KR20070032381A - Dental Compositions Containing Carbosilane Polymers - Google Patents

Abstract

No Si-O bonds; More than one repeat unit; At least four Si-arylene bonds; At least one (meth) acrylate residue, Si-H residue, or both; Carbosilane containing polymers (including oligomers) are disclosed which preferably have at least four silicon atoms and have structural features in which two silicon atoms are separated by one arylene group in each repeating unit.

Polymerizable carbosilane polymer (oligomer), (meth) acrylate, dental composition, volume shrinkage, filler system, initiator system, additive

Description

Dental Compositions Containing Carbosilane Polymers

Carbosilane polymers and dental compositions comprising such polymers

It is well known that volume shrinkage of dental compositions upon curing results in fine cracking and high stress of the composite. Such defects can cause clinical failure of composite materials. Therefore, it is important to develop dental composites with reduced volume shrinkage while maintaining the excellent physical properties of current materials.

Current commercial (meth) acrylate based composites exhibit a volume shrinkage of 2 to 4 percent (%) upon polymerization. It is an object to reduce shrinkage to less than 2% while maintaining other desired physical properties such as compressive strength and viscosity. Although many types of components have been developed for reducing polymeric shrinkage for use in dental composites, especially (meth) acrylate-based composites, composites based on them are available from 3M (St. Paul, Minn., USA). Compared to commercial products such as the trade name FILTEK Z250, these generally exhibit reduced physical properties.

Therefore, there is still a need for new ingredients that can be added to (meth) acrylate-based dental compositions to provide reduced shrinkage.

<Overview of invention>

The present invention provides carbosilane polymers for use in dental compositions. Carbosilane polymers (ie carbosilane containing polymers) are materials having one or more repeat units. Herein, within the scope of polymers and polymeric materials, relatively low molecular weight oligomeric materials are included. Preferably, the carbosilane polymer comprises a carbosilane containing oligomeric material. Such materials are preferably free of Si-O bonds; More than one repeating unit; At least four Si-arylene bonds; At least one (meth) acrylate residue, Si-H residue or both; And preferably structural features having at least four silicon atoms. Such materials typically also include two silicon atoms separated by one arylene group in each repeating unit.

In certain embodiments, the carbosilane polymer is formed from the reaction of aromatic silanes, in particular arylene disilane and ethylenically unsaturated compounds. Such materials may be crystalline or amorphous, depending on the desired balance of before and after curing properties of the composition. Dental compositions comprising such materials typically have low volumetric shrinkage upon curing. The resulting cured composites also have potentially higher antifouling properties compared to current composites.

Dental compositions of the invention also typically include an initiator system, such as a photoactive free radical source (preferably a source activated by blue light). In certain embodiments, the dental composition also includes a filler system and preferably comprises up to 80% by weight filler system (preferably including inorganic filler) based on the total weight of the composition. Other optional ingredients include, for example, colorants, flavors, drugs, stabilizers, viscosity modifiers, diluents, flow control additives, thixotropic agents, antibacterial agents and polymer thickeners. For the desired effect, various combinations of each of the ingredients listed above can be used.

In certain embodiments, carbosilane-containing polymers of the invention follow formula (I).

In the above formula,

Each Ar is independently an arylene group,

Each R is independently an aliphatic group, a cycloaliphatic group, or a combination thereof, optionally comprising one or more O, Br, Cl, or Si atoms or combinations thereof,

Each Q is independently an aliphatic group, a cycloaliphatic group, an aromatic group, or a combination thereof, which optionally includes a bond or, optionally, one or more O, Br, Cl, or Si atoms or combinations thereof Optionally comprises at least one (meth) acrylate group,

Each R ¹ To R ⁴ groups are independently aliphatic groups, cycloaliphatic groups, aromatic groups or combinations thereof, optionally substituted with one or more (meth) acrylate groups,

Each R ⁵ And R ⁶ groups are independently hydrogen or aliphatic groups, cycloaliphatic groups, aromatic groups or combinations thereof, optionally substituted with one or more (meth) acrylate groups,

n is greater than one.

In certain embodiments, carbosilane polymers of the invention conform to Formula II.

In the above formula,

Each Ar is independently an arylene group,

Each Q is independently an aliphatic group, a cycloaliphatic group, an aromatic group, or a combination thereof, which optionally includes a bond or, optionally, one or more O, Br, Cl, or Si atoms or combinations thereof Is optionally substituted with one or more (meth) acrylate groups,

Each R ¹ To R ⁴ group is methyl,

Each R ⁵ And R ⁶ groups independently include hydrogen, or optionally an aliphatic group, a cycloaliphatic group, an aromatic, optionally substituted with one or more O, Br, Cl or Si atoms or combinations thereof, and one or more (meth) acrylate groups Groups or a combination thereof,

n is greater than one.

Justice

The term "curable" refers to a material that can be cured or solidified, for example by heating to remove solvent, heating to induce polymerization, chemical crosslinking, radiation-induced polymerization or crosslinking, and the like.

The term "arylene" as used herein includes a carbocyclic aromatic ring or ring system, which aromatic ring may be optionally connected by oxygen, nitrogen, sulfur or alkylene groups or combinations thereof and optionally halogen, alkyl Or an alkoxy group or a combination thereof. Examples of arylene groups include phenylene, naphthylene, biphenylene, fluorenylene, indenylene, diphenylene ether, optionally substituted with alkyl and / or alkoxy groups.

"Crystallizable" means that a substance with alone or other monomers exhibits a crystalline melting point of 20 ° C. or higher, as measured by differential scanning calorimetry (DSC). The temperature of the observed endothermic peak is taken as the crystalline melting point. The crystalline phase comprises multiple lattice in which the material takes on a highly ordered listing of adjacent chemical residues that the material builds up. The packing arrangement in the grating (short order orientation) is highly regular in both chemical and geometric aspects. The crystalline component may be in a "semicrystalline state" in that long segments of the polymer chain appear above 20 ° C. in both amorphous and crystalline states or phases. Thus, the "crystalline" component herein includes a semicrystalline material.

The term "non-crystallizable" refers to a material composed of irregularly oriented atoms, ions, or molecules that do not form a defined pattern, lattice structure, or long-term alignment (ie, amorphous). Amorphous materials do not show a crystalline melting point above 20 ° C. as measured by differential scanning calorimetry (DSC).

The term "comprising" and variations thereof are not meant to be limiting where such terms are set forth in the specification and claims.

As used herein, "a", "the", "at least one" and "one or more" are used interchangeably. Thus, for example, a dental composition comprising "one" carbosilane-containing component may be interpreted in the sense of a dental composition comprising "one or more" carbosilane-containing component. Similarly, a composition comprising "one" filler may be interpreted in the sense of a composition comprising a filler of "one or more" type.

Also herein, reference to numerical ranges by endpoints includes all numbers included within that range (eg, 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, 5, etc.). ).

 The above summary of the present invention is not intended to describe all embodiments of the present invention or each disclosed embodiment. The following techniques illustrate exemplary embodiments in more detail. In several places throughout the specification, guidance is provided, and these examples may be used in various combinations. In each case, the cited lists serve only as representative groups and should not be construed as limiting lists.

The present invention particularly provides carbosilane polymers (including oligomers) for use in dental compositions with other (meth) acrylate-based components. Carbosilane polymers (ie carbosilane containing polymers) are preferably free of Si—O bonds; More than one repeating unit; At least two Si-arylene bonds; At least one (meth) acrylate residue, Si-H residue or both (preferably at least two (meth) acrylate residues); It preferably comprises structural features having at least four silicon atoms, wherein the two silicon atoms are separated by one arylene group in each repeating unit.

