阅读说明：本技术 牙科组合物 (Dental composition ) 是由 H·里特 J·E·科里 吕辉 K·纽豪斯 于 2020-04-09 设计创作，主要内容包括：本文公开了一种牙科材料,其含有可聚合的水解稳定的多环酰胺单体。本公开涉及可聚合的水解稳定的多环酰胺单体的制造方法及其用于制备牙科可聚合的水解稳定的多环酰胺单体组合物的用途。本公开进一步涉及通过聚合牙科材料而获得的固化的牙科材料。(Disclosed herein is a dental material comprising a polymerizable hydrolytically stable polycyclic amide monomer. The present disclosure relates to a method of making polymerizable hydrolytically stable polycyclic amide monomers and their use to prepare dental polymerizable hydrolytically stable polycyclic amide monomer compositions. The present disclosure further relates to a cured dental material obtained by polymerizing a dental material.)

1. A dental material comprising:

(i) a polymerizable hydrolytically stable polycyclic amide monomer comprising a compound of formula (I):

wherein

R₁、R₂、R₃And R₄Are independent of each other and represent hydrogen, C_1-4Alkyl or C₅-C₁₈An aryl group;

R₅is a hydrogen atom, C_1-6Alkyl radical, C_3-10Cycloalkyl radical, C₇-C₁₂Aralkyl group; wherein each group R₅Optionally via C_1-4Alkyl radical, C_1-4One or more of alkoxy or hydroxy;

R₆is a hydrogen atom, C_1-6Alkyl radical, C_3-10Cycloalkyl radical, C₇-C₁₂Aralkyl radical, C₆-C₁₀An aryl, ester or amide group,

x is alkylene, O, S or CO;

n is an integer from 0 to 1;

m is an integer of 1 to 6; and

z is (m +1) -valent unsubstituted or substituted C₁-C₁₈Alkylene, unsubstituted or substituted C₃-C₈Cycloalkylene, unsubstituted or substituted aralkylene, unsubstituted or substituted C₅-C₁₈Arylene or unsubstituted or substituted C₃-C₁₈A heteroarylene group; it is composed ofEach unsubstituted or substituted group Z optionally includes at least one of the following: 1-6 oxygen, silicon, sulfur atoms or NR₉Wherein R is₉Represents a hydrogen atom, a linear or branched or cyclic C_1-6An alkyl group;

(ii) at least one polymerizable resin monomer having at least one (meth) acrylate group, (meth) acrylamide group, allyl group, or vinyl group;

(iii) optionally a particulate filler; and

(iv) at least one of a photoinitiator and a redox initiator.

2. The dental material of claim 1 wherein R₁、R₂、R₃、R₄And R₆Is hydrogen; x is alkylene and n is 1.

3. The dental material of claim 1 wherein R₁、R₂、R₃、R₄、R₅And R₆Is hydrogen; x is alkylene, m is 1 and n is 1.

4. The dental material of claim 1 wherein Z represents a group of formula IV, V or VI;

wherein

R^a、R^b、R^c、R^d、R^eAnd R^fIndependently are the same or different hydrogen atoms, C_1-6Linear or branched alkyl or C_4-10An aryl group;

R₈represents a linear, branched or cyclic alkyl group;

X₃and X₄Independently being the same or different oxygen, sulfur or a group NR₉Wherein R is₉Is a hydrogen atom or C_1-4An alkyl group;

L₃is a divalent hydrocarbon radical selected from linear or branched C_2-3Alkylene or C₅-C₁₈An arylene group;

L₄and L₅Independently are the same or different C_2-20An alkylene group;

a is an integer from 1 to 18;

b is an integer from 1 to 10;

c is an integer of 1 to 10;

d is an integer of from 0 to 1,

e is an integer from 1 to 10; and

f is an integer from 0 to 1.

5. The dental material according to claim 1, wherein the compound of formula (I) is obtained by reacting a mixture comprising:

(i) x equivalents of at least one component A having the formula (II):

wherein

R₁、R₂、R₃And R₄Are independent of each other and represent hydrogen, C_1-4Alkyl or C₅-C₁₈An aryl group;

R₆is a hydrogen atom, C_1-6Alkyl radical, C_3-10Cycloalkyl radical, C₇-C₁₂Aralkyl radical, C₆-C₁₀An aryl, ester or amide group,

x is alkylene, O, S or CO;

n is an integer from 0 to 1; and

t is a hydroxyl group or a halogen atom;

(ii) y equivalents of component B having at least one of a primary amine functional group and a secondary amine functional group of the compound of formula III:

wherein

R₇Is an (r +1) -valent aliphatic C_2-10Radical, cycloaliphatic C₃-C₆A radical or aralkylene having 7 to 24 carbon atoms, where each radical R₇Optionally containing oxygen or sulfur atoms, and each radical R₇Optionally via C_1-4Alkyl substitution;

R₅is a hydrogen atom, C_1-6Alkyl radical, C_3-10Cycloalkyl radical, C₇-C₁₂An aralkyl or (meth) acryloyl group; wherein each group R₅Optionally via C_1-4Alkyl radical, C_1-4One or more of alkoxy or hydroxy;

L₁and L₂Independently are the same or different straight or branched chain alkylene groups having 1 to 4 carbons;

X₁is a direct bond or via R₅A substituted nitrogen atom;

X₂is an oxygen atom;

p and q are integers from 0 to 4; and

r is an integer from 1 to 6;

wherein x and y are the molar equivalents of components (i) and (ii).

6. The dental material of claim 1 wherein the at least one polymerizable resin monomer is selected from 2,2' -bis [4- (3-methacryloyloxy-2-hydroxypropoxy) -phenyl]Propane (bis-GMA), tetraethylene glycol di (meth) acrylate (TEGDMA), Urethane Dimethacrylate (UDMA), trimethylolpropane trimethacrylate, C (meth) acrylate₁-C₂₀Alkyl esters, aromatic methacrylates, and hydroxyalkyl (meth) acrylates.

7. The dental material of claim 1, wherein the polymerizable hydrolytically stable polycyclic amide monomer is present in an amount of 1-99% w/w based on the total weight of the dental material.

8. The dental material of claim 1, wherein the at least one of a photoinitiator and a redox initiator is present in an amount of 0.01-5% w/w based on the total weight of the dental material.

9. The dental material of claim 1, wherein the at least one polymerizable resin monomer is present in an amount of 1-99% w/w based on the total weight of the dental material.

10. The dental material of claim 1 wherein the dental material is a dental composite or dental cement and includes a particulate filler.

11. The dental material of claim 10 wherein the particulate filler is present in an amount of 10-90% w/w based on the total weight of the dental composite.

12. The dental material of claim 1 further comprising a stabilizer, one or more polymerization inhibitors, one or more solvents, and combinations thereof.

13. A cured dental material obtained by polymerizing a mixture comprising:

(i) a polymerizable hydrolytically stable polycyclic amide monomer comprising a compound of formula (I):

wherein

R₁、R₂、R₃And R₄Are independent of each other and represent hydrogen, C_1-4Alkyl or C₅-C₁₈An aryl group;

R₅is a hydrogen atom, C_1-6Alkyl radical, C_3-10Cycloalkyl radical, C₇-C₁₂Aralkyl group; wherein each group R₅Optionally via C_1-4Alkyl radical, C_1-4Alkoxy radicalOr one or more of hydroxyl;

R₆is a hydrogen atom, C_1-6Alkyl radical, C_3-10Cycloalkyl radical, C₇-C₁₂Aralkyl radical, C₆-C₁₀An aryl, ester or amide group,

x is alkylene, O, S or CO;

n is an integer from 0 to 1;

m is an integer of 1 to 6; and

z is (m +1) -valent unsubstituted or substituted C₁-C₁₈Alkylene, unsubstituted or substituted C₃-C₈Cycloalkylene, unsubstituted or substituted aralkylene, unsubstituted or substituted C₅-C₁₈Arylene or unsubstituted or substituted C₃-C₁₈A heteroarylene group; wherein each unsubstituted or substituted group Z optionally comprises at least one of the following: 1-6 oxygen, silicon, sulfur atoms or NR₉Wherein R is₉Represents a hydrogen atom, a linear or branched or cyclic C_1-6An alkyl group;

(ii) at least one polymerizable resin monomer having at least one (meth) acrylate group, (meth) acrylamide group, allyl group, or vinyl group;

(iii) optionally a particulate filler; and

(iv) at least one of a photoinitiator and a redox initiator.

Technical Field

The present disclosure relates to a dental material containing a polymerizable hydrolytically stable polycyclic amide monomer. The present disclosure relates to a method of making the polymerizable hydrolytically stable polycyclic amide monomers and their use to prepare dental polymerizable hydrolytically stable polycyclic amide monomer compositions. The present disclosure further relates to a cured dental material obtained by polymerizing the dental material.

