CA1152279A - Enclosure member substantially impermeable to the transmission of solvents and fuels - Google Patents
Enclosure member substantially impermeable to the transmission of solvents and fuelsInfo
- Publication number
- CA1152279A CA1152279A CA000370747A CA370747A CA1152279A CA 1152279 A CA1152279 A CA 1152279A CA 000370747 A CA000370747 A CA 000370747A CA 370747 A CA370747 A CA 370747A CA 1152279 A CA1152279 A CA 1152279A
- Authority
- CA
- Canada
- Prior art keywords
- weight
- enclosure member
- permeability
- enclosure
- concentration
- Prior art date
- Legal status (The legal status 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 status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2461/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
- Y10T428/1397—Single layer [continuous layer]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
- Y10T428/2495—Thickness [relative or absolute]
- Y10T428/24967—Absolute thicknesses specified
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
- Y10T428/269—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension including synthetic resin or polymer layer or component
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31678—Of metal
- Y10T428/31692—Next to addition polymer from unsaturated monomers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/31909—Next to second addition polymer from unsaturated monomers
- Y10T428/31913—Monoolefin polymer
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/31909—Next to second addition polymer from unsaturated monomers
- Y10T428/31928—Ester, halide or nitrile of addition polymer
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/31938—Polymer of monoethylenically unsaturated hydrocarbon
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Treatments Of Macromolecular Shaped Articles (AREA)
- Sealing Material Composition (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Containers Having Bodies Formed In One Piece (AREA)
Abstract
ABSTRACT
The present application relates to enclosure members consisting essentially of solid polyolefins that have a linear carbon to carbon backbone structure and having a plurality of free hydrogen atoms attached to the carbon atoms with a permeability to wet solvents and fuels of less than 1/7, optionally less than 1/40 of the permeability of untreated enclosure members having a thickness of 1 mm. Said low permeability is due to the presence of a layer of an iron phenanthroline complex on at least the inner surface of said enclosure members, having a portion of the hydrogen atoms replaced by sulphonic acid or sulphonate groups.
The present application relates to enclosure members consisting essentially of solid polyolefins that have a linear carbon to carbon backbone structure and having a plurality of free hydrogen atoms attached to the carbon atoms with a permeability to wet solvents and fuels of less than 1/7, optionally less than 1/40 of the permeability of untreated enclosure members having a thickness of 1 mm. Said low permeability is due to the presence of a layer of an iron phenanthroline complex on at least the inner surface of said enclosure members, having a portion of the hydrogen atoms replaced by sulphonic acid or sulphonate groups.
Description
" ~5Z27~ 1 , An enclosure member substantially impermeable to the transmission of solvents and fuels.
The present invention relates to an enclosure member substantially impermeable to the transmissio~ of solvents and fuels consisting essentially of solid polyolefins that have a linear carbon to carbon backbone structure and have a plurality of free hydrogen atoms attached to the carbon atomsJ the enclosure having an inner and outer surface, at least the inner surface having a portion of the hydrogen atoms replaced by sulphonic acid groups and a process for preparing it.
Generally the above type of enclosure members have excellent properties, being light in weight, strong, resistant to impact and unaffected by a wide range of chemicals. However, polyethylene, for example, has inherently a high permeability to many orgànic solvents, particularly hydrocarbons and chlorinated hydrocarbons. This has prevented them from being used extensively in, for example, petrol lS tanks for vehicles or shipping containers where these solvents are present in the product to be packed.
Several methods of reducing said permeability are known and one of the most successful of these is to sulphonate the surface of the container by treatment with sulphur trioxide and neutralise the sulphonic acids formed on the polyethylene surface. (Vide USP 2 793 964 3 613 957 and 3 740 25B).
Although the permeability for dry solvents is much reduced by means of sulphonation it has been found that a sulphonated surface will loose the barrier properties achieved, if it is in contact with a solvent that contains a significant proportlon of water ~or a period of some days. If such a sulphonated polyethylene surface is in contact with a wet solvent for some weeks the permeability may rise to an unacceptable level.
The effect of water in various solvents on the permeability of sulphonated polyethylene is shown in Table A. Solvents which permeate at a faster rate appear to be affected by water to a greater extent.
