CN104610529A - Epoxy resin composition, preparation method of epoxy resin composition and composite material for wind power blade - Google Patents
Epoxy resin composition, preparation method of epoxy resin composition and composite material for wind power blade Download PDFInfo
- Publication number
- CN104610529A CN104610529A CN201510058667.1A CN201510058667A CN104610529A CN 104610529 A CN104610529 A CN 104610529A CN 201510058667 A CN201510058667 A CN 201510058667A CN 104610529 A CN104610529 A CN 104610529A
- Authority
- CN
- China
- Prior art keywords
- epoxy resin
- component
- parts
- composition epoxy
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Epoxy Resins (AREA)
Abstract
The invention relates to an epoxy resin composition, a preparation method of the epoxy resin composition, as well as a composite material prepared by using the composition and used for a wind power blade and a preparation method of the composite material. The epoxy resin composition comprises epoxy resin, a diluting agent, polyether amine and alicyclic amine; by virtue of the synergistic effect of all the components, the composition has low viscosity, low exothermic peak time and long exothermic peak time and is applicable to a vacuum assisted resin infusion technique; a wind power blade composite material prepared from the composition and a carbon fiber reinforced material has relatively light weight and relatively high mechanical property, is applicable to large-scale production of the wind power blade and has bright application prospect and high market value.
Description
Technical field
The present invention relates to a kind of resin material, matrix material for wind electricity blade relating more specifically to a kind of composition epoxy resin and preparation method thereof and use this composition epoxy resin to prepare and preparation method thereof, belongs to wind electricity blade Material Field.
Background technology
In current Wind Power Generation Industry, the wind electricity blade of nearly all business level all adopts matrix material as manufacture main body, especially adopts glass fiber compound material.The method preparing matrix material then mainly adopts lower-cost Liquid molding techniques, i.e. vacuum infusion molding technology.This technology is imported by epoxy resin to be provided with in the vacuum systems of strongthener, and epoxy resin is infiltrated in strongthener, through overcuring, and the matrix material that the two forming property final is good.
In order to meet energy demand growing in productive life, improve generating efficiency, Wind Power Generation Industry is inexorable trend to wind electricity blade large scale development.But, in the process that blade maximizes, glass fiber compound material is used to run into bottleneck: blade is larger, and in matrix material, the weight of glass fibre reinforcement is larger, more difficultly meet the demand of blade to intensity, this limits the maximization of blade to a certain extent.Therefore, in order to alleviate leaf weight, meeting the requirement of strength of blade, adopting carbon-fibre composite to replace glass fiber compound material to be comparatively effective means.
But when using vacuum infusion molding technology to prepare carbon-fibre composite, there is again following problem: first, because carbon fiber surface is level and smooth, active function groups is few, and surface energy is low, presents surface chemistry inertia.Therefore, the wetting property between carbon fiber and epoxy resin-base is poor; Secondly, carbon fibre fabric degree of compactness is higher, the common epoxy resin for sized glass fibres strongthener can not be had multilayer carbon fiber and well soak into.
Therefore, develop that a kind of viscosity is lower, operable time is longer, excellent in mechanical performance, carbon fiber had to the epoxy resin of ability of well soaking into, can become the key of the good carbon-fibre composite of processability.Researcher has carried out large quantifier elimination, and achieves many achievements, such as:
CN101880443A discloses a kind of low viscosity epoxy resin system for resin transfer molding and preparation and application thereof, this epoxy-resin systems comprises according to the epoxy resin of certainweight number proportioning, response type thinner, defoamer and solidifying agent, but its operable time is shorter, is not still suitable for and prepares carbon-fibre composite.
CN101693765B discloses a kind of organic silicon perfusion resin and preparation method thereof, and this vacuum infusion resin is modifying epoxy resin by organosilicon system, but this system exists the shortcomings such as adhesive property difference, cured article intensity is lower.
CN104151780A discloses a kind of wind electricity blade vacuum diversion composition epoxy resin, use the epoxy resin of number of different types to reduce the viscosity of said composition, but said composition also exists the shorter problem of operable time simultaneously.
In sum, although disclosed the multiple resin system for wind electricity blade in prior art, but these materials or not there is comparatively low viscosity, or after obtained matrix material, do not possess higher intensity, or not there is longer operable time, be unsuitable for the preparation technology of carbon-fibre composite.
Therefore, the defect that the present invention is intended to for existing in prior art is improved resin system, develop a kind of new composition epoxy resin, make it have lower viscosity and longer operable time, the requirement of strength of wind turbine blade to matrix material can be met.
Summary of the invention
In order to solve the problems of the technologies described above, contriver is paying a large amount of creative works and after going deep into experimental exploring, is developing a kind of composition epoxy resin with low viscosity and longer operable time.
Specifically, the present invention relates generally to following four aspects.
First aspect, the present invention relates to a kind of composition epoxy resin, described composition comprises component (A) and component (B), and described component (A) comprises epoxy resin and thinner, and described component (B) comprises polyetheramine and cycloaliphatic amines.
In described composition epoxy resin of the present invention, with parts by weight, in component (A), the content of each component is as follows:
Epoxy resin 60-95
Thinner 5-40
With parts by weight, in component (B), the content of each component is as follows:
Polyetheramine 50-90
Cycloaliphatic amines 5-50
In described composition epoxy resin of the present invention, relate to " comprising " of composition, both contained open " comprising ", " comprising " etc. and similar meaning thereof, also contains enclosed " by ... composition " etc. and similar meaning thereof.
In described composition epoxy resin of the present invention, the parts by weight of described component (A) are 80-100 part, such as, can be 80 parts, 85 parts, 90 parts, 95 parts or 100 parts.The parts by weight of described component (B) are 10-50 part, such as, can be 10 parts, 15 parts, 18 parts, 20 parts, 25 parts, 28 parts, 30 parts, 32 parts, 35 parts, 38 parts or 40 parts, 42 parts, 45 parts or 50 parts; Namely the weight ratio of described component (A) and described component (B) is 80-100: 10-50.
Wherein, be in the restriction of 80-100: 10-50 in the weight ratio of described component (A) and described component (B), " 80-100 " that relate to component (A) includes the concrete point value of any one enumerating above-mentioned, and " 10-50 " that relate to component (B) includes the concrete point value of any one enumerating above-mentioned.
Wherein, in described component (A), the parts by weight of described epoxy resin are 60-95 part, such as, can be 60 parts, 65 parts, 70 parts, 75 parts, 80 parts, 85 parts, 90 parts or 95 parts.
Described epoxy resin is any one in glycidyl ether type epoxy resin, glycidyl ester epoxy resin, glycidyl amine epoxy resin, linear aliphatic based epoxy resin, alicyclic ring based epoxy resin or any several mixture.
Preferably, described epoxy resin is glycidyl ether type epoxy resin, most preferably is bisphenol A type epoxy resin.
