1 weight percent to about 5.0 weight percent, and
wherein all weight percents are based on the total weight of the curable antimicrobial composition.
0. 21. A curable antimicrobial composition according to claim 20, comprising
about 80 weight percent of a glass filler having a particle size of from about 10 nm to about 100 microns; and
wherein the imidazolium-based polymerizable resin is present from about 0.9 weight percent to about 1.8 weight percent, and
wherein all weight percents are based on the total weight of the curable antimicrobial composition.
0. 22. A curable antimicrobial composition according to claim 12,
wherein the imidazolium-based polymerizable resin has a formula of:

(A-X)n—Z—(Y—B—QR)m
wherein A is a polymerizable moiety selected from the group consisting of methacrylate, acrylate, epoxy and vinylether,
wherein B is an imidazole or a methyl imidazole,
wherein R is a hydrogen atom or an alky group having from 1 to 22 carbon atoms,
wherein Q is an imidazolium counter ion,
wherein X and Y are the same or different and are an ether, ester, amide, imide, direct link, alkyl, or aromatic,
wherein Z is an alkyl or an aromatic, and
wherein n and m are integers of at least 1.
0. 23. A curable antimicrobial composition according to claim 22, wherein Q is a halogen.
0. 24. A curable antimicrobial composition according to claim 22, wherein Q is selected from chlorine, bromine, and iodine.
0. 27. A curable antimicrobial composition according to claim 26, wherein the imidazole based polymerizable resin has a formula selected from:
(a) a bisimidazole-dimethacrylate resin that has a formula selected from:
a isosorbide-based bisimidazole-dimethacrylate resin
e####
##STR00013##
a TCDC-based bisimidazole-dimethacrylate resin
##STR00014##
CDI-based reaction pathways to bisimidazole-dimethacrylate resins
##STR00015##
a butanediol-based bisimidazole-dimethacrylate resin
##STR00016##
a paraxylenediol-based bisimidazole-dimethacrylate resin
##STR00017##
(b) a monoimidazole-dimethacrylate resin that has a formula:
a HEMA-based monoimidazole-dimethacrylate resin
##STR00018##
(c) a monoimidazole-methacrylate resin that has a formula selected from:
a AMAHP-based monoimidazole-methacrylate resin
##STR00019##
a EGAMA-based monoimidazole-methacrylate resin
##STR00020##

A: polymerizable moiety like methacrylate, acrylate, epoxy, vinylether, etc; n=1, 2, 3, 4 . . . .

B: substituted imidazole moiety like imidazole, methylimidazole, etc, m=1, 2, 3, 4, . . . .

R: a hydrogen atom or an alkyl group having 1-22 carbon atoms

Q: counter ion groups such as halogen atom, chlorine, bromine, iodine, etc

X, Y: equal or different, ether, ester, amide, imide, direct link, alkyl, aromatic, etc,

Z: alkyl, aromatic, etc.

Furthermore, formulated dental compositions, including composite or cements, from this invented polyimidazolium resin are able to offer balanced antibacterial effectiveness and mechanical property without causing any severe cytotoxicity. Such resins may be formulated with conventional resins to provide an improved adhesive to hard tissues in a prepared tooth cavity.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 depicts isosorbide-based bisimidazole-dimethacrylate resins.

FIG. 2 depicts a CDI-based reaction pathway to monoimidazole-dimethacrylate resin.

FIG. 3 depicts CDI-based reaction pathways to bisimidazole-dimethacrylate resins.

FIG. 4 depicts a butanediol-based bisimidazole-dimethacrylate resin.

FIG. 5a depicts a TCDC-based bisimidazole-dimethacrylate resin.

FIG. 5b depicts a paraXylenediol-based bisimidazole-dinnethacrylate resin.

FIG. 6 depicts an imidazole-based reaction pathway to monoimidazole-monomethacrylate resin.

FIG. 7 depicts an imidazole-based reaction pathway to monoimidazole-monomethacrylate resin.

FIG. 8 depicts typical monoimidazole resins.

FIG. 9 depicts other polyimidazole(meth)acrylate resins.

FIG. 10 depicts a reaction of 3-dodecanylimidazoliumbromide-dimethacrylate resin.

FIG. 11 depicts typical alkylimidazoliumbromide-dimethacrylate resins.

FIG. 12 depicts an isosorbide-based bis(3-butylimidazoliumbromide)-dimethacrylate resin.

FIG. 13 depicts a 1,6-hexane-bisimidazoliumbromide-dimethacrylate resin.

FIG. 14 depicts a bis(3-butylimidazoliumbromide)bisacrylate resin.

FIG. 15 depicts a bis(3-dodecanylimidazoliumbromide)bisacrylate resin.

FIG. 16 depicts a 3-dodecanylimidazoliumbromide-monomethacrylate resin.

FIG. 17 depicts the antibacterial effectiveness of polymerizale antibacterial resin against S. mutans.

