CA1090498A - Degradable disposable polyolefine compositions - Google Patents
Degradable disposable polyolefine compositionsInfo
- Publication number
- CA1090498A CA1090498A CA157,334A CA157334A CA1090498A CA 1090498 A CA1090498 A CA 1090498A CA 157334 A CA157334 A CA 157334A CA 1090498 A CA1090498 A CA 1090498A
- Authority
- CA
- Canada
- Prior art keywords
- carboxylic acid
- metal
- composition according
- free carboxylic
- thermoplastics
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
Thermoplastics compositions, especially poly-olefine compositions, contain a metal carboxylate plus a free carboxylic acid as a synergistic prodegradant. Iron stearate plus extra stearic acid is an effective mixture for low and high density polyethylene. The compositions are useful for making disposable plastic wrappings, containers and the like.
Thermoplastics compositions, especially poly-olefine compositions, contain a metal carboxylate plus a free carboxylic acid as a synergistic prodegradant. Iron stearate plus extra stearic acid is an effective mixture for low and high density polyethylene. The compositions are useful for making disposable plastic wrappings, containers and the like.
Description
105~0~38 This invention relates to thermoplastics compositions.
The use of disposable plastics wrappings, containers and the like and their subsequent discarding, either intentionally or accidentally, has led to the problem of plastics litter. This invention relates to a plastics composition the use of which can alleviate the problem.
According to the invention a thermoplastics composition contains as prodegradant a free carboxylic acid and a metal salt of a carboxylic acid said metal having an atomic number of 22 to 29, each being present in such a concentration that; ~-(a) The total amount of metal salt ~ free carboxylic acid is between 0.001~ and 40% by weight based on the total composition;
(b) the amount of free carboxylic acid is from 10% up to 95~ by weight, preferably from 50% up to 90% by weight, of the total amount of metal salt plus free carboxylic acid.
The metals with atomic numbers 22 to 29 are Ti, V, Cr, Mn, Fe, Co, Ni and Cu; of these the preferred metals are iron and manganese.
The thermoplastics compositions described above include both end-use compositions and masterbatch
The use of disposable plastics wrappings, containers and the like and their subsequent discarding, either intentionally or accidentally, has led to the problem of plastics litter. This invention relates to a plastics composition the use of which can alleviate the problem.
According to the invention a thermoplastics composition contains as prodegradant a free carboxylic acid and a metal salt of a carboxylic acid said metal having an atomic number of 22 to 29, each being present in such a concentration that; ~-(a) The total amount of metal salt ~ free carboxylic acid is between 0.001~ and 40% by weight based on the total composition;
(b) the amount of free carboxylic acid is from 10% up to 95~ by weight, preferably from 50% up to 90% by weight, of the total amount of metal salt plus free carboxylic acid.
The metals with atomic numbers 22 to 29 are Ti, V, Cr, Mn, Fe, Co, Ni and Cu; of these the preferred metals are iron and manganese.
The thermoplastics compositions described above include both end-use compositions and masterbatch
- 2 -s '~ .
1090~98 compositions, i.e. compositions which contain high concentr-ations of additives and the utility of which is that they can be added to the pure polymer to give an end-use composition.
In the case of end-use compositions concentration (a) above is usually between 0.01% and 2%, preferably between 0.1% and 1%. The composition may contain a single polymer or it may contain a blend of several polymers.
The free carboxylic acid is preferably, but not necessarily, the same as that of the metal carboxylate.
However both are preferably selected from the group of those with the formula R.COOH where R is a hydrocarbon group with up to 30 carbon atoms. Particularly suitable acids are those in which R iS a straight chain hydrocarbon group with 8 up to 21 carbon atoms and having less than
1090~98 compositions, i.e. compositions which contain high concentr-ations of additives and the utility of which is that they can be added to the pure polymer to give an end-use composition.
In the case of end-use compositions concentration (a) above is usually between 0.01% and 2%, preferably between 0.1% and 1%. The composition may contain a single polymer or it may contain a blend of several polymers.
The free carboxylic acid is preferably, but not necessarily, the same as that of the metal carboxylate.
However both are preferably selected from the group of those with the formula R.COOH where R is a hydrocarbon group with up to 30 carbon atoms. Particularly suitable acids are those in which R iS a straight chain hydrocarbon group with 8 up to 21 carbon atoms and having less than
3 double bonds.
The prodegradant according to the invention is particularly suitable for increasing the rate of degradation of olefine polymers, olefine copolymers with other monomers copolymerisable with olefine monomers and blends of the olefine polymers and/or copolymers.
The preferred olefine polymers are: ;
(1) Homopolymers of ethylene, propylene, butene-1,
The prodegradant according to the invention is particularly suitable for increasing the rate of degradation of olefine polymers, olefine copolymers with other monomers copolymerisable with olefine monomers and blends of the olefine polymers and/or copolymers.
The preferred olefine polymers are: ;
(1) Homopolymers of ethylene, propylene, butene-1,
4-methyl pentene-l and styrene.
:
.. . . .. . .
: : .
1()90~98 ~
(2) Copolymers of these with one another and other ~-olefines. ~ :
The preferred olefine copolymers are those which contain at least 50~ by weight of ethylene, propylene, butene-l, 4-methyl pentene-l and/or styrene together with at least one of the following comonomers:
vinyl chloride vinyl acetate -methyl acrylate methyl methacrylate ~ :
acrylic acid methacrylic acid hydroxyethyl methacrylate The preferred olefine copolymers include the ionomers ~ ~
produced by neutralising or partially neutralising the : --carboxylic groups of those copolymers which contain ~; ~
carboxylic groups. .- .`
Copolymers which contain at least 50% by weight :~
of ethylene are particularly suitable. .
In addition to the polymer and the prodegradant a composition according to the invention may also include .~-other additives~which are conventionally incorporated in ~ :
thermoplastics polymer compositions, for example in the : -~
case of polyolefines they may incorporate anti-blocking : agents, slip agents, anti:static agents, stabilisers to -` ~ ' :
- 4 _ ~-: .
., : ;
lV90~98 stabilise the composition during processiny as well as stabilisers to stabilise the composition during use (i.e. after processing has finished).
The invention includes wrapping material, string and containers (including lids for containers) made of the plastics composition described above. The following are examples of containers; bags, sacks, boxes, cartons, bottles, sachets, cups and cartridge cases.
The invention also includes an item of merchandise packed in a material made of a plastics composition as described above.
Several compositions according to the invention will now be described by way of example. In all the examples powdered ferric stearate and a powdered carboxylic -acid or a liquid carboxylic acid dissolved in an alcohol (and in some cases an antioxidant) were milled with po~yeth-ylene. Milling was continued for lO minutes after mixing had been achieved so as to form a crepe. The crepe was compression moulded between polyethylene terephthalate foils at a suitable temperature to give a coherent film 125 ~m thick.
Samples 1 cm x 3 cm were cut from the foil and tested in the FS/BL Test.
FS/B~ Test The samples were exposed to W irradiati~n using a combination of equal numbers of 20 watt fluorescent :~;
~O~V~98 ~unlamp~ and 20 watt black lamps. '~he samples circulated around the lamps at a distance of 10 cm from the lamps. (~he circulation help~ to obtain uniform irradiation). The samples were inspected daily and tested for flex-crack failure. The time to failure indicates the effect of the prodegradant, a shorter time indicating a more effective prodegradant.
Table 1 gives embrittlement times in the FS/~
~est (in days) on high density polyethylene samples which contained the stated quantities of ferric ~tearate (metal saltj and free stearic acid. ~able 1 also includes results on samples which also contained 0.02~/o w/w of BHT. (BHT is a conventional "name" for a common antioxidant the full chemical name of which is 2,6-ditertiarybutyl-4-methyl phenol).
~ABLE 1 Metal Salt Free Acid ~otal Pro- Free Acid Life in days ~ w/w % w/w degradant as % of at BHT conc.
~ w/w total Pro-degradant NONE %.ow2fw . ,, 0.008 0.002 0.01 20 23 ~
0.008 0.102 0.11 93 12 11 ;:
0.08 0.02 0.1 20 14 13 ~' ~
0.0~ 0.12 0.2 60 ~ 15 0.08 0.22 0.3 73 2 6 0.08 0. 52 0 . 6 86 . 5 2 _ ~ ,` ~,.
'~ .
.
''' , ' .' . ' ~.~ , .:~ '. ' , ~oso~gs P.24502 (The blank, i.e. high density polyethylene with no additives, was 23 days.) ~able 2 gives similar re~ults on low density polyethylene whioh contained the stated quantities of ferric ~tearate (metal salt) and free stearic acid.
TAB~E 2 - . .
Metal Salt ~ree Acid Total Pro- ~ree Acid ~ife % w/w % w/w degradant as % of in % w/w total Pro- days degradant .
Nil Nil Nil _ 5o 0.008 0.002 0.01 20 35 0 . 08 0 . 02 0 . 1 20 20 0.20 Nil 0.2 0 24 0.10 0.10 0. 2 50 19 0.08 0.12 0.2 60 17 ~il 0. 20 0. 2 100 35 0.08 0.22 0.3 73-4 15 0. 08 0~ 6 86. 5 18 The four results at 0.2% total prodegradant show that both the acid and the salt have prodegradant activity but the two together give an enhanced effect.
- 10 Table 3 shows the effect of adding a variety of other acids to the seme base mixture. In all caæes the mixture contains:
.
- ~ -: . . .
. ~ ' -' ' .
1090~98 P.24502 0~08% w/w of ferric stearate o.o~h w/w of stearic acid 0.1% w/w of the other acid (as stated) (i.e. O.Z~ w/w total prodegradant and 60% free acid based on the total prodegradant.) ~ '~.
=
~ame of Acid No. of C-atoms qype Life in days _ :.
Benzoic 7 aromatic 19 ;~
Pelargonic 9 saturated 14 ~auric 12 saturated 13 Stearic 18 saturated 18 Oleic 18 1 double bond 15 ~inoleic 18 2 double bonds ~18 -Behenic 22 saturated ~ 18 able 3 suggests that in the case of acids R.COOH
where R is hydrocarbon, the nature of R does not have a .
large influence on the rate of degradation.
A result was obtained for the degradation of high : .
density polyethylene u8ing manganese stearate as prodegradant. With 0.6% wjw of manganese stearate and 1% w/w of stearic acid (i.e. 1.6% total prodegradant ~: 6~h of which is acid) the life in the ~S/BL test was 2 days;
: , ' .:, . . , ' . ~ :
1090~91~
-~ithout the acid the life was 9 days. The manganese stearate gave less colour than the iron.
The prodegradant effect of the synergistic combination of 0.0~ ferric stearate and 0.02% stearic acid is exemplified by the results shown in Table 4 for a series of thermoplastics when exposed to FS~B~ radiation.
_ Life in Days Polymer Prodegradant Control composition .
7 1~2% vinyl Acetate/
Ethylene a) 34 75 -~
Polypropylene homopolymer b) 46 10 "Surlyn" Trade Mark A 1555 c) 13 71 a) MFI 2.0; density 0.926 g/cc.
The film was compression moulded to 125~ m.
b) The polypropylene was stabilised by 0.1% of calcium stearate and 0.1% of 2:6 di-tertbutyl-4-methyl phenol and blown at 220~C. to 20 ~m. ~-~
c) A partially neutralised copolymer of ethylene and methacrylic acid compression moulded to 125 ~m thick film.
., .
:
.. . . .. . .
: : .
1()90~98 ~
(2) Copolymers of these with one another and other ~-olefines. ~ :
The preferred olefine copolymers are those which contain at least 50~ by weight of ethylene, propylene, butene-l, 4-methyl pentene-l and/or styrene together with at least one of the following comonomers:
vinyl chloride vinyl acetate -methyl acrylate methyl methacrylate ~ :
acrylic acid methacrylic acid hydroxyethyl methacrylate The preferred olefine copolymers include the ionomers ~ ~
produced by neutralising or partially neutralising the : --carboxylic groups of those copolymers which contain ~; ~
carboxylic groups. .- .`
Copolymers which contain at least 50% by weight :~
of ethylene are particularly suitable. .
In addition to the polymer and the prodegradant a composition according to the invention may also include .~-other additives~which are conventionally incorporated in ~ :
thermoplastics polymer compositions, for example in the : -~
case of polyolefines they may incorporate anti-blocking : agents, slip agents, anti:static agents, stabilisers to -` ~ ' :
- 4 _ ~-: .
., : ;
lV90~98 stabilise the composition during processiny as well as stabilisers to stabilise the composition during use (i.e. after processing has finished).
The invention includes wrapping material, string and containers (including lids for containers) made of the plastics composition described above. The following are examples of containers; bags, sacks, boxes, cartons, bottles, sachets, cups and cartridge cases.
The invention also includes an item of merchandise packed in a material made of a plastics composition as described above.
Several compositions according to the invention will now be described by way of example. In all the examples powdered ferric stearate and a powdered carboxylic -acid or a liquid carboxylic acid dissolved in an alcohol (and in some cases an antioxidant) were milled with po~yeth-ylene. Milling was continued for lO minutes after mixing had been achieved so as to form a crepe. The crepe was compression moulded between polyethylene terephthalate foils at a suitable temperature to give a coherent film 125 ~m thick.
Samples 1 cm x 3 cm were cut from the foil and tested in the FS/BL Test.
FS/B~ Test The samples were exposed to W irradiati~n using a combination of equal numbers of 20 watt fluorescent :~;
~O~V~98 ~unlamp~ and 20 watt black lamps. '~he samples circulated around the lamps at a distance of 10 cm from the lamps. (~he circulation help~ to obtain uniform irradiation). The samples were inspected daily and tested for flex-crack failure. The time to failure indicates the effect of the prodegradant, a shorter time indicating a more effective prodegradant.
Table 1 gives embrittlement times in the FS/~
~est (in days) on high density polyethylene samples which contained the stated quantities of ferric ~tearate (metal saltj and free stearic acid. ~able 1 also includes results on samples which also contained 0.02~/o w/w of BHT. (BHT is a conventional "name" for a common antioxidant the full chemical name of which is 2,6-ditertiarybutyl-4-methyl phenol).
~ABLE 1 Metal Salt Free Acid ~otal Pro- Free Acid Life in days ~ w/w % w/w degradant as % of at BHT conc.
~ w/w total Pro-degradant NONE %.ow2fw . ,, 0.008 0.002 0.01 20 23 ~
0.008 0.102 0.11 93 12 11 ;:
0.08 0.02 0.1 20 14 13 ~' ~
0.0~ 0.12 0.2 60 ~ 15 0.08 0.22 0.3 73 2 6 0.08 0. 52 0 . 6 86 . 5 2 _ ~ ,` ~,.
'~ .
.
''' , ' .' . ' ~.~ , .:~ '. ' , ~oso~gs P.24502 (The blank, i.e. high density polyethylene with no additives, was 23 days.) ~able 2 gives similar re~ults on low density polyethylene whioh contained the stated quantities of ferric ~tearate (metal salt) and free stearic acid.
TAB~E 2 - . .
Metal Salt ~ree Acid Total Pro- ~ree Acid ~ife % w/w % w/w degradant as % of in % w/w total Pro- days degradant .
Nil Nil Nil _ 5o 0.008 0.002 0.01 20 35 0 . 08 0 . 02 0 . 1 20 20 0.20 Nil 0.2 0 24 0.10 0.10 0. 2 50 19 0.08 0.12 0.2 60 17 ~il 0. 20 0. 2 100 35 0.08 0.22 0.3 73-4 15 0. 08 0~ 6 86. 5 18 The four results at 0.2% total prodegradant show that both the acid and the salt have prodegradant activity but the two together give an enhanced effect.
- 10 Table 3 shows the effect of adding a variety of other acids to the seme base mixture. In all caæes the mixture contains:
.
- ~ -: . . .
. ~ ' -' ' .
1090~98 P.24502 0~08% w/w of ferric stearate o.o~h w/w of stearic acid 0.1% w/w of the other acid (as stated) (i.e. O.Z~ w/w total prodegradant and 60% free acid based on the total prodegradant.) ~ '~.
=
~ame of Acid No. of C-atoms qype Life in days _ :.
Benzoic 7 aromatic 19 ;~
Pelargonic 9 saturated 14 ~auric 12 saturated 13 Stearic 18 saturated 18 Oleic 18 1 double bond 15 ~inoleic 18 2 double bonds ~18 -Behenic 22 saturated ~ 18 able 3 suggests that in the case of acids R.COOH
where R is hydrocarbon, the nature of R does not have a .
large influence on the rate of degradation.
A result was obtained for the degradation of high : .
density polyethylene u8ing manganese stearate as prodegradant. With 0.6% wjw of manganese stearate and 1% w/w of stearic acid (i.e. 1.6% total prodegradant ~: 6~h of which is acid) the life in the ~S/BL test was 2 days;
: , ' .:, . . , ' . ~ :
1090~91~
-~ithout the acid the life was 9 days. The manganese stearate gave less colour than the iron.
The prodegradant effect of the synergistic combination of 0.0~ ferric stearate and 0.02% stearic acid is exemplified by the results shown in Table 4 for a series of thermoplastics when exposed to FS~B~ radiation.
_ Life in Days Polymer Prodegradant Control composition .
7 1~2% vinyl Acetate/
Ethylene a) 34 75 -~
Polypropylene homopolymer b) 46 10 "Surlyn" Trade Mark A 1555 c) 13 71 a) MFI 2.0; density 0.926 g/cc.
The film was compression moulded to 125~ m.
b) The polypropylene was stabilised by 0.1% of calcium stearate and 0.1% of 2:6 di-tertbutyl-4-methyl phenol and blown at 220~C. to 20 ~m. ~-~
c) A partially neutralised copolymer of ethylene and methacrylic acid compression moulded to 125 ~m thick film.
., .
Claims (18)
1. A thermoplastics composition comprising an olefine polymer or copolymer and as prodegradant a free carboxylic acid and a metal salt of a carboxylic acid, said metal having an atomic number of 22 to 29 and in which the free carboxylic acid and the carboxylic acid of the metal carboxylate are both selected from the group R.COOH where R is a hydrocarbon group with up to 30 carbon atoms, each of said free acid and metal salt being present in such a concentration that: (a) the total amount of metal salt + free carboxylic acid is between 0.001% and 40% by weight based on the total composition; (b) the amount of free carboxylic acid is from 10% to to 95% by weight of the total amount of metal salt plus free carboxylic acid.
2. A thermoplastics composition according to Claim 1 in which the amount of free carboxylic acid is from 50% up to 90% by weight of the total amount of metal salt plus free carboxylic acid.
3. A thermoplastics composition according to Claim 1 where R is a straight chain hydrocarbon group with 8 up to 21 carbon atoms and having less than 3 double bonds.
4. A thermoplastics composition according to Claim 3 where R is the group C17H35.
5. A thermoplastics composition according to Claim 1 in which the free carboxylic acid is the same as that of the metal carboxylate,
6. A thermoplastics composition according to Claim 1 in which the metal of the carboxylate is iron.
7. A thermoplastics composition according to Claim 1 in which the metal of the carboxylate is manganese.
8. A thermoplastics composition according to claim 1 in which the olefine polymer or copolymer is an ethylene polymer or copolymer which contains at least 50% by weight of ethylene monomer.
9. A thermoplastics composition according to claim 8 in which the polyolefine is a homopolymer of ethylene.
10. A thermoplastics composition according to Claim 1 in which concentration (a) is between 0.01% and 2% by weight.
11. A thermoplastics composition according to Claim 10 in which concentration (a) is between 0.1% and 1% by weight.
12. An environmentally degradable composition of a major proportion of ethylene homopolymer or copolymer where the ethylene fraction is predominant and between 0.001% and 40.0%
by weight based on the total composition of the prodegradants:
a) a free carboxylic acid having the structure R-COOH where R is a hydrocarbon with up to 30 carbon atoms, and b) a polyvalent metal salt of R-COOH where R is a hydrocarbon group with up to 30 carbon atoms and where the metal is selected from Ti, V, Cr, Mn, Fe, Co, Ni and Cu;
the amount of free carboxylic acid being from 10% to 90% by weight of the total amount of metal salt plus free carboxylic acid.
by weight based on the total composition of the prodegradants:
a) a free carboxylic acid having the structure R-COOH where R is a hydrocarbon with up to 30 carbon atoms, and b) a polyvalent metal salt of R-COOH where R is a hydrocarbon group with up to 30 carbon atoms and where the metal is selected from Ti, V, Cr, Mn, Fe, Co, Ni and Cu;
the amount of free carboxylic acid being from 10% to 90% by weight of the total amount of metal salt plus free carboxylic acid.
13. The composition of Claim 12 which additionally contains an anti-oxidant for said ethylene polymer.
14. The composition of Claim 12 in which the acid is the unsaturated acid, oleic acid.
15. The composition of Claim 12 in which the metal of the salt is iron.
16. The composition of Claim 12 in which the salt is ferric stearate.
17. The composition of Claim 12 in which the metal of the salt is manganese.
18. The composition according to Claim 13 in which the antioxidant is 2,6-di tertiary butyl-p-cresol.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB5456671A GB1401418A (en) | 1971-11-24 | 1971-11-24 | Plastics composition |
| GB54566/71 | 1971-11-24 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1090498A true CA1090498A (en) | 1980-11-25 |
Family
ID=10471438
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA157,334A Expired CA1090498A (en) | 1971-11-24 | 1972-11-23 | Degradable disposable polyolefine compositions |
Country Status (9)
| Country | Link |
|---|---|
| JP (1) | JPS568053B2 (en) |
| AU (1) | AU473461B2 (en) |
| BE (1) | BE791912A (en) |
| CA (1) | CA1090498A (en) |
| DE (1) | DE2257730A1 (en) |
| FR (1) | FR2160945B1 (en) |
| GB (1) | GB1401418A (en) |
| NL (1) | NL7215159A (en) |
| SE (1) | SE396084B (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5136783B2 (en) * | 1972-03-29 | 1976-10-12 | ||
| ES432731A1 (en) * | 1973-11-28 | 1976-12-01 | Coloroll Ltd | Method of preparation of a biodegradable composition. (Machine-translation by Google Translate, not legally binding) |
| IT1178605B (en) * | 1984-10-31 | 1987-09-09 | Fiocchi Munizioni Spa | HUNTING, SHOOTING AND SIMILAR COMPONENTS IN PHOTODEGRADABLE SYNTHETIC PLASTIC MATERIAL |
| BR8606562A (en) * | 1985-03-27 | 1987-08-04 | Scient Cartridge Developments | CARTRIDGE FOR CACA SHOTGUN |
| US4780319A (en) * | 1985-07-08 | 1988-10-25 | Merck & Co., Inc. | Organic acids as catalysts for the erosion of polymers |
| GB8712009D0 (en) * | 1987-05-21 | 1987-06-24 | Folk Drive Eng Ltd | Degradable plastics |
| BE1002431A4 (en) * | 1987-07-07 | 1991-02-05 | Lilaran & Sons Uk Ltd B | In the air biodegradable ethylene polymers. |
| GB9108555D0 (en) * | 1991-04-22 | 1991-06-05 | Kent Cartridge Mfg | Improvements in cartridge cases |
| FR2741627B1 (en) * | 1995-11-27 | 1997-12-19 | Poudres & Explosifs Ste Nale | FULLY BIODEGRADABLE COMPOSITIONS USEFUL FOR MAKING HUNTING AND SHOOTING CARTRIDGES |
| FR2754265B1 (en) * | 1996-10-04 | 1998-12-18 | France Cheddite | COLORED PHOTODEGRADABLE PLASTIC MATERIAL, PIECE SUCH AS SOCKET, PAD AND PROJECTILE, OBTAINED FROM SUCH MATERIAL |
| NO324368B1 (en) * | 2003-04-23 | 2007-10-01 | Normors As | Process for preparing additive for thermoplastics and such prepared additive as well as thermoplastics containing such additive. |
| GB2464285A (en) * | 2008-10-08 | 2010-04-14 | Wells Plastics Ltd | Transition metal additives for enhancing polymer degradation |
-
0
- BE BE791912D patent/BE791912A/en unknown
-
1971
- 1971-11-24 GB GB5456671A patent/GB1401418A/en not_active Expired
-
1972
- 1972-11-07 AU AU48615/72A patent/AU473461B2/en not_active Expired
- 1972-11-09 NL NL7215159A patent/NL7215159A/xx not_active Application Discontinuation
- 1972-11-22 FR FR7241436A patent/FR2160945B1/fr not_active Expired
- 1972-11-23 CA CA157,334A patent/CA1090498A/en not_active Expired
- 1972-11-23 SE SE1527272A patent/SE396084B/en unknown
- 1972-11-24 JP JP11725372A patent/JPS568053B2/ja not_active Expired
- 1972-11-24 DE DE19722257730 patent/DE2257730A1/en not_active Ceased
Also Published As
| Publication number | Publication date |
|---|---|
| BE791912A (en) | 1973-05-24 |
| JPS4864130A (en) | 1973-09-05 |
| JPS568053B2 (en) | 1981-02-21 |
| FR2160945B1 (en) | 1978-01-06 |
| DE2257730A1 (en) | 1973-05-30 |
| FR2160945A1 (en) | 1973-07-06 |
| AU4861572A (en) | 1974-05-09 |
| AU473461B2 (en) | 1976-06-24 |
| SE396084B (en) | 1977-09-05 |
| NL7215159A (en) | 1973-05-28 |
| GB1401418A (en) | 1975-07-16 |
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