WO1981001706A1 - Novel secondary and tertiary amines and the use thereof in compositions and in stabilization of polymers against ultraviolet light degradation - Google Patents
Novel secondary and tertiary amines and the use thereof in compositions and in stabilization of polymers against ultraviolet light degradation Download PDFInfo
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- WO1981001706A1 WO1981001706A1 PCT/US1980/001499 US8001499W WO8101706A1 WO 1981001706 A1 WO1981001706 A1 WO 1981001706A1 US 8001499 W US8001499 W US 8001499W WO 8101706 A1 WO8101706 A1 WO 8101706A1
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- independently selected
- alkyl
- aralkyl
- hydroxy substituted
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- 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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
- C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D211/06—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
- C07D211/36—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D211/56—Nitrogen atoms
- C07D211/58—Nitrogen atoms attached in position 4
Definitions
- the Field of the Invention - This invention relates to novel compounds, compositions containing such compounds and methods for the stabilization of UV sensitive polymers. More specifically, this invention is directed to novel secondary and tertiary amines, stabilized polymer compositions containing such novel compounds and methods for the UV stabilization of photodegradable polymers.
- Description of the Prior Art - Polymers have in the past and continue to provide an attractive -substitute for the more traditional types of structural materials (e.g. wood or metals) because of relatively inexpensive materials and fabrication cost. As polymers continue to find new applications in, for example, the fabrication of automotive parts and building materials, they must also become more durable and capable of withstanding prolonged exposure to a variety of degradative forces.
- Degradation of polymers can be caused by exposure to light, heat, moisture and/or air. Such degradation is usually manifest by either a partial or total loss of structural integrity, changes in light transmission properties, changes in color, loss or reduction of flexibility and/or resiliency, or any combination of the above phenomena.
- Those attempting to avoid polymer degradation have generally selected from among three possible approaches: (a) elimination or reduction of the degradative forces; (b) isolation of the sensitive material from the degradative forces; or (c) modification of the polymer composition to enhance its resistance to the degradative forces. The latter approach is generally preferable since it does not require elaborate engineering nor structural changes in the polymer product environment.
- the problems associated with the stabilization of different polymeric materials are affected to a greater extent by the functionality of the polymer and any unsaturation that may be present along the backbone or the side chains of such materials.
- the polymer contains unsaturation along its backbone and/or side chains, it is highly sensitive to oxidative degradation.
- Materials that are suitable to prevent oxidative degradation of dienic or unsaturated polymers do not necessarily have similar beneficial effects when incorporated within a polymeric materials lacking such unsaturation.
- stabilizers which are effective for polyolefins, such as polyethylene may have little, if any, stabilizing effect upon dienic polymers or polymers having unsaturation along their backbone or side chain.
- additives which have been disclosed in the past as suitable for enhancing polymer resistance to one or more degradative forces described hereinabove.
- These additives (hereinafter collectively referred to as "stabilizers") can usually be physically combined with or engrafted upon the environmentally sensitive polymer thereby prolonging its useful life in its hostile degradative environment.
- stabilizers can usually be physically combined with or engrafted upon the environmentally sensitive polymer thereby prolonging its useful life in its hostile degradative environment.
- polymers i.e. a stabilizer package
- One of the more difficult to control of the degradative forces is the irradiation of polymers by ultraviolet light.
- the impact of such irradiation will, of course, vary depending upon the intensity and duration of exposure and thus, may manifiest itself only after a prolonged interval.
- the irradiation of polymers with ultraviolet light can oftentimes cause crosslinking of these materials, thereby reducing its resiliency and/or impact resistance. Changes in color and opacity are often effected by prolonged exposure of polymers to UV irradiation. While many materials are known and commercially available as stabilizers against ultraviolet light degradation, the degree of protection afforded by such agents is generally concentration dependent and may be geared to a particular limited class of material.
- the stabilizer is a polyurea having piperdinyl functional moieties appended from its backbone.
- the '248 patent is similar in its disclosure in that the piperidinyl functional moieties are appended from a polymer backbone composed of alkalene groups. While each of the foregoing stabilizer materials would appear to be attractive from the standpoint of low mobility, (due to its size) the presence of other components of the polymer backbone tends to increase the amount by weight, in relation to polymer, of such stabilizer that must be present in order to insure a sufficient number of stabilizer functional groups to adequately protect the ultraviolet light sensitive polymer against degradation.
- the stabilization of polymers against changes in their physical, chemical and/or electrical properties can be readily achieved by the incorporation of one or more stabilizer compounds within the environmentally sensitive material.
- the specific stabilizer materials which have been discussed herein- above are effective to a degree in the prevention of UV degradation of many widely used polymeric materials.
- such stabilization with the aforementioned materials can apparently result in some alteration in the stabilized polymer properties due to the amount of materials which must be included therein to achieve the desired degree of protection of the host polymer from the degradative agent.
- R and R' being independently selected from the group consisting of alkyl, hydroxy substituted alkyl, aryl, amino or hydroxy substituted aryl, aralkyl and amino or hydroxy substituted aralkyl;
- R 1 and R 2 being independently selected from hydrogen, alkyl, aralkyl;
- R 3 and R 4 being independently selected from from alkyl of 1 to 4 carbon atoms and capable of collectively forming a cycloalkyl substituent;
- a and A' being independently selected from the group consisting of alkylene of 1 to 12 carbon atoms; and m is 0 - 4 n is 1 - 3.
- the amount of stabilizer compounds which can effect satisfactory stabilization of ultraviolet light sensitive polymers is in the range of about 0.1 to about 5 parts by weight of stabilizer per 100 parts by weight of polymer.
- novel compounds of this invention can be routinely prepared using standard equipment, techniques and readily available starting materials.
- a typical synthesis of such materials stoichiometric quantities of an appropriately substituted piperidone and a primary amine are reacted with one another in an alcoholic medium in the presence of a catalyst such as platinum.
