WO1995021204A1 - Copolymeres chlorosulfones d'ethylene et d'olefines alpha a greffe de monomeres - Google Patents

Copolymeres chlorosulfones d'ethylene et d'olefines alpha a greffe de monomeres Download PDF

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Publication number
WO1995021204A1
WO1995021204A1 PCT/US1995/000560 US9500560W WO9521204A1 WO 1995021204 A1 WO1995021204 A1 WO 1995021204A1 US 9500560 W US9500560 W US 9500560W WO 9521204 A1 WO9521204 A1 WO 9521204A1
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WO
WIPO (PCT)
Prior art keywords
ethylene
copolymers
chlorosulfonated
composition
units
Prior art date
Application number
PCT/US1995/000560
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English (en)
Inventor
Royce Elton Ennis
Original Assignee
E.I. Du Pont De Nemours And Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by E.I. Du Pont De Nemours And Company filed Critical E.I. Du Pont De Nemours And Company
Publication of WO1995021204A1 publication Critical patent/WO1995021204A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
    • C08F255/023—On to modified polymers, e.g. chlorinated polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond

Definitions

  • Graft-modification of the ethylene alpha-olefm copolymer base resins is accomplished by free radical-initiated addition of ethylenically unsaturated carboxylic acids, ethylenically unsaturated carboxylic acid anhydrides, copolymers of ethylene and C J-C JO alkyl esters of acrylic acid, or copolymers of ethylene and C 1 -C ⁇ 0 alkyl esters of methacrylic acid.
  • Bulk, solution, or suspension processes may be utilized. Bulk processes are characterized by reaction of the polymer and grafting agent in the presence of a free radical-generating compound at elevated temperatures, generally 150-180°C, in an extruder or mixer.
  • the polymer, grafting agent, and free radical generator are dissolved, generally in an organic solvent, and reaction takes place at temperatures around 100°C.
  • An aqueous suspension process has also been disclosed for use under conditions wherein the grafting agents are not subject to hydrolysis. In that method the polymer, grafting agent, and l o free radical generator are contacted at temperatures of 60- 100°C, sometimes in the presence of a surfactant.
  • the bulk process is most generally used on a commercial scale.
  • the graft-modified ethylene alpha-olefin copolymers are converted to the chlorosulfonated compositions of the present invention by reaction with a chlorosulfonating agent at temperatures of about 50-150°C, preferably 80-110°C, in a solvent substantially inert to chlorination.
  • suitable solvents include carbon tetrachloride, chloroform, methylene chloride, trichlorofluoromethane, dibromofluoromethane, difluorotrichloroethane, tetrafluorotrichloropropane, 1 , 1 ,2-trichloroethane, pentafluorodichloropropane, monochlorobenzene, dichlorobenzene, fluorobenzene, and monochloromonofluorobenzene.
  • the reaction is preferably run at pressures of 0.10-0.35 MPa.
  • the chlorosulfonated graft-modified polymers may also be prepared by the alternative method of chlorosulfonation of the ethylene alpha-olefin base resin with subsequent grafting of the chlorosulfonated product. In such cases, the chlorosulfonation proceeds as described above. Free radical initiated addition of grafting agent may occur following completion of the chlorosulfonation reaction in the same reactor or the grafting reaction may be a separate process performed subsequent to isolation of the chlorosulfonated product.
  • a particularly useful class of polymers which falls within the scope of the present invention is that comprising chlorosulfonated ethylene alpha-olefin graft copolymers wherein the chlorine level is 20-35 percent by weight, preferably 22-32 percent by weight.
  • These compositions exhibit unusually enhanced oil resistance in combination with excellent low temperature properties, particularly low temperature fracture resistance and resiliency. This combination of properties is a result of the presence of the pendant alkyl groups introduced by copolymerization of ethylene and higher alpha-olefins and a balance in the level of chlorine and highly polar graft units.
  • the polymers are rubbery at low chlorine content due to the modification of crystallinity brought about by copolymerization.
  • Example 1 The reactor system described in Example 1 was charged with 4 lbs. (1.82kg) of a maleic anhydride- grafted ethylene/octene/butene copolymer (melt flow index 5.2g/10 minutes, density 0.918g/cc, maleic anhydride content 0.91%, weight ratio 90.6/4.7/4.7 before grafting) and 70 lbs. (31.8kg) of carbon tetrachloride.
  • the reaction mixture was heated to 110°C and a reactor pressure of 0.3 IMPa.
  • a 1% solution of 2, 2'- azobis(isobutyronitrile) in chloroform was added continuously at a rate of 2.3g/minute throughout the reaction.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Graft Or Block Polymers (AREA)

Abstract

Copolymères chlorosulfonés d'éthylène et d'oléfines alpha C4-C10 à greffe d'unités de monomères choisies parmi un groupe consistant en acides carboxyliques non saturés en éthylène, en anhydrides d'acides carboxyliques non saturés en éthylène, en copolymères d'éthylène et d'alkyle esters C1-C10 de l'acide acrylique, et en copolymères d'éthylène et alkyle esters C1-C10 de l'acide méthacrylique. Lesdits copolymères chlorosulfonés se caractérisent par leur excellent comportement dynamique et à basse température.
PCT/US1995/000560 1994-02-02 1995-01-31 Copolymeres chlorosulfones d'ethylene et d'olefines alpha a greffe de monomeres WO1995021204A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US19076394A 1994-02-02 1994-02-02
US08/190,763 1994-02-02

Publications (1)

Publication Number Publication Date
WO1995021204A1 true WO1995021204A1 (fr) 1995-08-10

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1995/000560 WO1995021204A1 (fr) 1994-02-02 1995-01-31 Copolymeres chlorosulfones d'ethylene et d'olefines alpha a greffe de monomeres

Country Status (1)

Country Link
WO (1) WO1995021204A1 (fr)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0511635A1 (fr) * 1991-04-30 1992-11-04 Ministero Dell' Universita' E Della Ricerca Scientifica E Tecnologica Système adhésif à plusieurs constituants
WO1993020161A1 (fr) * 1992-04-06 1993-10-14 E.I. Du Pont De Nemours And Company Latex resinique chlorosulfone stable

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0511635A1 (fr) * 1991-04-30 1992-11-04 Ministero Dell' Universita' E Della Ricerca Scientifica E Tecnologica Système adhésif à plusieurs constituants
WO1993020161A1 (fr) * 1992-04-06 1993-10-14 E.I. Du Pont De Nemours And Company Latex resinique chlorosulfone stable

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