CA1062723A - Polycarbonate stabilizers - Google Patents
Polycarbonate stabilizersInfo
- Publication number
- CA1062723A CA1062723A CA261,717A CA261717A CA1062723A CA 1062723 A CA1062723 A CA 1062723A CA 261717 A CA261717 A CA 261717A CA 1062723 A CA1062723 A CA 1062723A
- Authority
- CA
- Canada
- Prior art keywords
- cyano
- compound
- beta
- alpha
- methyl
- 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
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
-
- 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
- C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
-
- 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
- C08K5/315—Compounds containing carbon-to-nitrogen triple bonds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A B S T R A C T
Polycarbonate is effectively stabilized against degradation by ultraviolet radiation by a compound of the formula:
wherein A is cyclohexyl or the group wherein Z
is methoxy or ethoxy; R os CH3- or -CH2CH2CN and R1 is CN
or -COOC2H5.
Polycarbonate is effectively stabilized against degradation by ultraviolet radiation by a compound of the formula:
wherein A is cyclohexyl or the group wherein Z
is methoxy or ethoxy; R os CH3- or -CH2CH2CN and R1 is CN
or -COOC2H5.
Description
25,~0~1 qZ3 This invention relates to a novel compound and to its use to stabilize polycl~rbonates against degrada-tion on exposure to ultraviolet radiation.
Polycarbonates can be formed into useful art-icles, such as pipje, hollow objects (e~g. bottles, tumb-lers, etc.), film, sheet, lenses, hard hats, etc. by suchprocess as in~ection molding, extrusion, blow-molding, etc. Because o~ their desirable properties and ease of forming m to useful articles, polycarbonates have attain- -ed wide commercial utilization. In some of these uses, ~ -the polycarbonate is exposed to ultraviolet radiation, su~h as in sunlight. As is well known, such exposure causes degradation of the polyoarbonate, leading to dis- ~ -coloration and embrittlement. It is an ob~ect of this invention to provide a novel compound URefUl, when in-corporated in-~polycarbonates, for inhibiting degradation .
~ 2 - ~ ~
, .~ .. ... . .. .
~Z7;~3 1 caused by ul ~aviolet radia-tion.
In accordance with the present invention, it has been Eound that a compo~nd having the formula:
CN
5A-N-CH=C /
wherein A is cyclohexyl or the group Z ~ wherein z is methoxy or ethoxy; R is CH3- or -CH2CH2CN and Rl is CN or -COOC2H5, is effective for inhibiting degradation of polycarbona~e on exposure to ultraviolet radiation.
This compound may be incorporated into poly-carbonate by any of the standard techniques, including milling, screw extruding, Banbury mixing, swelling, etc.
This compound is effective over a wide concentration range of about 0.1 to about 5.0 percent based on weight of polycarbonate. Preferably, it is used at a concen-tration of about 0.5 to about 2.0 percent on weight of polycarbonate. Other additives, such as dyes, foaming agents, pigments~ plasticizers, thermal stabilizers, etc.
may also be added to the polycarbonate for their usual , fun~tionsO
This invention is further illustrated in the following examples, wherein all parts are by weight un-less otherwise stated.
, ,. , :
Example 1 A mixture of 7.21 grams (0.064 mole) of N--methyl-M-cyclohexylamine and 10.3 grams (0~07 mole) of triethyl orthoformate was heated to 105C. and 6.9 grams -~
(0.06 mole) vf ethyl cyanoacetate was slowly added there- -to. The temperature gradually rose until ethanol began .. : , . .
27~3 1 to distill ov~r. After 11.4 milliliters of distillate was coll~cted, the reaction mixture was cooled to room temperature and poured into water. The aqueous mixture was extracted with diethyl ether, dried over anhydrous magnesium sulfate, and evaporated to obtain 14.0 grams of a dark oil. The oil was heated under vacuum to remove some distillable material and the remainder was extracted with three portions of hot cyclohexane which, on cooling, ~ave a total of 5.7 grams of light tan powder. ~he powder was recrystallized from cyclohexane, yie~ing 4.0 grams melting at 65-70C. Further recrystallization from pet-xoleum ether gave ethyl a-cyano-~-(N-methyl-N-cyclohexyl-amino)acrylate as fine white plates, melting point 71--72C.. AnalySiS: Calculated for Cl3H20N2o2: C~ 66-07;
H, 8.53; N, 11.86. Found: C, 65.98; H, 8.54; N, 11.72.
