CN105777971A - Preparation method of composite porous organic carrier - Google Patents
Preparation method of composite porous organic carrier Download PDFInfo
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Abstract
The invention relates to a composite carrier composed of a copolymer of divinyl benzene and hydroxyalkyl methacrylate and inorganic layered silicate. The composite carrier is characterized in that inorganic layer silicate is added during the copolymerization process between divinyl benzene and hydroxyalkyl methacrylate, the ratio of added inorganic layered silicate to monomers is 0.5-10:100; and the inorganic layer silicate particles are montmorillonite or metal ion modified montmorillonite with enlarged interlayer spacing. During the process of copolymerization, inorganic layered silicate is added, due to the polar adsorption effect of inorganic layer silicate, polar functional monomers can be absorbed on the surface of inorganic layer silicate, thus the yield of copolymerized monomers in in-situ copolymerization is increased, and moreover, the composite carrier particles can be filtered more easily.
Description
Technical field
The preparation method that the present invention relates to a kind of olefin polymerization catalysis organic carrier.
Background technology
At present, the business olefin polymerization catalysis overwhelming majority uses loaded catalyst, catalyst generally uses inorganic matter to carry out the load of catalyst, US Patent No. 4, 808, 561, US5, 026, 797, US5, 763, 543, US5, 661, 098, US6, 455, 647, US4540679, Chinese patent CN98126385, CN1174549, CN1356343 reports with inorganic matter such as magnesium chloride, silicon dioxide, aluminium oxide, magnesium carbonate etc. prepare support type Ziegler-Natta and metallocene catalyst for carrier, but these inorganic carriers can affect polyolefinic performance after introducing polymer.And in recent years owing to the organic polymer carrier containing loose structure has the performance (such as high activity, good copolymerization performance, the especially prepared inorganic ash of polymeric articles is relatively low) of uniqueness, just it is being increasingly subject to the concern of industrial quarters and academia.
At present, the polymer as catalyst carrier has a lot, and being typically based on organic source can be divided into: (1) natural polymer, and especially the natural polymer such as cyclodextrin of some particular functional group is contained on surface；null(2) artificial-synthetic copolymer，Mainly include polyethylene (PE) such as international monopoly WO2001036096 and WO2004092230，Polypropylene (PP) is such as international monopoly WO6,152,543 and WO6,403,519，Poly-1,2-polybutadiene WO4,161,462，Polysiloxanes and styrene、Divinyl benzene crosslinked monomer (optional) and another function monomer such as ethylene nitrile、The copolymerization carrier of methyl methacrylate etc.，Such as US Patent No. 4,623,707、US4,623,912、US5,139,985、US5,463,000、US5,498,582、European patent EP 344,755 and Chinese patent CN101440137A，And divinylbenzene and function monomer copolymerization carrier，Such as US Patent No. 5,168,104 use gas phase silica gel as porogen，Adopt suspension polymerisation，Carry out divinylbenzene and hydroxyethyl methylacrylate copolymer，Then the grain diameter macroporous polymeric beads more than 0.1 μm is obtained after being etched by silica gel with highly basic；US6,583,082 and US6,750,303, adopt suspension polymerization, obtain polymer support by after hydroxyethyl methylacrylate function monomer and divinylbenzene monomers copolymerization, obtain specific surface area more than 10m2/ g, grain diameter at 0.1-1000 μm, the pore volume polymer support more than 0.2ml/g.But adopting the grain diameter prepared of suspension polymerization and distribution relatively big, granular size can reach more than 200 μm, generally the carrier of preparation carries out the load of olefin polymerization catalysis after needing to screen out the granule of 30-100 μm.
Summary of the invention
The present invention adopts dispersion copolymerization method, prepares the copolymer of divinylbenzene and hydroxyalkyl methacrylate and the complex carrier of inorganic laminated silicate.Organic and inorganic function carrier prepared by the present invention, particle size distribution is narrow, carrier granular specific surface area and particle shape can be regulated and controled by inorganic laminated silicate addition, the addition of polarity phyllosilicate makes the polymer prepared can be easily separated, improve comonomer and generate the productivity of solid particle, obtain the polymer that particle shape is good.
The present invention provides a kind of organic-inorganic porous sexual function carrier and preparation method thereof.This organic-inorganic porous sexual function carrier can as the carrier of metallocene catalyst.Organic carrier moieties is binary or multiple copolymer, and this copolymer is divinylbenzene and hydroxyalkyl methacrylate copolymerization forms, and inorganic carrier part is phyllosilicate.
