SU1016304A1 - Process for producing polyisobutylene - Google Patents

Abstract

1. METHOD OF OBTAINING POLYISOBUTYLENE by polymerization of isobutylene .9, -i - l, h / D X - :: -:; on at (-78) - (in an organic.-solvent in the presence of alkdvinium-containing catalysis, molecular mass regulator, from one to another, so that, in order to simplify the technology and produce the output. and high molecular weight alkylphenols based on the desired product, in as a regulator or regulator, and solvent, 16-6 O O% are used from isobutylene of trialkylbenzenes of the general formula 1.3.5-CHERKc 1h, where R, R-C -C-alkyl, as a catalyst 0.45-1.6% Beci,% of isobutylene alkyl alkylphenyl chlorides of the general formula 8 R AeCf-, (O where.-Alkyl. 2. The method according to Claim 1, of t and h an-; iu and and with it, which is used as isobu.

Description

The invention relates to methods for producing polyisobutylene and can be used in the petrochemical industry, and polyisobutylene as additives for mineral oils, lubricants, feedstock for the production of antioxidants, surface active substances PLV. There is a known method for producing low molecular weight polybutylene octols by polymerization of a C / butched butane-butylene fraction in the presence of a forgtula catalyst: L1Cl1. H, O C / H) 2. G13. The disadvantage of this method is a high catalyst consumption of 10–14%, the products obtained have a low C-C bond number. The polymer has a molar polymer of 0.33–0.4, which, with subsequent modification of polyisobutylene with maleic anhydride, leads to a low yield of the additive. In addition, the products obtained have an irregular structure, which affects the quality of the succinimide additive based on polymers (poorly dispersed 1 die properties). A known method for producing polyiso butylene polymerization, isobutylene or isobutylene containing fractions in the presence of 0.99–20 wt.% As a catalyst is from the monomer of sulfonic acid resins in the H-form, activated by addition of alkyl aluminum chlorides of the general formula KLESC2, where R is Co-C d- alkyl at 1-78) - (-10) ° C. The process can be carried out in mesitylene medium. In this case, the products obtained have a B1t1 high unsaturation, which in turn leads to a high yield of the additive. A disadvantage of the known method is that the obtained polyisobutylenes have insufficiently high peak temperature of 140-150 ° C. Increasing this rate would extend the temperature range of oil and additive operation. The closest to the technical essence is the method of producing polyisobutylene by polymerization of isobutylene at C-78) - (- 10) C in an ORGANIC solvent in the presence of an aluminum-containing catalyst, molecular regulator masses. Diisobuylene (, 2, 4, 4-trimethylpentene-1) Gz1 is used as a regulator. The disadvantage of this method is the relatively high consumption of catalyst, with further modification of polyisobutylene (production by syls.) K to surfactant lubricating oils), it was impossible to obtain products of modification with high yield. Process: the process has several disadvantages associated with the use of diisobutylene as a regulator. 2,4, 4-Trimethylpentene-1 has a strong regulatory action at low concentrations (. Percent share). This imposes a harsh requirement on dosage accuracy and leads to difficulties in obtaining strictly specified values of the molecular weight of polyisobutylene. In addition, 85-90% of unspent diisobutylene remains in the reaction medium, which creates certain frontiers in the purification of the components of the reaction medium for their further use. 2,4,4-Trimethylpentane € n-1 bp 101.4 ° C, the other isomer 2,4,4-trimethylene-2 has t „kip. 104.9 ° C and is always present in a mixture with the first, regardless of the method of preparation. 2,4,4-Trimethylpenthen-2 (although it is a weak regulator.) Is a catalyst house, which implies a laborious separation of it from 2,4,4-trimethylpentene-1. When using diisobutylene, the next one enters the polyisobutylene (PIB) polygon chain, which creates difficulties for further modification. PIB (due to the presence of volumetric groupings J. The aim of the invention is to simplify the technology and increase the yield of additives and high molecular weight alkylphenols based on the desired product. The goal is achieved by the fact 1HT according to the method of producing polyisobutylene by polymerizing isobutylene at (-78) - ( -10) with in an organic solvent in the presence of an aluminum-containing catalyst, molecular weight regulator, 6–600% by volume of isobutylene of trialkylbenzenes are used as a regulator or regulator and solvent. Formulas I 1,3,5-СНЗРЯС Нз, where RR is С -, - С4-alkyl, as a catalyst О, 45-1.6 wt.% of isobutylene alkyl aluminum chloride of the general formula Aese2 where R is C2-C4-alkyl It is possible to use isobutylene-containing fractions C as isobutylene. Despite the fact that in order to achieve a tangible regulatory effect, it is necessary to use replenishing amounts of the regulating additive (not less than 6% by volume against 0.5% by weight to isobutylene by a known method), this is not a disadvantage. On the contrary, the use of soft-regulating trialkylbenzenes makes it unnecessary to comply with the stringent requirements imposed on the dosage of the regulator. : Due to its good dissolving ability as well as chemical inertness to aluminum chloride, symmetric trialkylbenzenes can be used as a solvent.

Examples 1-4. Isobutylene is polymerized at -78 ° C in a glass reactor equipped with a chalk constantan tergiopar and an addition funnel. 50 ml of the solvent, isopentane, are introduced into the dry, purged with nitrogen, reactor. 3.3 ml of liquefied isobutylene and a certain amount of 1,3,5-trimethylbenzene (mesitylene. To the mixture is added a catalytic solution of C2 HjAlC2 in isopentane (examples 2-4 I. Polymerization time is 10 min.

The resulting TID is re-precipitated twice from the solution with ethyl alcohol and subjected to a lyol bag. Molecular masses (MM) are determined viscrimetrically in cyclohexane. The number of double bonds per mole of the PNU (C – C is determined ozonometrically. The results of the examples are shown in Table 1.

Table 1

Example 1 is comparative. From Table 1, it can be seen that the use of the low temperature in process. By limiting the isobutylene of mesitylene in quantities of 15–120 By.% to isobutylene as an additive regulator (Examples 2–4), it is possible to obtain unsaturated PIB pars with a regulated MM. Examples 5-9. A batch-type bar, equipped with a thermostatic jacket, is charged with 50 ml of a mixture of isopentane with mesitylene (examples 6-8) or an individual mesitylene (-example 9), and the catalyst is added. The table is led in the absence of meytylene. A C H AlClo solution in isopentane and at a temperature in two streams and isobutylene and nitrogen are passed through for 30 minutes. From the reaction mixture after water forging of the catalyst, drying with CaClg and distilling, isopentane on a rotary evaporator at 100 ° / 5 mm Hg. Mesitylene is distilled off. The average product yield is 6-7 g. Characteristics of low molecular weight PIB are listed in Table 2. When using trialkylbenzenes, it is possible to carry out the complete regeneration of solvents according to a waste-free scheme. Isopentane 93 72: 0 Mesitylene 92 820 Calculated per volume of liquefied gas per reaction. MM of low molecular weight TID specific Comparative: an example in the absence. ; .. . Table 2 suggests that using mesitylene as a regulating additive (Examples 6-8) and as a reaction medium (Example 9), in the polymerization process of isobutylene at -10 ° C, it is possible to produce unsaturated PIB octols with MM 700 -1000. According to the data of IR-spectroscopy, end and pre-terminal double bonds of CH, and -CH 9-CH3 are contained in the product, respectively Jnc, "but. The catalyst consumption is 0.45-0.5% by weight. Example 10. The method is carried out as in Example 6. The consumption of catalyst is 0.5% by weight for isobutylen. The difference is that it takes as an aromatic hydrocarbon. t -1,3,5-gdimetil-tert-butylenzole. The output of the PIB-6,5 g. Conversion on isobutylene 93%, U 950, p .... 1.04. The infrared radiation of the product contains the characteristic frequencies of stretching and deformation vibrations and s CH 3 iH e groups, i.e. the regulator is not included in the polymer chain. Example 11 The method is carried out as in Example b. The difference is that 1,3,5-methyldi-tert-butylenzole is taken as the aromatic hydrocarbon. Vuhod PIV 6.8 g Convert to isobutILEN 95%, MM 840, 1.00. In the IR spectrum of the product are present harster and -. Catalyst consumption 0.47 wt.% Per isobutylen. PRI me R 12 .. Method osui.est. In yut in a reactor equipped with a thermocouple. And a dropping funnel. Download 11 ml of liquefied isobutylene, 5.6 ml of 1,3,5-trimethylVenzene, and at a temperature of 10 ° C, add 1.0 ml of catalytic solution of C-HjAlClj (2.5-10 Mol) in mesitylle gradually. The total amount of mesylen is 60 bIST to isobutylene. Reaction time 30 min. From the reaction mixture after water from washing the catalyst, drying with

Continued table. 2 0.97. 0,; 5 1,03 0,5 ilena (P 0,66 g / cm), entered. Rioscopically in benzene. itiena ... -. . . . . CaCl2 and mesitylene stripping get polyisobutylene. Mark octol with MM-700, s with 1 / 0.1. Conversion lio to isobutylene 98%. In the H-spectrum of the product, there are characteristic vibration frequencies and (CH3) 2 groups. СНз Catalyst consumption O, 49 wt. % isobutylen .... Example 13: The method is carried out as in Example 12. However, the difference is that mesitylene, distilled in Example 12 b, is used as the reaction medium: without further purification. Received TID with MM 810 PS-1.01. Conversion to isobutylene 93%. The IR spectrum of the product contains characteristic frequencies of valence and deformation vibrations and -. (CH3) 2 groups. Catalyst consumption is 0.46 wt.% For isobutylen. Example 14. The method is provided, as in example 12. The difference is that mesitylene is loaded in the amount of 2.3 ml, and 25 ml of the isobutylene fraction of the isobutylene composition,% CjHfl 0.8,, 4, iso-C H pva 55;; 4, nC. l, C.Nv 0.4, iso-C Nd 39.5, -C4No1.9. About “its amount is 33 of.%. The PIB of the brand name has been obtained with I1M 190, 1. Conversion to 95% isobutylene. In the infrared spectrum of the product are present, the oscillation frequency of-C CHj and -CH C (CH3) 2 groups. Catalyst consumption 0.5 wt.% (La isobutylen. Butylenes do not take part in the reaction. EXAMPLE 15 The method is carried out as in Example 6. The difference is that iso-C is used as a catalyst. HdA1C12a and the reaction temperature is. The yield of PIB with t 750 nt Q, B1 is 8 g, and the isobene conversion is 97%. In the IR spectrum of the product

vibration frequencies of -C-CHg and -CH-C (CH) 2 groups are present. Consumption

bnz

catalyst 0.7 wt.% on eosoutilen. .

ten

Example

Example 16 (control). An example is given for comparing the reactivity capacity (quality) of a product obtained under the conditions of Example 6 in the presence of mesitylene and a product with the same MM obtained according to a known method (in the presence of 2,4,4-trimethylpentene-1). The quality criterion is the yield of alkenylsuccinic anhydride synthesized as a result of the condensation of the compared products with maleic anhydride (T 200 ° C, reaction time 8 hours, 1.5 mole of anhydride per mole of PIB). After removal of the maleic anhydride from the protein by precipitation with gasoline of the grade B1-1 and distillation with, the reaction products are analyzed for the content of alkenylsuccinan1 drida using elemental analysis and IR spectroscopy. The course of alkenylsuccinic succinic anhydride intermediate for the synthesis of succinimide additives is 60% and 33%, respectively. Thus, the PIB obtained in the presence of mesitylene, according to the Proposed method, is of higher quality than the ecu product synthesized in the presence of 2,4,4-trimethylpentene-1.

Example 17 (control, received one According to the known fl 1 method). The method is carried out by Tc1kzhe, as in example 7, the difference is that instead of mesitylene use t-xyl. The yield of 6.9 g 18 3

9500 0.96 0.2 1000 1.02 0.1

19 6

Low molecular weight PIB, obtained by the proposed method, have a temperature of (t) equal to 170180 ° С. The data on the temperature of the peak are presented in Table 3.

T a b l and c a 3

eleven

14

fW 700, p., (0.3. Conversion to isobutylene 96%. Unsaturated product unsaturation is due to the inclusion of dial; kilbenzene in the polymer chain as an end group, which is confirmed by UV absorption band spectra at 265.271 nm. V

From the data of the control example, it can be seen that the use of dialkyl benzene in the polymerization process of isobutylene leads to the formation of products with low Unsaturation (0.3 mol / mol PIB instead of 1.05 mol / mol PIB, according to the proposed method).

Examples 18-21. Examples are given to compare the reactivity (quality) of PIB, obtained according to the proposed and known methods. The quality criterion is the yield of high molecular weight alkylphenols obtained by alkylation of phenol (3 lyons) with 1 mol of isobutylene 1 mol in n-nonane in the presence of benzenesulfonic acid for 4 hours. The yield of high molecular alkyl alkyl phenols is determined by the residual unsaturation of the product by the ozonometric method. The content of low molecules rnph-. alkylphenols estimate the method of gas-liquid chromatography.

Data on the alkylation of phenols with isobutylene polymers is summarized in. table.4. IT a b l it.ts. .a 4.

65 50

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Claims (2)

1. METHOD FOR PRODUCING POLYISOBUTILE ON THE POLYMERIZATION OF ISOBUTYLENE AT (-78) - (-10) ^p C in an organic, “solvent in the presence of aluminum- ^; . containing a catalyst, a molecular weight regulator, due to the fact that, in order to simplify the technology and increase the yield of λ additives and high molecular weight alkyl phenols based on the target product, they are used as a regulator or regulator and solvent; 6-600 vol.% Of isobutylene trialkylbenzenes of the general formula * 1.3,5-CH ₃ RR'c _fe H ₃ , where R, R'-C ^ -C ₄ -alkyl, as a catalyst 0.45-1.6 veaL from isobutylene alkylaluminium chlorides of the general formula _ w RAece ₂ , where R is -C „-C ^ -alkyl. 2. The method according to claim 1, about t and with the n I with the fact that as an isob ·. of thylene use isobutylene-containing fractions C ^ .. ... 8 · /