Epoxy resin composition with low viscosity, long open period, rapid curing and difficult crystallization

Abstract

The invention discloses an epoxy resin composition with low viscosity, long open period, rapid curing and difficult crystallization, which comprises a component A and a component B. The component A comprises the following components in parts by weight: 73-81 parts of epoxy resin, 8-12 parts of novolac epoxy resin, 11-15 parts of diluent decyl glycidyl ether and 1 part of defoaming agent BYK530; the component B is prepared from 23 to 30 parts of alicyclic amine curing agent, 62 to 75 parts of polyether amine curing agent and 2 to 8 parts of tertiary amine accelerant. The epoxy resin composition at least has the following beneficial effects that the epoxy resin composition with low viscosity, long open period, rapid curing and difficult crystallization is provided, and the resin components in the composition comprise bisphenol A, novolac epoxy resin and decyl glycidyl ether as main raw materials, so that the viscosity of the perfusion resin is reduced, and meanwhile, the viscosity of the perfusion resin is reduced; and the anti-crystallization performance of the resin component is enhanced. The curing agent is composed of alicyclic amine, polyether amine and tertiary amine, and meets the pouring process requirements of rapid curing and low heat release during the long open period of the large wind turbine blade.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of vacuum infusion resin for wind power generation blades, and particularly relates to an epoxy resin composition with low viscosity, long open time and fast curing and not easy to crystallize. BACKGROUND

[0002] As a key component of a wind power generation system, a wind power generation blade directly affects the performance of the entire system, and is mainly composed of resin and fiber core material, etc., wherein the resin accounts for about 33% of the cost of the entire blade system. With the continuous increase in the size of the wind power generation blade, which gradually increases from dozens of meters to more than one hundred meters, the size of the blade gradually increases, and the thickness of the blade layer becomes thicker and thicker, which requires the resin to have a longer open time. The problem brought about by the increase in the open time is that the curing time is correspondingly prolonged, which is contrary to the actual requirement of increasing efficiency by speeding up and reducing cost of the blade. Although the resin for pouring wind power generation blades in the prior art has certain long open time or low heat release performance, it cannot achieve the requirements of fast establishment of Tg (glass transition temperature) of the resin, low viscosity and not easy to crystallize while maintaining the above two performances.

[0003] For example, Chinese Patent CN110564110A discloses an epoxy resin composition suitable for a vacuum infusion process and a preparation method thereof, wherein the epoxy composition A is composed of a bisphenol A epoxy resin, a 1,4-butanediol diglycidyl ether and a bisphenol F epoxy resin blend, and the curing agent B is composed of a polyetheramine, an alicyclic amine and a tertiary amine type accelerator. The disadvantage is high heat release, high viscosity and short open time; Chinese Patent CN112029237 discloses an epoxy resin composition suitable for a vacuum infusion process and a preparation method thereof, wherein the epoxy composition A is composed of a bisphenol A epoxy resin, a 1,6-hexanediol diglycidyl ether and a bisphenol F epoxy resin blend, and the curing agent B is composed of a polyetheramine, a dimethyl dipropyl triamine and a coupling agent. The Tg is slow to establish, the heat release is high, and the composite material is prone to discoloration; Chinese Patent CN101735564 discloses a vacuum infusion resin for wind power generation blades and a preparation method thereof, wherein the epoxy composition A is composed of a bisphenol A epoxy resin, an organic silicon modified epoxy resin and a diluent, a defoaming agent and a coupling agent blend, and the curing agent B is composed of an alicyclic amine, an aliphatic polyamine, an accelerator and a dye. The viscosity is large, and the heat release is high; Chinese patent CN200910201435 discloses a megawatt wind power blade vacuum infusion resin and its preparation method, its epoxy composition A is composed of bisphenol A epoxy resin, trifunctional epoxy of trisglycidyl-p-aminophenol (AFG-90), 4,5-epoxy cyclohexyl-1,2-dicarboxylic acid diglycidyl ester (TDE-85) and diluent polyol glycidyl ether blend, curing agent B is composed of alicyclic amine, fatty amine, its cost is higher, the open period is short; Chinese patent CN102702686A discloses a megawatt wind power blade epoxy resin system and its preparation method, its epoxy composition A is composed of bisphenol A epoxy resin, bisphenol F epoxy resin, low viscosity epoxy resin and diluent, thixotropic agent, functional additive blend, curing agent B is composed of alicyclic amine, fatty amine and aromatic amine, functional additive, thixotropic agent, pigment, its viscosity is high, the open period is short; Chinese patent CN103694637 discloses a high toughness vacuum slow epoxy resin for wind power blades and its preparation method, its epoxy composition A is composed of epoxy resin, vinyl-terminated epoxy polyether, active diluent, coupling agent, defoaming agent blend, curing agent B is composed of one or a mixture of two of aliphatic amine, alicyclic amine, aromatic amine, its open period is short, shrinkage is large, Tg is slow to establish; Chinese patent CN118126495A discloses a double-system infusion resin system and its preparation method and application, which includes resin part, curing agent part and catalyst part, the resin part is composed of epoxy resin, ring olefin composition composed of one or more ring olefins containing dicyclopentadiene, the curing agent is composed of aliphatic anhydride curing agent, epoxy accelerator, the catalyst is composed of ruthenium carbene catalyst, storage solvent, non-ionic surfactant, stabilizer and antioxidant, its smell is large, fiber infiltration is poor; Chinese patent CN115926377A describes a vacuum infusion process epoxy resin system and its preparation method, which includes resin component and curing agent component, the resin component includes main resin, polyurethane modified epoxy resin, silicone modified epoxy resin, diluent, the curing agent is composed of polyether amine, polyether polyol, alicyclic amine, fatty amine, its viscosity is large, the open period is short; In order to solve the problem that the existing wind power blade infusion resin cannot simultaneously consider low viscosity, long open period, rapid curing and not easy to crystallize, the present application obtains a low viscosity, long open period, rapid curing and not easy to crystallize wind power blade infusion resin through a special infusion system formula combination, which solves the requirements of long open period, good infiltration and low exothermic, rapid curing after infusion for large-scale blade resin. SUMMARY

[0004] An object of the present application is to solve at least the above problems and / or drawbacks and to provide at least the advantages later described.

[0005] To achieve these objects and other advantages of the present application, there is provided an epoxy resin composition with low viscosity, long open time, fast curing and less crystallization, comprising component A and component B, in terms of weight parts, the component A comprising: 73-81 parts of epoxy resin, 8-12 parts of phenolic epoxy resin, 11-15 parts of diluent decyl glycidyl ether, 1 part of defoaming agent BYK-530; the component B comprising: 23-30 parts of alicyclic amine curing agent, 62-75 parts of polyether amine curing agent, 2-8 parts of tertiary amine accelerator.

[0006] Preferably, the epoxy resin is one or more of bisphenol A epoxy resin E58, bisphenol A epoxy resin E54, bisphenol A epoxy resin E51, bisphenol A epoxy resin E44.

[0007] Preferably, characterized in that the phenolic epoxy resin is one or more of o-cresol novolac epoxy resin with a molecular weight less than 1100, bisphenol A novolac epoxy resin, phenol novolac epoxy resin, diphenyl novolac epoxy resin.

[0008] Preferably, characterized in that the alicyclic amine curing agent is one or more of 1,2-cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine (CHDA), methylcyclopentanediamine, methylcyclohexanediamine.

[0009] Preferably, characterized in that the polyether amine curing agent is one or more of T403 polyether amine, D400 polyether amine, D230 polyether amine, D2000 polyether amine, D200 polyether amine.

[0010] Preferably, characterized in that the tertiary amine accelerator is one or more of N,N-dimethylbenzylamine, N,N-dimethylcyclohexylamine, tetramethylguanidine, 3-diethylaminopropylamine, 3-dimethylaminopropylamine.

[0011] The present application also provides a preparation method of an epoxy resin composition with low viscosity, long open time, fast curing and less crystallization, the preparation method of the component A being: after weighing the epoxy resin, the phenolic epoxy resin, the diluent decyl glycidyl ether and the defoaming agent BYK-530 in terms of weight parts, all are added into a reaction kettle, heated to 60-80℃, stirred for 3-6h, then packed into a packaging barrel and sealed for storage; the preparation method of the component B being: after weighing the alicyclic amine curing agent, the polyether amine curing agent and the tertiary amine accelerator in terms of weight parts, all are added into a reaction kettle, heated to 40-60℃, stirred for 3-6h, then packed into a packaging barrel and sealed for storage.

[0012] The present application at least includes the following beneficial effects: the present application provides an epoxy resin composition with low viscosity, long open time and fast curing, and the combination of phenolic epoxy resin and decyl glycidyl ether in resin component A reduces the crystallization of the resin and provides lower viscosity characteristics, which can reduce the viscosity of the pouring resin while enhancing the anti-crystallization performance of the resin component; and the combination of phenolic epoxy resin in component A and alicyclic amine curing agent and tertiary amine accelerator in component B accelerates the curing rate of the resin and prolongs the open time of the resin system, solving the requirements of large wind turbine blades for long open time, fast curing (Tg rapid establishment) and low exothermic pouring process. DETAILED DESCRIPTION The present application will be further described in detail below so that those skilled in the art can implement it according to the description.

[0013] Example 1 An epoxy resin composition with low viscosity, long open time and fast curing, the preparation method of component A is: weigh bisphenol A epoxy resin E54 76 kg, phenolic epoxy resin 10 kg, diluent decyl glycidyl ether 13 kg, defoamer BYK-530 1 kg into the reaction kettle, warm to 80℃, stir for 3h; then put into a packaging barrel, seal and store; the preparation method of component B is: weigh polyether amine with molecular weight of 230 64 kg, 1,4-cyclohexanediamine (CHDA) 30 kg, N,N-dimethylcyclohexylamine 6 kg into the reaction kettle, warm to 60℃, stir for 3h and cool; put into a packaging barrel, seal and store.

[0014] Example 2 The preparation methods of component A and component B are the same as in example 1, wherein the composition of component A is: bisphenol A epoxy resin E5476 kg, phenolic epoxy resin 10 kg, decyl glycidyl ether 13 kg, defoamer BYK-530 1 kg; the composition of component B is: polyether amine with molecular weight of 230 66 kg, 1,4-cyclohexanediamine (CHDA) 30 kg, N,N-dimethylcyclohexylamine 4 kg.

[0015] Example 3 The preparation methods of component A and component B are the same as in example 1, wherein the composition of component A is: bisphenol A epoxy resin E5476 kg, phenolic epoxy resin 10 kg, decyl glycidyl ether 13 kg, defoamer BYK-530 1 kg; the composition of component B is: polyether amine with molecular weight of 230 64 kg, 1,4-cyclohexanediamine (CHDA) 28 kg, N,N-dimethylcyclohexylamine 8 kg.

[0016] Example 4 The preparation method of component A and component B is the same as that in Example 1, wherein the component A is composed of bisphenol A epoxy resin E54 76 kg, phenol novolac epoxy resin 10 kg, decyl glycidyl ether 13 kg, and defoaming agent BYK-530 1 kg; and the component B is composed of polyether amine with a molecular weight of 230 67 kg, 1,4-cyclohexane diamine (CHDA) 27 kg, and N,N-dimethylcyclohexylamine 6 kg.

[0017] Example 5 The preparation method of component A and component B is the same as that in Example 1, wherein the component A is composed of bisphenol A epoxy resin E54 78 kg, phenol novolac epoxy resin 8 kg, decyl glycidyl ether 13 kg, and defoaming agent BYK-530 1 kg; and the component B is composed of polyether amine with a molecular weight of 230 61 kg, 1,4-cyclohexane diamine (CHDA) 33 kg, and N,N-dimethylcyclohexylamine 6 kg.

[0018] Example 6 The preparation method of component A and component B is the same as that in Example 1, wherein the component A is composed of bisphenol A epoxy resin E54 74 kg, phenol novolac epoxy resin 10 kg, decyl glycidyl ether 15 kg, and defoaming agent BYK-530 1 kg; and the component B is composed of polyether amine with a molecular weight of 230 61 kg, 1,4-cyclohexane diamine (CHDA) 33 kg, and N,N-dimethylcyclohexylamine 6 kg.

[0019] Comparative Example 1 An epoxy resin composition comprises component A and component B, the preparation method of the component A is that bisphenol A epoxy resin E54 76 kg, phenol novolac epoxy resin 10 kg, diluent 1,4-butanediol glycidyl ether 13 kg, and defoaming agent BYK-530 1 kg are weighed into a reaction kettle, heated to 80°C, and stirred for 3 h; then the mixture is loaded into a packaging barrel and stored in a sealed state; the preparation method of the component B is that polyether amine with a molecular weight of 230 64 kg, 1,4-cyclohexane diamine (CHDA) 30 kg, and N,N-dimethylcyclohexylamine 6 kg are weighed into a reaction kettle, heated to 60°C, and stirred for 3 h before cooling; then the mixture is loaded into a packaging barrel and stored in a sealed state.

[0020] Comparative Example 2 An epoxy resin composition comprising component A and component B, the preparation method of component A is: take bisphenol A epoxy resin E54 86 kg, diluent 1,6-butanediol glycidyl ether 13 kg, defoaming agent BYK-530 1 kg into the reaction kettle, warm to 80℃, stir for 3h; Then put into a packaging barrel, seal and store; The preparation method of component B is: take polyether amine with molecular weight of 230 64 kg, 1,4-cyclohexanediamine (CHDA) 30 kg, N,N-dimethylcyclohexylamine 6 kg into the reaction kettle, warm to 60℃, stir for 3h and then cool; Put into a packaging barrel, seal and store.

[0021] Comparative example 3 An epoxy resin composition comprising component A and component B, the preparation method of component A is: take bisphenol A epoxy resin E54 86 kg, diluent 1,6-butanediol glycidyl ether 13 kg, defoaming agent BYK-530 1 kg into the reaction kettle, warm to 80℃, stir for 3h; Then put into a packaging barrel, seal and store; The preparation method of component B is: take polyether amine with molecular weight of 230 64 kg, 1,4-cyclohexanediamine (CHDA) 30 kg, N,N-dimethylcyclohexylamine 6 kg into the reaction kettle, warm to 60℃, stir for 3h and then cool; Put into a packaging barrel, seal and store.

[0022] Comparative example 4 An epoxy resin composition comprising component A and component B, the preparation method of component A is: take bisphenol A epoxy resin E54 76 kg, phenol novolac epoxy resin 10 kg, diluent decyl glycidyl ether 13 kg, defoaming agent BYK-530 1 kg into the reaction kettle, warm to 80℃, stir for 3h; Then put into a packaging barrel, seal and store; The preparation method of component B is: take polyether amine with molecular weight of 230 64 kg, isophorone diamine (IPDA) 36 kg into the reaction kettle, warm to 60℃, stir for 3h and then cool; Put into a packaging barrel, seal and store.

[0023] Comparative example 5 An epoxy resin composition comprising component A and component B, the preparation method of component A is: take bisphenol A epoxy resin E54 76 kg, phenol novolac epoxy resin 10 kg, decyl glycidyl ether 13 kg, defoaming agent BYK-530 1 kg into the reaction kettle, warm to 80℃, stir for 3h; Then put into a packaging barrel, seal and store; The preparation method of component B is: take polyether amine with molecular weight of 230 64 kg, 4,4-diamino dicyclohexyl methane (PACM) 36 kg into the reaction kettle, warm to 60℃, stir for 3h and then cool; Put into a packaging barrel, seal and store.

[0024] Comparative example 6 Example 1, wherein component A comprised bisphenol A epoxy resin E5 476 kg, phenol novolak epoxy resin 10 kg, decyl glycidyl ether 13 kg, and defoamer BYK-530 1 kg; and component B comprised polyetheramine with a molecular weight of 230 64 kg, 1,4-cyclohexanediamine (CHDA) 34 kg, and N,N-dimethylcyclohexylamine 2 kg.

[0025] Comparative Example 7 Example 1, wherein component A comprised bisphenol A epoxy resin E5 476 kg, phenol novolak epoxy resin 14 kg, decyl glycidyl ether 9 kg, and defoamer BYK-530 1 kg; and component B comprised polyetheramine with a molecular weight of 230 64 kg, 1,4-cyclohexanediamine (CHDA) 35 kg, and N,N-dimethylcyclohexylamine 1 kg.

[0026] Comparative Example 8 Example 1, wherein component A comprised bisphenol A epoxy resin E5 476 kg, phenol novolak epoxy resin 7 kg, decyl glycidyl ether 16 kg, and defoamer BYK-530 1 kg; and component B comprised polyetheramine with a molecular weight of 230 64 kg, 1,4-cyclohexanediamine (CHDA) 34 kg, and N,N-dimethylcyclohexylamine 2 kg.

[0027] Comparative Example 9 Example 1, wherein component A comprised bisphenol A epoxy resin E5 476 kg, phenol novolak epoxy resin 6 kg, decyl glycidyl ether 17 kg, and defoamer BYK-530 1 kg; and component B comprised polyetheramine with a molecular weight of 230 64 kg, 1,4-cyclohexanediamine (CHDA) 35 kg, and N,N-dimethylcyclohexylamine 1 kg.

[0028] Comparative Example 10 Example 1, wherein component A comprised bisphenol A epoxy resin E5 476 kg, phenol novolak epoxy 16 kg, decyl glycidyl ether 7 kg, and defoamer BYK-530 1 kg; and component B comprised polyetheramine with a molecular weight of 230 64 kg, 1,4-cyclohexanediamine (CHDA) 34 kg, and N,N-dimethylcyclohexylamine 2 kg.

[0029] Performance test: the resin samples of examples 1-6 (A:B=100:26) and comparative examples 1-10 (A:B=100:26) were prepared and tested for performance according to the following steps: the A component and the B component were mixed according to the weight ratio, stirred for 4-6 minutes, and whether the stirring was uniform was observed. If there was no filament, the stirring was uniform. If there was, the stirring was continued until the stirring was uniform. 20 parts of the stirred resin were subjected to a mixed viscosity test (in accordance with standard GB / T 22314). 400 parts of the stirred resin were placed in a vacuum oven for bubble removal treatment. After the bubble-removed resin was poured into a mold, a curing system of 25℃ / 24h-70℃ / 8h was used for post-curing, and then the resin sample was cut and tested for mechanics (in accordance with standard ISO527-2). 100 parts of the stirred resin were used for low-temperature crystallinity test, and whether crystallization occurred was observed after the resin was stored at-15℃ / 12h-5℃ / 12h for one month. 100 parts of the stirred resin were placed in a 35℃ environment for exothermic test (in accordance with standard ASTM D 2471), and the time when the exothermic peak reached 50℃ was defined as the open period. 10 parts of the stirred resin were placed in a 75℃ oven, and the curing time of the resin to reach the glass transition temperature (Tg) was defined as the Tg establishment time (in accordance with standard GB / T 19466.2). The results are shown in Table 1.

[0030] Table 1 From the experimental data in Table 1, it can be seen that, by comparing examples 1-6 and comparative examples 1-5, it can be seen that the combination of bisphenol A epoxy, phenolic novolac epoxy resin and decyl glycidyl ether in the resin of examples 1-6 of the present application, and the combination of tertiary amine and 1,4-cyclohexanediamine in the curing agent, enable the epoxy resin composition obtained by the present application to have excellent performance, such as low viscosity, long open period, fast curing and low crystallization. While providing high strength and low viscosity, the long open period and fast Tg establishment rate are achieved, and the crystallization property of the resin is reduced. Compared with example 1, comparative example 1-2 uses conventional diluents 1,4-butanediol glycidyl ether or 1,6-butanediol glycidyl ether, and comparative example 3 does not add phenolic novolac epoxy resin. The resin prepared by comparative example 1-3 has crystallization phenomenon after the A and B components are mixed, which indicates that the anti-crystallization property is not good, and the viscosity of the product prepared by comparative example 1-3 is high. Comparative examples 4-5 do not use aliphatic amine and tertiary amine accelerators, and the open period of the product prepared after the A and B components are mixed is short, and the Tg establishment time is long. Comparative examples 6-10 do not strictly add the components according to the amount, which leads to defects in some properties such as viscosity, open period and Tg establishment time of the product prepared.

[0031] While embodiments of the application have been disclosed in connection with the preferred embodiments of the application, it should be understood that there can be other embodiments which fall within the broad concept of the application as defined in the claims and their equivalents.

Claims

1. An epoxy resin composition having low viscosity, long open period, fast curing and not easy to crystallize, characterized in that: The invention comprises component A and component B. In parts by weight, component A comprises: 73-81 parts of epoxy resin, 8-12 parts of phenolic epoxy resin, 11-15 parts of diluent decyl glycidyl ether, and 1 part of defoamer BYK-530; component B comprises: 23-30 parts of alicyclic amine curing agent, 62-75 parts of polyetheramine curing agent, and 2-8 parts of tertiary amine accelerator.

2. The epoxy resin composition having low viscosity, long open period, fast curing and not easy to crystallize as claimed in claim 1, characterized in that: The epoxy resin is one or more of bisphenol A epoxy resin E58, bisphenol A epoxy resin E54, bisphenol A epoxy resin E51, and bisphenol A epoxy resin E44.

3. The epoxy resin composition having low viscosity, long open period, fast curing and not easy to crystallize as claimed in claim 1, characterized in that: The novolac epoxy resin is one or more of o-cresol novolac epoxy resin, bisphenol A novolac epoxy resin, phenol novolac epoxy resin and biphenyl novolac epoxy resin with a molecular weight less than 1100.

4. The epoxy resin composition having low viscosity, long open period, fast curing and not easy to crystallize as claimed in claim 1, characterized in that: The alicyclic amine curing agent is one or more of 1,2-cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, methylcyclopentanediamine, and methylcyclohexanediamine.

5. The epoxy resin composition having low viscosity, long open period, fast curing and not easy to crystallize as claimed in claim 1, characterized in that: The polyetheramine curing agent is one or more of T403 polyetheramine, D400 polyetheramine, D230 polyetheramine, D2000 polyetheramine, and D200 polyetheramine.

6. The epoxy resin composition having low viscosity, long open period, fast curing and not easy to crystallize as claimed in claim 1, characterized in that: The tertiary amine accelerator is one or more of N,N-dimethylbenzylamine, N,N-dimethylcyclohexylamine, tetramethylguanidine, 3-diethylaminopropylamine, and 3-dimethylaminopropylamine.

7. A method for preparing an epoxy resin composition having low viscosity, long open period, fast curing and non-crystallization properties as claimed in any one of claims 1 to 6, characterized in that: The preparation method of the component A is as follows: after weighing epoxy resin, novolac epoxy resin, diluent decyl glycidyl ether and defoamer BYK-530 by weight, all of them are added into a reactor, heated to 60-80° C., stirred for 3-6 hours, and then packed into a packaging barrel and sealed for storage; the preparation method of the component B is as follows: after weighing alicyclic amine curing agent, polyether amine curing agent and tertiary amine accelerator by weight, all of them are added into a reactor, heated to 40-60° C., stirred for 3-6 hours, and then packed into a packaging barrel and sealed for storage.

Images