CN104014368B - A kind of condensation polymer type pearl macroporous resin catalyst and preparation method thereof - Google Patents
A kind of condensation polymer type pearl macroporous resin catalyst and preparation method thereof Download PDFInfo
- Publication number
- CN104014368B CN104014368B CN201410267373.5A CN201410267373A CN104014368B CN 104014368 B CN104014368 B CN 104014368B CN 201410267373 A CN201410267373 A CN 201410267373A CN 104014368 B CN104014368 B CN 104014368B
- Authority
- CN
- China
- Prior art keywords
- parts
- polymer type
- condensation polymer
- catalyst
- macroporous resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Phenolic Resins Or Amino Resins (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The present invention relates to a kind of condensation polymer type pearl macroporous resin catalyst and preparation method thereof, belong to technical field of polymer materials.The resin catalyst of the present invention includes following raw materials by weight: tripolycyanamide 15 25 parts, 35 50 parts of formaldehyde, polyhydric phenols 5 10 parts, solid catalyst 20 30 parts, porogen 5 10 parts, distilled water 5 10 parts, disperse medium 300 500 parts, Ba Lafu network 35 parts.Condensation polymer type pearl macroporous resin of the present invention can embed polytype solid catalyst, the condensation polymer type pearl macroporous resin catalyst of the present invention directly uses tripolycyanamide to be synthesis material, it is effectively improved the mechanical strength of resin, increases the service life of this resin catalyst.Additionally, due to the employing of porogen, make the resin catalyst of preparation have macroporosity, improve the catalytic efficiency of resin catalyst.
Description
Technical field
The present invention relates to a kind of resin catalyst and preparation method thereof, it is more particularly related to a kind of condensation polymer type
Pearl macroporous resin catalyst and preparation method thereof, belongs to technical field of polymer materials.
Background technology
Condensation polymer type ion exchange resin is class exploitation relatively morning, the ion exchanging function macromolecule material that application is the widest
Material.It is widely used in the industries such as water process, medical industry, food industry at present.
This resinoid is prepared as main preparation methods by polycondensation reaction technique.Condensation resin is to use earlier
Bulk technique first makes bulk polymer, more size-reduced, sieve, obtain amorphous granular.Obtained by this kind of preparation method
Resin be not pearl because of shape, hydraulic performance is poor, is difficult to obtain preferable effect in column operation.Additionally, due to
The monomer that condensation polymer type resin is used is water miscible, it is impossible to adopts and uses water as suspension polymerisation disperse medium to prepare pearl tree
Fat, can only use non-water-soluble medium as disperse medium.All these all giving is prepared condensation polymer type bead-like resin and is brought tired
Difficulty, also makes the research be subject to people's attention, and becomes a research field the most active.
Additionally, solid catalyst is as a big branch of catalysis technical field, due to its in specific catalyst system and catalyzing not
Dissolubility, can make traditional liquid liquid catalytic process become liquid/solid catalytic process, decrease processing step, improves technique effect
Rate.But owing to solid catalyst typically uses with powder, bring inconvenience to technical process.
(Liu Yongning, Shi Zuoqing, Zhang Qing, He Ping Lin, Spherical Macroporous Polycondensate-type Resins synthesis and decoloration performance grind Liu Yongning et al.
Study carefully, ion exchange and absorption, 1990,6(4)), a kind of condensation polymer type resin be applied to sweet with formaldehyde, phenol as Material synthesis
The decolouring of leaf chrysanthemum sweeting agent.This research work explores the synthesis technique of condensation polymer type pearl macroporous resin, and its product is mainly used in
The decolouring of natural materials.Owing to copolymerization component is less, limit the range of application of product.UNITICA company of Japan is by phenol, first
Aldehyde and imino group ethanedioic acid utilize Mannish that O-hydroxyl benzyl group imino group ethanedioic acid base be synthesized to obtain, more common with phenol, formaldehyde
The aqueous solution of the poly-monomer prepared is dispersed in suspension within organic media halogenated hydrocarbons constantly steaming moisture from spheroid through polycondensation process,
Directly form spherical condensation polymer type chelating resin.Wang Jiaxing et al. (Wang Jiaxing, Yu Renrong, " powder embedding " type ion exchange resin
Research, ion exchange and absorption, 1992,8(3)), with formaldehyde, tripolycyanamide as Material synthesis, one can embed powder
The condensation resin of chemical substance.The major defect one of this resin is that intensity is poor, is in use easily broken, and service life is short；
Two are the failure to be prepared as macroporous type, and resin service efficiency is poor.
