EP1414799A2 - Amines empechees stabilisatrices de l'action de la lumiere, a base de composes carbonyle pluri-fonctionnels de carbonyle, et leur procede d'elaboration - Google Patents

Amines empechees stabilisatrices de l'action de la lumiere, a base de composes carbonyle pluri-fonctionnels de carbonyle, et leur procede d'elaboration

Info

Publication number
EP1414799A2
EP1414799A2 EP01994383A EP01994383A EP1414799A2 EP 1414799 A2 EP1414799 A2 EP 1414799A2 EP 01994383 A EP01994383 A EP 01994383A EP 01994383 A EP01994383 A EP 01994383A EP 1414799 A2 EP1414799 A2 EP 1414799A2
Authority
EP
European Patent Office
Prior art keywords
compound
hydrogen
group
alkyl
reaction mixture
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.)
Withdrawn
Application number
EP01994383A
Other languages
German (de)
English (en)
Inventor
Thomas Patrick Sassi
Ram Baboo Gupta
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.)
Cytec Technology Corp
Original Assignee
Cytec Technology 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 Cytec Technology Corp filed Critical Cytec Technology Corp
Priority claimed from PCT/US2001/049873 external-priority patent/WO2002057232A2/fr
Publication of EP1414799A2 publication Critical patent/EP1414799A2/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • C07D211/40—Oxygen atoms
    • C07D211/44—Oxygen atoms attached in position 4
    • C07D211/46—Oxygen atoms attached in position 4 having a hydrogen atom as the second substituent in position 4

