CA1116339A - Stabilization of propylene polymers - Google Patents
Stabilization of propylene polymersInfo
- Publication number
- CA1116339A CA1116339A CA000321125A CA321125A CA1116339A CA 1116339 A CA1116339 A CA 1116339A CA 000321125 A CA000321125 A CA 000321125A CA 321125 A CA321125 A CA 321125A CA 1116339 A CA1116339 A CA 1116339A
- Authority
- CA
- Canada
- Prior art keywords
- stabilization
- polymer composition
- polymer
- bis
- olefin
- 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
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/529—Esters containing heterocyclic rings not representing cyclic esters of phosphoric or phosphorous acids
-
- 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
Abstract
Abstract Olefin polymers stabilized against deterioration caused by exposure to ultraviolet light. The stabilization is effected by means of 3.9-bis(2,2,6,6-tetramethyl-4-piperidinyl-oxy)-2,4,8,10,3,9-tetraoxadiphospha(5,5)spiroundecane.
Description
3~
Bis-(Piperidinyl)Pentite This invention relates to the stabilization of polymers.
More particularly, it relates to the stabilization of olefin polymers against the deteriorating influence of ultraviolet radiation.
Ultrav;olet light has a degradative effect on olefin `polymers, the severity of which is dependent on the particular polymer and the geographical location of exposure. The degradation -may take the form of discoloration, loss of tensile and impact strength, distortion of initial flexibility, dimensional change, surface craze, cracking, powdering or increased electrical con-ductivity. All of these effects may result from the breaking of carbon-to-carbon bonds in the po1ymer chain followed by immediate oxidation of the chain fragments.
`15 . It is well known that the addition of certain materials to an olefin polymer will impart a degree of stabilization to that polymer with respect to its resistance to the destructive forces of ultraviolet radiation. These materials, in one instance, function as preferential acceptors of incident ultraviolet radiation because they have a much higher affinity for such ` radiation than does the olefin polymer. ~t appears that they ;~ absorb harmful radiation and dissipate it as harmless energy.They thus form a protective shield for the polymer in which they are present.
U.S. 3S640,928 (Murayama et al.) shows the stabilization of synthetic polymers by the presence therein of certain piperidine compounds wherein the ~wo carbon atoms adjacent to the ring nitrogen each contain two alkyl substituents. The piperidi:ne compounds contain also an oxy substituent in the four-position and, in many instances, two or more piperidine nuclei are joined to ~: .
" .
':
, ~ ~
7 ~r 3~
one another by means of polyfunctional ether, ester, carbamate,sulfonate, etc. groups.
West German Patent No. 2,500,314 (Ciba-Geigy) like-wise shows the stabilization of polyolefins (which contain inorganic pigments) by means of substituted piperidines. The broad description (and most pertinent disclosure) of the in-ventions is found on pages 2 and 6 and in Claim 1.
Japanese Patent Publication No. 1977-22578, published February 19, 1977, shows the stabilization of a wide variety of organic materials, including "synthétic resins" (page 1) such as "polypropylene" (page 11), by means of any of a large number of organic phosphites, including substituted pentites, i.e., penta-erythritol diphosphites. Formula No. ~2 on page 8 is pertinent.
The stabilized polymer compositions of the present in-vention comprise olefin polymers stabilized against deterioration due to ultraviolet light and heat by the presence therein of a . minor proportion, sufficient to provide such stabiliza~ion, of - an additive which is 3,9-bis(2,2,6,6-tetramethyl-4-piperidinyloxy)-
Bis-(Piperidinyl)Pentite This invention relates to the stabilization of polymers.
More particularly, it relates to the stabilization of olefin polymers against the deteriorating influence of ultraviolet radiation.
Ultrav;olet light has a degradative effect on olefin `polymers, the severity of which is dependent on the particular polymer and the geographical location of exposure. The degradation -may take the form of discoloration, loss of tensile and impact strength, distortion of initial flexibility, dimensional change, surface craze, cracking, powdering or increased electrical con-ductivity. All of these effects may result from the breaking of carbon-to-carbon bonds in the po1ymer chain followed by immediate oxidation of the chain fragments.
`15 . It is well known that the addition of certain materials to an olefin polymer will impart a degree of stabilization to that polymer with respect to its resistance to the destructive forces of ultraviolet radiation. These materials, in one instance, function as preferential acceptors of incident ultraviolet radiation because they have a much higher affinity for such ` radiation than does the olefin polymer. ~t appears that they ;~ absorb harmful radiation and dissipate it as harmless energy.They thus form a protective shield for the polymer in which they are present.
U.S. 3S640,928 (Murayama et al.) shows the stabilization of synthetic polymers by the presence therein of certain piperidine compounds wherein the ~wo carbon atoms adjacent to the ring nitrogen each contain two alkyl substituents. The piperidi:ne compounds contain also an oxy substituent in the four-position and, in many instances, two or more piperidine nuclei are joined to ~: .
" .
':
, ~ ~
7 ~r 3~
one another by means of polyfunctional ether, ester, carbamate,sulfonate, etc. groups.
West German Patent No. 2,500,314 (Ciba-Geigy) like-wise shows the stabilization of polyolefins (which contain inorganic pigments) by means of substituted piperidines. The broad description (and most pertinent disclosure) of the in-ventions is found on pages 2 and 6 and in Claim 1.
Japanese Patent Publication No. 1977-22578, published February 19, 1977, shows the stabilization of a wide variety of organic materials, including "synthétic resins" (page 1) such as "polypropylene" (page 11), by means of any of a large number of organic phosphites, including substituted pentites, i.e., penta-erythritol diphosphites. Formula No. ~2 on page 8 is pertinent.
The stabilized polymer compositions of the present in-vention comprise olefin polymers stabilized against deterioration due to ultraviolet light and heat by the presence therein of a . minor proportion, sufficient to provide such stabiliza~ion, of - an additive which is 3,9-bis(2,2,6,6-tetramethyl-4-piperidinyloxy)-
2,4,8,10,3,9-tetraoxadiphospha(5,5)spiroundecane or a salt thereof.
The structural formula of this compound is as follows:
(CH3 ~ C- C ~ / OC ~ / CH20 \ / CH2 C \H3)2 HN \ / CHOP \ / C POCH / NH
(CH3)2C' CH2 OCH2 CH20 CH2--C~CH3)2 Salts of the above compound are, as indicated, also contemplated. These include inorganic acid salts such as phosphate, - carbonate and the like, as well as organic acid salts such as citrate, stearate, benzoate and the like.
The olefin poiymers contempalted herein ;nclude homo-polymers and copolymers of monoolefins, preferably those monoolefins con~aining 1 4 carbon atoms. Illustratlve examples include , . , ,,.:
~ 3 polyethylene (both low and high density), polypropylene, poly-isobutylene, and copolymers of ethylene, propylene and iso-butylene; EPDM polymers are also contemplated. Polypropylene is preferred.
The amount of the above additive which should be used in the polyolefin compositions of this invention may vary widely depending upon the type, properties and particular uses of the polyolefin to be stabilized. In general, it is added to the poly-olefin in such amount as to provide a concentration of from about 0.01% to about 5.0% based on the eight of polyolefin, preferably ~rom about 0.05% to about 2.0%. It may be used as above, i.e., as the only additive in the polymer composition, but generally it will be used in combination with one or more additives.
Other such additives include metal soaps such as calcium, zinc, barium, cadmium, tin, magnesium and aluminum soaps, i.e., polyvalent metal salts of fatty acids. These coact with the additive of this invention to impart improved properties to olefin polymers upon prolonged exposure to atmospheric conditions.
They should each be used, when such use is indicated, in con-centrations of from about 0.05% to about 3.0%,based on the weightof olefin polymer.
Phenolic antioxidants may also be used in combination with the nitrogen compound of this invention. Those phenolic antioxidants embraced by the structural formula:
r l .
R>~
HO ~ CH2CHCOO - ~ A
_ _ n :
~6;33~ ~
~ere R and R' are lower alkyl, i.e., al~yl of 1-10 carbon atoms, R" is lower alkyl or hydrogen, n is 1-4, and A is the residue I of an alkanol or alkane polyol, are preferred. Illustrative ` examples of A include CH
~; CH2 - C - CH2, C18H37, CH2CH2, CH2CHCH2, and (CH3)2C
~' .
A contains 2-24 carbon atoms. Preferably, A is C18H37. The - relative proportions of antioxidant used in the stabilized poly-olefins of this invention range from about 0.01% to about 3.0%, ; based on the polyolefin.
Other additives contemplated herein include phosphites, fillers, pigments, antistatic agents, etc.
The above add;tive rnay be prepared by reaction of 4-hydroxy-2,2,6,6-tetramethylpiperidine with bis(3,9-dimethylamino)-2,4,8,10,3,9-tetraoxadiphospha(5,5)spiroundecane, according to the -,`~ following equation:
;~ (CH3 ~C C ~ / OC ~ j CH2 \
~ HN \ / CHOH (CH3)2N-P \ / C \ P-N(CH3)2 >
,~ ~ (CH3)2C CH2 OCH2 CH20 ',' :
I I
,.. ~: .
,: , .
HN ~ ~ 'HO P / ~ / 2 \ / 2 5 3)2 + 2(CH3) NH
, ~ (CH3)2C CH2 \OCH2 CH2 ' CH2~C(CH3)2 ,, .
~,....
, ., .
~, .
:;i ,~;
~ L~L~L~.~3~3 07~002-M _ 5 _ Alternatively, bis(3,9-dimethoxy)- or bis(3,9-diphenoxy)-2,4~8, 10,3,9-tetraoxadiphospha(5,5)spiroundecane may be substituted in the above e~uation for the bis(3,9-dimethylamino)-compound, also, the bis(3,9'dichloro)- compound may be used in such a reaction, in ~hich case a hydrogen chloride acceptor is required, e.g., triethyl amine. The method illustrated above, however, is preferred because the reaction proceeds smoothly, with good yields, and the resulting product is easily isolated and purified.
The method of preparation is illustrated by the follow-ing example:
'Example A mixture of 12 grams (0.0425 mol) of II (in the aboveequation) and 16 grams (0.1019 mol) of 4-hydroxy-2,2,6,6-tetra-methylpiperidine (I) is heated with stirring in a nitrogen at-mosphere at 15~C until 3.4 grams (9OY0 of the theory) ofdimethyl amine is collected (by means of a methanol-dry ice condenser). Then, the unreacted piperidine compound is distilled away by continued heating at 150~C/20 mm. The cooled residue is warmed and stirred wi~h 75 ml. of heptane, then filtered.
The cooled filtrate deposits 16 grams of a solid, M.P., 133-138C.
Evaporation of the riltrate from this crystallization yields an . additional 2 grams, M.P. 9 128-136C.
The efficacy of the additive of this invention as a stabilizer against detericration of polymers caused by ultra--violet light is shown by data obtained from tests carried out ina h'eather-Ometer. Test samples are prepar~d by dry-blending in a Waring elendor and then extruding from ~ raber,der extruder havin~ a 3/4-inch screw diameter. A sheet die is used which can be adJusted to produce a film 10 mils thick and 2 inches wide. The extruder is heated so that the temperature of the extruded film is about 500F as it leaves'the die. The éxtruded .... .. .......................................................................... ....
~ 1~633~
078002 ~ - 6 -material is pulled by a set of chrome rolls which are heatPd atabout 50C and which polish the film and assure its uniform thickness. Care is taken not to pull the film too fast as it leaves the extruder so that the polymer remains unoriented.
The extrusion of polypropylene under these conditions produces an extrudate having a tensile strength of about 5000 psi.
The Weather-Ometer is an enclosed box containing xenon lamps, the light from whicn simulates the ultraviolet radiation from the sun. Water is sprayed on the test samples, so as to simulate rain, for 20 minutes of each hour. The test samples are suspended in this environment by means of metal clamps and removed at periodic intervals for testing as regards deterioration Gf tensile strength.
Three test samples are tested each time and the average result of these three is taken as the tensile strength. They are pulled at a rate oF ten inches per minute on an Instron, which records the stretch or elongation of the sample and the force required to produce that elongation. When the sample yields and again when it breaks, the force and elongation are no'ed. The force (in pounds) is divided by the cross^sectional area (in square inches) to give the tensile strength. When the tensile stren~th has diminished to 50% of the original value, the sample is rated a failure.
The product of the Example is subjected to such testing at periodic intervals after exposure to ultraviolet light in the Weather-Ometer as above. The formulation (A) tested consisted of 100 parts of polypropylene containing 0.05 part of calcium stearate, 0.1 part of~Irganox 1076 (octadecyl-3-(3',-5'-ditertiarybutyl-4'-hydroxyphenyl)propionate), and 0.3 part of the product of the Example. A second sample (B) is prepared and tested, of similar composition, except that it contains no product of the Example.
The resu1ts are as follows:
: ......................................................................................................................................................
078002-M _ 7 ' TABLE I
Time'to Failure A 4150 hours B 700 hours Similar tests on formulations containing varying proportions of the additive of this invention are rated somewhat ' differently. The test samples are 2.5 mils thick and are analyzed for carbonyl content (a measure of relative deterioration) by means of infrared curves. That is, the area under the peak at 5.8 microns is tàken as a quantitative indication of the carbonyl content of the test sample. When the test sample is shown to have ~; ~ developed an inc~ease of 0.1 percent in carbonyl content, it is ; regarded as havinq failed and the hours of exposure in the Weather-Ometer until such failure is a measure of the efficacy ~ ~ 15 of the test sample as an ultraviolet stabilizer. The test '~ samples in Table II each contain 100 parts of polypropylene, -~ ~ 0.10 part of Irganox 1076, O.lO'part of distearyl pentaerythritol ~ diphosphite and varying proportions (or none), as indicated, of ;- the additive `of the invention.
~.
` ~ ' 20 TABLE'II
Sample ''Product of'the'Example ''Time to Failure C O ~ 35 hours D 0.25 ~ 275 hours E ~ 0.50 275 hours All parts and pércentages herein are by weight unless otherwise speclfically defi~ned.
. ~ :
., ~
,, , ~ .
'.~.. ,,.. , .,,.. ,,.. ,.. ,.. ,.,.,,.. ,,.. ,.. ,.. .................... ................... `.. ' "
, . . .
,.. .
The structural formula of this compound is as follows:
(CH3 ~ C- C ~ / OC ~ / CH20 \ / CH2 C \H3)2 HN \ / CHOP \ / C POCH / NH
(CH3)2C' CH2 OCH2 CH20 CH2--C~CH3)2 Salts of the above compound are, as indicated, also contemplated. These include inorganic acid salts such as phosphate, - carbonate and the like, as well as organic acid salts such as citrate, stearate, benzoate and the like.
The olefin poiymers contempalted herein ;nclude homo-polymers and copolymers of monoolefins, preferably those monoolefins con~aining 1 4 carbon atoms. Illustratlve examples include , . , ,,.:
~ 3 polyethylene (both low and high density), polypropylene, poly-isobutylene, and copolymers of ethylene, propylene and iso-butylene; EPDM polymers are also contemplated. Polypropylene is preferred.
The amount of the above additive which should be used in the polyolefin compositions of this invention may vary widely depending upon the type, properties and particular uses of the polyolefin to be stabilized. In general, it is added to the poly-olefin in such amount as to provide a concentration of from about 0.01% to about 5.0% based on the eight of polyolefin, preferably ~rom about 0.05% to about 2.0%. It may be used as above, i.e., as the only additive in the polymer composition, but generally it will be used in combination with one or more additives.
Other such additives include metal soaps such as calcium, zinc, barium, cadmium, tin, magnesium and aluminum soaps, i.e., polyvalent metal salts of fatty acids. These coact with the additive of this invention to impart improved properties to olefin polymers upon prolonged exposure to atmospheric conditions.
They should each be used, when such use is indicated, in con-centrations of from about 0.05% to about 3.0%,based on the weightof olefin polymer.
Phenolic antioxidants may also be used in combination with the nitrogen compound of this invention. Those phenolic antioxidants embraced by the structural formula:
r l .
R>~
HO ~ CH2CHCOO - ~ A
_ _ n :
~6;33~ ~
~ere R and R' are lower alkyl, i.e., al~yl of 1-10 carbon atoms, R" is lower alkyl or hydrogen, n is 1-4, and A is the residue I of an alkanol or alkane polyol, are preferred. Illustrative ` examples of A include CH
~; CH2 - C - CH2, C18H37, CH2CH2, CH2CHCH2, and (CH3)2C
~' .
A contains 2-24 carbon atoms. Preferably, A is C18H37. The - relative proportions of antioxidant used in the stabilized poly-olefins of this invention range from about 0.01% to about 3.0%, ; based on the polyolefin.
Other additives contemplated herein include phosphites, fillers, pigments, antistatic agents, etc.
The above add;tive rnay be prepared by reaction of 4-hydroxy-2,2,6,6-tetramethylpiperidine with bis(3,9-dimethylamino)-2,4,8,10,3,9-tetraoxadiphospha(5,5)spiroundecane, according to the -,`~ following equation:
;~ (CH3 ~C C ~ / OC ~ j CH2 \
~ HN \ / CHOH (CH3)2N-P \ / C \ P-N(CH3)2 >
,~ ~ (CH3)2C CH2 OCH2 CH20 ',' :
I I
,.. ~: .
,: , .
HN ~ ~ 'HO P / ~ / 2 \ / 2 5 3)2 + 2(CH3) NH
, ~ (CH3)2C CH2 \OCH2 CH2 ' CH2~C(CH3)2 ,, .
~,....
, ., .
~, .
:;i ,~;
~ L~L~L~.~3~3 07~002-M _ 5 _ Alternatively, bis(3,9-dimethoxy)- or bis(3,9-diphenoxy)-2,4~8, 10,3,9-tetraoxadiphospha(5,5)spiroundecane may be substituted in the above e~uation for the bis(3,9-dimethylamino)-compound, also, the bis(3,9'dichloro)- compound may be used in such a reaction, in ~hich case a hydrogen chloride acceptor is required, e.g., triethyl amine. The method illustrated above, however, is preferred because the reaction proceeds smoothly, with good yields, and the resulting product is easily isolated and purified.
The method of preparation is illustrated by the follow-ing example:
'Example A mixture of 12 grams (0.0425 mol) of II (in the aboveequation) and 16 grams (0.1019 mol) of 4-hydroxy-2,2,6,6-tetra-methylpiperidine (I) is heated with stirring in a nitrogen at-mosphere at 15~C until 3.4 grams (9OY0 of the theory) ofdimethyl amine is collected (by means of a methanol-dry ice condenser). Then, the unreacted piperidine compound is distilled away by continued heating at 150~C/20 mm. The cooled residue is warmed and stirred wi~h 75 ml. of heptane, then filtered.
The cooled filtrate deposits 16 grams of a solid, M.P., 133-138C.
Evaporation of the riltrate from this crystallization yields an . additional 2 grams, M.P. 9 128-136C.
The efficacy of the additive of this invention as a stabilizer against detericration of polymers caused by ultra--violet light is shown by data obtained from tests carried out ina h'eather-Ometer. Test samples are prepar~d by dry-blending in a Waring elendor and then extruding from ~ raber,der extruder havin~ a 3/4-inch screw diameter. A sheet die is used which can be adJusted to produce a film 10 mils thick and 2 inches wide. The extruder is heated so that the temperature of the extruded film is about 500F as it leaves'the die. The éxtruded .... .. .......................................................................... ....
~ 1~633~
078002 ~ - 6 -material is pulled by a set of chrome rolls which are heatPd atabout 50C and which polish the film and assure its uniform thickness. Care is taken not to pull the film too fast as it leaves the extruder so that the polymer remains unoriented.
The extrusion of polypropylene under these conditions produces an extrudate having a tensile strength of about 5000 psi.
The Weather-Ometer is an enclosed box containing xenon lamps, the light from whicn simulates the ultraviolet radiation from the sun. Water is sprayed on the test samples, so as to simulate rain, for 20 minutes of each hour. The test samples are suspended in this environment by means of metal clamps and removed at periodic intervals for testing as regards deterioration Gf tensile strength.
Three test samples are tested each time and the average result of these three is taken as the tensile strength. They are pulled at a rate oF ten inches per minute on an Instron, which records the stretch or elongation of the sample and the force required to produce that elongation. When the sample yields and again when it breaks, the force and elongation are no'ed. The force (in pounds) is divided by the cross^sectional area (in square inches) to give the tensile strength. When the tensile stren~th has diminished to 50% of the original value, the sample is rated a failure.
The product of the Example is subjected to such testing at periodic intervals after exposure to ultraviolet light in the Weather-Ometer as above. The formulation (A) tested consisted of 100 parts of polypropylene containing 0.05 part of calcium stearate, 0.1 part of~Irganox 1076 (octadecyl-3-(3',-5'-ditertiarybutyl-4'-hydroxyphenyl)propionate), and 0.3 part of the product of the Example. A second sample (B) is prepared and tested, of similar composition, except that it contains no product of the Example.
The resu1ts are as follows:
: ......................................................................................................................................................
078002-M _ 7 ' TABLE I
Time'to Failure A 4150 hours B 700 hours Similar tests on formulations containing varying proportions of the additive of this invention are rated somewhat ' differently. The test samples are 2.5 mils thick and are analyzed for carbonyl content (a measure of relative deterioration) by means of infrared curves. That is, the area under the peak at 5.8 microns is tàken as a quantitative indication of the carbonyl content of the test sample. When the test sample is shown to have ~; ~ developed an inc~ease of 0.1 percent in carbonyl content, it is ; regarded as havinq failed and the hours of exposure in the Weather-Ometer until such failure is a measure of the efficacy ~ ~ 15 of the test sample as an ultraviolet stabilizer. The test '~ samples in Table II each contain 100 parts of polypropylene, -~ ~ 0.10 part of Irganox 1076, O.lO'part of distearyl pentaerythritol ~ diphosphite and varying proportions (or none), as indicated, of ;- the additive `of the invention.
~.
` ~ ' 20 TABLE'II
Sample ''Product of'the'Example ''Time to Failure C O ~ 35 hours D 0.25 ~ 275 hours E ~ 0.50 275 hours All parts and pércentages herein are by weight unless otherwise speclfically defi~ned.
. ~ :
., ~
,, , ~ .
'.~.. ,,.. , .,,.. ,,.. ,.. ,.. ,.,.,,.. ,,.. ,.. ,.. .................... ................... `.. ' "
, . . .
,.. .
Claims (5)
1. A polymer composition stabilized against deterioration due to ultraviolet light and heat comprising a propylene polymer and a minor proportion, sufficient to provide such stabilization, of 3,9-bis(2,2,6,6-tetramethyl-4-piperidinyloxy)-2,4,8,10,3,9-tetraoxadiphospha(5,5)spiroundecane.
2. The polymer composition of Claim 1 wherein the olefin polymer is polypropylene.
3. The polymer composition of Claim 1 characterized further in that it also contains a polyvalent metal salt of a fatty acid.
4. The polymer composition of Claim 1 characterized further in that it also contains a phenolic antioxidant.
5. The polymer composition of Claim 4 wherein the phenolic antioxidant has the structural formula:
where R and R' are lower alkyl, R" is lower alkyl or hydrogen, n is 1-4, and A is the residue of an alkanol or alkane polyol.
where R and R' are lower alkyl, R" is lower alkyl or hydrogen, n is 1-4, and A is the residue of an alkanol or alkane polyol.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US87813778A | 1978-02-15 | 1978-02-15 | |
| US878,137 | 1978-02-15 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1116339A true CA1116339A (en) | 1982-01-12 |
Family
ID=25371458
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000321125A Expired CA1116339A (en) | 1978-02-15 | 1979-02-08 | Stabilization of propylene polymers |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JPS54114553A (en) |
| CA (1) | CA1116339A (en) |
| DE (1) | DE2905808A1 (en) |
| FR (1) | FR2417523A1 (en) |
| GB (1) | GB2014586A (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2258866B (en) * | 1991-08-13 | 1995-06-21 | Ciba Geigy Ag | N-methylated bis-4-piperidylphosphite |
| US5230816A (en) * | 1992-05-05 | 1993-07-27 | Ciba-Geigy Corporation | 3,9-bis(dialkylamino)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecanes and stabilized compositions |
| TW251307B (en) * | 1992-10-05 | 1995-07-11 | Ciba Geigy | |
| US7442732B2 (en) | 2005-03-29 | 2008-10-28 | Crompton Corporation | Hindered amine light stabilizers comprising neoalkanediol phosphites |
| CN107987402A (en) * | 2017-12-26 | 2018-05-04 | 河南驼人医疗器械集团有限公司 | A kind of medical clear acrylic of resistance to electron beam irradiation and preparation method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2656766A1 (en) * | 1975-12-19 | 1977-07-07 | Ciba Geigy Ag | NEW PHOSPHITE STABILIZERS |
| GB1513629A (en) * | 1975-12-19 | 1978-06-07 | Ciba Geigy Ag | Piperidyl phosphites |
| BE851424A (en) * | 1977-02-15 | 1977-08-16 | Argus Chem | ORGANIC STABILIZING COMPOUNDS |
-
1979
- 1979-02-08 CA CA000321125A patent/CA1116339A/en not_active Expired
- 1979-02-13 GB GB7905103A patent/GB2014586A/en not_active Withdrawn
- 1979-02-14 FR FR7903779A patent/FR2417523A1/en not_active Withdrawn
- 1979-02-15 DE DE19792905808 patent/DE2905808A1/en not_active Withdrawn
- 1979-02-15 JP JP1668879A patent/JPS54114553A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| GB2014586A (en) | 1979-08-30 |
| DE2905808A1 (en) | 1979-08-16 |
| FR2417523A1 (en) | 1979-09-14 |
| JPS54114553A (en) | 1979-09-06 |
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