CN112480598A - Preparation method and application of modified phenolic resin - Google Patents
Preparation method and application of modified phenolic resin Download PDFInfo
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Abstract
The invention provides a preparation method and application of modified phenolic resin, wherein the preparation method comprises the following steps: (1) mixing Al2O3Sol, ZrO2Uniformly mixing the sol to obtain mixed sol; slowly adding the modified phenolic aldehyde prepolymer into the mixtureMixing the sol, continuing stirring after the addition is finished, slowly heating to 80-85 ℃ in vacuum, and stirring at constant temperature to obtain a mixture; (2) putting the mixture, tall oil, tung oil and polyamine catalyst into a reaction kettle, heating to 135-class sand 145 ℃, and carrying out heat preservation reaction to obtain phenolic aldehyde slurry; (3) adding hydrogenated castor oil and silane coupling agent modified graphene oxide into the phenolic aldehyde slurry, slowly heating to 230 ℃ for 220-; (4) vacuum drying to obtain the final product. The modified phenolic resin prepared by the invention has the advantages of high heat resistance, high carbon residue rate, high strength, good toughness and wide application range.
Description
Technical Field
The invention relates to the field of high polymer materials, in particular to a preparation method and application of modified phenolic resin.
Background
Phenolic resins are thermoplastic/thermosetting resins synthesized by polycondensation of phenols and aldehydes, which were the first resins to be used by humans and produced industrially. The material is easy to obtain and industrially produce, and has the advantages of excellent high temperature resistance, ablation resistance, high carbon residue rate, friction resistance, excellent mechanical performance and the like, so that the material is widely applied to the fields of aerospace, material chemical industry and the like.
With the increasing demand in industry, the application of phenolic resin is more and more extensive. For example, in the grinding process, resin grinding tools produced by using phenolic resin as a binding agent have excellent performance and are widely used. However, phenolic resins also have some disadvantages, phenolic hydroxyl groups and methylene groups are easily oxidized; the cured phenolic resin is significantly brittle due to poor flexibility and poor brittleness caused by the structure in which aromatic nuclei are connected only by methylene groups. These factors greatly limit the current applications of phenolic resins, so it is very important to toughen and modify phenolic resins.
At present, the main toughening methods are divided into an internal toughening method and an external toughening method, wherein the internal toughening method is characterized in that an aliphatic compound with a soft and smooth long chain, alkylphenol, rubber, certain resins and the like are added in the reaction process, and a flexible chain exists in the molecular structure through chemical chain connection, so that the brittleness is reduced, and the impact strength is improved. The external toughening mainly utilizes a blending method, rubber, resin, a toughening agent and certain superfine inorganic particles are added into the phenolic resin, and the modified substances are uniformly dispersed in a phenolic resin matrix to form a sea-island structure, thereby playing a role in improving the impact strength.
Meanwhile, the phenolic resin is widely used as a main matrix of an ablation-resistant composite material due to excellent heat resistance and mature processing technology, but phenolic hydroxyl and methylene in the phenolic resin are easily oxidized by heat and cannot meet the requirement of the current high-ablation-resistant material, so that the phenolic resin needs to be modified, and the thermal stability of the phenolic resin in a high-temperature environment is improved.
The preparation method of the melamine and cardanol modified phenolic resin with the application number of CN201510779407.3 comprises the steps of firstly reacting cardanol, phenol and formaldehyde under an acidic condition, then washing with water, adding a resin dispersing agent after washing with water, and then adding the rest formaldehyde and melamine under an alkaline condition to prepare the modified phenolic resin; the method is simple and easy to implement, the synthesis steps and the reaction end point are easy to control, and the method is a good process method for synthesizing the melamine and cardanol modified phenolic resin. The resin synthesized by the method has good toughness and heat resistance, and is suitable for the fields of phenolic molding compounds, friction materials and the like.
However, with the development of the industry, the requirements on the heat resistance and the mechanical properties of the phenolic resin are higher and higher, so that the continuous development of the phenolic resin with more excellent properties has a greater prospect.
Disclosure of Invention
The invention aims to provide a preparation method and application of modified phenolic resin, and the prepared modified phenolic resin has the advantages of high heat resistance, high carbon residue rate, high strength, good toughness and wide application range.
In order to achieve the purpose, the invention is realized by the following technical scheme:
a preparation method of the modified phenolic resin comprises the following steps:
(1) mixing Al2O3Sol, ZrO2Uniformly mixing the sol to obtain mixed sol; slowly adding the modified phenolic aldehyde prepolymer into the mixed sol, continuously stirring for 2-3h after the addition is finished, slowly heating to 80-85 ℃ in vacuum, and stirring for 2-3h at constant temperature to obtain a mixture;
(2) putting the mixture, tall oil, tung oil and polyamine catalyst into a reaction kettle, heating to 135-class sand 145 ℃, and carrying out heat preservation reaction for 3-4h to obtain phenolic aldehyde slurry;
(3) adding hydrogenated castor oil and silane coupling agent modified graphene oxide into the phenolic aldehyde slurry, slowly heating to 230 ℃ for 220-;
(4) and (4) drying the product obtained in the step (3) at 80-85 ℃ for 3-4h in vacuum to obtain the modified phenolic resin.
Preferably, the modified phenolic resin comprises the following raw materials in parts by weight: 100 parts of modified phenolic aldehyde prepolymer, 20-30 parts of mixed sol, 4-6 parts of tall oil, 2-3.5 parts of tung oil, 0.7-1 part of polyamine catalyst, 70-90 parts of hydrogenated castor oil, 1.3-1.8 parts of silane coupling agent modified graphene oxide and 1.5-2 parts of esterification catalyst.
Preferably, in step (1), the Al2O3The solid content of the sol is 15-20%; the ZrO2The solid content of the sol is 18-25%;
preferably, the Al2O3Sol, ZrO2The mass ratio of the sol is 1: 3-5.
Preferably, the synthetic method of the modified phenolic aldehyde prepolymer comprises the following steps:
(1) adding p-tert-octylphenol and a NaOH solution with the concentration of 1mol/L into a reaction kettle, heating until the materials are completely melted, adding 2-hydroxy-2-propanesulfonic acid sodium, stirring for reaction for 30-40min, then cooling to 55-60 ℃, slowly dropwise adding a formaldehyde solution, and keeping the temperature for reaction for 3-4.5 h;
the mol ratio of the p-tert-octylphenol, the formaldehyde, the 2-hydroxy-2-propanesulfonic acid sodium salt and the NaOH is 1: 1.6-2.2: 0.2-0.3: 0.1-0.15;
(2) adding acetic acid solution to adjust the pH value of the system to 6.5-7, and stirring and vacuum drying the obtained product at 80-85 ℃ for 3-4h to obtain the modified phenolic aldehyde prepolymer.
Preferably, the formaldehyde solution is a formaldehyde aqueous solution with the mass fraction of 33-37%.
Preferably, the silane coupling agent modified graphene oxide is prepared by the following method: adding graphene oxide and toluene into a reaction kettle, heating to 80-85 ℃, adding a silane coupling agent, continuously stirring for 5-6h, filtering, washing with ethanol, and then placing at 70-80 ℃ for vacuum drying to obtain silane coupling agent modified graphene oxide;
the mass ratio of the toluene to the graphene oxide to the silane coupling agent is 10: 0.3-0.5: 1-1.5.
Preferably, the silane coupling agent is KH550 or KH 560.
The invention has the beneficial effects that:
1. in the invention, the modified phenolic aldehyde prepolymer is a phenolic aldehyde prepolymer modified by 2-hydroxy-2-sodium propane sulfonate, so the modified phenolic aldehyde prepolymer has certain solubility in water, after the modified phenolic aldehyde prepolymer is premixed with the mixed sol, the mixing uniformity of the modified phenolic aldehyde prepolymer and the mixed sol is high, and then vacuum drying is carried out, so that the nano Al can be prepared2O3Nano ZrO 22High dispersion in the system, no agglomeration, thus leading the nano Al2O3Nano ZrO 22The modified phenolic resin has higher reinforcing effect on subsequent phenolic resin, so that the strength, toughness and high temperature resistance of the modified phenolic resin are improved to a higher degree.
2. In the invention, nano Al is mixed with2O3Nano ZrO 22The modified phenolic prepolymer is modified together with tall oil, tung oil, hydrogenated castor oil and the like, and under the action of a proper catalyst and the like, molecules in the tall oil and the tung oil are grafted by the phenolic resin, so that a molecular chain is expanded, phenolic resin groups are not easy to oxidize, the obtained modified phenolic resin acid ester is low, and the toughness of the phenolic resin can be effectively improved.
3. The invention adds silane for couplingThe agent modified graphene oxide can be highly dispersed in a system and is mixed with nano Al2O3Nano ZrO 22The phenolic resin has the advantages of effectively conducting heat conduction, improving the heat resistance of the phenolic resin, and simultaneously having remarkable effects of improving the thermal decomposition temperature of the phenolic resin and increasing the thermal residue rate.
4. According to the invention, through reasonably setting the raw materials in each step and reasonably controlling reaction parameters, the prepared modified phenolic resin has high heat resistance and high carbon residue rate, can be used for preparing high-requirement ablation-resistant materials, has high strength and good toughness, can also be used for preparing the automobile brake pad adhesive, and has a wide integral application range.
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 with reference to the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. 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.
Example 1:
a synthetic method of a modified phenolic aldehyde prepolymer comprises the following steps:
(1) adding p-tert-octylphenol and a NaOH solution with the concentration of 1mol/L into a reaction kettle, heating until the materials are completely molten, adding 2-hydroxy-2-propanesulfonic acid sodium, stirring for reacting for 40min, then cooling to 60 ℃, slowly dropwise adding a formaldehyde solution (a formaldehyde aqueous solution with the weight fraction of 33-37%), and reacting for 3h while keeping the temperature;
the molar ratio of p-tert-octylphenol, formaldehyde (formaldehyde contained in the formaldehyde solution), sodium 2-hydroxy-2-propanesulfonate and NaOH (NaOH contained in the NaOH solution) is 1: 2: 0.25: 0.15.
(2) adding acetic acid solution to adjust the pH value of the system to 7, and stirring and vacuum drying the obtained product at 85 ℃ for 4 hours to obtain the modified phenolic aldehyde prepolymer.
Example 2:
a synthetic method of a modified phenolic aldehyde prepolymer comprises the following steps:
(1) adding p-tert-octylphenol and a NaOH solution with the concentration of 1mol/L into a reaction kettle, heating until the materials are completely molten, adding 2-hydroxy-2-propanesulfonic acid sodium, stirring for reaction for 30min, then cooling to 55 ℃, slowly dropwise adding a formaldehyde solution (a formaldehyde aqueous solution with the weight fraction of 33-37%), and keeping the temperature for reaction for 4.5 h;
the molar ratio of p-tert-octylphenol, formaldehyde (formaldehyde contained in the formaldehyde solution), sodium 2-hydroxy-2-propanesulfonate and NaOH (NaOH contained in the NaOH solution) is 1: 2.2: 0.2: 0.1.
(2) adding acetic acid solution to adjust the pH value of the system to 6.5, and stirring and vacuum drying the obtained product at 80 ℃ for 3 hours to obtain the modified phenolic aldehyde prepolymer.
(2) Adding acetic acid solution to adjust the pH value of the system to 7, and stirring and vacuum drying the obtained product at 85 ℃ for 4 hours to obtain the modified phenolic aldehyde prepolymer.
Example 3:
a synthetic method of a modified phenolic aldehyde prepolymer comprises the following steps:
(1) adding p-tert-octylphenol and a NaOH solution with the concentration of 1mol/L into a reaction kettle, heating until the materials are completely molten, adding 2-hydroxy-2-propanesulfonic acid sodium, stirring for reacting for 35min, then cooling to 60 ℃, slowly dropwise adding a formaldehyde solution (a formaldehyde aqueous solution with the weight fraction of 33-37%), and reacting for 4h while keeping the temperature;
the molar ratio of p-tert-octylphenol, formaldehyde (formaldehyde contained in the formaldehyde solution), sodium 2-hydroxy-2-propanesulfonate and NaOH (NaOH contained in the NaOH solution) is 1: 1.6: 0.3: 0.12.
(2) adding acetic acid solution to adjust the pH value of the system to 7, and stirring and vacuum drying the obtained product at 85 ℃ for 4 hours to obtain the modified phenolic aldehyde prepolymer.
Example 4:
a preparation method of the modified phenolic resin comprises the following steps:
(1) mixing Al2O3Sol, ZrO2Uniformly mixing the sol to obtain mixed sol; high-quality Al2O3The solid content of the sol was 20%, ZrO2Of solsThe solid content is 20 percent; al in mixed sol2O3Sol, ZrO2The mass ratio of the sol is 1: 5.
weighing the following raw materials in parts by weight: 100 parts of modified phenolic aldehyde prepolymer (prepared by the synthesis method in example 1), 25 parts of mixed sol, 6 parts of tall oil, 3 parts of tung oil, 1 part of diethylenetriamine, 80 parts of hydrogenated castor oil, 1.7 parts of silane coupling agent modified graphene oxide and 1.8 parts of lithium oxide.
Slowly adding the modified phenolic aldehyde prepolymer into the mixed sol, continuously stirring for 3 hours after the addition is finished, slowly heating to 85 ℃ in vacuum, and stirring for 3 hours at constant temperature to obtain a mixture.
(2) And putting the mixture, tall oil, tung oil and diethylenetriamine into a reaction kettle, heating to 140 ℃, and reacting for 3.5 hours under the condition of heat preservation to obtain the phenolic aldehyde pulp.
(3) Adding hydrogenated castor oil and silane coupling agent modified graphene oxide into the phenolic aldehyde slurry, slowly heating to 230 ℃, stirring for 35min, adding lithium oxide, heating to 260 ℃ while stirring, and stirring at constant temperature for reaction for 8 h.
(4) And (4) drying the obtained product in the step (3) at 85 ℃ for 3h in vacuum to obtain the modified phenolic resin.
The silane coupling agent modified graphene oxide is prepared by the following method: adding graphene oxide and toluene into a reaction kettle, heating to 85 ℃, adding a silane coupling agent KH560, continuously stirring for 6 hours, filtering, washing with ethanol, and then placing at 80 ℃ for vacuum drying to obtain the silane coupling agent modified graphene oxide.
The mass ratio of the toluene to the graphene oxide to the silane coupling agent KH560 is 10: 0.3: 1.
example 5:
a preparation method of the modified phenolic resin comprises the following steps:
(1) mixing Al2O3Sol, ZrO2Uniformly mixing the sol to obtain mixed sol; high-quality Al2O3The solid content of the sol was 15%, ZrO2The solid content of the sol was 25%; al in mixed sol2O3Sol, ZrO2Sol gelThe mass ratio of (1): 4.
weighing the following raw materials in parts by weight: 100 parts of modified phenolic aldehyde prepolymer (prepared by the synthesis method in example 2), 20 parts of mixed sol, 5 parts of tall oil, 2 parts of tung oil, 1 part of hexamethylenetetramine, 90 parts of hydrogenated castor oil, 1.6 parts of silane coupling agent modified graphene oxide and 1.8 parts of lithium oxide.
Slowly adding the modified phenolic aldehyde prepolymer into the mixed sol, continuously stirring for 3 hours after the addition is finished, slowly heating to 85 ℃ in vacuum, and stirring for 2 hours at constant temperature to obtain a mixture.
(2) And (3) putting the mixture, tall oil, tung oil and hexamethylenetetramine into a reaction kettle, heating to 145 ℃, and carrying out heat preservation reaction for 3 hours to obtain the phenolic aldehyde slurry.
(3) Adding hydrogenated castor oil and silane coupling agent modified graphene oxide into the phenolic aldehyde slurry, slowly heating to 230 ℃, stirring for 35min, adding lithium oxide, heating to 265 ℃ while stirring, and stirring at constant temperature for reaction for 8 h.
(4) And (4) drying the obtained product in the step (3) at 85 ℃ for 3h in vacuum to obtain the modified phenolic resin.
The silane coupling agent modified graphene oxide is prepared by the following method: adding graphene oxide and toluene into a reaction kettle, heating to 80 ℃, adding a silane coupling agent KH550, continuously stirring for 5 hours, filtering, washing with ethanol, and then placing at 70 ℃ for vacuum drying to obtain silane coupling agent modified graphene oxide; the mass ratio of the toluene to the graphene oxide to the silane coupling agent KH550 is 10: 0.5: 1.5.
example 6:
a preparation method of the modified phenolic resin comprises the following steps:
(1) mixing Al2O3Sol, ZrO2Uniformly mixing the sol to obtain mixed sol; high-quality Al2O3The solid content of the sol was 20%, ZrO2The solid content of the sol is 20%; al in mixed sol2O3Sol, ZrO2The mass ratio of the sol is 1: 3.
weighing the following raw materials in parts by weight: 100 parts of modified phenolic aldehyde prepolymer (prepared by the synthesis method in example 1), 30 parts of mixed sol, 4 parts of tall oil, 3 parts of tung oil, 0.7 part of hexamethylenetetramine, 80 parts of hydrogenated castor oil, 1.8 parts of silane coupling agent modified graphene oxide and 1.5 parts of magnesium oxide.
Slowly adding the modified phenolic aldehyde prepolymer into the mixed sol, continuously stirring for 2 hours after the addition is finished, slowly heating to 80 ℃ in vacuum, and stirring for 3 hours at constant temperature to obtain a mixture.
(2) And putting the mixture, tall oil, tung oil and hexamethylenetetramine into a reaction kettle, heating to 135 ℃, and carrying out heat preservation reaction for 4 hours to obtain the phenolic aldehyde slurry.
(3) Adding hydrogenated castor oil and silane coupling agent modified graphene oxide into the phenolic aldehyde slurry, slowly heating to 220 ℃, stirring for 30min, adding magnesium oxide, heating to 260 ℃ while stirring, and stirring at constant temperature for reaction for 6 h.
(4) And (4) drying the obtained product in the step (3) at 80 ℃ for 4h in vacuum to obtain the modified phenolic resin.
The preparation method of the silane coupling agent modified graphene oxide is the same as that of example 4.
Example 7:
a preparation method of the modified phenolic resin comprises the following steps:
(1) mixing Al2O3Sol, ZrO2Uniformly mixing the sol to obtain mixed sol; high-quality Al2O3The solid content of the sol was 20%, ZrO2The solid content of the sol was 18%; al in mixed sol2O3Sol, ZrO2The mass ratio of the sol is 1: 5.
weighing the following raw materials in parts by weight: 100 parts of modified phenolic aldehyde prepolymer (prepared by the synthesis method in example 2), 20 parts of mixed sol, 6 parts of tall oil, 3.5 parts of tung oil, 1 part of diethylenetriamine, 80 parts of hydrogenated castor oil, 1.3 parts of silane coupling agent modified graphene oxide and 2 parts of lithium oxide.
Slowly adding the modified phenolic aldehyde prepolymer into the mixed sol, continuously stirring for 3 hours after the addition is finished, slowly heating to 85 ℃ in vacuum, and stirring for 2 hours at constant temperature to obtain a mixture.
(2) And putting the mixture, tall oil, tung oil and diethylenetriamine into a reaction kettle, heating to 140 ℃, and reacting for 3.5 hours under the condition of heat preservation to obtain the phenolic aldehyde pulp.
(3) Adding hydrogenated castor oil and silane coupling agent modified graphene oxide into the phenolic aldehyde slurry, slowly heating to 225 ℃, stirring for 40min, adding lithium oxide, heating to 265 ℃ while stirring, and stirring at constant temperature for reaction for 7 h.
(4) And (4) drying the obtained product in the step (3) at 80 ℃ for 4h in vacuum to obtain the modified phenolic resin.
The preparation method of the silane coupling agent modified graphene oxide is the same as that of example 4.
Example 8:
a preparation method of the modified phenolic resin comprises the following steps:
(1) mixing Al2O3Sol, ZrO2Uniformly mixing the sol to obtain mixed sol; high-quality Al2O3The solid content of the sol was 15%, ZrO2The solid content of the sol is 20%; al in mixed sol2O3Sol, ZrO2The mass ratio of the sol is 1: 5.
weighing the following raw materials in parts by weight: 100 parts of modified phenolic aldehyde prepolymer (prepared by the synthesis method in example 3), 22 parts of mixed sol, 5.5 parts of tall oil, 3.5 parts of tung oil, 0.7 part of hexamethylenetetramine, 75 parts of hydrogenated castor oil, 1.6 parts of silane coupling agent modified graphene oxide and 2 parts of magnesium oxide.
Slowly adding the modified phenolic aldehyde prepolymer into the mixed sol, continuously stirring for 2 hours after the addition is finished, slowly heating to 85 ℃ in vacuum, and stirring for 3 hours at constant temperature to obtain a mixture.
(2) And putting the mixture, tall oil, tung oil and hexamethylenetetramine into a reaction kettle, heating to 145 ℃, and carrying out heat preservation reaction for 4 hours to obtain the phenolic aldehyde slurry.
(3) Adding hydrogenated castor oil and silane coupling agent modified graphene oxide into the phenolic aldehyde slurry, slowly heating to 225 ℃, stirring for 30min, adding magnesium oxide, heating to 260 ℃ while stirring, and stirring at constant temperature for reaction for 8 h.
(4) And (4) drying the obtained product in the step (3) at 80 ℃ for 4h in vacuum to obtain the modified phenolic resin.
The preparation method of the silane coupling agent modified graphene oxide is the same as that of example 5.
Example 9:
a preparation method of the modified phenolic resin comprises the following steps:
(1) mixing Al2O3Sol, ZrO2Uniformly mixing the sol to obtain mixed sol; high-quality Al2O3The solid content of the sol was 15%, ZrO2The solid content of the sol was 25%; al in mixed sol2O3Sol, ZrO2The mass ratio of the sol is 1: 3.
weighing the following raw materials in parts by weight: 100 parts of modified phenolic aldehyde prepolymer (prepared by the synthesis method in example 2), 20 parts of mixed sol, 6 parts of tall oil, 3.5 parts of tung oil, 0.8 part of hexamethylenetetramine, 85 parts of hydrogenated castor oil, 1.5 parts of silane coupling agent modified graphene oxide and 2 parts of magnesium oxide.
Slowly adding the modified phenolic aldehyde prepolymer into the mixed sol, continuously stirring for 2 hours after the addition is finished, slowly heating to 85 ℃ in vacuum, and stirring for 3 hours at constant temperature to obtain a mixture.
(2) And putting the mixture, tall oil, tung oil and hexamethylenetetramine into a reaction kettle, heating to 135 ℃, and reacting for 3.5 hours under the condition of heat preservation to obtain the phenolic aldehyde pulp.
(3) Adding hydrogenated castor oil and silane coupling agent modified graphene oxide into the phenolic aldehyde slurry, slowly heating to 225 ℃, stirring for 35min, adding magnesium oxide, heating to 265 ℃ while stirring, and stirring at constant temperature for reaction for 7 h;
(4) and (4) drying the obtained product in the step (3) at 85 ℃ for 3.5 hours in vacuum to obtain the modified phenolic resin.
The preparation method of the silane coupling agent modified graphene oxide is the same as that of example 5.
And (3) performance testing:
1. determination of thermal stability of phenolic resin
TG/DSC thermal analyzer was used. TG analysis was performed on the modified phenolic resin at a temperature rise rate of 10 ℃/min under argon atmosphere. The modified phenolic resin was tested for thermal stability. Specific results are shown in table 1.
Table 1:
| T5％(℃) | T10％(℃) | R800℃(％) | |
| example 4 | 463.5 | 541.0 | 75.2 |
| Example 5 | 452.6 | 535.1 | 74.3 |
| Example 6 | 458.6 | 536.9 | 73.5 |
| Example 7 | 443.6 | 523.9 | 72.2 |
| Example 8 | 449.2 | 527.8 | 72.7 |
| Example 9 | 460.2 | 537.2 | 71.2 |
As shown in Table 1, the modified phenolic resin prepared by the invention has excellent thermal stability and strong heat resistance.
2. Mechanical Property test
The bending strength is measured according to the method GB/T9341-. Specific test results are shown in table 2.
Table 2:
| impact Strength/KJ/m2 | Flexural strength/MPa | Hardness HBR | |
| Example 4 | 18.3 | 86.3 | 136.3 |
| Example 5 | 17.1 | 83.2 | 132.0 |
| Example 6 | 17.7 | 84.5 | 131.3 |
| Example 7 | 16.3 | 82.3 | 129.3 |
| Example 8 | 18.0 | 85.1 | 125.2 |
| Example 9 | 16.9 | 83.9 | 123.5 |
As shown in Table 2, the modified phenolic resin prepared by the invention has excellent mechanical properties and toughness.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. The preparation method of the modified phenolic resin is characterized by comprising the following steps:
(1) mixing Al2O3Sol, ZrO2Uniformly mixing the sol to obtain mixed sol; slowly adding the modified phenolic aldehyde prepolymer into the mixed sol, continuously stirring for 2-3h after the addition is finished, slowly heating to 80-85 ℃ in vacuum, and stirring for 2-3h at constant temperature to obtain a mixture;
(2) putting the mixture, tall oil, tung oil and polyamine catalyst into a reaction kettle, heating to 135-class sand 145 ℃, and carrying out heat preservation reaction for 3-4h to obtain phenolic aldehyde slurry;
(3) adding hydrogenated castor oil and silane coupling agent modified graphene oxide into the phenolic aldehyde slurry, slowly heating to 230 ℃ for 220-;
(4) and (4) drying the product obtained in the step (3) at 80-85 ℃ for 3-4h in vacuum to obtain the modified phenolic resin.
2. The preparation method of the modified phenolic resin according to claim 1, wherein the modified phenolic resin comprises the following raw materials in parts by weight: 100 parts of modified phenolic aldehyde prepolymer, 20-30 parts of mixed sol, 4-6 parts of tall oil, 2-3.5 parts of tung oil, 0.7-1 part of polyamine catalyst, 70-90 parts of hydrogenated castor oil, 1.3-1.8 parts of silane coupling agent modified graphene oxide and 1.5-2 parts of esterification catalyst.
3. The method for producing a modified phenolic resin according to claim 1, wherein in the step (1), the Al is2O3The solid content of the sol is 15-20%; the ZrO2The solid content of the sol is 18-25%.
4. The method for producing a modified phenolic resin according to claim 3, wherein said Al is2O3Sol, ZrO2The mass ratio of the sol is 1: 3-5.
5. The preparation method of the modified phenolic resin as claimed in claim 1, wherein the synthesis method of the modified phenolic prepolymer comprises the following steps:
(1) adding p-tert-octylphenol and a NaOH solution with the concentration of 1mol/L into a reaction kettle, heating until the materials are completely melted, adding 2-hydroxy-2-propanesulfonic acid sodium, stirring for reaction for 30-40min, then cooling to 55-60 ℃, slowly dropwise adding a formaldehyde solution, and keeping the temperature for reaction for 3-4.5 h;
the mol ratio of the p-tert-octylphenol, the formaldehyde, the 2-hydroxy-2-propanesulfonic acid sodium salt and the NaOH is 1: 1.6-2.2: 0.2-0.3: 0.1-0.15;
(2) adding acetic acid solution to adjust the pH value of the system to 6.5-7, and stirring and vacuum drying the obtained product at 80-85 ℃ for 3-4h to obtain the modified phenolic aldehyde prepolymer.
6. The method for preparing a modified phenolic resin according to claim 5, wherein the formaldehyde solution is a 33-37% formaldehyde aqueous solution by mass.
7. The method for preparing the modified phenolic resin according to claim 1, wherein the silane coupling agent modified graphene oxide is prepared by the following method: adding graphene oxide and toluene into a reaction kettle, heating to 80-85 ℃, adding a silane coupling agent, continuously stirring for 5-6h, filtering, washing with ethanol, and then placing at 70-80 ℃ for vacuum drying to obtain silane coupling agent modified graphene oxide;
the mass ratio of the toluene to the graphene oxide to the silane coupling agent is 10: 0.3-0.5: 1-1.5.
8. The method for producing a modified phenolic resin according to claim 7, wherein the silane coupling agent is KH550 or KH 560.
9. The method for preparing the modified phenolic resin according to claim 1, wherein the polyamine catalyst is diethylenetriamine or hexamethylenetetramine; the esterification catalyst is lithium oxide or magnesium oxide.
10. Use of the modified phenolic resin prepared according to the preparation method of any one of claims 1 to 9 in the preparation of ablation-resistant materials.
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