Example 2 A mixture of 35.2 grams (0.2 mole) of N-cyano-ethyl-p~methoxyaniline, 29.6 grams (0.2 mole) of triethyl orthoformate, and 13.2 grams (0.2 mole) of malononitrile was heated to 160C. over a period of thirty minute5 and then heated at 165C. for an additional thirty minutes.
Theresulting solution was cooled to room temperature and 100 milliliters of ethanol was added thereto. Fur-ther cooling of tha resulting solution in dry ice cau~ed an oil to separate. After separating the oil from the remainder of the material~ methanol was added to the oil causing it to crystallize. The crude product (5.5 grams, melting point 164-165C.) was;recrystallized from a mix~
tu.re of 125 mill:iliters o methanol and 25 milliliters of mathyl cellosolve to obtain 3 grams of product melting - .
:, ' 1 at 174--175C. This latter product was recrystallized from 50 milliliters of ethyl acetatP to obtain ~he de-sired ~-cyano~ N-cyanoethyl-p-methoxyanilino)acryloni-trile (Formula I, supra), melting at 175-177C.
Example 3 _ A mixkure of 62.5 grams (0.5 mole) of N-methyl--p-aminophenol, 74.0 grams (0.5 mole) of triethyl ortho- -formate, and 33.5 grams (0.5 mole) of malononitrile in 400 milliliters of 99.5% ethanol was prepared under a nitrogen atmosphere and heated at 75-78C. for seventeen hours~ The reaction mixture was cooled to room temper-ature, diluted with 1.5 liters of wa~er ~lus ice and al lowed to stand one-half hour. The precipitate was filt-ered to obtain 44 grams of a-cyano-~-tN-methyl-p-hydroxy~
anilino)acrylonitrile, melting point 187-189C. Five grams of this precipitate was treated with diethylsul~ate ; in aqueous sodium hydroxide to obtain 0.5 gram of a-cy-ano ~-(N-methyl-p-ethoxyanilino)acrylonitrile as a solid which melts at 147-148C. after recrystalli7.ation from ethyl acetate.
- Example 4 ~ .
Test films were prepared by adding the stabil- ;~
iæer, identif.ied in the Table below, to a ten percent so-lution of water-free unstablized polycarbonate in chloro-form~ casting, and drying at 20-25C. to obtain films one mil thick. The quantity of stabili~er added was one ~:
percent on weight of polycarbonate~ The films were ex-posed to ultraviolet light in an Atlas Xenon Weather--Ometer (no water spray in the Weather-Gmeter) until they became embrittled to the point of complete destructionO
.
- s - .
.
.
1 The ef~iciency of the stabili~ers in preventing degrada-tion is measured in terms of the time in hours to fail-ure of the film over a control sample which contains no stabilizer. The results were as follows:
Increase in Hours to Test Stabilizer* Failure over Control A I 3250**
B II 2750**
C I~I 2500**
D PA 1500***
Notes: *Stabilizer I was a-cyano-~-(M-cyanomethyl-p--methoxyanilino)acrylonitrile.
Stabilizer II was ~-cyano-~-~N-m~thyl-p-ethoxy-anilino)acrylonitrile.
Stabilizer PA was the prior art compound a-cyano-~-(N-methyl-p-mathoxyanilino)acrylonitrile of column S, lines 71-74 of Boyle et al., United ~tates Patent 3,079,366~
S~abili~er III was a~-cyano~ N-methyl-N-cyclo-hexylamino)acrylate.
**Average of two test~
*~*Single test These data show that the compoundR of the pre~-ent invention are about twice as effective in prolonging ~5 the resistance to ultraviolet radiation of polycarbonate when compared to the prior art compound of closest struc~
tural similari~y.
!
.
, , . ~
Polycarbonates can be formed into useful art-icles, such as pipje, hollow objects (e~g. bottles, tumb-lers, etc.), film, sheet, lenses, hard hats, etc. by suchprocess as in~ection molding, extrusion, blow-molding, etc. Because o~ their desirable properties and ease of forming m to useful articles, polycarbonates have attain- -ed wide commercial utilization. In some of these uses, ~ -the polycarbonate is exposed to ultraviolet radiation, su~h as in sunlight. As is well known, such exposure causes degradation of the polyoarbonate, leading to dis- ~ -coloration and embrittlement. It is an ob~ect of this invention to provide a novel compound URefUl, when in-corporated in-~polycarbonates, for inhibiting degradation .
~ 2 - ~ ~
, .~ .. ... . .. .
~Z7;~3 1 caused by ul ~aviolet radia-tion.
