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  • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
  • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
  • C07D307/26—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
  • C07D307/30—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member 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
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  • C07C67/00—Preparation of carboxylic acid esters
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  • C07C67/31—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of functional groups containing oxygen only in singly bound form
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  • C07C69/62—Halogen-containing esters
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  • C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
  • C07C69/73—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of unsaturated acids
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  • 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
  • C08F20/04—Acids, Metal salts or ammonium salts thereof
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  • 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
  • C08F20/62—Monocarboxylic acids having ten or more carbon atoms; Derivatives thereof
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  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F22/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides or nitriles thereof
  • C08F22/10—Esters
  • C08F22/12—Esters of phenols or saturated alcohols
  • C08F22/18—Esters containing halogen
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  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—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
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/22—Esters containing halogen
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  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/17—Amines; Quaternary ammonium compounds
  • C08K5/18—Amines; Quaternary ammonium compounds with aromatically bound amino groups
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
  • C11C1/00—Preparation of fatty acids from fats, fatty oils, or waxes; Refining the fatty acids
  • C11C1/08—Refining
  • C11C1/10—Refining by distillation
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
  • C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2601/00—Systems containing only non-condensed rings
  • C07C2601/18—Systems containing only non-condensed rings with a ring being at least seven-membered
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  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2603/00—Systems containing at least three condensed rings
  • C07C2603/56—Ring systems containing bridged rings
  • C07C2603/58—Ring systems containing bridged rings containing three rings
  • C07C2603/60—Ring systems containing bridged rings containing three rings containing at least one ring with less than six members
  • C07C2603/66—Ring systems containing bridged rings containing three rings containing at least one ring with less than six members containing five-membered rings
  • C07C2603/68—Dicyclopentadienes; Hydrogenated dicyclopentadienes

Definitions

• This invention relates to the preparation of vicinal acryloxy-halo long-chain aliphatic compounds. More specifically, this invention relates to the preparation of long-chain vicinal 'acryloxy-halo compounds by the reaction of an acid acrylic compound and an alkyl hypohalite with a long-chain unsaturated compound, i.e., a haloacylation reaction in which a halogen and an acyloxy group are introduced in one reaction on adjacent carbon atoms.
• the electrophilic nature of the carboxy group of the alpha, beta-ethylenically unsaturated monocarboxylic acid and the presence of two such electrophilic groups in the halfesters of alpha, beta-ethylenically unsaturated dicarboxylic acids renders the ethylenic double bond in these acid acrylic compounds surprisingly resistant to attack by alkyl hypohalites.
• R is hydrogen, halogen or alkyl of from 1 to 4 carbon atoms; and Y is an aliphatic or aromatic monovalent radical of up to 18 carbon atoms.
• One principal object of this invention is to provide a process of making novel vicinal acryloxy-halo aliphatic reaction products, which comprises reacting a long-chain ethylenically unsaturated compound, an acid acrylic compound and an alkyl hypohalite.
• Another principal object of this invention is the provision of novel acryloxy-halo long-chain aliphatic reaction products, which have utility in the preparation of useful resinous homopolymers and/ or copolymers.
• Another, and somewhat more general object of this invention is a process of making vicinal acryloxy-halo aliphatic compounds, which comprises reacting an alkyl hypohalite, an acid acrylic compound and an ethylenically unsaturated compound.
• this invention is a process of reacting an alkyl hypohalite, an acid acrylic compound and a longchain ethylenically unsaturated compound to introduce halogen and an acyloxy group in one reaction on adjacent carbon atoms.
• the half-esters of alpha, beta-ethylenically unsaturated alpha, beta-dicarboxylic acids are not articles of commerce since they undergo dismutation whereby a mixture of diester and free dicarboxylic acid forms within a short time after their preparation.
• the only commercially feasible method of preparing these compounds in good yields is to react a monohydroxy compound and the anhydride of the dicarboxylic acid. Since fumaric acid by its very nature cannot exist as an anhydride, its halfester cannot be prepared in this manner. This is a serious problem since the products of this invention that are based on the fumaric acid half-esters are among the most important commercially.
• an important object of this invention is a commercially feasible method of preparing acryloXy-halo long-chain aliphatic compounds, wherein the acryloxy group is the residue of a half-ester of fumaric acid.
• this invention is a process of reacting a monohydroxy organic compound with maleic anhydricle to form a half-ester, isomerizing the maleic acid half-ester to a fumaric acid half-ester and then reacting the fumaric acid half-ester, an alkyl hypohalite and a long-chain ethylenically unsaturated compound.
• the products of this invention are prepared by reacting an acid acrylic compound (as defined above), an ethylenically unsaturated long-chain aliphatic compound (as defined above) and an alkyl hypohalite.
• the carbonium ion then seemingly attracts the negative anion of the acid acrylic compound to form a vicinal acryloXy-halo compound.
• the alkoXy anion, from the alkyl hypohalite, and the hydrogen ion of the acid acrylic compound combine to form an alkanol as a by-product.
• R, R and R are as defined above; R is alkyl and X is halogen.
• the acylating acid acrylic compounds of this invention all have an ethylenically unsaturated double bond, which is itself a theoretical point of haloacylation.
• this ethylenically unsaturated double bond is quite stable in the presence of a long-chain ethylenically unsaturated compound.
• acrylic acid itself, and methacrylic acid as well this resistance seems to be due in part to the terminal position of the ethylenic double bond, but more importantly to the presence of an electrophilic carboxyl group attached to a carbon atom of the ethylenic group, which makes the ethylenic double bond part of a conjugated double bond system.
• Alpha-chloroacrylic acid and the half-esters of maleic and furnaric acid are even less prone to undergo haloacylation because of the presence of a second electrophilic group on one of the carbon atoms of the ethylenic group. Any small amount of reaction between the acid acrylic compound and another molecule of acid acrylic compound yields product that is compatible with the main reaction products and polymers thereof or in most cases may be removed in an alkaline wash.
• hypohalite reactant While various alkyl hypohalites can be used in the instant invention for the haloacylatio-n reaction, tertiary alkyl hypoha-lites, such as tertiary butyl hypochlorite and tertiary amyl hypochlorite, are preferred, since they are considerably more stable than the normal and secondary alkyl hypohalites.
• tertiary butyl hypochlorite can be distilled at about 79 C.; or further, even without distillation, it can be stored (in the dark) at room temperature for months Without decomposing.
• Tertiary butyl hypoch-lorite is particularly adv-antageous because it can be produced easily and inexpensively.
• the long-chain unsaturated reactant in somewhat greater detail can contain various other groups such as hydroxyl groups, carboxyl groups, carboxyl'ate groups, carbamyl groups, amino groups, nitrilo groups, car-bamato groups, halo groups, acy-loxy groups, mercapto groups, alkoxy groups, aryloxy groups, etc.
• the preferred long-chain ethylenically unsaturated compounds of this invention are the readily available, naturally occurring glyceride oils (which are considered as having carboxy'late groups), such as soybean, corn oil, cottonseed oil, hempseed oil, tung oi-l, safiiower oil, peanut oil, linseed oil, tobacco seed oil, cod oi-l, hearing (or menhaden) oil, castor oil, etc.
• Esters of other unsaturated long-chain acids are also advantageous as starting materials, such as the methyl ester of oleic acid, the 2-ethylhexyl ester of linoleic acid, various esters of tall oil fatty acids, etc.
• the glycerides and other esters generally are stable in the reaction of this invention although small proportions of secondary products (other than those previously mentioned) may be produced during the reaction in accordance with this invention.
• Z is the residue of a hydroxyl compound, in is a number ranging from 0 to 5
• n is a number ranging from 0 to 5
• the sum of m and n+1 is 1 to 6, the number of hydroxyl groups in the original hydroxyl compound
• each R is independently a group selected from the group consisting of hydrogen, monovalent aliphatic groups having from 1 to 24 carbon atoms and monovalent aromatic groups having from 6 to 18 carbon atoms.
• the alcohols from which Z in the preceding formula may be derived can contain from 1 to 6 hydroxyl groups and from 1 to 24,carbon atoms. They can be saturated or ethylenically unsaturated. They may be open chain compounds such as n-butanol, glycerol, and sorbitol, or cyclic compounds such as furfury-l alcohols, cyclohexanol, and inositol.
• suitable alcohols for this purpose are the monohydric alcohols ranging from methyl to lignoceryl, including the isomers in which the hydroxyl groups may be primary, secondary, or tertiary.
• dihydric alcohols ethylene glycol, trimethylene glycol, and the polyoxyalkylene glycols in which the oxyalkylene groups have 1 to 3 carbon atoms, i.e., the polymethylene glycols, the polyethylene glycols and the polypropylene glycols.
• additional suitable higher polyhydric alcohols are pentaerythritol, arabitol, mannitol, tr-imethylol propane, trimethylol ethane, trimethylol methane, etc.
• Suitable esters may also be obtained from aromatic hydroxy compounds such as phenol, the cresols, resorcinol, hydroquinone, naphthol, etc.
• ester consists of a polyhydric alcohol only partially esterfield with a long-chain carboxylic acid, e.g. monoglycerides and diglycerides.
• esters of a polyhydric alcohol acylated in part by saturated acids.
• the glyceryl hydroxy groups in the foregoing monoglycerides and diglycerides may be esterified with acids such as acetic acid, benzoic acid, stearic acid, etc.
• the acid acrylic compound The following compounds are representative of the various acid acrylic compounds, which can be used as acylating agents in this invention: acrylic acid; methacrylic acid; ethacrylic acid; alpha-chloroacrylic acid; alphabromoacrylic acid; alpha-iodoacrylic acid; alpha-phenylacrylic acid; alpha-benzylacrylic acid; alpha-propoxyacrylic acid; methyl hydrogen itaconate; methyl hydrogen maleate; methyl hydrogen fumarate; methyl hydrogen mesaconate; methyl hydrogen citraconate; ethyl hydrogen maleate; ethyl hydrogen fumarate; n-propyl hydrogen maleate; isopropyl hydrogen fumarate; n-butyl hydrogen maleate; tertiary-butyl hydrogen fumarate; isoa-myl hydrogen fumarate; 4-methyl-2-pentyl hydrogen fumarate; n-octyl hydrogen maleate; 2-ethylhexyl hydrogen fuma
• Half-esters of alpha, beta-ethylenically unsaturated dicarboxylic acids An important characteristic of the half-esters of the unsubstituted alpha, beta-ethylenically unsaturated alpha, beta-dicarboxylic acids (maleic acid and fumaric acid) is that the properties of the acryloxy-halo polymerizable products based on these half-esters can be readily and inexpensively varied by selecting the proper alcohol from which the half-ester is made.
• the half-ester when the half-ester is based on a lower alcohol, such as isopropanol, copolymerization products of the compounds of this invention with monomers such as styrene, are more rigid than when the half-ester is based on a higher alcohol, such as Z-ethylhexanol.
• a higher alcohol such as Z-ethylhexanol.
• the flexibility of the copolymers increases as the number of carbon atoms in the alcohol increases.
• aryl half-esters form harder, copolymerization products than the corresponding alkyl half-esters.
• the half-ester-derived haloacryloxy compounds of this invention are frequently as cheap or cheaper than the acrylic acid-and methacrylic acid-derived compounds of this invention.
• products based on the isopropyl half-ester of fumaric or maleic acid have a decided cost advantage over the monocarboxylic acid acrylic compounds. While the halfesters of substituted alpha, beta-ethylenically unsaturated alpha, betadicarboxylic acids and the half-ester of itaconic acid offer the same product flexibility as the maleate and fumarate half-esters, the cost makes their use less attractive.
• the halo-acryloxy compounds based on the fumaric acid half-esters are an important class of polymerizable compounds of this invention. This is particularly true of the alkyl hydrogen fumarates having from 2 to 13 carbon atoms in the alkyl group.
• the copolymers based on the fumarate half-esters are clearer, tougher, and have higher tensile strength than the corresponding products based on the maleate half-esters.
• the fumaric acid half-esters are prepared by reacting substantially equal molar quantities of maleic anhydride and a monohydric alcohol at a temperature of from about 20 C. to about 200 C., and isomerizing the maleic acid half-ester to the fumaric acid half-ester using heat and/or an isomerization catalyst.
• esterification catalysts such as 3P p-toluenesulfonic acid, etc.
• 3P p-toluenesulfonic acid etc.
• the esterification-reaction product from maleic anhydride contains a mixture of diester, monoester, dicarboxylic acid (both maleic and fumaric) and possibly some unreacted anhvdride.
• unreactive maleic diester can be tolerated as it only adds to the cost of the final product.
• free maleic anhydride, or free dicarboxylic acid, in the reaction mixture raises a serious problem, since these compounds can cross-link prematurely materials having more than one ethylenically unsaturated group per molecule into an infusible mass, (Where there is only one ethylenically unsaturated group per molecule, free maleic anhydride or dicarboxylic acid raises no problem.
• fumaric acid which is also present is so inert and insoluble, and has such a high melting point that it often precipitates from the monomeric reaction product and/ or final polymer masses made from it.
• an esterification catalyst of the above type when used in the preparation of the half-ester, it is preferred to use an excess of monohydroxy com pound and/or to separate the half-ester from any anhydride or dicarboxylic acid formed during esterification.
• the half-ester can be prepared directly from the cis or trans dicarboxylic acid or the acid halide, and, in this case, the aforementioned esterification catalysts are ad- In this case too, the esterification-reaction product will usually contain a mixture of all the compounds that can occur with the maleic anhydride and an esterification catalyst and the same precautions should be observed.
• the monohydroxy compound and maleic anhydride are preferably used in substantially equal molar proportions, it is possible to use either compound in excess.
• maleic anhydride is used in a molar excess of 25% or more over the monohydroxy compound (i.e., a ratio of more than 1.0 to 0.8)
• the half-ester should be isolated from the reaction mixture before reacting it with a polyunsaturated compound, since any dicarboxylic acid formed from the unreacted anhydride can cross-link the polyunsaturated compound into an infusible mass, as pointed out previously.
• alcohols can be used in a substantial excess (e.g., 3 or 4 moles to 1 mole anhydride), provided no esterification catalyst is present.
• the free excess alcohol should be removed prior to the haloacylation, since, if it is not removed, it will compete with the acid acrylic compound in its reaction with the carbonium ion, thereby decreasing the yield of acryloxyhalo groups.
• the mole ratio of alcohol to anhydride should be no more than 1.5 to l.
• Aromatic hydroxy compounds such as phenol or cresol, should not be used in an excess unless the unreacted hydroxy compound is removed, since any unreacted portion of these aromatic hydroxy compounds can inhibit the subsequent copolymerization of their monomeric haloacylation reaction prod- -ucts.
• the half-esters can be prepared at a temperature of from about 20 C to 200 C. However, it is usually preferable to carry out this reaction at moderately elevated temperatures (e.g., 80 C.150 C.) in order to get a rapid reaction Without having the half-ester undergo dismutation (i.e., forming diester and dicarboxylic acid).
• moderately elevated temperatures e.g. 80 C.150 C.
• the half-ester of maleic acid can be rapidly converted to the half-ester of fumaric acid at a temperature of from 50 C. to 150 C. without any significant dismutation.
• the isomerization is complete in from about 5 to 60 minutes.
• the following compounds can be used as isomerization catalysts: phosphorus oxychloride, phosphorus trichloride, thionyl chloride, phosphorus oxybromide, phosphorus oxyiodide, phosphorus oxyfluoride, phosphorus tribromide, phosphorus triiodide, phosphorus trifluoride, Z-ethylhexyl phosphoryl dichloride, di (2 ethylhexyl) phosphoryl rnonochloride, phosphorus thiobromide, phosphorus thiochloride, thionyl bromide, thionyl fluoride, hexadecane, sulfone chloride, toluene sulfone chloride, chlorosulfonic acid, sulfur monobromide, sulfur monochloride, sulfur dichloride, sulfuryl chloride, iodine, bromine, aluminum chloride, diethyl amine, sulfur dioxide, zinc
• catalysts can be used in an amount equal to from 0.0001 mole to 0.1 mole per mole of half-ester. Larger concentrations only increase the cost of the product without assisting the reaction.
• Thionyl chloride, aluminum chloride, phosphorus trichloride and phosphorus oxychloride are the preferred catalysts because of their availability and efiiciency.
• Temperature and optional catalyst for the haloacylation reaction Vicinal acyloxy-halo compounds of this invention are prepared by reacting the acid acrylic compound, a longchain ethylenically unsaturated compound, and the .alkyl hypohalite at a temperature of from about -50 C. to about C.
• the reaction is strongly exothermic and the reaction mixture, particularly in large scale operations, should be cooled to prevent damaging temperature rise.
• Useful reaction rates without objectionable product discoloration and without decomposition are obtained in the range of 0-100 C. and the preferred range is about 25 -75 C.
• the reaction is substantially complete in 1-5 hours, the vapor pressure of the preferred hypohalite (tertiary butyl hypochlorite) is moderate, product discoloration is nil, and side reactions of the acid arcylic compound with tertiary alkyl hypochlorite is suppressed.
• Higher reaction temperatures lead to product discoloration and to problems stemming from higher vapor pressure of the hypochlorite necessitating the use of pressure vessels.
• the chief disadvantage of lower temperatures is reduced reaction rate and correspondingly longer reaction time.
• useful products are obtained in %8 hours. Over the broader temperature range of -50 C. to 150 C., the reaction time will vary from virtually instantaneous reaction to reaction of several weeks duration.
• a catalyst such as a tetraalkyl ammonium salt or a tetraalkyl phosphonium salt can be employed.
• these catalysts can be employed in a concentration of 0.0001 to 0.1 mole per equivalent of ethylenic unsaturation in the ethylenically unsaturated compound.
• Tetramethyl ammonium chloride is particularly efiicacious.
• the acid acrylic compound, alkyl hypohalite and long chain ethylenically unsaturated compound can be present in the reaction mixture in virtually any proportions.
• a higher proportion of the alkyl hypohalite accelerates the reaction only slightly and may create the inconvenience of having to remove excess hypohalite and/or alcoholic by-products' from the reaction product. However, this inconvenience may be compensated for the copolymers of the reaction product having increased toughness and/ or rigidity.
• copolymers of styrene with the reaction product of tertiary butyl hypochlorite, soybean oil and acrylic acid in a ratio of 1.20:1.00:1.35 are stronger and more rigid than when the ratio is 1.00: 1.00: 1.35.
• a lower proportion of the alkyl hypohalite reduces the number of ethylenic groups that are haloacylated.
• useful products are obtained over the range of about 0.1 to about 3 moles of alkyl hypohalite per equivalent of ethylenic unsaturation.
• the acid acrylic compound should be used in the preferred proportion of about 1.2 to 2 moles per equivalent of ethylenic unsaturation in the ethylenically unsaturated compound, and the most effective concentration varies with temperature. For example, at about 45 C., a ratio 1.7 to 1 is most effective, while at about 65 C., a ratio of 1.35 to 1 is most effective. Compared with results at a l to 1 ratio, the preferred proportions provide a significantly higher reaction rate and yield of acryloxy-halo compound.
• the residual acid acrylic 4 compound may be removed along with the alcoholic by-products by alkaline aqueous washing or by vacuum distillation.
• a polymerization inhibitor such as metallic copper, an amine, a phenolic or a quinoid compound, should be present in the haloacylation in the proportion of from about 0.001 to 0.5 weight percent of the reactants when an acid acrylic compound having terminal ethylenic unsaturation is employed as the acylating agent.
• the inhibitor should be used in the proportion of from about 0.01 to 0.1 weight percent of the reactants.
• the phenolic compounds are preferred since they have less tendency to produce undesirable color than the amines do; also the amines tend to react with alkyl hypohalites.
• sufiicient phenolic inhibitor is usually present in the commercially available monocarboxylic acids, and in this event it is unnecessary to add additional inhibitor.
• Acid acrylic compounds having an esterified carboxyl group on the beta carbon atom e.g. maleic acid halfesters and fumaric acid half-esters
• the physical and chemical characteristics of the novel vicinal acryloxy-halo-compound reaction products contemplated by this invention, and more particularly the polymers and resins derived therefrom, are capable of wide variation by selecting properly the reactants, i.e. the unsaturated compound and the acid acrylic compound, and the extent of .acylation.
• the reaction products of this invention may be polymerized through the ethylenic groups in the acylating acid with known catalysts, either ionic or free radical, to form useful homopolymers, or they may be polymerized with other vinylidene compounds to form useful copolymers.
• vinylidene monomers with which the acryloxy-halo-compound reaction products of this invention may be copolymerized are methyl methacrylate, ethyl acrylate, butyl methacrylate, stearyl acrylate, acrylic acid, methacrylic acid, styrene, alpha-methyl styrene, allyl alcohol, vinyl acetate, vinyl stearate, vinyl chloride, vinylidene chloride, acrylamide, acrylonitrile, butadiene, etc.
• the acryloxy- -halo products of this invention may also be copolymerized with a wide variety of monomers having internal ethylenic unsaturation, using conventional catalysts and polymerizing conditions, to yield useful copolymers.
• monomers having internal ethylenic unsaturation include maleic anhydride, crotonic acid, cinnamic acid, dipentene, myrcene, etc.
• the copolyme-rs thus produced range from viscous liquids through soft gels to tough rubbery products and hard resins.
• the polymers are useful broadly in the manufacture of cast, molded and extruded forms, as fiber-reinforced laminating and molding resins, as surface coatings, adhesives, plasticizers, and as paper and textile treating agents.
• the products of this invention are useful broadly in the production of homopolymers and copolymers.
• T-he methacryloxy and acryloxy compounds are photo-sensitive and must be stored in the dark to prevent premature polymerization. In the absence of light, they are stable for months at room temperature.
• the stored acryloxy-halo monomers should contain about 0.05 percent to 5 percent by weight of a stabilizer such as barium-cadmium soap, epoxidized soybean oil, or a tin mercaptide.
• a stabilizer such as barium-cadmium soap, epoxidized soybean oil, or a tin mercaptide.
• any of the stabilizers used for polyvinyl chloride, chlorinated polyethylene or polyolefins prepared with a Zieglertype catalyst can be incorporated in these products, just so the stabilizer does not prevent their subsequent polymerization.
• the instant invention is primarily directed to the haloacylation of long chain ethylenically unsaturated compounds, it can also be used to introduce an acryloxy group into a wide variety of other ethylenically unsaturated compounds, such a ethylene, propylene, butene-l, -butene-2, hexene-l, heptene-3, diisobutylene, nonene-3, octadecene-l, butadiene, isoprene, tetramethylethylene, cyclohexene, cyclooctene, alpha-pinene styrene, alphamethyl styrene, p-methyl styrene, o-octyl styrene, 2,5-dichlorostyrene, vinyl chloride, vinyl bromide, allyl chloride, chloroprene, allyl alcohol, diallyloxypenta
• those compounds, which contain an internal ethylenic double bond, such as cyclohexene or nonene-3, can be haloacylated under the same conditions as the preferred long-chain ethylenically unsaturated compounds of this invention.
• those compounds which contain only terminal unsaturation, such as ethylene and propylene require temperatures in excess of about 20 C. and/ or a haloacylation catalyst (e.g., tetramethyl ammonium chloride) since terminal ethylenic double bonds are somewhat harder to haloacylate than internal ethylenic double bonds.
• a haloacylation catalyst e.g., tetramethyl ammonium chloride
• the tendency for the ethylenic double bond of the acid acrylic compound to be haloacylated increases and, accordingly, this by-product is formed in increased amount in the reaction product.
• This reaction product is compatible with the various other products formed during the haloacylation and the polymers thereof.
• the haloacylated acid acrylic compound can be extracted with alkali.
• acylating acids such as chloroacrylic acid and the half-esters of maleic acid and fumaric acid are less susceptible to attack by alkyl hypohalite than acrylic acid itself, and methacrylic acid. Accordingly, the amount of the by-products formed by the haloacylation of the acylating acid can be controlled by the choice of acylating acid.
• Example I One hundred and seventy-four grams (2 moles) of methacrylic acid containing 0.025 percent by weight pmethoxy phenol and 204 grams of soybean oil (1.00 equivalent of ethylenic unsaturation) were weighed into a Morton flask equipped with a stirrer, thermometer, reflux condenser and dropping funnel with an inlet tube extending to the bottom of the flask. One hundred and twelve grams of 97 percent pure tertiary butyl hypochlorite (1.0 mole) was added gradually from the dropping funnel over a 15 minute period to the stirred reaction mixture, while cooling the reaction mixture to hold its temperature at 40 C. Stirring at the same temperature, with heating as required, was continued for 5 hours.
• NIR near infrared absorption band method
• the total ethylenic unsaturation was determined by the pyridine sulfate dibromide method described at page 203 of the 1954 edition of Monomeric Acrylic Esters" by E. H. Riddle.
• Example 11 Example 11 was repeated except that 1.7 mole of methacryli c was used instead of 2.0 mole and the reaction was run for 2 hours instead of 5 hours. Before the alkaline extraction was carried out, the sample was vacuum distilled at 25 mm. pressure and 50 C. in order to remove all the tertiary butyl alcohol and some of the unreacted methacrylic acid. This sample is identified as product B.
• Example III Example I was repeated except that acrylic acid was used instead of methacrylic acid. Sixty-one and ninetenths mole percent of the ethylenic double bonds in the soybean oil had vicinal acryloxy and chloro groups.
• Example IV Example II was repeated except that acrylic acid was used in place of methacrylic acid and the reaction was carried out at 65 C. for 1.5 hours. Fifty-nine and seventenths mole percent of the ethylenic double bonds in the soybean oil were substituted with vicinal acryloxy and chloro groups.
• Example V Ninety-six and four-tenths grams of acrylic acid (1.32 mole) containing 0.02 percent by weight p-methoxy phenol and 300 grams of soybean oil (1.50 equivalents of'ethylenic unsaturation) were weighed into a Morton flask equipped as described in Example 1. One hundred and sixty-eight grams of 97 percent pure tertiary butyl hypochlorite (1.5 mole) was added gradually from the dropping funnel over a 15 minute period to the stirred mixture, while cooling the reaction mixture to hold its temperature at 65-70 C. Stirring at the same temperature, with heating as required was continued for minutes.
• Example V1 Example V was repeated except that 1.13 moles of acrylic acid was reacted for 65 minutes instead of 1.32 moles of acrylic acid.
• Example VII 7 Example V was repeated except that 0.99 mole of acrylic acid and 1.13 moles tertiary butyl hypochlorite were reacted for 55 minutes instead of 1.32 moles of acrylic acid and 1.5 moles of tertiary butyl :hypochlorite.
• Example Example IX V VI VII 5 Example VIII was repeated except that the lsomeriza- Weight of sample before vacuum distillation, g. 564 545 503 non Step was Omltted' Weight ofresidue, g 444 442 42a icigigy beiore vacuum distillation, nne 0.87 0. 51 0.
• Example XI 15 Example X was repeated except that the lsomerlza- The results of next ten examples are set forth in Step was Omltted' Table IV.
• Example XII I Example The isopropyl half-ester product was prepared using the One and one-half moles of maleic anhydride (147 mfithod and 111016 Proportion of Tea tant5 0f Example grams) was weighed into a flask equipped with a stirrer, except that h -Q Was ⁇ Someflled at f thermometer, condenser and dropping funnel, and then 9 for 30 minutes 1151118 Welght 'p thlonyl heated to 1105 C o d o h 1f moles f methanol chloride and the haloacylation was carried out at 40 C.
• Example XI-I (48 grams) was added slowly from the dropping funnel Over a 90 minute P while mlintaining the teni lperaturle of the reaction mixture Examp 1,; X111 at 90-1 0
• su Clem was i generated
• Example XI-I was repeated except that the isomerizaby the reaction, the external heating was discontinued and o tlon step was omitted.
• the temperature rose to l35-140 C.
• the reaction mixture was allowed to cool to 100 C. and maintained at Example XIV this temperature for 1 hour.
• An analytical sample of the The -P PY half-ester Product Was P p 115mg the reaction product had an acid value of 7.58 meq./ig.
• Example VIII A portion of product (B) was mixed with 33 percent by except that the half-ester was isomerized at 90-100 C. weight styrene, 1 percent Advastab BC10-5 heat stabifor 30 minutes using 0.50 weight percent P01 as the isomlizer (a metal soap) and 1 percent benzoyl peroxide and erization catalyst and the haloacylation was carried out placed in an aluminum weighing cup. By covering with at C. over a minute period.
• Example XVIII One mole of maleic anhydride (98 grams) was weighed into a Morton flask equipped as before. One mole of methyl amyl alcohol (4-methyl-2-pentanol) (102 grams) was added slowly over 35 minutes from a dropping funnel while maintaining the reaction mixture at 110 C. Sixty-eight hundredths of a gram of PCl (0.005 mole) was added to the reaction mixture while maintaining the reactants at 110 C. for minutes. Immediately thereafter, two hundred grams of soybean oil (1.0 equivalent of ethylenic unsaturation) was added to the reaction mixture and the temperature of the reaction mixture was adjusted to 65 C.
• Example XIX Example XVIII was repeated except 1.2 moles of methylamyl alcohol and 1.2 moles of maleic anhydride were used.
• Example XX Example XVIII was repeated except that A of the methylamyl alcohol was replaced by A mole of isobutanol. 7
• Example XXI The 2-ethylhexyl half-ester reaction product was prepared using the method and proportions of Example XVIII.
• Example XXII using the method and proportions of Example XVIII.
• methacrylic acid (0.425 mole) containing 0.025 percent by weight p-methoxy phenol and 27.1 g. of 99.6 percent tertiary butyl hypochlorite (0.25 mole) were reacted for 90 minutes at 65 C.
• the reaction mixture was stripped at 25 mm. pressure and 50 C. Acidity and infrared analysis showed 46.7 mole percent of the oil uns-aturation had methacryloxy and chloro substituents. Further analysis indicated that 14 mole percent of the oil unsaturation was al-lylic chloro groups and that 30 mole percent of the oil unsaturation had butoxy and chloro substituents.
• a copolymer with 33 percent by weight styrene was reddish brown, transparent, hard and brittle.
• Example XXV Thirty-three and two-tenths grams of linseed oil (0.25 equivalent of ethylenic unsaturation) was used in place of the 0.25 equivalent of menhaden oil in Example XXIV. Fifty-seven and one-half mole percent of the ethylenic groups in the oil had methacryloxy and chloro substituents, 14.4 mole percent of the ethylenic groups in the oil were chloro allylic groups and 12 mole percent of the ethylenic groups in the oil had butoxy and chloro substituents. A copolymer with 33 percent by weight styrene was amber-colored, transparent, hard and rigid.
• Example XXVI Thirty-one and five-tenths grams of tung oil (0.300 equivalent of ethylenic unsaturation) was mixed with 43.9 grams (0.510 mole) of methacrylic acid containing 0.025 percent p-methoxy phenol. This mixture was reacted with 32.6 grams (0.300 mole) of tertiary butyl hypochlorite for 90 minutes at 65 C. The reaction product was stripped at 25 mm. Hg and 50 C. to remove the t butyl alcohol by-product. Infrared spectrophotometric analyses showed 45.7 mole percent of the oil unsaturation was converted to vicinal methacryloxy-chloro substituents. A copolymer of the oil product containing 33 percent by weight styrene was clear, light yellow, quite hard and rigid.
• the stripped product was copolymerized with 33 percent by weight styrene, using 1 percent benzoyl peroxide and 1 percent barium-cadmium carboxylate at 65 C. for 4 hours.
• the cast sheet was yellow, slightly opaque, semi-hard .and slightly flexible.
• Example XXIV Thirty-six and one-fourth grams of menhaden oil (0.25 q ival n of' e hylenic unsaturation), 36.55 grams of Example XXVII Four hundred and forty-five grams of methyl oleate (1.5 equivalents of ethy-lenic unsaturation) was used in place of the 1.5 equivalents of castor oil in Example XXIII. Analysis of the product showed that 60 mole percent of. the ethylenically unsaturated groups in the ester had chloro and methacryloxy substituents. A copolymer with 33 percent by weight styrene, which had been cured at C. for 1 hour after the initial copolymerization at 65 C. for 3 hours, was a tough, quite flexible solid which adhered to the aluminum mold.
• Example XX VIII thru XXX VI A series of tall oil esters were reacted with tertiary butyl hypochlorite and methacrylic acid containing 0.05 percent p-meth-oxy phenol at 45 C. using a concentration of 1.7 moles of methacrylic acid, 1.0 mole tertiary butyl hypochlorite and sufficient tall oil ester to contain 1.0 equivalent of ethylenic unsaturation. A portion of the sample was stripped at 50 C. and 50 mm. pressure and a second portion was alkali extracted by the method of Example I.
• Table VI lists the characteristics of the tall oil esters which were prepared by conventional esterification techniques.
• Table VII lists the characteristics of the haloacylated product and Table VIII lists the properties 1 7 of a copolymer of the vacuum stripped reaction product with 33 percent by weight styrene.
• A is the crude reaction product
• B is the vacuum stripped product
• C is the alkali washed product
• Pentaerythritol 12. 3. 04 Rigid, tough, and hard.
• Ethylene 13. 1 64 Hard. tough, and slightly flexible.
• Example XXXVII A commercially available soybean oil monoglyceride having 3.87 meq./ g. of ethylenic unsaturation was haloacylated using the same conditions and proportions employed in the preceding nine examples. The product had 33.7 mole percent acryloxy-chloro groups, 23.5 mole percent butoxychloro groups, 14.3 mole percent of the oil unsaturation were allylic chloro groups and 0.45 acryloxy groups per molecule. A copolyrner of the vacuum stripped product with 33 percent by weight styrene was hard, tough and slightly flexible.
• Example XXXVIII This example illustrates the use of tertiary amyl hypochlorite.
• Sample Sample Acidity meqJg. 1. 05 0. 18 0. 03 Saponitication, meqJg-.- 6. 06 6. 75 6. 63 Total chlorine, meqjg..- 2. 40 3. 05 3. 14 Allyllc chlorine, meqJg 0. 48 0. 61 0. 58 t-Arnyl Alcohol, wt. percent (by G.L. P.
• Example XXXIX This example illustrates the use of aluminum chloride as an isomerization catalyst.
• Maleic anhydride (98.0 g.E1.00 mole) was heated to 110 C. in a reaction vessel equipped with a stirrer, a condenser, and a reactant addition port.
• Aluminum trichloride (1.00 .50.0075 mole) was added and the temperature was controlled at 90 C. for 25 minutes.
• the product was a clear, pale-yellow liquid having a viscosity of 5000 c.p.s. at 25 C.
• Copolymerization with styrene yielded a flexible resin having a tensile strength of 500 p.s.i. and a Clash-Berg elastic modulus T value of 20 C.
• the soy oil product (66 parts) was combined with styrene (33 parts) and benzoyl peroxide (1 part), cast in a inch sheet, and cured 16 hours at 65 C. and 0.5 hour at 110 C.
• the copolymer had the following physical characteristics:
• the soy oil product copolymerized with 33 percent styrene had the following physical characteristlcsz Flexural modulus, p.s.i 28,600 Flexural strength, p.s.i 630 Tensile strength, p.s.i 1,390 Elastic modulus, Clash-Berg T C 29 Heat distortion, 66 p.s.i. C. 24 Shore hardness -93
• Example X Ll A mixture of high purity heptene-3 (49.0 g.E0.50 mole), methacryrlic acid (43.3 g.z0.50 mole), and pmethoxy phenol (0.022 g.E0.05 percent of the methacrylic acid) was heated to 60 C.
• Tertiary butyl hypochlorite (54.5 g.z0.50 mole) was added slowly while maintaining the exothermic reaction at 65 C. by external cooling. After minutes at 65 C. the mixture gave a negative potassium iodide test for hypochlorite. A sample of the total reaction products was labeled A.
• Example XLII This example illustrates the haloacylation of methacrylic with a second methacrylic acid molecule.
• Tertiary butyl hypochlorite 27 g.E0.2S mole
• methacrylic acid 43 g.E0.50 mole
• the liquid B product was homopolymerized using benzoyl peroxide and 65 C. heating. It produced a soft, clear, fairly tough solid.
• Example XLIII This example illustrates the preferential haloacylation of methacrylic acid by a second molecule of methacrylic acid in the presence of tetrachloroethylene.
• a mixture of 4.0 g. of the liquid distillation residue and 0.05 g. of benzoyl peroxide was cast in a mold to form a inch thick sheet. After heating 16 hours at 65 C. and 0.5 hour at 120 C. a clear, hard, brittle resin was obtained.
• Example XLV Tertiary butyl hypochlorite (54.5 g.E0.50 mole) was combined with a mixture of octadecene-l (126.0 g.E0.50 mole), acrylic acid (36.3 g.E0.50 mole), and p-methoxy phenol (0.05 wt. percent of the acrylic acid).
• the reaction procedure and product isolation outlined in Example XLI was followed. This reaction, however, was slower and took 210 minutes at 65 C.
• Example XLVI Tertiary butyl hypochlorite (54.5 g.E0.50 mole) was combined with a mixture of cyclooctene (55 g.E0.50 mole), acrylic acid (36.3 g.E0.50 mole), and p-methoxyphenol (0.05 percent of the acrylic acid). The reaction procedure and product isolation described in Example XLI was followed. This reaction was complete in 50 minutes.
• Example XLVII Tertiary butyl hypochlorite (54.5 g.z0.50 mole) was combined with a mixture of styrene (52050.50 mole). acrylic acid (36.3 g.E0.50 mole), and p-methoxy phenol (0.05 wt. percent of the acrylic acid). The reaction procedure and product isolation described in Example XLI was followed. This reaction was complete within 60 minutes.
• Example XLVIII Tertiary butyl hypochlorite (54.5 g.E0.50 mole) was combined with a mixture of dicyclopentadiene (66.0 g.EO.50 mole), methacrylic acid (43.3 g.E0.50 mole), and p-methoxy phenol 0.05 wt. percent of the methacrylic acid). The reaction procedure and product isolation described in Example XLI was followed. This reaction was complete in 30 minutes.
• Example IL A mixture of methacrylic acid (86.5 g.E1.00 mole), p-methoxy phenol (0.0432 .E0.05% of the methacrylic acid), and tertiary butyl hypochlorite (109.0 g.s1.00 mole) was heated to 37 C. in a reaction flask equipped with a stirrer, a gas dispersion inlet tube, a thermometer, and a Dry Ice-methanol cooled condenser. Ethylene (11.0 g.E0.393 mole) was added to the reaction mixture at the rate of 0.073 g./min. The exothermic reaction was controlled at 40-44 C. by ice water bath cooling.
• Example L A mixture of methacrylic acid (86.5 gELOO mole) p-cresol (0.065E0.075% of the methacrylic acid), and t-butyl hypochlorite (109.0 g.E1.00 mole) was heated to 39 C. Propylene (17.3 g.E0.412 mole) was added at the rate of 0.25 g./ min. while controlling the exothermic reaction at 45 C.
• the process of preparing a polymerizable long chain compound which comprises reacting at a temperature of from C. to 100 C. an ethylenically un saturated compound having the structure wherein is an open chain of from to 24 carbon atoms and R is selected from the group consisting of hydrogen and a monovalent aliphatic group, a tertiary alkyl hypochlorite and an acid acrylic compound having the structure wherein R is selected from the group consisting of hydrogen and 0 II COY when R is a hydrogen, R is selected from the group R is selected from the group consisting of hydrogen, halogen and alkyl of from 1 to 4 carbon atoms; and Y is selected from the group consisting of a monovalent aliphatic group of from 1 to 18 carbon atoms and a monovalent aromatic group of from 6 to 18 carbon atoms.
• the process of preparing a polymerizable long chain compound which comprises reacting an ethylenically unsaturated compound having the structure is an open chain of from 10 to 24 carbon atoms and R is selected from the group consisting of hydrogen and a monovalent aliphatic group, a tertiary butyl hypochlorite and an acid acrylic compound having the structure at a temperature of from 50 C. to 150 C.

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