The preparation method of above-mentioned resin is for the purpose of preparing ion exchange resin, but product exists number of drawbacks, due to contracting
In interpolymer system, the existence of pressed powder, brings difficulty to polymerization technique.
Summary of the invention
Present invention seek to address that the problem of condensed macropore resin in prior art, it is provided that a kind of condensation polymer type pearl macropore tree
Fat catalyst, solid catalyst can be embedded in wherein, have the function of solid catalyst by the resin in this resin catalyst, can
Being widely used in various catalytic field, and intensity is high, service efficiency is high.
For achieving the above object, its concrete technical scheme is as follows:
A kind of condensation polymer type pearl macroporous resin catalyst, it is characterised in that: include following raw materials by weight:
Tripolycyanamide 15-25 part
Formaldehyde 35-50 part
Polyhydric phenols 5-10 part
Solid catalyst 20-30 part
Porogen 5-10 part
Distilled water 5-10 part
Disperse medium 300-500 part
Ba Lafu network 3-5 part.
Preferably, a kind of condensation polymer type pearl macroporous resin catalyst, it is characterised in that: include following in parts by weight
Raw material:
Tripolycyanamide 18-22 part
Formaldehyde 35-45 part
Polyhydric phenols 5-8 part
Solid catalyst 25-28 part
Porogen 8-10 part
Distilled water 8-10 part
Disperse medium 350-450 part
Ba Lafu network 4-5 part.
Polyhydric phenols of the present invention is hydroquinone or resorcinol.
Solid catalyst of the present invention is that the catalyst of this area all solids powder is (such as various metal-oxides
Microgranule, nanoparticle), preferably MgO, TiO2、AuTiO2、Rh/ZrO2。
Porogen of the present invention is NaCl, Na2CO3、CaCl2、NaHCO3、K2SO4, KCl, methanol, n-butyl alcohol or
Isopropanol.
Disperse medium of the present invention is No. 30 machine oil, No. 40 machine oil or silicone oil.
Ba Lafu network (paraflow) of the present invention is the anticoagulant of a kind of lubricating oil, has help water-soluble substances
Scattered effect in oil-phase medium, can be condensed by chlorinated paraffin and naphthalene and form, and is a kind of green and has honorable viscous of reflection
Property oil.
A kind of preparation method of condensation polymer type pearl macroporous resin catalyst, it is characterised in that: comprise the following steps that:
A, weigh tripolycyanamide, formaldehyde, polyhydric phenols, solid catalysis according to the formula of condensation polymer type pearl macroporous resin catalyst
Agent, porogen and distilled water, make each raw material the most miscible with stirring, obtain miscible solution；
B, miscible solution step A obtained are placed in 35-40 DEG C of water-bath, carry out prepolymerization 20-30 minute, obtain pre-polymerization
Close solution system；
C, weigh disperse medium and Ba Lafu network, mix homogeneously, obtain inverse suspension polymerization Medium Oil phase system, reheat
To 40-45 DEG C, pre-polymer solution system step B obtained joins in described inverse suspension polymerization Medium Oil phase system,
Start stirring, be dispersed into bead；
D, the temperature of reaction system being dispersed into bead in step C is risen to 50-60 DEG C, continue stirring, be incubated 10-20min；
Again temperature is risen to 60-70 DEG C, be polymerized, after shaping to be solidified, be incubated 1-2 hour；The most further temperature is risen to 75
DEG C, it is incubated 2-3 hour；Further temperature is risen to 85 DEG C, be incubated 2-3 hour；Finally temperature is risen to 90 DEG C, be incubated 2-3
Hour；
E, the system temperature in step D is risen to 100 DEG C, be incubated 2-4 hour, slough the moisture in reaction system, then
Cool the temperature to 40-50 DEG C, leach resin bead, the resin bead leached is carried out, obtain condensation polymer type pearl macropore tree
Fat catalyst.