In accordance with the present invention, it has been Eound that a compo~nd having the formula:
CN
5A-N-CH=C /
wherein A is cyclohexyl or the group Z ~ wherein z is methoxy or ethoxy; R is CH3- or -CH2CH2CN and Rl is CN or -COOC2H5, is effective for inhibiting degradation of polycarbona~e on exposure to ultraviolet radiation.
This compound may be incorporated into poly-carbonate by any of the standard techniques, including milling, screw extruding, Banbury mixing, swelling, etc.
This compound is effective over a wide concentration range of about 0.1 to about 5.0 percent based on weight of polycarbonate. Preferably, it is used at a concen-tration of about 0.5 to about 2.0 percent on weight of polycarbonate. Other additives, such as dyes, foaming agents, pigments~ plasticizers, thermal stabilizers, etc.
may also be added to the polycarbonate for their usual , fun~tionsO
This invention is further illustrated in the following examples, wherein all parts are by weight un-less otherwise stated.
, ,. , :
Example 1 A mixture of 7.21 grams (0.064 mole) of N--methyl-M-cyclohexylamine and 10.3 grams (0~07 mole) of triethyl orthoformate was heated to 105C. and 6.9 grams -~
(0.06 mole) vf ethyl cyanoacetate was slowly added there- -to. The temperature gradually rose until ethanol began .. : , . .
27~3 1 to distill ov~r. After 11.4 milliliters of distillate was coll~cted, the reaction mixture was cooled to room temperature and poured into water. The aqueous mixture was extracted with diethyl ether, dried over anhydrous magnesium sulfate, and evaporated to obtain 14.0 grams of a dark oil. The oil was heated under vacuum to remove some distillable material and the remainder was extracted with three portions of hot cyclohexane which, on cooling, ~ave a total of 5.7 grams of light tan powder. ~he powder was recrystallized from cyclohexane, yie~ing 4.0 grams melting at 65-70C. Further recrystallization from pet-xoleum ether gave ethyl a-cyano-~-(N-methyl-N-cyclohexyl-amino)acrylate as fine white plates, melting point 71--72C.. AnalySiS: Calculated for Cl3H20N2o2: C~ 66-07;
H, 8.53; N, 11.86. Found: C, 65.98; H, 8.54; N, 11.72.
Example 2 A mixture of 35.2 grams (0.2 mole) of N-cyano-ethyl-p~methoxyaniline, 29.6 grams (0.2 mole) of triethyl orthoformate, and 13.2 grams (0.2 mole) of malononitrile was heated to 160C. over a period of thirty minute5 and then heated at 165C. for an additional thirty minutes.
Theresulting solution was cooled to room temperature and 100 milliliters of ethanol was added thereto. Fur-ther cooling of tha resulting solution in dry ice cau~ed an oil to separate. After separating the oil from the remainder of the material~ methanol was added to the oil causing it to crystallize. The crude product (5.5 grams, melting point 164-165C.) was;recrystallized from a mix~
tu.re of 125 mill:iliters o methanol and 25 milliliters of mathyl cellosolve to obtain 3 grams of product melting - .
:, ' 1 at 174--175C. This latter product was recrystallized from 50 milliliters of ethyl acetatP to obtain ~he de-sired ~-cyano~ N-cyanoethyl-p-methoxyanilino)acryloni-trile (Formula I, supra), melting at 175-177C.
Example 3 _ A mixkure of 62.5 grams (0.5 mole) of N-methyl--p-aminophenol, 74.0 grams (0.5 mole) of triethyl ortho- -formate, and 33.5 grams (0.5 mole) of malononitrile in 400 milliliters of 99.5% ethanol was prepared under a nitrogen atmosphere and heated at 75-78C. for seventeen hours~ The reaction mixture was cooled to room temper-ature, diluted with 1.5 liters of wa~er ~lus ice and al lowed to stand one-half hour. The precipitate was filt-ered to obtain 44 grams of a-cyano-~-tN-methyl-p-hydroxy~
anilino)acrylonitrile, melting point 187-189C. Five grams of this precipitate was treated with diethylsul~ate ; in aqueous sodium hydroxide to obtain 0.5 gram of a-cy-ano ~-(N-methyl-p-ethoxyanilino)acrylonitrile as a solid which melts at 147-148C. after recrystalli7.ation from ethyl acetate.
- Example 4 ~ .
Test films were prepared by adding the stabil- ;~
iæer, identif.ied in the Table below, to a ten percent so-lution of water-free unstablized polycarbonate in chloro-form~ casting, and drying at 20-25C. to obtain films one mil thick. The quantity of stabili~er added was one ~:
percent on weight of polycarbonate~ The films were ex-posed to ultraviolet light in an Atlas Xenon Weather--Ometer (no water spray in the Weather-Gmeter) until they became embrittled to the point of complete destructionO
.
- s - .
.
.
1 The ef~iciency of the stabili~ers in preventing degrada-tion is measured in terms of the time in hours to fail-ure of the film over a control sample which contains no stabilizer. The results were as follows:
Increase in Hours to Test Stabilizer* Failure over Control A I 3250**
B II 2750**
C I~I 2500**
D PA 1500***
Notes: *Stabilizer I was a-cyano-~-(M-cyanomethyl-p--methoxyanilino)acrylonitrile.
Stabilizer II was ~-cyano-~-~N-m~thyl-p-ethoxy-anilino)acrylonitrile.
Stabilizer PA was the prior art compound a-cyano-~-(N-methyl-p-mathoxyanilino)acrylonitrile of column S, lines 71-74 of Boyle et al., United ~tates Patent 3,079,366~
S~abili~er III was a~-cyano~ N-methyl-N-cyclo-hexylamino)acrylate.
**Average of two test~
*~*Single test These data show that the compoundR of the pre~-ent invention are about twice as effective in prolonging ~5 the resistance to ultraviolet radiation of polycarbonate when compared to the prior art compound of closest struc~
tural similari~y.
!
.
, , . ~
Claims (9)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A polycarbonate composition stabilized against the deteriorating effects of ultraviolet radia-tion by incorporating therein an effective amount of a compound having the formula:
wherein A is cyclohexyl or the group wherein Z is methoxy or ethoxy; R is CH3- or -CH2CH2CN and R1 is CN or -COOC2H5.
wherein A is cyclohexyl or the group wherein Z is methoxy or ethoxy; R is CH3- or -CH2CH2CN and R1 is CN or -COOC2H5.
2. A composition as defined in Claim 1 where-in said stabilizer is present in an amount of 0.1 to 5.0 percent on weight of polycarbonate.
3. A composition as defined in Claim 1 where-in said stabilizer is .alpha.-cyano-.beta.-(N-cyanoethyl-p-methoxy-anilino)acrylonitrile.
4. A composition as defined in Claim 1 where-in said stabilizer is .alpha.-cyano-.beta.-(N-methyl-p-ethoxyanilino) acrylonitrile.
5. A composition as defined in Claim 1 where-in said stabilizer is .alpha.-cyano-.beta.-(N-methyl-N-cyclohexyl-amino)acrylate ethyl ester.
6. A compound of the following formula:
wherein A is cyclohexyl or the group wherein Z is methoxy or ethoxy; R is CH3- or -CH2CH2CN and R1 is CN or -COOC2H5.
wherein A is cyclohexyl or the group wherein Z is methoxy or ethoxy; R is CH3- or -CH2CH2CN and R1 is CN or -COOC2H5.
