US3639329A - Benzene polycarboxylic acid esters - Google Patents

Benzene polycarboxylic acid esters Download PDF

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Publication number
US3639329A
US3639329A US732028A US3639329DA US3639329A US 3639329 A US3639329 A US 3639329A US 732028 A US732028 A US 732028A US 3639329D A US3639329D A US 3639329DA US 3639329 A US3639329 A US 3639329A
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film
acid
propyl
radicals
coating
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US732028A
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Morice William Thompson
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Imperial Chemical Industries Ltd
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Imperial Chemical Industries Ltd
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00Preparation of carboxylic acid esters
    • C07C67/08Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00Preparation of carboxylic acid esters
    • C07C67/24Preparation of carboxylic acid esters by reacting carboxylic acids or derivatives thereof with a carbon-to-oxygen ether bond, e.g. acetal, tetrahydrofuran
    • C07C67/26Preparation of carboxylic acid esters by reacting carboxylic acids or derivatives thereof with a carbon-to-oxygen ether bond, e.g. acetal, tetrahydrofuran with an oxirane ring
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/76Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/76Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
    • C07C69/80Phthalic acid esters

Definitions

  • n is an integer from 1 to 3
  • X and X are straight or branched chain alkylene radicals the same or different containing from 2 to 4 carbon atoms and R and R are alkyl, cycloalkyl, aralkyl, aromatic or heterocyclic radicals, the same or different and containing from 1 to 18 carbon atoms in the alkyl radical.
  • esters are those wherein the substituent in the benzene ring of variable position is in one or more of the positions numbered 2, 4, 5 with respect to the substitutent of specified position in the above structural formula.
  • the most preferred esters are those in which the substituents of the benzene ring are in the 1, 2, the 1, 2, 4, or the 1, 2, 4, 5 positions, that is they are derivatives of o-phthalic acid, trimellitic acid or pyromellitic acid. They may also be derivatives of the other phthalic acid isomers.
  • alkylene radicals X and X which may be the same or different in each subsituent, may be for example ethylene, propylene, isopropylene, butylene and isobutylene.
  • the radicals R and R which may be the same or different in each substituent, may be straight or branched chain saturated or unsaturated alkyl radicals and contain up to 18 carbon atoms for example ethyl, propyl, butyl, amyl, hexyl, 2-ethyl hexyl, octyl, iso-octyl, nonyl, decyl, lauryl, tetradecyl, allyl or oleyl radicals.
  • the preferred alkyl radicals are saturated straight or branched chain containing from 6 to 10 carbon atoms.
  • radicals R and R may alternatively be a cyclo-alkyl radical for example cyclopentyl, cyclohexyl or cycloheptyl; or an aralkyl radical, for example benzyl, or phenyl ethyl; or an aromatic radical for exam ple phenyl, naphthyl; or a heterocyclic radical, for example pyridyl. It is particularly preferred that R and/ or R are phenyl radicals.
  • esters may be prepared by any suitable method known in the art, they are preferably prepared by esterifying the appropriate benzene polycarboxylic acid with a hydroxy ester and according to a further feature of the invention we provide a process of preparing esters of benzene polycarboxylic acids which comprises completely esterifying a benzene polycarboxylic acid of struc ture:
  • Preferred benzene polycarboxylic acids are phthalic, trimellitic and pyromellitic acids and we include the use of the acid anhydrides.
  • Suitable alkylene oxides include ethylene oxide, 1,2- propylene oxide and 1,2-butylene oxide, and mixtures thereof but 1,2-propylene oxide is preferred.
  • Suitable carboxylic acids include acetic acid, butyric acid, octoic acid, lauric acid, cycloheptylic acid, benzoic acid and mixtures thereof. Particularly preferred acids are those in which R represents a straight or branched carbon chain of 6-10 carbon atoms and more particularly, 8 carbon atoms, that is octoic acid.
  • octoic acid may be reacted with propylene oxide to form a hydroxy ester which is then reacted with phthalic acid or the anhydride thereof to form the benzene polycarboxylic acid ester.
  • the ester produced is in fact a mixture of two isomers which may be separated only with difliculty.
  • ethylene oxide is employed an ester of unambiguous structure is obtained.
  • the individual isomers may only be separated and characterised with great difiiculty but for most applications the mixture of isomeric esters is found to be 'quite suitable.
