US2130507A - High molecular weight iso-olefine polymers and process of producing the same - Google Patents

Description

Patented Sept. 20, 1938 HIGH MOLECULAR WEIGHT ISO-OLEFINE POLYMERS THE SAME AND PROCESS OF PRODUCING Michael Otto and Martin Mueller-Onnradi, Ludwigshafen-on-the-Ilhine, Germany, asaignorl to I. G. Farbenindnstrie Aktlengeseilschaft, Frankfort-on-the-Main, Germany No Drawing.

Original application July 21, 1932,

Serial No. 623,812. Divided and this application April 2, 1935, Serial No. 14,273.

many July 25, 1031 '1 Claims.

The present invention relates to the preparation of valuable hydrocarbon products, more particularly those of higher boiling point.

' We have found that hydrocarbon mixtures, in particular those having a boiling point above 200 0.. and especially those boiling above about 325 C. at ordinary pressure, for example lubricating oils or greases or hard or soft paraffin wax, are considerably improved and that in particular the viscosity of these materials is much increased by adding thereto high molecular hydrocarbons having a molecular weight of for example 1000 or 2000 or even more, which are obtained by polymerizing iso-olefines and in particular iso-butylene.

By the addition of these high molecular hydrocarbons obtained by polymerizing iso-oleflnes (which hydrocarbons for the sake of brevity are hereinafter referred to as polymerized iso-olefines) also the temperature-viscosity curve of the hydrocarbon mixtures to be improved is remarkably flattened in many cases. Furthermore the electric properties of these hydrocarbon mixtures are considerably changed so that for example by the addition of only l per cent of polymerized iso-oleflnes the disruptive strength of the hydrocarbon mixtures is increased to double its height and that this effect even remains after artificial ageing. The hydrocarbon mixtures so improved may therefore be employed with great advantage as insulating oils for transformers and switches. Hard and soft paraflin wax is rendered transparent by the addition of the said polymerized isoolei'lnes; furthermore the formation of fissures and cracks is prevented thereby. In many cases it is sufiicient to add the polymerized iso-oleflnes in an amount of from a fraction of none per cent up to about 10 per cent with reference to the hydrocarbon mixtures to be improved, but the amount added may also be much higher, as for example about 20 or or even per cent.

For many purposes, as for example for lubricating automobile motors'. it is well known that oils are necessary which on the one hand still have a satisfactory viscosity at high temperatures, as

for example from to C., and on the other hand are still so thinly liquid at low temperatures that the friction is not too great for the automobile motor to be set in motion directly by the starting device. According to the present invention oils can be prepared which correspond to a great extent to these requirements and which are far superior to the special automobile oils hitherto in commerce.

- The effect of the addition of the said polymer- In Gerized iso-oleflnes is shown in the following table of examples. The oils used in experiments A, B, C. D and E are mineral oils of the type of the commercial light to medium machine oils. Experiments A. B, C, C", D and E show the effect of the addition of an iso-butylene polymerization product. Experiments F, G and H are the tests of special automobile oils. In all cases the temperatures are given in degrees C.

The viscosity index indicates the value of the oil in that as the index value increases, the quality of the oil improves.

P ggeentlage Viscosity in degrees Engler at iso uty ene 223? polytmeri- Zll inn 0 o o o o a product 0 20 38 50 m0 150 0 125 25 8.3 1.0 Help 1.2 6 42 15.6 8.8 2. 25 1.44 0 46 11 5.3 3.0 1.45 Below 1.2 4 98 29.5 12.9 7.7 2.25 1.47 U l 3.3 2.1 1.3 l 4 I10 33 13.9 8.2 2.32 1.4.; 13 280 84 35.2 2L8 5.0 3.18 0 12 4.8 2.55 2.0 1.3 6 55 20.5 9.8 6.5 2.25 1.52 0 225 41 12.9 7.0 LS 1.22 1 About 58 l9.l 10.3 2.3 1. 42

280 F 0 Abgg'l; 03 20.2 11.1 2.3 1.4 G 0 0335 73.5 21.8 11 2.12 1.32 H 0 Over 83 25.3 13 2.5 1.45

- Viscosity Setting Flush Densitv Expenment index point point at 20 Degrees below zero Degree 8 242 0.880 i3 242 0.880 6 215 0. 870 12 215 0. 870 50 0.885 45 180 0.885 9 0.860 12 185 0.860 2. 5 221 0 0H 5 222 0.014 7 231 0. 7481i 16 235 0.90!

From the table it can be seen that the addition of the highly polymerized isobutylene prodducts considerably improves the oils. The resulting improved oils have even a higher viscosity index than special automobile oils of high value.

On account of the low coke test of the polymerized iso-olefines the lubricating oils the vis- Viscosity Conradson Addn'ions at C. coke test l, 56 0. 08 4.0 per cent of lyinerizcd iso-butylene 3. 0 0.09 33.0 per cent 0 bright stock oil l. 0 0. 52 33.0 per cent of hot steam cylinder olL l. 9 0. 71

The effect of the addition of polymerized isoolefines to greases is shown by the following example:

1200 grams of a lubricating oil for freezing machines having a viscosity of 7 Engler at 20 C. and a setting point of 45 below zero C. is mixed after dissolution therein of 60 grams of polymerized iso-butylene with 250 grams of oleic acid glyceride, 30 grams of hydrate of lime and 20 grams of a 20 per cent solution of caustic soda, the mixture being stirred for about 5 hours at 100 C. The resulting grease is soft and of a great adhesive power.

Also hard and soft paraffin wax is considerably improved by the addition of polymerized isobutylene as will be seen from the following example:

Polymerized iso-butylene is added in an amount of from 1 to 4 per cent to paraflin wax having a strong tendency to form crystals and which when employed for casting candles causes the formation of fissures. The candles cast with the mixture thus obtained do not show fissures to a substantial degree and fissures or points of crystallization still formed disappear after 1 or 2 days. The candles are uniformly transparent.

The production of the polymerized iso-olefines to be added to the hydrocarbon products is effected by polymerization of the iso-olefines in the presence of suitable catalysts, preferably volatilizable inorganic halides, such as boron fluoride, boron fluoride charged with hydrofluoric acid, phosphorus trifluoride, phosphorus pentafluoride, aluminium chloride, preferably in statu nascendi, such as aluminium chloride as is formed by allowing hydrogen chloride to act on aluminium, or solutions or double compounds of the said halides, while cooling so strongly that no sudden substar tial increase in temperature occurs. The said catalysts may be employed as such or together with substances such as phenol or cresol, in which they dissolve without decomposition, whether with the formation of real solutions, or with the formation of double compounds. The strong cooling prevents the undesired too rapid reaction, which leads to products not having the desired molecular weight, and furthermore the loss in iso-butylene which would occur by a sudden superheating. It may be advantageous not to bring the catalyst into contact with the isobutylene at once but gradually. By moving the iso-butylene, for example by stirring, the removal of the reaction heat'is favoured and local superheating is avoided. The polymerization of iso-butylene is a strongly exothermic reaction. Corresponding to the different intensity of the catalytic action of the diflerent catalysts it is necessary tovary the intensity of cooling. For

active boron fluoride it is necessary to keep the temperature during the reaction below 5 C. Temperatures as low as 10 below zero 0. or still lower temperatures may be employed.

The cooling may be effected externally by means of cooling baths or internally by adding to the reacting substances cold materials which have no favourable influence on the reaction, as for example solid carbon dioxide.

The catalysts may be employed in very small amounts; for example less than 1 per cent of catalyst is suflicient when boron fluoride is employed. It is, however, possible to use also higher percentages of catalysts, for example 3 or 5 per cent of aluminium chloride.

Solvents, such as pentane, may be present during the reaction. The resulting product is very viscous and of a from sticky to semi-solid or solid or rubber-like consistency; it is "colorless and clear, soluble in liquid hydrocarbons in any proportion and may easily be depolymerized, without the formation of coke, to form gaseous and lower boiling hydrocarbons by heating, for example to a temperature of 300 C. Of particular value are the polymerized products having a molecular weight of more than 2,000, as for example up to 10,000 and more. The Conradsoncoke-test of these products is very low and not far from zero; it amounts for example to 0.01.

The following examples further illustrate the preferred preparation of the said polymerized iso-olefines; the preparation of these products is, however, not restricted to the particular operations there described.

Example 1 About 0.5 part of boron fluoride is led into 100 parts of liquid iso-butylene which is cooled by a bath of carbon dioxide at 80 below zero C. The polymerization soon sets in vigorously. By intense stirring while maintaining the cooling, the considerable heat of reaction is led away so well that the temperature does not rise above 20 below zero C. The reaction product has a mean molecular weight of 3500. It is extremely viscous, may be drawn out into long threads and,

even at 200 C., it is still not liquid.

Example 2 Example 3 A 20 per cent solution of iso-butylene in pentane is kept at 40 below zero C. while leading in boron fluoride. After expelling volatile constituents with steam the product has a molecular weight of 2500. The product is much more soft and more sticky than that obtained according to Example 2; it is colorless and clear and may be drawn into long threads.

Example 4 A mixture of grams of iso-butylene and 110 grams of normal butylene (mainly a-butylene) is polymerized as described in Example 2. After' example, in the employment of the extremely distilling oil the normal butylene 20 g ams of a [Ill residue having a molecular weight of about 4000 are obtained.

Example 5 A mixture of 50 grams oi iso-butyiene and 250 grams oi normal butylene are polymerized as described in Example 2. After distilling oil a residue oi 58 grams is obtained. From this residue ll grams may be distilled 03 under a pressure oi. 0.1 millimeter mercury gauge and at a temperature up to 200 0., 47 grams 0! a product having a molecular weight of about 3000 thus being obtained.

Example 6 A mixture consisting of 900 grams of natural gas gasoline (distilling almost completely up to 60 C.) 60 grams of iso-butylene and 290 grams of normal butylene, which mixture is liquid under a slight superatmospheric pressure, is polymerized as described in Example 2.

After distilling oil '19 grams of a polymerizatlon product are obtained, of which 16 grams, under a pressure oi 15 millimeters mercury gauge, boil up to 200 C., and further 18 grams boil up to this temperature, under a pressure or 0.0? millimeter mercury gauge, 45 grams of a residue having a mean molecular weight of 3500 remain in the still. 7

The molecular weight may be increased by depolymerlzing either the said 79 grams of polymerization product or the said grams of residue into iso-butylene by heating, ii desired, in the presence of catalysts and then again polymerizing the depolymerlzed products. For example the said polymerization product or the said residue is heated to a temperature oi 300 C. in the presence of phosphoric acid while allowing the condensable vapors evolved from the heating zone to return. The resulting iso-butylene, when polymerized as described in Example 2 furnishes a polymerization product having a molecular weight of more than 5000.

This application has been divided out irom our copending application Ser. No. 623,812 filed July 21st, 1932.

What we claim is:

1. The process of producing a high molecular polymerization product of an iso-oleflne which comprises polymerizing an iso-oleflne in the presence of a volatilizable inorganic halide polymerization catalyst while continuously maintaining the temperature oi the reaction mixture below 10 below zero 0. throughout the reaction period.

2. The process of producing a high molecular polymerization product or iso-butylene which comprises polymerizing iso-butylene in the presence ofia volatilizable inorganic halide polymerization catalyst while continuously maintaining the temperature of the reaction mixture below 10" below zero C. throughout the reaction period.

3. The process oi producing a high molecular polymerization product of an iso-oleflne which comprises polymerizing an iso-oleilne in the presence oi boron fluoride while continuously maintaining the temperature of the reaction mixture below 10 below zero C. throughout the reaction period.

4. The process oi producing a high-molecular polymerization product oi iso-butylene which comprises polymerizing lso-butylene in the presence of boron fluoride while continuously maintaining the temperature of the reaction mixture below 10 below zero 0. throughout the reaction period.

5. A polymerization product of an aliphatic lso-oleflne which is, substantially saturated, and has a from viscous, sticky to solid consistency at ordinary temperature, which product by heating is depolymerizable to gaseous or low boiling hydrocarbons without substantial formation of coke, which has a molecular weight of more than 3000 and which is soluble in liquid hydrocarbons in any proportion obtained according to the process 01' claim 3. l

6. A polymerization product 0! iso-butylene which is substantially saturated, and has a from viscous, sticky to solid consistency at ordinary temperature, which product by heating is depolymerlzable to gaseous or low boiling hydrocarbons without substantial formation of coke, which has a molecular weight of more than 3000 and which is soluble in liquid hydrocarbons in any proportion obtained according to the process 01 claim 4.

7. The process of producing a high molecular polymerization product of an iso-oleflne which comprises polymerizing an iso-oleiine in the presence of a volatilizable inorganic halide polymerization catalyst selected from the class consisting of boron fluoride, boron fluoride charged with hydrofiuoric acid, phosphorous trifiuoride, phosphorous pentailuorlde, aluminum chloride and the double compounds of said halides, while continuously maintaining the temperature of the reaction mixture below 10 below zero 0. throughout the reaction period.

MICHAEL O'I'l'O. MARTIN MUmlE'R-CUNR'ADI.

CERTIFICATE OF CORRECTION Patent No. 2,150,507.

September 20, 1958.

MICHAEL OTTO, ET AL.

It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows 2 Page 5 second column,

line 50, claim 5, for the claim reference numeral "5" read 1; line 59, Cl im 6, for the claim reference numeral "1 read 2; and that the said Letters Patent shouldbe read with this correction therein that thesame may conform to the record of the case in the Patent Office.

Signed and sealed this 6th day of December, A. D. 1958.

(Seal) Henry Van Arsdale Acting Comlesioner of Patents.

residue having a molecular weight of about 4000 are obtained.

Example 5 A mixture of 50 grams oi iso-butyiene and 250 grams oi normal butylene are polymerized as described in Example 2. After distilling oil a residue oi 58 grams is obtained. From this residue ll grams may be distilled 03 under a pressure oi. 0.1 millimeter mercury gauge and at a temperature up to 200 0., 47 grams 0! a product having a molecular weight of about 3000 thus being obtained.

Example 6 A mixture consisting of 900 grams of natural gas gasoline (distilling almost completely up to 60 C.) 60 grams of iso-butylene and 290 grams of normal butylene, which mixture is liquid under a slight superatmospheric pressure, is polymerized as described in Example 2.

After distilling oil '19 grams of a polymerizatlon product are obtained, of which 16 grams, under a pressure oi 15 millimeters mercury gauge, boil up to 200 C., and further 18 grams boil up to this temperature, under a pressure or 0.0? millimeter mercury gauge, 45 grams of a residue having a mean molecular weight of 3500 remain in the still. 7

The molecular weight may be increased by depolymerlzing either the said 79 grams of polymerization product or the said grams of residue into iso-butylene by heating, ii desired, in the presence of catalysts and then again polymerizing the depolymerlzed products. For example the said polymerization product or the said residue is heated to a temperature oi 300 C. in the presence of phosphoric acid while allowing the condensable vapors evolved from the heating zone to return. The resulting iso-butylene, when polymerized as described in Example 2 furnishes a polymerization product having a molecular weight of more than 5000.

This application has been divided out irom our copending application Ser. No. 623,812 filed July 21st, 1932.

What we claim is:

1. The process of producing a high molecular polymerization product of an iso-oleflne which comprises polymerizing an iso-oleflne in the presence of a volatilizable inorganic halide polymerization catalyst while continuously maintaining the temperature oi the reaction mixture below 10 below zero 0. throughout the reaction period.

2. The process of producing a high molecular polymerization product or iso-butylene which comprises polymerizing iso-butylene in the presence ofia volatilizable inorganic halide polymerization catalyst while continuously maintaining the temperature of the reaction mixture below 10" below zero C. throughout the reaction period.

3. The process oi producing a high molecular polymerization product of an iso-oleflne which comprises polymerizing an iso-oleilne in the presence oi boron fluoride while continuously maintaining the temperature of the reaction mixture below 10 below zero C. throughout the reaction period.

4. The process oi producing a high-molecular polymerization product oi iso-butylene which comprises polymerizing lso-butylene in the presence of boron fluoride while continuously maintaining the temperature of the reaction mixture below 10 below zero 0. throughout the reaction period.

5. A polymerization product of an aliphatic lso-oleflne which is, substantially saturated, and has a from viscous, sticky to solid consistency at ordinary temperature, which product by heating is depolymerizable to gaseous or low boiling hydrocarbons without substantial formation of coke, which has a molecular weight of more than 3000 and which is soluble in liquid hydrocarbons in any proportion obtained according to the process 01' claim 3. l

6. A polymerization product 0! iso-butylene which is substantially saturated, and has a from viscous, sticky to solid consistency at ordinary temperature, which product by heating is depolymerlzable to gaseous or low boiling hydrocarbons without substantial formation of coke, which has a molecular weight of more than 3000 and which is soluble in liquid hydrocarbons in any proportion obtained according to the process 01 claim 4.

7. The process of producing a high molecular polymerization product of an iso-oleflne which comprises polymerizing an iso-oleiine in the presence of a volatilizable inorganic halide polymerization catalyst selected from the class consisting of boron fluoride, boron fluoride charged with hydrofiuoric acid, phosphorous trifiuoride, phosphorous pentailuorlde, aluminum chloride and the double compounds of said halides, while continuously maintaining the temperature of the reaction mixture below 10 below zero 0. throughout the reaction period.

MICHAEL O'I'l'O. MARTIN MUmlE'R-CUNR'ADI.

CERTIFICATE OF CORRECTION Patent No. 2,150,507.

September 20, 1958.

MICHAEL OTTO, ET AL.

It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows 2 Page 5 second column,

line 50, claim 5, for the claim reference numeral "5" read 1; line 59, Cl im 6, for the claim reference numeral "1 read 2; and that the said Letters Patent shouldbe read with this correction therein that thesame may conform to the record of the case in the Patent Office.

Signed and sealed this 6th day of December, A. D. 1958.

(Seal) Henry Van Arsdale Acting Comlesioner of Patents.

h CERTIFICATE OF CORRECTION.

Patent No. 2,150, 507- September 20, 1958.

MICHAEL o'r'ro, ET AL.

It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows: Page 2, first column, line 65, before the word "molecular" insert high; and second col mun, line 8, for "favourable" read unfavourable; and that the said Letters Patent should be read with this correction therein that the same may conform to the record of the case in the Patent Office.

Signed and sealed this 16th day of May, A. D. 1959.

Henry Van Arsdale (Seal) Acting Commissioner of Patents.