US2166981A

US2166981A - Process for esterifying polymerized olefines

Info

Publication number: US2166981A
Application number: US164494A
Authority: US
Inventors: Rosen Raphael; Peter J Gaylor
Original assignee: Standard Oil Development Co
Current assignee: Standard Oil Development Co
Priority date: 1937-09-18
Filing date: 1937-09-18
Publication date: 1939-07-25
Anticipated expiration: 1956-07-25

Description

ass son 'reterr.

ch, NewYor-k, N. a, and Rapl Bosen, both. N. 1.; we wimvmi by in i e or to Eeter J. Gaylcr;

ore to Standard il llevelopmentcompany, a corporation oi Delaware 7 No Drawing. pplication Septeber 18, 193?,

This invention relates to improved detergent aids and method of preparing the same. It particularly relates to detergent aids prepared from olefin polymers, and especially to those olefin polymers having from 10 to 30 carbon atoms in the molecule secured by polymerizing olefins having from 3 to 6 carbon atoms in the molecule.

By the term detergent aids" it is meant to inand emulsifying agents atoms and secured by the polymerization of lowmolecular weight olefins is not exactly known, it is reasonably certain that these compounds contain a number of carbon side chains. This feature makes the detergent aids derived from such compounds particularly desirable in that they have a lower melting point, they are more oil and less water soluble, and their germicidal value is considerably higher than that of detergent aids produced from substantially-straight chain olefins.

These detergent aids are prepared by treating a low molecular weight polymerized olefin such as isobutylene dimer, trimer and tetramer, amylene dimers and trimers and the dimers and trimersof hexylene with a strong mineral polybasic g acid such as sulphuric acid, and then neutralizing with an alkali as, for example, sodium hydromde. Th we highly branched olefin polymers, preferably those having from 12 to 20 carbon atoms in the molecule and still'containing one double bond 40 per molecule, are treated preferably with sulphuric acid under conditions to form a satisfactory olefin polymer sulphuric acid reaction product, and then neutralized-with an alkali such as sodium hydromde, potassium'carbonate, onium bases, etc. in order to produce the desired detergent.

The olefin polymers may be prepared from oleethylene, acetylene, buene, isoprene or extracted 01 or po trom vapor (Cl. 260-d) cracked gasoline and the like, maybe polymerized to produce polymers having from 5 to 30 carbon atoms in the molecule. Gaseous olefins such as ethylene, propylene, butylenes and amylenes and mixtures of these, which are present in refinery gases from cracking, distilling and naphtha re-' forming operations may also be polymerized to secure satisfactory polymers. materials are ethylene, propylene, butylene, amylene and hexylene. The term polymers is intended to also include co-polymers of these compounds, 1. e., a polymer of twodissimilar monomers, such as a polymer of isobutylene and normal butylene.

. These olefins may be polymerized in any manner which will give the desired polymer. One method is to polymerize olefins by means of catalysts such as boron fluoride, aluminum chloride or other volatile metallic halides above about 32 F. or by treating with dilute or strong sulphuric acid or liquid phosphoric acid. olefins may also be polymerized by heating under suitable pressure and temperature conditions, at about 500-900 F. for example, and 200-3000 pounds per square inch or more. Catalytic masses such as clay, alumina, charcoal, sodium metaphosphate, anhydrous ferric chloride, baumte and silica gel, may be employed, as well as catalysts of the types of charcoal impregnated with phosphoric acid. Liquid catalysts such as sulphuric acid and phosphoric acid or the sulfates or chlorides of various metals may be employed. The conditions of the polymeri'zation reaction may be widely varied in order to secure a' satisfactory polymer product. For instance, in the case of iso-olefin polymerization, dilute acids at elevated temperatures are em-- ployed. For example, with isobutylene polymerization is carried out with sulphuric acid at -200 F., say F. F

The polymers are then treated with strong polybasic mineral acid as, for example, strong or fuming sulphuric acid, chlorsulphonic acid, phosphoric acid, and the like. The treating agent is preferably strong sulphuric acid oi approximately 90% concentration or fuming sulphuric acid containing as high as 20% '-oleum. The reaction is preferably carried out at a' temperature from 10 to --20C. although if the time of contact is reduced, somewhat higher temperatures may be employed. The reacted olefin reaction product is neutralized with alkali to produce neutralized olefin polymer acid reaction product having desirable wetting and detergent properties.

The following examples serve to illustrate meth- 65 The preferred raw 0.2% solution of the soap in water.

100 parts by weight oi a cracked petroleum.

butane type fraction containing 10.6% isobutylene was treated in a tower with parts of sulphuric acid at 28 to 32 F. and atmospheric pressure. The acid extract containing 9 parts isobutylene was then separated and heated in a packed copper tube having an exit temperature 01' 248' F. About 7 parts of polymer were separated from the acid, the polymer containing 12% dimer and 88% trimer of isobutylene. These productswere then separated by distillation.

To parts of. the tri-isobutylene was added slowly 61 parts of sulphuric acid containing 20% sulphur tri-oxide. The mixture was vigorously stirred and the reaction temperature kept below F. during the addition of the fuming sulphuric acid. After the acid was entirely added,

the temperature was increased to about to F. 'and maintained at this temperature for about 1 hours, during which it was vigorously stirred for the first three-quarters of an hour. The material was then neutralized by adding 133 parts of 30% sodium hydroxide solution. To this solution was then added 123 parts of 91% isopropyl alcohol and the entire mixture heated under reflux conditions for two hours. The mixture was then allowed to stand at room temperatures for approximately 48 hours, during which it separated into three distinct layers. The upper layer was unreacted material while the middle layer was a neutralized olefin polymer'sulphuric acid reaction product consisting mainly water 193 0.2% solution in hard water, (C a++-300 parts/million) 126 Wetting number ismeasured bythedisc method and represents the number of seconds it takes for a small .circular disc (2 cm. diam.) oi. cotton canvas to become completely wetted when gently laid on the surface of an Example 2 A charge of cracked petroleum butane type fraction was agitated at 35-40 F. under 3 pounds gauge pressure. Boron fluoride gas was led into the mass at a rate equal to 40 in. of water pressure drop through a a, in. orifice. When the reaction had started, the feed wasadded at a rate of 250 gala/hr. until the agitator overfiowed into a still, then the rate was cut to 100 gala/hr. During the reaction the temperature increased to 100 F. and the pressure went up to 7-8 pounds gauge. The polymer obtained was fractionated by distillation and the tri-isobutylene separated.

To 100 parts of tri-isobutylene was added 60.7 parts of 96% sulphuric acid. The acid was added slowly and the reaction temperature was maintained below 120 F. and vigorous stirring employed during the addition of the sulphuric acid. After the sulphuric acid was added, the reaction mixture was heated to a temperature between 140 and 160 r. for 1% hours in which vigorous stirring was employed for the first three-quarters of an hour. To this mixture was then added gradually 133 parts or 30% sodium hydroxide solution. To the neutralized solution was then added 123 parts of 91% isopropyl alcohol, and the entire mixture was heated under reflux oondi;;- tions for 2 hours. The product was then allowed to stand and a three-layer separation occurred. The neutralized isobutylene polymer sulphuric acid reaction product middle layer was separated by means of dec'antation. The upper layer was 're-extracted with 91% isopropyl alcohol and the extracts were combined with the separated middle detergent layer which was then evaporated to dryness in a steam bath. A yield of 8.8 parts of semi-solid pasty material 01 a light brown color resulted, which as seen from the following data. possesses excellent wetting characteristics in dilute acid and in hard water:

Wetting number seconds 0.2% solution in distilled water 0.2% solution inhard water (Ca++--300- parts/million) 0.2% solution in acid water (.3% sulphuric acid) Wetting number is measured by the disc method and represents the number of seconds it takes for a small circular disc (2 cm. diam.) of cotton canvas to become completely wetted when gently laid on the surface of an 0.2% solution of. the sea in water. Pure water enerally has a wetting number 0 between 70,000 to 100, 00.

Other suitable polymer materials which can be converted to excellent detergent aids are:

Polymers of gaseous oleflns obtained by treating the latter with phosphoric acid at 200-250 F. and 400-500 pounds pressure.

Polymers of propylene obtained by treating the olefin with alumina-silica catalysts or activated or raw clays.

Polymers of lower oleiins obtained by polymerization with acid treated bentonites.

Polymers obtained by depolymerization of higher hydrocarbon polymers.

The above invention is not to be limited by any theory or method of operation but only, by the iollowing claims in which it is desired to claim all novelty in so far as the prior art permits.

We claim:

1..Process for preparing detergent aids comprising polymerizing an olefin thenseparating a polymer fraction having from 10 to 30 carbon atoms in the molecule and treating the olefin polymer fraction with astrong p lybasic mineral acid, and neutralizing the olefin polymer acid reaction product to secure, a product having detergent and wetting p operties.

2. Process for preparing detergent aids comprising polymerizing olefins having from 3 to 8 carbon atoms in the molecule separating therefrom polymer fractions having from 12 to 20 carbon atoms in the molecule then treating said polymer fractions with a strong polybasic mineral acid followed by' neutralization ot the olefin polymer acid reaction product with an alkali to produce a reaction product having detergent and wetting properties.

3. Process in accordance with claim 2 in which said strong polybasic mineral acid is sulphuric acid andsaid alkali is sodium hydroxide.

. 4: Process in accordance with claim 2 in which said strong polybasic mineral acid is fuming sulphuric'acid and said alkali is sodium hydroxide.

5. Process comprising polymerizing a butane cracked petroleum fraction to give a product predominating in trimer, separating the trimer by distillation, sulfating said trimer, and neutralizing the product to produce a detergent aid.

6. The process comprising the steps of separating from a cracked petroleum product an olefin compound, treating the olefin compound with a polymerizing agent, separating the polymerized product into a fraction containing substantially pure trimer, treating the trimer with concentrated sulphuric acid to produce a sulphonate, and neutralizing the sulphonate to produce the sodium salt of a polymerized iso-olefin 'sulphonic acid as a detergent.

7. The process comprising the steps of polymerizing a cracked petroleum product, separating the polymerized product into a fraction containing substantially pure trimer, treating the trimer with concentrated sulphuric acid at a low temperature to produce a s'ulphonate, and neutralizing the sulphonate to produce the sodium salt of a polymerized iso-olefln sulphonic acid as a detergent.

B. The process comprising the steps of polymerizing isobutylene, separating 4 the polymerized product into a fraction containing substantially pure trimer, treating the trimer with concentrated sulphuric acid at a low temperature to produce a s'ulphonate and neutralizing the sulphonate to produce the sodium salt of a polymerized iso-oleiin sulphonic acid as a detergent.

PETER J. wmza'vrcrr.v prism