Background

During a dental composite restorative procedure, polymerization shrinkage stresses occur from the composite resin polymerization. This transfer of polymerization stress to the interface with the dental cavity leads to a number of clinical problems such as enamel cracking, impaired binding, post-operative sensitivity and secondary caries.

In this context, it is known from the prior art that cyclic monomers, such as monofunctional vinylcyclopropane derivatives, react with significantly lower polymerization stresses than linear monomers, such as (meth) acrylates. During the polymerization, the monofunctional vinylcyclopropane derivative polymerizes with a ring-opening mechanism. However, in general, monofunctional vinyl cyclopropane esters have slow polymerization kinetics.

U.S. patent No. 6136887 discloses polymerizable vinylcyclopropane derivatives, and U.S. patent No. 7365222 discloses bicyclic cyclopropane derivatives; which exhibits low volume shrinkage during polymerization and at the same time is free-radically copolymerizable with (meth) acrylates.

U.S. patent application No. 2018/0036209 discloses a free-radically polymerizable dental material containing at least one vinylcyclopropane, which shrinks only slightly upon free-radical polymerization, and which has a high free-radical polymerization reactivity, in particular upon photopolymerization.

U.S. patent application No. 2008/0058443 discloses dental materials with low polymerization shrinkage and comparable mechanical properties comprising at least one polymerizable calix [ n ] arene having a polymerizable group, wherein the polymerizable group is a group capable of polymerizing under free radical conditions such as a (meth) acrylate or a (meth) acrylamide capable of polymerizing by ring opening under free radical conditions, a cyclic group, or a group capable of polymerizing under cationic conditions such as a cycloaliphatic epoxide or an oxetane group or a polyreactive nitrone group.

U.S. patent No. 9580524 discloses vinylcyclopropane exhibiting volume expansion upon homopolymerization and capable of improving solvent solubility, a monomer composition comprising the vinylcyclopropane, a polymer of vinylcyclopropane, a polymer composition comprising the polymer, and an article obtainable by curing the monomer composition. The vinylcyclopropane may be suitably used for producing optical materials, molding materials, composite materials, casting materials, sealing materials, medical materials, dental materials, recording materials, cement, coating materials, adhesives, materials for holographic optical recording media, and the like.

Alupei et al (Polymer 45(2004), 2111-2117) have shown 3-ethoxycarbonyl-tricyclo [3.2.1.0 ]^2,4]Oct-6-ene can be converted in the presence of a free radical initiator into a stable polymer having recurring backbone units of nortricyclene (nortricyclene). Instead of the normal vinyl polymerization, the polymerization mechanism is based on intramolecular cyclopropanation, accompanied by a ring opening process, and reduces the polymerization stress.

By using monofunctional vinylcyclopropanecarboxamides, the polymerization rate is increased.

Bis (polycyclic amide) compounds are suitable for this monofunctional vinylcyclopropane structure. The amide structure is hydrolytically stable and has sufficient polymerization kinetics.

Disclosure of Invention

There is a continuing need to develop bulk-filled restoratives that simultaneously have well-maintained bonding, ease of handling, and desirable aesthetics, such as by having polymerizable hydrolytically stable polycyclic amide monomers as additives in dental compositions.

It is an object of the present disclosure to provide a polymerizable hydrolytically stable polycyclic amide monomer and its use as an additive for dental compositions in order to significantly reduce the polymerization stress compared to (meth) acrylates having a comparable double bond content. The compositions containing polymerizable hydrolytically stable polycyclic amide monomers are particularly suitable as dental materials, in particular as dental composites, dental glass ionomers, dental sealants, dental adhesives, adhesion promoters, anti-adhesive materials, cement, crown-forming materials or impression materials.

In a first aspect of the present disclosure, there is provided a dental material comprising:

(i) a polymerizable hydrolytically stable polycyclic amide monomer comprising a compound of formula (I):

wherein

R₁、R₂、R₃And R₄Are independent of each other and represent hydrogen, C_1-4Alkyl or C₅-C₁₈An aryl group;

R₅is a hydrogen atom, C_1-6Alkyl radical, C_3-10Cycloalkyl radical, C₇-C₁₂Aralkyl group; wherein each group R₅Optionally via C_1-4Alkyl radical, C_1-4One or more of alkoxy or hydroxy;

R₆is a hydrogen atom, C_1-6Alkyl radical, C_3-10Cycloalkyl radical, C₇-C₁₂Aralkyl radical, C₆-C₁₀An aryl, ester or amide group,

x is alkylene, O, S or CO;

n is an integer from 0 to 1;

m is an integer of 1 to 6; and

z is (m +1) -valent unsubstituted or substituted C₁-C₁₈Alkylene, unsubstituted or substituted C₃-C₈Cycloalkylene, unsubstituted or substituted aralkylene, unsubstituted or substituted C₅-C₁₈Arylene or unsubstituted or substituted C₃-C₁₈A heteroarylene group; wherein each unsubstituted or substituted group Z optionally comprises at least one of the following: 1-6 oxygen, silicon, sulfur atoms or NR₉Wherein R is₉Represents a hydrogen atom, a linear or branched or cyclic C_1-6An alkyl group;

(ii) at least one polymerizable resin monomer having at least one (meth) acrylate group, (meth) acrylamide group, allyl group, or vinyl group;

(iii) optionally a particulate filler; and

(iv) at least one of a photoinitiator and a redox initiator.

The present disclosure provides for the use of the polymerizable hydrolytically stable polycyclic amide monomers for the preparation of dental materials.

In a second aspect of the disclosure, a method of preparing a polymerizable hydrolytically stable polycyclic amide monomer comprising a compound of formula (I) is provided. The method comprises reacting a mixture comprising:

(i) x equivalents of at least one component A having the formula (II):

wherein

R₁、R₂、R₃And R₄Are independent of each other and represent hydrogen, C_1-4Alkyl or C₅-C₁₈An aryl group;

R₆is a hydrogen atom, C_1-6Alkyl radical, C_3-10Cycloalkyl radical, C₇-C₁₂Aralkyl radical, C₆-C₁₀An aryl, ester or amide group,

x is alkylene, O, S or CO;

n is an integer from 0 to 1; and

t is a hydroxyl group or a halogen atom.

(ii) y equivalents of component B having at least one of a primary amine functional group and a secondary amine functional group of the compound of formula III:

wherein

R₇Is an (r +1) -valent aliphatic C_2-10Radical, cycloaliphatic C₃-C₆A radical or aralkylene having 7 to 24 carbon atoms, where each radical R₇Optionally containing oxygen or sulfur atoms, and each radical R₇Optionally via C_1-4Alkyl substitution;

R₅is a hydrogen atom, C_1-6Alkyl radical, C_3-10Cycloalkyl radical, C₇-C₁₂Aralkyl or (meth) acryloyl; wherein each group R₅Optionally via C_1-4Alkyl radical, C_1-4One or more of alkoxy or hydroxy;

L₁and L₂Independently are the same or different straight or branched chain alkylene groups having 1 to 4 carbons;

X₁is a direct bond or via R₅A substituted nitrogen atom;

X₂is an oxygen atom;

p and q are integers from 0 to 4; and

r is an integer from 1 to 6;

wherein x and y are the molar equivalents of components (i) and (ii).

To form a polymerizable hydrolytically stable polycyclic amide monomer comprising a compound of formula (I)

Wherein

R₁、R₂、R₃And R₄Are independent of each other and represent hydrogen, C_1-4Alkyl or C₅-C₁₈An aryl group;

R₅is a hydrogen atom, C_1-6Alkyl radical, C_3-10Cycloalkyl radical, C₇-C₁₂Aralkyl group; wherein each group R₅Optionally via C_1-4Alkyl radical, C_1-4One or more of alkoxy or hydroxy;

R₆is a hydrogen atom, C_1-6Alkyl radical, C_3-10Cycloalkyl radical, C₇-C₁₂Aralkyl radical, C₆-C₁₀An aryl, ester or amide group,

x is alkylene, O, S or CO;

n is an integer from 0 to 1;

m is an integer of 1 to 6; and

z is (m +1) -valent unsubstituted or substituted C₁-C₁₈Alkylene, unsubstituted or substituted C₃-C₈Cycloalkylene, unsubstituted or substituted aralkylene, unsubstituted or substituted C₅-C₁₈Arylene or unsubstituted or substituted C₃-C₁₈A heteroarylene group; wherein each unsubstituted or substituted group Z optionally comprises at least one of the following: 1-6 oxygen, silicon, sulfur atoms or NR₉Wherein R is₉Represents a hydrogen atom, a linear or branched or cyclic C_1-6An alkyl group.

Drawings

FIG. 1 depicts in CDCl₃Of bis (norbornene cyclopropaneamido) Compound 1¹H NMR spectrum.

FIG. 2 depicts a comparison of polymerization shrinkage stress data for bis (norbornene cyclopropaneamido) compound 1(HLU18-150-N5T5) for CMX-resins.

Curve 1: t00182 Nov 62018211 pm tensiometer HLU18-150-N5T5_ L103118 _ QHL-2min _ S1.tsd

0 is the number of lines in the bundle file,

curve 2: t00183 Nov 62018425 pm tensiometer HLU18-150-N5T5_ L103118 _ QHL-2min _ S2.tsd

0 is the number of lines in the bundle file,

curve 3: t00008 Oct 120181024 am tensiometer CMX-resin _ K900833_ L1802000718 post-treatment (PostRepair) _ s1.tsd,

curve 4: t00009 Oct 120181131 am tensiometer CMX-resin _ K900833_ L1802000718 post-treatment (PostRepair) _ s2.tsd,

curve 5: t00011 Oct 12018250 pm tensiometer CMX-resin _ K900833_ L1802000718-post-treatment (PostRepiair) _ S3. tsd.

Detailed Description

The above aspects and other aspects, features and advantages of the present disclosure are described below in connection with various embodiments and with reference to the following drawings. Some terms used in this disclosure are defined as follows:

unless otherwise specified, the term "alkyl" refers to a mono-radical branched or unbranched saturated hydrocarbon chain having 1 to 18 carbon atoms. This term can be exemplified by groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, n-decyl, dodecyl, tetradecyl, and the like. The alkyl group may be further substituted with one or more substituents selected from the group consisting of alkenyl group, alkoxy group and hydroxyl group.

Unless otherwise specified, the term "alkylene" refers to a linear saturated divalent hydrocarbon group of 1 to 18 carbon atoms or a branched saturated divalent hydrocarbon group of 3 to 18 carbon atoms, such as methylene, ethylene, 2-dimethylethylene, propylene, 2-methylpropylene, butylene, and the like, preferably methylene, ethylene, or propylene.

The term "alkoxy" is a functional group containing an alkyl group bonded to an oxygen atom. C_1-4The alkoxy group may include linear or branched alkoxy groups having 1 to 4 carbon atoms, such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy and tert-butoxy.

The term "arylene" is a divalent moiety of "aryl". The term "aryl" refers to C₅-C₁₈A ring system of a meta-aromatic, heterocyclic, fused aromatic, fused heterocyclic, bi-aromatic or bi-heterocyclic ring. As used herein, the broadly defined "aryl" includes 5-, 6-, 7-, 8-, 9-and 10-membered monocyclic aromatic groups, which may include 0-4 heteroatoms, e.g., benzene, pyridinePyrrole, furan, thiophene, imidazole,Oxazole, thiazole, triazole, pyrazole, pyridine, pyrazine, pyridazine, pyrimidine, and the like. Those "aryl" groups having heteroatoms in the ring structure may also be referred to as "heteroaryl" or "heterocycle" or "heteroarene". The aromatic ring may be substituted at one or more ring positions with one or more substituents including, but not limited to: halogen, azide, alkyl, aralkyl, alkenyl, alkynyl, cycloalkyl, hydroxy, alkoxy, amino (or quaternized amino), nitro, mercapto, imino, amido, phosphonate, phosphinate, carbonyl, carboxyl, silyl, ether, alkylthio, sulfonyl, sulfonamido, ketone, aldehyde, ester, heterocyclyl, aromatic or heteroaromatic moieties, - - -CF₃-CN and combinations thereof.

The term "aryl" also includes polycyclic ring systems having two or more cyclic rings in which two or more carbons are common to two adjoining rings (i.e., "fused rings"), wherein at least one of the rings is aromatic, e.g., another cyclic ring can be cycloalkyl, cycloalkenyl, cycloalkynyl, aryl, and/or heterocyclyl. Examples of heterocyclic rings include, but are not limited to, benzimidazolyl, benzofuranyl, benzothiofuranyl, benzothiophenylAzolyl radical, benzoOxazolinyl, benzothiazolyl, benzotriazolyl, benzotetrazolyl, benzisoxazolylAzolyl, benzisothiazolyl, benzimidazolinyl, carbazolyl, 4aH carbazolyl, carbolinyl, chromanyl, chromenyl, cinnolinyl, decahydroquinolinyl, 2H,6H-1,5, 2-dithiazinyl, dihydrofluorenyl [2,3b ] group]Tetrahydrofuran, furyl, furazanyl, imidazolidinyl, imidazolinyl, imidazolyl1H-indazolyl, indolylenyl, indolinyl, indolizinyl, indolyl, 3H-indolyl, isatinoyl, isobenzofuranyl, isobenzopyranyl, isoindolyl, isoquinolyl, isothiazolyl, isoindolinylOxazolyl, methylenedioxyphenyl, morpholinyl, naphthyridinyl, octahydroisoquinolinyl,oxadiazolyl, 1,2,3-Oxadiazolyl, 1,2,4-Oxadiazolyl, 1,2,5-Oxadiazolyl, 1,3,4-(ii) a diazolyl group,an oxazolidinyl group, which is a group of,oxazolyl, oxindolyl, pyrimidinyl, phenanthridinyl, phenanthrolinyl, phenazinyl, phenothiazinyl, phenoxythienyl, phenazinyl, phthalazinyl, piperazinyl, piperidinyl, piperidonyl, 4-piperidonyl, piperonyl, pteridinyl, purinyl, pyranyl, pyrazinyl, pyrazolidinyl, pyrazolinyl, pyrazolyl, pyridazinyl, pyridoAzoles, pyridoimidazoles, pyridothiazoles, pyridyl (pyridinyl), pyridyl (pyridil), pyrimidyl, pyrrolidinyl, piridolPyrrolinyl, 2H-pyrrolyl, quinazolinyl, quinolinyl, 4H-quinolizinyl, quinoxalinyl, quinuclidinyl, tetrahydrofuranyl, tetrahydroisoquinolinyl, tetrahydroquinolinyl, tetrazolyl, 6H-1,2, 5-thiadiazinyl, 1,2, 3-thiadiazolyl, 1,2, 4-thiadiazolyl, 1,2, 5-thiadiazolyl, 1,3, 4-thiadiazolyl, thianthrenyl, thiazolyl, thienyl, thienothiazolyl, thienoAzolyl, thienoimidazolyl, thiophenyl and xanthenyl.

The term "heteroarylene" is a divalent moiety of "heteroaryl".

The term "aralkylene" is a divalent moiety of "aralkyl". The term "aralkyl" refers to a group of the formula-R '-aryl, wherein R' is an alkylene group as defined above, e.g., methylene, ethylene, and the like. The aryl moiety is optionally substituted as described above for aryl.

The term "cycloalkylene" is a divalent moiety of "cycloalkyl". The term "cycloalkyl" refers to a monocyclic or polycyclic cycloalkyl group. Examples of monocyclic cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. Examples of polycyclic cycloalkyl radicals include, for example, adamantyl, norbornyl, decahydronaphthyl, 7-dimethyl-bicyclo [2.2.1]Heptyl, tricyclo [5.2.1.0^2,6]Decyl groups, and the like. Unless the specification expressly states otherwise, the term "cycloalkyl" denotes a cycloalkyl group including a single ring or multiple rings, which is optionally substituted with one or more substituents selected from alkyl, halogen, oxy or alkylene chain.

The term "cycloalkylalkylene" refers to the group-R '-cycloalkyl- ", wherein R' is an alkylene group as defined above, e.g., methylene, ethylene, and the like. As used herein, C₁-C₈Cycloalkylalkylene is understood to be a radical of formula I through C_1-C₈Alkylene-linked cycloalkyl groups.

The term "divalent hydrocarbon group" refers to a divalent hydrocarbon group having 2 to 18 carbon atoms, and includes alkylene groups such as ethylene, methylmethylene, propylene, butylene, pentylene, hexylene, and octadecylene; alkylene groups such as vinylene group, allylene group, and butadienylene group; cycloalkylene groups such as cyclobutyl, cyclopentylene, and cyclohexylene groups; cycloalkylene groups such as cyclopentenylene and cyclohexenylene; arylene groups such as phenylene and xylylene (xenylene); aralkylene such as benzylidene; and alkylarylene radicals such as tolylene radicals.

With respect to free radical polymerization, the term "polymerizable moiety" often refers to any double bond capable of addition polymerization, such as a carbon-carbon double bond.

The term "(meth) acrylate" means in the context of the present disclosure acrylate as well as the corresponding methacrylate.

The term "(meth) acryl" means in the context of the present disclosure acryl as well as corresponding methacryl.

The present disclosure relates to a dental material containing a polymerizable hydrolytically stable polycyclic amide monomer. The present disclosure relates to methods of making the polymerizable hydrolytically stable polycyclic amide monomers. The present disclosure relates to the use of the polymerizable hydrolytically stable polycyclic amide monomers for the preparation of dental polymerizable hydrolytically stable polycyclic amide monomer compositions. The compositions containing polymerizable hydrolytically stable polycyclic amide monomers are particularly suitable as dental materials, in particular dental composites, dental glass ionomers, dental sealants, dental adhesives, adhesion promoters, anti-adhesive materials, cement, crown-forming materials or impression materials.

