CN1569334A - Thermostable strong acid cation resin catalyst and its preparing method - Google Patents

Thermostable strong acid cation resin catalyst and its preparing method Download PDF

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CN1569334A
CN1569334A CN 200410008779 CN200410008779A CN1569334A CN 1569334 A CN1569334 A CN 1569334A CN 200410008779 CN200410008779 CN 200410008779 CN 200410008779 A CN200410008779 A CN 200410008779A CN 1569334 A CN1569334 A CN 1569334A
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product
agent
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divinylbenzene
styrene
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CN1240477C (en
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刘文飞
毛进池
张勇
姚远东
吴玉林
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Kairui Environmental Protection Technology Co ltd
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JIZHONG CHEMICAL PLANT CANGZHOU CITY
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Abstract

The present invention solves the problem that the existing strong acid resin catalyst has bad high temperature mechanical intensity and complex hole purification technics, brings forward a simple preparing method for pressurization polymerization and hole purification method, the pressurization polymerization improves the uniformity of polymer bead body structure and the high temperature mechanical stability for resin, the extraction is executed by solvent naphtha first and the boiling is executed by halogeno-alkane, the hole purification method is simplified. The prepared strong acid cation resin catalyst has high temperature resistant and excellent catalytic activity and its high temperature stability is better than same kind of product.

Description

High temperature resistant strong acid cation resin Catalysts and its preparation method
Technical field
The present invention relates to a kind of high temperature resistant strong acid cation resin Catalysts and its preparation method, specifically a kind of uniformity by pressure polymerization process modification polymer Archon, thus significantly improve the manufacture method of the fire resistant resin catalyst of the high-temperature machinery stability of resin and heat endurance.
Background technology
Polystyrene strong resin catalyst has been widely used in organic synthesis industry such as etherificate, hydration, esterification, alkylation.This resinoid catalyst can be divided into constant temperature catalyzing agent and heatproof catalyst according to the difference of serviceability temperature.Its serviceability temperature of heatproof catalyst is 130～200 ℃, and common polystyrene sulfonic acid resin sulfonic group in the time of 120 ℃ just significantly comes off.Therefore, must carry out halogenation, nitrated introducing electron-withdrawing group to phenyl ring, as F, Cl, Br, NO 2Deng.At concrete manufacturing process, many patents are disclosed.As patent JP73-8675 and GB1393594 describe with core by the first polymerization of the monomer of halogenation again sulfonation produce the heatproof resin.But raw material sources are few.
Patent CN1076385A has described and has used the benzene series solvent 130～200 ℃ of processing earlier styrene-divinylbenzene copolymer, uses 3～20 hours hole purification method of Ethanol Treatment again, reaches bromination, process for sulfonation.This patent hole purification method is very complicated.
Patent US4269943 has then described the method for polymer with carbon tetrachloride swelling afterchlorinate, and processing, process for sulfonation and the aftertreatment technology of chlorine ball.This patent aftertreatment technology complexity needs special treatment facility.
Except, mechanical strength of resin that above-mentioned patent is made or high-temperature machinery less stable cause that broken phenomenon appears in resin under the condition of high temperature.
Summary of the invention
Resin high-temperature machinery intensity difference, the hole process for purifying complicated problems of the present invention in order to solve above-mentioned existence proposed a kind of pressure polymerization and the simple preparation method of hole purification method, and made high temperature resistant strong acid cation resin catalyst thus.
In order to achieve the above object, the present invention proposes a kind of high temperature resistant strong acid cation resin catalyst, and its preparation method has two kinds, is divided into the method for using pore-foaming agent and the method for not using pore-foaming agent.Use the preparation method of pore-foaming agent as follows:
(1) carry out the polymerisation of styrene-divinylbenzene under sealing and pressurized state: the oil phase that will comprise the water of water, dispersant and dispersion aids and comprise styrene, divinylbenzene, pore-foaming agent and initator adds polymerization reaction kettle respectively, feeding compressed air or nitrogen to the reactor gas-phase space remains under the barotropic state less than 1.0Mpa the gas phase gauge pressure, carry out suspension polymerisation, make the matrix polymer of resin with better high-temperature machinery stability and heat endurance; Be that 1 weight portion is a benchmark with styrene and divinylbenzene weight sum in the described oil phase, the parts by weight of described pore-foaming agent are: 0.6 〉=pore-foaming agent＞0.
