CN108948299A - A kind of bisphenol A formaldehyde phenolic resin and its synthetic method - Google Patents
A kind of bisphenol A formaldehyde phenolic resin and its synthetic method Download PDFInfo
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- CN108948299A CN108948299A CN201810940081.1A CN201810940081A CN108948299A CN 108948299 A CN108948299 A CN 108948299A CN 201810940081 A CN201810940081 A CN 201810940081A CN 108948299 A CN108948299 A CN 108948299A
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- bisphenol
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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
- C08G8/20—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with polyhydric phenols
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
- C09J161/04—Condensation polymers of aldehydes or ketones with phenols only
- C09J161/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
- C09J161/12—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols with polyhydric phenols
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Abstract
The invention discloses a kind of bisphenol A formaldehyde phenolic resin and its synthetic method, the molecular weight of affiliated bisphenol A formaldehyde phenolic resin is 2000-3000, and molecular weight is higher than existing bisphenol A formaldehyde phenolic resin；This method, which is polymerize with bisphenol-A with Formaldehyde Radical, prepares bisphenol A formaldehyde phenolic resin, has excellent glueability, on the one hand uses and remains the original hydroxyl of bisphenol-A and phenyl ring and its active site, while improving the molecular weight of bisphenol-A again；On the other hand, due to containing a large amount of active site in polymer architecture, in adhesive process, can occur to chemically react or be added the insoluble polymer that curing agent reaction generates tridimensional network；Simultaneously as bisphenol-A and formaldehyde carry out condensation reaction, methylene bridges bisphenol-A is formed.So considerably increasing the relative molecular mass of polymer, then reacted with Nian Jie substrate, can be reacted by active group, be bonded it rapidly, reach gluing purpose.
Description
[technical field]
The invention belongs to field of adhesive technology, and in particular to a kind of bisphenol A formaldehyde phenolic resin and its synthetic method.
[background technique]
Since phenolic resin has excellent corrosion resistance, mechanicalness, electrical insulating property, molding processibility, anti-flammability, size
Stability and less toxic mist, and its cheap, production technology and equipment are simple, therefore in aircraft and space field, military dress
It is played an important role in the industry such as standby, transport, mining, building and microelectronics, is the indispensable macromolecule material of industrial circle
Material.Phenolic resin has adhesive strength height, water-fast, heat-resisting, antifriction scrape along good chemical stability.However, phenolic resin
Adhesive is there is also color depth, solidification glue-line hard crisp, the disadvantages of being easily cracked, is at high cost, toxicity is big, especially the adhesive curing temperature
Height, curing rate are slow, cause production efficiency low, energy consumption is high, so that the range of synvaren is subject to certain restrictions.
Bisphenol-A has obtained more and more concerns as a kind of novel novolak resin in recent years.Bisphenol A formaldehyde phenol
Urea formaldehyde is to realize industrialized synthetic resin earliest in the world, and product is related to bonding wood, moulding compound, friction material, insulation
The fields such as product, coating, ink, casting.Bisphenol-A is a kind of resource of sustainable development, have it is from a wealth of sources, side effect is small,
It is cheap, the outstanding features such as be readily synthesized, be easily modified, is environmental-friendly, there are many scholars to attempt bisphenol-A both at home and abroad at present
Adhesive applications are done in various adhesive, but because its is not soluble in water, can only be dissolved in organic solvent, under acidic catalyst easily
Macromolecule is formed in polymerization, and does not destroy its active hydroxy group, it is convenient that it is modified.So domestic and international research hotspot
It is modified bisphenol A formaldehyde phenolic resin, improves its application range.The bisphenol A formaldehyde phenolic resin synthesized currently on the market
Molecular weight is small (2000), and free formaldehyde content is big, and product separating-purifying has very big difficulty, and it is low to be not easy bonding surface polarity
Substrate, such as substrate made of PP, PE material.
The advantage of bisphenol-A how is played, while under the premise of guaranteeing the excellent physics of bisphenol-A, chemical property, shortening it
Curing time reduces production cost, reduces free formaldehyde content therein, promotes the molecular weight of bisphenol A formaldehyde phenolic resin, increases
Its big bonding low to surface polarity substrate is the Important Problems studied now.
