CN115386094A - High-toughness phenolic epoxy vinyl ester resin and preparation method thereof - Google Patents
High-toughness phenolic epoxy vinyl ester resin and preparation method thereof Download PDFInfo
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
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Abstract
The invention discloses a high-toughness phenolic epoxy vinyl ester resin and a preparation method thereof, belonging to the technical field of resin synthesis and comprising the following components in percentage by mass: 68 to 90 percent of phenolic epoxy resin, 9 to 30 percent of long-chain polyether unsaturated monocarboxylic acid and 0.1 to 2 percent of catalyst; the long-chain polyether unsaturated monocarboxylic acid comprises the following components: unsaturated acyl chloride, saturated acyl chloride and polyether dihydric alcohol. The phenolic epoxy vinyl ester resin with high toughness, high thermal stability and high elongation is prepared by synthesizing the phenolic epoxy resin with low elongation with long-chain polyether unsaturated resin, and introducing a polyether long chain into the unsaturated side chain of the phenolic epoxy skeleton, so that the high heat deformation temperature of the phenolic vinyl ester resin is effectively maintained, the elongation is improved, the hydroxyl content of matrix resin is not reduced, the wettability of the matrix resin on fibers is maintained to the maximum extent.
Description
Technical Field
The invention relates to the technical field of resin synthesis, in particular to the technical field of epoxy vinyl ester resin, further relates to high-toughness phenolic epoxy vinyl ester resin, and further relates to a preparation method of the high-toughness phenolic epoxy vinyl ester resin.
Background
Epoxy vinyl ester resins, referred to simply as vinyl ester resins or vinyl ester resins, are resins obtained by ring-opening addition polymerization of epoxy resins and monocarboxylic acids containing unsaturated double bonds, mainly methacrylic acid. The epoxy resin has the advantages of high mechanical strength and chemical corrosion resistance of the epoxy resin and good processing property of the unsaturated polyester resin, is an important matrix resin of a fiber reinforced composite material, and is widely applied to the fields of chemical industry, ships, coal and electricity and the like.
Although vinyl ester resin has higher mechanical strength, the vinyl ester resin also has the brittleness problem, namely the defects of low impact strength, low elongation at break and the like, the elongation of a general bisphenol A epoxy vinyl ester resin casting body is 5-6 percent, the elongation of a phenolic aldehyde type is lower and only 2.5-4 percent, although the phenolic aldehyde type can obtain higher thermal deformation temperature due to large crosslinking density and can reach 150 ℃, the prepared composite material has the defects of poor bending resistance, insufficient high-temperature bending property and the like, and the toughening modification of the phenolic aldehyde type composite material has important significance for widening the application field, in particular to the field with high fatigue resistance and high toughness requirements on resin matrix composite materials, such as high-speed railways, high-speed boats, sports equipment, novel non-pneumatic tire framework materials and the like.
The conventional methods for toughening vinyl ester resin at present comprise active liquid rubber toughening, nanoparticle filling toughening, polyurethane modification and the like, wherein the liquid rubber toughening is researched most and applied most mature, and the problem mainly to be overcome is the compatibility problem of the liquid rubber and an active diluent, so that the final stability of the product is ensured. Nanoparticle filled toughening also needs to face the above problems.
Patent CN103304749a discloses a synthesis method of a modified high-toughness epoxy vinyl ester resin, wherein the synthesis route is that bisphenol a type epoxy resin, unsaturated monocarboxylic acid and long-chain saturated dicarboxylic acid are subjected to a ring-opening reaction, and after a diluent is added, polymethylene polyphenyl isocyanate is used for a chain extension reaction. Patent CN113024770a discloses a preparation method of a high-strength and high-toughness vinyl ester resin, which comprises reacting diisocyanate with polyether diol to prepare isocyanate-terminated polyurethane Prepolymer (PUR), reacting the polyurethane Prepolymer (PUR) with hydroxyl of epoxy resin to obtain polyurethane-segmented modified epoxy resin (UE), and reacting with unsaturated monocarboxylic acid to obtain polyurethane-modified Vinyl Ester Resin (VER).
