CA1244597A - Polymeric hindered amines - Google Patents
Polymeric hindered aminesInfo
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- CA1244597A CA1244597A CA000482119A CA482119A CA1244597A CA 1244597 A CA1244597 A CA 1244597A CA 000482119 A CA000482119 A CA 000482119A CA 482119 A CA482119 A CA 482119A CA 1244597 A CA1244597 A CA 1244597A
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- olefin polymer
- tetramethylpiperidine
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Abstract
POLYMERIC HINDERED AMINES
Abstract of Disclosure Disclosed is a new class of polymeric hindered amine light stabilizers based on maleic anhydride modified poly-olefins reacted with tetramethyl piperidine derivatives.
These materials are more effective than most of the generally used hindered amine light stabilizers, but due to their higher molecular weights and the polyolefin backbone, they are more compatible with polyolefins.
Abstract of Disclosure Disclosed is a new class of polymeric hindered amine light stabilizers based on maleic anhydride modified poly-olefins reacted with tetramethyl piperidine derivatives.
These materials are more effective than most of the generally used hindered amine light stabilizers, but due to their higher molecular weights and the polyolefin backbone, they are more compatible with polyolefins.
Description
5~7 This invention relates to novel high-molecular-weight polymeric amines that have light-stabilizing properties for alpha-olefins.
One of the greatest problems in the commercial use of polyolefins such as polyethylene, polypropylene and related olefin copolymers has been their poor light stability. In sunlight or any other light containing a significant amount of ultraviolet radiation, fibers, films and molded objects of polyolefin degrade to the point of being totally useless unless the polymer is protected by an effective stabilizer system.
Among the most successful light stabilizers presently in use are the "hindered" amine compounds, i.e., compounds con-taining secondary amine groups having two alkyl substituents on each of the carbon atoms attached to an amine group.
Examples of a hindered amine compounds which function well as light stabilizers are 2,2,6,6-tetramethyl piperidine (TMP) and certain synthetic compounds of medium molecular weight of similar conEiguration. Commercially available examples of such synthetic compounds include a) O O
HN ~-O-C-(CH2)8-C-O- ~ NH
I
One of the greatest problems in the commercial use of polyolefins such as polyethylene, polypropylene and related olefin copolymers has been their poor light stability. In sunlight or any other light containing a significant amount of ultraviolet radiation, fibers, films and molded objects of polyolefin degrade to the point of being totally useless unless the polymer is protected by an effective stabilizer system.
Among the most successful light stabilizers presently in use are the "hindered" amine compounds, i.e., compounds con-taining secondary amine groups having two alkyl substituents on each of the carbon atoms attached to an amine group.
Examples of a hindered amine compounds which function well as light stabilizers are 2,2,6,6-tetramethyl piperidine (TMP) and certain synthetic compounds of medium molecular weight of similar conEiguration. Commercially available examples of such synthetic compounds include a) O O
HN ~-O-C-(CH2)8-C-O- ~ NH
I
- 2 ~ L~ 7 and b) H H
l l 5- ~ N ~ r N--(CH2)6-t--C8--H17--NH II
10 It has been theorized that the tetramethyl piperidine acts as a free radical scavenger in effecting light stabili-zation. The hindered amine moiety is readily converted to an oxygenated free radical form, N-0-, which, in turn, reacts with the free radical polyolefin degradation products. This reaction product is then oxidized to polyolefin nonradical products and the hindered amine product reverts to the oxy-genated free radical form whereupon the process starts over.
The hindered amine moiety is sufficiently activated by the methyl groups on the adjacent carbons that a free radical can form on the substituent attached to the nitrogen atom where R' is any of the nonfree radical substituents specified.
Thus, each is capable of participating in the light stabili-zation in the manner explained.
The stabilizing effect of such amines is discussed in an article by V. Ya. Shlyapintokh and V. B. Ivanov in Developments in Polymer Stabilization-5, Applied Science Publishers, (1982).
