RU2690169C2 - Polymer protective composition - Google Patents
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- RU2690169C2 RU2690169C2 RU2016152679A RU2016152679A RU2690169C2 RU 2690169 C2 RU2690169 C2 RU 2690169C2 RU 2016152679 A RU2016152679 A RU 2016152679A RU 2016152679 A RU2016152679 A RU 2016152679A RU 2690169 C2 RU2690169 C2 RU 2690169C2
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3225—Polyamines
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3225—Polyamines
- C08G18/325—Polyamines containing secondary or tertiary amino groups
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3802—Low-molecular-weight compounds having heteroatoms other than oxygen having halogens
- C08G18/3814—Polyamines
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/46—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/46—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen
- C08G18/4615—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/61—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/02—Polyureas
Abstract
Description
Изобретение относится к области химии, а именно: к композиции для получения покрытия, защищающего изделия и конструкции из разных материалов, в том числе, из резины, и обладающего хорошими физико-механическими свойствами (в частности, прочностью при растяжении, адгезией, стойкостью в широком диапазоне температур от минус 50°С до плюс 200°С), а также атмосферостойкостью и стойкостью к воздействию химических агентов - минеральных кислот, щелочей и углеводородных сред.The invention relates to the field of chemistry, namely: to a composition for obtaining a coating, protecting products and structures from different materials, including rubber, and having good physical and mechanical properties (in particular, tensile strength, adhesion, durability in a wide temperature range from minus 50 ° C to plus 200 ° C), as well as weather resistance and resistance to chemical agents - mineral acids, alkalis and hydrocarbon media.
Для оценки новизны заявленного решения рассмотрим ряд известных технических средств аналогичного назначения, характеризуемых совокупностью сходных с заявленным покрытием признаков.To assess the novelty of the claimed solution, we consider a number of well-known technical means of a similar purpose, characterized by a set of features similar to the stated coverage.
Известна композиция по патенту РФ №2440374 для покрытия на основе полимочевины, полученной из реакционной смеси, которая содержит изоцианат, (мет)акрилированный амин и, дополнительно, амин как продукт реакции между полиамином и полиэпоксидом. Введение эпоксигрупп увеличивает адгезию покрытия и его стойкость в химических средах. Однако из-за высокого уровня реакционной способности между компонентами время жизнеспособности композиции ограничено. Полимочевинная композиция по патенту РФ №2571136 включает, кроме полиизоцианата, изоцианатсилан или метакрилосилан. Композиция имеет низкую вязкость, что позволяет улучшить ее текучесть, а покрытия получают повышенную адгезию. Но отмечено снижение эффективности в обеспечении надежности защиты, низкая прочность при длительном воздействии ультрафиолетового облучения и влаги.Known composition according to the patent of Russian Federation №2440374 for coating on the basis of polyurea, obtained from the reaction mixture, which contains isocyanate, (meth) acrylated amine and, additionally, amine as a reaction product between polyamine and polyepoxide. The introduction of epoxy groups increases the adhesion of the coating and its durability in chemical environments. However, due to the high level of reactivity between the components, the pot life of the composition is limited. The polyurea composition according to the patent of the Russian Federation No. 2571136 includes, in addition to the polyisocyanate, isocyanatesilane or methacrylosilane. The composition has a low viscosity, which allows it to improve its fluidity, and coatings receive increased adhesion. But there was a decrease in efficiency in ensuring the reliability of protection, low durability with prolonged exposure to ultraviolet radiation and moisture.
Известно покрытие по патенту РФ №2448986 на основе полимочевины, полученной из реакционной смеси, содержащей изоцианат, амин(мет)акрилатный олигомерный продукт реакции между полиамином, поли(мет)акрилатом и моно(мет)акрилатом, которое обладает коррозионной стойкостью, ударопрочностью и структурной целостностью.Known coating on the patent of the Russian Federation No. 2448986 based on polyurea obtained from the reaction mixture containing isocyanate, amine (meth) acrylate oligomeric reaction product between polyamine, poly (meth) acrylate and mono (meth) acrylate, which has corrosion resistance, impact resistance and structural integrity.
Все полимочевинные системы являются двухкомпонентными. Скорость реакции между компонентами может составлять 2-1000 секунд в зависимости от состава, условий синтеза и других обстоятельств. Этим временем ограничена жизнеспособность композиции. Поэтому способ получения полимочевины и ее нанесения базируется на использовании специальных установок высокого давления с двухкомпонентным дозатором, позволяющих одновременное, равномерное, но раздельное распыление обоих компонентов.All polyurea systems are two-component. The reaction rate between the components can be 2-1000 seconds, depending on the composition, synthesis conditions and other circumstances. This time is limited by the viability of the composition. Therefore, the method of producing polyurea and its application is based on the use of special high-pressure installations with a two-component dispenser, which allow simultaneous, uniform, but separate spraying of both components.
В последнее время разработаны полимочевинные композиции «ручного нанесения», состоящие из фторполимера на основе изоцианата и отвердителя полиаспартического типа, отличающиеся тем, что, являясь достаточно реакционноспособными, обеспечивают более длительную жизнеспособность реакционной смеси, иногда до 1 часа. Это позволяет производить нанесение композиции с помощью валиков, кистей или распылителями, не требующими раздельного распыления обоих компонентов мочевинной композиции. Так, в патенте РФ №2411256 рассмотрен способ получения (мет)акрилат/аспартатного аминового отвердителя, описаны полимочевинная композиция «ручного нанесения», содержащая продукт реакции между полученным отвердителем и изоцианатом, а также покрытия на основе этой композиции. Эти покрытия характеризуются стойкостью к коррозии, воздействию химических веществ, ультрафиолетового излучения, нагревания и других факторов окружающей среды.Recently, “manual deposition” polyurea compositions have been developed, consisting of an isocyanate-based fluoropolymer and a polyaspartic type hardener, characterized in that, being sufficiently reactive, they provide a longer viability of the reaction mixture, sometimes up to 1 hour. This allows the composition to be applied using rollers, brushes or sprays that do not require separate spraying of both components of the urea composition. Thus, in the patent of the Russian Federation No. 2411256 a method for the preparation of (meth) acrylate / aspartate amine hardener is described, a “manual deposition” polyurea composition containing the reaction product between the obtained hardener and isocyanate, as well as coatings based on this composition are described. These coatings are characterized by resistance to corrosion, chemicals, ultraviolet radiation, heat and other environmental factors.
Эта полимочевинная композиция принята в качестве прототипа заявленного изобретения.This polyurea composition is adopted as the prototype of the claimed invention.
Задача изобретения заключается в создании композитного покрытия, обладающего хорошей адгезией к различным материалам, в том числе, к резине, повышенной эластичностью, атмосферостойкостью и стойкостью к действию химических агентов - минеральных кислот, щелочей, углеводородных сред.The objective of the invention is to create a composite coating with good adhesion to various materials, including rubber, high elasticity, weather resistance and resistance to the action of chemical agents - mineral acids, alkalis, hydrocarbon media.
Согласно изобретению полимерная защитная композиция, состоящая из полимочевинной двухкомпонентной композиции «ручного нанесения», характеризуется тем, что в нее дополнительно введена модифицирующая добавка, в качестве которой использован полидиметилфенилсилоксан (ПДМФС) в количестве 15-30 масс. %.According to the invention, a polymeric protective composition consisting of a polyurea two-component “manual deposition” composition is characterized by the fact that a modifying additive is additionally introduced in it, in which polydimethylphenylsiloxane (PDMFS) is used in an amount of 15-30 wt. %
Заявленная совокупность существенных признаков обеспечивает достижения технического результата, заключающегося в том, что покрытия из заявленной композиции на основе полимочевины с дополнительным содержанием ПДМФС имеют улучшенную адгезию, повышенную эластичность, твердость и термостойкость по сравнению с покрытиями из чистой полимочевины. Образующиеся в цепи полимера полимочевинные связи обеспечивают покрытиям высокие показатели, выгодно отличающие их от покрытий на основе пленкообразующих других классов - эпоксидных, полиэфирных, акриловых и пр. Исследование взаимосвязи между реакционными составами, условиями синтеза, строением и свойствами получаемого мочевинно-силоксанового композита показали возможность образования гибридных полимочевинных систем, содержащих дополнительно элементы кремнийорганических полимеров. Синтез композитных полимочевинно-силоксановых гибридов позволяет направленно улучшать механические и физико-химические свойства покрытий.The claimed set of essential features ensures the achievement of the technical result, namely, that the coatings of the claimed composition based on polyurea with an additional content of PDMFS have improved adhesion, increased elasticity, hardness and heat resistance compared to pure polyurea coatings. Polyurea bonds formed in the polymer chain provide coatings with high indicators that favorably distinguish them from coatings based on film-forming other classes - epoxy, polyester, acrylic, etc. The study of the relationship between the reaction compositions, synthesis conditions, the structure and properties of the resulting urea-siloxane composite showed the possibility of hybrid polyurea systems containing additionally elements of organosilicon polymers. Synthesis of composite polyurea-siloxane hybrids allows you to purposefully improve the mechanical and physicochemical properties of coatings.
Заявленную полимерную защитную композицию получают путем введения в полимочевинную композицию «ручного нанесения» при интенсивном механическом перемешивании полидиметилфенилсилоксана (ПДМФС) в количестве 15-30% от массы полимочевинной композиции, после чего результирующую полимерную композицию выдерживают под вакуумом в течение 2-5 мин. для удаления пузырей.The stated polymer protective composition is obtained by introducing into the polyurea composition a “manual deposition” with intensive mechanical stirring of polydimethylphenylsiloxane (PDMP) in an amount of 15-30% by weight of the polyurea composition, after which the resulting polymer composition is kept under vacuum for 2-5 minutes. to remove bubbles.
Композиция на защищаемые покрытия наносится методами лакокрасочной технологии - валиком, кистью, пульверизатором. Отверждение покрытий проводится по одному из двух режимов: 1- холодное отверждение (х/о) при температуре окружающего воздуха; до начала испытаний или эксплуатации покрытий рекомендуется их выдержка не менее 3-х суток; 2 - горячее отверждение (г/о) при температуре 120°С в течение 4 часов.The composition on the protected coating is applied by the methods of paint and varnish technology - roller, brush, spray. Curing of coatings is carried out in one of two modes: 1 - cold curing (x / o) at ambient temperature; prior to the start of testing or operation of coatings, their exposure for at least 3 days is recommended; 2 - hot curing (g / o) at a temperature of 120 ° C for 4 hours.
В табл.1 приведены составы композиций, подтверждающие указанные пределы содержания ПДМФС результатами испытаний. Испытания проведены по утвержденным методикам: адгезия (балл) - ГОСТ15140, метод решетчатых надрезов; жизнеспособность (мин) - ГОСТ 27890; прочность при изгибе (мм) - ГОСТ 6806; твердость по маятниковому прибору типа ТМЛ (отн. ед) - ГОСТ 5233; термостойкость - ГОСТ 9406; относительное удлинение(%), предел прочности при разрыве (МПа) - ГОСТ18299; маслостойкость (%) - ГОСТ IEC60811-2-1.Table 1 shows the compositions, confirming the specified limits of the content of PDMFS test results. Tests were carried out according to approved methods: adhesion (point) - GOST15140, the method of lattice cuts; viability (min) - GOST 27890; flexural strength (mm) - GOST 6806; the hardness of the pendulum device type TML (Rel. units) - GOST 5233; heat resistance - GOST 9406; relative elongation (%), tensile strength at break (MPa) - GOST 18299; oil resistance (%) - GOST IEC60811-2-1.
Данные табл. 2 характеризуют свойства резины В-14-1-НТА без покрытия и с покрытием из предлагаемой полимерной защитной композиции состава №3 (см. табл. 1) при испытаниях в разных условиях старения. Старение образцов резины при испытании механических свойств проведено при температуре 100°С в течение 72 часов. При определении маслостойкости использованы минеральные масла IRM 901 и IRM 903. Степень набухания и объемный износ оценены после выдержки образцов в минеральных средах в течение 72 часов.The data table. 2 characterize the properties of rubber B-14-1-NTA without coating and with a coating of the proposed polymer protective composition of composition No. 3 (see Table 1) when tested in different aging conditions. Aging of rubber samples when testing mechanical properties was carried out at a temperature of 100 ° C for 72 hours. In determining the oil resistance, mineral oils IRM 901 and IRM 903 were used. The degree of swelling and volumetric wear were evaluated after exposure of the samples in mineral media for 72 hours.
Результаты испытаний свидетельствуют, что покрытия из полимерной защитной композиции по предлагаемому изобретению на основе полимочевинной композиции «ручного нанесения» с дополнительным содержанием ПДМФС имеют улучшенную адгезию, повышенную эластичность, твердость и термостойкость по сравнению с покрытиями из чистой полимочевинной. Отмеченное влияние отразилось на свойствах образцов резины В-14-1-НТА, покрытых заявляемой полимерной защитной композицией: повысилась прочность при растяжении после термостарения, уменьшилась степень набухания в углеводородных средах.The test results show that the coatings of the polymeric protective composition according to the invention based on the “manual application” polyurea composition with an additional content of PDMP have improved adhesion, increased elasticity, hardness and heat resistance compared to pure polyurea coatings. This effect affected the properties of rubber specimens B-14-1-NTA coated with the inventive polymer protective composition: the tensile strength after thermal aging increased, the degree of swelling in hydrocarbon media decreased.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007003264A2 (en) * | 2005-07-02 | 2007-01-11 | Lanxess Deutschland Gmbh | Polyaspartic acid derivatives in covering agents containing polysiloxane |
| WO2009143003A1 (en) * | 2008-05-19 | 2009-11-26 | Ppg Industries Ohio, Inc. | Coating compositions comprising polyurea and a polysiloxane |
| RU2411256C1 (en) * | 2006-12-18 | 2011-02-10 | Ппг Индастриз Огайо, Инк. | Acrylate/aspartate amine curing agents and coatings and articles containing same |
| RU2012117800A (en) * | 2009-09-29 | 2013-11-10 | Ппг Индастриз Огайо, Инк. | SUBSTRATES COVERED BY TRANSPARENT FILM-FORMING POLYOREA COMPOSITIONS |
-
2016
- 2016-12-29 RU RU2016152679A patent/RU2690169C2/en not_active Application Discontinuation
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007003264A2 (en) * | 2005-07-02 | 2007-01-11 | Lanxess Deutschland Gmbh | Polyaspartic acid derivatives in covering agents containing polysiloxane |
| RU2411256C1 (en) * | 2006-12-18 | 2011-02-10 | Ппг Индастриз Огайо, Инк. | Acrylate/aspartate amine curing agents and coatings and articles containing same |
| WO2009143003A1 (en) * | 2008-05-19 | 2009-11-26 | Ppg Industries Ohio, Inc. | Coating compositions comprising polyurea and a polysiloxane |
| RU2012117800A (en) * | 2009-09-29 | 2013-11-10 | Ппг Индастриз Огайо, Инк. | SUBSTRATES COVERED BY TRANSPARENT FILM-FORMING POLYOREA COMPOSITIONS |
Also Published As
| Publication number | Publication date |
|---|---|
| RU2016152679A (en) | 2018-07-02 |
| RU2016152679A3 (en) | 2018-07-02 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FA92 | Acknowledgement of application withdrawn (lack of supplementary materials submitted) |
Effective date: 20180731 |
|
| FZ9A | Application not withdrawn (correction of the notice of withdrawal) |
Effective date: 20180731 |