[summary of the invention]
It is an object of the invention to overcome the above-mentioned prior art, provide a kind of bisphenol A formaldehyde phenolic resin and its
Synthetic method is polymerize with Formaldehyde Radical using bisphenol-A and prepares bisphenol A formaldehyde phenolic resin, has excellent glueability.
In order to achieve the above objectives, the present invention is achieved by the following scheme:
A kind of bisphenol A formaldehyde phenolic resin, the chemical formula of the bisphenol A formaldehyde phenolic resin are as follows:
Wherein, molecular weight 2000-3000.
A kind of synthetic method of bisphenol A formaldehyde phenolic resin, comprising the following steps:
Step 1, mixing bisphenol-A and n-butanol, stir and heat up, form transparent reaction system；
Formalin and p-methyl benzenesulfonic acid, formation mixed solution after reaction system cooling for reflux, will be added in step 2；It stirs
It mixes and the mixed solution that heats up, aubergine liquid is generated after reaction；
Step 3, distillation decompression aubergine liquid, generate aubergine viscous product；
Step 4 decompression dehydration and will dry after the washing of aubergine viscous product, and bisphenol A formaldehyde phenolic resin is made.
A further improvement of the present invention is that:
Preferably, in step 1, the solid-liquid ratio of bisphenol-A and n-butanol is (10-13) g:(20-30) mL；It stirs and is warming up to
60-80℃。
Preferably, in step 2, reaction system cooling for reflux to room temperature, the concentration of formalin is 37%.
Preferably, in step 2, formalin and bisphenol-A mass ratio are 1:(2-4.5)；Formalin with to toluene
The mass ratio of sulfonic acid is 1:(0.02-0.08).
Preferably, in step 2, mixed solution stirs and is warming up to 85-95 DEG C, and reaction 5-8h generates aubergine liquid.
Preferably, it in step 3, is decompressed to that reaction system is anhydrous to drip back stream, generates aubergine viscous product.
Preferably, it in step 4, is washed aubergine viscous product 3-5 times by boiling water, decompression dehydration after washing, decompression is de-
Dialysis step is had additional between water and drying；Drying temperature is 100-120 DEG C, and drying environment is vacuum.
Preferably, dialysis step are as follows: the crude product after decompression dehydration is dissolved in acetone solvent, mixed solution is formed,
Mixed solution is put into bag filter and is dialysed, after dialysis, dialysis product is put in draught cupboard, acetone solvent is vapored away,
It is again to be dried in 100-120 DEG C of vacuum oven in temperature.
Compared with prior art, the invention has the following advantages:
The invention discloses a kind of bisphenol A formaldehyde phenolic resin, and molecular weight is between 2000-3000；Molecular weight is at this
The phenolic resin bonded effect of bisphenol A formaldehyde in range is preferable, can the efficiently low substrate of bonding surface polarity, such as PP, PE
The low substrate material of the surface polarity of preparation.
The invention also discloses a kind of synthetic method of bisphenol A formaldehyde phenolic resin, this method is free with bisphenol-A and formaldehyde
Base polymerization prepares bisphenol A formaldehyde phenolic resin, has excellent glueability, on the one hand uses and remains the original hydroxyl of bisphenol-A
Base and phenyl ring and its active site；On the other hand, due to containing a large amount of active site in polymer architecture, in adhesive process
In, it can occur to chemically react or be added the insoluble polymer that curing agent reaction generates tridimensional network；Simultaneously as bisphenol-A
Condensation reaction is carried out with formaldehyde, forms methylene bridges bisphenol-A, p-methyl benzenesulfonic acid improves the degree of polymerization of bisphenol-A and formaldehyde,
The relative molecular mass of polymer is considerably increased, then is reacted with Nian Jie substrate, can be reacted by active group, glue it rapidly
It connects, reaches gluing purpose.