FIG. 18 depicts the antibacterial effectiveness of cured composite containing antibacterial resin against S. aureus.
DETAILED DESCRIPTION

During the attempt to prepare a carbonate-based polymerizable resin (FIG. 1) by using an acrylate-methacrylate resin (AMAHP) and 1,1-carbonyl-diimidazole (CDI), it was surprisingly discovered that a chemically bonded imidazole resin was formed exclusively in the resulting resin. It has been elucidated that the formation of the imidazole resin was the result of a Michael adduct between the acrylate group in AMAHP and the CDI in-situ generated by-product (imidazole) in the absence of any catalysts. The imidazole was found to react exclusively toward the acrylate group. Thus a variety of polymethacrylated resins containing at least one polyimidazole moiety could be readily prepared by proper hybrid acrylate-methacrylate resins or even polyacrylate resins with proper control of the conversion of the imidazole addition. Therefore, this is an effective method to incorporate an imidazole moiety into a polymerizable resin as novel functional resins for acid-free adhesive resins. Furthermore, such polymerizable imidazole-containing resins may be further chemically modified by reaction with a variety of halogenated alkyls to form polymerizable resins with ionic moiety of imidazolium, which may be new class of polymerizable ionic liquid resins.

Accordingly from such a reaction platform, other derivatives may be readily prepared as illustrated in FIGS. 2 through 5: a variety of polymethacrylate resins with polyimidazoles are able to be prepared via the precursor as showed in FIGS. 2 and 3 by coupling with different mono, di, tri, or polyols or polyamines.

Further, in order to streamline the process of making such imidazole-based polymerizable resins for use in making imidazolium-based polymerizable resins, a facile process based on imidazole and acrylated resins were investigated as illustrated in FIGS. 6 and 7. Thus a variety of imidazole-based polymerizable resins are able to be prepared, as shown in FIGS. 8 and 9.

Furthermore, as illustrated in FIGS. 10 through 15, a variety of imidazolium-based polymerizable resins may be prepared from a wide range of imidazole-based polymerizable resins as discussed previously. The preferred imidazolium-based polymerizable resin contains at least one polymerizable group such as methacrylate or acrylate and at least one imidazolium moiety bearing linear long alkyl chain of C8-C14. The most preferred resin contains two methacrylate group and at least one imidazolium moiety bearing a C12 linear alkyl chain.

Such imidazolium-based polymerizable resin was found highly effective in killing bacteria such as S. mutans as showed in FIG. 17. It was also demonstrated that such imidazolium-based polymerizable resins are also very effective in inhibiting MMP even at low concentration. Matrix metalloproteinases (MMP) bond to dentin and are thought to contribute to the progressive degradation of collagen fibrils in hybrid layers formed during dentin bonding. The dentin matrix contains MMP-2, MMP-8, MMP-9, and MMP-20. It is known that chlorhexdine (CHX) has broad anti-MMP activity in addition to antimicrobial activity. However, the long term anti-MMP activity for CHX is not effective, which has been attributed to possible leaching out of the CHX. It has been shown that cationic quaternary ammonium methacrylates (QAS) may exhibit dentin MMP inhibition comparable with that of CHX, but require higher concentrations.

Such effectiveness in killing bacteria for the imidazolium-based polymerizable resins were further demonstrated by the formulated dental composites as showed in Table V and FIG. 18. More importantly it was discovered that a low level loading (less than 1%, wt/wt) of such an imidazolium-based polymerizable resin may remain effective in killing bacteria as showed in Table VI. Furthermore, with optimized compositions not only highly effective antibacterial activity is achieved but also excellent mechanical properties were yielded as shown in Tables VII through XIV. The effectiveness in antibacterial properties of this novel polymerizable imidazolium resin offers another crucial benefit without causing severe cytotoxicity. Conventional QAS-based polymerizable resins, on the other hand, are less effective and high dose loading (up to 30%) is needed, which usually leads to decreases in mechanical property and increases cytotoxicity.

Obviously from the resin disclosed herein a variety of applications could be found as photopolymerizable dental products. Certainly, it can also be polymerized by heat, and/or redox initiation process. In addition, due to the nature of the imidazole moiety, it is also expected that the disclosed polymerizable resin can also find application in forming a complex with acidic resins or polymers, including PENTA, OEMA, methacrylic acid, polyacrylic acid or reactive acidic glass powders to form a soluble liquid resin, soft gel or hard gel structures or highly-crosslinked solids.

Disclosed herein is a composition and method of making and using such compositions in dental restorations. The composition disclosed herein includes novel polymerizable resins. More specifically, the composition disclosed herein is related to a method of preparing such polymerizable resins that contains multiple imidazole groups and multiple radically polymerizable groups as shown in the following formula:
(A-X)n—Z—(Y—BQR)m

A: polymerizable moiety like methacrylate, acrylate, epoxy, vinylether, etc; n=1, 2, 3, 4 . . . .

B: substituted imidazole moiety like imidazole, methylimidazole, etc, m=1, 2, 3, 4, . . . .

R: a hydrogen atom or an alkyl group having 1-22 carbon atoms

Q: counter ion groups such as halogen atom, chlorine, bromine, iodine, etc

X, Y: equal or different, ether, ester, amide, imide, direct link, alkyl, aromatic, etc,

Z: alkyl, aromatic, etc.

