RU2028319C1 - Polymethyl-1-methylenesiloxy-4,4′-dipyridylium chloride of copper (ii) acetate (cobalt ii) as a modifying addition to the rubber mixture on the basis of nonpolar, unsaturated, carbon-chain rubbers - Google Patents
Polymethyl-1-methylenesiloxy-4,4′-dipyridylium chloride of copper (ii) acetate (cobalt ii) as a modifying addition to the rubber mixture on the basis of nonpolar, unsaturated, carbon-chain rubbers Download PDFInfo
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- RU2028319C1 RU2028319C1 SU5036358A RU2028319C1 RU 2028319 C1 RU2028319 C1 RU 2028319C1 SU 5036358 A SU5036358 A SU 5036358A RU 2028319 C1 RU2028319 C1 RU 2028319C1
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- copper
- cobalt
- acetate
- dipyridylium
- chloride
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- 230000000051 modifying effect Effects 0.000 title claims abstract description 9
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 title claims abstract 8
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract 3
- 239000010941 cobalt Substances 0.000 title claims abstract 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract 3
- 229920001971 elastomer Polymers 0.000 title claims description 12
- 239000005060 rubber Substances 0.000 title claims description 12
- 239000000203 mixture Substances 0.000 title claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 title abstract description 3
- 239000010949 copper Substances 0.000 claims description 7
- 239000000654 additive Substances 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 230000000996 additive effect Effects 0.000 claims description 4
- 230000004048 modification Effects 0.000 claims description 2
- 238000012986 modification Methods 0.000 claims description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims 2
- 239000000126 substance Substances 0.000 abstract description 8
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical compound [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 abstract description 7
- 239000002244 precipitate Substances 0.000 abstract description 5
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 abstract description 4
- MWVTWFVJZLCBMC-UHFFFAOYSA-N 4,4'-bipyridine Chemical group C1=NC=CC(C=2C=CN=CC=2)=C1 MWVTWFVJZLCBMC-UHFFFAOYSA-N 0.000 abstract description 3
- 229920000642 polymer Polymers 0.000 abstract description 3
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 abstract description 2
- 230000003993 interaction Effects 0.000 abstract description 2
- 238000001556 precipitation Methods 0.000 abstract description 2
- 238000005406 washing Methods 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 229940043232 butyl acetate Drugs 0.000 abstract 1
- 230000000694 effects Effects 0.000 abstract 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 abstract 1
- 238000002844 melting Methods 0.000 abstract 1
- 230000008018 melting Effects 0.000 abstract 1
- 238000000034 method Methods 0.000 abstract 1
- 150000002894 organic compounds Chemical class 0.000 abstract 1
- 239000000047 product Substances 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- MBEBBSNWIOVTHQ-UHFFFAOYSA-M copper;acetate Chemical compound [Cu+2].CC([O-])=O MBEBBSNWIOVTHQ-UHFFFAOYSA-M 0.000 description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229940011182 cobalt acetate Drugs 0.000 description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 2
- 238000010668 complexation reaction Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- SVMCDCBHSKARBQ-UHFFFAOYSA-N acetic acid;cobalt Chemical compound [Co].CC(O)=O SVMCDCBHSKARBQ-UHFFFAOYSA-N 0.000 description 1
- QSYBDNNHWODCCJ-UHFFFAOYSA-N buta-1,3-diene;prop-1-en-2-ylbenzene Chemical compound C=CC=C.CC(=C)C1=CC=CC=C1 QSYBDNNHWODCCJ-UHFFFAOYSA-N 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
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Abstract
Description
Изобретение относится к новым химическим соединениям, а именно полиметил-1-метиленсилокси-4,4'-дипиридилийхлорид уксуснокислой меди (II) и полиметил-1-метиленсилокси-4,4' -дипиридилийхлорид уксуснокислого кобальта (II), общей формулы
В промышленности в качестве модифицирующей добавки используют диафен ФП (1), который обладает недостаточными модифицирующими свойствами и покупается за рубежом. In industry, the FP diaphhen is used as a modifying additive (1), which has insufficient modifying properties and is bought abroad.
Целью изобретения является получение новых модифицирующих добавок, обеспечивающих повышение модифицирующих свойств вулканизированных резиновых смесей. The aim of the invention is to obtain new modifying additives, providing an increase in the modifying properties of vulcanized rubber compounds.
Эта задача решается веществами общей формулы:
Эти вещества получают путем сплавления олигохлорметил(метил)силоксана с избытком 4,4'-дипиридила с последующим высаживанием и промыванием образовавшегося осадка полимера горячим бутилацетатом и взаимодействия полученного дипиридилиевого силоксана с уксуснокислой медью (II) (вещество I) и кобальта (II) (вещество 2) в этанольном растворе. These substances are obtained by fusion of oligochloromethyl (methyl) siloxane with an excess of 4,4'-dipyridyl followed by precipitation and washing of the resulting polymer precipitate with hot butyl acetate and the interaction of the obtained dipyridylium siloxane with copper acetate (II) (substance I) and cobalt (II) (substance 2) in ethanol solution.
Сравнение ИК-спектров дипиридилиевого силоксана и его комплексов показало, что группы (Si-0), (Si-CH3) не принимают участие в комплексообразовании. Существенное изменение наблюдается в характере поглощения дипиридилиевых групп. При координировании металлов полоса валентных колебаний СН-групп (3030 см-1) смешается на 10-13 см-1 в область длинноволнового поглощения, происходит расщепление синглета их деформационных колебаний (713 см-1) в дуплет (716, 724 см-1). Скелетные колебания пиридиниевых и пиридиновых колец представлены группой полос в области 1639-1520 см-1. Комплексообразование приводит к изменению их интенсивности и сдвигу полос 1639 и 1520 на 8-10 см-1 в короткочастотную область спектра, а полосы 1600 на 13 см-1 в высокочастотную.A comparison of the IR spectra of dipyridylium siloxane and its complexes showed that the groups (Si-0), (Si-CH 3 ) do not participate in complexation. A significant change is observed in the nature of the absorption of dipyridylium groups. When metals are coordinated, the stretching vibration band of CH groups (3030 cm -1 ) is mixed by 10-13 cm -1 in the long-wavelength absorption region, the singlet of their deformation vibrations (713 cm -1 ) splits into a doublet (716, 724 cm-1) . Skeletal vibrations of pyridinium and pyridine rings are represented by a group of bands in the region of 1639-1520 cm -1 . Complexation leads to a change in their intensity and a shift of the bands 1639 and 1520 by 8-10 cm -1 to the short-frequency region of the spectrum, and the bands 1600 by 13 cm -1 to the high-frequency.
Вычислено, % : С 42,76; Н 4,93; О 17,80; N 6,23; Сl 7,89; Si 6,24; Сu 14,14. Calculated,%: C 42.76; H 4.93; About 17.80; N, 6.23; Cl 7.89; Si 6.24; Cu 14.14.
С16Н22О5N2ClSiCu.C 16 H 22 O 5 N 2 ClSiCu.
Найдено, % : С 42,96; Н 5,03; О 17,66; N 6,86; Сl 7,57; Si 6,31; Сu 14,23. Found,%: C 42.96; H 5.03; O 17.66; N, 6.86; Cl 7.57; Si 6.31; Cu 14.23.
Вычислено, % : С 37,40; Н 6,30; О 28,02; N 5,54; Сl 6,90; Si 5,46; Со 11,47;
С16Н27О9N2ClSiCo.Calculated,%: C 37.40; H, 6.30; O 28.02; N 5.54; Cl 6.90; Si 5.46; C 11.47;
C 16 H 27 O 9 N 2 ClSiCo.
Найдено, % : С 37,91; Н 5,22; О 27,98; N 5,40; Сl 5,99; Si 5,15; Со 11,11. Found,%: C 37.91; H 5.22; About 27.98; N, 5.40; Cl 5.99; Si 5.15; C 11.11.
Изобретение иллюстрируется следующими примерами. The invention is illustrated by the following examples.
В стеклянных ампулах запаивают по 2 г (1,84 мэкв) олигохлорметилметил)силоксана/кинематическая вязкость по ВПЖ-1 1,39х103мм/с, nD 20 = 1,4645, Мn = 1500 (определена на эбулиографе ЭП-68 в хлороформе) и 8,51 (5,52 мэкв) 4,4'-дипиридила (с т. пл. 114оС). Реакцию проводят в течение 0,5 ч при 115оС. После окончания реакции смесь высаживают в 100-150 мл бутилацетата. Для удаления исходных мономеров осадок полимера промывают горячим (50-60оС) бутилацетатом. Сушат в вакууме при 60оС до постоянного веса.In glass ampoules, 2 g (1.84 meq) of oligochloromethylmethyl) siloxane / kinematic viscosity according to VPZh-1 1.39 × 10 3 mm / s, n D 20 = 1.4645, Mn = 1500 (determined on an EP-68 euliograph chloroform) and 8.51 (5.52 meq) of 4,4'-dipyridyl (mp mp 114 ° C). The reaction is carried out for 0.5 h at 115 about C. After the reaction is complete, the mixture is planted in 100-150 ml of butyl acetate. To remove the starting monomers of the polymer precipitate was washed with hot (50-60 ° C) with butyl acetate. Dry in vacuo at 60 C to constant weight.
Навеску 1 г дипиридилиевого силоксана - полиметил-1-метиленсилокси-4,4'-дипиридилийхлорида растворяют в 20-25 мл этанола и приливают к раствору 3-кратного эквивалента ацетата меди или кобальта, находящегося в колбе Эрленмейера с магнитной мешалкой. Наблюдается выделение обильного творожистого осадка (вещество 1,2), его отфильтровывают и промывают небольшими порциями этанола для удаления избытка ионов ацетата меди или кобальта. Сушат в вакууме при 60оС до постоянной массы.A portion of 1 g of dipyridylium siloxane - polymethyl-1-methylenzyloxy-4,4'-dipyridyl chloride is dissolved in 20-25 ml of ethanol and added to a solution of 3 times the equivalent of copper or cobalt acetate in an Erlenmeyer flask with a magnetic stirrer. A copious precipitate of cheesy precipitate is observed (substance 1.2), it is filtered off and washed with small portions of ethanol to remove excess copper or cobalt acetate ions. Dry in vacuo at 60 C to constant weight.
Выход: вещество 1 93%
вещество 2 100%.Yield:
Модификация эластомерных композиций. Modification of elastomeric compositions.
Резиновые смеси готовят в лабораторном резиносмесителе со скоростью вращения роторов 30 об/мин и объемом смесительной камеры 2х10-3 м3. Серу вводят на лабораторных вальцах. Модифицирующие добавки вводят совместно с сыпучими ингредиентами.Rubber compounds are prepared in a laboratory rubber mixer with a rotor speed of 30 rpm and a mixing chamber volume of 2x10 -3 m 3 . Sulfur is introduced on a laboratory roll. Modifying additives are administered in conjunction with bulk ingredients.
Резиновые смеси вулканизуют в электропрессе при температуре 142±2оС.Rubber mixture in a machine for vulcanized at a temperature of 142 ± 2 ° C.
Для проведения испытаний свойств резиновых смесей были изготовлены по известной технологии составы, приведенные в табл.1,2. To test the properties of rubber compounds, the compositions shown in Table 1.2 were made according to the well-known technology.
Затем по ГОСТ 269-86 были проведены испытания вулканизатов, результатов испытаний физико-механических свойств приведены в табл.3,4. Then, according to GOST 269-86, tests of vulcanizates were carried out, the results of tests of physical and mechanical properties are given in Table 3.4.
Claims (1)
где n=14;
Mt=Cu2 +, Co2 +,
в качестве модифицирующей добавки в резиновые смеси на основе неполярных, ненасыщенных, карбоцепных каучуков.Copper (II) (cobalt (II) poly (methyl) 1-methylenzyloxy-4,4 1- dipyridyl chloride of copper (II) acetate
where n = 14;
Mt = Cu 2 + , Co 2 + ,
as a modifying additive in rubber compounds based on non-polar, unsaturated, carbochain rubbers.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| SU5036358 RU2028319C1 (en) | 1992-02-11 | 1992-02-11 | Polymethyl-1-methylenesiloxy-4,4′-dipyridylium chloride of copper (ii) acetate (cobalt ii) as a modifying addition to the rubber mixture on the basis of nonpolar, unsaturated, carbon-chain rubbers |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| SU5036358 RU2028319C1 (en) | 1992-02-11 | 1992-02-11 | Polymethyl-1-methylenesiloxy-4,4′-dipyridylium chloride of copper (ii) acetate (cobalt ii) as a modifying addition to the rubber mixture on the basis of nonpolar, unsaturated, carbon-chain rubbers |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| RU2028319C1 true RU2028319C1 (en) | 1995-02-09 |
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| SU5036358 RU2028319C1 (en) | 1992-02-11 | 1992-02-11 | Polymethyl-1-methylenesiloxy-4,4′-dipyridylium chloride of copper (ii) acetate (cobalt ii) as a modifying addition to the rubber mixture on the basis of nonpolar, unsaturated, carbon-chain rubbers |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2149879C1 (en) * | 1995-09-28 | 2000-05-27 | Вакер-Хеми ГмбХ | Mesoscopic organopolysiloxane particles with chemically bound metal compounds |
| RU2390533C2 (en) * | 2008-04-15 | 2010-05-27 | Общество с ограниченной ответственностью "Совтех" | Processing additive for rubber mixtures based on carbon-chain rubber |
-
1992
- 1992-02-11 RU SU5036358 patent/RU2028319C1/en active
Non-Patent Citations (1)
| Title |
|---|
| Химические добавки к полимерам. Справочник, 2-е издание. М.: Химия, 1981, с.24,25. * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2149879C1 (en) * | 1995-09-28 | 2000-05-27 | Вакер-Хеми ГмбХ | Mesoscopic organopolysiloxane particles with chemically bound metal compounds |
| RU2390533C2 (en) * | 2008-04-15 | 2010-05-27 | Общество с ограниченной ответственностью "Совтех" | Processing additive for rubber mixtures based on carbon-chain rubber |
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