CN107383294B - A kind of two acid catalyzed preparation method for synthesizing light o-cresol-formaldehyde resin - Google Patents
A kind of two acid catalyzed preparation method for synthesizing light o-cresol-formaldehyde resin Download PDFInfo
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- 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
- C08G8/12—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with monohydric phenols having only one hydrocarbon substituent ortho on para to the OH group, e.g. p-tert.-butyl phenol
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Abstract
The present invention provides a kind of two acid catalyzed production method for synthesizing light o-cresol-formaldehyde resin, the following steps are included: the formalin of certain mol proportion and o-cresol are added in the transposed reactor of high pure nitrogen, it is uniformly mixed, certain amount of organic acid catalyst is added under conditions of nitrogen protection and is reacted 1~4 hour at 90~120 DEG C, it adds a certain amount of inorganic acid catalyst and improves catalytic rate, organic solvent is added after the reaction was continued 1~4 hour dissolves resin, make material liquid pH value 6~7 by repeatedly washing, use infiltration evaporation film device recycling design, up to light o-cresol-formaldehyde resin.The organic acid and inorganic acid that the present invention uses are total to catalysis technique, can make reaction mitigate and it is easily controllable, reduce the coloration of product, and finally improve the conversion ratio and yield of raw material, the separation of recycling azeotropic mixture system organic solvent is realized using saturating vaporization film, energy consumption can be reduced, recovery efficiency is improved, can be used for the industrialized production of light o-cresol-formaldehyde resin.
Description
Technical field
The present invention relates to the methods for using organic acid and inorganic acid co-catalysis to synthesize light o-cresol-formaldehyde resin, belong to phenol
Urea formaldehyde macromolecule synthesising technology field.
Background technique
O-cresol formaldehyde epoxy resin is the primary structural material of integrated antenna package, with the close phase of numerous high-tech industries
Even, development level directly affects the development of integrated antenna package technology, has very importantly in IC industry
Position.O-cresol-formaldehyde resin can obtain o-cresol formaldehyde ring after base catalysis epoxidation later by the way that etherification reaction occurs with epoxychloropropane
Oxygen resin.
With the fast development of electronic product, the market demand of o-cresol formaldehyde epoxy resin is also stepped up, to neighbour
The performance requirement of cresol novolac epoxy resins also increases accordingly.O-cresol-formaldehyde resin is main as synthesizing o-cresol formaldehyde epoxy resin
Resin raw material, shade directly influence the form and aspect of o-cresol formaldehyde epoxy resin, the final quality for influencing final products and
Price.
In existing technical report, in order to reduce the coloration of o-cresol-formaldehyde resin, it is often used the progress of reproducibility organic acid
Catalysis, which can preferentially react with oxygen, simultaneously because its catalytic capability is weaker, be conducive to control polycondensation process, generation
The general color of naval stores is shallower.However, merely using organic acid since reaction rate is slower, in the short time, o-cresol raw material is very
Rare to reaction completely, the production cycle is longer, so developing a kind of effectively control polycondensation process, improves polymerization rate, contracting
Short reaction time, but can reduce the o-cresol-formaldehyde resin of product coloration to improve resin quality and reduce production cost have it is important
Meaning.
In addition, organic solvent obtained by extraction aftercut is usually organic solvent and water azeotropic mixture, using conventional extraction
The methods of rectifying, azeotropic distillation are separated, and process is complicated, and energy consumption is high, higher cost.It is realized according to novel membrane technology organic
The hardly possible such as aqueous solvent azeotropic mixture system divides the separation of object system, then has many advantages, such as that easy to operate, low energy consumption, pollution-free, high-efficient, have compared with
Big development potentiality and commercial value.
