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US4148839A Expired / Lapsed US ⏱️ 0.0 years remaining

Graft co-polymers

Assignee: Department of National Defence
•
Filing: 1976-02-20
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Granted: 1979-04-10
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Expires: 1996-02-20
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Abstract

Abstract Polymeric materials are disclosed in which a synthetic essentially hydrophobic base polymer has at least in its surface region a crosslinked polar comonomer graft in the surface region at least of which there are metal atoms or ions which are chemically bound and which cannot be removed by solution processes. There are also disclosed three processes by which such materials may be produced. The deposition of a complex metal compound, the contacting of the graft with a metal compound both followed by heating, and graft copolymerization with a metal containing comonomer. There is also disclosed a method of ensuring a good bond between a polymeric material and a coating which includes a preliminary surface graft with a polar comonomer.

Inventors

  • 👤 Peter J. Fydelor

Bibliographic Details

Application Number —
Jurisdiction US
Data Source google_patents
Last Synchronized 2026-10-29 09:47
CPC Classifications
C; C08; C08J; C08J7/00; C08J7/12; C08J7/16; C08F; C08F8/00; C08F8/42

Claims Analysis

Total Claims: 37
Claim 1
Independent Claim 92 words
A composition of matter which is produced by contacting with a metal compound a synthetic substantially hydrophobic base polymer selected from polyolefins, copolyolefins, polyamides, copolyamides, halogenated polyolefins, polyesters, unsaturated polyesters, having a cross-linked copolymer graft at least in its surface region, the graft comonomer being selected from ethylenic carboxylic acids, amine esters of ethylenic carobxylic acids acrylamides and methacrylamides, followed by heating to cause reaction so that metal atoms or ions are chemically bound in the form of a stable inorganic glass in at least the surface region of the said graft.
Claim 2
Dependent Claim 92 words
A composition of matter which is produced by contacting with a metal compound a synthetic substantially hydrophobic base polymer selected from polyolefins, copolyolefins, polyamides, copolyamides, halogenated polyolefins, polyesters, unsaturated polyesters, having a cross-linked copolymer graft at least in its surface region, the graft comonomer being selected from ethylenic carboxylic acids, amine esters of ethylenic carobxylic acids acrylamides and methacrylamides, followed by heating to cause reaction so that metal atoms or ions are chemically bound in the form of a stable inorganic glass in at least the surface region of the said graft.
Claim 3
Dependent Claim 34 words
A composition of matter as claimed in claim 1 and wherein the metal atoms or ions are selected from aluminium, iron, chromium, titanium, lead nickel, zinc, silver, cadmium, alkali metals and alkaline earth metals.
Claim 4
Dependent Claim 35 words
A composition of matter as claimed in claim 1 and wherein the metal atoms or ions are in a surface region of the said graft copolymer having a depth within the range 0.05μ to 2μ.
Claim 5
Dependent Claim 20 words
A composition of matter as claimed in claim 3 and wherein the depth is within the range 0.1μ to 0.2μ.
Claim 6
Dependent Claim 51 words
A composition of matter as claimed in claim 1 and wherein the said synthetic substantially hydrophobic base polymer is selected from low, medium or high density polyethylene, polypropylene, poly-4-methylpentene-1, a copolymer of any of the foregoing, nylon, polyvinyl chloride, polytetrafluoroethylene, polychlorofluoroethylene or a mixture of two or more of the foregoing.
Claim 7
Dependent Claim 24 words
A composition of matter as claimed in claim 1 and wherein the graft comonomer is selected from acrylic acid, methacrylic acid, and butylamine acrylate.
Claim 8
Dependent Claim 42 words
A composition of matter as claimed in claim 1 and which is a film material, the extent of the graft polymerisation being within the range 8% by weight and 70% by weight based upon the total weight of the graft copolymerised material.
Claim 9
Dependent Claim 32 words
A composition of matter as claimed in claim 1 and which is a film material, the extent of the graft copolymerisation being within the range 0.1% by weight to 5% by weight.
Claim 10
Dependent Claim 53 words
A composition of matter as claimed in claim 1 and wherein the said hydrophobic base polymer is selected from high density polyethylene, low density polyethylene, polypropylene, polytetrafluoroethylene and polyvinylchloride, the graft comonomer being selected from acrylic acid and butylamine acrylate and the metal atoms or ions being selected from chromium, aluminum and iron.
Claim 11
Independent Claim 99 words
A method of applying a layer of metal containing inorganic glassy material to the surface of a polymeric material which comprises the steps of graft copolymerising the said polymeric material with a reactive vinyl monomer selected from ethylenic carboxylic acids, amine esters of ethylenic carboxylic acids, acrylamides and methacrylamides, contacting the said graft copolymer with a metal compound, and heating to cause reaction between the metal compound and the said graft copolymer whereby meatl atoms or ions are chemically bound in the form of a stable inorganic glass in at least the surface region of the said graft copolymer.
Claim 12
Independent Claim 99 words
A method of applying a layer of metal containing inorganic glassy material to the surface of a polymeric material which comprises the steps of graft copolymerising the said polymeric material with a reactive vinyl monomer selected from ethylenic carboxylic acids, amine esters of ethylenic carboxylic acids, acrylamides and methacrylamides, contacting the said graft copolymer with a metal compound, and heating to cause reaction between the metal compound and the said graft copolymer whereby meatl atoms or ions are chemically bound in the form of a stable inorganic glass in at least the surface region of the said graft copolymer.
Claim 13
Dependent Claim 41 words
A method as claimed in claim 10 and wherein the polymeric material is selected from synthetic substantially hydrophobic base polymer selected from polyolefins, copolyolefins, polyamides, copolyamides, halogenated polyolefins, polyesters, unsaturated polyesters or a mixture of two or more of the foregoing.
Claim 14
Dependent Claim 45 words
A method as claimed in claim 10 and wherein the polymeric material is selected from low, medium or high density polyethylene, polypropylene, poly-4-methylpentene-1, a copolymer of any of the foregoing, nylon, polyvinyl chloride, polytetrafluoroethylene, polychlorofluoroethylene or a mixture of two or more of the foregoing.
Claim 15
Dependent Claim 23 words
A method as claimed in claim 10 and wherein the reactive vinyl monomer is selected from acrylic acid, methacrylic acid and butylamine acrylate.
Claim 16
Dependent Claim 109 words
A process for the production of a composition of matter wherein a graft copolymer having a synthetic substantially hydrophobic base polymer selected from polyolefins, copolyolefins, polyamides, copolyamides, halogenated polyolefins, polyesters, unsaturated polyesters, having a cross-linked copolymer graft at least in its surface region, the graft comonomer being selected from ethylenic carboxylic acids, amine esters of ethylenic carboxylic acids, acrylamides and methacrylamides is contacted with a metal compound followed by heating to cause reaction between the metal compound and the said graft copolymer whereby metal atoms or ions are chemically bound in the form of a stable inorganic glass in at least the surface region of the said graft copolymer.
Claim 17
Dependent Claim 109 words
A process for the production of a composition of matter wherein a graft copolymer having a synthetic substantially hydrophobic base polymer selected from polyolefins, copolyolefins, polyamides, copolyamides, halogenated polyolefins, polyesters, unsaturated polyesters, having a cross-linked copolymer graft at least in its surface region, the graft comonomer being selected from ethylenic carboxylic acids, amine esters of ethylenic carboxylic acids, acrylamides and methacrylamides is contacted with a metal compound followed by heating to cause reaction between the metal compound and the said graft copolymer whereby metal atoms or ions are chemically bound in the form of a stable inorganic glass in at least the surface region of the said graft copolymer.
Claim 18
Dependent Claim 114 words
A process for chemically bonding metal atoms or ions in the region of the surface of a graft copolymmer having a synthetic substantially hydrophobic base polymer selected from the group consisting of polyolefins, copolyolefins, polyamides, copolyamides, halogenated polyolefins, saturated polyesters and unsaturated polyesters, said copolymer having a cross-linked copolymer graft at least in its surface region, the graft comonomer being selected from ethylenic carboxylic acids, acrylamides and methacrylamides, said process comprising contacting by spraying or dipping the said graft copolymer with a solution containing a metal compound which is a complex aluminium, iron, chromium or titanium phosphate, and heating the resulting product to cause reaction between the metal compound and the said graft copolymer.
Claim 19
Dependent Claim 114 words