Dental composition disclosed herein may be composed of (1) the functional polymerizable resins contains imidazole group or imidazolium groups described herein in amount of from about 0.5 weight percent to about 99 weight percent of the dental composition, (2) conventional polymerizable resin in amounts of from about 10 weight percent to about 99 weight percent of the dental composition, (3) initiators and other additives in amounts of from about 0.001 weight percent to about 5.0 weight percent of the dental composition, (4) a plurality of filler particles having a size of from about 10 nm to about 100 micron of the dental composition, and (5) an optional inert solvent in amounts not to exceed 1 weight percent of the dental composition.

HEMA and HPMA are typical monomethacrylate resins; BisGMA, TEGDMA, UDMA are typical conventional dimethacrylate resins, which are polymerizable/curable by heat, light and redox initiation processes. CQ and LTPO are typical photoinitaiors. Tertiary aromatic amines, such as EDAB, may be included as an accelerator for CQ-based photoinitiator. Other additives such as inhibitors, UV stabilizers or fluorescent agents may also be used. In addition, a variety of particles, polymeric, inorganic, organic particles may be incorporated to reinforce the mechanical properties, rheological properties and sometime biological functionalities.

The following abbreviations may be used:

  • BisGMA: 2,2-bis(4-(3-methacryloyloxy-2-hydroxypropoxy)-phenyl)propane
  • HEMA: 2-hydroxyethyl methacrylate
  • HPMA: 2-hydroxypropyl methacrylate
  • TEGDMA: triethylene glycol dimethacrylate
  • UDMA: di(methacryloxyethyl)trimethyl-1,6-hexaethylene-diurethane
  • BHT: butylhydroxytoluene
  • CQ; camphorquinone
  • LTPO: lucirin TPO/2,4,6-trimethylbenzoyldiphenylphosphine oxide
  • EDAB: 4-Ethyl dimethylaminobenzonate
  • AMAHP: 3-(acryloyloxy)-2-hydroxypropyl methacrylate
  • EGAMA: ethyleneglycol acrylate methacrylate
  • TCDC: 4,8-bis(hydroxymethyl)-tricyclo[5,2,1,02.6]
  • CDI: 1,1-carbonyl-diimidazole
  • SR295: pentaerythritol tetraacrylate

EXAMPLES
Example 1

Isosorbide-based Bisimidazole-dimethacrylate Resin (XJ8-9/FIG. 1) was prepared via a two-step process as described in the following: to a 1000 ml 3-nech round flask, 98.88 g of 1,1-carbonyl-diimidazole (CDI), 550 g of methylene dichloride and 43.9 g of isosorbide was charged and soon the system turned clear at room temperature. Then the crystal was developed as a result of imidazole formation. After 2 hrs reacting at RT, 131.1 g of 3-(acryloyloxy)-2-hydroxypropyl methacrylate (AMAHP), 40.0 g of potassium carbonate and 4.0 g of terabutylamoniumbromide was added. The reaction proceeded at room temperature for an additional 10-12 hrs prior to 200 ml of DI water being added to stop the reaction. The resulting solution was extracted several times with DI water to remove all of imidazole and catalysts. Then it was dried over magnesium sulfate overnight at RT prior to being filtrated. Solvent was removed via Rotovapor at 35-40° C. under vacuum. 240 g of liquid resin was collected with a yield of 89%.

Example 2

TCDC-based Bisimidazole-dimethacrylate Resin (XJ8-13/FIG. 5a) was prepared via a two-step process as described in the following: to a 1000 ml 3-nech round flask, 74.45 g of CDI, 400 ml of methylene dichloride and 98.36 g of AMAHP was charged and soon the system turned clear at room temperature. After 6 hrs reacting at RT, 45.0 g of 4,8-bis(hydroxymethyl)-tricyclo[5,2,1,02.6](TCDC) and 40.0 g of potassium carbonate and 3.8 g of terabutylamoniumbromide was added. The reaction continued at room temperature for an additional 10-12 hrs prior to 250 ml of DI water being added to stop the reaction. The resulting solution was extracted several times with DI water to remove all of imidazole and catalysts. Then it was dried over magnesium sulfate overnight at RT prior to it being filtrated. The solvent was removed via Rotovapor at 35-40° C. under vacuum.

Example 3a

HEMA-based Monoimidazole-dimethacrylate Resin (XJ8-6/FIG. 2) was prepared via a two-step process as described in the following: to a 1000 ml 3-nech round flask, 81.8 g of CDI, 450 ml of methylene dichloride and 107.5 g of AMAHP was charged and soon the system turned clear at room temperature. After a 6 hrs reaction at RT, 66.5 g of 2-hydroxyethyl methacrylate (HEMA), 40.0 g of potassium carbonate and 4.0 g of terabutylamoniumbromide was added. The reaction continued at room temperature for an additional 10-12 hrs prior to 200 ml of DI water being added to stop the reaction. The resulting solution was extracted several times with DI water to remove all of the imidazole and catalysts. Then the solution was dried over magnesium sulfate overnight at RT prior to being filtrated. The solvent was removed via Rotovapor at 35-40° C. under vacuum.