Summary of the invention
The technical problem to be solved by the present invention is to be directed to the deficiency of single acid catalytic systems, a kind of two acid catalyzed conjunction is provided
At the preparation method of light o-cresol-formaldehyde resin.Organic acid, which is added, keeps o-cresol-formaldehyde resin color shallower, and reaction is mild controllable, adds
Entering inorganic acid accelerates polymerization rate, improves the conversion ratio of raw material, can effectively shorten the reaction time, and effect is reduced and is produced into
This.The separation that azeotropic mixture system organic solvent is realized using dimethyl silicone polymer/aluminium oxide infiltrating and vaporizing membrane can simplify separation stream
Journey significantly reduces energy consumption, improves recovery efficiency.
In order to solve the above technical problems, the technical solution adopted by the present invention is that: a kind of light o-cresol of two acid catalyzed synthesis
The preparation method of urea formaldehyde, including following steps:
Step 1: in a nitrogen atmosphere, the formalin of o-cresol and 37% being added in reactor, is heated to 40~60
DEG C stirring makes o-cresol dissolve and be uniformly mixed, and obtains transparent reaction liquid, o-cresol and formaldehyde mole ratio are 1:0.9~1:
1.05；
Step 2: organic acid catalysis is added to the resulting transparent reaction liquid of step 1 in normal pressure under conditions of nitrogen protection
Agent reacts 1~4 hour under conditions of 90~120 DEG C, obtains milky polymer solution；
Step 3: inorganic acid is added into the resulting milky polymer solution of step 2 under conditions of nitrogen protection
Catalyst, the reaction was continued under conditions of 90~120 DEG C 1~4 hour, obtains milky thick liquid；
Crude resin product is dissolved Step 4: organic solvent is added in the resulting milky thick liquid of step 3, is led to
Crossing repeatedly washing makes material liquid pH value 6~7, and subsequently into infiltration vaporization membrane module, recycling design obtains light o-cresol formaldehyde tree
Rouge；Using dimethyl silicone polymer/aluminium oxide infiltrating and vaporizing membrane.
Organic acid catalyst described in step 2 be oxalic acid, formic acid, acetic acid, butyric acid, benzoic acid, ethanedioic acid it is one or more
The mixture of arbitrary proportion；The dosage of the organic acid catalyst is 1~3% of o-cresol quality described in step 1.
Inorganic acid catalyst described in step 3 is one or more any ratios of concentrated hydrochloric acid, concentrated nitric acid, the concentrated sulfuric acid, phosphoric acid
The mixture of example；The dosage of the inorganic acid catalyst is 1~3% of o-cresol quality described in step 1.
Organic solvent described in step 4 is one kind or more of methyl iso-butyl ketone (MIBK), toluene, n-butanol, isopropanol, dimethylbenzene
The mixed liquor of kind arbitrary proportion, the volume of organic solvent used are the 1~5 of the resulting milky thick liquid volume of step 3
Times.
Washing described in step 4 carries out extracting and washing, water temperature control to crude resin solution using plural serial stage centrifugal extractor
At 70~95 DEG C, unreacted o-cresol raw material and acidic catalyst in resin are removed.
Dimethyl silicone polymer described in step 4/aluminium oxide infiltrating and vaporizing membrane, operating pressure 0.3MPa, film permeation flux
3.5kg·m-2·h-1。
The rate of the polycondensation reaction of o-cresol and formaldehyde is related with the type of acidic catalyst and concentration, different types of acid
Property catalyst directly affect the generating rate of resin, also influence the performance of resin.Inorganic acid hydrogen ion extent of dissociation is big, and catalysis is anti-
Answer rate quickly, but very exothermic is difficult to control reaction in polycondensation process, and product is made to be easy crosslinking, the naval stores of production
Color is also deep.Organic acid hydrogen ion dissociating power is weak, and catalytic capability is also weaker, but reacts mild controllable.In addition, reduction
The organic acid of property can be reacted with the oxygen in reaction system, can also be restored the phenolic hydroxyl group for being oxidized resin, can be significantly reduced resin
The coloration of product improves its appearance.The present invention is catalyzed jointly using organic acid and inorganic acid, and this method can be tied effectively
The advantages of closing two kinds of acidic catalysts.In addition, organic solvent obtained by extraction aftercut is usually organic solvent and water vapor of mixture
Object, the methods of conventional extraction rectifying, azeotropic distillation separating energy consumption are larger.The present invention uses newest seepage slope method extractant
Recycling, can significantly simplify separation process, reduce separation costs.
