Ultra-low shrinkage composite resins based on blended nematic liquid crystal monomers
AssigneeThe University of Texas System
InventorsBarry K. Norling, Neera Satsangi
Life of this patent
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Abstract
A novel method of making liquid crystal monomers, novel monomer blends, and novel secondary monomers for use in such blends. The blends remain in a nematic state after additing inorganic filler, and exhibit low cure shrinkage.
Claims180
A method comprising:
- providing a 4-hydroxyl benzoic acid comprising a carboxyl substituent;
- providing an alkylene group comprising an α-hydroxyl group and an ω-halide group;
- condensing said 4-hydroxyl of said benzoic acid with said ω-halide group under conditions effective to produce a hydroxyl terminated alkyloxy comprising said α-hydroxyl group at a first terminus and said carboxyl substituent of said 4-hydroxyl benzoic acid at a second terminus.
A method comprising:
- providing a 4-hydroxyl benzoic acid comprising a carboxyl substituent;
- providing an alkylene group comprising an a-hydroxyl group and an ω-halide group;
- condensing said 4-hydroxyl of said benzoic acid with said ω-halide group under conditions effective to activate said carboxyl group and to produce a hydroxyl terminated alkyloxy comprising said α-hydroxyl group at a first terminus and an activated carboxyl substituent of said 4-hydroxyl benzoic acid at a second terminus;
- reacting a polymerizable group with said first terminus under conditions effective to produce an ethereal benzoic acid comprising said activated carboxyl substituent in a position para- to a polymerizable terminus;
- and,
- providing a hydroquinone comprising a bulky organic group and comprising a first hydroxyl group para- to a second hydroxyl group, at least one of said first hydroxyl group and said second hydroxyl group being an ionically activated hydroxyl group;
- condensing said at least one ionically activated hydroxyl group of said hydroquinone with said activated carboxyl substituent of said ethereal benzoic acid under conditions effective to produce a compound comprising at least two aromatic rings joined by an ester linkage and comprising a polymerizable terminus and a terminus selected from the group consisting of a second polymerizable terminus and said second hydroxyl group of said hydroquinone.
A method comprising:
- providing a 4-hydroxy benzoic acid comprising a carboxyl substituent;
- providing an alkylene group comprising an α-hydroxyl group and an ω-halide group;
- condensing said 4-hydroxyl substituent of said benzoic acid with said ω-halide group under conditions effective to produce a hydroxyl terminated alkyloxy comprising said α-hydroxyl group of said alkylene group at a first terminus and said carboxyl substituent of said benzoic acid at a second terminus;
- reacting a polymerizable group with said first terminus under conditions effective to produce an ethereal benzoic acid comprising said activated carboxyl substituent in a position para- to a polymerizable terminus;
- and,
- providing a hydroquinone comprising a bulky organic group and comprising a first hydroxyl group para- to a second hydroxyl group, at least one of said first hydroxyl group and said second hydroxyl group being an ionically activated hydroxyl group;
- condensing said at least one ionically activated hydroxyl group of said hydroquinone with said activated carboxyl substituent of said ethereal benzoic acid under conditions effective to produce a nematic liquid crystal comprising three aromatic rings joined by an ester linkage and comprising at least a first polymerizable terminus.
A resin blend comprising inorganic filler and a primary liquid crystal monomer at a ratio to a secondary monomer, said secondary monomer and said ratio being adapted to maintain said resin blend in a nematic liquid crystalline state for about 30 minutes or more after addition of an inorganic filler at a temperature of 20° C.
The resin blend of claim 42 wherein R2 is selected from the group consisting of t-butyl groups, phenyl groups, isopropyl groups, and secondary butyl groups.
The resin blend of claim 42 wherein R2 is a t-butyl group.
The resin blend of claim 46 wherein A has 6 carbon atoms.
A resin blend comprising inorganic filler and a primary liquid crystal monomer at a ratio to a secondary monomer, said ratio and said secondary monomer being adapted to maintain said resin blend in a nematic liquid crystalline state for about 30 minutes or more after addition of an inorganic filler at a temperature of 20 ° C., wherein said blend exhibits about 4 vol. % or less polymerization shrinkage.
