CA1118139A - Light-stable polypropylene compositions - Google Patents
Light-stable polypropylene compositionsInfo
- Publication number
- CA1118139A CA1118139A CA000342491A CA342491A CA1118139A CA 1118139 A CA1118139 A CA 1118139A CA 000342491 A CA000342491 A CA 000342491A CA 342491 A CA342491 A CA 342491A CA 1118139 A CA1118139 A CA 1118139A
- Authority
- CA
- Canada
- Prior art keywords
- light
- polypropylene
- pentaerythritol
- polyphosphite
- stable
- 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
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3432—Six-membered rings
- C08K5/3435—Piperidines
-
- 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
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
-
- 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
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
-
- 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
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/527—Cyclic esters
Abstract
LIGHT-STABLE POLYPROPYLENE COMPOSITIONS
Abstract Light-stable polypropylene fibers containing a combination of a hindered piperidinyl compound and a pentaerythritol polyphosphite.
Abstract Light-stable polypropylene fibers containing a combination of a hindered piperidinyl compound and a pentaerythritol polyphosphite.
Description
- 1118~
077168~
LIGHT-STABLE POLYPROPYLENE CO~OSITIONS
.
Description The invention of this application relates, as indicated, to polypropylene compositions. I~lore parti-cularly, it relates to such compositions which are stabilized against deterioration that ordinarily results from prolonged exposure to sunlight. Still more parti-cularly, it relates to the stabilization of polypropylene compositions by means of the combination of small pro-portions of additives.
Ultraviolet light has a degradative effect uponolefin polymers, the severity of which is dependent - primarily on the degree of exposure. The effect is es-pecially se~ere on polypropylene, probably because of the high concentration of tertiary carbon atoms which are peculiarly susceptible to oxidative attack.
Ordinarily, polypropylene is characterized by high tensile strength, i.e., higher than that of other olefin polymers, as well as by high abrasion resistance and a lustrous surface which is resistant to acid, alkali, solvent and other chemical attack. It is also very light in weight, i.e., it has a specific gravity of about 0.90. All of these physical properties, plus the fact that, as a fiber, it can be oriented so as to significantly increase its tensile strength, are highly desirable and, as expected, it finds wide usage in many applications.
Unfortunately, these desirable qualities are accompanied by a tendency of the polypropylene to deteriorate rapidly by means of photooxidation upon exposure to sunlight.
The result is discoloration, reduced molecular weight and embrittlement. It is accordingly necessary to stabilize 077168~ 2 -the polymer against such deterioration, and this is done by the addition of small amounts of chemical agents which are effective for this purpose. Hydroxybenzophenones, hydroxyphenylbenzotriazoles and phenylsalicylates are thus effective and are used in this manner. They operate by absorbing harmful ultraviolet energy and reemitting it at a different energy level which does not adversely affect the polymer.
The relative instability of polypropylene is due to the presence of tertiary carbon atoms in the polymer chain; these are subject to oxidative attack which is catalyzed by heat and light. In the case of fiber compo-sitions, for example, light is an especially important factor because of the relatively large amount of surface area of the polypropylene.
Japanese Patent Publication No. 66551/77 shows the stabilization of certain synthetic resins, including polypropylene, by the combination of a substituted piperidine, a triorganophosphite and a secondary organophosphite. The secondary organophosphite is an essential component of the stabilizer combination.
U.S. 3,640,928 (Murayama et al), which deals with the stabilization of a wide variety of synthetic polymers, shows the use of certain piperidine derivatives for that purpose. Included among such piperidine derivatives is bis(2,2,6,6-tetramethyl-4-piperidyl)adipate. It is stated that these compounds can be used alone or in co~bination with other known stabilizers, fillers, pigments and the like.
U.S. 3,840,494 (Murayama et al) shows much the same thing.
West German Patent Publication No. ~5 00 314 deals with the stabilization of pigmented polyolefin compositions.
Stabilization is accomplished by means of cyclic di-tert-alkylamines; these are defined very broadly and illustrated profusely, and include bis-(2,2,6,6-tetramethyl-4-piperidinyl-l-oxyl)-sebacate (see page 15). It is also stated that 07716S~ 3 ~
these cyclic di-tert-amines can be used for their intended purpose in combination with other known additives.
