WO2014142637A1 - Method for producing thermoplastic elastomers - Google Patents
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- WO2014142637A1 WO2014142637A1 PCT/KZ2013/000003 KZ2013000003W WO2014142637A1 WO 2014142637 A1 WO2014142637 A1 WO 2014142637A1 KZ 2013000003 W KZ2013000003 W KZ 2013000003W WO 2014142637 A1 WO2014142637 A1 WO 2014142637A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L17/00—Compositions of reclaimed rubber
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- the invention relates to the field of chemical technology of polymers, in particular, technology for producing composite materials.
- the objective of the invention is to develop an effective method for producing thermoplastic elastomers (TEC) for the production of technical products and parts, cable insulation and modifiers of asphalt - bitumen mixtures.
- TEC thermoplastic elastomers
- a composition containing high density polyethylene (PE) or polypropylene (PP), styrene butadiene rubber (BSK) and the surface-activated product for the regeneration of car tires and rubber products (PARR) is obtained by mechanochemical polymerization on a single screw extruder in one technological stage.
- thermoplastic elastomers Glukhovskoy V.S., Litvin Yu.A., Sitnikova V.V., Kulakova K.A., Fil V.G., Kudryavtsev L.D., Molodyka A.V., Privalov V.
- Thermoplastic elastomers are obtained by block copolymerization of styrene or a - methylstyrene and diene in an organic solvent medium under the action of a primary organolithium initiator in the presence of a modifier - methyl tert.-butyl ether.
- a complex soluble in hydrocarbon solvents is used, obtained by reacting ethyl chloride with lithium dispersion in a molar ratio of 1: 2.05-2.10, respectively, at a temperature of 323 — ZZZK followed by the introduction of monomer into the reaction mass.
- the monomer is selected from the group: ethylene, butadiene, isoprene, piperylene, styrene or a mixture of butadiene with styrene, with a molar ratio of monomer from the group: ethyl lithium 0.25 - 1.00: 1, respectively, at a dosage of initiator 4.5 ⁇ 10 "5 - 1, 2-10 "4 moles of active lithium per 1 g of vinyl aromatic monomer upon receipt of thermoplastic elastomers.
- the method allows to reduce the synthesis time of the first polystyrene or poly-a-methylstyrene block, to reduce the initiator consumption.
- a disadvantage of the known composition is multi-stage, labor-intensive technological process, consisting of separate and unrelated cycles and insufficient physical and mechanical properties for the production of technical products and parts, cable insulation and modifiers of asphalt - bitumen mixtures.
- thermoplastic elastomers Glukhovskoy V. S; Litvin Yu. A.; Sitnikova V.
- a stainless steel apparatus with a volume of 16 m, equipped with a paddle mixer, a circulation pump, a thermostatic jacket with a coolant, inert gas, solvent, monomers, and catalyst supply systems
- 7000 l of hydrocarbon solvent is supplied in a stream of dried nitrogen (mixture of cyclohexane and gasoline in a ratio of 70: 30 wt.h) containing 0.1% methyl tert-butyl ether (MTBE)
- the catalytic complex obtained in example 1 is dosed in an amount of 29.8 l (55 mol by active lithium).
- 460 kg of styrene is supplied.
- Styrene polymerization proceeds in adiabatic mode with an increase in temperature to -313K for 20 minutes. The conversion of styrene is 100%. Then, 1020 kg of butadiene, cooled to a temperature of 268K, is fed into the apparatus, the temperature of the reaction mixture first drops to 281-283K, then sharply increases to 368-375K within 15-20 minutes, butadiene polymerization ends with the formation of a living two-block copolymer of polystyrene-polybutadienyl lithium.
- a multifunctional coupling agent is fed into the apparatus - 2.8 kg of tetraethoxysilane, the combination reaction of two-block copolymers is carried out for 20 minutes, the polymerizate is sent to the averager and, after stabilization, the polymer is isolated by water degassing.
- the specified method is a multi-stage process, which leads to the high cost of DST-30R. Physico - mechanical indicators of the properties of the branched DST-ZOR are tested according to standard methods.
- TECs are produced in continuous and continuous mode on rollers or syringe machines, followed by extrusion on twin-screw extruders.
- the advantage of this method is the combination of the mixing and crosslinking process in order to obtain TEC.
- the disadvantage of this method is the multi-stage process and the presence of a vulcanization process, which increases the duration of the process.
- a significant difference of the present invention is the use of a twin - screw extruder for the production of TEC, one - stage and reduction of the duration of the technological process, the absence of vulcanization during the processing of compositions and the use of modified rubber regenerates.
- Example 1-6 (a method of obtaining TEC according to the prototype).
- May 20.0 is loaded into the hopper of the main extruder for mixing.
- h software (LDPE or PC); May 40.5-52.5.
- h of modified PARP is introduced into a high-speed agglomerator mixer and mixed at a speed of rotation of the agglomerator rotor of 2000 rpm; The resulting mixture is loaded into the hopper of the main extruder and from May 25.0 to 35.0.
- h BSK or SKEPT extruded at a screw speed of 40-50 rpm (the formulation of the compositions are presented in table 1);
- Granulation is carried out at a rotational speed of the knife drive of 15-20 rpm. granulating head rotor.
- Surface modification of PRR is carried out in an agglomerator by the introduction of May 0.5. h SKIN by weight of PRR.
- volumetric modification of the PRR is carried out in the sinter by the introduction of May 3.0. h DOF by weight of PRR.
- the composition of the vulcanizing group is presented in table.2.
- the measurement results of the physico - mechanical parameters of the compositions and the duration of the technological cycle ( ⁇ ) are presented in table 3.
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Abstract
Description
СПОСОБ ПОЛУЧЕНИЯ ТЕРМОЭЛАСТОПЛАСТОВ METHOD FOR PRODUCING THERMOELASTOPLASTES
Изобретение относится к области химической технологии полимеров, в частности, технологии получения композиционных материалов. The invention relates to the field of chemical technology of polymers, in particular, technology for producing composite materials.
Задача изобретения заключается в разработке эффективного способа получения термоэластопластов (ТЭП) для производства технических изделий и деталей, кабельной изоляции и модификаторов асфальто - битумных смесей. The objective of the invention is to develop an effective method for producing thermoplastic elastomers (TEC) for the production of technical products and parts, cable insulation and modifiers of asphalt - bitumen mixtures.
Композицию, содержащую полиэтилен высокой плотности (ПЭ) или полипропилен (ПП), бутадиенстирольный каучук (БСК) и поверхностно активированный продукт регенерации автомобильных шин и резинотехнических изделий (ПАРР) получают механохимической полимеризацией на одношнековом экструдере в одну технологическую стадию. A composition containing high density polyethylene (PE) or polypropylene (PP), styrene butadiene rubber (BSK) and the surface-activated product for the regeneration of car tires and rubber products (PARR) is obtained by mechanochemical polymerization on a single screw extruder in one technological stage.
Известен способ получения ТЭП [Патент РФ. JNb 2141976. Способ получения термоэластопластов. Глуховской В. С, Литвин Ю. А., Ситникова В. В., Кулакова К. А., Филь В. Г., Кудрявцев Л. Д., Молодыка А. В., Привалов В. A known method of obtaining TEC [RF Patent. JNb 2141976. A method of producing thermoplastic elastomers. Glukhovskoy V.S., Litvin Yu.A., Sitnikova V.V., Kulakova K.A., Fil V.G., Kudryavtsev L.D., Molodyka A.V., Privalov V.
A. , Гусев А. В., Навроцкий Ю.В., Степанова И. А. , Опубл. 27. 1 1. 1999]. Термоэластопласты получают путем блок - сополимеризации стирола или а - метилстирола и диена в среде органического растворителя под действием первичного литийорганического инициатора в присутствии модификатора - метил-трет.-бутилового эфира. В качестве первичного литийорганического инициатора используют растворимый в углеводородных растворителях комплекс, получаемый взаимодействием хлористого этила с дисперсией лития в молярном соотношении 1 :2,05-2,10 соответственно при температуре 323 - ЗЗЗК с последующим введением в реакционную массу мономера. Мономер выбран из группы: этилен, бутадиен, изопрен, пиперилен, стирол или смесь бутадиена со стиролом, при молярном соотношении мономер из группы: этиллитий 0,25 - 1,00: 1 соответственно, при дозировке инициатора 4,5· 10"5 - 1 ,2- 10"4 молей активного лития на 1 г винилароматического мономера при получении термоэластопластов. Способ позволяет сократить время синтеза первого полистирольного или поли-а-метилстирольного блока, снизить расход инициатора. A., Gusev A.V., Navrotsky Yu.V., Stepanova I.A., Publ. 27. 1 1. 1999]. Thermoplastic elastomers are obtained by block copolymerization of styrene or a - methylstyrene and diene in an organic solvent medium under the action of a primary organolithium initiator in the presence of a modifier - methyl tert.-butyl ether. As the primary organolithium initiator, a complex soluble in hydrocarbon solvents is used, obtained by reacting ethyl chloride with lithium dispersion in a molar ratio of 1: 2.05-2.10, respectively, at a temperature of 323 — ZZZK followed by the introduction of monomer into the reaction mass. The monomer is selected from the group: ethylene, butadiene, isoprene, piperylene, styrene or a mixture of butadiene with styrene, with a molar ratio of monomer from the group: ethyl lithium 0.25 - 1.00: 1, respectively, at a dosage of initiator 4.5 · 10 "5 - 1, 2-10 "4 moles of active lithium per 1 g of vinyl aromatic monomer upon receipt of thermoplastic elastomers. The method allows to reduce the synthesis time of the first polystyrene or poly-a-methylstyrene block, to reduce the initiator consumption.
Недостатком известной композиции является многостадийность, трудоем-кость технологического процесса, состоящий из раздельных и не связанных циклов и недостаточные физико - механические свойства для производства технических изделий и деталей, кабельной изоляции и модификаторов асфальто - битумных смесей. A disadvantage of the known composition is multi-stage, labor-intensive technological process, consisting of separate and unrelated cycles and insufficient physical and mechanical properties for the production of technical products and parts, cable insulation and modifiers of asphalt - bitumen mixtures.
Известен способ получения ТЭП [Патент РФ N«2172747. Способ получения термоэластопластов. Глуховской В. С; Литвин Ю. А.; Ситникова В. A known method of obtaining TEC [RF Patent N "2172747. A method of producing thermoplastic elastomers. Glukhovskoy V. S; Litvin Yu. A.; Sitnikova V.
B. ; Филь В. Г.; Митин И. П.; Свиридов С. Н.; Кретинина Е. С; Куликов Е. П.; Гусев А. В.; Привалов В. А.; Рачинский А. В.; Гудков В. В.; Конюшенко В. Д. , Опубл. 27.08.2001]. Синтез разветвленного бутадиен-стирольного термоэластопласта ДСТ-30Р. В аппарат из нержавеющей стали объемом 16 м , снабженный лопастной мешалкой, циркуляционным насосом, термостатирующей рубашкой с теплоносителем, системами подвода инертного газа, растворителя, мономеров, катализатора, подают в токе осушенного азота 7000 л углеводородного растворителя (смесь циклогексана и бензина в соотношении 70:30 мас.ч), содержащего 0,1% метил -трет - бутилового эфира (МТБЭ), дозируют каталитический комплекс, полученный по примеру 1 , в количестве 29,8 л (55 моль по активному литию). После усреднения смеси в течение 15 мин при температуре 298-ЗОЗК подают 460 кг стирола. Полимеризация стирола протекает в адиабатическом режиме с повышением температуры до -313К в течение 20 мин. Конверсия стирола 100%. Затем, в аппарат подают 1020 кг бутадиена, охлажденного до температуры 268К, температура реакционной массы сначала снижается до 281- 283К затем резко возрастает до 368-375К в течение 15-20 мин, полимеризация бутадиена завершается образованием "живущего" двублочного сополимера полистиролполибутадиениллития. Через 10-15 мин после достижения максимальной температуры в аппарат подают полифункциональный сочетающий агент - 2,8 кг тетраэтоксисилана, реакцию сочетания двублочных сополимеров проводят в течение 20 мин, направляют полимеризат в усреднитель и после стабилизации выделяют полимер методом водной дегазации. Указанный способ является многостадийным процессом, что приводит к высокой себестоимости ДСТ-30Р. Физико - механические показатели свойств, полученного разветвленного ДСТ-ЗОР испытывают по стандартным методикам. B.; Fil V.G .; Mitin I.P .; Sviridov S.N .; Kretinina E. S; Kulikov E.P .; Gusev A.V .; Privalov V.A .; Rachinsky A.V .; Gudkov V.V .; Konyushenko V.D., Publ. 08/27/2001]. Synthesis of branched butadiene-styrene thermoplastic elastomer DST-30R. In a stainless steel apparatus with a volume of 16 m, equipped with a paddle mixer, a circulation pump, a thermostatic jacket with a coolant, inert gas, solvent, monomers, and catalyst supply systems, 7000 l of hydrocarbon solvent is supplied in a stream of dried nitrogen (mixture of cyclohexane and gasoline in a ratio of 70: 30 wt.h) containing 0.1% methyl tert-butyl ether (MTBE), the catalytic complex obtained in example 1 is dosed in an amount of 29.8 l (55 mol by active lithium). After averaging the mixture for 15 minutes at a temperature of 298-CLC, 460 kg of styrene is supplied. Styrene polymerization proceeds in adiabatic mode with an increase in temperature to -313K for 20 minutes. The conversion of styrene is 100%. Then, 1020 kg of butadiene, cooled to a temperature of 268K, is fed into the apparatus, the temperature of the reaction mixture first drops to 281-283K, then sharply increases to 368-375K within 15-20 minutes, butadiene polymerization ends with the formation of a living two-block copolymer of polystyrene-polybutadienyl lithium. 10-15 minutes after reaching the maximum temperature, a multifunctional coupling agent is fed into the apparatus - 2.8 kg of tetraethoxysilane, the combination reaction of two-block copolymers is carried out for 20 minutes, the polymerizate is sent to the averager and, after stabilization, the polymer is isolated by water degassing. The specified method is a multi-stage process, which leads to the high cost of DST-30R. Physico - mechanical indicators of the properties of the branched DST-ZOR are tested according to standard methods.
Наиболее близким к заявленному техническому решению является способ получения динамически вулканизованных ТЭП [Вольфсон С. И. Динамически вулканизованные термоэластопласты. - М.: Наука, 2004,-С. 17-24.- ISBN N°5- 02- 032951-7]- прототип. По данному способу получают ТЭП в прерывном и непрерывном режиме на вальцах или шприц - машинах с последующей экструзией на двухшнековых экструдерах. Достоинством названного способа является совмещение процесса смешение и сшивки с целью получения ТЭП. Недостатком этого способа является много -стадийность технологического процесса и наличие процесса вулканизации, который увеличивает продолжительность технологического процесса. Closest to the claimed technical solution is a method for dynamically vulcanized TEC [Wolfson S. I. Dynamically vulcanized thermoplastic elastomers. - M .: Nauka, 2004, p. 17-24.- ISBN N ° 5-02-032951-7] - prototype. According to this method, TECs are produced in continuous and continuous mode on rollers or syringe machines, followed by extrusion on twin-screw extruders. The advantage of this method is the combination of the mixing and crosslinking process in order to obtain TEC. The disadvantage of this method is the multi-stage process and the presence of a vulcanization process, which increases the duration of the process.
Существенным отличием предлагаемого изобретения является исполь - зование двухшнекового экструдера для получения ТЭП, одностадийность и сокращение продолжительности технологического процесса, отсутствие про- цесса вулканизации при переработке композиций и использование модифици - рованных регенератов резины. A significant difference of the present invention is the use of a twin - screw extruder for the production of TEC, one - stage and reduction of the duration of the technological process, the absence of vulcanization during the processing of compositions and the use of modified rubber regenerates.
Предложенный способ получения композиций позволяет достичь высокого технического результата при заявляемом использовании механохимической поли-меризации ПО или ПК с бутадиен стирольным каучуком, а именно сократить продолжительность технологического процесса полимеризации за счет одно -стадийности процесса производства ТЭП . Пример 1-6. (способ получения ТЭП по прототипу). В бункер основного экструдера для смешения загружают 20,0 мае. ч ПО (ПЭВД или ПК); 40,5-52,5 мае. ч модифицированного ПАРР вводят в высокоскоростной смеситель - агломератор и смешивают при скорости вращения ротора агломератора 2000 об/мин; Полученную смесь загружают в бункер основного экструдера и с 25,0- 35,0 мае. ч БСК или СКЭПТ экструдируют при скорости вращения шнеков 40- 50 об/мин (рецептура композиций представлена в таблице 1); Температуры зоны загрузки (Т3 = 353-363 К); температуры зоны пластикации -2-9 зоны ( Тп = 373-413К), температуры фильеры (Тф = 433-453К), давления головки (Р = 7-12 МПа), направление шнеков -односторонее. Грануляцию проводят при скорости вращения привода ножа 15-20 об/мин. ротора гранулирующей головки. Модификацию поверхности ПРР проводят в агломераторе введением 0,5 мае. ч КОЖ от массы ПРР. Объемную модификацию ПРР проводят в агломераторе введением 3,0 мае. ч ДОФ от массы ПРР. Состав вулканизующей группы представлен в табл.2. Из полученных композиций, прямым прессованием получают образцы для испытаний физико - механических свойств композиций при Т=473-483К и Р=100кг/см2. Результаты измерений физико - механических показателей композиций и продолжительности технологического цикла (τ) представлены в таблице 3. The proposed method for producing compositions allows to achieve a high technical result with the claimed use of mechanochemical polymerization of PO or PC with styrene butadiene rubber, namely, to reduce the duration of the polymerization process due to the one-stage process of manufacturing TEC. Example 1-6. (a method of obtaining TEC according to the prototype). May 20.0 is loaded into the hopper of the main extruder for mixing. h software (LDPE or PC); May 40.5-52.5. h of modified PARP is introduced into a high-speed agglomerator mixer and mixed at a speed of rotation of the agglomerator rotor of 2000 rpm; The resulting mixture is loaded into the hopper of the main extruder and from May 25.0 to 35.0. h BSK or SKEPT extruded at a screw speed of 40-50 rpm (the formulation of the compositions are presented in table 1); The temperature of the loading zone (T 3 = 353-363 K); the temperature of the plasticization zone is 2–9 zones (T p = 373-413K), the temperature of the die (T f = 433-453K), the pressure of the head (P = 7-12 MPa), the direction of the screws is one-sided. Granulation is carried out at a rotational speed of the knife drive of 15-20 rpm. granulating head rotor. Surface modification of PRR is carried out in an agglomerator by the introduction of May 0.5. h SKIN by weight of PRR. Volumetric modification of the PRR is carried out in the sinter by the introduction of May 3.0. h DOF by weight of PRR. The composition of the vulcanizing group is presented in table.2. Samples for testing the physicomechanical properties of the compositions at T = 473-483K and P = 100kg / cm 2 are obtained from the obtained compositions by direct compression. The measurement results of the physico - mechanical parameters of the compositions and the duration of the technological cycle (τ) are presented in table 3.
Таблица 1- Рецептура композиций по прототипу и предлагаемому способу Table 1 - Formulation of the compositions of the prototype and the proposed method
Таблица 2 - Рецептура вулканизующих систем на 100 мае, ч. СК +ПРРTable 2 - The recipe for vulcanizing systems on May 100, h. SK + PRR
Компоненты мае. ч. Components May. hours
ZnO 1,80 ZnO 1.80
Сера 0,70 Sulfur 0.70
Стеариновая кислота 0,75 Stearic acid 0.75
Тиурам Д 0,55 Tiuram D 0.55
Альтакс 0,20 Altax 0.20
Перекись бензоила 0,25 Таблица 3. Технологический режим механохимической полимеризации ТЭП и их физико - механические свойства на двухшнековом экструдере с L/d = 30 Benzoyl Peroxide 0.25 Table 3. Technological regime of mechanochemical polymerization of TEC and their physical and mechanical properties on a twin-screw extruder with L / d = 30
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| EP1338619A1 (en) * | 2002-02-26 | 2003-08-27 | Mitsui Chemicals, Inc. | Method for manufacturing olefinic thermoplastic elastomer composition |
| RU2276167C1 (en) * | 2005-03-18 | 2006-05-10 | Открытое акционерное общество Научно-производственное объединение "КОМПОЗИТНЫЕ МАТЕРИАЛЫ" | Thermoplastic elastomeric composition and method for its preparing |
| RU2431641C2 (en) * | 2009-11-11 | 2011-10-20 | Институт Катализа Им. Г.К. Борескова Сибирского Отделения Российской Академии Наук | Method of producing modified rubber mixtures |
-
2013
- 2013-03-14 WO PCT/KZ2013/000003 patent/WO2014142637A1/en not_active Ceased
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2139893C1 (en) * | 1997-10-07 | 1999-10-20 | Государственное унитарное предприятие Научно-исследовательский институт синтетического каучука им.акад.С.В.Лебедева | Method of preparing thermoplastoelastic material |
| EP1338619A1 (en) * | 2002-02-26 | 2003-08-27 | Mitsui Chemicals, Inc. | Method for manufacturing olefinic thermoplastic elastomer composition |
| RU2276167C1 (en) * | 2005-03-18 | 2006-05-10 | Открытое акционерное общество Научно-производственное объединение "КОМПОЗИТНЫЕ МАТЕРИАЛЫ" | Thermoplastic elastomeric composition and method for its preparing |
| RU2431641C2 (en) * | 2009-11-11 | 2011-10-20 | Институт Катализа Им. Г.К. Борескова Сибирского Отделения Российской Академии Наук | Method of producing modified rubber mixtures |
Non-Patent Citations (1)
| Title |
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| VOLFSON SI .: "Dinamicheski vulkanizovannye termoelastoplasty.", POLUCHENIE, PERERABOTKA, SVOISTVA. M., NAUKA, 2004, pages 17 - 24 * |
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