CN109337027A - A method of using Caprolactam basic ionic liquid as catalyst preparation phenolic resin - Google Patents
A method of using Caprolactam basic ionic liquid as catalyst preparation phenolic resin Download PDFInfo
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- CN109337027A CN109337027A CN201811091757.0A CN201811091757A CN109337027A CN 109337027 A CN109337027 A CN 109337027A CN 201811091757 A CN201811091757 A CN 201811091757A CN 109337027 A CN109337027 A CN 109337027A
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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
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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
- C08G8/12—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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- 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
- C08G8/22—Resorcinol
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- Phenolic Resins Or Amino Resins (AREA)
Abstract
The invention belongs to ionic liquid-catalyzed fields, and in particular to a method of using Caprolactam basic ionic liquid as catalyst preparation phenolic resin.This method uses phenol and formaldehyde for raw material, and using Caprolactam basic ionic liquid as catalyst, catalysis prepares phenolic resin.After reaction, phenolic resin bead is filtered to isolate while hot, filtrate water is cooled to 10 DEG C hereinafter, ionic liquid is automatically subjected to phase splitting with water, isolates caprolactam class ionic liquid reuse.The ionic liquid preparation process that the present invention uses is simple, cheap, as catalyst efficiency height, condensation reaction time is short, and ionic liquid may be reused, and the phenolic resin bead surface of preparation is smooth, sphere diameter is uniform, and the product yield of 0.3~0.5mm of target the small ball's diameter is high.
Description
Technical field
The invention belongs to ionic liquid-catalyzed fields, in particular to a kind of to use Caprolactam basic ionic liquid conduct
The method of catalyst preparation phenolic resin.
Background technique
As one of three big thermosetting resins, phenolic resin since raw material is easy to get, cheap, production process simply at
It is ripe, manufacture and process equipment small investment, molding be easy, the performance solidify in addition after can satisfy a variety of requirements and in industry
On be widely used.Currently, the technique of novolak resin ball all uses traditional handicraft (the just brave phenolic resin base of the Qin
The preparation of spherical activated charcoal and application [D] East China University of Science, 2012.), using inorganic acid alkali as catalyst, synthesize work
Skill is complicated, takes a long time, and condensation reaction is up to more than ten hour, can also generate largely containing acidic and alkaline waste water, cause one to environment
Fixed pollution.
Patent CN102862982 A discloses a kind of preparation method with narrow mesopore pore size distribution spheric active carbon,
It specifically discloses: preparing the aqueous solution of 5-10wt% dispersing agent, obtain dispersion liquid；By phenol, formaldehyde, sodium hydroxide and carboxyl function
Ionic liquid can be changed to be added in dispersion liquid, stir 10-60min.Then it is heated up under stirring with the rate of 0.5-2 DEG C/min
To 70-85 DEG C, and react 1-3h at this temperature to get phenolic resin ball, this method is needed using sodium hydroxide and carboxyl function
Ionic liquid can be changed as catalyst and prepare phenolic resin, and phenolic resin partial size obtained is smaller.
Summary of the invention
It is an object of the invention to overcome, catalyst activity existing in the prior art is lower, prepared by phenolic resin microspheres
The disadvantage that time-consuming for journey, target the small ball's diameter 0.3~0.5mm yield is low provides a kind of using alkali ionic liquid catalysis preparation
The method of phenolic resin bead.Idea of the invention is that using phenol and formaldehyde for raw material, caprolactam class alkali ion liquid is selected
Body is catalyst, under conditions of more mild, catalyzes and synthesizes phenolic resin bead.
The present invention uses method of the caprolactam class ionic liquid as catalyst preparation phenolic resin, and specific steps are such as
Under: 3.5wt% polyethylene of dispersing agent alcohol is added in four-hole boiling flask, is heated to 80 DEG C, sequentially adds phenol, formaldehyde and acyl in oneself
Amine ionic liquid catalyst, is stirred and heated to 60 DEG C~90 DEG C progress condensation reactions, and condensation reaction time 1~4 hour, then
4.0wt% hexamethylenetetramine curing agent is added, 95 DEG C is warming up to and continues stirring 4 hours, it is small to isolate phenolic resin while hot
Ball, filtrate are cooled to 10 DEG C hereinafter, caprolactam class ionic liquid is automatically subjected to phase splitting with water, isolate caprolactam class ionic liquid
Reuse.