Example 3b

HEMA-based Monoimidazole-dimethacrylate Resin (XJ8-48/FIG. 2) was prepared via a two-step process as described in the following: to a 1000 ml 3-nech round flask, 120.3 g of CDI and 200 ml of methylene dichloride were added. Then 159.3 g of AMAHP in 150 ml of methylene dichloride was charged and soon the system turned clear at room temperature. After an overnight reaction at RT, 100.1 g of HEMA, 40.0 g of potassium carbonate and 4.0 g of terabutylamoniumbromide were added. The reaction continued at room temperature for an additional 4 hrs prior to 200 ml of DI water being added to stop the reaction. The resulting solution was extracted several times with DI water to remove all of the imidazole and catalysts. Then the solution was dried over magnesium sulfate overnight at RT prior to being filtrated. The solvent was removed via Rotovapor at 35-40° C. under vacuum. 301 g of low viscosity liquid resin was collected.

Example 3c

AMAHP-based monosimidazole-methacrylate Resin (XJ8-111/FIG. 6) was prepared via a one-step solution process as described in the following: to a 2000 ml 3-neck flask, 800 ml of methylene dichloride, 161.1 g of AMAHP and 102.2 g of imidazole were charged. Soon the imidazole got dissolved and the clear solution was mixed at room temperature overnight prior to 200 ml of DI water being added to stop the reaction. The resulting solution was extracted several times with DI water to remove all of the excess imidazole and catalysts. Then the solution was dried over magnesium sulfate overnight at RT prior to being filtrated. The solvent was removed via Rotovapor at 35-40° C. under vacuum. 200 g of low viscosity liquid resin was collected, from which a reversible gel-like resin is formed once the temperature down to RT.

Example 3d

EGAMA-based monosimidazole-methacrylate Resin (XJ8-157/FIG. 7) was prepared via a one-step bulk process as described in the following: to a 500 ml 3-nech round flask, 184.5 g of ethyleneglycol acrylate methacrylate (EGAMA) and 69.3 g of imidazole were charged. This slurry was mixed at room temperature for 60 hrs. 250 g of low viscosity liquid resin was collected.

Example 4

HEMA-based Monoimidazoliumbromide-dimethacrylate Resin (XJ8-45/FIG. 10) was prepared by a one-step condensation reaction from the imidazole precursor prepared as described in Example 3b. To a 250 ml 3-neck round flask, 61.7 g of HEMA-based monoimidazole-dimethacrylate resins (XJ8-38) and 40.2 g of 1-bromododecane and 200 ml of methylene dichloride was charged. The reaction continued at 40° C. for 7 days. Added 135 grams of hexane to the system and it is immiscible. After separated the hexane solution part, the resin was dissolved in methylene dichloride and extracted with water for several times. The solvent was removed via Rotovapor at 35-40° C. under vacuum. 80 grams of clear liquid resin was collected, which had a viscosity of 140 Pa·s at 20° C.

Example 5

Isosorbide-based Bisimidazoliumbromide-dimethacrylate Resin (XJ8-31/FIG. 12) was prepared by a one-step solution reaction from the imidazole precursor prepared as described in Example 1. To a 500 ml 3-neck round flask, 42.4 g of Isosorbide-based bisimidazole-dimethacrylate resins (XJ8-9), 13.7 g of 1-bromobutane, 200 ml of methylene dichloride and 8.65 g of triethylene glycol dimethacrylate (TEGDMA) were charged. The reaction continued at 40° C. for 2 days. Finally 65 g of highly viscose liquid resin was collected. The RI of this resin is 1.5130.

Example 6

HEMA-based Monoimidazoliumbromide-dimethacrylate Resin (XJ8-40/FIG. 11) was prepared by a one-step condensation reaction from the imidazole precursor prepared as described in Example 3b. To a 250 ml 3-neck round flask, 21.92 g of HEMA-based monoimidazole-dimethacrylate resins (XJ8-38) and 8.22 g of 1-bromobutane and 200 ml of methylene dichloride was charged. The reaction continued at 40° C. for 2 days. 25.6 grams of viscose liquid resin was collected, which had a RI of 1.5098.

Example 7

HEMA-based Monoimidazoliumbromide-dimethacrylate Resin (XJ8-54/FIG. 11) was prepared by a one-step condensation reaction from the imidazole precursor prepared as described in Example 3b. To a 250 ml 3-neck round flask, 60.2 g of HEMA-based monoimidazole-dimethacrylate resins (XJ8-48), 26.5 g of 1-bromooctane, 150 ml of methylene dichloride was charged. The reaction continued at 40° C. for 6 days. Finally 79 g of liquid resin was collected, which had a viscosity of 245 Pa·s at 20° C.

Example 8

HEMA-based Monoimidazoliumbromide-dimethacrylate Resin (XJ8-80/FIG. 10) was prepared by a one-step condensation reaction from the imidazole precursor prepared as described in Example 3b. To a 250 ml 3-neck round flask, 65.9 g of HEMA-based monoimidazole-dimethacrylate resins (XJ8-48) and 37.4 g of 1-bromododecane and 200 ml of methylene dichloride was charged. The reaction continued at 40° C. for 7 days. 99.5 grams of liquid resin was collected, which had a viscosity of 175 Pa·s at 20° C.