The invention of this application is a light-stable polypropylene composition comprising polypropylene and minor proportions sufficient to improve the light stability of said polypropylene of each of a piperidinyl compound having the formula r CH
7 ~ A
CHX--~ 3 CH3 i_ Y
where R is alkyl of 1-4 carbon atoms or hydrogen, y is 1-4 and A is an organic radical or a phosphorus acid residue, and a pentaerythritol polyphosphite. The organic radical or phosphorous acid residue may be an ester, carbonate, ether, thiocarbonate, sulfinate, sulfonate, phosphite or phosphate radical, as shown more particularly in U.S.
3,640,928.
~ore narrowly, the invention comprises polypropylene compositions containing a piperidinyl compound having the formula Rl~ O--CO . (CH2)h~--~ Nn _ x where R is alkyl of 1-4 carbon atoms or hydrogen, m is 1-4, x i~ 2-3 and n is 0 or 1, and a pentaerythritol polyphosphite.
077168~ 4 _ It will be noted that the above piperidinyl compound may comprise three substituted piperidinyl groups bound to one another through a nitrogen atom, as well as one where two substituted piperidinyl groups are bound to one another through the residue of an aliphatic dicarboxylic acid. In the first instance, such a compound may be prepared by the reaction of a lower alkyl ester of a tricarboxylic acid having the formula N [ (CH2)mCOOH~
where m is 1-4, with 4-hydroxy-2,2,6,6-tetramethylpiperidine.
In the other instance, the piperidinyl compound of the invention may be prepared by reaction of a di-(lower)alkyl dicarboxylate with the 4-hydroxy-2,2,6,6-tetramethylpiperidine. Illustrative di-(lower)alkyl di-carboxylates include dimethyl and diethyl, glutarates, suberates, sebacates, adipates and pimelates. The methods of preparation shown in the above Murayama et al patents are suitable here.
The pentaerythritol polyphosphite preferably is a dialkyl pentasrythritol diphosphite. It may be prepared by the reaction of pentaerythritol and two mols of triphenyl phosphite, followed by transesterification of the resulting diphenyl pentaerythritol diphosphite with a relatively non-volatile alcohol such as stearyl alcohol. Other suitable pentaerythritol polyphosphites may be prepared by reacting various proportions of pentaerythritol and triphenyl phosphite with one another. Thus, the reaction of three mols of pentaerythritol and four mols of triphenyl phosphite results in tripentaerythritol tetraphosphite, i.e., a product wherein all of the phosphorus valences are attached through oxygen to a pentaerythritol residue. It will be understood 3g 077168-~ - 5 -that products of this type, being derived from two polyfunctional reactants, are necessarily a mixture of several products and that the term "product" is used herein to designate the product obtained in principal amounts.
Other proportions of the above two reactants may be employed to obtain, on the one hand, products having free hydroxyl groups attached to the pentaerythritol residue and, on the other hand, products having un-reacted phenyl ester groups; these phenyl ester groupscan, of course, be transesterified with relatively non-volatile alcohols such as stearyl alcohol, dodecyl alcohol, decyl alcohol and the like.
The details of method of preparation of these pentaerythritol polyphosphites may be gleaned from the disclosures of U.S. 3,205,250; U.S. 3,281,381;
U.S. 3,310,609; and U.S. 3,928,505.
The piperidinyl compound of the invention should be used in concentrations ranging from about 0.03% to about 1.0% based on the polypropylene content. The pentaerythritol polyphosphite should be used in concentrations ranging from about 0.05% to about 1.0% on the same basis.
The piperidinyl compounds herein are known to impart good ultraviolet stability to polymer compositions. Un-fortunately, they are expensive because of the number ofprocessing steps required in their manufacture. The invention of this application permits substitution of a much less expensive additive, viz., the pentaerythritol polyphosphite, for a large proportion, i.e., up to about 75%, of the piperidinyl compound, without loss of ultraviolet stabilizing activity. ~s a matter of fact, in many instances there is a considerable increase in such activity upon 1118~3~
077168-.~l - 6 -addition of ,he pentaerythritol polyphosphite.
Other stabilizing agents can be added to the polypropylene compositions herein. These include neutralizers such as metal oxides and metal salts of higher molecular weight carboxylic acids such as calcium stearate, barium laurate, etc.; phenolic oxidation inhibitors such as those described in U.S. 3,285,855; U.S. 3,644,482;
and U.S. 3,531,483; and various fillers, pigments, etc.
The efficacy of the polypropylene compositions of the invention is shown by data collected from tests carried out on 200/16 denier natural polypropylene multifilament.
