CN112538183A - Preparation method of surface hydroxylated polystyrene resin - Google Patents
Preparation method of surface hydroxylated polystyrene resin Download PDFInfo
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- CN112538183A CN112538183A CN202011162241.8A CN202011162241A CN112538183A CN 112538183 A CN112538183 A CN 112538183A CN 202011162241 A CN202011162241 A CN 202011162241A CN 112538183 A CN112538183 A CN 112538183A
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- polystyrene resin
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- 229920005990 polystyrene resin Polymers 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000004005 microsphere Substances 0.000 claims abstract description 58
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 39
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 26
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 13
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 230000004048 modification Effects 0.000 claims abstract description 12
- 238000012986 modification Methods 0.000 claims abstract description 12
- 238000001914 filtration Methods 0.000 claims abstract description 10
- 230000008961 swelling Effects 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910021642 ultra pure water Inorganic materials 0.000 claims abstract description 7
- 239000012498 ultrapure water Substances 0.000 claims abstract description 7
- 239000002245 particle Substances 0.000 claims abstract description 6
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000005457 ice water Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 9
- PUGUQINMNYINPK-UHFFFAOYSA-N tert-butyl 4-(2-chloroacetyl)piperazine-1-carboxylate Chemical compound CC(C)(C)OC(=O)N1CCN(C(=O)CCl)CC1 PUGUQINMNYINPK-UHFFFAOYSA-N 0.000 claims description 9
- 239000003153 chemical reaction reagent Substances 0.000 claims description 7
- 230000033444 hydroxylation Effects 0.000 claims description 7
- 238000005805 hydroxylation reaction Methods 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 10
- 238000006116 polymerization reaction Methods 0.000 abstract description 10
- 229920005989 resin Polymers 0.000 abstract description 10
- 239000011347 resin Substances 0.000 abstract description 10
- 239000000178 monomer Substances 0.000 abstract description 6
- 238000009826 distribution Methods 0.000 abstract description 4
- 238000005727 Friedel-Crafts reaction Methods 0.000 abstract description 3
- 238000001291 vacuum drying Methods 0.000 abstract 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- 230000004584 weight gain Effects 0.000 description 3
- 235000019786 weight gain Nutrition 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 238000002715 modification method Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 238000007265 chloromethylation reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000012844 infrared spectroscopy analysis Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000009828 non-uniform distribution Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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- 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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/02—Chemical treatment or coating of shaped articles made of macromolecular substances with solvents, e.g. swelling agents
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- 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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
-
- 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
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention provides a preparation method of surface hydroxylated polystyrene resin, wherein the used unmodified resin is large-particle size polystyrene resin, and the monomer for modification is 4-chlorophenol. Firstly, swelling polystyrene resin microspheres by using dichloromethane, then sequentially washing and filtering by using tetrahydrofuran, ultrapure water, absolute ethyl alcohol and methanol for a plurality of times, and finally carrying out vacuum drying; then the pre-treated resin and 4-chlorophenol are subjected to Friedel-crafts reaction to obtain the hydroxylated polystyrene resin microspheres. The invention solves the problems of complex and unstable reaction process, low polymerization degree of surface hydroxyl and uneven distribution when the surface of the traditional polystyrene resin microsphere is grafted with hydroxyl.
Description
[ technical field ] A method for producing a semiconductor device
The invention relates to a surface hydroxylated polystyrene resin and a preparation method thereof.
[ background of the invention ]
The polystyrene resin microspheres are rigid beads prepared by using styrene as a monomer and divinylbenzene as a crosslinking agent, and the diameters of the rigid beads are different from dozens of nanometers to hundreds of micrometers. The different sizes determine the different physical properties of the microspheres. The nano-scale polystyrene resin microspheres are usually used as a carrier of a catalyst because of their relatively small surface energy. The micron-level polystyrene resin microspheres have larger surface energy, and the reaction activation energy cannot be effectively reduced when the micron-level polystyrene resin microspheres are used as catalyst carriers, but the effect of using the micron-level polystyrene resin microspheres as adsorbents is better. Compared with the pure solid resin microspheres, the resin microspheres with porous structures have higher specific surface areas and higher adsorption properties.
The unmodified polystyrene resin microspheres cannot meet the specific adsorption application requirements, and the modification of polystyrene resin to enable the polystyrene resin to meet the use under specific conditions is the key point and the main direction of the research and development of the current polystyrene resin microspheres. At present, there are two main methods for preparing surface hydroxylated polystyrene resin microspheres, one is to perform chloromethylation on polystyrene resin and then perform hydroxylation modification (Chinese patent CN104492402B), and the disadvantages are that the preparation process is complicated and the cost is high. The other method is to use soap-free emulsion polymerization, add hydroxyethyl acrylate and other medicines to copolymerize with styrene to obtain hydroxylated polystyrene composite microspheres, which mainly has two defects, firstly, the addition of auxiliary monomer for copolymerization can cause the steric hindrance effect in the polymerization process to be aggravated, thus causing the polymer on the surface to be unevenly distributed and the degree of polymerization to be lower; secondly, the method is susceptible to unstable factors in the copolymerization process, so that the distribution of hydroxyl groups on the microspheres is not uniform.
Functional groups can be directly grafted on the surface of the polystyrene resin microsphere by utilizing Friedel-crafts reaction, compared with the traditional modification method, the grafted functional groups are more in number and are uniformly distributed, the experimental steps are simple, and the reaction process is stable and easy to obtain.
The traditional polystyrene resin microsphere surface modification method adopts the polystyrene resin with smaller grain diameter, and the modification is easier. The resin microspheres with larger size are more convenient in application, but for polystyrene resin microspheres with the size of hundreds of micrometers or even larger, the surface area is larger, and the chemical modification is difficult. The existing polystyrene resin microsphere surface modification usually adopts monomer direct polymerization, and a steric hindrance effect exists in the polymerization process to influence the further polymerization of the monomer, so that the polymer on the resin microsphere surface is unevenly distributed and has low polymerization degree.
[ summary of the invention ]
The technical problem to be solved by the invention is to provide a preparation method of polystyrene resin with hydroxyl on the surface, which solves the problems of low surface hydroxyl content and uneven distribution caused by steric hindrance effect in the polymerization process of the existing large-particle-size polystyrene resin microspheres, complex polymerization process by adding auxiliary monomers, difficult control, low resin microsphere strength and high cost.
The invention is realized by the following steps:
a method for preparing a surface hydroxylated polystyrene resin, the method comprising the steps of:
step 2, hydroxylation modification of polystyrene resin microspheres: putting the polystyrene resin obtained in the step 1 into a container, adding a carbon disulfide reagent for swelling, then putting the container into an ice-water bath, and sequentially adding aluminum bromide and 4-chlorophenol; continuously placing in ice water bath for 20-30 minutes, and then placing in a water bath shaking table at 20-40 ℃ for reaction; after the reaction is finished, washing and filtering the mixture for a plurality of times by tetrahydrofuran, diluted hydrochloric acid, water and methanol respectively, and finally drying the mixture in vacuum at the temperature of between 20 and 40 ℃ to constant weight.
Further, the polystyrene resin microspheres adopted in the step 1 are polystyrene resin microspheres with the particle size of 300-500 μm.
Further, the weight parts of each reactant in the step 2 are as follows: 1 part of polystyrene resin microspheres, 60-220 parts of carbon disulfide, 2-7 parts of 4-chlorophenol and 1-9 parts of aluminum bromide.
Further, the reaction time in the water bath shaker in the step 2 is 2 to 15 hours.
The method of the invention has the following advantages:
the hydroxylated polystyrene resin microspheres prepared by the invention have the advantages of large particle size, high strength, high surface hydroxyl content and uniform hydroxyl distribution on the surfaces of the resin microspheres, and the problems of complex and unstable reaction process, low surface hydroxyl polymerization degree and nonuniform distribution when hydroxyl is grafted on the surfaces of the traditional large-particle size polystyrene resin microspheres are solved.
The hydroxylated polystyrene resin microspheres prepared by the invention can be used for wastewater treatment, ion exchange, photocatalysis, catalyst carriers and the like, and are functional polystyrene resin microspheres with excellent performance.
[ description of the drawings ]
The invention will now be further described with reference to the following examples.
FIG. 1 is a chart of IR spectrum analysis of polystyrene resin microspheres with hydroxyl groups on the surface prepared in example 1 of the present invention.
[ detailed description ] embodiments
The invention discloses a preparation method of surface hydroxylated polystyrene resin, which comprises the following steps:
step 2, hydroxylation modification of polystyrene resin microspheres: putting the polystyrene resin obtained in the step 1 into a container, adding a carbon disulfide reagent for swelling, then putting the container into an ice-water bath, and sequentially adding aluminum bromide and 4-chlorophenol; continuously placing in ice water bath for 20-30 minutes, and then placing in a water bath shaking table at 20-40 ℃ for reaction; after the reaction is finished, washing and filtering the mixture for a plurality of times by tetrahydrofuran, diluted hydrochloric acid, water and methanol respectively, and finally drying the mixture in vacuum at the temperature of between 20 and 40 ℃ to constant weight.
The polystyrene resin microspheres adopted in the step 1 are polystyrene resin microspheres with the particle size of 300-500 mu m.
The weight parts of the reactants in the step 2 are as follows: 1 part of polystyrene resin microspheres, 60-220 parts of carbon disulfide, 2-7 parts of 4-chlorophenol and 1-9 parts of aluminum bromide.
The reaction time in the water bath shaking table in the step 2 is 2 to 15 hours.
Referring to fig. 1, the technical solution of the present invention will be described clearly and completely with reference to the accompanying drawings and the detailed description. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1: pretreatment of unmodified polystyrene resin: firstly, 0.5g of unmodified polystyrene resin microspheres are swelled in dichloromethane for 10 hours, then washed and filtered by tetrahydrofuran, ultrapure water, absolute ethyl alcohol and absolute methyl alcohol respectively for three times, and finally dried in vacuum at 20 ℃ to constant weight;
hydroxylation modification of polystyrene resin microspheres: taking 0.3g of the polystyrene resin obtained in the step 1, adding 100ml of carbon disulfide reagent for swelling, then placing the container in an ice-water bath, and sequentially adding 0.4g of aluminum bromide and 2g of 4-chlorophenol; continuously placing the mixture in an ice-water bath for 30 minutes, and then placing the mixture in a water bath shaking table at the temperature of 20 ℃ for reaction for 5 hours; after the reaction is finished, washing and filtering the mixture for a plurality of times by tetrahydrofuran, diluted hydrochloric acid, water and methanol respectively, and finally drying the mixture in vacuum at 40 ℃ to constant weight. Obtaining the hydroxylated polystyrene resin microspheres. The weight gain rate is 16.67%, and the grafting rate is 2.50%.
Example 2: pretreatment of unmodified polystyrene resin: firstly, 0.5g of unmodified polystyrene resin microspheres are swelled in dichloromethane for 5 hours, then washed and filtered by tetrahydrofuran, ultrapure water, absolute ethyl alcohol and absolute methyl alcohol respectively for three times, and finally dried in vacuum at 30 ℃ to constant weight;
hydroxylation modification of polystyrene resin microspheres: taking 0.3g of the polystyrene resin obtained in the step 1, adding 50ml of carbon disulfide reagent for swelling, then placing the container in an ice-water bath, and sequentially adding 0.6g of aluminum bromide and 2g of 4-chlorophenol; continuously placing the mixture in an ice-water bath for 25 minutes, and then placing the mixture in a water bath shaking table at the temperature of 30 ℃ for reaction for 10 hours; after the reaction is finished, washing and filtering the mixture for a plurality of times by tetrahydrofuran, diluted hydrochloric acid, water and methanol respectively, and finally drying the mixture in vacuum at 40 ℃ to constant weight. Obtaining the hydroxylated polystyrene resin microspheres. The weight gain rate is 20.48%, and the grafting rate is 3.10%.
Example 3: pretreatment of unmodified polystyrene resin: firstly, 0.5g of unmodified polystyrene resin microspheres are swelled in dichloromethane for 20 hours, then washed and filtered by tetrahydrofuran, ultrapure water, absolute ethyl alcohol and absolute methyl alcohol respectively for three times, and finally dried in vacuum at 40 ℃ to constant weight;
hydroxylation modification of polystyrene resin microspheres: taking 0.3g of the polystyrene resin obtained in the step 1, adding 50ml of carbon disulfide reagent for swelling, then placing the container in an ice-water bath, and sequentially adding 0.4g of aluminum bromide and 2g of 4-chlorophenol; continuously placing the mixture in an ice-water bath for 30 minutes, and then placing the mixture in a water bath shaking table at the temperature of 40 ℃ for reaction for 15 hours; after the reaction is finished, washing and filtering the mixture for a plurality of times by tetrahydrofuran, diluted hydrochloric acid, water and methanol respectively, and finally drying the mixture in vacuum at 40 ℃ to constant weight. Obtaining the hydroxylated polystyrene resin microspheres. The weight gain ratio was 23.33%, and the graft ratio was 3.50%.
FIG. 1 is a graph of infrared spectroscopic analysis of hydroxylated polystyrene resin microspheres (curve a in FIG. 1) and unmodified polystyrene resin microspheres (curve b in FIG. 1) prepared according to example 1. As can be seen from FIG. 1, the infrared spectrum of the modified resin microspheres is 1309cm-1The new absorption peak exists, the bending vibration frequency of-O-H is judged by analysis, the existence of-OH is proved, and in the reaction system, the-OH can only come from 4-chlorophenol, which indicates that the Friedel-crafts reaction is successfully carried out, and phenolic hydroxyl is successfully grafted on the resin microspheres.
Although specific embodiments of the invention have been described above, it will be understood by those skilled in the art that the specific embodiments described are illustrative only and are not limiting upon the scope of the invention, and that equivalent modifications and variations can be made by those skilled in the art without departing from the spirit of the invention, which is to be limited only by the appended claims.
Claims (4)
1. A preparation method of surface hydroxylated polystyrene resin is characterized in that: the method comprises the following steps:
step 1, pretreatment of unmodified polystyrene resin: swelling polystyrene resin microspheres in dichloromethane for 10-20 hours, washing and filtering with tetrahydrofuran, ultrapure water, absolute ethyl alcohol and absolute methyl alcohol for three times respectively, and finally drying in vacuum at 20-40 ℃ to constant weight;
step 2, hydroxylation modification of polystyrene resin microspheres: putting the polystyrene resin obtained in the step 1 into a container, adding a carbon disulfide reagent for swelling, then putting the container into an ice-water bath, and sequentially adding aluminum bromide and 4-chlorophenol; continuously placing in ice water bath for 20-30 minutes, and then placing in a water bath shaking table at 20-40 ℃ for reaction; after the reaction is finished, washing and filtering the mixture for a plurality of times by tetrahydrofuran, diluted hydrochloric acid, water and methanol respectively, and finally drying the mixture in vacuum at the temperature of between 20 and 40 ℃ to constant weight.
2. The method for preparing a surface-hydroxylated polystyrene resin according to claim 1, wherein: the polystyrene resin microspheres adopted in the step 1 are polystyrene resin microspheres with the particle size of 300-500 mu m.
3. The method for preparing a surface-hydroxylated polystyrene resin according to claim 1, wherein: the weight parts of the reactants in the step 2 are as follows: 1 part of polystyrene resin microspheres, 60-220 parts of carbon disulfide, 2-7 parts of 4-chlorophenol and 1-9 parts of aluminum bromide.
4. The method for preparing a surface-hydroxylated polystyrene resin according to claim 1, wherein: the reaction time in the water bath shaking table in the step 2 is 2 to 15 hours.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5466758A (en) * | 1994-04-13 | 1995-11-14 | Yoon-Sik; Lee | Process for preparing polystyrenes having β hydroxy group and polyglycol-grafted polystyrenes thereof |
| CN101440168A (en) * | 2007-11-20 | 2009-05-27 | 中国科学院过程工程研究所 | Surface hydrophilic modification of polystyrene material and product |
| CN105399969A (en) * | 2014-09-15 | 2016-03-16 | 天津工业大学 | Multi-walled carbon nano-tube/polystyrene composite material film preparation method |
| CN109053963A (en) * | 2018-07-12 | 2018-12-21 | 福建农林大学 | A kind of preparation method of cation polystyrene resin |
| CN110128571A (en) * | 2019-06-04 | 2019-08-16 | 厦门理工学院 | A kind of preparation method and application of modified polystyrene resin |
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- 2020-10-27 CN CN202011162241.8A patent/CN112538183B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5466758A (en) * | 1994-04-13 | 1995-11-14 | Yoon-Sik; Lee | Process for preparing polystyrenes having β hydroxy group and polyglycol-grafted polystyrenes thereof |
| CN101440168A (en) * | 2007-11-20 | 2009-05-27 | 中国科学院过程工程研究所 | Surface hydrophilic modification of polystyrene material and product |
| CN105399969A (en) * | 2014-09-15 | 2016-03-16 | 天津工业大学 | Multi-walled carbon nano-tube/polystyrene composite material film preparation method |
| CN109053963A (en) * | 2018-07-12 | 2018-12-21 | 福建农林大学 | A kind of preparation method of cation polystyrene resin |
| CN110128571A (en) * | 2019-06-04 | 2019-08-16 | 厦门理工学院 | A kind of preparation method and application of modified polystyrene resin |
Non-Patent Citations (1)
| Title |
|---|
| 唐迪: "聚苯乙烯—酚醛超高交联树脂的合成", 《中国优秀硕士学位论文全文数据库》 * |
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