,~ ~
15Z;~:79 TABLE A
The effect of water in different solvents on the permeability of sulphonated polyethylene bottles after 6 weeks storage at 20C.
_ .
Permeability ~g mm/m2/day) sulphonated un-treated .. _ xylene 0.6 : 20 xyl.ene + 1 % water 5.0 20 petrol 0.9 28 petrol + 1 % water 3.0 28 iso octane 0.1 1.4 iso octane + 1 % water0.1 ¦ 1.4 petroleum ether 1 0.3 5 11 ~petroleum ether + 1 % water l 0.6 , It has been found that actinic radiation, i.e. sunlight, affects the colour of sulphonated polyethylene. This explains why sulphonated polyethylene surfaces are affected by light when it is subJected to daylight behind a glass window. Contact of a sulphonated polyethylene surface in daylight with water promotes synergistically a deterioration of said sulphonated polyethylene surface. Probably such a surface is degraded by either water and/or light and residues absorbed by the liquid.
The de-colouration of sulphonated polyethylene by daylight may be eliminated by using a polyethylene that contains a black pigment and/or dye stuff. When exposed to daylight black polyethylene is less sensitive to the above effect than a natural polyethylene, as can be seen from Table B which relates the effect to increases, and therefore deterioration, in permeability properties.
-" llSZ279 .
TABLE B
Permeability of sulphonated polyethylene bottles to xylene - the effect of water in the xylene and daylight after 6 weeks storage at 20C.
~reatment ¦ Situation i Colour of ¦ Permcability (g mm/m2/day) bottle xylene 1 xylene+l % H20 . ~
Sulphonated Daylight ~ Natural ~ 0.6 9.8 ~ Black ~ 0.3 4.1 Sulphonated Dark I Natural 1 0.3 3.6 ¦ Black ~ 0.4 3.7 .
Untreated Daylight Natural ~ 17 17 l Black ~ 20 22 - ;
It has been observed that water or light separately reduce the concentration of sulphonate groups at the surface of a sulphonated polyethylene by about 30 % in 15 weeks. Water and light together reduce the sulphur concentration to zero in that time.
Even when a sulphonated polyethylene surface is not in contact with liquid, the presence of a solvent vapour or water vapour in the atmosphere will reduce the concentration o~f sulphonate groups if the samples are in daylight. However, in the absence of light the concentration is not significantly changed, as appears from Table C.
TABLE C
~ the sulphur concentration of sul.phonated polyethylene.
_ Sulphur concentration (g/m I
after 6 weeks storage at 20 C.
in daylight I in darkness _ _ _ Dry ai.r 0.9 ~ 1.0 Saturated water vapour 0.2 ~ 0.8 Saturated x lene va our I 0 3 1 1.0 Y P ~
-``` 1~5;2Z79 It was found, that enclosure members consisting essentially of solid poiyolefins that have a linear carbon to carbon backbone structure and having a plurality of free hydrogen atoms attached to the carbon atoms with a permeability to wet solvents and fuels of less than 1/7, optionally less than 1/40, of the permeability of untreated enclosure members having a thickness of 1 mm, may be obtained by subJecting at least the inner surface thereof having a portion of the hydrogen atoms replaced by sulphonic acid or sulphonate groups to a treatment with an aqueous solution comprising ferrous sulphate and phenantroline, both in a concentration of at least 0,05 weight % at 20C, at which at least a part of the cations of said surface has been replaced by said iron-phenantroline complex.
Preferably a mixture of a one weight % aqueous solution of ferrous sulphate and a one weight % aqueous solution of phenantroline is used.
Example l Polyehylene Samples A number of bottles were blow moulded by BP Chemicals Ltd.
from their Rigidex 00255. ~Trademark) Sulphonation The bottles were dried by passing dry air or nitrogen (less than 2 ppm water) through the bottle. Dry air or nitrogen containing 15 volume % S03 was then passed into the bottle until it had replaced the original air or nitrogen. After leaving the vapour in the bottle for 2 minutes it was removed by blowing dry air or nitrogen through the bottle for a few minutes. If neutralisation with ammonia gas was required this was then passed through the bottle, and blown out with air. Any remaining sulphur trioxide and/or ammonia was washed out with water. Where required neutralisation with 5 % ammonium hydroxide was carried out at this stage, and the bottle washed again and allowed to dry at ambient temperature.
