CN104672389B - A kind of processing mthod of white water from paper making cationic microspheres and the preparation method and application thereof - Google Patents
A kind of processing mthod of white water from paper making cationic microspheres and the preparation method and application thereof Download PDFInfo
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- 125000002091 cationic group Chemical group 0.000 title claims abstract description 43
- 238000012545 processing Methods 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000004793 Polystyrene Substances 0.000 claims abstract description 79
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- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000011347 resin Substances 0.000 claims abstract description 20
- 229920005989 resin Polymers 0.000 claims abstract description 20
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- 239000003999 initiator Substances 0.000 claims abstract description 10
- 239000000178 monomer Substances 0.000 claims abstract description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 10
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- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000012153 distilled water Substances 0.000 claims description 13
- 238000001291 vacuum drying Methods 0.000 claims description 12
- 238000010792 warming Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 10
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 9
- YXYZMHGSOKYZAF-UHFFFAOYSA-M [Cl-].C(C(=C)C)(=O)OCC[N+](C(C)(C)C)(C)C Chemical group [Cl-].C(C(=C)C)(=O)OCC[N+](C(C)(C)C)(C)C YXYZMHGSOKYZAF-UHFFFAOYSA-M 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 3
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 2
- 238000004132 cross linking Methods 0.000 claims description 2
- 239000002002 slurry Substances 0.000 claims description 2
- 150000001263 acyl chlorides Chemical class 0.000 claims 1
- 239000007789 gas Substances 0.000 claims 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 17
- 150000001768 cations Chemical class 0.000 abstract description 10
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- 125000000129 anionic group Chemical group 0.000 abstract description 2
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- 239000010813 municipal solid waste Substances 0.000 abstract 1
- 239000000123 paper Substances 0.000 description 27
- 239000000047 product Substances 0.000 description 17
- 229920000867 polyelectrolyte Polymers 0.000 description 13
- 239000000126 substance Substances 0.000 description 8
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000003456 ion exchange resin Substances 0.000 description 6
- 229920003303 ion-exchange polymer Polymers 0.000 description 6
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- -1 tertiary amine ion Chemical class 0.000 description 2
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- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
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- 238000005863 Friedel-Crafts acylation reaction Methods 0.000 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
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- 239000002253 acid Substances 0.000 description 1
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention discloses a kind of processing mthod of white water from paper making cationic microspheres and the preparation method and application thereof.This method is：Polystyrene resin Archon is taken, is put into dichloromethane and is swollen, filter wash is dry, obtains pretreated polystyrene Archon；Pretreated polystyrene Archon is taken, anhydrous methylene chloride and acryloyl chloride is added, anhydrous Aluminum chloride is added, is stirred to react, filter wash, it is dry, obtain loaded by polystyrene acryloyl chloride resin；Loaded by polystyrene acryloyl chloride resin is taken, DMF swollens are added, cationic monomer is added, initiator is added after logical nitrogen, heats up, reaction is dry then by product filter wash, obtains processing mthod of white water from paper making cationic microspheres.This method is made cation polystyrene microballoon and is applied to processing mthod of white water from paper making, and the cationic demand of plain boiled water can be greatly reduced, and reduces the content of anionic trash, and activated processing can be repeated as many times and use.
Description
Technical field
The invention belongs to polymeric material fields, and in particular to a kind of processing mthod of white water from paper making cationic microspheres and its preparation
Method and application.
Background technology
Paper industry is one of most important industry in the world, and various paper products are provided for our daily lifes.However,
With in global range the industrial structure and the big adjustment of the international division of labor, paper industry be faced with three major issues：There is lack of raw materials, the energy
It is nervous, seriously polluted.Clean manufacturing is the inexorable trend of paper industry sustainable development, and " 12th Five-Year Plan " is that China's paper industry turns
Become development pattern, builds the critical period of scientific and technical innovation type, resource-conserving and the industry of environmentally friendly modern paper.Country's hair
Exhibition reform committee announces《Paper Industry Development " 12th Five-Year Plan " is planned》Positive facilitation is played to the development of clean manufacturing.
