[1]Uni'ted States Patent Oflice j9765@884 3,705,884 VISCOUS COM[POSITIONS AND PROCESS FOR THE PRODUCTION THEREOF Albert Frese, Marl, Germany, assignor to Chemische Werke Huels, Aktiengesellschaft, Marl, Germany No Drawing. ]Rled June 19, 1970, Ser. No. 47,868 Claims priority, application Germany, June 20, 19699 P 19 31 421.7 Int. Cl. C08f 15140, ClOm 1118 U.S. Cl. 260-80.78 11 Claims ABSTRACT OF THE DISCLOSURE Viscous atactic polyolefin compositions having viscosities which are less temperature dependent and which have relatively low viscosities at 100' C., which are useful as lubricating oils, cable f!Hing compounds and in the manufacture of roofing board and sealiiig compounds, are produced from a mixture of polyolefins produced with a Ziegler catalyst and polyolefin produced with a FriedelCrafts catalyst, preferably produced by successively polymerizin.- an olefin mixture comprising butene-1, first with the Ziegler catalyst and then with the Friedel-Crafts catalyst. BACKGROUND OF THE INVENTION This invention relates to viscous mixtures of atactic polyolefins. For various fields of application, for example for cable filling compounds, atactic poly-a-olefins are required having low molecular weights and low viscosities, e.g., 10,010,000- centipoises at 100' C. The atactic poly-a-olefin, e.g., polybutene-1, obtained as a byproduct during the manufacture of isotactic poly-aolefins, exhibits a reduced specific viscosity of 0.3-1.0 (measured in a 0.03% decalin solution at 135' C.). However, their melt viscosity is high. For example, atactic polybutene-I has a viscosity at 100' C. of 100,000-200,000 cp. The substantially amorphous @polybutene-1 produced in polymerizations employing catalysts of low stereospecificity exhibits a reduced specific viscosity ranging above 0.5 and a melt viscosity at 100' C. above 100,000 ep. Thus, these products are unsuited for use as cable filling compounds, etc. It is not possible to produce low molecular weight polyImers with the desired properties in conventional polymerizations because the hydrogen control, which is normally effective in low-pressure polymerizations, fails even at a high partial hydrogen pressure, so that it is impossible to attain a value below a specific viscosity of 0.3. Also, due to thermal and/or radical degradation, the desired low viscosities cannot be regulated in an economical manner. Not only is such a process quite expensive, it has the disadvantage that the thus-obtained low-molecular polymers are contaminated by cracking products. OBJECTS OF THE INVENTION It is an object of this invention to provide a process for producing polymeric compositions having the above-'described properties, more specific@lly viscous atactic o:-olefin compositions, in an easy, simple, and reproducible fashion. It is another object to provide novel atactic a-olefin compositions. Other objects will be apparent to those skilled in the art to which this invention pertains. Patented Dec. 12, 1972 2 SUMMARY OF THE INVENTION According to this invention, viscous polyolefin compositions, especially those having a viscosity of 100-10,000 cp. at 100' C. are provided by a mixture of polyolefins consisting essentially of 5-95% by weight of mainly atactic poly-a-olefin or a polyolefin mixture comprising poly-aolefin with an atactic portion of 50-95% by weight and having a reduced specific viscosity of 0.05-5.0 and 95-5% 10 by weight of an atactic polyolefin or a polyolefin mixture comprising an atactic polyolefin and having a viscosity of 150- 60,000 cp. at 20' C. Such compositions can be produced by a process which comprises the steps of partially polymerizing a mixture of an a-olefin and an internally 15 unsaturated olefin with a Ziegler catalyst and thereafter further polymerizing the polymerizate with a FriedelCrafts catalyst. DETAILED DESCRIPTION 20 The compositions of this invention consist essentially of the products of two polymerizations, viz, one which produces a polyolefin having a reduced specific viscosity of 0.05-5.0, preferably 0.2-2.0, as a 0.03% decalin solution at 135' C., and one which produces a polyolefin 25 having a viscosity of 150-60,000 cp., preferably 300- 30,000 cp. at 20' C. The former ordinarily, i.e., at room temperature, is a solid of a viscosity too high to measure. The latter is a slightly to highly viscous fluid. The compositions of this invention include those ob30 tained by mixing two separately polymerized components having the properties described herein. Preferred are those obtained by first partially polymerizing an a-olefin or mixture of olefins comprising an a-olefin, with a Ziegler catalyst of low stereospecificity and then, optionauy after 35 replenishing the consumed olefin with the same or other olefin or olefins, continuing the polymerization with a FriedelCrafts catalyst. Suitable olefins are, for example, propene, butene, 4- 40 methyl-l-pentene, 1-dodecene, and mixtures comprising one or more of them. Preferably employed are butene-1 and. mixtures com ising butene-1 and other olefins, espePr cially iftixtures also comprising butene-2, e.g.,, n-tixtures of olefins containing but,ene-I and one or more of ethene, 45 propene, 4-methylpentene, and/or styrene in addition to butene-2, especially cis-butene-2. An especially preferred starting olefin mixture is a C4cut containing, e.g., 20-80%, preferably 30-60%, butene-1; 10- 30%, preferably 15-20%, cis-butene-2; 1.0- 50 30%, preferably, 20--25%, trans-butene-2; and 2-20%, preferably 5-15%, butane. The same or different olefin mixture can be used in the two polymerizations, e.g. when the two polymerizations are, conducted as separate polymerizations or addi55 tional olefins are added to the polymerizate of the first polymerization before conducting a second polymerizati6n thereof. Preferably a mixture of biltenes is present in both such polymerizations. The Ziegler catalyst is able to polymerize butene-I 60 only; butene-2 is practically not polymerized. The FriedelCrafts-catalyst polymerizes butene-2 and butene-1, t6o, if .,th,e latter is still present in the mixture. The first polymerizate contains 50-95% by weight atactic portions, the second polymer consists completely of 65 atactic material. The atactic portions are defined by their solubilit in boiling 4iethyl ether, y
[2]3)7051884 3 The poly-oc-olefm which is produced by the first polymerization step is soluted nearly completely under the conditions of the polymerization. It has a reduced specific viscosity ranging between 0.05 and 5.0, preferably between 0.2 and 2.0, and its solubility in boiling diethyl ether 5 ranges between 50 and 95%, preferably between 60 and 80%. In the especially preferred embodiment of this invention, the only olefins present at the beginning of the second polymerization are those present in the polymerizate of 10 the first polymerization. In this process aspect of this invention, the Cvcuts containing butene-I and butene-2 have the advantage that the butene-1 is first - polymerized into atactic polybutene with the Ziegler catalyst in the first polpmerization and thereafter the unreacted butene2 15 is polymerized with the Friedel-Crafts catalyst in the second polymerization into oily polybutenes. The Ziegler catalysts employed in the first polymerization are those of low stereospecificity, viz, the conventional mixed Ziegler catalysts, e.g', a mixture Of One or 20 more heavy metal compounds, e.g., titanium tetrachloride, vanadium tetrachloride, vanadium oxychloride, with an organoaluminum compound, e.g., trialkylene aluminum and dialkyl aluminum hydrides wherein the alkyl groups contain 2-12 carbon atoms, e.g., AI(C2H5)3, AI(C3H7)3, 25 Al (C4H9) 2H, Al (i-C4H9) 3. Furthermore, suitable are mixtures of heavy metal compounds, e.g., a mixture of TiCI4 with VC14 or VOC13. The polymerization to the atactic poly-a-olefins is usually conducted at elevated temperatures, e.g., 50-200' C., more preferably 70-150' C. 30 These mixed Ziegler catalysts are conventionally composed of heavy metal and aluminum compounds in a molar ratio of 0.1:1 to 10:1, preferably 0.5:1 to 5:1. They usually are employed in amounts of 0.1-0.5%, based on the monomer and solvent mixture. They are usually 35 employed in amounts of about 0,1 to 0.5%, preferably about 0.2 to 0.3 %, calculated on the total reaction mixture. Suitable Friedel-Crafts catalysts are, for example, AIC13, FeCI3, BF3, SbCls, SnCI4, TiCl,, ZnCl,, BCI,, BF3-etherate, - and AlCIB.BF3- They are usuafly employed in a large 40 molar excess, calculated on the Zeigler catalyst employed in the first polymerization, viz, in amounts of 100-2,000, preferably 200-1,000 mol percent, calculated on the alkyl aluminum compound, particularly when the polymerizate from the first polymerization is employed in the second 45 polymerization because the Friedel-Crafts catalyst, e.g., AIC13, reacts with the residual trialkyl aluminum of the Ziegler catalyst to form alkyl aluminum sesquichlorides. It is also possible to convert the residual Ziegler catalyst, after the desired polymerization;therewith, into a Friedel- @50 Crafts catalyst by adding a stoichiometric amount, or a small excess, of anhydrous hydrogen halide or halogen. An example is the reaction of AI(C2H5)3 with HCI or C12 as foflows: AI(C2H5)3+3HCI=AlCl,+3C,H6 55 AI(C2HB)3+3CI2@AICI,+3C,H5CI For this purpose, halogen or hydr.ogen halide is introduced under agitation into the partially polymerized charge,:e.g., at -20' C. to + 100' C., preferably at or below the tem- 60 perature to be employed 'm the second polymerization. The polymerization with the Friedel-Crafts catalysts can ,be conducted at temperatures of -20* C. to +1001 C., preferably 10 to 40' C. Especially suitable olefins for the Friedel-Crafts cata- 65 lyzed polymerization are the butenes, such as, for example, C4;-hydrocarbon cuts containing butene-I and butene-2. The conversion takes place ahnost quantitatively calculated on the butene-I and cis-butene-2 empl(jyed. T'he transbutene-2, usually also present in these C4-cuts, - polymerizes 70 somewhat more slowly. The Cccuts containing isobutene also can be employed. If desired, the a-olefins consumed in the first stage of the polymerization, or a part thereof, can be replenished, during the polymerizatiou, preferably when changing over 75 4 to the Friedel-Crafts catalyst, by adding the same or another a-olefin. For example, it is advantageous, after the polymerization of a raixture of butene-1 with methylpentene or dodecene with a Ziegler catalyst, to polymerize a mixture of bute-ne@l, butene-2 and isobutene with a Friedel-Crafts catalyst in the second polymerizatio-n. The polymerizations can be carried out batch-wise or continuously. In a continuous polymerization, the FriedelCrafts polymerization is conducted in one kettle and the polymerizate therefrom transferred continuously to a second kettle separate for the kettle in which the first polymerization is conducted. The compositions of this invention have a visrosity of 1000 to >100,000 ep. at 20' C. and 20 to 80,000 cp. at 100' C. The preferred compositions have a viscosity of 7,000 to >100,000 cp. at 20' C. and 100 to 10,000 ep. at 100' C. The compositions of this invention contain 5 to 95%, preferably 10 to 50%, of the polymerizate of the Ziegler catalyzed polymerization. As stated above, the preferred compositions are those resulting from the Friedel-Crafts catalyst catalyzed polymerization of the polymerizate of a Ziegler catalyst catalyzed partial polymerization of a mixture of olefins comprising an a-olefin, preferably butene-1, especially a Cvhydrocarbon cut comprising buterie-1 and butene-2, which mixture optionally also is added to the polymerizate of the first polymerization prior to the second polymerization. Compared to niixtures of atactic polyolefms with, for example, paraffin oil, the compositions produeed in accordance with this invention exhibit the surprising advantage that the components thereof are substantially more compatible, so that the low-molecular components, such as, for example, the polybutene offs, do not seep out. The compositions of this invention'havi'ng a lower proportion of first step polymerizate, for example less than 20%, are highly visco-us oils which exhibit very good lubricating properties and, surprisingly, their viscosity is relatively little temperature dependent. This temperature dependence is, for example, substantially less than that of a low molecular weight polyisobutene off. A polyisobutene oil, exbibiting a viscosity at 20' C. of 27,000 cp., has only a viscosity of 11,200 cp. at 30' C. In contrast thereto, the viscosity of a lubricating oil of the present invention is lowered, between 20 and 30' C., from 23,000 cp. to 15,000 cp., or from 29,000 to 20,000 cp. The rompositions of this invention are useful, inter alia, as lubricants having an improved viscosity characteristic, as additives to lubricating oils to improve the viscosity thereof, as rolling oils, as pore-controlling agents in foam production, and, when having a higher propgrtion of first step polyolefins, as sealing compounds, such as cable filling compounds. 'Without further elaboration, it is believed that one skiued in the art can, using the preceding description, utilize the present invention to its fullest extent. The following,preferred specific embodiments are, therefore, to construed as merely ibustrative, and not limitative of the remainder of the disclosure in any way whatsoever. EXAMPLE I Into a 40-liter pressurized polynierization kettle equipped with a stirrer, there is charged 18 parts by I a Cccut of 56% butene-1, 16% cis-butene-2, 20% trans-butene2, and 8% butane. By way of a charging valve, 0.015 part by weight of titanium tetrachloride and 0.057 part by weight of a 20% solution of triethylaluminum in hexane are added to the reaction mixture. The polymerization is conducted with this catalyst system for two hours at 130' C., under agitation. The polymerizate of the first polymerization has a reduced viscosity of 0.5 and is soluble in boiling diethyl ether in an amount of 74% by weight. Thereafter, the charge is quickly cooled to 20' C. After the addition of 0.2 part by weiolit of anhydrous 4urainura
[3]5 ,chloride by way of a charging valve, the polymerization is contixiued dt-20' -C. After eight hours the pol@meriiaiion is terminatdd. -After thO polymerization, the C4-cut has the followingt6mposition-. Percent Trans-butene-2 ------------------------------ 48.2 Cis-butene-2 ------- 1.7 -------------------- Butene-1 ---------------- ------- I --------- 0.2 Butane ------------------------------------- 49.8 o m6 . rization, the catalyst is washed out '.kfter ihe @oly with. watdr. Iii a simple refining distillation unit, the readily b6iling components and the residual watet are distilled off at 120' C./10 mm., leaving 12.4 parts by weight of a' viscous mass which, ai 301 C., exhibiis a viscosity of 52,000 cp. At 20' C., the viscosity amounts to 67,000 cp. The composition is suitable as rolling oil and lubricant. EXAMP,LE 2 In accordance with the procedure of Example 11 the polymerization is conducted in separate runs with the TiCI4/AI(C2H5)3 catalyst (KI) for one, 11/2, 3 and 4 hours, respectively. The polymerizate is amorphous essentially and hds a reduced viscosity of 0.5. After adding the AIC13, the polymerization is then conducted, in elach instance, for 8 hours at 20' C. The proper-ties of tfi6 highly viscous oils, or viscous compositions, thusobtained are set forth in Table 1. TABLE I Experiment nurnber poly lsobutene for 2.1 2.2 2.3 2.4 comparison Polymerization time (hrs.) withCatalyst KI ------------ I 1.6 3 4 ------ ------- Catalyst K2 ------------ 8 8 8 8 ------ ------- Viscosity st20' C. in ep ------------- 6,400 23,000 149,000 ------- 27,000 301 C. In ep ------------- 3,400 15,000 138,000 ------- 11,200 501 C In ep ------------ 1,050 4,600 42,000 ----- 212 100' C. iii ep ------------ 80 190 1,050 3, iao ---------- 00 These highly viscous oils exhibit satisfactory lubricating properties. They are suitable as lubricating oils, rouing oils, and serve as pore controlling agents during the foam material production. The highly viscous products of Experiments 2.3 and 2.4 are well suitable as cable fi.11ing compound. EXAMPLE3 In a pressure-resistant 40-liter kettle equipped with a stir@rer, 18 parts by weight of a C4-cut is provided, consisting of 34% butene-1, 30% trans-butene-2, 18% Cisbutene-2, and 18% butane. By way of a charging valve, 0.018 part by weight of TiCI4, 0.0095 part by weight of VC]4, and 0.08 part by weight of AI(C2HB)3 (as a 20% solution in hexane) are added to the reaction mixture. Th.6- polymerization takes place within 5 hours at 90' C. The polymerizate which is produced in this polymeriza on step has a reduced viscosity of 1.2. 76% by weight of it are soluble in boiling diethyl ether.@ After dooling to 10' C., 47 NI. of HCI is added. The kettle is inaintained at 10' C. by cooling. After 10 hours the catalyst is washed out with water and thereafter the composition is dried at 10 mm. Hg aiid 100' C. There is thus obtained 9.1 parts by weight of a viscous mass exhibiting a viscosity of 2,100 cp. at 100' C. It is especially suitable for use as a cable fflling compound. EXAMP@LE 4 15 parts by weight of a C4-cut of 50% butene-1, 24% trans-butene-2, 17% cis-butene2, and 9% butane, and 3 pgts by weight of 4-methyl-l-pentene are polymerized at 80' C. within 4 hours with a catalyst of 0.018 part by weight of TiCI4, 0.09 part by weight of VOC13, and 0.07 3 705,884 6 duced viscosity of 1.7 and 64% by weight of it are soluble in boiling diethyl ether. After cooling to 20' C., 41 NI. of HCI is added and thepolymerization is continued at 20' C. After workingup according to Example 3, 12.3 parts by weight of a viscous composition is obtained. It is suitable for use as a sealing compound and for the production of roofing board. EXAMPLE5 10 In a 40-liter pressure kettle equipped with agitator and level control and maintained at 100' C., are continuously introduced under stirring, per hour, 8 parts by weight of butene with a butene-I content of 50%, 1 part by weight 0 15 f 1-dodecene, and a catalyst suspension of 0.007 part by weight of titanium tetrachloride, 0.008 part by weight of triethylaluminum in 0.1 part by weight of hexane. The polymer solution from the first polymerization is continuously transferred from the kettle via a level-con-liter kettle, 20 trolled shut-off element, into a second 40 which is maintained at 30' C. by cooling. Into this kettle are continuously charged per hour 0.07 part by weight of aluminum chloride and 2 parts by weight of a C4-CUt, consisting of 40% isobutene, 30% butene-1, 24% butene25 2, and 6% butane. The product discharged from the seeond polymerization kettle is filtered, after the addition of 0.1 part by weight per hour of calcium hydroxide, at 120' C. and then freed of more readily boiling components at 10 mm. Hg and 120' C. There is obtained 5 parts by weight per hour of a viscous coffiposition which 30 is suitable for use as a sealing compound and for the manufacture of roofing board. The preceding examples can be repeated with similar success by substituting the generically or specifically de35 scribed reactants and/or operating conditions of this invention for those used in the preceding examples. From the foregoing description, one skilled in the art can easily ascertain the essential characteristir-s of this invention, and without departing from the spirit and scope 40 thereof, can make various changes and modifications of the invention to adapt it to various usages and conditions. What is