Definitions

  • This invention relates generally to novel hindered amine light stabilizers (HALS) and their use as a protectant against ultraviolet radiation or light (“UV light”). Also included are concentrates and articles including such stabilizers, and methods of making all of the above.
  • HALS hindered amine light stabilizers
  • UV light ultraviolet radiation
  • UV light or radiation can cause degradation of a variety of materials, especially polymeric materials. Often this results in embrittlement or yellowing of the materials, which may be in the form of molded articles, extruded articles, films, tapes, coatings, or the like. However, this degradation can be inhibited by the incorporation of light stabilizers in, or on, the polymeric articles.
  • the most commonly used stabilizers are UV-absorbers, hindered amine light stabilizers (“HALS”), and phenolic and non-phenolic antioxidants.
  • HALS scavenge free radicals formed in polymeric material when the material is exposed to UV light.
  • the functional component of the HALS molecule is typically the 2,2,6,6-tetraalkylpiperidine moiety.
  • the 2,2,6,6- tetraalkylpiperidine moiety is anchored to a carbonyl or melamine functional group (See, e.g., U.S. Patent ⁇ os. 4,331,586; 3,840,494; Re. 31,342; Re. 30,385; 3,640,928; 4,086,204; 4,265,805).
  • Anchoring the 2,2,6,6-tetraalkylpiperidine moiety to a carbonyl or melamine functional group typically lowers the volatility and extractability of a stabilizer.
  • Low volatility is an important characteristic of light stabilizers in applications where high temperatures are encountered, which occurs frequently in the processing of thermoplastics and in the curing of thermoset resins and coatings. Often, high temperatures are also present in the end-use applications for the stabilized material. Low volatility helps prevent loss of the stabilizer during processing, curing, and high temperature end uses.
  • HALS molecules containing the 2,2,6,6- tetraalkylpiperidine group anchored to a carbonyl group are made by reacting a 2,2,6,6- tetraalkylpiperidin-4-ol or 4-amino-2,2,6,6-tetramethylpiperidine with a carboxylic acid chloride or ester.
  • U.S. Patent Nos. Re. 31,342, 4,021,432 and 4,049,647 disclose a class of 1- and 4- substituted piperidines that are stabilizers for organic materials.
  • the stabilizers are produced by reacting the corresponding 1 -substituted piperidinols with acid chlorides, or the corresponding 4-substituted piperidines, with a compound introducing a residue into the 1 -position of the piperidine moiety.
  • U.S. Patent No. 3,840,494 discloses a polymer composition stabilized against photo- and thermal deterioration by incorporating therein acid esters of 4- piperidinol derivatives in an amount sufficient to prevent such deterioration.
  • the acid esters of the 4-piperidinol derivatives are prepared by reacting the 4-piperidinol derivative with a carboxylate ester in xylene with sodium hydroxide. For example, the reaction of 4-hydroxy-2,2,6,6-tetramethylpiperidine with ethyl benzoate produces 4- benzoyloxy-2 ,2,6, 6-tetramethylpiperidine .
  • 2,2,6,6-tetramethylpiperidin-4-ol can be reacted with diesters or diacid chlorides to produce diester-HALS. Also, the 2,2,6,6- tetramethylpiperidin-4-ol can be reacted with a diisocyanate to produce a diurethane-
  • alkoxycarbonylamino alkanoates are known for various other uses other than light stabilization and can be prepared by a variety of synthetic schemes (See, e.g., Effenberger, F.; Drauz, K.; Foerster, S.; Mueller, W., Chem. Ber., 114(1), 173-89; Dixit, A.; Tandel, S.; Rajappa, S.; Tett. Lett.; 35(33), 6133-4, Duong, et al., Aust. J.
  • U.S. Patent No. 5,574,162 discloses 1-hydrocarbyloxy substituted HALS, which also contain reactive functional groups that chemically attach to selected polymer substrates by condensation reactions.
  • TINUVIN 622 is a commercially available oligomeric HALS produced by Ciba Specialty Chemicals Inc. of Hawthorne, NY. TINUVIN 622 can be produced by the reaction of dimethyl succinate with N-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-piperidinol.
  • U.S. Patent No. 4,223,412 discloses condensation and addition polymers wherein the recurrent molecular unit contains a poly alky lpiperidine radical that are useful as light stabilizers for plastics.
  • the copolymer is formed by copolymerization or copolycondensation of polyalkylpiperidine containing monomers with polyalkylpiperidine free monomers such as caprolactam.
  • U.S. Patent No. 6,271,377 discloses HALS which are substituted on the N-atom by N-alkyloxy moieties containing one to three hydroxyl groups.
  • U.S. Patent No. 4,331,586 to Hardy discloses oligomers that contain at least one piperidyl moiety in the repeating unit for use as light stabilizers. While providing protection for polymeric materials, such as polypropylene, polymeric films containing the disclosed oligomeric HALS became brittle after exposure to UV light for about 1 ,700 hours.
  • HALS compounds may be used individually or in combination with other light stabilizers to inhibit photodegradation of polymers.
  • UV light absorbers such as benzotriazoles and benzophenones
  • HALS compounds were initially used to stabilize polymeric materials and to prevent degradation of such materials from exposure to UV light.
  • UV light absorbers were more effective than UV light absorbers alone, and thus, UV light absorbers are presently used in combination with at least one HALS compound in most conventional applications (See, e.g. , United States Patent Nos. 4,740,542; 4,619,956; 5,461,151; 5,721,298).
  • HALS compounds are often employed in combination with other stabilizers, such as antioxidants (See, e.g., United States Patent No.
  • U.S. Patent No. 4,619,956 discloses a method of stabilizing a polymer film, coating, or molded article against the action of light, moisture and oxygen by incorporating a HALS compound and a tris-aryl-s-triazine UV light absorber into a polymer.
  • the HALS compound is a 2,2,6,6-tetraalkylpiperidine compound, salt, or metal complex
  • the UV light absorber is a tris-aryl-2-triazine of formula
  • X, Y, and Z are each aromatic carbocyclic groups, and at least one of the aromatic groups has a hydroxy group ortho to the point of attachment to the triazine ring.
  • R 1 to R 9 is hydrogen, hydroxy, alkyl, alkoxy, sulfonic, carboxy, halo, haloalkyl, or acylamino.
  • Each of the UV light absorbers and HALS compound are used in an amount of from about 0.01 to 5 percent by weight, but only formulations having equal amounts of UV light absorber and HALS compound are exemplified. The compositions are effective in stabilizing the polymeric material, which does not begin to lose gloss or turn yellow until after about 1,000 to 2,400 hours of exposure to UV light.
  • the invention provides a new class of HALS.
  • the HALS of the invention have the formula (I):
  • n is an integer from 1 to 15, m is either 0 or 1;
  • R a , R b , R°, and R d are each a hydrogen or a hydrocarbyl group;
  • Y is CO-(CR e R f ) p wherein R e and R are each a hydrogen or hydrocarbyl group and p is zero or an integer from 1 to 20 or CO-C 6 H 4 -, wherein the substitution pattern on the phenylene group is an ortho, meta, or para substitution pattern and one or more of the hydrogens of the phenylene group may be substituted by a hydrocarbyl group or a functional group;
  • Z is -O- or -NG-, wherein G is H, C r C 12 alkyl or the radical R; wherein R is
  • R 1 is hydrogen, C r C 18 alkyl, O, OH, CH 2 CN.
  • R 2 is hydrogen, C r C 8 alkyl, or benzyl;
  • R 3 , R 4 , R 5 , and R 6 are each a hydrogen, C r C 8 alkyl, benzyl or phenethyl, or two geminal R moieties, which together with the carbon to which they are attached form a C 5 -C 10 cycloalkyl;
  • R is a H, C r C 4 alkyl, O, OH; C r C I8 alkoxy, C r C 18 hydroxyalkoxy, C 5 -C 12 cycloalkoxy or C 5 -C 12 hydroxycycloalkoxy, R 2 is H, or C r C 4 alkyl; R 3 , R 4 , R 5 , and R 6 are each H or C r C 4 alkyl; R a , R b , R c , and R d , are each a hydrogen, aromatic, or C r C 4 alkyl; and n is from 4 to 11.
  • R 1 is H or CH 3 ;
  • R 3 , R 4 , R 5 , and R 6 are each CH 3 ;
  • R 2 is hydrogen;
  • R a , R b , R c and R d are each a hydrogen;
  • Z is - O-;
  • m is 0 or 1; and
  • n is and integer from 4 to 10.
  • the invention also provides a method of forming the HALS of the invention.
  • the HALS of the invention may be prepared by combining one or more multifunctional carbonyl compounds of general structure:
  • n is an integer from 1 to 15, m is either 0 or 1;
  • R a , R , R c , and R are each a hydrogen or a hydrocarbyl group;
  • Y is CO-(CR e R f ) p , wherein R e and R f are each a hydrogen or hydrocarbyl group and p is zero or an integer from 1 to 20 or CO-C 6 H 4 -, wherein the substitution pattern on the phenylene group is an ortho, meta, or para substitution pattern and wherein one or more of the hydrogens of the phenylene group may be substituted by a hydrocarbyl group or a functional group;
  • R 1 is hydrogen, C r C I8 alkyl, O, OH, CH 2 CN, C r C 18 alkoxy, C,-C 18 hydroxyalkoxy, C 5 -C 12 cycloalkoxy, C 5 -C 12 hydroxycycloalkoxy, C 3 -C 6 alkenyl, C,-C 18 alkynyl, C 7 -C 9 phenylalkyl, unsubstituted or substituted on the phenyl with 1, 2 or 3 C r C 4 alkyls, or an aliphatic C,-C 8 acyl;
  • R 2 represents hydrogen, C r C 8 alkyl, or benzyl;
  • R 3 , R 4 , R 5 , and R 6 are each a hydrogen, C r C 8 alkyl, benzyl or phenethyl, or two geminal R moieties, which together with the carbon to which they are attached form a
  • the one or more multifunctional carbonyl compounds may be present in an amount of about 0.025 to 2.5 M and the molar ratio of the one or more multi-functional carbonyl compounds to the one or more 1 -substituted piperidin-4-ol or 4-aminopiperidines may be from about 20: 1 to 1:5.
  • the 4-piperidin-4-ol may be l,2,2,6,6-pentamethyl-4- piperidinol or 2,2,6,6-tetramethyl-4-piperidinol and the multi-functional carbonyl compound may be methyl 6-(methoxycarbonylamino)hexanoate, butyl 6- (butoxycarbonylamino) undecanoate, methyl 6-(butoxycarbonylamino)undecanoate, butyl 6-(methoxycarbonylamino)undecanoate, methyl 6-(methoxycarbonylamino)undecanoate, and combinations thereof.
  • the reaction mixture may include a solvent.
  • the solvent may be one or more of benzene, toluene, or one or more xylenes.
  • the reaction mixture may also include a catalyst.
  • the catalyst may be a base catalyst or an acid catalyst.
  • the base catalyst may be methoxide.
  • the acid catalyst may be a Lewis acid.
  • the Lewis acid may be aluminum trichloride, aluminum tribromide, trimethylaluminum, boron trifluoride, boron trichloride, l,3-diacetoxy-l,l,3,3-tetrabutyldistannoxane, zinc dichloride, titanium tetrachloride, titanium (IV) isopropoxide, tin dichloride, tin tetrachloride, a tetraalkoxytitanate, and mixtures thereof.
  • the catalyst may be present in an amount of less than about 30 mole percent based on the molar quantity of the multi-functional carbonyl compound.
  • n is an integer from 1 to 15 and R a , R b , R°, and R d are each a hydrogen or a hydrocarbyl group with one or more carbonyl compounds of general structure o
  • DO— (Y) m — C wherein m is either 0 or 1, D is a hydrocarbyl group and B is a hydrocarbyl group or OD and Y is CO-(CR e R f ) p , wherein R e and R f are each a hydrogen or hydrocarbyl group and p is zero or an integer from 1 to 20 or CO-C 6 H 4 -, and the substitution pattern on the phenylene group may be an ortho, meta, or para substitution pattern, and one or more of the hydrogens of the phenylene group may be substituted by a hydrocarbyl group or other functional group; and one or more 1 -substituted piperidin-4-ol or 4-aminopiperidines of general structure
  • R 1 is hydrogen, C r C 18 alkyl, O, OH, CH 2 CN, C r C 18 alkoxy, C,-C, 8 hydroxyalkoxy, C 5 -C 12 cycloalkoxy, C 5 -C 12 hydroxycycloalkoxy, C 3 -C 6 alkenyl, C r C 18 alkynyl, C 7 -C 9 phenylalkyl, unsubstituted or substituted on the phenyl with 1, 2 or 3 C r C 4 alkyls, or an aliphatic C r C 8 acyl;
  • R 2 represents hydrogen, C r C 8 alkyl, or benzyl;
  • R 3 , R 4 , R 5 , and R 6 are each a hydrogen, C r C g alkyl, benzyl or phenethyl, or two geminal R moieties, which together with the carbon to which they are attached, form
  • the carbonyl compound may be a dialkyl carbonate, a dialkyl oxalate, a dialkyl diester, an alkyl ester, or a mixtures thereof.
  • the reaction mixture may include a catalyst.
  • the catalyst may be a base catalyst or an acid catalyst.
  • the base catalyst may be methoxide.
  • the acid catalyst may be a Lewis acid.
  • the Lewis acid may be aluminum trichloride, aluminum tribromide, trimethylaluminum, boron trifluoride, boron trichloride, 1,3-diacetoxy-l ,1,3.3- tetrabutyldistannoxane, zinc dichloride, titanium tetrachloride, titanium (IN) isopropoxide, tin dichloride, tin tetrachloride, a tetraalkoxytitanate, and mixtures thereof.
  • the reaction mixture may also include a solvent.
  • the solvent may be one or more of benzene, toluene, or one or more xylenes.
  • concentration of lactam may be from about 0.025 to 10 M.
  • the ratio of lactam to carbonyl compound may be from about 2: 1 tol :4; the ratio of lactam to 1- substituted piperidin-4-ol or 4-aminopiperidine may be from about 1: 1; to 1:6; and the catalyst may be present in an amount of less than about 30 mole percent relative to the amount of carbonyl compound.
  • n is from 3 to 12 and the catalyst is a base catalyst or a Lewis acid.
  • the lactam comprises caprolactam or laurolactam.
  • the invention also provides for a method of forming a multi-functional carbonyl compound having the structure:
  • n is an integer from about 1 to 15, m is either 0 or 1;
  • R a , R b , R c , and R d are each a hydrogen or a hydrocarbyl group;
  • Y is CO-(CR e R) p , wherein R e and R f are each a hydrogen or hydrocarbyl group and p is an integer from about 0 to 20, preferably 0 to 10, or CO-
  • substitution pattern on the phenylene group is an ortho, meta, or para substitution pattern and one or more of the hydrogens of the phenylene group may be substituted by a hydrocarbyl group or a functional group; D is a hydrocarbyl group; and B is either OD or D.
  • the method involves combining one or more lactams of general structure
  • n and R ⁇ R b , R c , and R d are as defined above with one or more carbonyl compounds of general structure
  • D, B, Y, and m are as defined above; and a Lewis acid catalyst to provide a reaction mixture; reacting the reaction mixture for a sufficient time to produce the multi- functional carbonyl compound; and recovering the multi-functional carbonyl compound from the reaction mixture.
  • n is from about 3 to 12.
  • the Lewis acid catalyst may be aluminum trichloride, aluminum tribromide, trimethylaluminum, boron trifluoride, boron trichloride, zinc dichloride, titanium tetrachloride, titanium (IV) isopropoxide, tin dichloride, tin tetrachloride, a tetraalkoxytitanate, and mixtures thereof.
  • the reaction mixture may also include a solvent.
  • the solvent may be one or more of benzene, toluene, or one or more xylenes.
  • the concentration of the one or more lactams may be from about 0.075 M to 10 M.
  • the mole ratio of the one or more lactams to the one or more carbonyl compounds may be from about 1:10 to 5:1.
  • the catalyst may be present in an amount of less than about 30 mole percent relative to the amount of carbonyl compound.
  • the lactam may be caprolactam or laurolactam.
  • Another method for forming the multi-functional carbonyl compound involves combining one or more lactams of general structure
  • n, R a , R b , R c , and R d are as defined above with one or more carbonyl compounds of general structure
  • D, B, Y, and m are as defined above; and a basic catalyst to provide a reaction mixture; reacting the reaction mixture at a temperature less than about 20 °C for a sufficient time to produce the multi-functional carbonyl compound; and recovering the multi-functional carbonyl compound from the reaction mixture.
  • the temperature may less than about 15°C.
  • the reaction may be conducted in a solvent.
  • the base catalyst may be methoxide.
  • the HALS compounds of the present invention are based on the reaction of a lactam with the carbonyl group of a carbonyl compound.
  • the HALS compounds of the present invention include compounds where the functional component of the HALS compound, a piperidin-4-ol or 4 aminopiperidine group, is anchored to the terminus of a hydrocarbon chain by an ester functionality or an amide functionality and wherein the other end of the hydrocarbon chain terminates with an amide linkage that is not a HALS functionality. These may be referred to as
  • esters/amide HALS compounds and "amide/amide HALS compounds.”
  • both ends of the hydrocarbon chain can terminate with the piperidin-4-ol or 4 aminopiperidine group.
  • the HALS molecule is anchored to one terminus of the hydrocarbon chain by an ester functionality and to the other terminus by a urethane functionality. These may be referred to as “ester/urethane HALS compounds.”
  • the HALS molecule may be anchored to one terminus of the hydrocarbon chain by an amide functionality and to the other terminus by a urea functionality.
  • amide/urea HALS compounds These may be referred to as "amide/urea HALS compounds.”
  • the piperidin-4-ol or 4 aminopiperidine group is bonded by an ester linkage to one terminus of the hydrocarbon chain and by an oxamate linkage at the other terminus of the hydrocarbon chain to provide "ester/oxamate HALS compounds”