It may be since the weaker hydroxyl of alkalinity in Caprolactam basic ionic liquid has catalytic action, and oneself
The big steric hindrance of lactams group enables condensation reaction than more smoothly carrying out, to obtain the surface of appropriate particle size
Smooth target bead.
Wherein, the molar ratio of above-mentioned phenol, formaldehyde and caprolactam class ionic-liquid catalyst be 1:1.2~1.6:0.01~
0.06。
The phenol are as follows: phenol, Resorcino, 2, one in 4,6- trimethyls-phenol, p-methyl phenol or xylenol
Kind；
The Caprolactam basic ionic liquid catalyst, general formula are as follows:
Wherein, n is the integer of 1-8, and R is H or C1-C12Alkyl.
The preparation method of above-mentioned Caprolactam basic ionic liquid catalyst, steps are as follows:
(1) caprolactam substance and halogenated alkane (molar ratio 1.0:0.5~2) are dissolved in acetonitrile solvent, in N2Atmosphere
Middle synthetic intermediate is enclosed, then intermediate washes away its unreacted solution through ethyl acetate and ether, and rotary evaporation obtains purity
Higher intermediate；Wherein, solvent quality dosage is the 10%~50% of caprolactam substance quality, and synthesis reaction temperature is
70~120 DEG C, synthesising reacting time is 4~12h；
The caprolactam substance be caprolactam, N- methyl caprolactam, N- ethylcaprolactam, N- propyl oneself
Lactams, N- amyl caprolactam or N- hexyl caprolactam；Halogenated alkane is CnH2n+1- X or RX, wherein X is halogen, R H
Or C1-C12Alkyl.
(2) intermediate is dissolved in methanol, then reacts 12~28h at room temperature with inorganic alkali alcosol and oneself is prepared
Lactams ionic liquid, wherein the volume mass of intermediate and methanol ratio is 1~4ml/g, the volume matter of methanol and inorganic base
Measure 5~8ml/g of ratio.The inorganic base includes NaOH, KOH, NaHCO3、KHCO3Or Ca (OH)2One of which or at least two
Kind mixture.
The invention has the advantages that
(1) Caprolactam basic ionic liquid that the present invention uses prepares the catalyst of phenolic resin bead as catalysis
Catalytic activity is high, prepares phenolic resin relative to other catalyst (such as sodium hydroxide, ammonium hydroxide), the condensation time is short
(2-3h), product particle narrowly distributing, bead surface is smooth, and sphere diameter is uniform, and target 0.3~0.5mm of bead yield is high.
(2) alkali ionic liquid synthesis condition selected by is mild, the reaction time is short；Under alkaline ionic liquid catalyst low temperature
(10 DEG C or so) crystallizations, can be automatically with moisture phase, and convenient separation may be reused；And the alkaline ionic liquid catalyst
The problems such as there is no corrosion equipment and environmental pollutions, production process is environmentally protective, and cost of investment is lower.
Detailed description of the invention
Fig. 1 is the electron microscope for the phenolic resin bead that embodiment 4 synthesizes.
Specific embodiment
The present invention illustrates it with regard to following several caprolactam class ionic liquids and is catalyzing and synthesizing answering in phenolic resin
With.
Embodiment 1
It weighs 10g caprolactam and is dissolved in acetonitrile solvent and be put into four-hole boiling flask, acetonitrile content is quality of caprolactam
50%, it is placed in oil bath pan and is warming up to 120 DEG C, weigh bromomethane in constant pressure separatory funnel, caprolactam and bromomethane
Molar ratio is 1:2, and control rate of addition is slowly dropped into flask, while being passed through N2, insertion condenser pipe, thermometer, unlatching stirring, drop
Add end to take out constant pressure separatory funnel to continue to be stirred to react 12h, reaction terminates to pour out the unreacted solution in upper layer, uses ethyl acetate
Wash intermediate for several times, rotary evaporation is put into dry to constant weight in 70 DEG C of vacuum ovens and obtains the higher intermediate of purity.Claim
It takes intermediate in three-necked flask, solvent methanol wiring solution-forming is added, the methanol and intermediate volume mass ratio of addition are 4mL/
G, then the methanol solution of NaOH is weighed, wherein the volume mass of methanol and inorganic base ratio is 5mL/g, NaOH and intermediate molar ratio
For 1.5:1,28h is reacted at room temperature, filters and removes NaBr solid, and filtrate revolving removes most of methanol, and ether is added and ties again
Partial crystallization goes out unreacted solution NaOH and NaBr, be dried under vacuum to after revolving constant weight obtain the higher ionic liquid of purity (from
Sub- liquid 1).