Example 9

Bis(3-dodecanylimidazoliumbromide)-Bisacrylate Resin (XJ8-152-1/FIG. 15) was prepared via a two-step one-pot process as described in the following: to a 250 ml 3-nech round flask, 72.5 g of pentaerythritol tetraacrylate (SR295) and 9.5 grams of imidazole, mixed at RT for 1 hr, then 9.4 grams of imidazole was added for addition 1 hr reaction prior to addition of another 9.6 grams of imidazole. It was mixed overnight at RT. Then set the flask into an oil-bath of 40° C. with addition of 95.2 grams of 1-bromododecane and continued for 7 days at 40° C. 221 grams of highly viscose resin was collected.

Example 10

EGAMA-based monoimidazoliumbromide-monomethacrylate Resins (XJ8-160/FIG. 16) was prepared by a one-step condensation reaction from the imidazole precursor prepared as described in Example 3d. To a 250 ml 3-neck round flask, 127 grams of EGAMA-based monoimidazole-monomethacrylate resins (XJ8-157) and 124.0 grams of 1 -bromododecane were charged. The reaction continued at 40° C. for 10 days. Finally 245 g of liquid resin was collected, which had a viscosity of 50 Pa·s at 20° C.

Example 11

AMAHP-based monosimidazolium-methacrylate Resin (XJ8-88/FIG. 11) was prepared via a one-step solution process as described in the following: to a 500 ml 3-nech round flask, 65.9 g of AMAHP-based monoimidazole-methacrylate resins (XJ8-81) and 28.8 of 1-bromooctane and 200 ml of methylene dichloride were charged. The reaction continued at 40° C. for 6 days. 61.3 grams of liquid resin was collected, which had a viscosity of 170 Pa·s at 20° C.

Example 12

AMAHP-based monosimidazolium-methacrylate Resin (X18-94/FIG. 11) was prepared via a one-step solution process as described in the following: to a 500 ml 3-nech round flask, 56.5 g of AMAHP-based monoimidazole-methacrylate resins (XJ8-85) and 33.1 of 1-bromoohaxane and 200 ml of methylene dichloride were charged. The reaction continued at 40° C. for 7 days. 80 grams of viscose liquid resin was collected, which had a viscosity of 410 Pa·s at 20° C.

Example 13

AMAHP-based monosimidazolium-methacrylate Resin (XJ8-88/FIG. 11) was prepared via a one-step solution process as described in the following: to a 500 ml 3-nech round flask, 43.0 of AMAHP-based monoimidazole-methacrylate resins (XJ8-111) and 25.0 of 1,12-dibromododecane and 150 ml of methylene dichloride were charged. The reaction continued at 40° C. for 3 days. 60 grams of highly viscose liquid resin was collected.

Example 14-15

Light curable flowable dental composites (IJ1-84-2 and IJ1-85-2) containing polymerizable imidazlium resin (XJ8-80 at 2-4% wt/wt) were formulated with 60% of filler, which demonstrated effective antibacterial activities as showed in Table VI.

Example 16-17

Light curable universal dental composites (XJ8-136 and XJ8-137) containing polymerizable imidazlium resin (XJ8-80 at 20.9-1.8% wt/wt) were formulated with 82% of filler, which demonstrated effective antibacterial activities and excellent mechanical properties without causing severe cytotoxicityas as showed in Table VI.

Example 18-21

Light curable universal dental composites (IJ1-115, 117, 118, and 137) containing polymerizable imidazlium resin (XJ8-80 at 0.9-1.8% wt/wt) were formulated with 82% of filler, which demonstrated effective antibacterial activities and excellent mechanical properties without causing severe cytotoxicityas showed in Table VIII.

Example 22-25

Light curable universal dental composites (IJ2-39, 40, 41, and 42) containing polymerizable imidazlium resin (XJ8-152 at 0.9-1.8% wt/wt) were formulated with 82% of filler, which demonstrated excellent mechanical properties as showed in Table X.

Example 26-29

Light curable universal dental composites (IJ2-189, 190, 191, and 192) containing polymerizable imidazlium resin (XJ8-160 at 0.9-1.8% wt/wt) were formulated with 82% of filler, which demonstrated effective antibacterial activities and excellent mechanical properties as showed in Table XII.

Example 30

Light curable universal dental composites (IJ2-205) containing polymerizable imidazlium resin(XJ8-88 at 1.8% wt/wt) were formulated with 82% of filler, which demonstrated effective antibacterial activities as showed in Table XIV.

Example 31

Light curable universal dental composites (IJ2-206) containing polymerizable imidazlium resin(XJ8-94 at 1.8% wt/wt) were formulated with 82% of filler, which demonstrated effective antibacterial activities as showed in Table XIV.

Example 32

Light curable universal dental composites (IJ2-207) containing polymerizable imidazlium resin(XJ8-54 at 1.8% wt/wt) were formulated with 82% of filler, which demonstrated effective antibacterial activities as showed in Table XIV.

Example 33

Light curable universal dental composites (IJ2-208) containing polymerizable imidazlium resin(XJ8-114 at 1.8% wt/wt) were formulated with 82% of filler, which demonstrated effective antibacterial activities as showed in Table XIV.

Comparative Example 1-2

Light curable universal dental composites (IJ1-138 and 139) were formulated with 82% of filler, which demonstrated excellent mechanical properties as showed in Table VIII.

Comparative Example 3

Light curable universal dental composites (IJ1-171) were formulated with 82% of filler, which demonstrated excellent mechanical properties as showed in Table XIV.