Beneficial effects of the present invention:
1, the present invention is reproducibility organic acid in the catalyst that initial reaction stage is selected, and catalytic capability is weaker, mitigates reaction,
Initial reaction stage very exothermic is avoided to be crosslinked resin；Reproducibility organic acid plays reducing agent work within the entire production cycle simultaneously
With avoiding the phenolic hydroxyl group of product from being oxidized, the coloration of product be effectively reduced.
2, the present invention catalyst that the phase selects in the reaction is inorganic acid, and hydrogen dissociating power is big, and catalytic capability is stronger, can have
Effect further increases polycondensation reaction rate, improves the conversion ratio and yield of o-cresol, shortens reaction time, and reduction is produced into
This.
3, reproducibility is organic and inorganic acid it is two acid catalyzed, successfully solve simple reproducibility organic acid catalysis reaction rate
Slowly, the problems such as o-cresol conversion ratio is lower and the problem that simple mineral acid catalytic reactions are violent, product color is poor are made and divide
The product that son amount is high, softening point is controllable, coloration is low, while increasing reaction rate reduction production cost.
4, the separation of azeotropic mixture system organic solvent is realized using dimethyl silicone polymer/aluminium oxide infiltrating and vaporizing membrane, it can letter
Change separation process, significantly reduce energy consumption, improves recovery efficiency.
Specific embodiment
The following examples are used to illustrate the present invention, but are not intended to limit the scope of the present invention..
Embodiment 1
By evacuate repeatedly-nitrogen charging makes tri- mouthfuls of reactors of 1000mL full of nitrogen, then by 200g o-cresol and 135g37%
Formalin be added reaction vessel in, be heated to 40 DEG C, so that o-cresol is dissolved and is uniformly mixed using mechanical stirring, obtain
Bright reaction solution.Under conditions of nitrogen protection, mixed organic acid catalyst (solid oxalic acid 3g, formic acid is added to reaction solution in normal pressure
1g), reaction temperature control obtains milky polymer solution in 90 DEG C, heating reflux reaction 2 hours.Under nitrogen atmosphere, it is added
Inorganic acid catalyst (concentrated hydrochloric acid that 2.5g concentration is 37%), at 90 DEG C, the reaction was continued 4 hours for reaction temperature control, obtains milky white
Color thick liquid.Organic solvent methyl iso-butyl ketone (MIBK) is added, volume is 5 times of milky thick liquid volume, makes crude resin
Product dissolution；It reuses plural serial stage centrifugal extractor and extracting and washing is carried out to crude resin solution, deionized water 150mL is added,
70 DEG C of washings make material liquid pH value 6~7 three times.Subsequently into infiltration vaporization membrane module, recycling design, using dimethyl silicone polymer
(PDMS)/aluminium oxide infiltrating and vaporizing membrane, operating pressure 0.3MPa, film permeation flux 3.5kgm-2·h-1.Up to light adjacent first
Phenolic resin, sealing are placed in 5oC dry environment middle or short term saves.
O-cresol-formaldehyde resin color manufactured in the present embodiment is shallower, yield 203g, and o-cresol conversion ratio is 98.7%, adjacent
Cresol resin residual quantity is 0.08%, and softening point is 87 DEG C, and at 150 DEG C, the fugitive constituent of o-cresol-formaldehyde resin is 0.48%.
Embodiment 2
By evacuate repeatedly-nitrogen charging makes tri- mouthfuls of reactors of 1000mL full of nitrogen, then by 210g o-cresol and 150g37%
Formalin be added reaction vessel in, be heated to 60 DEG C makes o-cresol dissolve and be uniformly mixed using mechanical stirring, obtains
Bright reaction solution.Under conditions of nitrogen protection, solid oxalic acid 6g is added to reaction solution in normal pressure, and reaction temperature controls at 90 DEG C, adds
Obtain milky polymer solution within hot back flow reaction 4 hours.4g phosphoric acid inorganic acid catalyst is added, reaction temperature is controlled at 90 DEG C
The reaction was continued 4 hours, obtains milky thick liquid.Toluene organic solvent is added, volume is milky thick liquid volume
3 times, make crude resin product dissolve；It reuses plural serial stage centrifugal extractor and extracting and washing is carried out to crude resin solution, be added
Deionized water 200mL, washing four times for 70 DEG C makes material liquid pH value 6~7.Subsequently into infiltration vaporization membrane module, recycling design is used
Dimethyl silicone polymer (PDMS)/aluminium oxide infiltrating and vaporizing membrane, operating pressure 0.3MPa, film permeation flux 3.5kgm-2·h-1.Up to light o-cresol-formaldehyde resin, sealing is placed in 5oC dry environment middle or short term saves.
O-cresol-formaldehyde resin color manufactured in the present embodiment is shallower, yield 209g, and o-cresol conversion ratio is 97.6%, adjacent
Cresol resin residual quantity is 0.12%, and softening point is 84 DEG C, and at 150 DEG C, the fugitive constituent of o-cresol-formaldehyde resin is 0.37%.
Embodiment 3
By evacuate repeatedly-nitrogen charging makes tri- mouthfuls of reactors of 1000mL full of nitrogen, then by 160g o-cresol and 126g37%
Formalin be added reaction kettle in, being heated to 60 DEG C makes o-cresol dissolve and be uniformly mixed, and obtains transparent reaction liquid.In nitrogen
Under conditions of protection, formic acid 4g is added to reaction solution in normal pressure, and reaction temperature is controlled at 100 DEG C or so, and heating reflux reaction 3 is small
When, under nitrogen atmosphere, the hydrochloric acid solution that 4.8g concentration is 20% is slowly added dropwise, reaction temperature control continues anti-between 100 DEG C
It answers 4 hours, obtains milky thick liquid.Cyclohexanone organic solvent is added, volume is the 5 of milky thick liquid volume
Times, dissolve crude resin product.Reuse plural serial stage centrifugal extractor to crude resin solution carry out extracting and washing, addition go from
Sub- water 200mL, washing four times for 70 DEG C makes material liquid pH value 6~7.Subsequently into infiltration vaporization membrane module, recycling design, using poly- two
Methylsiloxane (PDMS)/aluminium oxide infiltrating and vaporizing membrane, operating pressure 0.3MPa, film permeation flux 3.5kgm-2·h-1.System
Obtain light o-cresol-formaldehyde resin product.
O-cresol-formaldehyde resin color manufactured in the present embodiment is shallower, yield 173g, and o-cresol conversion ratio is 98.9%, adjacent
Cresol resin residual quantity is 0.51%, and softening point is 92 DEG C, and at 140 DEG C, the fugitive constituent of o-cresol-formaldehyde resin is 0.76%.