Wherein, described bisphenol A type epoxy resin is a very known resinoid, buys obtain by commercial system, such as, can produce and the E-54 type of public offering, E-51 type or E-44 type epoxy resin for Wuxi resin processing plant.
In described component (A), the parts by weight of described thinner are 5-40 part, such as, can be 5 parts, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts or 40 parts.
Described thinner is any one of single epoxy active diluent or multi-epoxy reactive thinner or any multiple mixture.
Wherein, described single epoxy active diluent can be butylglycidyl ether, benzyl glycidyl ether, phenyl glycidyl ether, 2-hexyl glycidyl ether, ortho-cresol glycidyl ether, tert-butyl phenol glycidyl ether, n-Octanol glycidyl ether or C
12-c
14any one in alcohol glycidyl ether or any multiple mixture.
Described multi-epoxy reactive thinner can be any one in ethylene glycol diglycidylether, Diethylene Glycol glycidyl ether, butanediol diglycidyl ether, neopentyl glycol glycidyl ether, hexanediol diglycidyl ether, propanetriol-diglycidyl-ether, resorcinol diglycidyl ether, diglycidylaniline, trimethylolpropane triglycidyl ether, trishydroxymethyl third glycidyl ether or any multiple mixture.
Described thinner is preferably multi-epoxy reactive thinner, most preferably is BDDE or 1,6-hexanediol diglycidyl ether.
In described component (B), the parts by weight of described polyetheramine are 50-90 part, such as, be 50 parts, 55 parts, 60 parts, 65 parts, 70 parts, 75 parts, 80 parts, 85 parts or 90 parts.
Wherein, described polyetheramine is the known material in this area, can be obtained by business buying pattern, T403 type, D230 type or D400 type polyetheramine that such as U.S.'s Hensel Man produces.
In described component (B), the parts by weight of described cycloaliphatic amines are 5-50 part, such as, can be 5 parts, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, 45 parts or 50 parts.
Wherein, described cycloaliphatic amines be the Meng alkane diamines, isophorone diamine, N-aminoethyl piperazine, 3, two (the 3-aminopropyl)-2 of 9-, 4,8,10-tetra-oxaspiro undecane affixture, 1, two (aminoethyl) hexanaphthene, 3 of 3-, any one in 3-dimethyl-4,4-diamino cyclohexyl-methane or 4,4-diamino cyclohexyl-methane or any multiple mixture.
Described cycloaliphatic amines is preferably N-aminoethyl piperazine, 3,3-dimethyl-4, any one in 4-diamino-two cyclohexyl methane, 1,3-two (aminomethyl) hexanaphthene, 4,4-diamino-two cyclohexyl methane or isophorone diamine or any multiple mixture.
Described cycloaliphatic amines most preferably is N-aminoethyl piperazine and 3,3-dimethyl-4, the mixture, 1 of 4-diamino-two cyclohexyl methane, two (aminomethyl) hexanaphthene and 4 of 3-, the mixture of 4-diamino-two cyclohexyl methane or isophorone diamine and 3, the mixture of 3-dimethyl-4,4-diamino-two cyclohexyl methane.
In composition epoxy resin of the present invention, optionally, also mill base can be comprised in the described component (B) of described composition epoxy resin, the parts by weight of described mill base in described component (B) are 0-0.5 part, such as, can be 0 part, 0.1 part, 0.2 part, 0.3 part, 0.4 or 0.5 part; When for 0 part, namely now do not comprise mill base.
Wherein, described mill base comprises above-mentioned polyetheramine and pigment.
In described mill base, the parts by weight of polyetheramine are 95-99 part, such as, be 95 parts, 96 parts, 97 parts, 98 parts or 99 parts.In described mill base, the parts by weight of described pigment are 0.5-2 part, such as, be 0.5 part, 0.8 part, 1 part, 1.5 parts or 2 parts; Namely, in described mill base, the weight ratio of described polyetheramine and described pigment is 95-99: 0.5-2.Wherein, be in the restriction of 95-99: 0.5-2 in the weight ratio of described polyetheramine and described pigment, " 95-99 " that relate to described polyetheramine includes the concrete point value of any one enumerating above-mentioned, and " 0.5-2 " that relate to described pigment includes the concrete point value of any one enumerating above-mentioned.
Wherein, described pigment is known material, and be preferably solvent red pigment, solvent yellow pigment or solvent blue pigment, most preferably be solvent blue pigment, such as Huifeng, Shenzhen pigment company limited produces and solvent blue 35 pigment sold.
Second aspect, the present invention relates to the preparation method of described composition epoxy resin, and this preparation method comprises the steps:
(1) take each component according to the parts by weight of each component in said components (A), join in reactor by described epoxy resin, temperature control heats; Add described thinner again, stir, vacuumize eliminating bubble, continue stirring and make mixture even, vacuum breaker stops stirring, and after leaving standstill, obtains described component (A), and sealing is preserved;
(2) each component is taken according to the parts by weight of each component in said components (B), join in reactor by described polyetheramine and described cycloaliphatic amines, stirred at ambient temperature makes mixture even, after leaving standstill, obtain described component (B), sealing is preserved;
(3) the described component (B) that the described component (A) step (1) prepared and step (2) prepare is according to described component (A): the weight ratio of described component (B)=80-100: 10-50 joins in reactor, continue stirring until mixture even, namely obtain described composition epoxy resin.
In the preparation method of described composition epoxy resin of the present invention, in step (1), to described epoxy resin heating also control temperature≤70 DEG C, then add described thinner, stir 20-40 minute, vacuumize, make vacuum tightness≤80mbar, continue to stir after 1-2 hour, utilize nitrogen vacuum breaker, stop stir, leave standstill, leave standstill time >=0.5 hour.
Wherein, Heating temperature≤70 DEG C of described epoxy resin, such as 70 DEG C, 60 DEG C, 50 DEG C or 40 DEG C.
Wherein, after adding thinner, stir 20-40 minute, such as, stir 20 minutes, 25 minutes, 30 minutes, 35 minutes or 40 minutes.
Wherein, the vacuum tightness≤80mbar vacuumized, such as 80mbar, 70mbar, 60mbar, 50mbar or 40mbar.
Wherein, after vacuumizing, continue stir 1-2 hour, such as can continue stirring 1 hour, 1.2 hours, 1.5 hours or 2 hours.
Wherein, leave standstill time >=0.5 hour, such as 0.5 hour, 0.6 hour, 0.8 hour or 1 hour.
In the preparation method of described composition epoxy resin of the present invention, in step (2), the stirred at ambient temperature time is 1-2 hour, leave standstill time >=0.5 hour.
Wherein, churning time is 1-2 hour, such as, can stir 1 hour, 1.2 hours, 1.5 hours or 2 hours.
Wherein, leave standstill time >=0.5 hour, such as 0.5 hour, 0.8 hour, 1 hour or 2 hours.