TABLE I
Compositions for Various Bisimidazole Dimethacrylate Resins
Example 1 Example 2 Example 3a Example 3b
(XJ8-9) (XJ8-13) (XJ8-6) (XJ8-48)
Resin Isosorbide/ TCDC/ AMAHP/ AMAHP/
Composition AMAHP/ AMAHP/ HEMA HEMA
TEGDMA TEGDMA
BIDMA Resin, 90 90 100 100
TEGDMA, 10 10 0 0
(wt/wt, %)
Resin Form Liquid liquid Liquid liquid
Viscosity @ 690 40 3 40
20° C. Pa · s
Solubility @ partially partially partially partially
37° C. in water soluble soluble soluble soluble
Solubility @ soluble soluble soluble soluble
37° C. in
water/ethanol
(50:50, w/w %)

TABLE II
Compositions for Polymerizable Imidazolium-based Resins
Example 4 Example 5 Example 6 Example 7
(XJ8-45) (XJ8-31) (XJ8-40) (XJ8-54)
Imidazole-based Resin XJ8-9 XJ8-9 XJ8-9 XJ8-48
Alkyl Bromide C12 C4 C4 C8
Imidazolium-based 100 80 100 100
Resin/ 0 20 0 0
TEGDMA,
(Wt/wt, %)
Resin Form Liquid Wax-like Liquid Liquid
Viscosity @ 20° C. 140 N/A 740 250
Pa · s
Solubility @ 37° C. soluble soluble soluble soluble
in EtOH
Solubility @ 37° C. soluble soluble soluble soluble
in water/ethanol (50:50,
w/w %)
Refractive Index @ 25° C. N/A 1.5130 ± 0.0007 1.5098 ± 0.0019 N/A

TABLE III
Compositions for Polymerizable Imidazolium-based Resins
Example 8 Example 9 Example 10
(XJ8-80) (XJ8-152) (XJ8-160)
Imidazole-based Resin XJ8-48 XJ8-152-1 XJ8-157
Alkyl Bromide C12 C12 C12
Imidazolium-based 100 79 100
Resin/ 21
HEMA
(Wt/wt, %)
Resin Form Liquid Liquid Liquid
Viscosity @ 20° C. 175 50 50
Pa · s

TABLE IV
Compositions for Polymerizable Imidazolium-based Resins
Example 11 Example 12 Example 14
(XJ8-88) (XJ8-94) (XJ8-114)
Imidazole-based Resin XJ8-81 XJ8-9 XJ8-48
Alkyl Bromide C8 C6 1,12-C12
Imidazolium-based 80 100 100
Resin/ 20 0 0
TEGDMA,
(Wt/wt, %)
Resin Form Liquid Liquid Liquid
Viscosity @ 20° C. 170 410 N/A
Pa · s

TABLE V
Compositions of Formulated Resins and Composites
Composition XJ8-134 XJ8-135 XJ8-136 XJ8-137
Isosorbide-based 63% 90% 25.2% 36.0%
Urethane Resin
(999993/EBR10224)
TEGDMA  7% 10%  2.8%  4.0%
(487170/110207)
Antibacterial Resin 30%  0% 12.0%   0%
(XJ8-80)
Filler Blend  0%  0% 60.0% 60.0%
(DP3-34)
CFU at Time zero 1.27 × 105 1.27 × 105
CFU at 24 hrs <5 1.38 × 105
Reduction, % >99.999 none

TABLE VI
Compositions of Formulated Resins and Composites
Composition IJ1-138 IJ1-84-2 IJ1-85-2 IJ1-118 IJ1-137
Isosorbide-based Urethane Resin 90% 32.4% 34.2% 14.6% 15.4%
(999993/EBR10224)
TEGDMA 10%  3.6%  3.8%  1.6%  1.7%
(487170/110207)
Antibacterial Resin  0%  4.0%  2.0%  1.8%  0.9%
(XJ8-80)
Filler Blend  0% 60.0% 60.0% 82.0% 82.0%
Cytotoxicity Zone of 0 N/A N/A 0 0
(ISO Agarose Lysis(mm)
Overlay) Grade 0 N/A N/A 2 1
Reactivity 0 N/A N/A mild slight
Antibacterial/S. aureus CFU at 0 hr 1.75 × 105 1.75 × 105 1.75 × 105 1.75 × 105 1.75 × 105
(ISO 22196) CFU at 24 hrs 2.10 × 106 <5   <5   <5   5
(Reduction, %) >99.999 >99.999   >99.999   >99.999

TABLE VII
Cytotoxicity of Formulated Resins Containing Antibacterial Resin
Resin Compositions IJ1-107 IJ1-109 IJ1-108 IJ1-110 IJ1-112 (XJ8-135) IJ1-111
Isosorbide-based 81% 81% 85.5% 85.5% 90% 90%
Urethane Resin
(999993/EBR10224)
TEGDMA  9%  9%  9.5%  9.5% 10% 10%
(487170/110207)
Antibacterial 10% 10%   5%   5%  0%  0%
Resin(ABR)/(XJ8-80)
Agarose Overlay N/A Moderate N/A Moderate N/A Moderate
1XMEM Elute Severe N/A Mild N/A None N/A