The present invention is in step C, and the particle diameter of described bead is 0.2-1.2cm.
The present invention is in step E, and the described detailed process being carried out by the resin bead leached is: use industrial naptha
Resin bead is washed 3-5 time, then the gasoline on resin bead surface is air-dried at room temperature, finally wash with surfactant solution
Wash resin bead 3-5 time.
Beneficial effects of the present invention shows:
1, present invention seek to address that the condensation resin intensity that can embed powder chemistry material of the prior art is poor,
In use being easily broken, service life is short, the problem that resin service efficiency is poor.Condensation polymer type pearl macropore of the present invention
Resin can embed polytype solid catalyst, then possesses different catalysis, is applied to various technical process, the present invention
Condensation polymer type pearl macroporous resin catalyst directly use tripolycyanamide to be synthesis material, improve condensed macropore dropwise resin urge
In agent while the content of amido, moreover it is possible to be effectively improved the mechanical strength of resin, increase the service life of this resin catalyst.
Additionally, due to the employing of porogen, make the resin catalyst of preparation have macroporosity, improve the catalytic efficiency of resin catalyst.
Additionally, product is pearl, having good hydrodynamic performance, and processing technology is simple, cost is relatively low, expands application model
Enclose.
2, condensation polymer type pearl macroporous resin of the present invention can embed polytype solid catalyst, then possesses not
Same catalysis, is applied to various technical process.The present invention while preparing condensation polymer type pearl macroporous resin by solid catalysis
Agent embeds wherein, is successfully uniformly fixed on inside resin by solid catalyst, and the existence of porogen makes resin have macropore in addition
Performance, accelerates the transmission speed of catalysis object, improves the catalytic efficiency of system.The present invention uses polyhydric phenols single as the 3rd
Body, significantly increases the reactivity of polycondensation reaction, makes polymerization system energy rapid polymerization；It addition, with the addition of porogen, greatly carry
The high catalytic rate of resin.
3, the present invention is from macromolecule molecular design theory, utilizes Mannish to react, and uses the contracting of macromolecule anti-phase suspension
Close polymerization technique, be basic polymer raw with tripolycyanamide, formaldehyde and polyhydric phenols, embed solid catalyst, with machine oil or silicone oil
For disperse medium, with NaCl, Na2CO3、CaCl2, methanol, n-butyl alcohol or isopropanol be porogen, one-step polymerization reaction i.e. synthesizes
Go out condensation polymer type pearl macroporous resin catalyst.By prepolymerization, polymerization two-step method, effectively control the viscosity of pre-polymerization liquid, successfully will
Solid catalyst is uniformly distributed in polymerization system；The polymerization system liquid being scattered in oil-phase medium is made by reversed-phase polymerization technique
Pearl polymerizing curable, prepares the resin with catalysis that intensity is good, macroporous type is embedded with solid catalyst, for preparation embedding
Resin opens up a new way.
4, the present invention can be easily changed by mixing speed by the selection of polymerization technique and regulate resin bead
Particle diameter；On the other hand, condensation polymer type pearl macroporous resin can be conveniently adjusted by the change of the proportioning of raw materials various in formula
The pore structure parameters such as the content of middle tripolycyanamide, formaldehyde and polyhydric phenols and specific surface area, cell size and aperture, so that prepared
Condensation polymer type pearl macroporous resin have wider application surface and the suitability.
Detailed description of the invention
Embodiment 1
A kind of condensation polymer type pearl macroporous resin catalyst, including following raw materials by weight:
Tripolycyanamide 15 parts
35 parts of formaldehyde
Polyhydric phenols 5 parts
Solid catalyst 20 parts
Porogen 5 parts
Distilled water 5 parts
Disperse medium 300 parts
Ba Lafu network 3 parts.
Embodiment 2
A kind of condensation polymer type pearl macroporous resin catalyst, including following raw materials by weight:
Tripolycyanamide 25 parts
50 parts of formaldehyde
Polyhydric phenols 10 parts
Solid catalyst 30 parts
Porogen 10 parts
Distilled water 10 parts
Disperse medium 500 parts
Ba Lafu network 5 parts.
Embodiment 3
A kind of condensation polymer type pearl macroporous resin catalyst, including following raw materials by weight:
Tripolycyanamide 20 parts
42.5 parts of formaldehyde
Polyhydric phenols 7.5 parts
Solid catalyst 25 parts
Porogen 7.5 parts
Distilled water 7.5 parts
Disperse medium 400 parts
Ba Lafu network 4 parts.
Embodiment 4
A kind of condensation polymer type pearl macroporous resin catalyst, including following raw materials by weight:
Tripolycyanamide 21 parts
48 parts of formaldehyde
Polyhydric phenols 6.5 parts
Solid catalyst 23 parts
Porogen 9.5 parts
Distilled water 5.8 parts
Disperse medium 398 parts
Ba Lafu network 4.7 parts.
Embodiment 5
A kind of condensation polymer type pearl macroporous resin catalyst, including following raw materials by weight:
Tripolycyanamide 18 parts
35 parts of formaldehyde
Polyhydric phenols 5 parts
Solid catalyst 25 parts
Porogen 8 parts
Distilled water 8 parts
Disperse medium 350 parts
Ba Lafu network 4 parts.
Embodiment 6
A kind of condensation polymer type pearl macroporous resin catalyst, including following raw materials by weight:
Tripolycyanamide 22 parts
45 parts of formaldehyde
Polyhydric phenols 8 parts
Solid catalyst 28 parts
Porogen 10 parts
Distilled water 10 parts
Disperse medium 450 parts
Ba Lafu network 5 parts.
Embodiment 7
A kind of condensation polymer type pearl macroporous resin catalyst, including following raw materials by weight:
Tripolycyanamide 20 parts
40 parts of formaldehyde
Polyhydric phenols 6.5 parts
Solid catalyst 26.5 parts
Porogen 9 parts
Distilled water 9 parts
Disperse medium 400 parts
Ba Lafu network 4.5 parts.
Embodiment 8
A kind of condensation polymer type pearl macroporous resin catalyst, including following raw materials by weight:
Tripolycyanamide 19 parts
42 parts of formaldehyde
Polyhydric phenols 5.9 parts
Solid catalyst 27 parts
Porogen 9.6 parts
Distilled water 8.1 parts
Disperse medium 440 parts
Ba Lafu network 4.25 parts.
Embodiment 9
On the basis of embodiment 1-8, preferably:
Described polyhydric phenols is hydroquinone or resorcinol.
Described solid catalyst is MgO, TiO2、AuTiO2、Rh/ZrO2。
Described porogen is NaCl, Na2CO3、CaCl2、NaHCO3、K2SO4, KCl, methanol, n-butyl alcohol or isopropanol.
Described disperse medium is No. 30 machine oil, No. 40 machine oil or silicone oil.
Embodiment 10
A kind of condensation polymer type pearl macroporous resin catalyst, including following raw materials by weight:
Tripolycyanamide 15 parts
35 parts of formaldehyde
Hydroquinone 10 parts
MgO 25 parts
NaCl 5 parts
Distilled water 5 parts
350 parts of No. 30 machine oil
Ba Lafu network 3 parts.
Embodiment 11
A kind of condensation polymer type pearl macroporous resin catalyst, including following raw materials by weight:
Tripolycyanamide 20 parts
45 parts of formaldehyde
Hydroquinone 10 parts
TiO2 20 parts
Isopropanol 10 parts
Distilled water 10 parts
500 parts of No. 40 machine oil
Ba Lafu network 5 parts.
Embodiment 12
A kind of condensation polymer type pearl macroporous resin catalyst, including following raw materials by weight:
Tripolycyanamide 25 parts
45 parts of formaldehyde
Resorcinol 8 parts
AuTiO230 parts
Na2CO36 parts
Distilled water 8 parts
Silicone oil 350 parts
Ba Lafu network 4 parts
Embodiment 13
The preparation method of a kind of condensation polymer type pearl macroporous resin catalyst, comprises the following steps that:
A, weigh tripolycyanamide, formaldehyde, polyhydric phenols, solid catalysis according to the formula of condensation polymer type pearl macroporous resin catalyst
Agent, porogen and distilled water, make each raw material the most miscible with stirring, obtain miscible solution；
B, miscible solution step A obtained are placed in 35 DEG C of water-baths, carry out prepolymerization 20 minutes, obtain pre-polymer solution
System；
C, weigh disperse medium and Ba Lafu network, mix homogeneously, obtain inverse suspension polymerization Medium Oil phase system, reheat
To 40 DEG C, pre-polymer solution system step B obtained joins in described inverse suspension polymerization Medium Oil phase system, starts
Stirring, is dispersed into bead；
D, the temperature of reaction system being dispersed into bead in step C is risen to 50 DEG C, continue stirring, be incubated 10min；Again by temperature
Degree rises to 60 DEG C, is polymerized, after shaping to be solidified, is incubated 1 hour；The most further temperature rising to 75 DEG C, insulation 2 is little
Time；Further temperature is risen to 85 DEG C, be incubated 2 hours；Finally temperature is risen to 90 DEG C, be incubated 2 hours；
E, the system temperature in step D is risen to 100 DEG C, be incubated 2 hours, slough the moisture in reaction system, then will
Temperature is down to 40 DEG C, leaches resin bead, is carried out by the resin bead leached, and obtains the catalysis of condensation polymer type pearl macroporous resin
Agent.
Preferred:
In step C, the particle diameter of described bead is 0.2cm.
In step E, the described detailed process being carried out by the resin bead leached is: with industrial naptha to resin
Bead is washed 3 times, then is air-dried at room temperature by the gasoline on resin bead surface, finally with surfactant solution washing resin pearl
Body 3 times.
Embodiment 14
The preparation method of a kind of condensation polymer type pearl macroporous resin catalyst, comprises the following steps that:
A, weigh tripolycyanamide, formaldehyde, polyhydric phenols, solid catalysis according to the formula of condensation polymer type pearl macroporous resin catalyst
Agent, porogen and distilled water, make each raw material the most miscible with stirring, obtain miscible solution；
B, miscible solution step A obtained are placed in 40 DEG C of water-baths, carry out prepolymerization 30 minutes, obtain pre-polymer solution
System；
C, weigh disperse medium and Ba Lafu network, mix homogeneously, obtain inverse suspension polymerization Medium Oil phase system, reheat
To 45 DEG C, pre-polymer solution system step B obtained joins in described inverse suspension polymerization Medium Oil phase system, starts
Stirring, is dispersed into bead；
D, the temperature of reaction system being dispersed into bead in step C is risen to 60 DEG C, continue stirring, be incubated 20min；Again by temperature
Degree rises to 70 DEG C, is polymerized, after shaping to be solidified, is incubated 2 hours；The most further temperature rising to 75 DEG C, insulation 3 is little
Time；Further temperature is risen to 85 DEG C, be incubated 3 hours；Finally temperature is risen to 90 DEG C, be incubated 3 hours；
E, the system temperature in step D is risen to 100 DEG C, be incubated 4 hours, slough the moisture in reaction system, then will
Temperature is down to 50 DEG C, leaches resin bead, is carried out by the resin bead leached, and obtains the catalysis of condensation polymer type pearl macroporous resin
Agent.
Preferred:
In step C, the particle diameter of described bead is 1.2cm.
In step E, the described detailed process being carried out by the resin bead leached is: with industrial naptha to resin
Bead is washed 5 times, then is air-dried at room temperature by the gasoline on resin bead surface, finally with surfactant solution washing resin pearl
Body 5 times.
Embodiment 15
The preparation method of a kind of condensation polymer type pearl macroporous resin catalyst, comprises the following steps that:
A, weigh tripolycyanamide, formaldehyde, polyhydric phenols, solid catalysis according to the formula of condensation polymer type pearl macroporous resin catalyst
Agent, porogen and distilled water, make each raw material the most miscible with stirring, obtain miscible solution；
B, miscible solution step A obtained are placed in 37.5 DEG C of water-baths, carry out prepolymerization 25 minutes, obtain prepolymerization molten
Liquid system；
C, weigh disperse medium and Ba Lafu network, mix homogeneously, obtain inverse suspension polymerization Medium Oil phase system, reheat
To 42.5 DEG C, pre-polymer solution system step B obtained joins in described inverse suspension polymerization Medium Oil phase system, opens
Dynamic stirring, is dispersed into bead；
D, the temperature of reaction system being dispersed into bead in step C is risen to 55 DEG C, continue stirring, be incubated 15min；Again by temperature
Degree rises to 65 DEG C, is polymerized, after shaping to be solidified, is incubated 1.5 hours；The most further temperature is risen to 75 DEG C, be incubated 2.5
Hour；Further temperature is risen to 85 DEG C, be incubated 2.5 hours；Finally temperature is risen to 90 DEG C, be incubated 2.5 hours；
E, the system temperature in step D is risen to 100 DEG C, be incubated 3 hours, slough the moisture in reaction system, then will
Temperature is down to 45 DEG C, leaches resin bead, is carried out by the resin bead leached, and obtains the catalysis of condensation polymer type pearl macroporous resin
Agent.
Preferred:
In step C, the particle diameter of described bead is 0.7cm.
In step E, the described detailed process being carried out by the resin bead leached is: with industrial naptha to resin
Bead is washed 4 times, then is air-dried at room temperature by the gasoline on resin bead surface, finally with surfactant solution washing resin pearl
Body 4 times.
Embodiment 16
The preparation method of a kind of condensation polymer type pearl macroporous resin catalyst, comprises the following steps that:
A, weigh tripolycyanamide, formaldehyde, polyhydric phenols, solid catalysis according to the formula of condensation polymer type pearl macroporous resin catalyst
Agent, porogen and distilled water, make each raw material the most miscible with stirring, obtain miscible solution；
B, miscible solution step A obtained are placed in 39 DEG C of water-baths, carry out prepolymerization 21 minutes, obtain pre-polymer solution
System；
C, weigh disperse medium and Ba Lafu network, mix homogeneously, obtain inverse suspension polymerization Medium Oil phase system, reheat
To 41 DEG C, pre-polymer solution system step B obtained joins in described inverse suspension polymerization Medium Oil phase system, starts
Stirring, is dispersed into bead；
D, the temperature of reaction system being dispersed into bead in step C is risen to 52 DEG C, continue stirring, be incubated 18min；Again by temperature
Degree rises to 66.5 DEG C, is polymerized, after shaping to be solidified, is incubated 1.25 hours；The most further temperature is risen to 75 DEG C, insulation
2.75 hour；Further temperature is risen to 85 DEG C, be incubated 2.25 hours；Finally temperature is risen to 90 DEG C, be incubated 2.8 hours；
E, the system temperature in step D is risen to 100 DEG C, be incubated 3.25 hours, slough the moisture in reaction system, then
Cool the temperature to 47 DEG C, leach resin bead, the resin bead leached is carried out, obtain condensation polymer type pearl macroporous resin and urge
Agent.
Preferred:
In step C, the particle diameter of described bead is 0.35cm.
In step E, the described detailed process being carried out by the resin bead leached is: with industrial naptha to resin
Bead is washed 4 times, then is air-dried at room temperature by the gasoline on resin bead surface, finally with surfactant solution washing resin pearl
Body 5 times.
Claims (8)
1. a condensation polymer type pearl macroporous resin catalyst, it is characterised in that: include following raw materials by weight:
Tripolycyanamide 15-25 part
Formaldehyde 35-50 part
Polyhydric phenols 5-10 part
Solid catalyst 20-30 part
Porogen 5-10 part
Distilled water 5-10 part
Disperse medium 300-500 part
Ba Lafu network 3-5 part；
The preparation method of described condensation polymer type pearl macroporous resin catalyst, it is characterised in that: comprise the following steps that:
A, weigh according to the formula of condensation polymer type pearl macroporous resin catalyst tripolycyanamide, formaldehyde, polyhydric phenols, solid catalyst,
Porogen and distilled water, make each raw material the most miscible with stirring, obtain miscible solution；
B, miscible solution step A obtained are placed in 35-40 DEG C of water-bath, carry out prepolymerization 20-30 minute, obtain prepolymerization molten
Liquid system；
C, weigh disperse medium and Ba Lafu network, mix homogeneously, obtain inverse suspension polymerization Medium Oil phase system, be again heated to
40-45 DEG C, pre-polymer solution system step B obtained joins in described inverse suspension polymerization Medium Oil phase system, opens
Dynamic stirring, is dispersed into bead；
D, the temperature of reaction system being dispersed into bead in step C is risen to 50-60 DEG C, continue stirring, be incubated 10-20min；Again will
Temperature rises to 60-70 DEG C, is polymerized, and after shaping to be solidified, is incubated 1-2 hour；The most further temperature is risen to 75 DEG C, protect
Temperature 2-3 hour；Further temperature is risen to 85 DEG C, be incubated 2-3 hour；Finally temperature is risen to 90 DEG C, be incubated 2-3 hour；
E, the system temperature in step D is risen to 100 DEG C, be incubated 2-4 hour, slough the moisture in reaction system, then by temperature
Degree is down to 40-50 DEG C, leaches resin bead, is carried out by the resin bead leached, obtains condensation polymer type pearl macroporous resin and urge
Agent.
A kind of condensation polymer type pearl macroporous resin catalyst the most according to claim 1, it is characterised in that: include following according to
The raw material of parts by weight meter:
Tripolycyanamide 18-22 part
Formaldehyde 35-45 part
Polyhydric phenols 5-8 part
Solid catalyst 25-28 part
Porogen 8-10 part
Distilled water 8-10 part
Disperse medium 350-450 part
Ba Lafu network 4-5 part.
A kind of condensation polymer type pearl macroporous resin catalyst the most according to claim 1 and 2, it is characterised in that: described many
Unit's phenol is hydroquinone or resorcinol.
A kind of condensation polymer type pearl macroporous resin catalyst the most according to claim 1 and 2, it is characterised in that: described consolidates
Body catalyst is MgO, TiO2、AuTiO2、Rh/ZrO2。
A kind of condensation polymer type pearl macroporous resin catalyst the most according to claim 1 and 2, it is characterised in that: described cause
Hole agent is NaCl, Na2CO3、CaCl2、NaHCO3、K2SO4, KCl, methanol, n-butyl alcohol or isopropanol.
A kind of condensation polymer type pearl macroporous resin catalyst the most according to claim 1 and 2, it is characterised in that: described divides
Dispersion media is No. 30 machine oil, No. 40 machine oil or silicone oil.
A kind of condensation polymer type pearl macroporous resin catalyst the most according to claim 1, it is characterised in that: in step C, institute
The particle diameter of the bead stated is 0.2-1.2cm.
