CN110982026A - Preparation method of water-soluble phenolic resin - Google Patents
Preparation method of water-soluble phenolic resin Download PDFInfo
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Abstract
The invention relates to a preparation method of water-soluble phenolic resin, which comprises the following steps: (1) heating phenol, gradually raising the temperature and simultaneously adding a part of catalyst until the temperature is raised to the first reaction temperature and the addition of the catalyst is finished; (2) performing heat preservation reaction at the first reaction temperature, then dropwise adding part of formaldehyde, heating to the second reaction temperature, performing heat preservation reaction, then adding the rest part of catalyst, and continuously heating to the third reaction temperature; (3) keeping the temperature for reaction at the third reaction temperature, adding the rest part of formaldehyde, simultaneously heating to the fourth reaction temperature, keeping the temperature, stopping the reaction, cooling to below the fifth reaction temperature, and performing reduced pressure dehydration under stirring to obtain the water-soluble phenolic resin; the catalyst is sodium hydroxide. Compared with the prior art, the water-soluble phenolic resin prepared by the invention has high water solubility and low free phenol and free aldehyde content.
Description
Technical Field
The invention belongs to the technical field of thermosetting phenolic resin, and particularly relates to a preparation method of water-soluble phenolic resin.
Background
Phenol resin (PF), one of the three major thermosetting resins, is a high molecular compound synthesized from phenols and aldehydes under the action of a catalyst, is the resin synthesized by humans the earliest, and has many excellent properties, such as thermal stability, flame retardancy, carbon retention, electrical insulation and mechanical strength. They are widely used as ablative materials, refractory materials, foam materials, carbon materials and friction materials. According to the kind of catalyst participating in the reaction and the ratio of phenol to aldehyde, it can be divided into two types of thermoplastic and thermosetting phenol resins. The phenolic resin has some basic characteristics of high molecular compound, can be made into linear, branched and cross-linked phenolic resins under different conditions, and when the resin is in linear and branched structure state, it is soluble and flowable, and when it is converted into cross-linked structure state, it can be solidified, and is insoluble and infusible. The thermosetting phenolic resin is also called Resol, Resol phenolic resin, which is a resin containing hydroxymethyl active groups capable of further reaction, and can be crosslinked and cured under heating or acidic conditions. If the synthesis reaction is not controlled, the polycondensation reaction is allowed to proceed until an insoluble and infusible resin having a crosslinked structure is formed.
The traditional material feeding method for synthesizing the water-soluble phenolic resin mainly comprises the steps of adding formaldehyde, phenol and a catalyst together for reaction, and controlling the reaction time and the reaction temperature to realize the water-based reaction of the phenolic resin.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a preparation method of water-soluble phenolic resin, which adopts a feeding mode of a two-step catalyst and a two-step formaldehyde method to prepare the water-soluble phenolic resin with high water solubility and low contents of free phenol and free aldehyde.
The purpose of the invention can be realized by the following technical scheme:
a preparation method of water-soluble phenolic resin comprises the following steps:
(1) heating phenol, gradually raising the temperature and simultaneously adding a part of catalyst until the temperature is raised to the first reaction temperature and the addition of the catalyst is finished;
(2) performing heat preservation reaction at the first reaction temperature, then dropwise adding part of formaldehyde, heating to the second reaction temperature, performing heat preservation reaction, then adding the rest part of catalyst, and continuously heating to the third reaction temperature;
(3) keeping the temperature for reaction at the third reaction temperature, adding the rest part of formaldehyde, simultaneously heating to the fourth reaction temperature, keeping the temperature, stopping the reaction, cooling to below the fifth reaction temperature, and performing reduced pressure dehydration under stirring to obtain the water-soluble phenolic resin;
the catalyst is sodium hydroxide.
Preferably:
in the step (1), the first reaction temperature is 47-53 ℃;
in the step (2), the reaction time is kept at the first reaction temperature for 20-40 min, the second reaction temperature is 57-63 ℃, the reaction time is kept at the second reaction temperature for 40-60 min, and the third reaction temperature is 67-73 ℃;
in the step (3), the reaction time is kept at the third reaction temperature for 20-40 min, the fourth reaction temperature is 82-88 ℃, the reaction time is kept at the fourth reaction temperature for 20-40 min, and the fifth reaction temperature is 47-53 ℃.
Further preferably:
in the step (1), the first reaction temperature is 50 ℃;
in the step (2), the reaction time is kept at the first reaction temperature for 30min, the second reaction temperature is 60 ℃, the reaction time is kept at the second reaction temperature for 50min, and the third reaction temperature is 70 ℃;
in the step (3), the reaction time is 30min at the third reaction temperature, the reaction time is 85 ℃ at the fourth reaction temperature, the reaction time is 30min at the fourth reaction temperature, and the reaction temperature is 50 ℃.
Preferably, the addition of the materials is carried out simultaneously with the temperature rise, and the dropping rate of the materials is preferably such that the temperature of the reaction system does not rise significantly.
Preferably, the molar ratio of the phenol to the total formaldehyde to the total catalyst is 1 (1.2-3.0) to 0.25-0.35.
More preferably, the molar ratio of the phenol to the total formaldehyde to the total catalyst is 1 (1.2-3.0): 0.3.
Preferably, in the step (1), the part of the catalyst added is 60-70% of the total amount of the catalyst.
Further preferably, in step (1), the portion of the catalyst added is 2/3 of the total amount of the catalyst.
Preferably, part of the sodium hydroxide is added in the step (1) to make phenol generate phenoxy anion with stronger nucleophilicity.
Preferably, in the step (2), the added part of formaldehyde accounts for 75-85% of the total amount of formaldehyde.
Further preferably, in the step (2), the part of formaldehyde added is 80% of the total amount of formaldehyde.
Preferably, after part of the formaldehyde is added in the step (2), the system is refluxed with cold water.
And (3) adding formaldehyde in the step (2) to enable phenoxy anions generated in the step (1) to primarily react with formaldehyde to generate hydroxymethyl phenol.
And (3) continuously adding sodium hydroxide in the step (2) to enable the hydroxymethylphenol to generate ortho-position or para-position hydroxymethylphenoxy anions under the continuous catalysis of alkali.
And (3) adding the rest formaldehyde in the step (3), and reacting the o-position or p-position monomethyloxybenzene oxide negative ions in the step (2) with formaldehyde to generate dimethylol phenol, trihydroxy methyl phenol, polymethylol phenol containing dimethylene ether and water-soluble phenolic resin.
Preferably, the water-soluble phenolic resin belongs to the group of resins with low relative molecular mass and phenolic novolac resins, thus placing strict requirements on the amount of materials added, the manner of addition and the reaction progress. Since phenol has three active sites in the ortho-para position relative to the phenolic hydroxyl group, with a functionality of 3, and formaldehyde is a monomer with a functionality of 2, to ensure that a water-soluble phenolic resin is obtained, the phenol functionality must be in the range: a functionality of 1-2.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a preparation method of water-soluble phenolic resin, which adopts a two-step catalyst and a two-step formaldehyde method, namely, the feeding mode is that phenol and partial catalyst are added and stirred, phenoxy negative ions with stronger nucleophilicity are generated under the catalysis of alkali, starting to add formaldehyde at a certain temperature, dripping formaldehyde and heating at the same time to make phenoxy negative ions and formaldehyde initially react to generate hydroxymethyl phenol, heating to a certain value, adding the rest catalyst and continuing to heat, at this time, the o-position or p-position mono-hydroxymethyl phenoxy negative ion is generated by the mono-hydroxymethyl phenol under the continuous catalysis of alkali, and finally the rest part of formaldehyde is added and the temperature is kept at a certain temperature, so that the mono-hydroxymethyl phenoxy negative ion continuously reacts with the formaldehyde to generate the dihydroxymethyl phenol, the trihydroxymethyl phenol, the poly-hydroxymethyl phenol containing dimethylene ether and the water-soluble phenolic resin. Wherein the temperature increase is carried out simultaneously with the addition of the materials, preferably at a rate such that the temperature of the reaction system does not increase significantly.
Drawings
FIG. 1 is an infrared spectrum of different phenolic molar ratios of aqueous phenolic resin;
FIG. 2 is a schematic diagram of a molecule simulation of seven phenolic resins;
FIG. 3 shows the basic process of the reaction of aqueous phenolic resin.
Detailed Description
A preparation method of water-soluble phenolic resin comprises the following steps:
(1) heating phenol, gradually raising the temperature and simultaneously adding a part of catalyst until the temperature is raised to the first reaction temperature and the addition of the catalyst is finished;
(2) performing heat preservation reaction at the first reaction temperature, then dropwise adding part of formaldehyde, heating to the second reaction temperature, performing heat preservation reaction, then adding the rest part of catalyst, and continuously heating to the third reaction temperature;
(3) keeping the temperature for reaction at the third reaction temperature, adding the rest part of formaldehyde, simultaneously heating to the fourth reaction temperature, keeping the temperature, stopping the reaction, cooling to below the fifth reaction temperature, and performing reduced pressure dehydration under stirring to obtain the water-soluble phenolic resin;
the catalyst is sodium hydroxide.
Preferably:
in the step (1), the first reaction temperature is 47-53 ℃;
in the step (2), the reaction time is kept at the first reaction temperature for 20-40 min, the second reaction temperature is 57-63 ℃, the reaction time is kept at the second reaction temperature for 40-60 min, and the third reaction temperature is 67-73 ℃;
in the step (3), the reaction time is kept at the third reaction temperature for 20-40 min, the fourth reaction temperature is 82-88 ℃, the reaction time is kept at the fourth reaction temperature for 20-40 min, and the fifth reaction temperature is 47-53 ℃.
Further preferably:
in the step (1), the first reaction temperature is 50 ℃;
in the step (2), the reaction time is kept at the first reaction temperature for 30min, the second reaction temperature is 60 ℃, the reaction time is kept at the second reaction temperature for 50min, and the third reaction temperature is 70 ℃;
in the step (3), the reaction time is 30min at the third reaction temperature, the reaction time is 85 ℃ at the fourth reaction temperature, the reaction time is 30min at the fourth reaction temperature, and the reaction temperature is 50 ℃.
Preferably, the addition of the materials is carried out simultaneously with the temperature rise, and the dropping rate of the materials is preferably such that the temperature of the reaction system does not rise significantly.
Preferably, the molar ratio of the phenol to the total formaldehyde to the total catalyst is 1 (1.2-3.0) to 0.25-0.35.
More preferably, the molar ratio of the phenol to the total formaldehyde to the total catalyst is 1 (1.2-3.0): 0.3.
Preferably, in the step (1), the part of the catalyst added is 60-70% of the total amount of the catalyst.
Further preferably, in step (1), the portion of the catalyst added is 2/3 of the total amount of the catalyst.
Preferably, part of the sodium hydroxide is added in the step (1) to make phenol generate phenoxy anion with stronger nucleophilicity.
Preferably, in the step (2), the added part of formaldehyde accounts for 75-85% of the total amount of formaldehyde.
Further preferably, in the step (2), the part of formaldehyde added is 80% of the total amount of formaldehyde.
Preferably, after part of the formaldehyde is added in the step (2), the system is refluxed with cold water.
And (3) adding formaldehyde in the step (2) to enable phenoxy anions generated in the step (1) to primarily react with formaldehyde to generate hydroxymethyl phenol.
And (3) continuously adding sodium hydroxide in the step (2) to enable the hydroxymethylphenol to generate ortho-position or para-position hydroxymethylphenoxy anions under the continuous catalysis of alkali.
And (3) adding the rest formaldehyde in the step (3), and reacting the o-position or p-position monomethyloxybenzene oxide negative ions in the step (2) with formaldehyde to generate dimethylol phenol, trihydroxy methyl phenol, polymethylol phenol containing dimethylene ether and water-soluble phenolic resin.
Preferably, the water-soluble phenolic resin belongs to the group of resins with low relative molecular mass and phenolic novolac resins, thus placing strict requirements on the amount of materials added, the manner of addition and the reaction progress. Since phenol has three active sites in the ortho-para position relative to the phenolic hydroxyl group, with a functionality of 3, and formaldehyde is a monomer with a functionality of 2, to ensure that a water-soluble phenolic resin is obtained, the phenol functionality must be in the range: a functionality of 1-2.
The technical solutions of the present invention will be described clearly and completely through the following embodiments and the accompanying drawings, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the 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.
The invention adopts a 'two-step catalyst and two-step formaldehyde' method, namely, the reaction is carried out step by step, for example, in the basic reaction process of the water-based phenolic resin shown in figure 3, the phenol hydrolyzes hydrogen ions and hydroxyl radicals in phenolic hydroxyl groups under the action of partial basic catalysts, the phenolic hydroxyl groups are changed into oxygen anions, electrons in the oxygen anions tend to ortho positions in a benzene ring due to a conjugation effect, so that the density of ortho position electron clouds in the phenol is increased, the ortho position electron clouds in the phenol and formaldehyde undergo an ortho position electrophilic addition reaction to generate hydroxymethylphenol, the hydroxymethylphenol continues to undergo electron transfer under the action of the later added basic catalysts to generate hydroxymethylphenoxy anions, and the hydroxymethylphenoxy ions continue to undergo an ortho position electrophilic reaction with the later added formaldehyde to generate dimethylolphenol, thereby ensuring that 1 or 2 ortho positions of the phenol are all reacted, and along with the rise of the reaction temperature, then carrying out polycondensation reaction to generate the water-based phenolic resin.
If the method of 'two-step catalyst and two-step formaldehyde' is not adopted, electrophilic addition reaction occurs on two ortho positions and one para position of phenol, namely 3 functionalities, easily because the reaction degree is too fast, or the reaction does not occur on 3 functionalities of phenol because the reaction is insufficient, which affects the subsequent polycondensation reaction to generate the water-based phenolic resin.
The water-soluble phenolic resin with high water solubility and low contents of free phenol and free aldehyde is prepared by researching different charging molar ratios and combining molecular simulation and infrared spectroscopic analysis.
The raw materials used in the invention can be purchased in the market, and can be directly used without further treatment, wherein the used phenol, 37 percent of formaldehyde and sodium hydroxide (solid) are purchased from national drug group chemical reagent company Limited.
Example 1
In this example, a synthesis process for preparing a water-soluble phenol resin was determined by adjusting the addition mode of the added materials and the reaction temperature. The raw materials comprise phenol, formaldehyde and sodium hydroxide, wherein 0.2mol of phenol, 0.5mol of formaldehyde and 0.06mol of sodium hydroxide are added.
A preparation method for preparing water-soluble phenolic resin by adjusting the adding mode and the reaction temperature of added materials comprises the following specific steps:
(1) firstly, preheating and melting phenol, weighing phenol in a four-neck flask provided with an electric stirrer, a reflux condenser tube and a thermometer according to the molar ratio of the phenol to the formaldehyde to the sodium hydroxide of 1:2.5:0.3, starting the electric stirrer and heating in a water bath;
(2) gradually raising the temperature, simultaneously adding 2/3 sodium hydroxide catalyst until the temperature is raised to 50 ℃, and keeping the temperature for reaction for 30 min;
(3) after heat preservation, formaldehyde accounting for 80 percent of the total amount is dripped, the temperature is simultaneously raised to 60 ℃, heat preservation reaction is carried out for 50min, then the rest part of sodium hydroxide is added, and the temperature is simultaneously raised to 70 ℃;
(4) keeping the temperature at 70 ℃ for 30min for reaction, adding the rest part of formaldehyde, simultaneously heating to 85 ℃, keeping the temperature for reaction for 30min, stopping the reaction, keeping the temperature below 50 ℃, stirring, and finally performing reduced pressure dehydration to obtain the product.
Example 2
In the embodiment of the invention, the synthesis process for preparing the water-soluble phenolic resin is determined by adjusting the adding mode of the added materials and the reaction temperature. The raw materials comprise phenol, formaldehyde and sodium hydroxide, wherein 0.2mol of phenol, 0.4mol of formaldehyde and 0.06mol of sodium hydroxide are added.
A preparation method for preparing water-soluble phenolic resin by adjusting the adding mode and the reaction temperature of added materials comprises the following specific steps:
(1) firstly, preheating and melting phenol, weighing phenol in a four-neck flask provided with an electric stirrer, a reflux condenser tube and a thermometer according to the molar ratio of the phenol to the formaldehyde to the sodium hydroxide of 1:2.0:0.3, starting the electric stirrer and heating in a water bath;
(2) gradually raising the temperature, simultaneously adding 2/3 sodium hydroxide catalyst until the temperature is raised to 53 ℃, and keeping the temperature for reaction for 20 min;
(3) after heat preservation, formaldehyde accounting for 80 percent of the total amount is dripped, the temperature is simultaneously raised to 63 ℃, heat preservation reaction is carried out for 50min, then the rest part of sodium hydroxide is added, and the temperature is simultaneously raised to 72 ℃;
(4) keeping the temperature at 72 ℃ for reaction for 30min, adding the rest part of formaldehyde, simultaneously heating to 88 ℃, keeping the temperature for reaction for 30min, terminating the reaction, stirring below 53 ℃, and finally performing reduced pressure dehydration to obtain the product.
Example 3
In the embodiment of the invention, the synthesis process for preparing the water-soluble phenolic resin is determined by adjusting the adding mode of the added materials and the reaction temperature. The raw materials comprise phenol, formaldehyde and sodium hydroxide, wherein 0.2mol of phenol, 0.24mol of formaldehyde and 0.06mol of sodium hydroxide are added.
A preparation method for preparing water-soluble phenolic resin by adjusting the adding mode and the reaction temperature of added materials comprises the following specific steps:
(1) adding phenol, formaldehyde and sodium hydroxide with the molar ratio of 1:1.2:0.3 into a four-neck flask provided with an electric stirrer, a reflux condenser and a thermometer, starting the electric stirrer and heating in a water bath, and simultaneously dropwise adding 2/3 sodium hydroxide catalyst into the four-neck flask;
(2) heating to 46 ℃, keeping the temperature for 30min, dropwise adding 80% of formaldehyde, synchronously heating to 59 ℃, keeping the temperature for 50min, adding the rest sodium hydroxide, and heating to 68 ℃;
(3) keeping the temperature for reaction at 68 ℃ for 30min, adding the rest part of formaldehyde, simultaneously heating to 87 ℃, keeping the temperature for reaction for 30min, stopping the reaction, and finally performing reduced pressure dehydration under stirring when the temperature is below 48 ℃ to obtain the product.
Example 4
In the embodiment of the invention, the synthesis process for preparing the water-soluble phenolic resin is determined by adjusting the adding mode of the added materials and the reaction temperature. The raw materials comprise phenol, formaldehyde and sodium hydroxide, wherein 0.2mol of phenol, 0.3mol of formaldehyde and 0.06mol of sodium hydroxide are added.
A preparation method for preparing water-soluble phenolic resin by adjusting the adding mode and the reaction temperature of added materials comprises the following specific steps:
(1) adding phenol, formaldehyde and sodium hydroxide with the molar ratio of 1:1.5:0.3 into a four-neck flask provided with an electric stirrer, a reflux condenser and a thermometer, starting the electric stirrer and heating in a water bath, and simultaneously dropwise adding 2/3 sodium hydroxide catalyst into the four-neck flask;
(2) heating to 48 ℃, then preserving heat for 30min, dripping 80 percent of formaldehyde in total amount, synchronously preserving heat for 50min at 57 ℃, then adding the rest sodium hydroxide, and heating to 73 ℃;
(3) keeping the temperature at 73 ℃ for reaction for 30min, adding the rest part of formaldehyde, simultaneously heating to 83 ℃, keeping the temperature for reaction for 30min, stopping the reaction, and finally performing reduced pressure dehydration under stirring at the temperature below 52 ℃ to obtain the product.
Example 5
In the embodiment of the invention, the synthesis process for preparing the water-soluble phenolic resin is determined by adjusting the adding mode of the added materials and the reaction temperature. The raw materials comprise phenol, formaldehyde and sodium hydroxide, wherein 0.2mol of phenol, 0.6mol of formaldehyde and 0.06mol of sodium hydroxide are added.
A preparation method for preparing water-soluble phenolic resin by adjusting the adding mode and the reaction temperature of added materials comprises the following specific steps:
(1) firstly, preheating and melting phenol, weighing phenol in a four-neck flask provided with an electric stirrer, a reflux condenser tube and a thermometer according to the molar ratio of the phenol to the formaldehyde to the sodium hydroxide of 1:3.0:0.3, starting the electric stirrer and heating in a water bath;
(2) gradually raising the temperature, simultaneously adding 2/3 sodium hydroxide catalyst until the temperature is raised to 53 ℃, and keeping the temperature for reaction for 30 min;
(3) after heat preservation, formaldehyde accounting for 80 percent of the total amount is dripped, the temperature is simultaneously raised to 63 ℃, heat preservation reaction is carried out for 50min, then the rest part of sodium hydroxide is added, and the temperature is simultaneously raised to 69 ℃;
(4) keeping the temperature at 69 ℃ for reaction for 30min, adding the rest part of formaldehyde, simultaneously heating to 82 ℃, keeping the temperature for reaction for 30min, terminating the reaction, stirring below 47 ℃, and finally performing reduced pressure dehydration to obtain the product.
Example 6
In the embodiment of the invention, the synthesis process for preparing the water-soluble phenolic resin by directly adding materials into a blending reaction mode. The raw materials comprise phenol, formaldehyde and sodium hydroxide, wherein 0.2mol of phenol, 0.5mol of formaldehyde and 0.06mol of sodium hydroxide are added.
A method for preparing water-soluble phenolic resin by directly adding materials into a blending reaction mode comprises the following specific steps:
(1) preheating and melting phenol, weighing the phenol, the formaldehyde and the catalyst according to the molar ratio of the phenol to the formaldehyde to the sodium hydroxide of 1:2.5:0.3, putting the phenol, the formaldehyde and the catalyst into a four-neck flask provided with an electric stirrer, a reflux condenser tube and a thermometer, starting the electric stirrer and heating in a water bath;
(2) heating to 88 ℃ under stirring, condensing and refluxing by using a reflux condenser at the temperature, preserving heat for 2 hours, stopping the reaction, rapidly cooling to below 53 ℃, stirring, and performing reduced pressure dehydration to obtain the bright red brown water-soluble phenolic resin.
Example 7
In the embodiment of the invention, the synthesis process for preparing the water-soluble phenolic resin by adding materials into the water-soluble phenolic resin in batches for reaction. The raw materials comprise phenol, formaldehyde and sodium hydroxide, wherein 0.2mol of phenol, 0.4mol of formaldehyde and 0.06mol of sodium hydroxide are added.
A method for preparing water-soluble phenolic resin by adding materials into a reaction mode in batches comprises the following specific steps:
(1) preheating and melting phenol, weighing phenol, part of formaldehyde and a catalyst according to the molar ratio of the phenol to the formaldehyde to the sodium hydroxide of 1:2.0:0.3, putting the phenol, the part of the formaldehyde and the catalyst into a four-neck flask provided with an electric stirrer, a reflux condenser tube and a thermometer, starting the electric stirrer and heating in a water bath;
(2) heating to 60 ℃ under stirring, carrying out heat preservation reaction for 30min, adding the rest part of formaldehyde and catalyst, continuously heating to 85 ℃, condensing and refluxing at the temperature by using a reflux condenser pipe, carrying out heat preservation reaction for 1.5h, terminating the reaction, rapidly cooling to below 50 ℃, carrying out reduced pressure dehydration under stirring, and obtaining the bright brownish red water-soluble phenolic resin.
TABLE 1
| Examples | Feeding mode | Product traits |
| Example 1 | The two bases and the two aldehydes are added in portions | Water-soluble bright red brown |
| Example 2 | The two bases and the two aldehydes are added in portions | Water-soluble bright red brown |
| Example 3 | The two bases and the two aldehydes are added in portions | Water-soluble bright red brown |
| Example 4 | The two bases and the two aldehydes are added in portions | Water-soluble bright red brown |
| Example 5 | The two bases and the two aldehydes are added in portions | Water-soluble bright red brown |
| Example 6 | Non-two base two aldehyde process | Insoluble, infusible, red milky |
| Example 7 | Non-two base two aldehyde process | Slightly soluble, deep red viscous liquid |
FIG. 1 is an infrared spectrum of an aqueous phenolic resin, wherein a, b, c, d and e are aqueous phenolic resins corresponding to five different phenolic molar ratios.
FIG. 2 is a molecular simulation diagram of phenolic resins, A, B, C, D, E, F, G corresponds to examples 1-7 above, wherein A-E are prepared by adding materials in batches using "two bases and two aldehydes", and corresponds to examples 1-5, it can be seen from the molecular simulation that A-E are linear or branched, no obvious body crosslinking occurs, and are water-soluble phenolic resins. While F and G correspond to examples 6 and 7, the addition was not carried out in batch mode, and the reaction was too rapid, and it was observed that F and G began to undergo significant bulk crosslinking, thereby further illustrating the reason why the resins obtained in examples 6 and 7 had poor water solubility.
The embodiments described above are intended to facilitate the 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 (10)
1. The preparation method of the water-soluble phenolic resin is characterized by comprising the following steps:
(1) heating phenol, gradually raising the temperature and simultaneously adding a part of catalyst until the temperature is raised to the first reaction temperature and the addition of the catalyst is finished;
(2) performing heat preservation reaction at the first reaction temperature, then dropwise adding part of formaldehyde, heating to the second reaction temperature, performing heat preservation reaction, then adding the rest part of catalyst, and continuously heating to the third reaction temperature;
(3) keeping the temperature for reaction at the third reaction temperature, adding the rest part of formaldehyde, simultaneously heating to the fourth reaction temperature, keeping the temperature, stopping the reaction, cooling to below the fifth reaction temperature, and performing reduced pressure dehydration under stirring to obtain the water-soluble phenolic resin;
the catalyst is sodium hydroxide.
2. The method for preparing a water-soluble phenolic resin according to claim 1, characterized in that:
in the step (1), the first reaction temperature is 47-53 ℃;
in the step (2), the reaction time is kept at the first reaction temperature for 20-40 min, the second reaction temperature is 57-63 ℃, the reaction time is kept at the second reaction temperature for 40-60 min, and the third reaction temperature is 67-73 ℃;
in the step (3), the reaction time is kept at the third reaction temperature for 20-40 min, the fourth reaction temperature is 82-88 ℃, the reaction time is kept at the fourth reaction temperature for 20-40 min, and the fifth reaction temperature is 47-53 ℃.
3. The method for preparing a water-soluble phenolic resin according to claim 2, characterized in that:
in the step (1), the first reaction temperature is 50 ℃;
in the step (2), the reaction time is kept at the first reaction temperature for 30min, the second reaction temperature is 60 ℃, the reaction time is kept at the second reaction temperature for 50min, and the third reaction temperature is 70 ℃;
in the step (3), the reaction time is 30min at the third reaction temperature, the reaction time is 85 ℃ at the fourth reaction temperature, the reaction time is 30min at the fourth reaction temperature, and the reaction temperature is 50 ℃.
4. The method for preparing the water-soluble phenolic resin according to claim 1, wherein the molar ratio of the phenol to the total formaldehyde to the total catalyst is 1 (1.2-3.0): 0.25-0.35.
5. The preparation method of the water-soluble phenolic resin as claimed in claim 4, wherein the molar ratio of the phenol to the total formaldehyde to the total catalyst is 1 (1.2-3.0): 0.3.
6. The method for preparing the water-soluble phenolic resin according to claim 1, wherein in the step (1), the part of the catalyst added is 60-70% of the total amount of the catalyst.
7. The method for preparing a water-soluble phenolic resin according to claim 6, wherein in the step (1), the part of the catalyst added is 2/3 of the total amount of the catalyst.
8. The method for preparing the water-soluble phenolic resin according to claim 1, wherein in the step (2), the added part of formaldehyde accounts for 75-85% of the total formaldehyde.
9. The method for preparing a water-soluble phenolic resin according to claim 8, wherein in the step (2), the part of the formaldehyde added is 80% of the total amount of the formaldehyde.
10. The method of claim 1, wherein the phenol functionality is in the range of: a functionality of 1-2.
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|---|---|---|---|---|
| CN103483515A (en) * | 2013-09-06 | 2014-01-01 | 中科院广州化学有限公司 | High-ortho-position phenol-formaldehyde resin prepolymer and preparation method thereof |
| CN108192055A (en) * | 2017-12-11 | 2018-06-22 | 安徽美克思科技有限公司 | A kind of synthesis technology of aramid fiber honeycomb nitrile rubber modified phenolic resin |
-
2019
- 2019-11-28 CN CN201911192771.4A patent/CN110982026A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103483515A (en) * | 2013-09-06 | 2014-01-01 | 中科院广州化学有限公司 | High-ortho-position phenol-formaldehyde resin prepolymer and preparation method thereof |
| CN108192055A (en) * | 2017-12-11 | 2018-06-22 | 安徽美克思科技有限公司 | A kind of synthesis technology of aramid fiber honeycomb nitrile rubber modified phenolic resin |
Non-Patent Citations (1)
| Title |
|---|
| 黎钢等: "水溶性酚醛树脂的合成及其性能研究", 《河北工业大学学报》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113860909A (en) * | 2021-10-22 | 2021-12-31 | 中国科学院金属研究所 | Preparation method of heat insulation-bearing integrated light carbon-based composite material |
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