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    • 1. 发明授权
    • Process for spin-dyeing of acid-modified polymers of copolymers of
acrylonitrile using rapid-fixing di-quaternary cationic dyes
    • 使用快速固定二季阳离子染料对丙烯腈共聚物酸改性聚合物进行染色的方法
    • US4607071A
    • 1986-08-19
    • US734442
    • 1985-05-15
    • Manfred HahnkeReinhard MohrKurt Hohmann
    • Manfred HahnkeReinhard MohrKurt Hohmann
    • C08K5/00C09B69/06D01F6/54C08K5/22C08J3/20D01F6/18
    • D01F6/54C08K5/0041C09B69/06Y10S8/927
    • Improvement of a process for spin-dyeing acid-modified polymers or copolymers of acrylonitrile in which cationic quaternary dyestuffs are added to the spinning mass and spun according to the wet-spinning procedure. The improvement is characterized by using dyestuffs characterized by a migration factor M of 20 or less than 20, by a combination index K of less than 2.5 and a cation weight of more than 310. Migration factor M and combination index K are known values in the dyestuff field or can be determined. The dyestuff to be used according to the invention can belong to the most different classes of dyestuffs; they fix rapidly on the polymer, and thus they do not color, or color only to a minor extent, the coagulation, stretching and washing baths although they are soluble in water and aqueous solutions of these baths. The fibers and filaments obtained by the process of the invention have outstanding fastnesses to wet processing and, owing to the absence of dyestuff aggregates at the surface of the fiber such as occur when spin-dyeing with pigments, very good fastnesses to dry and wet rubbing. The fibers are intense, absolutely transparent and free from specks.
    • 改进将染色酸改性聚合物或丙烯腈的共聚物的方法改进,其中将阳离子季染料加入到纺丝织物中并根据湿纺丝方法纺丝。 改进的特征在于使用迁移因子M为20或小于20的染料,组合指数K小于2.5,阳离子重量大于310.迁移因子M和组合指数K为 染料领域或可以确定。 根据本发明使用的染料可以属于最不同类型的染料; 它们快速固定在聚合物上,因此它们不会在凝固,拉伸和洗涤浴中颜色不浅或仅在较小程度上着色,尽管它们可溶于水和这些浴的水溶液。 通过本发明的方法获得的纤维和细丝具有优异的湿法加工牢度,并且由于在用颜料旋转染色时在纤维表面没有染料聚集体,因此具有非常好的干湿摩擦牢度 。 纤维是强烈的,绝对透明的,没有斑点。
    • 2. 发明授权
    • Zinc chloride complex compounds
    • US4423226A
    • 1983-12-27
    • US243876
    • 1981-03-16
    • Reinhard MohrRudolf Neeb
    • Reinhard MohrRudolf Neeb
    • C07F3/06C07D209/88C07D265/38C09B19/00C07D209/82
    • C07D265/38C07D209/88C09B19/00
    • Zinc chloride complex compounds to which the structure of the general formula (1) ##STR1## can be assigned, in which the individual radicals in the formula have the following meanings: Rhu 1 is a hydrogen atom or an optionally substituted lower alkyl group; R.sup.2 is a hydrogen atom, an optionally substituted lower alkyl group or an optionally substituted phenyl radical; R.sup.3 is a hydrogen atom or an optionally substituted lower alkyl group; R.sup.4 is a hydrogen atom, an optionally substituted lower alkyl group or an optionally substituted phenyl radical; R.sup.5 is a hydrogen atom or a halogen atom or a lower alkyl group or a lower alkoxy group, or R.sup.1 and R.sup.5 together form the o-phenylene radical; R.sup.6 is a hydrogen atom or a halogen atom or a lower alkyl group or a lower alkoxy group; Z is a hydrogen atom or a halogen atom or a lower alkyl group or a cyano, carboxylic acid, carbamoyl or sulfamoyl group or a carbamoyl or sulfamoyl group which is monosubstituted or disubstituted by lower alkyl, or a trifluoromethyl or lower carbalkoxy group, a lower alkoxy group which can be substituted by cyano, an acyloxy group, an acylamino group, a lower alkylamino group or a lower dialkylamino group. They are prepared by reacting a nitroso compound of the formula (2) ##STR2## in which R.sup.3, R.sup.4, R.sup.6 and Z have the meanings mentioned above, with an m-aminophenol of the formula (3) ##STR3## in which R.sup.1, R.sup.2 and R.sup.5 have the meanings mentioned above, in the presence of zinc chloride and in the absence of a base. The zinc chloride complex compounds of the formula (1) can be converted by eliminating the radical Z in the formula or by removing, by oxidative means, this radical Z, in the formula, which is in the ortho-position in relation to the nitrogen atom, or the other hydrogen atom which is in the ortho-position, into the phenoxazine dyestuffs of the formula (4) ##STR4## in which R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5 and R.sup.6 have the meanings mentioned above and Z.sub.1 denotes a halogen atom, a lower alkyl group, a cyano, carboxylic acid, carbamoyl or sulfamoyl group, a carbamoyl or sulfamoyl group which is monosubstituted or disubstituted by lower alkyl, or a trifluoromethyl or lower carbalkoxy group or a hydrogen atom and X.sup.(-) represents and anion.