TABLE VIII
Cytotoxicity, Antibacterial Activity and Mechanical Properties
of Formulated Composites Containing Antibacterial Resin
Composite Compositions IJ1-115 IJ1-118 IJ1-117 IJ1-137 IJ1-139 IJ1-138
Resin Blend IJ1-115 IJ1-118 IJ1-117 IJ1-137 IJ1-112 IJ1-111
17.83% 17.85% 17.75% 17.81% 17.84% 17.93%
Filler Blend 82.17% 82.15% 82.25% 82.19% 82.16% 82.07%
(XJ8-148)
Antibacterial  1.78%  1.78%  0.89%  0.89%    0%    0%
Resin(ABR)
(XJ8-80)
Compr. St. (MPa) 322 ± 12 310 ± 12 330 ± 14 318 ± 8  339 ± 10 353 ± 9 
Compr. Mod. (MPa) 6570 ± 150 6530 ± 230 6530 ± 100 6390 ± 330 6410 ± 40  6320 ± 380
Flex. St. (MPa) 99 ± 6 97 ± 6 114 ± 8  120 ± 13 119 ± 9  106 ± 8 
Flex. Mod. (MPa 8070 ± 640 9190 ± 940 9080 ± 670 10330 ± 1330 10600 ± 1310 11320 ± 1390
Agarose Overlay N/A Mild N/A Slight N/A None
1XMEM Elute Slight N/A Slight N/A None N/A
Antibacterial Activity 1.75 × 105 1.75 × 105 1.75 × 105
Vs S. aurues N/A <5   N/A 5   N/A 2.10 × 106
24 hrs/CFU Reduction, % >99.999 99.999 None

TABLE IX
Mechanical Properties of Formulated Resins Containing Antibacterial Resin
Resin Compositions IJ1-206 IJ1-208 IJ1-207 IJ2-1 IJ1-112 (XJ8-135) IJ1-111
Isosorbide-based   81%   81%  85.5% 85.5%   90%   90%
Urethane Resin
(999993/EBR10224)
TEGDMA    9%    9%  9.5%  9.5%   10%   10%
(487170/110207)
Antibacterial   10%   10%    5%   5%    0%    0%
Resin(ABR)/(XJ8-152)
CQ 0.165% 0.165% 0.165% 0.165%  0.165% 0.165%
EDAB 0.300%    0% 0.300%   0% 0.300%    0%
LTPO    0%  0.40%    0% 0.40%    0%  0.40%
BHT 0.030% 0.030% 0.030% 0.030%  0.030% 0.030%
Viscosity @ 20° C. 35 35 40 40 40 35
Pa · s
Compr. Mod. (MPa) 2530 ± 40  2550 ± 50  2620 ± 60  2640 ± 100 2640 ± 40  2680 ± 40 
Flex. St. (MPa) 68 ± 3 92 ± 2 74 ± 3 89 ± 3 80 ± 2 94 ± 2
Flex. Mod. (MPa 1740 ± 140 2430 ± 110 1680 ± 120 2160 ± 130 1850 ± 100 2190 ± 130

TABLE X
Mechanical Properties of Formulated Composites Containing Antibacterial Resin
Composite Compositions IJ2-39 IJ2-41 IJ2-40 IJ2-42 IJ1-139 IJ1-138
Resin Blend IJ1-206 IJ1-208 IJ1-207 IJ2-1 IJ1-112 IJ1-111
18.63% 18.31% 18.27% 18.57% 17.84% 17.93%
Filler Blend 81.37% 81.69% 81.76% 81.43% 82.16% 82.07%
(XJ8-148)
Antibacterial  1.86%  1.83%  0.92%  0.93%    0%    0%
Resin(ABR)
(XJ8-152)
Compr. St. (MPa) 300 ± 6 296 ± 20 313 ± 10 324 ± 12 339 ± 10 353 ± 9 
Compr. Mod. (MPa) 6300 ± 40 6250 ± 230 6450 ± 150 6570 ± 160 6410 ± 40  6320 ± 380
Flex. St. (MPa) 108 ± 8 115 ± 6  114 ± 8  120 ± 8  119 ± 9  106 ± 8 
Flex. Mod. (MPa  9800 ± 340 9910 ± 490 8790 ± 660 10800 ± 780  10600 ± 1310 11320 ± 1390

TABLE XI
Mechanical Properties of Formulated Resins Containing Antibacterial Resin
Resin Compositions IJ2-178 IJ2-180 IJ2-179 IJ2-181 IJ2-131 IJ2-132
Isosorbide-based   81%   81%  85.5% 85.5% 90%  90% 
Urethane Resin
(999993/EBR10224)
TEGDMA    9%    9%  9.5%  9.5% 10%  10% 
(487170/110207)
Antibacterial   10%   10%    5%   5% 0% 0%
Resin(ABR)
(XJ8-160)
CQ 0.165% 0.165% 0.165% 0.165%  0.165%    0%
EDAB 0.300%    0% 0.300%   0% 0% 0%
LTPO    0%  0.40%    0% 0.40% 0% 0.40%  
BHT 0.030% 0.030% 0.030% 0.030%  0.030%    0.030%   
Viscosity @ 20° C. 35 35 35 35 40 40
Pa · s
Compr. St. (MPa) 2500 ± 30  2440 ± 00  2290 ± 40  2580 ± 40  N/A 2640 ± 30
Compr. Mod. (MPa)
Flex. St. (MPa) 63 ± 6 77 ± 5 70 ± 4 82 ± 5 N/A  97 ± 1
Flex. Mod. (MPa 1560 ± 210 1850 ± 250 1690 ± 200 1850 ± 220 N/A 2280 ± 60