Significantly, the aromatic carbosilane polymer can be prepared, for example, using a simple silicon hydride addition procedure. The wide availability of starting materials (eg, aromatic silanes or more specifically arylene disilanes, and ethylenically unsaturated, or more specifically diolefin compounds) has been found to affect the structure, composition and functional groups of the carbosilane component. Allow for wider control. Thus, the repeat units of the carbosilane component typically comprise chemical moieties derived from the reaction product of an ethylenically unsaturated compound (typically a diolefin compound) and arylene disilane (with two Si-H moieties). Through this chemistry, it is possible, in one step, to prepare linear materials with polymerizable functional groups (preferably (meth) acrylate functional groups) along the main chain.

Carbosilane  Ingredients and their preparation

The material of the carbosilane component is typically a polymer, preferably an oligomer. That is, the carbosilane component comprises one or more polymerizable polymers, preferably oligomers.

Thus, as used herein, "polymer and polymeric" refers to any material having more than one repeating unit and thus includes oligomers. Thus, unless otherwise indicated, polymers generally include oligomers having a molecular weight of up to 20,000 grams per mole. Moreover, the term polymer as used herein includes both homopolymers and copolymers, and the term copolymer as used herein refers to materials having two or more different repeating units (eg, copolymers, terpolymers, Quaternary copolymers).

The molecular weight and viscosity of the polymeric material can be easily controlled by simply changing the building blocks used in the reaction. The number average molecular weight of the carbosilane material may vary over a wide range. Preferably, the molecular weight is 20,000 grams per mole (g / mol) or less, although the molecular weight may be higher if the material is a polymer. More preferably, the number average molecular weight of the carbosilane material is at most 10,000 grams per mole (g / mol), even more preferably at most 5000 g / mol. Preferably, the molecular weight is at least 500 g / mol, more preferably at least 750 g / mol. Starting materials for the polymerization can be selected to obtain a final product that is liquid or solid at room temperature.

Preferred carbosilane components can preferably be cured (eg polymerized and / or crosslinked) by free radical mechanisms. Carbosilane polymers may or may not be crystalline.

Carbosilane polymers (ie carbosilane containing polymers) are preferably free of Si—O bonds; At least two Si-arylene bonds; At least one (meth) acrylate residue, Si-H residue or both; And preferably structural features having at least four Si atoms and two silicon atoms separated by one arylene group in each repeating unit. Preferably, the carbosilane polymer has more than one, more preferably at least two functional groups. Preferably, the carbosilane polymer has at least two (meth) acrylate residues.

Preferably, the carbosilane component follows the general formula (I).

<Formula I>

In the above formula,

Each Ar is independently an arylene group,

Each R is independently an aliphatic group, a cycloaliphatic group, or a combination thereof, optionally comprising one or more O, Br, Cl, or Si atoms or combinations thereof,

Each Q is independently an aliphatic group, a cycloaliphatic group, an aromatic group, or a combination thereof, which optionally includes a bond or, optionally, one or more O, Br, Cl, or Si atoms or combinations thereof Optionally comprises at least one (meth) acrylate group,

Each R ¹ To R ⁴ groups are independently aliphatic groups, cycloaliphatic groups, aromatic groups or combinations thereof, optionally substituted with one or more (meth) acrylate groups,

Each R ⁵ And R ⁶ groups are independently hydrogen or aliphatic groups, cycloaliphatic groups, aromatic groups or combinations thereof, optionally substituted with one or more (meth) acrylate groups,

n (average value) is larger than 1, preferably 2 or more.

The term "arylene" as used herein includes a carbocyclic aromatic ring or ring system, which aromatic ring may optionally be connected by oxygen, nitrogen, sulfur, or alkylene groups or combinations thereof and optionally halogen , Alkyl or alkoxy groups or combinations thereof. Examples of arylene groups include phenylene, naphthylene, biphenylene, fluorenylene, indenylene, diphenylene ether, optionally substituted with alkyl and / or alkoxy groups.

Preferably, in formula (I), each arylene (Ar) group is independently optionally one or more halogen and / or alkyl groups, wherein alkyl preferably has from 1 to 10 carbon atoms, more preferably from 1 to 6 to 14 carbon atoms in the ring system. Aromatic groups in the ring system can be optionally linked by oxygen and / or alkylene groups. More preferably, arylene is phenylene or diphenylene ether (-C ₆ H ₄ -OC ₆ H _4- ), optionally substituted with one or more halogen and / or (C1-C3) alkyl groups.

Preferably, in formula (I), each R is ethylene.

For certain embodiments of formula I, each Q is independently preferably CH ₂ —O—Ar′—O—CH ₂ —, wherein Ar ′ is optionally one or more halogen and / or alkyl groups, wherein alkyl Is an arylene group having 6 to 14 carbon atoms, preferably substituted with 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms. Aromatic groups in the ring system can be optionally linked by oxygen and / or alkylene groups.

In certain embodiments of formula I, each Q is independently preferably -CH ₂ -O-alkylene-O-CH _2- , wherein alkylene (preferably C1-C4 alkylene) is (meth) Substituted with acrylate groups.

Preferably, in formula (I), each R ¹ To R ⁴ The groups are independently aliphatic groups having 1 to 6 carbon atoms, cycloaliphatic groups having 1 to 6 carbon atoms, aromatic groups having 6 to 14 carbon atoms, or combinations thereof. More preferably, each R ¹ To R ⁴ Groups are independently aliphatic groups having 1 to 6 carbon atoms (more preferably 1 to 3 carbon atoms).

Preferably, in formula (I), each R ⁵ And R ⁶ The groups are independently substituted with hydrogen, or optionally one or more (meth) acrylate groups, comprise one or more O, Br, Cl or Si atoms or combinations thereof and have from 1 to 10 carbon atoms which may comprise a bicyclic group Aliphatic groups, cycloaliphatic groups having 1 to 10 carbon atoms, aromatic groups having 6 to 14 carbon atoms, or combinations thereof. More preferably, each R ⁵ And R ⁶ The groups are independently hydrogen or aliphatic groups having from 1 to 10 carbon atoms (more preferably from 1 to 3 carbon atoms) substituted with one or more (meth) acrylate groups.

More preferably, the carbosilane component follows the formula II.

<Formula II>

In the above formula,

Each Ar is independently an arylene group,

Each Q is independently an aliphatic group, a cycloaliphatic group, an aromatic group, or a combination thereof, which optionally includes a bond or, optionally, one or more O, Br, Cl, or Si atoms or combinations thereof Is optionally substituted with one or more (meth) acrylate groups,

Each R ¹ To R ⁴ group is methyl,

Each R ⁵ and R ⁶ group is independently hydrogen or an aliphatic group, a cycloaliphatic group, optionally containing one or more O, Br, Cl or Si atoms or a combination thereof, optionally substituted with one or more (meth) acrylate groups , Aromatic groups or combinations thereof,

n (average value) is larger than 1, preferably 2 or more.

In formula (II), arylene is defined as above. Preferably, each arylene (Ar) group is independently optionally one or more halogen and / or alkyl groups (where alkyl preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms). Has from 6 to 14 carbon atoms in the ring system substituted with). Aromatic groups in the ring system can be optionally linked by oxygen and / or alkylene groups. More preferably, arylene is phenylene or diphenylene ether (-C ₆ H ₄ -OC ₆ H _4- ) substituted with one or more halogen and / or (C1-C3) alkyl groups.

For certain embodiments of formula II, each Q is independently preferably -CH ₂ -O-Ar'-O-CH _2- , wherein Ar 'is optionally one or more halogen and / or alkyl groups, wherein Alkyl is an arylene group having 6 to 14 carbon atoms, preferably substituted with 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms. Aromatic groups in the ring system can be optionally linked by oxygen and / or alkylene groups.

In certain embodiments of formula II, each Q is independently preferably -CH ₂ -O-alkylene-O-CH _2- , wherein alkylene (preferably C1-C4 alkylene) is (meth) Substituted with acrylate groups.

