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US3887650A Expired / Lapsed US ⏱️ 0.0 years remaining

Process for preparing block copolymers of olefins and vinylic monomers

Assignee: Individual
•
Filing: 1973-08-01
•
Granted: 1975-06-03
•
Expires: 1993-08-01
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Abstract

Abstract A process for synthesizing block copolymers of olefins, in particular ethylene or propylene, and vinylic monomers. The process consists of modifying an olefinic polymer or copolymer with terminal double bonds, using a compound of an element selected from boron and metals in columns II, III, IVA and VA of the periodic table of elements, in which at least one of the valencies of this element is saturated by a hydrogen atom, or a monovalent hydrocarbyl or hydrocarbyloxy radical, after which the modified polymer thus obtained is placed in contact with an oxygenated free-radical-producing initiator and one or more vinylic monomers, and polymerization of the monomer or monomers is left to take place.

Inventors

  • 👤 Elias Agouri
  • 👤 Robert Laputte
  • 👤 Yves Philardeau
  • 👤 Jacques Rideau

Bibliographic Details

Application Number —
Jurisdiction US
Data Source google_patents
Last Synchronized 2026-10-30 10:28
CPC Classifications
C; C08; C08F; C08F290/00; C08F290/02; C08F290/04; C08F290/044

Claims Analysis

Total Claims: 45
Claim 1
Independent Claim 115 words
A process for synthesizing block copolymers of olefins and vinylic monomers, comprising the steps of modifying in the absence of Ziegler-type catalysts, an olefinic polymer or copolymer containing terminal double bonds by the reaction with a compound of an element selected from boron and the metals in Columns II, III, IVA and VA of the periodic table of elements, in which at least one of the valencies of the element is saturated by a hydrogen atom or monovalent hydrocarbyl or hydrocarbyloxy radical, placing the resulting modified polymer in contact with an oxygenated free-radical-producing initiator and at least one vinylic monomer, and allowing polymerization of the monomer or monomers to take place within the resulting mixture.
Claim 2
Dependent Claim 115 words
A process for synthesizing block copolymers of olefins and vinylic monomers, comprising the steps of modifying in the absence of Ziegler-type catalysts, an olefinic polymer or copolymer containing terminal double bonds by the reaction with a compound of an element selected from boron and the metals in Columns II, III, IVA and VA of the periodic table of elements, in which at least one of the valencies of the element is saturated by a hydrogen atom or monovalent hydrocarbyl or hydrocarbyloxy radical, placing the resulting modified polymer in contact with an oxygenated free-radical-producing initiator and at least one vinylic monomer, and allowing polymerization of the monomer or monomers to take place within the resulting mixture.
Claim 3
Dependent Claim 113 words
A PROCESS FOR SYNTHESIZING BLOCK COPOLYMERS OF OLEFINS AND VINYL MONOMERS, COMPRISING THE STEPS OF MODIFYING IN THE ABSENCE OF ZIEGLER-TYPE CATALYST, AN OLEFINIC POLYMER OR COPOLYMER CONTAINING TERMINAL DOUBLE BONDS BY THE REACTION WITH A COMPOUND OF AN ELEMENT SELECTED FROM BORON AND THE METALS IN COLUMNS II,III,IVA AND VA OF THE PERIODIC TABLE OF ELEMENTS, IN WHICH AT LEAST ONE OF THE VALENCIES OF THE ELEMENT IS SATURATED BY A HYDROGEN ATOM OR MONOVALENT HYDROCARBYL OR HYDROCARBYLOXY RADICAL, PLACING THE RESULTING MODIFIED POLYMER IN CONTACT WITH AN OXYGENATED FRE-RADICAL-PRODUCING INITIATOR AND AT LEAST ONE VINYLIC MONOMER, AND ALLOWING POLYMERIZATION OF THE MONOMER OR MONOMERS TO TAKE PLACE WITHIN THE RESULTING MIXTURE.
Claim 4
Dependent Claim 113 words