TABLE XII
Properties of Formulated Composites Containing Antibacterial Resin
Composite Compositions IJ2-189 IJ2-191 IJ2-190 IJ2-192 IJ2-170 IJ2-171
Resin Blend IJ2-178 IJ2-180 IJ2-179 IJ2-181 IJ2-131 IJ2-132
17.52% 17.43% 17.57% 17.22% 17.48% 17.76%
Filler Blend 82.48% 82.57% 82.43% 82.78% 82.52% 82.24%
(XJ8-148)
Antibacterial  1.75%  1.74%  0.88%  0.86%    0%    0%
Resin(ABR)
(XJ8-160)
Compr. St. (MPa) 322 ± 11 313 ± 9  328 ± 14  339 ± 12 295 ± 13 332 ± 16
Compr. Mod. (MPa) 6350 ± 90  6520 ± 120 6140 ± 180 6610 ± 90 5690 ± 120 6350 ± 120
Flex. St. (MPa) 121 ± 3  138 ± 13 129 ± 13 136 ± 8 96 ± 8 118 ± 16
Flex. Mod. (MPa 9390 ± 610 11800 ± 690  10850 ± 1130 12320 ± 660 6720 ± 650 10840 ± 1170
Antibacterial Activity 1.65 × 105 1.65 × 105 1.65 × 105 1.65 × 105 1.65 × 105
Vs S. aurues 5   <5   <5   <5   N/A 1.85 × 104
24 hrs/CFU Reduction, % 99.973 >99.973 >99.973 >99.973 N/A

TABLE XIII
Compositions of Formulated Resins Containing Different Antibacterial
Resins
Resin Compositions IJ2-201 IJ12-202 IJ2-203 IJ2-204 IJ2-132
Isosorbide-based   81%   81%   81%   81%   90%
Urethane Resin
(999993/EBR10224)
TEGDMA    9%    9%    9%    9%   10%
(487170/110207)
Antibacterial
Resin (ABR)
XJ8-88   10%    0%
XJ8-94   10%
XJ8-54   10%
XJ8-114   10%
CQ 0.165% 0.165% 0.165% 0.165%    0%
EDAB    0%    0%    0%    0%    0%
LTPO  0.40%  0.40%  0.40%  0.40%  0.40%
BHT 0.030% 0.030% 0.030% 0.030% 0.030%
Viscosity @ 20° C. 40 40 40 40 40
Pa · s
Compr. St. (MPa) 2460 ± 30  2490 ± 70  2480 ± 50  N/A 2640 ± 30
Compr. Mod. (MPa)
Flex. St. (MPa) 80 ± 2 86 ± 3 86 ± 3 N/A  97 ± 1
Flex. Mod. (MPa 2030 ± 100 2330 ± 120 2210 ± 150 N/A 2280 ± 60

TABLE XIV
Antibacterial Activities and Properties of Formulated Composites
Containing Antibacterial Resin
Composite Compositions IJ2-205 IJ2-206 IJ2-207 IJ2-208 IJ2-171
Resin Blend IJ2-201 IJ2-202 IJ2-203 IJ2-204 IJ2-132
18.18% 18.23% 18..02%  18.57% 17.76%
Filler Blend 81.83% 81.77% 81.98% 81.43% 82.24%
(XJ8-148)
Antibacterial  1.82%  1.82%  1.80%  1.86%    0%
Resins (ABR)
Compr. St. (MPa) 335 ± 11 325 ± 14 328 ± 8 340 ± 15 332 ± 16
Compr. Mod. (MPa) 6620 ± 80  6520 ± 120  6560 ± 180 6380 ± 220 6350 ± 120
Flex. St. (MPa) 148 ± 11 146 ± 11 149 ± 7 147 ± 13 118 ± 16
Flex. Mod. (MPa 13840 ± 410  13390 ± 1390 11900 ± 880 11350 ± 1140 10840 ± 1170
Antibacterial Activity 2.05 × 105 2.05 × 105 2.05 × 105 2.05 × 105 2.05 × 105
Vs S. aurues 5 1.40 × 102 <5 1.84 × 103 2.40 × 105
24 hrs/CFU Reduction, % 99.998 99.942 >99.973 99.233 N/A

It will be appreciated that various of the above-disclosed and other features and functions, or alternatives thereof, may be desirably combined into many other different systems or applications. Also, various presently unforeseen or unanticipated alternatives, modifications, variations or improvements therein may be subsequently made by those skilled in the art, and are also intended to be encompassed by the following claims.

INVENTORS:

Jin, Xiaoming

THIS PATENT IS REFERENCED BY THESE PATENTS:
Patent Priority Assignee Title
THIS PATENT REFERENCES THESE PATENTS:
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