Stereolithography using vinyl ether-epoxide polymers

Claim 2

A polymer precursor composition for forming three-dimensional objects by stereolithography consisting essentially of (a) vinyl ether functionalized compounds; (b) epoxy functionalized compounds; (c) an effective amount of a cationic photoinitiator; said vinyl ether compounds and epoxy compounds both being curable by acids released by said photoinitiator and having proportions selected to provide a three-dimensional polymeric object having suitable green strength with minimal curl distortion when said composition is polymerized in stereolithography by a light source selected from the group consisting of UV and visible light lasers and defined by the formula M=F/E where M is the vinyl ether equivalent weight of the composition and has a value between 80 and 800 F is the total weight in grams of the composition E is the number of vinyl ether equivalents in the composition.

Claim 3

A polymer precursor composition of claim 1 wherein said vinyl ether compounds are derived from at least one member of the groups consisting of urethanes, phenols, esters, ethers, siloxanes, carbonates, and aliphatic or aromatic hydrocarbons.

Claim 4

The polymer precursor composition of claim 2 wherein the vinyl ether compounds comprise oligomers having the formula (R'CH═CR"--OZ).sub.n --A where R' and R" are H or an alkyl group having 1 to 10 carbon atoms A is a moiety derived from at least one of the group consisting of urethanes, phenols, polyesters, polyethers, polysiloxanes, polycarbonates and has a molecular weight of about 400 to 10,000 Z is a moiety derived from a saturated aliphatic or cyclo aliphatic hydrocarbon or a polyalkylene ether and has a molecular weight of about 28 to 250 n is an integer from 2 to 6.

Claim 5

The composition of claim 3 wherein said vinyl ether oligomers are derived from a urethane obtained by reacting (i) an hydroxyl terminated polyester having the formula ##STR14## where X and Y are divalent radicals having a molecular weight of 28 to about 500 and selected from the group consisting of alkylene, arylene, aralkylene, and cycloalkylene radicals m has an average value of 1 to about 100 and (ii) a diisocyanate having the formula OCN--Q--NCO where Q is a divalent radical selected from the group consisting of alkylene, arylene, aralkylene, and cycloalkylene radicals or a polyisocyanate having a functionality greater than 2 and (iii) a hydroxy monovinyl ether having the formula R'CH═CR"O--Z--OH where R' and R" are mono valent radicals selected from the group consisting of H and alkyl groups having 1-10 carbon atoms Z is a divalent radical having a molecular weight of 28 to about 250 and selected from the group consisting of alkylene, cycloalkylene, or polyalkylene ether radicals.

Claim 6

The composition of claim 3 wherein said vinyl ether oligomers are derived from a urethane obtained by reacting (i) an hydroxyl terminated polyether having the formula HO--X--(--O--X).sub.m --OH where m has an average value of 1 to about 100 X is a divalent radical having a molecular weight of 28 to about 500 and selected from the group consisting of alkylene, arylene, aralkylene, and cycloalkylene radicals and (ii) a diisocyanate having the formula OCN--Q--NCO where Q is a divalent radical selected from the group consisting of alkylene, arylene, aralkylene, and cycloalkylene radicals or a polyisocyanate having a functionality greater than 2 and (iii) a hydroxy monovinyl ether having the formula R'CH═CR"O--Z--OH where R' and R" are mono valent radicals selected from the group consisting of H and alkyl groups having 1-10 carbon atoms Z is a divalent radical having a molecular weight of 28 to about 250 and selected from the group consisting of alkylene, cycloalkylene, or polyalkylene ether radicals.

Claim 7

The composition of claim 3 wherein said vinyl ether oligomers are derived from a polyester obtained by reacting (a) a dicarboxylic acid having the formula ##STR15## where X and Y are divalent radicals having a molecular weight of about 28 to 500 and selected from the group consisting of alkylene, arylene, aralkylene, and cycloalkylene radicals m has an average value of about 1 to 100 (b) with a hydroxy monovinyl ether having the formula R'CH═CR"OZOH where R' and R" are monovalent radicals selected from the group consisting of H and alkyl groups having 1-10 carbon atoms Z is a divalent radical having a molecular weight of about 28 to 250 and selected from the group consisting of alkylene, cycloalkylene, or polyalkylene ether radicals.

Claim 8

The composition of claim 3 wherein said vinyl ether oligomers are derived from a polysiloxane defined as (R'CH═CR'--0--Z--).sub.n --A' where R', R", and Z are as defined above, n is an integer from 2 to 8 A' is a polysiloxane having n Si--H groups and a molecular weight of 140 to 5,000.

