KR20160137986A - Novel solvent for polyamide imides and polyimides - Google Patents

Abstract

The present invention relates to the use of 3-methoxy-N, N-dimethylpropanamide as a solvent for polyamide-imide and / or polyimide, the use of 3-methoxy-N, N-dimethylpropanamide, polyamide- And / or polyimide, and a process for preparing the composition using 3-methoxy-N, N-dimethylpropanamide.

Description

Novel solvents for polyamide-imides and polyimides are disclosed.

All documents cited in this application are incorporated herein by reference in their entirety.

The present application relates to novel solvents for polyamide-imides and polyimides and to their corresponding uses.

Background Art [0002]

Polyamide-imides are disclosed, for example, in US Pat. No. 3,554,984, DE 24 41 020, DE 25 56 523, DE 12 66 427 and DE 19 56 512, .

Likewise, polyimides are known and described, for example, in British Patent Publications GB 898,651, US 3,207,728, EP 0 274 602 and EP 0 274 121.

These types of resins are used in many fields, including for example wire enamels.

High-grade wire-coating materials, which are typically employed recently, are generally prepared by combining a solution containing a typical binder, such as polyamide-imide and polyimide, in a solvent, optionally in combination with a commercially typical hydrocarbon diluent .

The organic solvent for dissolving polyamide-imide and polyimide includes an amide solvent such as dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone (NMP). These solvents may be partially replaced by diluents. The prior art prefer to use a solvent comprising pure solvent or pure solvent mixture, or a diluent up to 40% by weight based on the total weight thereof.

In order to dissolve polyamides and / or polyimides, it is usually necessary to use NMP, especially when they are aromatic in their entirety.

However, the known and effective solvents of the prior art, especially NMP, have environmental, toxicity, and / or administrative (REACH) related problems.

problem:

Thus, the problem addressed by the present invention is that it is possible to dissolve polyamide-imide and / or polyimide very well and to solve the problems of the prior art solvents To provide a novel solvent or solvent composition that does not have the desired properties.

Another aspect of the problem addressed by the present invention is to provide a solvent in which the wholly aromatic polyamide-imide and / or the wholly aromatic polyimide can be dissolved.

Particularly intended is that NMP, which has been criticized for reasons including toxicity considerations, can be substituted, and compositions without NMP can be prepared.

Another problem addressed by the present invention is to provide a composition comprising polyamide-imide and / or polyimide, which can be formulated without NMP as a solvent, more specifically a wire enamel, and also a process for producing them .

solution:

The problem is 3-methoxy -N, N- dimethyl-a propanamide (CAS No .: 53185-52- 7) of polyamide-imide in the use and / or the polyimide solvent, 3-methoxy -N , N-dimethylpropanamide, polyamide-imide and / or polyimide, and also a process for preparing a composition using such 3-methoxy-N, N-dimethylpropanamide do.

Still other solutions will become apparent from the detailed description and claims.

Definitions:

In the context of the present invention, all quantitative data should be understood as weight data, unless otherwise indicated.

In the context of the present invention, the term "room temperature" refers to a temperature of 20 ° C. The temperature data is in degrees Celsius (° C) unless otherwise specified.

Unless otherwise indicated, the reactions and / or process steps mentioned are carried out at standard / atmospheric pressure, i.e. 1013 mbar.

In the context of the present invention, the phrase "and / or" includes any desired combination, as well as any combination of the elements mentioned in the respective list.

The overall aromatic polyamide-imide and the wholly aromatic polyimide are each one in which each of the structural components is composed of an aromatic compound.

details:

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

Surprisingly, both of the polyamide-imide and polyimide can be remarkably dissolved by this solvent.

Thus, the subject matter of the present invention includes for polyamide-imides, for polyimides, for mixtures of polyamide-imides and polyimides, and also for polyamide-imides, polyimides or mixtures of these resins 3-methoxy-N, N-dimethylpropanamide as a solvent for the composition.

