TW201540747A - New solvent for polyamide-imides and polyimides - Google Patents

Abstract

Use of 3-methoxy-N,N-dimethylpropanamide as solvent for polyamide-imides and/or polyimides, compositions comprising 3-methoxy-N,N-dimethylpropanamide, polyamide-imides and/or polyimides, and processes for producing such compositions using 3-methoxy-N,N-dimethylpropanamide.

Description

New solvent for polyamidimide and polyimine

All documents cited in the present application are hereby incorporated by reference in their entirety.

This invention relates to new solvents for polyamidoximines and polyimines and also to related applications.

Polyamides and imines are known and are described, for example, in US Pat. No. 3,554,984, DE 24,410,220, DE 2556523, DE 1266427 and DE 1956512.

Polyimine is also known and is described, for example, in GB 898,651, US 3,207,728, EP 0274602, EP 0274121.

Such resins are used in numerous parts, including, for example, wire enamels.

These high-grade wire coating materials which are currently commonly used are generally solutions of a typical binder such as polyamidamine and polyimine in a solvent, as appropriate, in combination with commercially available hydrocarbon diluents. Composition.

The organic solvent used to dissolve the polyamidimide and the polyimine includes guanamine solvents such as dimethylformamide, N,N-dimethylacetamide and N-methylpyrrolidone (NMP). ). These solvents may be partially replaced by a diluent. The prior art prefers to use a pure solvent or a pure solvent mixture, or a solvent containing up to 40% by weight (based on the total weight) of the diluent.

In order to dissolve the polyamidimide and/or the polyimine, especially if it is completely aromatic, it is usually necessary to use NMP.

However, prior art known and effective solvents, in particular NMP, present environmental, poison and/or management (REACH) problems.

problem:

Therefore, the problem solved by the present invention is to find a new solvent or solvent mixture which is very good at dissolving polyamidoximine and/or polyimine and no longer has problems with prior art solvents, and the manufacturing result is equivalent. They are currently in the prior art.

Another aspect of the problem addressed by the present invention is to find a solvent which will dissolve the fully aromatic polyamidoximine and/or fully aromatic polyimine.

In particular, the aim is to replace NMPs that have been criticized for reasons including toxicological considerations, and to obtain compositions that do not contain NMP.

Another problem addressed by the present invention is to find a composition comprising polyamidoximine and/or polyimine which can be formulated without the use of NMP as a solvent, more particularly an enamelled lacquer, and a process for its preparation.

Solution:

These problems are caused by the use of 3-methoxy-N,N-dimethylpropanamide (CAS No. 53185-52-7) as a solvent for polyamidoximine and/or polyimine. Including 3-methoxy-N,N-dimethylpropionamide, polyamidoximine and/or polyamidiamine related compositions, and using 3-methoxy-N,N-dimethyl The method of preparing these compositions by acrylamide is solved.

Other solutions can be understood by the embodiments and the scope of the patent application.

Definition of Terms:

In the context of the present invention, the full amount of data, unless otherwise indicated, is to be understood as weight data.

In the context of the present invention, the term "room temperature" means a temperature of 20 °C. Temperature data, in degrees Celsius (°C), unless otherwise indicated.

Unless otherwise indicated, the recited reactions and/or method steps are carried out at standard/atmospheric pressure (i.e., at 1013 mbar).

In the context of the present invention, the expression "and/or" includes not only any desired combination, but also all combinations of elements set forth in the respective listings.

The fully aromatic polyamidolimine and the fully aromatic polyimine are respectively composed of aromatic compounds in which individual structural components are all composed.

In the context of the present invention, it has been surprisingly found that the problems of the prior art can be solved by the use of 3-methoxy-N,N-dimethylpropanamide.

Using this solvent, surprisingly, both polyamidimide and polyimine can be significantly dissolved.

Accordingly, the gist of the present invention is to use 3-methoxy-N,N-dimethylpropionamide as the polyamidoximine, for the polyimine, for the polyamidoximine and A mixture of polyimine and a solvent for a composition comprising polyamidimide, polyimine or a mixture of such resins.

A further subject of the invention is the use or composition of 3-methoxy-N,N-dimethylpropionamide as a binder component thereof, including polyamidimide and/or polyimine. The solvent for the wire lacquer.

Similarly, the subject matter of the present invention includes polyamidoximine and/or polyimine as binder and pure 3-methoxy-N,N-dimethylpropionamide or at least 60% by weight. 3-methoxy-N,N-dimethylpropionamide and not more than 40% by weight of diluent, preferably at least 70% by weight of 3-methoxy-N,N-dimethylpropanamide and Not more than 30% by weight of diluent, more preferably at least 80% by weight of 3-methoxy-N,N-dimethylpropionamide and not more than 20% by weight of diluent and particularly preferably at least 90% by weight a composition of a mixture of 3-methoxy-N,N-dimethylpropionamide and no more than 10% by weight of a diluent as a solvent, in each case based on 3-methoxy-N The total weight of N-dimethylpropionamide and the diluent, and more particularly, the composition is an enameled wire lacquer.

