CN112759732B - Composite modified water-based phenolic resin and preparation method thereof - Google Patents
Composite modified water-based phenolic resin and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a composite modified water-based phenolic resin and a preparation method thereof, wherein the preparation method comprises the following steps: firstly, mixing phenol with a catalyst, and reacting for 10-30min at 47-53 ℃; adding formaldehyde and reacting at 57-63 deg.C for 20-30min; then adding a catalyst and formaldehyde, and reacting for 10-30min at 67-73 ℃; then adding boric acid, and reacting for 30-40min at 82-88 ℃; finally, adding epoxy resin, reacting for 30-40min at 82-88 ℃, and carrying out post-treatment to obtain the composite modified water-based phenolic resin. Compared with the prior art, the boric acid and the E20 epoxy resin are used as modifiers for carrying out composite modification, and the B-O bond and the epoxy group are introduced into the molecular chain of the water-based phenolic resin, so that the water-based phenolic resin with excellent temperature resistance and good stability is prepared.
Description
Technical Field
The invention belongs to the technical field of thermosetting phenolic resin, relates to composite modified water-based phenolic resin and a preparation method thereof, and particularly relates to water-based phenolic resin with good temperature resistance and long storage period and a preparation method thereof.
Background
Phenolic Resin (PR), which is considered to be a polymer product that is commercially produced from a simple compound having a low molecular weight as a monomer in the first place, has been developed for nearly a hundred years from the first discovery to the industrial production by doctor Baekeland to the appearance of a multi-component modified resin, and has been widely used in the fields of electrical engineering, automobile industry, wood adhesives, building materials, electronics, aerospace, molded parts, insulating varnish, laminates, industrial coatings, fiber bonding, wood products, microelectronic packaging, and the like, because of the advantages of low manufacturing cost, simple preparation method, excellent product performance, and the like.
In the field of aerospace, in order to prevent a spacecraft from being burnt out due to high temperature influence caused by high-speed friction when the spacecraft passes through the atmosphere, an ablation-resistant composite material is usually wrapped on the outer side of the spacecraft to serve as a thermal protection system of the spacecraft, and the composite material can absorb energy through high heat capacity or take away heat energy through ablation, so that the heat resistance and the heat insulation of the thermal protection system are improved. The phenolic resin used as a matrix of various composite materials has limited application in the field of heat-resistant and heat-insulating materials due to inherent performance defects of poor heat resistance, short storage period, severe volume shrinkage during processing, low yield of high-temperature coke and the like.
Since the 21 st century, the investment in infrastructure construction has been increased in all countries, the demand for phenolic resins has increased substantially, and higher requirements have been made on their properties. The conventional phenolic resin has the defects of higher production cost, serious pollution problem and the like because a large amount of organic solvent is used as a reaction system in the preparation process, and the water-based phenolic resin can adopt water which is non-toxic, harmless and wide in source as a solvent, so that the water-based phenolic resin gradually becomes a modified base material of reinforced resin and has important significance for expanding the application field of the phenolic resin.
The invention aims to break through the bottleneck of phenolic resin application and modify the traditional materials to prepare the water-based phenolic resin with economy, environmental protection, good temperature resistance and long storage period.
Disclosure of Invention
The invention aims to provide a composite modified water-based phenolic resin with excellent temperature resistance and longer storage period and a preparation method thereof.
The purpose of the invention can be realized by the following technical scheme:
a preparation method of composite modified water-based phenolic resin comprises the following steps:
1) Mixing phenol and a catalyst, and reacting at a first reaction temperature to obtain a first reaction product;
2) Heating the first reaction product to a second reaction temperature, adding formaldehyde in the temperature rise process, and then refluxing the system with cold water and carrying out heat preservation reaction to obtain a second reaction product;
3) Heating the second reaction product to a third reaction temperature, adding a catalyst and formaldehyde in the heating process, and then carrying out heat preservation reaction to obtain a third reaction product;
4) Heating the third reaction product to a fourth reaction temperature, adding boric acid in the temperature rise process, and then carrying out heat preservation reaction to obtain a fourth reaction product;
5) And adding epoxy resin into the fourth reaction product, carrying out heat preservation reaction, and carrying out post-treatment to obtain the composite modified water-based phenolic resin.
Furthermore, the molar ratio of the used amount of the phenol to the used amount of the formaldehyde to the used amount of the catalyst is 1 (1.0-2.5) to 0.3.
Further, in the step 1), the adding amount of the catalyst is 65-75% of the total using amount of the catalyst.
As a preferable technical scheme, in the steps 1) to 3), the pH of the reaction system is controlled to be 7-9.
Further, the catalysts all comprise sodium hydroxide or potassium hydroxide. Wherein the sodium hydroxide is used for catalyzing and synthesizing common phenolic resin; potassium hydroxide is used for the catalytic synthesis of the blend resin.
Further, in the step 1), the first reaction temperature is 47-53 ℃, and the reaction time is 10-30min;
in the step 2), the second reaction temperature is 57-63 ℃, and the reaction time is 20-30min;
in the step 3), the third reaction temperature is 67-73 ℃, and the reaction time is 10-30min;
in the step 4), the fourth reaction temperature is 82-88 ℃, and the reaction time is 30-40min;
in the step 5), in the heat preservation reaction, the reaction temperature is 82-88 ℃, and the reaction time is 30-40min.
Further, in the step 1), the phenol is preheated to be in a molten state and then mixed with the catalyst.
Further, in the step 2), the adding amount of the formaldehyde is 75-85% of the total using amount of the formaldehyde.
Further, in the step 4), the adding amount of the boric acid is 20-30% of the mass of the phenol;
in the step 5), the epoxy resin is E20 type epoxy resin, and the adding amount of the epoxy resin is 5-25% of the mass of the phenol.
Further, in the step 5), the post-treatment comprises cooling the reaction product mixed solution to 47-53 ℃, and then carrying out reduced pressure dehydration under a continuous stirring state to obtain the composite modified water-based phenolic resin.
The composite modified water-based phenolic resin is prepared by the method.
In the present invention, the formaldehyde is preferably added dropwise in synchronization with the temperature rise, and the rate of addition is preferably controlled so that the temperature of the reaction system does not rise significantly.
As shown in fig. 1, a synthesis route diagram of the composite modified aqueous phenolic resin of the present invention is shown, wherein firstly, under the action of a catalyst potassium hydroxide or sodium hydroxide, phenol is subjected to a reaction to obtain phenoxy anions; then carrying out addition reaction with formaldehyde to generate ortho-position or para-position hydroxymethyl phenol; then, additionally adding a catalyst and formaldehyde to generate 2,4, 6-trihydroxymethyl phenol;
after adding boric acid, reacting with hydroxymethyl and phenolic hydroxyl respectively to generate a B-O bond, and performing polycondensation reaction on hydroxymethyl phenol through the B-O bond;
the addition of the epoxy resin introduces epoxy groups into the molecular structure of the phenolic resin, and the epoxy groups are represented by a prepolymer of the epoxy resin and the phenolic resin or a copolymer of the epoxy resin and the phenolic resin.
In the obtained composite modified water-based phenolic resin, on one hand, the temperature resistance of the blended water-based phenolic resin is enhanced because the bond energy (775 kJ/mol) of a B-O bond is far greater than the bond energy (334 kJ/mol) of a-C-C bond; on the other hand, the boric acid and the epoxy resin attack phenolic hydroxyl groups in a molecular structure, so that rho-pi conjugation between the original phenolic hydroxyl groups and benzene rings is destroyed, and the content of the phenolic hydroxyl groups is reduced, thereby solving the problem that the resin has strong water absorption due to high content of the phenolic hydroxyl groups, and further causes poor storage property and alkali resistance.
Compared with the prior art, the invention has the following characteristics:
1) Aiming at the defects of poor temperature resistance and short storage period of the existing waterborne phenolic resin, boric acid and E20 epoxy resin are used as modifiers, and a synergistic effect between the two modifiers is utilized to introduce a new group into a molecular chain of the waterborne phenolic resin, so that the temperature resistance and the storage property of the material are obviously improved, and the application range of the material in the aerospace field is further expanded;
2) The method adopts a step-by-step method to synthesize the 2,4, 6-trihydroxymethyl phenol, compared with a one-step synthesis method, the method is more favorable for realizing the controllability of reaction temperature, avoids the condensation polymerization reaction of phenol and formaldehyde caused by local overheating in a reaction system, obtains thermosetting ethyl phenolic resin or propyl phenolic resin with poor water solubility, and solidifies the reaction system to cause that the subsequent boric acid modification and epoxy resin modification can not be carried out;
3) The invention also defines key process parameters such as phenolic aldehyde molar ratio, catalyst type and dosage, reaction temperature and the like, and has positive guiding function for industrial production of the material.
Drawings
FIG. 1 is a schematic diagram of the synthesis route of the composite modified aqueous phenolic resin of the present invention;
FIG. 2 is an infrared spectrum of a composite modified aqueous phenolic resin prepared in examples 1 to 6;
FIG. 3 is a thermogravimetric plot of composite modified aqueous phenolic resins prepared in examples 1-6;
FIG. 4 is a schematic diagram of the experimental apparatus for viscosity measurement in example 9.
Detailed Description
The invention is described in detail below with reference to the figures and the specific embodiments.
A preparation method of composite modified water-based phenolic resin comprises the following steps:
1) Preheating phenol to a molten state, adding catalyst potassium hydroxide or sodium hydroxide while heating, stopping adding the catalyst when the temperature reaches 47-53 ℃ (preferably 50 ℃), and carrying out heat preservation reaction for 10-30min (preferably 20 min) to obtain a first reaction product;
2) Heating the first reaction product to 57-63 ℃ (preferably 60 ℃), dropwise adding a formaldehyde solution in the temperature rise process, refluxing the system with cold water, and carrying out heat preservation reaction for 20-30min (preferably 20 min) to obtain a second reaction product;
3) Heating the second reaction product to 67-73 ℃ (preferably 70 ℃), adding a catalyst and a formaldehyde solution in the process of temperature rise, and then carrying out heat preservation reaction for 10-30min (preferably 20 min) to obtain a third reaction product;
4) Heating the third reaction product to 82-88 ℃ (preferably 80 ℃), adding boric acid with the mass of 20-30% (preferably 25%) of phenol in the process of temperature rise, and then carrying out heat preservation reaction for 30-40min (preferably 30 min) to obtain a fourth reaction product;
5) Adding E20 epoxy resin accounting for 5-25% of the mass of the phenol into the fourth reaction product, and carrying out heat preservation reaction at 82-88 ℃ (preferably 85 ℃) for 30-40min (preferably 30 min) to obtain a fifth reaction product;
6) And (3) cooling the fifth reaction product to 47-53 ℃ (preferably 50 ℃), and then dehydrating under reduced pressure in a continuous stirring state to obtain the composite modified waterborne phenolic resin.
Wherein the molar ratio of the phenol dosage, the total formaldehyde dosage and the total catalyst dosage is 1 (1.0-2.5) to 0.3; in the step 1), the adding amount of the catalyst is 65-75% (preferably 70%) of the total using amount of the catalyst; in step 2), the formaldehyde is added in an amount of 75-85% (preferably 80%) of the total amount of formaldehyde.
The following are more detailed embodiments, and the technical solutions and the technical effects obtained by the present invention will be further described by the following embodiments.
Phenol, formaldehyde, potassium hydroxide, sodium hydroxide and boric acid used in the following examples were purchased from national pharmaceutical group chemical agents, ltd, where formaldehyde was used as a 37% formaldehyde solution; the epoxy resin used is an E20 type epoxy resin.
Example 1:
the preparation method of the water-soluble phenolic resin comprises the following steps of:
1) Adding phenol into a four-neck flask provided with an electric stirrer, a condensation reflux pipe and a thermometer, stirring and heating to a molten state, then adding 0.04mol of NaOH (2/3 of the total amount) while heating, stopping adding a catalyst when the temperature reaches 50 ℃, and carrying out heat preservation reaction for 20min to obtain a first reaction product;
2) Slowly heating the first reaction product to 60 ℃, dropwise adding 0.32mol of formaldehyde (total amount is 80%) in the heating process, and then carrying out heat preservation reaction for 25min to obtain a second reaction product;
3) Slowly heating the second reaction product to 70 ℃, adding the rest 0.02mol of NaOH in the heating process, and then carrying out heat preservation reaction for 20min to obtain a third reaction product;
4) Slowly heating the third reaction product to 85 ℃, dropwise adding the rest 0.08mol of formaldehyde in the heating process, and then carrying out heat preservation reaction for 20min to obtain a fourth reaction product;
5) And cooling the fourth reaction product to below 50 ℃, and carrying out reduced pressure dehydration under a stirring state to obtain the water-soluble phenolic resin.
Example 2:
this example is used to prepare a composite modified water-soluble phenolic resin, and the raw materials used include 0.2mol of phenol, 0.4mol of formaldehyde, 0.06mol of catalyst KOH (i.e. the molar ratio of phenol, formaldehyde, and catalyst is 1.2), 4.7g of boric acid (corresponding to 25% of the mass of phenol) as the first modifier, and 0.9g of epoxy resin (corresponding to 5% of the mass of phenol), and the preparation method includes the following steps:
1) Adding phenol into a four-neck flask provided with an electric stirrer, a condensation reflux pipe and a thermometer, stirring and heating to a molten state, then adding 0.04mol of NaOH (2/3 of the total amount) while heating, stopping adding a catalyst when the temperature reaches 50 ℃, and carrying out heat preservation reaction for 20min to obtain a first reaction product;
2) Slowly heating the first reaction product to 60 ℃, dropwise adding 0.32mol of formaldehyde (total amount is 80%) in the heating process, and then carrying out heat preservation reaction for 20min to obtain a second reaction product;
3) Slowly heating the second reaction product to 70 ℃, adding the rest 0.02mol of KOH and 0.08mol of formaldehyde in the heating process, and then carrying out heat preservation reaction for 20min to obtain a third reaction product;
4) Slowly heating the third reaction product to 85 ℃, adding 4.7g of first modifier boric acid in the heating process, and then carrying out heat preservation reaction for 30min to obtain a fourth reaction product;
5) Adding 0.9g of second modifier epoxy resin into the fourth reaction product, carrying out heat preservation reaction for 30min, and obtaining a fifth reaction product after terminating the reaction;
6) And cooling the fifth reaction product to below 50 ℃, and performing reduced pressure dehydration under a stirring state to obtain the composite modified water-soluble phenolic resin.
Example 3:
this example is used to prepare a composite modified water-soluble phenolic resin, and the raw materials used include 0.2mol of phenol, 0.4mol of formaldehyde, 0.06mol of catalyst KOH (i.e. the molar ratio of phenol, formaldehyde, and catalyst is 1.2), 4.7g of boric acid (corresponding to 25% of the mass of phenol) as the first modifier, and 1.9g of epoxy resin (corresponding to 10% of the mass of phenol), and the preparation method includes the following steps:
1) Adding phenol into a four-neck flask provided with an electric stirrer, a condensation reflux pipe and a thermometer, stirring and heating to a molten state, then adding 0.04mol of NaOH (2/3 of the total amount) while heating, stopping adding a catalyst when the temperature reaches 50 ℃, and carrying out heat preservation reaction for 20min to obtain a first reaction product;
2) Slowly heating the first reaction product to 60 ℃, dropwise adding 0.32mol of formaldehyde (total amount is 80%) in the heating process, and then carrying out heat preservation reaction for 30min to obtain a second reaction product;
3) Slowly heating the second reaction product to 70 ℃, adding the rest 0.02mol of KOH and 0.08mol of formaldehyde in the heating process, and then carrying out heat preservation reaction for 20min to obtain a third reaction product;
4) Slowly heating the third reaction product to 85 ℃, adding 4.7g of first modifier boric acid in the heating process, and then carrying out heat preservation reaction for 30min to obtain a fourth reaction product;
5) Adding 1.9g of second modifier epoxy resin into the fourth reaction product, carrying out heat preservation reaction for 30min, and obtaining a fifth reaction product after terminating the reaction;
6) And cooling the fifth reaction product to below 50 ℃, and performing reduced pressure dehydration under a stirring state to obtain the composite modified water-soluble phenolic resin.
Example 4:
this example is used to prepare a composite modified water-soluble phenolic resin, and the raw materials used include 0.2mol of phenol, 0.4mol of formaldehyde, 0.06mol of catalyst KOH (i.e. the molar ratio of phenol, formaldehyde, and catalyst is 1.2), 4.7g of boric acid (corresponding to 25% of the mass of phenol) as the first modifier, and 2.8g of epoxy resin (corresponding to 15% of the mass of phenol), and the preparation method includes the following steps:
1) Adding phenol into a four-neck flask provided with an electric stirrer, a condensation reflux pipe and a thermometer, stirring and heating to a molten state, then adding 0.04mol of NaOH (2/3 of the total amount) while heating, stopping adding a catalyst when the temperature reaches 50 ℃, and carrying out heat preservation reaction for 20min to obtain a first reaction product;
2) Slowly heating the first reaction product to 60 ℃, dropwise adding 0.32mol of formaldehyde (total amount is 80%) in the heating process, and then carrying out heat preservation reaction for 20min to obtain a second reaction product;
3) Slowly heating the second reaction product to 70 ℃, adding the rest 0.02mol of KOH and 0.08mol of formaldehyde in the heating process, and then carrying out heat preservation reaction for 20min to obtain a third reaction product;
4) Slowly heating the third reaction product to 85 ℃, adding 4.7g of first modifier boric acid in the heating process, and then carrying out heat preservation reaction for 30min to obtain a fourth reaction product;
5) Adding 2.8g of second modifier epoxy resin into the fourth reaction product, carrying out heat preservation reaction for 30min, and obtaining a fifth reaction product after terminating the reaction;
6) And cooling the fifth reaction product to below 50 ℃, and performing reduced pressure dehydration under a stirring state to obtain the composite modified water-soluble phenolic resin.
Example 5:
this example is used to prepare a composite modified water-soluble phenolic resin, and the raw materials used include 0.2mol of phenol, 0.4mol of formaldehyde, 0.06mol of catalyst KOH (i.e. the molar ratio of phenol, formaldehyde, and catalyst is 1.2), 4.7g of boric acid (corresponding to 25% of the mass of phenol) as the first modifier, and 3.7g of epoxy resin (corresponding to 20% of the mass of phenol), and the preparation method includes the following steps:
1) Adding phenol into a four-neck flask provided with an electric stirrer, a condensation reflux pipe and a thermometer, stirring and heating to a molten state, then adding 0.04mol of NaOH (2/3 of the total amount) while heating, stopping adding a catalyst when the temperature reaches 50 ℃, and carrying out heat preservation reaction for 20min to obtain a first reaction product;
2) Slowly heating the first reaction product to 60 ℃, dropwise adding 0.32mol of formaldehyde (total amount is 80%) in the heating process, and then carrying out heat preservation reaction for 20min to obtain a second reaction product;
3) Slowly heating the second reaction product to 70 ℃, adding the rest 0.02mol of KOH and 0.08mol of formaldehyde in the heating process, and then carrying out heat preservation reaction for 20min to obtain a third reaction product;
4) Slowly heating the third reaction product to 85 ℃, adding 4.7g of first modifier boric acid in the heating process, and then carrying out heat preservation reaction for 30min to obtain a fourth reaction product;
5) Adding 3.7g of second modifier epoxy resin into the fourth reaction product, carrying out heat preservation reaction for 30min, and obtaining a fifth reaction product after terminating the reaction;
6) And cooling the fifth reaction product to below 50 ℃, and performing reduced pressure dehydration under a stirring state to obtain the composite modified water-soluble phenolic resin.
Example 6:
this example is used to prepare a composite modified water-soluble phenolic resin, and the raw materials used include 0.2mol of phenol, 0.4mol of formaldehyde, 0.06mol of catalyst KOH (i.e. the molar ratio of phenol, formaldehyde, and catalyst is 1.2), 4.7g of boric acid (corresponding to 25% of the mass of phenol) as the first modifier, and 4.7g of epoxy resin (corresponding to 25% of the mass of phenol), and the preparation method includes the following steps:
1) Adding phenol into a four-neck flask provided with an electric stirrer, a condensation reflux pipe and a thermometer, stirring and heating to a molten state, then adding 0.04mol of NaOH (2/3 of the total amount) while heating, stopping adding a catalyst when the temperature reaches 50 ℃, and carrying out heat preservation reaction for 20min to obtain a first reaction product;
2) Slowly heating the first reaction product to 60 ℃, dropwise adding 0.32mol of formaldehyde (total amount is 80%) in the heating process, and then carrying out heat preservation reaction for 20min to obtain a second reaction product;
3) Slowly heating the second reaction product to 70 ℃, adding the rest 0.02mol of KOH and 0.08mol of formaldehyde in the heating process, and then carrying out heat preservation reaction for 20min to obtain a third reaction product;
4) Slowly heating the third reaction product to 85 ℃, adding 4.7g of first modifier boric acid in the heating process, and then carrying out heat preservation reaction for 30min to obtain a fourth reaction product;
5) Adding 4.7g of second modifier epoxy resin into the fourth reaction product, carrying out heat preservation reaction for 30min, and obtaining a fifth reaction product after terminating the reaction;
6) And cooling the fifth reaction product to below 50 ℃, and performing reduced pressure dehydration under a stirring state to obtain the composite modified water-soluble phenolic resin.
Example 7:
in this example, the water-soluble phenol resins prepared in examples 1 to 6 were subjected to infrared spectroscopic analysis, and the results are shown in FIG. 2. As can be seen, the epoxy resins used in the amounts of 5%, 10% and 15% are in the range of 3440-3245cm -1 The peak of broadened hydroxyl group is present, but no diffusion occurs, which is probably because the hydroxyl groups in the resin have stronger hydrogen bonds, and the epoxy resin with the dosage of 20 percent and 25 percent is in the range of 2925-2855cm -1 Is provided with stronger-CH 2 -methylene peak position, wherein the higher vibration frequency is-CH 2 -antisymmetric telescopic vibration, the lower frequency of vibration being-CH 2 Symmetric stretching vibration, and the five resins with different proportions are all 912-910cm -1 The characteristic peak of epoxy functional group appears, 1250-1300cm -1 Is corresponding to B-O bond at 3100-3000cm -1 The stretching vibration frequency is C-H bond, but the absorption is weak, and is 1594-1487cm -1 The position is the stretching vibration of a C = C bond of a benzene ring skeleton, and a band is in 1280-11 parts due to the conjugated pi electrons of an aromatic ring in a phenol molecule and O atom lone pair electrons in a C-O group50cm -1 C-O stretching vibration occurs.
Example 8:
this example was conducted to examine the temperature resistance of the water-soluble phenol resin prepared in examples 1 to 6 by thermogravimetric analysis, and the results are shown in fig. 3.
It can be seen from the figure that on the basis of boric acid modified phenolic resin, epoxy resin can effectively enter into phenolic resin, the maximum weight loss temperature of the composite modified resin can reach about 530 ℃, and before the maximum weight loss temperature, the weight loss rate is increased along with the increase of the EP dosage, but near the maximum pyrolysis temperature, the weight loss rate of the composite modified resin is reduced along with the increase of the EP dosage. Before 220 ℃, the weight loss rate of the common water-based phenolic resin (example 1, PR) is fastest, and compared with the common water-based phenolic resin (example 1, PR), the thermogravimetric curve of the composite modified resin is gentle and only has a difference of about 17% near the highest pyrolysis temperature, while the curve fall of the common resin is larger and has a difference of over 60%, which shows that the weight loss rate of the composite modified resin is lower near the highest pyrolysis temperature, the fluctuation is not greatly influenced by the pyrolysis temperature, after 900 ℃, the carbon residue rate of the blended resin can reach more than 35%, and the common water-based phenolic resin is only about 10%.
Example 9:
this example was conducted to examine the pot life resistance of the water-soluble phenolic resins prepared in examples 1 to 6 by a viscosity test using a coat-4 cup test (GB/T1723-93) and using an experimental set-up as shown in FIG. 4, with reference to GB/T14074-2006, following the specific test procedure:
firstly testing the initial viscosity of each water-soluble phenolic resin, then respectively placing the resins into a water bath container at 60 ℃ for heating, starting to record time, taking out samples after a period of time, cooling to room temperature, then measuring the viscosity, ensuring that the liquid level of the water bath is over the liquid level of the sample in the whole process until the viscosity is increased to 200% of the initial viscosity, and recording processing time t (h), wherein t represents the storage stability time of the resins, and 6t is equivalent to the storage period of the hermetically packaged resins when the resins are not directly irradiated by sunlight at 10-20 ℃.
TABLE 1 viscosity and pot life of the blended resins
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (7)
1. The preparation method of the composite modified water-based phenolic resin is characterized by comprising the following steps:
1) Mixing phenol and a catalyst, and reacting at 47-53 ℃ for 10-30min to obtain a first reaction product;
2) Heating the first reaction product to 57-63 ℃, adding formaldehyde in the temperature rise process, and then carrying out heat preservation reaction for 20-30min to obtain a second reaction product;
3) Heating the second reaction product to 67-73 ℃, adding a catalyst and formaldehyde in the heating process, and then carrying out heat preservation reaction for 10-30min to obtain a third reaction product;
4) Heating the third reaction product to 82-88 ℃, adding boric acid in the temperature rise process, and then carrying out heat preservation reaction for 30-40min to obtain a fourth reaction product; wherein, the adding amount of the boric acid is 20-30% of the mass of the phenol;
5) Adding epoxy resin into the fourth reaction product, carrying out heat preservation reaction, and carrying out post-treatment to obtain the composite modified water-based phenolic resin;
wherein, in the heat preservation reaction, the reaction temperature is 82-88 ℃, and the reaction time is 30-40min;
the epoxy resin is E20 type epoxy resin, and the addition amount of the epoxy resin is 5-25% of the mass of the phenol; the molar ratio of the phenol dosage, the total formaldehyde dosage and the total catalyst dosage is 1 (1.0-2.5) to 0.3.
2. The method for preparing the composite modified waterborne phenolic resin as claimed in claim 1, wherein in the step 1), the adding amount of the catalyst is 65-75% of the total using amount of the catalyst.
3. The preparation method of the composite modified water-borne phenolic resin as claimed in claim 1 or 2, wherein the catalyst is potassium hydroxide or sodium hydroxide.
4. The method for preparing the composite modified waterborne phenolic resin as claimed in claim 1, wherein in the step 1), the phenol is preheated to be in a molten state and then mixed with the catalyst.
5. The method for preparing the composite modified waterborne phenolic resin as claimed in claim 1, wherein in the step 2), the formaldehyde is added in an amount of 75-85% of the total amount of formaldehyde.
6. The method for preparing the composite modified waterborne phenolic resin as claimed in claim 1, wherein in step 5), the post-treatment comprises: after the reaction is finished, cooling the mixed solution of the reaction products to 47-53 ℃, and then decompressing and dehydrating under the state of continuous stirring to obtain the composite modified water-based phenolic resin.
7. A composite modified aqueous phenolic resin, characterised in that it is prepared by a process as claimed in any one of claims 1 to 6.
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Citations (6)
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|---|---|---|---|---|
| CN103588942A (en) * | 2013-11-07 | 2014-02-19 | 吉林化工学院 | High-performance phenolic resin composition and preparation method thereof |
| CN104449499A (en) * | 2014-11-13 | 2015-03-25 | 山东永泰化工有限公司 | Phenolic resin adhesive and preparation method thereof |
| CN104877302A (en) * | 2015-06-15 | 2015-09-02 | 黑龙江省科学院石油化学研究院 | Waterborne epoxy modified phenolic resin emulsion, preparation method thereof and adhesive prepared by using same as raw material |
| CN105001387A (en) * | 2015-07-13 | 2015-10-28 | 贵阳学院 | Composite modified phenolic resin preparation method |
| CN107513144A (en) * | 2017-07-26 | 2017-12-26 | 常熟东南塑料有限公司 | A kind of boron modified phenolic resin and preparation method thereof |
| CN111171255A (en) * | 2020-01-22 | 2020-05-19 | 上海应用技术大学 | Temperature-resistant water-based phenolic resin and preparation method thereof |
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2020
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103588942A (en) * | 2013-11-07 | 2014-02-19 | 吉林化工学院 | High-performance phenolic resin composition and preparation method thereof |
| CN104449499A (en) * | 2014-11-13 | 2015-03-25 | 山东永泰化工有限公司 | Phenolic resin adhesive and preparation method thereof |
| CN104877302A (en) * | 2015-06-15 | 2015-09-02 | 黑龙江省科学院石油化学研究院 | Waterborne epoxy modified phenolic resin emulsion, preparation method thereof and adhesive prepared by using same as raw material |
| CN105001387A (en) * | 2015-07-13 | 2015-10-28 | 贵阳学院 | Composite modified phenolic resin preparation method |
| CN107513144A (en) * | 2017-07-26 | 2017-12-26 | 常熟东南塑料有限公司 | A kind of boron modified phenolic resin and preparation method thereof |
| CN111171255A (en) * | 2020-01-22 | 2020-05-19 | 上海应用技术大学 | Temperature-resistant water-based phenolic resin and preparation method thereof |
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