    • 3. 发明授权
    • Quaternary and basic azamethine compounds and their use as colorants
    • US4344879A
    • 1982-08-17
    • US204323
    • 1980-11-05
    • Reinhard MohrManfred Hahnke
    • Reinhard MohrManfred Hahnke
    • C09B23/00C08K5/3417C09B23/16C09B26/02C09B26/04C09B69/06D06P1/38C07D209/14
    • C09B26/02C08K5/3417C09B23/162C09B26/04C09B69/06
    • Novel azamethine compounds of the formula (1) ##STR1## in which R is alkyl of from 1 to 4 carbon atoms optionally substituted, Alk is alkyl of from 1 to 4 carbon atoms, Y is the methine radical or a nitrogen atom, R.sub.1 is hydrogen or alkyl of from 1 to 4 carbon atoms optionally substituted, alkylene is an alkylene group of from 2 to 6 carbon atoms, Z is a group of the formula (2a) or 2(b) ##STR2## in which R.sub.2 is alkyl of from 1 to 4 carbon atoms optionally substituted, R.sub.3 is alkyl of from 1 to 4 carbon atoms optionally substituted, or is phenyl unsubstituted or substituted by chlorine, alkyl of from 1 to 4 carbon atoms, alkoxy of from 1 to 4 carbon atoms, nitro, carbalkoxy of from 2 to 5 carbon atoms and/or carbamoyl, R.sub.4 is hydrogen or alkyl of from 1 to 4 carbon atoms optionally substituted, or R.sub.2 and R.sub.3 together with the nitrogen atom form a heterocyclic ring containing optionally nitrogen, oxygen or sulfur as a further hetero atom, or R.sub.2 and R.sub.3 or R.sub.2, R.sub.3 and R.sub.4 together with the positive nitrogen form a heterocyclic ring containing optionally nitrogen, oxygen or sulfur as a further hetero atom, the benzene nucleus A is unsubstituted or substituted by halogen, nitro, cyano, sulfamoyl, alkyl of from 1 to 4 carbon atoms, alkoxy of from 1 to 4 carbon atoms and/or carbalkoxy of from 2 to 5 carbon atoms, the benzene nucleus B is unsubstituted or substituted by halogen, nitro, alkyl of from 1 to 4 carbon atoms, alkoxy of from 1 to 4 carbon atoms and/or carbalkoxy of from 2 to 5 carbon atoms, n is the integer 1 or 2, and X.sup.(-) is the equivalent of a colorless anion.These novel compounds can be prepared in usual manner analogously to known processes using the corresponding indoline and alkoxyaniline derivatives as starting compounds with optional subsequent alkylation.The novel azamethine compounds are well suitable as dyestuffs, soluble in water and in acids as well as in various organic solvents, for the dyeing of preferably acid-modified aromatic polyesters, acid-modified polyamides and acid-modified polyacrylonitrile materials, especially those in the form of fibres or in the mass by means of a spin-dyeing procedure.