Claim 9

The composition of claim 3 wherein said vinyl ether oligomers are derived from a phenol defined as (R'CH═CR"--O--Z--O).sub.n --A" where A" is a polyvalent aromatic radical having a molecular weight of about 152 to 5,000 R', R" and Z are as defined above n is 2 to 6.

Claim 10

The composition of claim 3 wherein said vinyl ether oligomers are derived from a polyether by reacting at least one of the groups consisting of poly(ethylene oxy), poly(propylene oxy), or poly(butylene oxy) glycols, where m has an average value from about 2 to 50 with acetylene or a vinyl oxy alkyl halide.

Claim 11

The polymer precursor composition of claim 3 wherein the vinyl ether oligomers are derived from a carbonate defined as ##STR16## where p is 4 to 10 Z is a divalent radical having a molecular weight of about 28 to 250 and selected from the group consisting of alkylene, cycloalkylene or polyalkylene ether radicals X is a diester, diol, or polyol moiety.

Claim 12

The composition of claim 2 wherein R' and R" are hydrogen.

Claim 13

The composition of claim 2 wherein R' is methyl and R" is hydrogen.

Claim 14

The polymer precursor composition of claim 2 wherein the vinyl ether compounds comprise monomers having the formula (R'CH═CR"--0--Z).sub.n --B where R' and R" are H or an alkyl group having 1 to 10 carbon atoms Z is a moiety derived from a saturated aliphatic or cyclo aliphatic hydrocarbon or a poly alkylene ether and has a molecular weight of about 28 to 250 n is an integer from 1 to 4 B is derived from at least one of the group consisting of aliphatic and aromatic hydrocarbons, esters, ethers, siloxanes, urethanes, and carbonates and has a molecular weight of about 60 to 400.

Claim 15

The composition of claim 13 wherein R' and R" are hydrogen.

Claim 16

The composition of claim 13 wherein R' is methyl and R" is hydrogen.

Claim 17

The composition of claim 13 wherein said vinyl ether monomers are derived from esters and having the formula ##STR17## where n is 1 to 4, M 1 is a mono, di, tri, or tetra functional radical having a molecular weight of 15 to 180 and selected from the group consisting of alkylene, arylene, aralkylene and cycloalkylene radicals Z is a divalent radical having a molecular weight of 28 to 290 and selected from the group consisting of alkylene, cycloalkylene, or polyalkylene ether radicals R' and R" are monovalent radicals selected from the group consisting of H and alkyl groups having 1-10 carbon atoms.

Claim 18

The composition of claim 13 wherein said vinyl ether monomers are derived from ethers by reacting at least one of the group consisting of poly(ethyleneoxy), poly(propyleneoxy), or poly(butyleneoxy) glycols, where m has an average value from about 1 to about 5 with acetylene or a vinyl oxy alkyl halide.

Claim 19

The composition of claim 13 wherein said vinyl ether monomers are derived from aliphatic hydrocarbons described by the formula M.sub.2 --(--OZ--OCR"═CHR').sub.n where n is 1 to 4 M 2 is a mono, di, tri, or tetra functional aliphatic or cycloaliphatic radical having a molecular weight of about 56 to 500 Z is a divalent radical having a molecular weight of 28 to about 250 and selected from the group consisting of alkylene, cycloalkylene or polyalkylene ether radicals R' and R" are monovalent radicals selected from the group consisting of H and alkyl groups having 1-10 carbon atoms.

Claim 20

The composition of claim 13 wherein said vinyl ether monomers are derived from aromatic hydrocarbons described by the formula M.sub.3 --(--OZ--OCR"--CHR').sub.n where n is 1 to 4 M 3 is a mono, di, tri, or tetrafunctional aromatic radical having a molecular weight of about 77 to 500 Z is a divalent radical having a molecular weight of 28 to about 250 and selected from the group consisting of alkylene, cycloalkylene or polyalkylene ether radicals R' and R" are monovalent radicals selected from the group consisting of H and alkyl groups having 1-10 carbon atoms.

Claim 21

The composition of claim 13 wherein said vinyl ether monomers are derived from a polysiloxane defined as (R'CH═CR'--0--Z--).sub.n --A' where R', R", and Z are defined above n is an integer from 2 to 8 A' is a polysiloxane having n Si--H groups and a molecular weight of 140 to 500.

Claim 22

The composition of claim 13 wherein said vinyl ether monomers are derived from a carbonate defined as ##STR18## where p is 0 to 3 Z is a divalent radical having a molecular weight of about 28 to 250 and selected from the group consisting of alkylene, cycloalkylene or polyalkylene ether radicals X is a diester, diol, or polyol moiety.

Claim 23

A polymer precursor composition of claim 1 wherein said epoxy compounds are derived from at least one member of the group consisting of phenols, novolacs, aliphatic or cycloaliphatic polyols, and polyether polyols and siloxanes.