" planning " is distinctly claimed paper industry to year ends 2015, and the average water withdrawal of ton paper pulp, paper and cardboard was by 85m in 20103Under
It is down to 70m3, decline 18%.Currently, in paper industry, the circulating and recovering of white-water system is an important clean manufacturing way
Diameter.The closed circulation of plain boiled water can not only solve the pollution problem of draining, moreover it is possible to reduce fiber, thermal energy, clear water consumption, improve enterprise
Environmental image.But along with the closed circulation of plain boiled water, a large amount of dissolving and colloidal substance can be accumulated in paper manufacturing systems
（Dissolved and colloidal substances, abbreviation DCS）, these pollutants can seriously affect the operation of paper machine
Property, influence paper physical property, influence additive for paper making using effect.
Dissolving in paper manufacturing systems is divided into four kinds with colloidal substance according to the difference in source：Lignin from paper pulp raw material spreads out
Biology, hemicellulose, extract come from the stickums such as the adhesive, latex, macromolecule resin of regenerated fiber, come from
Metal ion in the dyestuff of chemical addition agent, carboxymethyl cellulose, starchy material and engineering water（Calcium, magnesium, aluminium）、
Minerals etc..How to be effectively removed DCS is the important link that plain boiled water recycles.
It in recent years, can using the sticking agent of high charge density, low molecular weight for the DCS in paper-making process Recirculating white water
DCS is fixed on fiber, on fiber fines, white-water system is taken out of, but the DCS substances being affixed in page can also influence paper machine
Maneuverability, especially squeezing and drying section.Other filtering embrane methods and biological enzyme, due to harsh service condition and higher life
Produce cost so that promote the use of and be restricted.Currently, absorption resin is since it is good with adsorption effect, desorption and regeneration is easy, property
It can be stable, the scope of application is wide, practicability is good, achievable comprehensive utilization the features such as, is widely used in water treatment industry.It will inhale
Attached resin-encapsulated can more easily remove the DCS in plain boiled water in a fluidized bed reactor.
Traditional ion exchange resin, especially anionic ion exchange resin, surface carry the season of a large amount of short chains
Ammonium, tertiary amine ion can be acted on by charge neutrality, adsorb the dissolving in plain boiled water and colloidal substance, utilize conventional organic solvent
It can be with regenerative adsorption resin.How the task performance of resin is improved（Such as adsorbance, the rate of adsorption）It is many engineers and technicians
Concern, processing mthod of white water from paper making are as the same.Using crosslinked polystyrene Archon as base material, by surface graft modification, in polyphenyl
Cationic polyelectrolyte is introduced on ethylene Archon, is creatively prepared a kind of capture dissolving and is preferably inhaled with colloidal substance effect
Attached resin.
Invention content
According to the technical characterstic of heterogeneous reaction, present invention is primarily aimed at provide a kind of processing mthod of white water from paper making it is positive from
Sub- microballoon and the preparation method and application thereof.Method and process mild condition in the present invention, obtained novel polyphenyl ethylene microballoon tool
Have impurity it is few, load cationic polyelectrolyte content it is high the features such as.
The present invention causes cation mono by introducing acryloyl chloride group on crosslinked polystyrene microsphere, with ammonium persulfate
The cation polystyrene microballoon is made in body MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride.
For achieving the above object, the present invention adopts the following technical scheme that.