In the preparation method of described composition epoxy resin of the present invention, in step (2), when comprising mill base, then preparation method is as follows: first, each component is taken according to the parts by weight of component each in described mill base, described polyetheramine in described mill base and described pigment are joined in reactor, mixes, obtain described mill base; Then, each component is taken according to the parts by weight of each component in said components (B), after described polyetheramine in described component (B) and described cycloaliphatic amines are joined reactor, first stir 10-30 minute, add described mill base again, at room temperature stir and within 1-2 hour, make mixture even, leave standstill at least 0.5 hour, obtain described component (B), sealing is preserved.
Wherein, the churning time added after described polyetheramine and described cycloaliphatic amines is 10-30 minute, such as, can be 10 minutes, 15 minutes, 20 minutes, 25 minutes or 30 minutes.
Wherein, after adding mill base, stir 1-2 hour, such as, can stir 1 hour, 1.2 hours, 1.5 hours or 2 hours.
Wherein, leave standstill time >=0.5 hour, such as 0.5 hour, 0.8 hour, 1 hour or 2 hours.
3rd aspect, the present invention relates to a kind of matrix material for the manufacture of wind electricity blade, and described matrix material comprises strongthener and described composition epoxy resin.
In described matrix material of the present invention, described strongthener is the one in glass fibre reinforcement or carbon fibre reinforcement, is preferably carbon fibre reinforcement.
Wherein, the weight part of described strongthener is 70-80 part, such as, can be 70 parts, 72 parts, 75 parts, 78 parts or 80 parts; The weight part of described composition epoxy resin is 20-30 part, such as, can be 20 parts, 22 parts, 25 parts, 28 parts or 30 parts.
Wherein, described glass fibre reinforcement or carbon fibre reinforcement are all the known materials in this area, and this is no longer going to repeat them.
4th aspect, the present invention relates to the preparation method of described matrix material, described preparation method comprises the following steps:
S1: prepare described composition epoxy resin and described strongthener according to the parts by weight of above-mentioned composition epoxy resin and strongthener;
S2: utilize vacuum infusion molding technology, is placed in vacuum systems by described strongthener, is imported in described vacuum systems by described composition epoxy resin by glue inlet tube, infiltrates described strongthener, after solidification, obtains described matrix material.
Further, in S2 step, first, described strongthener is layed on mould; Secondly, above described strongthener, lay stripping release cloth, flow-guiding cloth successively, and insert described glue inlet tube, vapor pipe; Then, seal with film under vacuum coating mould; Finally, under condition of negative pressure, import in described mould by described composition epoxy resin by described glue inlet tube, infiltrate strongthener, after having infiltrated, solidification, the demoulding, obtain described matrix material.
Wherein, described strongthener is the one in glass fibre reinforcement or carbon fibre reinforcement, is preferably carbon fibre reinforcement.
Wherein, described condition of negative pressure is vacuum tightness >=60KPa, such as 60KPa, 70KPa, 80KPa, 90KPa or 95KPa.
Wherein, the 7.5-9.5 hour set time of cure stage, preferably 8.5 hours; The solidification value in this stage is 70-90 DEG C, preferably 85 DEG C.
Composition epoxy resin of the present invention, by selecting suitable thinner kind and parts by weight, suitable solidifying agent kind and parts by weight thereof, thus optimize the parameter such as viscosity, mechanical property of composition epoxy resin, make it for the manufacture of in the process of carbon-fibre composite, there is the longer exothermic peak time, lower exothermic peak temperature, can improve the over-all properties of final obtained matrix material simultaneously.
Especially, vacuum infusion molding technology is utilized to prepare in the process of carbon-fibre composite, composition epoxy resin of the present invention can be good at infiltrating carbon fibre reinforcement, while making final obtained carbon-fibre composite keep lighter in weight, there is higher mechanical strength, thus be applicable to the manufacture of maximization wind electricity blade.
As mentioned above, the invention provides a kind of composition epoxy resin, its preparation method, comprise its matrix material for the manufacture of wind electricity blade and the preparation method of described matrix material, by the selection etc. of suitable ingredients and consumption, and make described composition epoxy resin have excellent properties, and then lightweight, that intensity is high carbon-fibre composite can be obtained, more so can be used to prepare wind turbine blade, in technical field of wind power, there is good industrial applications prospect and value.
Embodiment
Below by specific embodiment, the present invention is described in detail, should be understood that, these embodiments are only used for exemplifying the present invention, not forms any type of any restriction to real protection scope of the present invention.
In all embodiments below, unless otherwise specified, " part " of relating to amounts of components is weight part.
Embodiment 1: the preparation of composition epoxy resin of the present invention
(1) 60 parts of E-54 type bisphenol A epoxide resins and 40 part 1 is taken according to the parts by weight of each component in component (A), 4-butanediol diglycidyl ether, join in reactor by E-54 type bisphenol A epoxide resin, temperature control heats, and Heating temperature is 70 DEG C; Add BDDE again, stir 30 minutes, be evacuated to vacuum tightness and equal 80mbar, get rid of bubble, continue stirring and within 2 hours, make mixture even, stop stirring after utilizing nitrogen vacuum breaker, leave standstill 0.5 hour, obtain component (A), sealing is preserved;
(2) 70 parts of T403 type polyetheramines, 10 parts of N-aminoethyl piperazines and 20 part 3 is taken according to the parts by weight of each component in component (B), 3-dimethyl-4,4-diamino-dicyclohexyl methyl hydride, T403 type polyetheramine, N-aminoethyl piperazine and 3,3-dimethyl-4,4-diamino-dicyclohexyl methyl hydride are joined in reactor, stirred at ambient temperature makes mixture even in 2 hours, leave standstill 0.5 hour, obtain component (B), sealing is preserved;
(3) component (B) that the component (A) step (1) prepared and step (2) prepare is according to component (A): the weight ratio of component (B)=100: 40 joins in reactor, continue stirring until mixture even, namely composition epoxy resin is obtained, called after SZ-1.
Composition epoxy resin obtained in the present embodiment, the exothermic peak temperature of 100g said composition at 25 DEG C is less than 50 DEG C, and the exothermic peak time is greater than 450 minutes.
