RU2114128C1 - Method for synthesis of oil-filled cis-1,4-polybutadiene - Google Patents
Method for synthesis of oil-filled cis-1,4-polybutadiene Download PDFInfo
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Abstract
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Изобретение относится к технологии получения маслонаполненного цис-1,4-полибутадиена под влиянием каталитических систем Циглера-Натта и может быть использовано в промышленности синтетического каучука, а получаемый полимер - в резинотехнической и шинной отраслях народного хозяйства. The invention relates to a technology for the production of oil-filled cis-1,4-polybutadiene under the influence of Ziegler-Natta catalyst systems and can be used in the synthetic rubber industry, and the resulting polymer in the rubber and tire industries.
Известны способы получения маслонаполненного цис-1,4-полибутадиена под действием каталитических систем Циглера-Натта на основе соединений титана и соединений редкоземельных элементов (РЗЭ). Known methods for producing oil-filled cis-1,4-polybutadiene under the action of Ziegler-Natta catalyst systems based on titanium compounds and rare earth compounds (REE).
Наиболее близким по технической сущности к описываемому изобретению является способ, в соответствии с которым полимеризацию бутадиена осуществляют на батарее из шести полимеризаторов, куда подают шихту, представляющую собой раствор бутадиена в толуоле, толуольный раствор триизобутилалюминия и толуольный раствор смешанного галогенида титана. В последний полимеризатор подают ароматическое масло Пластар-20К [1]. The closest in technical essence to the described invention is a method in which the polymerization of butadiene is carried out on a battery of six polymerizers, which serves a mixture, which is a solution of butadiene in toluene, a toluene solution of triisobutylaluminum and a toluene solution of mixed titanium halide. Aromatic oil Plastar-20K is fed into the last polymerizer [1].
Недостатком прототипа является то, что маслонаполненный цис-1,4-полибутадиен, полученный по указанному способу, характеризуется высокой пластичностью и хладотекучестью. Высокая хладотекучесть не позволяет с достаточной степенью надежности сохранения формы брикетов транспортировать полученный полимер потребителю, а повышенная пластичность требует дополнительных затрат на выделение его из раствора. Кроме того, указанный полибутадиен характеризуется низкими физико-химическими показателями вулканизатов и относительно низким содержанием цис-1,4-звеньев, что неприемлемо для отдельных зарубежных потребителей. The disadvantage of the prototype is that the oil-filled cis-1,4-polybutadiene obtained by the specified method is characterized by high ductility and cold flow. High cold flow does not allow the polymer to be transported to the consumer with a sufficient degree of preservation of the shape of the briquettes, and increased ductility requires additional costs for isolating it from the solution. In addition, this polybutadiene is characterized by low physicochemical parameters of vulcanizates and a relatively low content of cis-1,4 units, which is unacceptable for some foreign consumers.
Общим приемом для всех способов получения маслонаполненного цис-1,4-полибутадиена является получение заведомо высоковязкой основы (полибутадиена) с 50 - 100 ед. Муни и смешение ее с маслом по окончании процесса полимеризации. Поэтому недостатком прототипа является также необходимость транспортировать раствор высоковязкого полибутадиена (с Муни 50 - 100 ед.) из аппарата в аппарат полимеризационной батареи и, следовательно, невозможность получать высоконаполненные маслом каучуки. A common technique for all methods of obtaining oil-filled cis-1,4-polybutadiene is to obtain a known high viscosity base (polybutadiene) with 50-100 units. Mooney and mixing it with oil at the end of the polymerization process. Therefore, the disadvantage of the prototype is the need to transport a solution of high viscosity polybutadiene (with Mooney 50-100 units) from the apparatus to the apparatus of the polymerization battery and, therefore, the inability to obtain highly filled rubbers.
Целью изобретения является получение высокомаслонаполненных каучуков с высоким содержанием цис-1,4-звеньев, пониженной пластичностью и хладотекучестью и высокими физико-механическими показателями вулканизатов. The aim of the invention is to obtain high oil-filled rubbers with a high content of CIS-1,4-units, low ductility and cold flow and high physical and mechanical properties of vulcanizates.
Поставленная цель достигается тем, что в предложенном способе получения маслонаполненного цис-1,4-полибутадиена полимеризацию бутадиена под влиянием лантаноидного катализатора осуществляют на батарее из шести полимеризаторов, причем в последний полимеризатор вводят ароматическое масло и толуольный раствор О,О'-бис(1,3,5-три-трет-бутилгексадиен-2,5-OH-4-ил)-n- бензохинондиоксим) (далее хиноловый эфир)
где R - третбутил,
после чего полимеризат заправляют антиоксидантом и подают на дегазацию и выделение полимера. В предложенном способе вязкость по Муни основы (полибутадиена) составляет 40 - 45 ед., поскольку вводимая добавка, хиноловый эфир, способствуют разветвлению и структурированию уже сформировавшихся макромолекул эластомера при его термической обработке. Высокомаслонаполненный цис-1,4-полибутадиен, полученный в соответствии указанным способом, характеризуется пониженной пластичностью и хладотекучестью, высоким содержанием цис-1,4-звеньев и высокими физико-механическими показателями вулканизатов.This goal is achieved by the fact that in the proposed method for the production of oil-filled cis-1,4-polybutadiene, the polymerization of butadiene under the influence of a lanthanide catalyst is carried out on a battery of six polymerizers, and aromatic oil and toluene solution O, O'bis are introduced into the last polymerizer (1, 3,5-tri-tert-butylhexadiene-2,5-OH-4-yl) -n-benzoquinone dioxime) (hereinafter quinol ether)
where R is tert-butyl,
after which the polymerizate is seasoned with an antioxidant and served for degassing and isolation of the polymer. In the proposed method, the Mooney viscosity of the base (polybutadiene) is 40 - 45 units, since the added additive, quinol ether, promotes the branching and structuring of the already formed elastomer macromolecules during its heat treatment. High oil filled cis-1,4-polybutadiene obtained in accordance with the specified method is characterized by reduced ductility and cold flow, a high content of cis-1,4-units and high physical and mechanical properties of vulcanizates.
Сущность заявляемого способа и его преимущества по сравнению с прототипом (пример 1) раскрыты в примерах 2 и 3. The essence of the proposed method and its advantages compared with the prototype (example 1) are disclosed in examples 2 and 3.
Пример 1. Полимеризацию бутадиена осуществляют на батарее из шести полимеризаторов, куда подают 30 т/ч шихты, представляющей собой 10%-ный (мас.) раствор бутадиена (3 т/ч) в толуоле (27 т/ч), 195 л/ч толуольного раствора триизобутилалюминия (ТИБА) (42 моль ТИБА/ч) и 161,5 л/ч толуольного раствора дииоддихлортитана (ДДТ) (10,5 моль ДДТ/ч). В шестой полимеризатор подают масло Пластар-20К в количестве 0,9 т/ч. Конверсия мономера в шестом полимеризаторе 80%. Обрыв процесса полимеризации осуществляют раствором антиоксиданта (0,5 мас. % агидола-2), отмывку полимеризата - частично умягченной водой в соотношении 1:1. Example 1. The polymerization of butadiene is carried out on a battery of six polymerizers, which serves 30 t / h of the mixture, which is a 10% (wt.) Solution of butadiene (3 t / h) in toluene (27 t / h), 195 l / h of a toluene solution of triisobutylaluminum (TIBA) (42 mol TIBA / h) and 161.5 l / h of a toluene solution of diiododichlorotitan (DDT) (10.5 mol of DDT / h). Plastar-20K oil is supplied to the sixth polymerizer in an amount of 0.9 t / h. The conversion of the monomer in the sixth polymerizer is 80%. The termination of the polymerization process is carried out with an antioxidant solution (0.5 wt.% Agidol-2), the polymerizate is washed with partially softened water in a ratio of 1: 1.
Пример 2. Полимеризацию бутадиена под влиянием лантаноидного катализатора осуществляют на батарее из шести полимеризаторов, куда подают 30 т/ч шихты, представляющей собой 10%-ный (мас.) раствор бутадиена (3 т/ч) в толуоле (27 т/ч) и 407 л/ч (3,7 моль РЗЭ/ч) суспензии каталитического комплекса с содержанием РЗЭ 0,0091 моль/л. В шестой полимеризатор подают масло Пластар-20К в количестве 0,85 т/ч и 75 л/ч толуольного раствора хинолового эфира с содержанием 100 г/л (0,1 мас.% на мономер). Конверсия мономера в шестом полимеризаторе 95%. Стабилизация, отмывка и выделение полимера так же, как в примере 1. Example 2. The polymerization of butadiene under the influence of a lanthanide catalyst is carried out on a battery of six polymerizers, which serves 30 t / h of the mixture, which is a 10% (wt.) Solution of butadiene (3 t / h) in toluene (27 t / h) and 407 l / h (3.7 mol REE / h) of a suspension of the catalytic complex with a REE content of 0.0091 mol / l. Plastar-20K oil is fed into the sixth polymerization agent in an amount of 0.85 t / h and 75 l / h of a toluene solution of quinol ether with a content of 100 g / l (0.1 wt.% Per monomer). The conversion of the monomer in the sixth polymerizator 95%. Stabilization, washing and isolation of the polymer is the same as in example 1.
Пример 3. Полимеризацию бутадиена под влиянием лантаноидного катализатора осуществляют так же, как в примере 2. В отличие от примера 2 в шестой полимеризатор подают масло Пластар-20К в количестве 1,95 т/ч и 600 л/ч толуольного раствора хинолового эфира с содержанием 100 г/л (2,0 мас.% на мономер). Конверсия мономера в шестом полимеризаторе 93%. Example 3. The polymerization of butadiene under the influence of a lanthanide catalyst is carried out in the same way as in example 2. In contrast to example 2, Plastar-20K oil is supplied to the sixth polymerizator in an amount of 1.95 t / h and 600 l / h of toluene solution of quinol ether containing 100 g / l (2.0 wt.% Per monomer). The conversion of monomer in the sixth polymerization agent 93%.
Свойства маслонаполненного цис-1,4-полибутадиена, полученного в соответствии с примерами 1 - 3, представлены в таблице. Приготовление резиновых смесей и вулканизатов на их основе осуществляли по ГОСТ 19920.19-74, испытания вулканизатов - по ГОСТ 270-75. The properties of oil-filled CIS-1,4-polybutadiene obtained in accordance with examples 1 to 3 are presented in the table. Preparation of rubber compounds and vulcanizates based on them was carried out according to GOST 19920.19-74, testing of vulcanizates according to GOST 270-75.
Таким образом, в примерах 1 - 3 показано, что предложенный способ дает возможность получать цис-1,4-полибутадиен с высоким содержанием масла (до 70 мас. ч.) с пониженной пластичностью и хладотекучестью и более высокими физико-механическими показателями вулканизатов по сравнению с прототипом. Thus, in examples 1 to 3, it was shown that the proposed method makes it possible to obtain cis-1,4-polybutadiene with a high oil content (up to 70 parts by weight) with reduced ductility and cold flow and higher physical and mechanical properties of vulcanizates compared with the prototype.
Claims (1)
где R - трет-бутил,
в количестве 0,1 - 2,0 мас.% на монометр.The method of producing oil-filled cis-1,4-polybutadiene by polymerization of butadiene in an organic solvent in the presence of a stereospecific Ziegler-Natta catalyst in a polymerisation battery, followed by stopping, introducing an antioxidant and oil, washing and isolating rubber, characterized in that as a Ziegler-Natta catalyst use lanthanide compounds and organoaluminum compounds, and the introduction of oil is carried out in an amount of 30 - 70 wt. hours per 100 wt. hours rubber and combine it with the introduction of a regulator of plastoelastic properties of rubber, which reduces the plasticity and cold flow of the polymer, which is used as O, O '' - bis (1,3,5-tri-tert-butylhexadiene-2,5-OH-4-yl ) -p-benzoquinoidoxime of the formula
where R is tert-butyl,
in an amount of 0.1 - 2.0 wt.% per monometer.
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-
1996
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Non-Patent Citations (1)
Title |
---|
1. ТУ 38.103150-82. Каучук синтетический цис-1,4-бутадиеновый маслонаполн енный СКДМ. * |
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