The permeability was measured by filling the bottle with xylene sealing the top and weighing the sealed bottle. The bottle was stored at ambient temperature until a steady weight loss was recorded.
A similar test was conducted on another bottle with 1 weight ~ water added to the xylene.
.~ .
" 1152279 PerMeability to dry xylene 0.2 g mm/m /day Permeability to xylene + 1 weight ~ water 6.2 g mm/m2/day Permeability of unsulphonated bottle 20 g mm/m21day to dry xylene Example 2 Two bottles were treated as described in Example 1. Two further bottles were treated similarly except that after the sulphur trioxide had been flushed out with dry nitrogen the polyethylene surface was neutralised by passing ammonia gas into the bottle. This was then removed with nitrogen and the bottles washed and dried. One bottle of each type was treated further as described below.
A solution was made by mixing a 1 weight % aqueous solution of ferrous sulphate and a 1 weight % aqueous solution of phenanthroline.
The two bottles were filled with this solution and emptied after a few minutes. They were then rinsed with water and dried.
The permeability of all four bottles to xylene + 1 weight %
water was then measured as in Example 1 with the results shown in Table D.
TABLE D
~ 2 Post Treatment ¦ Permeability (g mm/m /day) after Sulphonation ~Aqueous Ammonia ¦ Aqueous Gas ~ . ~ I
None ~ 3.2 ¦ 5.1 Washed with iron ,~ ' phenanthrollne complex L l.o !! 0 5 Example 3.
Several bottles were sulphonated as descrlbed in Example 1.
The surface was either neutralised with aqueous ammonia, ammonia gas or in some cases not at all. The post treatment was as described in Example 2 but the time allowed for the reaction and the temperature of the solution were varied. The permeabili-ty to xylene containing 1 weight % water is shown in Table E.
-``" 1~5Z279 TABLE E
. . . _ Time and Temperature Permeability (g mm/m2¦day) !
of post treatment Unneutralised ~ Aqueous Ammonia I Ammonia Gas _ _ _.
20C/2 minutes 1.0 1.7 1.4 20C/30 minutes 1.0 0.5 0.4 50C/2 minutes 1 0.9 1.0 1.2 Example 4 Several polyethylene bottles were modified as described in Example 3 using ammonia gas to neutralise the sulphonated surface. The reaction time was maintained at 2 minutes at 20 C but the concentrations of ferrous sulphate and phenanthroline were varied. The results of permeability tests using xylene containing 1 weight ~ water are shown in Table F.
TABLE F
I Concentration Concentration Permeab~lity ! of Fe S04(weight%) tof phenanthroline (weight~) (g mm/m /day) 0.05 1 0.05 3.2 ~ 0.2 ~ 0.2 1.6 ~ 0.2 l 0'5 2.~
1 0.5 . 0.2 1.7 1 0~5 ~ 0.5 1.4
The present invention relates to an enclosure member substantially impermeable to the transmissio~ of solvents and fuels consisting essentially of solid polyolefins that have a linear carbon to carbon backbone structure and have a plurality of free hydrogen atoms attached to the carbon atomsJ the enclosure having an inner and outer surface, at least the inner surface having a portion of the hydrogen atoms replaced by sulphonic acid groups and a process for preparing it.
Generally the above type of enclosure members have excellent properties, being light in weight, strong, resistant to impact and unaffected by a wide range of chemicals. However, polyethylene, for example, has inherently a high permeability to many orgànic solvents, particularly hydrocarbons and chlorinated hydrocarbons. This has prevented them from being used extensively in, for example, petrol lS tanks for vehicles or shipping containers where these solvents are present in the product to be packed.
Several methods of reducing said permeability are known and one of the most successful of these is to sulphonate the surface of the container by treatment with sulphur trioxide and neutralise the sulphonic acids formed on the polyethylene surface. (Vide USP 2 793 964 3 613 957 and 3 740 25B).
Although the permeability for dry solvents is much reduced by means of sulphonation it has been found that a sulphonated surface will loose the barrier properties achieved, if it is in contact with a solvent that contains a significant proportlon of water ~or a period of some days. If such a sulphonated polyethylene surface is in contact with a wet solvent for some weeks the permeability may rise to an unacceptable level.
The effect of water in various solvents on the permeability of sulphonated polyethylene is shown in Table A. Solvents which permeate at a faster rate appear to be affected by water to a greater extent.
,~ ~
15Z;~:79 TABLE A
The effect of water in different solvents on the permeability of sulphonated polyethylene bottles after 6 weeks storage at 20C.
_ .
Permeability ~g mm/m2/day) sulphonated un-treated .. _ xylene 0.6 : 20 xyl.ene + 1 % water 5.0 20 petrol 0.9 28 petrol + 1 % water 3.0 28 iso octane 0.1 1.4 iso octane + 1 % water0.1 ¦ 1.4 petroleum ether 1 0.3 5 11 ~petroleum ether + 1 % water l 0.6 , It has been found that actinic radiation, i.e. sunlight, affects the colour of sulphonated polyethylene. This explains why sulphonated polyethylene surfaces are affected by light when it is subJected to daylight behind a glass window. Contact of a sulphonated polyethylene surface in daylight with water promotes synergistically a deterioration of said sulphonated polyethylene surface. Probably such a surface is degraded by either water and/or light and residues absorbed by the liquid.
The de-colouration of sulphonated polyethylene by daylight may be eliminated by using a polyethylene that contains a black pigment and/or dye stuff. When exposed to daylight black polyethylene is less sensitive to the above effect than a natural polyethylene, as can be seen from Table B which relates the effect to increases, and therefore deterioration, in permeability properties.
-" llSZ279 .
TABLE B
Permeability of sulphonated polyethylene bottles to xylene - the effect of water in the xylene and daylight after 6 weeks storage at 20C.
~reatment ¦ Situation i Colour of ¦ Permcability (g mm/m2/day) bottle xylene 1 xylene+l % H20 . ~
Sulphonated Daylight ~ Natural ~ 0.6 9.8 ~ Black ~ 0.3 4.1 Sulphonated Dark I Natural 1 0.3 3.6 ¦ Black ~ 0.4 3.7 .
Untreated Daylight Natural ~ 17 17 l Black ~ 20 22 - ;
It has been observed that water or light separately reduce the concentration of sulphonate groups at the surface of a sulphonated polyethylene by about 30 % in 15 weeks. Water and light together reduce the sulphur concentration to zero in that time.
Even when a sulphonated polyethylene surface is not in contact with liquid, the presence of a solvent vapour or water vapour in the atmosphere will reduce the concentration o~f sulphonate groups if the samples are in daylight. However, in the absence of light the concentration is not significantly changed, as appears from Table C.
TABLE C
~ the sulphur concentration of sul.phonated polyethylene.
_ Sulphur concentration (g/m I
after 6 weeks storage at 20 C.
in daylight I in darkness _ _ _ Dry ai.r 0.9 ~ 1.0 Saturated water vapour 0.2 ~ 0.8 Saturated x lene va our I 0 3 1 1.0 Y P ~
-``` 1~5;2Z79 It was found, that enclosure members consisting essentially of solid poiyolefins that have a linear carbon to carbon backbone structure and having a plurality of free hydrogen atoms attached to the carbon atoms with a permeability to wet solvents and fuels of less than 1/7, optionally less than 1/40, of the permeability of untreated enclosure members having a thickness of 1 mm, may be obtained by subJecting at least the inner surface thereof having a portion of the hydrogen atoms replaced by sulphonic acid or sulphonate groups to a treatment with an aqueous solution comprising ferrous sulphate and phenantroline, both in a concentration of at least 0,05 weight % at 20C, at which at least a part of the cations of said surface has been replaced by said iron-phenantroline complex.
Preferably a mixture of a one weight % aqueous solution of ferrous sulphate and a one weight % aqueous solution of phenantroline is used.
Example l Polyehylene Samples A number of bottles were blow moulded by BP Chemicals Ltd.
from their Rigidex 00255. ~Trademark) Sulphonation The bottles were dried by passing dry air or nitrogen (less than 2 ppm water) through the bottle. Dry air or nitrogen containing 15 volume % S03 was then passed into the bottle until it had replaced the original air or nitrogen. After leaving the vapour in the bottle for 2 minutes it was removed by blowing dry air or nitrogen through the bottle for a few minutes. If neutralisation with ammonia gas was required this was then passed through the bottle, and blown out with air. Any remaining sulphur trioxide and/or ammonia was washed out with water. Where required neutralisation with 5 % ammonium hydroxide was carried out at this stage, and the bottle washed again and allowed to dry at ambient temperature.
The permeability was measured by filling the bottle with xylene sealing the top and weighing the sealed bottle. The bottle was stored at ambient temperature until a steady weight loss was recorded.
A similar test was conducted on another bottle with 1 weight ~ water added to the xylene.
.~ .
" 1152279 PerMeability to dry xylene 0.2 g mm/m /day Permeability to xylene + 1 weight ~ water 6.2 g mm/m2/day Permeability of unsulphonated bottle 20 g mm/m21day to dry xylene Example 2 Two bottles were treated as described in Example 1. Two further bottles were treated similarly except that after the sulphur trioxide had been flushed out with dry nitrogen the polyethylene surface was neutralised by passing ammonia gas into the bottle. This was then removed with nitrogen and the bottles washed and dried. One bottle of each type was treated further as described below.
A solution was made by mixing a 1 weight % aqueous solution of ferrous sulphate and a 1 weight % aqueous solution of phenanthroline.
The two bottles were filled with this solution and emptied after a few minutes. They were then rinsed with water and dried.
The permeability of all four bottles to xylene + 1 weight %
water was then measured as in Example 1 with the results shown in Table D.
TABLE D
~ 2 Post Treatment ¦ Permeability (g mm/m /day) after Sulphonation ~Aqueous Ammonia ¦ Aqueous Gas ~ . ~ I
None ~ 3.2 ¦ 5.1 Washed with iron ,~ ' phenanthrollne complex L l.o !! 0 5 Example 3.
Several bottles were sulphonated as descrlbed in Example 1.
The surface was either neutralised with aqueous ammonia, ammonia gas or in some cases not at all. The post treatment was as described in Example 2 but the time allowed for the reaction and the temperature of the solution were varied. The permeabili-ty to xylene containing 1 weight % water is shown in Table E.
-``" 1~5Z279 TABLE E
. . . _ Time and Temperature Permeability (g mm/m2¦day) !
of post treatment Unneutralised ~ Aqueous Ammonia I Ammonia Gas _ _ _.
20C/2 minutes 1.0 1.7 1.4 20C/30 minutes 1.0 0.5 0.4 50C/2 minutes 1 0.9 1.0 1.2 Example 4 Several polyethylene bottles were modified as described in Example 3 using ammonia gas to neutralise the sulphonated surface. The reaction time was maintained at 2 minutes at 20 C but the concentrations of ferrous sulphate and phenanthroline were varied. The results of permeability tests using xylene containing 1 weight ~ water are shown in Table F.
TABLE F
I Concentration Concentration Permeab~lity ! of Fe S04(weight%) tof phenanthroline (weight~) (g mm/m /day) 0.05 1 0.05 3.2 ~ 0.2 ~ 0.2 1.6 ~ 0.2 l 0'5 2.~
1 0.5 . 0.2 1.7 1 0~5 ~ 0.5 1.4
Claims (8)
1. An enclosure member substantially impermeable to the transmission of solvents and fuels consisting essentially of solid polyolefins that have a linear carbon to carbon backbone structure and have a plurality of free hydrogen atoms attached to the carbon atoms with a permeability to wet solvents and fuels of less than 1/7 of the permeability of untreated enclosure members having a thickness of 1 mm, the enclosure having an inner ant outer surface, at least the inner surface having a portion of the hydrogen atoms replaced by sulfonic or sulfonate groups and being subjected to a treatment with an aqueous solution comprising ferrous sulfate and phenanthroline, both in a concentration of at least 0.05 weight % at 20°C, at which at least a part of the cations of said surfacehas been replaced by said iron-phenanthroline complex.
2. An enclosure member according to claim 1, wherein said solid poly-olefin is polyethylene.
3. An enclosure member according to claim 1, wherein a layer bearing non-neutralized sulfonic acid groups has been subjected to a treatment with an aqueous soluton comprising ferrous sulfate in a concentration of 0.5 weight % and phenanthroline in a concentration of 0.5 weight %.
4. A process for rendering impermeable to the transmission of wet or dry solvents, fuels, vapors and gases an enclosure member consisting essen-tially of solid polyolefins that have a linear carbon to carbon backbone structure and have a plurality of free hydrogen atoms attached to the carbon atoms, which process comprises treating the inner, outer or both the inner and outer surfaces of the enclosure member with sulfur tri-oxide, removing excess of sulfur trioxide with a stream of dry air followed by washing with an aqueous solution, then subjecting it to a treatment with an aqueous solution comprising ferrous and phenanthroline, both in a concentration of at least 0.05 weight % at 20°C.
5. A process according to claim 4 wherein said enclosure member consists of polyethylene.
6. A process according to claim 4, wherein said enclosure member bearing non-neutralized sulfonic acid groups is subjected to a treatment with an aqueous solution comprising ferrous sulfate in a concentration of 0.5 weight X and phenanthroline in a concentration of 0.5 weight %.
7. An enclosure member substantially impermeable to the transmission of solvents and fuels consisting essentially of solid polyolefins that have a linear carbon to carbon backbone structure and have a plurality of free hydrogen atoms attached to the carbon atoms with a permeability to wet solvents and fuels of less than 1/40 of the permeability of untreated enclosure membes having a thickness of 1 mm, the enclosure having an inner and outer surface, at least the inner surface having a portion of the hydrogen atoms replaced by sulfonic or sulfonate groups and being subjected to a treatment with an aqueous solution comprising ferrous sulfate and phenanthroline, both in a concentration of at least 0.05 weight X at 20°C, at which at least a part of the cations of said surfacehas been replaced by said iron-phenanthroline complex.
8. An enclosure member according to claim 7, wherein said solid poly-olefin is polyethylene.
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB8,004,570 | 1980-02-12 | ||
GB8004570 | 1980-02-12 | ||
US06/214,623 US4348436A (en) | 1980-02-12 | 1980-12-10 | Enclosure member substantially impermeable to the transmission of solvents and fuels |
US214,623 | 1980-12-10 |
Publications (1)
Publication Number | Publication Date |
---|---|
CA1152279A true CA1152279A (en) | 1983-08-23 |
Family
ID=26274462
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA000370747A Expired CA1152279A (en) | 1980-02-12 | 1981-02-12 | Enclosure member substantially impermeable to the transmission of solvents and fuels |
Country Status (8)
Country | Link |
---|---|
AR (1) | AR226201A1 (en) |
AU (1) | AU538912B2 (en) |
BR (1) | BR8100831A (en) |
CA (1) | CA1152279A (en) |
DE (1) | DE3168555D1 (en) |
DK (1) | DK58681A (en) |
ES (1) | ES499320A0 (en) |
PT (1) | PT72492B (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2606911A (en) * | 1949-04-01 | 1952-08-12 | Glidden Co | Preparation of etio-steroid acids |
-
1981
- 1981-02-06 DE DE8181200154T patent/DE3168555D1/en not_active Expired
- 1981-02-11 BR BR8100831A patent/BR8100831A/en unknown
- 1981-02-11 PT PT72492A patent/PT72492B/en unknown
- 1981-02-11 ES ES499320A patent/ES499320A0/en active Granted
- 1981-02-11 DK DK58681A patent/DK58681A/en not_active Application Discontinuation
- 1981-02-11 AU AU67190/81A patent/AU538912B2/en not_active Ceased
- 1981-02-12 CA CA000370747A patent/CA1152279A/en not_active Expired
- 1981-02-12 AR AR284275A patent/AR226201A1/en active
Also Published As
Publication number | Publication date |
---|---|
AU538912B2 (en) | 1984-08-30 |
AU6719081A (en) | 1981-08-20 |
PT72492A (en) | 1981-03-01 |
DE3168555D1 (en) | 1985-03-14 |
ES8201490A1 (en) | 1982-01-01 |
BR8100831A (en) | 1981-08-25 |
ES499320A0 (en) | 1982-01-01 |
AR226201A1 (en) | 1982-06-15 |
PT72492B (en) | 1983-02-08 |
DK58681A (en) | 1981-08-13 |
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Legal Events
Date | Code | Title | Description |
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MKEX | Expiry |