~ hese materials function well but have several disadvantages. a) their relatively high cost per equivalent of hindered amine group provided to the polymer; b3 since their unsu~stituted ~ydrocarbon c~ains are relatively short, they are ~ ~ y with the longer chain polyolefins and tend to exude from the polymer matrix; c) in textile ~x~
l l 5- ~ N ~ r N--(CH2)6-t--C8--H17--NH II
10 It has been theorized that the tetramethyl piperidine acts as a free radical scavenger in effecting light stabili-zation. The hindered amine moiety is readily converted to an oxygenated free radical form, N-0-, which, in turn, reacts with the free radical polyolefin degradation products. This reaction product is then oxidized to polyolefin nonradical products and the hindered amine product reverts to the oxy-genated free radical form whereupon the process starts over.
The hindered amine moiety is sufficiently activated by the methyl groups on the adjacent carbons that a free radical can form on the substituent attached to the nitrogen atom where R' is any of the nonfree radical substituents specified.
Thus, each is capable of participating in the light stabili-zation in the manner explained.
The stabilizing effect of such amines is discussed in an article by V. Ya. Shlyapintokh and V. B. Ivanov in Developments in Polymer Stabilization-5, Applied Science Publishers, (1982).
~ hese materials function well but have several disadvantages. a) their relatively high cost per equivalent of hindered amine group provided to the polymer; b3 since their unsu~stituted ~ydrocarbon c~ains are relatively short, they are ~ ~ y with the longer chain polyolefins and tend to exude from the polymer matrix; c) in textile ~x~
-3- 2212~-1644 applications, they are subject to being ext:racted during launderlng and dry cleaning; and d) they may cause dermatitis and therefore are too toxic to be used in film or molded containers that will be used for packaging :Eood~
According to the invention, a modified olefin polymer containing a 2,2,6,6-tetramethylpiperidine substituent, that has light stabilizing properties for alpha-olefins and tends to avoidthose disadvantages, is characterized in that it has one of the general formulas III or IV
_ _ l R-- HC-C
N--~R' III
H C- C
_ X
or R- --HC-C--O ~R' I ~
H2C-C - o~R~ y IV
.
in which R represents the residue of an alpha-olefin polymer or copolymer; and R' represents -H, -OH', ~ or -O-R", where R"
represents a lower alkyl and x and y are integers of a size relative to the molecular weight of R such that the total substitution of tetramethylpiperidine residue is between about pr~
5~17 -3a- 22124-1644 0,2 and 6% by weight~ based on the total weight of the modified olefin polymer.
The novel polymeric hindered amine compounds of this invention are highly useful as light stabilizers for polyolefins.
The incorporation of the2,~,6,6~etramethylpiperidine structure into a maleic anhydride-modified polyolefin molecule provides substantially improved light stabilizing abil.ity thereto; the polyolefin backbone is more compatible with the polyolefin matrix to which it is to be added, there is little or no tendency toward exudation or rejection of the D
~2~5~7 stabilizer molecules by the matrix, and there is a signifi~
cant reduction in extractability as compared to lower molecular weight hindered amines.
Another advantage of the polymeric hindered amine light stabilizers of the invention is improved reduced toxicity.
Some conventional hindered amine light stabilizers have been found to cause irreversible eye irritation in rabbits. As a result, operators working with these materials are required to take elaborate precautions against inhalation and against eye exposure to the dust.
The materials of this invention, when tested with laboratory rabbits, did not present the same irritation problems.
The residue R- in the above formula can represent any olefin polymer residue that is based on a preponderance o~
ethylene, propylene, or butene-l, and having a valence of x or y. Such residue can be either crystalline (stereoregular) or amorphous (random)~ Thus, it can be either a high or low density polyethylene residue, a polypropylene residue or a residue of a copolymer of ethylene with butene 1, a residue of a copolymer of ethylene and propylene, a residue of a propylene--butene copolymer or a residue of such a propylene copolymer with an olefin having up to about six carbon atoms.
The olefin polymer residue can also contain some unreacted or partially reacted maleic anhydride residue as it is not always required that all of the maleic anhydride modifier be reacted with the hindered amine containing residue. For example, Compound III may contain some groups of the structure.
H O
~ 11 , ~
-C-C-NH- ~ N-R' H2C-C-OH 7~
Il o The olefin polymer-based hindered amines of the inven-tion represented by formula III, in which R' is hydro~en, are prepared by graft-modifying the appropriate polymer backbone ~ ~J~ ~5 with maleic anhydride, and thereafter reacting said maleic an-hydride modified olefin polymer with 4-amino 2,2,6,6-tetra-~ethyl piperidine. To prepare the compounds of formula IV, in which R' is hydrogen, the maleic anhydride modified olefin polymer is reacted with 4-hydroxy-2,2,6,6-tetramethyl piper-idine.