3.5wt% polyethylene of dispersing agent alcohol solution 100mL is added in the four-hole boiling flask of 1000ml, is heated to 80 DEG C,
Adding 94.11g phenol, 90.25g formaldehyde, 2.0wt% ionic liquid (1), 500ml deionized water is heated to 70 DEG C,
4h is stirred under 200r/min mixing speed.It is constant to be kept stirring speed, 4.0wt% hexamethylenetetramine curing agent is added, and delay
Slowly 95 DEG C are warming up to, finally this mixing speed and at a temperature of react 4h, reaction terminating.It is unloaded after reaction temperature is reduced to room temperature
Material, is washed repeatedly with deionized water, until upper solution is limpid, is then filtered, and dry 4h, can be obtained phenolic aldehyde at 120 DEG C
Resin balls.Weighing phenolic resin microspheres quality be 60.25g, the following accounting 10.6% of the small ball's diameter 0.3mm, diameter 0.3~
0.5mm accounting 69.8%, 0.5mm or more accounting 19.6%, total recovery 70%.
Embodiment 2
Weigh 10g N- methyl caprolactam and be dissolved in alcohol solvent and be put into four-hole boiling flask, ethanol consumption be N- methyl oneself
The 10% of lactams quality is placed in oil bath pan and is warming up to 70 DEG C, weighs bromination of n-butane in constant pressure separatory funnel, N- methyl
Caprolactam and bromination of n-butane molar ratio are 1:0.8, and control rate of addition is slowly dropped into flask, while being passed through N2, it is inserted into cold
Solidifying pipe, thermometer open stirring, and completion of dropwise addition takes out constant pressure separatory funnel and continues to be stirred to react 4 hours, and reaction terminates to pour out
The unreacted solution of layer, washs intermediate for several times with ethyl acetate, rotary evaporation is put into 70 DEG C of vacuum ovens and dries to constant weight
Obtain the higher intermediate of purity.Intermediate is weighed in three-necked flask, solvent methanol wiring solution-forming, the methanol of addition is added
It is 1mL/g with intermediate volume mass ratio, then weighs the methanol solution of KOH, wherein the volume mass of methanol and inorganic base ratio is
8mL/g, KOH and intermediate molar ratio are 0.9:1, react 12h at room temperature, filter and remove KBr solid, it is dry that filtrate rotates vacuum
It is dry to obtain the higher ionic liquid of purity (ionic liquid 2) to constant weight.
3.5wt% polyethylene of dispersing agent alcohol solution 100mL is added in the four-hole boiling flask of 1000ml, is heated to 80 DEG C,
Adding 94.11g Resorcino, 82.73g formaldehyde, 3.0wt% ionic liquid (2), 500ml deionized water is heated to 60 DEG C,
3h is stirred under 200r/min mixing speed.It is constant to be kept stirring speed, 4.0wt% hexamethylenetetramine curing agent is added and delays
Slowly 95 DEG C are warming up to, finally this mixing speed and at a temperature of react 4h, reaction terminating.It is unloaded after reaction temperature is reduced to room temperature
Material, is washed repeatedly with deionized water, until upper solution is limpid, is then filtered, and dry 4h, can be obtained phenolic aldehyde at 120 DEG C
Resin balls.Weighing phenolic resin microspheres quality is 58.34g, the following accounting 9.8% of the small ball's diameter 0.3mm, 0.3~0.5mm of diameter
Accounting 68.4%, 0.5mm or more accounting 21.8%, total recovery 65%.
Embodiment 3
Weigh 10g N- amyl caprolactam and be dissolved in alcohol solvent and be put into four-hole boiling flask, ethanol consumption be N- amyl oneself
The 40% of lactams quality is placed in oil bath pan and is warming up to 90 DEG C, weighs bromination of n-butane in constant pressure separatory funnel, N- amyl
Caprolactam and bromination of n-butane molar ratio are 1:0.8, and control rate of addition is slowly dropped into flask, while being passed through N2, it is inserted into cold
Solidifying pipe, thermometer open stirring, and completion of dropwise addition takes out constant pressure separatory funnel and continues to be stirred to react 6 hours, and reaction terminates to pour out
The unreacted solution of layer, washs intermediate for several times with ethyl acetate, rotary evaporation is put into 70 DEG C of vacuum ovens and dries to constant weight
Obtain the higher intermediate of purity.Intermediate is weighed in three-necked flask, solvent methanol wiring solution-forming, the methanol of addition is added
It is 1mL/g with intermediate volume mass ratio, then weighs the methanol solution of KOH, wherein the volume mass of methanol and inorganic base ratio is
8mL/g, KOH and intermediate molar ratio are 0.9:1, are reacted at room temperature for 24 hours, filter and remove KBr solid, it is dry that filtrate rotates vacuum
It is dry to obtain the higher ionic liquid of purity (ionic liquid 3) to constant weight.
3.5wt% polyethylene of dispersing agent alcohol solution 100mL is added in the four-hole boiling flask of 1000ml, is heated to 80 DEG C,
Addition 94.11g 2,4,6- trimethyls-phenol, 105.30g formaldehyde, 1.0wt% ionic liquid (3), 500ml deionized water add
Heat stirs 2h under 200r/min mixing speed to 85 DEG C.It is constant to be kept stirring speed, it is solid that 4.0wt% hexamethylenetetramine is added
Agent is simultaneously to slowly warm up to 95 DEG C, finally this mixing speed and at a temperature of react 4h, reaction terminating.It is reduced to reaction temperature
Discharging after room temperature is washed repeatedly with deionized water, until upper solution is limpid, is then filtered, the dry 4h at 120 DEG C
Obtain phenolic resin ball.Weighing phenolic resin microspheres quality is 62.14g, the following accounting 14.9% of the small ball's diameter 0.3mm, diameter
0.3~0.5mm accounting 70.1%, 0.5mm or more accounting 15%, total recovery 75%.
Embodiment 4
It weighs 10g N- ethylcaprolactam and is dissolved in acetonitrile solvent and be put into four-hole boiling flask, acetonitrile content is N- ethyl hexyl
The 30% of lactams quality is placed in oil bath pan and is warming up to 110 DEG C, weighs bromination of n-butane in constant pressure separatory funnel, N- second
Base caprolactam and bromination of n-butane molar ratio are 1:1, and control rate of addition is slowly dropped into flask, while being passed through N2, it is inserted into cold
Solidifying pipe, thermometer open stirring, and completion of dropwise addition takes out constant pressure separatory funnel and continues to be stirred to react 8 hours, and reaction terminates to pour out
The unreacted solution of layer, washs intermediate for several times with ethyl acetate, rotary evaporation is put into 70 DEG C of vacuum ovens and dries to constant weight
Obtain the higher intermediate of purity.Intermediate is weighed in three-necked flask, solvent methanol wiring solution-forming, the methanol of addition is added
It is 3mL/g with intermediate volume mass ratio, then weighs the methanol solution of NaOH, wherein the volume mass of methanol and inorganic base ratio is
7mL/g, NaOH and intermediate molar ratio are 1.2:1, react 20h at room temperature, filter and remove NaBr solid, and filtrate revolving removes
Most of methanol is added Diethyl ether recrystallization and unreacted solution NaOH and NaBr is precipitated, is dried under vacuum to constant weight after revolving to obtain the final product
To the higher ionic liquid of purity (ionic liquid 4).