Preferably, in formula (II), each R ⁵ And the R ⁶ groups are independently substituted with hydrogen, or optionally one or more (meth) acrylate groups, and comprise one or more O, Br, Cl or Si atoms or combinations thereof, wherein one carbon atom may comprise a bicyclic group To aliphatic groups of 10 to 10 carbon atoms, cycloaliphatic groups of 1 to 10 carbon atoms, aromatic groups of 6 to 14 carbon atoms, or combinations thereof. More preferably, each R ⁵ And R ⁶ groups are independently hydrogen or aliphatic groups of 1 to 10 carbon atoms (preferably 1 to 3 carbon atoms) substituted with one or more (meth) acrylate groups.

The carbosilane component may be formulated into a dental composite that exhibits a total volumetric polymerization shrinkage of 2.0% or less (typically 1.4% to 2.0%) and preferably maintains good physical properties, said percentage being a composition before curing. It is based on the volume of.

Preferably, the total amount of carbosilane component in the dental composition is at least 1% by weight, more preferably at least 3% by weight and most preferably at least 5% by weight, based on the total weight of the composition. Preferably, the total amount of carbosilane component is up to 60% by weight, more preferably up to 50% by weight and most preferably up to 40% by weight based on the total weight of the composition.

Scheme 1 below outlines a preferred general procedure for the preparation of carbosilane containing materials. Such materials may be prepared with polymerizable end groups and optionally polymerizable groups pendant to the main chain of the polymer.

Although Scheme 1 shows the use of bis (dimethylsilyl) -arylene, substituents other than methyl may also be used in the arylene disilane reactant. Likewise, although the use of diolefins is shown in Scheme 1, other ethylenically unsaturated reactants may be used, including (meth) acrylate compounds. Furthermore, although Scheme 1 shows methacrylate functional olefin reactants in the end-capping step of the scheme, other ethylenically unsaturated compounds as well as acrylates can be used. Preferably, one of the reactants comprises a (meth) acrylate (ie acrylate or methacrylate) residue.

In Scheme 1, Ar, Q and n are as defined above. R 'is an aliphatic group, a cycloaliphatic group, an aromatic group, or a combination thereof, optionally comprising one or more O, Br, Cl or Si atoms, preferably an aliphatic group having 1 to 10 carbon atoms, 1 carbon atom To 10 individual cycloaliphatic groups or aromatic groups having 6 to 14 carbon atoms. More preferably, R 'is an aliphatic group having 1 to 10 carbon atoms (more preferably 1 to 3 carbon atoms).

As shown in Scheme 1, the bifunctional aromatic silane is reacted with a bifunctional ethylenically unsaturated compound via a silicon hydride addition reaction to produce a polymer (preferably oligomeric) product. The intermediate can then be reacted with a (meth) acrylate functional ethylenically unsaturated compound to obtain a polymerizable polymer with a methacrylate end group (preferably an oligomer). The stoichiometry of the initial reaction is typically chosen so that the polymer has silyl (Si-H) end groups that can be further functionalized with (meth) acrylate functional ethylenically unsaturated compounds. Alternatively, the bifunctional aromatic silane and / or diolefin compound may also contain a polymerizable group that produces a polymer with polymerizable groups pendant on the backbone of the chain. For example, stoichiometry may be selected to produce silane or vinyl end groups.

Typically, the starting aromatic silane and the ethylenically unsaturated starting material and the silicon hydride addition catalyst are reacted together in a solvent, typically at room temperature. Then optional final capping compound is added to the mixture. The catalyst can then be removed by filtration through silica gel to give the product or it can be obtained through crystallization or precipitation.

The silicon hydride addition catalyst used in the reaction may be any compound that will promote the addition reaction of, for example, a compound containing an olefinic double bond with a hydrogen atom bonded to silicon. Examples of suitable silicon hydride catalysts for the compositions of the present invention include many late transition elements such as cobalt, rhodium, iridium, nickel, palladium and platinum and organometallic complexes thereof. Preferred catalysts include metal platinum containing catalysts such as finely divided platinum metals, platinum metals on finely divided carriers such as charcoal or alumina, and platinum compounds such as chloroplatinic acid, platinum olefin complexes as described in US Pat. No. 3,159,601, US patents. Platinum alkyne complexes as described in US Pat. No. 4,603,215, reaction products of platinum chloride with a member selected from the group consisting of alcohols, ethers, aldehydes and mixtures thereof, as described in US Pat. No. 3,220,972, and US Pat. No. 3,715,334 A reaction product of chloroplatinic acid with tetravinylcyclotetrasiloxane in the presence of sodium bicarbonate in ethanol solution, as described in the foregoing. Particularly preferred catalysts are complexes prepared from chloroplatinic acid and certain unsaturated organosilicon compounds, such as those described in US Pat. Nos. 3,419,593, 3,775,452, 4,288,345 and 4,421,903. One particular example of such a catalyst is the reaction product of chloroplatinic acid with sym-divinyltetramethyldisiloxane. Another particularly preferred catalyst is a colloidal silicon hydride catalyst obtained by reaction of a silicon hydride or siloxane hydride with a platinum (0) or platinum (II) complex, such as described in US Pat. No. 4,705,765. . Another particularly preferred catalyst is (η ⁴ -1,5-cyclooctadiene) diarylplatinum and (η ⁵ -cyclopentadienyl) described in US Pat. Nos. 4,530,879, 4,510,094 and 4,600,484. There are those activated by actinic radiation, such as trialiphatic platinum complexes.

The catalyst should be present in an effective amount, ie, in an amount sufficient to promote the silicon hydride addition reaction. Satisfactory results can be obtained when the catalyst is present in an amount sufficient to supply as little as 1 part by weight of metal (eg platinum) per million parts by weight of the total composition. On the other hand, an amount of catalyst sufficient to supply as much as 1 to 10 parts by weight of metal per 1000 parts by weight of the total composition may also be used. Generally, however, it is preferable to use an amount of catalyst sufficient to supply 100 to 200 parts by weight of metal (eg platinum) per million parts by weight of the total composition.

H.N. Beck et al., J. Chem. Eng. Data, 8, 453 (1963), silane starting materials are typically prepared via Grignard reaction of halogenated aromatic compounds with chloro-dimethyl silanes (or other chloro-alkyl silanes). Preferred aromatic silane starting materials include 1,4-bis-dimethylsilyl benzene, 1,3-bis-dimethylsilyl benzene and bis- (p-dimethylsilyl) phenyl-ether.

Suitable difunctional ethylenically unsaturated precursors are 1,4-bis (allyloxy) benzene, 1,3-bis (allyloxy) benzene, bisphenol A di, which are commercially available or can be synthesized from methods known in the art. Allyl ether or tetrabromo bisphenol A diallyl ether. For example, aryl alkyl ether compounds such as allyl-phenyl-ether or but-2-enyl- (2-methoxy-phenyl) -ether are described in Houben-Weyl, Methoden der Organischen Chemie, volume VI / 3, p57. (Preparation Example 1) or p56 (Preparation Example 1), Georg Thieme Verlag, Stuttgart, 1965, 4th edition] or compounds such as allyl- (2-chloro-phenyl) -ether are described in [ D. Tarbell et al., J. Am. Chem. Soc. 64 (5), 1066-1070 (1942).

Difunctional ethylenically unsaturated precursors may be aromatic or aliphatic. Preferred aromatic compounds contain allyloxy substitution of the aromatic ring system. In addition, the vinyl compound may contain methacrylate functional groups.

If desired, the end groups of the polymer (formed in the first stage of Scheme 1) will be further reacted with a single or multifunctional group (in the second stage of Scheme 1). If a molar excess of carbosilane functional group is used in the polymerization (in the first step of Scheme 1), the polymer will contain carbosilane end groups that can further react with the compound containing ethylenically unsaturated groups. If a molar excess of ethylenically unsaturated functional group is used in the polymerization, the polymer will contain ethylenically unsaturated end groups that can further react with the carbosilane group containing compound. Typically, the polymerization is carried out with molar excess of carbosilane groups which further react with the ethylenically unsaturated (meth) acrylate compound in the end-capping reaction (second step in Scheme 1). The ethylenically unsaturated substituted (meth) acrylate component typically contains one olefin group and at least one (meth) acrylate group. Preferred such compounds include allyl methacrylate, 2- (5 / 6-methacryloyloxy-bicyclo [2.2.1] hept-2-yl) -ethene and (2-allyloxyethyl) methacrylate do.

Schemes 2-5 below generally follow Scheme 1 and outline the preparation schemes for preferred examples of carbosilane polymers, in which Ar and n are as defined above.

Secondary Polymerizable  matter

Additional polymerizable components other than the carbosilane polymers disclosed herein may optionally be added to the dental compositions of the present invention. To be suitable for use in the oral environment, these polymerizable components comprise one or more curable organic resins capable of forming a cured material having sufficient strength and hydrolytic stability. Preferably, at least some of the secondary polymerizable components comprise ethylenic unsaturations and may be addition polymerized. Suitable secondary polymerizable components preferably comprise at least one ethylenically unsaturated monomer (ie at least one carbon-carbon double bond).

The secondary polymerizable component of the present invention may be part of the curable resin. These resins are generally thermosetting materials that can be cured to form polymeric networks comprising, for example, acrylate functional materials, methacrylate functional materials, vinyl functional materials, and mixtures thereof. Typically, curable resins are prepared from one or more matrix forming oligomers, monomers, polymers or blends thereof.

One class of curable resins includes materials having polymerizable components with free radical activating functional groups. Examples of such materials include monomers having at least one ethylenically unsaturated group, oligomers with at least one ethylenically unsaturated group, polymers having at least one ethylenically unsaturated group, and combinations thereof.

In the class of curable resins with free radically active functional groups, polymerizable components suitable for use in the present invention contain at least one ethylenically unsaturated bond and may be addition polymerized. Such free radical ethylenically unsaturated compounds include, for example, methyl (meth) acrylate, ethyl acrylate, isopropyl methacrylate, n-hexyl acrylate, stearyl acrylate, allyl acrylate, glycerol triacrylate, Ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, 1,3-propanediol di (meth) acrylate, trimethylolpropane triacrylate, 1,2,4-butanetriol Trimethacrylate, 1,4-cyclohexanediol diacrylate, pentaerythritol tetra (meth) acrylate, sorbitol hexaacrylate, tetrahydrofurfuryl (meth) acrylate, bis [1- (2-acryloxy )]-p-ethoxyphenyldimethylmethane, bis [1- (3-acryloxy-2-hydroxy)]-p-propoxyphenyldimethylmethane, ethoxylated bisphenol A di (meth) acrylic Sites and tris-hydroxyethyl, di-or poly- (meth) acrylates (i.e., acrylates and methacrylates) isocyanurate trimethacrylate, such as mono-; (Meth) acrylamides (ie acrylamide and methacrylamide) such as (meth) acrylamide, methylene bis- (meth) acrylamide and diacetone (meth) acrylamide; Urethane (meth) acrylates; Bis- (meth) acrylates of polyethylene glycol (preferably molecular weight 200 to 500); Copolymerizable mixtures of acrylated monomers, such as in US Pat. No. 4,652,274 (Boettcher et al.); Acrylated oligomers such as in US Pat. No. 4,642,126 (Zador et al.); And vinyl compounds such as styrene, diallyl phthalate, divinyl succinate, divinyl adipate and divinyl phthalate. Other suitable free radically polymerizable compounds include, for example, International Publication No. 00/38619 (Guggenberger et al.), 01/92271 (Weinmann et al.), 01/07444 (Guggenberger et. al.), siloxane functional (meth) acrylates such as those disclosed in Guggenberger et al., and for example, US Pat. No. 5,076,844 (Fock et al.), US 4,356,296 ( Discordant as disclosed in Griffith et al., European Patent No. 0 373 384 (Wagenknecht et al.), No. 0 201 031 (Reiners et al.) And No. 0 201 778 (Reiners et al.). Polymeric functional (meth) acrylates are included. If desired, mixtures of two or more of the free radically polymerizable compounds can be used.

The secondary polymerizable component may also contain hydroxyl groups and free radical activating functional groups in a single molecule. Examples of such materials include hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; Glycerol mono- or di- (meth) acrylates; Trimethylolpropane mono- or di- (meth) acrylate; Pentaerythritol mono-, di- and tri- (meth) acrylates; Sorbitol mono-, di-, tri-, tetra- or penta- (meth) acrylates; And 2,2-bis [4- (2-hydroxy-3-methacryloxypropoxy) phenyl] propane (bisGMA). Suitable ethylenically unsaturated compounds are also available from a wide variety of commercial sources such as Sigma-Aldrich (St. Louis, MO). If desired, mixtures of ethylenically unsaturated compounds can be used.

The compounds listed above are typically amorphous (ie amorphous). Secondary polymerizable components may also include crystalline components. Such crystalline components may or may not have reactive groups that can polymerize (including crosslinking). Preferably, the crystalline component is polymerizable. Preferably, the crystalline component is a polymer (including oligomers). More preferably, the crystalline component is a polymerizable polymeric material. Secondary crystalline polymers (including oligomers) suitable for use in dental compositions may have crystalline main chain (ie linear) or pendant (ie side chain) segments. Preferred materials also contain reactive groups which can be polymerized and / or crosslinked. Particular preference is given to bicarbosilane crystalline oligomers or prepolymers having at least two reactive functional groups.

Examples of suitable secondary crystalline materials with crystalline main chain or backbone segments include polyesters (including polycaprolactones), polyethers, polythioethers, polyarylalkylenes, polysilanes, polyamides, (preferably lower) Polyolefins and polyurethanes, for example, formed from C2-C3 olefins.

Preferred secondary crystalline materials are saturated linear aliphatic polyester polyols (particularly diols) containing primary hydroxyl end groups. Examples of commercial materials useful as bicarbosilane crystalline components in the dental compositions of the present invention include some resins available under the trade name LEXOREZ of Inolex Chemical Co., Philadelphia, PA, USA. do. Examples of other polyester polyols useful in the compositions of the present invention are those available under the trade name RUCOFLEX of Ruco Polymer Corp., Huxville, NY. Examples of polycaprolactones useful in the present invention include those available under the trade names Tone 0230, Tone 0240 and Tone 0260 of Dow Chemical Co., Midland, Mich., USA. Particularly preferred materials are for example to introduce polymerizable unsaturated functional groups, such as, for example, polycaprolactone diol reacted with 2-isocyanatoethyl methacrylate, methacryloyl chloride or methacrylic anhydride (eg, Modified saturated linear aliphatic polyester polyols) via primary hydroxyl end groups.

Preferably, the total amount of secondary polymerizable components is at most 60 wt%, more preferably at most 50 wt%, most preferably at most 40 wt%, based on the total weight of the composition.

Initiator  system

The composition of the present invention is optionally an initiator system, ie one species, suitable for curing (eg, polymerization and / or crosslinking) of the resin system (eg carbosilane-containing component and optional (meth) acrylate component). May include an initiator or a mixture of two or more initiators. The initiator system preferably comprises free radical initiators which can be activated in various ways, for example heat and / or radiation. Thus, for example, the initiator system may include thermal initiators (eg, azo compounds and peroxides) or photoinitiators.

Preferably, the initiator system comprises at least one photoinitiator. More preferably, the initiator system is capable of promoting free radical polymerization and / or crosslinking of ethylenically unsaturated moieties when activated in the spectral range from 300 nanometers (nm) to 1200 nm and exposed to light of suitable wavelengths and intensities. At least one photoinitiator. A wide variety of such photoinitiators can be used. The photoinitiator is preferably soluble in the resin system. Preferably, the photoinitiator is sufficiently stable at room temperature and free of unwanted pigmentation to allow storage and use under typical dental laboratory and laboratory conditions. Visible light photoinitiators are preferred.

One type of suitable initiator (ie, initiator system) is described in US Pat. No. 5,545,676 (Palazzotto et al.), Which includes three component or three-way photoinitiator systems. The system ^{(e.g., Cl -, Br -, I} - or C ₂ H ₅ SO ₃ ^- and the anion containing the same), simple salt, or (e.g., SbF ₅ OH or AsF ₆ ^- containing) Iodonium salts, which may be metal complex salts, such as diaryliodonium salts. If desired, mixtures of iodonium salts can be used. The second component in the three-way photoinitiator system is a photosensitizer capable of absorbing light in the wavelength range of 400 nanometers (nm) to 1200 nm. The third component in the ternary photoinitiator system is the electron donor and is the amine (including aminoaldehydes and aminosilanes or other amines as described for the first initiator system), amides (including phosphoramides), ethers (including thioethers), Urea (including thiourea), ferrocene, sulfinic acid and salts thereof, salts of ferrocyanide, ascorbic acid and salts thereof, dithiocarbamic acid and salts thereof, salts of xanthate, salts of ethylene diamine tetraacetic acid and tetraphenylboron Salts of acids.

Examples of photosensitizers suitable for use in ternary photoinitiator systems include ketones, coumarin dyes (e.g. ketocoumarin), xanthene dyes, acridine dyes, thiazole dyes, thiazine dyes, oxazine dyes, azine dyes, Aminoketone dyes, porphyrins, aromatic polycyclic hydrocarbons, p-substituted aminostyryl ketone compounds, aminotriaryl methane, merocyanine, squarylium dyes and pyridinium dyes. Ketones (eg monoketones or alpha diketones), ketocoumarins, aminoarylketones and p-substituted aminostyryl ketone compounds are preferred photosensitizers. Examples of particularly preferred visible photosensitizers include camphorquinone, glyoxal, biacetyl, 3,3,6,6-tetramethylcyclohexanedione, 3,3,7,7-tetramethyl-1,2-cycloheptanedone , 3,3,8,8-tetramethyl-1,2-cyclooctanedione, 3,3,18,18,18-tetramethyl-1,2-cyclooctadecanedione, dipyvaloyl, benzyl, furyl, hydroxy Benzyl, 2,3-butanedione, 2,3-pentanedione, 2,3-hexanedione, 3,4-hexanedione, 2,3-heptanedione, 3,4-heptanedione, 2,3-octanedione , 4,5-octanedione and 1,2-cyclohexanedione. Of these, camphorquinone is the most preferred photosensitizer.

Another type of photoinitiator includes acylphosphine oxides such as those described in European Patent Application No. 173567 (Ying). Suitable acylphosphine oxides are preferably of the formula (R ⁴ ) ₂ -P (= 0) -C (= 0) -R ⁵ , wherein each R ⁴ is individually substituted with a halo group, an alkyl group or an alkoxy group. Hydrocarbon group, preferably an alkyl group, an alicyclic group, an aryl group and an aralkyl group, or two R ⁴ groups may combine to form a ring with a phosphorus atom, and R ⁵ is a hydrocarbon group, preferably Is a S, O or N containing 5- or 6-membered heterocyclic group or a -ZC (= O) -P (= O)-(R ⁴ ) ₂ group, Z is an alkylene having 2 to 6 carbon atoms or Divalent hydrocarbon groups such as phenylene. Examples of suitable acylphosphine oxides include, for example, bis (2,4,6-trimethylbenzoyl) phenyl phosphine oxide. Optionally, tertiary amine reducing agents can be used with the acylphosphine oxides. Exemplary tertiary amines useful in the present invention include ethyl 4- (N, N-dimethylamino) benzoate and N, N-dimethylaminoethyl methacrylate as well as those described above.

Monoketones and all ketones can also be used as photoinitiators. Examples of such systems are described in US Pat. No. 4,071,424 to Dart et al.

Another class of photoinitiators includes ionic dye-counter ion complex initiators including borate anions and complementary cationic dyes. Borate anions useful for such photoinitiators may generally be of the formula B (R ⁶ ) ₄ ⁻ , where each R ⁶ is independently alkyl, aryl, alkaryl, allyl, aralkyl, alkenyl, alkynyl, alicyclic And saturated or unsaturated heterocyclic groups. Cationic counterions may be cationic dyes, quaternary ammonium groups, transition metal coordination complexes, and the like. Useful cationic dyes as counter ions may be cationic methine, polymethine, triarylmethine, indolin, thiazine, xanthene, oxazine or acridine dyes. Quaternary ammonium groups useful as counter ions may be trimethylcetylammonium, cetylpyridinium and tetramethylammonium. Other lipophilic cations may include pyridinium, phosphonium and sulfonium. Cationic transition metal coordination complexes that may be useful as counter ions include pyridine, 2,2'-bipyridine, 4,4'-dimethyl-2,2'-bipyridine, 1,10-phenanthroline, 3,4, Complexes of cobalt, ruthenium, osmium, zinc, iron, and iridium with ligands such as 7,8-tetramethylphenanthroline, 2,4,6-tri (2-pyridyl-s-triazine) and the same ligands Can be.

Borate photoinitiators are described, for example, in US Pat. Nos. 4,772,530 to Gottschalkea et al., 4,954,414 to Adair et al. 5,057,393 to Shanklin et al.

Preferred visible-derived initiators are camphorquinone and optionally diaryliodonium simple salts or metal complex salts, chromophore-substituted halo in combination with a suitable hydrogen donor (e.g., an amine as described above for the first initiator system). Methyl-s-triazine or halomethyl oxadiazole. Particularly preferred visible-induced photoinitiators are combinations of alpha-diketones, for example camphorquinone and optionally diaryliodonium salts in combination with additional hydrogen donors, for example diphenyliodonium chloride, bromine Cargoes, iodides or hexafluorophosphates. Preferred ultraviolet-induced polymerization initiators include ketones such as benzyl and benzoin, acyloin and acyloin ethers. Preferred UV-induced polymerization initiators are 2,2-dimethoxy-2-phenylacetophenone available under the tradename IRGACURE 651 of Ciba Specialty Chemicals Corp., Terrytown, NY, USA. And benzoin methyl ether (2-methoxy-2-phenylacetophenone).

The initiator system is present in an amount sufficient to provide the desired rate of cure (eg, polymerization and / or crosslinking). In the case of a photoinitiator, this amount will depend in part on the light source, the thickness of the layer exposed to the radiant energy and the extinction coefficient of the photoinitiator. Preferably, the initiator system is present in a total amount of at least 0.01% by weight, more preferably at least 0.03% by weight, and most preferably at least 0.05% by weight, based on the weight of the composition. Preferably, the initiator system is present in a total amount of up to 10% by weight, more preferably up to 5% by weight and most preferably up to 2.5% by weight based on the weight of the composition.

Filling system

The composition of the present invention may optionally comprise a filler system (ie, at least one filler). Fillers for use in the filler system can be selected from a wide variety of common fillers for incorporation into the resin system. Preferably, the filler system comprises one or more common materials suitable for incorporation into the compositions used for medical applications, for example fillers currently used in dental restorative compositions. Therefore, the filler system used in the composition of the present invention is incorporated in the resin system.

The filler may be particulate or fibrous in nature. Particulate fillers may generally be defined as having a length to width ratio or aspect ratio of 20: 1 or less, more generally 10: 1 or less. Fibers can be defined as having an aspect ratio of greater than 20: 1 or more generally greater than 100: 1. The shape of the particles can vary from sphere to more planar, such as ellipses or flakes or discs. The macroscopic properties can depend largely on the shape of the filler particles, in particular the uniformity of the shape.

Preferred particulate fillers are finely divided and have an average particle size (preferably diameter) of less than 10 micrometers (ie, microns).

Preferred micron-sized particulate fillers have an average particle size of at least 0.2 microns to 1 micrometer or less. The average primary particle size of the nanoscale particles is less than 200 nm (0.2 micron). The filler may have a particle size distribution of single or multimodal (eg bimodal).

Micron-sized particles are very efficient at improving post cure abrasion. In contrast, nanoscale fillers are commonly used as viscosity and thixotropic modifiers. It is known that due to their small size, large surface area and associated hydrogen bonds these materials gather into aggregated reticular bodies. This type of material (“nanoscale” material) has an average primary particle size (ie, the largest dimension of the non-aggregated material, eg, diameter), up to 1000 nanometers (nm). Preferably, the average primary particle size of the nanoscale particulate material is at least 2 nanometers (nm), preferably at least 7 nm. Preferably, the average primary particle size of the nanoscale particulate material is at most 50 nm, more preferably at most 20 nm. The average surface area of such fillers is preferably at least 20 square meters per gram (m ² / g), more preferably at least 50 m ² / g, most preferably at least 100 m ² / g.

The filler system may comprise an inorganic material. It may also include crosslinked organic materials that are insoluble in the polymerizable resin and are optionally filled with inorganic fillers. The filler system is preferably generally nontoxic and suitable for use in the oral cavity.

Suitable fillers can be radiopaque, radiopaque or radiopaque. Fillers used in the dental field are typically ceramic in nature. Examples of suitable inorganic fillers include quartz, nitrides (eg silicon nitride), for example Ce, Sb, Sn, Zr, Sr, Ba or Al, colloidal silica, feldspar, borosilicate glass, kaolin, talc, titania And glass derived from zinc glass, zirconia-silica fillers; And low or Mohs hardness fillers such as those described in US Pat. No. 4,695,251 (Randklev). Examples of suitable organic filler particles include filled or unfilled ground polycarbonate and polyepcite and the like. Preferred filler particles are non-glass microparticles of the type described in US Pat. No. 4,503,169 (Randklev), quartz and silica up to micron. Combinations of fillers made from organic and inorganic materials as well as mixtures of these fillers may also be used.

Optionally, the surface of the filler particles may be treated with a surface treatment agent such as a silane coupling agent in order to strengthen the bond between the filler system and the resin system. The coupling agent may be functionalized with reactive curing groups such as acrylates and methacrylates.

The filler particles used to impart a non-covalent structure can be composed of silica, alumina, zirconia, titania or mixtures of these materials with each other or mixtures of these materials with carbon. In their synthetic state, the materials are generally hydrophilic due to the presence of surface hydroxyl groups. However, the materials can also be modified by treatment with a suitable agent such as alkyl silanes to modify the properties. For example, the surface of the filler particles can be made neutral, hydrophobic or reactive, depending on the desired properties. Fumed silica is a preferred compound for imparting self-support due to its low price, commercial availability and wide range of available surface properties.

Other suitable fillers are International Application Publication Nos. 01/30305 (Zhang et al.), 01/30306 (Windisch et al.), 01/30307 (Zhang et al.) And 03/063804. Wu et al., As well as US Pat. No. 6,387,981 to Zhang et al. And 6,572,693 to Wu et al. Filler components described in these references include nanosized silica particles, nanosized metal oxide particles, and combinations thereof. The nanofillers are also all US Patent Application No. 10 / 847,782, entitled "Nanofiller-Containing Dental Compositions and Related Methods," filed May 17, 2004, entitled "Nanozirconia Filler-Containing Dental Compositions." US Pat. No. 10 / 847,781 and US Pat. No. 10 / 847,803, entitled "Use of Nanoparticles for Adjusting the Refractive Index of Dental Compositions."

Preferably, the total amount of filler system is greater than 50 wt%, more preferably greater than 60 wt%, most preferably greater than 70 wt%, based on the total weight of the composition. If the filler system comprises fibers, the fibers are present in an amount of less than 20% by weight based on the total weight of the composition. Preferably, the total amount of filler system is at most 95% by weight, more preferably at most 80% by weight, based on the total weight of the composition.

Optional additives

The composition of the present invention may contain a surfactant system, i.e., one surfactant or a mixture of two or more surfactants. Such surfactants may be nonionic, anionic or cationic. The surfactant (s) may or may not be copolymerizable.

The composition may further comprise colorants (e.g. pigments or dyes commonly used for color control), flavorings, pharmaceuticals, stabilizers (such as butylated hydroxy toluene (BHT)), viscosity modifiers, diluents, flow control additives And optional agents such as thixotropic agents, antimicrobials and polymer thickeners. If desired, various combinations of the above optional additives can be used. Such formulations may optionally include reactive functional groups to copolymerize with the resin.

Preferably, the total amount of optional ingredients is up to 5.0 weight percent, more preferably up to about 2.5 weight percent, most preferably up to 1.5 weight percent based on the total weight of the composition.

How to use

The carbosilane containing monomers described above can preferably be used as components in dental compositions which are curable through radical polymerization of unsaturated groups, especially (meth) acrylate groups. The dental composition of the present invention can be used, for example, as a dental restoration or as a prefabricated denture design. Examples of restorative materials include dental composites and amalgams. Examples of prefabricated denture designs include crowns, bridges, veneers, inlays, onlays, columns and pins and the like.

The compositions of the present invention may also be shaped (eg molded) in various forms such as three-dimensional shapes, preformed sheets, arched plates, ropes, buttons and woven or nonwoven webs, and the like. The composition can be shaped (to form a first shape) in a variety of ways, including, for example, extrusion, injection molding, compression molding, thermoforming, vacuum molding, compression, calendering, and web processing using rollers. Typically, semifinished shapes are formed using templates of positive and negative patterns. Shaped forms can be used, for example, as dental crowns, dental bone dishes and orthodontic appliances. Examples of orthodontic appliances include tongue anchors, space anchors, hooks, buttons, splints, and bases for orthodontic supports.

Although the objects and advantages of the present invention will be further described in the following examples, the specific materials and amounts thereof recited in the following examples, as well as other conditions and details, should not be considered as unduly limiting the invention. Unless otherwise indicated, all parts and percentages are by weight, all water is deionized water, and all molecular weights are weight average molecular weight.

Compressive strength (CS) test method

The compressive strength of the test sample was determined by the American National Standards Institute / American Standards Association (ANSI / ASA) specification No. It was measured according to 27 (1993). The samples were packed in 4 mm (mm) (inner diameter) glass tubes (samples were heated if necessary for packing), the tubes were sealed with silicone rubber stoppers and pressed for 5 minutes with about 0.28 megapascals (Mpa) in the axial direction. . It was then exposed to two VISILUX Model 2500 blue light guns (3M, St. Paul, Minn., USA) arranged face-to-face, photocured for 90 seconds, followed by dentacolor XS units (180 seconds) Dentacolor XS unit) (Kulzer, Inc., Germany). The cured sample was cut with a diamond saw to form an 8 mm long cylindrical plug for the measurement of compressive strength. The stopper was stored in distilled water at 37 ° C. for 24 hours prior to testing. Measurements were performed using a 10 kilonewton (kN) load cell at a crosshead speed of 1 mm / min in an Instron tester (Instron 4505, Instron, Canton, Mass.). Five cylinders of cured samples were prepared and measured, and the results were reported in MPa as the average of five measurements.

diameter  The tensile strength ( DTS Test method

The tensile strength of the diameter of the test sample is ANSI / ASA Specification No. It was measured according to 27 (1993). Samples were pressed into glass tubes and cured as described for the CS test method. The cured sample was then cut into 2.2 mm thick disks for the measurement of DTS. Discs were stored in water as described above and measured using a 10 (kN) load cell at a crosshead speed of 1 mm / min in an Instron tester (Instron 4505, Instron). Five discs of the cured sample were prepared and measured, and the results were recorded in MPa as the average of five measurements.

Polymerization Shrinkage Test Method

Polymeric shrinkage of the test samples was measured using the Watts shrinkage test procedure (D.C. Watts et al., Meas. Sci. Technol., 2, 788-794 (1991)). This test was performed using a 3 mm glass slide.

Viscosity Test Method

The viscosity of the test sample was measured using an AR 2000 flow meter (TA Instruments, New Castle, Delaware, USA). About 1.2 grams (g) of sample was placed between the stage (25 ° C.) and a 40 mm aluminum plate. The plate was rotated according to the stepwise flow procedure of log shear force gradient from 1 to 1000 Pa (total 10 data points). Viscosity results were reported in centipoise (cP) as the mean value of 10 data points at 25 ° C.

Abbreviations, descriptions and suppliers of substances

Abbreviation Description and Source of Substance BHT 2,6-di-tert-butyl-4-methylphenol (Sigma-Aldrich, St. Louis, MO) Bisgma 2,2-bis [4- (2-hydroxy-3-methacryloyloxypropoxy) phenyl] propane CAS No. 1565-94-2 CPQ Campoquinone (Sigma-Aldrich) EDMAB Ethyl 4- (N, N-dimethylamino) benzoate (Sigma-Aldrich) STZ Silane-treated zirconia-silica fillers prepared as described in US Pat. No. 6,624,211 (Karim)  UDMA Diurethane Dimethacrylate (ROHAMERE 6661-0, Monomer-Polymer & Dajac Labs, Inc., Pisterville, Pennsylvania, USA) BisEMA-6 6 molar ethoxylated bisphenol A dimethacrylate (Sartomer CD541, Sartomer, Exton, Pa.)  DPIHFP Diphenyl Iodonium Hexafluorophosphate (Johnson Matthey, Alpha Aesar Division, Ward Hill, Mass.)  Benzotriazole 2- (2-hydroxy-5-methacryloxyethylphenyl) -2H-benzotriazole (Ciba Specialty Chemicals, Terrytown, NJ) TEGDMA Triethylene Glycol Dimethacrylate (Sigma-Aldrich) TAC Tricyclo [5.2.1.0 ^2,6 ] decanedimethanol diacrylate (Sigma-Aldrich)

Example  One

Carbosilane Oligomer  Synthesis (Scheme 4; Ar  = 1,4-double substitution Phenyl )

Glycerol diallyl ether (TCI America, Portland, OR) (30.0O g, 0.17 mol (mol)), methacrylic anhydride (Sigma-Aldrich) (29.55 g, 0.19 mmol (mmol)), triethylamine ( A mixture of Alpha Azure, Ward Hill, Mass., USA (17.76 g, 0.17 mol), 4-dimethylaminopyridine (Sigma-Aldrich) (1.05 g, 8.6 mmol), and tetrahydrofuran (70 ml) was prepared at room temperature 48 Stir for hours. An additional dose of 4-dimethylaminopyridine (1.05 g, 8.6 mmol) was added and the mixture was stirred at rt for 48 h. The reaction mixture was concentrated in vacuo and diluted with ethyl acetate (400 ml). The mixture was extracted with saturated aqueous sodium bicarbonate (200 ml) and three times saturated aqueous sodium chloride (100 ml). The organic phase was dried over MgSO ₄ and concentrated in vacuo. The residue was distilled under reduced pressure and two fractions collected (0.15 mm Hg, 20 Pascal, 7.48 g at 60-80 ° C. and 0.15 mm Hg, 20 Pascal, 8.57 g at 80-85 ° C.). The higher boiling fraction was combined with 4.6 g of the lower boiling fraction and purified by column chromatography on silica gel (30 wt% ethyl acetate in hexane) to give 2-methylacrylic acid 2-allyloxy-1-allyloxy as colorless oil. Methyl-ethyl ester (8.90 g) was obtained.

1,4-bis-dimethylsilylbenzene (Gelest, Tullytown, Pa.) (1.52 g, 7.9 mmol), 2-methylacrylic acid 2-allyloxy-1-allyloxymethyl-ethyl ester (2.88 g, 12 mmol), toluene (10 ml), and a mixture of two drops of a solution of the platinum-divinyltetramethyldisiloxane complex (gelist) in xylene were mixed at room temperature for 90 minutes. The mixture was loaded onto a silica gel column and eluted with a mixture of ethyl acetate (40 vol%) in hexane (60 vol%). The solvent was evaporated to give the product (4.20 g) as an oil. The viscosity of the oil was 812 cP.

Characterization of the oil by ¹ H nuclear magnetic resonance spectroscopy (NMR) and infrared spectroscopy (IR) spectroscopy was consistent with the structure shown in Scheme 4 (Ar = 1,4-disubstituted phenyl).

Example  2

Carbosilane Oligomer  Synthesis (Scheme 4; Ar  = 1,3-double substitution Phenyl )

A solution of 1,3-dibromobenzene (Sigma-Aldrich) (30.00 g, 0.13 mol) in anhydrous tetrahydrofuran (65 ml) was added to chlorodimethylsilane (Sigma-Aldrich) (40.10 g, 0.42 mol), tetrahydroante To the mixture of hydrofuran (100 ml), and magnesium flakes (24.31 g, 0.13 mol) was added dropwise over an hour. After complete addition, the mixture was refluxed for 2 hours. Then the solvent was removed under vacuum and the residue was diluted with hexane (200 ml). The solid was washed twice with hexane (200 ml) and filtered. The combined hexane solution was concentrated under vacuum and the residue was distilled under reduced pressure (2 mm Hg, 47-49 ° C. in 267 Pascal) to give 1,3-bis-dimethylsilylbenzene (17.41 g) as a colorless oil.

1,3-bis-dimethylsilylbenzene (1.63 g, 8.4 mmol), 2-methylacrylic acid 2-allyloxy-1-allyloxymethyl-ethyl ester (2.52 g, 12 mmol), toluene (10 ml), and xylene A mixture of two drops of a solution of the platinum-divinyltetramethyldisiloxane complex in water was mixed at room temperature for 90 minutes. The mixture was loaded onto a silica gel column and eluted with a mixture of ethyl acetate (40 vol%) in hexane (60 vol%). The solvent was evaporated to give the product (3.47 g) as an oil. The viscosity of the oil was 2277 cP. Characterization of the oil by ¹ H NMR and IR spectroscopy was consistent with the structure shown in Scheme 4 (Ar = 1,3-disubstituted phenyl).

Example  3

Carbosilane Oligomer  Synthesis (Scheme 3; molar ratio A)

Bisphenol A (Sigma-Aldrich) (16.78 g, 74 mmol), allyl bromide (Sigma-Aldrich) (24.00 g, 200 mmol), potassium carbonate (Sigma-Aldrich) (30.00 g, 217 mmol), 18-crown-6 A mixture of (Sigma-Aldrich) (0.10 g), and acetone (250 ml) was stirred by machine at 50 ° C. for 17 hours. The product was then filtered and the filtrate was concentrated in vacuo. The residue was purified by column chromatography on silica gel (10 wt% ethyl acetate in hexane) to give bisphenol A diallyl ether (20.00 g) as a colorless oil.

