ALPHAOLEFIN TERPOLYMER AND COATING COMPOSITION INCLUDING SAID TERPOLYMER

Abstract: Terpolymers of an anhydride either a lower alphaolefin, monoalkenyl aromatic compounds or mixtures thereof, and a higher alphaolefin; and aqueous dispersions of these ter­ polymers. A coating composition employing the terpolymer, an acrylic emulsion polymer and the balance of the composi­ tion being an aqueous vehicle which produces glosssy clear coatings is also prepared.

Description: This invention relates to terpolymers of maleic anhydride, at least one monomer selected from the group consisting of l-alkene having 4 to 16 carbon atoms, mono-alkenyl aromatic compounds and mixtures thereof and l-alkene having more than 18 carbon atoms, and novel coating compositions containing said terpolymers. Maleic anhydride alphaolefin copolymers are well known as are maleic anhydride alphaolefin terpolymers; see U.S. Patents 3,533,177, 3,560,455, 3,560,456, 3,560,457, 4,358,573, 4,151,069 and 4,240,916. The first four patents describe copolymers and the like anhydride with specific alphaolefins, such as C12 alphaolefin, C16-18 alphaolefin and C30+alpha- olefins. The last three patents describe terpolymers of maleic anhydride with mixtures of alphaolefins. Styrene maleic anhydride copolymers are described in a number of patents, including U.S. Patent 3,423,373, 3,277,116 and 3,256,296. These patents, however, are directed to copolymers of styrene and maleic anhydride and do not disclose terpolymers. U.S. Patent 3,723,375, describes terpolymers of styrene and maleic anhydride along with a termonomer having the formula EMI1.1 where R2 is an organic radical containing 6 to 35 carbon atoms, Y is hydrogen, halogen, alkyl or phenyl and X is oxygen, sulphur, carboxy, carbonaBido or a chemical bond, Tt Column 4 this patent describes possible monomers having the above formula, including five alphaolefins from l-decene to l-eicosene. The terpolymers as described in this patent have a relatively small amount of the termonomer, that is, less than 15 mole per cent and the example where the termonomer is a l-olefin no more than 3.5 mole per cent. It has been surprisingly found that terpolymers comprising from 49 to 60 mole per cent of an anhydride, from about 20 to 40 mole per cent of at least one monomer selected from the group consisting of l-alkene having from 4 to 16 carbon atoms, monoalkenyl aromatic compounds and mixtures thereof, and from about 40 to 20 mole per cent of at least l-alkene having at least 18 carbon atoms can be prepared. Said terpolymer can also be prepared as an aqueous dispersion having low viscosity in alkali and other bases. This invention also relates to novel coating compositions which include the terpolymers described herein. Attempts have been made to prepare substrate coatings containing terpolymers such as overprint varnishes and inks which have good slip and non-blocking characteristics. By this is meant the coating will not, under the effect of temperature, pressure or a combination of temperature and pressure, soften or otherwise adhere to the surrounding coating, substrates and/or films. In high-speed manufacturing processes of coated material, the substrate is quickly stacked after coating and if the non-blocking characteristic of the coating is poor, the articles may not properly stack or may adhere to surrounding coatings and substrates thereby ruining a portion of the product. Surprisingly, a coating composition which com rises from 0.5 to 30 per cent by weight of the inventive terpolymer, from 1 to 55 per cent by weight of an acrylic emulsion polymer having a weight average molecular weight of greater than 20,000 and the balance aqueous vehicle, will impart excellent coating properties to the substrate such as clarity, gloss, rub resistance, etc. and also form a non-blocking coating with good slip characteristics. It is therefore the primary object of the present invention to provide a novel terpolymer of styrene, maleic anhydride and an alphaolefin. Further advantages of the present invention include providing an aqueous alkaline dispersion of a terpolymer of styrene, maleic anhydride and an alphaolefin; providing a novel terpolymer of styrene, maleic anhydride and an alphaolefin which can be incorporated in an aqueous coating composition having good slip and non-blocking characteristics and providing a terpolymer composition which has good waxy properties characteristic of C18 and higher alphaolefins and yet has water dispersibility and good hardness which provides a coating composition with good water resistance and dry-rub characteristics. Still further advantages of the composition of the present invention will become more apparent from the following more detailed description. According to the present invention there is provided a terpolymer of from about 49 to 60 mole per cent of an anhydride, from about 20 to 40 mole per cent of at least one monomer selected from the group consisting of l-alkene having from 4 to 16 carbon atoms, mono-alkenyl aromatic compounds and mixtures thereof, and from about 40 to 20 mole per cent of at least one l-alkene having at least 18 carbon atoms. The terpolymer composition of the present invention also relates to an aqueous dispersion of a terpolymer of from about 49 to 60 mole per cent of an anhydride, from about 20 to 40 mole per cent of at least one monomer selected from the group consisting of l-alkene having from 4 to 16 carbon atoms, monoalkenyl aromatic compounds and mixtures thereof; and from about 40 to 20 mole per cent of at least one l-alkene having at least 18 carbon atoms, this dispersion having a viscosity at 250C. of less than 20 centipoise at 10 per cent solids content and having a pH within the range from about 6.5 to 10. It is noted above the terpolymers of the present invention include an anhydride. In addition to the preferred anhydride, maleic anhydride, certain other anhydrides can be utilized in the formation of the terpolymers of the present invention such di-methyl maleic anhydride, flouro maleic anhydride, methyl ethyl maleic anhydride and the like. It is preferred that the anhydride be substantially free of acid and the like before polymerization. As noted above, the preferred anhydride is maleic anhydride. A second component of the terpolymers of the present invention is a higher l-alkene, i.e., a l-alkene having at least 18 carbon atoms. These materials may be pure materials such as l-octadecene or may be mixtures of various of l-alkenes such as mixed C2D, C22 and C24 l-alkenes and the like. Suitable l-alkenes for use in the terpolymers of the present invention include the following: l-octadecene l-eicosene l-docosene l-tetracosene l-hexacosene l-octacosene l-triacontene l-dotriacontene l-tetratriacontene l-hexatriaconter.e l-octatriacontene l-tetracontene l-dotetracontene l-tetratetracontene l-hexatetracontene l-octatetracontene l-pentacontene l-hexacontene and mixtures thereof Both pure alkenes and mixed alkenes can be utilized. Typical mixtures of C30+ l-alkenes are described in U.S. Patent 3,553,177. Typically, these mixed higher alkenes are primarily even chain alphaolefins. The higher l-alkene should essentially be free of di-olefins as these materials can cause gel formation and cross linking. Although small amounts of di-olefins, typically less than 2 per cent, can be tolerated as impurity in the higher l-alkene monomer, it is preferred that the level of saturates in the monomer be kept to a miniumum generally less than 1 per cent and preferably less than 0.3 per cent, as the resulting polymer dispersions are hazy. The preferred higher l-alkenes are l-eiocene, mixed C20-24 l-alkenes and mixtures thereof. A third monomer in the terpolymers of the present invention is at least one monomer selected from the group of l-alkenes having 4 to 16 carbon atoms, aromatic monoalkenyl compounds or mixtures thereof. Suitable monomers include styrene, alpha methyl styrene, vinyl toluene and the like. The preferred monomer is styrene. Generally, the monomers of the lower alkenes are included in minor portions less than 3 mole percent; The purpose of these monomers is to modify one or more properties of the resulting terpolymer. Suitable alkene monomers include divinylbenzene and the like. Each of the above three monomers must be present in the terpolymers of the present invention in certain specific amounts in order to achieve the desired result. In other words, if too much aromatic monoalkenyl monomer is included, the waxy properties of the resultant terpolymers is reduced while if sufficient l-alkene is not included, the materials do not have the appropriate waxy and slip properties. As is well known in the art, polymers including maleic anhydride are essentially alternating polymers with maleic anhydride alternating between random comonomers. The alternating backbone occurs without regard to the relative ratio of the reactants. This phenomenon is described in various patents noted below relating to the process of preparing polymers of the instant application. Accordingly, terpolymers of the present invention will contain from 49 to 60 mole per cent of anhydride preferably maleic anhydride. Under some conditions such as very high initiator levels it is possible to include some small excess of maleic anhydride relative to the comonomers in these polymers. The amount of monomer selected from the group of l-alkenes having 4 to 16 carbon atoms, aromatic monoalkenyl compounds or mixtures thereof are present in the terpolymers of the present invention is from 20 to 40 mole per cent while the amount of l-alkene having at least 18 carbon atoms, is similarly from 20 to 40 mole per cent. The preferred terpolymers of the present invention include from 49 to 55 mole per cent maleic anhydride and from to 20 to 30 mole per cent of aromatic monoalkenyl monomer and 20 to 30 mole per cent higher l-alkene. The polymers of the present invention may be prepared by any of a number of conventional polymerization processes including polymerization processes as set forth in U.S. re-issue patent 28475, U.S. 3,553,177, 3,560,455, 3,560,456, 3,560,457 and 3,488,311. The terpolymers of the present invention are generally low molecular weight materials having a number average of molecular weight within the range of from 2,000 to 15,000 and preferably within the range of from 2,000 to 10,000. One unexpected benefit of the terpolymers of the present invention is the ease with which solubilization of these polymers occurs. These polymers can be characterized as alkali soluble materials and can be prepared as alkali cuts having a solids content of up to 25 per cent polymer. Suitable alkali materials include ammonium hydroxide, potassium hydryoxide and sodium hydroxide. The preferred base for solubilizing these polymers is ammonium hydroxide. It is surprising that compositions containing substantial percentages of alphaolefin can be solubilized at a relatively low viscosity over a relatively short period of time. This is contrasted with materials outside the scope of the present invention whereby those containing high percentages of alphaolefin are difficulty soluble and do not produce a stable viscosity for an extended period of time. These dispersions have a relatively low viscosity at moderate solids. Generally the viscosity of a 10 per cent solids aqueous solution of the terpolymer will be less than 20 centipoise and preferably these dispersions will be less than 10 centipoise. These viscosities are to be measured at room temperature. In some instances, it is necessary to heat the polymer to get it completely solubilized. It is theorized that one reason for this solubility is that the terpolymers of the present invention go directly to a fluid system without passing through a gel region characteristic of polymers containing higher 1-alkenes. This greatly increases the flexibility in preparing solutions of these terpolymers for end uses. The dispersions of the terpolymers of the present invention are useful to a wide range of coatings including use as release agents, slip agents, anti-blocking agents and the like. According to the present invention there is provided a coating composition from about 0.5 to 30 per cent of the inventive terpolymer; from about 1 to 55 per cent by weight of an emulsion polymer having a weight average molecular weight of greater than 20,000 and the balance being an aqueous vehicle. As used in the instant specification and claims, the term "aqueous vehicle" includes water and mixtures of water with various water missible solvents such as 2-butoxyethanol, 2-ethoxyethyl acetate, ethanol, n-propanol, 2-ethoxyethanol, aromatic petroleum distilates such as Solvesso 100 and Solvesso 150 from Exxon Corp., esters such as isopropyl acetate, ketones such as methylethylketone, etc. The coating compositions of the present invention include from 0.5 to 30 per cent by weight of a terpolymer comprising from 49 to 60 mole per cent of at least one anhydride, from 20 to 40 per cent by weight of at least one monomer selected from the group consisting of l-alkene having 4 to 16 carbon atoms, mono-alkenyl aromatic compounds and mixtures thereof, and from 20 to 40 mole per cent of at least on 1 alkene having at least 18 carbon atoms. The preferred terpolymers for use in the coating compositions of the present invention include those terpolymers wherein the anhydride is maleic anhydride and the second monomer is styrene or a l-alkene having from 4 to 10 carbon atoms such as l-butene, l-pentene, l-hexene, l-heptene, l-octene, l-noeme and l-decene. Most preferred terpolymers include polymers where the second monomer is styrene. These most preferred terpolymers add better scratch resistance and better adhesion to the coating. Preferred terpolymers comprise from 49 to 55 per cent by weight maleic anhydride, 20 to 30 per cent by weight styrene and 20 to 30 per cent by weight higher 1-alkene. Examples of suitable terpolymers include terpolymers of maleic anhydride, styrene and l-eicosene; maleic anhydride, styrene and mixed C20-24 l-alkene; maleic anhydride, styrene and 1octadecene and the like. As noted above, the terpolymers are present in the composition in the amount of from 0.5 to 30 per cent by weight and are present as alkali dispersions. These dispersions are found using any suitable base such as sodium, potassium or ammonium hydroxide. Ammonium hydroxide is the preferred base as this material is fugitive and can leave the coating after application to make a more water-resistant coating. Typically these dispersions comprise from 10 to 40 per cent by weight terpolymer in an aqueous system and have a pH within the range of from 6.5 to 10.0. The compositions of the present invention should comprise from 0.5 to 30 per cent by weight terpolymer. It is preferred the compositions include 2 to 10 per cent by weight terpolymer and preferably from 2 to 7.5 per cent by weight of terpolymer. The second component of the coating compositions of the present invention comprises an acrylic emulsion polymer. These emulsion polymers must have a weight average molecular weight as determined by gel permeation chromatography of greater than 20,000. Suitable acrylic emulsion polymers include polymers containing the following monomers: methyl methacrylate, methylacrylate, methylacrylic acid, acrylic acid, itaconic acid, ethyl acrylate, butyl acrylate, ethyl hexyl acrylate, ethyl methacrylate, butyl methacrylate, hy droxy acrylates, hydroxy methacrylates, styrene, alpha-methyl styrene, acrylonitrile, etc. Specific acrylic emulsion polymers include polymers with the following monomer content: copolymers of styrene, ethyl acrylate, 2-ethyl hexyl acrylate and acrylic acid; styrene, butyl methacrylate and methacrylic acid; styrene, methylmethacrylate, ethyl acrylate and methacrylic acid; styrene, methylmethacrylate, ethyl acrylate, butyl acrylate, methacrylic acid and acrylic acid; styrene, methyl methacrylate, butylacrylate and methacrylic acid; styrene, butylmethacrylate and methacrylic acid; styrene, acrylonitrile, 2-ethyl hexyl acrylate and methacrylic acid; methyl methacrylate, 2-ethyl hexyl acrylate and methacrylic acid; etc. Typically, the above acrylic emulsion pa1- mers contain from 15-75% by weight of at least one hard monomers1 i.e. those monomers which produce homopolymers having a Tg of greater than 200C; 20-70% by weight of at least one soft monomer, i.e. those monomers which produce homopolymers having a Tg of less than 20 C and 3-25% by weight of an acid monomer, i.e. those monomers having carboxyl functionality. In addition to the acrylic emulsion polymers, other suitable acrylic emulsion polymers include polymers formed by emulsion polymerization in the presence of a low molecular weight resin. These materials include polymers having monomers as listed above which polymerized using an emulsion polymerization action technique in the presence of a low moleular weight, i.e. number average of less than 7,000, resin. Typical resins contain styrene, alpha methyl styrene, acrylates, methacrylates and carbonyl containing rno- mers and have an acid number within the range of 100-300. Examples of these resins include: styrene and acrylic acid; styrene, alpha methyl styrene and acrylic acid; styrene, butylacrylate and acrylic acid; alphamethylstyrene, butylacrylate and acrylic acid; styrene, ethylacrylate and acrylic acid; alphamethylstyrene, ethylacrylate and acrylic acid; styrene, methylmethacrylate and acrylic acid and the like including mixtures. The acrylic emulsion polymers typically contain methylmethacrylate, 2-ethylhexyl acrylate and butylacrylate; styrene and 2-ethylhexyl acrylate; styrene; methylmethacrylate, butyl acrylate and isobutyl methacrylate; and the like. The preferred acrylic emulsion polymers are those prepared by emulsion polymerization in the presence of a low molecular weight acrylic polymer. These materials, when neutralized, have less sensitivity to high pH's and accordingly retain their viscosity characteristics at the pH's of the composition of the present invention. The preferred emulsion polymers include the following: polymers prepared by emulsion polymerization of at least one of methylmethacrylate, butyl methacrylate, styrene, butyl acrylate and 2ethylhexyl acrylate in the presence of a low molecular weight polymer having number average molecular weight of less than 5,000 and an acid value of 150 to 270. The emulsion polymers can be prepared in any of a number of conventional emulsion polymerization processes. Suitable processes for producing the emulsion polymers in the presence of the low molecular weight polymer are disclosed in U.S. 4,062,823. As noted above, emulsion polymers are to be present in an amount of from 1 to 55 per cent by weight. It is preferred that the emulsion polymer of the present in an amount of from 20 to 40 per cent by weight and most preferably from 25 to 35 per cent by weight. The compositions of the present invention also include an aqueous vehicle. The aqueous vehicle includes water and mixtures of water with various water missible solvents such as 2-butoxyethanol, 2-ethoxyethyl acetate, ethanol, n-propanol, isopropanol 2ethoxyethanol, aromatic petroleum distilates such as Solvesso 100 and Solvesso 150 from Exxon Corp., esters such as isopropyl acetate, ketones such as methylethylketone, etc. and mixtures thereof. The aqueous vehicle forms the balance of the composition. The preferred aqueous vehicles are mixtures of water, 2-ethoxyethyl acetate, 2-butoxyethanol, mixtures of water and 2-ethoxyethanol, mixtures of water and 2ethoxyethyl acetate, and mixtures of water, 2-butoxyethanol, and aromatic petroleum distilates. As coated above, water is utilized as a carrier in the composition of the present invention, however, the amount of water should be kept at a minimum, especially if the substrate to be coated is essentially impermeable such as polyethylene film or aluminum or other metal foils. Certain of the above solvents are more water missible than others. For those solvents with a low degree of water missibility the amount used as part of the aqueous vehicle should be such that the solvent will not interfere with the stability of the composition. For papers and other cellulosic substrates the water content may be higher as the water can be absorbed by the substrate allowing faster drying times. In addition to the above three components, the compositions of the present invention can include from 0 to 25 per cent by weight of a slip aid. Suitable slip aids include polyethylene wax emulsions, polytetrafluoroethylene, paraffin wax emulsions, silicone fluids and emulsions and mixtures thereof. These materials are all well known in the coatings industry and are available commercially. Certain slip aid emulsions can be prepared using polyethylene wax and conventional pressure emulsification techniques. Typically, emulsions useful as slip-aids contain from 20 to 50 per cent non-volatiles. These slip-aids are used in the conventional manner in older to improve the slip and handling characteristics of the films. The compositions of the present invention also can include up to 10 per cent by weight of other optional ingredients including pigments, dyes, fragrance, germicides, fillers, defoamers, surfactants, wetting agents and the like. These components are conventionally used in the industry and can be incorporated into the compositions of the present invention in their conventional additive amounts. The compositions of the present invention are suitable for coating a wide variety of substrates, including various cellulose substrates such as paper, clay-coated paper, kraft paper, bonded kraft paper, poster board, folding cartons, wood and the like, as well as impermeable substrates such as polyethylene films, polypropylene films, aluminum foil and other metal foils, and other porous and non-porous substrates. The compositions of the present invention can be coated on these substrates using a variety of methods including roll-coating, flexographic coating, gravure coating, knife coating, squeegee coating, curtain coating and rod coating. The compositions of the present invention can be prepared by mixing the components together. This mixing can be done at room temperature and elevated pressures or special mixing equipment are not required. The terpolymers, dispersions and coating compositions of the present invention will now be more fully illustrated by way of the following examples. These examples are for illustration only and are in no way to be considered as limiting. EXAMPLE 1 Charge 224 grams of l-eicosene and 234 grams of cellosolve acetate to a 2000 milliliter reaction flask. Begin stirring and heat the mixture to 1400C. Melt 196 grams of maleic anhydride and then transfer it to a heated dropping funnel. Maintain the maleic anhydride in a molten state. Combine 125 grams of styrene and 15.52 grams of tertiarybutylperbenzoate and then transfer to a second dropping funnel. o Maintain 140 C. and run the reaction under a nitrogen head with continuous stirring, adding the contents of both dropping funnels at an even pace over a one-hour addition period. Upon completion of the addition, maintain 140 C. for a 45 minute hold period. Pour the contents of the flask into a container. Strip off the solvent by use of a wiped film evaporator to form dry polymer. An ammonia cut of this polymer is prepared at 10 per cent solids by mixing 200 grams of the polymer prepared above with 89.1 grams of 28 per cent aqueous ammonia and 1710.9 grams distilled water at 700C. This mixture was stirred for one hour at 700C. The solution was cooled to room temperature, about 250C. and had a viscosity of approximately 5.0 centipoise. EXAMPLE 2 Using the procedure of Example 1, the polymers as described in Table 1 were prepared: TABLE 1 C20-24 C30+ Maleic Polymer l-Eicosene l-Alkene l-Alkene Styrene Anhydride A -- -- - - - 1.0 1.0 B 0.2 - - - - 0.8 1.0 C 0.4 - - - - 0.6 1.0 D 0.6 - - - - 0.4 1.0 E 0.8 - - - - 0.2 1.0 F 1.0 - - - - - - 1.^ G - - 0.2 - - 0.8 1.0 H - - 0.4 - - 0.6 1.0 I - - 0.6 - - 0.4 1.0 J - - 0.8 - - 0.2 1.0 K - - 1.0 - - - - 1.0 L - - - - 0.2 0.8 1.0 M - - - - 0.4 0.6 1.0 N - - - - 0.6 0.4 1.0 0 - - - - 0.8 0.2 1.0 P - - - - 1.0 - - 1.0 Each of the polymers were dried either using a wipe film evaporator or evaporating the solvent off in an oven. The molecular weights of the polymers were determined by Gel Permeation Chromatography. The polymers had the molecular weights as shown below in Table 2. TABLE 2 Polymer M M M n w z A 1390 2680 4790 B 2150 4940 8910 C 2990 7500 16740 D 3030 6990 13220 E 3140 6450 11000 F 2640 4610 6910 G 4250 15660 43750 H 3900 14550 41470 I 3300 11800 29500 J 2640 8980 20160 K 1850 5420 10130 L 3820 14750 39440 M 2850 10750 26880 N 2620 8360 18400 O 1870 5650 12380 P 1530 3950 8100 EXAMPLE 3 10 per cent of the polymers described in Table 1 were neutralized using 28 per cent ammonia to 100 per cent neutralization. The polymers were neutralized at three temperatures: 270C, 4OOC, and 700C. After one hour of shaking or stirring, the viscosity was measured at 25 0C. using both the Brookfield viscometer and the Nametre viscometer. The viscosity readings are shown in Table 2. For those polymers which had a relatively low viscosity at low temperature, the runs were not repeated at higher temperatures since the viscosity, once it reaches the range from 5 to 20 centipoise, stablizes and shows no further decrease. Further more, once the viscosity was reduced to within the above range by heating, the cooled solution maintained that low viscosity. TABLE 3 Viscosity Temp. Cps. Polymer OC Brookfield Nametre Time A 27 5.0 2.8 1 hour B 27 20.4 18.1 1 hour C 27 460,000 5,800 1 hour D 27 6,000 57.6 1 hour E 27 22.2 10.0 1 hour F 27 59.0 30.8 1 hour C 40 2,600 -- 1 hour D 40 9.3 6.9 1 hour E 40 6.4 3.9 1 hour F 40 6.5 3.9 1 hour C 70 5.0 2.8 1 hour G 70 11.5 8.6 2 hours H 70 12.8 5.7 1 hour I 70 6.0 2.5 1 hour J 70 5.5 2.0 1 hour K 70 7.0 4.6 1.5 hours L 70 79,250 1740 1.5 hours M 70 880 96.5 1 hour N 70 8.8 5.6 1 hour O 70 12.5 3.0 1 hour P 70 6.3 2.4 2 hours Except for Polymers K, N, 0, and P, each of the polymer resin cuts described in Table 2 were clear indicating complete solubilization. It is interesting to note that even the very viscous cuts were substantially clear. EXAMPLE 4 Charge 224 grams of l-eicosene and 244 grams of cellosolve acetate to a 2000 milliliter reaction flask. Begin stirring and heat the mixture to 140 C. Melt 204.2 grams of maleic anhydride and then trans fer it to a heated dropping funnel. Maintain the maleic anhydride in a molten state. Combine 125 grams of styrene, 15.52 grams of tertiarybutylperbenzoate and 5.45 grams of divinyl benzene (9.90 grams of 55 per cent material) and then transfer to a second dropping funnel. Maintain 140 C. and run the reaction under a nitrogen head with continuous stirring, adding the contents of both dropping funnels at an even pace over a one-hour addition period. Upon completion of the addition, maintain 140 C. for a 45 minute hold period. Pour the contents of the flask into a container. Strip off the solvent by use of a wiped film evaporator to form the dry polymer. An ammonia cut of this polymer was prepared at 10 per cent solids by mixing 200 grams of the above polymer with 89.1 grams of 28 per cent aqueous ammonia and 1710.9 grams of distilled water. This mixture was stirred for one hour at 70 C. The resulting solution was cooled to room temperature and had a viscosity of about 5.0 centipoise at 250C. EXAMPLE 5 Using the procedure of Example 4, the following polymers, as set forth in Table 4, were prepared. TABLE 4 Maleic Divinyl Styrene l-Eicosene Anhydride Benzene Polymer (mules) (mules) (Moles) (% by Weight) Q 1.0 0.0 1.0 1.0 R 0.8 0.2 1.0 1.0 S 0.6 0.4 1.0 1.0 T 0.4 0.6 1.0 1.0 U 0.2 0.8 1.0 1.0 V 0.0 1.0 1.0 1.0 The molecular weight of the above resins were determined by gel permeation chromatography and have the number average molecular weight, weight average molecular weight and Z average molecular weight as shown in Table 5. TABLE 5 Polymer Mn Mw Mz Q 1810 4320 9100 R 3240 10550 42980 S 3410 11620 66570 T 3580 10210 35910 U 3340 7850 16370 V 2940 5850 9920 EXAMPLE 6 1Q per cent non-volatile ammonia cuts of the polymers of Example 5 were made by using 28 per cent aqueous ammonia to obtain 100 per cent neutralization. These materials were neutralized at three temperatures: 27 0C., 400C., and 70 C. At lower temperatures certain of the resins, as noted in Table 6, did not dissolve fully after one day. For those polymer solutions with a viscosity of less than 70 centipoise, the viscosity at 25 C. remained low after cooling to room temperature. TABLE 6 Viscosity Temp. Cps. Polymer C Brookfield Nametre Time Notes Q 27 F 27 5 0 3.6 1 hour S 27 67.4 30.0 1 hour T 27 710.000 22,400 1 hour 1,2 U 27 288,000 1,680 1 hour 1,3 V 27 - - - - 1 hour 4 S 40 625 67 1 hour T 40 2600 - - 1 hour 5 U 40 9.3 6.9 1 hour V 40 6.4 3.9 1 hour 6.5 3.9 1 hour 3.8 2.5 1 hour Notes: 1 - Not all dissolved after one day. 2 - Brookfield viscosity after 2 months = 7,300 cps. 3 - Brookfield viscosity after 2 months = 11,500 cps. 4 - Not all dissolved after one day, no one hour reading taken, Brookfield viscosity after 2 months = 540 cps. 5 - Brookfield viscosity after 4 days = 30.0 cps. EXAMPLE 7 Charge 224 grams of l-eicosene and 244 grams of ethoxyethanol acetate to a 2000 milliliter reaction flask. Begin stirring and heat the mixture to 14 OOC. Melt 204.2 grams of maleic anhydride and then transfer it to a heated dropping funnel. Maintain the maleic anhydride in a molten state. Combine 125 grams of styrene, 15.52 grams of tertiary butyl perbenozoate and 9.90 grams of divinyl benzene (55% active) and then transfer to a second dropping funnel. Maintain 140 C. and run the reaction under a nitrogen head with continuous stirring, adding the contents of both dropping funnels at an even pace over a one-hour addition period. Upon completion of the addition, maintain 1400C. for a 45 minute hold period. Pour the contents of the flask into a container. Strip off the solvent by use of a wiped film evaporator to form the dry polymer. An ammonia cut of this polymer was prepared at 25 per cent solids by mixing 200 grams of the above polymer with 89.1 grams of 28 per cent aqueous ammonia and 510.9 grams of distilled water. This mixture was stirred for one hour at 70 C. The resulting solution was cooled to room temperature and had a viscosity of about 430 centipoise measured at 250C. EXAMPLE 8 A non-blocking overprint varnish having the following composition was prepared: Polymer of Example 7 (25% Solids) 13.00% Polyethylene Wax Emulsion (25% Solids) (JONWAX 26 available from S.C. Johnson & Son, Inc.) 5.00 Paraffin-Polyethylene Wax Emulsion (34% Solids) (JONWAX 120 available from S.C. Johnson & Son, Inc.) 10.00 Emulsion polymer containing styrene, 2-ethylhexyl acrylate alpha methylstryene and acrylic acid (Joncryl 537 available from S.C. JOHNSON & Son, Inc.) (46% Solids) 63.00 2 -butoxyethanol 6.30 Solvesso 150 (Petroleum Naphtha Exxon Corp) 0.70 HV-490 (50% Silicone Emulsion Dow Corning) 2.00 The above formulation was coated on card stock at a coating weight of about 0.5 pounds per 1,000 square feet dry coating weight. This coating was clear and had a good gloss with good slip properties. This coated stock was subjected to a blocking test and did not block when stacked coating face to coating face and coating face to noricoated stock at 20 psi at 1500F for 24 hours. A second blocking test at 250 F under 30 psi for 2 seconds also did not cause blocking. It also demonstrated high slip (low static slide angle) when tested coated surface to coated surface. The slide angle was determined by placing a sample of the coated card stock on a 500 gram block and a second sample of coated card stock on the bed of a Cenco Incline Plane. The block is placed on the plane and the plane is gradually elevated; the angle at which the block begins to slide is the static slide angle. Readings of 90 to 120 are achieved with this coating as compared to 150 to 180 for acrylic systems without the polymer of Example 7. EXAMPLE 9 A further overprint formulation with the following formulation was prepared: Polymer of Example 7 (25% Solids) 15.00 Emulsion polymer containing styrene, acrylonitile, 2-ethylhexylacrylate and methacrylic acid (RHOPLEX WL-91 from Rohm & Haas) (50% Solids) 62.00 2 -butoxyethanol 6.00 HV-490 Silicone Emulsion (50% Solids) 2.00 Polyethylene wax emulsion (25% Solids) (JONWAX 26) 5.00 Paraffin polyethylene wax emulsion (34% Solids) (JONWAX 120) 10.00 This formulation when coated on card stock had better solvent resistance than the formulation of Example 8. Other properties were similar. EXAMPLE 10 A formulation which is useful as an ink is prepared having the following formulation: Polymer of Example 7 (25% Solids) 10.00% Emulsion polymer* (40% Solids) 58.77 Urea 11.25 67% Styrene/33% Acylic Acid resin (Mw 4,000) (27% Solids) 19.98 * 10% Methacrylic acid, 5% acrylic acid, 22% methymethacrylate, 4% Styrene, 57% Ethyl acrylate and 2% butyl acrylate. This formulation when used as an ink had good scuff and rub resistance and had similar blocking properties as the formula of Example 8. EXAMPLE 11 Example 8 was repeated except the emulsion polymer was replaced by the following commercially available emulsion polymers. a) Acrysol 153 from Rohm & Haas; b) 22-1271 from Zimchem; and c) 1052 from Polyvinyl Chemicals The above formulations were coated on card stock and evaluated as in Example 8. The 153 polymer had fair slip and non-blocking properties but had lower gloss than Example 8. The 22-1271 polymer had good slip and non-blocking properties but had only fair gloss. The 1052 polymer had good slip, nonblocking and gloss properties.

Claims: CLAIM$ 1. A terpolymer characterized by comprising frcm 49 to 60 mole percent of an anhydride, from about 2Q to 40 mole percent of at least one monomer selected from the group consisting of 1-alkene having from 4 to 16 carbon atoms, monaikenyl aromatic compounds and mixtures thereof; and from about 40 to 20 mole percent of at least one 1-alkene having at least 18 carbon atoms, 2. The terpolymer of claim 1 characterized in that the terpolymer is an aqueous alkaline dispersion having a viscosity at 250C of less than 20 centipoise of 10 per cent terpolymer and having a pH within the range of from 6.5 to 10, 3. The terpolymer of claim 1 or 2 characterized in that the anhydride is maleic anhydride. 4. The terpolymer of claim 1, 2 or 3 char- acterized in that the aromatic mono-alkenyl monomer is selected from the group consisting of styrene, alphamethyl styrene or mixtures thereof. 5. The terpolymer of any of claims 1 to 4 characterized in that the higher l-alkene is l-eicosene or a mixture of 1-alkenes having from 20 to 24 carbon atoms. 6. The terpolymer of any of the preceding claims characterized by comprising from about 4 to 60 mole per cent maleic anhydride, 20 to 40 mole per cent styrene and from 40 to 20 mole per cent of at least X- alkene having at least 18 carbon atoms. 7. A coating composition characterized by comprising: (a) from about .5 to 308 by weight of a terpolymer which comprises: (i) from about 49 to 60 mole percent of an anhydride; (ii) from about 20 to 40 mole percent of at least one monomer selected from the group consisting of l-alkene having from 4 to 16 carbon atoms, monoalkenyl aromatic compounds and mixtures thereof; and (iii) from about 20 to 40 mole percent of at letst one l-alkene having at least 18 carbon atoms; (b) from about I to 55 percent by weight of an emulsion polymer having a weight average molecular weight of greater than 20,000; and (c) the balance being an aqueous vehicle. 8. The composition of clam 7, characterized in that they anhydride is maleic anhydride. 9. The aomposition of claim 7 or 8, characterized in that the monomer is selected from the group consisting of l-alkenes having 4 to 10 carbon atoms, styrene and mixtures thereof. 10. The composition of claim 7 or 8,-characterized in that the monomer is styrene. 11. The composition of any of claims 7 to 10, tharacterizsd in that the terpolymer is present in an. amount from 2 to 10 per cent, preferably 2 to 7.5 per cent, the emulsion polymer is present in an amount of from 20 to 40 percent preferably from 25 to 35 per cent, and the balance being an aqueous vehicle. 12. The composition of any of claims 7 to 11, characterized in that the composition includes an effective amount of a slip aid.

Inventors: HANSEN, FREDERICK C., KIEHLBAUCH, RICHARD A., VERBRUGGE, CALVIN J.
Applicants: S.C. JOHNSON & SON, INC.
Application year: 1984
Main classification: C08F222
IPC codes: C08F210, C08F222