In one aspect of the present disclosure, there is provided a dental material comprising:

(i) a polymerizable hydrolytically stable polycyclic amide monomer comprising a compound of formula (I):

wherein

R₁、R₂、R₃And R₄Are independent of each other and represent hydrogen, C_1-4Alkyl or C₅-C₁₈An aryl group;

R₅is a hydrogen atom, C_1-6Alkyl radical, C_3-10Cycloalkyl radical, C₇-C₁₂Aralkyl group; wherein each group R₅Optionally via C_1-4Alkyl radical, C_1-4One or more of alkoxy or hydroxy;

R₆is a hydrogen atom, C_1-6Alkyl radical, C_3-10Cycloalkyl radical, C₇-C₁₂Aralkyl radical, C₆-C₁₀An aryl, ester or amide group,

x is alkylene, O, S or CO;

n is an integer from 0 to 1;

m is an integer of 1 to 6; and

z is (m +1) -valent unsubstituted or substituted C₁-C₁₈Alkylene, unsubstituted or substituted C₃-C₈Cycloalkylene, unsubstituted or substituted aralkylene, unsubstituted or substituted C₅-C₁₈Arylene or unsubstituted or substituted C₃-C₁₈A heteroarylene group; wherein each unsubstituted or substituted group Z optionally comprises at least one of the following: 1-6 oxygen, silicon, sulfur atoms or NR₉Wherein R is₉Represents a hydrogen atom, a linear or branched or cyclic C_1-6An alkyl group;

(ii) at least one polymerizable resin monomer having at least one (meth) acrylate group, (meth) acrylamide group, allyl group, or vinyl group;

(iii) optionally a particulate filler; and

(iv) at least one of a photoinitiator and a redox initiator.

I. Polymerizable hydrolytically stable polycyclic amide monomers

The polymerizable hydrolytically stable polycyclic amide monomers are compounds of formula (I)

Wherein

R₁、R₂、R₃And R₄Are independent of each other and represent hydrogen, C_1-4Alkyl or C₅-C₁₈An aryl group;

R₅is a hydrogen atom, C_1-6Alkyl radical, C_3-10Cycloalkyl radical, C₇-C₁₂Aralkyl group; wherein each group R₅Optionally via C_1-4Alkyl radical, C_1-4One or more of alkoxy or hydroxy;

R₆is a hydrogen atom, C_1-6Alkyl radical, C_3-10Cycloalkyl radical, C₇-C₁₂Aralkyl radical, C₆-C₁₀An aryl, ester or amide group,

x is alkylene, O, S or CO;

n is an integer from 0 to 1;

m is an integer of 1 to 6; and

z is (m +1) -valent unsubstituted or substituted C₁-C₁₈Alkylene, unsubstituted or substituted C₃-C₈Cycloalkylene, unsubstituted or substituted aralkylene, unsubstituted or substituted C₅-C₁₈Arylene or unsubstituted or substituted C₃-C₁₈A heteroarylene group; wherein each unsubstituted or substituted group Z optionally comprises at least one of the following: 1-6 oxygen, silicon, sulfur atoms or NR₉Wherein R is₉Represents a hydrogen atom, a linear or branched or cyclic C_1-6An alkyl group.

The term "polymerizable hydrolytically stable polycyclic amide monomer" means a monomer that contains more than one cyclic moiety containing a cyclopropyl group and an amide group. The polycyclic amide monomer is hydrolytically stable. Specifically, the polymerizable polycyclic amide monomer does not contain a group such as an ester in the main chain, which is hydrolyzed in an aqueous medium under acidic conditions at a temperature of about 23 to 27 ℃ within 1 month. Acidic conditions refer to a pH of 1-5, e.g. 2-4 or a pH of 3.

In certain embodiments, the polymerizable polycyclic amide monomer is a cyclopropyl-containing polycyclic olefin of a compound having formula I, wherein R₁，R₂，R₃，R₄And R₆Is hydrogen; x is alkylene and n is 1.

In one embodiment, the polymerizable polycyclic amide monomer is a norbornene-type moiety containing a cyclopropyl group, a compound having formula I, wherein R is₁，R₂，R₃，R₄And R₆Is hydrogen; x is methylene and n is 1.

In one embodiment, the polymerizable polycyclic amide is a substituted tricyclic [3.2.1.0 ]^2,4]Monomers of oct-6-ene.

In one embodiment, the polymerizable polycyclic amide monomer is a compound of formula I, wherein m is 1 and R is₅Is hydrogen.

In certain embodiments of the compounds of formula I, Z is unsubstituted or substituted C₁-C₁₈Alkylene groups, which may optionally include at least one of the following: 1-6 oxygen, silicon, sulfur atoms or NR₉Wherein R is₉Represents a hydrogen atom, a linear or branched or cyclic C_1-6An alkyl group.

In one embodiment, Z represents a group according to formula IV:

wherein

R^aAnd R^bIndependently are identical or different hydrogen atoms, C_1-6Linear or branched alkyl or C_4-10An aryl group; and

a is an integer from 1 to 18.

In one embodiment, Z is selected from:

in certain embodiments, Z represents a group according to formula V:

wherein

R^c、R^d、R^eAnd R^fIndependently are identical or different hydrogen atoms, C_1-6Linear or branched alkyl or C_4-10An aryl group;

X₃and X₄Independently being the same or different oxygen atoms, sulfur atoms and groups NR₉Wherein R is₉Is a hydrogen atom or C_1-4An alkyl group;

L₃is a divalent hydrocarbon radical selected from linear or branched C_2-3Alkylene or C₅-C₁₈An arylene group.

b is an integer from 1 to 10;

c is an integer of 1 to 10; and

d is an integer from 0 to 1.

In certain embodiments, Z represents a group according to formula VI:

wherein

R₈Represents a linear, branched or cyclic alkyl group.

L₄And L₅Independently are the same or different C_2-20An alkylene group;

e is an integer from 1 to 10; and

f is an integer from 0 to 1.

The compound of formula I may be a compound selected from the group consisting of:

in one embodiment of the dental material disclosed herein, the polymerizable hydrolytically stable polycyclic amide monomer may be present in an amount of 1 to 99 percent based on the total weight of the dental material. Alternatively 2-95%; alternatively 5-90% or any value, range, or subrange therebetween, based on the total weight of the dental material.

In one aspect of the disclosure, a method of preparing a polymerizable hydrolytically stable polycyclic amide monomer having a compound of formula I is described.

In one embodiment, the compound of formula (I) is obtained by reacting a mixture comprising:

(i) x equivalents of at least one component A having the formula (II):

wherein

R₁、R₂、R₃And R₄Are independent of each other and represent hydrogen, C_1-4Alkyl or C₅-C₁₈An aryl group;

R₆is a hydrogen atom, C_1-6Alkyl radical, C_3-10Cycloalkyl radical, C₇-C₁₂Aralkyl radical, C₆-C₁₀An aryl, ester or amide group,

x is alkylene, O, S or CO;

n is an integer from 0 to 1; and

t is a hydroxyl group or a halogen atom;

(ii) y equivalents of component B having at least one of a primary amine functional group and a secondary amine functional group of the compound of formula III:

wherein

R₇Is an (r +1) -valent aliphatic C_2-10Radical, cycloaliphatic C₃-C₆A radical or aralkylene having 7 to 24 carbon atoms, where each radical R₇Optionally containing oxygen or sulfur atoms, and each radical R₇Optionally via C_1-4Alkyl substitution;

R₅is a hydrogen atom, C_1-6Alkyl radical, C_3-10Cycloalkyl radical, C₇-C₁₂Aralkyl or (meth) acryloyl; wherein each group R₅Optionally via C_1-4Alkyl radical, C_1-4One or more of alkoxy or hydroxy;

L₁and L₂Independently are the same or different straight or branched chain alkylene groups having 1 to 4 carbons;

X₁is a direct bond or via R₅A substituted nitrogen atom;

X₂is an oxygen atom;

p and q are integers from 0 to 4; and

r is an integer from 1 to 6;

wherein x and y are the molar equivalents of components (i) and (ii).

In one embodiment, component a of the compound having formula (II) may be a norbornene cyclopropanecarboxylic acid or a norbornene cyclopropanecarbonyl halide.

The halide may be selected from bromine or chlorine.

In one embodiment, component a of the compound having formula (II) may be norbornene cyclopropanecarbonyl chloride.

