# US 2019/0167533 A1 · Dental materials based on urethane-group-containing vinylcyclopropane derivatives

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- Number: US 2019/0167533 A1
- Document ID: US20190167533A1
- Status: Published application
- Kind: A1
- Application number: 16/322,827
- Filed: 2017-08-01
- Published: 2019-06-06
- Earliest claimed: 2016-08-03
- Assignees: Ivoclar Vivadent AG
- Applicants: Ivoclar Vivadent AG
- Inventors: Norbert MOSZNER; Yohann CATEL; Urs Karl FISCHER; Sven TAUSCHER
- Web page: https://patentgrep.com/patent/US20190167533A1

## CPC

- A61K 6/887: Compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C08F 22/14: Esters having no free carboxylic acid groups
- C08L 35/02: Homopolymers or copolymers of esters (C08L35/06, C08L35/08 take precedence)
- C08L 2203/02: for biomedical use
- A61K: PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES (devices or methods specially adapted for bringing pharmaceutical products into particular physical or administering forms A61J3/00; chemical aspects of, or use of materials for deodorisation of air, for disinfection or sterilisation, or for bandages, dressings, absorbent pads or surgical articles A61L; soap compositions C11D)
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)

## Abstract

Vinylcyclopropane of general formulae I in which X, Y in each case are O or NH, wherein X and Y cannot have the same meaning, R1 is a linear or branched C1-C8-alkyl radical, which can be interrupted by O, S, an ester group or a urethane group, R2 is a linear or branched C2-C10-alkylene radical, which can be interrupted by O, S, an ester group or a urethane group, R3 is a hydrocarbon radical with 1 to 20 carbon atoms, which additionally can contain one or more N, O or S atoms, and n is 1, 2, 3 or 4, preferably 1 or 2. The vinylcyclopropanes are characterized by a low shrinkage and a high reactivity on radical polymerization and are suitable in particular for the preparation of dental materials.

## Claims

### Claim 1

A vinylcyclopropane of general formulae I
in which
X, Y in each case are O or NH, wherein X and Y cannot have the same meaning,
R1 is a linear or branched C1-C8-alkyl radical, which can be interrupted by O, S, an ester group or a urethane group,
R2 is a linear or branched C2-C10-alkylene radical, which can be interrupted by O, S, an ester group or a urethane group,
R3 is a hydrocarbon radical with 1 to 20 carbon atoms, which additionally can contain one or more N, O or S atoms, and
n is 1, 2, 3 or 4.

### Claim 2 (depends on 1)

The vinylcyclopropane according to claim 1,
in which R3 is an aliphatic linear or branched C1-C20-hydrocarbon radical, which can be interrupted by O, S or an ester group, an alicyclic or aromatic C6-C14-radical or an aromatic or non-aromatic heterocyclic radical, which can contain 4 to 20 carbon atoms and 1 to 6 heteroatoms, which are selected from N, O and/or S atoms, wherein the cyclic radicals can be mono- or polycyclic groups and wherein R3 can also be formed by a combination of the named radicals.

### Claim 3 (depends on 1)

The vinylcyclopropane according to claim 1, in which the variables have the following meanings:
X, Y in each case O or NH, wherein X and Y cannot have the same meaning,
R1 a branched or linear C1-C4-alkyl radical,
R2 a branched or linear C2-C4-alkyl radical,
R3 an aliphatic linear or branched C1-C20-hydrocarbon radical, an aromatic C6-C14 radical, an aromatic or non-aromatic heterocyclic radical, which contains 4 to 12 carbon atoms and 1 to 2 heteroatoms, which are selected from N or O atoms, an alicyclic C6-C12-hydrocarbon radical, wherein in all cases the cyclic radicals can be mono- or polycyclic groups, or an aliphatic-aromatic C7-C20 radical,
n 1 or 2.

### Claim 4 (depends on 1)

A dental material, which comprises at least one vinylcyclopropane according to claim 1.

### Claim 5 (depends on 4)

The dental material according to claim 4, which additionally comprises at least one further radically polymerizable monomer and an initiator for the radical polymerization.

### Claim 6 (depends on 5)

The dental material according to claim 5, which comprises, as additional monomer, at least one compound, which is selected from 1,1-di(ethoxycarbonyl)- or 1,1-di(methoxycarbonyl)-2-vinylcyclopropane, bis(2-vinylcyclopropane-1-carboxylic acid ethyl ester-1-carbonamido)-2,2-dimethyl-4-methylhexane, 1,8-bis(2-vinylcyclopropane-1-carboxylic acid ethyl ester-1-carbonyloxy)-3,6-dioxaoctane (VCP 5), the esters of 1-ethoxycarbonyl- or 1-methoxycarbonyl-2-vinylcyclopropanecarboxylic acid with ethylene glycol, 1,1,1-trimethylolpropane, 1,4-cyclohexanediol or resorcinol, bis-(2-vinyl-1,1-dicarboxylic acid monoethyl ester)resorcinyl ester (VCP 4), bicyclic cyclopropane derivatives, 2-(bicyclo[3.1.0]hex-1-yl)acrylic acid methyl or ethyl ester or the disubstitution products in 3-position thereof, (3,3-bis(ethoxy-carbonyl)-bicyclo-[3.1.0]-hex-1-yl)acrylic acid methyl or ethyl ester.

