Patent EP0367445A2 successfully refreshed from Google Patents.
EP0367445A2
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EP
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Extruder polymerization of polyurethanes
Assignee: 3M Co
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Filing: 1989-10-18
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Granted: —
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Expires: 2009-10-18
Abstract
Abstract Bulk polymerization process for making radiation curable polyurethanes which comprises: A) providing the following raw materials: 1) diisocyanate; 2) oligomeric diol ≧ 400 molecular weight; and 3) ≧ 1 chain extending monomer; B) reacting the raw materials in a twin screw extruder under the following conditions: 1) molar ratio of isocyanate to hydroxy moieties of about 1; 2) ratio of chain extending monomer to other monomers sufficient to yield a polymer having chain extender incorporated at 0.1 to 10 weight percent; 3) extruder temperature sufficient to initiate and maintain reaction; and 4) residence time sufficient to obtain substantially complete reaction of diisocyanate; C) cooling product polymer. Polyurethane product has weight average molecular weight greater than 80,000 and acrylate or methacrylate functionality. Process permits continuous production of radiation curable polyurethanes having narrow molecular weight distribution and high tensile strength.
Inventors
- 👤 Jimmie L. C/O Minnesota Mining And Echols
- 👤 Walton J. C/O Minnesota Mining And Hammar
- 👤 Thomas A. C/O Minnesota Mining And Kotnour
Bibliographic Details
Application Number
—
Jurisdiction
EP
Data Source
google_patents
Last Synchronized
2026-11-09 22:35
CPC Classifications
C; C08; C08G; C08G18/00; C08G18/06; C08G18/08; C08G18/0895; B; B29; B29C; B29C48/00; B29C48/001; B29C48/0012; C08G18/28; C08G18/67; C08G18/675; C08G18/677
Claims Analysis
Total Claims: 11
Claim 1
Independent Claim
223 words
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 (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 2
Dependent Claim
223 words
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 (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 3
Dependent Claim
17 words
The process of Claim 1 which further comprises curing the product polymer by exposing it to radiation.
Claim 4
Dependent Claim
20 words
The process of Claim 1 wherein a prepolymer of the diisocyanate and the oligomeric diol is made before step (B).
Claim 5
Dependent Claim
93 words
The process of Claim 1 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; and diisocyanates with the formula wherein R₃ is -CH₃ or C₂H₅; alicyclic diisocyanates selected from 1,4-cyclohexane bis(methyleneisocyanate); dicyclohexylmethane 4,4′ diisocyanate; and 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 - - where R is an alkyl radical of 1 to 5 carbon atoms.
Claim 6
Dependent Claim
98 words
The process of Claim 1 wherein the oligomeric diol is selected from the group consisting of linear hydroxyl containing compounds having the following formula HO[(CH₂) n O] x1 H wherein n is an integer from 2 to 6 and x₁ 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 formula wherein n₂ = 2-800 and y = 0-11.
Claim 7
Dependent Claim
48 words
The process of Claim 1 wherein the chain extending monomer is selected from the group consisting of monomers having the formulas: wherein m = 0-4 n₁ = 1-4 R₁ is -H or -CH₃ R₇ is -H, -CH₃, or -C₂H₅ A is -NH- -, -O -, or -SO₂- and
Claim 8
Dependent Claim
29 words
The process of Claim 1 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 9
Dependent Claim
32 words
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 10
Dependent Claim
26 words
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 11
Dependent Claim
31 words
The process of Claim 1 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.
References Cited (Backward Citations)
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