The fiber compositions are prepared by dry blending the various components and then extruding the mixture at 475F. Fibers are spun at 540 F, drawn at a ratio of 7:1 and given one twist per inch. The test consists of exposure of the test fiber to conditions of ordinary weather in the Caribbean. The tensile strength of the fiber is measured at periodic intervals and the percent retention of the original tensile strength after 140 kilolangleys ("KL") is taken as a measure of the resistance of the fiber to deterioration. Test data for various polypropylene fibers are shown in the following table.
Each fiber composition contains 100 parts of poly-propylene, 0.05 phr (parts per hundred parts of resin) of calcium stearate, 0.15 phr of octadecyl 3-(4-hydroxy-3, 5-ditertiarybutylphenyl)propionate and the indicated amounts (phr) of toher additives.
Table % Retention of A B C D Tensile Strength after 140 KL
1. 0.2 43
077168~
LIGHT-STABLE POLYPROPYLENE CO~OSITIONS
.
Description The invention of this application relates, as indicated, to polypropylene compositions. I~lore parti-cularly, it relates to such compositions which are stabilized against deterioration that ordinarily results from prolonged exposure to sunlight. Still more parti-cularly, it relates to the stabilization of polypropylene compositions by means of the combination of small pro-portions of additives.
Ultraviolet light has a degradative effect uponolefin polymers, the severity of which is dependent - primarily on the degree of exposure. The effect is es-pecially se~ere on polypropylene, probably because of the high concentration of tertiary carbon atoms which are peculiarly susceptible to oxidative attack.
Ordinarily, polypropylene is characterized by high tensile strength, i.e., higher than that of other olefin polymers, as well as by high abrasion resistance and a lustrous surface which is resistant to acid, alkali, solvent and other chemical attack. It is also very light in weight, i.e., it has a specific gravity of about 0.90. All of these physical properties, plus the fact that, as a fiber, it can be oriented so as to significantly increase its tensile strength, are highly desirable and, as expected, it finds wide usage in many applications.
Unfortunately, these desirable qualities are accompanied by a tendency of the polypropylene to deteriorate rapidly by means of photooxidation upon exposure to sunlight.
The result is discoloration, reduced molecular weight and embrittlement. It is accordingly necessary to stabilize 077168~ 2 -the polymer against such deterioration, and this is done by the addition of small amounts of chemical agents which are effective for this purpose. Hydroxybenzophenones, hydroxyphenylbenzotriazoles and phenylsalicylates are thus effective and are used in this manner. They operate by absorbing harmful ultraviolet energy and reemitting it at a different energy level which does not adversely affect the polymer.
The relative instability of polypropylene is due to the presence of tertiary carbon atoms in the polymer chain; these are subject to oxidative attack which is catalyzed by heat and light. In the case of fiber compo-sitions, for example, light is an especially important factor because of the relatively large amount of surface area of the polypropylene.
Japanese Patent Publication No. 66551/77 shows the stabilization of certain synthetic resins, including polypropylene, by the combination of a substituted piperidine, a triorganophosphite and a secondary organophosphite. The secondary organophosphite is an essential component of the stabilizer combination.
U.S. 3,640,928 (Murayama et al), which deals with the stabilization of a wide variety of synthetic polymers, shows the use of certain piperidine derivatives for that purpose. Included among such piperidine derivatives is bis(2,2,6,6-tetramethyl-4-piperidyl)adipate. It is stated that these compounds can be used alone or in co~bination with other known stabilizers, fillers, pigments and the like.
U.S. 3,840,494 (Murayama et al) shows much the same thing.
West German Patent Publication No. ~5 00 314 deals with the stabilization of pigmented polyolefin compositions.
Stabilization is accomplished by means of cyclic di-tert-alkylamines; these are defined very broadly and illustrated profusely, and include bis-(2,2,6,6-tetramethyl-4-piperidinyl-l-oxyl)-sebacate (see page 15). It is also stated that 07716S~ 3 ~
these cyclic di-tert-amines can be used for their intended purpose in combination with other known additives.
The invention of this application is a light-stable polypropylene composition comprising polypropylene and minor proportions sufficient to improve the light stability of said polypropylene of each of a piperidinyl compound having the formula r CH
7 ~ A
CHX--~ 3 CH3 i_ Y
where R is alkyl of 1-4 carbon atoms or hydrogen, y is 1-4 and A is an organic radical or a phosphorus acid residue, and a pentaerythritol polyphosphite. The organic radical or phosphorous acid residue may be an ester, carbonate, ether, thiocarbonate, sulfinate, sulfonate, phosphite or phosphate radical, as shown more particularly in U.S.
3,640,928.
