US3639329A - Benzene polycarboxylic acid esters - Google Patents
Benzene polycarboxylic acid esters Download PDFInfo
- 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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- United States
- Prior art keywords
- film
- acid
- propyl
- radicals
- coating
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 title abstract description 39
- 239000002253 acid Substances 0.000 title abstract description 21
- 150000002148 esters Chemical class 0.000 title description 21
- 239000004014 plasticizer Substances 0.000 abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 8
- 229910001868 water Inorganic materials 0.000 abstract description 8
- 150000007513 acids Chemical class 0.000 abstract description 7
- 230000032050 esterification Effects 0.000 abstract description 2
- 238000005886 esterification reaction Methods 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 description 26
- 239000008199 coating composition Substances 0.000 description 17
- 239000000203 mixture Substances 0.000 description 17
- 125000004432 carbon atom Chemical group C* 0.000 description 16
- 238000000576 coating method Methods 0.000 description 16
- 239000011248 coating agent Substances 0.000 description 12
- 239000004922 lacquer Substances 0.000 description 12
- 125000001557 phthalyl group Chemical group C(=O)(O)C1=C(C(=O)*)C=CC=C1 0.000 description 11
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 10
- 229920001577 copolymer Polymers 0.000 description 9
- 229920001519 homopolymer Polymers 0.000 description 8
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical class OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 7
- IRIAEXORFWYRCZ-UHFFFAOYSA-N Butylbenzyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCC1=CC=CC=C1 IRIAEXORFWYRCZ-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- -1 ethylene, propylene Chemical group 0.000 description 6
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 5
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 239000000049 pigment Substances 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 239000004923 Acrylic lacquer Substances 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 229920006217 cellulose acetate butyrate Polymers 0.000 description 3
- 125000000753 cycloalkyl group Chemical group 0.000 description 3
- 239000003085 diluting agent Substances 0.000 description 3
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229920006254 polymer film Polymers 0.000 description 3
- 229940090181 propyl acetate Drugs 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 125000005250 alkyl acrylate group Chemical group 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 125000004076 pyridyl group Chemical group 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- RBACIKXCRWGCBB-UHFFFAOYSA-N 1,2-Epoxybutane Chemical compound CCC1CO1 RBACIKXCRWGCBB-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 229920001944 Plastisol Polymers 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 125000005395 methacrylic acid group Chemical class 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000003021 phthalic acid derivatives Chemical class 0.000 description 1
- 239000004999 plastisol Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 125000001919 trimellityl group Chemical group C(=O)(O)C=1C=C(C(=O)*)C=CC1C(=O)O 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/24—Preparation of carboxylic acid esters by reacting carboxylic acids or derivatives thereof with a carbon-to-oxygen ether bond, e.g. acetal, tetrahydrofuran
- C07C67/26—Preparation 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
- C07C69/80—Phthalic 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.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Paints Or Removers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Laminated Bodies (AREA)
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 |
Family
ID=10219464
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US732028A Expired - Lifetime US3639329A (en) | 1967-05-30 | 1968-05-27 | Benzene polycarboxylic acid esters |
Country Status (6)
Country | Link |
---|---|
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)
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 |
-
1967
- 1967-05-30 GB GB24926/67A patent/GB1171829A/en not_active Expired
-
1968
- 1968-05-27 US US732028A patent/US3639329A/en not_active Expired - Lifetime
- 1968-05-30 ES ES354504A patent/ES354504A1/es not_active Expired
- 1968-05-30 BE BE715913D patent/BE715913A/xx unknown
- 1968-05-30 FR FR1567564D patent/FR1567564A/fr not_active Expired
- 1968-05-30 DE DE19681768580 patent/DE1768580A1/de active Pending
Cited By (2)
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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