TW201323411A - Improved method of producing polymeric phenazonium compounds - Google Patents

Abstract

A process of making a polymeric phenazonium compound having the general formula: Wherein R1, R2, R4, R5, R6, R8 and R9 are the same or different, and represent hydrogen, a low alkyl or a substituted aryl, R3 starts as NH2 and is diazotized followed by polymerization, R5 and R8 may alternatively represent monomeric or polymeric polymeric phenazonium radicals, R7 is a carbon in the aromatic ring, and wherein Rx-N-RY represent a substituted amine, and RX and RY represent any combination of CH3, C2H5, , and hydrogen, except that RX and RY cannot both be hydrogen, A is an acid radical, and n is an integer from 2 to 100. The polymeric phenazonium compound is usable in as an additive in a metal plating bath. The method includes the steps of; (a) dissolving an effective amount of an amino compound in a formic acid solution; (b) adding a nitrite salt to diazotize the amino compound; and (c) adding sulfamic acid to neutralize any excess nitrous acid that may be formed in step (b), whereby a polymeric phenazonium compound is produced.

Description

Improved method for producing polymeric non-nathene compounds Cross-references to related applications

This application is filed on September 24, 2010. In the current application, part of the serial application of the application No. 12/890,013, the subject matter of which is incorporated herein by reference.

The present invention is generally directed to an improved process for the manufacture of polymeric phenanthrene compounds.

It is known in the art to add an organic material to an acid copper electrolysis bath (including, for example, a copper sulfate electrolyte) to deposit a bright copper layer in place of the crystalline matte deposit. These additives include, for example, polyethylene glycol, thiourea and its derivatives, thioglycolide, thiocarbamate and phosphorothioate, safranin, thiourea-formaldehyde condensate and some C= S compound. The aforementioned additives have conventionally been used as additives for acidic copper electrolytes (including copper sulfate electrolytes) to obtain bright copper plating. In addition, polymeric non-nathene compounds have also been developed for use in acid copper electrolytes to deposit bright, flat copper coatings, and can be used alone or in combination with other organic materials.

For example, as described in U.S. Patent No. 3,743,584, the entire disclosure of which is incorporated herein in A polymeric non-nadonium compound is prepared.

The diazotization of an amine compound is usually accomplished by suspending the monomer in a strong acid solution, such as sulfuric acid, hydrochloric acid, acetic acid, fluoroboric acid, phosphoric acid. And / or another suitable acid. These acids form diazo acid free radicals. The diazonium salt formed by boiling is generally present in a temperature range of from about 5 to 100 ° C, preferably from about 10 to 25 ° C. The reaction product is precipitated from the acidic reaction solution or precipitated from the solution by neutralization with a base such as ammonia or a hydroxide such as potassium hydroxide.

The polymeric non-nadonium compounds prepared in accordance with the present methods generally have the following general formula: Wherein R ¹ , R ² , R ⁴ , R ⁵ , R ⁶ , R ⁸ and R ⁹ are the same or different and represent hydrogen, lower alkyl or substituted aryl, R ³ starts with NH ₂ and is subsequently polymerized To diazotize, R ⁵ and R ⁸ may additionally represent a monomer or a polymerized phenanthrene radical, R ⁷ is a carbon in the aromatic ring, and wherein R ^X -NR ^Y represents a substituted amine, and R ^X and R ^Y stands for CH ₃ , C ₂ H ₅ , And any combination of hydrogen, but R ^X and R ^Y cannot be hydrogen at the same time, A is an acid radical, and n is an integer between 2 and 100.

In the case of lower alkylene groups, it may include methyl, ethyl and propyl groups.

As the aryl group, a phenyl group substituted with a methyl group, an ethyl group, a methoxy group, an ethoxy group or the like can be used.

Examples of such non-polymerized quinone compounds include poly(6-methyl-7-dimethylamino-5-phenylphenazinium sulphate); poly(2-methyl) -7-diethylamino-5-phenylphenazinium chloride; poly(2-methyl-7-dimethylamino-5-phenylphenazine sulfonate); poly( 5-methyl-7-dimethylaminopyrazine acetate; poly(2-methyl-7-anilino-5-phenylphenazinium sulfate); poly(2-methyl -7-dimethylamino quinazolam sulfate; poly(7-methylamino-5-phenylphenazinium acetate); poly(7-ethylamino-2,5- Diphenylphenazinium chloride; poly(2,8-dimethyl-7-diethylamino-5-tolylphenazolan chloride); poly(2,5,8-three) Phenyl-7-dimethylaminopyrazine sulfate; and poly(7-dimethylamino-5-phenylphenazine chloride) are by way of example and not limitation.