A PROCESS FOR SYNTHESIZING BLOCK COPOLYMERS OF OLEFINS AND VINYL MONOMERS, COMPRISING THE STEPS OF MODIFYING IN THE ABSENCE OF ZIEGLER-TYPE CATALYST, AN OLEFINIC POLYMER OR COPOLYMER CONTAINING TERMINAL DOUBLE BONDS BY THE REACTION WITH A COMPOUND OF AN ELEMENT SELECTED FROM BORON AND THE METALS IN COLUMNS II,III,IVA AND VA OF THE PERIODIC TABLE OF ELEMENTS, IN WHICH AT LEAST ONE OF THE VALENCIES OF THE ELEMENT IS SATURATED BY A HYDROGEN ATOM OR MONOVALENT HYDROCARBYL OR HYDROCARBYLOXY RADICAL, PLACING THE RESULTING MODIFIED POLYMER IN CONTACT WITH AN OXYGENATED FRE-RADICAL-PRODUCING INITIATOR AND AT LEAST ONE VINYLIC MONOMER, AND ALLOWING POLYMERIZATION OF THE MONOMER OR MONOMERS TO TAKE PLACE WITHIN THE RESULTING MIXTURE.
Claim 5
Dependent Claim 106 words
A process as defined in claim 1, in which the compound reacting with the olefinic polymer or copolymer with terminal double bonds has the general formula M(H)y(X)x(R)n (x y) where M represents one of the elements boron, aluminium, germanium, tin, lead, antimony, magnesium, zinc and cadmium, X is a hologen, and R represents identical or different alkyl, aryl, cycloalkyl, alkylaryl, aralkyl and alcoxy radicals containing from 1 to 12 carbon atoms, n represents the valency of M, and y and x represent whole numbers, between 0 and n for y and between 0 and (n-1) for x, the sum of x+y being not more than n.
Claim 6
Dependent Claim 25 words
A process as defined in claim 2, in which the alkyl, aryl, cycloalkyl, alkylaryl, aralkyl and alcoxy radicals contain from 1 to 9 carbon atoms.
Claim 7
Dependent Claim 50 words
A process as defined in claim 1, in which the proportion of compound reacting with the olefinic polymer or copolymer is such that the relation of the number of molecules of the compound to the number of terminal double bonds in the copolymer or polymer is between 0.01 and 40.
Claim 8
Dependent Claim 36 words
A process as defined in claim 4, in which the ratio of the number of molecules in the compound to the number of terminal double bonds in the polymer or copolymer is between 0.3 and 10.
Claim 9
Dependent Claim 29 words
A process as defined in claim 1, in which the olefinic polymers or copolymers with terminal double bonds are derived from alpha-olefins containing from 2 to 18 carbon atoms.
Claim 10
Dependent Claim 29 words
A process as defined in claim 6, in which the olefinic polymers or copolymers with terminal double bonds are derived from alpha-olefins containing from 2 to 12 carbon atoms.
Claim 11
Dependent Claim 22 words
A process as defined in claim 1, in which modification of the olefinic polymer or copolymer takes place in an inert liquid.
Claim 12
Dependent Claim 22 words
A process as defined in claim 8, in which modification of the olefinic polymer or copolymer takes place in an inert atmosphere.
Claim 13
Dependent Claim 26 words
A process as defined in claim 1, in which modification of the olefinic polymer or copolymer takes place at a temperature of between -30* and 200*C.
Claim 14
Dependent Claim 26 words
A process as defined in claim 10, in which modification of the olefinic polymer or copolymer takes place at a temperature of between -20* and 120*C.
Claim 15
Dependent Claim 31 words
A process as defined in claim 1, in which modification of the olefinic polymer or copolymer is carried out in the presence of a complexing agent of the Lewis base type.
Claim 16
Dependent Claim 25 words
A process as defined in claim 1, in which the oxygenated free-radical-producing initiator belongs to the group comprising peroxides, hydroperoxides, hydrogen peroxide, oxygen and air.
Claim 17
Dependent Claim 32 words
A process as defined in claim 1, in which the initiator and vinylic monomer or monomers are added directly to the reaction mixture in which modification of the olefinic polymer takes place.
Claim 18
Dependent Claim 38 words
A process as defined in claim 1, in which the olefinic polymer treated with the modifying agent is separated from the modification reaction mixture before being brought into contact with the oxygenated free-radical-producing initiator and monomer or monomers.
Claim 19
Dependent Claim 69 words
A process as defined in claim 15, in which the modified polymer is brought into contact with the initiator and vinylic monomer or monomers for polymerization in an inert liquid phase, which may be an aqueous phase if the modified polymer is not affected by water or if the contact is made before the combination of the polymer, initiator and monomer or monomers is placed in the liquid phase.
Claim 20
Dependent Claim 35 words
A process as defined in claim 15, in which the modified polymer is brought into contact with the initiator and vinylic monomer or monomers for polymerization, using the monomer or monomers as a suspension medium.
Claim 21
Dependent Claim 37 words
A process as defined in claim 1, in which polymerization of the vinylic monomer or monomers in the presence of the modified olefinic polymer and initiator is carried out at a temperature of between -78* and +180*C.
Claim 22
Dependent Claim 20 words
A process as defined in claim 18, in which polymerization takes place at a temperature of between -40* and +100*C.
Claim 23
Dependent Claim 22 words
A process as defined in claim 18, in which polymerization takes place below the temperature of thermal decomposition of the initiator used.
Claim 24
Dependent Claim 31 words
A process as defined in claim 16, in which polymerization of the vinylic monomer or monomers is performed in the presence of a complexing agent of the weak Lewis acid type.
Claim 25
Dependent Claim 18 words
A process as defined in claim 21, in which polymerization is performed in the presence of ethyl acetate.
Claim 26
Dependent Claim 27 words
A process as defined in claim 1, in which the vinylic monomers belong to the group comprising chlorovinylic, acrylic, methacrylic, vinylaromatic, vinylpyridines, vinylpyrrolidones, butadiene, and vinylic esters.
Claim 27
Dependent Claim 91 words
A process for preparing olefinic polymers with peroxide end-groups, comprising the steps of modifying an olefinic polymer or copolymer containing terminal double bonds by reaction with the compound of an element selected from boron and metals in Columns II, III, IVA and VA of the periodic table of elements, in which at least one of the valencies of the element is saturated by a hydrogen atom or monovalent hydrocarbyl or hydrocarbyloxy radical, placing the resulting modified polymer in contact with an oxygenated free-radical-producing initiator, and collecting the peroxidized polymer that forms.
Claim 28
Dependent Claim 91 words
A process for preparing olefinic polymers with peroxide end-groups, comprising the steps of modifying an olefinic polymer or copolymer containing terminal double bonds by reaction with the compound of an element selected from boron and metals in Columns II, III, IVA and VA of the periodic table of elements, in which at least one of the valencies of the element is saturated by a hydrogen atom or monovalent hydrocarbyl or hydrocarbyloxy radical, placing the resulting modified polymer in contact with an oxygenated free-radical-producing initiator, and collecting the peroxidized polymer that forms.
Claim 29
Dependent Claim 97 words
A process as defined in claim 24, in which the compound reacting with the olefinic polymer or copolymer with terminal double bonds has the general formula M(H)y(X)x(R)n (x y) germanium, tin, lead, antimony, magnesium, zinc and cadmium, X is a halogen, and R represents identical or different alkyl, aryl, cycloalkyl, alkylaryl, aralkyl and alcoxy radicals containing from 1 to 12 carbon atoms, n represents the valency of M, and y and x represent whole numbers, between 0 and n for y and between 0 and (n-1) for x, the sum of x+y being not more than n.
Claim 30
Dependent Claim 24 words
A process as defined in claim 25, in which the alkyl, aryl, cycloarkyl, alkylaryl, aralkyl and alcoxy radicals contain from 1 to 9 atoms.
Claim 31
Dependent Claim 50 words
A process as defined in claim 24, in which the proportion of compound reacting with the olefinic polymer or copolymer is such that the relation of the number of molecules of the compound to the number of terminal double bonds in the polymer or copolymer is between 0.01 and 40.
Claim 32
Dependent Claim 36 words
A process as defined in claim 27, in which the ratio of the number of molecules in the compound to the number of terminal double bonds in the polymer or copolymer is between 0.3 and 10.
Claim 33
Dependent Claim 29 words
A process as defined in claim 24, in which the olefinic polymers or copolymers with terminal double bonds are derived from alpha-olefins containing from 2 to 18 carbon atoms.
Claim 34
Dependent Claim 29 words
A process as defined in claim 29, in which the olefinic polymers or copolymers with terminal double bonds are derived from alpha-olefins containing from 2 to 12 carbon atoms.
Claim 35
Dependent Claim 22 words
A process as defined in claim 24, in which modification of the olefinic polymEr or copolymer takes place in an inert liquid..
Claim 36
Dependent Claim 22 words
A process as defined in claim 31, in which modification of the olefinic polymer or copolymer takes place in an inert atmosphere.
Claim 37
Dependent Claim 26 words
A process as defined in claim 24, in which modification of the olefinic polymer or copolymer takes place at a temperature of between -30* and 200*C.
Claim 38
Dependent Claim 26 words
A process as defined in claim 33, in which modification of the olefinic polymer or copolymer takes place at a temperature of between -20* and 120*C.
Claim 39
Dependent Claim 31 words
A process as defined in claim 24, in which modification of the olefinic polymer or copolymer is carried out in the presence of a complexing agent of the Lewis base type.
Claim 40
Dependent Claim 25 words
A process as defined in claim 24, in which the oxygenated free-radical-producing initiator belongs to the group comprising peroxides, hydroperoxides, hydrogen peroxide, oxygen and air.
Claim 41
Dependent Claim 32 words
A process as defined in claim 24, in which the initiator and vinylic monomer or monomers are added directly to the reaction mixture in which modification of the olefinic polymer takes place.
Claim 42
Dependent Claim 34 words
A process as defined in claim 24, in which the olefinic polymer treated with the modifying agent is separated from the modification reaction mixture before being brought into contact with the oxyginated free-radical-producing initiator.
Claim 43
Dependent Claim 39 words
A process as defined in claim 38, in which the modified polymer is brought into contact with the initiator in an inert liquid phase, which may be an aqueous phase when the modified polymer is not affected by water.
Claim 44
Dependent Claim 27 words
A process as defined in claim 24, in which the peroxidized polymer resulting from the peroxidation treatment by the oxygenated free-radical-producing initiator is then subjected to hydrolysis.
Claim 45
Dependent Claim 26 words
A process as defined in claim 40, in which hydrolysis is performed in an aqueous or slightly acid phase, at a temperature of 0* to 100*C.

References Cited (Backward Citations)

US3739042A Cited
US3458598A Cited
US3652724A Cited
US3699190A Cited
US3769368A Cited
US3734978A Cited

USPTO Annuity & Maintenance Windows

Annuity Stage Window Opens Payment Deadline Surcharge Period Until Estimated Fee Status
3.5 Years (Year 4) 1978-06-02 1978-12-02 1979-06-03 $2000.00 Window Closed / Lapsed
7.5 Years (Year 8) 1982-06-02 1982-12-02 1983-06-03 $3760.00 Window Closed / Lapsed
11.5 Years (Year 12) 1986-06-02 1986-12-02 1987-06-03 $7700.00 Window Closed / Lapsed

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