  • the piperidin-4-ol or 4 aminopiperidine group is bonded by an amide linkage to one terminus of the hydrocarbon chain and by an oxamide linkage at the other terminus of the hydrocarbon chain to provide "amide/oxamide HALS compounds.”
  • n is an integer from 1 to 15, preferably 4 to 11; m is either 0 or 1; R ⁇ R b , R°, and R d , are each a hydrogen or a hydrocarbyl group; Y is CO-(CR e R f ) p , wherein R e and R f are each a hydrogen or hydrocarbyl group and p is zero or an integer from 1 to 20 or CO-C 6 H 4 -, and the substitution pattern on the phenylene group, i.e., -C 6 H 4 -, may be an ortho, meta, or para substitution pattern, in addition one or more of the hydrogens of the phenylene group may be substituted by a hydrocarbyl group or other functional group commonly found in organic molecules; Z is -O- or NG, wherein G is H, C r C 12 alkyl or the radical R; wherein the radical R represents:
  • R 1 is hydrogen, C,-C lg alkyl, O, OH, CH 2 CN, C,-C 18 alkoxy, C r C lg hydroxyalkoxy, C 5 -C 12 cycloalkoxy, C 5 -C 12 hydroxycycloalkoxy, C 3 -C 6 alkenyl, C r C 18 alkynyl, C 7 -C 9 phenylalkyl, unsubstituted or substituted on the phenyl with 1, 2 or 3 C,-C 4 alkyls, or an aliphatic C r C 8 acyl;
  • R 2 is hydrogen, C r C 8 alkyl, or benzyl;
  • R 3 , R 4 , R 5 , and R 6 are each a hydrogen, C r C 8 alkyl, benzyl or phenethyl, or two geminal R moieties, which together with the carbon to which they are attached, form a C 5 -C 10 cyclo
  • hydrocarbyl is a monovalent hydrocarbon group in which the valency is derived by extraction of a hydrogen from a carbon.
  • Hydrocarbyl includes, for example, aliphatics (straight and branched chain), cycloaliphatics, aromatics and mixed character groups (e.g. , aralkyl and alkaryl). Hydrocarbyl also includes groups with internal unsaturation and activated unsaturation.
  • hydrocarbyl includes, but is not limited to, alkyl, cycloalkyl, aryl, aralkyl, alkaryl, alkenyl, cycloalkenyl, and alkynyl, typically having from about 1 to 24 carbon atoms, preferably having from about 1 to 12 carbon atoms.
  • a hydrocarbyl may contain one or more carbonyl groups (which is/are included in the carbon count) and/or a heteroatom or heteroatoms (such as at least one oxygen, nitrogen, sulfur, or silicon) in the chain or ring.
  • a hydrocarbyl may have one or more of the hydrogens of the hydrocarbon group replaced by a functional group commonly found in organic molecules.
  • the phrase "functional group commonly found in organic molecules” means non-hydrocarbyl groups that are typically found in organic molecules including, but not limited to, halides, cyano groups, amino groups, thiol groups, carboxylate groups, hydroxyl groups, sulfonate groups, nitroso groups, nitro groups, and the like.
  • hydrocarbylene in the context of the present invention is a divalent hydrocarbon group in which both valencies derive by abstraction of hydrogens from carbon atoms. Included within the definition of hydrocarbylene are the same groups as indicated above for hydrocarbyl and functional hydrocarbyl with, of course, the extra valency (for example, alkylene, alkenylene, arylene, etc.).
  • R 1 is H, C r C 4 alkyl,C r C 18 alkoxy, C 5 -C 12 cycloalkoxy, O, or OH;
  • R 2 is H, or C r C 4 alkyl;
  • R 3 , R ⁇ R 5 , and R 6 are H or C l -C 4 alkyl;
  • R a , R b , R c , and R d are each a hydrogen, aromatic, or C r C 4 alkyl; and
  • n is from about 2 to 10.
  • R represents the 2,2,6,6- tetramethylpiperidine radical (i.e.
  • R 3 , R 4 , R 5 , R 6 are methyl and R 2 is hydrogen) or 1,2,2,6,6-pentamethylpiperidine radical (i.e. , R 2 , R 3 , R 4 , R 5 , and R 6 are methyl); R a , R b , R c , and R d are each a hydrogen; Z is -O-; m is 0 or 1; and n is 4 to 10.
  • HALS compounds of the formula (I) are typically prepared by the reaction of a multi-functional carbonyl compound with a 4-piperidin-ol or a 4- aminopiperidine moiety.
  • the multi-functional carbonyl compound has the general structure:
  • n is an integer from 1 to 15, preferably 4 to 11; m is either 0 or 1; R a , R b , R° and R d , are each a hydrogen or a hydrocarbyl group; Y is CO-(CR e R f ) p , wherein R e and R f are each a hydrogen or hydrocarbyl group, and p is zero or an integer from about 1 to 20 or CO-C 6 H 4 -, and the substitution pattern on the phenylene group, i.e.
  • -C 6 H 4 - is an ortho, meta, or para substitution pattern, in addition one or more of the hydrogens of the phenylene group may be substituted by a hydrocarbyl group or a functional group commonly found in organic molecules; D is a hydrocarbyl group; and B is either OD or D; and reacting the carbonyl compound with a 1 -substituted piperidin-4-ol or 4- aminopiperidine of general structure:
  • Z is OH or NHG, wherein G is H or C r C 12 alkyl or the radical R (wherein R is defined above); and R 1 is hydrogen, C,-C 18 alkyl, O, OH, CH 2 CN, C r C 18 alkoxy, C,-C 18 hydroxyalkoxy, C 5 -C 12 cycloalkoxy, C 5 -C 12 hydroxycycloalkoxy, C 3 -C 6 alkenyl, C--C lg alkynyl, C 7 -C 9 phenylalkyl, unsubstituted or substituted on the phenyl with 1, 2 or 3 C r C 4 alkyls, or an aliphatic C r C 8 acyl; R 2 is hydrogen, C r C 8 alkyl, or benzyl; R 3 , R 4 , R 5 , and R 6 are each a hydrogen, C r C 8 alkyl, benzyl or phenethyl, or two
  • the reaction between the multi-functional carbonyl compound and the 4- piperidin-ol or 4-aminopiperidine moiety is conducted for a sufficient time for the compound of formula (I) to be formed.
  • the phrase "conducted for a sufficient time for the compound of [a given formula] to be formed” means that after the reactants are combined they are allowed to react for sufficient time to produce a detectable amount of the desired compound, i.e. , the compound of a given formula.
  • detectable amount of a compound is meant an amount of the compound that can be detected by any means readily available to those of ordinary skill in the art.
  • Means for detecting the formation of a compound in a reaction mixture include, but are not limited to, thin layer chromatography (TLC), high performance liquid chromatography (HPLC), gas chromatography (GC), column chromatography, nuclear magnetic resonance spectroscopy (NMR), infra-red (IR) spectroscopy, ultra-violet (UV) or visible (VIS) spectroscopy, and wet-chemical analysis, for example.
  • TLC thin layer chromatography
  • HPLC high performance liquid chromatography
  • GC gas chromatography
  • NMR nuclear magnetic resonance spectroscopy
  • IR infra-red
  • UV ultra-violet
  • VIS visible
  • wet-chemical analysis for example.
  • the length of time for the desired compound to be produced is dependent on a number of variables and, thus, cannot be generalized.
  • the reaction time is dependent on the temperature, the pressure, the specific reactants (i.e.
  • the reaction may be carried out in the absence of a solvent or in the presence of a solvent.
  • a solvent either the multi-functional carbonyl compound or the 4-piperidin-ol or 4-aminopiperidine may be present in an excess and employed as the reaction medium.
  • the multifunctional carbonyl compound and 4-piperidin-ol or 4-aminopiperidine can be present in a stoichiometric amount.
  • the multi-functional carbonyl compound and 4-piperidin-ol or 4- aminopiperidine may be present in a melt.
  • the reaction is carried out in an organic solvent. Any solvent compatible with the reagents may be used.
  • Preferred solvents for use in the method of the invention include, but are not limited to, hydrocarbon solvents such as a saturated alkanes; benzene; toluene; xylenes; halogenated hydrocarbons; ethers such as ethyl ether; cyclic ethers such as tetrahydrofuran and dioxane; amides such as dimethylformamide; sulfoxides such as dimethylsulf oxide; ketones such as 2-butanone or methyl isobutyl ketone; and the like; or combinations thereof.
  • the more preferred solvents include toluene, benzene, and xylenes.
  • the concentration of the multifunctional carbonyl in the organic solvent is generally from about 0.025 M to 2.5 M, preferably from about 0.125 M to 2 M, and more preferably from about 0.25 M to 1.35 M.
  • the molar ratio of the 1 -substituted piperidin-4-ol or 4-aminopiperidine to the multifunctional carbonyl compound is between about 20:1 and 1:5, preferably between about 10:1 and 1:3, and more preferably between about 5:1 and 1:5.
  • the reaction of the multi-functional carbonyl compound and 4-piperidin-ol or 4-aminopiperidine produces an alcohol of structure DOH.
  • the alcohol is removed from the reaction mixture as it is formed to help drive the reaction to completion.
  • the alcohol may be removed by any means available to those of ordinary skill in the art such as distillation and or azeotropic distillation.
  • the reaction is conducted in the presence of a catalyst.
  • the optional catalyst may be a basic or an acidic catalyst.
  • the phrase "base catalyst" means any compound that can abstract a proton.
  • Base catalysts suitable for the invention include, but are not limited to, alkoxide ions; hydroxide ion; amide ion; and amines such as triethylamine, DBU (1,8-diazabicyclo [5.4.0] undec-7-ene), or DBN (1,5-diazabicyclo [4.3.0] non-5-ene).
  • DBU 1,8-diazabicyclo [5.4.0] undec-7-ene
  • DBN 1,5-diazabicyclo [4.3.0] non-5-ene
  • the phrase "acid catalyst” means any inorganic or organic acid with at least one acidic proton or a Lewis acid.
  • the organic acids include any organic compound that contains at least one acidic functional group, including one or more of RCO 2 H, RSO 3 H, RSO 2 H, RSH, ROH, RPO 3 H, RPO 2 H, wherein R is a hydrocarbyl group.
  • Preferred protic acids include HC1, HBr, HI, HNO 3 , HNO 2 , H 2 S, H 2 SO 4 , H 3 PO 4 , H 2 CO 3 , acetic acid, formic acid, propionic acid, butanoic acid, benzoic acid, phthalic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, methanesulfonic acid, and p- toluenesulfonic acid, or mixtures thereof.
  • Lewis acids suitable for the method of the invention include, but are not limited to, aluminum halides, alkylalummum halides, boron halides, dialkyl tin oxides and derivatives thereof, tin halides, titanium halides, lead halides, zinc halides, iron halides, gallium halides, arsenic halide, copper halides, cadmium halides, mercury halides, antimony halides, and the like.
  • Preferred Lewis acids include aluminum trichloride, aluminum tribromide, 1,3,-diacetoxy-l, 1,3,3- tetrabutyldistannoxane, trimethylaluminum, boron trifluoride, boron trichloride, zinc dichloride, titanium tetrachloride, titanium (IV) isopropoxide, tin dichloride, tin tetrachloride, a tetraalkoxytitanate or a mixture thereof.
  • the acid or base catalyst may also be a solid supported catalyst such as amberlyst catalysts.
  • the catalyst is typically added in an amount of less than about 30 mole percent based on the molar quantity of the multi-functional carbonyl compound, preferably less than about 20 mole percent based on the molar quantity of the multifunctional carbonyl compound, more preferably less than about 10 mole percent based on the molar quantity of the multi-functional carbonyl compound, and most preferably less than about 5 mole percent by weight based on the weight of the multi-functional carbonyl compound.
  • the preferred base catalyst for use in the method of the invention is methoxide ion.
  • the preferred acid catalyst is a Lewis acid.
  • the preferred Lewis acid is 1,3-diacetoxy-l, 1,3,3- tetrabutyldistannoxane.
  • the reaction is allowed to proceed for a time that is less than about 20 hours and more preferably less than aboutlO hours.
  • the reaction temperature is from about room temperature to 150 °C, for example, up to the boiling point of the solvent.
  • the reactions are ran at atmospheric pressure.
  • Representative reaction conditions for forming the compound of formula (I) are provided in the examples.
  • the compound of formula (I) is formed, it is recovered from the reaction mixture by any means available to those of ordinary skill in the art. Methods for recovering compounds from a reaction mixture include, but are not limited to, chromatography, recrystallization, distillation, extraction, and the like. More than one method may be used to recover a compound from the reaction mixture.
  • the substituted 4-piperidin-4-ol is 1,2,2,6,6- pentamethyl-4-piperidinol or 2,2,6,6-tetramethyl-4-piperidinol and the multi-functional carbonyl compound is methyl 6-(methoxycarbonylamino)hexanoate, butyl 6- (butoxycarbonylamino) undecanoate, methyl 6-(butoxycarbonylamino)undecanoate, butyl 6-(methoxycarbonylamino)undecanoate, or methyl 6- (methoxycarbonylamino)undecanoate .
  • the multi-functional carbonyl compounds can be prepared by any method available to those of ordinary skill in the art.
  • the multi-functional carbonyl compound is prepared by reacting a lactam with a carbonyl compound.
  • the multi-functional carbonyl compound can be prepared by the base catalyzed reaction of a lactam and a carbonyl compound according to the method disclosed in U.S. Patent No. 5,300,678, the contents of which are expressly incorporated herein by reference thereto.
  • lactam may be used according to the method of the invention.
  • the size of the lactam ring is from about 4 to 13 atoms. More preferably the lactam is caprolactam or laurolactam.
  • the carbonyl compound must include at least one reactive carbonyl group.
  • "Reactive carbonyl group” means any carbonyl group that is attached to a good leaving group and, thus, is activated towards nucleophilic acyl substitution.
  • the reactive carbonyl group may be, for example, an ester or acid chloride.
  • the carbonyl compound is an ester.
  • More preferred carbonyl compounds include dialkyl carbonates, dialkyl oxalates, dialkyl diesters, or alkyl esters.
  • the general structure of the carbonyl compound is Q— (Y)m— ⁇
  • m is either 0 or 1
  • Q is a good leaving group, such as chloride or OD
  • D is a hydrocarbyl group, preferably methyl
  • B is Q or a hydrocarbyl group
  • Y is CO-(CR e R f ) p
  • R e and R f are each a hydrogen or hydrocarbyl group and p is zero or an integer from about 1 to 20 or CO-C 6 H 4 -
  • the substitution pattern on the phenylene group, i.e., -C 6 H 4 - may be an ortho, meta, or para substitution pattern, in addition one or more of the hydrogens of the phenylene group may be substituted by a hydrocarbyl group or other functional group commonly found in organic molecules.
  • the resulting multifunctional carbonyl compound is a hydrocarbon chain that terminates on one end with an ester functionality and the other end with a urethane functionality.
  • the carbonyl compound is a dialkyl oxalate
  • the resulting multi-functional carbonyl compound is a hydrocarbon chain that terminates on one end with an ester functionality and the other end with an oxamate functionality.
  • the carbonyl compound is a dialkyl ester
  • the resulting multi-functional carbonyl compound is a hydrocarbon chain that includes an amide linkage and terminates on each end with an ester functionality.
  • the carbonyl compound is an alkyl ester
  • the resulting multi-functional carbonyl compound is a hydrocarbon chain that terminates on one end with an ester functionality and the other end with an amide functionality.
  • the reaction of the lactam with the carbonyl compound can be conducted in a solvent or in the absence of a solvent.
  • excess carbonyl compound may be employed as the reaction medium and, thus, the carbonyl compound may be present in an excess compared to the lactam.
  • the lactam may also be present in an excess and employed as the reaction medium.
  • the lactam and carbonyl compound can be present in a stoichiometric amount.
  • the lactam and carbonyl compound may be present in a melt.
  • the excess carbonyl compound or lactam may be recovered by, for example, distillation and reused.
  • one or more different lactams are reacted with one or more different carbonyl compounds.
  • two lactam molecules can be reacted with 1 molecule of carbonyl compound.
  • Solvents suitable for the method of the invention include, but are not limited to, hydrocarbon solvents such as a saturated alkane; benzene; toluene; xylenes; halogenated hydrocarbons; ethers such as ethyl ether; cyclic ethers such as tetrahydrofuran and dioxane; amides such as dimethylformamide; sulfoxides such as dimethylsulfoxide; ketones such as 2-butanone or methyl isobutyl ketone; alcohols; and the like; or mixtures thereof.
  • hydrocarbon solvents such as a saturated alkane
  • benzene toluene
  • xylenes halogenated hydrocarbons
  • ethers such as ethyl ether
  • cyclic ethers such as tetrahydrofuran and dioxane
  • amides such as dimethylformamide
  • sulfoxides such as dimethylsulfoxide
  • the concentration of the lactam in the solvent is from about 0.025 M to 10 M, preferably from about 0.375 M to 6 M, and more preferably from about 0.25 M to 4 M.
  • the mole ratio of lactam to carbonyl compound is typically from about 1:10 to 5:1, preferably from about 1:5 to 2:1, and more preferably from about 1:2.5 to 1.5:1.
  • the reaction is allowed to proceed for a sufficient time to form a detectable amount of the multi-functional carbonyl compound. In general the reaction time is less than about 12 hours.
  • the reaction temperature is from about room temperature to 150°C, for example, up to the boiling point of the solvent, when a solvent is used.
  • the reaction is typically conducted at room temperature.
  • the present invention also provides an improved method for preparing the multi-functional carbonyl compound.