### Claim 7 (depends on 6)

The dental material according to claim 6, which contains, as additional monomer, at least one mono- or polyfunctional (meth)acrylic acid derivative, which is selected from methyl, ethyl, 2-hydroxyethyl, butyl, benzyl, tetrahydrofurfuryl or isobornyl (meth)acrylate, p-cumylphenoxyethylene glycol methacrylate (CMP-1E), bisphenol A di(meth)acrylate, bis-GMA (an addition product of methacrylic acid and bisphenol A diglycidyl ether), ethoxylated or propoxylated bisphenol A dimethacrylate, bisphenol A dimethacrylate 2-[4-(3-methacryloyloxyethoxyethyl)phenyl]-2-[4-(3-methacryloyloxyethyl)phenyl]propane (SR-348c) with 3 ethoxy groups, 2,2-bis[4-(2-(meth)acryloxypropoxy)phenyl]propane, UDMA (an addition product of 2-hydroxyethyl methacrylate (HEMA) and 2,2,4-trimethylhexamethylene diisocyanate), TMX-UDMA (an addition product of a mixture of HEMA and hydroxypropyl methacrylate (HPMA) with α,α,α′,α′-tetramethyl-m-xylylene diisocyanate (TMXDI)), di-, tri- or tetraethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, glycerol di- and trimethacrylate, 1,4-butanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate (D3MA), 1,12-dodecanediol di(meth)acrylate and acid-group-containing monomers.

### Claim 8 (depends on 4)

The dental material according to claim 4, which additionally comprises at least one particulate filler.

### Claim 9 (depends on 4)

The dental material according to claim 4, which additionally comprises at least one additive, which is selected from solvents, stabilizers, flavouring agents, dyes, microbiocidal active ingredients, fluoride-ion-releasing additives, optical brighteners, plasticizers and/or UV absorbers.

### Claim 10 (depends on 4)

Dental material according to claim 4, which comprises
a) 2 to 95 wt.-% of at least one vinylcyclopropane of general formula I,
b) 0.01 to 5 wt.-% of at least one initiator for the radical polymerization,
c) 0 to 80 wt.-%, of other monomer(s), and optionally
d) 0 to 85 wt.% filler(s),
in each case relative to the total mass of the material.

### Claim 11 (depends on 10)

The dental material according to claim 10, which comprises 0 to 40 wt.-% filler(s), for use as coating material, or which comprises 10-70 wt.-% filler(s), for use as cement, or which comprises 10-85 wt.-% filler(s), for use as filling composite.

### Claim 12 (depends on 11)

The dental material according to claim 11 for use as filling material, which contains
a) 2 to 60 wt.-% of at least one vinylcyclopropane of general formula I,
b) 0.1 to 3 wt.-% of at least one initiator for the radical polymerization,
c) 0 to 50 wt.-% of other monomer(s), and
d) 10 to 85 wt.-% filler(s),
in each case relative to the total mass of the material.

### Claim 13 (depends on 1)

A method of using a dental material which comprises at least one vinylcyclopropane according to claim 1 comprising manufacturing or repairing dental restorations, prostheses, artificial teeth, inlays, onlays, crowns or bridges.

### Claim 14 (depends on 1)

A method of using a dental material which comprises at least one vinylcyclopropane according to claim 1 comprising manufacturing molded articles by a generative process.

### Claim 15

(canceled)

### Claim 16 (depends on 9)

The dental material according to claim 9,
wherein the solvents comprise water, ethanol or a mixture thereof and the stabilizers comprise polymerization stabilizers.

### Claim 17 (depends on 4)

The dental material according to claim 4, which comprises
a) 2 to 90 wt.-% of at least one vinylcyclopropane of general formula I,
b) 0.1 to 3.0 wt.-% of at least one initiator for the radical polymerization,
c) 0 to 60 wt.-% of other monomer(s), and optionally
d) 0 to 80 wt.-% filler(s),
in each case relative to the total mass of the material.

### Claim 18 (depends on 4)

The dental material according to claim 4, which comprises
a) 10 to 85 wt.-% of at least one vinylcyclopropane of general formula I,
b) 0.2 to 2 wt.-% of at least one initiator for the radical polymerization comprising a photoinitiator,
c) 0 to 50 wt.-% of other monomer(s), and optionally
d) 0 to 80 wt.-% filler(s),
in each case relative to the total mass of the material.

### Claim 19 (depends on 11)

Dental material according to claim 11 for use as filling material, which comprises
a) 5 to 60 wt.-% of at least one vinylcyclopropane of general formula I,
b) 0.2 to 3.0 wt.-% of at least one initiator for the radical polymerization which comprises a photoinitiator,
c) 0 to 40 wt.-% of other monomer(s), and
d) 10 to 80 wt.-% filler(s),
in each case relative to the total mass of the material.

### Claim 20 (depends on 11)

Dental material according to claim 11 for use as filling material, which comprises
a) 10 to 60 wt.-% of at least one vinylcyclopropane of general formula I,
b) 0.2 to 1 wt.-% of at least one initiator for the radical polymerization,
c) 0 to 30 wt.-% of other monomer(s), and
d) 10 to 80 wt.-% filler(s),
in each case relative to the total mass of the material.