(2) with industrial naptha the product of step (1) is carried out extracting;
(3) product of step (2) is carried out thermophilic digestion adding to depress with halogenated alkane, temperature is 80～120 ℃, and the time is 5～24 hours, and gauge pressure is 0.01MPa～1.0MPa;
(4) with halogenating agent or nitrating agent the product of step (3) is carried out halogenation or nitrated;
(5) with sulfonating agent the product of step (4) is carried out sulfonation;
(6) product to step (5) is washed till neutrality with hot pure water.
Do not use the preparation method of pore-foaming agent as follows:
(1) carry out the polymerisation of styrene-divinylbenzene under sealing and pressurized state: the oil phase that will comprise the water of water, dispersant and dispersion aids and comprise styrene, divinylbenzene and initator adds polymerization reaction kettle respectively, feeding compressed air or nitrogen to the reactor gas-phase space remains under the barotropic state less than 1.0Mpa the gas phase gauge pressure, carry out suspension polymerisation, make the matrix polymer of resin with better high-temperature machinery stability and heat endurance;
(2) product of step (1) is carried out thermophilic digestion adding to depress with halogenated alkane, temperature is 80～120 ℃, and the time is 5～24 hours, and gauge pressure is 0.01MPa～1.0MPa;
(3) with halogenating agent or nitrating agent the product of step (2) is carried out halogenation or nitrated;
(4) with sulfonating agent the product of step (3) is carried out sulfonation;
(5) product to step (4) is washed till neutrality with hot pure water.
Preparation method of the present invention is described in further detail as follows:
(1) prepares water and oil phase adding polymerization reaction kettle respectively according to following prescription, in reactor, feed clean compressed air or nitrogen, and the maintenance gaseous pressure is 0.01～1.0MPa in whole polymerization process, be warming up to 80 ℃, be incubated 10 hours, be warming up to 95～100 ℃ again, be incubated 12 hours.Through washing, dry, screening, collecting granularity is the ball of 0.35～1.12mm.
Described water constitutes: pure water 1000 weight portions, dispersant 0.5～5.0 weight portion, dispersion aids 0.01～0.5 weight portion;
Be that 1 weight portion is a benchmark with styrene and divinylbenzene weight sum in the described oil phase, each component and weight portion thereof are: styrene 0.70～0.98 weight portion, divinylbenzene 0.02～0.30 weight portion, pore-foaming agent 0～0.60 weight portion, initator 0.003～0.01 weight portion.
Described oil phase and water weight ratio are 1: 3～6.
Described dispersant is a gelatin, and described dispersion aids is a magnesium carbonate.
Described pore-foaming agent be white oil, liquid wax, solid wax, toluene or in them more than a kind of mixture, the weight ratio of following mixture is:
White oil: Gu wax is 4～12: 0～1,
Liquid wax: Gu wax is 4～12: 0～1,
White oil: toluene is 3～10: 0～1.
Described initator is a benzoyl peroxide.
In the preparation method who uses pore-foaming agent, add industrial naptha, preferred 120 to above-mentioned qualified ball #Industrial naptha, extracting goes out pore-foaming agent.
(2) in the thermophilic digestion process, the product that obtains to the step in front adds the halogenated alkane of 5 times of volumes, boiling under certain pressure.Used alkyl halide is that dichloroethanes, carbon tetrachloride, dichloroethanes and carbon tetrachloride are 2～6: 0.5～1 mixture of forming with weight ratio.Boiling temperature is 80～120 ℃, and gauge pressure is 0.01～1.0MPa, and the time is 5～24 hours.
(3) product with boiling carries out chlorination, bromination or nitrated with traditional technology.
The preferred chlorine of described halogenating agent, bromine or fluorine gas;
The mixed acid of the preferred nitric acid of described nitrating agent, nitrous acid, nitrate, nitrite or nitric acid and sulfuric acid, wherein HNO 3: H 2SO 4Be 2～15%: 50～98%, all the other are H 2O.
Preferred 0 ℃～20 ℃ of described halogenation, nitrated temperature.
