CN107446115B - Preparation method of nano modified bisphenol A epoxy resin - Google Patents
Preparation method of nano modified bisphenol A epoxy resin Download PDFInfo
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- CN107446115B CN107446115B CN201610378899.XA CN201610378899A CN107446115B CN 107446115 B CN107446115 B CN 107446115B CN 201610378899 A CN201610378899 A CN 201610378899A CN 107446115 B CN107446115 B CN 107446115B
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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
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
- C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
- C08G59/063—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols with epihalohydrins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0862—Nickel
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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Abstract
The invention discloses a preparation method of nano modified bisphenol A epoxy resin, which uses a modified titanium dioxide precursor (precursor) prepared by an organic homogeneous phase deposition method, wherein the substance is powdery, can be self-dispersed in an organic solvent and water, and can be reassembled into modified titanium dioxide; in the bisphenol A epoxy resin synthesis method, a modified titanium dioxide precursor prepared by an organic homogeneous phase deposition method is dispersed in a reactant, namely epichlorohydrin or sodium hydroxide, and in-situ polymerization modification is carried out on the bisphenol A epoxy resin, so that the prepared resin is combined with modified inorganic nanoparticles in the in-situ reaction process.
Description
Technical Field
The invention relates to a bisphenol A epoxy resin coating, belongs to the technical field of coatings, and particularly relates to a preparation method for carrying out nano in-situ modification on bisphenol A epoxy resin in the preparation process of the resin.
Background
The epoxy resin refers to a high molecular prepolymer containing two or more epoxy groups and having a fatty acid, an alicyclic segment or an aromatic segment in the main chain. Bisphenol A epoxy resins are favored by users because of their low cost and high yield. The bisphenol A epoxy resin has better manufacturability, can be used together with various curing agents and additives, and can be designed into various formulas to meet various requirements; the low-pressure forming agent has the advantages of low-pressure forming, stable performance of a cured product, good adhesive force, strong corrosion resistance and good chemical resistance.
However, it is found that the alloy has disadvantages of poor toughness and heat resistance in daily use. This limits the application of bisphenol a epoxy resin, and people only improve the toughness and heat resistance of bisphenol a epoxy resin by modifying it.
The appearance of the nano particles provides a new idea for modifying the bisphenol A epoxy resin. The nano particles have special properties such as surface effect, small-size effect, quantum effect and the like, and if the nano materials are used as the additive materials, the mechanical property and the corrosion resistance of the coating can be greatly improved. However, since the inorganic nanoparticles have different interface properties with epoxy resin and are poor in compatibility, the surfaces of the rigid particles are in a thermodynamically unstable state and are easily aggregated, and thus, when the inorganic nanoparticles are combined with epoxy resin, problems such as poor binding force and easy separation are easily caused. In addition, the problems of complex preparation process, high price, no mass production and the like of the nano material also restrict the popularization and application of the nano modified epoxy resin.
Therefore, the invention aims to provide a method for carrying out in-situ polymerization on a modified nano material in the process of synthesizing bisphenol A resin on the premise of developing a simple process capable of producing the nano material in large scale at low cost and fully dispersing the nano material in the bisphenol A epoxy resin.
Disclosure of Invention
In view of the above, the present invention is directed to a method for preparing a modified nanomaterial by organic homogeneous deposition, wherein the modified nanomaterial is added during the synthesis of bisphenol a epoxy resin to achieve in-situ polymerization modification of the bisphenol a epoxy resin.
The in-situ preparation method of the modified bisphenol A epoxy resin comprises the following steps:
the method is characterized in that an inorganic modified nano titanium dioxide precursor (precursor) prepared by an organic homogeneous phase deposition method is added in the process of synthesizing the bisphenol A epoxy resin, and the in-situ polymerization of inorganic modified nano titanium dioxide precursor powder and the bisphenol A epoxy resin is achieved by adjusting reaction parameters to generate the monodisperse nano modified bisphenol A epoxy resin. The inorganic modified nano titanium dioxide precursor powder is added at two links in the reaction process, one is dispersed in epoxy chloropropane, the other is dispersed in sodium hydroxide solution, and one is selected, and the specific steps are described.
The method comprises the following specific steps:
(1) stirring and dispersing modified titanium dioxide precursor powder prepared by an organic homogeneous phase deposition method in epoxy chloropropane, adding bisphenol A, fully stirring, heating to 75-80 ℃ in a water bath, controlling the temperature to be 70 ℃ when the temperature reaches 70 ℃, adding a sodium hydroxide solution with the concentration of 20%, finishing dropwise adding within half an hour, continuously heating after finishing dropwise adding, heating to 75-80 ℃, continuously reacting for 1.5-2 hours, and stopping heating; adding benzene, stirring for 20 minutes, standing, removing a water layer until the washing wastewater is neutral by using a pH test paper, and separating an organic layer after detecting no chloride ions by using a silver nitrate solution; pouring the upper layer solution into a distillation device, distilling off benzene at normal pressure, removing all benzene, and then distilling under reduced pressure to remove all volatile matters; finally pouring out the bisphenol A type resin to obtain the modified bisphenol A type epoxy resin.
(2) Stirring and dispersing modified titanium dioxide precursor powder prepared by an organic homogeneous phase deposition method in a sodium hydroxide solution with the concentration of 20%, and keeping the powder in a suspension state in the sodium hydroxide solution for subsequent addition; fully stirring epoxy chloropropane and bisphenol A, heating in a water bath to 75-80 ℃, controlling the temperature to be 70 ℃ when the temperature reaches 70 ℃, adding a sodium hydroxide solution containing 20% of titanium dioxide powder, finishing dropwise adding within half an hour, continuing to heat after dropwise adding is finished, heating to 75-80 ℃, continuing to react for 1.5-2 hours, and stopping heating; adding benzene, stirring for 20 minutes, standing, removing a water layer until the washing wastewater is neutral by using a pH test paper, and separating an organic layer after detecting no chloride ions by using a silver nitrate solution; pouring the upper layer solution into a distillation device, distilling off benzene at normal pressure, removing all benzene, and then distilling under reduced pressure to remove all volatile matters; finally pouring out the bisphenol A type resin to obtain the modified bisphenol A type epoxy resin.
(3) In the two steps, the addition amount of the modified titanium dioxide precursor powder is 0.01-0.5g, the addition amount of bisphenol A is 0.1mol (22g), the addition amount of epichlorohydrin is 0.3mol (28.02g), the addition amount of 20% sodium hydroxide solution at 70 ℃ is 40ml, the addition amount of benzene is 60ml, and the concentration of silver nitrate is 0.1 mol/L.
The method has the advantages that:
the nano material prepared by the preparation method of the nano material is a titanium dioxide precursor, which can be hydrolyzed, dispersed and reassembled in an organic solvent and water to form the titanium dioxide nano material, if metal salt is added in the process of preparing the precursor, the nano material is a nano titanium dioxide material modified by doping corresponding metal, the nano titanium dioxide precursor is directly added in the process of synthesizing bisphenol A epoxy resin, and due to the characteristics of dispersion in the organic solvent and water and reassembly, the in-situ modification of the nano material and the bisphenol A epoxy resin can be realized, so that the mechanical properties of the resin, such as toughness, hardness and the like, are enhanced, and the problem of poor compatibility of the nano material and the bisphenol A epoxy resin is solved.
Drawings
FIG. 1 is a flow chart of a method for synthesizing a nano-modified bisphenol A epoxy resin.
Detailed Description
Example 1
Preparation of 1% nickel-doped modified bisphenol A epoxy resin
Sequentially adding 0.05g of 1% nickel-doped modified titanium dioxide precursor powder prepared by an organic homogeneous deposition method, 28.02g of epichlorohydrin solution and 22g of bisphenol A particles into a 250ml three-neck flask provided with a stirrer, a dropping funnel and a thermometer; heating in water bath, heating to 70 ℃, stirring the solution to fully dissolve bisphenol A particles and 1% nickel-doped modified titanium dioxide precursor powder, dispersing in an epichlorohydrin solution, keeping the temperature unchanged at 70 ℃, dropwise adding 40ml of 20% sodium hydroxide solution, continuously heating to 75-80 ℃ after dropwise adding is finished at a controlled dropping speed for 30min, continuously reacting for 1.5-2h, stopping heating, cooling to room temperature, adding 60ml of benzene solution, stirring to fully dissolve the solution, transferring into a separating funnel, standing, removing a water layer, washing with distilled water for multiple times until pH test paper detects that washing wastewater is neutral and no chloride ion exists in silver nitrate solution detection wastewater, pouring an upper layer of benzene solution into a reduced pressure distillation device, distilling at normal pressure to remove benzene at 80 ℃, starting reduced pressure distillation when the temperature rises to more than 80 ℃, distilling to remove all volatile matters, observing the distilled liquid, and stopping reduced pressure distillation when the distilled liquid does not boil violently and only small bubbles appear in the liquid and slowly rise; and pouring the residual liquid into a beaker and standing to normal temperature to obtain the 1% nickel-doped modified bisphenol A epoxy resin.
Example 2
Preparation of 1% nickel-doped modified bisphenol A epoxy resin
0.05g of 1% nickel-doped modified titanium dioxide precursor powder prepared by an organic homogeneous phase deposition method is stirred and dispersed in 40ml of 20% sodium hydroxide solution, and the modified titanium dioxide precursor powder is kept in a suspension state in the sodium hydroxide solution to be added subsequently; then 28.02g of epichlorohydrin solution and 22g of bisphenol A particles are sequentially added into a 250ml three-neck flask which is provided with a stirrer, a dropping funnel and a thermometer; heating in water bath, heating to 70 ℃, stirring the solution to fully dissolve bisphenol A particles and 1% nickel-doped modified titanium dioxide precursor powder, dispersing the bisphenol A particles and the 1% nickel-doped modified titanium dioxide precursor powder in an epichlorohydrin solution, keeping the temperature unchanged at 70 ℃, dropwise adding 40ml of sodium hydroxide solution containing 1% nickel-doped modified titanium dioxide precursor powder and the concentration of 20%, controlling the dropping speed for 30min, continuously heating to 75-80 ℃, continuously reacting for 1.5-2h, stopping heating, cooling to room temperature, adding 60ml of benzene solution, stirring, transferring the solution into a separating funnel after full dissolution, standing, removing a water layer, washing with distilled water for multiple times until the pH test paper detects that the washing wastewater is neutral and no chloride ion exists in silver nitrate solution detection wastewater, pouring an upper layer of benzene solution into a reduced pressure distillation device, distilling at normal pressure to remove benzene at 80 ℃, starting reduced pressure distillation when the temperature rises to over 80 ℃, distilling to remove all volatile matters, observing the distilled liquid, and stopping reduced pressure distillation when the distilled liquid does not boil violently and only small bubbles appear in the liquid and rise slowly; and pouring the residual liquid into a beaker and standing to normal temperature to obtain the 1% nickel-doped modified bisphenol A epoxy resin.
The modified epoxy resin prepared by examples 1-2 was mixed with an equal mass of a curing agent, and hardness tests were performed by varying the amount of 1% nickel-doped titanium dioxide precursor added to the epoxy resin, as shown in table 1 below, which shows the effect of different amounts of addition on resin hardness during the synthesis of the resin for 1% nickel-doped titanium dioxide precursor.
TABLE 1 Effect of different 1% Ni-doped Titania precursor additions on epoxy resin hardness
The above examples only show two embodiments of the present invention, and the description thereof is specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (2)
1. A preparation method of nanometer modified bisphenol A type epoxy resin is mainly characterized in that nanometer titanium dioxide particles are generated in situ in the process of resin synthesis reaction, so as to realize in-situ polymerization of nanometer materials and bisphenol A type epoxy resin, and the nanometer titanium dioxide particles are organically combined with epoxy molecules and uniformly and monodispersed in the resin;
the nano modified titanium dioxide material is 1% nickel-doped modified titanium dioxide precursor powder prepared by an organic homogeneous deposition method, and can be hydrolyzed, dispersed and reassembled in an organic solvent and water to form the titanium dioxide nano material; the nano modified titanium dioxide precursor material has two adding positions in the process of synthesizing bisphenol A type epoxy resin, so that one of the two positions is selected, and the preparation method comprises the following steps:
(1) stirring and dispersing modified titanium dioxide powder prepared by a nano material preparation method in epoxy chloropropane, adding bisphenol A, fully stirring, heating to 75-80 ℃ in a water bath, controlling the temperature to be 70 ℃ when the temperature reaches 70 ℃, adding a sodium hydroxide solution with the concentration of 20%, dropwise adding within half an hour, continuously heating after dropwise adding is finished, heating to 75-80 ℃, continuously reacting for 1.5-2 hours, and stopping heating; adding benzene, stirring for 20 minutes, standing, removing a water layer until the washing wastewater is neutral by using a pH test paper, and separating an organic layer after detecting no chloride ions by using a silver nitrate solution; pouring the upper layer solution into a distillation device, distilling off benzene at normal pressure, removing all benzene, and then distilling under reduced pressure to remove all volatile matters; finally pouring out the liquid to obtain the modified bisphenol A type epoxy resin;
(2) stirring and dispersing modified titanium dioxide powder prepared by a nano material preparation method in a sodium hydroxide solution with the concentration of 20%, and keeping the powder in the sodium hydroxide solution in a suspension state for subsequent addition; fully stirring epoxy chloropropane and bisphenol A, heating in a water bath to 75-80 ℃, controlling the temperature to be 70 ℃ when the temperature reaches 70 ℃, adding a sodium hydroxide solution containing 20% of titanium dioxide powder, finishing dropwise adding within half an hour, continuing to heat after dropwise adding is finished, heating to 75-80 ℃, continuing to react for 1.5-2 hours, and stopping heating; adding benzene, stirring for 20 minutes, standing, removing a water layer until the washing wastewater is neutral by using a pH test paper, and separating an organic layer after detecting no chloride ions by using a silver nitrate solution; pouring the upper layer solution into a distillation device, distilling off benzene at normal pressure, removing all benzene, and then distilling under reduced pressure to remove all volatile matters; finally pouring out the liquid to obtain the modified bisphenol A type epoxy resin;
the addition amount of the modified titanium dioxide powder is 0.01-0.5g, the bisphenol A is 0.1mol, the epichlorohydrin is 0.3mol, the addition amount of 20 percent sodium hydroxide solution at 70 ℃ is 40ml, the benzene is 60ml, and the silver nitrate concentration is 0.1 mol/L;
adding 20 percent sodium hydroxide solution at 70 ℃ by mass fraction.
2. The method for preparing nano-modified bisphenol A epoxy resin according to claim 1, wherein the sodium hydroxide solution with a concentration of 20% is prepared from sodium hydroxide particles and distilled water at 70 ℃; except that the concentration of silver nitrate is constant, the addition amount of other related substances can be adjusted in multiple times, and the prepared modified bisphenol A epoxy resin is the same, only has different yield, and can be used for large-scale production.
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| CN108976715A (en) * | 2018-07-27 | 2018-12-11 | 青岛理工大学 | A kind of epoxy resin and preparation method thereof that nano-oxide is modified |
| CN109134824B (en) * | 2018-07-27 | 2021-07-13 | 青岛理工大学 | Graphene/nano TiO-containing material2Epoxy resin of composite material and preparation method thereof |
| CN113698849B (en) * | 2021-08-23 | 2022-08-02 | 厦门百安兴新材料有限公司 | Epoxy resin composite material and preparation method and application thereof |
Citations (2)
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|---|---|---|---|---|
| CN1417246A (en) * | 2002-11-28 | 2003-05-14 | 浙江大学 | In-situ and inclusion polymerization process of preparing composite particle/epoxy resin nano material |
| CN103044657A (en) * | 2012-12-14 | 2013-04-17 | 徐世前 | Nano-modified epoxy resin and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1417246A (en) * | 2002-11-28 | 2003-05-14 | 浙江大学 | In-situ and inclusion polymerization process of preparing composite particle/epoxy resin nano material |
| CN103044657A (en) * | 2012-12-14 | 2013-04-17 | 徐世前 | Nano-modified epoxy resin and preparation method thereof |
Non-Patent Citations (2)
| Title |
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| "Molecular Crystals and Liquid Crystals Science and Technology. Section A. Molecular Crystals and Liquid Crystals";Helmut K. Schmidt;《Mnl Cyst. ondLiy. Cryr.》;20060924;第353卷;第165-179页 * |
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