Embodiment 2: the preparation of composition epoxy resin of the present invention
(1) 95 parts of E-51 type bisphenol A epoxide resins and 5 part 1 is taken according to the parts by weight of each component in component (A), 4-butanediol diglycidyl ether, join in reactor by E-51 type bisphenol A epoxide resin, temperature control heats, and Heating temperature is 60 DEG C; Add BDDE again, stir 30 minutes, be evacuated to vacuum tightness and equal 70mbar, get rid of bubble, continue stirring and within 2 hours, make mixture even, stop stirring after utilizing nitrogen vacuum breaker, leave standstill 0.5 hour, obtain component (A), sealing is preserved;
(2) according to the parts by weight of each component in component (B) take 50 parts of D403 type polyetheramines, 20 part 1, two (aminomethyl) hexanaphthene of 3-and 30 part 4,4-diamino-two cyclohexyl methane, D403 type polyetheramine, 1,3-two (aminomethyl) hexanaphthene and 4,4-diamino-two cyclohexyl methane are joined in reactor, stirred at ambient temperature makes mixture even in 2 hours, leave standstill 0.5 hour, obtain component (B), sealing is preserved;
(3) component (B) that the component (A) step (1) prepared and step (2) prepare is according to component (A): the weight ratio of component (B)=100: 30 joins in reactor, continue stirring until mixture even, namely composition epoxy resin is obtained, called after SZ-2.
Composition epoxy resin obtained in the present embodiment, the exothermic peak temperature of 100g said composition at 25 DEG C is less than 50 DEG C, and the exothermic peak time is greater than 450 minutes.
Embodiment 3: the preparation of composition epoxy resin of the present invention
(1) 60 parts of E-44 type bisphenol A epoxide resins and 40 part 1 is taken according to the parts by weight of each component in component (A), 6-hexanediol diglycidyl ether, join in reactor by E-44 type bisphenol A epoxide resin, temperature control heats, and Heating temperature is 70 DEG C; Add 1,6-hexanediol diglycidyl ether again, stir 25 minutes, be evacuated to vacuum tightness and equal 60mbar, get rid of bubble, continue stirring and within 2 hours, make mixture even, stop stirring after utilizing nitrogen vacuum breaker, leave standstill 0.8 hour, obtain component (A), sealing is preserved;
(2) 50 parts of D400 type polyetheramines, 15 parts of isophorone diamines and 35 part 3 is taken according to the parts by weight of each component in component (B), 3-dimethyl-4,4-diamino-dicyclohexyl methyl hydride, D400 type polyetheramine, isophorone diamine and 3,3-dimethyl-4,4-diamino-dicyclohexyl methyl hydride are joined in reactor, stirred at ambient temperature makes mixture even in 1.5 hours, leave standstill 0.8 hour, obtain component (B), sealing is preserved;
(3) component (B) that the component (A) step (1) prepared and step (2) prepare is according to component (A): the weight ratio of component (B)=100: 42 joins in reactor, continue stirring until mixture even, namely composition epoxy resin is obtained, called after SZ-3.
Composition epoxy resin obtained in the present embodiment, the exothermic peak temperature of 100g said composition at 25 DEG C is less than 50 DEG C, and the exothermic peak time is greater than 450 minutes.
Embodiment 4: the preparation of composition epoxy resin of the present invention
(1) 80 parts of E-54 type bisphenol A epoxide resins and 20 part 1 is taken according to the parts by weight of each component in component (A), 4-butanediol diglycidyl ether, join in reactor by E-54 type bisphenol A epoxide resin, temperature control heats, and Heating temperature is 50 DEG C; Add BDDE again, stir 40 minutes, be evacuated to vacuum tightness and equal 80mbar, get rid of bubble, continue stirring and within 1 hour, make mixture even, stop stirring after utilizing nitrogen vacuum breaker, leave standstill 1 hour, obtain component (A), sealing is preserved;
(2) first, 99 parts of D230 type polyetheramines and 1 part of solvent blue 35 pigment (this pigment is produced by Huifeng, Shenzhen pigment company limited and sold) is taken according to the parts by weight of component each in mill base, D230 type polyetheramine and solvent blue 35 pigment are joined in reactor, mix, obtain mill base; Then, according to the parts by weight of each component in component (B) take 70 parts of D230 type polyetheramines, 15 parts of isophorone diamines, 15 part 3,3-dimethyl-4,4-diamino-dicyclohexyl methyl hydride and 0.1 part of above-mentioned obtained mill base, by D230 type polyetheramine, isophorone diamine and 3,3-dimethyl-4,4-diamino-dicyclohexyl methyl hydride joins in reactor, stirs 15 minutes; Add above-mentioned obtained mill base again, stirred at ambient temperature makes mixture even for 2 hours, leaves standstill 0.5 hour, obtains component (B), and sealing is preserved;
(3) component (B) that the component (A) step (1) prepared and step (2) prepare is according to component (A): the weight ratio of component (B)=100: 32 joins in reactor, continue stirring until mixture even, namely composition epoxy resin is obtained, called after SZ-3.
Composition epoxy resin obtained in the present embodiment, the exothermic peak temperature of 100g said composition at 25 DEG C is less than 50 DEG C, and the exothermic peak time is greater than 450 minutes.
Embodiment 5: the preparation of matrix material of the present invention
S1: prepare obtained SZ-1 and the 70 part carbon fibre reinforcement of 30 parts of embodiments 1 (this carbon fibre reinforcement is the A 3K-01 type carbon cloth being opened up the sale of Tianxiang matrix material company limited by Shenzhen);
S2: utilize vacuum infusion molding technology, first, is layed in strongthener on mould; Secondly, above strongthener, lay stripping release cloth, flow-guiding cloth successively, and be inserted into sebific duct, vapor pipe; Then, seal with film under vacuum coating mould; Finally, be under the condition of 90KPa in vacuum tightness, imported in mould by SZ-1, infiltrate above-mentioned strongthener by described glue inlet tube, after having infiltrated, solidify 8.5 hours under the condition of 85 DEG C, the demoulding, obtains the matrix material of embodiment 5, called after FH-1.
Embodiment 6: the preparation of matrix material of the present invention
Except selecting the obtained SZ-2 of embodiment 2 to replace the obtained SZ-1 of embodiment 1 to infiltrate except strongthener as composition epoxy resin, obtain the matrix material of embodiment 6 with the method identical with embodiment 5, gained matrix material called after FH-2.
Embodiment 7: the preparation of matrix material of the present invention
Except selecting the obtained SZ-3 of embodiment 3 to replace the obtained SZ-1 of embodiment 1 to infiltrate except strongthener as composition epoxy resin, obtain the matrix material of embodiment 6 with the method identical with embodiment 5, gained matrix material called after FH-3.
Comparative example 1: the preparation of the composition epoxy resin of prior art
(1) 70 parts of E-54 type bisphenol A epoxide resins and 20 part 1 is taken according to the parts by weight of each component in component (A), 4-butanediol diglycidyl ether, join in reactor by E-54 type bisphenol A epoxide resin, temperature control heats, and Heating temperature is 70 DEG C; Add BDDE again, stir 30 minutes, be evacuated to vacuum tightness and equal 80mbar, get rid of bubble, continue stirring and within 2 hours, make mixture even, stop stirring after utilizing nitrogen vacuum breaker, leave standstill 0.5 hour, obtain component (A), sealing is preserved;
(2) first, 99 parts of T403 type polyetheramines and 1 part of solvent blue 35 pigment (this pigment is produced by Huifeng, Shenzhen pigment company limited and sold) is taken according to the parts by weight of component each in mill base, D230 type polyetheramine and solvent blue 35 pigment are joined in reactor, mix, obtain mill base; Then, according to the parts by weight of each component in component (B) take 60 parts of T403 type polyetheramines, 20 parts of isophorone diamines, 10 part 1,3-two aminomethyl cyclohexane, 10 parts of tetramethyl guanidines and 0.1 part of above-mentioned obtained mill base, by T403 type polyetheramine, isophorone diamine, 1, the two aminomethyl cyclohexane of 3-and tetramethyl guanidine join in reactor, stir 15 minutes, add above-mentioned obtained mill base again, stirred at ambient temperature makes mixture even in 2 hours, leave standstill 0.5 hour, obtain component (B), sealing is preserved;
(3) component (B) that the component (A) step (1) prepared and step (2) prepare is according to component (A): the weight ratio of component (B)=100: 25 joins in reactor, continue stirring until mixture even, namely composition epoxy resin is obtained, called after D-1.
Composition epoxy resin obtained in this comparative example, the exothermic peak temperature of 100g said composition at 25 DEG C is less than 70 DEG C, and the exothermic peak time is greater than 240 minutes.
Comparative example 2
Adopt Hensel to step Huntsman company to produce and the LY1564/XB3486 type composition epoxy resin sold as a comparison case 2, gained composition epoxy resin called after D-2.
Comparative example 3: the preparation of the matrix material of prior art
Except the D-2 that selects in comparative example 2 replaces SZ-1 in embodiment 1 as composition epoxy resin for infiltrating except strongthener, obtain the matrix material of comparative example 3 with the method identical with embodiment 5, gained matrix material called after D-3.
Comparative example 4: the preparation of the matrix material of prior art
Except selecting glycerin triglycidyl ether and replacing BDDE, obtain composition epoxy resin with the method identical with embodiment 2; Except selecting this composition epoxy resin and replacing SZ-2, obtain the matrix material of comparative example 4 with the method identical with embodiment 5, gained matrix material called after D-4.
Comparative example 5: the preparation of the matrix material of prior art
Replace except selecting trimethylolpropane triglycidyl ether, outside 1,6-hexanediol diglycidyl ether, obtaining composition epoxy resin with the method identical with embodiment 3; Except selecting this composition epoxy resin and replacing SZ-3, obtain the matrix material of comparative example 5 with the method identical with embodiment 5, gained matrix material called after D-5.
Comparative example 6: the preparation of the matrix material of prior art
Except only selecting N-aminoethyl piperazine to replace the mixture of N-aminoethyl piperazine and 3,3-dimethyl-4,4-diamino-two cyclohexyl methane as outside cycloaliphatic amines as cycloaliphatic amines, obtained composition epoxy resin in the same manner as in Example 1; Except selecting this composition epoxy resin and replacing SZ-1, obtain the matrix material of comparative example 6 with the method identical with embodiment 5, gained matrix material called after D-6.
Comparative example 7: the preparation of the matrix material of prior art
Except only selecting 4,4-diamino-dicyclohexyl methyl hydride replaces 1 as cycloaliphatic amines, the mixture of two (aminomethyl) hexanaphthene of 3-and 4,4-diamino-dicyclohexyl methyl hydride, as outside cycloaliphatic amines, obtains composition epoxy resin with the method identical with embodiment 2; Except selecting this composition epoxy resin and replacing SZ-2, obtain the matrix material of comparative example 7 with the method identical with embodiment 5, gained matrix material called after D-7.
Comparative example 8: the preparation of the matrix material of prior art
Except selecting Meng alkane diamines to replace the mixture of isophorone diamine and 3,3-dimethyl-4,4-diamino-dicyclohexyl methyl hydride as outside cycloaliphatic amines as cycloaliphatic amines, obtain composition epoxy resin with the method identical with embodiment 3; Except selecting this composition epoxy resin and replacing SZ-3, obtain the matrix material of comparative example 8 with the method identical with embodiment 5, gained matrix material called after D-8.
Performance test
1, the performance test of composition epoxy resin
Test according to concerned countries standard method of test, test the various performance parameters of the SZ-1 to SZ-4 that above-mentioned comparative example 1 obtained D-1 and embodiment 1-4 obtains respectively, experimental result sees the following form 1:
Table 1: the performance test of different rings epoxy resin composition
As shown in Table 1, the exothermic peak temperature of composition epoxy resin of the present invention between 35-50 DEG C, exothermic peak time >=450min, mixing viscosity between 210-250mPa.s, be all better than the relevant parameter in comparative example.In addition, known by the contrast of table 1, the mechanical property of composition epoxy resin of the present invention is also better than the mechanical property of comparative example.
2, the wetting capacity test of composition epoxy resin
Respectively the SZ-1 that the D-2 in comparative example 2 and embodiment 1 obtain is filled in strongthener (this carbon fibre reinforcement is the A3K-01 type carbon cloth being opened up the sale of Tianxiang matrix material company limited by Shenzhen), at interval of certain hour, utilize the infiltration weight of electronic balance record two kinds of composition epoxy resins in filling process.Wherein, the infiltration weight of D-2 and SZ-1 is all benchmark with 3000g, judges by the infiltration weight recording D-2 and SZ-1 the time stopping perfusion.Namely the time of initial timing is the time starting to pour into, and the time stopping timing is the time that D-2 and SZ-1 infiltrates about 3000g respectively, now, stops perfusion.Experimental result sees the following form 2:
The wetting capacity of table 2. different rings epoxy resin composition
In upper table 2, the implication of "--" is, when the infiltration weight of SZ-1 has reached about 3000g (being specially 3038g), namely stops the perfusion to SZ-1.Therefore, 53 minutes time, do not need the infiltration weight recording SZ-1 again, thus do not need the infiltration weight difference calculating SZ-1 and D-2 more yet.In addition, 53 minutes time, the infiltration weight of D-2 also reaches about 3000g (being specially 2958g), now stops the perfusion to D-2, and experiment terminates.
As above shown in table 2, in identical infusion time, the infiltration weight of composition epoxy resin of the present invention in strongthener is all many than the infiltration weight of comparative example 2 composition epoxy resin, shows that composition epoxy resin of the present invention has wetting velocity, better wetting capacity faster in strongthener.
3, the performance test of matrix material
(1) test according to concerned countries standard GB/T 2567-2008 testing method, respectively the various performance parameters of the obtained D-3 of above-mentioned the comparative example 3 and obtained FH-1 of embodiment 5 is carried out to twice parallel test test of the same terms, experimental result sees the following form 3:
The performance test 1 of table 3. matrix material
As above shown in table 3, the matrix material that the matrix material that composition epoxy resin of the present invention obtains obtains in mechanical property and in comparative example 3 is in same level, in tensile strength and compressive strength, be even more better than the matrix material that comparative example 3 is obtained, prove that the matrix material that composition epoxy resin of the present invention obtains has excellent mechanical property, the mechanical property requirements making wind electricity blade can be met.
(2) test according to concerned countries standard GB/T 2567-2008 testing method, respectively the various performance parameters of the obtained D-4 to D-5 of above-mentioned comparative example 4 to comparative example 5 and embodiment 6 and the obtained FH-2 to FH-3 of embodiment 7 is carried out to twice parallel test test of the same terms, experimental result sees the following form 4, table 5:
Table 4: the performance test 2 of matrix material
Table 5: the performance test 3 of matrix material
As above shown in table 4 and table 5, after adopting thinner of the present invention to obtain composition epoxy resin, recycle the matrix material that this composition epoxy resin is obtained, the mechanical property parameters such as its tensile modulus, compressive strength and shearing resistance are all higher than the mechanical property parameters of comparative example 4 to 5 matrix material, prove that the matrix material that composition epoxy resin of the present invention obtains has excellent mechanical property, meet the mechanical property requirements making wind electricity blade.
(3) test according to concerned countries standard GB/T 2567-2008 testing method, respectively the various performance parameters of the D-6 to D-8 that above-mentioned comparative example 6 to comparative example 8 obtains is carried out to twice parallel test test of the same terms, and the various performance parameters of the FH-1 to FH-3 experimental result and embodiment 5 to embodiment 7 obtained compares, experimental result sees the following form 6 to 8:
Table 6: the performance test 4 of matrix material
Table 7: the performance test 5 of matrix material
Table 8: the performance test 6 of matrix material
As above shown in table 6 to table 8, after adopting cycloaliphatic amines of the present invention to obtain composition epoxy resin, recycle the matrix material that this composition epoxy resin is obtained, the mechanical property parameters such as its tensile modulus, compressive strength and shearing resistance are all higher than the mechanical property parameters of comparative example 6 to 8 matrix material, prove that the matrix material that composition epoxy resin of the present invention obtains has excellent mechanical property, meet the mechanical property requirements making wind electricity blade.
From above-mentioned experimental result, compared with prior art, composition epoxy resin of the present invention has following excellent properties:
1, composition epoxy resin of the present invention has lower exothermic peak temperature and longer exothermic peak time, when this makes to utilize vacuum infusion molding technology to prepare using said composition and strongthener as the matrix material of wind electricity blade, said composition has sufficiently long operable time in vacuum systems, can infiltrate strongthener more fully.
2, the viscosity of composition epoxy resin of the present invention is very low, is conducive to said composition and flows in strongthener, improves the effect of impregnation to strongthener, especially has good wetting capacity to carbon fibre reinforcement.
3, the matrix material utilizing the present composition to prepare has good mechanical property, can meet the requirement of wind turbine blade to intensity.
In sum, the invention provides a kind of composition epoxy resin, it comprises epoxy resin, thinner, polyetheramine and cycloaliphatic amines, described composition epoxy resin is made to have low viscosity by the synergy between component, low exothermic peak time and longer exothermic peak time, be applicable to vacuum infusion molding technology, especially this technology is utilized to prepare the matrix material of material based on carbon fibre reinforcement and the present composition, final obtained matrix material is made to have compared with light weight and stronger mechanical property, the maximization being applicable to wind electricity blade is produced, have a good application prospect and marketable value.
Should be appreciated that the purposes of these embodiments is only not intended to for illustration of the present invention limit the scope of the invention.In addition; also should understand; after having read technology contents of the present invention, those skilled in the art can make various change, amendment and/or modification to the present invention, and these all equivalent form of values fall within the protection domain that the application's appended claims limits equally.
Claims (10)
1. a composition epoxy resin, it is characterized in that: described composition comprises component (A) and component (B), described component (A) comprises epoxy resin and thinner, and described component (B) comprises polyetheramine and cycloaliphatic amines.
2. composition epoxy resin as claimed in claim 1, it is characterized in that: with parts by weight, in component (A), the content of each component is as follows:
Epoxy resin 60-95
Thinner 5-40
With parts by weight, in component (B), the content of each component is as follows:
Polyetheramine 50-90
Cycloaliphatic amines 5-50
The weight ratio of described component (A) and described component (B) is 80-100: 10-50.
3. composition epoxy resin as claimed in claim 1 or 2, is characterized in that: described epoxy resin is any one in glycidyl ether type epoxy resin, glycidyl ester epoxy resin, glycidyl amine epoxy resin, linear aliphatic based epoxy resin, alicyclic ring based epoxy resin or any multiple mixture.
4. composition epoxy resin as claimed in claim 1 or 2, is characterized in that: described thinner is any one of single epoxy active diluent or multi-epoxy reactive thinner or any multiple mixture.
5. composition epoxy resin as claimed in claim 1 or 2, is characterized in that: described single epoxy active diluent is butylglycidyl ether, benzyl glycidyl ether, phenyl glycidyl ether, 2-hexyl glycidyl ether, ortho-cresol glycidyl ether, tert-butyl phenol glycidyl ether, n-Octanol glycidyl ether or C
12-c
14the mixture of one or more in alcohol glycidyl ether; Described multi-epoxy reactive thinner is any one in ethylene glycol diglycidylether, Diethylene Glycol glycidyl ether, butanediol diglycidyl ether, neopentyl glycol glycidyl ether, hexanediol diglycidyl ether, propanetriol-diglycidyl-ether, resorcinol diglycidyl ether, diglycidylaniline, trimethylolpropane triglycidyl ether, trishydroxymethyl third glycidyl ether or any multiple mixture.
6. composition epoxy resin as claimed in claim 1 or 2, it is characterized in that: described cycloaliphatic amines be the Meng alkane diamines, isophorone diamine, N-aminoethyl piperazine, 3, two (the 3-aminopropyl)-2 of 9-, 4,8,10-tetra-oxaspiro undecane affixture, 1, two (aminoethyl) hexanaphthene, 3 of 3-, any one in 3-dimethyl-4,4-diamino cyclohexyl-methane or 4,4-diamino cyclohexyl-methane or any multiple mixture.
7. composition epoxy resin as claimed in claim 1 or 2, it is characterized in that: also comprise mill base in the described component (B) of described composition epoxy resin, the parts by weight of described mill base in described component (B) are 0-0.5 part.
8. the preparation method of the composition epoxy resin as described in any one of claim 1-7, is characterized in that:
(1) take each component according to the parts by weight of each component in described component (A), join in reactor by described epoxy resin, temperature control heats; Add described thinner again, stir, vacuumize eliminating bubble, continue stirring and make mixture even, vacuum breaker stops stirring, and after leaving standstill, obtains described component (A), and sealing is preserved;
(2) each component is taken according to the parts by weight of each component in described component (B), join in reactor by described polyetheramine and described cycloaliphatic amines, stirred at ambient temperature makes mixture even, after leaving standstill, obtain described component (B), sealing is preserved;
(3) the described component (B) that the described component (A) step (1) prepared and step (2) prepare is according to described component (A): the weight ratio of described component (B)=80-100: 10-50 joins in reactor, continue stirring until mixture even, namely obtain described composition epoxy resin.
9. the matrix material for the manufacture of wind electricity blade, it is characterized in that: described matrix material comprises strongthener and the composition epoxy resin described in any one of claim 1-7, the parts by weight of described strongthener are 70-80 part, and the parts by weight of described composition epoxy resin are 20-30 part.
10. for the manufacture of a preparation method for the matrix material of wind electricity blade, it is characterized in that, comprise the following steps:
S1: prepare composition epoxy resin and strongthener according to the parts by weight of component each in matrix material as claimed in claim 9;
S2: utilize vacuum infusion molding technology, is placed in vacuum systems by described strongthener, is imported in described vacuum systems by described composition epoxy resin by glue inlet tube, infiltrates described strongthener, after solidification, obtains described matrix material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510058667.1A CN104610529A (en) | 2015-02-04 | 2015-02-04 | Epoxy resin composition, preparation method of epoxy resin composition and composite material for wind power blade |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510058667.1A CN104610529A (en) | 2015-02-04 | 2015-02-04 | Epoxy resin composition, preparation method of epoxy resin composition and composite material for wind power blade |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104610529A true CN104610529A (en) | 2015-05-13 |
Family
ID=53145199
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510058667.1A Pending CN104610529A (en) | 2015-02-04 | 2015-02-04 | Epoxy resin composition, preparation method of epoxy resin composition and composite material for wind power blade |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104610529A (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105885356A (en) * | 2016-06-21 | 2016-08-24 | 固德电材系统（苏州）股份有限公司 | Vacuum infusion resin and preparation method and application thereof |
| CN106186828A (en) * | 2016-07-01 | 2016-12-07 | 吉林重通成飞新材料股份公司 | Utilize the method that retired wind electric blade composite prepares square brick |
| WO2017150521A1 (en) * | 2016-02-29 | 2017-09-08 | 三菱ケミカル株式会社 | Epoxy resin composition, molding material, and fiber-reinforced composite material |
| CN109503812A (en) * | 2017-09-15 | 2019-03-22 | 万华化学集团股份有限公司 | A kind of epoxide resin material and its preparation method and application |
| CN110343443A (en) * | 2019-06-10 | 2019-10-18 | 宜昌市三峡天润纳米材料工程技术研究中心有限公司 | A kind of graphene coating and preparation method thereof |
| CN113501930A (en) * | 2021-06-23 | 2021-10-15 | 四川东树新材料有限公司 | Cast polyurethane resin for wind power blade and preparation method thereof |
| CN113817291A (en) * | 2021-09-30 | 2021-12-21 | 广东博汇新材料科技股份有限公司 | Carbon fiber vacuum infusion epoxy resin |
| US11332571B2 (en) | 2017-09-18 | 2022-05-17 | Aditya Birla Chemicals (Thailand) Ltd. | Epoxy resin system for structural composites |
| CN114656619A (en) * | 2022-05-05 | 2022-06-24 | 四川东树新材料有限公司 | Vacuum infusion epoxy resin composition and preparation method thereof |
| CN114907291A (en) * | 2022-05-16 | 2022-08-16 | 厦门市宜帆达新材料有限公司 | Modified reactive diluent and preparation method thereof, and epoxy resin for carbon fibers and preparation method thereof |
| CN117362598A (en) * | 2023-11-09 | 2024-01-09 | 四川东树新材料有限公司 | Epoxy resin composition with low viscosity, high strength and difficult crystallization |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101418070A (en) * | 2008-12-10 | 2009-04-29 | 北京玻钢院复合材料有限公司 | Epoxy resin combination, composite material and preparation method thereof |
| CN102020831A (en) * | 2010-11-16 | 2011-04-20 | 上海康达新能源材料有限公司 | Composite material for wind power generation blades |
| CN102604045A (en) * | 2012-03-22 | 2012-07-25 | 华东理工大学 | Epoxy resin composition and method for preparing glue film, prepreg and composite material by using same |
| CN102746621A (en) * | 2012-07-18 | 2012-10-24 | 中国石油化工股份有限公司 | Low-viscosity epoxy resin system for rapid repair and reinforcement and preparation method of low-viscosity epoxy resin system |
| CN102977557A (en) * | 2012-12-11 | 2013-03-20 | 蓝星(北京)化工机械有限公司 | Room temperature curing epoxy resin composition and preparation method thereof |
| CN104277418A (en) * | 2013-07-09 | 2015-01-14 | 上海杰事杰新材料(集团)股份有限公司 | Carbon fiber reinforced toughened epoxy resin composite material and preparation method thereof |
-
2015
- 2015-02-04 CN CN201510058667.1A patent/CN104610529A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101418070A (en) * | 2008-12-10 | 2009-04-29 | 北京玻钢院复合材料有限公司 | Epoxy resin combination, composite material and preparation method thereof |
| CN102020831A (en) * | 2010-11-16 | 2011-04-20 | 上海康达新能源材料有限公司 | Composite material for wind power generation blades |
| CN102604045A (en) * | 2012-03-22 | 2012-07-25 | 华东理工大学 | Epoxy resin composition and method for preparing glue film, prepreg and composite material by using same |
| CN102746621A (en) * | 2012-07-18 | 2012-10-24 | 中国石油化工股份有限公司 | Low-viscosity epoxy resin system for rapid repair and reinforcement and preparation method of low-viscosity epoxy resin system |
| CN102977557A (en) * | 2012-12-11 | 2013-03-20 | 蓝星(北京)化工机械有限公司 | Room temperature curing epoxy resin composition and preparation method thereof |
| CN104277418A (en) * | 2013-07-09 | 2015-01-14 | 上海杰事杰新材料(集团)股份有限公司 | Carbon fiber reinforced toughened epoxy resin composite material and preparation method thereof |
Cited By (25)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20200140633A1 (en) * | 2016-02-29 | 2020-05-07 | Mitsubishi Chemical Corporation | Epoxy resin composition, molding material, and fiber-reinforced composite material |
| US10920027B2 (en) | 2016-02-29 | 2021-02-16 | Mitsubishi Chemical Corporation | Epoxy resin composition, molding material, and fiber-reinforced composite material |
| WO2017150521A1 (en) * | 2016-02-29 | 2017-09-08 | 三菱ケミカル株式会社 | Epoxy resin composition, molding material, and fiber-reinforced composite material |
| JPWO2017150521A1 (en) * | 2016-02-29 | 2018-03-08 | 三菱ケミカル株式会社 | Molding materials and fiber reinforced composite materials |
| CN108603009A (en) * | 2016-02-29 | 2018-09-28 | 三菱化学株式会社 | Composition epoxy resin, moulding material and fibre reinforced composites |
| CN108603009B (en) * | 2016-02-29 | 2020-10-20 | 三菱化学株式会社 | Epoxy resin composition, molding material, and fiber-reinforced composite material |
| CN105885356B (en) * | 2016-06-21 | 2019-01-04 | 固德电材系统（苏州）股份有限公司 | A kind of vacuum imports resin and its preparation method and application |
| CN105885356A (en) * | 2016-06-21 | 2016-08-24 | 固德电材系统（苏州）股份有限公司 | Vacuum infusion resin and preparation method and application thereof |
| CN106186828B (en) * | 2016-07-01 | 2018-11-02 | 吉林重通成飞新材料股份公司 | The method for preparing square brick using retired wind electric blade composite |
| CN106186828A (en) * | 2016-07-01 | 2016-12-07 | 吉林重通成飞新材料股份公司 | Utilize the method that retired wind electric blade composite prepares square brick |
| CN109503812B (en) * | 2017-09-15 | 2020-08-28 | 万华化学集团股份有限公司 | Epoxy resin material and preparation method and application thereof |
| CN109503812A (en) * | 2017-09-15 | 2019-03-22 | 万华化学集团股份有限公司 | A kind of epoxide resin material and its preparation method and application |
| US11248085B2 (en) | 2017-09-15 | 2022-02-15 | Wanhua Chemical Group Co., Ltd. | Epoxy resin material, preparation method therefor and application thereof |
| US11332571B2 (en) | 2017-09-18 | 2022-05-17 | Aditya Birla Chemicals (Thailand) Ltd. | Epoxy resin system for structural composites |
| CN110343443A (en) * | 2019-06-10 | 2019-10-18 | 宜昌市三峡天润纳米材料工程技术研究中心有限公司 | A kind of graphene coating and preparation method thereof |
| CN110343443B (en) * | 2019-06-10 | 2021-12-07 | 宜昌三峡中润纳米材料有限公司 | Graphene coating and preparation method thereof |
| CN113501930A (en) * | 2021-06-23 | 2021-10-15 | 四川东树新材料有限公司 | Cast polyurethane resin for wind power blade and preparation method thereof |
| CN113501930B (en) * | 2021-06-23 | 2022-04-01 | 四川东树新材料有限公司 | Cast polyurethane resin for wind power blade and preparation method thereof |
| CN113817291A (en) * | 2021-09-30 | 2021-12-21 | 广东博汇新材料科技股份有限公司 | Carbon fiber vacuum infusion epoxy resin |
| CN114656619A (en) * | 2022-05-05 | 2022-06-24 | 四川东树新材料有限公司 | Vacuum infusion epoxy resin composition and preparation method thereof |
| CN114656619B (en) * | 2022-05-05 | 2024-04-30 | 四川东树新材料有限公司 | Vacuum-introduced epoxy resin composition and preparation method thereof |
| CN114907291A (en) * | 2022-05-16 | 2022-08-16 | 厦门市宜帆达新材料有限公司 | Modified reactive diluent and preparation method thereof, and epoxy resin for carbon fibers and preparation method thereof |
| CN114907291B (en) * | 2022-05-16 | 2024-01-12 | 厦门市宜帆达新材料有限公司 | Modified reactive diluent and preparation method thereof, and epoxy resin for carbon fiber and preparation method thereof |
| CN117362598A (en) * | 2023-11-09 | 2024-01-09 | 四川东树新材料有限公司 | Epoxy resin composition with low viscosity, high strength and difficult crystallization |
| CN117362598B (en) * | 2023-11-09 | 2024-08-09 | 四川东树新材料有限公司 | Epoxy resin composition with low viscosity, high strength and difficult crystallization |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104610529A (en) | Epoxy resin composition, preparation method of epoxy resin composition and composite material for wind power blade | |
| CN102020831B (en) | Composite material for wind power generation blades | |
| CN102746621B (en) | Low-viscosity epoxy resin system for rapid repair and reinforcement and preparation method of low-viscosity epoxy resin system | |
| CN105670223B (en) | Epoxy resin composition for wind turbine blade and composite material | |
| CN107815070A (en) | A kind of room temperature-curing low-viscosity high strength epoxy resin castable and preparation method | |
| WO2011037895A1 (en) | Curable epoxy resin compositions and composites made therefrom | |
| CN101818037A (en) | Room-temperature curing epoxy structural adhesive composition and preparation method thereof | |
| CN108699219A (en) | Blend for Cured epoxy resin compositions | |
| CN105086376B (en) | A kind of carbon fiber/epoxy resin composite material and preparation method thereof | |
| CN105038224A (en) | Benzoxazine prepreg composite and preparation method | |
| CN107011657A (en) | A kind of high-ductility bimaleimide resin and its preparation method and application | |
| CN103694637B (en) | A kind of High-tenacity vacuum slow epoxy resin for wind power blade and preparation method thereof | |
| CN112795143B (en) | High-performance pultrusion epoxy resin composite material for wind power and preparation method thereof | |
| CN106589837A (en) | Heat-resisting epoxy resin and carbon fiber composite cured at medium and low temperature and preparation method of composite | |
| CN107903587A (en) | A kind of carbon fibre reinforcement epoxy-resin systems | |
| CN111004472B (en) | Epoxy resin prepolymer with phase-splitting structure and preparation method and application thereof | |
| CN101589127B (en) | Toughened binder compositions for use in advance processes | |
| CN108384497A (en) | A kind of low viscosity repairing concrete crack potting compound and preparation method thereof | |
| CN110041702A (en) | Hot melt prepreg lower shrinkage cyanate ester resin system and preparation method thereof | |
| CN111087754B (en) | High-modulus high-toughness resin matrix for winding and preparation method and application thereof | |
| CN114230973A (en) | Epoxy resin composition for OOA process and preparation method of composite material thereof | |
| WO2024152750A1 (en) | Epoxy resin system for vacuum infusion process and preparation method therefor | |
| CN107083025A (en) | A kind of preparation method of carbon fiber Automobile Part rapid shaping fire resistant resin system | |
| EP3652233B1 (en) | Improvements in resin curative systems | |
| CN105754451A (en) | Konjac fly powder based epoxy resin, preparation method thereof and coating prepared from konjac fly powder based epoxy resin |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information |
Address after: 511400 Guangdong Province, Zhaoqing high tech Zone of Zhaoqing City, North River Road No. 9 Guangdong Bo new Mstar Technology Ltd office building Applicant after: Guangdong Bo new materials Polytron Technologies Inc Address before: 511400 Guangdong city of Guangzhou province Panyu District Panyu Avenue North, No. 555 Tian technology industrial building B, room 1008 Applicant before: GUANGDONG BROADWIN ADVANCED MATERIALS CO., LTD. |
|
| COR | Change of bibliographic data | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20150513 |