A composition having the following general structure:
- 23
- wherein
- n is selected from the group of 0 and 1;
- X and Y independently are selected from the group consisting of linear and branched alkyl groups having from about 2 to about 12 carbon atoms;
- Z is selected from the group consisting of linear and branched alkyl groups having from about 2 to about 12 carbon atoms;
- provided that, when n is 0, Z is further selected from the group consisting of 2-alkyl-1,4-bis[-4-(alkyl-6-yl-1-oxo)-benzoyloxy]-benzene and, when n is 1, Z is further selected from the group consisting of 4-oxoalkyl-benzoyl groups, wherein said alkyl groups independently have from about 2 to about 12 carbon atoms;
- R7 is a bulky organic group having a bulk greater than R1 and R3, said bulk being adapted to provide sufficient steric hindrance for said liquid crystal monomer to achieve a nematic state at room temperature while suppressing crystallization of said blend at 20° C.;
- R6 and R8 are selected from the group consisting of hydrogen atoms and methyl groups;
- R5 and R9 are polymerizable groups selected from the group consisting of nucleophiles and groups comprising an electron deficient alkene.
A composition having the following general structure:
- 24
- wherein
- R is selected from the group consisting of hydrogen and a methyl group;
- and
- n and m independently are selected from the group consisting of from about 2 to about 11.
The composition α,ω-bis-4-[4-{4-(ω-R-acryloxy-alkyloxy)-benzoyloxy}-2-R7-phenoxy carbonyl]-phenoxy-alkane wherein:
- R is selected from the group consisting of H and CH3.
- said alkyls have from about 2 to about 12 carbon atoms;
- and
- R7 independently is selected from the group consisting of t-butyl groups, phenyl groups, isopropyl groups, and secondary butyl groups.
A composition having the following general structure:
- 25
The compound n-[4-({n-[(2-(R7)-4-{4-[n-(2-R-prop-2-noyloxy)alkyloxy]phenylcarbonyloxy}phenyl)oxycarbonyl]alkyl}oxycarbonyl)phenoxy]alkyl 2-R-prop-2-enoate wherein:
- R is selected from the group consisting of H and CH3,
- said alkyls have from about 2 to about 12 carbon atoms;
- and
- R7 is selected from the group consisting of a t-butyl group, a phenyl group, an isopropyl group, and a secondary butyl group.
A composition having the following general structure:
- 26
- wherein
- R is selected from the group consisting of H and CH3;
- and
- n and m independently are selected from the group consisting of from about 2 to about 12.
A composition having the following general structure:
- 27
A composition having the following general structure:
- 28
- wherein
- R is selected from the group consisting of H and CH3;
- and
- n and m independently are selected from the group consisting of from about 2 to about 12.
A composition having the following general structure:
- 29
- wherein
- n and m independently are selected from the group consisting of from about 2 to about 12;
- and
- R is selected from the group consisting of H and CH3.
The composition nonanedioic acid bis-(2-R7-4-{4-[6-(2-R-acryloyloxy)-alkyloxy]-benzoyloxy}-phenyl) ester wherein:
- R is selected from the group consisting of H and CH3;
- said alkyls have from about 2 to about 12 carbon atoms;
- and
- R7 is selected from the group consisting of a t-butyl group, a phenyl group, an isopropyl group, and a secondary butyl groups.
The composition of claim 143 wherein R7 is selected from the group consisting of a t-butyl group and a phenyl group.
A method for making a composition comprising
- providing a 4-hydroxyl benzoic acid comprising a carboxyl substituent;
- providing an alkylene group comprising an α-halide group and an ω-halide group;
- condensing said 4-hydroxyl of said benzoic acid with said ω-halide group under first conditions effective to activate said carboxyl substituent and to produce a hydroxyl terminated alkyloxy comprising said α-hydroxyl group at a first terminus and an activated carboxyl substituent of said 4-hydroxyl benzoic acid at a second terminus;
- providing a hydroquinone comprising a bulky organic group and comprising a first hydroxyl group para- to a second hydroxyl group, at least one of said first hydroxyl group and said second hydroxyl group being an ionically activated hydroxyl group;
- condensing said activated carboxyl substituent with said at least one ionically activated hydroxyl group of said hydroquinone under second conditions effective to produce α,ω-bis-4-[4-{4-(ω-R-acryloxy-alkyloxy)-benzoyloxy}-2-R7-phenoxy carbonyl]-phenoxy-alkane.
A method for making a composition comprising
- providing a 4-hydroxyl benzoic acid comprising a carboxyl substituent;
- providing an alkylene group comprising an α-halide group and an ω-halide group and comprising from about 2 to about 12 carbon atoms;
- condensing said 4-hydroxyl of said benzoic acid with said ω-halide group under first conditions effective to activate said carboxyl substituent and to produce a hydroxyl terminated alkyloxy comprising said α-hydroxyl group at a first terminus and an activated carboxyl substituent of said 4-hydroxyl benzoic acid at a second terminus;
- providing a 2-(R7)-4-[4-(6-acryloxy-alkyloxy)-benzoyloxy]-phenol comprising a bulky organic group and an ionically activated hydroxyl group para- to said [4-(6-acryloxy-alkyloxy)-benzoyloxy] group;
- condensing said activated carboxyl substituent with said ionically activated hydroxyl group under second conditions effective to produce nonanedioic acid-α,ω-bis-(2-R7)-4-[4-{ω-(2-R-acryloyloxy)-alkyloxy}-benzoyloxy]-phenyl ester.
