• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    Disclosed are silicon-containing nitro dyes for dying organic polymers or organosiloxanes, which are reactive dyes for synthetic or natural fibers of vegetable or animal origin, having the formula: <IMAGE> wherein the chromophore component is bonded with the Si-atom by homopolar bonds and wherein X represents the same or different hydrolyzable groups or a siloxane radical, Z is a bivalent alkylene radical with 1-10 carbon atoms which may be interrupted by NR' groups, R is a monovalent organic radical, R' is hydrogen, alkyl with 1-10 carbon atoms, aryl, aralkyl or said substituted radicals, Ar is a substituted or unsubstituted aryl radical, and a and b are integers from 1-3, and a process for making said dyes. Said dyes may be built into a large number of organic and inorganic molecules and color the same without fixation.
    公开号:SU1017706A1
    申请号:SU797770488
    申请日:1979-03-07
    公开日:1983-05-15
    发明作者:Бодо Хирш；Гюнтер Хорн；Хеллмут Реутер
    申请人:Феб Хемиверк Нюнхритц Форшунгсштелле Радебеул (Инопредприятие)；
    IPC主号:
    专利说明:

    The invention relates to silicon-containing nitro colorants for dyeing polymeric organic compounds, in particular for dyeing silicone products, as well as inorganic materials and reactive dyes for synthetic or natural fibers of plant or animal origin. Dyes can be incorporated into the polymer molecule or deposited on the fibers without additional fixation.
    The production and use of dyes based on an organic amino silicon compound for dyeing silicone and other polymers is known. Organic siliceous compounds are readily available and are involved in many reactions. For example, it is possible to obtain azo dyes by reacting amino arylalkylsilanes with suitable dye intermediates. For dyeing glass fibers, the surface hydroxyl groups of the glass fibers are first treated with a solution of reactive silane and then with a diazotized solution (US patent specification 2 934 459).
    It is possible to obtain silicon-containing azo dyes by diazotization of amino-arylalkylsilanes, followed by combination with aromatic compounds (description of the invention to US patent 2,927,839).
    Triazine dyes are known, which are obtained by reacting a inoalkylalkoxysilanes with aminoazo-colors and cyanur chloride (U.S. Patent 2,963,338 invented thiazin dyes obtained by oxidizing a mixture of aryl alkanoicaphenylsilane, p-diaminoazobenzene and thiosulfate (description of the invention). , as well as triarylmethane dyes from arylaminoalkylsilane with aryl aldehyde or aryl ketone (patent specification ShA 2 955 899).
    Hemaavi and Jones (I. Soc. Dyers and Colorists 85 (9) 40 (1969); presented anthrazinone dyes that contain an aminoalkylsilyl group.
    In accordance with the specifications of U.S. Patents 3,888,891, 3,963,744, and 3,981,859, silicon-containing dyes must be particularly well compatible with silicones if they contain a tris (trimethylsiloxy) silylalkylamine radical, quinone, indigo, thioindigum as the silicon component phthalocyanine and azo dyes).
    However, the preparation of the known silicon-containing dyes is very expensive as it requires complex working steps. At the same time, silicone functional groups in the starting components are wound for compatibility with other materials, acting as. active groups in the dyeing process. From this it follows that due to the effect of syneresis during curing or crosslinking, for example, of silicone resins, silicone rubbers and other silicone products, these dyes will make their durable coloring difficult.
    Since the tris-trimethylsiloxy-silyl group is no longer capable of reactions with suitable functional groups in polymers, retention of these dyes in the polymer is ensured only by physical nature (without chemical interaction).
    The aim of the invention is to obtain new dyes in a simple manner from readily available starting materials with a good yield. Dye components should, if possible, be bound to the substrate using homeopolar bonds. In terms of their durability, the dyes must meet the requirements of the specific and highest requirements for silicones and must be durable in dyeing of polymeric materials, especially silicone products.
    . Silicon containing nitro dyes of the general formula -, {- (Ji-7-- f X- -2-: S-AT (SQ,}
     u
    3-Ь
    where X is the same or different hydrolyzable groups or a silicone radical;
    Z alkylene radical with 2-10 C-atoms} - "
    IV - monovalent organic
    , radix)} hydrogen, alkyl with 1-10 C-atoms, unsubstituted or substituted aryl, argshyl; 5 ag - substituted sludge not substituted
    aromatic radical; a, b - integers from 1 to 3, can permanently dye polymeric materials, especially SILICONE 0 products, while satisfying such high demands on silicone products as, for example, heat resistance. ;
    Application according to the invention, 5, silicon-containing nitro dyes
    carried out by the simple reaction of .i new or siloxanes of the general formula
     i-z-HHR
    0.h-b

    where X, Z, R.R, b have the indicated values,
    (with a nitro compound of the general formula 5 iHal- r Oj), where ar and a have the above values} Hal is a halogen atom; - the group reacts with the gal nitroaromatic gene and is linked to cleavage of IS1. In most cases, it is enough to simply mix the starting materials at a normal temperature, and the nitroso compounds, which are basically crystalline compounds, dissolve in the silane due to the released heat. Low heat can promote the reaction. The reaction is stoichimetrically, which means that one amino group reacts with one molecule of nitroaromatic compounds. Similar compounds with other substitutes, such as -50 3 H substituents, can also be used as aromatic compounds. Possible substituents are -ROH, -RCH, -CHMN-XOOH, etc. may also be carried out in a solvent, with water and organic solvents being suitable, for example alkanols, toluene or dimethylformamide. The solvent can also be used for the reaction of nitroaromatic compounds with partially condensed polyorganosiloxanes, since siloxane groups are condensed with -Z-NHR-radicals. These products are suitable as tinting pastes for dyeing silicone products. The nitro dyes obtained according to the invention are particularly suitable for dyeing organopolysiloxanes. The concentration of the dye in the silicone polymers may be in the range of 0.1-5% by weight and is preferably chosen between 0.2 and 2% by weight. The nitro dyes according to the invention have the advantage that the dye components are built into the half-dimensional molecule through a homeopoly bond. In principle, the dye itself, by virtue of the groups capable of being hydrolyzed and condensed on the silicon atom, can be polymerized into silicone oil, silicone rubber, or silicone resin, in accordance with the functionality of IC-. coupling connection. Since the functional groups on the silicon atom are retained, then with these; dyes are all possible modifications known to silanes (for example, silicic acids). The nitro dyes obtained according to the invention, embedded by means of a homeopolar bond in a silicone molecule, are thermally stable, only extremely long heating can cause a slight color change from yellow to brownish tones. To organopolysiloxanes dyed with such nitro dyes, ordinary dilutions can be added (extenders, for example, calcium carbonate, zinc oxide, clay, quartz powder, glass or metal fibers, amorphous silicic acid, etc.) complicate the process, the dye does not suffer from this. Nitro dyes obtained according to the invention are active dyes suitable for dyeing — natural or synthetic fibers, such as wool, silk, cotton fiber, regenerated polyamide fibers, polyester fibers, etc., as well as dyeing inorganic materials, for example highly dispersed silicic acid, fiberglass, etc. It is advisable to carry out the staining of the named materials with a dye solution, for example, in water, alcohol or in aromatic compounds by simple immersion followed by rinsing and rinsing. Additional fixation is not required, since reactive groups that are contained in the dye molecule form a homeopolar bond with the substrate. Example 1. In a beaker with a gentle shake, 20.3 parts by weight are mixed. 2,4-dinitrochlorobenzene I 23 weight.h. aminopropyltriethoxysilane. In this case, the mixture is quickly heated and the 2,4-dinitrochlorobenzene is dissolved in the silane with evolution of gas. By cooling to room temperature, a yellow liquid dye of the following t structure is obtained - (CH,), - NH - (,, j to silicone rubber paste, consisting of 100 weight parts polydimethylsiloxane with hydroxyl groups of viscosity 5000 cSt, 50 weight. of amorphous silica and 1 part by weight of water, 2 parts by weight of the dye described are added, 3 parts by weight of a mixture of tin dibutyl diaurate and tetraoxysilane are added to crosslink the rubber paste. This results in silicone rubber which is intensely colored in yellow the color that is subjected to warming up for at 24 hours the color does not change.If the silicone rubber paste without the addition of cross-links, its agent only partially condenses with the dye, then it is possible to use the product as a tinting paste for mixtures of silicone rubbers. Example 2. 20.3 parts by weight 2,4-dinitrochlorobenzene are dissolved
    When heated in ethanol in a round bottom flask. To this solution was added, 2 ppm by weight. amLnoethylaminopropyltrimethoxysilane. The solution of the sodra is oily to a deep red color. After distilling off the ethanol, a dark yellow liquid remains.
    5 g of the obtained dye is dissolved in 95 g of water, and this solution is immersed in 5 g of cotton fiber, 5 g of wool, 5 g of polyamide fiber, 5 polyacrylic fiber, 5 g of polyester silk, and 5 g of cellulose fibers, with -. than each fiber immersed for 5 min.
    15
    After rinsing and repeated washing in a molar solution, these fibers retain the yellow color obtained from the yellow dye.
    PRI me R 3. 20.3 weight.h.
    20 2,4-dinitrochlorobeneol is dissolved by heating in ethanol in a round bottom flask. 10.4 parts by weight are added to this solution. Gminoethylaminopropyl- (methyl) -dimethoxysilane
    25 and creep liquid deep yellow.