    • 5. 发明授权
    • Certain 6-amino-4-hydrocarbyl-nicotinamides
    • 某些6-氨基-4-烃基 - 烟酰胺
    • US3980659A
    • 1976-09-14
    • US521442
    • 1974-11-06
    • Erwin FleckensteinErnst HeinrichReinhard Mohr
    • Erwin FleckensteinErnst HeinrichReinhard Mohr
    • C07D401/06C07D401/12C07D413/04C07D213/44
    • C07D413/04C07D401/06C07D401/12Y10S8/922
    • Compounds of the formula ##SPC1##Wherein X is aliphatic, cycloaliphatic, aromatic, aralkyl, hetaryl, hetarylalkyl or hydrogen; Y is aliphatic, aromatic, aralkyl, --COOR.sub.1, --COR.sub.2, ##EQU1## --SO.sub.2 R.sub.2, ##EQU2## --CN, --NH.sub.2, --NO, --NO.sub.2 or hydrogen with the proviso that when Y is hydrogen, X is other than hydrogen; Z.sub.1 is cyano, ##EQU3## --NH--OR.sub.10, ##EQU4## --OR.sub.12, --SR.sub.12 or --SO.sub.2 R.sub.12 and Z.sub.2 is chlorine, bromine, cyano, hydroxy, mercapto, --OR.sub.12, --SR.sub.12, --SO.sub.2 R.sub.12, ##EQU5## --NH--OR.sub.10 or ##EQU6## R.sub.1 is aliphatic; R.sub.2 is aliphatic, cycloaliphatic, aromatic, aralkyl or heterocyclic; R.sub.3 and R.sub.4 when taken separately are hydrogen, aliphatic, cycloaliphatic, aromatic or aralkyl; R.sub.3 and R.sub.4 when taken together with the nitrogen atom to which they are attached form a heterocyclic moiety; R.sub.5 and R.sub.6 when taken separately are aliphatic, aromatic, aralkyl, heterocyclic or hydrogen; R.sub.5 and R.sub.6 when taken together with the nitrogen atom to which they are attached are heterocyclic; R.sub.7 is hydrogen, aliphatic or aromatic; R.sub.8 and R.sub.9 are aliphatic or aromatic, R.sub.10 is hydrogen, aliphatic or aralkyl, R.sub.11 is aliphatic and R.sub.12 is aliphatic, aromatic or aralkyl; R.sub.10 and R.sub.11 when taken together with the nitrogen atom to which they are attached are heterocyclic.
    • 式WH的化合物是脂族,脂环族,芳族,芳烷基,杂芳基,杂芳基烷基或氢; Y是脂族的,芳族的,芳烷基,-COOR 1,-COR 2,R 3 -CO-N角,R 4 -SO 2 R 2,R 3 -SO 2 -N取代基,R 4 -CN,-NH 2,-NO,-NO 2或氢,条件是 当Y是氢时,X不是氢; Z 1是氰基,R 5 R 7 R 8 -N取代基,ANGLE NN ANGLE,R 6 R 9 -NH-OR 10,OR 10 -N ANGLE,R 11 -OR 12,-SR 12或-SO 2 R 12,Z 2是氯,溴,氰基,羟基,巯基,-OR 12 - SR12,-SO2R12,R5R7R8-AN,ANGLE NN ANGLE,R6R9 -NH-OR10或OR10 -N ANGLE; R11 R1是脂肪族的; R2是脂族,脂环族,芳族,芳烷基或杂环; 单独使用时,R 3和R 4为氢,脂族,脂环族,芳族或芳烷基; 当与它们所连接的氮原子一起形成杂环部分时,R 3和R 4; R5和R6分别为脂族,芳族,芳烷基,杂环或氢时; 当与它们所连接的氮原子一起取代时,R 5和R 6是杂环的; R7是氢,脂族或芳族; R8和R9是脂族或芳族的,R10是氢,脂族或芳烷基,R11是脂族的,R12是脂族的,芳族的或芳烷基; 当与它们所连接的氮原子一起取代时,R 10和R 11是杂环的。
    • 7. 发明授权
    • Process for the preparation of chlorozincate salts of benzo thiazolium
azo dyestuffs by alkylating with dialkylsulfate in aqueous medium in
the presence of Zn-containing acid acceptor at pH.ltoreq.7
    • 在含有Zn的酸受体的pH7中存在下,通过在含水介质中与二烷基硫酸盐烷基化制备苯并噻唑鎓偶氮染料的氯酸锌盐的方法
    • US4638053A
    • 1987-01-20
    • US775111
    • 1985-09-11
    • Rudolf NeebReinhard Mohr
    • Rudolf NeebReinhard Mohr
    • C09B44/00C09B44/20C09B69/06C09B29/045C09B43/11
    • C09B44/005C09B44/20C09B69/065
    • Chlorozincate salts of benzothiazonium azo compounds are prepared by reacting benzothiazolium azo compounds with an dialkylsulfate having from 1 to 4 carbon atoms in the alkyl radicals, which process comprises carrying out the reaction in an aqueous medium at a temperature of from 10.degree. to 80.degree. C. in the presence of an acid acceptor and the alkylation with the use of from 1.8 to 2.5 mols of the dialkylsulfate, calculated on the starting azo dyestuff, at a pH not exceeding 7. The prepared benzothiazolium azo compound is precipitated as chlorozincate salt, especially with the use of an alkali metal chloride. According to this process, the chlorozincate salts are obtained in higher purity. A perceptible decomposition of the benzothiazolium azo compound does not occur. Chemicals, for example the alkylation agent and acid-binding agents need be used in a small quantity. In addition to this economy and to the less pollution of the waste water, the process has the advantage that it can be carried out with the use of a small reaction volume.
