SU726110A1 - Method of producing high-molecular weight polypiperylene - Google Patents

Description

(54) METHOD FOR RECEIVING A VOLUME-MOLECULAR PIPINPER LENA DKHKHTHKHKHKHKHKHKHKHKHKHKHKHKHKHKH Formula K K Ktoykonektoykuyuuuuuuuuuuuuuuuto phytoxyphaone ohmone ethoku Formula ki самых кт кт кт наиболее наиболее наиболее наиболее наиболее cytotransferential lactanoic acid (their ln CSg chlorides) with mi as the complex forming agents (K) of the cheapest and most affordable cyvTb chytotransmitter (ohmoneg)), the most cheap and affordable cyvTb chytothenetehycone, ohmg LSO) or dialkyl sulfoxides (DASO) makes it much cheaper to prepare a LnC j3K catalytic complex soluble in y-hydrogen hydrogen, the cost of, for example, sulfonic acid complexes of Ln MF is 1.5–2 times lower than the cost of naphthenates, octeno-atoms c, adyl acetonates and other solution derivatives of lanthanides. Petroleum sulfoxides are mixtures of cyclic sulfoxidoses of a seismic structure, semi-oxidized with hydrogen peroxide, petroleum sulphides (petrochemical production waste), separated by sulfuric acid extraction from diesel fuel, Oxide. It is also easy to obtain a dialkyl sulfide sulfide Dy. Tributyl phosphate (TBP) is a product of industrial production. Sulfoxide or tributyl phosphate complexes of Ln CC are easily obtained and well dissolved in aliphatic or apoMaTH4ecKfLx hydrocarbons, in which the polyglurization process is carried out. The presence of complexing agents in the catalytic system increases its activity, and their presence in the ready-made material improves its plasticization, and its plasticization can improve its plasticization in the finished material, and its plasticization can be improved. Used items. The essence of the proposed invention of COX7SL is that piperylene is polymerized in an inert solvent (aliphatic HecKifx or aromatic hydrocarbons or their mixtures) on a two-component catalytic system consisting of a hydrocarbon-soluble complex of the lanthanide chloride (or mixtures of lanthanides and an alantide compound and a lanthanide mixture and a mixture of the lanthanides and the lanthanide mixture soluble in hydrocarbons (or lanthanide mixtures and the lanthanide mixtures) de R. where P is cycloalkyl alkyls, in the presence or absence of monomer The polymerization process is usually carried out at 20-5 ° C with practically 100% conversion in 6-8 hours. The resulting rubber contains 80% 1,4- cis units, has a high intrinsic viscosity (3-7 dL / g) and a low glass transition temperature (-30) - (- 50) ° C, Example 1. Control experiments. and) Vtrenirovanny glass reactor equipped with magnetic using a stirrer, successively with stirring, inert gas in aTMoCixvpe, in addition toluene solutions of pcetyl letonate nconjp .ta, trnobot lalumti and dyutpatyumnium chloride, so that the molar ratio Mb: Cy; AR equals 1: 2.5: 40. The resulting precipitate is allowed to stand for 1 hour at room temperature and a trans-piperylene 159 ° heptane solution is added to it, so that the concentration of 1H of the solution is 2 mmol V / 1OO g P1sheralen. The yield of polytyperylene is 48%, the intrinsic viscosity is 2.7 dl / g, the content of 1,4-cis-units is 78%, 1,2-trans-eve 1b is 22%, the glass transition temperature is () -42 ° C. b) Under similar conditions, a complex is prepared from praseodymium stearate, diethyl aluminumium chloride and triethyl aluminum at a molo.m ratio of 1: 3: 50 and kept for 1 hour at room temperature. A 15% toluene solution is added to the complex. piperylene, so that the concentration of the solution corresponds to 2 mmol of Pp / 10 O g pt perylene. Polymerization is carried out at 20 ° C for 4 hours. The polypiperylene withdrawal is 48%, and the 1,4-cis-chain content is 80%. 1.2-trans-, EvenB2O%, D) 2.2dl / g, tc -40 ° C, M a rm 2..a) a toluene solution of a complex of neodymium chloride with a carbon dioxide is introduced into the reactor in an inert gas atmosphere and a triisobutylaluminum toluene solution, so that the molar ratio A / MO is 40. The complex matures for 1 hour at room temperature, then a solution of trans-piperylene in heptane is added, so that the concentration of the complex is 0.75 μl N61 / 100 g piperylene . Polymerization is carried out for 4 hours at 20 ° C. The yield of polypiperylene is 60%, T | 4.3 dl / g, 1,4-cis-units of 8O9o, 1,2-trans-links 20%, tc, b) In analogous conditions, a catalytic complex of diamyl sulfoxide of neodymium chloride and triethylaluminium is prepared at a molar ratio of components A / An NS of 50 is kept for 1 hour and a 15% solution of piperylene in toluene is added to it, so that the concentration of the complex is 0.75 ME / 100 g of piperylene. Polymer time-. for 6 h at 20 ° C, polymer yield 72%, f) 3.7 dl / g, content of 1.4 cyto-doubles 78% c 1,2-trans-units 22%, tc -40 ° С. 572 c) Under similar conditions, a catalytic complex of peft sulfox dusts of {NacCg-SHCO) and triheptylaluminium is prepared at a molar ratio of ACh / Wd 50 and added 1.5% pf of transBrc transgrcleni in heptane to it at a concentration of 0.5. mmol Nd / lOO g of pilerilen. The polymerization is carried out for 4 hours. The yield of the polypipericle is 64%, g - 4.7 dl / g, the content of 1,4-cis-units is 82%, 1,2-tranny units is 18%,:, In the table. Figure 1 shows the effect of the Nd / At ratio on the yield, D) and the microstructure of fullpiperylene under the same other conditions of epitapation. As can be seen in Table 1, the optimal polymerization conditions (good yield with a high i) are observed with AE / N5 ratio of 40- 60 The microstructure of the polypscherylene does not depend on the ratio of D. / H61, Table. Figure 2 shows the effect of polymerization time on the yield, n, and microstructure of polypiperylene. As can be seen from Yes 1 table. 2, with an increase in the time of polymerization, the yields and values of Γ increase, and the content of links of a single fi sh structure remains constant. In tab. Figure 3 shows the effect of the temperature of the polymerization on the yield, f and the microstructure of polypiperylene. As can be seen from the table. 3, an increase in the temperature of half a day leads to an increase in the output of the .nDavmunepLncHanpH while simultaneously reducing n without changing the microstructure of the polypiperilep. Example Z. In a reactor in an inert gas atmosphere, a toluene solution of a complex of neodymium chloride with tributyl phosphate and a toluene solution of triisobutylaluminum with n -sherklene at a ratio of A2 / N3 40 and K3 / piperylene 1 is introduced. In this case, no precipitate forms in the homogeneous catalytic complex it is easy to dose. The complex ages for 1 h at room temperature and is introduced into a 15% transpiperylene heptane solution {concentration 0.75 mmol. Ko1 / 1OO g piperylene). Polymerization is carried out for 4 hours at 20 ° C. Polypiperylene yield is 67%, 4.4 dl / g, 1,4-cis-unit content is 80%, 1,2-trans-20%, 4-. , 6; When comparing DONNIEH of this example with the results of the example. It is hypothesized that the addition of monomer during the molding of the catalytic complex leads to the homogenization of the system {which is more convenient for the technological design of the process) with a slightly larger increase in its activity, but the microstructure is different. lipiperipylene and remain the same in both cases. Example 4. a) Toluene solutions of the cerium chloride complex with petroleum sulfoxides and triisobutylaluminum are introduced into the reactor in an inert atmosphere, so that the Au / Ce molar ratio is 50. The complex matures for 1 hour at room temperature and it is added 15% solution of trans-p1triegten in heptane in such an amount that the molar concentration of the complex is 1 mmol of Ce / 10 O g of schirylene. Polymerization is carried out for 6 hours at 20 ° C. The polymer yield is 52%, i). 3.8 dl / g, tg-4bS, the content of 1,4-cis-units is 80%, and 1,2-trans-oveni is 20%. b) Under similar conditions, a catalytic complex of a tributyl phosphate complex of praseodymium chloride (PP C ZTBP) and aluminum triethyl is prepared at a molar ratio of A / Pr 60 and maintained for 1 hour at room temperature. Then a 15% solution of piperylene in toluene was introduced into the reactor so that the concentration of the complex was 0, 5 mmol of Pr / 1OO g of piperylene. The polymerization is carried out for 4 hours at. Polymer yield 75%, D) 4.7 dl / g, s -42 C, the content of 1,4 1c-units 81%. c) Under similar conditions, a catalytic complex of the mishmetal.t chloride complex is prepared (an industrial sample of a mixture of lanthanides of the composition,%: La 40, Ce 5 O, Fe 7 and the sum of the remaining lanthanides {MD, Pr, etc.) 3%, with oil sulfoxides and triheptyl-aluminum. The A / Mischmetal ratio is 6O. The complex matures for 1 hour at 20 ° C, then a 15% heptane solution of trans-piperidene is introduced into the reactor in such an amount that the concentration of the complex is 1 mmol of mischetal / 1OO g of piperylene. Post-qualification during 77776110

put a getheir; 6 h 1; ri 50 ° С, Vkop n.olpmera 82%, D) 3.2 ll / g, t, the content of 1,4-i-units 81%,

In tab. 4 shows the influence of nature.

lantaioipov HQ activity and stersospet: a feature of lytic systems based on complexes of lanthanide chlorides with THFHbllvfl SULFOX NECTS.

Trace polymer

101.08O20

202.18119

453.0802О

524.07921

603,3802О

622,78218

622,37921

-45 -45 -47 -5 О -50 -40 -45

table 2

Table

Claims (2)

1. A method for producing a high molecular weight polypiplene by polymerization of a pililen in a hydrocarbon solvent medium at -60 ° C in the presence of a reaction product of lanthanide compounds and organo-aluminum compounds as a catalyst, characterized in that, in order to increase the rate of polymerization, increase eco-efficiency of the process and simplification of its technology, carbohydrate-dissolving (sulphrite or alkylphosphate complexes of lan10 726110 Table 4 tanoids or mixtures thereof at a molar ratio of the organoaluminum compound to the lanthanide compound from 15: 1 to 100: 1. 2. The method according to claim 1, wherein the interaction of the catalyst components is carried out in the presence of piperylene. Sources of information taken into account in the examination 1.Patent UK No. 961269, 1СЛ, С 3 Р, published. 1964. 2, UK Patent N; 93190О, KJU 2/6 / Р, published. 1963. ZGPatent - CUJA - №37t; r4f304, cl. 252-431, publ. 1974 (prototype).