Another subject of the present invention is the use of 3-methoxy-N, N-dimethylpropanamide as a solvent for wire enamel having a binder component comprising polyamide-imide and / or polyimide, or a binder component thereof .

Likewise, the subject matter of the present invention is to provide polyimide-imides and / or polyimides as binders and to provide pure 3-methoxy-N, N-dimethylpropanamide, or 60 wt.% Or more of 3-methoxy- , N-dimethylpropanamide and up to 40% by weight of a diluent, preferably not less than 70% by weight of 3-methoxy-N, N-dimethylpropanamide and up to 30% by weight of diluent, more preferably not less than 80% Methoxy-N, N-dimethylpropanamide and up to 20% by weight of a diluent, particularly preferably not less than 90% by weight of 3-methoxy-N, N-dimethylpropanamide and up to 10% by weight of a diluent, 3-methoxy-N, N-dimethylpropanamide and a diluent), said composition being particularly preferably wire enamel.

The main subject of the present invention is a method for preparing a composition, more specifically a wire enamel, by mixing constituents, wherein the binder component comprises or consists of polyamide-imide and / or polyimide Methoxy-N, N-dimethylpropanamide or 60 wt.% Or more of 3-methoxy-N, N-dimethylpropanamide and up to 40 wt.% Of a diluent, preferably 70 Methoxy-N, N-dimethylpropanamide and not more than 30% by weight of diluent, more preferably not less than 80% by weight of 3-methoxy-N, N-dimethylpropanamide and not more than 20% , Particularly preferably at least 90% by weight of 3-methoxy-N, N-dimethylpropanamide and up to 10% by weight of a diluent, said percentages being based on the total weight of 3-methoxy-N, N-dimethylpropanamide and diluent Lt; / RTI > as a standard) The.

The desired 3-methoxy-N, N-dimethylpropanamide solvent of the present invention may be any desired polyamide-imide and / or polyamide-imide, including polyamide-imides which are entirely aromatic and / As it can be employed in polyimide, the present invention applies to any desired polyamide-imide and / or polyimide.

It is of course also possible in the context of the present invention that the wholly aromatic polyamide-imides and / or polyimides are used in the form of mixtures with polyimide-imides and / or polyimides which are not aromatic in their entirety.

With respect to polyamide-imides and polyimides which can be used in the context of the present invention, the following may be mentioned by way of example:

The polyamide-imide can be obtained, for example, from polycarboxylic acids or their anhydrides, in which two carboxyl groups are in adjacent positions and which must additionally have one or more other functional groups, and from one or more primary amino groups Can be prepared from polyamines by known methods. Instead of an amine group, an isocyanate group can be used to form an imido ring. The polyamide-imide may also be a polyamide; A polyisocyanate containing at least two NCO groups; And cyclic dicarboxylic acid anhydride containing at least one other group capable of condensation or addition reaction.

Furthermore, if one of the constituents already contains an imide group, it is also possible to prepare polyamide-imides from diisocyanates or diamines and dicarboxylic acids. Thus, it is particularly possible, first, to react the tricarboxylic acid anhydride with a diprimary amine to provide the corresponding diimidocarboxylic acid which is then reacted with a diisocyanate to form a polyamide- Can be provided.

For polyamide-imides, it is preferred to use tricarboxylic acids in which the carboxyl groups are adjacent to each other, and / or anhydrides thereof. Trimellitic anhydride and naphthalenetricarboxylic acid anhydride are preferred and corresponding aromatic tricarboxylic acid anhydrides such as biphenyltricarboxylic anhydride are preferred and also, as in the examples listed in DE-OS 19 56 512, Tricarboxylic acids having two benzene rings in the molecule and two adjacent carboxyl groups are preferred. Trimellitic anhydride is very particularly preferably used.

The carboxylic acid anhydride is typically reacted with a diisocyanate in a suitable solvent, wherein the amide is formed from a carboxyl group, the imide is formed from an anhydride structure, and the carbon dioxide is removed.