The present invention organic-inorganic porous sexual function support preparation method is as follows:
(1) configuration of dispersion soln: dispersion liquid adopts the mass ratio of the lower alcohol by 1-4 carbon atom and aqueous systems, alcohol and water addition to be 5-15:1, and in dispersion liquid, alcohol is methanol, ethanol, propanol, isopropanol, n-butyl alcohol, isobutanol.It is mass ratio without the following addition ratio of specified otherwise.
(2) adding reaction monomers: be at room temperature added sequentially in above-mentioned dispersion liquid by comonomer divinylbenzene and hydroxyalkyl methacrylate, it is 1:5-20 that monomer adds the mass ratio of total amount and dispersion liquid, makes system be uniformly dispersed.In monomer addition, hydroxyalkyl methacrylate and divinylbenzene mass ratio are 0.2-1.5:1.Can also adding Third monomer such as styrene or the styrene containing alkyl or halogen substiuted, prepare multiple copolymer, Third monomer and divinylbenzene mass ratio are 0-1.5:1.
(3) adding stabilizer, make stabilizer be dissolved in system at 20-60 DEG C, stabilizer is poly(propylene oxide)-polyethylene oxide copolymer or PVAC polyvinylalcohol.Stabilizer molecular weight control is 6,000-100, and between 000, stabilizer addition and monomer add total amount ratio for 1-3:100.
(4) adding inorganic laminated silicate granules, the ratio that inorganic laminated silicate addition adds total amount with monomer is 0.5-10:100.
(5) add radical initiator, common radical initiator, including azodiisobutyronitrile or dibenzoyl peroxide, be then warming up to 60-85 DEG C again, stirring, react 3-12 hour.The ratio that the addition of initiator adds total amount with monomer is 0.5-3:100.The polymer washing being obtained by reacting removes impurity, obtains organic-inorganic porous sexual function carrier after drying.
In course of reaction of the present invention, the 3rd comonomer can be added and prepare multiple copolymer, 3rd comonomer generally includes styrene, the styrene that alkyl the replaces styrene as replaced containing 1-6 carbon atom, such as the styrene that methyl, propyl group, butyl replace, halogenated styrenes, such as 1-chlorostyrene etc., and the styrene containing alkyl and halogen functional group, such as p-chloromethyl styrene etc..
Comonomer divinylbenzene in the present invention, english abbreviation is DVB, and hydroxyalkyl methacrylate includes but not limited to the positive butyl ester of hydroxyethyl methylacrylate, Hydroxypropyl methacrylate, hydroxyethyl methacrylate, hydroxyethyl methacrylate isobutyl ester etc..Hydroxyethyl methylacrylate english abbreviation is HEMA, Hydroxypropyl methacrylate english abbreviation is HPMA, all can using commodity monomers, as divinylbenzene can with the commodity monomers of 55% or 80%DVB content, hydroxyethyl methylacrylate monomer adopts commercial concentration more than 98% reagent.Above-mentioned monomer is both needed to pretreatment before using, and re-uses after first removing polymerization inhibitor.Remove in the method prior art of polymerization inhibitor and have a lot, can use such as divinylbenzene sodium hydroxide solution and distilled water wash, hydroxyethyl methylacrylate, Hydroxypropyl methacrylate that neutral alumina column can be used to use after removing polymerization inhibitor.Third monomer, uses after removing polymerization inhibitor such as styrene, use sodium hydroxide solution and distilled water wash, and chloro-styrene can use alkali alumina post to use after removing polymerization inhibitor.
In the present invention, inorganic laminated silicate is montmorillonite, the phyllosilicate crystal being made up of two-layer Si-O tetrahedron and one layer of Al-O octahedron, and layer is contained within cation and is mainly sodium ion, magnesium ion, calcium ion, next has potassium ion, lithium ions etc., its average wafer thickness is less than 25nm.In the present invention, montmorillonite can also use the modified montmorillonoid after metal cation exchange, as used magnesium ion, aluminium ion that montmorillonite is modified, modified montmorillonite can be made to have bigger interlamellar spacing.
The present invention uses the binary for preparing of dispersion copolymerization method or multiple copolymer, solvent need to be used to wash, the impurity such as unreacted comonomer, stabilizer are removed, solvent can be the lower alcohol (such as ethanol, propanol etc.) of 1-4 carbon atom, and the alkane (such as isopentane, hexane etc.) of alcohol/aqueous systems solvent and 1-6 carbon atom carries out washing impurity removing.
The present invention can also add porogen such as n-butyl phthalate or diisobutyl phthalate compounds in dispersion, the aperture of polymer is adjusted.
In the present invention, the grain diameter of porous carrier adopts Malvern laser particle particle size analyzer Mastersizer2000 to test, and first ultrasonic disperse 150 seconds before test, mean particle size D (50) is between 15-60 μm；The specific surface area of carrier adopts Nova2000e to use BET nitrogen adsorption methods to test, and carrier specific surface area prepared by the control present invention is more than 100m2/ g, polymer pore volume is more than 0.20ml/g.
In the present invention, preparation method is simple and environmentally-friendly, adopt alcohol-water system dispersion, carrying out binary or polynary in-situ copolymerization, be typed on polydivinylbenezene skeleton by hydroxyalkyl methacrylate function monomer, in-situ polymerization prepares organic-inorganic porous sexual function carrier.The addition of inorganic laminated silicate in the present invention, due to its polar adsorption, is adsorbed on inorganic laminated silicate surfaces by polar functionalities monomer, when carrying out in-situ copolymerization, not only improves the productivity of comonomer, and makes complex carrier granule be easier to filter.Relative to existing organic carrier, the carrier of preparation has bigger specific surface area, and microsphere supported relative to porous prepared by existing employing suspension polymerization, the grain diameter size of its carrier is uniform, disperseing narrow, polymer supported body aperture is concentrated mainly on the mesoporous of 2-50nm；In the present invention, the organic-inorganic porous sexual function carrier specific surface area of preparation is more than 100m2/ g, pore volume is more than 0.20ml/g.
Accompanying drawing explanation
Fig. 1 is the copolymer complex carrier scanning electron microscope sem figure with inorganic laminated silicate of divinylbenzene and methacrylate.
Detailed description of the invention
The organic-inorganic porous property prepared gathers (divinylbenzene-hydroxyethyl methylacrylate) bipolymer/montmorillonite carrier, is designated as MMT/P (DVB-co-HEMA)；The organic-inorganic porous property obtained gathers (divinylbenzene-Hydroxypropyl methacrylate)/montmorillonite carrier, is designated as MMT/P (DVB-co-HPMA)；The organic-inorganic porous property obtained gathers (styrene-divinylbenzene-hydroxyethyl methylacrylate)/montmorillonite carrier, is designated as MMT/P (St-co-DVB-co-HEMA).
Azodiisobutyronitrile english abbreviation is AIBN, and dibenzoyl peroxide english abbreviation is BPO.
Embodiment 1
The process of comonomer: polymerization inhibitor is first removed before using by divinylbenzene with 10%NaOH solution, then uses with after deionized water wash 3 times；Hydroxyethyl methylacrylate, Hydroxypropyl methacrylate etc. use chromatography on neutral alumina post to use after removing polymerization inhibitor.Specified otherwise comonomer is not all used by following example after treatment.
nullThe preparation of the organic porous carrier of function: in 250ml glass reactor，Add 108ml ethanol and 12ml deionized water，It is subsequently adding 4.8g divinylbenzene (Aladdin reagent，55%) and 3.2g hydroxyethyl methylacrylate polymerization single polymerization monomer，Stir 5min at normal temperatures，It is subsequently adding the montmorillonite K-10 granule (Aladdin reagent 240m2/g) of 5% monomer mass，And 2% the polyvinyl alcohol (degree of polymerization is 1788) of monomer mass at 50 DEG C，Stirring 1h，Polyvinyl alcohol stabilizer is dissolved，Add the AIBN of 2% monomer mass，It is warming up to 70 DEG C，React 3 hours，Then temperature is risen to 80 DEG C，After reacting 5 hours，Speed of agitator is 360 revs/min，Ethanol/water (1:1) is used to wash 3 times，Use 400 order 316 stainless steel filter screen multiple filtrations (lower same)、Obtain 5.4g porous MMT/P (DVB-co-HEMA) complex carrier A1 after drying.
Embodiment 2
nullThe preparation of the organic porous carrier of function: in 250ml glass reactor，Add 126ml ethanol and 14ml deionized water，It is subsequently adding 4.7g divinylbenzene (Aladdin reagent，55%) and 3.1g hydroxyethyl methylacrylate (98%) polymerization single polymerization monomer，Stir 5min at normal temperatures，It is subsequently adding the montmorillonite K-10 (Aladdin reagent) of 3% monomer mass，And 2% the polyvinyl alcohol (degree of polymerization is 1788) of monomer mass at 50 DEG C，Stirring 1h，Polyvinyl alcohol stabilizer is dissolved，Add the AIBN of 2% monomer mass，It is warming up to 70 DEG C，React 3 hours，Then temperature is risen to 80 DEG C，After reacting 5 hours，Speed of agitator is 360 revs/min，Use washing with alcohol 3 times，Obtain 5.2g porous MMT/P (DVB-co-HEMA) complex carrier A2 after drying.
Embodiment 3
In embodiment 3 preparation of organic porous carrier different except montmorillonite K-10 consumption from embodiment 2 except, preparation process is identical with other reagent dosage, adds and 1% replace addition 3% in embodiment 3.Prepare 4.1g porous MMT/P (DVB-co-HEMA) complex carrier A3.
Embodiment 4
In embodiment 4 preparation of organic porous carrier different except the montmorillonite trade mark from embodiment 2 except, preparation process is identical with other reagent dosage, adds 7% montmorillonite KSF (Aladdin reagent 20-40m in embodiment 42/g).Prepare 5.5g porous MMT/P (DVB-co-HEMA) complex carrier A4.
Embodiment 5
nullThe preparation of the organic porous carrier of function: in 250ml glass reactor，Add 117ml ethanol and 13ml deionized water，It is subsequently adding 4.8g divinylbenzene (Aladdin reagent，55%) and 3.2g hydroxyethyl methylacrylate polymerization single polymerization monomer，Stir 5min at normal temperatures，It is subsequently adding the montmorillonite K-10 of 3% monomer mass，And 2% poly(propylene oxide)-the polyethylene oxide copolymer (BASF AG F127) of monomer mass stir 0.5h at normal temperatures，F127 is dissolved，Add the AIBN of 2% monomer mass，It is warming up to 70 DEG C，React 3 hours，Then temperature is risen to 80 DEG C，After reacting 5 hours，Speed of agitator is 360 revs/min，Use washing with alcohol 3 times，Obtain 5.3g porous MMT/P (DVB-co-HEMA) complex carrier A5 after drying.
Embodiment 6
nullThe preparation of the organic porous carrier of function: in 250ml glass reactor，Add 117ml ethanol and 13ml deionized water，It is subsequently adding 4.0g divinylbenzene (Aladdin reagent，55%) and 4.0g hydroxyethyl methylacrylate polymerization single polymerization monomer，Stir 5min at normal temperatures，It is subsequently adding the montmorillonite K-10 of 5% monomer mass，And 2% the polyvinyl alcohol (degree of polymerization is 1788) of monomer mass at 50 DEG C，Stirring 1h，Polyvinyl alcohol stabilizer is dissolved，Add the AIBN of 2% monomer mass，It is warming up to 70 DEG C，React 3 hours，Then temperature is risen to 80 DEG C，After reacting 5 hours，Speed of agitator is 360 revs/min，Use washing with alcohol 3 times，Filter slightly slow，Obtain 4.5g porous MMT/P (DVB-co-HEMA) complex carrier A6 after drying.
Embodiment 7
The preparation of magnesium salt modified montmorillonoid: in 250ml glass reactor, add 100ml ethanol and water-soluble (1:1) agent, add 4.0g montmorillonite K-10 and 1.0g magnesium sulfate solid particle, react 4h at normal temperatures, then, use ethanol/water (1:1) solvent alkene 3 times, after washing with acetone 3 times, obtain the montmorillonite that magnesio is modified after drying.
nullThe preparation of the organic porous carrier of function: in 250ml glass reactor，Add 117ml ethanol and 13ml deionized water，It is subsequently adding 4.7 divinylbenzene (Aladdin reagent，55%) and 3.1g hydroxyethyl methylacrylate polymerization single polymerization monomer，Stir 5min at normal temperatures，It is subsequently adding the modified montmorillonoid of 3% monomer mass，And 2% the polyvinyl alcohol (degree of polymerization is 1788) of monomer mass at 50 DEG C，Stirring 1h，Polyvinyl alcohol stabilizer is dissolved，Add the AIBN of 2% monomer mass，It is warming up to 70 DEG C，React 3 hours，Then temperature is risen to 80 DEG C，After reacting 5 hours，Speed of agitator is 360 revs/min，Ethanol/water (1:1) is used to wash 3 times，Filter slightly slow，Obtain 5.5g porous Mg-MMT/P (DVB-co-HEMA) complex carrier A7 after drying.
Embodiment 8
nullThe preparation of the organic porous carrier of function: in 250ml glass reactor，Add 126ml ethanol and 14ml deionized water，It is subsequently adding 4.9g divinylbenzene (Aladdin reagent，80%) and 3.3g hydroxyethyl methylacrylate (98%) polymerization single polymerization monomer，Stir 5min at normal temperatures，It is subsequently adding the montmorillonite K-10 of 5% monomer mass，And 2% the polyvinyl alcohol (degree of polymerization is 1788) of monomer mass at 50 DEG C，Stirring 1h，Polyvinyl alcohol stabilizer is dissolved，Add the AIBN of 2% monomer mass，It is warming up to 70 DEG C，React 3 hours，Then temperature is risen to 80 DEG C，After reacting 5 hours，Speed of agitator is 350 revs/min，Ethanol/water (1:1) is used to wash 3 times，Obtain 7.0g porous MMT/P (DVB-co-HEMA) complex carrier A8 after drying.
Embodiment 9
In embodiment 9, the preparation of organic porous carrier and embodiment 8 are except different copolymer monomer and consumption, preparation process is identical with other reagent dosage, embodiment 9 adds 4.8g divinylbenzene (Aladdin reagent, 80%) and 3.2g Hydroxypropyl methacrylate (98%) polymerization single polymerization monomer.Prepare 7.1g porous MMT/P (DVB-co-HPMA) complex carrier A9.
Embodiment 10
nullThe preparation of the organic porous carrier of function: in 250ml glass reactor，Add 126ml ethanol and 13ml deionized water，It is subsequently adding 3.8g divinylbenzene (Aladdin reagent，80%) and 3.0g hydroxyethyl methylacrylate polymerization single polymerization monomer，And 1.8g styrene Third monomer，Stir 5min at normal temperatures，It is subsequently adding the montmorillonite K-10 of 3% monomer mass，And 2% the polyvinyl alcohol (degree of polymerization is 1788) of monomer mass at 50 DEG C，Stirring 1h，Polyvinyl alcohol stabilizer is dissolved，Add the AIBN of 2% monomer mass，It is warming up to 70 DEG C，React 3 hours，Then temperature is risen to 80 DEG C，After reacting 5 hours，Speed of agitator is 360 revs/min，Ethanol/water (1:1) is used to wash 3 times，Obtain 6.3g porous MMT/P (St-co-DVB-co-HEMA) complex carrier A10 after drying.
Comparative example 11
nullThe preparation of the organic porous carrier of function: in 250ml glass reactor，Add 108ml ethanol and 12ml deionized water，It is subsequently adding 3.9g divinylbenzene (Aladdin reagent，55%) and 2.5g hydroxyethyl methylacrylate polymerization single polymerization monomer，Stir 5min at normal temperatures，It is subsequently adding the polyvinyl alcohol (degree of polymerization is 1788) of 2% monomer mass at 50 DEG C，Stirring 1h，Polyvinyl alcohol stabilizer is dissolved，Add the AIBN of 2% monomer mass，It is warming up to 70 DEG C，React 3 hours，Then temperature is risen to 80 DEG C，After reacting 5 hours，Speed of agitator is 360 revs/min，Ethanol/water (1:1) is used to wash 3 times，It is more difficult to filter，Obtain 3.4g porous P (DVB-co-HEMA) organic carrier B11 after drying.
Comparative example 12
In embodiment 12, the preparation of organic porous carrier and embodiment 6 are except not adding montmorillonite K-10, and monomer addition difference outer (ratio is identical), and preparation process is identical with other reagent dosage.Embodiment 12 adds 4.8g divinylbenzene (Aladdin reagent, 55%) and 4.8g hydroxyethyl methylacrylate polymerization single polymerization monomer, but cannot being filtrated to get solid particulate matter smoothly, it is B12 that postscript is dried in bottom solids P (DVB-co-HEMA).
Comparative example 13
nullThe preparation of the organic porous carrier of function: in 250ml glass reactor，Add 117ml ethanol and 13ml deionized water，It is subsequently adding 3.7g divinylbenzene (Aladdin reagent，80%) and 3.3g hydroxyethyl methylacrylate polymerization single polymerization monomer，And 1.8g styrene Third monomer，Stir 5min at normal temperatures，It is subsequently adding the polyvinyl alcohol (degree of polymerization is 1788) of 2% monomer mass at 50 DEG C，Stirring 1h，Polyvinyl alcohol stabilizer is dissolved，Add the AIBN of 2% monomer mass，It is warming up to 70 DEG C，React 3 hours，Then temperature is risen to 80 DEG C，After reacting 5 hours，Speed of agitator is 360 revs/min，Use washing with alcohol 3 times，Filter slightly slow，Obtain 5.9g porous P (St-co-DVB-co-HEMA) organic carrier B13 after drying.
In embodiment and comparative example 1-13, the organic porous carrier specific surface area of preparation, pore volume, mean particle size and particle size distribution result are shown in table 1 below.
The specific surface area of table 1 organic carrier, pore volume and particle diameter and distribution
As can be seen from the test results, complex carrier prepared by the present invention easily filters, and polymerization single polymerization monomer productivity improves the addition of phyllosilicate montmorillonite, it is possible to the specific surface area and pore volume preparing carrier is regulated and controled.Using specific surface area and the pore volume of the function organic carrier that 80%DVB and methyl methacrylate monomer copolymerization prepare, than using, the 55%DVB carrier prepared is much higher, this be due to the carrier degree of cross linking of preparation higher caused by.Using polyvinyl alcohol to use poly(propylene oxide)-polyethylene oxide copolymer F127 as dispersin polymerization stabilizer ratio in the present invention, specific surface area and the pore volume of preparation resulting vehicle want height.
Grain diameter and distribution change with test condition change, and result is not as carried out specified otherwise for disperseing at ethanol, and the test result that ultrasonic disperse is after 150 seconds.From above-mentioned organic carrier grain diameter and particle size distribution it can be seen that use preparation method the present invention can prepare the organic carrier that particle size distribution is narrower, particle size distribution value Span can control within 2.0.
Claims (7)
1. the preparation method of a composite porous organic carrier, it is characterised in that prepared by following method:
(1) configuration dispersion soln: dispersion liquid adopts the mass ratio of the lower alcohol by 1-4 carbon atom and aqueous systems, alcohol and water addition to be 5-15:1, is mass ratio without the following addition ratio of specified otherwise；
(2) reaction monomers is added: be at room temperature added sequentially in above-mentioned dispersion liquid by comonomer divinylbenzene and hydroxyalkyl methacrylate, it is 1:5-20 that monomer adds the mass ratio of total amount and dispersion liquid, making system be uniformly dispersed, in monomer addition, hydroxyalkyl methacrylate and divinylbenzene mass ratio are 0.2-1.5:1；
(3) adding stabilizer, make stabilizer be dissolved in system at 20-60 DEG C, stabilizer is poly(propylene oxide)-polyethylene oxide copolymer or polyvinyl alcohol, stabilizer molecular weight control is 6,000-100, between 000, stabilizer addition and monomer add total amount ratio for 1-3:100；
(4) adding inorganic laminated silicate granules, the ratio that inorganic laminated silicate addition adds total amount with monomer is 0.5-10:100, and described inorganic laminated silicate granules is montmorillonite or the metal ion-modified montmorillonite expanding interlamellar spacing；
(5) add radical initiator, be then warming up to 60-85 DEG C again, stirring, react 3-12 hour, the ratio that the addition of initiator adds total amount with monomer is 0.5-3:100, and the scrubbed removing impurity of polymer being obtained by reacting obtains complex carrier after drying.
2. the preparation method of composite porous organic carrier according to claim 1, it is characterized in that the reaction monomers described in preparation process adds the 3rd reaction monomers further except divinylbenzene and hydroxyalkyl methacrylate, Third monomer and divinylbenzene mass ratio are 0-1.5:1.
3. the preparation method of composite porous organic carrier according to claim 2, it is characterised in that the 3rd reaction monomers described in preparation process is styrene, the styrene of alkyl replacement, halogenated styrenes and the styrene containing alkyl and halogen functional group.
4. the preparation method of composite porous organic carrier according to claim 1, it is characterised in that add porogen in preparation process further, the aperture of polymer is adjusted.
5. the preparation method of composite porous organic carrier according to claim 4, it is characterised in that the described porogen added in preparation process is n-butyl phthalate or diisobutyl phthalate compounds.
6. the preparation method of composite porous organic carrier according to claim 1, it is characterised in that the described metal cation in metal cation modified montmorillonoid is magnesium ion, aluminium ion.
7. the preparation method of composite porous organic carrier according to claim 1, it is characterised in that described hydroxyalkyl methacrylate is selected from methacrylate, hydroxypropyl methacrylate.
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