It would be desirable to provide a process for making these polymeric non-nathene compounds which requires fewer steps and produces an additive which has a lower amount of unreacted monomer in the end product than the conventional manufacturing process.

One of the objects of the present invention is to provide an improved method of forming a non-nathene monomer which overcomes the deficiencies of the prior art.

Another object of the present invention is to provide a method of forming a non-nathene monomer which is capable of improving the synthesis of a polymer dye.

Another object of the present invention is to provide a method of forming a polymeric phenacetin compound which requires fewer processing steps.

Still another object of the present invention is to provide a process for forming a polymeric phenergazine compound having a higher percentage concentration of polymeric material contained in the end product than in the conventional process.

To this end, the present invention generally relates to a process for the manufacture of a polymeric non-nadonium compound having the following general formula: Wherein R ¹ , R ² , R ⁴ , R ⁵ , R ⁶ , R ⁸ and R ⁹ are the same or different and represent hydrogen, lower alkyl or substituted aryl, R ³ starts with NH ₂ and is subsequently polymerized To diazotize, R ⁵ and R ⁸ may additionally represent a monomer or a polymerized phenanthrene radical, R ⁷ is a carbon in the aromatic ring, and wherein R ^X -NR ^Y represents a substituted amine, and R ^X and R ^Y stands for CH ₃ , C ₂ H ₅ , And any combination of hydrogen, but R ^X and R ^Y cannot be hydrogen at the same time, A is an acid radical, and n is an integer between 2 and 100. The method comprises the steps of: a) an effective amount of an amine compound Dissolving in a formic acid solution; b) adding nitrite to diazotize the amine compound; and c) adding sulfamic acid to neutralize any excess nitrous acid that may be formed in step b), thereby producing a polymerization Ancestral compound.

The present invention takes the form of a synthetic non-nathene compound in a manner not used in conventional methods (e.g., as described in U.S. Patent No. 3,743,584), and provides several advantages in the ease of synthesizing the polymer dye.

The present invention is generally directed to an improved method for the polymerization of phenanthrene compounds and their manufacture. These polymeric non-nathene compounds are used, for example, for acid In the electrolyte, a bright, flat copper coating is deposited.

The inventors of the present invention have surprisingly found that the amine based compound and the resulting polymeric phenergazine dye are quite soluble in the formic acid solution. Although U.S. Patent No. 3,743,584 discloses the use of acetic acid as a strong acid for the polymerization of non-nathene compounds, the use of acetic acid still requires many of the steps set forth in the patent. However, the inventors of the present invention have found surprising results when using formic acid due to the solubility of the amine compound in formic acid. Thus, the steps required to produce a polymerized quinone compound are less by the methods described herein.

In particular, it is possible to dissolve the amine compound in a formic acid solution, and then add the nitrite in a usual manner at a low temperature to diazotize the amine compound. Thereafter, sulfamic acid is added to neutralize any excess nitrous acid. The result is a highly concentrated solution of the polymerized non-nathene dye which does not require any additional steps prior to use in the acidic copper electrolytic solution and is in the form: Wherein R ¹ , R ² , R ⁴ , R ⁵ , R ⁶ , R ⁸ and R ⁹ are the same or different and represent hydrogen, lower alkyl or substituted aryl, R ³ starts with NH ₂ and is subsequently polymerized To diazotize, R ⁵ and R ⁸ may additionally represent a monomer or a polymerized phenanthrene radical, R ⁷ is a carbon in the aromatic ring, and wherein R ^X -NR ^Y represents a substituted amine, and R ^X and R ^Y stands for CH ₃ , C ₂ H ₅ , And any combination of hydrogen, but R ^X and R ^Y cannot be hydrogen at the same time, A is an acid radical, and n is an integer between 2 and 100.

More particularly, the invention relates generally to a process for the manufacture of a polymeric non-nadonium compound having the following general formula: Wherein R ¹ , R ² , R ⁴ , R ⁵ , R ⁶ , R ⁸ and R ⁹ are the same or different and represent hydrogen, lower alkyl or substituted aryl, R ³ starts with NH ₂ and is subsequently polymerized To diazotize, R ⁵ and R ⁸ may additionally represent a monomer or a polymerized phenanthrene radical, R ⁷ is a carbon in the aromatic ring, and wherein R ^X -NR ^Y represents a substituted amine, and R ^X and R ^Y stands for CH ₃ , C ₂ H ₅ , And any combination of hydrogen, but R ^X and R ^Y cannot be hydrogen at the same time, A is an acid radical, and n is an integer between 2 and 100, wherein the polymerized non-nathene compound can be used as a metal plating bath An additive comprising the steps of: a) dissolving an effective amount of an amine compound in a low temperature formic acid solution; b) adding a nitrite to diazotize the amine compound; and c) adding a sulfamic acid to neutralize Any excess nitrous acid that may be formed in step b), thus producing a polymeric non-nadonium compound.

Examples of the amine-based compound suitable for practical use in the present invention include 2-methyl-3-amino-7-dimethylamino-5-phenylphenazinium sulfate, 3-amino-6-methyl Benzyl-7-dimethylamino-5-phenylphenazinium hydrogensulfate, 2-methyl-3-amino-7-diethylamino-5-phenylphenazinium chloride , 3-Amino-7-dimethylamino-5-methylphenazone acetate, 2-methyl-3-amino-7-anilino-5-phenylphenazinium hydrogen sulfate Salt, 2-methyl-3-amino-7-dimethylaminopyrazine sulphate, 3-amino-7-methylamino-5-phenylphenazinium acetate, 2-phenyl-3-amino-7-ethylamino-5-phenylphenazinium chloride, 1,2,6,9-tetramethyl-3-amino-7-diethyl Amino-5-phenylphenazinium hydrogensulfate, 2,8-dimethyl-3-amino-7-diethylamino-5-tolyphenephthalide chloride, and 2, 9-Diphenyl-3-amino-6-methyl-7-dimethylamino-5-phenylphenazinium hydrogensulfate. These compounds preferably have an amine at the three positions and a substituted amine at the seven position.

In a preferred embodiment, the amine compound is 2-methyl-3-amino-7-dimethylamino-5-phenylphenazinium chloride having the structure:

In another preferred embodiment, the amine compound is 2-methyl-3-amino-7-diethylamino-5-phenylphenazinium chloride having the structure:

Based on this, the polymeric non-nadonium compound produced from these amine compounds comprises a polymeric non-nadonium compound selected from this type, including poly(6-methyl-7-dimethyl), according to the methods described herein. Amino-5-phenylphenazinium sulfonate); poly(2-methyl-7-diethylamino-5-phenylphenazinium chloride); poly(2-methyl-7) - dimethylamino-5-phenylphenazinium sulphate); poly(5-methyl-7-dimethylaminophenyl phenacetamidine acetate); poly(2-methyl- 7-anilino-5-phenylphenazone sulfate; poly(2-methyl-7-dimethylaminophenazone); poly(7-methylamino-5-) Phenylphenazide acetate; poly(7-ethylamino-2,5-diphenylphenazinium chloride); poly(2,8-dimethyl-7-diethylamine) Benz-5-tolylphenazinium chloride; poly(2,5,8-triphenyl-7-dimethylaminophenazone); and poly(7-dimethylamine) Groups consisting of benzyl-5-phenylphenazinium chlorides, these are by way of example only and not limitation.

While various nitrites are useful in the practice of the invention, the preferred nitrite is sodium nitrite, which is used as a diazotizing agent. Another diazotizing agent useful in the practice of this invention is nitrosyl sulfate.

The reaction is usually warmed to at least 20 ° C in order to completely produce the reaction product (polymer).

In a preferred embodiment, the metal plating bath contains copper. Usually copper is in the form of copper sulfate. However, other copper salts can also be used. For example, in one embodiment, in an electrolyte for depositing a copper plating layer and adding the polymerized phenanthrene compound of the present invention, a copper sulfate sulfate solution having the following composition may be used:

Other copper salts may also be used in place of copper sulfate, at least partially. The sulfuric acid may be partially or fully substituted with fluoroboric acid, phosphoric acid and/or other suitable acid. The electrolyte may be free of chloride or may generally contain a chloride such as an alkali metal chloride or hydrochloric acid in an amount of from 0.001 to 0.2 g/liter in order to facilitate improvement in gloss and flatness.

Preferably, the concentration of the amine compound in the formic acid solution is between about 100 grams per liter and about 200 grams per liter, more preferably between about 110 grams per liter and about 185 grams per liter, and is optimal. The system is between about 110 and about 122 grams per liter.

As previously discussed, the methods claimed herein do not require additional processing steps as compared to the methods described in, for example, U.S. Patent No. 3,743,584. For example, the process of the invention does not require and does not include a neutralization step of polymerizing the phenanthrene compound with a base to precipitate the polymerized phenanthrene compound, and an additional purification and separation step for the manufacture of the final product. More specifically, in a preferred embodiment of the invention, it is not necessary to neutralize the polymerization of the phenanthrene compound with ammonia, potassium hydroxide or sodium hydroxide. Also do not filter the final product before use. Finally, the use of formic acid can also produce a polymerized non-nathene product without any significant nitrogen emissions. Conversely, in the manufacture of aggregates In the case of products, if other strong acids such as sulfuric acid, hydrochloric acid and acetic acid are used, significant nitrogen emissions will be produced.

The examples cited in U.S. Patent No. 3,743,584 are described in terms of the yield of the wet cake, and Table 1 below provides the properties of the materials prepared in accordance with these examples.

All of the above materials may also contain some alkali metal salts (KCl, NaCl, K ₂ SO ₄ , Na ₂ SO ₄ , (NH ₄ ) ₂ SO ₄ , NH ₄ Cl, etc.).

Conversely, the methods described herein do not include a neutralization step, therefore, There will be no inorganic salts.

Because of the salt content of the precipitate, the percentage of monomer is difficult to predict. However, the inventors of the present invention have determined that the monomer is initially 0.1 mole (36.45 grams), and after passing the process described herein, the entire reaction mass is diluted with one liter of aqueous deionized water. The properties of this material are quite excellent. If there is no polymerization procedure, the monomer is subjected to performance evaluation, and the result is at most bad.

When the polymerized quinone compound is added to the copper electrolyte as described herein, the generally dim crystalline precipitate becomes bright over a relatively wide range of current densities. The current density is preferably maintained at a level between about 0.1 and about 8.0 ASD.

The materials produced according to the invention are also particularly suitable for use with other conventional gloss formers and/or wetting agents to deposit coatings which are free of turbidity and high brightness. Gloss forming agents and/or wetting agents (as described, for example, in U.S. Patent No. 3,743,584) may also be added to the copper electrolyte of the present invention within the preset limits.

Further, the concentration ratio of each compound in the copper electrolytic solution can be varied within a relatively large range.

The polymeric phenacetal compound produced in accordance with the methods described herein can be used in an acidic copper electrolyte at a concentration of between about 0.0001 g/liter and 0.5 g/l, preferably between about 0.002 g/ The rise is between about 0.015 g/l.

Example 1:

36.45 g (0.1 mol) of the amine compound C ₂₁ H ₂₁ N ₄ Cl (2-methyl-3-amino-5-phenyl-7-dimethylaminophenazone chloride), Available from several dye manufacturers, it is dissolved in about 300 ml of 90% by weight of formic acid. The solution was then cooled to between about -10 and 0 ° C and the diazotized solution was slowly added (7.59 grams of sodium nitrite dissolved in 25.00 grams of deionized water, approximately 0.11 moles) while maintaining the temperature at the specified Within the scope. After the addition was completed, the reaction mass was stirred at the specified temperature for about 2 hours. Any excess nitrous acid is then destroyed by mixing with a sulfamic acid solution which is 1.20 grams of sulfamic acid dissolved in 10 grams of deionized water. When the solution was warmed to about 20 ° C, almost no gas evolution was observed.

The reaction was complete at this point and the dye concentration was diluted with deionized water and mixed for four hours. It is now ready for use directly in acid copper electrolytes without any additional intermediate steps.

Comparative example:

36.45 g (0.1 mol) of the amine compound (2-methyl-3-amino-5-phenyl-7-dimethylaminophenazone chloride) was dissolved in 423 ml of deionized water And then suspended in 210 ml of 37% hydrochloric acid (12.0 N solution). Thereafter, the solution was diazotized by mixing with a solution of 7.59 g of sodium nitrite dissolved in 35.00 g of deionized water. Any excess nitrous acid is then destroyed by mixing with a sulfamic acid solution which is 1.20 grams of sulfamic acid dissolved in 10 grams of deionized water. The solution was warmed to approximately 20 °C.

However, significant gas release was observed as a result. After the nitrogen evolution was complete, the dye was neutralized by mixing a solution of 315.00 grams of 45% potassium hydroxide with 95.32 grams of deionized water. Neutralizing dye It was filtered off from the solution in the form of a precipitate, dried in an oven, and then ground to a fine powder. Finally, the resulting dye was dissolved in sulfuric acid and then diluted with deionized water to form a bath.

The dried polymeric non-nathene product also contains residual inorganic salts. Therefore, when the desired product is produced in hydrochloric acid and then neutralized with sodium or potassium to form sodium chloride or potassium chloride, it is necessary to avoid the salt/product ratio exceeding the consumption of the plating bath.

As described herein, the process of the present invention produces a polymeric non-nathene compound that can be fabricated in a simpler manner, requires fewer processing steps, and does not produce any significant outgassing.

Although the present invention has been described with reference to the specific embodiments thereof, it is obvious that many modifications, improvements and changes may be made without departing from the scope of the invention. Accordingly, the present invention is intended to embrace all such modifications, modifications and All patent applications, patents, and other publications cited herein are hereby incorporated by reference in their entirety.

Claims (12)

A method of making a polymeric non-nathene compound having the following general formula: Wherein R ¹ , R ² , R ⁴ , R ⁵ , R ⁶ , R ⁸ and R ⁹ are the same or different and represent hydrogen, lower alkyl or substituted aryl, R ³ starts with NH ₂ and is subsequently polymerized To diazotize, R ⁵ and R ⁸ may additionally represent a monomer or a polymerized phenanthrene radical, R ⁷ is a carbon in the aromatic ring, and wherein R ^X -NR ^Y represents a substituted amine, and R ^X and R ^Y stands for CH ₃ , C ₂ H ₅ , And any combination of hydrogen, but R ^X and R ^Y cannot be hydrogen at the same time, A is an acid radical, and n is an integer between 2 and 100. The method comprises the steps of: a) dissolving an effective amount of an amine compound In a formic acid solution; b) adding a nitrite to diazotize the amine compound; and c) adding a sulfamic acid to neutralize any excess nitrous acid that may be formed in step b), thereby producing a polymeric non-nafene鎓 compound. The method of claim 1, wherein n is an integer between 2 and 20. The method of claim 1, wherein the amine compound is selected from the group consisting of 2-methyl-3-amino-7-dimethylamino-5-phenylphenazine Acid salt, 3-amino-6-methyl-7-dimethylamino-5-phenylphenazinium hydrogensulfate, 2-methyl-3-amino-7-diethylamino -5-phenylphenazinium chloride, 3-amino-7-dimethylamino-5-methylphenazinium acetate, 2-methyl-3-amino-7-anilino -5-phenylphenazone bismuth hydrogensulfate, 2-methyl-3-amino-7-dimethylaminobisphenazine hydrogensulfate, 3-amino-7-methylamino group- 5-phenylphenazone acetate, 2-phenyl-3-amino-7-ethylamino-5-phenylphenazine chloride, 1,2,6,9-tetramethyl 3-amino-7-diethylamino-5-phenylphenazinium hydrogensulfate, 2,8-dimethyl-3-amino-7-diethylamino-5-toluene a group consisting of chlorpheniramine and 2,9-diphenyl-3-amino-6-methyl-7-dimethylamino-5-phenylphenazinium hydrogensulfate In the group. The method of claim 1, wherein the nitrite is sodium nitrite. The method of claim 1, wherein the amine compound is dissolved in formic acid having a temperature between about -10 and about 0 °C. The method of claim 1, wherein after step b), the reaction is warmed to at least 20 °C. The method of claim 1, further comprising the step of adding the polymerized phenanthrene compound to the acid copper electrolytic bath. The method of claim 1, wherein the concentration of the amine compound in the formic acid solution is between about 100 g/liter and about 200 g/liter. The method of claim 8, wherein the concentration of the amine compound in the formic acid solution is between about 120 g/L and about 185 g/L. between. The method of claim 1, wherein the method of producing a polymerized phenanthrene compound does not include the step of neutralizing the phenanthrene compound by alkali. The method of claim 1, wherein substantially no outgas of nitrogen occurs. The method of claim 1, wherein the concentration of the polymerized phenanthrene in the polymerized quinone compound is between about 30 g/liter and about 34 g/liter. .