Hydrolysable and polymerizable oxetane silanes

• US 6,284,898 B1
• Filed: 06/09/2000
• Issued: 09/04/2001
• Est. Priority Date: 03/25/1997
• Status: Expired due to Term

• Current Assignee: Ivoclar AG
• Original Assignee: Ivoclar AG
• Inventors: Voelkel, Thomas, Rheinberger, Volker, Moszner, Norbert, Stein, Sabine
• Primary Examiner(s): Trinh, Ba K.
• Application Number:
  US09/591,358
• Time in Patent Office: 452 Days
• Field of Search: 549/214, 549/510, 549/511, 522/168, 522/172
• US Class Current: 549/214
• CPC Class Codes: A61K 6/20 Protective coatings for natural or artificial teeth, e.g. sealings, dye coatings or varnish
• CPC Class Codes: A61K 6/30 Compositions for temporarily or permanently fixing teeth or palates, e.g. primers for dental adhesives
• CPC Class Codes: A61K 6/896 Polyorganosilicon compounds
• CPC Class Codes: C07F 7/1804 Compounds having Si-O-C linkages Si-O-acyl linkages C07F7/1896
• CPC Class Codes: C08G 77/22 containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen C08G77/045 takes precedence
• CPC Class Codes: C08G 77/58 Metal-containing linkages C08G77/485 takes precedence
• CPC Class Codes: C08L 83/12 containing polyether sequences

Abstract

Polymerizable and hydrolysable oxetane silanes and in particular silicic acid condensates which can be prepared therefrom are described, which exhibit only a low volume shrinkage on polymerization and produce polymers with high mechanical strength and therefore can be used above all as dental material or constituent thereof.

Claims

1. A dental material comprising a polymer of an oxetane silane of the general formula (I) and stereoisomers thereof

in which the variables R⁰, R¹, R², R³, R⁴, R⁵, R⁶, X, Y, a, b, c, and x, unless otherwise stated, independently of one another have the following meanings:

R⁰=hydrogen or substituted or unsubstituted C₁ to C₁₀ alkyl;

R¹=missing or represents substituted or unsubstituted C₁ to C₁₈ alkylene, C₆ to C₁₈ arylene, C₇ to C₁₈ alkylenearylene, or arylenealkylene, these radicals being able to be interrupted by at least one group selected from the group consisting of ether, thioether, ester, carbonyl, amide, and urethane groups;

R²=missing or represents substituted or unsubstitituted C₁ to C₁₈ alkylene, C₆ to C₁₈ arylene, C₇ to C₁₈ alkylenearylene, or C₇ to C₁₈ arylenealkylene, these radicals being able to be interrupted by at least one group selected from the group consisting of ether, thioether, ester, thioester, carbonyl, amide, and urethane groups or being able to bear these in the terminal position;

R³=missing or represents substituted or unsubstitituted C₁ to C₁₈ alkyl, C₂ to C₁₈ alkenyl, C₆ to C₁₈ aryl, C₇ to C₁₈ alkylaryl, or C₇ to C₁₈ arylalkyl, these radicals being able to be interrupted by at least one group selected from the group consisting of ether, thioether, ester, carbonyl, amide, and urethane groups;

R⁴=missing or represents substituted or unsubstituted —

CHR⁶—

CHR⁶, —

CHR⁶—

CHR⁶—

S—

R⁵—

, —

S—

R⁵—

, —

Y—

CO—

NH—

R⁵—

, or —

CO—

O—

R⁵—

;

R⁵=substituted or unsubstitituted C₁ to C₁₈ alkylene, C₆ to C₁₈ arylene, C₆ to C₁₈ alkylenearylene, or C₆ to C₁₈ arylenealkylene, these radicals being able to be interrupted by at least one group selected from the group consisting of ether, thioether, ester, carbonyl, amide, and urethane groups;

R⁶=hydrogen or substituted or unsubstituted C₁ to C₁₈ alkyl or C₆ to C₁₀ aryl;

X=a hydrolysable group, namely halogen, hydroxy, alkoxy, or acyloxy;

Y=O or S;

a=1, 2, or 3;

b=1, 2, or 3;

c=1 or 2; and

x=1, 2, or 3;

and with the proviso that

(i) a+x=2, 3, or 4 and

(ii) a and/or b 1.

2. A dental material comprising a polymerizable silicic acid condensate of a hydrolysable and polymerizable oxetane silane of the general formula (I) and stereoisomers thereof

in which the variables R⁰, R¹, R², R³, R⁴, R⁵, R,⁶, X, Y, a, b, c, and x, unless otherwise stated, independently of one another have the following meanings:

R⁰=hydrogen or substituted or unsubstituted C₁ to C₁₀ alkyl;

R¹=missing or represents substituted or unsubstituted C₁ to C₁₈ alkylene, C₆ to C₁₈ arylene, C₇ to C₁₈ alkylenearylene, or arylenealkylene, these radicals being able to be interrupted by at least one group selected from the group consisting of ether, thioether, ester, carbonyl, amide, and urethane groups;

R²=missing or represents substituted or unsubstitituted C₁ to C₁₈ alkylene, C₆ to C₁₈ arylene, C₇ to C₁₈ alkylenearylene, or C₇ to C₁₈ arylenealkylene, these radicals being able to be interrupted by at least one group selected from the group consisting of ether, thioether, ester, thioester, carbonyl, amide, and urethane groups or being able to bear these in the terminal position;

R³=missing or represents substituted or unsubstitituted C₁ to C₁₈ alkyl, C₂ to C₁₈ alkenyl, C₆ to C₁₈ aryl, C₇ to C₁₈ alkylaryl, or C₇ to C₁₈ arylalkyl, these radicals being able to be interrupted by at least one group selected from the group consisting of ether, thioether, ester, carbonyl, amide, and urethane groups;

R⁴=missing or represents substituted or unsubstituted —

CHR⁶—

CHR⁶—

, —

CHR⁶—

CHR⁶—

S—

R⁵—

, —

S—

R⁵—

, —

Y—

CO—

NH—

R⁵—

, or —

CO—

O—

R⁵—

;

R⁵=substituted or unsubstitituted C₁ to C₁₈ alkylene, C₆ to C₁₈ arylene, C₆ to C₁₈ alkylenearylene, or C₆ to C₁₈ arylenealkylene, these radicals being able to be interrupted by at least one group selected from the group consisting of ether, thioether, ester, carbonyl, amide, and urethane groups;

R⁶=hydrogen or substituted or unsubstituted C₁ to C₁₈ alkyl or C₆ to C₁₀ aryl;

X=a hydrolysable group, namely halogen, hydroxy, alkoxy, or acyloxy;

Y=O or S;

a=1, 2, or 3;

b=1, 2, or 3;

c=1 or 2; and

x=1, 2, or 3;

and with the proviso that

(i) a+x=2, 3, or 4 and

(ii) a and/or b=1.

3. A dental material comprising a polymer of the silicic acid condensate according to claim 2.

4. A method of producing a dental material comprising:

providing a hydrolysable and polymerizable oxetane silane of the general formula (I) and stereoisomers thereof

in which the variables R⁰, R¹, R², R³, R⁴, R⁵, R⁶, X, Y, a, b, c, and x, unless otherwise stated, independently of one another have the following meanings;

R⁰=hydrogen or substituted or unsubstituted C₁ to C₁₀ alkyl;

R¹=missing or represents substituted or unsubstituted C₁ to C₁₈ alkylene, C₆ to C₁₈ arylene, C₇ to C₁₈ alkylenearylene, or arylenealkylene, these radicals being able to be interrupted by at least one group selected from the group consisting of ether, thioether, ester, carbonyl, amide, and urethane groups;

R²=missing or represents substituted or unsubstitituted C₁ to C₁₈ alkylene, C₆ to C₁₈ arylene, C₇ to C₁₈ alkylenearylene, or C₇ to C₁₈ arylenealkylene, these radicals being able to be interrupted by at least one group selected from the group consisting of ether, thioether, ester, thioester, carbonyl, amide, and urethane groups or being able to bear these in the terminal position;

R³=missing or represents substituted or unsubstitituted C₁ to C₁₈ alkyl, C₂ to C₁₈ alkenyl, C₆ to C₁₈ aryl, C₇ to C₁₈ alkylaryl, or C₇ to C₁₈ arylalkyl, these radicals being able to be interrupted by at least one group selected from the group consisting of ether, thioether, ester, carbonyl, amide, and urethane groups;

R⁴=missing or represents substituted or unsubstituted —

CHR⁶—

CHR⁶—

, —

CHR⁶—

CHR⁶—

S—

R⁵—

, —

S—

R⁵—

, —

Y—

CO—

NH—

R⁵—

, or —

CO—

O—

R⁵—

;

R⁵=substituted or unsubstitituted C₁ to C₁₈ alkylene, C₆ to C₁₈ arylene, C₆ to C₁₈ alkylenearylene, or C₆ to C₁₈ arylenealkylene, these radicals being able to be interrupted by at least one group selected from the group consisting of ether, thioether, ester, carbonyl, amide, and urethane groups;

R⁶=hydrogen or substituted or unsubstituted C₁ to C₁₈ alkyl or C₆ to C₁₀ aryl;

X=a hydrolysable group, namely halogen, hydroxy, alkoxy, or acyloxy;

Y=O or S;

a=1, 2, or 3;

b=1, 2, or 3;

c=1 or 2; and

x=1, 2, or 3;

and with the proviso that

(i) a+x=2, 3, or 4 and

(ii) a and/or b=1 and

polymerizing the oxetane silane under conditions effective to produce the dental material.

5. A method of producing a dental material comprising:

providing a polymerizable silicic acid condensate of a hydrolysable and polymerizable oxetane silane of the general formula (I) and stereoisomers thereof

in which the variables R⁰, R¹, R², R³, R⁴, R⁵, R⁶, X, Y, a, b, c, and x, unless otherwise stated, independently of one another have the following meanings;

R⁰=hydrogen or substituted or unsubstituted C₁ to C₁₀ alkyl;

R¹=missing or represents substituted or unsubstituted C₁ to C₁₈ alkylene, C₆ to C₁₈ arylene, C₇ to C₁₈ alkylenearylene, or arylenealkylene, these radicals being able to be interrupted by at least one group selected from the group consisting of ether, thioether, ester, carbonyl, amide, and urethane groups;

R²=missing or represents substituted or unsubstitituted C₁ to C₁₈ alkylene, C₆ to C₁₈ arylene, C₇ to C₁₈ alkylenearylene, or C₇ to C₁₈ arylenealkylene, these radicals being able to be interrupted by at least one group selected from the group consisting of ether, thioether, ester, thioester, carbonyl, amide, and urethane groups or being able to bear these in the terminal position;

R³=missing or represents substituted or unsubstitituted C₁ to C₁₈ alkyl, C₂ to C₁₈ alkenyl, C₆ to C₁₈ aryl, C₇ to C₁₈ alkylaryl, or C₇ to C₁₈ arylalkyl, these radicals being able to be interrupted by at least one group selected from the group consisting of ether, thioether, ester, carbonyl, amide, and urethane groups;

R⁴=missing or represents substituted or unsubstituted —

CHR⁶—

CHR⁶—

, —

CHR⁶—

CHR⁶—

S—

R⁵—

, —

S—

R⁵—

, —

Y—

CO—

NH—

R⁵—

, or —

CO—

O—

R⁵—

;

R⁵=substituted or unsubstitituted C₁ to C₁₈ alkylene, C₆ to C₁₈ arylene, C₆ to C₁₈ alkylenearylene, or C₆ to C₁₈ arylenealkylene, these radicals being able to be interrupted by at least one group selected from the group consisting of ether, thioether, ester, carbonyl, amide, and urethane groups;

R⁶=hydrogen or substituted or unsubstituted C₁ to C₁₈ alkyl or C₆ to C₁₀ aryl;

X=a hydrolysable group, namely halogen, hydroxy, alkoxy, or acyloxy;

Y=O or S;

a=1, 2, or 3;

b=1, 2, or 3;

c=1 or 2; and

x=1, 2, or 3;

and with the proviso that

(i) a+x=2, 3, or 4 and

(ii) a and/or b=1 and

polymerizing the silicic acid condensate under conditions effective to produce the dental material.