    • 苯并噻唑偶氮化合物的氯化锌盐通过苯并噻唑鎓偶氮化合物与烷基中具有1至4个碳原子的二烷基硫酸盐反应来制备,该方法包括在水介质中在10至80℃的温度下进行反应 在酸性受体的存在下进行烷基化,并使用1.8-2.5摩尔在起始偶氮染料上计算的二烷基硫酸盐在pH不超过7的条件下进行烷基化。制备的苯并噻唑鎓偶氮化合物作为氯酸锌沉淀,特别是 使用碱金属氯化物。 根据该方法,得到较高纯度的氯锌酸盐。 不会发生苯并噻唑鎓偶氮化合物的可察觉的分解。 化学品,例如烷基化剂和酸结合剂需要少量使用。 除了这种经济之外,对废水的污染较少,该方法的优点是可以使用小的反应体积进行。
    • 8. 发明授权
    • Process for dyeing, in the gel state, fiber material composed of wet
spun acrylonitrile polymers using dyes with two basic groups
    • 在凝胶状态下染色的方法是使用具有两个碱性基团的染料由湿纺丙烯腈聚合物组成的纤维材料
    • US4563191A
    • 1986-01-07
    • US647269
    • 1984-09-04
    • Manfred HahnkeReinhard MohrKurt Hohmann
    • Manfred HahnkeReinhard MohrKurt Hohmann
    • D06P3/76C09B69/00D01F1/06D01F6/18D06P3/70C09B23/16D06F1/06D06P1/41
    • D06P3/702C09B69/001D01F1/06D01F6/18Y10S8/927
    • Fiber material composed of acid-modified homopolymers or copolymers of acrylonitrile (PAC fibers) which has been obtained by a wet spinning process, has not been dried and is still in a swollen condition (gel form), can be dyed advantageously and in fast colors by means of soluble dyes, the molecule of which contains several groups, namely more than one quaternary grouping and/or a strongly basic grouping carrying no charge, which exert a basic action towards the acid groups of the fiber substance. The chromophore of this colorant can belong to the category of monoazo or diazo dyes, methine, azamethine or diazamethine dyes or naphthalactam dyes.In accordance with the invention, after substantially removing the non-aqueous spinning solvent by washing, the spun material, as a moist gel, is dyed continuously or discontinuously from an aqueous dyebath; the fibers can be stretched before the dye is applied, during the dyeing process itself or immediately afterwards.By virtue of their special nature, the dyes of the type designated above, which have a strong fixing action, produce optimum fixing rates when dyeing PAC gels and, in the subsequent production stages, do not cause any noticeable soiling, as a result of dye which has bled out, on components of machines and operating baths, such as stretching or after-treatment baths. Investigations of penetration of the fiber by the dye, of the fixing rate and of the resulting fastness properties, such as fastness to wet processing, have shown no disadvantages compared with conventional dyes.
    • 由湿法纺丝法得到的酸改性均聚物或丙烯腈共聚物(PAC纤维)所组成的纤维材料未经干燥,仍处于溶胀状态(凝胶形式),可以有利地以快速染色 通过可溶性染料,其分子含有几个基团,即多于一个四元组和/或不带电荷的强碱基,其对纤维物质的酸基发挥基本作用。 这种着色剂的发色团可以属于单偶氮或重氮染料,次甲基,氮杂酮或二氮杂吗啉染料或萘胺染料。 根据本发明,通过洗涤基本上除去非水性纺丝溶剂后,作为湿凝胶的纺丝材料从水性染浴中连续或不连续地染色; 在染色过程本身之前或之后,纤维可以在施加染料之前被拉伸。 由于其特殊性质,具有强固定作用的上述类型的染料在染色PAC凝胶时产生最佳定影率,并且在随后的生产阶段中不会引起明显的污染,因为染料 已经排出了机器和操作浴的部件,如拉伸或后处理浴。 通过染料对纤维的渗透性,定影率和所得到的坚牢度性能的研究,例如湿法加工的坚牢度,与常规染料相比,没有显示出缺点。
    • 10. 发明授权
    • Substituted pyridine compounds
    • 取代的吡啶化合物
    • US3956294A
    • 1976-05-11
    • US521443
    • 1974-11-06
    • Erwin EleckensteinErnst HeinrichReinhard Mohr
    • Erwin EleckensteinErnst HeinrichReinhard Mohr
    • C07D401/06C07D401/12C07D413/04C07D295/12
    • C07D413/04C07D401/06C07D401/12
    • Compounds of the formula ##SPC1##Wherein X is aliphatic, cycloaliphatic, aromatic, aralkyl, hetaryl, hetarylalkyl or hydrogen; Y is aliphatic, aromatic, aralkyl, --COOR.sub.2, --COR.sub.2, ##EQU1## --CN, --NH.sub.2, --NO, --NO.sub.2 or hydrogen with the proviso that when Y is hydrogen, X is other than hydrogen; Z.sub.1 is cyano, ##EQU2## --OR.sub.12, --SR.sub.12 or --SO.sub.2 R.sub.12 and Z.sub.2 is chlorine, bromine, cyano, hydroxy, mercapto, ##EQU3## R.sub.1 is aliphatic; R.sub.2 is aliphatic, cycloaliphatic, aromatic, aralkyl or heterocyclic; R.sub.3 and R.sub.4 when taken separately are hydrogen, aliphatic, cycloaliphatic, aromatic or aralkyl; R.sub.3 and R.sub.4 when taken together with the nitrogen atom to which they are attached form a heterocyclic moiety; R.sub.5 and R.sub.6 when taken separately are aliphatic, aromatic, aralkyl, heterocyclic or hydrogen; R.sub.5 and R.sub.6 when taken together with the nitrogen atom to which they are attached are heterocyclic; R.sub.7 is hydrogen; aliphatic or aromatic; R.sub.8 and R.sub.9 are aliphatic or aromatic, R.sub.10 is hydrogen, aliphatic or aralkyl, R.sub.11 is aliphatc and R.sub.12 is aliphatic, aromatic or aralkyl; R.sub.10 and R.sub.11 when taken together with the nitrogen atom to which they are attached are heterocyclic.
    • 式WH的化合物是脂族,脂环族,芳族,芳烷基,杂芳基,杂芳基烷基或氢; Y是脂族,芳族,芳烷基,-COOR 2,-COR 2,R 3,R 3 -COOR 1,-COR 2,-CO-N ANGLE,-SO 2 R 2,-SO 2 -N取代基,R 4 R 4 -CN,-NH 2,-NO,-NO 2 或氢,条件是当Y是氢时,X不是氢; Z 1是氰基,R 5 R 7 R 8 OR 10 -N角,角NN,-NH-OR 10,-N角,R 6 R 11 R 11 -OR 12,-SR 12或-SO 2 R 12,Z 2是氯,溴,氰基,羟基,巯基, OR 12,-SR 12,-SO 2 R 12,-N ANGLE,R 6 R 7 R 8 OR 10 ANGLE NN ANGLE,-NH-OR 10或-N ANGLE R 9 R 11 R 1是脂族基; R2是脂族,脂环族,芳族,芳烷基或杂环; 单独使用时,R 3和R 4为氢,脂族,脂环族,芳族或芳烷基; 当与它们所连接的氮原子一起形成杂环部分时,R 3和R 4; R5和R6分别为脂族,芳族,芳烷基,杂环或氢时; 当与它们所连接的氮原子一起取代时,R 5和R 6是杂环的; R7是氢; 脂肪族或芳香族; R 8和R 9是脂族或芳族,R 10是氢,脂族或芳烷基,R 11是脂族基,R 12是脂族,芳族或芳烷基; 当与它们所连接的氮原子一起取代时,R 10和R 11是杂环的。