Embodiment 4
By evacuate repeatedly-nitrogen charging makes 100L reactor full of nitrogen, then by the first of 20kg o-cresol and 13.5kg37%
Aldehyde solution is added in reaction kettle, and being heated to 60 DEG C of stirrings makes o-cresol dissolve and be uniformly mixed, and obtains reaction solution.In nitrogen protection
Under conditions of, on normal pressure disposably to answer liquid be added mixed organic acid catalyst aqueous solution (0.2kg formic acid, 0.2kg oxalic acid,
0.2kg acetic acid), the heating reflux reaction 1 hour under conditions of 120 DEG C.In order to further increase o-cresol conversion ratio, to system
The aqueous solution (0.2kg37% hydrochloric acid, 200mL water) of mixing inorganic acid catalyst is added.In order to keep reaction controllable, inorganic acid catalysis
The small flow of agent mixed liquor is continuously added into polymerization system, and addition flow is 15mL/min.It is heated back under conditions of 120 DEG C
Stream reaction 1 hour, obtains milky thick liquid.Toluene is added and isopropanol solvent, volume are milky thick liquid bodies
Long-pending 1 times, crude resin product is dissolved；Reuse plural serial stage centrifugal extractor to crude resin solution carry out extracting and washing, 95
DEG C washing makes material liquid pH value rise to 6~7 four times.Subsequently into infiltration vaporization membrane module, recycling design, using polydimethylsiloxanes
Alkane (PDMS)/aluminium oxide infiltrating and vaporizing membrane, operating pressure 0.3MPa, film permeation flux 3.5kgm-2·h-1.It is adjacent to obtain light color
Cresols urea formaldehyde, sealing are placed in 5oC dry environment middle or short term saves.
O-cresol-formaldehyde resin color manufactured in the present embodiment is shallower, yield 20.2kg, and o-cresol conversion ratio is 99.1%,
O-cresol resin residue amount is 0.01%, and softening point is 89 DEG C, is 0.1% in the fugitive constituent of 150 DEG C of o-cresol-formaldehyde resins.
Comparative example 1
By evacuate repeatedly-nitrogen charging makes tri- mouthfuls of reactors of 1000mL full of nitrogen, then by 200g o-cresol and 135g
37% formalin is added in reaction vessel, and be heated to 40 DEG C makes o-cresol dissolve and be uniformly mixed using mechanical stirring, obtains
Transparent reaction liquid.Under conditions of nitrogen protection, mixed organic acid catalyst (3g solid oxalic acid, 1g is added to reaction solution in normal pressure
Acetic acid), reaction temperature is controlled at 90 DEG C, can obtain milky polymer solution within heating reflux reaction 6 hours.Under nitrogen atmosphere,
Organic acid catalyst 3g solid oxalic acid and 1g acetic acid are added, the reaction was continued 4 hours at 90 DEG C for reaction temperature control, obtains milky white
Color thick liquid.Organic solvent methyl iso-butyl ketone (MIBK) is added, volume is 5 times of milky thick liquid volume, makes crude resin
Product dissolution；It reuses plural serial stage centrifugal extractor and extracting and washing is carried out to crude resin solution, deionized water 150mL is added,
Washing makes material liquid pH value 6~7 three times, using film enrichment facility high-temperature pressure-reduction recycling design, under 150 DEG C of nitrogen protections
0.05KPa Vacuum discharge is placed in 5 to get light o-cresol-formaldehyde resin, sealingoC dry environment middle or short term saves.
The o-cresol-formaldehyde resin color of this comparative example preparation is shallower, yield 198g, and o-cresol conversion ratio is 94.7%, adjacent
Cresol resin residual quantity is 0.18%, and softening point is 83 DEG C, the o-cresol-formaldehyde resin for this comparative example preparation surveyed at 150 DEG C
Fugitive constituent is 0.56%.
The o-cresol-formaldehyde resin and comparative example 1 that 1 synthetic method obtains through the embodiment of the present invention are compared, and can be seen
Out, synthetic method of the invention, it is available with comparative example coloration similar in o-cresol formaldehyde product while, can dramatically speed up
Polymerization rate improves the conversion ratio of o-cresol, reduces the residual of o-cresol, shortens the reaction time.Simultaneously using using poly-
Dimethyl siloxane/aluminium oxide infiltration vaporization separation film technology realizes o-cresol-formaldehyde resin product water-organic solvent azeotropic mixture system
Etc. difficulties divide the separation of object system, it is easy to operate, low energy consumption, pollution-free, high-efficient, have biggish development potentiality and commercial value.