A process for chemically bonding metal atoms or ions in the region of the surface of a graft copolymmer having a synthetic substantially hydrophobic base polymer selected from the group consisting of polyolefins, copolyolefins, polyamides, copolyamides, halogenated polyolefins, saturated polyesters and unsaturated polyesters, said copolymer having a cross-linked copolymer graft at least in its surface region, the graft comonomer being selected from ethylenic carboxylic acids, acrylamides and methacrylamides, said process comprising contacting by spraying or dipping the said graft copolymer with a solution containing a metal compound which is a complex aluminium, iron, chromium or titanium phosphate, and heating the resulting product to cause reaction between the metal compound and the said graft copolymer.
Claim 20
Dependent Claim 81 words
A process as claimed in claim 14 annd wherein a solution of a metal compound selected from alkali metal hydroxides, alkaline earth metal hydroxides, copper nitrates, copper sulphates, copper chlorides, lead sulphates and salts of iron, nickel, chromium, zinc, silver, cadmium and aluminium is applied to the said graft copolymer followed by heating to remove the solvent and by flash heating to cause chemical binding of individual metal atoms or ions within or upon the surface of the said graft copolymer.
Claim 21
Dependent Claim 44 words
A process as claimed in claim 16 and wherein the time of contact between metal compound solution and the said graft copolymer is controlled so that the penetration of the said metal compound into the said graft copolymer takes place to a perdetermined extent.
Claim 22
Dependent Claim 23 words
A process as claimed in claim 17 and wherein the flash heating is by flaming, induction heating or by hot electrically sustained flames.
Claim 23
Dependent Claim 45 words
A process as claimed in claim 14 and wherein the metal compound is a metal containing polymerisable comonomer which is contacted with the said graft copolymer in solution followed by polymerisation of the metal containing copolymerisable comonomer by radiation, ionic or free radical initiated process.
Claim 24
Dependent Claim 17 words
A process as claimed in claim 19 and wherein the metal containing polymerisable comonomer is vinyl ferrocene.
Claim 25
Dependent Claim 21 words
The composition of matter of claim 1 wherein the hydrophobic base polymer is polyethylene and the graft monomer is acrylic acid.
Claim 26
Dependent Claim 135 words
A process for the production of a composition of matter which is a polymeric material having metal atoms or ions at least in the surface region thereof wherein a graft copolymer having a synthetic substantially hydrophobic base polymer selected from polyolefins, copolyolefins, polyamides, copolyamides, halogenated polyolefins, polyesters, unsaturated polyesters, having a cross-linked copolymer graft at least in its surface region, the graft comonomer being selected from ethylenic carboxylic acids, amine esters of ethylenic carboxylic acids, acrylamides and methacrylamides is contacted with a solution of a complex aluminum, iron, chromium or titanium phosphate which is applied to the said graft copolymer by dipping or spraying followed by heating so removing the solvent and further heating to decompose the metal complex to a stable inorganic glass bonded within or on the surface of the said graft copolymer.
Claim 27
Dependent Claim 135 words
A process for the production of a composition of matter which is a polymeric material having metal atoms or ions at least in the surface region thereof wherein a graft copolymer having a synthetic substantially hydrophobic base polymer selected from polyolefins, copolyolefins, polyamides, copolyamides, halogenated polyolefins, polyesters, unsaturated polyesters, having a cross-linked copolymer graft at least in its surface region, the graft comonomer being selected from ethylenic carboxylic acids, amine esters of ethylenic carboxylic acids, acrylamides and methacrylamides is contacted with a solution of a complex aluminum, iron, chromium or titanium phosphate which is applied to the said graft copolymer by dipping or spraying followed by heating so removing the solvent and further heating to decompose the metal complex to a stable inorganic glass bonded within or on the surface of the said graft copolymer.
Claim 28
Dependent Claim 44 words
A process as claimed in claim 22 and wherein the time of contact between metal compound solution and the said graft copolymer is controlled so that the penetration of the said metal compound into the said graft copolymer takes place to a predetermined extent.
Claim 29
Dependent Claim 152 words
A process for the production of a composition of matter which is a polymeric material having metal atoms or ions at least in the surface region thereof wherein a graft copolymer having a synthetic substantially hydrophobic base polymer selected from polyolefins, copolyolefins, polyamides, copolyamides, halogenated polyolefins, polyesters, unsaturated polyesters, having a cross-linked copolymer graft at least in its surface region, the graft comonomer being selected from ethylenic carboxylic acids, amine esters of ethylenic carboxylic acids, acrylamides and methacrylamides is contacted with a solution of a metal compound selected from alkali metal hydroxides, alkaline earth metal hydroxides, copper nitrates, copper sulphates, copper chlorides, lead sulphates and salts of iron, nickel, chromium, zinc, silver, cadmium and aluminium applied to the said graft copolymer followed by heating to remove the solvent and by flash heating to cause chemical binding of individual metal atoms or ions within or upon the surface of the said graft copolymer.
Claim 30
Dependent Claim 152 words
A process for the production of a composition of matter which is a polymeric material having metal atoms or ions at least in the surface region thereof wherein a graft copolymer having a synthetic substantially hydrophobic base polymer selected from polyolefins, copolyolefins, polyamides, copolyamides, halogenated polyolefins, polyesters, unsaturated polyesters, having a cross-linked copolymer graft at least in its surface region, the graft comonomer being selected from ethylenic carboxylic acids, amine esters of ethylenic carboxylic acids, acrylamides and methacrylamides is contacted with a solution of a metal compound selected from alkali metal hydroxides, alkaline earth metal hydroxides, copper nitrates, copper sulphates, copper chlorides, lead sulphates and salts of iron, nickel, chromium, zinc, silver, cadmium and aluminium applied to the said graft copolymer followed by heating to remove the solvent and by flash heating to cause chemical binding of individual metal atoms or ions within or upon the surface of the said graft copolymer.
Claim 31
Dependent Claim 44 words
A process as claimed in claim 24 and wherein the time of contact between metal compound solution and the said graft copolymer is controlled so that the penetration of the said metal compound into the said graft copolymer takes place to a predetermined extent.
Claim 32
Dependent Claim 23 words
A process as claimed in claim 25 and wherein the flash heating is by flaming, induction heating or by hot electrically sustained plasma.
Claim 33
Dependent Claim 106 words
A process for the production of a composition of matter which is a polymeric material having metal atoms or ions at least in the surface region thereof wherein a graft copolymer having a synthetic substantially hydrophobic base polymer selected from polyolefins, copolyolefins, polyamides, copolyamides, halogenated polyolefins, polyesters, usaturated polyesters, having a cross-linked copolymer graft at least in its surface region, the graft comonomer being selected from ethylenic carboxylic acids, amine esters of ethylenic carboxylic acids, acrylamides and methacrylamides is contacted with a solution of a metal containing polymerizable comonomer followed by polymerization of the metal containing copolymerizable comonomer by radiation, ionic or free radical initiated process.
Claim 34
Dependent Claim 106 words
A process for the production of a composition of matter which is a polymeric material having metal atoms or ions at least in the surface region thereof wherein a graft copolymer having a synthetic substantially hydrophobic base polymer selected from polyolefins, copolyolefins, polyamides, copolyamides, halogenated polyolefins, polyesters, usaturated polyesters, having a cross-linked copolymer graft at least in its surface region, the graft comonomer being selected from ethylenic carboxylic acids, amine esters of ethylenic carboxylic acids, acrylamides and methacrylamides is contacted with a solution of a metal containing polymerizable comonomer followed by polymerization of the metal containing copolymerizable comonomer by radiation, ionic or free radical initiated process.
Claim 35
Dependent Claim 17 words
A process as claimed in claim 19 and wherein the metal containing polymerizable comonomer is vinyl ferrocene.
Claim 36
Dependent Claim 44 words
A process as claimed in claim 15 and wherein the time of contact between metal compound solution and the said graft copolymer is controlled so that the penetration of the said metal compound into the said graft copolymer takes place to a predetermined extent.
Claim 37
Dependent Claim 22 words
A process as claimed in claim 15 wherein the flash heating is by flaming, induction heating or by hot electrically sustained plasma.

References Cited (Backward Citations)

US3376168A Cited
US3297471A Cited
US3522223A Cited
US3951924A Cited

USPTO Annuity & Maintenance Windows

Annuity Stage Window Opens Payment Deadline Surcharge Period Until Estimated Fee Status
3.5 Years (Year 4) 1982-04-09 1982-10-09 1983-04-10 $2000.00 Window Closed / Lapsed
7.5 Years (Year 8) 1986-04-09 1986-10-09 1987-04-10 $3760.00 Window Closed / Lapsed
11.5 Years (Year 12) 1990-04-09 1990-10-09 1991-04-10 $7700.00 Window Closed / Lapsed

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