Copolymers, compositions, and articles, and methods for making same

Claim 2

A polyester diol/monomer composition which is convertible by reaction with a polyisocyanate to a polyurethane and which is polymerizable in the presence of a vinyl polymerization catalyst comprising (A) a polyester diol comprising: (a) aliphatically saturated divalent diacyl moieties of the formula ##STR8## wherein R is a single bond connecting the two carbonyl groups or a divalent organic group free of aliphatic unsaturation, and olefinically unsaturated divalent diacyl moieties of the formula ##STR9## wherein R' is a divalent olefinically unsaturated organic group, said diacyl moieties being present in a mole ratio of 0.25 to 3 moles of said diacyl moieties essentially free of aliphatic unsaturation per mole of said olefinically unsaturated diacyl moieties; and (b) divalent dioxy moieties having the formula: --OR"O--wherein R" is a divalent organic group interconnecting the oxy groups shown in said formula and each oxy group shown by said formula is bonded to a non-carboxyl atom of said R" group; said diacyl moieties being bonded through ester linkages to said dioxy moieties in a mole ratio of at least 1.75 moles of all said dioxy moieties per mole of all said diacyl moieties; and said polyester diol (i) being end-blocked essentially only by non-carboxylic hydroxyl groups bonded to dioxy moieties as defined in (b) hereinabove; and (ii) having an acid number of less than 3, (B) a polymerizable ethylenically unsaturated monomer present in an amount providing about 1 to about 6 ethylenically unsaturated groups of said monomer per olefinically unsaturated group of said polyester diol, (C) a catalyst capable of catalyzing polyurethaneforming reactions of polyisocyanates and polyhydroxy compounds, and (D) a vinyl polymerization inhibitor.

Claim 3

Composition as claimed in claim 1 wherein said vinyl polymerization inhibitor is present in amounts of at least 250 parts per million parts of said composition.

Claim 4

Composition as claimed in claim 1 wherein said polymerizable ethylenically unsaturated monomer contains one ethylenic group per molecule.

Claim 5

Composition as claimed in claim 3 wherein said monomer is present in an amount providing about 2 moles of monomer per olefinically unsaturated group of said polyester diol.

Claim 6

Composition as claimed in claim 4 wherein the amount of vinyl polymerization inhibitor ranges from about 500 to about 1000 parts per million parts of said composition.

Claim 7

Composition as claimed in claim 1 wherein said polymerizable ethylenically unsaturated monomer is styrene and said polyester diol is claimed in claim 6.

Claim 8

Tough polyurethane/vinyl polymer copolymer of (I) a polyester diol comprising: (a) aliphatically saturated divalent diacyl moieties of the formula ##STR10## wherein R is a single bond connecting the two carbonyl groups or a divalent organic group free of aliphatic unsaturation, and olefinically unsaturated divalent diacyl moieties of the formula ##STR11## wherein R' is a divalent olefinically unsaturated organic group, said diacyl moieties being present in a mole ratio of 0.25 to 3 moles of said diacyl moieties essentially free of aliphatic unsaturation per mole of said olefinically unsaturated diacyl moieties; and (b) divalent branched dioxy moieties having the formula: --OR"'O--wherein R"' is a divalent branched chain composed of carbon and hydrogen or carbon, hydrogen and oxygen and containing 2 to 8 consecutive atoms of carbon and oxygen interconnecting the oxy groups shown in said formula and having alkyl groups of one to eight carbon atoms bonded to one or more carbon atoms of said consecutive atoms, and divalent linear dioxy moieties having the formula: --OR""O--wherein R"" is a linear chain composed of carbon and hydrogen or carbon, hydrogen and oxygen and containing 2 to 8 consecutive atoms of carbon or carbon and oxygen interconnecting the oxy groups shown in said formula, said dioxy moieties being present in a mole ratio of 0.3 to 3 moles of said branched dioxy moieties per mole of said linear dioxy moieties; said diacyl moieties being bonded through ester linkages to said dioxy moieties in a mole ratio of at least 1.75 moles of all said dioxy moieties per mole of all said diacyl moieties; and said polyester diol (i) being end-blocked essentially only by alcoholic hydroxyl groups formed from oxy atoms of dioxy moieties as defined in (b) hereinabove; and (ii) having an acid number of less than 3, (II) a polymerizable ethylenically unsaturated monomer present in an amount providing about 1 to about 6 ethylenically unsaturated groups of said monomer per olefinically unsaturated group of said polyester diol, and (III) a polyisocyanate present in an amount providing about 0.9 to about 1.2 isocyanate groups per hydroxyl group of said polyester diol.

Claim 9

Tough polyurethane/vinyl polymer copolymer of (I) a polyester diol comprising: (a) aliphatically saturated divalent diacyl moieties of the formula ##STR10## wherein R is a single bond connecting the two carbonyl groups or a divalent organic group free of aliphatic unsaturation, and olefinically unsaturated divalent diacyl moieties of the formula ##STR11## wherein R' is a divalent olefinically unsaturated organic group, said diacyl moieties being present in a mole ratio of 0.25 to 3 moles of said diacyl moieties essentially free of aliphatic unsaturation per mole of said olefinically unsaturated diacyl moieties; and (b) divalent branched dioxy moieties having the formula: --OR"'O--wherein R"' is a divalent branched chain composed of carbon and hydrogen or carbon, hydrogen and oxygen and containing 2 to 8 consecutive atoms of carbon and oxygen interconnecting the oxy groups shown in said formula and having alkyl groups of one to eight carbon atoms bonded to one or more carbon atoms of said consecutive atoms, and divalent linear dioxy moieties having the formula: --OR""O--wherein R"" is a linear chain composed of carbon and hydrogen or carbon, hydrogen and oxygen and containing 2 to 8 consecutive atoms of carbon or carbon and oxygen interconnecting the oxy groups shown in said formula, said dioxy moieties being present in a mole ratio of 0.3 to 3 moles of said branched dioxy moieties per mole of said linear dioxy moieties; said diacyl moieties being bonded through ester linkages to said dioxy moieties in a mole ratio of at least 1.75 moles of all said dioxy moieties per mole of all said diacyl moieties; and said polyester diol (i) being end-blocked essentially only by alcoholic hydroxyl groups formed from oxy atoms of dioxy moieties as defined in (b) hereinabove; and (ii) having an acid number of less than 3, (II) a polymerizable ethylenically unsaturated monomer present in an amount providing about 1 to about 6 ethylenically unsaturated groups of said monomer per olefinically unsaturated group of said polyester diol, and (III) a polyisocyanate present in an amount providing about 0.9 to about 1.2 isocyanate groups per hydroxyl group of said polyester diol.

Claim 10

Tough polyurethane/vinyl polymer copolymer as claimed in claim 7 wherein said polyisocyanate is an aromatic polyisocyanate.

Claim 11

Tough polyurethane/vinyl polymer copolymer as claimed in claim 8 wherein said polymerizable ethylenically unsaturated monomer is present in an amount providing 1 to 3 ethylenically unsaturated groups per olefinically unsaturated group of said polyester diol.

Claim 12

Tough polyurethane/vinyl polymer copolymer as claimed in claim 9 wherein said polyester diol has an acid number of less than one, said polymerizable ethylenically unsaturated polymer is styrene and said aromatic polyisocyanate is a diphenyl methylene diisocyanate or polyisocyanate derivative thereof.

Claim 13

Tough polyurethane/vinyl polymer copolymer as claimed in claim 10 wherein said aromatic polyisocyanate is tolylene diisocyanate or polyisocyanate derivative thereof.

Claim 14

Tough polyurethane/vinyl polymer copolymer as claimed in claim 7 wherein a reinforcing agent is dispersed throughout said copolymer.

Claim 15

Tough polyurethane/vinyl polymer copolymer as claimed in claim 12 wherein said reinforcing agent comprises glass fibers.

Claim 16

Method of producing a tough polyurethane/vinyl polymer copolymer by reacting a mixture comprising (a) a polyester diol as defined in claim 1; (b) an organic polyisocyanate; and (c) a polymerizable ethylenically unsaturated monomer in the presence of (d) a catalyst for the reaction of (a) and (b); (e) a catalyst for the reaction of (a) and (c).

Claim 17

Method as claimed in claim 14 wherein said reaction is conducted in the presence of a vinyl polymerization inhibitor in an amount sufficient to inhibit substantial vinyl polymerization until the reaction of (a) and (b) is at least 50% complete.

Claim 18

Method as claimed in claim 15 wherein said inhibitor is present in an amount of about 500 to about 1000 ppm of the composition of (a), (b), (c), (d) and (e).

Claim 19

Method as claimed in claim 14 wherein said reaction is conducted in the presence of a reinforcing agent dispersed throughout said mixture.

Claim 20

Method as claimed in claim 17 wherein said reinforcing agent is glass fibers present in said mixture in an amount of about 5 to about 70 wt. % of the weight of said mixture.

Claim 21

Method as claimed in claim 14 wherein said polyester diol, said polymerizable ethylenically unsaturated monomer is styrene, said catalyst for (a) and (b) is a tin catalyst and said catalyst for (a) and (c) is a peroxide catalyst.

Claim 22

Method as claimed in claim 19 wherein the mixture of (a), (c) and (d) is continuously mixed and reacted with the mixture of (b) and (e) in a machine and continuously molded into shaped articles.

Claim 23

Method of producing shaped, tough plastic articles comprising the steps of mixing a polyester diol as claimed in claim 7, a polyisocyanate and a polymerizable ethylenically unsaturated monomer to form a polymerizable composition, shaping said composition by molding to form said article and subjecting said composition to polyurethane polymerization conditions.

Claim 24

Method as claimed in claim 21 wherein said composition is maturated prior to molding to reach a suitable molding viscosity.

Claim 25

Method as claimed in claim 22 wherein evaporation of volatiles from the composition during maturation is prevented.

Claim 26

Method as claimed in claim 21 wherein said composition is shaped by injection molding.

Claim 27

Method as claimed in claim 21 wherein said composition is shaped by transfer molding.

Claim 28

Method as claimed in claim 24 wherein said composition is shaped by compression molding.

Claim 29

Method as claimed in claim 22 wherein said maturated composition is formed into a sheet and said sheet is cut and formed into the desired size and shape prior to subjecting it to polyurethane forming conditions and vinyl polymerization conditions.

Claim 30

Method as claimed in claim 27 wherein reinforcing fibers are distributed on the upper surface of said sheet, a second sheet of said maturated composition is laid over said reinforcing fibers to form a sandwich and said sandwich is compressed to merge said sheets and reinforcing fibers together, and cutting and forming said merged sheets into the desired shape and size.

Claim 31

Method as claimed in claim 21 the polyester diol/monomer composition claimed in claim 1 is rapidly mixed with a mixture of a polyisocyanate and vinyl polymerization catalyst and quickly molded in the shape of the desired article.

Claim 32

Method as claimed in claim 29 wherein said molding is conducted in a reaction injection molding machine.