This method forms reaction intermediate under the action of p-methyl benzenesulfonic acid is catalyst, the intermediate and raw material of generation or
Condensation reaction occurs for precursor product, forms the structure connected with methylene or methylene ether two types bridge, while discharging one
The catalyst of molecule, continuous cross reaction forms product bisphenol A formaldehyde phenolic resin, so that the production of bisphenol A formaldehyde phenolic resin
Extracting rate improves, and reduces purification difficulty.It, first should will be anti-before formalin and catalyst p-methyl benzenesulfonic acid is added to reaction system
It answers system temperature cooling for reflux to room temperature, prevents formalin and n-butanol at a suitable temperature, a molecule is sloughed in reaction
Water, generate a kind of colourless liquid, there is the smell of similar chloroform, paralysis irritant to the mucous membrane of human body effect sucks human body
Nose and larynx can be caused to stimulate, there is the dimethoxymethane of damage to eye.Therefore first is added in room temperature in temperature of reaction system control
Aldehyde solution and catalyst p-methyl benzenesulfonic acid facilitate the positive of reaction and carry out, reduce the generation of by-product, react the double of generation
The output capacity of phenol A formaldehyde phenolic resin is higher, and the molecular weight of the product of generation controls between 2000-3000 well, bonding
Effect reaches most preferably, and the residual quantity of bisphenol-A and free formaldehyde is minimum.Utilize the method for dialysis separating-purifying, effective solution
The problem of bisphenol-A, residues of formaldehyde.And under certain solvent burden ratio, bisphenol A formaldehyde phenolic resin can efficient bonding surface
The low substrate of polarity, such as the low substrate material of surface polarity of PP, PE preparation.
[Detailed description of the invention]
Fig. 1 is the preparation process schematic diagram of bisphenol A formaldehyde phenolic resin of the present invention；
Fig. 2 is the infrared contrast schematic diagram of Fourier of bisphenol A formaldehyde phenolic resin prepared by the present invention；
Fig. 3 is influence of the reaction time of the invention to bisphenol A residues amount and free formaldehyde content.
[specific embodiment]
The invention will be described in further detail combined with specific embodiments below, and the invention discloses a kind of bisphenol A formaldehydes
Phenolic resin synthetic method, specific preparation process the following steps are included:
Step 1, in the 50ml three neck round bottom flask equipped with mechanical stirring and reflux condensate device, be added bisphenol-A with just
The additional amount ratio of butanol, bisphenol-A and n-butanol is (10-13) g:(20-30) mL；It stirs and is warming up to 60-80 DEG C, to bis-phenol
A is completely dissolved, and reaction system is clear and transparent.
Step 2 is water-cooled and is back to room temperature.Then be added at one time 37% formalin, formalin with
The mass ratio of bisphenol-A is 1:(2-4.5), catalyst p-methyl benzenesulfonic acid, the mass ratio of formalin and p-methyl benzenesulfonic acid is added
For 1:(0.02-0.08), mixed solution is formed；It is stirred solution, while being heated to 85-95 DEG C, stirring rate is
450r/min；5-8h is reacted at this temperature, generates aubergine liquid.
N-butanol and a small amount of water is distilled off in step 3 under normal pressure, and then removed under reduced pressure residue water drips back to anhydrous
Stream, product become aubergine thick liquid.
Step 4 washs the 3-5 unreacted bisphenol-A of removing with boiling water, and last decompression dehydration will be thick after decompression dehydration
Product is dissolved in acetone solvent, and putting dialysis pore diameter mol amount into is to carry out acetone soln in the bag filter of 800-1000 or more
Dialysis three days, after terminating, product is placed in draught cupboard, after vaporing away acetone, then in 100-120 DEG C of temperature of vacuum drying
It is dried in case, obtains the solid bisphenol A formaldehyde phenolic resin of aubergine, wait being cooled to room temperature that move to storage bottle spare.
The chemical formula of bisphenol A formaldehyde phenolic resin obtained through the invention are as follows:
Wherein, molecular weight 2000-3000.
The synthesis process of bisphenol A formaldehyde phenolic resin of the present invention is as shown in Figure 1, using n-butanol as solvent, bisphenol-A and formaldehyde
For reactive agent, in the case where p-methyl benzenesulfonic acid makees catalyst, the higher phenol hydroxyl of carbonium ion attack cloud density of formaldehyde formation
The ortho position of base forms hydroxymethyl phenol, then forms reaction intermediate under the action of catalyst, the intermediate and raw material or precursor of generation
Condensation reaction occurs for product, forms the structure connected with methylene or methylene ether two types bridge, while discharging a molecule
Catalyst.So constantly cross reaction forms product bisphenol A formaldehyde phenolic resin.
As shown in Fig. 2, in the infrared spectroscopy of bisphenol A formaldehyde phenolic resin, υ=1696.80cm-1It is bent for CH in phenyl ring
Vibration absorption peak, in υ=1603.40cm-1/1505.05cm-1/1434.80cm-1For phenyl ring skeletal vibration absorption peak, υ=
1364.50cm-1The dual vibration absorption peak of the feature being connected with carbon atom for two methyl, in υ=1107.05cm-1It is taken for contraposition
For CH out-of-plane vibration absorption peak in benzene, in υ=1011.34cm-1For ehter bond vibration absorption peak, in υ=887.05cm-1For contraposition
The characteristic absorption peak of substituted benzene, in υ=1735-1710cm-1There is not the vibration absorption peak of carbonyl, therefore without dialysis solvent third
Ketone.The product for proving synthesis is bisphenol A formaldehyde phenolic resin.
Fig. 3 is influence of the reaction time to bisphenol A residues amount and free formaldehyde content, is speculated by reaction dynamics law,
The suitable reaction time will necessarily promote conversion of the reactant to target product, for this purpose, the mass fraction for having studied catalyst is
Influence of 20% the reaction time to product property.The result shows that the reaction time extends to 6 hours, residual content of bisphenol A is most
Low, the content of free formaldehyde is minimum, surveys the bisphenol A formaldehyde phenolic resin yield that bisphenol-A is reacted with formaldehyde and is up to
80% or so.But after reaction carries out to a certain extent, due to reactant concentration very little in reaction system at this time, continue to extend
Time is unfavorable for positive reaction progress, side reaction is increased instead, so that the content of the residual quantity of bisphenol-A and free formaldehyde
With the extension of reaction time, increase instead.In conclusion most preferably 6 hours in reaction time, the residual quantity and trip of bisphenol-A
It is minimum from content of formaldehyde, yield highest.
Embodiment 1
Step 1, in the 50ml three neck round bottom flask equipped with mechanical stirring and reflux condensate device, 11.4g bisphenol-A is added
With n-butanol 25mL, stirs and be warming up to 60 DEG C, be completely dissolved to bisphenol-A, reaction system is clear and transparent.
Step 2 is water-cooled and is back to room temperature, 37% formalin 4.5g is then added at one time, to toluene sulphur
Sour 0.13g forms mixed solution；It is stirred solution, while being heated to 95 DEG C, stirring rate 450r/min；Herein
At a temperature of react 7h, generate aubergine liquid.
N-butanol and a small amount of water is distilled off in step 3 under normal pressure, and then removed under reduced pressure residue water drips back to anhydrous
Stream, product become aubergine thick liquid.
Step 4 is washed with boiling water and removes unreacted bisphenol-A for 3 times, and last decompression dehydration is dry in 120 DEG C of temperature of vacuum
It is dried in dry case, obtains the solid bisphenol A polymer of aubergine, wait being cooled to room temperature that move to storage bottle spare.
Embodiment 2
Step 1, in the 50ml three neck round bottom flask equipped with mechanical stirring and reflux condensate device, be added 10g bisphenol-A with
N-butanol 20mL is stirred and is warming up to 70 DEG C, is completely dissolved to bisphenol-A, reaction system is clear and transparent.
Step 2 is water-cooled and is back to room temperature, is then added at one time 37% formalin 5g, p-methyl benzenesulfonic acid
0.4g forms mixed solution；It is stirred solution, while being heated to 80 DEG C, stirring rate 450r/min；In this temperature
Lower reaction 5h generates aubergine liquid.
N-butanol and a small amount of water is distilled off in step 3 under normal pressure, and then removed under reduced pressure residue water drips back to anhydrous
Stream, product become aubergine thick liquid.
Step 4 is washed with boiling water and removes unreacted bisphenol-A for 5 times, and last decompression dehydration is dry in 100 DEG C of temperature of vacuum
It is dried in dry case, obtains the solid bisphenol A polymer of aubergine, wait being cooled to room temperature that move to storage bottle spare.
Embodiment 3
Step 1, in the 50ml three neck round bottom flask equipped with mechanical stirring and reflux condensate device, be added 30g bisphenol-A with
N-butanol 30mL is stirred and is warming up to 80 DEG C, is completely dissolved to bisphenol-A, reaction system is clear and transparent.