- the reaction vessel in which such synthesis is carried out is pressurized and hydrogen introduced therein while the temperature of the reaction mass is elevated (preferably to the refluxing temperature of the alcohol). After the consumption of hydrogen gases essentially ceases, the reaction mass is cooled and filtered.
- the starting materials which can be used in the synthesis of such novel compounds are either commercially available or can be prepared from readily available materials using standard equipment and techniques.
- piperazine and piperidone is commercially available from Aldrich Chemical Co.
- Representative piperazine and piperidone reactants which are suitable for use in the synthesis of the compounds of this invention are N,N'-bis (3-aminopro- pyl) piperazine, N,N'-bis (3-aminopropyl) -2, 5-dimethyl piperazine, 2, 2,6, 6-tetramethyl-4-piperidone and 1,2,2,6, 6-pentamethyl-4-piperidone.
- the primary amines which are suitable for use in the synthesis of the novel compounds of this, invention are readily available from Dow Chemical Co. or Union Carbide Corp.
- Representative of the amine reactants which are suitable for use in the synthesis of the compounds of this invention are diethylenetriamine, triethylenetetramine, tetraethylene- pentamine, 3,3-diamino-N-methyldipro ⁇ ylamine, 3,3- diamino-N-ethyldipropylamine and 3, 3-diamino-N-pro ⁇ yl- dipropylamine.
- the reaction is preferably carried out in the presence of a suitable catalyst, such as platinum.
- Catalyst concentration is preferably in the range of from about 0.01g to 0.10g of 10% Pt on carbon, per 0.1 mole piperidone reactant.
- novel compounds can be represented by the following structural formulae:
- R, R' , A, A' , R, , R 2 and m are the same as previously defined.
- Typical compounds falling within the scope of the foregoing formulae are bis [3-(2, 2, 6, 6-tetramethylpiperidin-4-yl) aminopropyl]methylamine, bis [3-(2, 2, 6,6- tetramethylpiperidin-4-yl) aminopropyl] ethylamine, bis [3- (2,2,6,6-tetramethylpiperdin-4-yl) aminopropyl] propyl amine, N,N*-bis [3- (2, 2, 6, 6-tetramethylpiperidin-4- yl) aminopropyl] piperazine, N,N'-bis [3-(2, 2, 6, 6-tetra- methylpiperidin-4-yl) aminopropyl] -2, 5-dimethylpiperazine, N,N' -bis [3- (2, 2, 6, 6-tetramethylpiperidin-4-yl) amino- propyl] -2,3,5, 6-tetramethylpiperazine, bis [2-(2, 2, 6, 6- tetramethylpi
- Ultraviolet light sensitive polymers of the compositions of this invention can include any polymeric material that manifests some degradation upon exposure to UV irradiation. Virtually all polymeric materials are sensitive, at least to some degree, to photodegradation by ultraviolet light.
- photodegradation as used herein with reference to ultraviolet light sensitive polymeric materials, is intended to be inclusive of any photo-induced change in the physical, chemical and/or electrical properties of the polymer or articles prepared therefrom.
- UV sensitive polymeric materials are the polyurethanes, PVC resins, ABS resins, polystyrene, polyacfylonitrile, polymethacrylate, polycarbonates, phenol-formaldehyde resins, polyepoxides, polyesters, and polyolefins (especially homopolymers and copolymers of polyethylene, polypropylene, ethylene-propylene copolymers, ethylene-vinyl acetate copolymers), and the like.
- the ultraviolet light sensitive polymers are derived from ⁇ - monoolefin monomers such as ethylene, propylene, isobutylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-l- pentene, and the like.
- the stabilized polymeric compositions prepared from the above materials can contain, in addition to the stabilizers and polymers described hereinabove, a variety of optional ingredients.
- Such optional ingredients can include metal oxides, such as zinc, calcium and magnesium oxides; fatty acids, such as stearic, lauric and salts thereof; fillers such as calcium and magnesium carbonate, calcium and barium, sulfonates, aluminum silicates, asbestos, and the like; plasticizers and extenders, such as dialkyl and diaryl organic acids, such as diisobutyl, diisooctyl, diisodecyl and dibenzyl oleates, stearates, sebacates, azelates, phthalates, and the like; ASTM Type 2 petroleum oils, paraffinic oils, castor oil, tall oil, glycerine, and the like; antioxidants, such as 2,6-di-t- butyl-para-cresol, 2,2'-methylene-bis-(4-ethyl-6-t-butyl phenol), 2, 2' -thio-bis-(4-methyl-6-t-butyl phenol), 2, 2'- m
- antioxidants are the antioxidants.
- antioxidants can be present within the polymer composition at a concentration within the range of from about 0.1 to about 10 parts by weight per 100 parts by weight polymer, and preferably from about 0.2 to about 5 parts by weight per 100 parts by weight polyer.
- the phenolic antioxidants are preferred for use in conjunction with the UV stabilizers of this invention.
- This combination of UV stabilizer and phenolic antioxidants is especially suitable for use in conjunction with polyolefins; that is, in an environment in which the polyolefin is subjected to a plurality of degradative forces, including heat, oxygen and ultraviolet light.
- the photodegradable polymers of the compositions of this invention can be compounded with the various stabilizers and additives described hereinabove in accord with standard mixing techniques and equipment; such as in a Banbur.y mixer, Henschel mixer, a rubber mill, an extruder mixer or other equivalent device.
- the various components of such a composition may be physically and intimately blended either in the absence of, or in the presence of, a common solvent; or in a solvent which is capable of dissolving the polymer component of the composition yet substantially incapable of dissolving the stabilizer ingredients.
- solvents/dispersing agents include hexane or benzene.
- the dispersing agent (if any) can be removed by selective evaporation and the resultant resin compounded and recovered.
- the resin compound may thereafter be formed into useful products by a variety of molding techniques.