~ore narrowly, the invention comprises polypropylene compositions containing a piperidinyl compound having the formula Rl~ O--CO . (CH2)h~--~ Nn _ x where R is alkyl of 1-4 carbon atoms or hydrogen, m is 1-4, x i~ 2-3 and n is 0 or 1, and a pentaerythritol polyphosphite.
077168~ 4 _ It will be noted that the above piperidinyl compound may comprise three substituted piperidinyl groups bound to one another through a nitrogen atom, as well as one where two substituted piperidinyl groups are bound to one another through the residue of an aliphatic dicarboxylic acid. In the first instance, such a compound may be prepared by the reaction of a lower alkyl ester of a tricarboxylic acid having the formula N [ (CH2)mCOOH~
where m is 1-4, with 4-hydroxy-2,2,6,6-tetramethylpiperidine.
In the other instance, the piperidinyl compound of the invention may be prepared by reaction of a di-(lower)alkyl dicarboxylate with the 4-hydroxy-2,2,6,6-tetramethylpiperidine. Illustrative di-(lower)alkyl di-carboxylates include dimethyl and diethyl, glutarates, suberates, sebacates, adipates and pimelates. The methods of preparation shown in the above Murayama et al patents are suitable here.
The pentaerythritol polyphosphite preferably is a dialkyl pentasrythritol diphosphite. It may be prepared by the reaction of pentaerythritol and two mols of triphenyl phosphite, followed by transesterification of the resulting diphenyl pentaerythritol diphosphite with a relatively non-volatile alcohol such as stearyl alcohol. Other suitable pentaerythritol polyphosphites may be prepared by reacting various proportions of pentaerythritol and triphenyl phosphite with one another. Thus, the reaction of three mols of pentaerythritol and four mols of triphenyl phosphite results in tripentaerythritol tetraphosphite, i.e., a product wherein all of the phosphorus valences are attached through oxygen to a pentaerythritol residue. It will be understood 3g 077168-~ - 5 -that products of this type, being derived from two polyfunctional reactants, are necessarily a mixture of several products and that the term "product" is used herein to designate the product obtained in principal amounts.
Other proportions of the above two reactants may be employed to obtain, on the one hand, products having free hydroxyl groups attached to the pentaerythritol residue and, on the other hand, products having un-reacted phenyl ester groups; these phenyl ester groupscan, of course, be transesterified with relatively non-volatile alcohols such as stearyl alcohol, dodecyl alcohol, decyl alcohol and the like.
The details of method of preparation of these pentaerythritol polyphosphites may be gleaned from the disclosures of U.S. 3,205,250; U.S. 3,281,381;
U.S. 3,310,609; and U.S. 3,928,505.
The piperidinyl compound of the invention should be used in concentrations ranging from about 0.03% to about 1.0% based on the polypropylene content. The pentaerythritol polyphosphite should be used in concentrations ranging from about 0.05% to about 1.0% on the same basis.
The piperidinyl compounds herein are known to impart good ultraviolet stability to polymer compositions. Un-fortunately, they are expensive because of the number ofprocessing steps required in their manufacture. The invention of this application permits substitution of a much less expensive additive, viz., the pentaerythritol polyphosphite, for a large proportion, i.e., up to about 75%, of the piperidinyl compound, without loss of ultraviolet stabilizing activity. ~s a matter of fact, in many instances there is a considerable increase in such activity upon 1118~3~
077168-.~l - 6 -addition of ,he pentaerythritol polyphosphite.
Other stabilizing agents can be added to the polypropylene compositions herein. These include neutralizers such as metal oxides and metal salts of higher molecular weight carboxylic acids such as calcium stearate, barium laurate, etc.; phenolic oxidation inhibitors such as those described in U.S. 3,285,855; U.S. 3,644,482;
and U.S. 3,531,483; and various fillers, pigments, etc.
The efficacy of the polypropylene compositions of the invention is shown by data collected from tests carried out on 200/16 denier natural polypropylene multifilament.
The fiber compositions are prepared by dry blending the various components and then extruding the mixture at 475F. Fibers are spun at 540 F, drawn at a ratio of 7:1 and given one twist per inch. The test consists of exposure of the test fiber to conditions of ordinary weather in the Caribbean. The tensile strength of the fiber is measured at periodic intervals and the percent retention of the original tensile strength after 140 kilolangleys ("KL") is taken as a measure of the resistance of the fiber to deterioration. Test data for various polypropylene fibers are shown in the following table.
