Impregnating resin system for sealing materials in distribution devices

FIELD: chemistry.

SUBSTANCE: resin contains methyl nadic anhydride and/or hydrogenated methyl nadic anhydride and imidazole of formula , where R1, R2, R3 and R4 are given in claim 1.

EFFECT: obtained resin has significantly higher glass transition temperature with high quality mechanical characteristics and tracking resistance.

3 dwg, 7 cl, 1 ex

 

The present invention relates to the field of insulating resins for switchgear.

In electric switchgear, especially in a compact design, plays an important role insulating material.

When this is used, in particular, resins, which are used, for example, as an impregnating resin suitable for semi-finished products, for example, nonwovens, impregnated with epoxy resin.

The advantage of these resins is a high glass transition temperature, but often there are also high demands for favourable mechanical properties, high field strength and good resistance to the formation of tracks.

Thus, the task is an alternative to the existing solutions to create an insulating resin for switchgear, which increased the glass transition temperature will be different at the same time a good or even improved other properties, in particular with regard to the resistance to the formation of tracks.

This problem is solved by an insulating resin according to paragraph 1 of this application. Accordingly, it is proposed an insulating resin on the basis of complex pilgramage air for insulation materials in switching devices formed from the feedstock, including

a) material containing methylenedi-ngered and/or hydrogenated methylenedi-anhydride

(b) a material containing imidazole the following structure:

and R1selected from the group consisting of alkyl, long-chain alkyl, alkenyl, cycloalkyl, halogenated, aryl;

R2, R3, R4independently from each other selected from the group consisting of hydrogen, alkyl, long-chain alkyl, alkenyl, cycloalkyl, halogenated, aryl,

moreover, the matching of residues of one or more non-adjacent CH2groups independently from each other may be replaced by-O-, -S-, -NH-, -NR°-, -SiR°R°°-, -CO-, -COO-, -OCO-, -OCO-O-, -SO2-, -CN, -S-CO-, -CO-S-, -CY1=CY2-or-C≡C-in such a way that O atoms and/or S were not directly related to each other, as well as optional substituted aryl or heteroaryl, preferably containing from 1 to 30 C atoms (end of CH3groups are understood as CH2-group in the sense of CH2-H, R° and R°° = alkyl).

The General definition of groups: In the description and the claims declared and described generalized groups, such as alkyl, alkoxy, aryl, etc. If not written otherwise, in the framework of the present invention preferably applies the following groups as described in the General groups:

alkyl: linear and branched C1-C8-alkali;

long-chain alkali: linear and branched C5-C20 alkali;

alkenyl: C2-c6alkenyl;

cycloalkyl: C3-C8-cycloalkyl;

al is safe: selected from the group containing methylene, 1,1-ethylene, 1,2-ethylene, 1,1-propylidene, 1,2-propylene, 1,3-propylene, 2,2-propylidene; butane-2-ol-1,4-diyl, propane-2-ol-1,3-diyl, 1,4-butylene, cyclohexane-1,1-diyl, cyclohexane-1,2-diyl, cyclohexane-1,3-diyl, cyclohexane-1,4-diyl, cyclopentane-1,1-diyl, cyclopentane-1,2-diyl and cyclopentane-1,3-diyl, vinyl, cyanoethyl, undecyl, hydroxymethyl;

aryl: selected from aromatic compounds with molecular weight less than 300 daltons;

halogenated: selected from the group consisting of mono, di, tri-, poly - and perhalogenated linear and branched C1-C8-alkali.

Unless otherwise stated, within the General definition of groups, more preferred are the following groups:

alkyl: linear and branched Cl-C6-alkali, in particular, methyl, ethyl, propyl, isopropyl;

aryl: selected from the group consisting of phenyl, biphenyl, naphthalenyl, anthracene, phenanthrene, benzyl.

Unexpectedly, it was found that in the presence of both components result in a kind of synergistic effect in many applications it is possible to obtain an insulating resin according to the present invention, which have a much higher glass transition temperature compared with the previous solutions with very high mechanical properties.

In the spirit of the present invention, the term "insulating resin" includes and/or covers, in particular, impregnating malaney system (preferably low viscosity) on the basis of epoxy resin and anhydrite component with controlled reactivity.

In the spirit of the present invention, the term "switchgear" includes and/or covers, in particular, devices for low, medium and high voltage.

In the spirit of the present invention, the term "on the basis of complex pilgramage ether" includes and/or covers, in particular, that as the source component, in particular, the main component, is used glycidyloxy polyester resin. This can be applied all known in the prior art resins.

In the spirit of the present invention, the term "formed from the source component(s)" includes and/or covers, in particular, that the insulating resin obtained from this/these components.

In the spirit of the present invention, the term "methylenedi-anhydride includes and/or covers, in particular, the following connection:

According to one preferred form of implementation of the present invention, the ratio of material a to material b) is (weight/weight) ≥50:1 to ≤300:1. In practice, it has proved advantageous, as it is often possible to further increase the glass transition temperature.

Preferably, the ratio of material a to material b) (weight/weight) is ≥100:1 to ≤250:1, more preferably ≥150:1 to ≤220:1.

According to one preferred form of implementation of the present invention, the proportion of material a) with the OLE (weight to weight glycidyloxy broadcasting Foundation) is ≥0,8:1 to ≤1:1. It is also often proved to be advantageous to increase the glass transition temperature.

Preferably, the ratio of the material (a) material a) in the resin (weight-to-weight glycidyloxy broadcasting Foundation) is ≥0,85:1 to ≤0,98:1, even more preferably from ≥0.92 to ≤0,97:1.

According to one preferred form of implementation of the present invention, the proportion of material b) in the resin (weight-to-weight glycidyloxy broadcasting Foundation) is ≥0.01:l to ≤0,1:1, more preferably from ≥0,02:1 to ≤0,09:1, and most preferably from 0.04:1 to ≤0,07:1.

According to one preferred form of implementation of the present invention, component b) is selected from the group consisting of 1-Mei, 1-ethylimidazole, 1-propylimidazol, 1-isopropylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-ethylimidazole, imidazole, 1-benzyl-2-phenylimidazole, 1-vinylimidazole, 2-Mei, the 2-getdelimiter, and mixtures thereof.

According to one preferred form of implementation of the present invention, the insulating resin obtained by curing process containing a step of curing at ≥140°C, preferably at ≥150°C, with a duration of curing ≥12 h, preferably ≥14 h, and most preferably ≥16 PM

The present invention relates, in addition to insulating the part containing the insulating resin according to the present invention.

In the spirit nastojasih the invention, the term "insulating part includes and/or covers, in particular, a composite material containing an insulating resin and/or non-woven material/fabric-based polyester, glass or aramid.

When the insulating resin is preferably introduced into a polyester non-woven material.

In the spirit of the present invention, the term "polyester non-woven material" includes and/or covers, in particular, the materials on the basis of [RETR] (polyethylene terephthalate) or RHT (polybutylene terephthalate). Preferred [RETR].

In the spirit of the present invention, the term "introduced" includes and/or covers, in particular, that non-woven material impregnated with resin. From the point of view of the dielectric properties of the preferred vacuum impregnation.

The present invention relates, furthermore, to use a resin system based on complex pilgramage ester formed from the initial components containing

a) material containing methylenedi-anhydride and/or hydrogenated methylenedi-anhydride,

(b) a material containing imidazole the following structure:

and R1selected from the group consisting of alkyl, long-chain alkyl, alkenyl, cycloalkyl, halogenated, aryl;

R2, R3, R4independently from each other selected from the group consisting of hydrogen, alkyl, long-chain alkyl, alkenyl, cycloalkyl, halogenated, aryl,

moreover, p is Chadasha residues of one or more non-adjacent CH 2groups independently from each other may be replaced by-O-, -S-, -NH-, -NR°-, -SiR°R°°-, -CO-, -COO-, -OCO-, -OCO-O-, -SO2-, -S-CO-, -CO-S-, -CY1=CY2-or-C≡C-in such a way that O atoms and/or S were not directly related to each other, as well as optional substituted aryl or heteroaryl, preferably containing from 1 to 30 C atoms (end of CH3groups are understood as CH2-group in the sense of CH2-H, R° and R°° = alkyl)

as an insulating system for switchgear.

The above, as well as claimed and described in the examples of implementation details used according to the invention, are not subject to any special restrictions on their size, design, material selection and technical ideas, so that you can without exception be applied well-known in the field of application of the selection criteria.

The following details, features and advantages of the object of the invention emerge from the dependent claims and from the following description of the respective examples.

Example 1

The present invention is examined purely illustrative and without intent to limit, in this example I according to the invention. When this resin was obtained, formed of the following components:

ComponentThe relative weight fraction
Bis(2, 3-epoxypropoxy)100
ether 1,2-
cyclohexanedicarboxylic acid
methylenedi-anhydride95
1-Mei0,5

The resin was utverjdali 2 h at 80°C followed by 2 h at 100°C, then 1 h at 130°C, and the conclusion 16 h at 150°C.

In addition, there were obtained two comparative resin (not of the invention).

Comparative example I:

In comparative example I methylenedi-anhydride was replaced by the anhydride methylhexadecanoic acid. In the rest of the conditions for obtaining were identical.

Comparative example II:

In comparative example II 1-Mei was replaced by dimethylbenzylamine. In the rest of the conditions for obtaining were identical.

Then determined the glass transition temperature of these three resins. The results are presented below.

ResinThe glass transition temperature Tg
example I140°C
comparative example I114°C
comparative example II99°C

Thus, it is seen that the glass transition temperature of the sample according to the invention is considerably higher.

In addition, polyester non-woven fabric was impregnated with the resin in example I. using a standard non-woven material of polypropylene fibers on the basis of PETP weighing 150 g/m2.

The sheet has the following options:

lengthwidthunit
DensityISO 1183-11,32 ± 0,01g/cm3
Fiber contentH QM - AA
571
50 ± 5%
Flexural strengthISO 178≥120≥150MPa
Module E (bend)ISO 17831003300 MPa
The tensile strengthISO 527-4≥75≥85MPa
Elongation at breakISO 527-4≥4≥7%
Module E (tensile)ISO 527-435003800MPa
Compressive strengthISO 604≥250MPa
Splitting effortDIN 53463≥3500N
Impact strengthISO 179-1
an15
≥25≥35kJ/m2
The impact strength of the specimen with notchISO 179-1
ak10
≥5kJ/m2
The hardness at which daliani ball ISO 2039-1135 ± 5N/mm2
The shore hardness DDIN 5350577 ± 2Shore D
Moisture absorptionISO 62≤30mg

It is seen that the requirements for the sheet-like insulating material for wiring devices (in particular, in respect of tensile strength, splitting efforts and strength in bending) very well satisfied.

The sheet has, in addition, the following electrical properties:

Resistance to breakdownEN 60243-1
1 mm
1 mm ┴
≥30
≥50
kV/mm
kV/mm
The dielectric constant εrIEC 602503,2 ± 0,1
The specific flow resistanceIEC 600931017Ohm·cm
Surface resistivity PsIEC 600931017Ohms
Pulse the resistance of the electric arcTVH-IA 104to 0.032
The fatigue strength of the electric arcTVH-IA 1041,2mA
Resistance to diffusion breakdown24h/H2O/100°C
100h/H2O/100°C
100h/4%HF/23°C
≥ 8,5
≥ 6,6
≥31
kV/cm
kV/cm
kV/cm

Furthermore, the material has a very high compressive strength. Testing for long-term strength at elevated temperatures have a very low tendency to creep. This is especially important for parts under pressure. In addition, the material has excellent resistance to the formation of tracks.

In the experience of thermal aging (20000 h at 155°C) was used plate from thermal class F.

Thus, visible advantageous properties of insulating resins according to the invention.

1. An insulating resin on the basis of complex pilgramage ether for isolatio the materials in the distribution device, formed using the initial components containing
a) methylenedi-anhydride and/or hydrogenated methylenedi-anhydride,
b) an imidazole of the following structure:

where R1selected from the group consisting of linear and branched C1-C8-alkali, long-chain alkali selected from the group consisting of linear and branched C5-C20-alkali, C2-C6-alkenyl, C3-C8-cycloalkyl, halogenated selected from the group consisting of mono, di, tri-, poly - and perhalogenated linear and branched C1-C8-alkali, aryl selected from aromatic compounds with molecular weights below 300 Yes;
R2, R3, R4independently from each other selected from the group consisting of hydrogen, linear and branched C1-C8-alkali, long-chain alkali selected from the group consisting of linear and branched C5-C20-alkali, C2-C6-alkenyl, C3-C8-cycloalkyl, halogenated selected from the group consisting of mono, di, tri-, poly - and perhalogenated linear and branched C1-C8-alkali, aryl selected from aromatic compounds with molecular weights below 300 Da.

2. The insulating resin according to claim 1, where the ratio of component a) to component (b) (weight/weight.) is ≥50:1 to ≤300:1.

3. The insulating resin according to claim 1 or 2, where the proportion of the component (a) in the resin (weight-to-weight glycidyloxy broadcasting Foundation) is ≥0,8:1 to ≤:1.

4. The insulating resin according to claim 1 or 2, where the proportion of the component (b) in the resin (weight-to-weight glycidyloxy broadcasting Foundation) is ≥0.01:1 to ≤0,1:1.

5. The insulating resin according to claim 1 or 2, where component b) is selected from the group consisting of 1-Mei, imidazole, 1-ethylimidazole, 1-propylimidazol, 1-isopropylimidazole, 2-Mei, 1,2-dimethylimidazole, 2-ethyl-4-ethylimidazole, imidazole, 1-benzyl-2-phenylimidazole, 1-vinylimidazole, 2-Mei, the 2-getdelimiter, 2-vinylimidazole, and mixtures thereof.

6. The insulating resin according to claim 1 or 2, where the insulating resin obtained in the method of curing, containing stage curing at ≥140°C and the duration of the curing ≥12 hours

7. Insulating part containing an insulating resin according to one of claims 1 to 6.

8. The insulating part according to claim 7, where the insulating resin is introduced into a polyester non-woven material.

9. The use of resin systems based on complex pilgramage ether formed using the initial components containing
a) methylenedi-anhydride and/or hydrogenated methylenedi-anhydride,
b) an imidazole of the following structure:

where R1selected from the group consisting of linear and branched C1-C8-alkali, long-chain alkali selected from the group consisting of linear and branched C5-C20-alkali, C2-C6-alkenyl, C3-C8-cycloalkyl, halogenated, SEL the p group, containing mono, di, tri-, poly - and perhalogenated linear and branched C1-C8-alkali, aryl selected from aromatic compounds with molecular weights below 300 Yes;
R2, R3, R4independently from each other selected from the group consisting of hydrogen, linear and branched C1-C8-alkali, long-chain alkali selected from the group consisting of linear and branched C5-C20-alkali, C2-C6 - alkenyl, C3-C8-cycloalkyl, halogenated selected from the group consisting of mono, di, tri-, poly - and perhalogenated linear and branched C1-C8-alkali, aryl selected from aromatic compounds with molecular weights below 300 Yes;
as insulating material in electrical switchgear.



 

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