CN107759812A - Cross-linked polymer based on waste polystyrene and preparation method and application - Google Patents

Cross-linked polymer based on waste polystyrene and preparation method and application Download PDF

Info

Publication number
CN107759812A
CN107759812A CN201710936463.2A CN201710936463A CN107759812A CN 107759812 A CN107759812 A CN 107759812A CN 201710936463 A CN201710936463 A CN 201710936463A CN 107759812 A CN107759812 A CN 107759812A
Authority
CN
China
Prior art keywords
cross
waste polystyrene
linked polymer
polystyrene
preparation
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.)
Granted
Application number
CN201710936463.2A
Other languages
Chinese (zh)
Other versions
CN107759812B (en
Inventor
刘长坤
伏振宇
雷晓斌
贾继珍
王琳
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shenzhen University
Original Assignee
Shenzhen University
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Shenzhen University filed Critical Shenzhen University
Priority to CN201710936463.2A priority Critical patent/CN107759812B/en
Publication of CN107759812A publication Critical patent/CN107759812A/en
Priority to PCT/CN2018/108310 priority patent/WO2019072105A1/en
Application granted granted Critical
Publication of CN107759812B publication Critical patent/CN107759812B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
    • B01J20/267—Cross-linked polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/504—Carbon dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
    • C08J2325/02—Homopolymers or copolymers of hydrocarbons
    • C08J2325/04—Homopolymers or copolymers of styrene
    • C08J2325/06—Polystyrene
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Abstract

The invention discloses a kind of cross-linked polymer based on waste polystyrene and preparation method and application, including：Step A, by weight percentage, waste polystyrene 1 6%, organic solvent 80 90%, crosslinking agent 1 6% and catalyst 2 8% are mixed, under protective atmosphere, 10 50min is stirred at room temperature, be then heated to 80 90 DEG C of 6 24h of reaction；Step B, in through the reacted solution of step A, alcoholic solution terminating reaction is added, room temperature and purified processing is subsequently cooled to, obtains cross-linked polymer.For the present invention using discarded polystyrene as raw material, cost is low, and effective way is provided for the recovery of waste polystyrene；While present invention employs crosslinking agent and it is aided with catalyst, through single step reaction so that polystyrene forms highly cross-linked 3 D stereo reticulated porous structures, it can be applied to solid adsorption material field.

