Process for producing high molecular weight polyethylene

Patent metadata

Field	Value
Publication number	US-9290629-B2
Application number	US-201514670742-A
Country	US
Kind code	B2
Filing date	Mar 27, 2015
Priority date	Nov 6, 2007
Publication date	Mar 22, 2016
Grant date	Mar 22, 2016

Abstract

The invention relates to a process for producing an (ultra) high molecular weight polyethylene (HMWPE) article comprising:
incorporating into the HMWPE resin a Hindered Amine Light Stabilizer (HALS) and cross-link the (U)HMWPE during or after molding the (U)HMWPE resin.

In particular the invention relates to a process comprising the following steps:
a) incorporating into (U)HMWPE resin a Hindered Amine Light Stabilizer (HALS) according to one of the following general formulas or combinations hereof:

 wherein R 1 up to and including R 5 are herein independent substituents; for example containing hydrogen, ether, ester, amine, amide, alkyl, alkenyl, alkynyl, aralkyl, cycloalkyl and/or aryl groups, which substituents may in turn contain functional groups, for example alcohols, ketones, anhydrides, imines, siloxanes, ethers, carboxyl groups, aldehydes, esters, amides, imides, amines, nitriles, ethers, urethanes and any combination thereof;
b) molding the (U)HMWPE resin comprising the HALS, resulting in an article;
c) cross-linking and sterilizing the article via gamma radiation or electron beam radiation;
d) optionally, if step b results in a stock shape, machining the stock shape into an article;
wherein step c and step d can be performed in either order.

First claim

The invention claimed is:

1. A process for producing an (ultra)high molecular weight polyethylene ((U)HMWPE) article comprising:
(a.) forming a composition by incorporating a stabilizer consisting of one or more Hindered Amine Light Stabilizers selected from the group consisting of 2,2,6,6-tetramethyl-4-piperidone; 2,2,6,6-tetramethyl-4-piperidinol; bis-(1,2,2,6,6-pentamethylpiperidyl)-(3′,5′-di-tert-butyl-4′-hydroxybenzyl) butylmalonate; di-(2,2,6,6-tetramethyl-4-piperidyl) sebacate; oligomer of N-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-piperidinol and succinic acid; bis-(2,2,6,6-tetramethyl-4-piperidinyl) succinate; bis-(1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate; bis-(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate; N,N′-bis-(2,2,6,6-tetramethyl-4-piperidyl) hexane-1,6-diamine; N-butyl-2,2,6,6-tetramethyl-4-piperidinamine; 2,2′-[(2,2,6,6-tetramethylpiperidinyl)imino]-bis-[ethanol]; poly((6-morpholine-S-triazine-2,4-diyl)(2,2,6,6-tetramethyl-4-piperidinyl)-iminohexamethylene-(2,2,6,6-tetramethyl-4-piperidinyl)-imino); 5-(2,2,6,6-tetramethyl-4-piperidinyl)-2-cycloundecyloxazole); 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro(4,5)decane-2,4-dione; polymethylpropyl-3-oxy[4(2,2,6,6-tetramethyl)piperidinyl)siloxane; copolymer of α-methylstyrene-N-(2,2,6,6-tetramethyl-4-piperidinyl)maleimide and N-stearylmaleimide; 1,2,3,4-butanetetracarboxylic acid, polymer with beta,beta,beta′,beta′-tetramethyl-2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-diethanol, 1,2,2,6,6-pentamethyl-4-piperidinyl ester; 2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-diethanol,beta,beta,beta′,beta′-tetramethyl-, polymer with 1,2,3,4-butanetetracarboxylic acid, 2,2,6,6-tetramethyl-4-piperidinyl ester; D-glucitol, 1,3:2,4-bis-O-(2,2,6,6-tetramethyl-4-piperidinylidene)-; oligomer of 7-oxa-3,20-diazadispiro[5.1.11.2]heneicosan-21-one,2,2,4,4-tetramethyl-20-(oxiranylmethyl); propanedioic acid, [(4-methoxyphenyl)methylene]-bis(1,2,2,6,6-pentamethyl-4-piperidinyl) ester; formamide, N,N′-1,6-hexanediylbis[N-(2,2,6,6-tetramethyl-4-piperidinyl; 1,3,5-triazine-2,4,6-triamine, N,N′″-[1,2-ethanediylbis[[[4,6-bis[butyl(1,2,2,6,6-pentamethyl-4-iperidinyl)amino]-1,3,5-triazine-2-yl]imino]-3,1-propanediyl]]-bis[N′,N″-dibutyl-N′,N″-bis(1,2,2,6,6-pentamethyl-4-piperidinyl); 1,5-dioxaspiro (5,5) undecane 3,3-dicarboxylic acid, bis (2,2,6,6-tetramethyl-4-piperidinyl) ester; 1,5-dioxaspiro (5,5) undecane 3,3-dicarboxylic acid, bis (1,2,2,6,6-pentamethyl-4-peridinyl) ester; N-2,2,6,6-tetramethyl-4-piperidinyl-N-amino-oxamide; 4-acryloyloxy-1,2,2,6,6-pentamethyl-4-piperidine; 1,3-benzenedicarboxamide,N,N′-bis(2,2,6,6-tetramethyl-4-piperidinyl); 3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidyl)-pyrrolidin-2,5-dione; 1,3-Propanediamine, N,N-1,2-ethanediylbis-,polymer with 2,4,6-trichloro-1,3,5-triazine, reaction products with N-butyl-2,2,6,6-tetramethyl-4-piperidinamine; 1,1′-(1,2-ethane-di-yl)-bis-(3,3′,5,5′-tetra-methyl-piperazinone); 1,1′,1″-(1,3,5-triazine-2,4,6-triyltris ((cyclohexylimino)-2,1-ethanediyl)tris(3,3,5,5-tetramethylpiperazinone); 1,1′,1″-(1,3,5-triazine-2,4,6-triyltris((cyclohexylimino)-2,1-ethanediyl)tris(3,3,4,5,5-tetramethylpiperazinone); 1,2,3,4-Butanetetracarboxylic acid, tetrakis(2,2,6,6-tetramethyl-4-piperidinyl) ester; 1,2,3,4-Butane-tetra-carboxylic acid, 1,2,3-tris-(1,2,2,6,6-penta-methyl-4-piperidyl)-4-tridecylester; mixture of esters of 2,2,6,6-tetra-methyl-4-pipiridinol and several fatty acids; Propanedioic acid, [(4-methoxyphenyl)methylene]-,bis(2,2,6,6-tetramethyl-4-piperidinyl) ester; 3-Dodecyl-1-(2,2,6,6-tetramethyl-4-piperidyl)-pyrrolidin-2,5-dione; 3-Dodecyl-1-(1,2,2,6,6-pentamethyl-4-piperidyl)-pyrrolidin-2,5-dione; 1,2,3,4-Butanetetracarboxylic acid, tetrakis(1,2,2,6,6-pentamethyl-4-piperidinyl)ester; 1,2,3,4-Butane-tetra-carboxylic acid, 1,2,3-tris-(2,2,6,6-tetra-methyl-4-piperidyl)-4-tridecylester; mixture of: 2,2,4,4 tetramethyl-21-oxo-7-oxa-3.20-diazadispiro[5.1.11.2]-heneicosane-20-propionic acid dodecylester and 2,2,4,4 tetramethyl-21-oxo-7-oxa-3.20-diazadispiro[5.1.11.2]-heneicosane-20-propionicacid tetradecylester; Poly[[6-[(1,1,3,3-tetramethylbutyl)amino]-s-triazine-2,4-diyl][2,2,6,6-tetramethyl-4-piperidinyl)-imino]hexamethylene[(2,2,6,6-tetramethyl-4-piperidinyl) iminol]}; 1,3,5-Triazine-2,4,6-triamine, N,N′″-[1,2-ethanediylbis[[[4,6-bis[butyl(1,2,2,6,6-pentamethyl-4-piperidinyl)amino]-1,3,5-triazine-2-yl]mino]-3,1-propanediyl]]-bis[N′,N″-dibutyl-N′,N″-bis(1,2,2,6,6-pentamethyl-4-piperidinyl); Poly[(6-morpholino-s-triazine-2,4-diyl)[1,2,2,6,6-penta-methyl-4-piperidyl)imino]-hexamethylene[(1,2,2,6,6 penta-methyl-4-piperidyl)iminol]1,6-Hexanediamine, N,N′-bis(1,2,2,6,6-pentamethyl-4-pipiridinyl)-, Polymers with morpholine-2,4,6-trichloro-1,3,5-triazine; Poly-methoxypopyl-3-oxy[4(1,2,2,6,6-pentamethyl)-piperidinyl]-siloxane; 1,6-Hexanediamine, N,N′-bis(2,2,6,6-tetramethyl-4-piperidinyl)-polymer with 2,4,6-trichloro-1,3,5-triazine, reaction products with N-butyl-1-butanamine and N-butyl-2,2,6,6-tetramethyl-4-piperidinamine; reaction products of N,N′-ethane-1,2-diylbis (1,3-propanediamine), cyclohexane, peroxidized 4-butylamino-2,2,6,6-tetramethylpiperidine and 2,4,6-trichloro-1,3,5-triazine; and 1,6-hexanediamine, N,N′-bis(2,2,6,6-tetramethyl-4-piperidinyl)-, polymer with 2,4,6-trichloro-1,3,5-triazine, reaction products with 3-bromo-1-propene, n-butyl-1-butanamine and N-butyl-2,2,6,6-tetramethyl-4-piperidinamine, oxidized, hydrogenated into a (U)HMWPE resin having a molecular weight distribution (Mw/Mn) of between 2 and 18, wherein Hindered Amine Light Stabilizers are the only stabilizers in the composition; and
(b.) cross-linking the composition during or after molding by irradiating the composition with an irradiation dose of from 30 to 250 kGy, thereby forming an article with a cross-link density of 0.09 mol/dm 3 or more.

2. The process according to claim 1 , wherein the one or more Hindered Amine Light Stabilizers comprise N,N′″-[1,2-ethanediylbis[[[4,6-bis[butyl(1,2,2,6,6-pentamethyl-4-iperidinyl)amino]-1,3,5-triazine-2-yl]imino]-3,1-propanediyl]]bis[N′,N″-dibutyl-N′,N″-bis(1,2,2,6,6-pentamethyl-4-piperidinyl) or poly{[[6[(1,1,3,3-tetramethylbutyl)amino]-s-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidinyl)imino]-hexamethylene[(2,2,6,6-tetramethyl-4-piperidinyl)imino]]}.

3. The process according to claim 1 , wherein the composition consists of (U)HMWPE resin having a molecular weight distribution (Mw/Mn) of between 2 and 18 and poly{[[6-[(1,1,3,3-tetramethylbutyl)amino]-s-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidinyl)imino]-hexamethylene[(2,2,6,6-tetramethyl-4-piperidinyl)imino]]}.

4. The process according to claim 1 , wherein the (U)HMWPE resin has an intrinsic viscosity of 8 dl/g or more.

5. The process according to claim 1 , wherein the one or more Hindered Amine Light Stabilizers are incorporated into the (U)HMWPE resin by mixing the one or more Hindered Amine Light Stabilizers with the (U)HMWPE resin or a melt of the (U)HMWPE resin, by impregnating the (U)HMWPE resin with a solution comprising the one or more Hindered Amine Light Stabilizers, or by spraying a solution comprising the one or more Hindered Amine Light Stabilizers on the (U)HMWPE resin.

6. The process according to claim 1 , wherein the Hindered Amine Light Stabilizers are present in an amount between 0.02 and 1% by weight, based on the total weight of the composition.

7. The process according to claim 3 , wherein the Hindered Amine Light Stabilizers are present in an amount between 0.02 and 1% by weight, based on the total weight of the composition.

8. The process according to claim 1 , wherein the irradiation dose is between 40 and 130 kGy.

9. The process according to claim 2 , wherein the irradiation dose is between 40 and 130 kGy.

10. The process according to clai

Assignees

• Dsm Ip Assets Bv

Inventors

• Smelt Harold Jan
• Gijsman Pieter
• Van Duin Martin

Classifications

• C08K5/3435 Primary

  Piperidines · CPC title

• C08J3/28 Primary

  Treatment by wave energy or particle radiation · CPC title

• C08L2666/02

  Organic macromolecular compounds, natural resins, waxes or and bituminous materials · CPC title

• C08F110/02

  Ethene · CPC title

• C08F8/00

  Chemical modification by after-treatment (graft polymers, block polymers, crosslinking with unsaturated monomers or with polymers C08F251/00 - C08F299/00; of conjugated diene rubbers C08C) · CPC title