GB974111A - Organic compositions incorporating ultra-violet light absorbers - Google Patents

Organic compositions incorporating ultra-violet light absorbers

Info

Publication number
GB974111A
GB974111A GB965961A GB965961A GB974111A GB 974111 A GB974111 A GB 974111A GB 965961 A GB965961 A GB 965961A GB 965961 A GB965961 A GB 965961A GB 974111 A GB974111 A GB 974111A
Authority
GB
United Kingdom
Prior art keywords
methylene malononitrile
malononitrile
methylene
phenyl
ultra
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
Application number
GB965961A
Inventor
Albert Frederick Strobel
Sigmund Charles Catino
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
GAF Chemicals Corp
Original Assignee
General Aniline and Film Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by General Aniline and Film Corp filed Critical General Aniline and Film Corp
Priority to GB965961A priority Critical patent/GB974111A/en
Publication of GB974111A publication Critical patent/GB974111A/en
Expired legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K15/00Anti-oxidant compositions; Compositions inhibiting chemical change
    • C09K15/04Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds
    • C09K15/16Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing nitrogen

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

4, 41-dichlorodiphenylmethylenemalononitrile is made by condensation of 4, 41-dichlorobenzophenone with malononitrile: <FORM:0974111/C1/1> The reaction mixture, containing also ammonium acetate, glacial acetic acid, and benzene, is refluxed for 12 hours, the benzene distilled off, the residue diluted with water and filtered, crushed, slurried in water, filtered, washed with water, air-dried, distilled at 0.5 mm. at 185 DEG -200 DEG C, decolourized and recrystallized from an alcohol-water mixture.ALSO:An ultra-violet absorbing composition comprises an organic plastic material and, as ultra-violet absorber, a compound of the formula:- <FORM:0974111/C3/1> where Ar and Ar1 are aromatic carbocyclic nuclei devoid of nitro substituents and nuclear bonded amino groups. Preferably, from 0.1%-10% by weight of the ultra-violet absorber, based on the weight of the organic plastic material, is present. Ar and Ar1 may be benzene nuclei which may or may not be substituted. Specified compounds include:- diphenyl methylene malononitrile, phenyl-(4-n-dodecyloxyphenyl)-methylene malononitrile, 4, 41-ditolyl-methylene malononitrile, 3, 4-dimethyl diphenyl methylene malononitrile, 2, 41-dichlorodiphenyl methylene malononitrile, 4-41-dichlorodiphenyl methylene malononitrile, 4, 41-dibromodiphenyl methylene malononitrile, 4-chloro phenyl-41-methoxy phenyl methylene malononitrile, phenyl-(4-methoxy phenyl)-methylene malononitrile, phenyl-4-hydroxy phenyl methylene malononitrile, di-(4-hydroxyphenyl)-methylene malononitrile, phenyl-(4-biphenyl)-methylene malononitrile, di-(4-methoxyphenyl)-methylene malononitrile, di(benzene sulphonyl) methylene malononitrile, p-anisyl-3-4-xylyl methylene malononitrile and bis-(p-anisyl)-methylene malononitrile. A long list of other suitable compounds is given. Polyoxyalkylated derivatives of those compounds containing at least one reactive hydrogen atom e.g. phenols and amides, made by reaction with alkylene oxides, may also be used, such compounds having the formula <FORM:0974111/C3/2> where X represents the hydrocarbon residue of the oxyalkylating agent and n and m are integers from 0-100, at least one of these being at least one. Examples describe the preparation of ethoxylated derivatives of phenyl-4-hydroxy phenyl methylene malononitrile. The organic plastic material may be transparent or coloured. Materials specified include nitrocellulose, cellulose acetate, polyethylene, polyesters, e.g. polyethylene terephthalate, nylon, methyl methacrylate polymers, polyvinyl chloride and polyurethane foams, (see Division C2) formaldehyde polymers, synthetic rubber and carnauba wax compositions (see Divisions B1 and B2). Examples describe the preparation of (I) a nitrocellulose lacquer including diphenyl methylene malononitrile, "Cellolyn" (Registered Trade Mark), dibutyl phalate, butyl acetate, butanol and toluene, a nitro-cellulose lacquer (11) containing di-(4-methoxyphenyl) methylene malononitrile, or phenyl-4-hydroxyphenyl methylene malononitrile (14), or 3, 4-dimethyl diphenyl methylene malononitrile (14c) cellulose acetate sheet material from a composition containing 4, 41-dichlorodiphenyl methylene malononitrile (2)4, 41-dibromomodiphenyl methylene malononitrile (11), or phenyl (4-biphenyl) methylene malononitrile (10) or phenyl-4-hydroxyphenyl methylene malononitrile (14) or 3, 4-dimethyl diphenyl methylene malononitrile (14B) ethanol, ethyl acetate and methyl "Cellosolve" (Registered Trade Mark), (3) polyethylene sheet material from a composition containing phenyl-(4-n-dodecyloxyphenyl) methylene malononitrile, (5) polyester sheet material from a composition containing 2, 41-dichlorodiphenyl methylene-malononitrile (6) a leather coating composition (see also Divisions B1 and B2) including methyl methacrylate and phenyl-(4-methoxy phenyl) methylene malononitrile, (7) a synthetic rubber composition containing acrylonitrile-butadiene latex and 4, 41-ditolyl methylene malononitrile, and formaldehyde polymers containing 3, 4-dimethyl diphenyl methylene malononitrile (19), (20), and 4, 41-dichlorodiphenyl methylene malononitrile (21). Diphenyl methylene malononitrile, di-(4-hydroxyphenyl)-methylene malononitrile, and di(benzene sulphonyl) methylene malononitrile, preparations for which are given, may be used for the preparation of polyurethane and polyvinyl chloride foams against ultra-violet light, the foam material being immersed in a 5% solution of the ultra-violet light absorbing compound in methyl "Cellosolve" (Registered Trade Mark), squeezed and dried in a vacuum oven.ALSO:Leather is sprayed with an emulsion containing methyl methacrylate, and phenyl-4-(methoxyphenyl)-methylene malononitrile, as an ultra-violet light absorber, a dispersing agent, ammonium persulphate and water. The leather is then pressed and dried. Leather so treated shows less tendency to yellowing. In general, the ultra-violet light absorbers are compounds of the formula <FORM:0974111/B1-B2/1> where AR and AR1 are aromatic carbocyclic nuclei devoid of nitro substituents and nuclear bonded amino groups. Preferably, from 0,1-10% by weight of the ultra-violet absorber, based on the weight of the organic plastic material, is present. AR and AR1 may be benzene nuclei which may or may not be substituted. Specified compounds include diphenylmethylene malononitrile, phenyl-(4-n-dodecyloxy phenyl)-methylene malononitrile, 4,41-ditolylmethylene malononitrile, 3,4-dimethyl diphenyl methylene malononitrile, 2,41-dichlorodiphenyl methylene malononitrile, 4,41-dichlorodiphenyl methylene malononitrile, 4,41-dibromodiphenyl methylene malononitrile, 4-chloro phenyl-41-methoxy phenyl methylene malononitrile, phenyl-(4-methoxyphenyl)-methylene malononitrile, phenyl-4-hydroxy phenyl methylene malononitrile di-(4-hydroxyphenyl)-methylene malononitrile, phenyl-(4-biphenyl)-methylene malononitrile di(4-methoxyphenyl)-methylene malononitrile, di-(benzene sulphonyl) methylene malononitrile, p-anisyl-3,4-xylyl methylene malononitrile and bis-(p-anisyl)-methylene malononitrile. A long list of other suitable compounds is given. These compounds may also be incorporated in the translucent or transparent backings of pressure-sensitive adhesive tapes, or may be used as an overcoating in a transparent or translucent film coating base using any suitable material which will adhere to the tape back as the film former, e.g. a regenerated cellulose tape may be coated with a nitrocellulose or cellulose acetate lacquer containing the compound (see Examples 1 and 2). Further examples describe the preparation of emulsion furniture polishes containing the ultraviolet light absorbing compounds. Thus 4-chloro-41-methoxybenzophenone is included in a composition containing carnauba wax, turpentine, soap and water, and 3,4-dimethyl diphenyl methylene malononitrile is included in a composition containing carnauba wax, turpentine, sodium lauryl sulphate and water. Such polishes prevent the darkening of varnished wood on exposure to actinic radiation.ALSO:Polyethylene terephthalate and nylon fibres are dyed in a bath containing the disperse dye Celliton Turquoise MG at 190 DEG C. for 1 hour, and 0.05 gms of p-anisyl-3-4-xylylmethylene malononitrile dissolved in 5 mls. dimethyl formamide is added and dyeing continued for 1 hour. (Examples 22, 23). Fibres dyed in the presence of p-anisyl-3-4-xylylmethylene malononitrile, which is an ultra violet light absorber, show enhanced fastness to light. Similar results are obtained by dyeing polyethylene terephthalate fibres with a disperse dye of the formula:- <FORM:0974111/D1-D2/1> bis-(-p-anisyl) methylene malonotrile being used as the ultra violet light absorber. Hydrophilic materials e.g. paper and other cellulosic products e.g. cotton and jute may be proofed against ultra-violet light by treatment with polyoxyalkylated derivatives of phenyl-4-hydroxy phenyl methylene malonoitrile. (Example 15). In general, the ultra-violet absorbers are compounds of the formula:- <FORM:0974111/D1-D2/2> where AR and AR1 are aromatic carbocyclic nuclei devoid of nitro substituents and nuclear bonded amino groups. Preferably, from 0.1%-10% by weight of the ultra-violet absorber, based on the weight of the orgainic plastic material, is present. AR and AR1 may be benzene nuclei which may or may not be substituted. Specified compounds include:- diphenyl methylene malononitrile, phenyl-(4-n-dodecyloxy phenyl)-methylene malononitrile, 4, 41-ditolyl-methylene malononitrile, 3, 4-dimethyl diphenyl methylene malononitrile, 2, 41-dichlorodiphenyl methylene malononitrile, 4-41dichlorodiphenyl methylene malononitrile, 4, 41dibromodiphenyl methylene malononitrile, 4-chlorophenyl-41-methoxyphenyl methylene malononitrile, phenyl-(-4-methoxyphenyl)-methylene malononitrile, pheny-4-hydroxy phenyl methylene malononitrile di-(4-hydroxyphenyl)-methylene malononitrile, phenyl-(4-biphenyl)-methylene malononitrile di-(4-methoxyphenyl)-methylene malononitrile, di (benzene sulphonyl) methylene malononitrile, p-anisyl-3-4-xylyl methylene malononitrile and bis-(p-anisyl)-methylene malononitrile. A long list of other suitable compounds is given. Polyoxyalkylated derivatives of those compounds containing at least one reactive hydrogen atom, e.g. phenols and amides made by reaction with alkylene oxides, may also be used, such compounds having the formula <FORM:0974111/D1-D2/3> where X represents the hydrocarbon residue of the oxyalkylating agent and n and m are integers from 0-100, at least one of these being at least one.
GB965961A 1961-03-16 1961-03-16 Organic compositions incorporating ultra-violet light absorbers Expired GB974111A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
GB965961A GB974111A (en) 1961-03-16 1961-03-16 Organic compositions incorporating ultra-violet light absorbers

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB965961A GB974111A (en) 1961-03-16 1961-03-16 Organic compositions incorporating ultra-violet light absorbers

Publications (1)

Publication Number Publication Date
GB974111A true GB974111A (en) 1964-11-04

Family

ID=9876269

Family Applications (1)

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GB965961A Expired GB974111A (en) 1961-03-16 1961-03-16 Organic compositions incorporating ultra-violet light absorbers

Country Status (1)

Country Link
GB (1) GB974111A (en)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1208150A1 (en) * 1999-06-11 2002-05-29 Sydney Hyman Image making medium
US7225095B2 (en) 2005-06-10 2007-05-29 S.O.I.Tec Silicon On Insulator Technologies S.A. Thermal processing equipment calibration method
US8669325B1 (en) 1999-06-11 2014-03-11 Sydney Hyman Compositions image making mediums and images
US8921473B1 (en) 2004-04-30 2014-12-30 Sydney Hyman Image making medium
US9744800B2 (en) 1999-06-11 2017-08-29 Sydney Hyman Compositions and image making mediums
US9786194B2 (en) 1999-06-11 2017-10-10 Sydney Hyman Image making medium compositions and images
US11355027B2 (en) 2004-04-30 2022-06-07 Sydney Hyman Image making medium compositions and images

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1208150A1 (en) * 1999-06-11 2002-05-29 Sydney Hyman Image making medium
EP1208150A4 (en) * 1999-06-11 2005-01-26 Sydney Hyman Image making medium
US7629400B2 (en) 1999-06-11 2009-12-08 Sydney Hyman Image making medium
US8669325B1 (en) 1999-06-11 2014-03-11 Sydney Hyman Compositions image making mediums and images
US9744800B2 (en) 1999-06-11 2017-08-29 Sydney Hyman Compositions and image making mediums
US9786194B2 (en) 1999-06-11 2017-10-10 Sydney Hyman Image making medium compositions and images
US11341863B2 (en) 1999-06-11 2022-05-24 Sydney Hyman Compositions and image making media
US8921473B1 (en) 2004-04-30 2014-12-30 Sydney Hyman Image making medium
US11355027B2 (en) 2004-04-30 2022-06-07 Sydney Hyman Image making medium compositions and images
US7225095B2 (en) 2005-06-10 2007-05-29 S.O.I.Tec Silicon On Insulator Technologies S.A. Thermal processing equipment calibration method

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