Step 2 is water-cooled and is back to room temperature, 37% formalin 6.7g is then added at one time, to toluene sulphur
Sour 0.3g forms mixed solution；It is stirred solution, while being heated to 85 DEG C, stirring rate 450r/min；It is warm herein
Degree is lower to react 8h, generates aubergine liquid.
N-butanol and a small amount of water is distilled off in step 3 under normal pressure, and then removed under reduced pressure residue water drips back to anhydrous
Stream, product become aubergine thick liquid.
Step 4 is washed with boiling water and removes unreacted bisphenol-A for 4 times, and last decompression dehydration is dry in 110 DEG C of temperature of vacuum
It is dried in dry case, obtains the solid bisphenol A polymer of aubergine, wait being cooled to room temperature that move to storage bottle spare.
Embodiment 4
Step 1, in the 50ml three neck round bottom flask equipped with mechanical stirring and reflux condensate device, be added 14g bisphenol-A with
N-butanol 25mL is stirred and is warming up to 70 DEG C, is completely dissolved to bisphenol-A, reaction system is clear and transparent.
Step 2 is water-cooled and is back to room temperature, 37% formalin 4.7g is then added at one time, to toluene sulphur
Sour 0.28g forms mixed solution；It is stirred solution, while being heated to 95 DEG C, stirring rate 450r/min；Herein
At a temperature of react 6h, generate aubergine liquid.
N-butanol and a small amount of water is distilled off in step 3 under normal pressure, and then removed under reduced pressure residue water drips back to anhydrous
Stream, product become aubergine thick liquid.
Step 4 is washed with boiling water and removes unreacted bisphenol-A for 4 times, and last decompression dehydration is dry in 100 DEG C of temperature of vacuum
It is dried in dry case, obtains the solid bisphenol A polymer of aubergine, wait being cooled to room temperature that move to storage bottle spare.
Embodiment 5
Step 1, in the 50ml three neck round bottom flask equipped with mechanical stirring and reflux condensate device, be added 18g bisphenol-A with
N-butanol 22mL is stirred and is warming up to 65 DEG C, is completely dissolved to bisphenol-A, reaction system is clear and transparent.
Step 2 is water-cooled and is back to room temperature, 37% formalin 7.2g is then added at one time, to toluene sulphur
Sour 0.5g forms mixed solution；It is stirred solution, while being heated to 92 DEG C, stirring rate 450r/min；It is warm herein
Degree is lower to react 8h, generates aubergine liquid.
N-butanol and a small amount of water is distilled off in step 3 under normal pressure, and then removed under reduced pressure residue water drips back to anhydrous
Stream, product become aubergine thick liquid.
Step 4 is washed with boiling water and removes unreacted bisphenol-A for 5 times, and last decompression dehydration is dry in 120 DEG C of temperature of vacuum
It is dried in dry case, obtains the solid bisphenol A polymer of aubergine, wait being cooled to room temperature that move to storage bottle spare.
Embodiment 6
Step 1, in the 50ml three neck round bottom flask equipped with mechanical stirring and reflux condensate device, be added 22g bisphenol-A with
N-butanol 28mL is stirred and is warming up to 75 DEG C, is completely dissolved to bisphenol-A, reaction system is clear and transparent.
Step 2 is water-cooled and is back to room temperature, 37% formalin 5.5g is then added at one time, to toluene sulphur
Sour 0.22g forms mixed solution；It is stirred solution, while being heated to 88 DEG C, stirring rate 450r/min；Herein
At a temperature of react 5h, generate aubergine liquid.
N-butanol and a small amount of water is distilled off in step 3 under normal pressure, and then removed under reduced pressure residue water drips back to anhydrous
Stream, product become aubergine thick liquid.
Step 4 is washed with boiling water and removes unreacted bisphenol-A for 3 times, and last decompression dehydration is dry in 110 DEG C of temperature of vacuum
It is dried in dry case, obtains the solid bisphenol A polymer of aubergine, wait being cooled to room temperature that move to storage bottle spare.