  • compositions are those in which the film-forming polymer contains polar groups.
  • Filmforming polymers which contain polar groups and which are commonly employed in coating compositions include homopolymers and copolymers of the lower alkyl acrylates and methacrylates, for example methyl methacrylate, homopolymers and copolymers of vinyl acetate and homopolymers and copolymers of vinyl chloride.
  • Film-forming polymers which are suitable in most respects for use in surface coatings, for example by virtue of their durability and ease of application, are frequently deficient in that they provide coatings which, for example, although hard may be brittle and may have poor adhesion to a substrate. It is therefore common practice to incorporate with such polymers a plasticiser which will lessen the brittleness. However, when it is necessary to repair a damaged coating, particularly a coating based on an acrylic polymer, by a method in which the original coating is exposed to a solvent the repaired coating may suffer from crazing.
  • Crazing is characterised by the appearance in the coating of minute surface cracks which cause a difference in the appearance of the repaired and the unrepaired areas of the coating, and is due primarily to the loss of plasticiser from the coating either by volatilisation or by migration into an adjacent coating.
  • plasticisers commonly employed in compositions which comprise a film-forming polymer are certain esters of phthalic acid, such as dibutyl phthalate and butyl benzyl phthalate, which may be used in the presence of other modifiers for the film-forming polymer.
  • These plasticisers suffer from several disadvantages, in particular their tendency to volatilise from the coating film and to migrate into an adjacent substrate. Lacquer coatings containing these plasticisers are also liable to become marked when spots of rain water are allowed to dry upon them particularly in the sun.
  • the new plasticisers may be employed in coating compositions where film-forming is present in solution and/or in dispersion.
  • the composition may comprise a solution of a polymer of methyl methacrylate in a solvent such as toluene or alternatively it may comprise a fine particle-size dispersion of a polymer of methyl methacrylate in a diluent such as an aliphatic hydrocarbon.
  • the new plasticisers may be readily incorporated into the composition so that the characteristics of the final polymer film are improved.
  • the new plasticisers are also useful in the preparation of plastisols.
  • the new plasticisers are not in any way to be limited We find that they are particularly suitable in coating compositions which contain as a filmformer a polymer of methyl methacrylate.
  • the polymer of methyl methacrylate may be a homopolymer or it may be a copolymer of methyl methacrylate with a minor proportion of other ethylenically unsaturated compolymerisable monomers, for example up to of monomers such as acrylic or methacrylic acids and/or up to of the lower alkyl esters of these acids, for example ethyl acrylate or butyl methacrylate.
  • One typical film-forming methyl methacrylate polymer consists of a copolymer of 80% methyl methacrylate, 18% of ethyl acrylate and 2% of methacrylic acid.
  • the new plasticisers have particularly good compatibility with the methyl methacrylate polymers and that there is very little migration of plasticiser from the polymer film into the undercoat over which the film is applied.
  • the final coating is produced by reflow of the lacquer coating on a substrate, a good gloss is obtained and there is little loss of plasticiser.
  • the proportion of the plasticiser to be used will depend largely on the nature of the film-forming polymer and other materials present in the coating composition and on the characteristics required in the final film. In general it is preferred to use at least 5% and not more than 60% by weight of plasticiser based on the weight of film-forming polymer.
  • plasticiser are from 15% to 40% by weight based on the weight of film-forming polymer.
  • pigments there may be present for example pigments, fillers, other conventional plasticisers, or modifiers for the main film-forming polymer or an additional film-forming polymer such as for example cellulose acetate butyrate.
  • Solvents and/ or diluents which may be present in the coating composition include ketones alcohols, xylene, butyl acetate and aliphatic hydrocarbons.
  • EXAMPLE 1 720 parts of n-caprylic acid and 5.27 parts of the dimethyl derivative of an amine obtained by hydrogenating the amide of coconut oil fatty acids were mixed in a pressure vessel under a nitrogen atmosphere and heated under pressure to C. whilst 333.5 parts of propylene oxide were passed into the mixture. The temperature was maintained at 85 C. and the pressure maintained at 60 pounds per square inch until the acid value was less than 5 mg. KOH/ gm. Excess propylene oxide was removed from the resulting crude mixture of the two stereo-isomers of 5- hydroxy propyl octoate.
  • EXAMPLE 2 Benzene polycar- Aliphatic or Benzene polycarboxylic acid/acid aromatic boxylic acid anhydride monocarester boxylic acid Phtlgilic anhydride. Acetic acid Phthalyl bis(;3-propyl acetate).
  • Butyrie acid Phthalyl bis(
  • pigmented with rutile titanium dioxide in a pigment: binder ratio of 0.5 :l by weight The total solids of the pigmented lacquer was 40.0% by weight, the volatile fraction of the lacquer consisting of a mixture of solvents in the relative proportions toluenezacetonezxylol of 3.5 :1:1 by weight.
  • the lacquer was reduced for application with a thinner containing 30 parts acetone, 40 parts toluene and 30 parts cellosolve acetate to give a viscosity of 30 seconds in a British Standard Type B No. 3 cup at 25 C.
  • Three double coats were then applied by spray to a mild steel panel coated with a baked, high pigment volume epoxy surfacer. The panel was then baked for 15 minutes at 200 F.
  • the film weights on the panel were 1.2 thou. of surfacer and 2.0 thou. of acrylic lacquer.
  • the lacquer film was then sanded with 600 grade abrasive paper using white spirit as lubricant and baked for 30 minutes at 275 F.
  • volrtiles at 310F 1:1 Cold crack cycle as de- No failure No failure.
  • pigmented with rutile titanium dioxide in a pigment:binder ratio of 0.5 :1 by Weight The total solids of the pigmented lacquer was 40.0% by weight and the volatile fraction of the lacquer consisted of a mixture of solvents in the relative proportions toluenezacetone-xylol or 3.5:111 by weight.
  • Example 1 A test was prepared by the procedure described in Example 1 having a smooth glossy film after being refiowed for 30 minutes at 275 F.
  • the film had excellent refiow potential, chip resistance, intercoat adhesion and stain resistance.
  • the petrol resistance was very good.
  • Panels prepared for the G-cycle cracking test over a nitrocellulose undercoat were subjected to the cycle described in ASTM Method D2246-64T and were free from film breakdown after 15 cycles.
  • a conventional lacquer coating as control was cracked after the same treatment.
  • the volatility of the plasticiser was that of a similar lacquer in which the plasticiser was butyl benzyl phthalate.
  • the new ester also gave improved results when incorporated in coatings which contained polyvinyl acetate and polyvinyl chloride respectively as the film-forming materials.
  • a coating composition which comprises a film-forming polymer selected from the group consisting of homopolymers and copolymers of lower alkyl acrylates and methacrylates, homopolymers and copolymers of vinyl acetate and homopolymers and copolymers of vinyl chloride, and 5-60%, based on the weight of said film-forming polymer, of a plasticizer having the formula wherein n is an integer from 1 to 3, X and X are straight or branched chain alkylene radicals the same or diiferent containing from 2 to 4 carbon atoms and R and R are each saturated straight or branched chain alkyl radicals containing from 6 to 10 carbon atoms, benzyl, phenylethyl, phenyl, naphthyl and pyridyl.
  • a coating composition according to claim 1 wherein the film-forming polymer is a homopolymer or copolymer of methyl methacrylate.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Paints Or Removers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Laminated Bodies (AREA)
US732028A 1967-05-30 1968-05-27 Benzene polycarboxylic acid esters Expired - Lifetime US3639329A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB24926/67A GB1171829A (en) 1967-05-30 1967-05-30 Benzene Polycarboxylic Acid Esters Plasticisers

Publications (1)

Publication Number Publication Date
US3639329A true US3639329A (en) 1972-02-01

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US (1) US3639329A (en:Method)
BE (1) BE715913A (en:Method)
DE (1) DE1768580A1 (en:Method)
ES (1) ES354504A1 (en:Method)
FR (1) FR1567564A (en:Method)
GB (1) GB1171829A (en:Method)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4053681A (en) * 1976-02-26 1977-10-11 Standard Oil Company (Indiana) Additives for improved polyester and vinyl polymer compositions
US5302650A (en) * 1990-08-06 1994-04-12 Riken Vinyl Industry Co., Ltd. Vinyl chloride resin composition

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4053681A (en) * 1976-02-26 1977-10-11 Standard Oil Company (Indiana) Additives for improved polyester and vinyl polymer compositions
US5302650A (en) * 1990-08-06 1994-04-12 Riken Vinyl Industry Co., Ltd. Vinyl chloride resin composition

Also Published As

Publication number Publication date
GB1171829A (en) 1969-11-26
FR1567564A (en:Method) 1969-05-16
ES354504A1 (es) 1969-11-16
DE1768580A1 (de) 1972-02-17
BE715913A (en:Method) 1968-12-02

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