FI73896B - ORGANOFILT LERGELNINGSMEDEL OCH FOERFARANDE FOER OEKNING AV ETT FLYTANDE ORGANISKT SYSTEMS VISKOSITET. - Google Patents

Description

73896

This invention relates to organophilic organic clay complexes which are dispersible in and form a gel in organic liquids. Depending on the composition of the gel, such gels can be used as lubricating greases, oil-based slurries, oil-based sealants, paint and alkyd varnish and cellulose coating removers, paints, binders in foundry sand, polyester grease and sealants, printing inks, polyac The invention also relates to a method for increasing the viscosity of a liquid organic system by means of such clay gel formers.

It is well known that organophilic compounds containing a cation react under preferred conditions by ion exchange with clays containing a negative layer lattice and containing. . ·. 20 exchangeable cations to form products of organophilic organic compound and clay. If the organic cation contains at least one alkyl group,. . containing at least 10 carbon atoms, such • organic clays are characterized by swelling in certain organic liquids. See. for example, U.S. Patent 2,531,427 and U.S. Patent 2,966,506, which are incorporated herein by reference, and Grim. R.E., Clay Mineralogy, Second Edition, McGraw-Hill Book Company, Inc., 1968, especially: Chapter 10, Clay-Mineral-Organic Reactions; pages 30 356-368, Ionic Reactions, Smectite; and pages 392-401,

Organophilic Clay-Mineral Complexes.

Whereas, since the introduction of organo-clays on the market as commercial products in the early 1950s, it has become well known that the greatest efficiency of gel formation (pak-35 decay) with these organo-clays is obtained by adding to the composition a low molecular weight polar; organic matter. Such polar organic materials have alternatively been referred to as dispersants, dispersants, solvents, dispersants, and the like. See, for example, the following patents: 0'Halloran 2,677,661; McCarthy et al. 2,704,276; Stratton 2,833,720; Stratton 2,879,229; Stansfield et al. 3,294,683. The use of such dispersants was found to be unnecessary with the use of 10 specially designed organophilic clays derived from substituted quaternary ammonium compounds. See U.S. Patents: Finlayson et al. 4,105,578 and Finlayson 4,208,218.

Low molecular weight alcohols and ketones, especially methanol and acetone, have been found to be the most effective and accepted dispersants for use as polar materials. However, these dispersers have very low flash points and require the use of refractory equipment. Dispersers which boil higher and have a higher flash point can be used but are less effective and often produce gels with poor secondary properties such as mechanical stability, poor thickening or storage stability.

Most previously produced organophilic clays have had limited utility as a gel, primarily due to varying dispersion and viscosity properties. Finlaysonin et al. Although the materials disclosed in U.S. Patent 4,105,578 have not had such deficiencies, the production of these materials is relatively difficult and additional costs are incurred in selecting benzyl starting materials.

Thus, there is a need for an organophilic clay gel form that is easy to prepare yet inexpensive and can be easily dispersed in organic systems to gel them without the substantial presence of a polar dispersant other than perhaps small amounts of water.

Unexpectedly, it has been found that an organophilic clay gelling agent with increased dispersibility in anhydrous liquid systems is obtained as a reaction product of a smectite-type clay and a certain type of organic cationic compound. According to the invention, such a gelling agent is an organophilic clay gelling agent containing a reaction product of an organic cationic compound and a smectite-10 ti-type clay (having a cation exchange capacity of at least 75 milliequivalents per 100 g of said clay), wherein the organic cationic compound has the general formula f R 1 V, 15 1 R 4 -X + -r2 m ”= .. ^ L ^ 20 wherein R. ^ is a β, ^" - unsaturated alkyl group or a hydroxy; ·. · An alkyl group having 2-6 carbon atoms, or a mixture thereof? R2 is a long chain alkyl group, R 12 and R 4 are selected from the group consisting of R 1 -, an aralkyl group having 1 to 22 carbon atoms in the alkyl moiety, and an alkyl group having 1 to 22 carbon atoms, and mixtures thereof, X is nitrogen, and M is Cl, I, Br, NO 2, OH- and <'2H 3 ^ 2' 3 the amount of said organic cationic compound is 90 to 140 milliequivalents / 100 g of said 30 clays based on 100% into active clay.

The invention further relates to a method for increasing the viscosity of a liquid organic system without a polar organic dispersant. In this method, an organophilic clay gelling agent as defined above is mixed into said liquid organic system in an amount sufficient to increase said viscosity.

4,7386 The clays used in the preparation of the organophilic clay gel formers of this invention are smectite-type clays having a cation exchange capacity of at least 75 milliequivalents per 100 g of clay. Particularly preferred types of clays are Wyoming variants of naturally occurring swellable bentonites and similar clays and hectorite, swellable magnesium lithium silicate.

The cation exchange capacity of smectite-type clays can be determined by a well-known ammonium acetate method.

Clays, especially bentonite-type clays, are preferably converted to the sodium form if they are not already in this form. This can be easily accomplished by preparing a 15-mile aqueous clay slurry and passing the slurry through a cation exchange resin layer in sodium form. Alternatively, the clay may be mixed with water and a soluble sodium compound such as sodium carbonate, sodium hydroxide or the like and then mixed with a clay mixer or extruder.

Smectite-type clays which have been prepared naturally or synthetically, either pneumolytically or, preferably, by a hydrothermal synthetic process, can also be used in the preparation of these organophilic clays. Typical examples of such clays are montmorillonite, bentonite, beidellite, hectorite, saponite and stevensite. Synthetic clays can be synthesized hydrothermally by forming an aqueous reaction mixture as a slurry containing the desired desired *. Aqueous oxides or hydroxides of the metal, with or without sodium fluoride (or alternative exchangeable cations or mixtures thereof), in appropriate proportions for the synthetic smectite desired in each case. The slurry is then placed in an autoclave and heated under autogenous pressure to a temperature in the range of about 100-325 ° C, preferably 274-300 ° C, for a time long enough to form the desired product.

The organic cationic compounds useful in this invention can be selected from a wide variety of materials capable of forming an organophilic sa-5 defect by cation exchange with a smectite-type clay, as defined above by the general formula.

The unsaturated alkyl group may be selected from a wide variety of substances. These compounds may be cyclic or acyclic, unsubstituted or substituted by aliphatic radicals having up to 3 carbon atoms, so that the total number of aliphatic carbons in the p, unsaturated radical is 6 or less. The β, β-unsaturated alkyl radical may be substituted by an aromatic ring which is similarly conjugated to the unsaturation of the β, β-moiety, or the β, β-radical is substituted by both an aliphatic radical and aromatic rings.

Typical examples of cyclic β, β-unsaturated alkyl groups include 2-cyclohexyl and 2-cyclopentenyl. Typical examples of acyclic β, β-unsaturated alkyl groups containing 6 carbons or less include propargyl; allyl (2-propenyl); crotyl (2-butenyl); 2-pentenyl; 2-hexenyl; 3-methyl- 2-butenyl, 3-methyl-2-penten-25-yl, 2,3-dimethyl-2-butenyl, 1,1-dimethyl-2-propenyl, 1,2-dimethylpropenyl, 2,4-pentadienyl, and Typical examples of acyclic aromatically substituted compounds include Kinnamyl (3-phenyl-2-propenyl), 2-enyl-2-propenyl, and 3- (4-methoxyphenyl) -2- Typical examples of aromatically and aliphatically substituted substances include 3-phenyl-2-cyclohexenyl, 3-phenyl-2-cyclopentenyl, 1,1-dimethyl-3-phenyl-2-propenyl, 1,1,2-trimethyl- 3-phenyl-2-propenyl, 2,3-dimethyl-3-35-phenyl-2-propenyl, 3,3-dimethyl-2-phenyl-2-propenyl and 3-phenyl-2-butenyl.

6 73896

The hydroxyalkyl group is selected from a hydroxyl-substituted aliphatic radical in which the hydroxyl is not substituted on the carbon adjacent to the positively charged atom, and the group has 2 to 6 aliphatic carbons. The alkyl group may be substituted on the aromatic ring independently of 2 to 6 aliphatic carbons. Typical examples include 2-hydroxyethyl (ethanol); 3-hydroxypropyl; 4-hydroxypentyl; 6-hydroxy-hexyl; 2-hydroxypropyl (isopropanol); 2-hydroxybu-10 style; 2-hydroxypentyl; 2-hydroxyhexyl; 2-hydroxycyclohexyl; 3-hydroxycyclohexyl; 4-hydroksisyklo-hexyl; 2-hydroxycyclopentyl; Hydroksisyklopentyy-3-yl; 2-methyl-2-hydroxypropyl; 1,1,2-trimethyl-2-hydr-propyl; 2-phenyl-2-hydroxyethyl; 3-methyl-2-15 hydroxybutyl; and 5-hydroxy-2-pentenyl.

Long chain alkyl radicals may be branched or unbranched, saturated or unsaturated, substituted or unsubstituted, and should have from 12 to 60 carbon atoms in the straight chain portion of the radical.

Long-chain alkyl radicals can be derived from naturally occurring oils, including various vegetable oils such as corn oil, peanut oil, soybean oil, cottonseed oil, castor oil and the like, as well as 25 different animal oils and fats such as tallow oil.

Alkyl radicals can be petrochemically derived in the same way as those derived from alpha-olefins.

Examples of useful branched saturated radicals include 12-methylstearyl and 12-ethylstearyl. Typical examples of useful branched, unsaturated radicals include 12-methyloleyl and 12-ethyloleyl. Typical examples of unbranched saturated radicals include lauryl; stearyl; tridecyl; myristal 35 (tetradecyl); pentadecyl; hexadecyl; hydrogenated tallow; dokosonyyli. Typical examples of unbranched, unsaturated and 7,73396 unsubstituted radicals include oleyl; & Linol yl; linolenyl; soybeans and tallow.

Typical examples of aralkyl groups attached to a positively charged atom, i. benzyl and 5 substituted benzyl groups include benzyl and radicals derived from, e.g., benzyl halides, benzhydryl halides, trityl halides, X-halo-OL-phenylalkanes, and having 1 to 22 carbon atoms in the alkyl chain such as 1-halo-1-halo. phenylethane; 1-halogen-1-phenylpropane; and 1-halo-1-phenyloctadecane; substituted benzyl groups which can be derived from ortho-, meta- and para-chlorobenzyl halides, para-methoxybenzyl halides; ortho-, meta- and para-nitrilobenzyl halides and ortho-, meta- and para-alkylbenzyl halides having 1 to 22 carbon atoms in the alkyl chain; and benzyl-type radicals containing fused rings, such as radicals which can be derived from 2-halomethylnaphthalene, 9-halomethylanthracene and 9-halomethylphenanthrene, wherein the halogen group is defined as chlorine, bromine, iodine or any such group as a leaving group in a nucleophilic reaction of a benzyl-type group such that the nucleophile replaces the leaving group in the benzyl-type group.

Typical examples of useful alkyl groups, which may be linear or branched, cyclic or acyclic, include methyl; ethyl; propyl; 2-propyl; isobutyl; cyclopentyl; and cyclohexyl.

Alkyl radicals can also be derived from other natural oils, both substituted and unsubstituted as described above, including various vegetable oils such as hydrogenated vegetable oil, corn oil, soybean oil, cottonseed oil, castor oil and the like as well as various animal oils.

35 Many methods are known for preparing salts of an organic cation. For example, in the preparation of a quaternary ammonium salt, it is possible to prepare a secondary dialkylamine, for example, by hydrogenation of nitriles, see U.S. Patent 2,355,356; and then forms a tertiary methyldialkylamine by reductive alkylation using formaldehyde as the source of the methyl radical. See also Shapiro et al. U.S. Pat. No. 3,136,819, which discloses the formation of a quaternary amine by adding benzyl chloride or benzyl bromide to a tertiary amine, see also Shapiro et al. U.S. Patent No. 10,775,617.

The salt anion is preferably selected from the group consisting of chloride and bromide and mixtures thereof, and is most preferably chloride, although other anions such as acetate, hydroxide, nitrite, etc. may be present in the organic cationic compound to neutralize the cation.

The organophilic smoke of this invention can be prepared by mixing clay, a quaternary ammonium compound and water together, preferably at a temperature in the range of 20 to 100 ° C and most preferably at a temperature in the range of 35 to 77 ° C for a sufficient time to coat the clay particles. then filtered, washed, dried and ground. When organophilic clays are used in emulsions, the drying and grinding steps can be omitted. When mixing the clay, the quaternary ammonium compound and water 25 at concentrations such that no sludge is formed, the filtration and washing steps can be omitted.

The clay is preferably mixed with water to a concentration of about 1-80% and preferably 2-7%, the slurry is optionally removed by centrifugation of non-clay impurities that make up about 10-50% of the starting wort composition, the slurry is mixed and heated to a temperature in the range of 35-77 ° C. The quaternary amine salt is then added in the desired milliequivalent ratio, preferably as a liquid in isopropanol or dispersed in water, and stirring is continued to enhance the reaction.

li 9 73896 For convenience of handling, it is recommended that the total organic matter content of the organophilic clay reaction products of this invention should be less than about 50% by weight of the organic clay. When higher amounts of mouth-5 are used, it is difficult to filter, dry and grind the reaction product.

For purposes of this invention, the amount of organic cation added to the clay should be sufficient to provide the clay with the desired improved dispersion properties.

This amount is determined as the milliequivalence ratio, which is the number of milliequivalents (M.E.) of the organic cation in the organic clay per 100 g of clay per 100% of active clay base. The organophilic clays of this invention should have a milliequivalence ratio of 90-140 and preferably 100-130. Organophilic clays produced at lower milliequivalent ratios are not effective in gelling form, although they may be good gelling agents when mixed with a polar organic dispersant in a conventional manner. At higher milliequivalent ratios-20a, organophilic clays are poor gelling agents.

. However, it should be noted that the recommended milliequivalence ratio in the range of 90-140 varies according to the properties of the organic system to which the organophilic clay is incorporated. . to form a gel.

The manner in which the organic cation acts in the reaction products of the organophilic clay of this invention is not fully known. However, the unique properties associated with the compositions of this invention are believed to be associated with the electron-withdrawing and electron-donating effect of various portions of the cation, and in particular the presence of at least one long chain alkyl group together with a β · unsaturated alkyl group and / or hydroxyalkyl group. When attached to a positively charged atom, the long chain alkyl group acts as an electron donor to aid in the delocalization of the positive charge. More importantly, it provides sufficient separation of the clay flakes to ensure further separation under reasonable mixing conditions. the unsaturated alkyl group, on the other hand, appears to cause delocalization of the positive charge; this may be due to the resonance and / or inductive power that occurs with the unsaturated alkyl group. This phenomenon does not occur to a significant extent with other saturated alkyl groups in the prior art. The enhanced effect of the lower hydroxyalkyl group appears to be related to an internal covalently bonded polar activating moiety, namely the hydroxyl group, if it is not adjacent to a positively charged atom. This effect is impossible when the hydroxyl moiety is localized to the 15 carbon atoms adjacent to the positively charged atom or to the aliphatic carbon of the alkyl chain longer than 6 carbon atoms.

The compositions of the invention set forth above have extensive use as rheological additives in generally anhydrous fluid systems. Anhydrous liquid compositions in which self-activating organophilic clays are useful include paints, varnishes, enamels, waxes, epoxies, mastics, adhesives, cosmetics, inks, polyester laminating resins, polyester gel coatings, and the like. These liquids can be prepared by any conventional method as disclosed in U.S. Patent 4,208,218, including colloid mills, roller mills, ball mills, high speed mixers in which the pigments become well mixed with the organic solvent using a high mixing speed in the processing.

The organophilic clay gelling agent is used in such compositions in an amount sufficient to provide the desired theological properties such as high viscosity at low mixing speeds, control of film shrinkage, and prevention of separation and hard packaging of pigments present in the anhydrous liquid composition. The amount of organophilic clay gelling agent used in the anhydrous liquid system should preferably be about 0.1-15% based on the weight of the treated anhydrous liquid system and preferably 0.3-5.0% to obtain the desired theological properties.

The following examples are provided to illustrate the invention, but are not intended to limit it. All percentages given in the examples are by weight unless otherwise indicated.

The smectite-type clays used in the examples were hectorite and Wyoming bentonite. Hectorite-10 clay was slurried in water and centrifuged to remove essentially all non-clay impurities. Wyoming bentonite was slurried in water, centrifuged, and substantially removed to remove all non-clay impurities, and deionized to the sodium form by passing the slurry through a cation-exchange resin pad in sodium form.

Examples 1-17 illustrate the preparation of various organic cationic compounds, which can be used as starting materials with organoclay to form the organophilic clay reaction products of this invention.

The organic cationic compounds used in accordance with the invention were prepared by early methods by standard methods starting from an amine having the desired number of long chain alkyl groups attached to a nitrogen atom. This long chain al-25 alkylamine was then reacted by reductive alkylation with an aldehyde and / or in an nucleophilic displacement reaction of the alkyl halide to form the desired quaternary ammonium compound.

The organic cationic compounds given in the examples. Teas are typical examples of cations used in accordance with the invention and are not intended to include all useful compounds.

...* Example 1

Allylethanol (hydrogenated tallow) ammonium chloride ... · 35 (abbreviation AE2HT) 852.9 g ethanol (hydrogenated tallow) amine, 130.7 g 12,7896 allyl chloride, 18.1 g allyl bromide (as catalyst), 13 g sodium bicarbonate and solvent about 400 ml of isopropyl alcohol was placed in a 2-liter autoclave. The temperature was maintained at 100 ° C and the mixture was allowed to react overnight.

A sample was taken, filtered and analyzed using HCl and NaOH. The sample contained 4.2% amine and 1.2% amine * HCl. 5 g of sodium bicarbonate was added to neutralize the amine HCl. The autoclave was sealed and the temperature was allowed to rise to 120 ° C. Methyl chloride was introduced into the autoclave and added periodically until the pressure remained constant (550 kPa, 65 psig) for one hour. In this case, the reaction was considered complete. Final analyzes showed an effective molecular weight of 966.97.

Example 2 Allylmethyl dide (hydrogenated tallow) ammonium chloride (abbreviation AM2HT)

824.7 g of methyldi (hydrogenated tallow) amine, about 350 ml of isopropyl alcohol, 250 g of NaHCO 3, 191.3 g of allyl chloride and 10 g of allyl bromide (as catalyst) were added. 20 in a 4-liter reaction vessel connected to a condenser and a mechanical stirrer. The mixture was heated and refluxed slowly. A sample was taken, filtered and titrated with HCl and NaOH. The reaction was considered complete with 0.0% amine HCl and 1.8 g amine.

25 The final analysis showed an effective molecular weight of 831.17.

Example 3

Allylbenzylide (hydrogenated tallow) ammonium chloride (abbreviation AB2HT) 30 This reaction involves two steps - the formation of a tertiary amine and the preparation of quaternary ammonium chloride.

759.3 g of di (hydrogenated tallow) amine, 168.0 g of sodium bicarbonate and about 400 ml of isopropyl alcohol were placed in a 4-liter reaction vessel connected to a condenser, a mechanical stirrer, a thermometer and an addition funnel. Mixture 73896 was heated to 50 ° C until the amine dissolved. 153.1 g of allyl chloride were added dropwise over one hour at 50 ° C. After about two hours at 50 ° C, two samples were taken and filtered, and the other was reacted with phenyl isocyanate. Both were then titrated with HCl. An additional 153.1 g of allyl chloride was added dropwise to the reaction mixture. The mixture was heated to reflux for one hour before being sampled again. In this case, the reaction was considered complete. Excess allyl chloride was distilled off.

208.9 g of benzyl chloride was placed in a 4-liter reaction vessel containing the reaction mixture described above. The reaction mixture was heated to reflux for 4 days. A sample was taken, filtered and analyzed. It was found to contain 0.18% amine * HCl and 10.75% amine. 25 g of benzyl chloride and a further 50 g of NaHCO 3 were added and the mixture was heated to reflux for two days. Analyzes of the sample showed 10.17% amine and 0.0% amine »HCl. The reaction mixture was placed in a 1 liter autoclave, heated to 100 ° C and methyl chloride was added. When the pressure did not drop after the addition of MeCl, the reaction was complete. A sample was taken, filtered and analyzed.

· * "· The sample still contained 2.86% amine, but the reaction was then considered complete. Final analysis showed an effective molecular weight of 1423.17.

Example 4

Allylbenzylethanol (hydrogenated tallow) ammonium chloride (abbreviation ABEHT) A 2-liter autoclave was charged with benzylethanol-30 (hydrogenated tallow) amine (632.2 g; 1.5 mol), 133.9 g of allyl chloride, 18.1 g of allyl bromide, 160 g of sodium bicarbonate and 175 ml of isopropyl alcohol. The mixture was allowed to react at 100 ° C overnight. A sample was taken and found to contain 61.2% amine. The apparently slow reaction rate was due to a leak in the autoclave. After correcting the 14,73886 error, 133.9 g of allyl chloride and 18.1 g of allyl bromide were added. The reaction was allowed to proceed overnight. A sample was taken and analyzed. It contained 16.1% amine and 0.4% amine · HCl. An additional 36 g of allylvyl bromine-5 dia was added. The next day, a sample was taken, analyzed, and found to contain 7% amine and 0.5% amine HCl. Allyl bromide (15 g) and 25 g of sodium bicarbonate were added and the reaction was allowed to proceed overnight. Analyzes of the sample showed it to contain 0.0% amine-10 n-HCl and 5.2% amine. Methyl chloride was added to the autoclave to complete the quaternization reaction. The final analysis showed an effective molecular weight of 780.7.

Example 5

Allylbenzylmethyl (hydrogenated tallow) ammonium chloride (abbreviation ABMHT) In a 2-liter autoclave was charged 436.8 g (1.17 mol) of benzylmethyl (hydrogenated tallow) amine, 133.9 g (1.75 mol) of allyl chloride, 14 .5 g (0.12 mol) of allyl bromide, 150 g of sodium bicarbonate and 150 ml of isopropyl alcohol. The mixture was allowed to react at 100 ° C overnight. Sample-20 te was taken, analyzed and found to contain approx. ; 10.8% amine and 0.7% amine hydrochloride. An additional 30 g of allyl chloride was added. The mixture was allowed to continue to react overnight. The second sample was taken, filtered and analyzed. It contained 22.8% amine and 0.0% amine-25 N * HCl. The increase in the percentage of amine was perhaps due to the presence of amine carbonate. Therefore, the reaction mixture was filtered and 10 g of sodium hydroxide in 10 ml of water was added. An additional 30 g of allyl bromide was added and the mixture was allowed to continue reacting at 100 overnight.

Analysis of the sample showed 3.0% amine, and 1.3% sodium bicarbonate (30 g) was added and quaternization was stopped using methyl chloride. A sample was taken and analyzed. It contained 0.0% amine. HCl and 2.8% amine. About 50 g of sodium bicarbonate was added to the mixture, stirred and the reaction was considered complete. Final analyzes showed an effective molecular weight of 826.09.

Il 15 73896

Example 6

Allyldiethanoloctadecylammonium chloride (abbreviation A2EAlk) 755.6 g (2.1 mol) of diethanoloctadecylamine, 191.3 g (2.5 mol) of allyl chloride, 12.7 g (0.105 mol) of allyl bromide, 390 ml of isoprop were charged to a 2-liter autoclave. -pyl alcohol and 20.8 g of sodium bicarbonate. The mixture was allowed to react at 100 ° C overnight. A sample was taken, filtered and analyzed. It was found to contain 3.3% 10 amine HCl and 0.5% amine. An additional 20.0 g of sodium bicarbonate and 20.0 g of allyl chloride were added and the mixture was allowed to proceed at 100 ° C. The reaction was considered complete the next day. Final analysis showed an effective molecular weight of 656.49.

15 Example 7

Allyldimethyloctadecylammonium chloride (abbreviation A2MAlk) Into a 2-liter reaction vessel equipped with a mechanical stirrer and reflux condenser was charged 660.0 g of dimethyl-20-octadecylamine, 199.0 g (2.19 mol) of allyl chloride, 13.3 g (0.11 mol). allyl bromide, 20 g of sodium bicarbonate and 350 ml of isopropyl alcohol. This mixture was refluxed overnight. Analysis of the filtered sample showed that the reaction was complete.

The mixture was filtered and analysis showed an effective molecular weight of 496.74.

Example 8

Diallylmethyl (hydrogenated tallow) ammonium chloride (abbreviation 2AMHT) Into a 2-liter reaction vessel equipped with a reflux condenser, mechanical stirrer and addition funnel was charged 405.3 g (1.5 mol) of (hydrogenated tallow) amine, 112.0 g of sodium hydroxide. · ... · hydroxide, 42.0 g of sodium bicarbonate and 275 ml of iso-. . ·. propyl alcohol. The mixture was heated until the amine. · 35 dissolved. Allyl chloride (252.6 g? 3.3 mol) was added dropwise over about 1-1 / 2 hours. After the reaction mixture was gently heated to reflux for 22 hours, a sample was taken and filtered. A portion of the sample was reacted with phenyl isocyanate and both portions were titrated with 0.100 N HCl. Results 5 showed about 75% tertiary amine. The reaction mixture was heated to reflux for an additional 2 hours before being analyzed again. In this case, the titration results showed about 90% tertiary amine. Excess allyl chloride was distilled off.

The above reaction mixture was placed in a 2-liter autoclave and reacted with methyl chloride. A sample was taken, filtered and analyzed. It contained 0.0% amine * HCl and 0.67% amine. The reaction mixture was filtered and analyzed to have an effective molecular weight of 635.34. 15 Example 9

Diallylide (hydrogenated tallow) ammonium chloride (abbreviation 2A2HT) In a 4-liter reaction vessel equipped with a reflux condenser, mechanical stirrer and addition funnel was charged 746.0 g of 20 di (hydrogenated tallow) amine, 400 mL of isopropyl alcohol and 175 g of sodium bicarbonate. The mixture was heated until the amine dissolved. Allyl chloride (344.4 g; 4.5 mol) was added dropwise over 1.5 hours. The rate and temperature of addition were monitored to maintain a slow recovery.

:: 25 After 4 days, a sample was taken, filtered and analyzed. The reaction rate was 38.9% complete (61.1% amine; 0.011% amine * HCl). An additional 250 mL of allyl chloride was added dropwise and the mixture was allowed to continue to reflux slowly overnight. A second sample was taken and found to contain 9.79% amine and 0.56% amine · HCl. An additional 100 g of allyl chloride was added. The next day, analysis showed 3.4% amine and 0.34% amine * HCl. 100 g of allyl chloride were added; this did not cause the reaction to continue any further. The reaction mixture was filtered and cooled to room temperature. Methyl iodide was added to stop quaternization. The final anal- ii.

17 73896 lysis showed an effective molecular weight of 1111.5; amine 0.397% and amine * HCl 0.0%.

Example 10

Triallyl (hydrogenated tallow) ammonium chloride (abbreviation 5 3AHT) 392.1 g (1.5 mol) of (hydrogenated tallow) amine, 355.9 g of allyl chloride, 18.2 g of allyl bromide, 120 g of sodium hydroxide were charged to a 2-liter autoclave, 84 g of sodium bicarbonate and 200 ml of isopropyl alcohol. The mixture was allowed to react at 100 ° C overnight. A sample was taken, filtered and analyzed. It was found to contain about 10% amine and 0.2% amine * HCl. An additional 56.2 g of allyl bromide was added and the mixture was allowed to continue reacting at 100 ° C. The sample was taken the next day. Analyzes 15 showed 1.97% amine and 3.4% amine HCl.

The reaction mixture was filtered. Sodium bicarbonate (10 g) was added and the mixture was stirred for 1/2 hour.

The mixture was filtered and 12.0 g of methyl iodide was added to stop the quaternization.

Analysis showed an effective molecular weight of 841.10.

- Example 11

Ethanolimethyloctadecylammonium chloride (abbreviated as E2M Alk) Dimethyloctadecylamine (779.35 g; 2.6 mol); * · '*' 257.63 g (3.2 mol) of 2-chloroethanol and about 400 ml of isopropanol were placed in a 4-liter reaction vessel equipped with a mechanical stirrer and a reflux condenser. The mixture was stirred at room temperature for about 2 weeks. Analyzes showed 67% amine and 0.7% amine · HCl. The mixture was heated with reflux for a week. A sample was taken, analyzed and found to contain 0.0% amine and 2.8% amine · HCl. Sodium bicarbonate (67 g) was added and the mixture was further heated to reflux. The next day, the sample was analyzed and contained 2.9% amine. The reaction mixture was filtered and cooled before adding iodomethane to quench the reaction. Final analysis showed 1.23% amine; amine HCl 0.409%; and an effective molecular weight of 567.9.

5 Example 12

Ethanolbenzylmethyl (hydrogenated tallow) ammonium chloride (abbreviation EBMHT) 632.2 g (1.5 mol) of benzylethanol (hydrogenated tallow) amine, 160 g of sodium bicarbonate and 175 ml of isopropyl alcohol were charged to a 2-liter autoclave. The temperature was allowed to rise to 100 ° C. Methyl chloride was introduced and added periodically until the pressure remained constant for one hour. A sample was taken and analyzed. It was found to contain 18.4% amine and 3.0% amine-15 * HCl. The autoclave was refilled with methyl chloride and heated to 100 ° C overnight. A second sample was taken, filtered and found to contain 4.8% amine and 3.2% amine · HCl. The reaction mixture was filtered, stirred with added sodium bicarbonate and refiltered. It was recrystallized twice from acetone. Final analysis showed 0.33% amine; amine HCl 0.29%; and an effective molecular weight of 393.9.

- * I Example 13

Ethanol benzylide (hydrogenated tallow) ammonium chloride '/ 25 (abbreviation EB2HT)

Ethanol (hydrogenated) amine (823.7 g, 1.5 mol), 215.2 g of benzyl chloride (1.7 mol), 25.7 g of benzyl bromide (0.15 mol), 15.0 g of sodium bicarbonate and 430 ml of isopropyl alcohol was placed in a 2-liter flask equipped with a mechanical stirrer and a reflux condenser. This mixture was heated to reflux.

After two days, the sample was taken, filtered and analyzed. It was found to contain 3.9% amine and 5.6% amine HCl. An additional 20.0 g of sodium bi-35 carbonate was added and the reaction mixture was transferred to a 2-liter autoclave. The quaternization was stopped with methyl chloride. The standard method of methylation was used except that the temperature was maintained at -80 ° C. The reaction was complete. The final analysis showed an effective molecular weight of 941.1.

5 Example 14

Diethanolbenzyloctadecylammonium chloride (abbreviation 2EB Alk) In a 4-liter reaction vessel equipped with a reflux condenser and a mechanical stirrer were charged 10,719.6 g (2.0 mol) of diethanoloctadecylamine, 278.5 g (2.2 mol) of benzyl chloride, 20 g of sodium bicarbonate and about 400 ml of isopropyl alcohol. The reaction mixture was heated to reflux overnight. A sample was taken, analyzed and found to contain 7.4% amine 15 and 1.7% amine · HCl. The mixture was allowed to continue to react overnight. A second sample was analyzed and found to contain 4.1% amine and 3.7% amine · HCl. An additional 20 g of sodium bicarbonate and 30 g of benzyl chloride were added. After a week, the reaction had not progressed any longer. The mixture was placed in an autoclave and the quaternization was stopped with methyl chloride. Final analyzes showed 0.0% amine; amine.HCl <1%; and an effective molar mass of 834.4.

Example 15 Diethanolmethyloctadecylammonium chloride (abbreviation 2EM Alk) 858.3 g (2.4 mol) of diethanoloctadecylamine, 20 g of sodium bicarbonate and 420 ml of isopropyl alcohol were placed in a 2-liter autoclave. The temperature was raised to 30,100 ° C. Methyl chloride was introduced and added periodically until the pressure remained constant (550 kPa, 65 psig) for one hour.

A sample was taken and filtered. Analyzes showed 2.67% amine. The reaction mixture was filtered and 18.0 g of iodomethane was added to stop the quaternization. Final analyzes showed 1.64% amine 20 7 3 8 9 6 and 0.0% amine »HCl and an effective molecular weight of 725.27.

Example 16

Diethanolide (hydrogenated tallow) ammonium chloride 5 (abbreviation 2E2HT) In a 4-liter reaction vessel equipped with a condenser and a mechanical stirrer was charged 812.5 g of ethanol (hydrogenated tallow) amine, 144.9 g of 2-chloroethanol and about 500 g of ml of isopropyl alcohol. This mixture was scrubbed-10 at reflux for 2 weeks.

A sample was taken, analyzed and found to contain about 47% amine and 12% amine · HCl. An additional 100 g of 2-chloroethanol was added and the mixture was further heated to reflux. After five days, 15 second samples were taken. It was found to contain 21% amine and 10% amine · HCl. The amine * HCl was neutralized by the addition of 75 g of NaHCO 3. The reaction mixture was placed in a 2-liter autoclave and reacted with methyl chloride to complete the quaternization. Final analyzes are 0.0% amine-20; 1.9% amine · HCl; and an effective molecular weight of 1246.55.

: ·: Example 17

Triethanoloctadecylammonium chloride (abbreviation 3E Alk)

175.6 g of diethanoloctadecylamine, 120.8 g of 2-chloroethanol, 200 ml of isopropyl alcohol and a few crystals of potassium bromide (as catalyst) were placed in a 1-liter flask equipped with a condenser and a mechanical stirrer. The mixture was heated to reflux for 10 days.

Analyzes were performed by titrating the sample with 0.100 N HCl (to determine amine%) and 0.100 N NaOH (to determine amine · HCl%). After 10 days, the reaction was 10% complete (79.8% amine; 10.2% amine · HCl). The reaction was allowed to proceed at reflux.

After another ten days, analyzes showed 20.22% amine and 29.76% amine hydrochloride. Additional 2-chloroethanol (48.3 g, 0.6 mol) was added and the amine * HCl was neutralized with 27.7 g (0.33 mol) of sodium bicarbonate. The mixture was then heated to Palau-5 under reflux for another week. It contained 4.92% amine HCl and 8.05% amine. The resulting material was then recrystallized twice from a mixture of acetone and toluene.

The final analyzes were as follows: amine 0.32%; amine * HCl 1.97%; and an effective molecular weight of 452.04. 10 Examples 18-67 and Comparative Examples A-G

These examples illustrate the use of the organophilic clay preparations of this invention in various solvent systems. The compositions are shown in Table I and the solvent miscibility results in Table II.

Organophilic clay reaction products were prepared by loading a suitably sized container of 3% clay slurry (sodium form of Wyoming bentonite or hectorite) which was heated to 60 ° C with stirring. A solution of the organic cationic compound 20 was added to the clay slurry and stirred long enough to complete the reaction (usually 10-60 minutes). The organoclay was collected on a vacuum filter. The filter cake was washed with hot (40-80 ° C) water and dried at 60 ° C. Dried organo-; · ‘The clay was ground using a hammer mill or similar grinding device to reduce the particle size and then screened’ through a 200 mesh screen before use. The amounts of starting materials used are shown in Table 1. The density of the screen is expressed in US standard mesh.

The improved dispersion properties of the organoflitic clays of this invention are illustrated by a solvent miscibility test. This test demonstrates any results that may be obtained using the compositions of the invention. The solvent miscibility test is performed by taking a sample of the organophilic clay, which is sprinkled in separate 10 ml batches of 10 ml in different 10 ml beakers. The organophilic clay is added at such a rate that the particle cartridges are wetted evenly and no clumping occurs. The samples are allowed to equilibrate after all the organophilic clay has been added (approximately 30 minutes). The volume taken up by the organophilic clay is then recorded in tenths of a milli-5 liter; this figure is called the swelling state volume.

The mixture is stirred vigorously 50 times, 10 times horizontally and 40 times vertically and allowed to stand overnight. The volume taken up by the organophilic clay is again recorded as tenths of a milliliter; this value is called the landing volume.

The swelling volume indicates the miscibility of the organic part of the organophilic clay with the solvents tested; the settling volume indicates the ease of dispersion of the orga-15 nophilic clay into that solvent at low agitation rates.

Due to variations in the rate of scattering of organic clay in the solvent and variations in the mixing strength of the sample, the figures are not absolute. Small differences in 20 volumes are not considered significant. Rather, the values are for comparison purposes only.

The results show that the compositions of this invention have broad dispersibility in a variety of solvent systems and that the materials of the invention are more dispersible than similar conventional quaternary amine reaction products. The solvent systems used are typically three main solvent systems: aliphatic, aromatic and moderately polar. These systems cover a wide range of systems in which the rheological additives of this invention are used.

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Claims (8)

An organophilic clay gelling agent comprising the reaction product of an organic cationic compound and a smectite-type clay (with a cation exchange capacity of at least 75 milliequivalents per 100 g of the clay in question), characterized in that the organic cationic compound has the general formula R 10 h R 4 - X + --- R_ M ~ 4 ik * 3 wherein R 2 is a / 3, -, - unsaturated alkyl group or a hydroxyalkyl group having 2-6 carbon atoms or a mixture thereof; R 2 is a long chain alkyl group of 12 to 60 carbon atoms; R 2 and: · R 2 is selected from a group containing the R 2 group, an aralkyl group having 1-22 carbon atoms in the alkyl moiety and an alkyl group - having 1-22 carbon atoms and mixtures thereof; X is nitrogen -. and M is Cl ”, I, Br, NC ^, OH and ₂HH₂, and the amount of the organic cationic compound in question is . 90-140 milliequivalents / 100 g of clay calculated as 100% active clay. 2. A composition according to claim 1, characterized in that the clay of the smectite type is hectorite or sodium bentonite. Composition according to claim 1, characterized in that the Y-unsaturated alkyl group is an unsubstituted or substituted cyclic or acyclic alkyl group having less than 7 carbon atoms, acyclic alkyl group substituted with aromatic groups, or aromatic group substituted with aliphatic groups. 4. A composition according to claim 1, characterized in that the hydroxyalkyl group is a substituted or unsubstituted cyclic or aliphatic group of 2-6 carbon atoms and the hydroxyl substitution is present at the carbon atom C2-C2. A process for increasing the viscosity of a liquid organic system without a polar organic dispersant, characterized in that a sufficient amount of an organophilic clay yellowing agent is added to the organic system, which increases the viscosity of the organic product. cationic compound and a smectite-type clay (with a cation exchange capacity of at least 75 milliequivalents per 100 g of clay), in which the reaction product of the organic cationic compound has the n general form 15 (1) + - wherein R 1 is a f'-unsaturated alkyl group or a hydroxy alkyl group of 2-6 carbon atoms or a mixture thereof; 1 * 2 is a long chain alkyl group of 12-60 carbon atoms; and R 2 is selected from a group containing the R 2 group, an aralkyl group having 1-22 carbon atoms in the alkyl moiety and an alkyl group having 1-22 carbon atoms and mixtures thereof; X is nitrogen and M is Cl 2, I, Br, NO 2 / OH and C 2 H 3 ° 2 'and that the amount of clay in question is 90-140 milliequivalents / 100 g of clay calculated as 100% active clay. 6. A process according to claim 5, characterized in that the clay of the smectite type is hectorite or sodium bentonite. 7. A process according to claim 6, characterized in that the *>, unsaturated alkyl group is an unsubstituted or substituted cyclic or acyclic alkyl group having less than 7 carbon atoms, acyclic alkyl group substituted by aromatic groups or aromatic li