CN115181276A - Modified epoxy resin and preparation method thereof, epoxy resin coating and preparation method and application thereof - Google Patents

Modified epoxy resin and preparation method thereof, epoxy resin coating and preparation method and application thereof Download PDF

Info

Publication number
CN115181276A
CN115181276A CN202211031442.3A CN202211031442A CN115181276A CN 115181276 A CN115181276 A CN 115181276A CN 202211031442 A CN202211031442 A CN 202211031442A CN 115181276 A CN115181276 A CN 115181276A
Authority
CN
China
Prior art keywords
epoxy resin
modified epoxy
fluorine
containing polymer
modified
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
Application number
CN202211031442.3A
Other languages
Chinese (zh)
Inventor
王通
李强
荆晓杰
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Weifang Ruitong Environmental Protection Technology Co ltd
Original Assignee
Weifang Ruitong Environmental Protection Technology Co ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Weifang Ruitong Environmental Protection Technology Co ltd filed Critical Weifang Ruitong Environmental Protection Technology Co ltd
Priority to CN202211031442.3A priority Critical patent/CN115181276A/en
Publication of CN115181276A publication Critical patent/CN115181276A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • 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
    • C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
    • C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C08G81/024—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F120/10—Esters
    • C08F120/22—Esters containing halogen
    • C08F120/24—Esters containing halogen containing perhaloalkyl radicals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D187/00—Coating compositions based on unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
    • C09D187/005—Block or graft polymers not provided for in groups C09D101/00 - C09D185/04
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/18—Fireproof paints including high temperature resistant paints
    • 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
    • C08G2150/00—Compositions for coatings
    • C08G2150/90—Compositions for anticorrosive coatings

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Epoxy Resins (AREA)

Abstract

The invention provides a modified epoxy resin and a preparation method thereof, an epoxy resin coating and a preparation method and application thereof, and relates to the technical field of high-molecular anticorrosive materials.