Solution of platinum-divinyltetramethyldisiloxane complex in bisphenol A diallyl ether (2.00 g, 6.5 mmol), 1,4-bis-dimethylsilylbenzene (2.52 g, 13 mmol), toluene (15 ml), and xylene One drop of the mixture was mixed at room temperature for 90 minutes. Allyl methacrylate (Sigma-Aldrich) (1.64 g, 13 mmol) is added and the mixture is stirred for 3 hours. Then one drop of the platinum-divinyltetramethyldisiloxane complex in xylene was added and the mixture was stirred for an additional 17 hours. The mixture was loaded onto a silica gel column and eluted with a mixture of ethyl acetate (30 vol%) in hexane (70 vol%). The solvent was evaporated to give the product (4.47 g) as a waxy solid. Characterization of the waxy solids by ¹ H NMR and IR spectroscopy was consistent with the structure shown in Scheme 3.

Example  4

Carbosilane Oligomer  Synthesis (Scheme 3; molar ratio B)

Bisphenol A diallyl ether (2.16 g, 7.0 mmol), 1,4-bis-dimethylsilylbenzene (2.52 g, 13 mmol), toluene (15 ml), and the platinum-divinyltetramethyldisiloxane complex in xylene A drop of solution was mixed at room temperature for 90 minutes. Allyl methacrylate (Sigma-Aldrich) (1.50 g, 12 mmol) is added and the mixture is stirred for 3 hours. Then one drop of the platinum-divinyltetramethyldisiloxane complex in xylene was added and the mixture was stirred for an additional 17 hours. The mixture was loaded onto a silica gel column and eluted with a mixture of ethyl acetate (30 vol%) in hexane (70 vol%). The solvent was evaporated to give the product (3.50 g) as a waxy solid. Characterization of the waxy solids by ¹ H NMR and IR spectroscopy was consistent with the structure shown in Scheme 3.

Example  5-12

Polymerizable  Composition

Polymerizable compositions (Examples 5-12) were prepared according to the following general procedure. The photoinitiator / stabilizer component was first dissolved in BisGMA and the resulting mixture was mixed with other monomer components of the composition. (BisEMA-6, UDMA, TEGDMA, and carbosilane oligomer (selected from Examples 1-4)). The concentration of photoinitiator / stabilizer component used (parts per 100 parts of BisGMA (ie resin), phr) was CPQ (0.176 phr), EDMAB (1.55 phr), DPIHFP (0.517 phr), BHT (0.155 phr) and benzotriazole (1.552 phr). The blended monomer and filler ingredients STZ are weighed into a MAX 20 plastic mixing cup with screw caps (Flakteck, Randham, SC, USA), close the cup and place in an oven at 85 ° C. for 30 minutes. Heated. The cup was placed in a DAC 150 FV Speed Mixer (Plactech) and rotary mixed at 3000 rpm for 1 minute. The cup was then reheated at 85 ° C. for 30 minutes and then mixed for another 1 minute at 3000 rpm to obtain the final blended composition. The amount of components in each example is shown in Table 1 below. The weight of BisGMA includes the weight of the photoinitiator / stabilizer component.

Example Carbosilane Oligomers (Examples) Carbosilane oligomer (g) BisGMA (g) BisEMA-6 (g) UDMA (g) TEGDMA (g) TAC (g) STZ (g) 5 One 0.36 0.42 0.49 0.14 0 0 6.37 6 One 0.56 0.43 0.21 0 0.07 0 6.37 7 2 0.35 0.42 0.49 0.15 0 0 6.37 8 3 0.40 1.64 0 0 0 0 8.01 9 3 0.40 1.20 0 0 0 0.40 8.01 10 3 0.40 0.40 0.56 0.56 0.08 0 8.01 11 4 0.40 1.60 0 0 0 0 8.01 12 4 0.40 1.20 0 0 0 0.40 8.01

Evaluation of the properties of the composition

Polymerization shrinkage, compressive strength and diameter tensile strength of the composition samples (Examples 5-12) were evaluated according to the test methods described herein. The results are shown in Table 2 below.

Example Shrinkage (% by volume) Compressive strength, MPa (standard deviation) Diameter Tensile Strength, MPa (Standard Deviation) 5 1.58 Do not test Do not test 6 1.48 Do not test Do not test 7 1.40 Do not test Do not test 8 Do not test 267 (14) 47 (6) 9 Do not test 272 (24) 62 (9) 10 Do not test 305 (22) 72 (14) 11 Do not test 266 (9) 47 (7) 12 Do not test 297 (7) 61 (10)

The complete disclosures of patents, patent documents, and publications cited herein are hereby incorporated by reference in their entirety as if each were individually incorporated. Various modifications and variations of the present invention will be apparent to those skilled in the art without departing from the spirit and scope of the invention. It is to be understood that the invention is not unduly limited by the embodiments and examples described herein and that such examples and embodiments are provided by way of example only, and the scope of the invention is limited only by the claims that follow. do.

Claims (14)

No Si-O bonds, More than one repeat unit, At least four Si-arylene bonds, At least one (meth) acrylate residue, Si-H residue, or both, and Two silicon atoms separated by one arylene group in each repeating unit Carbosilane-containing polymer comprising a. The polymer of claim 1 comprising at least four silicon atoms. The polymer of claim 1 or 2 comprising at least two ethylenically unsaturated moieties. The polymer according to any one of claims 1 to 3, wherein the number average molecular weight is 20,000 grams or less per mole. The polymer according to any one of claims 1 to 4, wherein the polymer is of formula (I). <Formula I>

Where Each Ar is independently an arylene group, Each R is independently an aliphatic group, a cycloaliphatic group, or a combination thereof, optionally comprising one or more O, Br, Cl or Si atoms, or a combination thereof, and which may include a bicyclic group, Each Q is independently an aliphatic group, a cycloaliphatic group, an aromatic group, or a combination thereof, which optionally includes a bond, or optionally one or more O, Br, Cl, or Si atoms or combinations thereof, Optionally comprises at least one (meth) acrylate group, Each R ¹ To R ⁴ groups are independently aliphatic groups, cycloaliphatic groups, aromatic groups or combinations thereof, optionally substituted with one or more (meth) acrylate groups, Each R ⁵ And R ⁶ groups are independently hydrogen, aliphatic groups, optionally substituted with one or more (meth) acrylate groups, cycloaliphatic groups, aromatic groups or combinations thereof. n is greater than one. 6. The polymer of claim 5, wherein the polymer is of formula II. <Formula II>

Where Each Ar is independently an arylene group, Each Q is independently an aliphatic group, a cycloaliphatic group, an aromatic group, or a combination thereof, which optionally includes a bond, or optionally one or more O, Br, Cl, or Si atoms or combinations thereof, Is optionally substituted with one or more (meth) acrylate groups, Each R ¹ To R ⁴ group is methyl, Each R ⁵ And the R ⁶ groups are independently hydrogen or optionally an aliphatic group, a cycloaliphatic group, an aromatic group, optionally containing one or more O, Br, Cl or Si atoms or a combination thereof, and optionally substituted with one or more (meth) acrylate groups Or a combination thereof. n is greater than one. Dental composition comprising the carbosilane-containing polymer according to any one of claims 1 to 6 and the initiator system. The dental composition of claim 7 wherein the carbosilane-containing polymer is crystalline. The dental composition of claim 7 or 8 further comprising a filler system. 10. The additive according to any one of claims 7 to 9, wherein the additive is selected from the group consisting of colorants, flavors, pharmaceuticals, stabilizers, viscosity modifiers, diluents, flow control additives, thixotropic agents, antibacterial agents, polymeric thickeners and combinations thereof. Dental composition further comprising. The dental composition of claim 7 further comprising a polymerizable component different from the carbosilane containing polymer. 12. The dental composition of claim 11 wherein the polymerizable component different from the carbosilane-containing polymer is a (meth) acrylate component. The dental composition according to claim 7, wherein the polymerization shrinkage is 2.0% or less based on the volume of the composition before curing. The dental composition of claim 7 comprising 1% to 60% by weight carbosilane component, based on the total weight of the composition.