Extruder polymerization of polyurethanes

Claim 2

A process for bulk polymerization of polyurethanes which comprises: (A) providing the following raw materials: (1) at least one diisocyanate; (2) at least one oligomeric diol having a molecular weight of at least 400; and (3) at least one chain extending monomer having an acrylate or methacrylate moiety; (B) continuously conveying the above raw materials to a twin screw extruder and reacting them together to the desired degree of conversion in the extruder while conveying the reacting mass through the extruder under the following conditions: (1), molar ratio of isocyanate to hydroxy moieties 1.00±0.05; (2) ratio of chain extending monomer to other monomers sufficient to yield a polymer product having such chain extender incorporated therein to a level of from 0.1 to less than about 10 weight percent; (3) extruder barrel temperature sufficient to initiate and maintain reaction between the raw materials; and a residence time (4) extruder configured to have sufficient to obtain substantially complete reaction of the diisocyanate as measured by infrared spectrometry of the extrudate; and (C) cooling the resulting product polymer from the discharge of the extruder; to yield a polyurethane having the following properties: (i) weight average molecular weight greater than 80,000; and (ii) acrylate or methacrylate functionality in the polymer molecule resulting from the chain extending monomer and which functionality survived the extruder reaction conditions.

Claim 3

A process for bulk polymerization of polyurethane which comprises: (A) providing the following raw materials: (1) at least one diisocyanate; (2) at least one oligomeric diol having a molecular weight of at least 400; and (3) at least one chain extending monomer having an acrylate or methacrylate moiety and selected from the group consisting of monomers having the formulas: ##STR7## wherein m=0-4 n 1 =1-4 R1 is --H or --CH 3 R 7 is --H, --CH 3 , or --C 2 H 5 A is ##STR8## Y is ##STR9## (B) continuously conveying the above raw materials to a twin screw extruder and reacting them together to a desired degree of conversion in the extruder while conveying the reacting mass through the extruder under the following conditions: (1) molar ratio of isocyanate to hydroxy moieties 1.00±0.05; (2) ratio of chain extending monomer to other monomers sufficient to yield a polymer product having such chain extender incorporated therein to a level of from 0.5 to less than about 10 weight percent; (3) extruder barre 1 temperature sufficient to initiate and maintain reaction between the raw materials; and (4) extruder configured to have a residence time sufficient to obtain substantially complete reaction of the diisocyanate as measured by infrared spectrometry of the extrudate; and (C) cooling the resulting product polymer from the discharge of the extruder; to yield a polyurethane having the following properties: (i) weight average molecular weight greater than 80,000; and (ii) acrylate or methacrylate functionality in the polymer molecule resulting from the chain extending monomer and which functionality survived the extruder reaction conditions.

Claim 4

A process for bulk polymerization of polyurethane which comprises: (A) providing the following raw materials: (1) at least one diisocyanate; (2) at least one oligomeric diol having a molecular weight of at least 400; and (3) at least one chain extending monomer having an acrylate or methacrylate moiety and selected from the group consisting of monomers having the formulas: ##STR7## wherein m=0-4 n 1 =1-4 R1 is --H or --CH 3 R 7 is --H, --CH 3 , or --C 2 H 5 A is ##STR8## Y is ##STR9## (B) continuously conveying the above raw materials to a twin screw extruder and reacting them together to a desired degree of conversion in the extruder while conveying the reacting mass through the extruder under the following conditions: (1) molar ratio of isocyanate to hydroxy moieties 1.00±0.05; (2) ratio of chain extending monomer to other monomers sufficient to yield a polymer product having such chain extender incorporated therein to a level of from 0.5 to less than about 10 weight percent; (3) extruder barre 1 temperature sufficient to initiate and maintain reaction between the raw materials; and (4) extruder configured to have a residence time sufficient to obtain substantially complete reaction of the diisocyanate as measured by infrared spectrometry of the extrudate; and (C) cooling the resulting product polymer from the discharge of the extruder; to yield a polyurethane having the following properties: (i) weight average molecular weight greater than 80,000; and (ii) acrylate or methacrylate functionality in the polymer molecule resulting from the chain extending monomer and which functionality survived the extruder reaction conditions.

Claim 5

The process of claim 2 which further comprises curing the product polymer by exposing it to radiation.

Claim 6

The process of claim 2 wherein a prepolymer of the diisocyanate and the oligomeric diol is made before step (B).

Claim 7

The process of claim 2 wherein the diisocyanate is selected from the group consisting of: aliphatic diisocyanates selected from hexamethylene diisocyanate; 1,6-diisocyanato-2,2,4,4-tetramethylhexane; 1,6-diisocyanato-2,4,4-trimethylhexane; diisocyanates with the formula ##STR10## wherein R 3 is --CH 3 or C 2 H 5 ; alicyclic diisocyanates selected from 1,4-cyclohexane bis(methyleneisocyanate); dicyclohexylmethane 4,4'-diisocyanate; 1,4-cyclohexyl diisocyanate; and aromatic diisocyanates having the formula OCN-Ar-Y-Ar-NCO wherein Ar is cyclic, and Y may be a carbon-to-carbon valence bond, an alkylene radical containing 1 to 5 carbon atoms, oxygen, sulfur, sulfoxide, sulfone or ##STR11## where R is an alkyl radical of 1 to 5 carbon atoms.