Examples of suitable diisocyanates are trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, propylene diisocyanate, ethylene ethylene 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-tolylene diisocyanate , 2,6-tolylene diisocyanate, 4,4'-biphenylene diisocyanate, 1,5-naphthylene diisocyanate, 1,4-naphthylene diisocyanate, 1-isocyanatomethyl- Bis (4-isocyanatocyclohexyl) methane, bis (4-isocyanatophenyl) methane, 4,4'-di SOCCIA Ney Todi ether and 2,3-bis (8-isocyanuric Ney took butyl) -4-octyl-5-hexyl cyclohexene. It is preferred to use isomeric mixtures of tolylene diisocyanate and also bis (4-isocyanatophenyl) methane.

The imide structure can also be prepared by the reaction of an anhydride group with a diamine. As the amine component, a di-primary diamine that reacts first with 2 moles of polycarboxylic acid can be used. This is then configured with the diisocyanate on the remaining free carboxyl groups to provide polyamide-imides.

As both polyamide-imides and polyimides are well known to those skilled in the art, no further detailed description is required herein.

In one variant of the invention, it is preferred that the polyamide-imide and / or polyimide are entirely aromatic.

In the context of the present invention, in addition to 3-methoxy-N, N-dimethylpropanamide, the diluent which can be optionally used consists preferably of a pure hydrocarbon compound and / or a mixture thereof - Atoms other than hydrogen are present as technical impurities at most.

Diluent used in the context of the present invention, more preferably, toluene, xylene, solvent naphtha (solvent naphtha), toluene, ethylbenzene, cumene, heavy (heavy) benzene, for example, Solvesso ^(R) in the table of various types of C ₁₀ - C ₁₃ aromatic mixtures, for example various types of hydrocarbons of the Deasol ^(R) table, aromatic-rich hydrocarbon mixtures, and mixtures thereof.

The diluent used in the context of the present invention is particularly preferably selected from the group consisting of xylene, solvent naphtha, toluene, ethylbenzene, cumene, heavy benzene, C ₁₀ -C ₁₃ aromatic mixtures, aromatic-rich hydrocarbon mixtures, Lt; / RTI >

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

In one variant of the invention, up to 20% by weight of the diluent can be replaced by dimethylacetamide. Thus, in variations of the present invention it is possible to use a diluent / dimethylacetamide mixture in a weight ratio of 99: 1 to 80:20 in place of the diluent.

The composition of the present invention particularly preferably does not contain NMP, i.e. the amount of NMP is less than 1 wt%, preferably less than 0.5 wt%, more preferably less than the detection limit.

Surprisingly and unexpectedly, 3-methoxy-N, N-dimethylpropanamide may be suitable for solving the problems addressed by the present invention and produces very good results.

The compositions of the present invention, and more particularly the wire enamel, may contain any desired mixtures of polyamide-imide alone, polyimide alone, or both.

Furthermore, the composition of the present invention, and more particularly the wire enamel, may comprise additional components as required and / or preferred, depending on the respective application. These components can be cross-linking agents, pigments and a wide variety of optional additives, such as wetting agents, dispersion aids, stabilizers, and the like.

Various implementations of the invention, including but not limited to implementations of various dependent claims, may be combined with one another in any desired manner.

The present invention is now illustrated with reference to the following non-limiting examples.

Example:

Example 1 - Preparation of polyamide-imide resin in NMP:

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

The resulting mixture was allowed to react at 85 캜 for 2 hours, followed by further reaction at 95 캜 for 2 hours, and finally at an increased temperature of 125 캜 for 4 hours.

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

This resulted in a solution of polyamide-imide resin having a resin concentration of 36% (weight percent based on the weight of the total solution) and a viscosity of 1900 mPas at 20 占 폚.

Example 2 - Preparation of polyamide-imide resin in 3-methoxy-N, N-dimethylpropanamide:

A 2 l four-necked flask equipped with a stirrer, a cooling tube and a thermometer was charged with 192 g (1 mole) of trimellitic anhydride, 250 g (1 mole) of 4,4'-diphenylmethane diisocyanate and 500 g of 3- Methoxy-N, N-dimethylpropanamide.

The resulting mixture was allowed to react at 85 DEG C for 5 hours.

The mixture was then cooled to 50 DEG C and then 20 g of 3-methoxy-N, N-dimethylpropanamide, 50 g of dimethylacetamide and 200 g of aromatic hydrocarbons (1: 1 of xylene and solvent naphtha Mixture) was added to the reaction mixture.

This resulted in a solution of polyamide-imide resin with a resin concentration of 37% (weight percent based on the weight of the total solution) and a viscosity of 1500 mPas at 20 占 폚.

Example 3 - Preparation of polyamide-imide resin in 3-methoxy-N, N-dimethylpropanamide:

A 2 l four-necked flask equipped with a stirrer, a cooling tube and a thermometer was charged with 192 g (1 mole) of trimellitic anhydride, 250 g (1 mole) of 4,4'-diphenylmethane diisocyanate and 500 g of 3- Methoxy-N, N-dimethylpropanamide.

The resulting mixture was allowed to react at 85 DEG C for 5 hours to react at an elevated temperature of 115 DEG C for 1 hour.

The mixture was then cooled to 50 DEG C and 340 g of 3-methoxy-N, N-dimethylpropanamide and 295 g of aromatic hydrocarbons (1: 1 mixture of xylene and solvent naphtha) .

This resulted in a solution of the polyamide-imide resin having a resin concentration of 25.6% (weight percent based on the weight of the total solution) and a viscosity of 1300 mPas at 20 占 폚.

Example 4 - Preparation of polyimide resin in NMP:

A 2 l four-necked flask equipped with a stirrer, a cooling tube and a thermometer was charged with 198 g (1 mole) of 4,4'-methylenedianiline, 322 g (1 mole) of 3,3 ', 4,4'-benzophenone Tetracarboxylic dianhydride and 2100 g of NMP.

The resulting mixture was allowed to react at 35 DEG C for 5 hours.

This resulted in a solution of polyimide resin having a resin concentration of 20% (weight percent based on the weight of the total solution) and a viscosity of 700 mPas at 20 占 폚.

Example 5 - Preparation of polyimide resin in 3-methoxy-N, N-dimethylpropanamide:

A 2 l four-necked flask equipped with a stirrer, a cooling tube and a thermometer was charged with 198 g (1 mole) of 4,4'-methylenedianiline, 322 g (1 mole) of 3,3 ', 4,4'-benzophenone Tetracarboxylic dianhydride and 2100 g of 3-methoxy-N, N-dimethylpropanamide.

The resulting mixture was allowed to react at 30 DEG C for 6 hours.

This resulted in a solution of polyimide resin with a resin concentration of 20% (weight percent based on the weight of the total solution) and a viscosity of 2000 mPas at 20 占 폚.

Example  6 - Experimental wire (Control wire) 1 CW 1 ):

The polyamide-imide resin (PAI 1) from Example 1 was applied to a copper wire having a diameter of 0.71 mm at a temperature of 500 to 550 캜 in a baking oven at a speed of 32 m / min.

The total thickness of the applied insulating layer was approximately 65 to 75 mu m.

Example  7 - Experimental wire  2( CW 2 ):

The polyamide-imide resin (PAI 2) from Example 2 was applied to a copper wire having a diameter of 0.71 mm in a baking oven at a temperature of 500 to 550 ° C at a speed of 32 m / min.

The total thickness of the applied insulating layer was approximately 65 to 75 mu m.

Example  8 - Experimental wire  3 ( CW 3 ):

The polyamide-imide resin (PAI 3) from Example 3 was applied to a copper wire having a diameter of 0.71 mm in a baking oven at a temperature of 500 to 550 占 폚 at a speed of 32 m / min.

The total thickness of the applied insulating layer was approximately 65 to 75 mu m.

Example  9 - Experimental wire  4( CW 4 ):

The polyimide resin (PI 4) from Example 4 was applied to a copper wire having a diameter of 0.71 mm at a temperature of 500 to 550 캜 in a baking oven at a speed of 28 m / min.

The total thickness of the applied insulating layer was approximately 60 to 65 mu m.

Example  10 - Experimental wire  5 ( CW 5 ):

The polyimide resin (PI 5) from Example 5 was applied to a copper wire having a diameter of 0.71 mm at a temperature of 500 to 550 占 폚 in a baking oven at a rate of 28 m / min.

The total thickness of the applied insulating layer was approximately 60 to 65 mu m.

The results are summarized in Table 1 below:

CW 1 CW 2 CW 3 CW 4 CW 5 Resin type PAI PAI PAI PI PI Enamelling Machine * MAG HEL 4/5 MAG HEL 4/5 MAG HEL 4/5 MAG HEL 4/5 MAG HEL 4/5 Type and strength (degree) Single coating; Strength 2 Single coating; Strength 2 Single coating; Strength 2 Single coating; Strength 2 Single coating; Strength 2 Number of passes 14 14 14 14 14 Application type Nozzle Nozzle Nozzle Nozzle Nozzle Average Total Diameter (mm) Total: 0.78
Conductor: 0.703 Total: 0.775
Conductor: 0.703 Total: 0.768
Conductor: 0.703 Total: 0.763
Conductor: 0.703 Total: 0.764
Conductor: 0.703 Film formation (mm) Formation: 0.075 Formation: 0.072 Formation: 0.065 Formation: 0.060 Formation: 0.061 Maximum speed (m / min) 48 48 48 48 48 Surface condition Acceptable Acceptable Acceptable Acceptable Acceptable flexibility Height 20% Ok1x Height 20% Ok1x Height 20% Ok1x Height 20% Ok1x Height 20% Ok1x Tangent delta (° C) 266 265 265 271 274 Breakdown voltage (KV) at ambient temperature 10 9.8 10 6 6.2 Thermal pressure (℃) 390 390 390 > 550 > 550 Thermal shock (1/2 hour) 1D 260 ° C 1D 260 ° C 1D 260 ° C 1D 300 ° C 1D 300 ° C

* Enamelling conditions:

Annealing zone temperature: 630 ° C

Fan rotation speed: 2800 rpm

Oven temperature: 520 ° C

Nozzle order (mm): 0.75x2, 0.76x2, 0.77x2, 0.78x2, 0.79x2, 0.80x2, 0.81

Testing of the wires was always carried out in accordance with IEC 60851 standard.

The 3-methoxy-N, N-dimethylpropanamide-containing enamel exhibited the same level of properties as the prior art NMP-containing enamel.

Claims (7)

For polyamide-imides, for polyimides, for mixtures of polyamide-imides and polyimides, and for mixtures of polyamide-imides, polyimides or polyamide-imides and polyimides Use of 3-methoxy-N, N-dimethylpropanamide as a solvent for the composition. The use according to claim 1, wherein the composition is a wire enamel having a binder component comprising polyamide-imide and / or polyimide or a binder component thereof. Polyamide-imide and / or polyimide and pure 3-methoxy-N, N-dimethylpropanamide; or
60% by weight or more of 3-methoxy-N, N-dimethylpropanamide and up to 40% by weight of a diluent (these percentages being based on the total weight of 3-methoxy-N, N- dimethylpropanamide and diluent) ≪ / RTI > The composition of claim 3, wherein the polyamide-imide and / or polyimide is a binder of the composition. 5. The composition of claim 3 or 4, wherein the composition is wire enamels. A process for producing a composition comprising a binder, a solvent and optionally further components, wherein the composition has a binder component comprising polyamide-imide and / or polyimide, or a binder component thereof,
Pure 3-methoxy-N, N-dimethylpropanamide; or
60% by weight or more of 3-methoxy-N, N-dimethylpropanamide and up to 40% by weight of a diluent (these percentages being based on the total weight of 3-methoxy-N, N- dimethylpropanamide and diluent) Is used as the solvent. 7. The method of claim 6, wherein the composition is a wire enamel.