3.5wt% polyethylene of dispersing agent alcohol solution 100mL is added in the four-hole boiling flask of 1000ml, is heated to 80 DEG C,
Add 94.11g phenol, 97.77g formaldehyde, 5.0wt% ionic liquid (4), 500ml deionized water, at that same temperature,
1h is stirred under 200r/min mixing speed.It is constant to be kept stirring speed, 4.0wt% hexamethylenetetramine curing agent is added and delays
Slowly 95 DEG C are warming up to, finally this mixing speed and at a temperature of react 4h, reaction terminating.It is unloaded after reaction temperature is reduced to room temperature
Material, is washed repeatedly with deionized water, until upper solution is limpid, is then filtered, and dry 4h, can be obtained phenolic aldehyde at 120 DEG C
Resin balls.Weighing phenolic resin microspheres quality is 68.56g, the following accounting 3.7% of the small ball's diameter 0.3mm, 0.3~0.5mm of diameter
Accounting 81.3%, 0.5mm or more accounting 15%, total recovery 91.3%.
Embodiment 5
Weigh 10g N- propyl caprolactam and be dissolved in acetonitrile solvent and be put into four-hole boiling flask, acetonitrile content be N- propyl oneself
The 20% of lactams quality is placed in oil bath pan and is warming up to 80 DEG C, weighs bromination of n-butane in constant pressure separatory funnel, N- propyl
Caprolactam and bromination of n-butane molar ratio are 1:1, and control rate of addition is slowly dropped into flask, while being passed through N2, insertion condensation
Pipe, thermometer open stirring, and completion of dropwise addition takes out constant pressure separatory funnel and continues to be stirred to react 5 hours, and reaction terminates to pour out upper layer
Unreacted solution washs intermediate for several times with ethyl acetate, and rotary evaporation is put into 70 DEG C of vacuum ovens and dries to constant weight i.e.
Obtain the higher intermediate of purity.Intermediate is weighed in three-necked flask, be added solvent methanol wiring solution-forming, the methanol of addition with
Intermediate volume mass ratio is 3mL/g, then weighs the methanol solution of NaOH, and wherein the volume mass of methanol and inorganic base ratio is
7mL/g, NaOH and intermediate molar ratio are 1.2:1, react 18h at room temperature, filter and remove NaBr solid, and filtrate revolving removes
Most of methanol is added Diethyl ether recrystallization and unreacted solution NaOH and NaBr is precipitated, is dried under vacuum to constant weight after revolving to obtain the final product
To the higher ionic liquid of purity (ionic liquid 5).
3.5wt% polyethylene of dispersing agent alcohol solution 100mL is added in the four-hole boiling flask of 1000ml, is heated to 80 DEG C,
Addition 94.11g p-methyl phenol, 120.37 formaldehyde, 4.0wt% ionic liquid (5), 500ml deionized water are heated to 90 DEG C,
2h is stirred under 200r/min mixing speed.It is constant to be kept stirring speed, addition 4.0wt% hexamethylenetetramine curing agent is simultaneously slow
Be warming up to 95 DEG C, finally this mixing speed and at a temperature of react 4h, reaction terminating.It is unloaded after reaction temperature is reduced to room temperature
Material, is washed repeatedly with deionized water, until upper solution is limpid, is then filtered, and dry 4h, can be obtained phenolic aldehyde at 120 DEG C
Resin balls.Weighing phenolic resin microspheres quality be 63.53g, the following accounting 13.5% of the small ball's diameter 0.3mm, diameter 0.3~
0.5mm accounting 73.9%, 0.5mm or more accounting 12.6%, total recovery 80%.
Embodiment 6
Weigh 10g N- hexyl caprolactam and be dissolved in acetonitrile solvent and be put into four-hole boiling flask, acetonitrile content be N- hexyl oneself
The 45% of lactams quality is placed in oil bath pan and is warming up to 120 DEG C, weighs bromination of n-butane in constant pressure separatory funnel, N- oneself
Base caprolactam and bromination of n-butane molar ratio are 1:1, and control rate of addition is slowly dropped into flask, while being passed through N2, it is inserted into cold
Solidifying pipe, thermometer open stirring, and completion of dropwise addition takes out constant pressure separatory funnel and continues to be stirred to react 5 hours, and reaction terminates to pour out
The unreacted solution of layer, washs intermediate for several times with ethyl acetate, rotary evaporation is put into 70 DEG C of vacuum ovens and dries to constant weight
Obtain the higher intermediate of purity.Intermediate is weighed in three-necked flask, solvent methanol wiring solution-forming, the methanol of addition is added
It is 3mL/g with intermediate volume mass ratio, then weighs the methanol solution of NaOH, wherein the volume mass of methanol and inorganic base ratio is
7mL/g, NaOH and intermediate molar ratio are 1.2:1, react 16h at room temperature, filter and remove NaBr solid, and filtrate revolving removes
Most of methanol is added Diethyl ether recrystallization and unreacted solution NaOH and NaBr is precipitated, is dried under vacuum to constant weight after revolving to obtain the final product
To the higher ionic liquid of purity (ionic liquid 6).