Claim 8

The process of claim 2 wherein the oligomeric diol is selected from the group consisting of linear hydroxyl containing compounds having the following formula HO[(CH.sub.2).sub.n O].sub.x1 H wherein n is an integer from 2 to 6 and x 1 is an integer from 5 to 600; hydroxyl terminated poly(1,2-propylene oxides); hydroxy terminated poly(1,2-butylene oxide); hydroxy-substituted tetrahydrofuran; and hydroxyl terminated ethylene oxide copolyethers; polyesters prepared by polymerization of esters of dicarboxylic acids or their anhydrides with at least one glycol having 2-10 carbon atoms and silicone diols having the following ##STR12## where in n 2 =2-800 and y=0-11.

Claim 9

The process of claim 2 wherein the raw materials further comprise a short chain glycol selected from aliphatic, cycloaliphatic and aromatic glycols having a molecular weight less than 400.

Claim 10

The process of claim 7 wherein the short chain diol is selected from the group consisting of ethylene diol, propylene diol, 1,6-hexanediol, 2-ethylhexanediol, 1,6-neopentyl diol, 1,4-butanediol, 2-butene-1,4-diol, diethylene glycol, cyclohexanedimethanol, and bis-1,4-(hydroxyethoxy)benzene.

Claim 11

The process of claim 7 wherein the amount of short chain diol used is from greater than 0 to 10 moles per mole of oligomeric diol.

Claim 12

The process of claim 2 which further comprises making an interpenetrating polymer network by adding to the twin screw extruder near the discharge end a monomer selected from acrylates and methacrylates.

Claim 13

The process of claim 2 wherein the concentration of chain extender within the reacting mass in the twin screw extruder is maintained at or below 5 weight percent.

Claim 14

A process for bulk polymerization of polyurethanes which comprises: (A) providing the following raw materials: (1) at least one diisocyanate; (2) at least one oligomeric diol having a molecular weight of at least 400; and (3) at least one chain extending monomer having an acrylate or methacrylate moiety and selected from the group consisting of monomers having the formulas: ##STR13## wherein m=0-4 n 1 =1-4 R1 is --H or --CH 3 R 7 is --H, --CH 3 , or --C 2 H 5 A is ##STR14## and Y is ##STR15## (B) continuously conveying the above raw materials to a thin screw extruder and reacting them together to the desired degree of conversion in the extruder while conveying the reacting mass through the extruder under the following conditions: (1) molar ratio of isocyanate to hydroxy moieties 1.00±0.05; (2) ratio of chain extending monomer to other monomers sufficient to yield a polymer product having such chain extender incorporated therein to a level of from 0.5 to less than about 10 weight percent; (3) extruder barrel temperature sufficient to initiate and maintain reaction between the raw materials; and (4) extruder configured to have a residence time sufficient to obtain substantially complete reaction of the diisocyanate as measured by infrared spectrometry of the extrudate; and (C) cooling the resulting product polymer from the discharge of the extruder; to yield a polyurethane having the following properties: (i) weight average molecular weight greater than 80,000; and (ii) acrylate or methacrylate functionality in the polymer molecule in which said functionality survived the extruder reaction conditions.

Claim 15

A process for bulk polymerization of polyurethanes which comprises: (A) providing the following raw materials: (1) at least one diisocyanate; (2) at least one oligomeric diol having a molecular weight of at least 400; and (3) at least one chain extending monomer having an acrylate or methacrylate moiety and selected from the group consisting of monomers having the formulas: ##STR13## wherein m=0-4 n 1 =1-4 R1 is --H or --CH 3 R 7 is --H, --CH 3 , or --C 2 H 5 A is ##STR14## and Y is ##STR15## (B) continuously conveying the above raw materials to a thin screw extruder and reacting them together to the desired degree of conversion in the extruder while conveying the reacting mass through the extruder under the following conditions: (1) molar ratio of isocyanate to hydroxy moieties 1.00±0.05; (2) ratio of chain extending monomer to other monomers sufficient to yield a polymer product having such chain extender incorporated therein to a level of from 0.5 to less than about 10 weight percent; (3) extruder barrel temperature sufficient to initiate and maintain reaction between the raw materials; and (4) extruder configured to have a residence time sufficient to obtain substantially complete reaction of the diisocyanate as measured by infrared spectrometry of the extrudate; and (C) cooling the resulting product polymer from the discharge of the extruder; to yield a polyurethane having the following properties: (i) weight average molecular weight greater than 80,000; and (ii) acrylate or methacrylate functionality in the polymer molecule in which said functionality survived the extruder reaction conditions.