Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
  • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
  • C07D471/10—Spiro-condensed systems
• • 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
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
  • C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
  • C07D211/06—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
  • C07D211/36—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
  • C07D211/56—Nitrogen atoms
  • C07D211/58—Nitrogen atoms attached in position 4
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
  • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
  • C08F20/10—Esters
  • C08F20/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
  • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
  • C08F20/52—Amides or imides
  • C08F20/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
  • C08F20/60—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing nitrogen in addition to the carbonamido nitrogen
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L101/00—Compositions of unspecified macromolecular compounds

Definitions

• the present invention relates to acrylate homopolymers and copolymers bearing pendant N-heterocyclic rings and to their use as light stabilizers in organic polymers.
• R 7 and R 8 are C 1 ⁇ C 12 alkyl, for example methyl, ethyl, isopropyl, n-butyl, isobutyl, t-butyl, isopentyl, n -Octyl or n-dodecyl, R 7 and R 8 are preferred C 1 ⁇ C 4 alkyl.
• R 7 is as C 3 ⁇ C 8 alkenyl, for example allyl, 2-butenyl or 2-hexenyl.
• R 7 is as C 7 ⁇ C 8 aralkyl, for example benzyl or ⁇ -phenylethyl.
• Y means -0- or preferably -0-.
• the homopolymers characterized by the definition given above are good light stabilizers. Nevertheless, in many cases it is advantageous to modify these homopolymers by copolymerization with at least one compound which has one or more polymerizable double bonds. This enables the properties, such as the solubility or the softening point of the additive, to be influenced in a simple manner.
• suitable copolymerizable components are styrene, divinylbenzene, 2- or 4-vinylpyridine, compounds from the acrylic acid series, such as esters or amides, which are derived from acrylic acid or methacrylic acid, e.g.
• Preferred copolymerizable components are styrene, acrylonitrile, acrylic or methacrylic acid esters, vinyl esters, vinyl ethers or acrylic or methacrylamides.
• Copolymers can also be made from two different piperidyl monomers.
• Compounds in soft R 1 and R 2 together represent a group of the formula VIII are particularly suitable for copolymerization reactions, be it with other piperidinyl monomers or other above-mentioned polymerizable components.
• the compound specifically chosen as the co-monomer component plays a minor role, i.e.
• the connections listed above are largely interchangeable.
• the measures which must be taken in order to obtain copolymers of similar molecular weight and similar properties are known to the person skilled in the art.
• copolymers of more than two monomeric components e.g. Terpolymers can be used.
• the molecular weight of the homo- or copolymers according to the invention is more than 500; however, it can make up to 150,000.
• Preferred compounds have a molecular weight of 500 to 50,000 and in particular 1000-20,000.
• the copolymerizable component can be completely absent or up to a 10-fold excess.
• the molar ratio of the side-containing N-heterocyclic ring-containing compound to the co-component is therefore preferably about 1: 0.001 to 1:10, in particular 1: 0.001 to 1: 5.
• the amount of the Co component can be very small (eg 0.1% based on the component of the formula 1). This will be the case in particular if the Co component has two polymerizable double bonds, such as divinylbenzene or bisacrylates or bismethacrylates with which branched or crosslinked additives are formed.
• the monomers which are suitable as starting materials for the polymerization reaction correspond to the general formula IX wherein R 1 , R 2 , R 3 and R 4 have the meaning defined above.
• R 1 is a group of the formula II in which Y is -0- or -NH and R 5 and R 6 are hydrogen, and R 2 and R 3 are hydrogen or methyl and R 4 is hydrogen
• the monomers are new and therefore also constitute an object of the invention.
• the monomers of the formula IX are themselves light stabilizers for organic material.
• the monomers of the formula IX used for the polymerization are prepared in a manner known per se, for example analogously to that in US Pat. 3,705,166 methods described. For example, it becomes a reactive derivative of an unsaturated carboxylic acid of the formula X. with one of the compounds of the formulas XI, XII, XIII or XIV wherein all the substituents have the meaning defined above, preferably implemented in an inert organic solvent.
• Reactive derivatives of an unsaturated carboxylic acid are, for example, an acid halide of the formula Xa wherein Hal, bromine or especially chlorine, or an acid anhydride of the formula Xb
• About one mole of a compound of the formula Xa or Xb is preferably used per mole of one of the compounds of the formulas XI, XII, XIII or XIV.
• R 2 , R 3 and R 4 in the formulas Xa and Xb correspond to the definition given above.
• an acid halide of the formula Xa When using an acid halide of the formula Xa, one works in the presence of a base, for example in the presence of a tertiary amine, such as triethylamine, di-isopropylethylamine, N, N-diethylaniline or pyridine; or in the presence of an anhydrous alkali metal or alkaline earth metal carbonate, or alkali metal bicarbonate such as MgCO 3 , NaHCO 3 , Na 2 CO 3 or K 2 CO 3 .
• a base for example in the presence of a tertiary amine, such as triethylamine, di-isopropylethylamine, N, N-diethylaniline or pyridine; or in the presence of an anhydrous alkali metal or alkaline earth metal carbonate, or alkali metal bicarbonate such as MgCO 3 , NaHCO 3 , Na 2 CO 3 or K 2 CO 3 .
• Aliphatic hydrocarbons such as hexane or ligroin are suitable, for example; aromatic hydrocarbons such as benzene, toluene or xylene; chlorinated hydrocarbons such as methylene chloride or chloroform; Amides such as hexamethylene phosphoric triamide; or ethers such as dioxane, 1,2-dimethoxyethane, diethyl ether or tetrahydrofuran.
• the temperature of this reaction is preferably -20 to + 120 ° C, but especially -10 ° C to + 80 ° C.
• a further process variant consists in that an ester of the formula Xc is used as the reactive derivative of a carboxylic acid of the formula X.
• R 2 , R 3 and R 4 have the meaning given above and R * C 1 ⁇ C 4 alkyl is used.
• the reactants of the formulas XI, XII, XIII or XIV, in which m and n are 1 and the other symbols have the meaning given above, can be reacted in approximately stoichiometric amounts or with an excess of Xc.
• transesterification catalyst e.g. an acid or preferably a base takes place.
• the temperature is preferably 20-170 ° C, in particular 50-150 ° C.
• An ion exchange resin can also be used as a catalyst.
• the compounds of the formula Xc are liquid compounds, a solvent can optionally be dispensed with.
• the reaction component Xc is optionally before the transesterification reaction with one of the known stabilizers, such as. Hydroquinone, hydroquinone monomethyl ether, 2,6-di-tert-butyl-p-cresol, another 2,6-di-tert-butyl-phenyl derivative or phenothiazine.
• the compounds of the formulas X, Xa, Xb and Xc used as starting materials are compounds known to the person skilled in the art and, if not commercially available, can be prepared in a simple manner.
• the piperidinyl derivatives used as reactants are also known compounds.
• the preparation of the compounds of formula XI is, for example, DT-OS 2,352,658 (4-hydroxypiperidine) or in US Pat. 3,684,765 (4-aminopiperidines).
• the compounds of the formulas XI, XII, XIII and XIV which have different substituents in the piperidyl ring in the 2- and 6-position can be prepared by reacting a ketone of the formula CH 3 ⁇ CO ⁇ CH 2 ⁇ R 6 with ammonia.
• the pyrimidine formed is, as in Helv. Chim. Acta 30, 114 (1947), hydrolyzed to an amino ketone of formula XV.
• the compounds of the formula XV are reacted in a second process step with ammonia and a ketone CH 3 ⁇ CO ⁇ CH 2 ⁇ R 6 , as described, for example, in Monthly Chemistry 88, 464 (1957) (R B has the formulas given the above meaning).
