US2084501A - Valuable hydrocarbon products - Google Patents
Valuable hydrocarbon products Download PDFInfo
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- US2084501A US2084501A US676680A US67668033A US2084501A US 2084501 A US2084501 A US 2084501A US 676680 A US676680 A US 676680A US 67668033 A US67668033 A US 67668033A US 2084501 A US2084501 A US 2084501A
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- US
- United States
- Prior art keywords
- isobutylene
- grams
- polymerized
- molecular weight
- iso
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- 229930195733 hydrocarbon Natural products 0.000 title description 19
- 150000002430 hydrocarbons Chemical class 0.000 title description 19
- 239000004215 Carbon black (E152) Substances 0.000 title description 14
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 24
- 239000000203 mixture Substances 0.000 description 21
- 239000000047 product Substances 0.000 description 20
- 239000003921 oil Substances 0.000 description 14
- 229920000642 polymer Polymers 0.000 description 12
- 238000007792 addition Methods 0.000 description 10
- 238000009835 boiling Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 229910015900 BF3 Inorganic materials 0.000 description 7
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 7
- 239000001993 wax Substances 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000010687 lubricating oil Substances 0.000 description 5
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000000571 coke Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical group CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000010727 cylinder oil Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229960002050 hydrofluoric acid Drugs 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910001502 inorganic halide Inorganic materials 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000010721 machine oil Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- AYOOGWWGECJQPI-NSHDSACASA-N n-[(1s)-1-(5-fluoropyrimidin-2-yl)ethyl]-3-(3-propan-2-yloxy-1h-pyrazol-5-yl)imidazo[4,5-b]pyridin-5-amine Chemical compound N1C(OC(C)C)=CC(N2C3=NC(N[C@@H](C)C=4N=CC(F)=CN=4)=CC=C3N=C2)=N1 AYOOGWWGECJQPI-NSHDSACASA-N 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- OBCUTHMOOONNBS-UHFFFAOYSA-N phosphorus pentafluoride Chemical compound FP(F)(F)(F)F OBCUTHMOOONNBS-UHFFFAOYSA-N 0.000 description 1
- WKFBZNUBXWCCHG-UHFFFAOYSA-N phosphorus trifluoride Chemical compound FP(F)F WKFBZNUBXWCCHG-UHFFFAOYSA-N 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M1/00—Liquid compositions essentially based on mineral lubricating oils or fatty oils; Their use as lubricants
- C10M1/08—Liquid compositions essentially based on mineral lubricating oils or fatty oils; Their use as lubricants with additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
- C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
- C07C2/08—Catalytic processes
- C07C2/14—Catalytic processes with inorganic acids; with salts or anhydrides of acids
- C07C2/20—Acids of halogen; Salts thereof ; Complexes thereof with organic compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
- C09J123/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
- C09J123/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
- C09J123/22—Copolymers of isobutene; Butyl rubber ; Homo- or copolymers of other iso-olefines
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/06—Halogens; Compounds thereof
- C07C2527/08—Halides
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
- C10M2205/026—Butene
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/14—Electric or magnetic purposes
- C10N2040/16—Dielectric; Insulating oil or insulators
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/14—Electric or magnetic purposes
- C10N2040/17—Electric or magnetic purposes for electric contacts
Definitions
- Rhine, Germany assiznors to E. Farhe'nindusttie dirtiengeeellschatt, Frankfort cn themriain, Germany ,No Drawing. Originai application July 21, 1932,
- hydrocarbon mixtures in particular those having a boiling point above 200 C., and especially those boiling above about 325 C. at ordinary pressure, for example lubril0 eating oils or greases or hard or soft parafiln wax,
- the polymer- A 40 ized iso-olefines in an amount of from a fraction of one 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 35 or even 545 per cent.
- oils are necessary which on the one hand still have a satisfactory viscosity at high tempera- 5'0 tures, as for example from to 150 C., and;
- the'present invention oils can be prepared which correspond to a great extent to these require ments and which are far superior to the special automobile oils hitherto in commerce.
- the effect of the addition of the said polymerized iso-olefines 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 efiect 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 qual ity of the oil improves.
- Viscosity Setting Flash- Density Ekpt' index point point at 20 From the table it can be seen that the addition of the highly polymerized isobutylene products considerably improves the oils.. The resulting improved oils have even a higher viscosity index than special automobile oils or high value.
- Polymerized isobutylene is added in an amount of from 1 to 4 per cent to paraffin 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 hydro fluoric acid, phosphorus tri-fluoride, phosphorus pentafluoride, aluminum chloride, preferably in statu nascendi, such as aluminum 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 substantial increase in temperature occurs.
- suitable catalysts preferably Volatilizable inorganic halides, such as boron fluoride, boron fluoride charged with hydro fluoric acid, phosphorus tri-fluoride, phosphorus pentafluoride, aluminum chloride, preferably in statu nascendi, such as aluminum chloride as is formed by allowing hydrogen chlor
- 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 high molecular weight, and furthermore the loss in isobutylene which would occur by a It may be advantageous not to bring the catalyst into contact with the isobutylene at once but gradually.
- By moving the isobutylene for example by stirring, the removal of the reaction heat is favoured and local superheating is avoided;
- the polymerization of isobutylene is a strongly exothermic reaction.
- the cooling may be effected externally by means of cooling baths or internally by adding to the reacting substances cold materials which have no unfavourable 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 sufficient 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.
- the polymerized products having a molecular weight of more than 2000, as for example up to 10000 and more.
- the Coni'adsoncoke-test of these products is very low and not far from zero; it amounts for example to 0.01.
- Example 1 About 0.5 part of boron fluoride is led into 100 parts of liquid isobutylene which is cooled by a bath of carbon dioxide at 80 below zero 0. The polymerization soon sets in vigorously. By in tense 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 threads and, even at 200 C., it is still not liquid.
- Example 2 The process is similar to that in Example 1 except that before and during the leading in of boron fluoride solid carbon dioxide is thrown into the reaction material in order to maintain the temperature below from 60 to 70 below zero C. A product having a mean molecular weight of about 5000 is obtained. The product is as viscous as normal rubber masticated at 70 C. It is slightly sticky, colorless and clear.
- Example 3 A 20 per cent solution of isobutylene 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 Ex ample 2; it is colorless and clear and may be drawn into long threads.
- Example 4 A mixture of grams of isobutylene and 110 grams of normal butylene (mainly a-butylene) is polymerized as described in Example 2. After distilling off the normal butylene grams of a residue having a molecular weight of about 4000 are obtained.
- normal butylene mainly a-butylene
- Example -6 A mixture consisting of 900 grams of natural gas gasoline (distilling almost completely up to 60C., 60 grams of isobutylene and 290 grams of normal butylene. which mixture is liquid under a slight, super-atmospheric pressure, is polymerized as described in Example 2.
- the molecular weight may be increased by dc densable vapors evolved from the heating zone to return.
- the resulting isobutylene, when polymerized as described in Example 2 furnishes a polymerization product having a molecular weight of more than 5000.
- composition of matter comprising an un- For example the said polymerized hydrocarbon product boiling above 200 C. and an iso-oleiinic hydrocarbon polymer having a molecular weight of at least 1000 in. a viscosity improving amount.
- composition of matter comprising a petroleum lubricating oil and an iso-olefinic hydrocarbon polymer having a molecular weight of at least 3000 in a viscosity improving amount.
- composition of matter comprising an unpolymerized hydrocarbon product boiling about 200 C. and an isobutylene polymer having a molecular weight in excess oi 1000 in a viscosity improving amount.
- composition of matter comprising a pctroleum lubricating oil and a polymer of isobutylene having a molecular weight in excess of 5000 in a viscosity improving amount.
- a composition of matter comprising troleum lubricating oil and a polymer of isobutylene having a molecular weight between about 2000 and 10,000 in a viscosity improving amount.
- a composition of matter comprising an unpolymerized hydrocarbon product boiling above 200 C. and a polymer oi isobutylene having a molecular-weight between 2000 and 10,000 in a viscosity improving amount.
- composition of matter essentially comprising a parailln wax and a small amount 01 isobutylene polymer having a molecular weight of at least 1000.
- composition of matter essentially comprising a hydrocarbon insulating oil and a small amount of an isobutylene polymer having a molecular weight of at least 1000.
- a composition of matter essentially comprising a wax selected from the group consisting 01 hard and soft paraflln waxes. and a polymer oi" iso-olefine having a molecular weight oif at least 1,000, the amount of polymer not exceeding that of the wax.
- composition according to claim 9 in which the iso-oleiine polymer is a polymer .0! isobutylene.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
assist t @FFWE itdtiibfidl.
/ VALUAELE ZKYIDRQQARBON PEG'DUCTS Michaei Otto and. Martin ltiuellen-tiunradi, Lud
Rhine, Germany, assiznors to E. Farhe'nindusttie dirtiengeeellschatt, Frankfort cn themriain, Germany ,No Drawing. Originai application July 21, 1932,
Serial No. 623,812.
many July 25, 1931 Divided and this application June 20, 1938, Serial No. 676,680.
In Ger- Claims. (01. ice-151) This is a divisional application of our application Ser. No. 623,812, filed July 21st, 1932, which 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 C., and especially those boiling above about 325 C. at ordinary pressure, for example lubril0 eating oils or greases or hard or soft parafiln 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 measured by the eflect of markably flattened in many cases. Furthermore the hydrocarbon mixtures is increased to double the material on the boiling or freezing point of benzol. winch are obtained by polymerizing isoolefines and in particular iso-butylene.
the addition of these high molecular hydrocarbons obtained by polymerizing iso-olefines (which hydrocarbons for the sake of brevity are hereinafter referred to as polymerized iso-olefines) also the temperature-viscosity curve of the hydrocarbon mixture to be improved is rethe electric properties of these hydrocarbon mix tures are considerably changed so that for example by the addition of only 1 per cent of polymerized iso-olefines the disruptive strength of switches. Hard and soft paraflln wax is rendered transparent by the addition of the said polymerized iso-olefines; furthermore the formation of fissures and cracks is prevented thereby. In
many cases it is suflicient to add the polymer- A 40 ized iso-olefines in an amount of from a fraction of one 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 35 or even 545 per cent.
For many purposes, as for example for lubrieating automobile motors, it is well known that oils are necessary which on the one hand still have a satisfactory viscosity at high tempera- 5'0 tures, as for example from to 150 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 thestarting device. According to 55 the'present invention oils can be prepared which correspond to a great extent to these require ments and which are far superior to the special automobile oils hitherto in commerce.
The effect of the addition of the said polymerized iso-olefines 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 efiect 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 qual ity of the oil improves.
Percentage Viscosity in Englcr at isobutylenc Expt. pplytrlner- I 011 o o o o o 0 product 0 20 38 50 100 A 0 125 25 8.3 1.6 Below 1.2 A 0 42 15.6 8.8 2.25 1:44 B 0 40 11 5.3 3.0 1.45 Below 1.2 B' 4 98 29.5129 7.7 2.25 1.47 O 0 3.3 2.1 1.3 C' 4 110 33 13.0 8.2 2.32 1.43 C- 13 280 84 36.2 21.8 5.0 2.18 D 0 12 4.8 2.55 2.0 1.3 0 55 20.5 9.8 6.5 2.25 1.52 0 41 12.0 7.0 1.8 1.22 1 About 280 58 10.1 10.3 2.3 1.42 0 About300 53 21.2 11.1 2.3 1.4 0 Over 300 73.52L8 11 2.12 1.32 0 Over 300 83 25.3 13 2.5 1.45
Viscosity Setting Flash- Density Ekpt' index point point at 20 From the table it can be seen that the addition of the highly polymerized isobutylene products considerably improves the oils.. The resulting improved oils have even a higher viscosity index than special automobile oils or high value.
On account of the low coke test of the polymerized iso-oleflnes the lubricating oils the viscosity sudden superheating.
bid
of which has been incremd by the addition of the said polymerized iso-oleflnes instead of by Vlscosit Oonradson Additions at coke test 1. 66 0.08 4.0 percent of l erlzed isobutylene. 3. 0 0. 09 83.0 percent 0 br ght stock oil l. 0 0. 52 33.0 percent of hot steam cylinder oil 1. 0 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 isobutylene 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 parafiin wax is considerably improved by the addition of polymerized isobutylene as will be seen from the following example:
Polymerized isobutylene is added in an amount of from 1 to 4 per cent to paraffin 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 hydro fluoric acid, phosphorus tri-fluoride, phosphorus pentafluoride, aluminum chloride, preferably in statu nascendi, such as aluminum 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 substantial 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 high molecular weight, and furthermore the loss in isobutylene which would occur by a It may be advantageous not to bring the catalyst into contact with the isobutylene at once but gradually. By moving the isobutylene, for example by stirring, the removal of the reaction heat is favoured and local superheating is avoided; The polymerization of isobutylene is a strongly exothermic reaction. Corresponding to the different intensity of the catalytic action of the different catalysts it is necessary to vary the intensity of cooling. For example, in the employment of the extremely active boron fluoride it is necessary to keep the temperature during the reaction below 5 C. Temperatures as low as 10 below zero C. 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 unfavourable 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 sufficient 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 2000, as for example up to 10000 and more. The Coni'adsoncoke-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 isoolefines; 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 isobutylene which is cooled by a bath of carbon dioxide at 80 below zero 0. The polymerization soon sets in vigorously. By in tense 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 threads and, even at 200 C., it is still not liquid.
Example 2 The process is similar to that in Example 1 except that before and during the leading in of boron fluoride solid carbon dioxide is thrown into the reaction material in order to maintain the temperature below from 60 to 70 below zero C. A product having a mean molecular weight of about 5000 is obtained. The product is as viscous as normal rubber masticated at 70 C. It is slightly sticky, colorless and clear.
Example 3 A 20 per cent solution of isobutylene 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 Ex ample 2; it is colorless and clear and may be drawn into long threads.
Example 4 A mixture of grams of isobutylene and 110 grams of normal butylene (mainly a-butylene) is polymerized as described in Example 2. After distilling off the normal butylene grams of a residue having a molecular weight of about 4000 are obtained.
Example A mixture oi. 50 grams of isobutylene and 250 grams 01 normal butylene are polymerized as described in Example 2. After distilling of! a residue of 58 grams is obtained. From this residue 11 grams may be distilled oil under a pressure of 0.1 millimetre mercury gauge and at a temperature up to 200 C., 47 grams of 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 60C., 60 grams of isobutylene and 290 grams of normal butylene. which mixture is liquid under a slight, super-atmospheric pressure, is polymerized as described in Example 2.
After distilling off 79 grams of a polymerization product are obtained, of which 16grams, under a pressure of 15 millimetres mercury gauge, boil. up to 200 0., and further. 18 grams boil up-to this temperature under a pressure 010.07 millimetre mercury gauge. 45 grams of a residue having a mean molecular weight of 3500 remain in the still.
The molecular weight may be increased by dc densable vapors evolved from the heating zone to return. The resulting isobutylene, when polymerized as described in Example 2 furnishes a polymerization product having a molecular weight of more than 5000.
What we claim is:-
1. A composition of matter comprising an un- For example the said polymerized hydrocarbon product boiling above 200 C. and an iso-oleiinic hydrocarbon polymer having a molecular weight of at least 1000 in. a viscosity improving amount.
2. A composition of matter comprising a petroleum lubricating oil and an iso-olefinic hydrocarbon polymer having a molecular weight of at least 3000 in a viscosity improving amount.
3. A composition of matter comprising an unpolymerized hydrocarbon product boiling about 200 C. and an isobutylene polymer having a molecular weight in excess oi 1000 in a viscosity improving amount.
4. A composition of matter comprising a pctroleum lubricating oil and a polymer of isobutylene having a molecular weight in excess of 5000 in a viscosity improving amount.
5. A composition of matter comprising troleum lubricating oil and a polymer of isobutylene having a molecular weight between about 2000 and 10,000 in a viscosity improving amount.
6. A composition of matter comprising an unpolymerized hydrocarbon product boiling above 200 C. and a polymer oi isobutylene having a molecular-weight between 2000 and 10,000 in a viscosity improving amount.
7; A composition of matter essentially comprising a parailln wax and a small amount 01 isobutylene polymer having a molecular weight of at least 1000.
8. A composition of matter essentially comprising a hydrocarbon insulating oil and a small amount of an isobutylene polymer having a molecular weight of at least 1000.
9. A composition of matter essentially comprising a wax selected from the group consisting 01 hard and soft paraflln waxes. and a polymer oi" iso-olefine having a molecular weight oif at least 1,000, the amount of polymer not exceeding that of the wax.
10. Composition according to claim 9 in which the iso-oleiine polymer is a polymer .0! isobutylene.
MICHAEL OTTO. MARTIN MUEILER-CUNRADI.
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
NL35995D NL35995C (en) | 1932-07-21 | ||
DEI42157D DE641284C (en) | 1931-07-26 | 1931-07-26 | Process for the preparation of high molecular weight hydrocarbons from isobutylene |
US676680A US2084501A (en) | 1932-07-21 | 1933-06-20 | Valuable hydrocarbon products |
US14273A US2130507A (en) | 1932-07-21 | 1935-04-02 | High molecular weight iso-olefine polymers and process of producing the same |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US62381232A | 1932-07-21 | 1932-07-21 | |
US676680A US2084501A (en) | 1932-07-21 | 1933-06-20 | Valuable hydrocarbon products |
Publications (1)
Publication Number | Publication Date |
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US2084501A true US2084501A (en) | 1937-06-22 |
Family
ID=27089535
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US676680A Expired - Lifetime US2084501A (en) | 1931-07-26 | 1933-06-20 | Valuable hydrocarbon products |
Country Status (2)
Country | Link |
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US (1) | US2084501A (en) |
NL (1) | NL35995C (en) |
Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2509203A (en) * | 1945-12-29 | 1950-05-30 | Standard Oil Dev Co | Polymerized alkyl fumarates and process |
US2525984A (en) * | 1946-04-19 | 1950-10-17 | Weston Charles Clark | Pattern composition |
US2560588A (en) * | 1945-12-29 | 1951-07-17 | Standard Oil Dev Co | Mineral oil containing polymers of esters of fumaric acid |
US2586345A (en) * | 1945-01-18 | 1952-02-19 | British Insulated Callenders | Electric cable having a nonmigratory insulating compound |
US2657246A (en) * | 1950-04-21 | 1953-10-27 | Standard Oil Dev Co | Selective polymerization of isobutylene |
US2819328A (en) * | 1954-04-08 | 1958-01-07 | Standard Oil Co | Propylene polymerization with pf5 |
US3172920A (en) * | 1965-03-09 | Catalytic process for the polymeri- zation of olefin hydrocarbons | ||
US3215154A (en) * | 1962-04-13 | 1965-11-02 | Dow Chemical Co | Method of reducing friction loss in flowing hydrocarbon liquids |
US3878115A (en) * | 1972-12-19 | 1975-04-15 | Labofina Sa | Lubricating compositions for marine diesel engines |
US4075113A (en) * | 1975-01-28 | 1978-02-21 | Labofina S.A. | Grease composition |
US4162985A (en) * | 1973-10-01 | 1979-07-31 | The Lubrizol Corporation | Multigrade lubricants containing interpolymers |
US4948522A (en) * | 1988-02-23 | 1990-08-14 | Exxon Chemical Patents Inc. | Dispersant for marine diesel cylinder lubricant |
-
0
- NL NL35995D patent/NL35995C/xx active
-
1933
- 1933-06-20 US US676680A patent/US2084501A/en not_active Expired - Lifetime
Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3172920A (en) * | 1965-03-09 | Catalytic process for the polymeri- zation of olefin hydrocarbons | ||
US2586345A (en) * | 1945-01-18 | 1952-02-19 | British Insulated Callenders | Electric cable having a nonmigratory insulating compound |
US2509203A (en) * | 1945-12-29 | 1950-05-30 | Standard Oil Dev Co | Polymerized alkyl fumarates and process |
US2560588A (en) * | 1945-12-29 | 1951-07-17 | Standard Oil Dev Co | Mineral oil containing polymers of esters of fumaric acid |
US2525984A (en) * | 1946-04-19 | 1950-10-17 | Weston Charles Clark | Pattern composition |
US2657246A (en) * | 1950-04-21 | 1953-10-27 | Standard Oil Dev Co | Selective polymerization of isobutylene |
US2819328A (en) * | 1954-04-08 | 1958-01-07 | Standard Oil Co | Propylene polymerization with pf5 |
US3215154A (en) * | 1962-04-13 | 1965-11-02 | Dow Chemical Co | Method of reducing friction loss in flowing hydrocarbon liquids |
US3878115A (en) * | 1972-12-19 | 1975-04-15 | Labofina Sa | Lubricating compositions for marine diesel engines |
US4162985A (en) * | 1973-10-01 | 1979-07-31 | The Lubrizol Corporation | Multigrade lubricants containing interpolymers |
US4075113A (en) * | 1975-01-28 | 1978-02-21 | Labofina S.A. | Grease composition |
US4948522A (en) * | 1988-02-23 | 1990-08-14 | Exxon Chemical Patents Inc. | Dispersant for marine diesel cylinder lubricant |
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