For example, temperature was reduced to 0 ℃～15 ℃ after boiling was finished, add the Catalyzed by Anhydrous Aluminium Chloride agent then, slowly add bromine down or feed chlorine or the mixed acid of adding sulfuric acid and nitric acid at 5～15 ℃, and under this temperature, reacted 6 hours, elimination dichloroethanes mother liquor, and with dichloroethanes washing three times, phenyl ring totally by bromination or chlorination or nitrated styrene cross-linked copolymer.
(4) sulfonation is carried out in halogenation or nitrated product.
Described sulfonating agent preferred mass percent concentration is 100～106% oleum or sulfur trioxide;
For example use 105% oleum in 110 ℃ of following sulfonation 20 hours, slowly add pure water and be diluted to sulfuric acid concentration less than 5%, massive laundering is to neutral.
(5) product with sulfonation added boiling pure water 24 hours in the reactor of reflux condenser is housed, and was washed till neutrality again and promptly got phenyl ring by halogenation or nitrated high temperature resistant strong acid cation resin product.
The product that the present invention obtains can be used in the propylene hydration preparing isopropanol, processes such as butene-1 hydration system sec-butyl alcohol, alkylation, nonyl phenol conversion.
The present invention has following characteristics:
1. adopt pressure polymerization technology, improved the gaseous phase partial pressure of each monomer component in the polymerization process, reduce the change of the part dispersion liquid pearl prescription that volatilization-condensation because of monomer-disperse again causes, thereby improved the uniformity of polymeric beads body structure, improved the high-temperature machinery stability of resin.
2. the polymeric beads body is after solvent extraction, halogenation or nitrated before, lower the temperature behind the thermophilic digestion carrying out under the suspension of halogenated alkane, directly enter halogenation or denitrification step then, not only reached the purpose of removing the low polymer in the polymeric beads body, and simplified operation, reduced cost.
Since copolymer pearl body halogenation or nitrated before low polymer is proposed, make that the post processing of resin is also very simple, only remove remaining acid in the resin with boiling under the pure water normal pressure, be washed till neutral getting final product then, the above hole purification method of this and other patent is diverse.
The specific embodiment
In order to describe resin catalyst of the present invention and preparation method thereof in more detail, further specify with embodiment below, but protection scope of the present invention is not limited to these embodiment.
Embodiment 1
(1) polymerization: in 50 liters polymeric kettle, add 20 liters of pure water, be heated to 45 ℃, under stirring, add 10g magnesium carbonate, 20g gelatin and 0.15g methine orchid respectively, stir evenly the back and add by 3kg styrene, 1kg divinylbenzene, 20g benzoyl peroxide the oil phase that 1kg white oil and 400g toluene mix.The capping still feeds clean compressed air to reactor, and keeping the interior gaseous pressure of still is 0.5 ± 0.05MPa, open and stir, the liquid pearl is transferred to suitable granularity, be warming up to 80 ℃, be incubated 10 hours, filtration, washing, drying, screening obtain the Archon 4.75kg that granularity is 0.315～1.120mm.
(2) solvent extraction: the Archon that step (1) is obtained is with 120# gasoline extracting 5 times, behind the defecation pore-foaming agent, and dry semi-finished product Archon 3.09kg.
(3) dichloroethanes boiling: above-mentioned Archon 3.09kg adding is equipped with in 50 liters of reactors of reflux condenser, adds 15 liters of dichloroethanes again, be warming up to 90 ℃, and kept still internal pressure 0.3MPa 10 hours, be cooled to 15 ℃.
(4) chlorination: add aluminum trichloride (anhydrous) 30g in aforesaid reaction vessel, stirring and dissolving is under 15 ± 3 ℃ in temperature, slowly feeds 3.5kg chlorine, is incubated 5 hours, extracts dichloroethanes out, and washs three times each 15 liters with fresh dichloroethanes.Washing lotion can be recycled after handling.
(5) sulfonation: above-mentioned chlorine ball is added in 50 liters of reactors, add 10kg 105% oleum, be warming up to 110 ℃, be incubated 20 hours, cooling slowly drips pure water, and still is full, extracts 1/3 out, continue to drip pure water, be operated to so that sulfuric acid concentration is less than 5% in the still, a large amount of pure water are washed till neutrality.
(6) resin preliminary treatment: add 30 liters of pure water in the reactor in step (5), normal pressure boiled 20 hours, reduced to normal temperature, be washed till neutrality with pure water again, blowing centrifugally removes surperficial moisture content, promptly get 12.1kg fire resistant resin catalyst finished product, physicochemical property is listed table 1 in.
This resin 10g is packed in the pressure vessel of 100ml liner tetrafluoro, add the 50ml pure water, under 155 ± 1 ℃, be incubated 500 hours, survey the changing down of its resin exchange capacity and ooze and grind rate of small round spheres (mechanical strength), the result lists table 2 in.
This resin catalyst butene-1 hydration qualification test device of packing under certain reaction condition, is measured butylene total conversion and selectivity, and the result lists table 3 in.
Embodiment 2
(1) polymerization: in 50 liters polymeric kettle, add 20 liters of pure water; be heated to 45 ℃; under stirring, add 10g magnesium carbonate, 20g gelatin and 0.15g methine orchid respectively, stir evenly the back and add the oil phase that mixes by 3kg styrene, 1kg divinylbenzene, 20g benzoyl peroxide.The capping still feeds clean compressed air to reactor, and keeping the interior gaseous pressure of still is 0.5 ± 0.05MPa, open and stir, the liquid pearl is transferred to suitable granularity, be warming up to 80 ℃, be incubated 10 hours, filtration, washing, drying, screening obtain the Archon 3.8kg that granularity is 0.315～1.120mm.
(2) dichloroethanes boiling: above-mentioned Archon 3.8kg adding is equipped with in 50 liters of reactors of reflux condenser, adds 15 liters of dichloroethanes again, be warming up to 90 ℃, and kept still internal pressure 0.3MPa 10 hours, be cooled to 15 ℃.
(3) chlorination: add aluminum trichloride (anhydrous) 25g in aforesaid reaction vessel, stirring and dissolving is under 15 ± 3 ℃ in temperature, slowly feeds 3.2kg chlorine, is incubated 5 hours, extracts dichloroethanes out, and washs three times each 15 liters with fresh dichloroethanes.Washing lotion can be recycled after handling.
(4) sulfonation: above-mentioned chlorine ball is added in 50 liters of reactors, add 10kg 105% oleum, be warming up to 110 ℃, be incubated 20 hours, cooling slowly drips pure water, and still is full, extracts 1/3 out, continue to drip pure water, be operated to so that sulfuric acid concentration is less than 5% in the still, a large amount of pure water are washed till neutrality.
(5) resin preliminary treatment: add 30 liters of pure water in the reactor in step (4), normal pressure boiled 20 hours, reduced to normal temperature, was washed till neutrality with pure water again, and blowing centrifugally removes surperficial moisture content, promptly gets 15kg fire resistant resin catalyst finished product.
Detect and evaluate with the resin catalyst finished product of the method identical, list table 1, table 2, table 3 respectively in embodiment 2 with embodiment 1.
Embodiment 3
Except that halogenation technology difference, polymerization, solvent extraction, dichloroethanes boiling, and sulfonation, resin preliminary treatment are all identical with embodiment 1.
The halogenating agent of embodiment 3 is a bromine, its technical process is: the 770g Archon after the dichloroethanes boiling is added in 10 liters of reactors, add the 4kg dichloroethanes again, 8g aluminum trichloride (anhydrous), stirring and dissolving, in temperature is under 15 ± 3 ℃, slowly drip bromine 1.9kg, and under this temperature, be incubated 6 hours, extract dichloroethanes out, and with fresh dichloroethanes washing three times, each 4kg.Washing lotion can be recycled after handling.The gained phenyl ring is carried out sulfonation and preliminary treatment by embodiment 1 identical method again by the styrene-divinylbenzene copolymer of bromination, obtains phenyl ring by the fire resistant resin catalyst of bromination.
Detect and evaluate with the sold resin catalyst of the method identical, list table 1, table 2, table 3 respectively in embodiment 3 with embodiment 1.
Embodiment 4
(1) polymerization and dichloroethanes boiling
Carry out polymerization and dichloroethanes boiling with the method identical with embodiment 2.
(2) nitrated
Pump dichloroethanes, the mixed acid of the nitric acid of the sulfuric acid of adding 20kg 98% and 10.5kg 30% in reactor, under stirring, temperature is controlled at 25-30 ℃, reacts 10 hours, extracts sulfate liquor out.
(3) ball after nitrated is added 10.5kg 102% oleum, be warming up to 110 ℃, be incubated 20 hours, cooling slowly drips pure water, and still is full, extracts 1/3 out, continues to drip pure water, is operated to so that sulfuric acid concentration is less than 5% in the still, and pure water are washed till neutrality in a large number.
(4) resin preliminary treatment: add 30 liters of pure water in the reactor after sulfonation, normal pressure boiled 20 hours, reduced to normal temperature, was washed till neutrality with pure water again, and blowing centrifugally removes surperficial moisture content, promptly gets the itrated fire resistant resin catalyst of 15.7kg phenyl ring finished product.
Comparative example 1
The fire resistant resin catalyst A that the phenyl ring that external certain factory is produced is chlorinated and embodiment 1 identical method detects and evaluates, and lists table 1, table 2, table 3 respectively in.
Comparative example 2
The phenyl ring that domestic certain factory is produced is used the method identical with embodiment 1 to detect and evaluate by the fire resistant resin catalyst B of bromination, lists table 1, table 2, table 3 respectively in.
The physicochemical property of table 1 resin catalyst
Project Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Comparative Examples 1 Comparative Examples 2
Exchange capacity mmol/g (H) the total pore volume ml/g of the apparent density g/ml specific area m that wets 2/ g average pore size μ m oozes mill rate of small round spheres % ???3.37 ???0.77 ???0.0299 ???25.338 ???0.0073 ???99.6 ???3.20 ???0.77 ???0.02531 ???19.354 ???0.0078 ???99.2 ???3.35 ???0.77 ???0.0354 ???27.887 ???0.0080 ???99.0 ???2.98 ???0.80 ???0.02349 ???20.563 ???0.0069 ???99.5 ???3.16 ???0.76 ???0.0444 ???23.459 ???0.0076 ???97.7 ????2.63 ????0.89 ????0.2611 ????25.314 ????0.1003 ????84.3
The heatproof test of table 2 resin catalyst
Project Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Comparative Examples 1 Comparative Examples 2
Exchange capacity mmol/g (H) takes off sulphur speed mmol/g (H) .h * 10 -5Ooze mill rate of small round spheres % and ooze mill intensity reduction percentage % ???3.34 ???6.0 ? ???99.0 ???0.6 ???3.18 ???4.0 ? ???99.0 ???0.2 ???3.32 ???6.0 ? ???98.5 ???0.5 ???2.96 ???4.0 ? ???99.0 ???0.5 ???3.13 ???6.0 ? ???95.4 ???2.3 ???2.61 ???4.0 ? ???82.8 ???1.5
The qualification test of the active butylene hydration system sec-butyl alcohol of table 3 resin catalyst
Reaction condition Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Comparative Examples 1 Comparative Examples 2
Raw material nC 4=content (%) reaction temperature (℃) reaction pressure (Mpa) water alkene is than the average one way nC of LHSV 1/h 4=conversion ratio (%) selectivity % running time/h ???82.07 ???150 ???8.0 ???2∶1 ???1.2 ???6.41 ???98.9 ???600 ????81 ????150 ????6.0 ????1∶1 ????2.0 ????6.53 ????98.9 ????120 ????93.37 ????1?50 ????8.0 ????2∶1 ????1.2 ????10.97 ????98.4 ????500 ????81 ????150 ????6.0 ????1∶1 ????2.0 ????6.74 ????98.8 ????120 ???93.37 ???150 ???8.0 ???2∶1 ???1.2 ???9.33 ???98.9 ???500 ????81 ????150 ????6.0 ????1∶1 ????2.0 ????5.75 ????98.6 ????120
Can find out that by table 1, table 2, table 3 the fire resistant resin catalyst that the present invention makes by technologies such as improvement polymerizations is guaranteeing its catalytic activity and durothermic while, its high-temperature machinery stability is apparently higher than like product, therefore, this resin catalyst will have longer service life than other catalyst in actual applications.

Claims (10)

1. fire resistant and highly acidic cation resin catalyzing agent is characterized in that it is made by following method:
(1) carry out the polymerisation of styrene-divinylbenzene under sealing and pressurized state: the oil phase that will comprise the water of water, dispersant and dispersion aids and comprise styrene, divinylbenzene, pore-foaming agent and initator adds polymerization reaction kettle respectively, feeding compressed air or nitrogen to the reactor gas-phase space remains under the barotropic state less than 1.0Mpa the gas phase gauge pressure, carry out suspension polymerisation, make the matrix polymer of resin with better high-temperature machinery stability and heat endurance; Be that 1 weight portion is a benchmark with styrene and divinylbenzene weight sum in the described oil phase, the parts by weight of described pore-foaming agent are: 0.6 〉=pore-foaming agent＞0.
(2) with industrial naptha the product of step (1) is carried out extracting;
(3) product of step (2) is carried out thermophilic digestion adding to depress with halogenated alkane, temperature is 80～120 ℃, and the time is 5～24 hours, and gauge pressure is 0.01MPa～1.0MPa;
(4) with halogenating agent or nitrating agent the product of step (3) is carried out halogenation or nitrated;
(5) with sulfonating agent the product of step (4) is carried out sulfonation;
(6) product to step (5) is washed till neutrality with hot pure water.
2. fire resistant and highly acidic cation resin catalyzing agent is characterized in that it is made by following method:
(1) carry out the polymerisation of styrene-divinylbenzene under sealing and pressurized state: the oil phase that will comprise the water of water, dispersant and dispersion aids and comprise styrene, divinylbenzene and initator adds polymerization reaction kettle respectively, feeding compressed air or nitrogen to the reactor gas-phase space remains under the barotropic state less than 1.0Mpa the gas phase gauge pressure, carry out suspension polymerisation, make the matrix polymer of resin with better high-temperature machinery stability and heat endurance;
(2) product of step (1) is carried out thermophilic digestion adding to depress with halogenated alkane, temperature is 80～120 ℃, and the time is 5～24 hours, and gauge pressure is 0.01MPa～1.0MPa;
(3) with halogenating agent or nitrating agent the product of step (2) is carried out halogenation or nitrated;
(4) with sulfonating agent the product of step (3) is carried out sulfonation;
(5) product to step (4) is washed till neutrality with hot pure water.
3. the preparation method of fire resistant and highly acidic cation resin catalyzing agent is characterized in that may further comprise the steps:
(1) carry out the polymerisation of styrene-divinylbenzene under sealing and pressurized state: the oil phase that will comprise the water of water, dispersant and dispersion aids and comprise styrene, divinylbenzene, pore-foaming agent and initator adds polymerization reaction kettle respectively, feeding compressed air or nitrogen to the reactor gas-phase space remains under the barotropic state less than 1.0Mpa the gas phase gauge pressure, carry out suspension polymerisation, make the matrix polymer of resin with better high-temperature machinery stability and heat endurance; Be that 1 weight portion is a benchmark with styrene and divinylbenzene weight sum in the described oil phase, the parts by weight of described pore-foaming agent are: 0.6 〉=pore-foaming agent＞0.
(2) with industrial naptha the product of step (1) is carried out extracting;
(3) product of step (2) is carried out thermophilic digestion adding to depress with halogenated alkane;
(4) with halogenating agent or nitrating agent the product of step (3) is carried out halogenation or nitrated;
(5) with sulfonating agent the product of step (4) is carried out sulfonation;
(6) product to step (5) is washed till neutrality with hot pure water.
4. the preparation method of fire resistant and highly acidic cation resin catalyzing agent is characterized in that may further comprise the steps:
(1) carry out the polymerisation of styrene-divinylbenzene under sealing and pressurized state: the oil phase that will comprise the water of water, dispersant and dispersion aids and comprise styrene, divinylbenzene and initator adds polymerization reaction kettle respectively, feeding compressed air or nitrogen to the reactor gas-phase space remains under the barotropic state less than 1.0Mpa the gas phase gauge pressure, carry out suspension polymerisation, make the matrix polymer of resin with better high-temperature machinery stability and heat endurance;
(2) product of step (1) is carried out thermophilic digestion adding to depress with halogenated alkane;
(3) with halogenating agent or nitrating agent the product of step (2) is carried out halogenation or nitrated;
(4) with sulfonating agent the product of step (3) is carried out sulfonation;
(5) product to step (4) is washed till neutrality with hot pure water.
5. according to claim 3,4 preparation method, it is characterized in that, be that 1 weight portion is a benchmark with styrene and divinylbenzene weight sum in the described oil phase, each component and weight portion thereof are: styrene 0.70～0.98 weight portion, divinylbenzene 0.02～0.30 weight portion, initator 0.003～0.01 weight portion;
Described water consists of: pure water 1000 weight portions, dispersant 0.5～5.0 weight portion, dispersion aids 0.01～0.5 weight portion;
Described oil phase and water weight ratio are 1: 3～6.
6. according to claim 3,4 preparation method, it is characterized in that:
Described dispersant is a gelatin, and described dispersion aids is a magnesium carbonate;
Described initator is a benzoyl peroxide;
Described halogenating agent is chlorine, bromine or fluorine gas;
Described sulfonating agent is that mass percent concentration is 100～106% oleum or sulfur trioxide;
Described nitrating agent is the mixed acid of nitric acid, nitrous acid, nitrate, nitrite or nitric acid and sulfuric acid, wherein HNO 3: H 2SO 4Be 2～15%: 50～98%, all the other are H 2O.
7. according to the preparation method of claim 3, it is characterized in that described pore-foaming agent be white oil, liquid wax, solid wax, toluene or in them more than a kind of mixture, the weight ratio of following mixture is:
White oil: Gu wax is 4～12: 0～1,
Liquid wax: Gu wax is 4～12: 0～1,
White oil: toluene is 3～10: 0～1.
8. according to claim 3,4 preparation method, it is characterized in that described thermophilic digestion temperature is 80～120 ℃, the time is 5～24 hours, and gauge pressure is 0.01MPa～1.0MPa.
9. according to claim 3,4 preparation method, it is characterized in that described halogenated alkane is dichloroethanes, carbon tetrachloride or dichloroethanes and carbon tetrachloride with weight ratio 2～6: 0.5～1 mixture of forming.
10. according to claim 3,4 preparation method, the industrial naptha that it is characterized in that described extraction steps is 120 #Industrial naptha, described halogenation, nitrated temperature are 0 ℃～20 ℃.
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USRE39902E1 (en) 1991-03-27 2007-10-30 Matsushita Electric Industrial Co., Ltd. Communication system
USRE39929E1 (en) 1991-03-27 2007-11-27 Matsushita Electric Industrial Co., Ltd. Communication system
US7352822B2 (en) 1992-03-26 2008-04-01 Matsushita Electric Industrial Co., Ltd. Telephone for transmitting an uplink signal to a base station and for receiving first and second downlink signals from the base station, and a base station for receiving an uplink signal from a telephone and transmitting first and second downlink signals to the telephone
USRE41146E1 (en) 1992-03-26 2010-02-23 Panasonic Corporation Communication system
US7894541B2 (en) 1992-03-26 2011-02-22 Panasonic Corporation Communication system
USRE42643E1 (en) 1991-03-27 2011-08-23 Panasonic Corporation Communication system
CN102161007A (en) * 2011-03-04 2011-08-24 凯瑞化工有限责任公司 Dimethyl ether catalyst and preparation method thereof
USRE43093E1 (en) 1992-03-26 2012-01-10 Panasonic Corporation Communication system
CN102319585A (en) * 2011-05-18 2012-01-18 凯瑞化工股份有限公司 High-temperature-resistant maleic anhydride (MAH) resin catalyst and preparation method thereof
US8160173B2 (en) 1992-03-26 2012-04-17 Panasonic Corporation Communication system
CN101757946B (en) * 2010-01-08 2012-07-18 凯瑞化工股份有限公司 Multi-functional group resin catalyst and preparation method thereof
CN102614916A (en) * 2012-02-28 2012-08-01 同济大学 Preparation method of high-acidity fluorination resin catalyst used for alkylating of isobutane and butene
CN103509591A (en) * 2012-06-28 2014-01-15 中国石油化工股份有限公司 Gasoline deep etherification modification method
CN103611572A (en) * 2013-12-10 2014-03-05 王金明 Catalyst for tert-butyl alcohol cleavage reaction and preparation method thereof
CN104324704A (en) * 2014-09-18 2015-02-04 宁波检验检疫科学技术研究院 Elimination method of sulfuryl fluoride
CN106349414A (en) * 2015-07-16 2017-01-25 中国石油天然气股份有限公司 Method for fluorinating hybrid resin solid acid as well as prepared product and application
CN107537570A (en) * 2017-09-26 2018-01-05 丹东明珠特种树脂有限公司 A kind of strong-acid type high temperature resistant cation resin catalyzing agent and preparation method thereof
CN114849784A (en) * 2022-06-02 2022-08-05 中海油天津化工研究设计院有限公司 Preparation method of heterogeneous catalyst for preparing carboxylic acid by aldehyde oxidation

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USRE40255E1 (en) 1991-03-27 2008-04-22 Matsushita Electric Industrial Co., Ltd. Communication system
USRE42643E1 (en) 1991-03-27 2011-08-23 Panasonic Corporation Communication system
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USRE39902E1 (en) 1991-03-27 2007-10-30 Matsushita Electric Industrial Co., Ltd. Communication system
USRE39929E1 (en) 1991-03-27 2007-11-27 Matsushita Electric Industrial Co., Ltd. Communication system
USRE39928E1 (en) 1991-03-27 2007-11-27 Matsushita Electric Industrial Co., Ltd. Communication system
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US7158577B1 (en) 1992-03-26 2007-01-02 Matsushita Electric Industrial Co., Ltd. Communication system
US7352822B2 (en) 1992-03-26 2008-04-01 Matsushita Electric Industrial Co., Ltd. Telephone for transmitting an uplink signal to a base station and for receiving first and second downlink signals from the base station, and a base station for receiving an uplink signal from a telephone and transmitting first and second downlink signals to the telephone
USRE43093E1 (en) 1992-03-26 2012-01-10 Panasonic Corporation Communication system
CN101757946B (en) * 2010-01-08 2012-07-18 凯瑞化工股份有限公司 Multi-functional group resin catalyst and preparation method thereof
CN102161007A (en) * 2011-03-04 2011-08-24 凯瑞化工有限责任公司 Dimethyl ether catalyst and preparation method thereof
CN102319585B (en) * 2011-05-18 2012-10-17 凯瑞化工股份有限公司 High-temperature-resistant maleic anhydride (MAH) resin catalyst and preparation method thereof
CN102319585A (en) * 2011-05-18 2012-01-18 凯瑞化工股份有限公司 High-temperature-resistant maleic anhydride (MAH) resin catalyst and preparation method thereof
CN102614916A (en) * 2012-02-28 2012-08-01 同济大学 Preparation method of high-acidity fluorination resin catalyst used for alkylating of isobutane and butene
CN103509591B (en) * 2012-06-28 2015-07-29 中国石油化工股份有限公司 A kind of method of gasoline deep etherificate upgrading
CN103509591A (en) * 2012-06-28 2014-01-15 中国石油化工股份有限公司 Gasoline deep etherification modification method
CN103611572A (en) * 2013-12-10 2014-03-05 王金明 Catalyst for tert-butyl alcohol cleavage reaction and preparation method thereof
CN103611572B (en) * 2013-12-10 2015-04-08 王金明 Catalyst for tert-butyl alcohol cleavage reaction and preparation method thereof
CN104324704A (en) * 2014-09-18 2015-02-04 宁波检验检疫科学技术研究院 Elimination method of sulfuryl fluoride
CN106349414A (en) * 2015-07-16 2017-01-25 中国石油天然气股份有限公司 Method for fluorinating hybrid resin solid acid as well as prepared product and application
CN107537570A (en) * 2017-09-26 2018-01-05 丹东明珠特种树脂有限公司 A kind of strong-acid type high temperature resistant cation resin catalyzing agent and preparation method thereof
CN114849784A (en) * 2022-06-02 2022-08-05 中海油天津化工研究设计院有限公司 Preparation method of heterogeneous catalyst for preparing carboxylic acid by aldehyde oxidation
CN114849784B (en) * 2022-06-02 2023-11-07 中海油天津化工研究设计院有限公司 Preparation method of heterogeneous catalyst for preparing carboxylic acid by aldehyde oxidation

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