A kind of preparation method of processing mthod of white water from paper making cationic microspheres, includes the following steps：
(1) pretreatment of polystyrene resin Archon：Polystyrene resin Archon is weighed, is put into dichloromethane and is swollen
With tetrahydrofuran filter wash 3~5 times after 2~4 hours, then with distilled water filter wash 3~5 times, then with absolute ethyl alcohol, each filter wash of methanol
2~3 times, drying 36~48 hours in 30~40 DEG C of vacuum drying chamber are finally put in, it is white to obtain pretreated polystyrene
Ball；
(2) prepared by loaded by polystyrene acryloyl chloride resin：Weigh 2.5~5.0g steps (1) obtain it is pretreated
Polystyrene Archon is added 20~100ml anhydrous methylene chlorides and 1.0~12.5g acryloyl chlorides, 1.8 is added at 5~30 DEG C
~21.0g anhydrous Aluminum chlorides under magnetic agitation, react 2~6 hours, then product is used successively absolute ethyl alcohol, 1% dilute salt
It is small to be finally put in 30~50 DEG C of vacuum drying chamber dry 24~48 by acid, distilled water, methanol filter wash 30~60 minutes for product
When, obtain flaxen spherical powder, i.e. loaded by polystyrene acryloyl chloride resin；
(3) preparation of cationization polystyrene microsphere：Weigh the loaded by polystyrene that 0.1~0.5g steps (2) obtain
Acryloyl chloride resin, is added 0.3g~36.5g DMF swollens 12~24 hours, is subsequently added into 0.2g~20.0g cationic monomers,
The initiator of 0.05mg~40mg is added after logical 30~60min of nitrogen, is warming up to 50~80 DEG C, reacts 12~24 hours, then
Product is used into distilled water, absolute ethyl alcohol, methanol filter wash 30~60 minutes successively, product is finally put in 30~50 DEG C of vacuum and is done
It is 24~48 hours dry in dry case, the spherical powder that surface is clear pale yellow color is obtained, that is, handles mthod of white water from paper making cationic microgel
Ball（Be cationized polystyrene microsphere）.
In the above method, step（1）In, the polystyrene resin Archon grain size is 200~400 μm, the degree of cross linking 5%
~10%.
In the above method, step（3）In, the cationic monomer is MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride,
Addition form is the aqueous solution that mass percent concentration is 60%~75%.
In the above method, step（5）In, the initiator is ammonium persulfate.
Nitrogen used above is High Purity Nitrogen, purity 99.99%.
It is a kind of cationization polystyrene microsphere be applied to processing mthod of white water from paper making, cationization polystyrene microsphere effect
In the Recirculating white water of APMP slurries, wherein cationization polystyrene microsphere is 5g/L~40g/ relative to the addition of plain boiled water
L。
The principle of the present invention is：First with friedel-crafts acylation, acryloyl is introduced on polystyrene resin Archon
Chlorine；Then it by cationic monomer MAC, is grafted on polystyrene microsphere by the method for free radical polymerization.
Compared with prior art, the present invention has the following advantages and beneficial effects：
Cationic polyelectrolyte is grafted on polystyrene microsphere by the present invention by heterogeneous initiation reaction, obtains sun
It ionizes the cationic polyelectrolyte content height of polystyrene microsphere and is more evenly distributed in Surfaces of Polystyrene Microparticles,
Graft modification is simple for process, dissolvent residual is less.The cation polystyrene microballoon can efficiently adsorb papermaking circulating plain boiled water
Middle dissolving and colloidal substance by simply elution action, and can be reused.
Description of the drawings
Fig. 1 is Fourier's infared spectrum of loaded by polystyrene polyelectrolyte microsphere prepared by embodiment 1, wherein a curves
For:Unmodified PS microballoons；B curves are:It is acylated PS microballoons；C curves are:Be cationized PS microballoons；
Fig. 2 is the electron scanning micrograph of unmodified PS microballoons in embodiment 1；
Fig. 3 is the electron scanning micrograph of cationization PS microballoons in embodiment 1；
Fig. 4 is the route map for preparing cationization polystyrene microsphere；
Fig. 5 is the variation that two kinds of absorption resins handle cationic demand after mthod of white water from paper making under different time；
Fig. 6 is two kinds and adsorbs being compared using repeatability for resin treatment mthod of white water from paper making.
Specific implementation mode
The present invention will be further specifically described in detail with reference to specific embodiments, but embodiments of the present invention are not
It is limited to this, for not specifically specified technological parameter, can refer to routine techniques progress.
Embodiment 1
(1) 100g polystyrene resin Archons are weighed, is put into dichloromethane and is swollen 4 hours, be then transferred to G2 sand cores
In funnel, with tetrahydrofuran filter wash 3 times, then with distilled water filter wash 3 times, absolute ethyl alcohol, each filter wash of methanol are then used 2 times, finally
Drying 48 hours in 40 DEG C of vacuum drying chamber are put in, pretreated polystyrene Archon is obtained；
(2) the pretreated Archon that 4.2g steps (1) obtain is weighed, 60ml anhydrous methylene chlorides and 7.2g third is added
11.6g anhydrous Aluminum chlorides are added in alkene acyl chlorides at 30 DEG C, under magnetic agitation, react 4 hours, then by product successively with anhydrous
Product is finally put in 50 DEG C of vacuum drying chamber dry 48 by ethyl alcohol, 1% dilute hydrochloric acid, distilled water, methanol filter wash 30 minutes
Hour, obtain flaxen spherical powder, i.e. loaded by polystyrene acryloyl chloride resin；
(3) weighing the load that 0.2g steps (2) obtain has the polystyrene microsphere of acryloyl chloride, and 1.2g DMF profits are added
Swollen 24 hours, being subsequently added into 1.3g MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chlorides, (addition form was：Mass percent concentration is
72% aqueous solution), lead to the ammonium persulfate solution of addition 0.04ml (25g/L) after nitrogen 30min, is warming up to 60 DEG C, reaction 4
Hour, then 80 DEG C are warming up to, keep the temperature 3 hours, then product is used to distilled water, absolute ethyl alcohol, methanol filter wash 30 minutes successively, most
Product is put in drying 48 hours in 50 DEG C of vacuum drying chamber afterwards, obtains the spherical powder that surface is clear pale yellow color, i.e., it is positive
Ionize polystyrene microsphere.
Cationization polystyrene microsphere testing result manufactured in the present embodiment is shown in Table 1.
Fig. 1 is Fourier's infared spectrum of cationization polystyrene microsphere manufactured in the present embodiment, from collection of illustrative plates
1733cm-1Ester group peak and 952cm-1Quaternary ammonium salt characteristic peak, show cationic polyelectrolyte（poly-MAC）Successfully
It is connected on polystyrene microsphere.
Fig. 2-Fig. 3 is the scanning electron microscopy that the present embodiment prepares each step product when cationization polystyrene microsphere
Mirror photo as can be seen from the figure without the Surfaces of Polystyrene Microparticles relative smooth of grafted cation polyelectrolyte, and is grafted
There is the Surfaces of Polystyrene Microparticles of cationic polyelectrolyte relatively rough.
Fig. 4 is the specific route map that the present embodiment prepares cationization polystyrene microsphere.First by paying a gram acylation
Reaction introduces acryloyl chloride molecule on polystyrene Archon surface, is eventually adding cationic monomer MAC, is to draw with ammonium persulfate
It sends out agent and carries out surface initiation free radical polymerization, prepare cationization polystyrene microsphere.
Embodiment 2
(1) method for preparing microsphere of loaded by polystyrene acryloyl chloride is the same as (1) in embodiment 1~(2).
(2) weighing the load that 0.2g steps (2) obtain has the polystyrene microsphere of acryloyl chloride, and 4.7g DMF profits are added
Swollen 24 hours, being subsequently added into 5.1g MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chlorides, (addition form was：Mass percent concentration is
72% aqueous solution), lead to the ammonium persulfate solution of addition 0.16ml (25g/L) after nitrogen 30min, is warming up to 60 DEG C, reaction 4
Hour, then 80 DEG C are warming up to, keep the temperature 3 hours, then product is used to distilled water, absolute ethyl alcohol, methanol filter wash 30 minutes successively, most
Product is put in drying 48 hours in 50 DEG C of vacuum drying chamber afterwards, obtains the spherical powder that surface is clear pale yellow color, i.e., it is positive
Ionize polystyrene microsphere.
Cationization polystyrene microsphere testing result manufactured in the present embodiment is shown in Table 1.
Embodiment 3
(1) method for preparing microsphere of loaded by polystyrene acryloyl chloride is the same as (1) in embodiment 1~(2).
(2) weighing the load that 0.2g steps (2) obtain has the polystyrene microsphere of acryloyl chloride, and 1.4g DMF profits are added
Swollen 24 hours, being subsequently added into 5.1g MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chlorides, (addition form was：Mass percent concentration is
72% aqueous solution), lead to the ammonium persulfate solution of addition 0.16ml (25g/L) after nitrogen 30min, is warming up to 60 DEG C, reaction 4
Hour, then 80 DEG C are warming up to, keep the temperature 3 hours, then product is used to distilled water, absolute ethyl alcohol, methanol filter wash 30 minutes successively, most
Product is put in drying 48 hours in 50 DEG C of vacuum drying chamber afterwards, obtains the spherical powder that surface is clear pale yellow color, i.e., it is positive
Ionize polystyrene microsphere.
Cationization polystyrene microsphere testing result manufactured in the present embodiment is shown in Table 1.
Embodiment 4
(1) method for preparing microsphere of loaded by polystyrene acryloyl chloride is the same as (1) in embodiment 1~(2).
(2) weighing the load that 0.2g steps (2) obtain has the polystyrene microsphere of acryloyl chloride, and 8.1g DMF profits are added
Swollen 24 hours, being subsequently added into 5.1g MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chlorides, (addition form was：Mass percent concentration is
72% aqueous solution), lead to the ammonium persulfate solution of addition 0.16ml (25g/L) after nitrogen 30min, is warming up to 60 DEG C, reaction 4
Hour, then 80 DEG C are warming up to, keep the temperature 3 hours, then product is used to distilled water, absolute ethyl alcohol, methanol filter wash 30 minutes successively, most
Product is put in drying 48 hours in 50 DEG C of vacuum drying chamber afterwards, obtains the spherical powder that surface is clear pale yellow color, i.e., it is positive
Ionize polystyrene microsphere.
Cationization polystyrene microsphere testing result manufactured in the present embodiment is shown in Table 1.
Embodiment 5
(1) method for preparing microsphere of loaded by polystyrene acryloyl chloride is the same as (1) in embodiment 1~(2).
(2) weighing the load that 0.2g steps (2) obtain has the polystyrene microsphere of acryloyl chloride, and 8.1g DMF profits are added
Swollen 24 hours, being subsequently added into 5.1g MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chlorides, (addition form was：Mass percent concentration is
72% aqueous solution), lead to the ammonium persulfate solution of addition 0.12ml (25g/L) after nitrogen 30min, is warming up to 60 DEG C, reaction 4
Hour, then 80 DEG C are warming up to, keep the temperature 3 hours, then product is used to distilled water, absolute ethyl alcohol, methanol filter wash 30 minutes successively, most
Product is put in drying 48 hours in 50 DEG C of vacuum drying chamber afterwards, obtains the spherical powder that surface is clear pale yellow color, i.e., it is positive
Ionize polystyrene microsphere.
Cationization polystyrene microsphere testing result manufactured in the present embodiment is shown in Table 1.
Embodiment 6
0.1g cationization polystyrene microspheres (embodiment 5), commodity ion exchange resin are weighed respectively（IRA-
900Cl）, it is added sequentially to 10ml and has been heated in 40 DEG C of mthod of white water from paper making, with magnetic stirrer suspension (100r/
Min), successively at 1 minute, 2 minutes, 5 minutes, 15 minutes, 30 minutes, 60 minutes, 120 minutes, 180 minutes, 240 minutes,
1ml supernatants are adsorbed, with particle charge analyzer（PCD-04）Measure its cationic demand.
Fig. 5 is that cation polystyrene microballoon (embodiment 5) and commodity ion exchange resin are chosen in embodiment 6（IRA-
900Cl）, the effect for handling mthod of white water from paper making compares.As can be seen from the figure homemade cation polystyrene microballoon handles papermaking
After plain boiled water, the cationic demand of plain boiled water declines fast compared with IRA-900Cl.When handling plain boiled water 15 minutes, homemade cation
Polystyrene microsphere can make plain boiled water cationic demand decline 58.28%, and IRA-900Cl can only make plain boiled water cationic demand
Decline 20.41%；After handling plain boiled water 120 minutes, after the two handles plain boiled water, cationic demand variation is all little.
Embodiment 7
0.1g cationization polystyrene microspheres (embodiment 5), commodity ion exchange resin are weighed respectively（IRA-
900Cl）, it is added sequentially to 10ml and has been heated in 40 DEG C of plain boiled water, with magnetic stirrer suspension (100r/min), according to
It is secondary over the course of 15 mins, adsorb 1ml supernatants, with particle charge analyzer（PCD-04）Its cationic demand is measured, then will
Suspension containing absorption resin pours into G2 sand core funnels, uses the sodium hydroxide of 0.1mol/L, dilute salt of 0.1mol/L successively
Twice, deionized water filter wash 3 times removes the moisture of resin surface, finally by wet resin to sour, 0.1mol/L sodium hydroxide filter wash
It places into 10ml to be heated in 40 DEG C of plain boiled water, operating procedure more than repetition executes 10 times, measures supernatant after each processing
The cationic demand of liquid.
Fig. 6 is cationic polystyrene microsphere (embodiment 5) and commodity ion exchange resin in embodiment 7（IRA-
900Cl）After handling mthod of white water from paper making, the comparison of repeatability is used.It can be seen from the figure that after two kinds of resin treatment plain boiled waters, plain boiled water
Cationic demand all has dropped, and with the increase of number of processes, processing capacity, which has, slightly to be declined.For the first time handle after sun from
Sub- polystyrene microsphere and IRA-900Cl make plain boiled water cationic demand decline 57.62%, 33.11% respectively；After processing 10 times,
Cation polystyrene microballoon and IRA-900Cl make plain boiled water cationic demand decline 49.67%, 15.89% respectively.
The testing result of loaded by polystyrene polyelectrolyte microsphere prepared by 1 embodiment 1 ~ 5 of table
| Sample | PS/MAC | MAC concentration | Initiator concentration | N% | Rate of body weight gain | Polyelectrolyte loading (mmol/g) |
| Embodiment 1 | 1:5 | 40% | 0.1% | 2.1 | 30.99% | 1.5 |
| Embodiment 2 | 1:20 | 40% | 0.1% | 2.45 | 49.61% | 1.75 |
| Embodiment 3 | 1:20 | 60% | 0.1% | 1.78 | 26.02% | 1.27 |
| Embodiment 4 | 1:20 | 30% | 0.1% | 2.32 | 48.27% | 1.66 |
| Embodiment 5 | 1:20 | 30% | 0.075% | 2.53 | 53.83% | 1.81 |
As it can be seen from table 1 under identical cationic monomer and initiator concentration, PS is 1 with cation mono body mass ratio:20
When, polyelectrolyte load capacity reaches 1.75mmol/g, and PS/MAC is 1:Load capacity when 5 only has 1.5mmol/g；Work as PS/MAC
It is not that cationic monomer MAC concentration more high load amount is higher when identical with initiator concentration, after comparison, cationic monomer
When MAC is 30%, the polyelectrolyte content loaded on PS microballoons is ideal；When PS/MAC is 1:When 20, MAC a concentration of 30%,
Compare different initiator concentrations to find, when initiator concentration is 0.075%, the loading highest of cationic polyelectrolyte reaches
1.81mmol/g。
The above embodiment of the present invention be only to clearly illustrate example of the present invention, and not be to the present invention
Embodiment restriction.For those of ordinary skill in the art, it can also make on the basis of the above description
Other various forms of variations or variation.There is no necessity and possibility to exhaust all the enbodiments.It is all the present invention
All any modification, equivalent and improvement etc., should be included in the protection of the claims in the present invention made by within spirit and principle
Within the scope of.
Claims (3)
1. a kind of preparation method of processing mthod of white water from paper making cationic microspheres, which is characterized in that include the following steps：
(1) pretreatment of polystyrene resin Archon：Polystyrene resin Archon is weighed, is put into dichloromethane and is swollen 2~4
With tetrahydrofuran filter wash 3~5 times after hour, then with distilled water filter wash 3~5 times, then with each filter wash of absolute ethyl alcohol, methanol 2~3
It is secondary, drying 36~48 hours in 30~40 DEG C of vacuum drying chamber are finally put in, pretreated polystyrene Archon is obtained；
(2) prepared by loaded by polystyrene acryloyl chloride resin：Weigh the pretreated polyphenyl that 2.5~5.0g steps (1) obtain
20~100ml anhydrous methylene chlorides and 1.0~12.5g acryloyl chlorides is added in ethylene Archon, it is added 1.8 at 5~30 DEG C~
21.0g anhydrous Aluminum chlorides under magnetic agitation, react 2~6 hours, then product is used successively absolute ethyl alcohol, 1% dilute hydrochloric acid,
Product is finally put in drying 24~48 hours in 30~50 DEG C of vacuum drying chamber by distilled water, methanol filter wash 30~60 minutes,
Obtain flaxen spherical powder, i.e. loaded by polystyrene acryloyl chloride resin；
(3) preparation of cationization polystyrene microsphere：Weigh the loaded by polystyrene propylene that 0.1~0.5g steps (2) obtain
Acyl chlorides resin, is added 0.3g~36.5g DMF swollens 12~24 hours, is subsequently added into 0.2g~20.0g cationic monomers, leads to nitrogen
The initiator of 0.05mg~40mg is added after 30~60min of gas, is warming up to 50~80 DEG C, reacts 12~24 hours, it then will production
Object uses distilled water, absolute ethyl alcohol, methanol filter wash 30~60 minutes successively, and product is finally put in 30~50 DEG C of vacuum drying chamber
Middle drying 24~48 hours obtains the spherical powder that surface is clear pale yellow color, that is, handles mthod of white water from paper making cationic microspheres；
The polystyrene resin Archon grain size is 200~400 μm, and the degree of cross linking is 5%~10%；
The cationic monomer is MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, and addition form is that mass percent concentration is
60%~75% aqueous solution；
The initiator is ammonium persulfate.
2. obtaining a kind of processing mthod of white water from paper making cationic microspheres by preparation method described in claim 1.
3. the cationic microspheres described in claim 2 are applied to processing mthod of white water from paper making, which is characterized in that cationic microspheres act on
In the Recirculating white water of APMP slurries, wherein cationic microspheres are 5g/L~40g/L relative to the addition of plain boiled water.
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| CN1931913A (en) * | 2005-09-14 | 2007-03-21 | 中国科学院过程工程研究所 | Surface functionalizing process of magnetic polystyrene microsphere |
| CN103159878A (en) * | 2013-04-03 | 2013-06-19 | 湖南科技大学 | Simple method for preparing monodisperse cationic polystyrene microspheres |
| CN103897120A (en) * | 2014-03-07 | 2014-07-02 | 浙江理工大学 | Synthesis method of cation cyclodextrin polymer and application in waster paper papermaking wet part |
| CN104311745A (en) * | 2014-10-15 | 2015-01-28 | 华南理工大学 | Preparation method of polystyrene-loaded cationic polyelectrolyte microsphere |
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| CN1931913A (en) * | 2005-09-14 | 2007-03-21 | 中国科学院过程工程研究所 | Surface functionalizing process of magnetic polystyrene microsphere |
| CN103159878A (en) * | 2013-04-03 | 2013-06-19 | 湖南科技大学 | Simple method for preparing monodisperse cationic polystyrene microspheres |
| CN103897120A (en) * | 2014-03-07 | 2014-07-02 | 浙江理工大学 | Synthesis method of cation cyclodextrin polymer and application in waster paper papermaking wet part |
| CN104311745A (en) * | 2014-10-15 | 2015-01-28 | 华南理工大学 | Preparation method of polystyrene-loaded cationic polyelectrolyte microsphere |
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