A kind of condensation polymer type pearl macroporous resin catalyst the most according to claim 1, it is characterised in that: in step E, institute
The detailed process being carried out by the resin bead leached stated is: wash resin bead 3-5 time with industrial naptha, then will tree
The gasoline on fat bead surface air-dries at room temperature, finally uses surfactant solution washing resin bead 3-5 time.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410267373.5A CN104014368B (en) | 2014-06-17 | 2014-06-17 | A kind of condensation polymer type pearl macroporous resin catalyst and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410267373.5A CN104014368B (en) | 2014-06-17 | 2014-06-17 | A kind of condensation polymer type pearl macroporous resin catalyst and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104014368A CN104014368A (en) | 2014-09-03 |
| CN104014368B true CN104014368B (en) | 2016-08-24 |
Family
ID=51431532
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410267373.5A Active CN104014368B (en) | 2014-06-17 | 2014-06-17 | A kind of condensation polymer type pearl macroporous resin catalyst and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104014368B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103012703A (en) * | 2012-12-14 | 2013-04-03 | 福建农林大学 | Mid-temperature cured phenolic resin and preparation method thereof |
| CN103319673A (en) * | 2013-05-30 | 2013-09-25 | 山东圣泉化工股份有限公司 | Modification method of melamine formaldehyde resin |
-
2014
- 2014-06-17 CN CN201410267373.5A patent/CN104014368B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103012703A (en) * | 2012-12-14 | 2013-04-03 | 福建农林大学 | Mid-temperature cured phenolic resin and preparation method thereof |
| CN103319673A (en) * | 2013-05-30 | 2013-09-25 | 山东圣泉化工股份有限公司 | Modification method of melamine formaldehyde resin |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104014368A (en) | 2014-09-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Ren et al. | Preparation and characterization of porous chitosan microspheres and adsorption performance for hexavalent chromium | |
| Jin et al. | Temperature and pH responsive hydrogels using methacrylated lignosulfonate cross-linker: synthesis, characterization, and properties | |
| Akelah | Functionalized polymeric materials in agriculture and the food industry | |
| RU2411081C2 (en) | Method of fabricating separation matrix | |
| CN103387629B (en) | A kind of high strength ionic of double hole channel macroporous structure exchanges tree and fat preparation method thereof | |
| JPS5998117A (en) | Manufacture of bridged copolymer beads | |
| WO2014079580A1 (en) | Method for the preparation of macroporous particles and macroporous particles obtained using such a method | |
| CN101670271B (en) | Condensation-type adsorbent resin microballon containing phenolic hydroxyl and preparation method thereof | |
| CN102627718A (en) | Preparation method for crosslinked polystyrene microspheres of 10-100 microns | |
| Ceylan et al. | Swelling–deswelling kinetics of ionic poly (acrylamide) hydrogels and cryogels | |
| CN104356258B (en) | Preparation method of rare earth element modified and aldehyde removed resin and application of rare earth element modified and aldehyde removed resin in ethylene glycol refining | |
| CN105566689B (en) | It is a kind of for starch based aquagel expanded material of sewage disposal and preparation method thereof | |
| CN101531742B (en) | Method for preparing nanometer composite aquagel using nanometer microsphere as junction | |
| Zhu et al. | Effect of Glycerol on the Properties of the Cross‐Linked Polyvinyl Alcohol Hydrogel Beads | |
| Savina et al. | Cryostructuration of polymer systems. XXIV. Poly (vinyl alcohol) cryogels filled with particles of a strong anion exchanger: Properties of the composite materials and potential applications | |
| CN101537375A (en) | Condensed macropore dropwise weak basic ion exchange resin and preparation method thereof | |
| CN104892851B (en) | A kind of preparation method of polymer hollow particles | |
| Guo et al. | Macroporous poly (calcium acrylate− divinylbenzene) bead a selective orthophosphite sorbent | |
| CN104014368B (en) | A kind of condensation polymer type pearl macroporous resin catalyst and preparation method thereof | |
| CN104017151A (en) | Polycondensation bead type macroporous resin extraction agent and preparation method thereof | |
| Zhang et al. | Microfibrillated cellulose reinforced poly (vinyl imidazole) cryogels for continuous removal of heavy metals | |
| Liang et al. | Stereoscopic porous gellan gum-based microspheres as high performance adsorbents for U (VI) removal | |
| Oliveira et al. | In‐Situ Incorporation of Amoxicillin in PVA/PVAc‐co‐PMMA Particles during Suspension Polymerizations | |
| Yamaguchi et al. | Methods for preparation of absorbent microspherical tannin resin | |
| CN102863646B (en) | Preparation method for rosin-based porous polymer microsphere |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |