Epoxy resin for long-term carbon fiber winding and preparation method thereof

Abstract

The invention discloses an epoxy resin for long-term carbon fiber winding and a preparation method thereof, comprising: component A and component B, wherein the mass ratio of component A to component B is 100:90-110, wherein component A is an epoxy resin component, and component B is a modified anhydride curing agent component. The invention uses biguanide compounds in the modified anhydride curing agent to greatly extend the service life of the epoxy resin, and can meet the requirement that the mixed viscosity is kept within 1000mPa.s for 30 hours at 40°C during the carbon fiber winding process, greatly ensuring the uniformity of the performance of the winding epoxy resin during use, and at the same time, the invention uses an additive BYK‑9920 for increasing wettability, which greatly increases the wettability of the epoxy resin to the carbon fiber.

Description

Technical Field

[0001] The invention belongs to the technical field of epoxy resin preparation, and more specifically, relates to an epoxy resin for carbon fiber winding with a long application period and a preparation method thereof. Background Art

[0002] With the rapid development of hydrogen energy, the demand for hydrogen cylinders for hydrogen storage is also increasing, and the performance requirements for hydrogen cylinders are gradually increasing. Hydrogen cylinders are mainly wrapped with carbon fiber around the outside of the cylinder to play a protective role. At this stage, hydrogen cylinders have developed into Type IV hydrogen cylinders, which have plastic inner liners and are mostly wrapped with epoxy resin on the outside of the hydrogen cylinders.

[0003] Currently, the epoxy resin used to wrap the outside of hydrogen cylinders cannot be used for a long time, does not have a long application period, and cannot guarantee the uniformity of the performance of the epoxy resin during use. Summary of the invention

[0004] An object of the present invention is to solve at least the above problems and / or disadvantages and to provide at least the advantages which will be described hereinafter.

[0005] In order to achieve these purposes and other advantages according to the present invention, a long-term application period epoxy resin for carbon fiber winding is provided, comprising: component A and component B, the mass ratio of component A to component B is 100:90-110, wherein component A is an epoxy resin component, and component B is a modified anhydride curing agent component.

[0006] Preferably, it is characterized in that the component A comprises 77-91% by mass of epoxy resin, 3-6% by mass of toughening agent, 3-5% by mass of diluent, 2-10% by mass of active diluent, and 1-2% by mass of wetting agent.

[0007] Preferably, the epoxy resin comprises 70-90% by mass of bisphenol A glycidyl ether resin and 10-30% by mass of alicyclic epoxy resin; wherein the bisphenol A glycidyl ether resin is one or a mixture of E-51 and E-54; and the alicyclic epoxy resin is one or more mixtures of 3,4-epoxycyclohexanecarboxylic acid-3',4'-epoxycyclohexanemethyl ester and 3,4-epoxy-6-methylcyclohexanecarboxylic acid-3',4'-epoxy-6-methylcyclohexanemethyl ester.

[0008] Preferably, the toughening agent is methyl methacrylate-butadiene-styrene toughening particles, the molecular weight distribution of the methyl methacrylate-butadiene-styrene toughening particles is 450-600 g / mol, and the particle size of the methyl methacrylate-butadiene-styrene toughening particles is required to be 500-1000 nm.

[0009] Preferably, the diluent is polyethylene glycol using ethylene glycol as an initiator, and the molecular weight distribution is 800-1000 g / mol.

[0010] Preferably, the active diluent is a monofunctional straight-chain alkyl glycidyl ether, and the carbon chain length of the straight-chain alkyl is C12 to C14.

[0011] Preferably, the wetting agent is BYK-9920.

[0012] Preferably, the B component comprises 80-90% by mass of an anhydride component, 5-10% by mass of a biguanide component, and 5-10% by mass of an accelerator.

[0013] Preferably, the acid anhydride component is a mixture of methyl hexahydrophthalic anhydride and hexahydrophthalic anhydride, wherein the mixing mass ratio of methyl hexahydrophthalic anhydride to hexahydrophthalic anhydride is 85-95:5-15;

[0014] The biguanide component is one or a mixture of 2-tolyl biguanide, 2-(2,5-dimethylphenyl) biguanide, phenyl biguanide, 2-benzyl biguanide, and 2,2'-ethylene biguanide;

[0015] The accelerator comprises 5-10% by mass of bisphenol A, 3-5% by mass of high orthophenyl ether type phenolic resin, and 85-92% by mass of imidazoline, wherein the imidazoline is a mixture of 2-phenylimidazoline and cycloalkylimidazoline or more.

[0016] A method for preparing an epoxy resin for long-term carbon fiber winding, wherein the preparation method of the A component comprises: adding epoxy resin, toughening agent, diluent, active diluent, and sizing agent into a high-speed dispersing container with a heating function, setting the temperature at 60-80°C, setting the stirring speed at 2000-2500 r / min, and stirring for 50-100 minutes, so as to obtain the required A component;

[0017] The preparation method of the B component comprises: adding the anhydride component, the biguanide component and the accelerator into a mixing container, introducing a certain amount of nitrogen, and then heating to 60-80° C. and stirring and mixing for 50-100 minutes to obtain the required B component.

[0018] The present invention includes at least the following beneficial effects: the use of biguanide compounds in the modified anhydride curing agent of the present invention greatly prolongs the applicability period of the epoxy resin, and can meet the requirement that the mixed viscosity is maintained within 1000 mPa.s for 30 hours at 40° C. during the carbon fiber winding process, thereby greatly ensuring the performance uniformity of the winding epoxy resin during use. At the same time, the present invention uses the additive BYK-9920 for increasing wettability, thereby greatly increasing the wettability of the epoxy resin to the carbon fiber.

[0019] Other advantages, objectives and features of the present invention will be embodied in part through the following description, and in part will be understood by those skilled in the art through study and practice of the present invention. DETAILED DESCRIPTION

[0020] The present invention is described in further detail below so that those skilled in the art can implement it according to the description.

[0021] It should be understood that the terms such as “having”, “including” and “comprising” used herein do not exclude the existence or addition of one or more other elements or combinations thereof.

[0022] Example 1

[0023] This embodiment provides an epoxy resin for carbon fiber winding with a long application period, comprising a component A and a component B, wherein the mass ratio of the component A to the component B is 100:100, wherein the component A is an epoxy resin component, and the component B is a modified acid anhydride curing agent component;

[0024] The preparation method of component A comprises: adding 65.36 g of E54 bisphenol A glycidyl ether resin, 20.64 g of 3,4-epoxycyclohexanecarboxylic acid-3',4'-epoxycyclohexane methyl ester, 5 g of methyl methacrylate-butadiene-styrene toughening particles, 3.5 g of polyethylene glycol PEG, 4 g of monofunctional linear alkyl glycidyl ether, and 1.5 g of BYK-9920 sizing agent into a high-speed dispersing container with a heating function, and raising the temperature to 100 °C. The temperature is set at 65°C, the stirring speed is set at 2000r / min, and the stirring is performed for 60 minutes to obtain the required component A; wherein the molecular weight of the methyl methacrylate-butadiene-styrene (MBS) toughened particles is 500g / mol, and the particle size is 800nm; the molecular weight of the polyethylene glycol (PEG) with ethylene glycol as the initiator is 1000g / mol; the linear alkane of the linear alkyl glycidyl ether is required to have a carbon chain length of C12 to C14;

[0025] The preparation method of component B comprises: adding 85.5g of methyl hexahydrophthalic anhydride, 4.5g of hexahydrophthalic anhydride, 5g of 2,2'-ethylene biguanide, 3g of 2-phenyl imidazoline, 1.5g of cycloalkyl imidazoline, 0.2g of high ortho-phenyl ether type phenolic resin and 0.3g of bisphenol A into a mixing container, introducing nitrogen, adjusting the flow rate to 5mL / min after the container is initially filled with nitrogen, and then heating to 60°C, stirring and mixing for 60min, and then obtaining the required component B.

[0026] When in use, component A and component B are mixed to obtain the epoxy resin for carbon fiber winding with a long application period.

[0027] The long-term applicable period carbon fiber winding epoxy resin prepared in this embodiment has a mixed viscosity of 926 mPa.s at 40°C during the carbon fiber winding process after 30 hours.

[0028] Example 2

[0029] This embodiment provides an epoxy resin for carbon fiber winding with a long application period, comprising a component A and a component B, wherein the mass ratio of the component A to the component B is 100:98, wherein the component A is an epoxy resin component, and the component B is a modified anhydride curing agent component;

[0030] The preparation method of component A comprises: adding 56.32 g of E54 bisphenol A glycidyl ether resin, 16.08 g of E51 bisphenol A glycidyl ether resin, 17.6 g of 3,4-epoxy-6-methylcyclohexanecarboxylic acid-3',4'-epoxy-6-methylcyclohexane methyl ester, 3 g of methyl methacrylate-butadiene-styrene toughening particles, 3 g of polyethylene glycol (PEG), 3 g of monofunctional linear alkyl glycidyl ether, and 1 g of BYK-9920 sizing agent to a mixture containing In a high-speed dispersion container with a thermal function, the temperature is set at 70°C, the stirring speed is set at 2000r / min, and the stirring is performed for 80 minutes to obtain the required component A; wherein the molecular weight of the methyl methacrylate-butadiene-styrene (MBS) toughened particles is 580g / mol, and the particle size is 1000nm; the molecular weight of the polyethylene glycol (PEG) with ethylene glycol as the initiator is 800g / mol; the linear alkane of the linear alkyl glycidyl ether is required to have a carbon chain length of C12 to C14;

[0031] The preparation method of component B includes: adding 81g of methyl hexahydrophthalic anhydride, 9g of hexahydrophthalic anhydride, 6g of 2-(2,5-dimethylphenyl)biguanide, 3.6g of cycloalkyl imidazoline, 0.16g of high ortho-phenylene ether type phenolic resin and 0.24g of bisphenol A into a mixing container, introducing nitrogen, and after the initial nitrogen fills the container, adjusting the flow rate to 5mL / min, and then heating to 75°C, stirring and mixing for 100min, the required component B can be obtained.

[0032] When in use, component A and component B are mixed to obtain the epoxy resin for carbon fiber winding with a long application period.

[0033] The long-usable-life carbon fiber winding epoxy resin prepared in this embodiment has a mixed viscosity of 963 mPa.s after being kept at 40°C for 30 hours during the carbon fiber winding process.

[0034] Example 3

[0035] This embodiment provides an epoxy resin for carbon fiber winding with a long application period, comprising a component A and a component B, wherein the mass ratio of the component A to the component B is 100:104, wherein the component A is an epoxy resin component, and the component B is a modified anhydride curing agent component;

[0036] The preparation method of component A comprises: adding 39.15 g of E54 bisphenol A glycidyl ether resin, 39.15 g of E51 bisphenol A glycidyl ether resin, 8.7 g of 3,4-epoxycyclohexanecarboxylic acid-3',4'-epoxycyclohexane methyl ester, 3 g of methyl methacrylate-butadiene-styrene toughening particles, 4 g of polyethylene glycol (PEG), 4 g of monofunctional linear alkyl glycidyl ether, and 2 g of BYK-9920 sizing agent into a high-speed heating device. In a dispersion container, the temperature is set at 80°C, the stirring speed is set at 2500r / min, and the stirring is carried out for 100min to obtain the required component A; wherein the molecular weight of the methyl methacrylate-butadiene-styrene (MBS) toughened particles is 600g / mol, and the particle size is 800nm; the molecular weight of the polyethylene glycol (PEG) with ethylene glycol as the initiator is 1000g / mol; the linear alkane of the linear alkyl glycidyl ether is required to have a carbon chain length of C12 to C14;

[0037] The preparation method of component B includes: adding 72.25g of methyl hexahydrophthalic anhydride, 12.75g of hexahydrophthalic anhydride, 8g of 2,2'-ethylene biguanide, 6.16g of cycloalkyl imidazoline, 0.28g of high ortho-phenylene ether type phenolic resin and 0.56g of bisphenol A into a mixing container, introducing nitrogen, and after the initial nitrogen fills the container, adjusting the flow rate to 5mL / min, and then heating to 75°C, stirring and mixing for 60min, the required component B can be obtained.

[0038] When in use, component A and component B are mixed to obtain the epoxy resin for carbon fiber winding with a long application period.

[0039] The long-term applicable carbon fiber winding epoxy resin prepared in this embodiment has a mixed viscosity of 988 mPa.s at 40°C during the carbon fiber winding process after 30 hours.

[0040] Comparative Example

[0041] This comparative example provides an epoxy resin for carbon fiber winding with a long application period, comprising a component A and a component B, wherein the mass ratio of the component A to the component B is 100:100, wherein the component A is an epoxy resin component, and the component B is a modified anhydride curing agent component;

[0042] The preparation method of component A comprises: adding 65.36g of E54 bisphenol A type glycidyl ether resin, 20.64g of 3,4-epoxycyclohexanecarboxylic acid-3',4'-epoxycyclohexane methyl ester, 5g of silicon-acrylate core-shell particles, 5g of polyethylene glycol PEG, and 4g of monofunctional straight-chain alkyl glycidyl ether into a high-speed dispersion container with a heating function, setting the temperature at 65°C, setting the stirring speed at 2000r / min, and stirring for 60min, so as to obtain the required component A; wherein the molecular weight of the silicon-acrylate core-shell particles is 450g / mol, and the particle size is required to be 1000nm; the molecular weight of polyethylene glycol (PEG) with ethylene glycol as the initiator is 800g / mol; the straight-chain alkane of the straight-chain alkyl glycidyl ether is required to have a carbon chain length of C12 to C14;

[0043] The preparation method of component B comprises: adding 95g of methyltetrahydrophthalic anhydride, 3g of benzyltriethylammonium chloride, 1.5g of cycloalkylimidazoline, 0.2g of high-orthophenyl ether type phenolic resin and 0.3g of bisphenol A into a mixing container, introducing nitrogen, and adjusting the flow rate to 5mL / min after the initial nitrogen fills the container, and then heating to 60°C and stirring and mixing for 60min to obtain the required component B.

[0044] When in use, component A and component B are mixed to obtain the epoxy resin for carbon fiber winding with a long application period.

[0045] The long-usable-life epoxy resin for carbon fiber winding prepared in this comparative example takes 10 to 15 hours for the mixed viscosity to reach 1000 mPa.s at 40° C. during the carbon fiber winding process.

[0046] The addition of biguanide compounds greatly extends the time, while the addition of the wetting agent BYK-9920 improves the wettability of the resin system to the carbon fiber and reduces the dry yarn defects that may occur as the winding time increases; the viscosity of a certain brand of commercially available winding epoxy resin is 916mPa.s after 10h, 2263mPa.s after 20h, and 4896mPa.s after 30h, while the viscosity of the resin system of the present invention has not reached 1000mPa.s after 30h, and the time required to reach 2000mPa.s is 42-45h, and the time required to reach 5000mPa.s is 58-60h, which greatly extends the applicable time of the resin.

[0047] The number of devices and processing scales described here are used to simplify the description of the present invention. Applications, modifications and variations of the present invention will be obvious to those skilled in the art.

[0048] Although the embodiments of the present invention have been disclosed as above, they are not limited to the applications listed in the specification and the implementation modes, and they can be fully applied to various fields suitable for the present invention. For those familiar with the art, additional modifications can be easily implemented. Therefore, without departing from the general concept defined by the claims and the scope of equivalents, the present invention is not limited to the specific details and the examples shown and described herein.

Claims

1. An epoxy resin for carbon fiber winding with a long application period, characterized in that: include: Component A and component B, the mass ratio of component A to component B is 100:90-110, wherein component A is an epoxy resin component, and component B is a modified anhydride curing agent component; The component A comprises 77-91% by mass of epoxy resin, 3-6% by mass of toughening agent, 3-5% by mass of diluent, 2-10% by mass of active diluent, and 1-2% by mass of wetting agent; The epoxy resin comprises 70-90% by mass of bisphenol A glycidyl ether resin and 10-30% by mass of alicyclic epoxy resin; wherein the bisphenol A glycidyl ether resin is one or a mixture of E-51 and E-54; and the alicyclic epoxy resin is one or a mixture of 3,4-epoxycyclohexanecarboxylic acid-3',4'-epoxycyclohexane methyl ester and 3,4-epoxy-6-methylcyclohexanecarboxylic acid-3',4'-epoxy-6-methylcyclohexane methyl ester; The toughening agent is methyl methacrylate-butadiene-styrene toughening particles, the molecular weight distribution of the methyl methacrylate-butadiene-styrene toughening particles is 450-600 g / mol, and the particle size of the methyl methacrylate-butadiene-styrene toughening particles is required to be 500-1000 nm; The diluent is polyethylene glycol using ethylene glycol as an initiator, and the molecular weight distribution is 800-1000 g / mol; The active diluent is a monofunctional straight-chain alkyl glycidyl ether, and the carbon chain length of the straight-chain alkyl is C12-C14; The B component includes 80-90% by mass of an anhydride component, 5-10% by mass of a biguanide component, and 5-10% by mass of an accelerator; The acid anhydride component is a mixture of methyl hexahydrophthalic anhydride and hexahydrophthalic anhydride, wherein the mixing mass ratio of methyl hexahydrophthalic anhydride to hexahydrophthalic anhydride is 85-95:5-15; The biguanide component is one or a mixture of 2-tolyl biguanide, 2-(2,5-dimethylphenyl) biguanide, phenyl biguanide, 2-benzyl biguanide, and 2,2'-ethylene biguanide; The accelerator comprises 5-10% by mass of bisphenol A, 3-5% by mass of high ortho-phenylene ether type phenolic resin, and 85-92% by mass of imidazoline, wherein the imidazoline is a mixture of one or more of 2-phenylimidazoline and cycloalkylimidazoline.

2. The long-usable-life carbon fiber winding epoxy resin according to claim 1, characterized in that: The sizing agent is BYK-9920.

3. A method for preparing an epoxy resin for long-term carbon fiber winding according to any one of claims 1 to 2, characterized in that: The preparation method of the component A comprises: adding epoxy resin, toughening agent, diluent, active diluent and impregnating agent into a high-speed dispersing container with a heating function, setting the temperature at 60-80° C., setting the stirring speed at 2000-2500 r / min, and stirring for 50-100 min, so as to obtain the required component A; The preparation method of the B component comprises: adding an anhydride component, a biguanide component and an accelerator into a mixing container, introducing a certain amount of nitrogen, and then heating to 60-80° C. and stirring and mixing for 50-100 min to obtain the required B component.