- the ultraviolet light stability of the compositions prepared in the above manner can be evaluated by exposing a sample thereof to a Xenon or Carbon arc light in a Weather-Ometer operated at a temperature of about 60°C. Degradation of similarly prepared samples is determined by measurement of the difference in tensile strength after exposure to UV light. Where the tensile strength of the sample is reduced to fifty percent (50%) of its original value, the sample is regarded as degraded.
- the protocol used in such evaluation is generally recognized as an accepted method for evaluation of photodegradation of plastics and correlate with other more elaborate techniques.
- Degradation of the sample can also be monitored periodically, by measuring the carbonyl absorption band at 1720cm 1 , using an IR spectrophotometer. The relatively rapid formation of carbonyl sites indicates photodegradation occurring within the sample.
- This test procedure is also a recognized method for evaluation of the efficacy of such UV stabilizers and is fully described in the open literature, see for example "Photodegradation, Photooxi- dation and Photostabilization of Polymers", by Ranby & Raybeck, John Wiley & Sons, New York City (1975) at page 125 et seq; and U.S. Patent 3,909,493.
- Photodegradation of the sample can also be visibly manifest as cracking of the sample upon prolonged heating at 180°C. Oxidative degradation and thermal stability of the sample can be verified by monitoring the time required to effect discoloration and/or embrittlement of the sample in a standard aging oven maintained at 149 °C.
- the concentrate is fractionated under reduced pressure for removal of 2,2,6,6-tetramethyl-4-piperidonol and the desired product isolated from the remaining fraction, boiling point 168 - 172°C @ 0.002mm Hg, total yield 12.9 grams or 72% based upon diethylenetriamine content of the charge. Elemental analysis yields the following results: Calculated for C 22 H 47 N 5 : C, 69.23;H,12.42;N,18.35. Found: C,68.41; H,12.38; N,18.03.
- the concentrate is fractionated under reduced pressure to remove 2,2,6,6-tetramethyl-4-piperidinol and to collect the desired product which boils at 220°C/0.7 mm Hg.
- the total weight of the desired product is 12.60 grams (59.2% yield based on triethylenetetramine). Elemental analysis gives the following results:
- Good-rite 3125 is 3,5- di-tert-butyl-4-hydroxy-hydrocinnamic acid triester with 1,3, 5-tris(2-hydroxyethyl-s- triazine)-2,4,6( IH,3H,5H)-trione.
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Abstract
Novel compounds, compositions and methods for stabilization of ultraviolet light sensitive polymers against photodegradation. The novel secondary and tertiary amines of this invention can be represented by the following structural formula: (FORMULA) with R and R' being independently selected from the group consisting of alkyl, hydroxy substituted alkyl, aryl, amino or hydroxy substituted aryl, aralkyl and amino or hydroxy substituted aralkyl; R1 and R2 being independently selected from hydrogen, alkyl, aralkyl; R3 and R4 being independently selected from alkyl of 1 to 4 carbon atoms and capable of collectively forming a cycloalkyl substituent; A and A' being independently selected from the group consisting of alkylene of 1 to 12 carbon atoms; and m is 0-4; n is 1-3. The above compounds are especially suitable in the stabilization of polyolefins (i.e. polypropylene) against the degradative forces of ultraviolet light.
Description
NOVEL SECONDARY AND TERTIARY AMINES AND THE USE THEREOF IN COMPOSITIONS AND IN STABILIZATION OF POLYMERS AGAINST ULTRAVIOLET LIGHT DEGRADATION
BACKGROUND OF THE INVENTION The Field of the Invention - This invention relates to novel compounds, compositions containing such compounds and methods for the stabilization of UV sensitive polymers. More specifically, this invention is directed to novel secondary and tertiary amines, stabilized polymer compositions containing such novel compounds and methods for the UV stabilization of photodegradable polymers. Description of the Prior Art - Polymers have in the past and continue to provide an attractive -substitute for the more traditional types of structural materials (e.g. wood or metals) because of relatively inexpensive materials and fabrication cost. As polymers continue to find new applications in, for example, the fabrication of automotive parts and building materials, they must also become more durable and capable of withstanding prolonged exposure to a variety of degradative forces. Degradation of polymers can be caused by exposure to light, heat, moisture and/or air. Such degradation is usually manifest by either a partial or total loss of structural integrity, changes in light transmission properties, changes in color, loss or reduction of flexibility and/or resiliency, or any combination of the above phenomena. Those attempting to avoid polymer degradation have generally selected from among three possible approaches: (a) elimination or reduction of the degradative forces; (b) isolation of the sensitive material from the degradative forces; or (c) modification of the polymer composition to enhance its resistance to the degradative forces. The latter
approach is generally preferable since it does not require elaborate engineering nor structural changes in the polymer product environment.
As one might readily expect, the problems associated with the stabilization of different polymeric materials are affected to a greater extent by the functionality of the polymer and any unsaturation that may be present along the backbone or the side chains of such materials. For example, where the polymer contains unsaturation along its backbone and/or side chains, it is highly sensitive to oxidative degradation. Materials that are suitable to prevent oxidative degradation of dienic or unsaturated polymers do not necessarily have similar beneficial effects when incorporated within a polymeric materials lacking such unsaturation. Similarly stabilizers which are effective for polyolefins, such as polyethylene, may have little, if any, stabilizing effect upon dienic polymers or polymers having unsaturation along their backbone or side chain. There are a variety of additives which have been disclosed in the past as suitable for enhancing polymer resistance to one or more degradative forces described hereinabove. These additives (hereinafter collectively referred to as "stabilizers") can usually be physically combined with or engrafted upon the environmentally sensitive polymer thereby prolonging its useful life in its hostile degradative environment. It is not uncommon for polymers to contain a variety of stabilizer materials, (i.e. a stabilizer package), each being present for prevention on a particular degradative reaction. One of the more difficult to control of the degradative forces is the irradiation of polymers by ultraviolet light. The impact of such irradiation will, of course, vary depending upon the intensity and duration of exposure and thus, may manifiest itself only after a prolonged interval. The irradiation of polymers
with ultraviolet light can oftentimes cause crosslinking of these materials, thereby reducing its resiliency and/or impact resistance. Changes in color and opacity are often effected by prolonged exposure of polymers to UV irradiation. While many materials are known and commercially available as stabilizers against ultraviolet light degradation, the degree of protection afforded by such agents is generally concentration dependent and may be geared to a particular limited class of material. The prior art is replete with technical articles and patents directed to resolving this complex problem, see for example, "Photodegradation, Photooxidation and Photostabilization of Polymers", B. Ranby & J. Raybeck, John Wiley & Sons, New York City (1975) at page 369 et seq. A number of hindered amine stabilizers had been previously disclosed as suitable in the prevention of photodegradation of polyolefins, such as polyethylene and polypropylene, see for example, U. S. Patents 4,006,207 and 4,104,248. Each of the above references discloses a piperdinyl functional compound which is suitable in the light stabilization of synthetic materials, such as polypropylene and polyethylene. In the case of the ' 207 patent, the stabilizer is a polyurea having piperdinyl functional moieties appended from its backbone. The '248 patent is similar in its disclosure in that the piperidinyl functional moieties are appended from a polymer backbone composed of alkalene groups. While each of the foregoing stabilizer materials would appear to be attractive from the standpoint of low mobility, (due to its size) the presence of other components of the polymer backbone tends to increase the amount by weight, in relation to polymer, of such stabilizer that must be present in order to insure a sufficient number of stabilizer functional groups to adequately protect the ultraviolet light sensitive polymer against degradation. In contrast to the above
approach, it would be preferable to somehow bind, either physically or chemically, stabilizer functional groups within the host material so as to achieve both the requisite amount of stabilization and the immobility or affixation of stabilizer necessary to prevent extraction thereof upon contact of the stabilized composition with solvents or exposure of the polymer to elevated temperatures.
In summary, the stabilization of polymers against changes in their physical, chemical and/or electrical properties can be readily achieved by the incorporation of one or more stabilizer compounds within the environmentally sensitive material. The specific stabilizer materials which have been discussed herein- above are effective to a degree in the prevention of UV degradation of many widely used polymeric materials. However, such stabilization with the aforementioned materials can apparently result in some alteration in the stabilized polymer properties due to the amount of materials which must be included therein to achieve the desired degree of protection of the host polymer from the degradative agent.
SUMMARY OF THE INVENTION Accordingly, it is the object of this invention to remedy the above as well as related deficiencies in the prior art.
More specifically, it is the principal object of this invention to provide a novel stabilizer material suitable for enhancing the resistance of ultraviolet light sensitive polymers to photodegradation.
Another object of this invention is to provide stabilized polymeric compositions which are resistant to photodegradation by ultraviolet light and yet possess processing characteristics essentially equivalent to the unstabilized material.
Another object of this invention is to provide a method for extending the useful life of environmentally sensitive polymers by enhancement in their resistance to photodegradation by ultraviolet light.
The above and related objects are achieved by providing a composition containing a stabilizer compound of the following formula:
A and A' being independently selected from the group consisting of alkylene of 1 to 12 carbon atoms; and m is 0 - 4 n is 1 - 3.
In the preferred embodiments of this invention, the amount of stabilizer compounds which can effect satisfactory stabilization of ultraviolet light sensitive polymers is in the range of about 0.1 to about 5 parts by weight of stabilizer per 100 parts by weight of polymer. DESCRIPTION OF THE INVENTION
INCLUDING PREFERRED EMBODIMENTS
The novel compounds of this invention can be routinely prepared using standard equipment, techniques and readily available starting materials. In a typical synthesis of such materials, stoichiometric quantities of an appropriately substituted piperidone and a primary amine are reacted with one another in an alcoholic medium in the presence of a catalyst such as platinum. The reaction vessel in which such synthesis is carried out is pressurized and hydrogen introduced therein while the temperature of the reaction mass is elevated (preferably to the refluxing temperature of the alcohol). After the consumption of hydrogen gases essentially ceases, the reaction mass is cooled and filtered.
The starting materials which can be used in the synthesis of such novel compounds are either commercially available or can be prepared from readily available materials using standard equipment and techniques. For example, appropriately substituted piperazine and piperidone is commercially available from Aldrich Chemical Co. Representative piperazine and piperidone reactants which are suitable for use in the synthesis of the compounds of this invention are N,N'-bis (3-aminopro- pyl) piperazine, N,N'-bis (3-aminopropyl) -2, 5-dimethyl piperazine, 2, 2,6, 6-tetramethyl-4-piperidone and 1,2,2,6, 6-pentamethyl-4-piperidone.
Similarly, the primary amines which are suitable for use in the synthesis of the novel compounds of this, invention are readily available from Dow Chemical Co. or Union Carbide Corp. Representative of the amine reactants which are suitable for use in the synthesis of the compounds of this invention are diethylenetriamine, triethylenetetramine, tetraethylene- pentamine, 3,3-diamino-N-methyldiproρylamine, 3,3- diamino-N-ethyldipropylamine and 3, 3-diamino-N-proρyl- dipropylamine.
As noted hereinabove, the reaction is preferably carried out in the presence of a suitable catalyst, such as platinum. Catalyst concentration is preferably in the range of from about 0.01g to 0.10g of 10% Pt on carbon, per 0.1 mole piperidone reactant.
In the preferred embodiments of this invention, the novel compounds can be represented by the following structural formulae:
wherein R, R' , A, A' , R, , R2 and m are the same as previously defined.
Typical compounds falling within the scope of the foregoing formulae are bis [3-(2, 2, 6, 6-tetramethylpiperidin-4-yl) aminopropyl]methylamine, bis [3-(2, 2, 6,6- tetramethylpiperidin-4-yl) aminopropyl] ethylamine, bis [3- (2,2,6,6-tetramethylpiperdin-4-yl) aminopropyl] propyl amine, N,N*-bis [3- (2, 2, 6, 6-tetramethylpiperidin-4- yl) aminopropyl] piperazine, N,N'-bis [3-(2, 2, 6, 6-tetra- methylpiperidin-4-yl) aminopropyl] -2, 5-dimethylpiperazine, N,N' -bis [3- (2, 2, 6, 6-tetramethylpiperidin-4-yl) amino- propyl] -2,3,5, 6-tetramethylpiperazine, bis [2-(2, 2, 6, 6-
tetramethylpiρeridin-4-yl) aminoethyl] amine, N 1 N 8 - bis (2, 2, 6 , 6-tetra methylpiperidin-4-yl) -3 , 6-diazaoctane-
1, 8-di-amine, N 1 ,N 1 1 -bis (2 , 2 , 6 , 6-tetramethylpiperidin-4- yl) -3 , 6 , 9-triazaundecane-l, 11-diamine, bis [3- ( l , 2 , 2 , 6 , 6- pent amethylpiperidin-4-yl) aminopropyl] methylamine ,
N,N'-bis [3-(l, 2,2,6,6-pentamethylpiperidin-4-yl) amino- propyl] piperazine, N 1,N8-bis (1, 2,2,6, 6-pentamethylpiperidin-4-yl)-3,6-diazaoctane -1,8-diamine, N 1 ,N 1 1-bis (1,2,2,
6, 6-pentamethylpiperidin-4-yl)-3,6, 9-triazaundecane-l, 11-diamine.
Ultraviolet light sensitive polymers of the compositions of this invention can include any polymeric material that manifests some degradation upon exposure to UV irradiation. Virtually all polymeric materials are sensitive, at least to some degree, to photodegradation by ultraviolet light. The term "photodegradation", as used herein with reference to ultraviolet light sensitive polymeric materials, is intended to be inclusive of any photo-induced change in the physical, chemical and/or electrical properties of the polymer or articles prepared therefrom.
Representative of the above UV sensitive polymeric materials are the polyurethanes, PVC resins, ABS resins, polystyrene, polyacfylonitrile, polymethacrylate, polycarbonates, phenol-formaldehyde resins, polyepoxides, polyesters, and polyolefins (especially homopolymers and copolymers of polyethylene, polypropylene, ethylene-propylene copolymers, ethylene-vinyl acetate copolymers), and the like. In the preferred stabilized compositions of this invention, the ultraviolet light sensitive polymers are derived from α- monoolefin monomers such as ethylene, propylene, isobutylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-l- pentene, and the like. The stabilized polymeric compositions prepared from the above materials can contain, in addition to the
stabilizers and polymers described hereinabove, a variety of optional ingredients. Such optional ingredients can include metal oxides, such as zinc, calcium and magnesium oxides; fatty acids, such as stearic, lauric and salts thereof; fillers such as calcium and magnesium carbonate, calcium and barium, sulfonates, aluminum silicates, asbestos, and the like; plasticizers and extenders, such as dialkyl and diaryl organic acids, such as diisobutyl, diisooctyl, diisodecyl and dibenzyl oleates, stearates, sebacates, azelates, phthalates, and the like; ASTM Type 2 petroleum oils, paraffinic oils, castor oil, tall oil, glycerine, and the like; antioxidants, such as 2,6-di-t- butyl-para-cresol, 2,2'-methylene-bis-(4-ethyl-6-t-butyl phenol), 2, 2' -thio-bis-(4-methyl-6-t-butyl phenol), 2, 2'- methylene-bis-(6-t-butyl-4-methyl phenol), 4,4'-butyli- dene-bis-6-t-butyl-m-cresol, 2-(4-hydroxy-3, 5-di-t- butylanilino-4, 6-bis-(octylthio)-1,3 ,5 triazine, hexa- hydro-1,3 ,5-tris-[β-(3, 5-di-t-butyl-4-hydroxyphenyl)- propionyl]-s-triazine, tris (3, 5-di-t-butyl-4-hydroxy- benzyl) isocyanurate, tetrakis-[methylene-3-(3'5'-di-t- butyl-4'-hydroxyphenyl) propionate] methane, distearylthiodipropionate, dilaurylthiodipropionate, tri- (nonylphenyl) phosphite, tin thioglycolate, and the like; and other ingredients such as pigments, tackifiers, flame retardants, fungicide and the like.
Optional compounding ingredients which are especially suitable for use in combination with the above stabilized compositions are the antioxidants. The inclusion within the composition of an antioxidant, in addition to the UV stabilizer, confers upon the polymer compositions stability against two of the more environmentally hostile degradative forces. Typically, antioxidants can be present within the polymer composition at a concentration within the range of from about 0.1 to about 10 parts by weight per 100 parts by weight
polymer, and preferably from about 0.2 to about 5 parts by weight per 100 parts by weight polyer. Generally, the phenolic antioxidants are preferred for use in conjunction with the UV stabilizers of this invention. This combination of UV stabilizer and phenolic antioxidants is especially suitable for use in conjunction with polyolefins; that is, in an environment in which the polyolefin is subjected to a plurality of degradative forces, including heat, oxygen and ultraviolet light.
The photodegradable polymers of the compositions of this invention can be compounded with the various stabilizers and additives described hereinabove in accord with standard mixing techniques and equipment; such as in a Banbur.y mixer, Henschel mixer, a rubber mill, an extruder mixer or other equivalent device. The various components of such a composition may be physically and intimately blended either in the absence of, or in the presence of, a common solvent; or in a solvent which is capable of dissolving the polymer component of the composition yet substantially incapable of dissolving the stabilizer ingredients. Typical of such solvents/dispersing agents include hexane or benzene. Subsequent to intimately dispersing the various components of the composition within one another, the dispersing agent (if any) can be removed by selective evaporation and the resultant resin compounded and recovered. The resin compound may thereafter be formed into useful products by a variety of molding techniques. The ultraviolet light stability of the compositions prepared in the above manner can be evaluated by exposing a sample thereof to a Xenon or Carbon arc light in a Weather-Ometer operated at a temperature of about 60°C. Degradation of similarly prepared samples is determined by measurement of the difference in tensile strength after exposure to UV light. Where the tensile
strength of the sample is reduced to fifty percent (50%) of its original value, the sample is regarded as degraded. The protocol used in such evaluation is generally recognized as an accepted method for evaluation of photodegradation of plastics and correlate with other more elaborate techniques. Degradation of the sample can also be monitored periodically, by measuring the carbonyl absorption band at 1720cm1, using an IR spectrophotometer. The relatively rapid formation of carbonyl sites indicates photodegradation occurring within the sample. This test procedure is also a recognized method for evaluation of the efficacy of such UV stabilizers and is fully described in the open literature, see for example "Photodegradation, Photooxi- dation and Photostabilization of Polymers", by Ranby & Raybeck, John Wiley & Sons, New York City (1975) at page 125 et seq; and U.S. Patent 3,909,493. Photodegradation of the sample can also be visibly manifest as cracking of the sample upon prolonged heating at 180°C. Oxidative degradation and thermal stability of the sample can be verified by monitoring the time required to effect discoloration and/or embrittlement of the sample in a standard aging oven maintained at 149 °C.
THE EXAMPLES The Examples which follow further define, describe and illustrate the preparation and evaluation of the compounds and stabilized compositions of this invention. Apparatus and procedures used in both the preparation and evaluation of such compounds and compositions are standard or as hereinbefore described. Parts and percentages appearing in such Examples are by weight unless otherwise stipulated.
EXAMPLE I
Preparation of bis [3-(2, 2, 6, 6-tetramethyIpiper- idin-4-yl) aminopropyl]methylamine: Into a 110 ml autoclave are charged 15.5 grams (0.1 mole) of 2,2,6,6-
tetramethyl-4-piperidone, 30 mis of methanol, 7.3 grams
(0.05 mole) of 3 ,3'-diamino-N-methyldipropylamine, and
0.05 grams of 10% platinum catalyst on carbon. The reaction mass is heated to about 80°C and the autoclave pressurized with hydrogen to about 800 psi. After about 3 hours, the reaction is terminated, the reaction mass is cooled and the catalyst was separated from the reaction product by filtration. The methanol medium is fractionated from the filtrate yielding a clear syrup product which is 99% pure by gas chromatographic techniques . The desired product has a boiling point between 227.5 and 228.9°C at 1.0 mm Hg. Elemental analysis yields the following results:
Calculated for C25H53N5: C,70.86; H,12.61; N, 16.53.
Found: C70.90; H,12.86; and N,16.35.
EXAMPLE II Preparation of N,N'-bis[3-(2, 2, 6 , 6-tetramethyl- piperidin-4-yl) aminopropyl] piperazine: Into a 110 ml autoclave are charged 15.5 grams (0.1 mole) of 2,2,6,6- tetramethyl-4-piperidone, 25 mis methanol, 5.0 grams (0.025 mole) of N,N' -bis (3-aminopropyl) piperazine, and 0.05 grams of 10% platinum on carbon. The reaction mass is heated to about 80°C and the autoclave pressurized with hydrogen to about 800 psi. After about 3 1/2 hours, the reaction is terminated, the reaction mass cooled and the catalyst was separated therefrom by filtration. The resultant product is fractionated for removal of 2,6,6,6- tetramethyl-4-piperidonol. 8.9 grams of a tan solid product is isolated from the pot residue. The melting point of this product is 95 to 96 °C. Elemental analysis of the product yields following results:
Calculated for C28H58N6:C,70.24,H,12.21, and
N,17.55. Found: C, 69.94;H, 12.30; N,17.40
EXAMPLE III
Preparation of bis [2- (2,2, 6 , δ-tetramethylpiper- idin^-yl) aminoethyl] amine : Into a 110 ml autoclave are charged 22.5 grams (0.145 mole) of 2, 2, 6, 6-tetramethyl-4- piperidone, 35 mis of methanol, 4.8 grams (0.047 mole) of diethylenetriamine, and 0.07 grams of 10% platinum on carbon. The reaction mass is heated to about 80°C, and the autoclave pressurized with hydrogen to about 1500 psi. After about 4 1/2 hours the reaction is terminated, the reaction mass is allowed to cool and the catalyst was separated from the reaction mass by filtration. The filtrate is thereupon concentrated on an evaporator. The concentrate is fractionated under reduced pressure for removal of 2,2,6,6-tetramethyl-4-piperidonol and the desired product isolated from the remaining fraction, boiling point 168 - 172°C @ 0.002mm Hg, total yield 12.9 grams or 72% based upon diethylenetriamine content of the charge. Elemental analysis yields the following results: Calculated for C22H47N5: C, 69.23;H,12.42;N,18.35. Found: C,68.41; H,12.38; N,18.03.
EXAMPLE IV Preparation of N 1,N8-bis(2,2, 6-tetramethyl- piperidin-4-yl)-3, 6-diazaoctane-l, 8-diamine: Into a 110 ml autoclave are charged 16.25 grams (0.105 mole) of 2, 2,6,6-tetramethyl-4-piperidone, 25 ml of methanol, 7.31 grams (0.05 mole) of triethylenetetramine, and 0.60 grams of 10% platinum on carbon. The above mixture is heated to 60°C, and the autoclave pressurized with hydrogen to about 1500 psi. After two hours, the reaction is terminated, cooled, and filtered to remove the catalyst. The filtrate is thereupon concentrated on an evaporator. The concentrate is fractionated under reduced pressure to remove 2,2,6,6-tetramethyl-4-piperidinol and to collect the desired product which boils at 220°C/0.7 mm Hg. The
total weight of the desired product is 12.60 grams (59.2% yield based on triethylenetetramine). Elemental analysis gives the following results:
Calculated for C24H52N6: C, 67.87; H, 12.34; N,19.79.
Found: C, 67.93; H, 12.32; N, 19.77.
Each of the foregoing compounds are evaluated for the stabilization of polypropylene with the following results:
**
A time to reach 50% of the original tensile strength. ***
2-Hydroxy-4-n-octoxybenzophenone
The foregoing Description and Examples have been provided as illustrative of the invention and not intended to delineate its scope which is set forth in the following claims.
Claims
1. Compounds of the formula
A and A' being independently selected from the group consisting of alkylene of 1 to 12 carbon atoms; and m is 0 - 4 n is 1 - 3.
Compounds of the formula
R1 and R2 being independently selected from hydrogen, alkyl, aralkyl;
R3 and R4 being independently selected from alkyl of 1 to 4 carbon atoms and capable of collectively forming a cycloalkyl substituent;
A and A' being independently selected from the group consisting of alkylene of 1 to 12 carbon atoms; and m is 0 - 4 n is 1 - 3.
3. Compounds of the formula
R3 and R4 being independently selected from
alkyl of 1 to 4 carbon atoms and capable of collectively forming a cycloalkyl substituent;
A and A' being independently selected from the group consisting of alkylene of 1 to 12 carbon atoms; and m is 0 - 4 n is 1 - 3.
4. A composition comprising a polymer which is sensitive to photodegradation by ultraviolet light a a UV stabilizer effective amount of a compound of the formula
A and A' being independently selected from the group consisting of alkylene of 1 to 12 carbon atoms; and m is 0 - 4 n is 1 - 3.
5. A composition comprising a polymer which is sensitive to photodegradation by ultraviolet light and a UV stabilizer effective amount of a compound of the formula
A and A' being independently selected from the group consisting of alkylene of 1 to 12 carbon atoms; and m is 0 - 4 n is 1 - 3.
6. A composition comprising a polymer which is sensitive to photodegradation by ultraviolet light and a UV stabilizer effective amount of a compound of the formula
R3 and R4 being independently selected from alkyl of 1 to 4 carbon atoms and capable of collectively forming a cycloalkyl substituent;
A and A' being independently selected from the group consisting of alkylene of 1 to 12 carbon atoms; and m is 0 - 4 n is 1 - 3,
7. A method for the stabilization of polymers which are sensitive to photodegradation by ultraviolet light, said method comprising incorporating within such photosensitive polymer a stabilizer effective amount of a compound of the formula
R3 and R4 being independently selected from alkyl of 1 to 4 carbon atoms and capable of collectively forming a cycloalkyl substituent;
A and A' being independently selected from the group consisting of alkylene of 1 to 12 carbon atoms; and m is 0 - 4 n is 1 - 3.
8. A method for the stabilization of polymers which are sensitive to photodegradation by ultraviolet light, said method comprising incorporating within such photosensitive polymer a stabilizer effective amount of a compound of the formula
A and A' being independently selected from the group consisting of alkylene of 1 to 12 carbon atoms; and m is 0 - 4 n is 1 - 3.
9. A method for the stabilization of polymers which are sensitive to photodegradation by ultraviolet light, said method comprising incorporating within such photosensitive polymer a stabilizer effective amount of a compound of the formula
A and A' being independently selected from the group consisting of alkylene of 1 to 12 carbon atoms; and m is 0 - 4 n is 1 - 3.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| BR8008958A BR8008958A (en) | 1979-12-10 | 1980-11-06 | NEW SECONDARY AND TERTIARY AMINES AND THEIR USE IN COMPOSITIONS AND IN THE STABILIZATION OF POLYMERS AGAINST DEGRADATION BY ULTRAVIOLET LIGHT |
| JP81500345A JPS56501681A (en) | 1979-12-10 | 1980-11-06 |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US10197279A | 1979-12-10 | 1979-12-10 | |
| US101972 | 1979-12-10 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO1981001706A1 true WO1981001706A1 (en) | 1981-06-25 |
Family
ID=22287446
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/US1980/001499 WO1981001706A1 (en) | 1979-12-10 | 1980-11-06 | Novel secondary and tertiary amines and the use thereof in compositions and in stabilization of polymers against ultraviolet light degradation |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0041555A4 (en) |
| JP (1) | JPS56501681A (en) |
| BE (1) | BE886428A (en) |
| BR (1) | BR8008958A (en) |
| ES (1) | ES497599A0 (en) |
| GR (1) | GR71618B (en) |
| WO (1) | WO1981001706A1 (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0061785A1 (en) * | 1979-01-15 | 1982-10-06 | Ciba-Geigy Ag | Use of polyalkylpiperidine polyamines as curing agent for epoxy resins |
| EP0213570A2 (en) * | 1985-08-28 | 1987-03-11 | BASF Aktiengesellschaft | Glycolurile derivatives and their use as polymer stabilizers |
| EP0224720A1 (en) * | 1985-11-01 | 1987-06-10 | The B.F. GOODRICH Company | Oligomeric light stabilizers with substituted piperidine ends |
| EP0272590A2 (en) * | 1986-12-22 | 1988-06-29 | BASF Aktiengesellschaft | Glycolurile derivatives and their use as polymer stabilizers |
| EP0376886A1 (en) * | 1988-12-23 | 1990-07-04 | Ciba-Geigy Ag | Piperidine-triazine compounds for use as stabilizers for organic materials |
| EP0410934A2 (en) * | 1989-07-28 | 1991-01-30 | Ciba-Geigy Ag | Piperazine-piperidine compounds for use as stabilizers for organic materials |
| US5112979A (en) * | 1990-11-29 | 1992-05-12 | Texaco Chemical Company | Polyoxyalkyleneamines containing tetraalkylpiperidine functionality and their use as light, heat and oxidation stabilizers |
| US5204474A (en) * | 1991-06-03 | 1993-04-20 | Ciba-Geigy Corporation | 2,6-diarylpiperidin-1-yl substituted 2-butene stabilizers |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3106552A (en) * | 1960-07-19 | 1963-10-08 | Geschickter Fund Med Res | Nu-substituted azaspiranes and azaspirane-diones and processes for their preparation |
| US3291808A (en) * | 1961-08-14 | 1966-12-13 | Parke Davis & Co | Naphthalene diamine compounds and methods for their production |
| US4104248A (en) * | 1975-03-21 | 1978-08-01 | Montefibre S.P.A. | Polyolefine-based polymeric compositions stabilized by organic polyamines, textile fibers obtained therefrom, and novel organic polyamines |
| US4240954A (en) * | 1979-02-26 | 1980-12-23 | American Cyanamid Company | Polymers stabilized against degradation by ultraviolet radiation |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3937711A (en) * | 1973-10-15 | 1976-02-10 | Ciba-Geigy Corporation | 4-(carboxamidoethyl) piperidines |
| CH592129A5 (en) * | 1973-10-18 | 1977-10-14 | Ciba Geigy Ag | Stabilising organic materials, esp. polymers - against light, oxygen and heat, with piperidine derivs. |
-
1980
- 1980-11-06 WO PCT/US1980/001499 patent/WO1981001706A1/en not_active Application Discontinuation
- 1980-11-06 EP EP19810900159 patent/EP0041555A4/en not_active Withdrawn
- 1980-11-06 BR BR8008958A patent/BR8008958A/en unknown
- 1980-11-06 JP JP81500345A patent/JPS56501681A/ja active Pending
- 1980-12-01 BE BE0/202996A patent/BE886428A/en unknown
- 1980-12-03 GR GR63542A patent/GR71618B/el unknown
- 1980-12-10 ES ES497599A patent/ES497599A0/en active Granted
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3106552A (en) * | 1960-07-19 | 1963-10-08 | Geschickter Fund Med Res | Nu-substituted azaspiranes and azaspirane-diones and processes for their preparation |
| US3291808A (en) * | 1961-08-14 | 1966-12-13 | Parke Davis & Co | Naphthalene diamine compounds and methods for their production |
| US4104248A (en) * | 1975-03-21 | 1978-08-01 | Montefibre S.P.A. | Polyolefine-based polymeric compositions stabilized by organic polyamines, textile fibers obtained therefrom, and novel organic polyamines |
| US4240954A (en) * | 1979-02-26 | 1980-12-23 | American Cyanamid Company | Polymers stabilized against degradation by ultraviolet radiation |
Non-Patent Citations (1)
| Title |
|---|
| See also references of EP0041555A4 * |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4528374A (en) * | 1979-01-15 | 1985-07-09 | Ciba-Geigy Corporation | Polyalkylpiperidines |
| EP0061785A1 (en) * | 1979-01-15 | 1982-10-06 | Ciba-Geigy Ag | Use of polyalkylpiperidine polyamines as curing agent for epoxy resins |
| EP0213570B1 (en) * | 1985-08-28 | 1992-04-08 | BASF Aktiengesellschaft | Glycolurile derivatives and their use as polymer stabilizers |
| EP0213570A2 (en) * | 1985-08-28 | 1987-03-11 | BASF Aktiengesellschaft | Glycolurile derivatives and their use as polymer stabilizers |
| EP0224720A1 (en) * | 1985-11-01 | 1987-06-10 | The B.F. GOODRICH Company | Oligomeric light stabilizers with substituted piperidine ends |
| EP0272590A2 (en) * | 1986-12-22 | 1988-06-29 | BASF Aktiengesellschaft | Glycolurile derivatives and their use as polymer stabilizers |
| EP0272590B1 (en) * | 1986-12-22 | 1994-03-09 | BASF Aktiengesellschaft | Glycolurile derivatives and their use as polymer stabilizers |
| EP0376886A1 (en) * | 1988-12-23 | 1990-07-04 | Ciba-Geigy Ag | Piperidine-triazine compounds for use as stabilizers for organic materials |
| US5039722A (en) * | 1988-12-23 | 1991-08-13 | Ciba-Geigy Corporation | Piperidine-triazine compounds for use as stabilizers for organic materials |
| EP0410934A2 (en) * | 1989-07-28 | 1991-01-30 | Ciba-Geigy Ag | Piperazine-piperidine compounds for use as stabilizers for organic materials |
| EP0410934A3 (en) * | 1989-07-28 | 1991-12-11 | Ciba-Geigy Ag | Piperazine-piperidine compounds for use as stabilizers for organic materials |
| US5332816A (en) * | 1989-07-28 | 1994-07-26 | Ciba-Geigy Corporation | Piperazine-piperidine compounds for use as stabilizers for organic materials |
| US5112979A (en) * | 1990-11-29 | 1992-05-12 | Texaco Chemical Company | Polyoxyalkyleneamines containing tetraalkylpiperidine functionality and their use as light, heat and oxidation stabilizers |
| US5204474A (en) * | 1991-06-03 | 1993-04-20 | Ciba-Geigy Corporation | 2,6-diarylpiperidin-1-yl substituted 2-butene stabilizers |
| US5290940A (en) * | 1991-06-03 | 1994-03-01 | Ciba-Geigy Corporation | 2,6-diarylpiperidin-1-yl substituted 2-butene stabilizers |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS56501681A (en) | 1981-11-19 |
| EP0041555A4 (en) | 1982-04-22 |
| GR71618B (en) | 1983-06-17 |
| ES8203344A1 (en) | 1982-04-01 |
| BR8008958A (en) | 1981-10-20 |
| ES497599A0 (en) | 1982-04-01 |
| EP0041555A1 (en) | 1981-12-16 |
| BE886428A (en) | 1981-04-01 |
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