A method for making a composition comprising
- providing a 4-hydroxyl benzoic acid comprising a carboxyl substituent;
- providing an alkanoyl halide comprising an ω-halide group and having from about 2 to about 12 carbon atoms;
- condensing said 4-hydroxyl of said benzoic acid with said ω-halide group under first conditions effective to activate said carboxyl substituent and to produce 4-(ω-R-acryloxy-alkyloxy) benzoic acid comprising an activated carboxyl substitutent;
- providing a hydroquinone comprising a bulky organic group and comprising a first hydroxyl group para- to a second hydroxyl group, at least one of said first hydroxyl group and said second hydroxyl group being an ionically activated hydroxyl group;
- condensing said activated carboxyl substituent of said 4-(ω-R-acryloxy-alkyloxy) benzoic acid with with said at least one ionically activated hydroxyl group of said hydroquinone under second conditions effective to produce 2-(R7)-1-[4-(ω-R-acryloxy-alkyl-α-oxy)-benzoyloxy], 4-(ω-halo-α-alkanoyloxy)-benzene.
A resin blend comprising a liquid crystal monomer at a 3:2 ratio to a secondary monomer said secondary monomer being 2-(t-butyl),1-[4-(6-acryloxy-hexyl-1-oxy)-benzoyloxy], 4-[4-{6-(3-acryl oxy-propionoxy)-hexyl-1-oxy}-benzoyloxy]-benzene, said liquid crystal monomer having the following general structure:
- 30
- wherein R2 is a t-butyl group;
- R1 and R3 are hydrogen atoms;
- A is 6;
- and R and R4 are methacryl groups.
A resin blend comprising an inorganic filler and a liquid crystal monomer at a ratio of 3:2 to a secondary monomer said secondary monomer being 2-(t-butyl), 1-[4-(6-acryloxy-hexyl-1-oxy)-benzoyloxy], 4-[4-{6-(3-acryl oxy-propionoxy)-hexyl-1-oxy}-benzoyloxy]-benzene, said liquid crystal monomer having the following general structure:
- 31
- wherein R2 is a t-butyl group;
- R1 and R3 are hydrogen atoms;
- A is 6;
- and R and R4 are methacrylgroups.
A resin blend comprising an inorganic filler and a liquid crystal monomer at a 3:2 ratio to a secondary monomer, said secondary monomer being 2-(t-butyl), 1-[4-(6-acryloxy-hexyl-1-oxy)-benzoyloxy], 4-[4-{6-(3-acryl oxy-propionoxy)-hexyl-1-oxy}-benzoyloxy]-benzene, said liquid crystal monomer having the following general structure:
- 32
- wherein R2 is a t-butyl group;
- R1 and R3 are hydrogen atoms;
- A is 6;
- and R and R4 are methacryl groups.
A resin blend comprising an inorganic filler and a liquid crystal monomer at a ratio of 3:2 to a secondary monomer, said secondary monomer being 2-(t-butyl), 1-[4-(6-acryloxy-hexyl-1-oxy)-benzoyloxy], 4-[4-{6-(3-acryl oxy-propionoxy)-hexyl-1-oxy}-benzoyloxy]-benzene, and said liquid crystal monomer has the following general structure:
- 33
- wherein R2 is a t-butyl group;
- R1 and R3 are hydrogen atoms;
- A is 6;
- and R and R4 are methacryl groups.
A resin blend comprising an inorganic filler and a liquid crystal monomer at a ratio to a secondary monomer, said secondary monomer and said ratio being adapted to produce a nematic to isotopic transition temperature for said resin blend of about 50° C. or more.
A method for delaying crystallization of a primary liquid crystal monomer which otherwise crystallizes in under 30 minutes after addition of inorganic filler at a temperature of 20° C., said method comprising providing a resin blend comprising said primary liquid crystal monomer and at least one secondary monomer, whereby upon addition of said inorganic filler to said resin blend at a temperature of 20° C., said resin blend maintains a nematic liquid crystallin state for about 30 minutes or more and exhibits about 4 vol. % or less polymerization shrinkage.
Dependencies are inferred from the claim text.