The subject matter of the present invention is, inter alia, a composition for preparing a composition by mixing the components, In particular, the method of enamelled wire lacquer, the binder component of which comprises or consists of polyamidimide and/or polyimine, and the solvent used is pure 3-methoxy-N,N- Dimethylpropionamide or 3-methoxyl containing at least 60% by weight of 3-methoxy-N,N-dimethylpropionamide and not more than 40% by weight of diluent, preferably at least 70% by weight Base-N,N-dimethylpropionamide and no more than 30% by weight of diluent, more preferably at least 80% by weight of 3-methoxy-N,N-dimethylpropanamide and no more than 20 % by weight of the diluent and particularly preferably at least 90% by weight of a mixture of 3-methoxy-N,N-dimethylpropionamide and no more than 10% by weight of the diluent, in each case based on The total weight of 3-methoxy-N,N-dimethylpropanamide and diluent.

The present invention is applicable to any desired polyamidoquinone imine and/or polyimine, since the 3-methoxy-N,N-dimethylpropionamine solvent of the present invention can be used for any desired aggregation. Amidoximine and/or polyimine, including, in particular, fully aromatic polyamidoximine and/or fully aromatic polyimine.

In the context of the present invention, fully aromatic polyamidoquinones and/or polyimines may of course also be used in combination with non-completely aromatic polyamidoquinones and/or polyimines.

With regard to the polyamidoximines and polyimines which can be used in the context of the present invention, for example, reference can be made to the following: polyamidoximines can be, for example, from polycarboxylic acids or their anhydrides in a known manner (two of them) The carboxyl group is in the ortho position and it must further have at least one other functional group) and is prepared from a polyamine having at least one amine group capable of undergoing a quinone imine linkage. Instead of the amine group, an isocyanate group can be used to form the quinone ring. The polyamidoximine may also be obtained by the reaction of polyamine, a polyisocyanate containing at least two NCO groups, and a cyclic dicarboxylic anhydride containing at least one other group capable of undergoing a condensation or addition reaction.

Further, the polyamidoquinone imides may also be prepared from diisocyanates or diamines and dicarboxylic acids, provided that one of the components already contains a quinone imine group. Thus, in particular, the tricarboxylic acid anhydride can be first reacted with a di-first-order diamine to obtain a corresponding diimine carboxylic acid, which is then reacted with a diisocyanate to obtain the polyamidoximine.

As the polyamidolimine, a tricarboxylic acid in which the carboxyl groups are ortho positions, and/or an anhydride thereof are preferably used. Preferred are corresponding aromatic tricarboxylic anhydrides such as trimellitic anhydride, naphthalene tricarboxylic anhydride, biphenyltricarboxylic anhydride, and other tricarboxylic acids having two benzene rings and two ortho-carboxy groups in one molecule. Examples such as those described in DE-OS 1956512. Extremely good use of trimellitic anhydride.

The carboxylic anhydrides are usually reacted with a diisocyanate in a suitable solvent, wherein the guanamine is formed from the carboxyl groups and the quinone imine is formed from the anhydride structure by removal of carbon dioxide.

Examples of suitable diisocyanates are trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, propyl diisocyanate, ethyl ethyl diisocyanate, 3, 3, 4-trimethylhexamethylene diisocyanate, 1,3-cyclopentyl diisocyanate, 1,4-cyclohexyl diisocyanate, 1,2-cyclohexyl diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,5-tolyl diisocyanate, 2,6-tolyl diisocyanate, 4,4'-strandy diisocyanate, 1,5-anthranyl Isocyanate, 1,4-naphthyl diisocyanate, 1-isocyanatomethyl-5-isocyanato-1,3,3-trimethylcyclohexane, bis(4-isocyanatecyclohexyl) Methane, bis(4-isocyanatophenyl)methane, 4,4'-diisocyanate diphenyl ether and 2,3-bis(8-isocyanatooctyl)-4-octyl-5-hexyl Cyclohexene. It is preferred to use a mixture of isomers of these tolyl diisocyanates, and bis(4-isocyanatophenyl)methane.

The quinone imine structures can also be prepared by the reaction of the anhydride groups with a diamine. With regard to the amine component, a di-first-diamine can be used, which is first reacted with a dimorone polycarboxylic acid. These are then constructed with the diisocyanate on the remaining free carboxyl groups to obtain the polyamidoximine.

Since both polyamidimide and polyimine are well known to those skilled in the art, no further details are required herein.

In a variant of the invention, the polyamidoquinones and/or polyimines are preferably completely aromatic.

In the context of the present invention, in addition to 3-methoxy-N,N-dimethylpropanamide, The diluent used is preferably composed of a pure hydrocarbon compound and/or a mixture thereof - in other words, atoms other than carbon and hydrogen are present as technical impurities.

The diluents used in the present invention are preferably selected from the group consisting of xylene, solvent naphtha, toluene, ethylbenzene, cumene, heavy benzene, and various Solvesso ^(R) trademarks. A C ₁₀ -C ₁₃ aromatic mixture (for example, various types of hydrocarbons such as the Deasol ^(R) brand, aromatic-rich hydrocarbon mixtures), and mixtures thereof.

Groups are selected from the group consisting of their particularly preferred diluent of the system used in the context of the present invention: xylene, solvent naphtha, toluene, ethylbenzene, cumene, heavy benzene, C ₁₀ -C ₁₃ aromatic Mixtures, aromatic-rich hydrocarbon mixtures, and mixtures thereof.

In a variation of the invention, the diluent used is a mixture of xylene and solvent naphtha, preferably in a ratio of 1:1.

In a variant of the invention, up to 20% by weight of the diluent can be substituted with dimethylacetamide. Thus, in a variation of the invention, the diluent can be replaced with a diluent/dimethylacetamide mixture in a weight ratio from 99:1 to 80:20.

In particular, the compositions of the present invention are free of NMP, meaning that the amount of NMP is less than 1% by weight, preferably less than 0.5% by weight, and more specifically below the detection limit.

3-Methoxy-N,N-dimethylpropanamide is suitable for solving the problems to be solved by the present invention and achieving very good results is surprising and unpredictable.

The compositions of the present invention, more particularly enamelled lacquers, may contain only polyamidimide, only polyimine or any desired mixture of the two.

Furthermore, the compositions of the present invention, and more particularly the enamelled lacquer, may include other ingredients that are necessary and/or desired for each field of use. These ingredients can be crosslinkers, pigments, and any of a wide variety of additives, examples being wetting agents, dispersing aids, stabilizers, and the like.

Various embodiments of the invention, including, but not limited to, the scope of the various dependent claims, may be combined in any desired manner.

The invention will now be elucidated with reference to the following non-limiting examples.

Example:

Example 1 - Preparation of Polyamidoximine Resin Resin in NMP:

Add 192 g (1 mol) of trimellitic anhydride, 250 g (1 mol) of 4,4'-diphenylmethane diisocyanate and 500 g of N-methylpyrrolidone to a 2 liter four-necked flask equipped with a stirrer, a cooling tube and a thermometer. (NMP).

The resulting mixture was allowed to stand at 85 ° C for 2 hours, then further reacted at 95 ° C for 2 hours, and finally at 450 ° C for 4 hours.

Thereafter, the mixture was cooled to 50 ° C, and then 25 g of NMP, 60 g of dimethylacetamide and 200 g of an aromatic hydrocarbon (1:1 mixture of xylene and solvent naphtha) were added to the reaction mixture.

This produced a polyamidoquinone imide resin solution having a resin concentration of 36% (by weight based on the total solution weight) and a viscosity of 1900 mPas at 20 °C.

Example 2 - Preparation of Polyamidoximine Resin Resin in 3-Methoxy-N,N-Dimethylpropionamide:

In a 2 liter four-necked flask equipped with a stirrer, a cooling tube and a thermometer, 192 g (1 mol) of trimellitic anhydride, 250 g (1 mol) of 4,4'-diphenylmethane diisocyanate and 500 g of 3-methoxy-N were added. , N-dimethylpropionamide.

The resulting mixture was allowed to stand at 85 ° C for 5 hours.

Thereafter, the mixture was cooled to 50 ° C, and then 20 g of 3-methoxy-N,N-dimethylpropanamide, 50 g of dimethylacetamide and 200 g of an aromatic hydrocarbon (xylene and solvent naphtha) were added. A 1:1 mixture) was added to the reaction mixture.

This produced a polyamidoquinone imide resin solution having a resin concentration of 37% (by weight based on the total solution weight) and a viscosity of 1500 mPas at 20 °C.

Example 3 - Preparation of a polyamidoximine resin in 3-methoxy-N,N-dimethylpropanamide:

In a 2 liter four-necked flask equipped with a stirrer, a cooling tube and a thermometer, 192 g (1 mol) of trimellitic anhydride, 250 g (1 mol) of 4,4'-diphenylmethane diisocyanate and 500 g of 3-methoxy-N were added. , N-dimethylpropionamide.

The resulting mixture was allowed to stand at 85 ° C for 5 hours and then at 115 ° C for 1 hour.

Thereafter, the mixture was cooled to 50 ° C, and then 340 g of 3-methoxy-N,N-dimethylpropionamide and 295 g of an aromatic hydrocarbon (1:1 mixture of xylene and solvent naphtha) were added to The reaction mixture.

This produced a polyamidoquinone imide resin solution having a resin concentration of 25.6% (by weight of the total solution weight) and a viscosity of 1300 mPas at 20 °C.

Example 4 - Preparation of Polyimine Resin in NMP:

Add 198g (1mol) of 4,4'-methylenediphenylamine and 322g (1mol) of 3,3',4,4'-diphenyl in a 2 liter four-necked flask equipped with a stirrer, cooling tube and thermometer. Ketotetracarboxylic dianhydride and 2100 g of NMP.

The resulting mixture was allowed to stand at 35 ° C for 5 hours.

This produced a polyimide resin solution having a resin concentration of 20% (by weight based on the total solution weight) and a viscosity of 700 mPas at 20 °C.

Example 5 - Preparation of Polyimine Resin in 3-Methoxy-N,N-Dimethylpropionamide:

Add 198g (1mol) of 4,4'-methylenediphenylamine and 322g (1mol) of 3,3',4,4'-diphenyl in a 2 liter four-necked flask equipped with a stirrer, cooling tube and thermometer. Ketotetracarboxylic dianhydride and 2100 g of 3-methoxy-N,N-dimethylpropanamide.

The resulting mixture was allowed to stand at 30 ° C for 6 hours.

This produced a polyimide resin solution having a resin concentration of 20% (by weight based on the total solution weight) and a viscosity of 2000 mPas at 20 °C.

Example 6 - Control Wire 1 (CW1):

The polyamidoquinone imide resin obtained in Example 1 in an oven at a temperature of 500 to 550 ° C (PAI 1) was applied to a copper wire having a diameter of 0.71 mm at a rate of 32 m/min.

The total thickness of the insulating layer applied is about 65 to 75 μm.

Example 7 - Control Wire 2 (CW2):

The polyamidoximine resin (PAI 2) obtained from Example 2 was applied to a copper wire having a diameter of 0.71 mm at a rate of 32 m/min in an oven at a temperature of 500 to 550 °C.

The total thickness of the insulating layer applied is about 65 to 75 μm.

Example 8 - Control Wire 3 (CW3):

The polyamidoximine resin (PAI 3) obtained from Example 3 was applied to a copper wire having a diameter of 0.71 mm at a rate of 32 m/min in an oven at a temperature of 500 to 550 °C.

The total thickness of the insulating layer applied is about 65 to 75 μm.

Example 9 - Control Wire 4 (CW4):

The polyimine resin (PI 4) obtained from Example 4 was applied to a copper wire having a diameter of 0.71 mm at a rate of 28 m/min in an oven at a temperature of 500 to 550 °C.

The total thickness of the insulating layer applied is about 60 to 65 μm.

Example 10 - Control Wire 5 (CW5):

The polyimine resin (PI 5) obtained from Example 5 was applied to a copper wire having a diameter of 0.71 mm at a rate of 28 m/min in an oven at a temperature of 500 to 550 °C.

The total thickness of the insulating layer applied is about 60 to 65 μm.

The results are summarized in Table 1 below:

The testing of these conductors is always carried out in accordance with the standard IEC60851.

The enamel containing 3-methoxy-N,N-dimethylpropionamide exhibits the same level of properties as the current prior art NMP-containing enamel.

Claims (7)

a 3-methoxy-N,N-dimethylpropionamide as a mixture for polyamidoximine, for polyimine, for a mixture of polyamidoximine and polyimine, And use of a solvent comprising a polyamidoximine, a polyimine or a composition of a mixture of a polyamidimide and a polyimide. The use of claim 1, wherein the composition is a binder component comprising or consisting of a polyamidimide and/or a polyimide. One comprises polyamidimide and/or polyimine and pure 3-methoxy-N,N-dimethylpropionamide or contains at least 60% by weight of 3-methoxy-N,N- A composition of a mixture of dimethylpropionamide and no more than 40% by weight of a diluent based on the total weight of 3-methoxy-N,N-dimethylpropanamide and a diluent. The composition of claim 3, wherein the polyamidimide and/or polyimide is a binder of the composition. The composition of claim 3 or 4, wherein the compositions are enamelled lacquers. A method for preparing a binder component thereof comprising a polyamidoximine and/or a polyimide or a composition thereof by mixing a binder, a solvent and optionally other components, characterized in that it is used Pure 3-methoxy-N,N-dimethylpropanamide or a mixture containing at least 60% by weight of 3-methoxy-N,N-dimethylpropionamide and no more than 40% by weight of diluent As a solvent, the percentages are based on the total weight of 3-methoxy-N,N-dimethylpropanamide and a diluent. The method of claim 6, wherein the composition is an enameled wire lacquer.