In one embodiment of the dental material disclosed herein, component B having at least one of a primary amine functional group and a secondary amine functional group is a compound of formula II:

wherein

R₇Is an (r +1) -valent aliphatic C_2-10Radical, cycloaliphatic C₃-C₆A radical or aralkylene having 7 to 24 carbon atoms, where each radical R₇Optionally containing oxygen or sulfur atoms, and each radical R₇Optionally via C_1-4Alkyl substitution;

R₅is a hydrogen atom, C_1-6Alkyl radical, C_3-10Cycloalkyl radical, C₇-C₁₂Aralkyl or (meth) acryloyl; wherein each group R₅Optionally via C_1-4Alkyl radical, C_1-4One or more of alkoxy or hydroxy;

L₁and L₂Independently are the same or different straight or branched chain alkylene groups having 1 to 4 carbons;

X₁is a direct bond or via R₅A substituted nitrogen atom;

X₂is an oxygen atom;

p and q are integers from 0 to 4; and

r is an integer from 1 to 6;

the expression "at least one of a primary amine function and a secondary amine function" should be understood to mean "primary amine function only", "secondary amine function only" or "both primary amine function and secondary amine function".

In one embodiment of formula III, R₇Is an (r +1) -valent aliphatic C_2-10Radical, alicyclic C₃-C₆A group or an aralkylene group having 7 to 24 carbon atoms. R₇May be divalent (r ═ 1), trivalent (r ═ 2), tetravalent (r ═ 3), pentavalent (r ═ 5), hexavalent (r ═ 5) or heptavalent (r ═ 6).

In certain embodiments of the dental materials disclosed herein, the compound of formula III can be a diamine of formula IIIa:

wherein R is₅As defined above; and

w is a divalent aliphatic radical C_2-10Radical, alicyclic C₃-C₆A group or an aralkylene group having 7 to 24 carbon atoms, wherein each group optionally contains an oxygen or sulfur atom, and which is optionally substituted by C_1-4Alkyl substitution.

In certain embodiments of the dental materials disclosed herein, the compound of formula III can be a compound of formula IIIb:

wherein R is₅And X₁As defined above.

In certain embodiments of the dental materials disclosed herein, the compound of formula III may be a monoamine of formula IIIc:

H₂N-R₅

formula IIIc

Wherein R is₅Is a monovalent aliphatic C_1-10Radical, alicyclic C₃-C₆A group or an aralkylene group having 7 to 24 carbon atoms.

In certain embodiments of the dental materials disclosed herein, the compound of formula III can be an amine of formula IIId:

wherein R is₅And R₇As defined above.

The compound of formula III may be selected from ethylenediamine, propylenediamine, butylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, tetramethylenediamine, octamethylenediamine, trimethylhexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, 4,7, 10-trioxa-1, 13-tridecanediamine, 2,2'- (ethyleneoxy) diethylamine, 1, 3-bis- (aminomethyl) cyclohexane, 1, 3-bis- (4-aminophenoxy) benzene, 4,4' -methylenebis-cyclohexylamine, 5-amino-1, 3, 3-trimethylcyclohexylmethylamine, Jeffamine T403, Jeffamine T3000, Jeffamine T5000, aminoalcohol, propanolamine, N, N '-dimethylethylenediamine, N, N' -dibenzylethylenediamine, n, N '-dibenzyl 5-oxanonanediamine-1, 9, N, N' -dibenzyl 3, 6-dioxaoctanediamine-1, 8, N, N '-diethylpropanediamine, N, N' -dimethylpropanediamine, N-butylamine, hexylamine, cyclohexylamine or benzylamine.

In certain embodiments of the method of preparing a polymerizable hydrolytically stable polycyclic amide monomer having a compound of formula I, x equivalents of at least one component a having a compound of formula (II) and y equivalents of component B (at least one of a primary amine functional group and a secondary amine functional group of a compound of formula III) can be dissolved in a solvent and stirred at reaction temperature.

In certain embodiments of the method of preparing a polymerizable hydrolytically stable polycyclic amide monomer having a compound of formula I, the solvent may be selected from the group consisting of dichloromethane, tetrahydrofuran, chloroform, dimethyl sulfoxide, and dimethylformamide. The reaction temperature may, for example, be from 0 ℃ to 60 ℃, e.g. from 30 ℃ to 55 ℃.

In the preparation of polymerizable hydrolytically stable polycyclic amide monomers having the compounds of formula I, a base may be used. The base is selected from triethylamine, 1, 4-diazabicyclo [2.2.2] octane, diisopropylethylamine and dimethylaminopyridine.

Filler material

The dental material of the present disclosure may include a particulate filler. "particulate fillers" are powdered metal oxides or hydroxides, mineral silicates or ionically leachable glasses or ceramics. Examples of particulate fillers may be selected from fillers commonly used in dental restorative compositions.

The particulate filler may have a monomodal or multimodal (e.g. bimodal) particle size distribution. The particulate filler may be an inorganic material. It may also be a crosslinked organic material which is insoluble in the polymerizable resin and optionally filled with an inorganic filler. The particulate filler may be radiopaque, radiolucent, or non-radiolucent.

Examples of suitable particulate inorganic fillers are naturally occurring or synthetic materials such as quartz, nitrides such as silicon nitride, glasses from, for example, Ce, Sb, Sn, Zr, Sr, Ba and Al, colloidal silica, feldspar, borosilicate glass, kaolin, talc, titanium dioxide and zinc glass, and submicron silica particles such as fumed silica.

Examples of suitable filler particles include, but are not limited to, strontium silicates, strontium borosilicates, barium silicates, barium borosilicates, barium fluoroaluminoborosilicate glass, barium aluminoborosilicate, calcium silicates, calcium alumino sodium fluorophosphosilicate, lanthanum silicates, aluminosilicates, and combinations comprising at least one of the foregoing fillers. The filler particles may further comprise fumed silica. Examples of fumed silicas include OX-50 from DeGussa AG (average particle size 40nm), Aerosil R-972 from DeGussa AG (average particle size 16nm), Aerosil 9200 from DeGussa AG (average particle size 20nm), other Aerosil fumed silicas can include Aerosil 90, Aerosil 150, Aerosil 200, Aerosil 300, Aerosil 380, Aerosil R711, Aerosil R7200 and Aerosil R8200, and Cab-O-Sil M5, Cab-O-Sil TS-720, Cab-O-Sil TS-610 from Cabot Corp. Examples of suitable particulate organic filler particles include powdered polycarbonate or polyepoxide, filled or unfilled.

The filler particles used in the materials disclosed herein may be surface treated prior to their blending with the organic compound. Surface treatments using silane coupling agents or other compounds are beneficial because they promote the bonding of the particulate filler and matrix and enable the filler particles to be more uniformly dispersed in the organic resin matrix, as well as improve physical and mechanical properties. Suitable silane coupling agents include 3-methacryloxypropyltrimethoxysilane, methacryloxyoctyltrimethoxysilane, styrylethyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, gamma-mercaptopropyltriethoxysilane, gamma-aminopropyltrimethoxysilane, and mixtures thereof.

The particulate filler typically has an average particle size of from 0.005 to 100 μm, for example from 0.01 to 40 μm, as measured, for example, by electron microscopy or by using conventional laser diffraction particle sizing as embodied by a MALVERN Mastersizer S or MALVERN Mastersizer 2000 apparatus.

The dental compositions of the present disclosure may comprise nano-sized particles. As the nano-sized particles in the present disclosure, any known nano-sized particles used in dental compositions may be used without any limitation. Preferred examples of the nano-sized particles include particles of inorganic oxides such as silica, alumina, titania, zirconia, particles of composite oxides of any of these oxides, and particles of calcium phosphate, hydroxyapatite, yttrium fluoride, and ytterbium fluoride. Preferably, the nano-sized particles are particles of silica, alumina, titania, which are prepared by flame pyrolysis.

The average particle size of the nano-sized particles is 1 to 50nm, for example 3 to 40 nm. The average particle size of the nano-sized particles may be measured by: an electron micrograph of these nano-sized particles was taken and the average of the diameters of 100 randomly selected nano-sized particles was calculated. It is desirable that the inorganic nano-sized particles are previously subjected to a surface treatment with a surface treatment agent to improve the affinity between the inorganic filler and the polymerizable composition of the present disclosure, and to increase the chemical bonding between the inorganic filler and the polymerizable composition to improve the mechanical strength of the cured product.

In one embodiment, the particulate filler may be organically modified silica nanoparticles diluted with ethoxylated bisphenol a dimethacrylate (Ormosil II).

The dental material of the present disclosure may comprise a particulate filler in an amount of 10-90% w/w, based on the total weight of the dental material. Alternatively 30-85% or any value, range, or subrange therebetween, based on the total weight of the dental material.

Photoinitiator

The dental material of the present disclosure includes at least one of a photoinitiator and a redox initiator.

The wording "at least one of a photoinitiator and a redox initiator" should be understood to mean "photoinitiator only", "redox initiator only" or "both photoinitiator and redox initiator".

Suitable photoinitiators include form I and form II. They can be used alone or as a mixture of different photoinitiators plus additional co-initiators. Some preferred photosensitizers may include monoketones and diketones (e.g., alpha diketones) that absorb some light in the range of about 300nm to about 800nm (preferably about 400nm to about 500nm), such as camphorquinone, benzil, furobinyl, 3,3,6, 6-tetramethylcyclohexanedione, phenanthrenequinone, and other cyclic alpha diketones. Among them camphorquinone is typically preferred. Preferred electron donor compounds include substituted amines, such as ethyl 4- (N, N-dimethylamino) benzoate, as promoters.