• R B has the formulas given the above meaning.
• the compounds of the formulas XI and XII, in which R 5 is hydrogen, can be obtained from the pyrimidine thus obtained by hydrolysis.
• the monomers of the formula IX can be polymerized by known methods, which are described, for example, in Houben-Weyl, 14 (1) 1010-1078 (1962).
• the reactions known under the names radical and ionic homo- or copolymerization are particularly suitable.
• the polymerization is controlled in a known manner by initiators and regulators or chain terminators. This makes it possible to obtain polymers of the desired molecular weight.
• the polyreaction can be carried out in bulk, in solution, in dispersion, in emulsion, in suspension or as a so-called bead polymerization.
• Per compounds are particularly suitable for radical homo- or copolymerization. Azo compounds and redox systems as initiators. Common organic or inorganic per-compounds include hydroperoxides, dialkyl peroxides, diacyl peroxides, peresters or peroxodisulfates. Examples of per compounds are hydrogen peroxide and potassium peroxodisulfate. Cumene hydroperoxide, di-t-butyl peroxide, ethyl methyl ketone peroxide, cyclohexanone peroxide or dibenzoyl peroxide optionally substituted by chlorine or bromine.
• Particularly suitable azo compounds are those in which the azo group is bound on both sides to tertiary carbon atoms which, in addition to alkyl groups, also carry nitrile or ester groups. If the polyreaction is triggered by means of a redox system, organic or inorganic per-compounds are suitable as oxidizing agents and either metal ions of low valence or metal-free compounds which can be easily oxidized are suitable as reducing agents. Examples of oxidizing agents are hydrogen peroxide. Peroxidisulfate or diacyl peroxides.
• the easiest way to control the molecular weight of the polymer is to use a suitable regulator.
• suitable regulator examples are mercaptans, such as n-butyl mercaptan or dodecyl mercaptan and other organic sulfur compounds, such as diisopropylxanthogen disulfide, and also aliphatic aldehydes and acetals or allyl compounds, such as allyl alcohol.
• the reaction temperatures are known to the person skilled in the art and, depending on the type of components used, are from -20 ° C. to + 200 ° C., preferably from + 20 ° C. to + 150 ° C., for the radical polymerization.
• the polymerization is ionic, it can be cationic, but preferably anionic.
• Suitable initiators are organometallic compounds such as diethyl zinc or diisobutyl zinc, naphthalene sodium, n-amyl sodium, cyclopentadienyl sodium, n-butyllithium or triethyl aluminum.
• Bases such as alkali metal hydroxides, alcoholates and amides also act as initiators.
• substances are used in ionic polymerization which react with the growing chain end; these include e.g. Water, alcohols, acids and amines.
• the temperature in this reaction variant is from -100 ° C to + 200 ° C, preferably -20 ° C to +1 50 ° C and is known to the person skilled in the art for the type of polymer desired in each case.
• the methods described are basically suitable for both homo- and copolymerization reactions. Depending on the choice of the copolymerization parameters, statistical copolymers or block copolymers are obtained in this way. It is essential for the present invention that only the physical properties such as softening point are added by adding co-monomer components. Solubility, etc. are influenced, but not their usefulness as light stabilizers for organic material. While the copolymerization of two monomers and the associated effects have been investigated particularly well and are known to the person skilled in the art, it is also useful in certain cases to use polymers of three or more polymerizable compounds. Such less known polymers are described, for example, in G.E. Ham, Copolymerization, High Polymers 18 (1964).
• the compounds of formula 1 can be used as stabilizers for plastics against their damage by the action of oxygen, heat and light.
• plastics are the polymers listed in DT-OS 2 456 864 on pages 12-14.
• polyolefins styrene polymers
• polyamides and of polyurethane for which the compounds of formula 1 are outstandingly suitable, examples being high and low density polyethylene, polypropylene, ethylene-propylene copolymers, polystyrene, styrene-butadiene Acrylonitrile terpolymers, mixtures of polyolefins or styrene polymers, polyurethanes based on polyether or polyester in the form of lacquers, threads, foils, plates, films, elastomers or foams.
• the homopolymeric or copolymeric stabilizers are added to the plastics in a concentration of 0.05 to 5% by weight, calculated on the material to be stabilized. 0.1 to 2.5% by weight of the compounds, calculated on the material to be stabilized, is preferably incorporated into the latter.
• the incorporation can take place after the polymerization, for example by mixing the compounds and, if appropriate, further additives into the melt by the methods customary in industry, before or during shaping, or else by applying the dissolved or dispersed ones gated compounds on the polymer, optionally with subsequent evaporation of the solvent.
• the new compounds can also be added to the plastics to be stabilized in the form of a masterbatch which contains these compounds, for example in a concentration of 2.5 to 25% by weight.
• the invention therefore also relates to the plastics stabilized by the addition of 0.01 to 5% by weight of a compound of the formula I, which may also contain other known and customary additives.
• the plastics stabilized in this way can be used in a wide variety of forms, e.g. as foils, fibers, tapes. Profiles or as binders for paints, adhesives or putties.
• the polymerization solution cooled to 80 ° C., was then poured into 1.3 liters of methanol at ⁇ 20 ° C. over approximately 5 minutes with vigorous turbination (Homorex) and the mixture was slowly warmed to room temperature within approximately 30 minutes. After the methanol solution had been decanted off, the resin-like deposited polymer was dissolved in a little dichloromethane and, as described, reprecipitated by pouring it into methanol. The poly-1,2,2,6,6-pentamethyl-4-methacryloxypiperidine thus purified was dried at 80 ° C. in a vacuum cabinet. The colorless, easily pulverizable polymer obtained has a softening point of ⁇ 190 ° C mol. M n) ⁇ 12,000.
• the polymerization solution cooled to about 70 ° C., was then poured into 800 ml of methanol pre-cooled to 0 ° C. with vigorous turbination (Ho morex), as a result of which the polymer precipitated out as a fine white powder. After turbinating for a further 30 minutes at room temperature, the copolymer was filtered off, washed well with methanol and dried in a vacuum cabinet at 70.degree. The colorless copolymer thus obtained has a softening point of 110 ° C.
• the 1-benzyl-2,2,6,6-tetramethyl-4-acryloyloxy-piperidine used as the monomeric component was obtained by reacting 1-benzyl-2,2,6,6-tetramethyl 4-hydroxypiperidine (m.p .: 156 ⁇ 157 ° C) with freshly distilled acrylic acid chloride in pure chloroform at 0 ° to 10 ° C in the presence of 1.1 equivalent of anhydrous triethylamine. Recrystallization from acetonitrile gave the analytically pure monomer with mp: 66 ⁇ 68 ° C.
• the exposure time up to 50% loss of tensile strength is the measure of the protective effect.

Applications Claiming Priority (2)

Publications (2)

Family

ID=4346229

Family Applications (1)

Country Status (7)

Cited By (9)

Families Citing this family (55)

Family Cites Families (9)

• 1978
  • 1978-07-11 EP EP78100360A patent/EP0000496B1/de not_active Expired
  • 1978-07-11 DE DE7878100360T patent/DE2861843D1/de not_active Expired
  • 1978-07-13 US US05/924,417 patent/US4210612A/en not_active Expired - Lifetime
  • 1978-07-17 CA CA000307495A patent/CA1147097A/en not_active Expired
  • 1978-07-18 BR BR7804636A patent/BR7804636A/pt unknown
  • 1978-07-18 AU AU38128/78A patent/AU517364B2/en not_active Expired
  • 1978-07-19 JP JP8821978A patent/JPS5421489A/ja active Granted
• 1980
  • 1980-01-25 US US06/115,277 patent/US4294949A/en not_active Expired - Lifetime

Also Published As

Similar Documents

Legal Events