Each fiber composition contains 100 parts of poly-propylene, 0.05 phr (parts per hundred parts of resin) of calcium stearate, 0.15 phr of octadecyl 3-(4-hydroxy-3, 5-ditertiarybutylphenyl)propionate and the indicated amounts (phr) of toher additives.
Table % Retention of A B C D Tensile Strength after 140 KL
1. 0.2 43
2. 0.4 ~6
3. 0.2 0 (at 44 KL)
4. 0.2 0.2 74 077168~
~ Retention of A B C D Tensile Strength after 40 KL
~ Retention of A B C D Tensile Strength after 40 KL
5. 0.3 0.1 64
6. 0.3 0.3 90
7. 0.2 0 (at 96 KL)*
8. 0.3 0 (at 48 KL)*
9. 0.6 64 A: bis-(2,2,6,6-tetramethyl-4-piperidyl)sebacate B: tris-(2,2,6,6-tetramethyl-4-piperidyl)nitriloacetate C: distearyl pentaerythritol diphosphite D: tripentaerythritol tetraphosphite * extrapolated values It will be seen that test fiber samples Nos. 4, 5 and 6, representing the combination of the claims, are rated quite high. ~oreover, No. 5 is rated as high (64) as No. 9 (64), although it has a lower overall additive content. Likewise, No. 4 is rated higher (74) than No. 2 (56), with which it is directly comparable. So also, No. 5 is rated higher (64) than No. 2 (56).
All parts and percentages herein, unless otherwise expressly stated, are by weight.
All parts and percentages herein, unless otherwise expressly stated, are by weight.
Claims (6)
1. A light-stable polypropylene composition comprising polypropylene and minor proportions sufficient to improve the light stability of said polypropylene of each of a piperidinyl compound having the formula wherein R is alkyl of 1-4 carbon atoms or hydrogen, y is 1-4 and A is an organic radical or phosphorus acid residue, and a pentaerythritol polyphosphite.
2. A light-stable polypropylene composition comprising polypropylene and minor proportions sufficient to improve the light stability of said polypropylene of each of a piperidinyl compound having the formula where m is 1-4, x is 2-3 and n is 0 or 1, and a penta-erythritol polyphosphite.
3. The light-stable polypropylene composition of Claim 2 wherein m is 1, x is 3 and n is 1.
4. The light-stable polypropylene composition of Claim 2 wherein m is 4, x is 2, and n is 0.
5. The light-stable polypropylene composition of Claim 1 wherein the pentaerythritol polyphosphite is distearyl pentaerythritol diphosphite.
6. The light-stable polypropylene composition of Claim 1 wherein the pentaerythritol polyphosphite is tripentaerythritol tetraphosphite.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US367579A | 1979-01-15 | 1979-01-15 | |
| US003,675 | 1979-01-15 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1118139A true CA1118139A (en) | 1982-02-09 |
Family
ID=21707026
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000342491A Expired CA1118139A (en) | 1979-01-15 | 1979-12-21 | Light-stable polypropylene compositions |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JPS5598237A (en) |
| CA (1) | CA1118139A (en) |
| DE (1) | DE3001114A1 (en) |
| FR (1) | FR2446300B1 (en) |
| GB (1) | GB2039494B (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4302383A (en) * | 1980-05-19 | 1981-11-24 | Borg-Warner Chemicals, Inc. | Stabilized olefin polymers |
| DE3167225D1 (en) * | 1980-11-17 | 1984-12-20 | Ciba Geigy Ag | Stabilisers against photo degradation |
| CA1164127A (en) * | 1981-02-23 | 1984-03-20 | Borg-Warner Chemicals, Inc. | Radiation-resistant olefin polymer |
| JPS58160333A (en) * | 1982-03-18 | 1983-09-22 | Toa Nenryo Kogyo Kk | Discoloration-resistant polyolefin composition |
| EP0155912A3 (en) * | 1984-03-20 | 1986-06-04 | Ciba-Geigy Ag | Radiation-stabilized polymer compositions |
| GB2156358A (en) * | 1984-03-23 | 1985-10-09 | Vyzk Ustav Chem Tech | Composition for heat and light stabilisation of polymers |
| EP0184191A3 (en) * | 1984-12-03 | 1987-08-19 | Phillips Petroleum Company | Stabilization of polyolefins |