According to a further preferred embodiment, the photoinitiator further comprises iodine of the formulaA compound:

R₁₀-I⁺-R₁₁A^-

wherein

R₁₀And R₁₁Are, independently of one another, an organic moiety, and

A^-is an anion;

for example diaryl iodidesThe salt may be selected from (4-methylphenyl) [4- (2-methylpropyl) phenyl ]]IodineHexafluoroantimonate, (4-methylphenyl) [4- (2-methylpropyl) phenyl]IodineTetrafluoroborate, diphenyl iodide(DPI) Tetrafluoroborate, bis (4-methylphenyl) iodide(Me2-DPI) Tetrafluoroborate, phenyl-4-methylphenyl iodideTetrafluoroborate, di- (4-tert-butylphenyl) -iodideHexafluorophosphate, bis (4-tert-butylphenyl) iodideP-toluenesulfonate, bis (4-heptylphenyl) iodideTetrafluoroborate, bis (3-nitrophenyl) iodideHexafluorophosphate, bis (4-chlorophenyl) iodideHexafluorophosphate, bis (naphthyl) iodideTetrafluoroborate, bis (4-trifluoromethylphenyl) iodideTetrafluoroborate, DPI hexafluorophosphate, Me2-DPI hexafluorophosphate; DPI hexafluoroarsenate, bis (4-phenoxyphenyl) iodideTetrafluoroborate, phenyl-2-thienyliodineHexafluorophosphate, 3, 5-dimethylpyrazolyl-4-phenyliodideHexafluorophosphate, DPI hexafluoroantimonate, 2,2' -DPI tetrafluoroborate, bis (2, 4-dichlorophenyl) iodideHexafluorophosphate, bis (4-bromophenyl) iodideHexafluorophosphate salt, di (a)4-methoxyphenyl) iodineHexafluorophosphate, bis (3-carboxyphenyl) iodideHexafluorophosphate, bis (3-methoxycarbonylphenyl) iodideHexafluorophosphate, bis (3-methoxysulfonylphenyl) iodideHexafluorophosphate, bis (4-acetamidophenyl) iodideHexafluorophosphate, bis (2-benzothienyl) iodideHexafluorophosphate and DPI hexafluorophosphate.

In particular, iodineThe compound comprises diphenyl iodide(DPI) hexafluorophosphate, bis (4-methylphenyl) iodide(Me2-DPI) hexafluorophosphate, bis- (4-tert-butylphenyl) -iodineHexafluorophosphate, diaryliodideHexafluoroantimonate, (4-methylphenyl) [4- (2-methylpropyl) phenyl]IodineHexafluoroantimonate, (4-methylphenyl) [4- (2-methylpropyl) phenyl]IodineHexafluorophosphate salts of (A), (B), (C) and C)250, k commercially available from BASF SE), (4-methylphenyl) [4- (2-methylpropyl) phenyl ]]IodineTetrafluoroborate, 4-octyloxyphenylphenyl iodideHexafluoroantimonate, 4- (2-hydroxytetradecyloxyphenyl) phenyliodideHexafluoroantimonate, and 4-isopropyl-4' -methyldiphenyliodideA borate salt.

According to a specific embodiment, iodineThe compound being bis (4-methylphenyl) iodide(Me2-DPI) hexafluorophosphate.

Other suitable photoinitiators for polymerizing free-radically photopolymerizable compositions may include phosphine oxides, which typically have a functional wavelength of about 380nm to about 1200 nm. Preferred phosphine oxide free radical initiators having a functional wavelength in the range of about 380nm to about 450nm are acyl and bisacylphosphine oxides.

Commercially available phosphine oxide photoinitiators capable of free radical initiation when irradiated in the wavelength range of greater than about 380nm to about 450nm may include 1-hydroxycyclohexyl phenyl ketone (IRGACURE 184), 2, 2-dimethoxy-1, 2-diphenylethan-1-one (IRGACURE 651), bis (2,4, 6-trimethylbenzoyl) phenyl phosphine oxide (IRGACURE 819), 1- [4- (2-hydroxyethoxy) phenyl ] -2-hydroxy-2-methyl-1-propan-1-one (IRGACURE 2959), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone (IRGACURE 369), 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropan-1-one (IRGACURE 907), 2-hydroxy-2-methyl-1-phenylpropan-1-one (DAROCUR 1173), bis (2,4, 6-trimethylbenzoyl) phenylphosphine oxide (IRGACURE 819), bis (2, 6-dimethoxybenzoyl) - (2,4, 4-trimethylpentyl) phosphine oxide (CGI 403), a 25:75 weight ratio mixture of bis (2, 6-dimethoxybenzoyl) -2,4, 4-trimethylpentylphosphine oxide and 2-hydroxy-2-methyl-1-phenylpropan-1-one (IRGACURE 1700), a 1:1 weight ratio mixture of bis (2,4, 6-trimethylbenzoyl) phenylphosphine oxide and 2-hydroxy-2-methyl-1-phenylpropan-1-one (DAROCUR 4265), and ethyl 2,4, 6-trimethylbenzylphenylphosphinate (LUCIRIN LR 8893X).

Suitable redox initiators comprise a reducing agent and an oxidizing agent, which typically react with each other or otherwise cooperate with each other to generate free radicals capable of initiating polymerization of the polymerizable double bond in a dark reaction independent of the presence of light. The reducing agent and oxidizing agent are selected such that the polymerization initiator system is sufficiently storage stable and free of undesirable discoloration to allow storage and use under typical dental conditions. In addition, the reducing agent and oxidizing agent are selected such that the polymerization initiator system is sufficiently miscible with the resin system to allow the polymerization initiator system to dissolve in the composition.

Useful reducing agents include ascorbic acid, ascorbic acid derivatives, and metal-complexed ascorbic acid compounds, as described in U.S. patent No. 5501727; amines, i.e. tertiary amines such as 4-tert-butyldimethylaniline. Other secondary reducing agents may include cobalt (II) chloride, ferrous chloride, ferric sulfate, hydrazine, hydroxylamine, salts of dithionite or sulfite anions, and mixtures thereof.

Suitable oxidizing agents include persulfuric acid and its salts, such as ammonium, sodium, potassium, cesium, and alkylammonium salts. Additional oxidizing agents include peroxides such as benzoyl peroxide, hydroperoxides such as cumene hydroperoxide, t-butyl peroxy (2-ethylhexyl) carbonate, t-butyl hydroperoxide, di (t-butyl) peroxide, t-butyl peroxy-3, 5, 5-trimethyl-hexanoate, amyl hydroperoxide, and potassium peroxydisulfate, as well as salts of transition metals such as cobalt (III) chloride and iron chloride, cerium (IV) sulfate, perboric acid and its salts, permanganic acid and its salts, perphosphoric acid and its salts, and mixtures thereof. One or more different oxidizing agents or one or more different reducing agents may be used in the polymerization initiator system.

Small amounts of transition metal compounds may also be added to accelerate the redox cure rate. The transition metal compound may be a salt of V, Fe, Cu, Ti, Mn, Ni and Zn. Most preferably, a transition metal salt of Fe or Cu. Tetravalent and/or pentavalent vanadium compounds are preferred, Including Vanadium (IV) oxide, vanadyl (IV) acetylacetonate, vanadyl (IV) oxalate, vanadyl (IV) sulfate, vanadyl (IV) oxybis (1-phenyl-1, 3-succinate), vanadyl (IV) bis (malate), vanadium (V) oxide, sodium (V) metavanadate and ammonium (V) metavanadate. Examples of the copper compound include copper acetylacetonate, copper (II) acetate, copper oleate, copper (II) chloride and copper (II) bromide.

The redox initiator system may optionally include a polymerization accelerator.

The polymerization accelerator is selected from the group consisting of aromatic sulfonate, sulfite, bisulfite and thiourea compounds.

Examples of aromatic sulfonates that can be used as polymerization promoters include, but are not limited to, p-toluene sulfonates such as sodium p-toluenesulfonate, potassium p-toluenesulfonate, calcium p-toluenesulfonate; benzene sulfinates such as sodium benzene sulfinate, potassium benzene sulfinate, calcium benzene sulfinate, 2,4, 6-triethylbenzene sulfinate, sodium 2,4, 6-triethylbenzene sulfinate, potassium 2,4, 6-triethylbenzene sulfinate, calcium 2,4, 6-triethylbenzene sulfinate, 2,4, 6-triisopropylbenzene sulfinate, sodium 2,4, 6-triisopropylbenzene sulfinate, potassium 2,4, 6-triisopropylbenzene sulfinate and calcium 2,4, 6-triisopropylbenzene sulfinate.

Examples of sulfites that may be used as polymerization promoters include, but are not limited to, sodium sulfite, potassium sulfite, calcium sulfite, ammonium sulfite, sodium bisulfite, and potassium bisulfite.

Examples of thioureas that can be used as polymerization promoters include, but are not limited to, 1-ethyl-2-thiourea, 1- (2-pyridyl) -2-thiourea, ethylthiourea, methylthiourea, N '-dimethylthiourea, N' -diethylthiourea, N '-di-N-propylthiourea, N' -dicyclohexylthiourea, trimethylthiourea, triethylthiourea, tri-N-propylthiourea, tricyclohexylthiourea, tetramethylthiourea, tetraethylthiourea, tetra-N-propylthiourea, tetracyclohexylthiourea, 3, 3-dimethylethylenethiourea, 4, 4-dimethyl-2-imidazolidinethione, 1, 1-dibutylthiourea, 1, 3-dibutylthiourea; and mixtures thereof.

The reducing agent and the oxidizing agent are present in amounts sufficient to allow for a sufficient radical reaction rate.

The reducing or oxidizing agent may be microencapsulated to improve the storage stability of the composition and allow the reducing and oxidizing agents to be packaged together if desired (U.S. patent No. 5154762). Proper selection of the encapsulant can allow the combination of the oxidizing and reducing agents and even the acidic functional component and optional filler to be combined in a storage stable state. Furthermore, proper selection of the water-insoluble encapsulant allows for the combination of the reducing agent and the oxidizing agent with the particulate reactive glass and water in a storage stable state.

Dual cure initiator systems combine a photoinitiator system and a redox initiator system.

In one embodiment of the dental material, at least one of the photoinitiator and the redox initiator may be present in an amount of 0.1% to about 5% by weight of the dental material.

Homo/co-polymerization

Polymerizable hydrolytically stable polycyclic amide monomers according to the present disclosure can be polymerized alone or in admixture with free radically polymerizable monomers.

Polymerizable monomer

In one embodiment of the dental material, the polymerizable monomer may be present in an amount of 1% to about 99% by weight of the dental material.

The polymerizable monomer may be an acrylic acid ester, a methacrylic acid ester, an ethylenically unsaturated compound, a carboxyl group-containing unsaturated monomer, C of (meth) acrylic acid_2-8Hydroxyalkyl esters, C of (meth) acrylic acid_1-24Alkyl or cycloalkyl esters, C of (meth) acrylic acid_2-18Alkoxyalkyl esters, olefin or diene compounds, mono/diesters, monoethers, adducts, vinyl monomers, styrene-based monomers, TPH resins, SDR resins, PBA resins and/or resins that do not contain BPA.

Examples of specific acrylate monomers include, but are not limited to, methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, 2-hydroxyethyl acrylate, hydroxypropyl acrylate, tetrahydrofurfuryl acrylate, glycidyl acrylate, glycerol monoacrylates and diacrylates, ethylene glycol diacrylate, polyethylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, monoacrylates, diacrylates, triacrylates, monoacrylates, 1, 3-butanediol diacrylate, 1, 4-butanediol diacrylate, 1, 6-hexanediol diacrylate, 2,2' -bis [3 (4-phenoxy) -2-hydroxypropane-1-acrylate ] propane, 2,2 '-bis (4-acryloyloxyphenyl) propane, 2,2' -bis [4 (2-hydroxy-3-acryloyloxyphenyl) ] propane, 2,2 '-bis (4-acryloyloxyethoxyphenyl) propane, 2,2' -bis (4-acryloyloxypropoxyphenyl) propane, 2,2 '-bis (4-acryloyloxydiethoxyphenyl) propane, 2' -bis [3 (4-phenoxy) -2-hydroxypropane-1-acrylate ] propane and dipentaerythritol pentaacrylate ester.

Examples of specific conventional methacrylate monomers include, but are not limited to, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, tetrahydrofurfuryl methacrylate, glycidyl methacrylate, diglycidyl methacrylate of bisphenol A (2, 2-bis [4- (2-hydroxy-3-methacryloyloxypropoxy) phenyl ] propane) (BisGMA), 4,4,6,16 (or 4,6,6,16) -tetramethyl-10, 15-dioxo-11, 14-dioxa-2, 9-diazepan-16-enoic acid 2- [ (2-methyl-1-oxo-2-propen-1-yl) oxy ] ethyl ester (CAS number 72869-86-4) (UDMA), glycerol monomethacrylate and dimethacrylate, ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, triethylene glycol dimethacrylate (TEGDMA), neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, monomethacrylate, dimethacrylate, trimethacrylate and tetramethacrylate of pentaerythritol and dipentaerythritol, 1, 3-butanediol dimethacrylate, 1, 4-butanediol dimethacrylate, bis [2- (methacryloyloxy) ethyl ] phosphate (BisMEP), 1, 6-hexanediol dimethacrylate, 2-2 '-bis (4-methacryloyloxyphenyl) propane, 2,2' -bis [4 (2-hydroxy-3-methacryloyloxy-phenyl) ] propane, 2,2 '-bis (4-methacryloyloxyethoxyphenyl) propane, 2,2' -bis (4-methacryloyloxypropoxyphenyl) propane, 2,2 '-bis (4-methacryloyloxydiethoxyphenyl) propane, 2,2' -bis [3 (4-phenoxy) -2-hydroxypropane-1-methacrylate ] propane, bis-2-methacryloyloxyethyl hexamethylene dicarbamate, bis-2-methacryloyloxyethyl trimethyl hexamethylene dicarbamate, bis-2-methacryloyloxyethyl dimethyl benzene dicarbamate, methylene-bis-2-methacryloyloxyethyl-4-cyclohexyl carbamate, bis-2-methacryloyloxyethyl-dimethyl cyclohexane dicarbamate, methylene-bis-2-methacryloyloxyethyl-4-cyclohexylcarbamate, di-1-methyl-2-methacryloyloxyethyl-trimethyl-hexamethylene dicarbamate, di-1-methyl-2-methacryloyloxyethyl-dimethylbenzenedicarbamate, di-1-methyl-2-methacryloyloxyethyl-dimethylcyclohexane dicarbamate, methylene-bis-1-methyl-2-methacryloyloxyethyl-4-cyclohexylcarbamate, di-1-chloromethyl-2-methacryloyloxyethyl-hexamethylene dicarbamate, di-1-chloromethyl-2-methacryloyloxyethyl-trimethylhexamethylene dicarbamate Formic acid esters, bis-1-chloromethyl-2-methacryloyloxyethyl-dimethylbenzenedicarbamate, bis-1-chloromethyl-2-methacryloyloxyethyl-dimethylcyclohexanedicarbamate, methylene-bis-2-methacryloyloxyethyl-4-cyclohexylcarbamate, bis-1-methyl-2-methacryloyloxyethyl-hexamethylenedicarbamate, bis-1-methyl-2-methacryloyloxyethyl-trimethylhexamethylenedicarbamate, bis-1-methyl-2-methacryloyloxyethyl-dimethylbenzenedicarbamate, bis-1-methyl-2-methacryloyloxyethyl-dimethylcyclohexanedicarbamate, methylene-bis-1-methyl-2-methacryloyloxyethyl-4-cyclohexylcarbamate, bis-1-chloromethyl-2-methacryloyloxyethyl-hexamethylene dicarbamate, bis-1-chloromethyl-2-methacryloyloxyethyl-trimethylhexamethylene dicarbamate, bis-1-chloromethyl-2-methacryloyloxyethyl-dimethylbenzene dicarbamate, bis-1-chloromethyl-2-methacryloyloxyethyl-dimethylcyclohexane dicarbamate, and methylene-bis-1-chloromethyl-2-methacryloyloxyethyl-4-cyclohexylcarbamate.

Examples of ethylenically unsaturated compounds include, but are not limited to, acrylates, methacrylates, hydroxy-functional acrylates, hydroxy-functional methacrylates, halogen-and hydroxy-containing methacrylates, and combinations thereof. Such radically polymerizable compounds include n-butyl, sec-butyl or tert-butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, decyl methacrylate, lauryl methacrylate, cyclohexyl methacrylate, stearyl (meth) acrylate, allyl (meth) acrylate, glycerol tri (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, 1, 3-propylene glycol di (meth) acrylate, 1,2, 4-butanetriol tri (meth) acrylate, 1, 4-cyclohexanediol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, sorbitol hexa (meth) acrylate, bis [1- (2-acryloyloxy) ] -p-ethoxyphenyl dimethyl methane, bis [1- (3-acryloyloxy-2-hydroxy) ] -p-propoxyphenyldimethylmethane, ethoxylated bisphenol a di (meth) acrylate, and trishydroxyethyl-isocyanurate tri (meth) acrylate; urethane (meth) acrylate; ((di) urethane dimethacrylate), bis (meth) acrylate of polyethylene glycol, and monomers containing a chlorine group, a bromine group, a fluorine group and a hydroxyl group such as 3-chloro-2-hydroxypropyl (meth) acrylate; the reaction product of 2, 2-bis [4- (2-hydroxy-3-methacryloxypropoxy) phenyl ] propane and hexamethylene diisocyanate (HMDI).

Examples of the carboxyl group-containing unsaturated monomer include, but are not limited to, for example, acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, and fumaric acid.

C of (meth) acrylic acid_2-8Examples of hydroxyalkyl esters include, but are not limited to, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and hydroxybutyl (meth) acrylate.

C of (meth) acrylic acid_2-18Examples of alkoxyalkyl esters include, but are not limited to, methoxybutyl methacrylate, methoxyethyl methacrylate, ethoxyethyl methacrylate, and ethoxybutyl methacrylate.

Olefin or diene compounds include, but are not limited to, ethylene, propylene, butylene, isobutylene, isoprene, chloropropene, fluoroolefins, and vinyl chloride.

Examples of the monoester may include a monoester between a polyether polyol (e.g., polyethylene glycol, polypropylene glycol or polytetramethylene glycol) and an unsaturated carboxylic acid (preferably methacrylic acid), a monoester or a diester between an unsaturated compound having an anhydride group (e.g., maleic anhydride or itaconic anhydride) and a diol (e.g., ethylene glycol, 1, 6-hexanediol or neopentyl glycol).

Examples of the monoether may include a monoether between a polyether polyol (e.g., polyethylene glycol, polypropylene glycol, or polybutylene glycol) and a hydroxyl group-containing unsaturated monomer (e.g., 2-hydroxy methacrylate).

Examples of the adduct may include, but are not limited to, an adduct between an unsaturated carboxylic acid and a monoepoxy compound; glycidyl (meth) acrylate (preferably glycidyl methacrylate), adducts between monobasic acids (e.g. acetic acid, propionic acid, p-tert-butyl benzoic acid or fatty acids).

Examples of vinyl monomers include, but are not limited to, aminopropyl vinyl ether, aminoethyl vinyl ether, N-vinyl formamide, vinylene carbonate, vinyl acetate, divinylbenzene, divinyl succinate, divinyl adipate, divinyl phthalate, vinyl pyridine, N-vinyl pyrrolidone, vinyl carbazole, vinylidene halides, and vinyl (meth) acrylate.

Examples of styrene-based monomers include, but are not limited to, styrene and 2-methylstyrene.

The (meth) acrylamide may be selected from the following compounds:

(meth) acrylamide, methylenebis- (meth) acrylamide, diacetone (meth) acrylamide,

additional Components

Dental compositions according to the present disclosure may include additional components such as ultraviolet light stabilizers, one or more polymerization inhibitors, one or more solvents, colorants, fluorescent agents, opacifiers, pigments, viscosity modifiers, fluoride releasing agents, and combinations thereof.

Examples of the ultraviolet stabilizer may include 2- (2' -hydroxy-5 ' -methylphenyl) -2H-benzotriazole, 2- (2' -hydroxy-5 ' -tert-octylphenyl) -2H-benzotriazole, 2-hydroxy-4-methoxybenzophenone (UV-9), 2- (2' -hydroxy-4 ',6' -di-tert-pentylphenyl) -2H-benzotriazole, 2-hydroxy-4-n-octyloxybenzophenone, 2- (2' -hydroxy-5 ' -methacryloyloxyethylphenyl) -2H-benzotriazole, phenothiazine and HALS (hindered amine light stabilizer).

Typical polymerization inhibitors for free radical systems may include hydroquinone Monomethyl Ether (MEHQ), Butylated Hydroxytoluene (BHT), Tertiary Butyl Hydroquinone (TBHQ), hydroquinone, phenol, 3, 5-di-tert-butyl-4-hydroxyanisole (2, 6-di-tert-butyl-4-ethoxyphenol), 2, 6-di-tert-butyl-4- (dimethylamino) methylphenol or 2, 5-di-tert-butylhydroquinone, butylhydroxyaniline, and the like. The polymerization inhibitor acts as a free radical scavenger to trap free radicals in the composition and extend the shelf life stability of the dental material. The polymerization inhibitor, if present, may be present in an amount of about 0.001% to about 1.5% by weight of the dental material, for example about 0.005% to about 1.1% or about 0.01% to about 0.08% by weight of the dental material. The dental material may include one or more polymerization inhibitors.

The dental material of the present disclosure comprises a solvent mixture comprising water and an organic solvent. The solvent mixture may comprise one or more organic solvents.

As used herein, the term "organic solvent" means any organic compound that is fluid or liquid at room temperature and that is capable of dissolving or at least partially dissolving a component of the dental composition of the present disclosure. The organic solvent is suitably selected in view of its volatility and physiological harmlessness. Preferably, the organic solvent is more volatile than water, that is, it has a higher vapor pressure than water at 20 ℃. Furthermore, it is preferred that the organic solvent is non-toxic to the patient to be treated, in particular to a human patient.

Preferably, the organic solvent of the solvent mixture is selected from the group consisting of n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, acetone and methyl ethyl ketone. Preferably, the dental material comprises the solvent mixture in an amount of 25-50 wt. -%, more preferably 27-47 wt. -%, most preferably 29-44 wt. -%, based on the total weight of the dental material.

It is preferred that the organic solvent comprised in the solvent mixture is n-propanol or isopropanol, preferably isopropanol.

Use of polymerizable hydrolytically stable polycyclic amide monomers as dental materials

Dental compositions are prepared by mixing the components of the dental compositions of the present disclosure. The components of the dental composition can be combined (e.g., mixed or blended) in various ways and amounts to form the dental compositions of the present disclosure.

The curable dental material composition may comprise:

a) 1-99% w/w of a polymerizable hydrolytically stable polycyclic amide monomer;

b) 0.01-5% w/w of a photoinitiator for free radical polymerization; and

c) 1-99% of polymerizable monomers.

The dental materials of the present disclosure may be composite materials and may include fillers in an amount of about 30 to about 90 weight percent.

The dental material of the present disclosure may be an adhesive and may include a filler in an amount of about 50 to about 65 weight percent, and a solvent in an amount of 0-70 weight percent.

Dental materials according to the present disclosure may be cement and may include fillers in an amount of about 50 to about 90 weight percent.

The dental composite may be formulated by mixing the polymerizable hydrolytically stable polycyclic amide monomer matrix and filler.

The disclosure will now be further illustrated by the following examples.

Example (b):

synthesis of hydrolytically stable bis (norbornene cyclopropaneamido) Compounds

5.9g (35mmol) of norbornene cyclopropanecarbonyl chloride were dissolved in 75mL of dichloromethane and placed in an ice bath. 2.7g (17mmol) of the mixture of diamine isomers, TMHDA (CAS 25620-58-0) and 3.44g (34mmol) of trimethylamine are dissolved in 20mL of dichloromethane and added dropwise to the reaction mixture. The reaction was carried out at room temperature for 30min and quenched by the addition of 150mL of water. The aqueous layer was separated and washed 3 times with 50mL dichloromethane. All organic layers were combined, dried and the solvent removed under reduced pressure. The bis (norbornene cyclopropaneamido) compound (1) is a colorless solid. Product passing¹H NMR spectrum characterization, as shown in figure 1.

Application example 1

Shrinkage stress:

the shrinkage stress was measured with a shrinkage stress measuring device called a tensiometer, which was designed and manufactured by the Paffenberger research center of the American dental institute Foundation (ADAF). This device is based on cantilever theory, i.e., the bending force generated by contracting the sample during polymerization causes the cantilever to flex. Dental resin or composite material was injected into the cell between two glass rods of 6.0mm diameter and 2.25mm thickness. The material was heated to 400mW/cm using QHL-75 halogen lamp²Light intensity of (c) for 60 seconds. A more detailed description, experimental procedures and characterization of the tensiometer are discussed in (H.Lu et al, Journal of Materials Science, Materials in Medicine, 2004, Vol.15, 1097-.

Copolymerization of bis (norbornene Cyclopropaneamido) Compound (1) with triethylene glycol dimethacrylate (TEGDMA)

For measurement of polymerization shrinkage and stress, mixtures of the components shown in table 1 were mixed and then irradiated with a visible light source.

The maximum shrinkage stress for the composition of HLU18-150-N5T5 was 1.5MPa (as shown in FIG. 2).

Comparative example

The CMX-resin was evaluated for shrinkage stress and a maximum shrinkage stress of 4.5MPa (as shown in FIG. 2) was observed; the CMX-resin also exhibits a significantly higher rate of shrinkage stress formation.

While the disclosure has been described with reference to one or more embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the scope of the disclosure. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the disclosure without departing from the essential scope thereof. Therefore, it is intended that the disclosure not be limited to the particular embodiment disclosed as the best mode contemplated for carrying out this disclosure, but that the disclosure will include all embodiments falling within the scope of the appended claims. Moreover, all numbers expressing quantities of ingredients, and so forth used in the detailed description are to be understood as being modified in all instances by the term "about.