7. A compound as defined in Claim 6 which is .alpha.-cyano-.beta.-(N-cyanoethyl-p-methoxyanilino)acrylonitrile.
8. A compound as defined in Claim 6 which is .alpha.-cyano-.beta.-(N-methyl-p-ethoxyanilino)acrylonitrile.
9. A compound as defined in Claim 6 which is .alpha.-cyano-.beta.-(N-methyl-N-cyclohexylamino)acrylate ethyl ester.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US05/615,872 US4076688A (en) | 1975-09-22 | 1975-09-22 | Polycarbonate stabilizers |
| US05/615,871 US3970639A (en) | 1975-09-22 | 1975-09-22 | Ethyl α-cyano β-(N-methyl-N-cyclohexylamino) acrylate stabilizer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1062723A true CA1062723A (en) | 1979-09-18 |
Family
ID=27087623
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA261,717A Expired CA1062723A (en) | 1975-09-22 | 1976-09-21 | Polycarbonate stabilizers |
Country Status (9)
| Country | Link |
|---|---|
| JP (1) | JPS5239749A (en) |
| AR (1) | AR209983A1 (en) |
| BR (1) | BR7606261A (en) |
| CA (1) | CA1062723A (en) |
| DE (1) | DE2641137A1 (en) |
| FR (1) | FR2324619A1 (en) |
| GB (1) | GB1553918A (en) |
| IT (1) | IT1066257B (en) |
| NL (1) | NL7609723A (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4216741A (en) * | 1979-03-05 | 1980-08-12 | Hazleton Systems, Inc. | Exposure chamber |
| JPS5852944U (en) * | 1981-09-30 | 1983-04-11 | 仁木 資浩 | Breeder cleaning equipment |
| JPS6074563U (en) * | 1983-10-28 | 1985-05-25 | 株式会社中西製作所 | Cabinet for laboratory animal cages |
| EP0675160A3 (en) * | 1994-03-29 | 1995-11-29 | Gen Electric | Ultraviolet light stabilized polyamide compositions. |
| DE10026628A1 (en) * | 2000-05-29 | 2001-12-06 | Bayer Ag | Transparent thermoplastic compositions |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE834104C (en) * | 1949-11-29 | 1952-03-17 | Farbwerke Hoechst Vormals Meis | Process for the production of condensation products |
| NL279734A (en) * | 1961-06-26 | |||
| NL137198C (en) * | 1961-12-21 | |||
| US3726662A (en) * | 1970-01-14 | 1973-04-10 | Monsanto Co | Herbicidal anilinomethylene-malononitriles |
-
1976
- 1976-08-19 GB GB34568/76A patent/GB1553918A/en not_active Expired
- 1976-08-25 AR AR264444A patent/AR209983A1/en active
- 1976-09-01 NL NL7609723A patent/NL7609723A/en not_active Application Discontinuation
- 1976-09-13 DE DE19762641137 patent/DE2641137A1/en not_active Withdrawn
- 1976-09-16 IT IT51301/76A patent/IT1066257B/en active
- 1976-09-20 JP JP51111926A patent/JPS5239749A/en active Pending
- 1976-09-21 CA CA261,717A patent/CA1062723A/en not_active Expired
- 1976-09-21 BR BR7606261A patent/BR7606261A/en unknown
- 1976-09-22 FR FR7628529A patent/FR2324619A1/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| NL7609723A (en) | 1977-03-24 |
| GB1553918A (en) | 1979-10-10 |
| BR7606261A (en) | 1977-06-14 |
| DE2641137A1 (en) | 1977-03-31 |
| FR2324619A1 (en) | 1977-04-15 |
| JPS5239749A (en) | 1977-03-28 |
| AR209983A1 (en) | 1977-06-15 |
| IT1066257B (en) | 1985-03-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US3678044A (en) | Substituted flavanones | |
| JP2597830B2 (en) | Crypto light stabilizers for coating materials. | |
| Reeve et al. | The reaction of styrene oxide with methanol | |
| US3153654A (en) | 3-pyrazolidinone carboxylic acid derivatives | |
| JPH0420913B2 (en) | ||
| CA1062723A (en) | Polycarbonate stabilizers | |
| US2739971A (en) | 5-benzal-3-n-cetyl-2-phenylimino-4-thiazolidone | |
| US3651091A (en) | Derivatives of 4-hydroxy coumarin and the preparation thereof | |
| US3231584A (en) | 1-phenyl-3, 3-dimethylspiro[(2'h-1'-benzopyran)-2', 2'-indoline] compound | |
| JPS6176483A (en) | Selected 2,2,6,6-tetramethyl-4-piperidinyl derivative | |
| US3970639A (en) | Ethyl α-cyano β-(N-methyl-N-cyclohexylamino) acrylate stabilizer | |
| US4076688A (en) | Polycarbonate stabilizers | |
| Koelsch | Electrophilic Properties of Ethyl 3-Phenylindone-2-carboxylate | |
| US4228067A (en) | UV Light stabilized polycarbonate composition | |
| US3117129A (en) | Salicyloyl pyridines | |
| Shriner et al. | Derivatives of Coumaran. IV. The Structure of Tectorigenin | |
| Katritzky et al. | An NMR study of the equilibria involved with benzotriazole, carbonyl compounds, and their adducts | |
| US4247692A (en) | Triazine derivatives | |
| DE1470171A1 (en) | Process for the preparation of dioxooctahydroanthracenes | |
| JPS6263576A (en) | Benzotriazole compound, composition and intermediate of same | |
| JP2000136176A (en) | Polymethine compound and its production and use | |
| US4147659A (en) | Novel antioxidant composition and process for making the same | |
| JP3163211B2 (en) | Chromane derivative and antioxidant composition | |
| US4115224A (en) | Radiation acid curable resin compositions and process for curing them | |
| Oki et al. | Estrogenic Biphenyls. II. 2′, 5′-Diethyl-4-methoxybiphenyl-4′-carboxylic Acid |