An epoxy anhydride impregnating resin, its preparation method and use

Abstract

The present application relates to the technical field of vacuum pressure impregnation, in particular to an epoxy anhydride impregnating resin, a preparation method and application thereof. The epoxy anhydride impregnating resin is prepared from A component and B component. The preparation raw materials of the A component include pretreated bisphenol A epoxy resin, pretreated bisphenol F epoxy resin, active diluent, dispersant and polymeric defoamer. The epoxy anhydride impregnating resin system has low viscosity, excellent cold and hot impact resistance and electrical properties. Meanwhile, the impregnating resin prepared by the present application is easy to obtain, convenient to prepare, low in cost and easy to industrialize compared with imported resin raw materials.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of vacuum pressure impregnation technology, in particular to an epoxy anhydride impregnating resin and a preparation method and application thereof. BACKGROUND

[0002] Vacuum pressure impregnation (VPI) impregnating resin is one of the key materials for realizing the vacuum pressure impregnation insulation treatment process. At present, the VPI impregnating resins mainly used at home and abroad include three types: epoxy ester styrene system, unsaturated polyester epoxy anhydride styrene system and pure epoxy anhydride impregnating resin system. Each of the impregnating resins has certain defects.

[0003] Firstly, the epoxy ester styrene system has long curing time, high curing temperature and high volatile content, and the electrical strength of the insulation structure made of the resin is not high, which is difficult to meet the manufacturing requirements of large high-voltage bushings. Secondly, the unsaturated polyester epoxy anhydride styrene system reduces the volatilization of styrene by reducing the curing temperature of the resin, thereby reducing the air gap of the insulation structure, forming a whole density and ensuring the electrical properties of the structure. The problem of this system is that the storage stability of the mixture of the components A and B at room temperature is not good, the resin is easy to absorb moisture, and the curing time is long at low temperature, and the curing is not sufficient, which requires post-curing. Thirdly, the epoxy anhydride VPI impregnating resin is a kind of impregnating resin without volatile diluents such as styrene, has small odor, and has zero VOC in the curing process. The whole insulation structure has good integrity, and the mechanical strength, especially the thermal mechanical strength, is high. The epoxy anhydride impregnating resin has been widely used in the manufacture of high-voltage bushings at home and abroad.

[0004] In the prior art, a normal-temperature impregnating type epoxy anhydride heat-resistant resin is disclosed in Chinese Patent No. 201010175005.X. The resin does not contain volatile styrene active diluent, and has good heat resistance, high mechanical strength, low dielectric loss factor, and can reduce the thickness of the coil insulation, which is beneficial to reduce the temperature rise of the motor, increase the service life of the motor, and reduce the volume of the motor.

[0005] Although this system is superior, the viscosity of the resin system mixture is still not ideal, which is not conducive to the penetration of the resin into the insulation paper, and finally leads to the decline of the electrical properties of the high-voltage bushing. Therefore, it is particularly important to develop a low-cost and low-viscosity epoxy resin impregnating system. SUMMARY

[0006] In order to solve the problems in the prior art, the present application provides an epoxy anhydride impregnating resin, and raw materials for preparing the epoxy anhydride impregnating resin, including an A component and a B component.

[0007] Preferably, the mass ratio of the A component to the B component is 1:1.

[0008] Preferably, the raw materials for preparing the A component include, by weight, 40-60 parts of the pretreated bisphenol A epoxy resin, 20-40 parts of the pretreated bisphenol F epoxy resin, 9-18 parts of the active diluent, 0.2-1 part of the dispersant, and 0.1-0.7 part of the polymeric defoaming agent.

[0009] Preferably, the pretreatment process of the pretreated bisphenol A epoxy resin and the pretreated bisphenol F epoxy resin includes: adding the bisphenol A epoxy resin and the bisphenol F epoxy resin into a molecular distillation device, and then distilling at 80-100 ℃ and 50-300 pa to obtain the pretreated bisphenol A epoxy resin and the pretreated bisphenol F epoxy resin.

[0010] Further, the pretreatment process of the pretreated bisphenol A epoxy resin and the pretreated bisphenol F epoxy resin includes: adding the bisphenol A epoxy resin and the bisphenol F epoxy resin into a molecular distillation device, and then distilling at 90 ℃ and 200 pa for 3 h to obtain the pretreated bisphenol A epoxy resin and the pretreated bisphenol F epoxy resin.

[0011] Preferably, the pretreated bisphenol A epoxy resin has an epoxy value of 0.50-0.52 mol / 100 g and a viscosity of 10000-13000 cps at 25 ℃, and the pretreated bisphenol F epoxy resin has an epoxy value of 0.58-0.60 mol / 100 g and a viscosity of 2000-5000 cps at 25 ℃.

[0012] Further, the pretreated bisphenol A epoxy resin has an epoxy value of 0.51 mol / 100 g and a viscosity of 10000-13000 cps at 25 ℃, and the pretreated bisphenol F epoxy resin has an epoxy value of 0.59 mol / 100 g and a viscosity of 2000-5000 cps at 25 ℃.

[0013] Further, the bisphenol A epoxy resin is NPEL-127E, which is purchased from Kunshan Nanya; and the bisphenol F epoxy resin is YDF-170, which is purchased from Guoduo Chemical.

[0014] Preferably, the weight ratio of the pretreated bisphenol A epoxy resin to the pretreated bisphenol F epoxy resin is (40-60):(20-40).

[0015] Further, the weight ratio of the pretreated bisphenol A epoxy resin to the pretreated bisphenol F type epoxy resin is 28:15.

[0016] Preferably, the active diluent is selected from one or more of carbon dodecyl-tetradecyl glycidyl ether, o-tolyl glycidyl ether, diethylene glycol diglycidyl ether, 1,2-cyclohexanediol diglycidyl ether.

[0017] Further, the active diluent is carbon dodecyl-tetradecyl glycidyl ether, o-tolyl glycidyl ether.

[0018] The carbon dodecyl-tetradecyl glycidyl ether is purchased from Hubei Green Home Material Technology Co., Ltd., and the model is LS-AGE; the o-tolyl glycidyl ether is purchased from Hubei Green Home Material Technology Co., Ltd., and the model is LS-691.

[0019] Preferably, the weight ratio of the carbon dodecyl-tetradecyl glycidyl ether to the o-tolyl glycidyl ether is (6-10):(3-8).

[0020] Further, the weight ratio of the carbon dodecyl-tetradecyl glycidyl ether to the o-tolyl glycidyl ether is 8:5.

[0021] Preferably, the dispersant is a copolymer containing an acidic group; further, the dispersant is BYK-W9011, purchased from BYK-Chemical.

[0022] Preferably, the polymeric defoamer is selected from one or more of BYK-333, BYK-307, BYK 057, BYK A535.

[0023] Further, the polymeric defoamer is BYK 057, purchased from BYK-Chemical.

[0024] Preferably, the raw materials for preparing the B component include anhydride curing agent, toughening agent, non-silicon defoamer, accelerator.

[0025] Preferably, the anhydride curing agent is selected from one or both of methyl tetrahydrophthalic anhydride and methyl nadic anhydride.

[0026] Further, the anhydride curing agent is methyl tetrahydrophthalic anhydride and methyl nadic anhydride.

[0027] Further, the mass ratio of the methyl tetrahydrophthalic anhydride to the methyl nadic anhydride is (70-80):(10-18).

[0028] Preferably, the raw materials for preparing the B component include 70-80 parts by weight of methyl tetrahydrophthalic anhydride, 10-18 parts by weight of methyl nadic anhydride, 5-10 parts by weight of a toughening agent, 0.1-0.7 parts by weight of a non-silicon defoaming agent, and 0.1-1 part by weight of an accelerator.

[0029] Preferably, the toughening agent is a nano core-shell rubber epoxy resin toughening agent.

[0030] Further, the toughening agent is MX-135, which is commercially available from Japan Kion.

[0031] Preferably, the non-silicon defoaming agent is BYK 057, which is commercially available from BYK-Chemie.

[0032] Preferably, the accelerator is a tertiary amine accelerator or an imidazole accelerator.

[0033] Further, the accelerator is a tertiary amine accelerator; the tertiary amine accelerator is selected from one or more of 2,4,6-tris(dimethylaminomethyl)phenol, benzyldimethylamine, triethanolamine, and o-hydroxybenzyl dimethylamine.

[0034] Further, the tertiary amine accelerator is 2,4,6-tris(dimethylaminomethyl)phenol.

[0035] The second aspect of the present application provides a preparation method of an epoxy anhydride impregnated resin, comprising the following steps:

[0036] S1: degassing the pretreated bisphenol A epoxy resin and bisphenol F epoxy resin, active diluent, dispersant, and defoaming agent at 60-80°C to obtain component A;

[0037] S2: degassing the anhydride curing agent, toughening agent, non-silicon defoaming agent, and accelerator at 60-80°C to obtain component B;

[0038] S3: preheating components A and B to 80°C, uniformly mixing them under stirring, and then degassing at 60-80°C and 800-1000 pa for 1 h before curing.

[0039] Further, the degassing temperature in S1 is 70°C; the degassing temperature in S2 is 70°C; and the degassing temperature in S3 is 70°C, and the degassing pressure is 900 pa.

[0040] Preferably, the degassing time in S1 is 2-3 h; further, the degassing time in S1 is 3 h.

[0041] Preferably, the degassing time in S2 is 2-3 h; further, the degassing time in S2 is 3 h.

[0042] Preferably, the curing conditions in S3 are 8h at 80℃, 8h at 100℃, 10h at 120℃, 10h at 150℃, respectively.

[0043] The third aspect of the present application provides the use of the above-mentioned epoxy anhydride impregnating resin in vacuum pressure impregnation.

[0044] Advantages

[0045] 1. The viscosity of conventional bisphenol A and F type epoxy resin is high, and the content of organic chlorine is high. In the present application, pretreated epoxy resin is used to obtain high-purity and low-organic chlorine content epoxy resin, which can improve the electrical properties of the impregnating resin.

[0046] 2. The bisphenol F type epoxy resin obtained by the specific pretreatment process in the present application has lower viscosity and better flexibility of the cured product than bisphenol A epoxy resin, because the bisphenol F epoxy resin has two fewer methyl groups on the chain segment, reducing the steric hindrance between molecules. Meanwhile, the specific active diluent can not only reduce the viscosity of the system, but also participate in the reaction of the epoxy group on the chain segment of the active diluent to improve the mechanical strength of the cured product.

[0047] 3. The specific toughening agent selected in the present application can form an island structure after the hydroxyl group on the chain segment participates in the system reaction, so that the cured product has excellent cold and hot impact resistance, and the system viscosity is reduced while the heat resistance of the cured product is improved.

[0048] 4. The impregnating resin prepared in the present application is easy to obtain, convenient to prepare, low in cost, and easy to produce industrially compared with imported resin raw materials. DETAILED DESCRIPTION

[0049] In order to make the purpose, technical scheme and advantages of the present application more clear, the present application will be further described in detail below with examples. It should be understood that the specific examples described herein are only used to explain the present application, and are not used to limit the present application. The experimental methods not specified in the examples are carried out according to the conventional conditions or the conditions recommended by the manufacturer. The reagents or instruments used are not specified by the manufacturer, and are all conventional products that can be purchased on the market.

[0050] Example 1

[0051] The first aspect of the present embodiment provides an epoxy anhydride impregnating resin, which is prepared from 100 parts of component A and 100 parts of component B. The preparation raw materials of the component A are 46 parts of pretreated bisphenol A epoxy resin, 40 parts of pretreated bisphenol F type epoxy resin, 13 parts of active diluent, 0.8 parts of dispersing agent and 0.2 parts of polymeric defoamer.

[0052] The pretreatment process of the pretreated bisphenol A epoxy resin and the pretreated bisphenol F epoxy resin comprises: adding the bisphenol A epoxy resin and the bisphenol F epoxy resin into a molecular distillation device, and distilling for 3h at 90℃ and 200pa.

[0053] The weight ratio of the pretreated bisphenol A epoxy resin to the pretreated bisphenol F epoxy resin is 46:40.

[0054] The bisphenol A epoxy resin is NPEL-127E, which is purchased from Kunshan Nanya; and the bisphenol F epoxy resin is YDF-170, which is purchased from Guoduo Chemical.

[0055] The active diluent is carbon dodecyl-tetradecyl glycidyl ether or o-tolyl glycidyl ether.

[0056] The weight ratio of the carbon dodecyl-tetradecyl glycidyl ether to the o-tolyl glycidyl ether is 10:3.

[0057] The dispersant is BYK-W9011, which is purchased from BYK-Chemie; and the polymeric defoamer is BYK 057, which is purchased from BYK-Chemie.

[0058] The raw materials for preparing the B component comprise, by weight, 73 parts of methyltetrahydrophthalic anhydride, 18 parts of methyl nadic anhydride, 7.5 parts of a toughening agent, 0.7 parts of a non-silicon defoamer, and 0.8 parts of an accelerator.

[0059] The mass ratio of the methyltetrahydrophthalic anhydride to the methyl nadic anhydride is 73:18.

[0060] The toughening agent is MX-135, which is purchased from Japan Zhongyuan.

[0061] The non-silicon defoamer is BYK 057, which is purchased from BYK-Chemie.

[0062] The accelerator is 2,4,6-tris(dimethylaminomethyl)phenol.

[0063] The second aspect of the embodiment provides a preparation method of an epoxy anhydride impregnated resin, which comprises the following steps:

[0064] S1: degassing the pretreated bisphenol A epoxy resin and the bisphenol F epoxy resin, the active diluent, the dispersant, and the defoamer at 70℃ for 3h to obtain the A component;

[0065] S2: degassing the anhydride curing agent, the toughening agent, the non-silicon defoamer, and the accelerator at 70℃ for 3h to obtain the B component;

[0066] S3: Preheat A, B components to 80℃, mix evenly under stirring, defoam at 70℃, 900pa for 1h, then cure at 80℃ for 8h, 100℃ for 8h, 120℃ for 10h, 150℃ for 10h.

[0067] The third aspect of the embodiment provides application of the above-mentioned epoxy anhydride impregnating resin in vacuum pressure impregnation.

[0068] Embodiment 2

[0069] The specific implementation of embodiment 2 is the same as that of embodiment 1, except that:

[0070] The raw materials for preparing the A component include 56 parts of pretreated bisphenol A epoxy resin, 30 parts of pretreated bisphenol F epoxy resin, 13 parts of active diluent, 0.6 parts of dispersant, and 0.4 parts of polymeric defoamer.

[0071] The weight ratio of the pretreated bisphenol A epoxy resin to the pretreated bisphenol F epoxy resin is 56:30.

[0072] The weight ratio of the carbon dodecyl to tetradecyl glycidyl ether to the o-tolyl glycidyl ether is 8:5.

[0073] The raw materials for preparing the B component include, by weight, 76 parts of methyl tetrahydrophthalic anhydride, 14 parts of methyl nadic anhydride, 9 parts of toughening agent, 0.4 parts of non-silicon defoamer, and 0.6 parts of accelerator.

[0074] The mass ratio of the methyl tetrahydrophthalic anhydride to the methyl nadic anhydride is 76:14.

[0075] Embodiment 3

[0076] The specific implementation of embodiment 3 is the same as that of embodiment 1, except that:

[0077] The raw materials for preparing the A component include 60 parts of pretreated bisphenol A epoxy resin, 25 parts of pretreated bisphenol F epoxy resin, 14 parts of active diluent, 0.3 parts of dispersant, and 0.7 parts of polymeric defoamer.

[0078] The weight ratio of the pretreated bisphenol A epoxy resin to the pretreated bisphenol F epoxy resin is 60:25.

[0079] The weight ratio of the carbon dodecyl to tetradecyl glycidyl ether to the o-tolyl glycidyl ether is 6:8.

[0080] The raw materials for preparing the B component include, by weight, 80 parts of methyl tetrahydrophthalic anhydride, 9.5 parts of methyl nadic anhydride, 9.7 parts of toughening agent, 0.5 parts of non-silicon defoamer, and 0.3 parts of accelerator.

[0081] The mass ratio of the methyltetrahydrophthalic anhydride and the methyl nadic anhydride is 80:9.5.

[0082] Comparative Example 1

[0083] The specific implementation of Comparative Example 1 is the same as that of Example 2, except that:

[0084] The raw materials for preparing the A component include 56 parts of an unpretreated bisphenol A epoxy resin, 30 parts of an unpretreated bisphenol F type epoxy resin, 13 parts of an active diluent, 0.6 parts of a dispersant, and 0.4 parts of a polymeric defoamer.

[0085] Comparative Example 2

[0086] The specific implementation of Comparative Example 2 is the same as that of Example 2, except that:

[0087] The raw materials for preparing the A component include 75 parts of a pretreated bisphenol A epoxy resin, 24 parts of a pretreated bisphenol F type epoxy resin, 0.6 parts of a dispersant, and 0.4 parts of a polymeric defoamer.

[0088] Comparative Example 3

[0089] The specific implementation of Comparative Example 3 is the same as that of Example 2, except that:

[0090] The raw materials for preparing the B component include, by weight parts, 85 parts of methyltetrahydrophthalic anhydride, 13 parts of methyl nadic anhydride, 1 part of a toughening agent, 0.4 parts of a non-silicon defoamer, and 0.6 parts of an accelerator.

[0091] The mass ratio of the methyltetrahydrophthalic anhydride and the methyl nadic anhydride is 85:13.

[0092] Performance test

[0093] Test sample:

[0094] The cured product prepared by Example 1-3 and Comparative Example 1-3 of the present application.

[0095] Test:

[0096] 1. Test of glass transition temperature Tg: use a differential scanning calorimeter DSC to test the glass transition temperature Tg, test twice, and take the average value.

[0097] 2. Test of flexural strength: refer to ISO 178, use an electronic tensile testing machine to test the flexural strength, test 5 sample strips each time, and take the average value.

[0098] 3. Test of tensile strength: refer to ISO 527, use an electronic tensile testing machine to test the tensile strength, test 5 sample strips each time, and take the average value.

[0099] 4. Test of linear expansion coefficient: refer to ISO 11359, use linear expansion coefficient tester to test linear expansion coefficient, 2 samples each time, take average value.

[0100] 5. Test of breakdown strength: refer to ISO 60243, use voltage resistance tester to test breakdown strength, 5 samples each time, take average value.

[0101] 6. Test of surface resistivity: refer to ISO 62631, use high resistance meter to test surface resistivity, 5 samples each time, take average value.

[0102] 7. Test of volume resistivity: refer to ISO 62631, use high resistance meter to test volume resistivity, 5 samples each time, take average value.

[0103] 8. Test of dielectric constant ε and dielectric loss angle tgδ: refer to ISO 62631, use Siheng bridge to test dielectric constant ε and dielectric loss angle tgδ at different temperatures, 5 samples each time, take average value.

[0104] The performance test results of each embodiment and the comparative example are shown in Table 1 and Table 2.

[0105] Table 1

[0106]

[0107]

[0108] Table 2

[0109]

[0110]

Claims

1. An epoxy anhydride impregnation resin characterized by, Its preparation raw materials, including A component, B component; the preparation raw materials of the A component, including 40-60 parts of pretreated bisphenol A epoxy resin, 20-40 parts of pretreated bisphenol F type epoxy resin, 9-18 parts of active diluent, 0.2-1 parts of dispersant, 0.1-0.7 parts of polymeric defoamer; the preparation raw materials of the B component, including 70-80 parts of methyl tetrahydrophthalic anhydride, 10-18 parts of methyl nadic anhydride, 5-10 parts of toughening agent, 0.1-0.7 parts of non-silicon defoamer, 0.1-1 parts of accelerator; The pretreatment process of the pretreated bisphenol A epoxy resin and the pretreated bisphenol F type epoxy resin comprises: adding bisphenol A type epoxy resin and bisphenol F type epoxy resin into a molecular distillation device, and distilling at 80-100 DEG C, 50-300 pa to obtain the pretreated bisphenol A type epoxy resin and the pretreated bisphenol F type epoxy resin; The epoxy value of the pretreated bisphenol A type epoxy resin is 0.51 mol / 100 g, and the viscosity at 25 DEG C is 10000-13000 cps; the epoxy value of the pretreated bisphenol F type epoxy resin is 0.59 mol / 100 g, and the viscosity at 25 DEG C is 2000-5000 cps; the bisphenol A type epoxy resin is NPEL-127E, and the bisphenol F type epoxy resin is YDF-170; The active diluent is carbon dodecyl-tetradecyl glycidyl ether or o-tolyl glycidyl ether; The weight ratio of the pretreated bisphenol A epoxy resin and the pretreated bisphenol F type epoxy resin is 46:40, the weight ratio of the carbon dodecyl-tetradecyl glycidyl ether and the o-tolyl glycidyl ether is 10:3, and the mass ratio of the methyl tetrahydrophthalic anhydride and the methyl nadic anhydride is 73:18; Or the weight ratio of the pretreated bisphenol A epoxy resin and the pretreated bisphenol F type epoxy resin is 56:30, the weight ratio of the carbon dodecyl-tetradecyl glycidyl ether and the o-tolyl glycidyl ether is 8:5, and the mass ratio of the methyl tetrahydrophthalic anhydride and the methyl nadic anhydride is 76:14; Or the weight ratio of the pretreated bisphenol A epoxy resin and the pretreated bisphenol F type epoxy resin is 60:25, the weight ratio of the carbon dodecyl-tetradecyl glycidyl ether and the o-tolyl glycidyl ether is 6:8, and the mass ratio of the methyl tetrahydrophthalic anhydride and the methyl nadic anhydride is 80:9.

5.

2. The epoxy-novolac resin according to claim 1, wherein, The toughening agent is nano core-shell rubber epoxy resin toughening agent.

3. A process for the preparation of an epoxy-novolac resin according to any one of claims 1-2, characterized in that, The method comprises the following steps: S1: degassing the pretreated bisphenol A type epoxy resin and bisphenol F type epoxy resin, active diluent, dispersant and polymeric defoamer at 60-80 DEG C to obtain the A component; S2: degassing the methyl tetrahydrophthalic anhydride, methyl nadic anhydride, toughening agent, non-silicon defoamer and accelerator at 60-80 DEG C to obtain the B component; S3: preheating the A and B components to 80 DEG C, uniformly mixing under stirring, and then degassing at 60-80 DEG C, 800-1000 pa for 1 h and curing.

4. Application of the epoxy anhydride impregnating resin according to any one of claims 1-2 in vacuum pressure impregnation.

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