3.5wt% polyethylene of dispersing agent alcohol solution 100mL is added in the four-hole boiling flask of 1000ml, is heated to 80 DEG C,
Entering 94.11g xylenol, 92.25g formaldehyde, 6.0wt% ionic liquid (6), 500ml deionized water is heated to 75 DEG C,
1.5h is stirred under 00r/min mixing speed.It is constant to be kept stirring speed, 4.0wt% hexamethylenetetramine curing agent is added and delays
Slowly 95 DEG C are warming up to, finally this mixing speed and at a temperature of react 4h, reaction terminating.It is unloaded after reaction temperature is reduced to room temperature
Material, is washed repeatedly with deionized water, until upper solution is limpid, is then filtered, and dry 4h, can be obtained phenolic aldehyde at 120 DEG C
Resin balls.Weighing phenolic resin microspheres quality is 65.32g, the following accounting 7.7% of the small ball's diameter 0.3mm, 0.3~0.5mm of diameter
Accounting 76%, 0.5mm or more accounting 16.3%, total recovery 85%.
Embodiment 7:
Alkali ionic liquid is carried out by the condition of example 4 and reuses test, and wherein alkali ionic liquid (4) is that recycling makes
With, and the fresh ionic liquid (4) of 5% (on the basis of ionic liquid quality) is supplemented, other conditions are constant.The results are shown in Table 1,
Alkali ionic liquid is repeated 4 times, and catalytic performance does not change much.
Since ionic liquid during reaction is as catalyst, after the separation of product bead, it is mainly water in liquid, does not have on a small quantity
There are the phenol and formaldehyde, ionic liquid of reaction, after freezing, most of alkali ionic liquid can crystallize precipitation, and structure does not have
It is destroyed, also there is same catalytic effect.
Table 1
| Bead total recovery % | Diameter < 0.3mm | 0.3~0.5mm of diameter | Diameter > 0.5mm | |
| Fresh ionic liquid | 91.3% | 3.7% | 81.3% | 15.0% |
| It reuses 1 time | 90.8% | 4.3% | 80.6% | 15.1% |
| It reuses 2 times | 89.9% | 3.8% | 79.7% | 16.5% |
| It reuses 3 times | 89.6% | 3.2% | 79.2% | 17.6% |
| It reuses 4 times | 88.9% | 4.3% | 78.4% | 17.3% |
Comparative example 1
By the experimental condition of embodiment 4, alkali ionic liquid (4) is changed to ammonium hydroxide, condensation reaction time extends to 16h.
That is: 3.5wt% polyethylene of dispersing agent alcohol solution 100mL is added in the four-hole boiling flask of 1000ml, is heated to 80 DEG C, adds
94.11g phenol, 97.77g formaldehyde, 5.0wt% ammonium hydroxide, 500ml deionized water are stirred at 200r/min at that same temperature
Mix 16 hours of condensation reaction.After reaction, 4.0wt% hexamethylenetetramine curing agent is added and is to slowly warm up to 95 DEG C,
4h, reaction terminating are finally reacted at this temperature.Phenolic resin bead is obtained by filtration, dry 4h, can be obtained phenol at 120 DEG C
Urea formaldehyde bead product.Weighing phenolic resin microspheres quality is 49.12g, the following accounting 20.1% of the small ball's diameter 0.3mm, diameter
0.3~0.5mm accounting 50.1%, 0.5mm or more accounting 29.8%, total recovery 54%.
Comparative example 2
Use Carboxyl-functional Ionic Liquid as catalyst preparation phenolic resin bead, specifically:
3.5wt% polyethylene of dispersing agent alcohol solution 100mL is added in the four-hole boiling flask of 1000ml, is heated to 80 DEG C,
Add 94.11g phenol, 97.77g formaldehyde, 5.0wt% ionic liquid 1- carboxyethyl -3- methyl imidazolium tetrafluoroborate,
500ml deionized water stirs 4h under 200r/min mixing speed at that same temperature；Six methine four of 4.0wt% is added
Amine hardener is simultaneously to slowly warm up to 95 DEG C, finally this mixing speed and at a temperature of react 4h, reaction terminating, without phenolic resin
Ball occurs.
Claims (8)
1. a kind of method using caprolactam class ionic liquid as catalyst preparation phenolic resin, it is characterised in that: described
Method prepares phenolic resin bead with formaldehyde condensation reaction using caprolactam class ionic liquid as catalyst phenol.
2. method of the caprolactam class ionic liquid as catalyst preparation phenolic resin is used as described in claim 1,
Be characterized in that: the method specific steps are as follows:
Poly-vinyl alcohol solution is added in four-hole boiling flask, is heated to 80 DEG C, sequentially adds phenol, formaldehyde and caprolactam class ion
Liquid catalyst is stirred and heated to 60 DEG C~90 DEG C progress condensation reactions, condensation reaction time 1~4 hour, then adds six
Methine tetramine is warming up to 95 DEG C and continues stirring 4 hours, isolates phenolic resin bead while hot, filtrate be cooled to 10 DEG C hereinafter,
Caprolactam class ionic liquid is automatically subjected to phase splitting with water, isolates caprolactam class ionic liquid reuse.
3. method of the caprolactam class ionic liquid as catalyst preparation phenolic resin is used as described in claim 1,
Be characterized in that: the molar ratio of the phenol, formaldehyde and caprolactam class ionic-liquid catalyst be 1:1.2~1.6:0.01~
0.06。
4. method of the caprolactam class ionic liquid as catalyst preparation phenolic resin is used as described in claim 1,
Be characterized in that: the phenol is phenol, Resorcino, 2, one in 4,6- trimethyls-phenol, p-methyl phenol or xylenol
Kind.
5. method of the caprolactam class ionic liquid as catalyst preparation phenolic resin is used as described in claim 1,
It is characterized in that: the Caprolactam basic ionic liquid, general formula are as follows:
Wherein, n is the integer of 1-8, and R is H or C1-C12Alkyl.
6. method of the caprolactam class ionic liquid as catalyst preparation phenolic resin is used as described in claim 1,
Be characterized in that: the Caprolactam basic ionic liquid the preparation method is as follows:
(1) caprolactam substance and halogenated alkane are dissolved in acetonitrile solvent according to the molar ratio of 1.0:0.5~2, N2In atmosphere
Then intermediate is washed away its unreacted solution through ethyl acetate and ether by synthetic intermediate, rotary evaporation obtain purity compared with
High intermediate, wherein solvent quality be caprolactam substance quality 10%~50%, synthesis reaction temperature be 70~
120 DEG C, synthesising reacting time is 4~12h；
(2) intermediate is dissolved in methanol, then reacts 12~28h at room temperature with inorganic alkali alcosol and acyl in oneself is prepared
Amine ionic liquid, wherein the volume mass of intermediate and methanol ratio is 1~4ml/g, the volume mass ratio of methanol and inorganic base
5~8ml/g.
7. method of the caprolactam class ionic liquid as catalyst preparation phenolic resin is used as claimed in claim 6,
Be characterized in that: caprolactam substance described in step (1) be caprolactam, N- methyl caprolactam, N- ethylcaprolactam,
Any one in N- propyl caprolactam, N- amyl caprolactam or N- hexyl caprolactam or compound；Described is halogenated
Alkane is CnH2n+1- X or RX, wherein X is halogen, and R is H or C1-C12Alkyl.
8. method of the caprolactam class ionic liquid as catalyst preparation phenolic resin is used as claimed in claim 6,
Be characterized in that: inorganic base described in step (2) is NaOH, KOH, NaHCO3、KHCO3Or Ca (OH)2One of or at least
Two kinds of mixtures.
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