  • the lactam and a carbonyl compound are reacted in the presence of an acid catalyst, preferably a Lewis acid catalyst.
  • any Lewis acid catalyst can be used according to the method of the invention.
  • any of the above-mentioned Lewis acid catalysts may be used.
  • the Lewis acid catalyst is titanium (IV) isopropoxide.
  • Lewis acids are a preferred catalyst since they can be easily removed from the reaction mixture.
  • many Lewis acids such as tetraorganotitanates, can be readily hydrolyzed with a stoichometric amount of water, leading to a highly insoluble titanium dioxide that can easily be removed from the reaction mixture by filtration.
  • Other Lewis acids such as, for example, boron trifluoride etherate, are sufficiently volatile that they can easily be removed from the reaction mixture by distillation.
  • using a Lewis acid can advantageously avoid having to extract the reaction mixture with an aqueous solvent to remove the catalyst. By avoiding an extraction step to remove the catalyst, the method of the invention generates less aqueous waste that ultimately has to be disposed of.
  • the lactam and carbonyl compound are allowed to react with an alkoxide anion as a basic catalyst, preferably methoxide anion.
  • the reaction is conducted at a temperature of less than about 20°C, preferably less than about 19°C, and more preferably less than about 15°C.
  • the lactam and carbonyl compound are allowed to react for less than about 5 hours, preferably less than about 2 hours, and more preferably less than about 1 hour. Conducting the reaction at a low temperature is preferred since temperatures can be kept below the flash point of many reagents and, thus, such low temperature reactions can be significantly safer.
  • dimethyl carbonate which is a common carbonyl compound for use in the method of the invention
  • the method is significantly safer than prior art methods that require higher temperatures.
  • the multi-functional carbonyl compound is formed, it can be recovered from the reaction mixture before it is reacted with the 1-substituted piperidin-4- ol or 4-aminopiperidine to form the HALS of the invention.
  • the multi-functional carbonyl compound may be recovered by any means available to those of ordinary skill in the art.
  • the multi-functional carbonyl compound is not recovered from the reaction mixture and instead the 1-substituted piperidin-4-ol or 4-aminopiperidine is added to the reaction mixture after a detectable amount of the multi-functional carbonyl compound is formed.
  • the 1-substituted piperidin-4-ol or 4-aminopiperidine and the multi-functional carbonyl compound can then react to form the HALS of the invention.
  • the compound of formula (I) is prepared by reacting the lactam, carbonyl compound, and 1-substituted piperidin-4-ol or 4-aminopiperidine in a single step.
  • the lactam, the carbonyl compound, and the 1-substituted piperidin-4-ol or 4-aminopiperidine are combined and allowed to react at the same time, rather than reacting the lactam and carbonyl compound to form the multi-functional carbonyl compound in a first step and then, in a subsequent step, reacting the multi-functional carbonyl compound with the 1-substituted piperidin-4-ol or 4-aminopiperidine.
  • the lactam, the carbonyl compound, and the 1-substituted piperidin-4-ol or 4-aminopiperidine are combined in a reaction vessel and allowed to react for sufficient time to form a detectable amount of the HALS of formula (I).
  • the ratio of lactam to carbonyl compound in this embodiment of the method is from about 2:1 to 1:4, preferably from about 1: 1 to 1:2; and the ratio of lactam to 1-substituted piperidin-4-ol or 4-aminopiperidine is from about 1:1 to 1:6, preferably from about 1:2 to 1:4.
  • the single step reaction can be conducted in a solvent or in the absence of a solvent.
  • a solvent any solvent that is compatible with the reagents may be used.
  • Representative solvents include, but are not limited to, those solvents described above for the reaction of a 1-substituted piperidin-4-ol or 4-aminopiperidine with a multifunctional carbonyl compound.
  • the reaction in this embodiment is carried out in the presence of a solvent.
  • the concentration of lactam is typically from about 0.025 M to 10 M, preferably from about 0.325 M to 6 M, and more preferably from about 0.75 M to 4 M.
  • the reaction is carried out in the presence of a catalyst.
  • the same catalysts may be used as were used in the reaction of a 1-substituted piperidin-4-ol or 4-aminopiperidine with a multi-functional carbonyl compound.
  • the catalyst is typically present in an amount of less than about 30 mole percent, preferably less than about 20 mole percent, and more preferably less than about 10 mole percent, and most preferably less than 5 mole percent, relative to the amount of carbonyl compound.
  • the alcohol is removed from the reaction mixture as it is formed to drive the reaction to completion.
  • the alcohol may be removed by any means available to those of ordinary skill in the art, such as distillation and/or azeotropic distillation.
  • the reaction time is less than about 20 hours and more preferably less than about 10 hours.
  • the reaction temperature is between about room temperature and 250°C.
  • the reactions are run at atmospheric pressure.
  • Representative reaction conditions for forming the HALS of formula (I) by the single step process are provided in the examples. When the HALS of formula (I) is formed it may be recovered from the reaction mixture by any means available to those of ordinary skill in the art.
  • Oligomeric HALS Compounds of the Invention The invention also includes oligomeric HALS having the general formula
  • i, j, k, and 1 are integers from about 0 to 300, preferably about 0 to 200, and more preferably 0 to about 100.
  • the sum of i, j, k, and 1 is greater than 2, preferably, the sum of i, j, k, and 1 is greater than about 3 and more preferably is greater than about 6.
  • i and j are integers from about 0 to 300, preferably about 0 to 200, and more preferably 0 to about 100.
  • the sum of i and j is greater than 2.
  • the sum of i and j is greater than about 3, more preferably greater than about 6.
  • at least two of i, j, k, and 1 are equal to or greater than 1.
  • E and E' are a piperidin-4-ol or 4-aminopiperidine moiety and F and F' are each a multi-functional carbonyl compound.
  • T can be F, F ⁇ or hydrogen and S can be E, E', or hydrogen.
  • E-F includes:
  • E-F' includes:
  • E'-F includes:
  • M is a diamino or a dihydroxy group that contains the 4- aminopiperidine group, R, as defined above.
  • diamino or a dihydroxy group is meant a group derived from a compound that contains at least two hydroxy groups, at least two amino groups, or at least one amino group and one hydroxy group.
  • the amino group can be either a primary or secondary amino group.
  • M-F includes:
  • M-F' includes:
  • the diamino or dihydroxy group that contains the 4-aminopiperidine group, i.e., M, is bonded to the multi-functional carbonyl compound by the hydroxy or amino group.
  • Formulas II and III may be a block copolymer or a random copolymer, i.e. , the units E-F, E-F', E'-F, and E'-F' or M-F and M-F' are distributed randomly throughout the polymer chain.
  • S is a hydrogen, or a unit derived from a piperidin-4-ol or a 4-aminopiperidine moiety and has the structure
  • T is a hydrogen or a unit derived from a multi-functional carbonyl compound and has the structure
  • D is a hydrocarbyl group
  • n is an integer from 1 to 15, preferably 4 to 11, m is either 0 or 1, s is 0 or an integer from about 1 to 10; R ⁇ R b , R c , and R d , are each a hydrogen or a hydrocarbyl group; Y is CO-(CR e R ⁇ p , wherein R and R f are each a hydrogen or hydrocarbyl group and p is zero or an integer from about 1 to 20 or CO-C 6 H 4 -, wherein the substitution pattern on the phenylene group is an ortho, meta, or para substitution pattern, and one or more of the hydrogens of the phenylene group may be substituted by a hydrocarbyl group or a functional group commonly found in organic molecules; Z is -O- or NG, wherein G is H or C r C 12 alkyl; R 2 is hydrogen,
  • E, E' and S are units derived from a piperidin-4-ol or a 4-aminopiperidine moiety and F, F' and T are units derived from a multi-functional carbonyl compound and in the HALS of formula (III) F and F' are derived from a multi-functional carbonyl compound and M is as defined above.
  • HALS of formula (II) it is preferably that the mole percent of the units derived from the multi-functional carbonyl compound is greater than the mole percent of the units derived from a piperidin-4-ol or a 4-aminopiperidine moiety.
  • the mole percent of the units derived from the multi-functional carbonyl compound is greater than die mole percent of the diamino or dihydroxy group that contains the 4-aminopiperidine group, i.e., M. This is advantageous since they are less expensive.
  • R 2 is H, or C r C 4 alkyl
  • R 3 , R 4 , R 5 , and R 6 are each H or C r C 4 alkyl
  • R a , R b , R c , and R d are each a hydrogen, aromatic, or C r C 4 alkyl
  • n is from about 4 to 11
  • s is from about 2 to 5.
  • R 2 is a hydrogen
  • R 3 , R 4 , R 5 , and R 6 are each methyl
  • R ⁇ R b , R°, and R d are each a hydrogen, Z is O, n is between 4 and 11, and s is 2, m is 0 and P is O.
  • R 2 is hydrogen
  • R 3 , R 4 , R 5 and R 6 are methyl
  • R a is hydrogen
  • R b , R c and R d are each hydrogen, Z is O, n is from 4 to 11 and s is 0.
  • M is N,N'- bis(2,2,6,6-tetramethyl-4-piperidinyl)-l,6-hexanediamine (BPIP) or N-(2,2,6,6- tetramethylpiperidinol) diethanolamine and n is from about 4 to 11.
  • BPIP 2,2,6,6-tetramethyl-4-piperidinyl
  • n is from about 4 to 11.
  • HALS compound of formula (II) and (III) is typically from about 400 to 20,000, preferably, from about 1,000 to 15,000, and more preferably from about 2,000 to 9,000.
  • the present invention also relates to a method of forming oligomeric
  • Oligomeric HALS of formula (II) are prepared by reacting a multi-functional carbonyl compound of general structure DO-CO-CR a R b -(-CR c R d -) n -NH-(Y) m -CO-OD (IV)
  • n is an integer from about 1 to 15, preferably 4 to 11, m is either 0 or 1;
  • R ⁇ R b , R c , and R d are each a hydrogen or a hydrocarbyl group;
  • Y is CO-(CR e R t ) p , wherein R e and R f are each a hydrogen or hydrocarbyl group and p is zero or an integer from about 1 to 20 or CO-C 6 H 4 -, wherein the substitution pattern on the phenylene group may be an ortho, meta, or para substitution pattern, and one or more of the hydrogens of the phenylene group may be substituted by a hydrocarbyl group or a functional group commonly found in organic molecules; and D is a hydrocarbyl group, with a 1-substituted piperidin-4-ol or 4-aminopiperidine of general structure:
  • Z is OH or or NHG, wherein G is H or -C ⁇ alkyl;
  • R 1 is -(CH 2 ) s -OH, -(CH 2 ) S -NH 2 , C r C 18 hydroxyalkoxy or C 5 -C 12 hydroxycycloalkoxy; wherein s is an integer from about 1 to 10, preferably 2 to 8;
  • R 2 represents hydrogen, C r C 8 alkyl, or benzyl;
  • R 3 , R 4 , R 5 , and R 6 are each a hydrogen, C r C 8 alkyl, benzyl or phenethyl, or two geminal R moieties, which together with the carbon to which they are attached, form a C 5 -C 10 cycloalkyl.
  • Oligomeric HALS of formula (III) are prepared by reacting a multifunctional carbonyl compound of general structure (IV) with a diamino or a dihydroxy compound that contains the 4-aminopiperidine group.
  • the diamino or dihydroxy compound includes N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)-l,6- hexanediamine (BPIP) or N-(2,2,6,6-tetramethylpiperidinol) diethanolamine.
  • the multi-functional carbonyl compounds are prepared by any method available to those of ordinary skill in the art.
  • the multi-functional carbonyl compounds are prepared by the method of the invention wherein a carbonyl compound is reacted with a lactam in the presence of a Lewis acid or wherein a carbonyl compound is reacted with a lactam and an alkoxide at a low temperature, i.e. , less than 20°C.
  • the carbonyl compound must have two reactive carbonyl groups or a single carbonyl group that is activated with two leaving groups (for example, phosgene or a dialkyl carbonate).
  • the leaving group is an ester.
  • Preferred carbonyl compound include dialkyl carbonates, dialkyl oxalates, and dialkyl esters.
  • the reaction can be carried out in the absence of a solvent or in the presence of an organic solvent.
  • either the multi-functional carbonyl compound or the 1-substituted piperidin-4-ol or 4-aminopiperidine (for compound (II)) or the diamino or dihydroxy compound that contains the 4-aminopiperidine group (for compound (III)) may be present in an excess and employed as the reaction medium.
  • the multi-functional carbonyl compound and the 1-substituted piperidin-4-ol or 4-aminopiperidine or the diamino or a dihydroxy compound that contains the 4-aminopiperidine group can be present in stoichiometric amounts.
  • the reaction can also be conducted in a melt.
  • the reaction is carried out in an organic solvent.
  • solvents compatible with the reagents include, but are not limited to, hydrocarbon solvents such as a saturated alkanes; benzene; toluene; xylenes; halogenated hydrocarbons; ethers such as ethyl ether; cyclic ethers such as tetrahydromran and dioxane; amides such as dimethylformamide; sulfoxides such as dimethylsulfoxide; ketones such as 2-butanone or methyl isobutyl ketone; and the like; or a mixture thereof.
  • the more preferred solvents include toluene, benzene, and xylenes, or a mixture thereof.
  • the concentration of the multi-functional carbonyl compound in the organic solvent is generally present in an amount of from about 0.025 M to 2.5 M, preferably from about 0.125 M to 0.2 M, and more preferably from about 0.25 M to 1.35 M.
  • oligomeric HALS of formula (III) is from about 5:1 to 1:5, preferably from about 2:1 to 1:2, and more preferably from about 1.2:1 to 1:1.2.
  • the substituted piperidin-4-ol or 4-aminopiperidine includes N-(2- hydroxyethyl)-2,2,6,6-tetramethyl-4-piperidinol.
  • the diamino or a dihydroxy compound that contains the 4-aminopiperidine group 4-aminopiperidine includes BPIP or N-(2,2,6,6-tetramethyl piperidinol) diethanolamine or a mixture thereof.
  • the reaction is conducted in the presence of a catalyst.
  • the catalyst may be a basic catalyst or an acid catalyst.
  • the base catalyst is methoxide ion.
  • the acid catalyst includes a Lewis acid.
  • the preferred Lewis acid includes 1, 3 -diacetoxy- 1,1,3,3- tetrabutyldistannoxane.
  • the catalyst is typically added in an amount of less than about 30 mole percent by weight based on the weight of the multi-functional carbonyl compound, preferably less than about 20 mole percent by weight based on the weight of the multi- functional carbonyl compound, more preferably less dian about 10 mole percent by weight based on the weight of the multi-functional carbonyl compound, and most preferably less than about 5 mole percent by weight based on the weight of the multifunctional carbonyl compound.
  • the reaction of the multi-functional carbonyl compound and the 1- substituted piperidin-4-ol or 4-aminopiperidine, used to prepare the oligomeric HALS of formula (II), or the diamino or dihydroxy compound that contains the 4-aminopiperidine group, used to prepare the oligomeric HALS of formula (III), is conducted for sufficient time to form a detectable amount of the oligomeric HALS of formula (II) or (III).
  • the reaction time temperature and pressure may readily be determined by one of ordinary skill in the art without undue experimentation. Typically, the reaction time is less than about 20 hours, preferably less than about 15 hours, and more preferably less than about 10 hours.
  • reaction temperature is from about room temperature to about 150°C, for example, up to the boiling point of the solvent.
  • reaction is carried out at atmospheric pressure.
  • Representative reaction conditions for forming the compound of formula (II) or (III) are provided in the examples.
  • oligomeric HALS of formula (II) or (III) are formed, they are recovered from the reaction mixture by any means available to those of ordinary skill in the art.
  • the oligomeric HALS of formula (II) and (III) are formed by reacting a lactam, a carbonyl compound of general structure
  • the lactam, carbonyl compound, and a 1-substituted piperidin-4-ol or 4- aminopiperidine or a diamino or a dihydroxy compound that contains the 4- aminopiperidine group are combined in a reaction vessel and allowed to react for sufficient time to form a detectable amount of the compound of formula (II) or (III).
  • the ratio of lactam to carbonyl compound is from about 2:1 to 1:4, preferably from about 1:1 to 1:2 and the ratio of lactam to 1-substituted piperidin-4-ol or 4-aminopiperidine or diamino or a dihydroxy compound is from about 2: 1 to 1:2, preferably about 1:1.
  • the single step reaction may be conducted in a solvent or in the absence of a solvent.
  • the reaction is conducted in the presence of a solvent.
  • a solvent any solvent that is compatible with the reagents may be used.
  • Representative solvents include, but are not limited to, those solvents described above for the reaction of a 1-substituted piperidin-4-ol or 4-aminopiperidine with a multi-functional carbonyl compound.