Description

Cross-linked polymer based on waste polystyrene and preparation method and application
Technical field
The present invention relates to porosu solid sorbing material field, more particularly to a kind of cross-linked polymeric based on waste polystyrene Thing and preparation method and application.
Background technology
At present, the carbon capture method of caused carbon dioxide mainly includes after fossil energy burning：Physical Absorption method, film Partition method, chemical absorption method etc..Consider the factors such as the technology, economy and environment of the adsorption treatment process of carbon dioxide, In above-mentioned separation method, the Physical Absorption method using cellular solid as absorbent receives much concern.Made using solid porous material There are many advantages come the carbon dioxide captured in waste gas for adsorbent：（1）Energy consumption is low, and solid porous material is to carbon dioxide Absorption is general by the way of pressure-variable adsorption and temp.-changing adsorption, and handling process is divided into capture with separating two processes, first, utilizes The big carbon dioxide adsorption of material captures the carbon dioxide in waste gas under high pressure or cryogenic conditions, in low pressure or the bar of high temperature The small carbon dioxide adsorption of material carrys out the carbon dioxide adsorbed in separation material under part, and the continuous reciprocation cycle of material uses next Handle the waste gas largely discharged.This can reduce the energy expenditure in acquisition procedure；Meanwhile solid material is selected to capture dioxy Change carbon and avoid energy resource consumption caused by regenerative process reclaimed water solvent absorption heat.（2）Easy to operate, solid material is as absorption Agent, avoids corrosion of the basic organic solution to equipment, and Operation and Maintenance process is simple.（3）Solid adsorption material is to carbon dioxide With the bigger adsorbance of relative monoethanolamine, this, which is attributed to material, has larger specific surface area and pore volume, can capture big The carbon dioxide of amount.
In recent years, the design of cellular solid achieved significant achievement in research with synthesis.In catching for carbon dioxide Application aspect is obtained, porosu solid sorbing material main at present concentrates on：Zeolite, silica, metal organic framework（MOFs）、 High molecular polymer and carbon based material etc..However, up to the present, the synthesis of most materials needs subtly to design reaction The structure of thing, select specific response path.In addition, in the course of reaction of cellular solid is prepared, it will usually use high Expensive transition-metal catalyst or poisonous solvent.These factors can increase the production cost of material, porous solid so as to restrict The industrialized production of body material and its carbon dioxide adsorption, trap and seal up for safekeeping aspect large-scale application.
Therefore, prior art has yet to be improved and developed.
The content of the invention
In view of above-mentioned the deficiencies in the prior art, it is an object of the invention to provide a kind of crosslinking based on waste polystyrene Polymer and preparation method and application, it is intended to solve complicated existing cellular solid preparation method, cost height, environment not The problems such as friendly.
Technical scheme is as follows：
A kind of preparation method of the cross-linked polymer based on waste polystyrene, including：
Step A, by weight percentage, by waste polystyrene 1-6%, organic solvent 80-90%, crosslinking agent 1-6%, catalyst 2-8% is mixed, and under protective atmosphere, 10-50min is stirred at room temperature, and is then heated to 80-90 DEG C of reaction 6-24h；
Step B, in through the reacted solution of step A, alcoholic solution is added（Such as methanol or ethanol solution）Terminate anti- Should, room temperature and purified processing are subsequently cooled to, obtains cross-linked polymer.
The preparation method of the described cross-linked polymer based on waste polystyrene, wherein, before the step A, first Waste polystyrene is cleaned up, and dried.
The preparation method of the described cross-linked polymer based on waste polystyrene, wherein, in the step A, the friendship Connection agent be carbon tetrachloride, dimethoxymethane, to benzyl dichloride, to one kind in dichloromethyl biphenyl and a benzotrichloride.
The preparation method of the described cross-linked polymer based on waste polystyrene, wherein, it is described to urge in the step A Agent is FeCl3And AlCl3In one kind.
The preparation method of the described cross-linked polymer based on waste polystyrene, wherein, it is described to have in the step A Solvent is one kind in toluene, ortho-xylene, ethylbenzene, dichloromethane, dichloroethanes, chloroform and p-nitrophenyl.
The preparation method of the described cross-linked polymer based on waste polystyrene, wherein, in the step B, the alcohol The concentration of solution is 40-60 V/V%.
The preparation method of the described cross-linked polymer based on waste polystyrene, wherein, it is described to carry in the step B Pure processing is specially：By the reacting liquid filtering after cooling, ethanol and dilute hydrochloric acid solution rinse are then used respectively, and use deionized water Much filtrate is finally used the apparatus,Soxhlet's equipped with methanol to extract 18-30h, dried, then by cleaning untill filter liquor is colourless 18-30h is dried in vacuo in 40-60 DEG C.
A kind of cross-linked polymer based on waste polystyrene, as above any described preparation method be made.
The described cross-linked polymer based on waste polystyrene, there is microcellular structure.
A kind of application of the cross-linked polymer based on waste polystyrene as described above, for CO2Absorption and separation.
Beneficial effect：The invention provides a kind of preparation of the cross-linked polymer based on waste polystyrene as described above Method, using discarded polystyrene as body material, not only wide material sources, cost are low, and operation is simple and easily controllable, and And the recycling for discarded polystyrene provides a kind of effective way, has expanded its application；The present invention adopts simultaneously With crosslinking agent and it is aided with catalyst, through single step reaction so that polystyrene forms the mesh structural porous knot of highly cross-linked 3 D stereo Structure, it can be applied to solid adsorption material field.
Brief description of the drawings
Fig. 1 is waste polystyrene foam photo；
Crosslinking agent is served as while Fig. 2 is using dichloroethanes as solvent with waste polystyrene foam reaction gained crosslinking to gather The scanning electron microscopic picture of compound；
Fig. 3 is the scanning that crosslinking agent and the superhigh cross-linking polymer of waste polystyrene foam reaction gained are done using carbon tetrachloride Electron microscopic picture；
Fig. 4 is the superhigh cross-linking polymer that crosslinking agent and waste polystyrene foam reaction gained are done using dimethoxymethane Scanning electron microscopic picture；
Fig. 5 is using the scanning that crosslinking agent and the superhigh cross-linking polymer of waste polystyrene foam reaction gained are done to benzyl dichloride Electron microscopic picture；
Fig. 6 is using the superhigh cross-linking polymer that crosslinking agent and waste polystyrene foam reaction gained are done to dichloromethyl biphenyl Scanning electron microscopic picture；
Fig. 7 is HCP-A, HCP-B, HCP-C, the HCP-D and business polystyrene prepared in embodiment 1,2,3,4（PS）Fu in Leaf transformation decay In situ ATR-FTIR figure；
Fig. 8 be embodiment 1,2,3,4 in prepare HCP-A, HCP-B, HCP-C and HCP-D nuclear magnetic resonance of carbon wave spectrum (13C NMR) figure；
Fig. 9 is HCP-A, HCP-B, HCP-C, HCP-D and business polystyrene for being prepared in embodiment 1,2,3,4 thermogravimetric analysis Figure（Test condition：N2Atmosphere, 10 DEG C/min of heating rate）；
Figure 10 is HCP-A, HCP-B, HCP-C and HCP-D for being prepared in embodiment 1,2,3,4 graph of pore diameter distribution；
Figure 11 is HCP-A, HCP-B, HCP-C and the HCP-D prepared in embodiment 1,2,3,4 in absorption of the 273K to carbon dioxide Thermoisopleth；
Figure 12 is adsorption isotherms of HCP-A, HCP-B, HCP-C and the HCP-D prepared in embodiment 1,2,3,4 in 273K to nitrogen Line.
Embodiment
The invention provides a kind of cross-linked polymer based on waste polystyrene and preparation method and application, to make this The purpose of invention, technical scheme and effect are clearer, clear and definite, and the present invention is described in more detail below.It should be appreciated that this The specific embodiment of place description is not intended to limit the present invention only to explain the present invention.
The invention provides a kind of preferred embodiment of the preparation method of the cross-linked polymer based on waste polystyrene, system Standby process is as follows：
By the waste polystyrene of recovery, cleaned up, be dried with baking oven rear standby with ethanol solution and deionized water.
According to percentage by weight, by the waste polystyrene 4% after cleaned processing, organic solvent dichloroethanes 86%, hand over Join agent dimethoxymethane 4% and catalyst AlCl3 6% is added in reaction vessel, is then charged into thermometer and condenser pipe, is protecting Protect atmosphere（Such as nitrogen）Under, 30min is stirred at room temperature, is again heated to 85 DEG C of reaction 16h.
After reaction to the time of setting, 50% ethanol solution terminating reaction is added, and is cooled to room temperature, then using cloth Family name's funnel filters to solution, and respectively with ethanol and 1% hydrochloric acid rinse, it is nothing then to be cleaned with deionized water to filter liquor Untill color, the apparatus,Soxhlet's equipped with methanol is used to extract 24h much filtrate, taking-up is dried, is subsequently placed in 50 DEG C of vacuum drying ovens 24h is dried, produces cross-linked polymer.
Polystyrene（PS）A kind of time-honored plastics variety, have good water resistance, chemical proofing, every The features such as hot, cost is cheap, widely used.According to statistics, the output of polystyrene is only second to polyethylene, polyvinyl chloride, occupies Plastics yield the 3rd.Because the rigid-skeleton of polystyrene is difficult to degrade under field conditions (factors), increasingly increased polyphenyl second Alkene the like waste has had resulted in serious " white pollution ".In order to reduce harm of the waste plastic to environment, traditional is discarded The processing method of polystyrene mainly includes：Landfill, burn, recycle.In countries in Europe, waste plastic recycling Ratio only have 30%, and in developing country, due to lacking corresponding equipment and facility, the recycling rate of polystyrene It is lower.
Therefore, the present invention prepares porosu solid sorbing material using discarded polystyrene as body material, and not only source is wide It is general, cost is low, and the recycling for discarded polystyrene provides a kind of effective way, is advantageous to the guarantor of ecological environment Shield.Waste polystyrene existing certain applications during recycling（Such as：Insulation material, water reducer, adhesive etc.）, the present invention Its application is expanded.
In this reaction, in the presence of catalyst and crosslinking agent Friedel-Crafts reaction occurs for waste polystyrene（Friedel– Crafts reaction）, crosslink to form the mesh structural porous micro-structural of 3 D stereo between phenyl ring therein, this structure energy Enough to CO2Produce suction-operated.The present invention solves traditional conjunction by having synthesized porosu solid sorbing material through single step reaction Into porosu solid sorbing material need to consume costliness transition-metal catalyst, can not industrial applications the problem of.
In this reaction system, if not adding crosslinking agent, only using dichloroethanes as solvent while serve as crosslinking agent, institute Obtain reactant and compare waste polystyrene material（As shown in Figure 1）Also crosslink, but loose irregular spherical is presented It is granular（As shown in Figure 2）；And add in addition crosslinking agent carbon tetrachloride, dimethoxymethane, to benzyl dichloride, to dichloromethyl biphenyl With one kind in benzotrichloride, then gained reactant highly cross-linked state is presented（As shown in Fig. 3, Fig. 4, Fig. 5, Fig. 6）, because This, the crosslinking agent that the present invention selects is formed to the pore passage structure of superhigh cross-linking polymer significant impact.
The cross-linked polymer based on waste polystyrene prepared according to the present invention, has good chemical stability, has Body surface is present：Insoluble in common organic solvents（Such as N,N-dimethylformamide, dimethyl sulfoxide (DMSO), tetrahydrofuran, toluene）And 1mol/L hydrochloric acid and 1mol/L sodium hydroxide solutions.Also, the cross-linked polymer has good heat endurance, 443 ℃（In thermogravimetric analysis, temperature that waste polystyrene decomposes completely）, only 13-28% superhigh cross-linking polymer decomposed. And its BET specific surface area reaches as high as 777m2/ g, micropore specific area reach as high as 382m2/ g, pore volume reach as high as 1.15cm3/g；Average pore size 3.11-6.86nm, pore-size distribution concentrate on micro-porous area and mesoporous region.
Present invention also offers a kind of application of above-mentioned cross-linked polymer.The present invention cross-linked polymer, due to Porous microstructure, under 273K and 1bar, to CO2Adsorbance reach as high as 2.521 mmol/g（Or 11.1 wt%）, to CO2 Heat of adsorption reach as high as 41.1 kJ/mol, to CO2：N2=15：Adsorptive selectivity in 85 mixed gas reaches as high as 37.8, therefore the cross-linked polymer of the present invention can be used as solid absorbent, applied to CO in factory smoke2Absorption and point From.
Below by embodiment, the present invention is described in detail.
Embodiment 1
（1）By waste polystyrene foam（WEPS）Recovery, is cleaned up with ethanol solution and deionized water, is done with baking oven It is standby after dry；（2）Waste polystyrene foam 2g, organic solvent dichloroethanes 80mL, crosslinking are separately added into reaction vessel Agent dimethoxymethane 1.5g and catalyst AlCl32g, load thermometer and condenser pipe, under nitrogen protection, be stirred at room temperature 30min, it is then heated to 80 DEG C of reaction 12h；（3）After reaction to setting time, 50% ethanol solution terminating reaction is added, it is cold But to room temperature, filter in Buchner funnel, respectively with ethanol and 1% hydrochloric acid rinse, then cleaned with deionized water to filter liquor Untill colourless, the apparatus,Soxhlet's equipped with methanol is used to extract 24h in polymer, taking-up is dried, and is subsequently placed in 50 DEG C of vacuum and is dried 24h is dried in case, produces waste polystyrene base superhigh cross-linking polymer（It is named as HCP-A）.HCP-A Fourier transformation declines Subtract In situ ATR-FTIR figure (ATR-FTIR) (in Fig. 7（a）Curve) and nuclear magnetic resonance of carbon wave spectrum (13C NMR)（In Fig. 8（a） Curve）Confirm that the superhigh cross-linking polymer is successfully prepared.
HCP-A has good chemical stability, is in particular in：Insoluble in common organic solvents（Such as N, N- dimethyl Formamide, dimethyl sulfoxide (DMSO), tetrahydrofuran, toluene etc.）And 1 mol/L hydrochloric acid and 1 mol/L sodium hydroxide solutions.Meanwhile HCP-A has good heat endurance, at 443 DEG C（In thermogravimetric analysis, temperature that polystyrene decomposes completely（In Fig. 9（e）It is bent Line））, only 27.7% HCP-A decomposed（In Fig. 9（a）Curve）.And its BET specific surface area is 777m2/ g, micropore ratio Surface area is 362m2/ g, pore volume 0.76cm3/g；Average pore size 3.90nm, pore-size distribution concentrate on micro-porous area and mesoporous Region（In Figure 10（a）Curve）.Under 273K and 1bar, to CO2Adsorbance be 2.521 mmol/g（Or 11.1 wt%）(figure In 11（a）Curve), to N2Adsorbance be 0.1483 mmol/g (in Figure 12（a）Curve)；To CO2Heat of adsorption be 40.4 kJ/mol；To CO2：N2=15：Adsorptive selectivity in 85 mixed gas is 37.8.
Embodiment 2
（1）By discarded ordinary polystyrene（WPS）Particle reclaims, and is cleaned up with ethanol solution and deionized water, is entered with baking oven Row is standby after drying；（2）Discarded ordinary polystyrene particle 2g, organic solvent p-nitrophenyl are separately added into reaction vessel 80mL, crosslinking agent dimethoxymethane 1.5g and catalyst AlCl34g, load thermometer and condenser pipe, under nitrogen protection, 30min is stirred at room temperature, is then heated to 80 DEG C of reaction 18h；（3）After reaction to setting time, 50% ethanol solution termination is added Reaction, is cooled to room temperature, is filtered in Buchner funnel, respectively with ethanol and 1% hydrochloric acid rinse, then cleaned with deionized water Untill filter liquor is colourless, the apparatus,Soxhlet's equipped with methanol is used to extract 24h in polymer, taking-up is dried, and places it into 50 24h is dried in DEG C vacuum drying oven, produces waste polystyrene base superhigh cross-linking polymer（It is named as HCP-B）.In HCP-B Fu Leaf transformation decay In situ ATR-FTIR figure (ATR-FTIR) is (in Fig. 7（b）Curve) and nuclear magnetic resonance of carbon wave spectrum (13C NMR) （In Fig. 8（b）Curve）Successfully confirm the preparation of the superhigh cross-linking polymer.
HCP-B has good chemical stability, is in particular in：Insoluble in common organic solvents（Such as N, N- dimethyl Formamide, dimethyl sulfoxide (DMSO), tetrahydrofuran, toluene etc.）And 1 mol/L hydrochloric acid and 1 mol/L sodium hydroxide solutions.Meanwhile HCP-B has good heat endurance, at 443 DEG C（In thermogravimetric analysis, temperature that polystyrene decomposes completely）, only 15.92% Superhigh cross-linking polymer HCP-B decomposed（In Fig. 9（b）Curve）.And its BET specific surface area is 768m2/ g, micropore ratio Surface area is 293m2/ g, pore volume 0.60cm3/g；Average pore size 3.11nm, pore-size distribution concentrate on micro-porous area and mesoporous Region（In Figure 10（b）Curve）.Under 273K and 1bar, to CO2Adsorbance be 2.149 mmol/g (in Figure 11（b）It is bent Line), the adsorbance to N2 is 0.1624 mmol/g (in Figure 12（b）Curve)；To CO2Heat of adsorption be 41.1kJ/mol；It is right CO2：N2=15：Adsorptive selectivity in 85 mixed gas is 24.7.
Embodiment 3
（1）By discarded high impact polystyrene（WHIPS）Particle reclaims, and is cleaned up with ethanol solution and deionized water, with baking Case is dried rear standby；（2）Discarded high impact polystyrene particle 3g, organic solvent dichloro are separately added into reaction vessel Ethane 90mL, crosslinking agent are to benzyl dichloride 1.75g and catalyst Fe Cl35g, load thermometer and condenser pipe, under nitrogen protection, 30min is stirred at room temperature, is then heated to 83 DEG C of reaction 24h；（3）After reaction to setting time, 50% ethanol solution termination is added Reaction, is cooled to room temperature, is filtered in Buchner funnel, respectively with ethanol and 1% hydrochloric acid rinse, then cleaned with deionized water Untill filter liquor is colourless, the apparatus,Soxhlet's equipped with methanol is used to extract 24h in polymer, taking-up is dried, and places it into 50 24h is dried in DEG C vacuum drying oven, produces waste polystyrene base superhigh cross-linking polymer（It is named as HCP-C）.In HCP-C Fu Leaf transformation decay In situ ATR-FTIR figure (ATR-FTIR) is (in Fig. 7（c）Curve) and nuclear magnetic resonance of carbon wave spectrum (13C NMR) （In Fig. 8（c）Curve）Successfully confirm the preparation of the superhigh cross-linking polymer.
HCP-C has good chemical stability, is in particular in：Insoluble in common organic solvents（Such as N, N- dimethyl Formamide, dimethyl sulfoxide (DMSO), tetrahydrofuran, toluene etc.）And 1 mol/L hydrochloric acid and 1 mol/L sodium hydroxide solutions.Meanwhile HCP-C has good heat endurance, at 443 DEG C（In thermogravimetric analysis, temperature that polystyrene decomposes completely）, only 18.26% Superhigh cross-linking polymer HCP-C decomposed（In Fig. 9（c）Curve）.And its BET specific surface area is 611m2/ g, micropore ratio Surface area is 256m2/ g, pore volume 0.91cm3/g；Average pore size 5.96nm, pore-size distribution concentrate on micro-porous area and mesoporous Region（In Figure 10（c）Curve）.Under 273K and 1bar, to CO2Adsorbance be 2.104 mmol/g (in Figure 11（c）It is bent Line), to N2Adsorbance be 0.2482 mmol/g (in Figure 12（c）Curve)；To CO2Heat of adsorption be 24.6 kJ/mol；It is right CO2：N2=15：Adsorptive selectivity in 85 mixed gas is 15.1.
Embodiment 4
（1）By discarded syndiotactic polytyrene（WSPS）Particle reclaims, and is cleaned up with ethanol solution and deionized water, is entered with baking oven Row is standby after drying；（2）Discarded syndiotactic polystyrene particles 4g, organic solvent ortho-xylene are separately added into reaction vessel 95mL, crosslinking agent are to dichloromethyl biphenyl 2.51g and catalyst AlCl36g, load thermometer and condenser pipe, protected in nitrogen Under, 30min is stirred at room temperature, is then heated to 85 DEG C of reaction 24h；（3）After reaction to setting time, 50% ethanol solution is added Terminating reaction, room temperature is cooled to, is filtered in Buchner funnel, respectively with ethanol and 1% hydrochloric acid rinse, then use deionized water Cleaning uses the apparatus,Soxhlet's equipped with methanol to extract 24h untill filter liquor is colourless, by polymer, and taking-up is dried, it is put 24h is dried in 50 DEG C of vacuum drying ovens, produces waste polystyrene base superhigh cross-linking polymer（It is named as HCP-D）.HCP-D's ATR-FTIR Spectrometry figure (ATR-FTIR) is (in Fig. 7（d）Curve) and nuclear magnetic resonance of carbon wave spectrum (13C NMR)（In Fig. 8（d）Curve）Successfully confirm the preparation of the superhigh cross-linking polymer.
HCP-D has good chemical stability, is in particular in：Insoluble in common organic solvents（Such as N, N- dimethyl Formamide, dimethyl sulfoxide (DMSO), tetrahydrofuran, toluene etc.）And 1 mol/L hydrochloric acid and 1 mol/L sodium hydroxide solutions.Meanwhile HCP-D has good heat endurance, at 443 DEG C（In thermogravimetric analysis, temperature that polystyrene decomposes completely）, only 14.22% Superhigh cross-linking polymer HCP-D decomposed（In Fig. 9（d）Curve）.And its BET specific surface area is 673m2/ g, micropore ratio Surface area is 382m2/ g, pore volume 1.15cm3/g；Average pore size 6.86nm, pore-size distribution concentrate on micro-porous area and mesoporous Region（In Figure 10（d）Curve）.Under 273K and 1bar, to CO2Adsorbance be 2.250 mmol/g (in Figure 11（d）It is bent Line), to N2Adsorbance be 0.2423 mmol/g (in Figure 12（d）Curve)；To CO2Heat of adsorption be 21.8kJ/mol；It is right CO2：N2=15：Adsorptive selectivity in 85 mixed gas is 15.2.
Embodiment 5
Gas absorption and separating experiment：The superhigh cross-linking polymer prepared is subjected to gas absorption experiment with gas absorption instrument, The measuring method of adsorbance is as follows：50 mg superhigh cross-linking polymer are put into sample cell, vacuumized, in certain temperature （273K or 298K）Under the conditions of, gas will be tested（CO2Or N2）Gas test port is accessed, measurement superhigh cross-linking polymer is to gas The adsorption isothermal curve of body molecule.Superhigh cross-linking polymer is calculated to CO according to Clausius-Clapeyron equations2Absorption Heat（Qst）.According to IAST（Ideal adsorption solution theory）Equation calculates superhigh cross-linking polymer to CO2With N2Adsorptive selectivity.
In summary, the invention provides a kind of cross-linked polymer based on waste polystyrene and preparation method thereof with answering With the present invention uses discarded polystyrene, and for body material, not only wide material sources, cost are low, and are discarded polyphenyl second The recycling of alkene provides a kind of effective way, is advantageous to the protection of ecological environment, has expanded its application；This hair simultaneously It is bright to employ crosslinking agent and be aided with catalyst, through single step reaction so that polystyrene to form highly cross-linked 3 D stereo netted more Pore structure, available for solid adsorption material field, solves the mistake that traditional synthesizing porous solid adsorption material need to consume costliness Cross metallic catalyst, can not industrial applications the problem of.
The cross-linked polymer of the present invention has good chemical stability, is in particular in：Insoluble in common organic solvents （Such as N,N-dimethylformamide, dimethyl sulfoxide (DMSO), tetrahydrofuran, toluene）And 1 mol/L hydrochloric acid and 1 mol/L hydroxides Sodium solution.The cross-linked polymer of the present invention has good heat endurance simultaneously, at 443 DEG C（In thermogravimetric analysis, polystyrene is complete The temperature decomposed entirely）, only 13-28% superhigh cross-linking polymer decomposed.And its BET specific surface area reaches as high as 777m2/ g, micropore specific area reach as high as 382m2/ g, pore volume reach as high as 1.15cm3/g；Average pore size 3.11- 6.86nm, pore-size distribution concentrate on micro-porous area and mesoporous region.Under 273K and 1bar, to CO2Adsorbance reach as high as 2.521 mmol/g（Or 11.1wt%）, to CO2Heat of adsorption reach as high as 41.1 kJ/mol；To CO2：N2=15：85 mixing Adsorptive selectivity in gas reaches as high as 37.8, can be applied to CO in factory smoke2Absorption and separation.
It should be appreciated that the application of the present invention is not limited to above-mentioned citing, for those of ordinary skills, can To be improved or converted according to the above description, all these modifications and variations should all belong to the guarantor of appended claims of the present invention Protect scope.

Claims (10)

  1. A kind of 1. preparation method of the cross-linked polymer based on waste polystyrene, it is characterised in that including：
    Step A, by weight percentage, by waste polystyrene 1-6%, organic solvent 80-90%, crosslinking agent 1-6%, catalyst 2-8% is mixed, and under protective atmosphere, 10-50min is stirred at room temperature, and is then heated to 80-90 DEG C of reaction 6-24h；
    Step B, in through the reacted solution of step A, alcoholic solution terminating reaction is added, is subsequently cooled to room temperature and through carrying Pure processing, obtains cross-linked polymer.
  2. 2. the preparation method of the cross-linked polymer according to claim 1 based on waste polystyrene, it is characterised in that Before the step A, first waste polystyrene is cleaned up, and dried.
  3. 3. the preparation method of the cross-linked polymer according to claim 1 based on waste polystyrene, it is characterised in that institute State in step A, the crosslinking agent be carbon tetrachloride, dimethoxymethane, to benzyl dichloride, to dichloromethyl biphenyl and three chloromethane One kind in benzene.
  4. 4. the preparation method of the cross-linked polymer according to claim 1 based on waste polystyrene, it is characterised in that institute State in step A, the catalyst is FeCl3And AlCl3In one kind.
  5. 5. the preparation method of the cross-linked polymer according to claim 1 based on waste polystyrene, it is characterised in that institute State in step A, the organic solvent is in toluene, ortho-xylene, ethylbenzene, dichloromethane, dichloroethanes, chloroform and p-nitrophenyl One kind.
  6. 6. the preparation method of the cross-linked polymer according to claim 1 based on waste polystyrene, it is characterised in that institute State in step B, the concentration of the alcoholic solution is 40-60 V/V%.
  7. 7. the preparation method of the cross-linked polymer according to claim 1 based on waste polystyrene, it is characterised in that institute State in step B, the purification processes are specially：By the reacting liquid filtering after cooling, ethanol and dilute hydrochloric acid solution are then used respectively Rinse, and cleaned with deionized water untill filter liquor is colourless, finally much filtrate is taken out with the apparatus,Soxhlet's equipped with methanol 18-30h is carried, is dried, is then dried in vacuo 18-30h in 40-60 DEG C.
  8. 8. a kind of cross-linked polymer based on waste polystyrene, it is characterised in that by any described preparations of claim 1-7 Method is made.
  9. 9. the cross-linked polymer according to claim 8 based on waste polystyrene, it is characterised in that there is micropore knot Structure.
  10. A kind of 10. application of the cross-linked polymer based on waste polystyrene as claimed in claim 8 or 9, it is characterised in that For CO2Absorption and separation.
CN201710936463.2A 2017-10-10 2017-10-10 Crosslinked polymer based on waste polystyrene, and preparation method and application thereof Active CN107759812B (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN201710936463.2A CN107759812B (en) 2017-10-10 2017-10-10 Crosslinked polymer based on waste polystyrene, and preparation method and application thereof
PCT/CN2018/108310 WO2019072105A1 (en) 2017-10-10 2018-09-28 Waste polystyrene-based crosslinked polymer, preparation method therefor and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710936463.2A CN107759812B (en) 2017-10-10 2017-10-10 Crosslinked polymer based on waste polystyrene, and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN107759812A true CN107759812A (en) 2018-03-06
CN107759812B CN107759812B (en) 2020-12-15

Family

ID=61267021

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710936463.2A Active CN107759812B (en) 2017-10-10 2017-10-10 Crosslinked polymer based on waste polystyrene, and preparation method and application thereof

Country Status (2)

Country Link
CN (1) CN107759812B (en)
WO (1) WO2019072105A1 (en)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019072105A1 (en) * 2017-10-10 2019-04-18 深圳大学 Waste polystyrene-based crosslinked polymer, preparation method therefor and application thereof
CN109701505A (en) * 2019-01-11 2019-05-03 武汉工程大学 A kind of crosslinked polystyrene adsorbent and its preparation method and application
CN110437489A (en) * 2019-08-30 2019-11-12 济南大学 A kind of method that waste and old expanded polystyrene (EPS) recycling prepares super cross-linked porous material
CN111876142A (en) * 2020-07-27 2020-11-03 西安奥德石油工程技术有限责任公司 High-temperature-resistant capsule gel breaker for fracturing and preparation method thereof
CN112341724A (en) * 2020-12-01 2021-02-09 贵州凯科特材料有限公司 Composition for preparing microcellular foam material, microcellular foam material and preparation method thereof
CN113856645A (en) * 2021-09-13 2021-12-31 山东大学 Tetraene silane-polystyrene adsorbent
CN113856644A (en) * 2021-09-13 2021-12-31 山东大学 Application of tetraene silane-polystyrene adsorbent in aspect of adsorbing aniline
CN114262425A (en) * 2021-12-31 2022-04-01 郑州大学 Naphthyl hypercrosslinked microporous polymer and preparation method and application thereof
CN116253321A (en) * 2023-04-13 2023-06-13 大连理工大学 Method for preparing porous carbon material by using polyvinyl chloride and polystyrene and application thereof

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2584207B (en) * 2019-05-13 2023-08-02 Indufil BV Method for removing a degraded component from a hydrocarbon fluid and a porous medium for achieving the same

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3822244A (en) * 1971-02-15 1974-07-02 Co Fr De Raffinage Process for the crosslinking of polystyrene
CN1269370A (en) * 1999-04-01 2000-10-11 王传玉 Petroleum resin modified with the by product of styrene and its paint material and production process
CN101003592A (en) * 2006-12-29 2007-07-25 南京工业大学 Polystyrene resin of containing double bond, and preparation method
CN101987291A (en) * 2010-11-05 2011-03-23 山东鲁抗立科药物化学有限公司 Macropore adsorption resin as well as preparation method and application thereof

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DD267033A1 (en) * 1987-12-28 1989-04-19 Friedrich Schiller Uni Jena Bf PROCESS FOR PRODUCING SUBSTITUTED AROMATES
CN1687152B (en) * 2005-04-08 2010-05-05 南京工业大学 Carrier of separating amino acid and preparation method thereof
CN101033305A (en) * 2007-02-06 2007-09-12 南京大学 Method of increasing hydrophilicity of complex function adsorption resin and reinforcing adsorbability of the complex function adsorption resin
CN100494231C (en) * 2007-02-09 2009-06-03 南开大学 Preparation of screening type adsorption resin and application thereof in separating panaxoside monomer Rb1
CN101633594B (en) * 2009-08-20 2012-12-05 镇江市海通化工有限公司 Environmental-friendly Friedel-Crafts reaction postprocessing method
KR101631536B1 (en) * 2011-08-09 2016-06-17 도레이 카부시키가이샤 Carrier for adsorption and method for producing same
CN102509629A (en) * 2011-09-29 2012-06-20 中山大学 High-specific-area layered pore carbon material as well as preparation method and application thereof
CN102500341B (en) * 2011-10-17 2013-12-25 河北工业大学 Three-dimensionally ordered macroporous material (3DOM) for adsorbing and separating organic molecules
CN103159886B (en) * 2013-04-03 2015-04-01 湖南科技大学 Preparation method of superhigh-specific-area monodisperse polymer microspheres
US20180050328A1 (en) * 2015-04-15 2018-02-22 Agency For Science, Technology And Research Modified porous hypercrosslinked polymers for co2 capture and conversion
CN107759812B (en) * 2017-10-10 2020-12-15 深圳大学 Crosslinked polymer based on waste polystyrene, and preparation method and application thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3822244A (en) * 1971-02-15 1974-07-02 Co Fr De Raffinage Process for the crosslinking of polystyrene
CN1269370A (en) * 1999-04-01 2000-10-11 王传玉 Petroleum resin modified with the by product of styrene and its paint material and production process
CN101003592A (en) * 2006-12-29 2007-07-25 南京工业大学 Polystyrene resin of containing double bond, and preparation method
CN101987291A (en) * 2010-11-05 2011-03-23 山东鲁抗立科药物化学有限公司 Macropore adsorption resin as well as preparation method and application thereof

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019072105A1 (en) * 2017-10-10 2019-04-18 深圳大学 Waste polystyrene-based crosslinked polymer, preparation method therefor and application thereof
CN109701505B (en) * 2019-01-11 2022-05-10 武汉工程大学 Crosslinked polystyrene adsorbent and preparation method and application thereof
CN109701505A (en) * 2019-01-11 2019-05-03 武汉工程大学 A kind of crosslinked polystyrene adsorbent and its preparation method and application
CN110437489A (en) * 2019-08-30 2019-11-12 济南大学 A kind of method that waste and old expanded polystyrene (EPS) recycling prepares super cross-linked porous material
CN111876142B (en) * 2020-07-27 2022-08-09 西安奥德石油工程技术有限责任公司 High-temperature-resistant capsule gel breaker for fracturing and preparation method thereof
CN111876142A (en) * 2020-07-27 2020-11-03 西安奥德石油工程技术有限责任公司 High-temperature-resistant capsule gel breaker for fracturing and preparation method thereof
CN112341724A (en) * 2020-12-01 2021-02-09 贵州凯科特材料有限公司 Composition for preparing microcellular foam material, microcellular foam material and preparation method thereof
CN112341724B (en) * 2020-12-01 2023-06-30 贵州凯科特材料有限公司 Composition for preparing microporous foam material, microporous foam material and preparation method of microporous foam material
CN113856645A (en) * 2021-09-13 2021-12-31 山东大学 Tetraene silane-polystyrene adsorbent
CN113856644A (en) * 2021-09-13 2021-12-31 山东大学 Application of tetraene silane-polystyrene adsorbent in aspect of adsorbing aniline
CN113856645B (en) * 2021-09-13 2022-10-14 山东大学 Tetraene silane-polystyrene adsorbent
CN113856644B (en) * 2021-09-13 2022-10-14 山东大学 Application of tetraene silane-polystyrene adsorbent in aspect of adsorbing aniline
CN114262425A (en) * 2021-12-31 2022-04-01 郑州大学 Naphthyl hypercrosslinked microporous polymer and preparation method and application thereof
CN116253321A (en) * 2023-04-13 2023-06-13 大连理工大学 Method for preparing porous carbon material by using polyvinyl chloride and polystyrene and application thereof

Also Published As

Publication number Publication date
WO2019072105A1 (en) 2019-04-18
CN107759812B (en) 2020-12-15

Similar Documents

Publication Publication Date Title
CN107759812A (en) Cross-linked polymer based on waste polystyrene and preparation method and application
CN107540801B (en) Covalent organic framework and preparation method thereof
Molavi et al. Enhancing CO2/N2 adsorption selectivity via post-synthetic modification of NH2-UiO-66 (Zr)
CN111001439A (en) Perylene bisimide and composite photocatalytic material thereof, preparation method and application thereof in removing organic pollutants in water body
Li et al. Phosphine-based covalent organic framework for highly efficient iodine capture
Chen et al. Stable nitrogen-containing covalent organic framework as porous adsorbent for effective iodine capture from water
CN111286010B (en) Lipophilic super-hydrophobic porous aromatic skeleton material and preparation method and application thereof
CN109575308A (en) A kind of fluorine-containing covalent organic frame compound of two dimension without catalysis high efficiency preparation method
CN110218301A (en) One kind being based on the organic microporous polymer of conjugation and preparation method thereof of 1,3,5- tri- (4- Fonnylphenyl) benzene
CN105597708B (en) The preparation method of PM2.5 cleansers in a kind of air
CN104056599A (en) Composite carbon dioxide adsorption material, preparation method and application thereof
CN105418938A (en) Hierarchical pore HKUST-1 material, preparation method and appliance
CN113042011B (en) Application of fluorine-containing conjugated microporous polymer
CN108483421A (en) A kind of N doping ordered mesoporous carbon material and its preparation and application
Jiang et al. Constructing an ultra-adsorbent based on the porous organic molecules of noria for the highly efficient adsorption of cationic dyes
CN109225138A (en) The modified activated carbon and preparation method thereof of AOCs in a kind of efficient absorption PTA waste water
Lei et al. SO3H-functionalized porous organic polymer with amphiphilic and swelling properties: A highly efficient solid acid catalyst for organic transformations in water
CN113683740A (en) Halogen ion functionalized organic porous material and preparation method and application thereof
CN110961084A (en) Preparation method of modified chitosan aerogel and application of modified chitosan aerogel in adsorption of lithium ions
Wang et al. Sulfonated Hollow Covalent Organic Polymer: Highly‐Selective Adsorption toward Cationic Organic Dyes over Anionic Ones in Aqueous Solution
CN107417913B (en) Nano organic microporous polymer and method for adsorbing heavy metals in drinking water
CN109232226B (en) Microporous metal organic framework material and preparation method and application thereof
CN105797596A (en) Preparation method of filter membrane for water purification
CN102671628A (en) Microporous molecular sieve-functionalized ionic liquid composite material and preparation method thereof
CN106964323B (en) A kind of CO containing imine linkage2Adsorbent material and its preparation method and application

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant