CN109535359A - A method of alkali resistance phenolic resin is synthesized based on control solution ph - Google Patents
A method of alkali resistance phenolic resin is synthesized based on control solution ph Download PDFInfo
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- CN109535359A CN109535359A CN201811465035.7A CN201811465035A CN109535359A CN 109535359 A CN109535359 A CN 109535359A CN 201811465035 A CN201811465035 A CN 201811465035A CN 109535359 A CN109535359 A CN 109535359A
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- phenolic resin
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- boric acid
- control system
- alkali resistance
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/28—Chemically modified polycondensates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
- C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
- C08G8/10—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with phenol
Abstract
The invention discloses a kind of methods based on control solution ph synthesis alkali resistance phenolic resin.The present invention first uses phenol and formaldehyde and catalyst in the uniform simultaneously control system pH value of heating stirring in three-necked flask between 7.5~9.0, then lead to cold water condensation, boric acid control system pH value is eventually adding between 5~7, last decompression dehydration is obtained based on boric acid modified phenolic resin.Boric acid modified phenolic resin obtained and phenolic resin are soaked in alkaline solution are compared respectively through the invention, measure its alkali resistance and significantly improve.
Description
Technical field
The present invention relates to thermosetting phenolic resins, and in particular to one kind synthesizes alkali resistance phenolic aldehyde tree based on control solution ph
The method of rouge.
Background technique
Phenolic resin (PF) is a kind of resin that the mankind synthesize earliest.It is original with phenolic compound and aldehyde compound
Material, under the action of catalyst, resin obtained by polycondensation are referred to as phenolic resin, react under alkaline condition, dissociate in synthesis
The key reaction approach of aldehyde has 2 kinds, and one is hydroxymethyl phenol is converted to phenol addition, this approach is to increase methylol group content
Key reaction；Another kind is that aldehyde is converted into methylene bridge, and the small molecule of dispersion is connected into macromolecular, increases average molecular
Quality.This two approach are all the main reactions of novolak resin.Phenolic resin has excellent anti-flammability, excellent mechanical property
Many advantages, such as energy, electrical insulating property, dimensional stability, bonding strength are high and chemical stability is good has been used as leaching pool in recent years
It is all that agent, adhesive, coating, plastics, ablator etc. are widely used in construction industry, transportation, war industry, mining industry etc.
It is multi-field, because raw material is easy to get, price is low, production technology and equipment are simple, still occupy in material circle so far of crucial importance
Status.But since traditional phenolic resin is there are fault of construction, its extensive use is limited, therefore, modified phenolic is always
In recent years research hotspot.Invention synthesis performance is better than the novel phenolic resins synthesis technology of traditional phenolic resin to meet different necks
Domain is needed with far reaching significance.
Summary of the invention
For overcome the deficiencies in the prior art, it is resistance to based on control solution ph synthesis that the purpose of the present invention is to provide one kind
The method of alkalescent phenol resin.The present invention is much higher than the activity of phenolic hydroxyl group using the activity of methylol, and high methylol group content can be with
Good reactive intermediate is provided for modified phenolic, and then boric acid is introduced into phenolic aldehyde molecular structure.The present invention passes through adjusting
PH value come control catalyst addition amount and boric acid be added amount to reach to the methylol and phenolic hydroxyl group in resol
Control, react boric acid targetedly with resol, precisely can effectively improve the alkaline-resisting of phenolic resin in this way
Property, modified cost is reduced, the content of free phenol and formaldehyde is greatly reduced, the unnecessary waste for not only avoiding reagent reduces life
Cost is produced, the discharge of the pollutants such as free phenol, free aldehyde is also reduced, is a kind of boric acid modified phenolic resin preparation of environment-friendly type
New method, meet the environmental protection concept of today's society.
The present invention synthesizes the higher phenolic resin of alkali resistance with two-step method, the first step according to phenol and formaldehyde molar ratio
Catalyst is added after phenol and formaldehyde is added on the basis of 1:1.5~1:1.8, cold water is cold after second step heating water bath and heat preservation
It is solidifying, it adds in boric acid and system and decompression dehydration obtains boric acid modified phenolic resin.The present invention is finally by product and common phenol
Urea formaldehyde is soaked in sodium hydroxide solution respectively and surveys its reduced gravity situations and is compared.
Technical solution of the present invention is specifically described as follows:
A method of alkali resistance phenolic resin is synthesized based on control solution pH value, the specific steps are as follows:
Step 1, by phenol and formaldehyde be added equipped with blender, reflux condensing tube, thermometer three-necked flask in, add
Ammonia spirit, the pH value of control system between 7.5~9.0, turn on agitator stir evenly and water bath heating temperature to 85~
95 DEG C, cold-water reflux is condensed to 50~60 DEG C after keeping the temperature 1.5~2.5h；
Step 2, boric acid is added into three-necked flask so that the pH value of system between 5~7, then proceed to stirring 1~
Alkali resistance phenolic resin is made in 2h, last decompression dehydration.
In the present invention, in step 1, the molar ratio of phenol and formaldehyde is 1:1.5~1:1.8.Step 1 obtains alkaline first rank phenol
Urea formaldehyde.
In the present invention, in step 1, the pH value of system is between 7.5~8.5；In step 2, the pH value of system is 5.
Compared to the prior art, the beneficial effects of the present invention are:
The present invention provides a kind of method based on control solution ph synthesis alkali resistance phenolic resin, and the present invention passes through control
PH value reacts boric acid targetedly with resol, hence it is evident that the alkali resistance for accurately improving phenolic resin avoids
The unnecessary waste of reagent and increase disposal of pollutants are a kind of new methods of the boric acid modified phenolic resin preparation of environment-friendly type.
Detailed description of the invention
Fig. 1 is influence of the boric acid additional amount to different system solution pH value.
Specific embodiment
Technical solution of the present invention will be clearly and completely described by embodiment below, it is clear that described reality
Applying example is only a part of the embodiments of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field skill
Art personnel every other embodiment obtained without making creative work belongs to the model that the present invention protects
It encloses.
The raw materials used in the present invention can be bought on the market, without being further processed, can be used directly, wherein benzene used
Phenol, formaldehyde, ammonium hydroxide and boric acid are purchased from Sinopharm Chemical Reagent Co., Ltd..Fig. 1 is boric acid additional amount to different system solutions
The influence of pH value.
Embodiment 1
Step 1: being 1:1.5 according to phenolic aldehyde molar ratio based on parts by weight, be added phenol and formaldehyde in equipped with blender,
Reflux condensing tube, thermometer three-necked flask in.Adding catalyst ammonia water control system pH value is 7.5；
Step 2: opening electric mixer after mixing evenly, and heating water bath control system temperature keeps the temperature 2h at 90 DEG C, will
Three-necked flask after heat preservation is condensed with cold-water reflux to being added in boric acid after 55 DEG C and system, control system pH value are 7, and decompression is de-
Water obtains boron modified phenolic resin, i.e. product.
Phenolic resin after will be boric acid modified is soaked under the conditions of 70 DEG C, measures mistake for 24 hours in 40% sodium hydroxide solution
Weigh 4.21%.
Embodiment 2
Step 1: being 1:1.6 according to phenolic aldehyde molar ratio based on parts by weight, be added phenol and formaldehyde in equipped with blender,
Reflux condensing tube, thermometer three-necked flask in.Adding catalyst ammonia water control system pH value is 8.5；
Step 2: opening electric mixer after mixing evenly, and heating water bath control system temperature keeps the temperature 2h at 90 DEG C, will
Three-necked flask after heat preservation is condensed with cold-water reflux to being added in boric acid after 55 DEG C and system, control system pH value are 7, and decompression is de-
Water obtains boron modified phenolic resin, i.e. product.
Phenolic resin after will be boric acid modified is soaked under the conditions of 70 DEG C, measures mistake for 24 hours in 40% sodium hydroxide solution
Weigh 3.57%.
Embodiment 3
Step 1: being 1:1.7 according to phenolic aldehyde molar ratio based on parts by weight, be added phenol and formaldehyde in equipped with blender,
Reflux condensing tube, thermometer three-necked flask in.Adding catalyst ammonia water control system pH value is 9；
Step 2: opening electric mixer after mixing evenly, and heating water bath control system temperature keeps the temperature 2h at 90 DEG C, will
Three-necked flask after heat preservation is condensed with cold-water reflux to being added in boric acid after 55 DEG C and system, control system pH value are 7, and decompression is de-
Water obtains boron modified phenolic resin, i.e. product.
Phenolic resin after will be boric acid modified is soaked under the conditions of 70 DEG C, measures mistake for 24 hours in 40% sodium hydroxide solution
Weigh 4.01%.
Embodiment 4
Step 1: being 1:1.8 according to phenolic aldehyde molar ratio based on parts by weight, be added phenol and formaldehyde in equipped with blender,
Reflux condensing tube, thermometer three-necked flask in.Adding catalyst ammonia water control system pH value is 7.5；
Step 2: opening electric mixer after mixing evenly, and heating water bath control system temperature keeps the temperature 2h at 90 DEG C, will
Three-necked flask after heat preservation is condensed with cold-water reflux to being added in boric acid after 55 DEG C and system, control system pH value are 6, and decompression is de-
Water obtains boron modified phenolic resin, i.e. product.
Phenolic resin after will be boric acid modified is soaked under the conditions of 70 DEG C, measures mistake for 24 hours in 40% sodium hydroxide solution
Weigh 3.57%.
Embodiment 5
Step 1: being 1:1.7 according to phenolic aldehyde molar ratio based on parts by weight, be added phenol and formaldehyde in equipped with blender,
Reflux condensing tube, thermometer three-necked flask in.Adding catalyst ammonia water control system pH value is 8.5；
Step 2: opening electric mixer after mixing evenly, and heating water bath control system temperature keeps the temperature 2h at 90 DEG C, will
Three-necked flask after heat preservation is condensed with cold-water reflux to being added in boric acid after 55 DEG C and system, control system pH value are 6, and decompression is de-
Water obtains boron modified phenolic resin, i.e. product.
Phenolic resin after will be boric acid modified is soaked under the conditions of 70 DEG C, measures mistake for 24 hours in 40% sodium hydroxide solution
Weigh 3.85%.
Embodiment 6
Step 1: being 1:1.7 according to phenolic aldehyde molar ratio based on parts by weight, be added phenol and formaldehyde in equipped with blender,
Reflux condensing tube, thermometer three-necked flask in.Adding catalyst ammonia water control system pH value is 9；
Step 2: opening electric mixer after mixing evenly, and heating water bath control system temperature keeps the temperature 2h at 90 DEG C, will
Three-necked flask after heat preservation is condensed with cold-water reflux to being added in boric acid after 55 DEG C and system, control system pH value are 6, and decompression is de-
Water obtains boron modified phenolic resin, i.e. product.
Phenolic resin after will be boric acid modified is soaked under the conditions of 70 DEG C, measures mistake for 24 hours in 40% sodium hydroxide solution
Weigh 3.53%.
Embodiment 7
Step 1: being 1:1.5 according to phenolic aldehyde molar ratio based on parts by weight, be added phenol and formaldehyde in equipped with blender,
Reflux condensing tube, thermometer three-necked flask in.Adding catalyst ammonia water control system pH value is 7.5；
Step 2: opening electric mixer after mixing evenly, and heating water bath control system temperature keeps the temperature 2h at 90 DEG C, will
Three-necked flask after heat preservation is condensed with cold-water reflux to being added in boric acid after 55 DEG C and system, control system pH value are 5, and decompression is de-
Water obtains boron modified phenolic resin, i.e. product.
Phenolic resin after will be boric acid modified is soaked under the conditions of 70 DEG C, measures mistake for 24 hours in 40% sodium hydroxide solution
Weigh 2.82%.
Embodiment 8
Step 1: being 1:1.6 according to phenolic aldehyde molar ratio based on parts by weight, be added phenol and formaldehyde in equipped with blender,
Reflux condensing tube, thermometer three-necked flask in.Adding catalyst ammonia water control system pH value is 8.5；
Step 2: opening electric mixer after mixing evenly, and heating water bath control system temperature keeps the temperature 2h at 90 DEG C, will
Three-necked flask after heat preservation is condensed with cold-water reflux to being added in boric acid after 55 DEG C and system, control system pH value are 5, and decompression is de-
Water obtains boron modified phenolic resin, i.e. product.
Phenolic resin after will be boric acid modified is soaked under the conditions of 70 DEG C, measures mistake for 24 hours in 40% sodium hydroxide solution
Weigh 2.38%.
Embodiment 9
Step 1: being 1:1.8 according to phenolic aldehyde molar ratio based on parts by weight, be added phenol and formaldehyde in equipped with blender,
Reflux condensing tube, thermometer three-necked flask in.Adding catalyst ammonia water control system pH value is 9；
Step 2: opening electric mixer after mixing evenly, and heating water bath control system temperature keeps the temperature 2h at 90 DEG C, will
Three-necked flask after heat preservation is condensed with cold-water reflux to being added in boric acid after 55 DEG C and system, control system pH value are 5, and decompression is de-
Water obtains boron modified phenolic resin, i.e. product.
Phenolic resin after will be boric acid modified is soaked under the conditions of 70 DEG C, measures mistake for 24 hours in 40% sodium hydroxide solution
Weigh 3.57%.
Embodiment 10
Step 1: in the three-necked flask that blender, thermometer, condenser pipe are housed, add according to phenolic aldehyde molar ratio for 1:1.6
Enter the ammonium hydroxide that phenol and formaldehyde starting blender are stirring evenly and then adding into.
Step 2: slowly heating, because addition reaction process belongs to exothermic reaction, the too fast system temperature that will lead to that heats up surpasses
Preset temperature is crossed, reaction 2h is kept after being heated to 90 DEG C, until " dulling " phenomenon occur obtains phenolic resin.
Under the conditions of phenolic resin is soaked in 70 DEG C, weightlessness 4.97% is measured for 24 hours in 40% sodium hydroxide solution.
In conclusion the weightless percentage that the boric acid modified phenolic resin of above-mentioned different pH value and phenolic resin are obtained
Than being listed in Table 1 below, it is known that under the experiment condition be added catalyst after control system pH value be 8.5, be added boric acid in and system
The boron modified phenolic resin alkali resistance that control pH value synthesizes for 5 is best.Table 1 be different pH value boric acid modified phenolic resin and
The percent weight loss and alkali resistance that phenolic resin obtains compare.
Table 1
In addition to illustrate that the methylol of oxyacid and ortho position or phenolic hydroxyl group carry out complexation reaction, rather than with it is lonely on aromatic ring
Vertical methylol or hydroxyl reaction, the present invention have selected the higher resol of methylol group content, phenol solution and water
Three kinds of systems, which investigate boric acid dosage, influences the pH value of three kinds of systems, and as can be seen from Figure 1: boric acid is to resol pH value shadow
It rings variation tendency and is different from other two system, there are a biggish mutation for it, this explanation is in the boric acid dosage and pH value model
In enclosing, resin is reacted with boric acid, and because ortho position steric hindrance is smaller, therefore this process only has ortho position methylol and ortho position phenol
Hydroxyl just can be carried out.
Claims (3)
1. a kind of method based on control solution ph synthesis alkali resistance phenolic resin, which is characterized in that specific step is as follows:
Step 1, by phenol and formaldehyde be added equipped with blender, reflux condensing tube, thermometer three-necked flask in, add ammonium hydroxide
Solution, the pH value of control system is between 7.5~9.0, and turn on agitator stirs evenly and water bath heating temperature is to 85~95 DEG C,
Cold-water reflux is condensed to 50~60 DEG C after 1.5~2.5h of heat preservation；
Step 2, boric acid is added into three-necked flask, so that the pH value of system between 5~7, then proceedes to 1~2h of stirring, most
Alkali resistance phenolic resin is made in decompression dehydration afterwards.
2. the method according to claim 1, wherein in step 1, the molar ratio of phenol and formaldehyde be 1:1.5~
1:1.8。
3. the method according to claim 1, wherein the pH value of system is between 7.5~8.5 in step 1；Step
In rapid 2, the pH value of system is 5.
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| CN201811465035.7A CN109535359A (en) | 2018-12-03 | 2018-12-03 | A method of alkali resistance phenolic resin is synthesized based on control solution ph |
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| CN201811465035.7A CN109535359A (en) | 2018-12-03 | 2018-12-03 | A method of alkali resistance phenolic resin is synthesized based on control solution ph |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110372414A (en) * | 2019-07-11 | 2019-10-25 | 上海应用技术大学 | The method of phenol-formaldehyde resin modified promotion impregnated graphite performance |
| CN114702633A (en) * | 2022-03-16 | 2022-07-05 | 陕西科技大学 | Modified resol and preparation method thereof |
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| WO2011034931A2 (en) * | 2009-09-15 | 2011-03-24 | Reactive Surface, Ltd. | Anti-fouling paints and coatings |
| CN102702930A (en) * | 2012-05-03 | 2012-10-03 | 盘锦中际特种管材制造有限公司 | Preparation method of boric high-heat-resistance wear-resistant heavy-duty inner coating for petroleum pipeline |
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2018
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011034931A2 (en) * | 2009-09-15 | 2011-03-24 | Reactive Surface, Ltd. | Anti-fouling paints and coatings |
| CN102702930A (en) * | 2012-05-03 | 2012-10-03 | 盘锦中际特种管材制造有限公司 | Preparation method of boric high-heat-resistance wear-resistant heavy-duty inner coating for petroleum pipeline |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110372414A (en) * | 2019-07-11 | 2019-10-25 | 上海应用技术大学 | The method of phenol-formaldehyde resin modified promotion impregnated graphite performance |
| CN114702633A (en) * | 2022-03-16 | 2022-07-05 | 陕西科技大学 | Modified resol and preparation method thereof |
| CN114702633B (en) * | 2022-03-16 | 2023-10-31 | 晶瓷(北京)新材料科技有限公司 | Modified resol resin and preparation method thereof |
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