Embodiment 7
Step 1, in the 50ml three neck round bottom flask equipped with mechanical stirring and reflux condensate device, be added 20g bisphenol-A with
N-butanol 25mL is stirred and is warming up to 80 DEG C, is completely dissolved to bisphenol-A, reaction system is clear and transparent.
Step 2 is water-cooled and is back to room temperature, 37% formalin 4.65g is then added at one time, to toluene sulphur
Sour 0.1g forms mixed solution；It is stirred solution, while being heated to 86 DEG C, stirring rate 450r/min；It is warm herein
Degree is lower to react 7h, generates aubergine liquid.
N-butanol and a small amount of water is distilled off in step 3 under normal pressure, and then removed under reduced pressure residue water drips back to anhydrous
Stream, product become aubergine thick liquid.
Step 4 is washed with boiling water and removes unreacted bisphenol-A for 5 times, and last decompression dehydration is dry in 100 DEG C of temperature of vacuum
It is dried in dry case, obtains the solid bisphenol A polymer of aubergine, wait being cooled to room temperature that move to storage bottle spare.
Embodiment 8
Step 1, in the 50ml three neck round bottom flask equipped with mechanical stirring and reflux condensate device, be added 25g bisphenol-A with
N-butanol 28mL is stirred and is warming up to 60 DEG C, is completely dissolved to bisphenol-A, reaction system is clear and transparent.
Step 2 is water-cooled and is back to room temperature, is then added at one time 37% formalin 9g, p-methyl benzenesulfonic acid
0.27g forms mixed solution；It is stirred solution, while being heated to 84 DEG C, stirring rate 450r/min；It is warm herein
Degree is lower to react 6h, generates aubergine liquid.
N-butanol and a small amount of water is distilled off in step 3 under normal pressure, and then removed under reduced pressure residue water drips back to anhydrous
Stream, product become aubergine thick liquid.
Step 4 is washed with boiling water and removes unreacted bisphenol-A for 3 times, and last decompression dehydration is dry in 120 DEG C of temperature of vacuum
It is dried in dry case, obtains the solid bisphenol A polymer of aubergine, wait being cooled to room temperature that move to storage bottle spare.
Embodiment 9
Step 1, in the 50ml three neck round bottom flask equipped with mechanical stirring and reflux condensate device, be added 28g bisphenol-A with
N-butanol 30mL is stirred and is warming up to 68 DEG C, is completely dissolved to bisphenol-A, reaction system is clear and transparent.
Step 2 is water-cooled and is back to room temperature, is then added at one time 37% formalin 13g, p-methyl benzenesulfonic acid
1g forms mixed solution；It is stirred solution, while being heated to 93 DEG C, stirring rate 450r/min；At this temperature
5h is reacted, aubergine liquid is generated.
N-butanol and a small amount of water is distilled off in step 3 under normal pressure, and then removed under reduced pressure residue water drips back to anhydrous
Stream, product become aubergine thick liquid.
Step 4 is washed with boiling water and removes unreacted bisphenol-A for 4 times, and last decompression dehydration is dry in 110 DEG C of temperature of vacuum
It is dried in dry case, obtains the solid bisphenol A polymer of aubergine, wait being cooled to room temperature that move to storage bottle spare.
Embodiment 10
Step 1, in the 50ml three neck round bottom flask equipped with mechanical stirring and reflux condensate device, be added 10g bisphenol-A with
N-butanol 30mL is stirred and is warming up to 72 DEG C, is completely dissolved to bisphenol-A, reaction system is clear and transparent.
Step 2 is water-cooled and is back to room temperature, is then added at one time 37% formalin 15g, p-methyl benzenesulfonic acid
0.3g forms mixed solution；It is stirred solution, while being heated to 90 DEG C, stirring rate 450r/min；In this temperature
Lower reaction 7h generates aubergine liquid.
N-butanol and a small amount of water is distilled off in step 3 under normal pressure, and then removed under reduced pressure residue water drips back to anhydrous
Stream, product become aubergine thick liquid.
Step 4 is washed with boiling water and removes unreacted bisphenol-A for 5 times, and last decompression dehydration is dry in 100 DEG C of temperature of vacuum
It is dried in dry case, obtains the solid bisphenol A polymer of aubergine, wait being cooled to room temperature that move to storage bottle spare.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Within mind and principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (9)
1. a kind of bisphenol A formaldehyde phenolic resin, which is characterized in that the chemical formula of the bisphenol A formaldehyde phenolic resin are as follows:
Wherein, molecular weight 2000-3000.
2. a kind of synthetic method of bisphenol A formaldehyde phenolic resin, which comprises the following steps:
Step 1, mixing bisphenol-A and n-butanol, stir and heat up, form transparent reaction system；
Formalin and p-methyl benzenesulfonic acid, formation mixed solution after reaction system cooling for reflux, will be added in step 2；Stirring is simultaneously
Heat up mixed solution, and aubergine liquid is generated after reaction；
Step 3, distillation decompression aubergine liquid, generate aubergine viscous product；
Step 4 decompression dehydration and will dry after the washing of aubergine viscous product, and bisphenol A formaldehyde phenolic resin is made.
3. a kind of synthetic method of bisphenol A formaldehyde phenolic resin according to claim 2, which is characterized in that in step 1,
The solid-liquid ratio of bisphenol-A and n-butanol is (10-13) g:(20-30) mL；It stirs and is warming up to 60-80 DEG C.
4. a kind of synthetic method of bisphenol A formaldehyde phenolic resin according to claim 2, which is characterized in that in step 2,
Reaction system cooling for reflux to room temperature, the concentration of formalin is 37%.
5. a kind of synthetic method of bisphenol A formaldehyde phenolic resin according to claim 2, which is characterized in that in step 2,
Formalin and bisphenol-A mass ratio are 1:(2-4.5)；The mass ratio of formalin and p-methyl benzenesulfonic acid is 1:(0.02-
0.08)。
6. a kind of synthetic method of bisphenol A formaldehyde phenolic resin according to claim 2, which is characterized in that in step 2,
Mixed solution stirs and is warming up to 85-95 DEG C, and reaction 5-8h generates aubergine liquid.
7. a kind of synthetic method of bisphenol A formaldehyde phenolic resin according to claim 2, which is characterized in that in step 3,
It is decompressed to that reaction system is anhydrous to drip back stream, generates aubergine viscous product.
8. a kind of synthetic method of bisphenol A formaldehyde phenolic resin, feature according to claim 2-7 any one exist
In, in step 4, by boiling water washing aubergine viscous product 3-5 times, decompression dehydration after washing, between decompression dehydration and drying
Have additional dialysis step；Drying temperature is 100-120 DEG C, and drying environment is vacuum.
9. a kind of bisphenol A formaldehyde phenolic resin synthetic method according to claim 8, which is characterized in that dialysis step are as follows:
Crude product after decompression dehydration is dissolved in acetone solvent, mixed solution is formed, mixed solution is put into bag filter and is dialysed,
After dialysis, dialysis product is put in draught cupboard, acetone solvent is vapored away；It is dried again.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810940081.1A CN108948299A (en) | 2018-08-17 | 2018-08-17 | A kind of bisphenol A formaldehyde phenolic resin and its synthetic method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810940081.1A CN108948299A (en) | 2018-08-17 | 2018-08-17 | A kind of bisphenol A formaldehyde phenolic resin and its synthetic method |
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| CN109810233A (en) * | 2019-02-28 | 2019-05-28 | 陕西科技大学 | A kind of glutaraldehyde modified bisphenol A formaldehyde phenolic resin and its synthetic method |
| CN112574371A (en) * | 2020-12-14 | 2021-03-30 | 陕西科技大学 | Bisphenol A paraformaldehyde phenolic resin and preparation method thereof |
| CN116589703A (en) * | 2023-05-24 | 2023-08-15 | 淄博金藏新材料科技有限公司 | Preparation method of novel low-viscosity resin hydrosol |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109810233A (en) * | 2019-02-28 | 2019-05-28 | 陕西科技大学 | A kind of glutaraldehyde modified bisphenol A formaldehyde phenolic resin and its synthetic method |
| CN112574371A (en) * | 2020-12-14 | 2021-03-30 | 陕西科技大学 | Bisphenol A paraformaldehyde phenolic resin and preparation method thereof |
| CN116589703A (en) * | 2023-05-24 | 2023-08-15 | 淄博金藏新材料科技有限公司 | Preparation method of novel low-viscosity resin hydrosol |
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Application publication date: 20181207 |