    100 weight. including proerachnoy methylenesilicone resin mixed: 0.2 weight.h. vzvezavannogo kori30 ate and then cured from at 200C
    within 2 hours. Get a solid transparent silicone resin yellow. If parts; The dyes are only partially condensed with particles of silicone resin, i.e. without curing, then this product can be used. As a tint silicone resin paste.
    Example 4. 82 weight.h. The polymethylsiloxane, which has a molecular weight of 820 and one elastic group per molecule, is mixed in small portions with 20.2 ppb. 2,4-dinitrochlorobenzene, the silicone liquid being colored yellow with heat.
    50 g of hydroxy-terminated polymethylsiloxane with a viscosity of approximately 5000 cSt are mixed with 0.05 g of a yellow silicone fluid and 3 g of a crosslinking agent, prepared by mixing 80 parts by weight of tetraethoxysilane and 20 parts by weight. dibutyldilaurate tin. After 24 hours at room temperature, transparent yellow silicone rubber is obtained.
    It is recognized as an invention according to the results of the examination carried out by the Office for the Invention of the German Democratic Republic.
    权利要求:
    Claims (3)
    [1]
    (57) 1. METHOD FOR PRODUCING SILICON-CONTAINING NITRO-DYES for Organosiloxanes, active dyes ^, for natural and synthetic f organic fibers or for organic materials of the general formula; V ~ Z - - Ar (K0 2 ) a ; K 'z-b where X is the same or different hydrolyzable groups or a silicone radical:
    Z is an alkylene radical with 2-10, C-atoms: R is a monovalent organic 1 a radical:
    R is hydrogen, alkyl with 1-10 C-atoms, unsubstituted or substituted aryl, aralkyl;
    ag is a substituted or unsubstituted aromatic radical;
    a, b are integers from 1 to 3, characterized in that the silanes or siloxanes of the general formula 'JY1- i iZ-TNHR 2 where: X, Z, R, R, b - have the indicated meanings, are subjected to interaction with the nitro compound of the general formulas | Hai-2r (NoJ a , where ar and a - have the indicated meanings;
    Hal is a halogen atom, ‘at ambient temperature or when heated in a stoichiometric ratio.
    [2]
    2. The method according to π. 1, characterized in that the process is carried out in a solvent environment.
    [3]
    3. The method according to p. 2, with the fact that the interaction is carried out on natural or synthetic fibers with the formation of a bond between the dye and the fiber.
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    同族专利:
    公开号 | 公开日
    BE875160A|1979-07-16|
    DD141678A1|1980-05-14|
    CS218886B1|1983-02-25|
    US4405801A|1983-09-20|
    GB2018797A|1979-10-24|
    DD141678B1|1980-12-24|
    JPS54148023A|1979-11-19|
    GB2018797B|1982-08-04|
    FR2421935A1|1979-11-02|
    DE2908205A1|1979-10-18|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US2756246A|1954-02-08|1956-07-24|Gen Electric|Nitro derivatives of organosilicon compounds|
    US2985680A|1959-08-03|1961-05-23|Union Carbide Corp|Nitro and nitrito derivatives of organosilicon compounds|
    US3375218A|1962-12-07|1968-03-26|Union Carbide Corp|Nitroarylsilanes and siloxanes|
    US3731205A|1972-03-23|1973-05-01|Embhart Corp|Sequence detector circuit|
    US4139403A|1977-08-19|1979-02-13|The United States Of America As Represented By The Secretary Of The Navy|Dinitroalkyl and fluorodinitroalkyl silicon compounds|EP0283206A3|1987-03-12|1990-08-22|Hewlett-Packard Company|Covalently labeled siloxane polymers|
    US5070158A|1987-03-12|1991-12-03|Hewlett-Packard Company|Covalently labeled siloxane polymers|
    FR2746102B1|1996-03-18|1998-04-30|SILOXANIC DYES, COMPOSITIONS CONTAINING THEM AND USES|
    US5789515A|1997-03-13|1998-08-04|Milliken Research Corporation|Polysiloxane-poly copolymer-substituted colorant|
    DE102006027533A1|2006-06-14|2007-12-20|Dystar Textilfarben Gmbh & Co. Deutschland Kg|Colored organopolysiloxanes|
    DE102006046465A1|2006-09-29|2008-04-03|Dystar Textilfarben Gmbh & Co. Deutschland Kg|Colored organopolysiloxanes useful e.g. in cosmetic, hair care and skin care products|
    WO2008138726A2|2007-05-11|2008-11-20|Basf Se|Polymeric dyes|
    JP5851336B2|2012-05-09|2016-02-03|オリンパス株式会社|Composite rubber material, molded body, and method for producing composite rubber material|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    DD20458878A|DD141678B1|1978-04-05|1978-04-05|SILICLE-CONTAINING NITROPYLENE|
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