Claims (6)
1. a kind of two acid catalyzed preparation method for synthesizing light o-cresol-formaldehyde resin, which is characterized in that this method includes following step
It is rapid:
Step 1: in a nitrogen atmosphere, the formalin of o-cresol and 37% being added in reactor, 40~60 DEG C is heated to and stirs
Mixing makes o-cresol dissolve and be uniformly mixed, and obtains transparent reaction liquid, and o-cresol and formaldehyde mole ratio are 1:0.9~1:1.05；
Step 2: organic acid catalyst is added to the resulting transparent reaction liquid of step 1 in normal pressure under conditions of nitrogen protection,
It is reacted 1~4 hour under conditions of 90~120 DEG C, obtains milky polymer solution；The dosage of the organic acid catalyst is step
The 1~3% of o-cresol quality described in rapid one
Step 3: inorganic acid catalysis is added into the resulting milky polymer solution of step 2 under conditions of nitrogen protection
Agent, the reaction was continued under conditions of 90~120 DEG C 1~4 hour, obtains milky thick liquid；The inorganic acid catalyst
Dosage is 1~3% of o-cresol quality described in step 1
Crude resin product is dissolved Step 4: organic solvent is added in the resulting milky thick liquid of step 3, it is used to have
The volume of solvent is 1~5 times of the resulting milky thick liquid volume of step 3, then makes material liquid pH value by repeatedly washing
It is 6~7, subsequently into infiltration vaporization membrane module, recycling design obtains light o-cresol-formaldehyde resin；Using polydimethylsiloxanes
Alkane/aluminium oxide infiltrating and vaporizing membrane.
2. the two acid catalyzed preparation method for synthesizing light o-cresol-formaldehyde resin of one kind according to claim 1, feature exist
In, organic acid catalyst described in step 2 be oxalic acid, formic acid, acetic acid, butyric acid, benzoic acid, ethanedioic acid it is one or more any
The mixture of ratio.
3. the two acid catalyzed preparation method for synthesizing light o-cresol-formaldehyde resin of one kind according to claim 1, feature exist
In inorganic acid catalyst described in step 3 is one or more arbitrary proportions of concentrated hydrochloric acid, concentrated nitric acid, the concentrated sulfuric acid, phosphoric acid
Mixture.
4. the two acid catalyzed preparation method for synthesizing light o-cresol-formaldehyde resin of one kind according to claim 1, feature exist
In, organic solvent described in step 4 be methyl iso-butyl ketone (MIBK), toluene, n-butanol, isopropanol, dimethylbenzene it is one or more any
The mixed liquor of ratio.
5. the two acid catalyzed preparation method for synthesizing light o-cresol-formaldehyde resin of one kind according to claim 1, feature exist
In washing described in step 4 carries out extracting and washing to crude resin solution using plural serial stage centrifugal extractor, and water temperature is controlled 70
~95 DEG C, remove unreacted o-cresol raw material and acidic catalyst in resin.
6. the two acid catalyzed preparation method for synthesizing light o-cresol-formaldehyde resin of one kind according to claim 1, feature exist
In, dimethyl silicone polymer described in step 4/aluminium oxide infiltrating and vaporizing membrane, operating pressure 0.3MPa, film permeation flux
3.5kg·m-2·h-1。
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| CN115109212B (en) * | 2022-07-15 | 2023-10-13 | 东营市赫邦化工有限公司 | Application of heteropolyacid and heteropolyacid salt as catalyst in catalytic preparation of o-cresol novolac resin |
| CN115124671B (en) * | 2022-07-15 | 2023-04-25 | 东营市赫邦化工有限公司 | Preparation method of phenol-formaldehyde resin and product obtained by preparation method |
| CN115181228B (en) * | 2022-07-19 | 2023-07-07 | 东营市赫邦化工有限公司 | Preparation method of low-chroma bisphenol A phenolic resin and product obtained by preparation method |
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