The maleic anhydride-modified polyolefins that form the substrate or carrier for the piperidine residue are known materials containing about 0.2 to 9~ by weight of combined maleic anhydride, preferably about 2 to 5~. In fact, one embodiment of these materials in which the polyolefin is either amorphous or crystalline polypropylene is a commer-cially available product, sold under the trademark "Herco prime( )" by Hercules Incorporated, Wilmington, Delaware.
Polyethylene modified with maleic anhydride is available commercially from Chemplex Company of Rolling Meadows, Illinois, under the trademark "Plexar(R)". Any polymer or copolymer of ethylene, propylene, or butene-l can be modiiied via the maleic anhydride moiety to form the substrate mole-cule, including polyethylene, polypropylene, ethylene--propy-lene copolymer, propylene--butene-l copolymer, or butene-l--ethylene copolymer. The most frequently encountered and the preferred maleic anhydride modified polyolefin is that based on crystalline or s-tereoregular polypropylene.
The preparation of maleic modified polypropylene is de-scribed in, inter alia, ~.S. Patent 3,483,276. Briefly, the preparation consists of treating the olefin polymer with a material or by a means that will induce the formation of active, free radical sites thereon with which maleic anhy-dride can react. Active centers can be induced, e.g., by subjecting the polymer to the action of high energy ionizing radiation such as gamma rays, x-rays, or high speed electrons;
by contacting it, either as a solid or a solution in a sol-vent, with a free radical producing material such as dibenzoyl peroxide, dilaurylperoxide, dicumyl peroxide or t-butyl per-benzoate; or by simply milling it in the presence of air.
The preferred method i9 the reaction of the polyolefin with maleic anhydride in solvent solution in the presence of a free radical initiator.
Preparation of the novel polymeric compounds of the in-vention i,5 accomplished via relatively simple, known chemical reactions. In the case of the compound __ R - - HC - C r ~
¦ N--~ NH
H2C _ C ~
_ O I x reaction of the maleic-modified polyolefin with 4-amino-2,216,6-tetramethyl piperidine is effected by refluxing in the presence of an aromatic solvent, such as, e.g., toluene, chlorobenzene, or xylene and removing water as it is formed.
The compound _ O
R ~ HC - C O - ~ N~
H2C - C-O - ~ NH
_ O Y
is prepared by refluxing the maleic-modified polyolefin with
According to the invention, a modified olefin polymer containing a 2,2,6,6-tetramethylpiperidine substituent, that has light stabilizing properties for alpha-olefins and tends to avoidthose disadvantages, is characterized in that it has one of the general formulas III or IV
_ _ l R-- HC-C
N--~R' III
H C- C
_ X
or R- --HC-C--O ~R' I ~
H2C-C - o~R~ y IV
.
in which R represents the residue of an alpha-olefin polymer or copolymer; and R' represents -H, -OH', ~ or -O-R", where R"
represents a lower alkyl and x and y are integers of a size relative to the molecular weight of R such that the total substitution of tetramethylpiperidine residue is between about pr~
5~17 -3a- 22124-1644 0,2 and 6% by weight~ based on the total weight of the modified olefin polymer.
The novel polymeric hindered amine compounds of this invention are highly useful as light stabilizers for polyolefins.
The incorporation of the2,~,6,6~etramethylpiperidine structure into a maleic anhydride-modified polyolefin molecule provides substantially improved light stabilizing abil.ity thereto; the polyolefin backbone is more compatible with the polyolefin matrix to which it is to be added, there is little or no tendency toward exudation or rejection of the D
~2~5~7 stabilizer molecules by the matrix, and there is a signifi~
cant reduction in extractability as compared to lower molecular weight hindered amines.
Another advantage of the polymeric hindered amine light stabilizers of the invention is improved reduced toxicity.
Some conventional hindered amine light stabilizers have been found to cause irreversible eye irritation in rabbits. As a result, operators working with these materials are required to take elaborate precautions against inhalation and against eye exposure to the dust.
The materials of this invention, when tested with laboratory rabbits, did not present the same irritation problems.
The residue R- in the above formula can represent any olefin polymer residue that is based on a preponderance o~
ethylene, propylene, or butene-l, and having a valence of x or y. Such residue can be either crystalline (stereoregular) or amorphous (random)~ Thus, it can be either a high or low density polyethylene residue, a polypropylene residue or a residue of a copolymer of ethylene with butene 1, a residue of a copolymer of ethylene and propylene, a residue of a propylene--butene copolymer or a residue of such a propylene copolymer with an olefin having up to about six carbon atoms.
The olefin polymer residue can also contain some unreacted or partially reacted maleic anhydride residue as it is not always required that all of the maleic anhydride modifier be reacted with the hindered amine containing residue. For example, Compound III may contain some groups of the structure.
H O
~ 11 , ~
-C-C-NH- ~ N-R' H2C-C-OH 7~
Il o The olefin polymer-based hindered amines of the inven-tion represented by formula III, in which R' is hydro~en, are prepared by graft-modifying the appropriate polymer backbone ~ ~J~ ~5 with maleic anhydride, and thereafter reacting said maleic an-hydride modified olefin polymer with 4-amino 2,2,6,6-tetra-~ethyl piperidine. To prepare the compounds of formula IV, in which R' is hydrogen, the maleic anhydride modified olefin polymer is reacted with 4-hydroxy-2,2,6,6-tetramethyl piper-idine.
The maleic anhydride-modified polyolefins that form the substrate or carrier for the piperidine residue are known materials containing about 0.2 to 9~ by weight of combined maleic anhydride, preferably about 2 to 5~. In fact, one embodiment of these materials in which the polyolefin is either amorphous or crystalline polypropylene is a commer-cially available product, sold under the trademark "Herco prime( )" by Hercules Incorporated, Wilmington, Delaware.
Polyethylene modified with maleic anhydride is available commercially from Chemplex Company of Rolling Meadows, Illinois, under the trademark "Plexar(R)". Any polymer or copolymer of ethylene, propylene, or butene-l can be modiiied via the maleic anhydride moiety to form the substrate mole-cule, including polyethylene, polypropylene, ethylene--propy-lene copolymer, propylene--butene-l copolymer, or butene-l--ethylene copolymer. The most frequently encountered and the preferred maleic anhydride modified polyolefin is that based on crystalline or s-tereoregular polypropylene.
The preparation of maleic modified polypropylene is de-scribed in, inter alia, ~.S. Patent 3,483,276. Briefly, the preparation consists of treating the olefin polymer with a material or by a means that will induce the formation of active, free radical sites thereon with which maleic anhy-dride can react. Active centers can be induced, e.g., by subjecting the polymer to the action of high energy ionizing radiation such as gamma rays, x-rays, or high speed electrons;
by contacting it, either as a solid or a solution in a sol-vent, with a free radical producing material such as dibenzoyl peroxide, dilaurylperoxide, dicumyl peroxide or t-butyl per-benzoate; or by simply milling it in the presence of air.
The preferred method i9 the reaction of the polyolefin with maleic anhydride in solvent solution in the presence of a free radical initiator.
Preparation of the novel polymeric compounds of the in-vention i,5 accomplished via relatively simple, known chemical reactions. In the case of the compound __ R - - HC - C r ~
¦ N--~ NH
H2C _ C ~
_ O I x reaction of the maleic-modified polyolefin with 4-amino-2,216,6-tetramethyl piperidine is effected by refluxing in the presence of an aromatic solvent, such as, e.g., toluene, chlorobenzene, or xylene and removing water as it is formed.
The compound _ O
R ~ HC - C O - ~ N~
H2C - C-O - ~ NH
_ O Y
is prepared by refluxing the maleic-modified polyolefin with
4 hydroxy-2,2,6,6-tetramethyl piperidine in aromatic solvent under catalytic acid conditions and removing water as it is formed. The acid condition can be created by any acid that is compatible with the aromatic solvent and does not partici-pate in the reaction. Para-toluene sulfonic acid is a pre-ferred acid.
Where the composition comprises a mixture of an olefin polymer and a modified olefin polymer, as above described9 it is found useful to utili~e modified olefin polymer in an amount sufEicient to provide a concentration of tetramethyl piperidine residue between 0~2 and 1.0% by weight.
Preparation of the compounds of the invention is illus-trated in the following examples.
"
~ 7 --Example 1 _ 2-[N-(2,2,6,6-Tetramethyl 4~piperidinyl)Succinimidyl]
_ Polyp~opylene A commerciaLly available maleic anhydride modified stereoregular polypropylene (Hercorprime G( ) Hercules In-corporated) was purified by refluxing in xylene and recrystal-lizing to remove water and free maleic anhydride. Combined maleic anhydride content of the purified material was about ~.6%.
A mixture of 49 grams of the purified maleic modified polymer in 450 ml of xylene was agitated and heated to reflux temperature. A solution of 4.69 grams of 4-amino-2,2,6,6-tetramethyl piperidine in xylene was added dropwise over about 15 minutes and reflux was maintained for about seven hours. Water was removed as it formed by azeotropic dis-tillation using a Dean-Stark trap, draining the water from the trap as soon as it was collected.
The product was allowed to cool overnight, at which time a solid, light tan product had precipitated. This product was separated and dried in a forced draft oven. About 48.9 grams was recovered.
Example 2 2-[Di-(2,2,6,6-Tetramethyl-4-Piperidinyl)Succinate]
Polypropyl_ne A mixture of 49 gms maleic anhydride modified polypropy-lene (Hercoprime G( ~ - ~ercules Incorporated - 3% combined maleic anhydride), 500 ml of chlorobenzene, 7.07 grams of 4-hydroxy-2,2,6,6-tetramethyl piperidine, and 1 gram of p-toluene sulfonic acid monohydrate was agitated and refluxed ~or seven hours under a Dean-Stark trap. Water was removed from the trap as the reaction proceeded.
After cooling and sitting overnight, the solid product that precipitated was isolated from the mass by vacuum fil-tration through sintered glass, pressed dry and washed with acetone~ The product was dried in air, then in an oven at 50 C f8r fifteen minutes. Dry weight of the product was 50.5 grams.
~2,~5~7 ~e~
Example 2 was repeated using xylene as the solvent and refluxing for five hours. About 50.3 grams of produ~t were recovered. IR spectra indicate the presence of some free carboxylic acid but showed that the diester was the over-whelmingly predominant product.
A mixture of 7 grams of a propylene--butene copolymer (14~ C43 containing about 5.1% combined maleic anhydride in 100 ml of xylene was agitated and heated at reflux (136C) under a Dean-Stark trap for about two hours until all traces of H2O were removed. The reaction mixture was cooled to about 100C and 0O9 gram of 4-amino-2,2,6,6-tetramethyl-piperidine in 15 ml of xylene was added dropwise over 15 minutes. The mixture was then agitated and refluxed for ten hours, the water being removed from the trap as it was collected.
The reaction product, a light tan solid, precipitated upon cooling~ This was worked up as described in Example 1.
In use as Light stabilizers for polyolefins, the poly-meric hindered amines of the invention are added in amounts such that the tetramethyl piperidine concentration in the total system is equivalent to that heretofore used with con-ventional monomeric tetramethyl piperidines, about 0.1 to 3 by weight.
Example 5 A series of modified polypropylenes prepared as described in the preceding examples were blended with polypropylene using a conventional laboratory extruder, then extruded and cut to molding powder. The molding powder pellets were pressed into ten mil films in a picture frame mold at 200C.
Films of each of the materials, along with a blank con-taining no light stabilizer and controls containing commer-cially available hindered amine light stabilizers, in amounts to provide e~uivalent amounts of tetramethyl piperidine, were subjected to accelerated aging in a Fade-O-Meter. Specimens were tested periodically for flexibility and embrittLement.
Average time to failure is recorded in Table 1.
g Table 1 Specimen Additive(l) _ ConcAveraqe L _e (hrs) Blank --- - - 80 Control 1 I 0.025 pph. 590
Where the composition comprises a mixture of an olefin polymer and a modified olefin polymer, as above described9 it is found useful to utili~e modified olefin polymer in an amount sufEicient to provide a concentration of tetramethyl piperidine residue between 0~2 and 1.0% by weight.
Preparation of the compounds of the invention is illus-trated in the following examples.
"
~ 7 --Example 1 _ 2-[N-(2,2,6,6-Tetramethyl 4~piperidinyl)Succinimidyl]
_ Polyp~opylene A commerciaLly available maleic anhydride modified stereoregular polypropylene (Hercorprime G( ) Hercules In-corporated) was purified by refluxing in xylene and recrystal-lizing to remove water and free maleic anhydride. Combined maleic anhydride content of the purified material was about ~.6%.
A mixture of 49 grams of the purified maleic modified polymer in 450 ml of xylene was agitated and heated to reflux temperature. A solution of 4.69 grams of 4-amino-2,2,6,6-tetramethyl piperidine in xylene was added dropwise over about 15 minutes and reflux was maintained for about seven hours. Water was removed as it formed by azeotropic dis-tillation using a Dean-Stark trap, draining the water from the trap as soon as it was collected.
The product was allowed to cool overnight, at which time a solid, light tan product had precipitated. This product was separated and dried in a forced draft oven. About 48.9 grams was recovered.
Example 2 2-[Di-(2,2,6,6-Tetramethyl-4-Piperidinyl)Succinate]
Polypropyl_ne A mixture of 49 gms maleic anhydride modified polypropy-lene (Hercoprime G( ~ - ~ercules Incorporated - 3% combined maleic anhydride), 500 ml of chlorobenzene, 7.07 grams of 4-hydroxy-2,2,6,6-tetramethyl piperidine, and 1 gram of p-toluene sulfonic acid monohydrate was agitated and refluxed ~or seven hours under a Dean-Stark trap. Water was removed from the trap as the reaction proceeded.
After cooling and sitting overnight, the solid product that precipitated was isolated from the mass by vacuum fil-tration through sintered glass, pressed dry and washed with acetone~ The product was dried in air, then in an oven at 50 C f8r fifteen minutes. Dry weight of the product was 50.5 grams.
~2,~5~7 ~e~
Example 2 was repeated using xylene as the solvent and refluxing for five hours. About 50.3 grams of produ~t were recovered. IR spectra indicate the presence of some free carboxylic acid but showed that the diester was the over-whelmingly predominant product.
A mixture of 7 grams of a propylene--butene copolymer (14~ C43 containing about 5.1% combined maleic anhydride in 100 ml of xylene was agitated and heated at reflux (136C) under a Dean-Stark trap for about two hours until all traces of H2O were removed. The reaction mixture was cooled to about 100C and 0O9 gram of 4-amino-2,2,6,6-tetramethyl-piperidine in 15 ml of xylene was added dropwise over 15 minutes. The mixture was then agitated and refluxed for ten hours, the water being removed from the trap as it was collected.
The reaction product, a light tan solid, precipitated upon cooling~ This was worked up as described in Example 1.
In use as Light stabilizers for polyolefins, the poly-meric hindered amines of the invention are added in amounts such that the tetramethyl piperidine concentration in the total system is equivalent to that heretofore used with con-ventional monomeric tetramethyl piperidines, about 0.1 to 3 by weight.
Example 5 A series of modified polypropylenes prepared as described in the preceding examples were blended with polypropylene using a conventional laboratory extruder, then extruded and cut to molding powder. The molding powder pellets were pressed into ten mil films in a picture frame mold at 200C.
Films of each of the materials, along with a blank con-taining no light stabilizer and controls containing commer-cially available hindered amine light stabilizers, in amounts to provide e~uivalent amounts of tetramethyl piperidine, were subjected to accelerated aging in a Fade-O-Meter. Specimens were tested periodically for flexibility and embrittLement.
Average time to failure is recorded in Table 1.
g Table 1 Specimen Additive(l) _ ConcAveraqe L _e (hrs) Blank --- - - 80 Control 1 I 0.025 pph. 590
5 5-A Imide 0.355 pph. 700 5-B diester 0.185 650 5-C Imide 0.215 960 Control 2 II 0.031 510 5-D Imide 0.30 840 0 (1~ - I is compound of formula I, hereinaboveO
II is compound of formula II, hereinabove.
5-A Imide is compound of formula III, hereinabove, where R
is homopolypropylene residue, R' is H, and combined maleic anhydride content is 3%. 5 5 B Diester is compound of formula IV, hereinabove, where R
is homopolypropylene residue, R' is H, and combined maleic anhydride content is 3%.
S-C Imide is compound of formula III, hereinabove, where R
is polypropylene-co-butylene residue, R' is ~, and com-bined maleic anhydride content is 5.1%.
5-D Imide is compound of formula III, hereinabove, where R
is homopolypropylene residue, R' is H, and combined maleic anhydride content is 3.6%.
From the data it will be apparent that the stabilizers of this invention are more effective than the conventional hindered amine light stabilizers based on tetramethyl piper-idine when used in tetramethyl piperidine- equivalent concen-trations.
II is compound of formula II, hereinabove.
5-A Imide is compound of formula III, hereinabove, where R
is homopolypropylene residue, R' is H, and combined maleic anhydride content is 3%. 5 5 B Diester is compound of formula IV, hereinabove, where R
is homopolypropylene residue, R' is H, and combined maleic anhydride content is 3%.
S-C Imide is compound of formula III, hereinabove, where R
is polypropylene-co-butylene residue, R' is ~, and com-bined maleic anhydride content is 5.1%.
5-D Imide is compound of formula III, hereinabove, where R
is homopolypropylene residue, R' is H, and combined maleic anhydride content is 3.6%.
From the data it will be apparent that the stabilizers of this invention are more effective than the conventional hindered amine light stabilizers based on tetramethyl piper-idine when used in tetramethyl piperidine- equivalent concen-trations.
Claims (11)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A modified olefin polymer containing a 2,2,6,6-tetra-methylpiperidine substituent, that has light stabilizing properties for alpha-olefins, characterized in that it has one of the general formulas III or IV
III
IV
wherein R represents the residue of an alpha-olefin polymer or copolymer; and R' represents -H, -OH, ?O, or -O-R", where R" is a lower alkyl group, and x and y are integers of a size relative to the molecular weight of R such that the total substitution of tetramethylpiperidine residue is between about 0.2 and 6% by weight, based on the total weight of the modified olefin polymer.
III
IV
wherein R represents the residue of an alpha-olefin polymer or copolymer; and R' represents -H, -OH, ?O, or -O-R", where R" is a lower alkyl group, and x and y are integers of a size relative to the molecular weight of R such that the total substitution of tetramethylpiperidine residue is between about 0.2 and 6% by weight, based on the total weight of the modified olefin polymer.
2. A polymer as claimed in claim 1, further characterized in that R is a polypropylene residue and R' is H.
3. A polymer as claimed in claim 1, further characterized in that the total concentration of tetramethylpiperidine residue is between about 0.2 and 1.0% by weight.
4. A polymer as claimed in claim 2, further characterized in that the total concentration of tetramethylpiperidine residue is between about 0.2 and 1.0% by weight.
5. 2-[N-(2,2,6,6-tetramethyl-4-piperidinyl)succinimidyl]-polypropylene.
6. 2-[Di-(2,2,6,6-tetramethyl-4-piperidinyl)succinate]-polypropylene.
7. A mixture of a modified olefin polymer containing a 2,2,6,6-tetramethylpiperidine substituent and an olefin polymer, characterized in that the modified olefin polymer is as claimed in claim 1 and the concentration of the tetramethylpiperidine residues in the mixture is between 0.2 and 6.0% by weight.
8. A mixture as claimed in claim 7 wherein the total concentration of tetramethylpiperidine residue is between about 0.2 and 1.0% by weight.
9. A mixture of a modified olefin polymer containing a 2,2,6,6-tetramethylpiperidine substituent and an olefin polymer, characterized in that the modified olefin polymer is as claimed in claim 5 or 6 and the concentration of the tetramethylpiperidine residues in the mixture is between 0.2 and 6.0% by weight.
10. A mixture of a modified olefin polymer containing a 2,2,6,6-tetramethylpiperidine substituent and an olefin polymer, characterized in that the modified olefin polymer is as claimed in claim 5 or 6 and the concentration of the tetramethylpiperidine residues in the mixture is between 0.2 and 1.0% by weight.
11. A mixture as claimed in claim 7 or 8, further character-ized in that the olefin polymer is polypropylene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000482119A CA1244597A (en) | 1985-05-23 | 1985-05-23 | Polymeric hindered amines |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000482119A CA1244597A (en) | 1985-05-23 | 1985-05-23 | Polymeric hindered amines |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1244597A true CA1244597A (en) | 1988-11-08 |
Family
ID=4130531
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000482119A Expired CA1244597A (en) | 1985-05-23 | 1985-05-23 | Polymeric hindered amines |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1244597A (en) |
-
1985
- 1985-05-23 CA CA000482119A patent/CA1244597A/en not_active Expired
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| MKEX | Expiry |