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide the high-toughness phenolic epoxy vinyl ester resin and the preparation method thereof.
In order to achieve the purpose, the invention adopts the technical scheme that:
in a first aspect of the invention, the invention provides a high-toughness novolac epoxy vinyl ester resin, which comprises the following components in percentage by mass: 68 to 90 percent of phenolic epoxy resin, 9 to 30 percent of long-chain polyether unsaturated monocarboxylic acid and 0.1 to 2 percent of catalyst;
the long-chain polyether unsaturated monocarboxylic acid comprises the following components: unsaturated acyl chloride, saturated acyl chloride and polyether dihydric alcohol;
the unsaturated acyl chloride comprises the following preparation raw materials: unsaturated monocarboxylic acids, thionyl chloride; the molar ratio of the unsaturated monocarboxylic acid to the thionyl chloride is 1: (1~3);
the saturated acyl chloride comprises the following preparation raw materials: saturated dicarboxylic acids, thionyl chloride; the molar ratio of the saturated dicarboxylic acid to the thionyl chloride is 1: (0.8 to 1.2);
the phenolic epoxy resin comprises at least one of F44 phenolic epoxy resin, F51 phenolic epoxy resin, F48 phenolic epoxy resin and F50 phenolic epoxy resin.
As a preferred embodiment of the present invention, the molar ratio of the unsaturated acid chloride, the saturated acid chloride and the polyether diol is 1: (0.8 to 1.2): (0.8 to 1.2).
As a preferred embodiment of the present invention, the molar ratio of the unsaturated acid chloride, the saturated acid chloride and the polyether diol is 1:1:1.
as a preferred embodiment of the present invention, the unsaturated monocarboxylic acid includes at least one of acrylic acid, methacrylic acid, crotonic acid and methylcrotonic acid.
As a preferred embodiment of the present invention, the saturated dicarboxylic acid includes at least one of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid.
In a preferred embodiment of the invention, the polyether glycol comprises at least one of polypropylene glycol and polyethylene glycol, wherein the molecular weight of the polypropylene glycol is 400 to 2000, and the molecular weight of the polyethylene glycol is 400 to 1000.
As a preferred embodiment of the present invention, the catalyst comprises at least one of benzyldimethylamine, benzyltriphenylphosphonium bromide, benzyltriethylammonium chloride, diethylamine, dimethylaniline, triethylamine or tributylamine.
In a second aspect of the present invention, the present invention provides a method for preparing the above-mentioned high toughness phenolic epoxy vinyl ester resin, comprising the steps of:
carrying out esterification reaction on unsaturated acyl chloride and polyether glycol to obtain hydroxyl-terminated unsaturated polyether, and carrying out esterification reaction on the hydroxyl-terminated unsaturated polyether and saturated acyl chloride to obtain long-chain polyether unsaturated monocarboxylic acid;
reacting long-chain polyether unsaturated monocarboxylic acid, phenolic epoxy resin and a catalyst until the acid value is lower than 10mgKOH/g, and obtaining the high-toughness phenolic epoxy vinyl ester resin.
The invention has the beneficial effects that: (1) According to the invention, the phenolic epoxy resin with low elongation is synthesized with the specific long-chain polyether unsaturated resin, and the polyether long chain is introduced into the unsaturated side chain of the phenolic epoxy skeleton, so that the high heat deformation temperature of the phenolic vinyl ester resin is effectively maintained, the elongation is improved, the hydroxyl content of matrix resin is not reduced, the wettability of the phenolic vinyl ester resin on fibers is maintained to the greatest extent, the phenolic epoxy vinyl ester resin with high toughness, high heat stability and high elongation is prepared, and the phenolic epoxy vinyl ester resin has good wettability on the fibers; (2) Compared with bisphenol A type resin commonly used in the world, the phenolic epoxy resin has lower elongation, has functional groups with better density, has obviously higher heat distortion temperature than the bisphenol A type resin, and does not reduce the wettability to fibers in the synthesis process. (3) The phenolic epoxy vinyl ester resin can be widely applied to the technical fields of high-speed railways, high-speed boats, sports equipment, novel non-pneumatic tire framework materials and fiber impregnation.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The specific dispersion and stirring treatment method is not particularly limited.
The reagents or instruments used in the present invention are not indicated by manufacturers, and are all conventional products commercially available.
The embodiment of the invention provides a high-toughness phenolic aldehyde type epoxy vinyl ester resin which comprises the following components in percentage by mass: 68 to 90 percent of phenolic epoxy resin, 9 to 30 percent of long-chain polyether unsaturated monocarboxylic acid and 0.1 to 2 percent of catalyst;
the long-chain polyether unsaturated monocarboxylic acid comprises the following components: unsaturated acyl chloride, saturated acyl chloride and polyether dihydric alcohol;
the unsaturated acyl chloride comprises the following preparation raw materials: unsaturated monocarboxylic acids, thionyl chloride; the molar ratio of the unsaturated monocarboxylic acid to the thionyl chloride is 1: (1~3);
the saturated acyl chloride comprises the following preparation raw materials: saturated dicarboxylic acids, thionyl chloride; the molar ratio of the saturated dicarboxylic acid to the thionyl chloride is 1: (0.8 to 1.2);
the phenolic epoxy resin comprises at least one of F44 phenolic epoxy resin, F51 phenolic epoxy resin, F48 phenolic epoxy resin and F50 phenolic epoxy resin.
According to the invention, the phenolic epoxy resin with low elongation is synthesized with the specific long-chain polyether unsaturated resin, and the polyether long chain is introduced into the unsaturated side chain of the phenolic epoxy skeleton, so that the high heat deformation temperature of the phenolic vinyl ester resin is effectively maintained, the elongation is improved, the hydroxyl content of matrix resin is not reduced, the wettability of the phenolic vinyl ester resin on fibers is maintained to the greatest extent, the phenolic epoxy vinyl ester resin with high toughness, high heat stability and high elongation is prepared, and the phenolic epoxy vinyl ester resin has good wettability on the fibers.
Compared with bisphenol A type resin commonly used in the world, the phenolic epoxy resin has lower elongation, has functional groups with better density, has obviously higher heat distortion temperature than the bisphenol A type resin, and does not reduce the wettability to fibers in the synthesis process.
The phenolic epoxy vinyl ester resin can be widely applied to the technical fields of high-speed railways, high-speed boats, sports equipment, novel non-pneumatic tire framework materials and fiber impregnation.
The inventor researches the influence of the using amounts of the phenolic epoxy resin and the long-chain polyether unsaturated monocarboxylic acid on the performance of the phenolic epoxy vinyl ester resin, and synthesizes the raw materials according to a specific proportion to prepare the phenolic epoxy vinyl ester resin with high toughness, high thermal stability and high elongation, and the phenolic epoxy vinyl ester resin has good wettability on fibers, so that if the using amounts of the long-chain polyether unsaturated monocarboxylic acid and the phenolic epoxy resin are not in the range of the invention, the tensile property, the elongation and the heat deformation temperature are reduced.
In one embodiment, the molar ratio of the unsaturated acid chloride, the saturated acid chloride and the polyether glycol is 1: (0.8 to 1.2): (0.8 to 1.2).
The long-chain polyether unsaturated monocarboxylic acid synthesized by taking unsaturated acyl chloride, saturated acyl chloride and polyether diol as raw materials has a specific polyether structure, unsaturated bonds and hydroxyl groups, can effectively improve the toughness, the thermal stability and the elongation of the phenolic epoxy vinyl ester resin, and improves the wettability to fibers.
In one embodiment, the molar ratio of the unsaturated acid chloride to the saturated acid chloride to the polyether diol is 1:1:1.
in one embodiment, the unsaturated monocarboxylic acid comprises at least one of acrylic acid, methacrylic acid, crotonic acid, and methylcrotonic acid.
In one embodiment, the saturated dicarboxylic acid comprises at least one of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid.
In one embodiment, the polyether glycol comprises at least one of polypropylene glycol and polyethylene glycol, wherein the molecular weight of the polypropylene glycol ranges from 400 to 2000, and the molecular weight of the polyethylene glycol ranges from 400 to 1000.
In one embodiment, the catalyst comprises at least one of benzyldimethylamine, benzyltriphenylphosphonium bromide, benzyltriethylammonium chloride, diethylamine, dimethylaniline, triethylamine or tributylamine.
An embodiment of the present invention provides a method for preparing the above high toughness phenolic epoxy vinyl ester resin, including the following steps:
carrying out esterification reaction on unsaturated acyl chloride and polyether dihydric alcohol to obtain hydroxyl-terminated unsaturated polyether, and carrying out esterification reaction on the hydroxyl-terminated unsaturated polyether and saturated acyl chloride to obtain long-chain polyether unsaturated monocarboxylic acid;
reacting long-chain polyether unsaturated monocarboxylic acid, phenolic epoxy resin and a catalyst until the acid value is lower than 10mgKOH/g, thereby obtaining the high-toughness phenolic epoxy vinyl ester resin.
The invention is further illustrated by the following specific examples:
example 1
A high-toughness phenolic aldehyde type epoxy vinyl ester resin comprises the following components in percentage by mass: 69% of phenolic epoxy resin, 30% of long-chain polyether unsaturated monocarboxylic acid and 1% of catalyst;
the long-chain polyether unsaturated monocarboxylic acid comprises the following components: unsaturated acyl chloride, saturated acyl chloride and polyether dihydric alcohol, wherein the molar ratio of the unsaturated acyl chloride to the saturated acyl chloride to the polyether dihydric alcohol is 1:1:1.
the unsaturated acyl chloride comprises the following preparation raw materials: methacrylic acid, thionyl chloride; the molar ratio of the methacrylic acid to the thionyl chloride is 1:1.5.
the saturated acyl chloride comprises the following preparation raw materials: oxalic acid, thionyl chloride; the molar ratio of the oxalic acid to the thionyl chloride is 1:1.
the polyether glycol comprises polypropylene glycol PPG400.
The phenolic epoxy resin is F44 phenolic epoxy resin.
The catalyst is benzyldimethylamine.
The preparation method of the high-toughness phenolic epoxy vinyl ester resin comprises the following steps:
(1) Adding methacrylic acid into a flask filled with thionyl chloride, building a tail gas absorption device with a drying tube, heating to 50 ℃, carrying out reflux reaction for 2 hours, distilling at normal pressure to remove excessive thionyl chloride to obtain unsaturated acyl chloride (methacryloyl chloride), and sealing and storing in a dryer;
(2) Filling thionyl chloride into a flask, building a tail gas absorption device with a drying tube, heating to 50 ℃ for reflux, dropwise and slowly adding oxalic acid into the flask, and sealing and storing the saturated acyl chloride (oxalyl chloride) after the reaction is finished.
(3) Filling polypropylene glycol PPG400 into a flask, building a tail gas absorption device with a drying tube, heating to 60 ℃ for reflux, dripping unsaturated acyl chloride into the flask, reacting for 0.5h after dripping is finished, then slowly adding saturated acyl chloride into the flask drop by drop, and reacting for 0.5h after dripping is finished to obtain long-chain polyether unsaturated monocarboxylic acid;
(4) Adding long-chain polyether unsaturated monocarboxylic acid, F44 novolac epoxy resin and benzyl dimethylamine into a reaction kettle, and reacting until the acid value is lower than 10mgKOH/g to obtain the high-toughness novolac epoxy vinyl ester resin.
Example 2
Example 2 is different from example 1 in that example 2 uses polypropylene glycol PPG600 instead of polypropylene glycol PPG400, and the rest is the same.
Example 3
Example 3 is different from example 1 in that example 3 uses polypropylene glycol PPG1000 instead of polypropylene glycol PPG400, and the rest is the same.
Example 4
Example 4 is different from example 1 in that example 4 uses polypropylene glycol PPG2000 instead of polypropylene glycol PPG400, but is otherwise the same.
Example 5
Example 5 is different from example 1 in that example 5 uses polyethylene glycol PEG1000 instead of polypropylene glycol PPG400, and the others are the same.
Example 6
A high-toughness phenolic aldehyde type epoxy vinyl ester resin comprises the following components in percentage by mass: 79 percent of phenolic epoxy resin, 20 percent of long-chain polyether unsaturated monocarboxylic acid and 1 percent of catalyst;
the long-chain polyether unsaturated monocarboxylic acid comprises the following components: unsaturated acyl chloride, saturated acyl chloride and polyether dihydric alcohol, wherein the molar ratio of the unsaturated acyl chloride to the saturated acyl chloride to the polyether dihydric alcohol is 1:1:1.
the unsaturated acyl chloride comprises the following preparation raw materials: methacrylic acid, thionyl chloride; the molar ratio of the methacrylic acid to the thionyl chloride is 1:1.5.
the saturated acyl chloride comprises the following preparation raw materials: oxalic acid, thionyl chloride; the molar ratio of the oxalic acid to the thionyl chloride is 1:1.
the polyether glycol comprises polypropylene glycol PPG1000.
The phenolic epoxy resin is F44 phenolic epoxy resin.
The catalyst is benzyldimethylamine.
The preparation method of the high-toughness phenolic epoxy vinyl ester resin comprises the following steps:
(1) Adding methacrylic acid into a flask filled with thionyl chloride, building a tail gas absorption device with a drying tube, heating to 50 ℃, carrying out reflux reaction for 2 hours, distilling at normal pressure to remove excessive thionyl chloride to obtain unsaturated acyl chloride (methacryloyl chloride), and sealing and storing in a dryer;
(2) Filling thionyl chloride into a flask, building a tail gas absorption device with a drying tube, heating to 50 ℃ for reflux, dropwise and slowly adding oxalic acid into the flask, and sealing and storing the saturated acyl chloride (oxalyl chloride) after the reaction is finished.
(3) Filling polypropylene glycol PPG1000 into a flask, building a tail gas absorption device with a drying tube, heating to 60 ℃ for reflux, dripping unsaturated acyl chloride into the flask, reacting for 0.5h after dripping, slowly adding saturated acyl chloride into the flask drop by drop, and reacting for 0.5h after dripping to obtain long-chain polyether unsaturated monocarboxylic acid;
(4) Adding long-chain polyether unsaturated monocarboxylic acid, F44 novolac epoxy resin and benzyl dimethylamine into a reaction kettle, and reacting until the acid value is lower than 10mgKOH/g to obtain the high-toughness novolac epoxy vinyl ester resin.
Example 7
A high-toughness phenolic aldehyde type epoxy vinyl ester resin comprises the following components in percentage by mass: 89% of phenolic epoxy resin, 10% of long-chain polyether unsaturated monocarboxylic acid and 1% of catalyst;
the long-chain polyether unsaturated monocarboxylic acid comprises the following components: unsaturated acyl chloride, saturated acyl chloride and polyether dihydric alcohol, wherein the molar ratio of the unsaturated acyl chloride to the saturated acyl chloride to the polyether dihydric alcohol is 1:1:1.
the unsaturated acyl chloride comprises the following preparation raw materials: methacrylic acid, thionyl chloride; the molar ratio of the methacrylic acid to the thionyl chloride is 1:1.5.
the saturated acyl chloride comprises the following preparation raw materials: oxalic acid, thionyl chloride; the molar ratio of the oxalic acid to the thionyl chloride is 1:1.
the polyether glycol comprises polypropylene glycol PPG1000.
The phenolic epoxy resin is F44 phenolic epoxy resin.
The catalyst is benzyldimethylamine.
The preparation method of the high-toughness phenolic epoxy vinyl ester resin comprises the following steps:
(1) Adding methacrylic acid into a flask filled with thionyl chloride, building a tail gas absorption device with a drying tube, heating to 50 ℃, carrying out reflux reaction for 2 hours, distilling at normal pressure to remove excessive thionyl chloride to obtain unsaturated acyl chloride (methacryloyl chloride), and sealing and storing in a dryer;
(2) Filling thionyl chloride into a flask, building a tail gas absorption device with a drying tube, heating to 50 ℃ for reflux, dropwise and slowly adding oxalic acid into the flask, and sealing and storing the saturated acyl chloride (oxalyl chloride) after the reaction is finished.
(3) Filling polypropylene glycol PPG1000 into a flask, building a tail gas absorption device with a drying tube, heating to 60 ℃ for reflux, dripping unsaturated acyl chloride into the flask, reacting for 0.5h after dripping, slowly adding saturated acyl chloride into the flask drop by drop, and reacting for 0.5h after dripping to obtain long-chain polyether unsaturated monocarboxylic acid;
(4) Adding long-chain polyether unsaturated monocarboxylic acid, F44 novolac epoxy resin and benzyl dimethylamine into a reaction kettle, and reacting until the acid value is lower than 10mgKOH/g to obtain the high-toughness novolac epoxy vinyl ester resin.
Example 8
Example 8 differs from example 6 in that example 8 uses methacrylic acid instead of methacrylic acid and malonic acid instead of oxalic acid, all other things being equal.
Example 9
Example 9 differs from example 6 in that example 9 uses crotonic acid instead of methacrylic acid and glutaric acid instead of oxalic acid, all other things being equal.
Example 10
Example 10 is different from example 6 in the kind of the novolac epoxy resin described in example 10 is different from example 6, and the others are the same.
The novolac epoxy resin described in this embodiment is F50 novolac epoxy resin.
Comparative example 1
Comparative example 1 differs from example 3 in the amount of novolac epoxy resin and long chain polyether unsaturated monocarboxylic acid used and is otherwise the same.
A high-toughness phenolic aldehyde type epoxy vinyl ester resin comprises the following components in percentage by mass: 94 percent of phenolic epoxy resin, 5 percent of long-chain polyether unsaturated monocarboxylic acid and 1 percent of catalyst.
Comparative example 2
Comparative example 2 differs from example 3 in the amount of novolac epoxy resin and long chain polyether unsaturated monocarboxylic acid used and is otherwise the same.
A high-toughness phenolic aldehyde type epoxy vinyl ester resin comprises the following components in percentage by mass: 59% of phenolic epoxy resin, 40% of long-chain polyether unsaturated monocarboxylic acid and 1% of catalyst.
Comparative example 3
Comparative example 3 is different from example 3 in that comparative example 3 uses E44 bisphenol a epoxy resin instead of novolac type epoxy resin (F44 novolac epoxy resin), and the others are the same.
Test example
The resin preparation samples prepared in the above examples and comparative examples were subjected to testing. The process is as follows: adding TPO initiator 1% (v/v) to the resin, standing at room temperature for 2.5h to remove air bubbles, pouring into dumbbell-shaped mold, and using 240mw/cm 2 And (4) carrying out ultraviolet irradiation with light intensity for 15s, naturally cooling to room temperature after curing is finished, and then carrying out performance test.
The tensile test and the bending test are determined according to the national standard GB/T2567-2021.
The heat distortion temperature HDT is determined according to the national standard GB/T1634-2014.
The test method of the complete fiber soaking time comprises the following steps: taking 5cm of glass fiber with the mark of E7DR17-2400-386H, flatly placing the fiber into a culture dish which is pre-filled with the resin, wherein the diameter of the culture dish is 10cm so as to ensure that the 5cm of fiber can be completely placed in the culture dish, and manually timing the time for the fiber to be completely soaked by the resin (namely, the fiber is transparent and does not see the primary color of the glass fiber).
Wherein the comparative product was a commercial product, fuchen 890, with the same curing procedure.
The test results are shown in table 1.
TABLE 1
As can be seen from Table 1, the epoxy vinyl ester resin of the present invention has high toughness, high thermal stability and high elongation, and the novolac epoxy vinyl ester resin has good wettability to fiber.
Comparing example 3 with comparative example 1~2, it can be seen that the amounts of the novolac epoxy resin and the long chain polyether unsaturated monocarboxylic acid significantly affect the properties of the epoxy vinyl ester resin, and if the amounts of the long chain polyether unsaturated monocarboxylic acid and the novolac epoxy resin are not within the range of the present invention, the tensile properties, elongation and heat distortion temperature are reduced, and the wettability of the fiber is reduced.
Comparing example 3 with comparative example 3, it can be seen that the phenolic epoxy resin adopted in the present invention can significantly improve the tensile property, elongation and heat distortion temperature, and also improve the wettability to the fiber, compared with bisphenol a type epoxy resin.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (7)
1. The high-toughness phenolic aldehyde type epoxy vinyl ester resin is characterized by comprising the following components in percentage by mass: 68 to 90 percent of phenolic epoxy resin, 9 to 30 percent of long-chain polyether unsaturated monocarboxylic acid and 0.1 to 2 percent of catalyst;
the long-chain polyether unsaturated monocarboxylic acid comprises the following components: unsaturated acyl chloride, saturated acyl chloride and polyether dihydric alcohol;
the unsaturated acyl chloride comprises the following preparation raw materials: unsaturated monocarboxylic acids, thionyl chloride; the molar ratio of the unsaturated monocarboxylic acid to the thionyl chloride is 1: (1~3);
the saturated acyl chloride comprises the following preparation raw materials: saturated dicarboxylic acids, thionyl chloride; the molar ratio of the saturated dicarboxylic acid to the thionyl chloride is 1: (0.8 to 1.2);
the phenolic epoxy resin comprises at least one of F44 phenolic epoxy resin, F51 phenolic epoxy resin, F48 phenolic epoxy resin and F50 phenolic epoxy resin.
2. The high toughness epoxy vinyl ester novolac resin of claim 1, wherein the molar ratio of unsaturated acid chloride, saturated acid chloride and polyether diol is 1: (0.8 to 1.2): (0.8 to 1.2).
3. The high toughness phenolic novolac epoxy vinyl ester resin of claim 1, wherein the unsaturated monocarboxylic acid comprises at least one of acrylic acid, methacrylic acid, crotonic acid and methylcrotonic acid.
4. The high toughness novolac-type epoxy vinyl ester resin as recited in claim 1, wherein said saturated dicarboxylic acid comprises at least one of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid.
5. The high-toughness phenolic aldehyde type epoxy vinyl ester resin as claimed in claim 1, wherein the polyether diol comprises at least one of polypropylene glycol and polyethylene glycol, the molecular weight of the polypropylene glycol is 400 to 2000, and the molecular weight of the polyethylene glycol is 400 to 1000.
6. The high toughness novolac-type epoxy vinyl ester resin of claim 1, wherein the catalyst comprises at least one of benzyldimethylamine, benzyltriphenylphosphonium bromide, benzyltriethylammonium chloride, diethylamine, dimethylaniline, triethylamine or tributylamine.
7. The process for preparing a high toughness phenolic epoxy vinyl ester resin as claimed in claim 1~6 comprising the steps of:
carrying out esterification reaction on unsaturated acyl chloride and polyether dihydric alcohol to obtain hydroxyl-terminated unsaturated polyether, and carrying out esterification reaction on the hydroxyl-terminated unsaturated polyether and saturated acyl chloride to obtain long-chain polyether unsaturated monocarboxylic acid;
reacting long-chain polyether unsaturated monocarboxylic acid, phenolic epoxy resin and a catalyst until the acid value is lower than 10mgKOH/g, and obtaining the high-toughness phenolic epoxy vinyl ester resin.
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