CA1295076C - Controllable and swiftly degradable polymer compositions and films and otherproducts made therefrom - Google Patents
Controllable and swiftly degradable polymer compositions and films and otherproducts made therefromInfo
- Publication number
- CA1295076C CA1295076C CA000528226A CA528226A CA1295076C CA 1295076 C CA1295076 C CA 1295076C CA 000528226 A CA000528226 A CA 000528226A CA 528226 A CA528226 A CA 528226A CA 1295076 C CA1295076 C CA 1295076C
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- Canada
- Prior art keywords
- complex
- metal
- polymer compositions
- polymer
- film
- Prior art date
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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
- C08K5/0091—Complexes with metal-heteroatom-bonds
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
- A01G13/00—Protecting plants
- A01G13/02—Protective coverings for plants; Coverings for the ground; Devices for laying-out or removing coverings
- A01G13/0256—Ground coverings
- A01G13/0268—Mats or sheets, e.g. nets or fabrics
- A01G13/0275—Films
-
- 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
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0033—Additives activating the degradation of the macromolecular compound
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K17/00—Soil-conditioning materials or soil-stabilising materials
- C09K17/52—Mulches
Abstract
ABSTRACT
Polymer compositions comprising a vinyl polymer and a combination of at least two metal complexes wherein the complexing agent of the first complex is attached to the metal through oxygen and the metal is a transition metal, and the complexing agent of the second complex is attached to the metal through sulphur and the metal is a transition metal or a metal of group II or IV of the periodic table of the elements, wherein the molar ratio of the second metal complex to the first metal complex is 0.5 or less. A film obtained from such polymer compositions and its use in agricultural processes are also claimed.
Polymer compositions comprising a vinyl polymer and a combination of at least two metal complexes wherein the complexing agent of the first complex is attached to the metal through oxygen and the metal is a transition metal, and the complexing agent of the second complex is attached to the metal through sulphur and the metal is a transition metal or a metal of group II or IV of the periodic table of the elements, wherein the molar ratio of the second metal complex to the first metal complex is 0.5 or less. A film obtained from such polymer compositions and its use in agricultural processes are also claimed.
Description
CONTROLLABLY AN~ SWIFTLY DEGRADABLE POLYMER COMPOSITI~NS
AND FILMS AND OTHER PRODUCTS MADE THEREFROM
This invention relates to photogradable and thermally stable compositions based on homopolymers and copolymers of vinyl or vinylidene monomers such as polyethylene, polypropylene, polymethylpentene, polyvinlchloride, ethylene-propylene co-polymers, condensation polymers, e.g. polyamides, polyesters, polyurethanes. etc., and intercopolymers containing unsaturation, as well as mixtures of such polymers, which degrade very rapidly on exposure to the environment owing to the presence of particular metal comple~es,. More particularly this invention relates to the ~,, pr~L~le6/r~Lc~ ,on O~ controlled ~b~44s~ .tmrof vinyl polymers wherein the induct;on^ `period, i.e. the duration between the exposure to sunlight (or the suitable radiation) and the beginning of said (legradation is predetermined and may be very short.
It is known that films of vinyl or vinylidene polymers and copolymers, especially ethylene polymers are widely used for many purposes including wraps and packaging materials and anyway for wrapping up different kind of products.
Inevitably certain of such films are discarded in areas of public accommodation and become objectionable litter which can accumula-te in substantial volunle by reason of the fact that such films are not readily degraded by natural environmental factors.
Owing to the unusual stability and to the resulting accumulation of such plastic materials, increasing attention is being given to the problem of producing wrapping and packaging polymer films which will degrade after use and upon exposure to other environ-mental including sunlight. Moreover agriculture and parti-,, ...
~2~ 6 cularly the field of crop protection has been requiring moreand more plastic materials for developing and manufacturing mulching films which must perform their service, namely to cover, enclose or protect the soil and the growing crops, under fully exposed outdoor conditions for a certain period of time or better, from a specific time to another specific time of the year. Subsequently9 certain agricultural operations, such as ploughing or gathering of the crop, must take place and the films constitute an obstacle to such operations and must be removed. Except for some cases in which the films can be re-used and is worth recovering, removal is a time consuming and costly operation.
Therefore the use of degraclable polymer films is a clesirable way of solving the problem of removal of mulching films as well as the problem of destroying plastic materials casually disposed after use.
In the case of wrapping or packaging films the environmental pollution caused by their residues may be avoided by compulsory use of cellulose-based materials which degrade fairly rapidly when exposed outdoors to the action of atmospheric agentsi this is not the case with mulching films whose life time will be as lông as may be desired and however for a given period of time and which have been normally removed after use. Such a problem was partially solved with the discovery of resin compositions containing particular agents which favour their degradation by causing their prior embrittlement followed by rapid decay and fornnation of oxidized and biodegradable production. Thus British Patent Specification n. 1,356,107 describes vinyl . . .
~g5~76 polymer conlpositions containing a complex of a transition metal, preferably iron, which can be activated by light of wavelength of less than 330 nm, U.V. radiation. This complex can be formed "in situ" from so called complexing agent and a salt oF the metal.
In the concentrations used the complex makes the composition stable in the manufacturing process in which it is brought to the molten state, usually extrusion or blow extrusion and during indooruseor in sufficiently sheltered places such as houses, shops, etc. On the contrary when the polymer material is disposed of` or exposecl to sunlight (outdoor envi-ronmen-t), the metal complex splits with release of the metal in a photoactivated state which causes the rapid degradation of the polymer. A film of degradable polymer containing metal cornplexes such as those claimed in the above mentioned patent, will pass upon being exposed to U.V. radiation, through a plurality of degradation stages, including a stage which is called "ernbrittlement" in which the film maintains its forms and continuity and therefore its protective character, substantially unaltered, but in which it will easily be broken up by means of any mechanical action. The embrittlement stage is characteri~ed by an elongation at break substantially equal to zero.
The lasting time between the exposure to U.V. radiation and the attainment of the embrittlenlent point constitutes the so called "induction period".
~;~95i~7~
The induction period may widely vary according to different environmental conditions and/or the type of polymer composition but is rather unpredictable and cannot be controllably pre-determined. This is the limit of the above mentioned invention.
The British patent specification no~l,586,34~ describes thermo-plastic polymer compositions in which the time to embrittlement can be predetermined and varied as one wishes with considerable precision especially in po1yolefin films, said compositions containing carefully controlled amount of a metal complex of the type described in the above mentioned British speci-fication (GB 1,356,107)incombination with an ultraviolet light stabilizing complex, preFerably a nickel complex.
The results which have been obtained by introducing ~he two types of complexes in the plastic compositions are very sur-prising since iron compounds alone and nickel compounds alone while both influencing the embrittlement time, do not permit, as above mentioned, to control and predict this latter with precision.
The single functions of the two types of complexes, namely the complexes of iron (or Mn or Ce) on one hand and the complexes of nickel (or Co or Cu, or Zn) on the other, are very different from one ano-ther. Iron complexes are power-ful activators of U.V. degradion of a ~eriety of polymers after a relatively short induction period whereas nickel-complexes are U.V. stabilizers.
~L2~
When simultaneously present in a polymer composition they act with a sor-t of synergistic effect which is not merely an enhancement of a certain property (such as a more rapid photogredation or an extension of the induction period) but a qualitative and complete change of behaviour. As a matter of fact the induction period is more complete and the stabi-lization of the polymer compositions which is promoted by the Ni-complex is enhanced during this period by reason of the comtemporary presence of the iron complex.
The composi-tions containing such a combination of the two aforementioned complexes are particularly useful for the pro-duction of fillns, especially mulching films which are allowed to remain on the soil for a certain and desired period of time and afterwards will degrade and will not interfere with the subsequent soil working operations such as ploughing or harvesting but actually will in fact be eliminated by those operations without the need of any change in them.
This type of polymer composition is very useful in agriculture and in countries with a very sunny climate such as are found in the Middle-East, where it is relatively easy to obtain fast degradation rates and it is necessary to extend the induction period to meet the needs of a particular crop. On the other hand the induction period would be in many cases absent without the synergistic action of the nickel-complex.
This was the purpose of British Patent 1,586,344. On the contrary in Northern Europe and similar northern latitudes, ~5~i ~6 where ~here is less sunshine the problem is the opposite of that one previously discussed.
In northern countries the scanty amount of radiation is not suf~icient to induce in a reasonable period of time the photoactivation and the degradation of polymer compositions either containing only one metal complex such as those mentioned in the B.P. 1,356,107 or containing a particular combination o~ two of them such as those mentioned in B.P. 1,568,344. ~he practical result of the unsufficient U.V. radiation is the difficulty to achieve a fast rate of degradation while the physical disintegration of the plastic materials occurs over a longer time than it would be needed as it should be the case of the mulching films in agriaulture.
This problem is exacerbated by the fact that in Europe and in other northerly climates with very limited sunshine, mulching ~ilms contain carbon black in order to aontrol and prevent the growth of weeds (in countries with very sunny climates mulching films are employed in order to prevent soil parching) and this additiYe behaves as an U.V. stabilizer for plastics thus extending the embrittlement time even further (see &.
Scott, Atmospheric Oxidation and Antioxidants, Elsevier, page 186 and 287).
In accordance with one aspect of the present invention, there is provided polymer compositions comprising a vinyl polymer and a combination of at least two metal complexes wherein the complexing agent of the first complex is attached to the metal through 3Q oxygen and the metal is a transition metal, and the complexing agent of the second complex is attached to the metal through sulphur and the metal is a transition metal or a metal of group II or IV of the periodic table of the elements, wherein the first metal complex is an activator for photodegradation and for thermal oxidation o~ the vinyl polymer and the second metal complex is a thermal stabilizer of the polymer, and wherein the molar ratio of the second metal complex to the ~irst metal complex is 005 or less.
It has been shown previously by olle of the present inventors that certain oxygen~containing metal-complexes of iron and cobalt, such as the B-diket:one complexe~
~29S;~76 ~H ~ M ( I ) \C - ""
_ ~ _ n where n is 2 or 3 are very powerful activators for the photodegradation of polyethylene [M.W. Amin and G. Scott, Europ. Polymer J., 10, 1019, (1974)] but that they cannot be used as additives for polymers in commercial practice, because they are also powerful activators for thermal oxidation of polymers during thermal conversion ancl processing operations such as extrusion or b10w extrusion. Polymer compositions based on polylefins and containing catalytic amounts of (I) when processed and extruded to films undergo severe and deleterious thermal degradation reactions which lead to technologically unaccept-able changes in melt flow index and other technological properties.
We have surprisingly and quite unexpectedly found, according to the present invention, that the above mentioned thermal degredation reactions which take place in polymer compositions containing (I) can be completely inhibited by surprisingly small molar proportions of thermal stabilizing dithiolate com-plexes of a transition metal or of a metal of group II or IV
...
~2~50~6 of the periodic table of the elements, notably zinc, nickel and cobalt dialkyl-dithiocarbamates. The thermal stabilization attainable by metal complexes based on sulphur compounds and other metal complexes is well known and has been already shown in British Patent 1,586,344, some of those complexes (Ni, Cu, Co) are U.V. stabilizers (G.B.
l,356,107; 1,586,34~).
On the contrary it is quite unexpected and unknown that very small amount of thermal stabilizers such as those of the present invention, when used in combination with complexes of type (I) and in molar ratios ranging from l:~ to l:S, actually increase the rate of photodegradation reactions, thus giving signlflcantly shorter embrittlement times than those attained with the oxygen complexes alone.
A second effect observed by combining very small amounts of at least one of the aforesaid thermostabilising complexes with complexes of type ~I) which are activators for the photodegradation of polymers, is ~he appearance of a very short but very well defined induction period upon exposure of degradable polymer compositions to sunlight.
That is to say that the induction period which in the case of complexes of the type (I) used alone is normally absent, in the case of the present invention is very short but the stability of the compositions is absolute and complete during the induction period. Afterwards the degradation phase is 5~76 .. g sharp and rapid with total decay of the thermoplastic material.
The above mentioned effects are however only observed when the molar ratio of the thermostabilising complex (for example Ni dithiocarbamate) to photoactiving complex ([) (for example iron acetylacetonate) is less than 0.5.
However, the most desirable ratios are lower than 0.3. When the molar ratio approaches 1 or is higher than 1, then the resulting observable effect is that of a noticable extension of induction period, with disappearance of the subsequent rapid and sharp decomposition.
This means that as the mo1ar ratio of stabilising to acti vating complex increases above 0.5 the very powerful and rapid phase of polymer degradation which is observable in the presence of complexes of type (I) either alone or in combination with very small amounts of thermal stabilising complexes is steadily disappearing.
The practical consequences of this new discovery are that much shorter embrittlement times can be obtained than it has been possible to achieve previously in polyethylene coupled with excellent stability of the polymer during processing.
The most characteristic aspects of the present invention are illustrated by means of the figures in the enclosed drawings ''' 5~76 wherein a comparison is made between the particular combin-ation of the two types of complexes when used in the desirable ratios and the same combination but at different ratios as wel~
as the iron dithiocarbamate referred to in Brit. Pat.
1,356,107. The first figure refers to low density poiyethylene (LPDE) films containing different amounts of iron dimethyl-dithiocarbamate (FeDMC), iron tris-acetylacetonate (FeAcAc) and zinc diethyldithiocarbamate (ZnDEC) and exposed in a weatherometer at the same time.
The abscissa (of fig. 1 and 2) represents the exposure-time and the ordinate (oF both figures) represents the variation of the carbonyl index (i.e. the ratio of the CO I.R. absorbance at a given time to the initial CO absorbanceJ as a measure o~ the polymer photodegradation. Two ditferent photodegradation activation complexes namely a complex of type (I) (FeAcAc=0,~005 moles/lOOg; curve A) and iron dimethyldithiocarbamate (FeDMC=0,0005 moles/100 9, curve B) contained at the same concentrations in LPDE behaves in a quite different way with respect to photodegradation contro1.
Iron acetylacetonate promotes the immediate start ot the degradative process while the second acts as a normal pho-toactivator (G.B. 1,356,107).
When iron acetylacetonate is combined with very small amounts of a thermal stabiliser (FeAcAc=O~OOU5 moles/lUO g + Zn DEC=
0,U01~5 moles/lUO g; R=~n = 0.25; curve ~) the degradation ~e 5~71~i rate is enhanced but the degradation process is preceded by a very short bu~ very complete induction period during which the stability is absolute as already mentioned.
When Zn to ~`e ratio is raised (R=l; FeAcAc=ZnDEC=0,00~5 moles/100 g; curve ~ the sharp trend of curve C turns into the steadily raising trend of curve D thus noticeably extend-ing the embrittlement time to values whlch are very similar to those observed in the case ot FeUMC alone (curve BJ. However, the comparison between curve C and curve D is the better visual explanation of the novelty and or1ginallty inherent to the present invention. The latter aspect of this invention is lllustrated in the second figure of the enclosed drawings, from which it can be seen that in an internal mixer the thermal stability of FeAcAc/ZnDEC (straight line C; FeAcAc=U,OU05 moles/
100 g + 7n DEC= 0,U0~125 moles/lou g or Fe~MC alone= U,OU25 moles/100 g) is very much better than that ot the control (curve B=no addltive) and as good as that of FeDM~ alone).
~eAcAc alone on the contrary (curve A; reAcAc=0,00~5 moles/1UO g causes very rapid oxidation of LD~E under these conditions.
This invention consequently relates to polymer composition which are very quickly degradable under the action of ultra-violet light and/or s~nlight wherein the induction period, namely, the delay time between the exposure to U.V. radiat-ion and the start of said degradation is predetermined and may be very small. The polymer compositions are characterized in that the photodegradation is promoted by means of the additional presence of at least one metal complex which is a powerful activator of said photo-degradation of polymers in combination with a very small amount o~ dithio1ate metal complex which is a stabiliser for thermal degradatlon. Molar ratios R of the activator complex to the thermal stabiliser are lower than 0.5 ancl preferably R \< 0.3.
Moreover this invention relates to any protectiYe or wrapping 3L~ 7~i membrane and/or mulching film obtainable from said compositions by means of usual manufacturing processe~ such as extrusion or blow extrusion.
The thermoplastic vinyl polymer is preferably a film or fibre-forming polymer or copolymer such as polyethylene, polypropylene, poly (4-methyl-1-penteneJ, or polystyrene or terpolymer which may contain unsaturation. Other vinyl polylners such as poly-vinylacetate, polyvinylchloride~ polymethyl methacrylate, and polycrylonitrile and copolymers of the corresponding monomers, including vinylchloride-vinyl acetate copolymers, including gra~t copolymers wlth unsaturated polymers, as well as miXtures of such polymers, particularly with unsalurated polymers, c~n also be used in the compositions of the present invention.
This process can also be used for condencation polymers such as polyesters, polyamides and polyurethanes.
The thermoplastic compositions of this invention may contain other cornpounding ingredients, such as blowing agents, various types of antioxidants, stabilisers, lubrificants, antistatic agents and antiblocking agents~ Antioxidants do not take part to the embrittlement process and therefore may be used in con-ventional amounts.
~nert pigments, dyes, other conventional additives and carbon black may also be added to the polymer compositions.
In general pigments act as U.V. screening agents and increase the embritt1ement time of the polymer and this is particularly true for carbon black as above already mentioned.
The photo-activating complex can be any organo-soluble trans-ition metal complex in which the ligand is attached to the metal through oxygen. PreFerred complexing agen~s are ~-di-ketones, ~-ketoesters and among them acetylacetone.
` 3~.;~g5i~76 Preferred transition metals are iron, coL,alt and manganese.
The thermal stabilising complex is preferably a groups lI, group IV or a transition mctal complex i~ which the complexing agent is any sulphur containing compound among the complexing agents disclosed in the earlier patents. In particular dialkyl dithiocarbamates, dialkyldithiophosphates, alkylxantates, mercaptobenzothiazoles and nitrogen coordinating compounds such as the salicylideneimides etc.
Rl\ ~ RlO
N-C-SH \ Il-SH
R2 R~O
dithiocarbamates dithiophosp~lates S S S
R~-C-~H HS-C-N-R3-N-~-SH
Rl ~2 bifunctionaldithiocarbamates S ' S
H-S-P-OR-~-P-SH R ~ C-SH
OR OR
bifunctional dithiophosphates benzthiazoles Where R, Kl, ~2' R3 each represent hydroyen or an alkyl, aralkyl or amyl group, which may be unsubstituted or substituted AS well as linked together to form heterocyclic lings.
1;;~9507G
Dlthiocarbamates and the above mentioned derivatlves thereof are the preferred complexing agents since they are substantially non toxic.
The preferred combinations of metal complexes in the thermopla-stic polymer compositions according to the present invention are iron-acetylacetonate and Ni or Zn dialkyldithiocarbamates.
The concentration of the oxygen complexes is generally from 0,0005 to 0,5% by weight and preferably from 0,OOCS to 0,2%
by weight.
The concentration of the thermal stabilising su'lphur containing metal complex depends on the desired relative mo'lar ratio R of stabilislng to actlvating complex. The molar ratio R is generally lower than 0,5 preferab'ly R ~ 0.3. However, the relative concentrations to be used of the two metal complexes depend largely on the intended use of the finished article.
The following examples further illustrate the present inven-tion. The starting material of the polymer compositions was a low density polyethylene L~PE with a melt flow index MFI=2.16Kg (lU' at l9UCj.
3L29~ 6 EXAMPLE I
Iron acetylacetonate was added in an internal mixer (feAcAc = 5.10 4 moI / 1dO gj to the aforesaid LDPE and a film was obtained using the blow extrusion technique which is conventional ln processing polyethylene. Maximum pro-cessing temperatures were in the order of 210C. The film thickness was ~0 mlcrons; however test carrie~ out with greater thicknesses, up to the practical maximum of 10U
microns, showed ~hat the behaviour of the material was sub-s~antially the same for all thicknesses in the said range.
, ~ , .
The films were then exposed in a Weatherometer~to U.V.
lrradiation. Iable I sunImarise the results obtained Prom films made using the same methodology but adding different complexes to the LDPE.
Table I.
~ehaviour of fllms of LDPE containing FeAcAc-Fe~MC complexes alone or in combination with ZnDEC or NiDEC and laid out.
. ~ . . __ ~ype of complexes (mol/lOU~) Lmbrittlement time (hours) FeAcAc (5-10 ) 425 FeAcAc (5-1U 4) +ZnDEC (1,25 10 4) 375 FeDMC (5-10 4) 130~
Fe~MC (1~5-1~-4) 900 FeDMC (~ 1~ 4) -~ ZnDEC (5-10 4)1200 FeDMC (2.5-1U 4) + NiDEC(0.25-10 4) 750 reference (LD~E ~Iithout aaditives) ~20u .. . _ EXhMPLE_I r Polypropylene samples containing NiDEC (2.5-1~4 mol/lOOg) amounts of FeAcAc variable and ranging from ~ to 15-104 mol/100 gI were processed in an internal mixer at 180C~
After 10 minutes processing the melt tlow index was measured ~ Trad~ r k , ~2~5~76 - lS
and the results are reported in table II.
This table shows that even the combination containing a six-fold excess of FeAcAc is as thermally stable as that containing NiDEC alone in Polypropylene which is notoriously subject to oxidative degredation during processing.
Table 11.
Ihermal stability of polypropylene containing NiDEC
(2.5'10 4 mol/lOOg) and FeAcAc (variable amounts) and processed in an internal mixer at 18uC and 10 mln.
. _ _ . ... _ . .. ..... . .. . _ _ _ .. ..... . .. . .. . _ . .. . . . _ _ . .
FeAcAc (Mol/lUOg) (MFI) 10 min _~
.64 7.5 1U 4 0.66 10.0-tU U.64 15 0 10~4 0.65
AND FILMS AND OTHER PRODUCTS MADE THEREFROM
This invention relates to photogradable and thermally stable compositions based on homopolymers and copolymers of vinyl or vinylidene monomers such as polyethylene, polypropylene, polymethylpentene, polyvinlchloride, ethylene-propylene co-polymers, condensation polymers, e.g. polyamides, polyesters, polyurethanes. etc., and intercopolymers containing unsaturation, as well as mixtures of such polymers, which degrade very rapidly on exposure to the environment owing to the presence of particular metal comple~es,. More particularly this invention relates to the ~,, pr~L~le6/r~Lc~ ,on O~ controlled ~b~44s~ .tmrof vinyl polymers wherein the induct;on^ `period, i.e. the duration between the exposure to sunlight (or the suitable radiation) and the beginning of said (legradation is predetermined and may be very short.
It is known that films of vinyl or vinylidene polymers and copolymers, especially ethylene polymers are widely used for many purposes including wraps and packaging materials and anyway for wrapping up different kind of products.
Inevitably certain of such films are discarded in areas of public accommodation and become objectionable litter which can accumula-te in substantial volunle by reason of the fact that such films are not readily degraded by natural environmental factors.
Owing to the unusual stability and to the resulting accumulation of such plastic materials, increasing attention is being given to the problem of producing wrapping and packaging polymer films which will degrade after use and upon exposure to other environ-mental including sunlight. Moreover agriculture and parti-,, ...
~2~ 6 cularly the field of crop protection has been requiring moreand more plastic materials for developing and manufacturing mulching films which must perform their service, namely to cover, enclose or protect the soil and the growing crops, under fully exposed outdoor conditions for a certain period of time or better, from a specific time to another specific time of the year. Subsequently9 certain agricultural operations, such as ploughing or gathering of the crop, must take place and the films constitute an obstacle to such operations and must be removed. Except for some cases in which the films can be re-used and is worth recovering, removal is a time consuming and costly operation.
Therefore the use of degraclable polymer films is a clesirable way of solving the problem of removal of mulching films as well as the problem of destroying plastic materials casually disposed after use.
In the case of wrapping or packaging films the environmental pollution caused by their residues may be avoided by compulsory use of cellulose-based materials which degrade fairly rapidly when exposed outdoors to the action of atmospheric agentsi this is not the case with mulching films whose life time will be as lông as may be desired and however for a given period of time and which have been normally removed after use. Such a problem was partially solved with the discovery of resin compositions containing particular agents which favour their degradation by causing their prior embrittlement followed by rapid decay and fornnation of oxidized and biodegradable production. Thus British Patent Specification n. 1,356,107 describes vinyl . . .
~g5~76 polymer conlpositions containing a complex of a transition metal, preferably iron, which can be activated by light of wavelength of less than 330 nm, U.V. radiation. This complex can be formed "in situ" from so called complexing agent and a salt oF the metal.
In the concentrations used the complex makes the composition stable in the manufacturing process in which it is brought to the molten state, usually extrusion or blow extrusion and during indooruseor in sufficiently sheltered places such as houses, shops, etc. On the contrary when the polymer material is disposed of` or exposecl to sunlight (outdoor envi-ronmen-t), the metal complex splits with release of the metal in a photoactivated state which causes the rapid degradation of the polymer. A film of degradable polymer containing metal cornplexes such as those claimed in the above mentioned patent, will pass upon being exposed to U.V. radiation, through a plurality of degradation stages, including a stage which is called "ernbrittlement" in which the film maintains its forms and continuity and therefore its protective character, substantially unaltered, but in which it will easily be broken up by means of any mechanical action. The embrittlement stage is characteri~ed by an elongation at break substantially equal to zero.
The lasting time between the exposure to U.V. radiation and the attainment of the embrittlenlent point constitutes the so called "induction period".
~;~95i~7~
The induction period may widely vary according to different environmental conditions and/or the type of polymer composition but is rather unpredictable and cannot be controllably pre-determined. This is the limit of the above mentioned invention.
The British patent specification no~l,586,34~ describes thermo-plastic polymer compositions in which the time to embrittlement can be predetermined and varied as one wishes with considerable precision especially in po1yolefin films, said compositions containing carefully controlled amount of a metal complex of the type described in the above mentioned British speci-fication (GB 1,356,107)incombination with an ultraviolet light stabilizing complex, preFerably a nickel complex.
The results which have been obtained by introducing ~he two types of complexes in the plastic compositions are very sur-prising since iron compounds alone and nickel compounds alone while both influencing the embrittlement time, do not permit, as above mentioned, to control and predict this latter with precision.
The single functions of the two types of complexes, namely the complexes of iron (or Mn or Ce) on one hand and the complexes of nickel (or Co or Cu, or Zn) on the other, are very different from one ano-ther. Iron complexes are power-ful activators of U.V. degradion of a ~eriety of polymers after a relatively short induction period whereas nickel-complexes are U.V. stabilizers.
~L2~
When simultaneously present in a polymer composition they act with a sor-t of synergistic effect which is not merely an enhancement of a certain property (such as a more rapid photogredation or an extension of the induction period) but a qualitative and complete change of behaviour. As a matter of fact the induction period is more complete and the stabi-lization of the polymer compositions which is promoted by the Ni-complex is enhanced during this period by reason of the comtemporary presence of the iron complex.
The composi-tions containing such a combination of the two aforementioned complexes are particularly useful for the pro-duction of fillns, especially mulching films which are allowed to remain on the soil for a certain and desired period of time and afterwards will degrade and will not interfere with the subsequent soil working operations such as ploughing or harvesting but actually will in fact be eliminated by those operations without the need of any change in them.
This type of polymer composition is very useful in agriculture and in countries with a very sunny climate such as are found in the Middle-East, where it is relatively easy to obtain fast degradation rates and it is necessary to extend the induction period to meet the needs of a particular crop. On the other hand the induction period would be in many cases absent without the synergistic action of the nickel-complex.
This was the purpose of British Patent 1,586,344. On the contrary in Northern Europe and similar northern latitudes, ~5~i ~6 where ~here is less sunshine the problem is the opposite of that one previously discussed.
In northern countries the scanty amount of radiation is not suf~icient to induce in a reasonable period of time the photoactivation and the degradation of polymer compositions either containing only one metal complex such as those mentioned in the B.P. 1,356,107 or containing a particular combination o~ two of them such as those mentioned in B.P. 1,568,344. ~he practical result of the unsufficient U.V. radiation is the difficulty to achieve a fast rate of degradation while the physical disintegration of the plastic materials occurs over a longer time than it would be needed as it should be the case of the mulching films in agriaulture.
This problem is exacerbated by the fact that in Europe and in other northerly climates with very limited sunshine, mulching ~ilms contain carbon black in order to aontrol and prevent the growth of weeds (in countries with very sunny climates mulching films are employed in order to prevent soil parching) and this additiYe behaves as an U.V. stabilizer for plastics thus extending the embrittlement time even further (see &.
Scott, Atmospheric Oxidation and Antioxidants, Elsevier, page 186 and 287).
In accordance with one aspect of the present invention, there is provided polymer compositions comprising a vinyl polymer and a combination of at least two metal complexes wherein the complexing agent of the first complex is attached to the metal through 3Q oxygen and the metal is a transition metal, and the complexing agent of the second complex is attached to the metal through sulphur and the metal is a transition metal or a metal of group II or IV of the periodic table of the elements, wherein the first metal complex is an activator for photodegradation and for thermal oxidation o~ the vinyl polymer and the second metal complex is a thermal stabilizer of the polymer, and wherein the molar ratio of the second metal complex to the ~irst metal complex is 005 or less.
It has been shown previously by olle of the present inventors that certain oxygen~containing metal-complexes of iron and cobalt, such as the B-diket:one complexe~
~29S;~76 ~H ~ M ( I ) \C - ""
_ ~ _ n where n is 2 or 3 are very powerful activators for the photodegradation of polyethylene [M.W. Amin and G. Scott, Europ. Polymer J., 10, 1019, (1974)] but that they cannot be used as additives for polymers in commercial practice, because they are also powerful activators for thermal oxidation of polymers during thermal conversion ancl processing operations such as extrusion or b10w extrusion. Polymer compositions based on polylefins and containing catalytic amounts of (I) when processed and extruded to films undergo severe and deleterious thermal degradation reactions which lead to technologically unaccept-able changes in melt flow index and other technological properties.
We have surprisingly and quite unexpectedly found, according to the present invention, that the above mentioned thermal degredation reactions which take place in polymer compositions containing (I) can be completely inhibited by surprisingly small molar proportions of thermal stabilizing dithiolate com-plexes of a transition metal or of a metal of group II or IV
...
~2~50~6 of the periodic table of the elements, notably zinc, nickel and cobalt dialkyl-dithiocarbamates. The thermal stabilization attainable by metal complexes based on sulphur compounds and other metal complexes is well known and has been already shown in British Patent 1,586,344, some of those complexes (Ni, Cu, Co) are U.V. stabilizers (G.B.
l,356,107; 1,586,34~).
On the contrary it is quite unexpected and unknown that very small amount of thermal stabilizers such as those of the present invention, when used in combination with complexes of type (I) and in molar ratios ranging from l:~ to l:S, actually increase the rate of photodegradation reactions, thus giving signlflcantly shorter embrittlement times than those attained with the oxygen complexes alone.
A second effect observed by combining very small amounts of at least one of the aforesaid thermostabilising complexes with complexes of type ~I) which are activators for the photodegradation of polymers, is ~he appearance of a very short but very well defined induction period upon exposure of degradable polymer compositions to sunlight.
That is to say that the induction period which in the case of complexes of the type (I) used alone is normally absent, in the case of the present invention is very short but the stability of the compositions is absolute and complete during the induction period. Afterwards the degradation phase is 5~76 .. g sharp and rapid with total decay of the thermoplastic material.
The above mentioned effects are however only observed when the molar ratio of the thermostabilising complex (for example Ni dithiocarbamate) to photoactiving complex ([) (for example iron acetylacetonate) is less than 0.5.
However, the most desirable ratios are lower than 0.3. When the molar ratio approaches 1 or is higher than 1, then the resulting observable effect is that of a noticable extension of induction period, with disappearance of the subsequent rapid and sharp decomposition.
This means that as the mo1ar ratio of stabilising to acti vating complex increases above 0.5 the very powerful and rapid phase of polymer degradation which is observable in the presence of complexes of type (I) either alone or in combination with very small amounts of thermal stabilising complexes is steadily disappearing.
The practical consequences of this new discovery are that much shorter embrittlement times can be obtained than it has been possible to achieve previously in polyethylene coupled with excellent stability of the polymer during processing.
The most characteristic aspects of the present invention are illustrated by means of the figures in the enclosed drawings ''' 5~76 wherein a comparison is made between the particular combin-ation of the two types of complexes when used in the desirable ratios and the same combination but at different ratios as wel~
as the iron dithiocarbamate referred to in Brit. Pat.
1,356,107. The first figure refers to low density poiyethylene (LPDE) films containing different amounts of iron dimethyl-dithiocarbamate (FeDMC), iron tris-acetylacetonate (FeAcAc) and zinc diethyldithiocarbamate (ZnDEC) and exposed in a weatherometer at the same time.
The abscissa (of fig. 1 and 2) represents the exposure-time and the ordinate (oF both figures) represents the variation of the carbonyl index (i.e. the ratio of the CO I.R. absorbance at a given time to the initial CO absorbanceJ as a measure o~ the polymer photodegradation. Two ditferent photodegradation activation complexes namely a complex of type (I) (FeAcAc=0,~005 moles/lOOg; curve A) and iron dimethyldithiocarbamate (FeDMC=0,0005 moles/100 9, curve B) contained at the same concentrations in LPDE behaves in a quite different way with respect to photodegradation contro1.
Iron acetylacetonate promotes the immediate start ot the degradative process while the second acts as a normal pho-toactivator (G.B. 1,356,107).
When iron acetylacetonate is combined with very small amounts of a thermal stabiliser (FeAcAc=O~OOU5 moles/lUO g + Zn DEC=
0,U01~5 moles/lUO g; R=~n = 0.25; curve ~) the degradation ~e 5~71~i rate is enhanced but the degradation process is preceded by a very short bu~ very complete induction period during which the stability is absolute as already mentioned.
When Zn to ~`e ratio is raised (R=l; FeAcAc=ZnDEC=0,00~5 moles/100 g; curve ~ the sharp trend of curve C turns into the steadily raising trend of curve D thus noticeably extend-ing the embrittlement time to values whlch are very similar to those observed in the case ot FeUMC alone (curve BJ. However, the comparison between curve C and curve D is the better visual explanation of the novelty and or1ginallty inherent to the present invention. The latter aspect of this invention is lllustrated in the second figure of the enclosed drawings, from which it can be seen that in an internal mixer the thermal stability of FeAcAc/ZnDEC (straight line C; FeAcAc=U,OU05 moles/
100 g + 7n DEC= 0,U0~125 moles/lou g or Fe~MC alone= U,OU25 moles/100 g) is very much better than that ot the control (curve B=no addltive) and as good as that of FeDM~ alone).
~eAcAc alone on the contrary (curve A; reAcAc=0,00~5 moles/1UO g causes very rapid oxidation of LD~E under these conditions.
This invention consequently relates to polymer composition which are very quickly degradable under the action of ultra-violet light and/or s~nlight wherein the induction period, namely, the delay time between the exposure to U.V. radiat-ion and the start of said degradation is predetermined and may be very small. The polymer compositions are characterized in that the photodegradation is promoted by means of the additional presence of at least one metal complex which is a powerful activator of said photo-degradation of polymers in combination with a very small amount o~ dithio1ate metal complex which is a stabiliser for thermal degradatlon. Molar ratios R of the activator complex to the thermal stabiliser are lower than 0.5 ancl preferably R \< 0.3.
Moreover this invention relates to any protectiYe or wrapping 3L~ 7~i membrane and/or mulching film obtainable from said compositions by means of usual manufacturing processe~ such as extrusion or blow extrusion.
The thermoplastic vinyl polymer is preferably a film or fibre-forming polymer or copolymer such as polyethylene, polypropylene, poly (4-methyl-1-penteneJ, or polystyrene or terpolymer which may contain unsaturation. Other vinyl polylners such as poly-vinylacetate, polyvinylchloride~ polymethyl methacrylate, and polycrylonitrile and copolymers of the corresponding monomers, including vinylchloride-vinyl acetate copolymers, including gra~t copolymers wlth unsaturated polymers, as well as miXtures of such polymers, particularly with unsalurated polymers, c~n also be used in the compositions of the present invention.
This process can also be used for condencation polymers such as polyesters, polyamides and polyurethanes.
The thermoplastic compositions of this invention may contain other cornpounding ingredients, such as blowing agents, various types of antioxidants, stabilisers, lubrificants, antistatic agents and antiblocking agents~ Antioxidants do not take part to the embrittlement process and therefore may be used in con-ventional amounts.
~nert pigments, dyes, other conventional additives and carbon black may also be added to the polymer compositions.
In general pigments act as U.V. screening agents and increase the embritt1ement time of the polymer and this is particularly true for carbon black as above already mentioned.
The photo-activating complex can be any organo-soluble trans-ition metal complex in which the ligand is attached to the metal through oxygen. PreFerred complexing agen~s are ~-di-ketones, ~-ketoesters and among them acetylacetone.
` 3~.;~g5i~76 Preferred transition metals are iron, coL,alt and manganese.
The thermal stabilising complex is preferably a groups lI, group IV or a transition mctal complex i~ which the complexing agent is any sulphur containing compound among the complexing agents disclosed in the earlier patents. In particular dialkyl dithiocarbamates, dialkyldithiophosphates, alkylxantates, mercaptobenzothiazoles and nitrogen coordinating compounds such as the salicylideneimides etc.
Rl\ ~ RlO
N-C-SH \ Il-SH
R2 R~O
dithiocarbamates dithiophosp~lates S S S
R~-C-~H HS-C-N-R3-N-~-SH
Rl ~2 bifunctionaldithiocarbamates S ' S
H-S-P-OR-~-P-SH R ~ C-SH
OR OR
bifunctional dithiophosphates benzthiazoles Where R, Kl, ~2' R3 each represent hydroyen or an alkyl, aralkyl or amyl group, which may be unsubstituted or substituted AS well as linked together to form heterocyclic lings.
1;;~9507G
Dlthiocarbamates and the above mentioned derivatlves thereof are the preferred complexing agents since they are substantially non toxic.
The preferred combinations of metal complexes in the thermopla-stic polymer compositions according to the present invention are iron-acetylacetonate and Ni or Zn dialkyldithiocarbamates.
The concentration of the oxygen complexes is generally from 0,0005 to 0,5% by weight and preferably from 0,OOCS to 0,2%
by weight.
The concentration of the thermal stabilising su'lphur containing metal complex depends on the desired relative mo'lar ratio R of stabilislng to actlvating complex. The molar ratio R is generally lower than 0,5 preferab'ly R ~ 0.3. However, the relative concentrations to be used of the two metal complexes depend largely on the intended use of the finished article.
The following examples further illustrate the present inven-tion. The starting material of the polymer compositions was a low density polyethylene L~PE with a melt flow index MFI=2.16Kg (lU' at l9UCj.
3L29~ 6 EXAMPLE I
Iron acetylacetonate was added in an internal mixer (feAcAc = 5.10 4 moI / 1dO gj to the aforesaid LDPE and a film was obtained using the blow extrusion technique which is conventional ln processing polyethylene. Maximum pro-cessing temperatures were in the order of 210C. The film thickness was ~0 mlcrons; however test carrie~ out with greater thicknesses, up to the practical maximum of 10U
microns, showed ~hat the behaviour of the material was sub-s~antially the same for all thicknesses in the said range.
, ~ , .
The films were then exposed in a Weatherometer~to U.V.
lrradiation. Iable I sunImarise the results obtained Prom films made using the same methodology but adding different complexes to the LDPE.
Table I.
~ehaviour of fllms of LDPE containing FeAcAc-Fe~MC complexes alone or in combination with ZnDEC or NiDEC and laid out.
. ~ . . __ ~ype of complexes (mol/lOU~) Lmbrittlement time (hours) FeAcAc (5-10 ) 425 FeAcAc (5-1U 4) +ZnDEC (1,25 10 4) 375 FeDMC (5-10 4) 130~
Fe~MC (1~5-1~-4) 900 FeDMC (~ 1~ 4) -~ ZnDEC (5-10 4)1200 FeDMC (2.5-1U 4) + NiDEC(0.25-10 4) 750 reference (LD~E ~Iithout aaditives) ~20u .. . _ EXhMPLE_I r Polypropylene samples containing NiDEC (2.5-1~4 mol/lOOg) amounts of FeAcAc variable and ranging from ~ to 15-104 mol/100 gI were processed in an internal mixer at 180C~
After 10 minutes processing the melt tlow index was measured ~ Trad~ r k , ~2~5~76 - lS
and the results are reported in table II.
This table shows that even the combination containing a six-fold excess of FeAcAc is as thermally stable as that containing NiDEC alone in Polypropylene which is notoriously subject to oxidative degredation during processing.
Table 11.
Ihermal stability of polypropylene containing NiDEC
(2.5'10 4 mol/lOOg) and FeAcAc (variable amounts) and processed in an internal mixer at 18uC and 10 mln.
. _ _ . ... _ . .. ..... . .. . _ _ _ .. ..... . .. . .. . _ . .. . . . _ _ . .
FeAcAc (Mol/lUOg) (MFI) 10 min _~
.64 7.5 1U 4 0.66 10.0-tU U.64 15 0 10~4 0.65
Claims (15)
1. Polymer compositions comprising a vinyl polymer and a combination of at least two metal complexes wherein the complexing agent of the first complex is attached to the metal through oxygen and the metal is a transition metal, and the complexing agent of the second complex is attached to the metal through sulphur and the metal is a transition metal ox a metal of group II or IV of the periodic table of the elements, wherein the first metal complex is an activator for photodegradation and for thermal oxidation of the vinyl polymer and the second metal complex is a thermal stabilizer of the polymer, and wherein the molar ratio of the second metal complex to the first metal complex is 0.5 or less.
2. Polymer compositions according to claim 1 in which the first complex is an iron complex or a cobalt complex.
3. Polymer composition according to claim 1 in which the second complex is a zinc or nickel or cobalt complex.
4. Polymer compositions according to claim 1 in which the complexing agent of the first complex is acetylacetone.
5. Polymer compositions according to claim 1 in which the complexing agent of the second complex is a dialkyl-dithiocarmate, dialkyldithiophosphate, alkylxantate, or mercaptobenzithiazole.
6. Polymer compositions according to claim 1 which contain 0.0001 to 0.5% by weight of the first complex.
7. Polymer compositions according to claim 1 which contain 0.00005 to 0.25% by weight of the second complex.
8. Polymer compositions according to claim 1 which include an antioxidant.
9. Polymer compositions according to claim 1 which include carbon black.
10. A film obtained from a composition as claimed in claim 1.
11. A film according to claim 10 which is a protective or mulching film.
12. A film according to claim 10 which is 30 to 100 microns thick.
13. An agricultural process which comprises laying out a protective or mulching film as claimed in claim 11 on a crop-growing soil area, allowing it to lay on the area at least until it has reached its embrittlement stage and subsequently carrying out soil working operations in said area thereby substantially to eliminate the film from the soil surface.
14. A process according to claim 13 in which the soil working operations are carried out when the embrittled film is still substantially continuous, whereby said film is broken up.
15. A process according to claim 13 in which the soil working operations are not carried out before the film has broken up.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8604849A GB2187193B (en) | 1986-02-27 | 1986-02-27 | Controllably and swiftly degradable polymer compositions and films and other products made therefrom |
| GB8604849 | 1986-02-27 |
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| Publication Number | Publication Date |
|---|---|
| CA1295076C true CA1295076C (en) | 1992-01-28 |
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ID=10593755
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000528226A Expired - Lifetime CA1295076C (en) | 1986-02-27 | 1987-01-27 | Controllable and swiftly degradable polymer compositions and films and otherproducts made therefrom |
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| Country | Link |
|---|---|
| US (1) | US4939194A (en) |
| EP (1) | EP0236005B1 (en) |
| JP (2) | JPH0662804B2 (en) |
| AR (1) | AR241193A1 (en) |
| AT (1) | ATE97149T1 (en) |
| AU (1) | AU602136B2 (en) |
| BR (1) | BR8700670A (en) |
| CA (1) | CA1295076C (en) |
| DE (1) | DE3788074T2 (en) |
| DK (1) | DK83987A (en) |
| EG (1) | EG19058A (en) |
| ES (1) | ES2007336A6 (en) |
| FI (1) | FI91417C (en) |
| GB (1) | GB2187193B (en) |
| GR (1) | GR870186B (en) |
| IL (1) | IL81069A (en) |
| IT (1) | IT1197825B (en) |
| MA (1) | MA20883A1 (en) |
| MX (1) | MX170812B (en) |
| NO (1) | NO168118C (en) |
| PT (1) | PT84372B (en) |
| TN (1) | TNSN87029A1 (en) |
| ZA (1) | ZA869758B (en) |
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| US20100229462A1 (en) * | 2010-05-26 | 2010-09-16 | Cerowa, Lp | Degradable and Compostable Plastic Films for Agriculture |
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| GB2207439B (en) * | 1987-07-27 | 1992-02-12 | Metal Box Plc | Improvements in and relating to packaging |
| FR2657353B1 (en) * | 1990-01-23 | 1993-07-02 | Bono Pierre | DEGRADABLE PLASTIC FILM COMPRISING AN ACTIVE VEGETABLE LOAD, LIGNIN. |
| US5274019A (en) * | 1990-10-25 | 1993-12-28 | Robinson Brothers Limited | Photodegradable compositions |
| US5145779A (en) * | 1991-05-03 | 1992-09-08 | Iowa State University Research Foundation, Inc. | Process of biodegradation of high molecular weight polyethylene by aerobic lignolytic microorganisms |
| US5518730A (en) | 1992-06-03 | 1996-05-21 | Fuisz Technologies Ltd. | Biodegradable controlled release flash flow melt-spun delivery system |
| KR960007311B1 (en) * | 1992-11-11 | 1996-05-30 | 대림산업주식회사 | Photo-degradable polyolefin film composition |
| JP3848077B2 (en) * | 2000-11-20 | 2006-11-22 | キヤノン株式会社 | Decomposable resin composition and method for treating the same |
| CN1233717C (en) * | 2000-12-06 | 2005-12-28 | 郝本忠 | Polynary composite for light and biological degraded plastic product and its use |
| US20040259974A1 (en) * | 2003-06-18 | 2004-12-23 | Gerald Scott | Biodegradable polymer compositions with controlled lifetimes |
| WO2005028558A1 (en) | 2003-09-22 | 2005-03-31 | Matsushita Electric Industrial Co., Ltd. | Flame-retardant resin composition, process for producing the same, and method of molding the same |
| US20090306452A1 (en) * | 2008-05-19 | 2009-12-10 | Payne Frederick C | Apparatus for treating a contaminated media with a sorbent |
| US20100068283A1 (en) * | 2008-09-16 | 2010-03-18 | Searete Llc, A Limited Liability Corporation Of The State Of Delaware | Ex VIVO modifiable particle or polymeric material medicament carrier |
| US20100068235A1 (en) * | 2008-09-16 | 2010-03-18 | Searete LLC, a limited liability corporation of Deleware | Individualizable dosage form |
| US20100068233A1 (en) * | 2008-09-16 | 2010-03-18 | Searete Llc, A Limited Liability Corporation Of The State Of Delaware | Modifiable dosage form |
| US20100068153A1 (en) * | 2008-09-16 | 2010-03-18 | Searete Llc, A Limited Liability Corporation Of The State Of Delaware | Ex vivo activatable final dosage form |
| US20100068152A1 (en) * | 2008-09-16 | 2010-03-18 | Searete Llc, A Limited Liability Corporation Of The State Of Delaware | Ex vivo modifiable particle or polymeric based final dosage form |
| US20100069821A1 (en) * | 2008-09-16 | 2010-03-18 | Searete Llc, A Limited Liability Corporation Of The State Of Delaware | Ex vivo modifiable medicament release-sites final dosage form |
| US20100068254A1 (en) * | 2008-09-16 | 2010-03-18 | Mahalaxmi Gita Bangera | Modifying a medicament availability state of a final dosage form |
| US20100068275A1 (en) * | 2008-09-16 | 2010-03-18 | Searete Llc, A Limited Liability Corporation Of The State Of Delaware | Personalizable dosage form |
| US20120310140A1 (en) | 2010-12-01 | 2012-12-06 | Spinal Modulation, Inc. | Directed delivery of agents to neural anatomy |
| JP2016507871A (en) | 2013-01-14 | 2016-03-10 | パワージェニックス・システムズ・インコーポレーテッドＰｏｗｅｒｇｅｎｉｘ Ｓｙｓｔｅｍｓ， Ｉｎｃｏｒｐｏｒａｔｅｄ | Paste-type nickel hydroxide electrodes and additives for rechargeable alkaline batteries |
| JP5890807B2 (en) * | 2013-08-12 | 2016-03-22 | みかど化工株式会社 | Agricultural multilayer multi-film |
| CA3074951A1 (en) | 2017-09-11 | 2019-03-14 | Sorrento Therapeutics, Inc. | Formulation of resiniferatoxin |
| KR20220161423A (en) | 2020-03-30 | 2022-12-06 | 소렌토 쎄라퓨틱스, 인코포레이티드 | Treatment of pulmonary inflammatory disease associated with COVID-19 by administering reginiferatoxin |
| AU2021292420A1 (en) | 2020-06-19 | 2023-02-09 | Sorrento Therapeutics, Inc. | Administration of resiniferatoxin for treatment of bladder pain or bladder cancer |
| JP2024507130A (en) | 2021-02-11 | 2024-02-16 | ソレント・セラピューティクス・インコーポレイテッド | Administration of resiniferatoxin for the treatment of prostate cancer |
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|---|---|---|---|---|
| GB965054A (en) * | 1961-12-28 | 1964-07-29 | Hercules Powder Co Ltd | Improvements in or relating to stabilization of polyolefins with nickel hydroxamates |
| GB1356107A (en) * | 1970-07-22 | 1974-06-12 | Scott G | Polymer compositions |
| US3941759A (en) * | 1972-03-01 | 1976-03-02 | Owens-Illinois, Inc. | Degradable plastics containing dual-function additive system |
| GB1423655A (en) * | 1972-05-18 | 1976-02-04 | Ici Ltd | Degradable polyvinyl chloride compositions |
| GB1400570A (en) * | 1972-11-23 | 1975-07-16 | Ici Ltd | Prodegradant compositions comprising vinyl chloride polymers |
| US4076689A (en) * | 1976-05-14 | 1978-02-28 | Phillips Petroleum Company | Ultraviolet light stabilizer combination for polymers |
| IL52974A0 (en) * | 1977-09-21 | 1977-11-30 | Plastopil Hazorea | Agricultural process film products for carrying out the process and controllably degradable polymer compositions for making said film products |
| US4519161A (en) * | 1977-09-21 | 1985-05-28 | Dan Gilead | Agricultural process using controllably degradable polymer composition film |
| DE3670855D1 (en) * | 1985-08-28 | 1990-06-07 | Akzo Nv | PHOTOSENSITIZING COMPOSITIONS AND THEIR CONTAINING LIGHT DEGRADABLE POLYMER COMPOSITION. |
-
1986
- 1986-02-27 GB GB8604849A patent/GB2187193B/en not_active Expired
- 1986-09-22 IT IT21782/86A patent/IT1197825B/en active
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- 1986-12-30 ZA ZA869758A patent/ZA869758B/en unknown
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1987
- 1987-01-15 AR AR87306483A patent/AR241193A1/en active
- 1987-01-26 JP JP62014302A patent/JPH0662804B2/en not_active Expired - Lifetime
- 1987-01-27 CA CA000528226A patent/CA1295076C/en not_active Expired - Lifetime
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- 1987-02-13 BR BR8700670A patent/BR8700670A/en not_active IP Right Cessation
- 1987-02-17 EP EP87301355A patent/EP0236005B1/en not_active Expired - Lifetime
- 1987-02-17 DE DE87301355T patent/DE3788074T2/en not_active Expired - Fee Related
- 1987-02-17 AT AT87301355T patent/ATE97149T1/en not_active IP Right Cessation
- 1987-02-19 MX MX005298A patent/MX170812B/en unknown
- 1987-02-19 DK DK083987A patent/DK83987A/en not_active Application Discontinuation
- 1987-02-23 AU AU69133/87A patent/AU602136B2/en not_active Ceased
- 1987-02-23 MA MA21118A patent/MA20883A1/en unknown
- 1987-02-26 EG EG10987A patent/EG19058A/en active
- 1987-02-26 TN TNTNSN87029A patent/TNSN87029A1/en unknown
- 1987-02-26 PT PT84372A patent/PT84372B/en not_active IP Right Cessation
- 1987-02-26 NO NO870801A patent/NO168118C/en unknown
- 1987-02-27 ES ES8700798A patent/ES2007336A6/en not_active Expired
-
1989
- 1989-08-04 US US07/391,703 patent/US4939194A/en not_active Expired - Fee Related
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1994
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100229462A1 (en) * | 2010-05-26 | 2010-09-16 | Cerowa, Lp | Degradable and Compostable Plastic Films for Agriculture |
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