Description

Modified epoxy resin and preparation method thereof, epoxy resin coating and preparation method and application thereof
Technical Field
The invention relates to the technical field of synthesis of high-molecular anticorrosive materials, in particular to modified epoxy resin and a preparation method thereof, and an epoxy resin coating and a preparation method and application thereof.
Background
The epoxy resin as a thermosetting resin has excellent performances such as adhesiveness, heat resistance, electrical insulation and high strength, and simultaneously has small curing shrinkage and expansion coefficient, excellent mechanical property and excellent comprehensive performance. Meanwhile, the monomer types for preparing the epoxy resin have diversity, so that the monomer types can be designed according to the performance of the actually required material. At present, epoxy resin is widely applied to the fields of adhesion of various metals and non-metals, electrical insulating materials, functional composite materials and the like, and plays an important role in the fields of electronics, mechanical manufacturing, aerospace and other industries.
However, amine compounds are often used in the curing process of epoxy resins, so that amino nitrogen atoms are introduced into the curing system, and the presence of the amino nitrogen atoms makes the epoxy resins susceptible to attack by acidic materials, so that the epoxy resins have poor acid resistance, so that the polymers of the epoxy resins are prone to chain scission and cracking and other problems when used under acidic conditions for a long time. In order to solve the problem, at present, the surface energy of the epoxy resin is reduced and the hydrophobicity is improved by grafting an epoxy resin molecular chain segment with an organic silicon chain segment and using a fluorine-containing micromolecule modified curing agent or doping hydrophobic materials such as graphene, so that the corrosion resistance to an acid medium is achieved, and the service life of the epoxy resin is prolonged.
Although the hydrophobicity of the epoxy resin can be improved by doping the hydrophobic material such as graphene, the graphene is expensive, and the filler such as graphene cannot be uniformly dispersed in the resin due to the high viscosity of the epoxy resin, which affects the uniformity of the performance of the composite epoxy resin; the fluorine-containing micromolecule modified curing agent can effectively perform curing reaction with the epoxy resin to form a uniform three-dimensional network structure and improve the hydrophobicity of the epoxy resin, but the fluorine atom content in the fluorine-containing curing agent molecules is low, so that the improvement of the hydrophobicity of the epoxy resin can only be limited.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a modified epoxy resin which has the characteristics of high thermal stability and strong hydrophobicity.
The second purpose of the invention is to provide a preparation method of the modified epoxy resin, which has simple process and easy operation.
The invention also aims to provide the epoxy resin coating which has good thermal stability and strong hydrophobicity, can prevent corrosive media from permeating into the resin, and has the characteristics of strong corrosion resistance and long service life.
The fourth purpose of the invention is to provide a preparation method of the epoxy resin coating, which has simple and high-efficiency process.
The fifth purpose of the invention is to provide the application of the epoxy resin coating, which can realize long-acting corrosion prevention.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
in a first aspect, a modified epoxy resin having a chemical structure represented by general formula (1):
Figure BDA0003817295150000031
wherein n is an integer of 10-20, and m is an integer of 4-12;
r comprises an epoxy group.
In a second aspect, a method for preparing a modified epoxy resin comprises the steps of:
carrying out grafting reaction on bisphenol A type epoxy resin and a fluorine-containing polymer to obtain the modified epoxy resin;
wherein the bisphenol A-type epoxy resin has a chemical structure represented by the general formula (2):
Figure BDA0003817295150000032
a is an integer of 4 to 12;
R 1 comprising a ringAn oxygen group;
wherein the fluorine-containing polymer has a chemical structure represented by general formula (3):
Figure BDA0003817295150000033
b is an integer of 10 to 20.
Further, the preparation method of the fluorine-containing polymer comprises the following steps:
and reacting the dodecafluoroheptyl methacrylate with a chain transfer agent to obtain the fluorine-containing polymer.
Further, the chain transfer agent has the following chemical structure:
Figure BDA0003817295150000041
further, the preparation method of the modified epoxy resin comprises the following steps:
and carrying out grafting reaction on the bisphenol A type epoxy resin and the fluorine-containing polymer in the solution under the action of a catalyst to obtain the modified epoxy resin.
Further, the catalyst comprises boron trifluoride;
the solvent for the grafting reaction comprises at least one of tetrahydrofuran, toluene and acetone;
the temperature of the grafting reaction is 100-120 ℃.
In a third aspect, an epoxy resin coating comprises the modified epoxy resin.
In a fourth aspect, a method for preparing an epoxy resin coating comprises the following steps:
and dissolving the modified epoxy resin to obtain the epoxy resin coating.
Further, the solvent in which the modified epoxy resin is dissolved includes at least one of acetone and tetrahydrofuran.
In a fifth aspect, an epoxy coating is used for corrosion protection.
Compared with the prior art, the invention has at least the following beneficial effects:
according to the modified epoxy resin provided by the invention, the fluorine-containing polymer with a specific structure is grafted on the chain segment of the bisphenol A type epoxy resin, so that the surface energy of the epoxy resin is obviously reduced, the hydrophobicity of the epoxy resin is enhanced, the permeation of corrosive media into the resin is effectively prevented, the corrosion resistance of the epoxy resin is further improved, and the service life of the epoxy resin is prolonged.
The preparation method of the modified epoxy resin provided by the invention is simple in process and easy to operate, and the fluorine content in the modified epoxy resin can be accurately regulated and controlled by regulating the proportion of the fluorine-containing polymer and the bisphenol A type epoxy resin in the reaction raw materials.
The epoxy resin coating provided by the invention has the characteristics of good thermal stability, strong hydrophobicity, strong corrosion resistance and long service life, and can prevent corrosive media from permeating into the resin.
The preparation method of the epoxy resin coating provided by the invention is simple in process and high in efficiency.
The epoxy resin coating provided by the invention can realize long-acting corrosion prevention and has an excellent application effect.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the embodiments or the prior art descriptions will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a schematic diagram illustrating the synthesis of a fluoropolymer according to one embodiment of the present invention;
FIG. 2 is a schematic diagram illustrating the synthesis of a modified epoxy resin according to one embodiment of the present invention;
FIG. 3 is a graph showing the thermogravimetric curves before and after modification of the epoxy resin obtained in test example 1 of the present invention;
FIG. 4 is a schematic view showing the contact angle between the epoxy resin obtained in test example 2 of the present invention and distilled water before and after modification;
FIG. 5 is a graph showing the change in water absorption before and after modification of the epoxy resin obtained in test example 2 of the present invention.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood 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.
According to a first aspect of the present invention, there is provided a modified epoxy resin having a chemical structure represented by general formula (1):
Figure BDA0003817295150000061
wherein n is an integer of 10 to 20, such as 10, 12, 14, 16, 18, 20, but not limited thereto; m is an integer of 4 to 12, and may be, for example, 4, 6, 8, 10, 12, but is not limited thereto; m and n are in the range, the comprehensive performance of the modified epoxy resin is better;
in the invention, the larger the value of n is, the higher the molecular weight of the hydrophobic segment of the fluorine-containing polymer is, so that the epoxy resin can show more excellent hydrophobicity, but the difficulty of grafting the fluorine-containing polymer to the epoxy resin in the synthesis process can be increased; the larger the value of m, the higher the viscosity of the epoxy resin, resulting in poorer flowability and reduced crosslinking density;
r includes, but is not limited to, an epoxy group.
According to the modified epoxy resin provided by the invention, fluorine-containing polymer with a specific structure is grafted on a chain segment of bisphenol A epoxy resin, so that introduction of fluorine element is realized, the thermal stability and hydrophobicity of the epoxy resin are effectively improved, the purpose of effectively preventing corrosive medium from permeating into the resin is realized, and the epoxy resin is endowed with excellent corrosion resistance and weather resistance.
According to the invention, the fluorine-containing polymer with a specific structure is grafted on the chain segment of the bisphenol A type epoxy resin, so that the surface energy of the epoxy resin is obviously reduced, the hydrophobicity of the epoxy resin is enhanced, the permeation of corrosive media into the resin is effectively prevented, and the corrosion resistance and the service life of the epoxy resin are further improved.
According to a second aspect of the present invention, there is provided a method for preparing a modified epoxy resin, comprising the steps of:
carrying out grafting reaction on bisphenol A type epoxy resin and a fluorine-containing polymer to obtain modified epoxy resin;
wherein the bisphenol A-type epoxy resin has a chemical structure represented by the general formula (2):
Figure BDA0003817295150000071
a is an integer of 4 to 12, and can be, for example, 4, 6, 8, 10, 12, but is not limited thereto;
R 1 including but not limited to epoxy groups;
wherein the fluorine-containing polymer has a chemical structure represented by general formula (3):
Figure BDA0003817295150000072
b is an integer of 10 to 20, and may be, for example, 10, 12, 14, 16, 18, 20, but is not limited thereto.
The preparation method of the modified epoxy resin provided by the invention is simple in process and easy to operate, and the fluorine content in the modified epoxy resin can be accurately regulated and controlled by regulating the proportion of the fluorine-containing polymer and the bisphenol A type epoxy resin in the reaction raw materials.
In a preferred embodiment, the process for the preparation of the fluoropolymer according to the invention comprises the following steps:
reacting dodecafluoroheptyl methacrylate with a chain transfer agent to obtain the fluorine-containing polymer.
The chemical structure of the chain transfer agent in the invention is as follows:
Figure BDA0003817295150000073
according to the invention, through the reaction of the dodecafluoroheptyl methacrylate and the chain transfer agent, the fluorine content in the fluorine-containing polymer can be controlled by controlling different reaction ratios of the dodecafluoroheptyl methacrylate and the chain transfer agent, and the controllable regulation of the reaction can be realized.
A typical method of making a fluoropolymer, see fig. 1, includes the steps of:
s1, preparation of a trithioester chain transfer agent:
dodecyl mercaptan, acetone, distilled water and tetrabutylammonium bromide (TBAB) are added into a flask to be dissolved, sodium hydroxide is added, carbon disulfide is added under the condition of ice-water bath stirring to react, a yellow product appears in the flask, 2-bromopropionic acid is added after the reaction is carried out for a period of time, then the reaction is carried out under the condition of room temperature, after the reaction is finished, rotary evaporation concentration and acidification are carried out, the yellow product is obtained by diluting with distilled water and filtering, then recrystallization and vacuum drying are carried out, and a bright yellow chain transfer agent S-dodecyl-S' -isopropyl acid-trithiocarbonate (DOPAT) is obtained;
s2: controllable polymerization for preparing fluorine-containing polymer containing terminal carboxyl:
adding dodecafluoroheptyl methacrylate (DFMA), DOPAT obtained in step S1, azodiisobutyronitrile (AIBN) and Tetrahydrofuran (THF) into a flask, mixing and dissolving, removing air in a reaction system by vacuumizing and filling nitrogen, then carrying out reaction under the protection of nitrogen, magnetically stirring at 65 ℃ for reaction for 18 hours, rapidly cooling after the reaction is finished, precipitating in diethyl ether to obtain a yellow precipitate, then washing, and vacuum drying to obtain the fluorine-containing polymer PDFMA-DOPAT containing terminal carboxyl.
The preparation method of the fluorine-containing polymer provided by the invention can effectively prepare the target product, is easy to control the fluorine content in the fluorine-containing polymer and can realize the controllable regulation of the reaction.
The invention adopts a controllable polymerization method to prepare the fluorine-containing polymer, and the prepared fluorine-containing polymer has a carboxyl functional group at the molecular chain end, and is endowed with certain reactivity so that the fluorine-containing polymer can be smoothly grafted to a chain segment of bisphenol A type epoxy resin.
In a preferred embodiment, the process for preparing the modified epoxy resin of the present invention comprises the steps of:
the bisphenol A epoxy resin and the fluorine-containing polymer are subjected to grafting reaction in the solution under the action of a catalyst to obtain the modified epoxy resin.
The preparation method of the modified epoxy resin provided by the invention can accurately regulate and control the fluorine content in the modified epoxy resin by regulating the proportion of the fluorine-containing polymer and the bisphenol A type epoxy resin in the reaction raw materials.
In the present invention, the catalyst for the grafting reaction is not particularly limited, and any catalyst having a corresponding catalytic effect may be used, and may be, for example, but not limited to, boron trifluoride, which is effective for catalyzing the grafting reaction of the bisphenol a type epoxy resin and the fluoropolymer.
In the present invention, the solvent for the grafting reaction is not particularly limited, and any solvent having a polymer dissolving ability that is commonly used in the art can be used as the solvent for the grafting reaction of the present invention, and for example, at least one of tetrahydrofuran, toluene, and acetone can be used.
In a preferred embodiment, the temperature of the grafting reaction of the present invention is in the range of 100 to 120 deg.C, which is typically, but not limited to, 100 deg.C, 105 deg.C, 108 deg.C, 112 deg.C, 115 deg.C, 118 deg.C, 120 deg.C, which facilitates the smooth grafting reaction of bisphenol A epoxy resin with fluoropolymer.
A typical preparation method of the modified epoxy resin, see fig. 2, comprises the following steps:
adding bisphenol A type epoxy resin and a tetrahydrofuran solution dissolved with PDFMA-DOPAT into a reaction kettle, mixing (controlling the molar ratio of epoxy group to PDFMA-DOPAT), heating under the protection of nitrogen, stirring thoroughly, and dissolving boron trifluoride (BF) 3 ) Is added into the reaction system, 12And (3) carrying out reaction at 0 ℃, and removing the solvent after the reaction is finished to obtain the fluoropolymer modified epoxy resin, namely the modified epoxy resin.
In the invention, a fluorine-containing polymer (PDFMA-DOPAT) and bisphenol A epoxy resin are reacted under the alkali catalysis condition, so that the fluorine-containing polymer is grafted to a molecular chain segment of the bisphenol A epoxy resin to obtain the epoxy resin modified by the fluorine-containing polymer.
The preparation method of the modified epoxy resin provided by the invention is simple in process and easy to operate, and the fluorine content in the modified epoxy resin can be accurately regulated and controlled by regulating the proportion of the fluorine-containing polymer and the bisphenol A type epoxy resin in the reaction raw materials.
According to a third aspect of the present invention, there is provided an epoxy resin coating comprising the modified epoxy resin described above.
The epoxy resin coating provided by the invention has the characteristics of good thermal stability, strong hydrophobicity, strong corrosion resistance and long service life, and can prevent corrosive media from permeating into the resin.
According to a fourth aspect of the present invention, there is provided a method for preparing an epoxy resin coating, comprising the steps of:
and dissolving the modified epoxy resin to obtain the epoxy resin coating.
In the present invention, the solvent used for dissolving the modified epoxy resin is not particularly limited, and any solvent having an ability to dissolve the polymer may be used as is common in the art, and may be, for example, at least one of acetone and tetrahydrofuran, but is not limited thereto.
A typical preparation method of an epoxy resin coating comprises the following steps:
and adding the modified epoxy resin into an acetone solvent to obtain the solvent type epoxy resin coating.
The preparation method of the epoxy resin coating provided by the invention is simple in process and high in efficiency.
According to a fifth aspect of the present invention, there is provided the use of an epoxy coating for corrosion protection.
The epoxy resin coating provided by the invention can realize long-acting corrosion prevention and has an excellent application effect.
The invention is further illustrated by the following examples. The materials in the examples are prepared according to known methods or are directly commercially available, unless otherwise specified.
Example 1
A modified epoxy resin has the following structure:
Figure BDA0003817295150000101
wherein m is 4, n is 10, and R is an epoxy group.
Example 2
A modified epoxy resin has the following structure:
Figure BDA0003817295150000111
wherein m is 8, n is 15, R is an epoxy group.
Example 3
A modified epoxy resin has the following structure:
Figure BDA0003817295150000112
wherein m is 12, n is 20, R is an epoxy group.
Example 4
This example is a method of preparing the modified epoxy resin of examples 1-3, comprising the steps of:
the first step is as follows: preparation of trithioester chain transfer agent:
18mL of dodecanethiol, 240mL of acetone, 30mL of distilled water and 1.62g of tetrabutylammonium bromide (TBAB) are sequentially added into a 500mL flask, then 3.0g of sodium hydroxide is added, 4.5mL of carbon disulfide is added under the stirring condition of an ice-water bath, a yellow product appears in the flask, 10.5g of 2-bromopropionic acid is dropwise added after 0.5h of reaction, the reaction is carried out for 15h at room temperature, rotary evaporation concentration is carried out after the reaction is finished, the solution is acidified by 300mL of hydrochloric acid with the concentration of 2mol/L, then the solution is diluted by 300mL of distilled water, and the yellow product is obtained by filtration and finally the solution is added with ethyl ether: petroleum ether =3:7 (volume ratio), and vacuum drying at 25 ℃ for 24h to obtain a bright yellow chain transfer agent S-dodecyl-S' -isopropyl acid-trithiocarbonate (DOPAT);
the second step is that: controllable polymerization for preparing fluorine-containing polymer containing terminal carboxyl:
adding dodecafluoroheptyl methacrylate (DFMA) and trithioester chain transfer agent (DOPAT) into a flask according to a certain proportion, adding Azobisisobutyronitrile (AIBN) and Tetrahydrofuran (THF), removing air in a reaction system by vacuumizing and filling nitrogen for three times, then magnetically stirring and reacting for 18h at 65 ℃ under the nitrogen protection atmosphere, rapidly cooling after the reaction is finished, then precipitating in diethyl ether to obtain yellow precipitate, then washing twice by using the diethyl ether, and finally vacuum-drying for 24h at 30 ℃ to obtain the fluorine-containing polymer (PDFMA-DOPAT) containing terminal carboxyl;
the third step: preparation of fluoropolymer modified epoxy resin:
adding bisphenol A type epoxy resin and a tetrahydrofuran solution dissolved with PDFMA-DOPAT into a reaction kettle, controlling the molar ratio of an epoxy group to the PDFMA-DOPAT, heating to 90 ℃ under the protection of nitrogen, fully and uniformly stirring, then adding an ether solution dissolved with boron trifluoride into the reaction kettle, heating to 120 ℃ after dropwise addition, stirring for reaction, cooling a reaction system to 60 ℃ after the reaction is finished, and removing a solvent through reduced pressure distillation to obtain a fluorine-containing polymer modified epoxy resin, namely the modified epoxy resin;
wherein, the bisphenol A type epoxy resin has the following structure:
Figure BDA0003817295150000121
a corresponds to m in examples 1 to 3, respectively, and R 1 Corresponding to R in examples 1-3, respectively.
Comparative example 1
The comparative example provides a bisphenol a epoxy resin, having the following structure:
Figure BDA0003817295150000122
wherein a is 5 1 Is an epoxy group.
Test example 1
In N 2 Thermal stability of the bisphenol A type epoxy resin (unmodified resin) of comparative example 1 and the modified epoxy resin of example 1 was respectively tested under atmosphere and at 30-550 ℃ by a thermogravimetric analyzer, and a thermal weight loss curve is shown in fig. 3, so that it can be seen that the epoxy resin provided by comparative example 1 starts to decompose at 220 ℃ (a in fig. 3), the temperature of the maximum weight loss rate is about 330 ℃, and when the temperature reaches 600 ℃, the residual carbon accounts for 15% of the resin proportion; in contrast, the modified epoxy resin provided in example 1 starts to decompose at 260 ℃ (b in fig. 3), the temperature of the maximum weight loss rate is about 390 ℃, and when the temperature reaches 600 ℃, the residual carbon accounts for 17% of the resin proportion; as can be seen from the above comparison, the decomposition temperature of the modified epoxy resin of example 1 is increased because fluorine has flame retardant property, so that the thermal stability of the resin can be improved after the fluorine is introduced.
The modified epoxy resins provided in examples 2 to 3 were analyzed by thermogravimetric analysis using the same temperature program as described above, and as a result, the modified resins of examples 2 to 3 also had better thermal stability.
Test example 2
In order to examine the hydrophobic effect of the modified epoxy resin provided by the present invention, the bisphenol a type epoxy resin (unmodified resin) and the modified epoxy resin of example 1 were tested for their surface contact angle with distilled water by dropping distilled water onto the surface of the resin coating and recording the image of the water drop, as shown in fig. 4, it can be seen that the contact angle of distilled water on the surface of the unmodified resin coating of comparative example 1 is 70.6 ° (a in fig. 4), and the contact angle on the surface of the modified epoxy resin of example 1 is 102.2 ° (b in fig. 4), and it can be seen that the contact angle is significantly increased, indicating that the hydrophobicity of the epoxy resin modified by the fluoropolymer is increased, mainly because the introduction of fluorine atoms can reduce the surface energy of the resin, making it more difficult for the liquid to spread on the surface of the resin, and thus can act as a stronger barrier to the permeation of corrosive acidic media into the interior, enhancing the corrosion resistance of the epoxy resin.
To further verify the hydrophobicity of the modified epoxy resin provided by the present invention, the water absorption of the bisphenol a type epoxy resin (unmodified epoxy resin) of comparative example 1 and the modified epoxy resin of example 1 were tested by the medium immersion method, and the water absorption of both resins was recorded for different times by immersing them in a 3.5% NaCl aqueous solution, and as a result, as shown in fig. 5, it can be seen that the water absorption of both resins was continuously increased with the extension of the immersion time, and after 30 days of immersion, the water absorption of the unmodified epoxy resin of comparative example 1 reached 1.58%, while the water absorption of the modified epoxy resin of example 1 was only 0.42%, and the water absorption at different immersion times was significantly lower than that of the unmodified epoxy resin of comparative example 1. The above results further demonstrate that the introduction of fluorine can increase the hydrophobicity of the resin and can effectively prevent the penetration of corrosive media into the resin.
The modified epoxy resins provided in examples 2 to 3 were verified for hydrophobicity in the same manner as described above, and as a result, the modified resins of examples 2 to 3 also had better hydrophobicity.
In conclusion, the fluorine-containing polymer is grafted to the chain segment of the epoxy resin to obtain the modified epoxy resin, so that the hydrophobicity and the thermal stability of the modified epoxy resin are improved, the corrosion resistance is enhanced, the technical problems of poor hydrophobicity, poor acid resistance and non-ideal modification effect of the epoxy resin in the prior art are solved, and the technical effects of improving the hydrophobicity and the thermal stability of the epoxy resin and enabling the epoxy resin to have stronger corrosion resistance are achieved.
Therefore, the invention designs and synthesizes the epoxy resin modified by the fluorine-containing polymer by utilizing the functional group characteristics of the epoxy resin, and can control the fluorine content in the epoxy resin material by designing reaction conditions, thereby controllably adjusting the acid resistance and the weather resistance of the epoxy resin material.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.

Claims (10)

1. A modified epoxy resin characterized by having a chemical structure represented by general formula (1):
Figure FDA0003817295140000011
wherein n is an integer of 10 to 20, and m is an integer of 4 to 12;
r comprises an epoxy group.
2. A method for preparing the modified epoxy resin according to claim 1, comprising the steps of:
carrying out grafting reaction on bisphenol A type epoxy resin and a fluorine-containing polymer to obtain the modified epoxy resin;
wherein the bisphenol A-type epoxy resin has a chemical structure represented by the general formula (2):
Figure FDA0003817295140000012
a is an integer of 4 to 12;
R 1 comprises an epoxy group;
wherein the fluorine-containing polymer has a chemical structure represented by general formula (3):
Figure FDA0003817295140000021
b is an integer of 10 to 20.
3. The method for producing a modified epoxy resin according to claim 2, wherein the method for producing a fluorine-containing polymer comprises the steps of:
and reacting the dodecafluoroheptyl methacrylate with a chain transfer agent to obtain the fluorine-containing polymer.
4. The method for preparing a modified epoxy resin according to claim 3, wherein the chain transfer agent has the following chemical structure:
Figure FDA0003817295140000022
5. the method for producing a modified epoxy resin according to any one of claims 2 to 4, characterized in that the method for producing a modified epoxy resin comprises the steps of:
and carrying out grafting reaction on the bisphenol A type epoxy resin and the fluorine-containing polymer in the solution under the action of a catalyst to obtain the modified epoxy resin.
6. The method for producing a modified epoxy resin according to claim 5, wherein the catalyst comprises boron trifluoride;
the solvent for the grafting reaction comprises at least one of tetrahydrofuran, toluene and acetone;
the temperature of the grafting reaction is 80-130 ℃.
7. An epoxy resin coating material comprising the modified epoxy resin according to claim 1.
8. A method for preparing the epoxy resin paint according to claim 7, characterized by comprising the steps of:
and dissolving the modified epoxy resin to obtain the epoxy resin coating.
9. The method according to claim 8, wherein the solvent in which the modified epoxy resin is dissolved includes at least one of acetone and tetrahydrofuran.
10. Use of the epoxy resin coating according to claim 7 for corrosion protection.
CN202211031442.3A 2022-08-26 2022-08-26 Modified epoxy resin and preparation method thereof, epoxy resin coating and preparation method and application thereof Pending CN115181276A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202211031442.3A CN115181276A (en) 2022-08-26 2022-08-26 Modified epoxy resin and preparation method thereof, epoxy resin coating and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202211031442.3A CN115181276A (en) 2022-08-26 2022-08-26 Modified epoxy resin and preparation method thereof, epoxy resin coating and preparation method and application thereof

Publications (1)

Publication Number Publication Date
CN115181276A true CN115181276A (en) 2022-10-14

Family

ID=83523471

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202211031442.3A Pending CN115181276A (en) 2022-08-26 2022-08-26 Modified epoxy resin and preparation method thereof, epoxy resin coating and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN115181276A (en)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1625571A (en) * 2001-12-21 2005-06-08 悉尼大学 Aqueous dispersions of polymer particles
CN101974138A (en) * 2010-10-26 2011-02-16 武汉理工大学 Method for preparing amphiphilic gradient copolymer
CN101982478A (en) * 2010-09-26 2011-03-02 北京印刷学院 Polymer surfactant and core-shell amphiphilic polymer microsphere as well as preparation method thereof
CN104789094A (en) * 2015-04-28 2015-07-22 中科院广州化学有限公司南雄材料生产基地 Carboxyl-terminated fluorine-containing prepolymer modified epoxy coating and preparation method and application thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1625571A (en) * 2001-12-21 2005-06-08 悉尼大学 Aqueous dispersions of polymer particles
CN101982478A (en) * 2010-09-26 2011-03-02 北京印刷学院 Polymer surfactant and core-shell amphiphilic polymer microsphere as well as preparation method thereof
CN101974138A (en) * 2010-10-26 2011-02-16 武汉理工大学 Method for preparing amphiphilic gradient copolymer
CN104789094A (en) * 2015-04-28 2015-07-22 中科院广州化学有限公司南雄材料生产基地 Carboxyl-terminated fluorine-containing prepolymer modified epoxy coating and preparation method and application thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
黄世德等: "《粘接和粘接技术手册》", 四川科学技术出版社, pages: 389 *

Similar Documents

Publication Publication Date Title
KR101582158B1 (en) Inorganic fiber reinforced organic-inorganic hybrid cationic exchange membrane with high dimensional stability and high thermal resistance and method for manufacturing the same
CN113956445B (en) Cationic polymer containing branched structure and preparation method and application thereof
CN108774310A (en) A kind of modified imidazole based epoxy resin latent curing agent, preparation method and application
CN111978771A (en) Modified graphene oxide, preparation method thereof, anticorrosive paint containing modified graphene oxide and preparation method
CN111499877A (en) Preparation method of organic silicon modified epoxy resin
CN1305935C (en) Serial electrically active polyaryl ether ketone polymers and their prepn process
CN112961354A (en) Reactive fluorosilicone resin and preparation method and application thereof
CN110746582B (en) High-temperature-resistant high-performance shape memory polymer and preparation method and application thereof
US20140170403A1 (en) Inorganic polymer material, method for forming the same, and inorganic polymer coating produced therefrom
CN115181276A (en) Modified epoxy resin and preparation method thereof, epoxy resin coating and preparation method and application thereof
CN112574352B (en) Preparation method of super-hydrophobic emulsion containing short fluorinated alkyl
CN112063263A (en) Super-hydrophobic rGO-Ag-modified epoxy resin anticorrosive paint and preparation method thereof
CN115505239B (en) Preparation method of polysiloxane modified epoxy resin material
CN114752337A (en) Waterproof MS sealant and preparation method thereof
CN115340651A (en) Norbornene-nitrile-siloxane type benzoxazine resin and preparation method thereof
CN110591376B (en) Bifunctional epoxy resin-silicon rubber block interpenetrating network material and preparation method thereof
CN114075366A (en) Bio-based epoxy resin composition, full bio-based flame-retardant composite material and preparation method thereof
CN117363148B (en) Graphene anticorrosive paint
CN114702813B (en) Oil-resistant and solvent-resistant rubber composite material, preparation method thereof and application thereof in cables
CN117659250A (en) Fluorosilicone resin, preparation method and application thereof
CN117004295A (en) Flame-retardant insulating electrophoretic paint and preparation method thereof
CN108727948B (en) Modified acrylic emulsion waterproof material and preparation process thereof
CN116693803A (en) Preparation method of polyurea polymer and epoxy resin composition
CN113105792A (en) Electronegativity-enhanced anti-aging fluorocarbon paint
CN117903087A (en) N-phenyl-p-phenylenediamine epoxy resin and preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination