CN112321881B - Polystyrene resin microsphere with surface rich in aldehyde groups and preparation method thereof - Google Patents

Polystyrene resin microsphere with surface rich in aldehyde groups and preparation method thereof Download PDF

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CN112321881B
CN112321881B CN202011162242.2A CN202011162242A CN112321881B CN 112321881 B CN112321881 B CN 112321881B CN 202011162242 A CN202011162242 A CN 202011162242A CN 112321881 B CN112321881 B CN 112321881B
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polystyrene resin
resin microspheres
microspheres
aldehyde
reaction
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CN112321881A (en
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苗庆显
蔡玉群
孟令超
张琛
陈礼辉
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Fujian Agriculture and Forestry University
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Fujian Agriculture and Forestry University
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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
    • 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
    • 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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Abstract

The invention provides a polystyrene resin microsphere with rich aldehyde group on the surface and a preparation method thereof, wherein an aldehyde reagent is p-chlorobenzaldehyde, methylene dichloride is used for swelling the resin microsphere, then tetrahydrofuran, ultrapure water, absolute ethyl alcohol and methanol are used for washing and filtering for a plurality of times in sequence, and finally vacuum drying is carried out until the weight is constant; swelling the pretreated polystyrene resin microspheres by using carbon disulfide, adding p-chlorobenzaldehyde in an ice water bath, adding aluminum bromide serving as a catalyst into a system after the benzaldehyde is completely dissolved, performing suction filtration after the reaction is finished, and performing washing filtration for a plurality of times by using tetrahydrofuran, dilute hydrochloric acid and ultrapure water respectively to obtain the polystyrene resin microspheres with surfaces rich in aldehyde groups. The invention solves the problems of complex synthesis process, high cost, difficult control of reaction process and the like of the existing aldehyde polystyrene resin.

Description

Polystyrene resin microsphere with surface rich in aldehyde groups and preparation method thereof
[ technical field ] A method for producing a semiconductor device
The invention relates to a polystyrene resin microsphere with an aldehyde group-rich surface and a preparation method thereof.
[ background of the invention ]
The polystyrene resin microsphere is a polymer prepared by using styrene as a main material and divinylbenzene as a cross-linking agent, and is a main framework material of the adsorption resin. Adding a precipitator, an inert organic solvent or a pore-foaming agent such as linear high polymer and the like when styrene and divinylbenzene are subjected to suspension copolymerization, and taking out the pore-foaming agent after the polymerization is finished to obtain the porous polystyrene resin microspheres. The polystyrene cross-linked adsorption resin has the characteristics of high strength, good swelling property, large specific surface area, stability to heat and chemical substances, easiness in regeneration, low price and the like, can introduce various functional groups by utilizing the high activity of a benzene ring, is very suitable for preparing resin microspheres with high selectivity and high adsorptivity, and is widely applied to adsorption of various substances.
The functionalization of polystyrene resin microspheres is usually completed by adding functional monomers or oligomers in the process of preparing polystyrene resin microsphere matrixes, functional groups of the obtained modified microspheres are usually distributed in the interior and on the surfaces of the microspheres, the number of the functional groups on the surfaces is small, the utilization rate of the functional groups in the application process is low, and the production cost is high. The central theory of the Friedel-crafts reaction is that a reagent containing halogen atoms is complexed under the action of Lewis acid to generate carbonium ions, and then the carbonium ions attack benzene rings to react. Although p-chlorobenzaldehyde contains benzene rings, aldehyde benzene rings and aluminum bromide still generate positive carbon ions under the action of aldehyde group passivation, and the positive carbon ions attack the benzene rings on the surface of the polystyrene resin microspheres to enrich the surfaces of the microspheres with aldehyde groups.
At present, the means for modifying polystyrene resin microspheres mainly comprises chloromethylation, and then the next reaction is carried out by utilizing the chloromethyl activity on the surfaces of the microspheres, and the reaction process is complicated and is difficult to control. The aldehyde group exists in the acyl group particularly, can perform oxidation reaction and reduction reaction, and has high reactivity so that other reactions can be performed. According to the invention, aldehyde groups are grafted to the surface of the polystyrene resin microspheres, the resin microspheres can be used as a reaction substrate, and oxidation/reduction reaction, condensation reaction and the like are carried out on the surfaces of the microspheres.
[ summary of the invention ]
The invention aims to solve the technical problem of providing a preparation method of a large-particle-size polystyrene resin microsphere with an aldehyde group-rich surface, and solving the problems of complex process, difficult control of the preparation process, high cost and the like of the existing preparation method.
The invention is realized by the following steps:
a preparation method of polystyrene resin microspheres with surfaces rich in aldehyde groups comprises the following steps: step 1, pretreatment of unmodified polystyrene resin microspheres: firstly, swelling polystyrene resin microspheres by using dichloromethane for 5-20 hours, sequentially washing and filtering by using tetrahydrofuran, ultrapure water, absolute ethyl alcohol and methanol for several times, and finally drying in vacuum at 20-40 ℃ to constant weight;
step 2, hydroformylation of polystyrene resin: swelling the polystyrene resin treated in the step 1 in a carbon disulfide solution for 5-12 hours, adding p-chlorobenzaldehyde under the condition of an ice water bath, adding aluminum bromide after the p-chlorobenzaldehyde is completely dissolved, keeping the mixture in the ice water bath for 1-3 hours, and placing the mixture in a gas bath shaker at 25-40 ℃ for reaction for a certain time after the ice water bath is finished; and (3) after the reaction is finished by suction filtration, washing and filtering the reaction product for a plurality of times by tetrahydrofuran, dilute hydrochloric acid and ultrapure water respectively, and drying the reaction product in vacuum at the temperature of between 20 and 40 ℃ until the weight is constant to obtain the aldehyde polystyrene resin microspheres.
Further, the polystyrene resin microspheres adopted in the step 1 are large-particle size polystyrene resin microspheres with the particle size of 300-500 microns.
Further, the weight parts of each reactant in the step 2 are as follows: 1 part of polystyrene resin microspheres, 250 parts of 150-carbon disulfide, 5-20 parts of p-chlorobenzaldehyde and 1-10 parts of aluminum bromide.
Further, in the step 2, the reaction time of the table concentrator is 3 to 15 hours at 40 ℃.
Further, the polystyrene resin microsphere with the surface being rich in aldehyde groups is prepared by the preparation method of the polystyrene resin microsphere with the surface being rich in aldehyde groups.
The invention has the following advantages:
when the method is used for performing the hydroformylation modification of the polystyrene resin microspheres, the large-particle-size polystyrene resin microspheres with surfaces rich in aldehyde groups are prepared by changing reagents used for hydroformylation. The method simplifies the traditional complex steps of chloromethylation and acylation to obtain aldehyde groups in the reaction process, and leads the microspheres to react in one step to directly prepare the aldehyde polystyrene resin microspheres. Solves the problems of complex reaction, difficult control and high cost of the traditional hydroformylation method.
The prepared aldehyde polystyrene resin microspheres can be used as a reaction substrate with the surface containing reducing groups, and are substrate type polystyrene resin microspheres with excellent performance.
[ description of the drawings ]
The invention will be further described with reference to the following examples with reference to the accompanying drawings.
FIG. 1 is a graph of IR spectrum analysis of polystyrene resin microspheres having surfaces rich in aldehyde groups prepared in example 1 of the present invention.
[ detailed description ] embodiments
The invention discloses a preparation method of aldehyde polystyrene resin microspheres, which comprises the following steps:
step 1, pretreatment of unmodified polystyrene resin microspheres: firstly, swelling polystyrene resin microspheres by using dichloromethane for 5-20 hours, sequentially washing and filtering by using tetrahydrofuran, ultrapure water, absolute ethyl alcohol and methanol for several times, and finally drying in vacuum at 20-40 ℃ to constant weight;
step 2, hydroformylation of polystyrene resin: swelling the polystyrene resin treated in the step 1 in a carbon disulfide solution for 5-12 hours, adding p-chlorobenzaldehyde under the condition of an ice water bath, adding aluminum bromide after the p-chlorobenzaldehyde is completely dissolved, keeping the mixture in the ice water bath for 1-3 hours, and placing the mixture in a gas bath shaker at 25-40 ℃ for reaction for a certain time after the ice water bath is finished; and (3) after the reaction is finished by suction filtration, washing and filtering the reaction product for a plurality of times by tetrahydrofuran, dilute hydrochloric acid and ultrapure water respectively, and drying the reaction product in vacuum at the temperature of between 20 and 40 ℃ until the weight is constant to obtain the aldehyde polystyrene resin microspheres.
The polystyrene resin microspheres adopted in the step 1 are large-particle-size polystyrene resin microspheres with the particle size of 300-500 microns.
The weight parts of the reactants in the step 2 are as follows: 1 part of polystyrene resin microspheres, 250 parts of 150-carbon disulfide, 5-20 parts of p-chlorobenzaldehyde and 1-10 parts of aluminum bromide.
In the step 2, the shaking table reaction time at 40 ℃ is 3-15 hours.
The invention also relates to the polystyrene resin microspheres with rich aldehyde groups prepared by the preparation method of the polystyrene resin microspheres with rich aldehyde groups on the surfaces.
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: weighing 0.5g of polystyrene resin microspheres, adding dichloromethane to swell for 20 hours, then sequentially washing and filtering with tetrahydrofuran, ultrapure water, absolute ethyl alcohol and methanol for a plurality of times, and finally drying in vacuum at 40 ℃ to constant weight.
Aldehyde group formation of polystyrene resin microspheres: weighing 0.3g of pretreated polystyrene resin white balls, putting the weighed white balls into a 250ml conical flask, adding 50ml of carbon disulfide, swelling for 12 hours, adding 5g of p-chlorobenzaldehyde under the condition of ice water bath, adding 2g of anhydrous aluminum bromide after the p-chlorobenzaldehyde is completely dissolved, continuously keeping the ice water bath for 3 hours, and then putting the mixture into a 40 ℃ gas bath shaking table for reaction for 12 hours. After the reaction is finished by suction filtration, the mixture is washed and filtered by tetrahydrofuran, diluted hydrochloric acid and ultrapure water respectively. Vacuum drying at 40 deg.c to constant weight to obtain aldehyde polystyrene resin microsphere. The weight gain rate is 17.32%, and the grafting rate is 1.54%.
Example 2: weighing 0.5g of polystyrene resin microspheres, adding dichloromethane to swell for 5 hours, washing and filtering with tetrahydrofuran, ultrapure water, absolute ethyl alcohol and methanol for several times, and finally drying in vacuum at 20 ℃ to constant weight.
Aldehyde group formation of polystyrene resin microspheres: weighing 0.3g of pretreated polystyrene resin white balls, putting the white balls into a 250ml conical flask, adding 50ml of carbon disulfide, swelling for 5 hours, adding 4g of p-chlorobenzaldehyde under the condition of ice water bath, adding 2g of anhydrous aluminum chloride after the p-chlorobenzaldehyde is completely dissolved, continuously keeping the ice water bath for 1 hour, and then putting the white balls into a 25 ℃ gas bath shaking table for reaction for 15 hours. After the reaction is finished by suction filtration, the mixture is washed and filtered by tetrahydrofuran, diluted hydrochloric acid and ultrapure water respectively. Vacuum drying at 20 deg.c to constant weight to obtain aldehyde polystyrene resin microsphere. The weight gain rate is 16.97%, and the grafting rate is 1.27%.
Example 3: weighing 0.5g of polystyrene resin microspheres, adding dichloromethane to swell for 20 hours, then sequentially washing and filtering with tetrahydrofuran, ultrapure water, absolute ethyl alcohol and methanol for a plurality of times, and finally drying in vacuum at 40 ℃ to constant weight.
Aldehyde group formation of polystyrene resin microspheres: weighing 0.3g of pretreated polystyrene resin white balls, putting the weighed white balls into a 250ml conical flask, adding 60ml of carbon disulfide, adding 6g of p-chlorobenzaldehyde under the condition of ice-water bath, adding 2.5g of anhydrous aluminum bromide after the p-chlorobenzaldehyde is completely dissolved, continuously keeping the ice-water bath for 3 hours, and then putting the mixture into a 40 ℃ gas bath shaking table for reaction for 13 hours. After the reaction is finished by suction filtration, the mixture is washed and filtered by tetrahydrofuran, diluted hydrochloric acid and ultrapure water respectively. Vacuum drying at 40 deg.c to constant weight to obtain aldehyde polystyrene resin microsphere. The weight gain rate is 19.54 percent, and the grafting rate is 1.98 percent.
FIG. 1 is a graph of IR spectrum analysis of the aldehyde-based polystyrene resin microspheres prepared in example 1, as can be seen from FIG. 1, at 1015cm-1And 1266cm-1The two absorption peaks are the characteristic absorption peak of-C-O-C-generated by crosslinking the chlorobenzaldehyde and the active double bonds in the polystyrene resin microspheres, and are 1700cm-1The absorption peak is the characteristic absorption peak of aldehyde group generated by grafting p-chlorobenzaldehyde on the surface of the polystyrene resin microsphere. Shows that the preparation of the aldehyde polystyrene resin microspheres by using the p-chlorobenzaldehyde grafted polystyrene resin microspheres is successful.
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 polystyrene resin microspheres with surfaces rich in aldehyde groups is characterized by comprising the following steps: the method comprises the following steps:
step 1, pretreatment of unmodified polystyrene resin microspheres: firstly, swelling polystyrene resin microspheres by using dichloromethane for 5-20 hours, sequentially washing and filtering by using tetrahydrofuran, ultrapure water, absolute ethyl alcohol and methanol for several times, and finally drying in vacuum at 20-40 ℃ to constant weight; the adopted polystyrene resin microspheres are large-particle-size polystyrene resin microspheres with the particle size of 300-500 microns;
step 2, hydroformylation of polystyrene resin: swelling the polystyrene resin treated in the step 1 in a carbon disulfide solution for 5-12 hours, adding p-chlorobenzaldehyde under the condition of an ice water bath, adding aluminum bromide after the p-chlorobenzaldehyde is completely dissolved, keeping the mixture in the ice water bath for 1-3 hours, and placing the mixture in a gas bath shaker at 25-40 ℃ for reaction for a certain time after the ice water bath is finished; and (3) after the reaction is finished by suction filtration, washing and filtering the reaction product for a plurality of times by tetrahydrofuran, dilute hydrochloric acid and ultrapure water respectively, and drying the reaction product in vacuum at the temperature of between 20 and 40 ℃ until the weight is constant to obtain the aldehyde polystyrene resin microspheres.
2. The method for preparing polystyrene resin microspheres with surfaces rich in aldehyde groups according to claim 1, wherein the method comprises the following steps: the weight parts of the reactants in the step 2 are as follows: 1 part of polystyrene resin microspheres, 250 parts of 150-carbon disulfide, 5-20 parts of p-chlorobenzaldehyde and 1-10 parts of aluminum bromide.
3. The method for preparing polystyrene resin microspheres with surfaces rich in aldehyde groups according to claim 1, wherein the method comprises the following steps: in the step 2, the shaking table reaction time at 40 ℃ is 3-15 hours.
4. The polystyrene resin microspheres with rich aldehyde groups on the surface prepared by the method for preparing the polystyrene resin microspheres with rich aldehyde groups according to any one of claims 1 to 3.
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