  • the concentration of the lactam is typically from about 0.075 M to 10 M, preferably from about 0.375 M to 6 M, and more preferably from about 0.75 M to 4 M.
  • the reaction is carried out in the presence of a catalyst.
  • the same catalysts may also be used as were used in the reaction of a 1- substituted piperidin-4-ol or 4-aminopiperidine with a multi-functional carbonyl compound.
  • the catalyst is typically present in an amount of less than about 30 mole percent, preferably less than about 20 mole percent, more preferably less than about 10 mole percent, and most preferably less than 5 mole percent relative to the amount of carbonyl compound.
  • the reaction time is less than about 20 hours, preferably less than about 15 hours, and more preferably less than about 10 hours.
  • the reaction temperature is from about room temperature to 250°C.
  • the reaction is carried out at atmospheric pressure.
  • Representative reaction conditions for forming the oligomeric HALS in a single step according to the method of the invention can readily be determined by one of ordinary skill in the art, but guidance is also provided in the examples.
  • oligomeric HALS of formula (II) or (III) When the oligomeric HALS of formula (II) or (III) is formed it may be recovered from the reaction mixture by any means available to those of ordinary skill in the art.
  • HALS of formula (I), (II), or (III) may be provided as neat compounds or may be provided in the form of a concentrate including from about 15 to 98 percent by weight, and preferably from about 20 to 95 percent by weight, preferably from about 25 to 90 percent by weight, and more preferably from about 40 to 70 percent of at least one of the HALS compounds of formula (I), (II), or (III) and a polymeric resin.
  • the HALS compounds of the present invention impart superior weatherability and yellowing resistance to polymers.
  • the HALS compounds of the present invention typically exhibit low volatility.
  • the present invention also provides polymeric articles stabilized by including an effective amount of the newly discovered HALS compounds to inhibit at least one of photo- or thermal degradation and methods of making the polymeric articles.
  • Any suitable polymer compatible with a HALS composition of the invention may be combined with one or more HALS of the invention to form a polymeric article protected from UV light.
  • the polymeric article includes at least one polymeric material and a sufficient amount of at least one HALS of formula (I), (II), or (III) to inhibit at least one of photo- or thermal degradation.
  • the polymeric article is stabilized by blending from about 0.01 percent to 10 percent by weight, preferably from about 0.03 percent to 1 percent by weight, and more preferably from about 0.05 percent to 0.5 percent by weight of at least one HALS of formula (I), (II), or (III) with a polymeric material used to form the article.
  • the article may be an extruded article, a molded article, a tape, a film, a fiber, or a coating, for example.
  • the method of making the polymeric articles includes blending a polymeric material with from about 0.01 percent to 10 percent by weight, preferably from about 0.03 percent to 1 percent by weight, and more preferably from about 0.05 percent to 0.5 percent by weight at least one HALS compounds of the present invention to form a stabilized polymeric composition, and forming an article from the polymeric composition.
  • the polymeric article may be formed by extrusion, sheet extrusion, injection molding, blow molding, injection blow molding, rotational or roto-molding, calendering, thermoforming, compression molding, vacuum molding, pressure molding, reaction injection molding, solvent casting, fiber spinning, and other similar techniques available to those of ordinary skill in the art.
  • the HALS of the invention may be added to the polymeric material by any means known in the art, and one of ordinary skill in the art may readily envision a variety of such ways to combine one or more HALS compounds and one or more polymeric materials to form polymeric articles according to the invention.
  • additives include, but are not limited to one or more of the following classes: a. Antioxidants
  • Alkylated monophenols such as 2,6-di-tert-butyl-4-methylphenol, 2-tert- butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl- 4-n-butylphenol, 2 , 6-di-tert-butyl-4-isobuty lphenol , 2 , 6-dicyclopentyl-4- methylphenol, 2-( ⁇ -methylcyclohexyl)-4,6-dimethylphenol, 2,6- dioctadecyl-4-methy lphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4- methoxymethylphenol; nonylphenols which are liner or branched in the side chains such as 2,6-di-nonyl-4-methylphenol, 2,4-dimethyl-6-(l- methylundec-l
  • IRGANOX ® 1010 Antioxidant and IRGANOX ® 1076 Antioxidant commercially available from of CIBA SPECIALTIES of Hawthorne, N.Y., and mixtures thereof;
  • Alkylthiomethylphenols such as 2,4-dioctylthiomethyl-6-tert-butylphenol,
  • Tocopherols such as ⁇ -tocopherol (vitamin E), ⁇ -tocopherol, ⁇ - tocopherol, ⁇ -tocopherol, and mixtures thereof;
  • Hydroxylated thiodiphenyl ethers such as 2,2'-thiobis(6-tert-butyl-4- methylphenol), 2,2'-thiobis(4-octylphenol), 4,4'-thiobis(6-tert-butyl-3- methylphenol) , 4,4 ' -thiobis(6-tert-butyl-2-methylphenol) , 4,4 ' -thiobis(3 , 6- di-sec-amylphenol),4,4'-bis(2,6-dimethyl-4-hydroxyphenyl)disulfide, and mixtures thereof;
  • Alkylidenebisphenols such as 2,2'-methylenebis(6-tert-butyl-4- methylphenol), 2,2'-m
  • Benzylphosphonates such as dimethyl-2,5-di-tert-butyl-4- hydroxybenzylphosphonate, diethyl-3 ,5-di-tert-butyl-4- hydroxybenzylphosphonate, dioctadecyl-3,5-di-tert-butyl-4- hydroxybenzylphosphonate, dioctadecyl-5-tert-butyl-4-hydroxy-3- methylbenzylphosphonate, the calcium salt of the monoethyl ester of 3,5- di-tert-butyl-4-hydroxybenzylphosphonic acid, and mixtures thereof;
  • Aminic antioxidants such as N,N'-diisopropyl- ⁇ -phenylenediamine, N,N'- di- sec-butyl-p-phenylenediamine, N,N'-bis(l,4-dimethylpentyl)-p- phenylenediamine, N,N'-bis(l-ethyl-3-methylpentyl)-p-phenylenediamine,
  • 2-Hydroxybenzophenones for example the 4-hydroxy, 4-methoxy, 4- octoxy CYASORB 8 UV-531 Light Stabilizer, commercially available from CYTEC INDUSTRIES), 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2' , 4 * - trihydroxy and 2'-hydroxy-4,4'-dimethoxy compounds, and mixtures thereof;
  • esters of substituted and unsubstituted benzoic acids or salicylic acid compounds such as 4-tert-butyl-phenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoyl resorcinol, bis(4-tert-butyIbenzoyl) resorcinol, benzoyl resorcinol, 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4- hydroxybenzoate, hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl 3 ,5-di-tert-butyl-4-hydroxybenzoate, and 2-methyl-4,6-di-tert-butylphenyl- 3,5-di-tert-butyl-4-hydroxybenzoate, and mixtures thereof;
  • PR-31 AND PR-32 commercially available from Clariant Corp. of Charlotte NC, and similar materials disclosed in GB-A-2269819, the reaction product of 7,7,9,9-tetramethyl-2-cycloundecyl-l-oxa-3,8-diaza-4- oxospiro[4.5]decane and epichlorohydrin.
  • tetramethylpiperidine derived HALS include CYASORB ® UV-3346 Light Stabilizer, commercially available from CYTEC INDUSTRIES, SANDUVOR ® 3055 HALS, SANDUVOR ® 3056 HALS, and
  • SANDUVOR ® 3058 HALS commercially available from SANDOZ Corporation of Charlotte, N.C., CHIMASORB" 944 Stabilizer, TINUVIN” 622 Stabilizer, and TINUVIN * 144 Stabilizer, each commercially available from CIBA SPECIALTIES, and mixtures thereof. See also generally U.S. Patent Nos. 5,106,891, 4,740,542, 4,619,956, 4,426,471, 4,426,472,
  • diphosphite bis(2,4-di-tert-butyl-6-methylphenyl)pentaerythritol diphosphite, bis(2,4,6-tris(tert-butyl)phenyl)pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis(2,4-di-tert-butylphenyl)-4,4'- biphenylene diphosphonite, 6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H- dibenzo[d,g]-l ,3,2-dioxaphosphocin, 6-fluoro-2,4,8, 10-tetra-tert-butyl-12- methyl-dibenzo[d,g]-l ,3 ,2-dioxaphosphocin, bis(2,4-di-tert-butyl-6- methy lphenyl)methylpho
  • any one or more of these additives may be combined, such as in CYANOX ® 2777 Antioxidant, commercially available from CYTEC INDUSTRIES, which combines a phenolic antioxidant and a phosphite antioxidant.
  • the composition may contain quenchers such as CYASORB ® UV-1084 Light Stabilizer, CYASORB ® UV-531 Light Stabilizer, each commercially available from CYTEC INDUSTRIES.
  • additives such as acid scavengers, antistatic agents, blowing agents, catalysts, clarifying agents, emulsifiers, fillers, flameproofing agents, fluorescent whitening agents, infrared absorbers, levelling assistants, lubricants, metal deactivators, mold release agents, nucleating agents, optical brighteners, pigments, plasticizers, rheological additives, and mixtures thereof.
  • the total amount of additives may be present in an amount up to about 10 percent, preferably from about 0.1 percent to about 5 percent by weight, and more preferably from about 0.2 percent to 3 percent by weight, based on the weight of the polymer.
  • the light-stabilized polymeric article may be formed from a polymeric material by incorporating the presently claimed compounds into polymeric materials, either chemically or physically.
  • polymeric materials that may be so stabilized are polyolefins; polyesters; poly ethers; polyketones; polyamides; natural and synthetic rubbers; polyurethanes; polystyrenes; high-impact polystyrenes; polyacrylates; polymethacrylates; polyacetals; poly aery lonitriles; polybutadienes; polystyrenes; ABS; SAN (styrene acrylonitrile); ASA (aery late styrene acrylonitrile); cellulosic acetate butyrate; cellulosic polymers; polyimides; polyamideimides; polyetherimides; polyphenylsulfides; PPO; polysulfones; polyethersulfones; poly viny .chlorides; polycarbonates; polyketones
  • the degradable polymer may be any polymer requiring stabilization, and includes homopolymers and copolymers of various monomers. It may be an addition polymer, a condensation polymer, a graft polymer, a thermosetting polymer, a photopolymer, a polymer blend or a thermoplastic polymer. It may be in the form of a fiber, a polymer film such as polypropylene films, a thin film such a solvent based coating, a water-based coating, a stoving lacquer, a powder coating, a gel coat, and the like, or it may be in the form of a molded article. Examples of degradable polymers which can be stabilized include, but are not limited to:
  • Homo- and copolymers of monoolefins and diolefins including, but not limited to, ethylene, propylene, isobutylene, butene, methy lpentene, hexene, heptene, octene, isoprene, butadiene, hexadiene, dicyclopentadiene, ethylidene, and cycloolefins such as cyclopentene and norbornene; for example, polyethylenes (which optionally can be cross-linked) such as high density polyethylene (HDPE), high density and high molecular weight polyethylene (HDPE-HMW), high density and ultrahigh molecular weight polyethylene (HDPE-UHMW), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), branched low density polyethylene (BLDPE) or polypropylene (PP) or polymers of ethylene propylene diene monomer (EP
  • Copolymers of one or more monoolefins and/or diolefins with carbon monoxide and/or with other vinyl monomers including acrylic and methacrylic acid, acrylates and methacrylates, acrylamides, acrylonitriles, styrenes, vinyl acetate (such as ethylene/ vinyl acetate copolymers (EVA)), vinyl halides, vinylidene halides, maleic anhydride, and allyl monomers such as allyl alcohol, allyl amine, allyl glycidyl ether and compounds thereof ; and blends thereof. 3.
  • vinyl monomers including acrylic and methacrylic acid, acrylates and methacrylates, acrylamides, acrylonitriles, styrenes, vinyl acetate (such as ethylene/ vinyl acetate copolymers (EVA)), vinyl halides, vinylidene halides, maleic anhydride, and allyl monomers such as allyl alcohol,
  • Hydrocarbon resins such as C 5 -C 9 including hydrogenated modifications thereof, and mixtures of polyalkylenes and starch ; and blends thereof.
  • Hydrocarbon resins such as C 5 -C 9
  • Homo- and copolymers of styrenes such as styrene, p-methylstyrene and - methylstyrene such as polystyrene, polyalphamethylstyrene, high impact polystyrene (HIPS); and blends thereof.
  • Copolymers of one or more styrenes with other vinyl monomers such as olefins and diolefins (e.g., ethylene, isoprene and/or butadiene), acrylic and methacrylic acid, acrylates and methacrylates, acrylamides, acrylonitriles, vinyl acetate (such as ethylene/ vinyl acetate copolymers), vinyl halides, vinylidene halides, maleic anhydride and allyl compounds such as allyl alcohol, allyl amine, allyl glycidyl ether; and blends thereof. 6.
  • olefins and diolefins e.g., ethylene, isoprene and/or butadiene
  • acrylic and methacrylic acid acrylates and methacrylates
  • acrylamides acrylonitriles
  • vinyl acetate such as ethylene/ vinyl acetate copolymers
  • vinyl halides vinylidene hal
  • ASA
  • Halogen-containing polymers such as poly vinyl chloride (PVC), chlorinated polyethylene (CPE), or polychloroprene; chlorinated rubbers; chlorinated and brominated isobutylene/isoprene copolymers; chlorinated or sulfochlorinated polyethylene; copolymers of ethylene and chlorinated ethylene; epichlorohydrin polymers and copolymers; and polymers and copolymers of halogen-containing vinyl compounds such as vinyl chloride, vinylidene chloride, vinyl fluoride and/or vinylidene fluoride, other vinyl monomers or other polyvinyl halides ; and blends thereof.
  • PVC poly vinyl chloride
  • CPE chlorinated polyethylene
  • CPE chlorinated polyethylene
  • polychloroprene chlorinated rubbers
  • chlorinated and brominated isobutylene/isoprene copolymers chlorinated or sulfochlorinated polyethylene
  • homo- and copolymers derived from unsaturated alcohols and amines or the acyl compounds or acetals thereof such as vinyl alcohol (including polyvinyl alcohol cross-linked polyvinyl alcohol), vinyl acetate, vinyl stearate, vinyl benzoate, vinyl maleate, vinyl butyral, allyl alcohol, allyl amine, allyl glycidyl ether, allyl phthalate and allyl melamine; as well as copolymers of such monomers with other ethylenic unsaturated monomers mentioned above ; and blends thereof.
  • vinyl alcohol including polyvinyl alcohol cross-linked polyvinyl alcohol
  • vinyl acetate vinyl stearate
  • vinyl benzoate vinyl maleate
  • vinyl butyral allyl alcohol
  • allyl amine allyl glycidyl ether
  • Polyacetals such as polyoxymethylene (POM) and those polyoxymethylenes which contain ethylene oxide as a comonomer; and polyoxymethylenes modified with thermoplastic polyurethanes, acrylates and/or MBS ; and blends thereof.
  • Polyesters derived from dicarboxylic acids, diols and/or hydroxy carboxylic acids or the corresponding lactones such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene terephthalate, glycol modified
  • PETG polyethylene terephthalate modified with 1,4-cyclohexanedimethanol
  • PCTG polyethylene terephthalate modified with 1,4-cyclohexanedimethanol
  • PCTG polyethylene terephthalate modified with 1,4-cyclohexanedimethanol
  • PCTG polyethylene terephthalate modified with 1,4-cyclohexanedimethanol
  • PCTG polyethylene terephthalate modified with 1,4-cyclohexanedimethanol
  • PCTG 1,4-cyclohexanedimethanol
  • poly-l,4-dimethylcyclohexane terepthalate polyhydroxybenzoates
  • block copolyether esters derived from hydroxyl-terminated ethers and also polyesters modified with polycarbonate or MBS; PEN, PTT; and blends thereof. 18.
  • PC and polyester carbonates such as resins are polycarbonates based on dihydric phenols such as 2,2-bis-(4-hydroxyphenyl)propane (bisphenol A); 2,4-bis (4-hydroxyphenyl)-2-methylbutane; l,l-bis-(4-hydroxyphenyl)- cyclohexane; 2,2-bis-(3-chloro-4-hydroxyphenyl)propane; 4,4 ' -sulfonyldiphenol; and l,l-bis-(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane ; and blends thereof.
  • dihydric phenols such as 2,2-bis-(4-hydroxyphenyl)propane (bisphenol A); 2,4-bis (4-hydroxyphenyl)-2-methylbutane; l,l-bis-(4-hydroxyphenyl)- cyclohexane; 2,2-bis-(3-chloro-4-hydroxyphenyl)propane; 4,4
  • polycarbonate copolymers incorporating two or more phenols, branched polycarbonates wherein a polyfunctional aromatic compound is reacted with a dihydric phenol(s) and carbonate precursor, and polymer blends of which polycarbonate comprises a significant portion of the blend (i.e. , more than 20% , preferably more than 50%).
  • Preferred resins for both layers are polycarbonates based on bisphenol A.
  • U.S. Patent No. 5,288,788 also describes polycarbonates and polyester carbonates, especially aromatic polycarbonates, for example those based on 2,2- bis(4-hydroxyphenyl)propane or l,l-bis(4-hydroxyphenyl)cyclohexane.
  • Mixtures (polyblends) of such polymers with one another or with other polymers, for example with polyolefins, polyacrylates, polydienes or other elastomers in the form of impact strength modifiers can also be stabilized wifli the HALS compounds of the invention.
  • A is a divalent phenolic radical. Suitable examples of A are given in U.S. Pat. No. 4,960,863 and DE-A-3 922,496 whose contents are incorporated herein by reference thereto.
  • A can be derived, for example, from hydroquinone, resorcinol, dihydroxybiphenylene or bisphenols in the broadest sense of the term, such as bis(hydroxyphenyl)alkanes, cycloalkanes, sulfides, ethers, ketones, sulfones, sulfoxides, ⁇ , ⁇ '-bis(hydroxyphenyl)- diisopropylbenzenes, for example the compounds 2,2-bis(4- hydroxyphenyl)propane , 2 , 2-bis(3 , 5-dimethyl-4-hydroxyphenyl)-propane , 2,2- bis(3 ,5-dichloro-4-hydroxyphenyl)propane, 1 , l-bis(4-
  • Polysulfones, poly ether sulfones and polyether ketones 19.
  • 20. Cross-linked polymers derived from aldehydes condensation resins such as phenol/formaldehyde resins, urea/formaldehyde resins and melamine/formaldehyde resins; and blends thereof.
  • Unsaturated polyester resins derived from copoly esters of saturated and unsaturated dicarboxylic acids with polyhydric alcohols and vinyl compounds as crosslmking agents, and also halogen-containing modifications thereof; and blends thereof.
  • Cross-linkable acrylic resins derived from substituted acrylates such as epoxy acrylates, hydroxy acrylates, isocyanato acrylates, urethane acrylates or polyester acrylates; and blends thereof.
  • Cross-linked epoxy resins derived from aliphatic, cycloaliphatic, heterocyclic and/or aromatic glycidyl compounds such as bisphenol A and bisphenol F, which are cross-linked with customary hardeners such as anhydrides or amines; and blends thereof.
  • Natural polymers such as cellulose, rubber, gelatin and chemically modified homologous compounds thereof, including cellulose acetates, cellulose propionates and cellulose butyrates, nitrocellulose, or the cellulose ethers such as methyl cellulose, as well as rosins and their compounds; and blends thereof.
  • PC/PBT PVC/CPE, PVC/acrylate, POM/thermoplastic PUR, PC/thermoplastic polyurethane, POM/acrylate, POM/MBS, PPO/HIPS, PPO/PA6.6 and copolymers, PA/HDPE, PP/HDPE, PP/LDPE, LDPE/HDPE, LDPE/EVA, LDPE/EAA, PA/PP, PA/PPO, PBT/PC/ABS, PBT/PET/PC and the like. 30.
  • Naturally occurring and synthetic organic materials which may be mixtures of compounds, including mineral oils, animal and vegetable fats, oils and waxes, or oils, fats or waxes based on synthetic esters (e.g., phthalates, adipates, phosphates or trimellitates) and also mixtures of synthetic esters with mineral oils in any ratio.
  • synthetic esters e.g., phthalates, adipates, phosphates or trimellitates
  • Aqueous emulsions of natural or synthetic rubber such as natural latex or latexes of carboxylated styrene/butadiene copolymers; and blends thereof.
  • Epoxymelamine resins such as light-stable epoxy resins cross-linked by an epoxy functional coetherified high solids melamine resin.
  • the aminoresin-cross-linked polymer may be an aminoresin-cross-linked thermoset acrylic or an aminoresin- cross-linked thermoset polyester.
  • the suitable aminoresins include alkylated and unalkylated melamine-formaldehyde resins, guanamine-formaldehyde resins, urea- formaldehyde resins, glycouril formaldehyde resins, and the like; and blends thereof.
  • Organic dyes such as azo dyes (diazo, triazo, and polyazo), anthraquinones, benzodifuranones, polycyclic aromatic carbonyl dyes, indigoid dyes, polymethines, styryl dyes, di- and triaryl carbonium dyes, phthalocyanines, quinophthalones, sulfur dyes, nitro and nitroso dyes, stilbene dyes, formazan dyes, quinacridones, carbazoles, and perylene tetracarboxylic diimides; and blends thereof.
  • Cosmetic products such as skin lotions, collagen creams, sunscreen, facial makeup, etc., comprising synthetic materials such as antioxidants, preservatives, lipids, solvents surfactants, colorants, antiperspirants, skin conditioners, moisturizers etc.; as well as natural products such as collagen, proteins, mink oil, olive oil, coconut oil, carnauba wax, beeswax, lanolin, cocoa butter, xanthan gum, aloe, etc; and blends thereof.
  • synthetic materials such as antioxidants, preservatives, lipids, solvents surfactants, colorants, antiperspirants, skin conditioners, moisturizers etc.
  • natural products such as collagen, proteins, mink oil, olive oil, coconut oil, carnauba wax, beeswax, lanolin, cocoa butter, xanthan gum, aloe, etc; and blends thereof.
  • Cellulose-based paper formulations for use e.g., in newsprint, cardboard, posters, packaging, labels, stationery, book and magazine paper, bond typing paper, multipurpose and office paper, computer paper, xerographic paper, laser and ink-jet printer paper, offset paper, currency paper, etc., and combinations thereof.
  • the term "copolymer,” as used herein, is a polymer of two or more different monomers.
  • the light-stabilized polymeric material is formed from a polyolefm homopolymer or copolymer, and more preferably a homopolymer or copolymer of polyethylene or polypropylene.
  • novel HALS of the present invention can also be employed in multilayer systems.
  • a polymer composition having from about 0.1 to 20 percent by weight and preferably having a relatively high content of the novel HALS of the invention, for example, from about 5 to 15 percent by weight, is applied in a thin film (typically between about 5 to 500 ⁇ m and preferably from about 10 to 100 ⁇ m thick) to a shaped article made from a polymer containing little or no ultraviolet stabilizers.
  • a thin film typically between about 5 to 500 ⁇ m and preferably from about 10 to 100 ⁇ m thick
  • Such composition may be applied at the same time as the shaping of the base structure, for example by coextmsion.
  • application can also be made to the ready-formed base structure, for example by lamination with a film or by coating with a solution.
  • the outer layer or layers of the finished article have the function of a UV filter, which protects the interior of the article from UV light.
  • the outer layer preferably contains about 0.1 to 20 percent, preferably about 1 to 15 percent and more preferably about 2 to 10 percent by weight of the outer layer composition, of at least one of the HALS of the present invention.
  • British Patent Appn. No. 2,290,745 describes a number of methods that have been developed to concentrate UV absorbers near or at the surface of polymeric materials. These include surface impregnation (see U.S. Patent Nos. 3,309,220, 3,043,709, 4,481,664 and 4,937,026) and coating a plastic article with solutions containing thermoplastic resins and UV absorbers (see U.S. Patent Nos.
  • the invention relates to thermoplastic articles coated with a thermoplastic layer about 0.1 to 10 mil (0.00254 mm to 0.254 mm) thick, preferable about 0.1 to 5 mil (0.00254 mm to 0.127 mm) thick, in which the layer contains between about 0.1 % to 20% by weight of one or more of the HALS of the invention.
  • Preferred concentrations are from about 2% to 15% by weight; most preferred are concentrations from about 5% to 10% by weight.
  • the HALS of the instant invention may be incorporated into the thermoplastics of the surface layer by standard methods, such as dry mixing the additives with a granular resin prior to extruding.
  • the HALS layer may be applied to one or more sides of a thermoplastic article according to the present invention.
  • Laminated thermoplastic articles corresponding to the present invention which contain additional layers such as a water resistant layer, as found in U.S. Pat. No. 4,992,322, are also within the scope of the present invention.
  • the core layer and the coating layer may be of the same thermoplastic resin or different.
  • thermoplastic resins include thermoplastic polyesters, polyester carbonates, polyphenylene oxide, polyvinyl chloride, polypropylene, polypropylene, polyethylene, polyacrylates, polymethacrylates and copolymers and blends such as styrene and acrylonitrile on polybutadiene and styrene with maleic anhydride; and blends thereof.
  • the polymers stabilized in this way are notable for high weathering resistance, especially for high resistance to UV light. This enables them to substantially retain their mechanical properties and their color and gloss for a long time even when used in harsh environments.
  • novel mixtures comprising at least one HALS of the invention can be used as stabilizers for coatings, for example for paints.
  • coatings and paints for the automobile industry are particularly interesting.
  • Coating means a free flowing composition that can be applied to the surface of an article in a thin film that then hardens to form a substantially solid surface on the article. Typically, the coating provides an interface between the article and the environment.
  • Such novel coating compositions comprise from about 0.01 to 20 percent, preferably from about 0.01 to 10 percent and more preferably from about 0.02 to 5 percent by weight of one or more of the HALS of the present invention.
  • the coating may be applied to the surface of the article in one or more than one layer to provide a multilayered system.
  • the concentration of the novel HALS compounds in the outer layer can be relatively high, for example from about 0.01 to 20 percent, preferably from about 0.01 to 10 percent, and more preferably from about 0.02 to 5 percent by weight.
  • the use of the novel stabilizer in coatings is accompanied by the additional advantage that it inhibits or prevents delamination, i.e. , the flaking-off of the coating from the substrate.
  • This advantage is particularly important in the case of metallic substrates, including multilayer systems on metallic substrates, which have such flaking tendencies.
  • the coatings typically include a binder that suspends pigments and other additives in the coating and allows attachment of the coating to the substrate.
  • the binder can in principle be any binder which is customary in industry, for example those described in Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, Vol. A18, pp. 368-426, VCH, Weinheim, 1991, which is incorporated herein by reference. In general, it is a film-forming binder based on a thermoplastic or thermosetting resin, predominantly on a thermosetting resin. Examples thereof are alkyd, acrylic, polyester, phenolic, melamine, epoxy, and polyurethane resins, and mixtures thereof. Such binders can be a cold-curable or hot-curable binder. Further, in some systems it may be advantageous to add a curing catalyst to such systems.
  • Suitable catalysts which accelerate curing of the binder are described, for example, in Ullmann's Encyclopedia of Industrial Chemistry, Vol. A18, p. 469, VCH Verlagsgesellschaft, Weinheim, 1991, which is incorporated herein by reference.
  • Preferred binders include those which comprise a functional acrylate resin and a crosslmking agent.
  • binders may be employed in such coating systems.
  • suitable coating compositions containing specific binders include but are not limited to: 1. paints based on cold- or hot-cross-linkable alkyd, acrylate, polyester, epoxy or melamine resins, or mixtures of such resins, if desired with addition of a curing catalyst;
  • polyurethane paints based on hydroxy 1-containing acrylate, polyester or polyether resins and aliphatic or aromatic isocyanates, isocyanurates or poly isocyanates; or mixtures thereof;
  • polyurethane paints based on blocked isocyanates, isocyanurates or poly isocyanates which are deblocked during baking; or mixtures thereof;
  • the coating composition according to the invention may further comprise one or more additional additives, such as an antioxidant or additional ultraviolet light absorber or stabilizer. Additional additives include, but are not limited to, those specifically listed above.
  • the additional additive is employed in coating compositions in an amount of from about 0.01 to 5 percent, preferably from about 0.02 to 2 percent by weight.
  • the coating composition can also comprise further components including, but not limited to, solvents, pigments, dyes, plasticizers, stabilizers, thixo tropic agents, drying catalysts and/or leveling agents, or combinations thereof.
  • solvents examples of possible components are those described in Ullmann's Encyclopedia of
  • Exemplary drying catalysts or curing catalysts are, for example, organometallic compounds, amines, amino-containing resins and/or phosphines.
  • organometallic compounds are metal carboxylates, especially those of the metals Pb, Mn, Co, Zn, Zr or Cu, or metal chelates, especially those of the metal Al, Ti or Zr, or organometallic compounds such as organotin compounds, for example, and mixtures thereof.
  • metal carboxylates are the stearates of Pb, Mn or Zn, the octoates of Co, Zn or Cu, the naphthenates of Mn and Co or the corresponding linoleates, resinates or tallates, and mixtures thereof.
  • metal chelates are the aluminum, titamum, or zirconium chelates of acetylacetone, ethyl acetylacetate, salicylaldehyde, salicylaldoxime, o- hydroxyacetophenone, or ethyl trifluoroacetylacetate, and the alkoxides of these metals, and mixtures thereof.
  • organotin compounds are dibutyltin oxide, dibutyltin dilaurate or dibutyltin dioctoate, and mixtures thereof.
  • amines are, in particular, tertiary amines, for example tributy lamine, triethanolamine, N-methyldiethanolamine, N-dimethylethanolamine, N- ethylmorpholine, N-methylmorpholine or diazabicyclooctane (triethylenediamine) and salts thereof, and mixtures thereof. Further examples are quaternary ammonium salts, for example trimethylbenzylammonium chloride.
  • Amino-containing resins are simultaneously a binder and a curing catalyst. Examples thereof are amino-containing acrylate copolymers.
  • the curing catalyst used can also be a phosphine, for example triphenylphosphine.
  • the novel coating compositions can also be radiation-curable coating compositions.
  • the binder includes monomeric or oligomeric compounds containing ethylenically unsaturated bonds, which after application are cured by actinic radiation, i.e. , converted into a crosslinked, high molecular weight form.
  • the system is UV-curable, it generally contains a photoinitiator as well.
  • the novel stabilizers can also be employed with or without additional UV light stabilizers, including sterically hindered amines.
  • the coating compositions according to the invention can be applied to any desired substrates, for example to metal, wood, plastic, or ceramic materials. They are preferably used as topcoats in the finishing of automobiles. If the topcoat comprises two layers, of which the lower layer is pigmented and the upper layer is not pigmented, the novel coating composition can be used for eitiier the upper or the lower layer or for both layers, but preferably for the upper layer.
  • the novel coating compositions can be applied to the substrates by any conventional methods available to those or ordinary skill in the art, for example by bmshing, spraying, pouring, dipping, or electrophoresis; see also Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, Vol. A 18, pp. 491-500, which is incorporated herein by reference.
  • the coatings can be cured at room temperature or may require heating. The coatings are preferably cured at a temperature of from about 50°C to 150°C, and in the case of powder coatings, even at higher temperatures.
  • the coatings obtained in accordance with the invention generally have excellent resistance to the damaging effects of light, oxygen, and heat.
  • the presently claimed coatings provide good light stability and weathering resistance.
  • the invention d erefore encompasses coatings, in particular a paint, which has been stabilized against the damaging effects of light, oxygen, and/or heat by a content of at least one of the HALS of the present invention incorporated into or onto an article.
  • the paint may be a pigmented mono-coat which includes a film-forming binder and an organic pigment or dye, an inorganic pigment, a metallic pigment, or a mixture thereof.
  • the paint may also be a composition which comprises a primer in adhesion to a metal or plastic substrate; a pigmented base coat that is in adhesion to the primer, and which comprises a film-forming binder and an organic pigment or dye, an inorganic pigment, a metallic pigment, or a mixture thereof; and a clear top coat that is in adhesion to the base coat, and which comprises a film-forming binder and optionally a transparent pigment.
  • the paint is preferably a topcoat for automobiles.
  • the invention furthermore relates to a process for stabilizing a coating based on organic polymers against damage by light, oxygen, and/or heat, which comprises mixing with the coating composition a mixture comprising one or more HALS of the present invention, as well as the use of mixtures comprising the one or more HALS of the present invention in coating compositions as stabilizers against damage by light, oxygen, and/or heat.
  • the coating compositions can comprise an organic solvent or solvent mixture in which the binder is soluble.
  • the coating composition can otherwise be an aqueous solution or dispersion.
  • the carrier can also be a mixture of organic solvent and water.
  • the coating composition may be a high-solids paint or can be solvent-free (e.g., a powder coating material).
  • the pigments can be inorganic, organic or metallic pigments.
  • the novel coating compositions preferably contain no pigments and preferably are used in clearcoat compositions.
  • the coating composition as a topcoat for applications in the automobile industry, especially as a pigmented or unpigmented topcoat of the paint finish. Its use for underlying coats, however, is also possible.
  • i, j, k, and 1 are integers and the sum of i, j, k, and 1 is greater than 2.
  • Compounds I and II were prepared from methyl 6-(methoxycarbonylamino) hexanoate (Compound A), compounds III and IV were prepared from butyl 6- butoxycarbonylaminoundecanoate (Compound B), compound V was prepared from methyl 6-[(methoxyoxoacetyl)amino]-hexanoate (Compound C) and compound VI was prepared from methyl 6-(octanoylamino)hexanoate (Compound D).
  • Compounds VII and Vi ⁇ were prepared from compound A and N-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4- piperidinol.
  • N-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-piperidinol was prepared by the hydrolysis of TINUVIN 622 with aqueous sodium hydroxide/tetrahydrofuran, removal of the tetrahydrofuran under reduced pressure, extraction of the aqueous layer with chloroform, drying and filtering the chloroform layer, and removal of the chloroform under reduced pressure.
  • the recovered N-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4- piperidinol had a melting point of 179-183 °C (literature melting point 182°C, DE 2,352,658).
  • the synthesis of Compounds A, B, C and D are described below.
  • the multifunctional carbonyl compound can be formed by nucleophilic acyl addition of a lactam anion at the carbonyl of a carbonate to produce an intermediate followed by reaction of a second lactam anion at the lactam carbonyl of the intermediate.
  • the resulting multifunctional carbonyl compounds can then be reacted with a 4-aminopiperidine radical to provide a HALS mixture which is an effective stabilizer.
  • the product produced in the lower temperature reactions are less colored.
  • Stark trap with a condenser, a thermometer, and a glass stopper was added 20 g (98.4 mmol) of Compound A, 46.3 g (0.295 mol) of 2,2,6,6-tetramethyl-4-piperidinol, and 150 mL of toluene. Under a slow nitrogen flow, 20 mL of toluene was distilled off and the trap drained. The glass stopper was removed and 1.0 g (1.67 mmol) of 1,3-diacetoxy- 1,1,3,3-tetrabutyldistannoxane was added. Another 75 mL of toluene was slowly distilled off over 8 hours.
  • a 250 mL single-necked reaction flask was equipped with a magnetic stirrer and a distillation head fitted with a thermometer, condenser, and receiving flask with a nitrogen inlet and outlet to a bubbler.
  • To this flask was charged 4.3 g (11.57 mmol) of Compound B, 7.27 g (46.3 mmol) of 2,2,6,6-tetramethyl-4- ⁇ iperidinol, and 200 mL of xylene. Under a slow nitrogen flow, 25 mL of xylene was distilled off and the trap drained.
  • a 250 mL single-necked reaction flask was equipped with a magnetic stirrer and a distillation head fitted with a thermometer, condenser, and receiving flask with a nitrogen inlet and outlet to a bubbler.
  • To this flask was charged 4.5 g (12.1 mmol) of Compound B, 8.3 g (48.4 mmol) of l,2,2,6,6-pentamethyl-4-piperidinol, and 200 mL of xylene. Under a slow nitrogen flow, 25 mL of xylene was distilled off and the trap drained.
  • a 250 mL single-necked reaction flask was equipped with a magnetic stirrer and a Dean-Stark trap fitted with a condenser and nitrogen inlet/outlet.
  • the flask was charged with 10.0 g (43.3 mmol) of compound C, 20.4 g (130 mmol) of 2,2,6,6- tetramethyl-4-piperidinol, and 150 mL of toluene. Under a slow nitrogen flow, 15 mL of toluene was distilled off and the trap drained.
  • a 250 mL single-necked reaction flask was equipped with a magnetic stirrer and a Dean-Stark trap fitted with a condenser and nitrogen inlet/outlet.
  • To this flask was charged 6.1 g (22.5 mmol) of compound D, 5.29 g (33.7 mmol) of 2,2,6,6- tetramethyl-4-pi ⁇ eridinol, and 150 mL of toluene. Under a slow nitrogen flow, 8 mL of toluene was distilled off and the trap drained.
  • Fraction A A 12 mL aliquot was removed from the reaction mixture (Fraction A), and was worked up as described below. The remaining reaction mixture was heated for an additional 2.5 hours, over which time 8 mL of solvent distilled off. After addition of 10 mL of xylenes, the temperature was increased so that 15 mL of additional solvent distilled off over 3 hours. The resulting reaction mixture (Fraction B) was worked up as described below. Workup of Fraction A: The 12 mL aliquot was diluted with methylene chloride, washed with water, dried (MgSO 4 ), filtered, and the solvent removed under reduced pressure. Further solvent removal in vacuo ( ⁇ 1 mm) at 50-60 °C gave 4.4 g of compound VII as a clear colorless semisolid.
  • HPSEC High Performance Size-Exclusion Chromatography
  • Example 8 Single step reaction to produce 2.2.6.6-tetramethyl-4-piperidine 6-(2.2.6.6- tetramethyl-4-piperidinoxycarbonyl amino)hexanoate (Compound I), base catalyzed.
  • a 100 mL three-necked round bottom flask equipped with a magnetic stir bar, an addition funnel containing anhydrous toluene, and a Dean-Stark trap fitted with a condenser and a nitrogen inlet/outlet was charged 1.69 g (15 mmol) of caprolactam, 2J4 g (15.75 mmol) of dibutyl carbonate, 4.94 g (31.5 mmol) of 2,2,6,6-tetramethyl-4- piperidinol, and 50 mL of toluene.
  • the mixture was heated to a heating mantle temperature of 142°C, so that 6 mL of solvent distilled into the trap.
  • the mixture was cooled and 75 mg (1.39 mmol) of sodium methoxide was added to the mixture.
  • the mixture was reheated to boiling and 20 mL distilled into the trap over 4 hours.
  • the trap was drained and 25 mL of toluene was added to the mixture through the addition funnel. After another 25 mL of solvent distilled off over 4 hours, 25 mL of anhydrous xylenes was added, and 35 mL of solvent removed over 6 hours.
  • Example 9 Single step reaction to produce 2.2.6.6-tetramethyl-4-piperidine 6-(2.2.6.6- tetramethyl-4-piperidinoxy carbonyl amino)hexanoate (Compound I). Lewis acid catalyzed.
  • the mixture was heated to reflux for one hour, after which the heat source was lowered, the Dean-Stark trap drained of 30 mL of xylenes which had collected, and 0.22 g (0.37 mmol) of 1,3-diacetoxy-l, 1 ,3,3-tetrabutyldistannoxane was added.
  • the mixture was reheated to the boiling point, and another 50 mL of solvent was allowed to collect over several hours.
  • Another 100 mL portion of anhydrous xylenes was added and distilled off over several hours.
  • the mixture was cooled to room temperature, diluted with methylene chloride, washed with water, dried (molecular sieves), filtered and the solvent removed under reduced pressure to give 12.1 g of compound IX as a tacky yellowish solid.
  • Example 11 Single Step Reaction to Produce Oligomeric HALS from Caprolactam. N- hydroxyethyl-2.2.6.6-tetramethyl-4-piperidinol. and Dibutyl Carbonate.
  • a 250 mL 3-necked reaction flask was equipped with a magnetic stirrer, a thermometer adapter, and a distillation head fitted with a condenser, a receiver, and a nitrogen inlet/outlet.
  • To this flask was charged 4.3 g (10.45 mmol) of the E/F mixture generated above, 7.27 g (46.3 mmol) of 2,2,6,6-tetramethyl-4-piperidinol, and 200 mL of xylenes. Under a slow nitrogen flow, 10 mL of xylenes were distilled off and the trap drained.
  • a 500 mL 3 -necked reaction flask was equipped with a magnetic stirrer, a thermometer adapter, and a distillation head fitted with a condenser, a receiver, and a nitrogen inlet/outlet.
  • To this flask was charged 7.9 g (19.2 mmol) of the E/F mixture generated above, 14.5 g (85.04 mmol) of l,2,2,6,6-pentamethyl-4-piperidinol, and 300 mL of xylenes. Under a slow nitrogen flow, 100 mL of xylenes were distilled off and the trap drained.
  • Composition Containing 1.2.2.6.6-pentamethyl-4-piperidine 6-(1.2.2.6.6-pentamethyl-4- piperidinoxycarbonylamino)hexanoate Compound II.
  • Compound II (1 % based on total resin solids) was pre-dissolved in the solvent mixture (5-10% solids) and added to the clear 2k acrylic urethane formulation given in Table I.
  • the 2k acrylic urethane is a two-component urethane formed by reacting a hydroxy functional acrylic polymer with an isocyanate cross linker. Components I and II were mixed just before use.
  • the clear coats were applied to cold roll steel panels, measuring 4" x 12" and pre-coated with an E-coat primer and white base-coat, obtained from ACT Laboratories, Inc. of Hillsdale, Michigan.
  • the draw-down technique using WC-60 WIRE-CATORSTM available from Leneta Co. of Ho-Ho-Kus, N. J. , was used to apply the clear coat to the pre-coated panels.
  • the clear coats were allowed to flash for 10 min at ambient temperature and cured for 30 min. at 120°C.
  • 'JONCRYL is commercially available from S.C. Johnson and Sons Inc. of Racine, WL b T-12 is commercially available from Air Products of Allentown, PA.
  • DESMODUR 0 1 % based on total resin solids d DESMODUR is commercially available from Bayer Corp. of Pittsburg, PA.
  • a 2k acrylic urethane clear coat stabilized with 1 % of Compound II showed superior percent gloss retention compared to the 2k urethane clear coat containing no stabilizer.
  • a 2k acrylic urethane clear coat stabilized with 1 % of Compound II showed superior percent DOI retention compared to the a 2k urethane clear coat containing no stabilizer.
  • Example 18 The performance of Compound II under Xenon WOM weathering is summarized in Examples 18-20.
  • the effect of Compound II on gloss retention is given in Example 18, the effect of Compound II on DOI retention is given in Example 19, and the effect on delta E is given in Example 20.
  • the effect of Compound II under natural weathering (Florida) on gloss retention, yellowing (delta b), and total color change (delta E) is given in Example 21.
  • Example 18 Xenon Weathering (SAE J1960 Automotive Exterior) of a 2k Polyurethane Acrylic Coating Stabilized with Compound II, Effect on Percent Gloss Retention
  • a 2k acrylic urethane clear coat stabilized with 1 % of Compound II showed superior gloss retention compared to the a 2k urethane clear coat containing no stabilizer.
  • Example 19 Xenon Weathering (SAE J1960 Automotive Exterior) of a 2k Polyurethane Acrylic Coatin Stabilized with Compound II, Effect on Percent DPI Retention
  • a 2k acrylic urethane clear coat stabilized with 1 % of Compound II showed superior percent DOI retention compared to the a 2k urethane clear coat containing no stabilizer.
  • a 2k acrylic urethane clear coat stabilized with 1 % of Compound II had a superior effect on total color change (Delta E) compared to the a 2k urethane clear coat containing no stabilizer.
  • An increase in Delta E indicates an unfavorable discoloration of the urethane coating.
  • Example 21 Florida Weathering (50° South, Direct, 18 Months) of a 2k Acrylic Urethane Clear Coat Stabilized with Compound II, Effect on Gloss Retention, Yellowing (Delta b , and Total Color Chan e (Delta E
  • Sample plaques were exposed in the xenon-arc weatherometer as determined by ASTM G-26 Standard using Test Method B with alternate exposure to light and darkness and intermittent exposure to water spray maintaining an atmosphere temperature of 63+3°C and a relative humidity of 30+5 percent (Miami, FL conditions).
  • Color ( ⁇ E) was determined with a Macbeth Color Eye Colorimeter (commercially available from Gretag-MacBeth LLC of New Windsor, NY) under laboratory conditions with illuminate C, 2° observer, specular component excluded, and UV component included. Specular gloss was measured according to ASTM D523 Standard using a Gardner black plate 60° Glossmeter measuring deviation loss to 50 percent.
  • Pellets were also injection-molded into tensile bars using an Arburg "Allrounder” hydraulic injection molder (commercially available from Arburg GmbH & Co. of Lossburg, Germany). Temperatures used were as follows: nozzle, 200°C; nozzle side, 220°C; middle, 225°C; feed, 210°C; and mold, 52°C. The blended material was also made into thin films. The thin films were prepared as described in Example 22.
  • Tinuvin 765 bis(l, 2, 2, 6, 6-pentamethyl-4-piperidyl) sebacate, CAS #41556-26-7
  • Tinuvin 770 bis(2, 2, 6, 6-tetramethyl-4- piperidyl) sebacate, CAS #52829-07-9)
  • Tinuvin 622 l-(2-hydroxyethyl)-4-hydroxy- 2, 2, 6, 6- tetramethyl piperidine-succininic acid, dimethyl ester, copolymer, CAS #65447-77-0) (commercially available from Ciba Specialties Corp., Hawthorne, NY
  • Chimasorb 944 poly[6-(l, 1, 3, 3-tetramethylbutyl)amino]-l, 3, 5-triazine-2, 4,-
  • Table IV shows a comparison of 50% Strength Retention, 50% Elongation Retention, and Hours to 50% Retention of Tensil Strength for the HALS of the invention and several commercially available HALS compounds in PROFAX polypropylene tensile bars.
  • Table III Performance of HALS of the Invention Relative to Conventional HALS in PROFAX 6501 Polypro ylene Pla ues and Pol ro lene Thin Films.
  • Example 22 a A product of Ciba Specialty Chemicals, Inc. of Hawthorne, NY Table IN: Performance of HALS of the Invention Relative to Conventional HALS in PROFAX 6501 Propylene Tensile Bars, Effect of Florida Weathering and Xenon Weathering.
  • Example 24 Performance of Compounds I-IV. VII- VIII Relative to Conventional HALS in Polyethylene Articles.
  • Compounds I-IV and VII- VIII, as well as several commercially available HALS compounds were each dry blended at a 0.1 percent loading level into a LLDPE prills (commercially available from Equistar Chemicals LP. of Houston TX) containing 0.01 percent zinc stearate (commercially available from Malinckrodt Chemicals of St. Louis, MO), and 0.07 percent Cyanox A-2777 (commercially available from Cytec Industries of West Paterson, NJ).
  • Blended material was melt-mixed in a Brabender PL-2000 torque rheometer base equipped with a single mixing screw extmder-5 zone, single pass at 50-75 rpm, with the temperature of zones 1-5 at 170°C, 175°C, 180°C, 185°C, and 190°C, respectively.
  • the extmdate was cooled, dried, and pelletized.
  • Pellets were compression molded into sample plaques (2 x 2.5 x 0.100 inches) using a PHI press at 177°C.
  • Sample plaques were exposed in the xenon-arc weatherometer as determined by ASTM G-26 Standard using Test Method B with alternate exposure to light and darkness and intermittent exposure to water spray maintaining an atmosphere temperature of 63 +3 °C and a relative humidity of 30+5 percent (Miami, FL conditions). Color ( ⁇ E) was determined with a Macbeth Color Eye Colorimeter under laboratory conditions with illuminate C, 2° observer, specular component excluded, and UV component included. The blended material was also made into thin films. The thin films were prepared as described in Example 22.
  • Table V Performance of HALS of the Invention Relative to Conventional HALS in LLDPE Pla ues and Thin Films.
  • Example 25 Performance of Compound VIII Relative to Conventional HALS in a Polypropylene Article.
  • Compound VIII, 1 1 blends of Compound VIII with Cyasorb R UV-3346,
  • Cyasorb R UV-3346, and several commercially available HALS compounds were each dry blended at a 0.2% loading level in PROFAX 6501 polypropylene flake (commercially available from Montel USA Inc. of Wilmington, DE) containing 0.07 percent calcium stearate (commercially available from Witco Corp. of Greenwich, CT), and 0.07 percent Cyanox A-2777 (commercially available from Cytec Industries of West Paterson, NJ). Blended material was melt-mixed in a Brabender PL-2000 torque rheometer base (commercially available from C.W.
  • Sample plaques were exposed in the xenon-arc weatherometer as determined by ASTM G-26 Standard using Test Method B with alternate exposure to light and darkness and intermittent exposure to water spray maintaining an atmosphere temperature of 63+3 °C and a relative humidity of 30 ⁇ 5 percent (Miami, FL conditions). Specular gloss was measured according to ASTM D523 Standard using a Gardner black plate 60° Glossmeter measuring deviation loss to 50 percent.
  • Example 25 Performance of Compound VIII of the Invention Relative to Conventional HALS in PROFAX 6501 Polypropylene Plaques.
  • Example 25 demonstrates that HALS of the invention showed equal or superior performance compared to commercially available HALS compounds.
  • Pellets were injection molded into sample plaques (2 x 2.5 x 0.100 inches) using an Arburg Allrounder 320- 210-750 injection molding machine (commercially available from Arburg GmbH & Co. of Lossburg, Germany) with the nozzle at 245°C, nozzle side at 260°C, middle at 270°C, feed at 270 °C, and mold at 82 °C.
  • Sample plaques were exposed in the xenon-arc weatherometer as determined by ASTM G-26 Standard using Test Method B with alternate exposure to light and darkness and intermittent exposure to water spray maintaining an atmosphere temperature of 63 +3 °C and a relative humidity of 30+5 percent (Miami, FL conditions). Color as measured by yellowing index (YI) and ⁇ E was determined with a Macbeth Color Eye Colorimeter under laboratory conditions with illuminate C, 2° observer, specular component excluded, and UV component included.
  • YI yellowing index
  • ⁇ E was determined with a Macbeth Color Eye Colorimeter under laboratory conditions with illuminate C,
  • Nylostab S-EED is a developmental product from Clariant Corp. of Charlotte, N.C. N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)isophthalamide)
  • Example 26 demonstrates that HALS of the invention outperformed the unstabilized system and showed equal or superior performance compared to the other HALS compounds.
  • the invention described and claimed herein is not to be limited in scope by the specific embodiments herein disclosed, since these embodiments are intended as illustrations of several aspects of the invention. Any equivalent embodiments are intended to be within the scope of this invention. Indeed, various modifications of the invention in addition to those shown and described herein will become apparent to those skilled in the art from the foregoing description. Such modifications are also intended to fall within the scope of the appended claims.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Hydrogenated Pyridines (AREA)

Abstract

L'invention porte sur des composés et des méthodes de préparation de composés de formule: (I) dans laquelle: n est un entier de 1 à 15, m est soit 0 ou 1; R?a, Rb, Rc, et Rd¿ sont chacun un hydrogène ou un groupe hydrocarbyle; Y est CO-(CReRf)p (dans lequel Re et Rf sont chacun un hydrogène ou un groupe hydrocarbyle et p est zéro ou un entier de 1 à 20 ou CO-C¿6?H4-); le schéma de substitution du groupe phénylène est une substitution ortho, méta, ou para et un ou plusieurs des hydrogènes du groupe phénylène peuvent être substitués par un groupe hydrocarbyle ou un groupe fonctionnel; Z est O- ou NG-; G est H, C1-C12alkyle, ou le radical R de formule (II) dans laquelle: R?1¿ est hydrogène, C¿1?-C18alkyle, O, OH, CH2CN, C1C18 alkoxy, C1-C18 hydroxyalkoxy, C5-C12 cycloalkoxy, C5-C12 hydroxycycloalkoxy, C3-C6 alcényle, C1-C18 alkynyle, C7-C9 phénylalkyle, non substitué ou substitué sur le phényle par 1, 2 ou 3 C1-C4 alkyles, ou un aliphatique C1-C8 acyle aliphatique; R?2¿ est hydrogène, C¿1?-C8 alkyle, ou benzyle; R?3, R4,R5, et R6¿ sont chacun un hydrogène, C¿1?-C8 acyle; R?2¿ est hydrogène, C¿1?-C8 alkyle, ou benzyle; R?3,R4,R5, et R6¿ sont chacun un hydrogène, C¿1?-C8 alkyle, benzyle, ou phénéthyle, ou deux fragments jumeaux R, formant ensemble avec le carbone auquel ils sont attachés un C5-C10 cycloalkyle; et A est soit ZR ou un groupe hydrocarbyle, et qui s'avèrent utiles pour stabiliser les compositions de polymères contre les dégradations sous l'effet de la lumière et de la chaleur.
EP01994383A 2000-11-03 2001-10-26 Amines empechees stabilisatrices de l'action de la lumiere, a base de composes carbonyle pluri-fonctionnels de carbonyle, et leur procede d'elaboration Withdrawn EP1414799A2 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US70479300A 2000-11-03 2000-11-03
US704793 2000-11-03
PCT/US2001/049873 WO2002057232A2 (fr) 2000-11-03 2001-10-26 Amines empechees stabilisatrices de l'action de la lumiere, a base de composes carbonyle pluri-fonctionnels de carbonyle, et leur procede d'elaboration

Publications (1)

Publication Number Publication Date
EP1414799A2 true EP1414799A2 (fr) 2004-05-06

Family

ID=24830876

Family Applications (1)

Application Number Title Priority Date Filing Date
EP01994383A Withdrawn EP1414799A2 (fr) 2000-11-03 2001-10-26 Amines empechees stabilisatrices de l'action de la lumiere, a base de composes carbonyle pluri-fonctionnels de carbonyle, et leur procede d'elaboration

Country Status (3)

Country Link
EP (1) EP1414799A2 (fr)
TW (1) TW583180B (fr)
ZA (1) ZA200302883B (fr)

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO02057232A3 *

Also Published As

Publication number Publication date
ZA200302883B (en) 2004-02-27
TW583180B (en) 2004-04-11

Similar Documents

Publication Publication Date Title
US6727300B2 (en) Polymeric articles containing hindered amine light stabilizers based on multi-functional carbonyl compounds
US6867250B1 (en) Non-yellowing ortho-dialkyl aryl substituted triazine ultraviolet light absorbers
US6365652B2 (en) Trisaryl-1,3,5-triazine ultraviolet light absorbers
US6492521B2 (en) Hindered amine light stabilizers based on multi-functional carbonyl compounds and methods of making same
AU1144899A (en) Morpholinones as light stabilizers
US6414155B1 (en) Oligomeric hindered amine light stabilizers based on multi-functional carbonyl compounds and methods of making same
CA2333324A1 (fr) Absorbeurs de rayonnement ultraviolet a la trisaryl-1,3,5-triazine avec phenols bloques
EP1089984B1 (fr) Absorbeurs de lumiere ultraviolette a base de triazine et de pyrimidine non sujets au jaunissement
WO2002062885A2 (fr) Articles polymeres contenant des photostabilisants a amine empechee formes a partir de composes carbonyle multi-fonctionnels
CA2427646A1 (fr) Photostabilisants oligomeres a amines inhibees a base de composes carbonyle multifonctionnels et procedes de production desdits stabilisants
US6001905A (en) Polyalkylene glycol group-containing hindered amines
US6545156B1 (en) Oligomeric hindered amine light stabilizers based on multi-functional carbonyl compounds and methods of making same
JP2004538340A (ja) 多官能カルボニル化合物が基になったヒンダードアミン系光安定剤を含有する高分子製品
EP1414799A2 (fr) Amines empechees stabilisatrices de l'action de la lumiere, a base de composes carbonyle pluri-fonctionnels de carbonyle, et leur procede d'elaboration
AU2002246783A1 (en) Hindered amine light stabilizers based on multi-functional carbonyl compounds and methods of making same
AU2002246745A1 (en) Oligomeric hindered amine light stabilizers based on multi-functional carbonyl compounds and methods of making same
AU2002246782A1 (en) Polymeric articles containing hindered amine light stabilizers based on multi-functional carbonyl compounds
EP1337580A2 (fr) Articles polymeres contenant des photostabilisants a amine empechee formes a partir de composes carbonyle multi-fonctionnels
AU2002246784A1 (en) Oligomeric hindered amine light stabilizers based on multi-functional carbonyl compounds and methods of making same
JPH10130236A (ja) アミンとエポキシドｈａｌｓからの付加物

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20030415

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE TR

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION HAS BEEN WITHDRAWN

18W Application withdrawn

Effective date: 20060628