| US4666959A (en) * | 1985-12-10 | 1987-05-19 | El Paso Products Company | Radiation sterilizable propylene polymer compositions and articles manufactured therefrom |
| CN114829042B (en) | 2019-12-19 | 2023-08-04 | 三菱综合材料株式会社 | Silver paste, method for producing same, and method for producing joined body |
| EP4059634A4 (en) | 2019-12-20 | 2023-08-23 | Mitsubishi Materials Corporation | Silver paste and method for producing same, and method for producing joined article |
Family Cites Families (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1325775A (en) * | 1970-06-10 | 1973-08-08 | Ciba Geigy Uk Ltd | Phosphorus-containing piperidine derivatives and their use as stabilisers for polymerica material |
| US4046737A (en) * | 1971-11-30 | 1977-09-06 | Ciba-Geigy Corporation | Piperidine derivatives |
| US3998784A (en) * | 1972-07-28 | 1976-12-21 | Ciba-Geigy Corporation | Compositions stabilized with piperidine derivatives |
| JPS4962543A (en) * | 1972-10-20 | 1974-06-18 | ||
| US4087404A (en) * | 1973-02-03 | 1978-05-02 | Ciba-Geigy Corporation | Polymers stabilized with substituted 2-(piperidinyl-4')-ethyl alcohol and salts thereof |
| US3992351A (en) * | 1973-02-15 | 1976-11-16 | Ciba-Geigy Corporation | Alkyl alkanoate derivatives of substituted piperazines and polymer compositions stabilized thereby |
| US3975357A (en) * | 1973-04-19 | 1976-08-17 | Sankyo Company Limited | Stabilized synthetic polymer compositions |
| JPS5058141A (en) * | 1973-06-09 | 1975-05-20 | ||
| US4001181A (en) * | 1973-12-28 | 1977-01-04 | Ciba-Geigy Corporation | Hindered piperidine carboxamide acids, metal salts thereof, and stabilized compositions |
| US3960809A (en) * | 1973-12-28 | 1976-06-01 | Ciba-Geigy Corporation | Compositions stabilized with hindered piperidine carboxylic acids |
| DE2500314A1 (en) * | 1974-01-10 | 1975-07-17 | Ciba Geigy Ag | Stabilisation of polyolefins contg inorganic pigments - by adding cyclic di-tert alkylamines |
| DK144796C (en) * | 1975-03-21 | 1982-10-25 | Montefibre Spa | STABILIZED ALKENE POLYMER MATERIAL OR ARTICLE AND STABILIZING AGENT FOR USE IN THE PREPARATION OF IT |
| US4101509A (en) * | 1976-03-29 | 1978-07-18 | Ciba-Geigy Corporation | Hindered piperidine carboxylic acids, metal salts thereof and stabilized compositions |
| JPS524546A (en) * | 1975-07-01 | 1977-01-13 | Mitsubishi Chem Ind Ltd | Polyolefin composition |
| JPS5266551A (en) * | 1975-12-01 | 1977-06-02 | Adeka Argus Chem Co Ltd | Stabilizer for plastics |
| JPS5952182B2 (en) * | 1976-03-19 | 1984-12-18 | アデカ・ア−ガス化学株式会社 | Stabilized synthetic resin composition |
| DE2630257C3 (en) * | 1976-07-06 | 1979-05-03 | Hoechst Ag, 6000 Frankfurt | New organic phosphites and their use as stabilizers |
| JPS5373241A (en) * | 1976-12-10 | 1978-06-29 | Adeka Argus Chem Co Ltd | Stabilized synthetic resin compositions |
| JPS5425951A (en) * | 1977-07-29 | 1979-02-27 | Adeka Argus Chem Co Ltd | Synthetic resin composition |
| JPS5497588A (en) * | 1978-01-19 | 1979-08-01 | Adeka Argus Chem Co Ltd | Phosphite compound |
-
1979
- 1979-12-21 CA CA000342491A patent/CA1118139A/en not_active Expired
-
1980
- 1980-01-03 GB GB8000122A patent/GB2039494B/en not_active Expired
- 1980-01-11 JP JP201480A patent/JPS5598237A/en active Granted
- 1980-01-14 FR FR8000694A patent/FR2446300B1/en not_active Expired
- 1980-01-14 DE DE19803001114 patent/DE3001114A1/en not_active Ceased
Also Published As
| Publication number | Publication date |
|---|---|
| FR2446300A1 (en) | 1980-08-08 |
| GB2039494B (en) | 1982-11-24 |
| DE3001114A1 (en) | 1980-07-24 |
| GB2039494A (en) | 1980-08-13 |
| FR2446300B1 (en) | 1985-12-20 |
| JPS6329703B2 (en) | 1988-06-15 |
| JPS5598237A (en) | 1980-07-26 |
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