Halogenated alkyl functionalized microspheres and preparation method thereof

Abstract

The invention provides a halogenated alkyl functionalized microsphere and a preparation method thereof, and the method comprises the following steps: in a reaction kettle, carrying out polymerization reaction on a polymerization reaction mixture containing a modified comonomer, an aromatic monomer, a halogenated aromatic monomer, an aliphatic monomer and polyether to generate the halogenated alkyl functionalized microsphere, the modified comonomer is polyether polyol modified by a modified compound, the aromatic monomer is an aromatic compound containing an alkenyl substituent group, and the halogenated aromatic monomer is an aromatic compound containing an alkenyl substituent group and a halogenated alkyl substituent group. The aliphatic monomer is an aliphatic ethylenically unsaturated compound containing a cyano group, a carboxyl group, an ester group or an acid anhydride group. According to the method disclosed by the invention, the halogenated alkyl functionalized microspheres which are stable in structure, uniform in particle size and excellent in performance can be synthesized through simple and efficient steps.

Description

Technical Field

[0001] The present application relates to the field of polymers, and more specifically to an improved method for preparing haloalkyl functionalized microspheres, and haloalkyl functionalized microspheres obtained by the method. Background Art

[0002] Microspheres modified with halogenated alkyl groups (e.g., polystyrene microspheres modified with chloromethyl groups) are an important class of polymer materials with a wide range of applications, mainly in the fields of adsorption separation, catalyst carriers, drug carriers, biomaterials, etc. The demand for such microspheres in these fields is growing, but the methods used to synthesize such microspheres in the prior art have significant defects.

[0003] Specifically, for example, a method for preparing chloromethyl modified polystyrene microspheres is to react polystyrene cross-linked microspheres with chloromethyl ether or dichloromethyl ether by Lewis acid catalysis. However, the chloromethyl ether and dichloromethyl ether reagents used in this method are strong carcinogens, and the chloromethylation reaction process produces a large amount of harmful substances such as formaldehyde, methylal, hydrogen chloride, and direct discharge can seriously pollute the environment. Another method is to directly prepare chloromethyl modified polystyrene microspheres by direct copolymerization of chloromethyl styrene monomer and styrene monomer. Although this method can avoid using the above-mentioned toxic reagents, this method inevitably needs to use emulsifiers (such as alkylbenzene sulfonates) to synthesize the target microspheres by emulsion polymerization, which will inevitably lead to the cost increase related to the emulsifier, and it is also necessary to remove the emulsifier from the product to avoid its impact on the performance of the product microspheres or the pollution caused by the emulsifier. People are eager to develop an improved haloalkyl modified microsphere synthesis method to eliminate the above-mentioned problems in the prior art, and it is best to make the obtained microspheres have better microscopic morphology, particle size uniformity and performance.

[0004] In view of the problems existing in the above-mentioned prior art, the inventors of the present application have unexpectedly developed a dispersion polymerization method suitable for preparing haloalkyl-modified microspheres through extensive and in-depth research. This method can simply and efficiently synthesize the above-mentioned microspheres, and the synthesized microspheres have a stable structure, uniform particle size, and a precisely modified microsphere surface, and the microspheres have excellent performance. Summary of the invention

[0005] The first aspect of the present application provides a method for preparing halogenated alkyl functionalized microspheres, the method comprising: in a reaction kettle, allowing a polymerization reaction mixture containing a modified comonomer, an aromatic monomer, a halogenated aromatic monomer, an aliphatic monomer, and a polyether to undergo a polymerization reaction to generate the halogenated alkyl functionalized microspheres; the modified comonomer is a polyether polyol modified with a modifying compound, and the modifying compound is a C4-C12 ethylenically unsaturated polycarboxylic acid or an anhydride thereof; the aromatic monomer is a C8-C18 aromatic compound containing at least one C2-C6 aliphatic alkenyl substituent; the halogenated aromatic monomer is a C9-C18 aromatic compound containing at least one C2-C6 aliphatic alkenyl substituent and at least one C1-C6 aliphatic halogenated alkyl substituent; the aliphatic monomer is a C3-C12 aliphatic ethylenically unsaturated compound and contains at least one functional group selected from the following: cyano, carboxyl, ester, anhydride.

[0006] According to one embodiment of the first aspect of the present application, the modified comonomer is obtained by the following steps: modifying the unmodified polyether polyol with a modifying compound, and then capping it with a capping compound, wherein the capping compound is selected from: C2-C6 alkylene oxide, C2-C6 polyol, or a combination thereof.

[0007] According to another embodiment of the first aspect of the present application, the unmodified polyether polyol has a functionality of 3-6 and a number average molecular weight of 6000-15000.

[0008] According to another embodiment of the first aspect of the present application, the molar ratio of the modified compound to the unmodified polyether polyol is 0.8:1 to 2:1.

[0009] According to another embodiment of the first aspect of the present application, the molar ratio of the modifying compound to the end-capping compound is 1:3 to 1:7.

[0010] According to another embodiment of the first aspect of the present application, the modified comonomer is prepared by the following steps:

[0011] i. activating a mixture of an unmodified polyether polyol and a catalyst at a temperature of 90-130° C., wherein the catalyst is an alkali metal hydroxide;

[0012] ii. reacting a mixture containing a modified compound, an unmodified polyether polyol and a catalyst at a temperature of 65-80°C;

[0013] iii. capping the product obtained in step ii with a capping compound at a temperature of 90-130 ° C;

[0014] iv. Aging at a temperature of 90-130°C.

[0015] According to another embodiment of the first aspect of the present application, the modifying compound is selected from one or more of the following: maleic acid / anhydride, fumaric acid / anhydride, glutaric acid / anhydride, hexamethylenediamine / anhydride, heptenedioic acid / anhydride, and octenedioic acid / anhydride.

[0016] According to another embodiment of the first aspect of the present application, the functionality of the polyether is 2-3, and the number average molecular weight is 3000-6000.

[0017] According to another embodiment of the first aspect of the present application, based on the total weight of the polymerization reaction mixture as 100 weight %, the content of the polyether is 40-60 weight %.

[0018] According to another embodiment of the first aspect of the present application, the aromatic monomer is selected from at least one of the following: styrene, methylstyrene, dimethylstyrene, ethylstyrene, propylstyrene, butylstyrene, divinylbenzene, propenylbenzene, and butenylbenzene.

[0019] According to another embodiment of the first aspect of the present application, the halogenated aromatic monomer is selected from at least one of the following: chloromethylstyrene, chloroethylstyrene, chloropropylstyrene, chlorobutylstyrene, chloromethylpropylenebenzene, and chloromethylbutylbenzene.

[0020] According to another embodiment of the first aspect of the present application, the aliphatic monomer is selected from at least one of the following: acrylonitrile, methacrylonitrile, acrylic acid, and methacrylic acid.

[0021] According to another embodiment of the first aspect of the present application, based on 100 wt % of the weight of the polymerization reaction mixture, the amount of the modified comonomer is 2-10 wt %.

[0022] According to another embodiment of the first aspect of the present application, based on 100 wt % of the weight of the polymerization reaction mixture, the amount of the aromatic monomer is 4-15 wt %.

[0023] According to another embodiment of the first aspect of the present application, based on 100 weight % of the weight of the polymerization reaction mixture, the amount of the halogenated aromatic monomer is 10-26 weight %.

[0024] According to another embodiment of the first aspect of the present application, based on 100 wt % of the weight of the polymerization reaction mixture, the amount of the aliphatic monomer is 9-20 wt %.

[0025] According to another embodiment of the first aspect of the present application, the mass ratio of the aromatic monomer to the halogenated aromatic monomer is 1:1 to 1:3.

[0026] According to another embodiment of the first aspect of the present application, the polymerization reaction mixture further contains a chain transfer agent and a free radical initiator. Based on the weight of the polymerization reaction mixture as 100 weight %, the amount of the chain transfer agent is 3-8 weight %, and the amount of the free radical initiator is 0.1-1 weight %.

[0027] According to another embodiment of the first aspect of the present application, the method is carried out without using an emulsifier.

[0028] The second aspect of the present application provides a haloalkyl functionalized microsphere, which is synthesized by the method of the present application.

[0029] In the following specific implementation section, the method and microspheres of the present application are further introduced in conjunction with the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] Figure 1 shows a scanning electron microscope image of the copolymer particles prepared in Example 4 of the present application;

[0031] Figure 2 shows a scanning electron microscope image of the copolymer particles prepared in Example 5 of the present application;

[0032] Figure 3 shows a scanning electron microscope image of the copolymer particles prepared in Example 6 of the present application;

[0033] Figure 4 A schematic diagram showing the catalytic reaction performed in Example 7 of the present application is shown;

[0034] Figure 5 The supported organic catalyst prepared by the haloalkyl functionalized microspheres obtained in Example 6 of the present application is shown, and the butylene carbonate product obtained by the catalytic reaction is 1 H NMR spectrum. DETAILED DESCRIPTION

[0035] "Range" disclosed herein is in the form of lower limit and upper limit. It can be one or more lower limits, and one or more upper limits respectively. A given range is defined by selecting a lower limit and an upper limit. The selected lower limit and upper limit define the boundaries of a particular range. All ranges that can be defined in this way are inclusive and combinable, i.e. any lower limit can be combined with any upper limit to form a range. For example, a range of 60-120 and 80-110 is listed for a particular parameter, and it is understood that a range of 60-110 and 80-120 is also expected. In addition, if the minimum range values ​​1 and 2 are listed, and if the maximum range values ​​3, 4 and 5 are listed, the following ranges can all be expected: 1-3, 1-4, 1-5, 2-3, 2-4 and 2-5.

[0036] In this application, unless otherwise specified, the numerical range "ab" represents an abbreviation of any real number combination between a and b, where a and b are real numbers. For example, the numerical range "0-5" means that all real numbers between "0-5" are listed in this document, and "0-5" is just an abbreviation of these numerical combinations.

[0037] In this application, unless otherwise specified, all embodiments and preferred embodiments mentioned herein can be combined with each other to form a new technical solution.

[0038] In this application, unless otherwise specified, all technical features and preferred features mentioned herein can be combined with each other to form a new technical solution.

[0039] In this application, if there is no special explanation, the "including" mentioned herein means open or closed. For example, the "including" may mean that other components not listed may also be included, or only the listed components may be included.

[0040] The most important feature of the method of the present invention is that a new method for synthesizing halogenated alkyl functionalized microspheres has been developed. In the method, a modified polyether (modified comonomer) is used as one of the comonomer raw materials, and it is dispersed polymerized together with an aromatic monomer, a halogenated aromatic monomer, an aliphatic monomer and a polyether, thereby unexpectedly achieving the synthesis of the target halogenated alkyl functionalized microspheres.

[0041] According to one embodiment of the present application, the dispersion polymerization method of the present invention does not use chloromethyl ether and / or dichloromethyl ether reagents conventionally used in the prior art, so a large amount of harmful substances such as formaldehyde and methylal are not generated during the method process as in the prior art. In addition, the dispersion polymerization method of the present invention does not use the emulsifier used in the emulsion polymerization method of the prior art, especially does not use the small molecule emulsifier known in the prior art (such as alkylbenzene sulfonate, etc.), thereby effectively avoiding the costs and defects associated with the emulsifier.

[0042] According to another embodiment of the present application, the modified comonomer used in the method of the present invention is obtained by modifying the polyether polyol with a modifying compound. According to a further embodiment of the present application, the modified comonomer is obtained by first modifying the polyether polyol with a modifying compound and then end-capping it with an end-capping compound.

[0043] According to another embodiment of the present application, the modified compound is a C4-C12 ethylenically unsaturated polycarboxylic acid or anhydride thereof, preferably a C4-C8 ethylenically unsaturated dicarboxylic acid or anhydride thereof, and more preferably a C4-C6 ethylenically unsaturated dicarboxylic acid or anhydride thereof. In the present invention, "ethylenically unsaturated" means that the compound contains at least one carbon-carbon double bond. According to an exemplary embodiment of the present application, the modified compound is selected from one or more of the following: maleic acid / anhydride, fumaric acid / anhydride, glutaric acid / anhydride, hexamethylenediamine / anhydride, heptenedioic acid / anhydride, octenedioic acid / anhydride; most preferably, the modified compound is maleic acid, maleic anhydride, or a combination thereof.

[0044] According to another embodiment of the present application, the hydroxyl functionality of the polyether polyol used as the raw material to be modified is 3-6, preferably 4-6; its number average molecular weight is 6000-15000, preferably 8000-14000, and more preferably 10000-12000.

[0045] According to one embodiment of the present application, in the process of modifying the polyether polyol using the modifying compound, the molar ratio of the added modifying compound to the added polyether polyol is 0.8:1 to 2:1, preferably 1:1 to 1.5:1.

[0046] According to a specific embodiment of the present application, the modification is carried out in the presence of a catalyst, and the catalyst is preferably an alkali metal hydroxide, such as potassium hydroxide, sodium hydroxide, lithium hydroxide, or a combination thereof, preferably potassium hydroxide. According to a specific embodiment of the present application, the catalyst is added to the modification reaction in the form of an aqueous solution. According to an exemplary embodiment of the present application, the amount (molar amount) of the catalyst added is 1-3 mol %, preferably 1.5-2.5 mol % of the molar amount of the modified compound.

[0047] According to another embodiment of the present application, the above-mentioned end-capping compound is selected from: C2-C6 alkylene oxide, C2-C6 polyol, or a combination thereof; preferably, the end-capping compound is ethylene oxide, propylene oxide, butylene oxide, pentyl oxide, hexyl oxide; more preferably, the end-capping compound is ethylene oxide. According to an exemplary embodiment of the present application, after the polyether polyol is modified using the modifying compound, the modified polyether polyol is end-capped with the end-capping compound, and the molar ratio of the molar amount of the end-capping compound added here to the molar amount of the modifying compound is 3:1 to 7:1, preferably 4:1 to 6:1. According to another independent embodiment of the present application, the weight ratio of the end-capping compound added here to the polyether polyol can be 1:100 to 5:100, preferably 1.5:100 to 3:100.

[0048] According to a specific embodiment of the present application, the modified comonomer can be carried out by the following steps: i. activating a mixture of unmodified polyether polyol and a catalyst; ii. further adding a modifying compound to react the mixture containing the modifying compound, the unmodified polyether polyol and the catalyst to modify the polyether polyol; iii. capping the product obtained in step ii with a capping compound; and iv. aging the capped material.

[0049] According to another embodiment of the present application, in the above step i, the activation is carried out at a temperature of 90-130° C., preferably 115-125° C. According to another embodiment of the present application, in the above step i, the duration of the activation is 1.5-2.5 hours, preferably 1.8-2 hours. According to another embodiment of the present application, the activation in the above step i is carried out under vacuum conditions, for example, vacuumed to a negative pressure of less than -0.098 MPa.

[0050] According to another embodiment of the present application, in the above step ii, the modification reaction is carried out at a temperature of 65-80° C., preferably 65-75° C. According to another embodiment of the present application, in the above step ii, the duration of the modification reaction is 2-4 hours, preferably 2.5-3 hours. According to another embodiment of the present application, the above step ii is carried out under vacuum environment or inert atmosphere (e.g., nitrogen).

[0051] According to another embodiment of the present application, in the above step iii, the end-capping reaction is carried out at a temperature of 90-130°C, preferably 110-120°C. According to another embodiment of the present application, in the above step ii, the duration of the end-capping reaction is 3-24 hours, preferably 3-6 hours. According to another embodiment of the present application, the above step iii is carried out under vacuum environment or inert atmosphere (such as nitrogen), preferably under high-pressure nitrogen; more preferably, nitrogen stamping is used to react under high-pressure conditions.

[0052] According to another embodiment of the present application, in the above step iv, aging is carried out at a temperature of 90-130°C, preferably 110-120°C. According to another embodiment of the present application, in the above step iv, the duration of aging is 10-15 hours, preferably 12-14 hours. According to another embodiment of the present application, the above step iv is carried out under vacuum environment or inert atmosphere (such as nitrogen). According to another embodiment of the present application, the aging is carried out in an inert atmosphere (such as nitrogen), and the pressure of the inert atmosphere is 0.3-0.5MPa, preferably 0.35-0.40MPa.

[0053] After the modified comonomer is prepared by the steps and process conditions described above, the modified comonomer is used in the dispersion polymerization method of the present application.

[0054] According to one embodiment of the present application, the method for preparing haloalkyl functionalized microspheres of the present invention comprises the following steps: in a reaction kettle, a polymerization reaction mixture containing a modified comonomer, an aromatic monomer, a halogenated aromatic monomer, an aliphatic monomer, and a polyether undergoes a polymerization reaction (dispersion polymerization) to generate the haloalkyl functionalized microspheres. According to another embodiment of the present application, the polymerization reaction mixture further contains a chain transfer agent and a free radical initiator.

[0055] According to another embodiment of the present application, based on the weight of the polymerization reaction mixture as 100 weight %, the amount of the modified comonomer is 2-10 weight %, preferably 3-5 weight %.

[0056] In the present invention, the polyether used for the polymerization reaction has not been modified or modified, so it is also referred to as a "basic polyether". According to one embodiment of the present application, the polymerization reaction uses polyether as a solvent for the polymerization reaction. According to another embodiment of the present application, the functionality (hydroxyl functionality) of the polyether used in the polymerization reaction is 2-3, preferably 3; its number average molecular weight is 3000-6000. According to another embodiment of the present application, based on the total weight of the polymerization reaction mixture as 100 weight%, the content of the polyether is 40-60 weight%, preferably 45-55 weight%, and more preferably 50 weight%.

[0057] According to one embodiment of the present application, the aromatic monomer used in the polymerization reaction (preferably a dispersion polymerization reaction) is a C8-C18 aromatic compound containing at least one C2-C6 aliphatic alkenyl substituent, preferably a C8-C12 aromatic compound containing at least one C2-C4 aliphatic alkenyl substituent, more preferably the aromatic monomer is selected from at least one of the following: styrene, methyl styrene, dimethyl styrene, ethyl styrene, propyl styrene, butyl styrene, divinyl benzene, propenyl benzene, butenyl benzene, and most preferably the aromatic monomer is styrene. According to another embodiment of the present application, based on the weight of the polymerization reaction mixture as 100 weight%, the amount of the aromatic monomer is 4-15 weight%, preferably 6-13 weight%.

[0058] According to one embodiment of the present application, the halogenated aromatic monomer used in the polymerization reaction (preferably a dispersion polymerization reaction) is a C9-C18 aromatic compound containing at least one C2-C6 aliphatic alkenyl substituent and at least one C1-C6 aliphatic haloalkyl substituent, preferably a C9-C12 aromatic compound containing at least one C2-C4 aliphatic alkenyl substituent and at least one C1-C3 aliphatic haloalkyl substituent, more preferably the halogenated aromatic monomer is selected from at least one of the following: chloromethylstyrene, chloroethylstyrene, chloropropylstyrene, chlorobutylstyrene, chloromethylpropylenebenzene, chloromethylbutylbenzene, and most preferably the halogenated aromatic monomer is chloromethylstyrene. According to another embodiment of the present application, based on the weight of the polymerization reaction mixture as 100 weight%, the amount of the halogenated aromatic monomer is 10-26 weight%, preferably 13-20 weight%.

[0059] According to another embodiment of the present application, the mass ratio of the halogenated aromatic monomer to the aromatic monomer is 1:1 to 3:1.

[0060] According to one embodiment of the present application, the aliphatic monomer used in the polymerization reaction (preferably a dispersion polymerization reaction) is a C3-C12 aliphatic ethylenically unsaturated compound, and contains at least one functional group selected from the following: cyano, carboxyl, ester, anhydride; preferably a C3-C6 aliphatic ethylenically unsaturated compound, and contains at least one functional group selected from the following: cyano, carboxyl, ester, anhydride, more preferably the aliphatic monomer is selected from at least one of the following: acrylonitrile, methacrylonitrile, acrylic acid, methacrylic acid, most preferably the aliphatic monomer is acrylonitrile. According to another embodiment of the present application, based on the weight of the polymerization reaction mixture as 100% by weight, the amount of the halogenated aromatic monomer is 9-20% by weight, preferably 12-16% by weight.

[0061] According to another embodiment of the present application, the weight ratio of the sum of the weights of the aromatic monomer and the halogenated aromatic monomer to the weight of the aliphatic monomer is: (aromatic monomer+halogenated aromatic monomer):aliphatic monomer=1:1 to 4:1, preferably 2:1 to 3:1.

[0062] According to another embodiment of the present application, the chain transfer agent used in the polymerization reaction (preferably a dispersion polymerization reaction) is water, C1-C16 alcohol, C2-C16 ether, C2-C12 carboxylic acid, C2-C16 carboxylate, C2-C12 aliphatic thiol, etc. According to a preferred embodiment of the present application, the chain transfer agent is a C1-C12 fatty alcohol, such as a C1-C6 fatty alcohol, more preferably isopropanol. According to another embodiment of the present application, based on the weight of the polymerization reaction mixture as 100 weight%, the amount of the chain transfer agent is 3-8 weight%, preferably 5-7 weight%.

[0063] According to another embodiment of the present application, the initiator used in the polymerization reaction (preferably a dispersion polymerization reaction) is a free radical initiator, such as an organic peroxide (cyclohexanone peroxide, dibenzoyl peroxide, tert-butyl hydroperoxide, etc.), an inorganic peroxide (potassium sulfate, sodium persulfate, ammonium persulfate, etc., which can be combined with a reducing agent to be used as an oxidation / reduction system), and an azo free radical initiator (azobisisobutyronitrile, azobisisoheptanenitrile, etc.). According to another embodiment of the present application, based on the weight of the polymerization reaction mixture as 100% by weight, the amount of the initiator is 0.1-1% by weight, preferably 0.4-0.5% by weight.

[0064] According to another embodiment of the present application, the polymerization reaction (preferably a dispersion polymerization reaction) is carried out at a temperature of 100-120° C., and the duration of the polymerization reaction is 0.5-2 hours.

[0065] According to another embodiment of the present application, the polymerization reaction (preferably a dispersion polymerization reaction) is treated at a temperature of 100-120° C. for 0.5-2 hours under negative pressure conditions to remove low-boiling substances from the polymerization product mixture.

[0066] According to one embodiment of the present application, the product synthesized by the polymerization method of the present invention is micron-sized beads, preferably micron-sized beads with uniform size.

[0067] According to one embodiment of the present application, the haloalkyl functionalized microspheres prepared in the present application can be effectively used as adsorption materials, catalyst carriers, drug carriers, biological culture carriers, etc.

[0068] The advantages of the present invention are:

[0069] 1. The method of the present invention does not require the use of chloromethyl ether and / or dichloromethyl ether reagents conventionally used in the prior art, so a large amount of harmful substances such as formaldehyde and methylal will not be generated during the method process as in the prior art; the dispersion polymerization method of the present invention does not use the emulsifier used in the emulsion polymerization method of the prior art, especially does not use the small molecule emulsifier known in the prior art (such as alkylbenzene sulfonate, etc.), thereby effectively avoiding the cost and defects associated with the emulsifier;

[0070] 2. This method can simply and efficiently synthesize the target product microspheres, and the synthesized microspheres have a stable structure, uniform particle size, precisely modified microsphere surface, and excellent performance.

[0071] The method of the present application is specifically described in the following examples, the purpose of which is to provide a better understanding of the content of the present application. It should be understood that these examples are merely illustrative and not restrictive.

[0072] Example

[0073] The water used in the examples is deionized water, and the reagents used are analytically pure products purchased from the market and used directly without further purification. The polyether polyol used in Examples 1-3 was purchased from Shanghai Dongda Chemical Co., Ltd., with a number average molecular weight of 12,000 and a hydroxyl functionality of 6; the basic polyether used in Examples 4-6 was purchased from Shandong Tunan New Materials Co., Ltd., with a number average molecular weight of 3,000 or 6,000, respectively, and a hydroxyl functionality of 3; the potassium hydroxide standard solution is an aqueous solution with a concentration of 1.00 mol / L.

[0074] Example 1

[0075] In this example the synthesis of a modified comonomer was carried out.

[0076] Specifically, 100 g of polyether polyol and 0.28 mL of a standard potassium hydroxide aqueous solution were added to a 150 mL autoclave, and a stirring device was started to stir the materials in the autoclave at a speed of 120 rpm. The autoclave was evacuated to a negative pressure of at least -0.098 MPa, and the materials in the autoclave were heated to 120° C. and maintained at this temperature for 2 hours for activation.

[0077] Then stop vacuuming, cool the contents in the reactor to 25°C, and then add 0.82g of maleic anhydride into the reactor. Then remove the air in the reactor and replace it with monomers, and repeat this process three times. Then heat the contents in the reactor to 70°C, and continue the reaction at this temperature for 3 hours, so that the polyether polyol is modified by maleic anhydride.

[0078] Then, the temperature of the materials in the reactor was raised to 115° C., and 1.83 g of ethylene oxide was introduced into the reactor. At the same time, nitrogen was charged into the reactor and pressurized to 0.4 MPa, and a capping reaction was carried out for 3 hours.

[0079] Then the material in the reactor was cooled to 25°C, nitrogen was introduced into the reactor and pressurized to 0.4 MPa, and then the temperature in the reactor was increased to 115°C, and the reaction was continued at this temperature for 12 hours to age the reaction product.

[0080] Then, the reactor is cooled to room temperature, and the materials in the reactor are discharged to obtain the modified comonomer.

[0081] The number average molecular weight was measured by gel permeation chromatography to be 13436 g / mol, and the molecular weight distribution was 1.12.

[0082] Example 2

[0083] In this example the synthesis of a modified comonomer was carried out.

[0084] Specifically, 100 g of polyether polyol and 0.34 mL of a standard aqueous solution of potassium hydroxide were added to a 150 mL autoclave, and a stirring device was started to stir the materials in the autoclave at a speed of 120 rpm. The autoclave was evacuated to a negative pressure of at least -0.098 MPa, and the materials in the autoclave were heated to 120° C. and maintained at this temperature for 2 hours for activation.

[0085] Then stop vacuuming, cool the contents in the reactor to 25°C, and then add 0.98g of maleic anhydride into the reactor. Then remove the air in the reactor and replace it with monomers, and repeat this process three times. Then heat the contents in the reactor to 70°C, and continue the reaction at this temperature for 3 hours, so that the polyether polyol is modified by maleic anhydride.

[0086] Then, the temperature of the materials in the reactor was raised to 115° C., and 2.2 g of ethylene oxide was introduced into the reactor. At the same time, nitrogen was charged into the reactor and pressurized to 0.4 MPa, and a capping reaction was carried out for 6 hours.

[0087] Then the material in the reactor was cooled to 25°C, nitrogen was introduced into the reactor and pressurized to 0.4 MPa, and then the temperature in the reactor was increased to 115°C, and the reaction was continued at this temperature for 12 hours to age the reaction product.

[0088] Then, the reactor is cooled to room temperature, and the materials in the reactor are discharged to obtain the modified comonomer.

[0089] The number average molecular weight was measured by gel permeation chromatography to be 14399 g / mol, and the molecular weight distribution was 1.20.

[0090] Example 3

[0091] In this example the synthesis of a modified comonomer was carried out.

[0092] Specifically, 100 g of polyether polyol and 0.28 mL of a standard potassium hydroxide aqueous solution were added to a 150 mL autoclave, and a stirring device was started to stir the materials in the autoclave at a speed of 120 rpm. The autoclave was evacuated to a negative pressure of at least -0.098 MPa, and the materials in the autoclave were heated to 120° C. and maintained at this temperature for 2 hours for activation.

[0093] Then stop vacuuming, cool the contents in the reactor to 25°C, and then add 1.22g of maleic anhydride into the reactor. Then remove the air in the reactor and replace it with monomers, and repeat this process three times. Then heat the contents in the reactor to 70°C, and continue the reaction at this temperature for 3 hours, so that the polyether polyol is modified by maleic anhydride.

[0094] Then, the temperature of the materials in the reactor was raised to 115° C., and 2.8 g of ethylene oxide was introduced into the reactor. At the same time, nitrogen was charged into the reactor and pressurized to 0.4 MPa, and a capping reaction was carried out for 12 hours.

[0095] Then the material in the reactor was cooled to 25°C, nitrogen was introduced into the reactor and pressurized to 0.4 MPa, and then the temperature in the reactor was increased to 115°C, and the reaction was continued at this temperature for 12 hours to age the reaction product.

[0096] Then, the reactor is cooled to room temperature, and the materials in the reactor are discharged to obtain the modified comonomer.

[0097] The number average molecular weight was measured by gel permeation chromatography to be 18824 g / mol, and the molecular weight distribution was 1.39.

[0098] Example 4

[0099] In this example, the modified comonomer prepared in Example 1 was used for dispersion polymerization.

[0100] A mechanically stirred reactor equipped with a mechanical stirring device, a thermocouple, and a pressure sensor was used for dispersion polymerization.

[0101] 50g of basic polyether with a number average molecular weight of 3000, 0.4g of azobisisobutyronitrile, 3.6g of the modified comonomer prepared in Example 1, 7.0g of isopropanol, 13.0g of chloromethylstyrene, 13.0g of styrene and 13.0g of acrylonitrile were added to a mixing bottle respectively. The autoclave was heated to 115°C, and the reaction mixture in the mixing bottle was slowly added to the autoclave. The feeding was completed within 1 hour under stirring, and then the polymerization reaction was continued for another 1 hour.

[0102] After the polymerization reaction is completed, the reactor is cooled to room temperature, the materials in the reactor are discharged, and the solid materials obtained by filtration are washed with 50 ml of ethanol, and then the obtained solid product is placed in a vacuum oven and maintained at 110° C. and a negative pressure of at least -0.098 MPa for 0.5 hours to remove a small amount of low-boiling point substances adsorbed on the solid product, thereby obtaining the final polymerization product. 1H NMR test showed that the monomers were completely converted during the polymerization process, the solid content of the product was 41.7, and the viscosity was 4500mPa·s. The microstructure was characterized by scanning electron microscopy, and the results are shown in Figure 1 .from Figure 1 It can be seen that the product obtained in this example is microspheres with extremely uniform particle size and complete structure.

[0103] Example 5

[0104] In this example, the modified comonomer prepared in Example 2 was used for dispersion polymerization.

[0105] A mechanically stirred reactor equipped with a mechanical stirring device, a thermocouple, and a pressure sensor was used for dispersion polymerization.

[0106] 50g of basic polyether with a number average molecular weight of 6000, 0.5g of azobisisobutyronitrile, 5.0g of the modified comonomer prepared in Example 2, 6.5g of isopropanol, 16.8g of chloromethylstyrene, 8.5g of styrene and 12.7g of acrylonitrile were added to a mixing bottle respectively. The autoclave was heated to 115°C, and the reaction mixture in the mixing bottle was slowly added to the autoclave. The feeding was completed within 1 hour under stirring, and then the polymerization reaction was continued for another 1 hour.

[0107] After the polymerization reaction is completed, the reactor is cooled to room temperature, the materials in the reactor are discharged, and the solid materials obtained by filtration are washed with 50 ml of ethanol, and then the obtained solid product is placed in a vacuum oven and maintained at 120° C. and a negative pressure of at least -0.098 MPa for 2 hours to remove a small amount of low-boiling point substances adsorbed on the solid product, thereby obtaining the final polymerization product. 1 H NMR test shows that the monomers are completely converted during the polymerization process, the solid content of the product is 41.9, and the viscosity is 4470mPa.s. The microstructure is characterized by scanning electron microscopy, and the results are shown in Figure 2 .from Figure 2 It can be seen that the product obtained in this example is microspheres with extremely uniform particle size and complete structure.

[0108] Example 6

[0109] In this example, the modified comonomer prepared in Example 3 was used for dispersion polymerization.

[0110] A mechanically stirred reactor equipped with a mechanical stirring device, a thermocouple, and a pressure sensor was used for dispersion polymerization.

[0111] 50g of basic polyether with a number average molecular weight of 3000, 0.4g of azobisisobutyronitrile, 4.6g of the modified comonomer prepared in Example 3, 5.0g of isopropanol, 20.0g of chloromethylstyrene, 6.7g of styrene and 13.3g of acrylonitrile were added to a mixing bottle respectively. The autoclave was heated to 120°C, and the reaction mixture in the mixing bottle was slowly added to the autoclave. The feeding was completed within 1 hour under stirring, and then the polymerization reaction was continued for another 1 hour.

[0112] After the polymerization reaction is completed, the reactor is cooled to room temperature, the materials in the reactor are discharged, and the solid materials obtained by filtration are washed with 50 ml of ethanol, and then the obtained solid product is placed in a vacuum oven and maintained at 120° C. and a negative pressure of at least -0.098 MPa for 2 hours to remove a small amount of low-boiling point substances adsorbed on the solid product, thereby obtaining the final polymerization product. 1 H NMR test shows that the monomers are completely converted during the polymerization process, the solid content of the product is 42.1, and the viscosity is 4520mPa.s. The microstructure is characterized by scanning electron microscopy, and the results are shown in Figure 3 .from Figure 3 It can be seen that the product obtained in this example is microspheres with extremely uniform particle size and complete structure.

[0113] Example 7

[0114] In this example, the microspheres prepared in Example 6 were used as carriers, on which the catalytically active component N-methylimidazole was loaded to prepare a supported catalyst, and Figure 4 The supported catalyst is used to catalyze the addition reaction of carbon dioxide and an alkylene oxide ring to synthesize the target product butylene carbonate.

[0115] N-methylimidazole (82g, 1.0mmol) and chloromethyl microspheres (0.40g) prepared in Example 6 were added to a 50mL three-necked flask with a condenser, and 10mL toluene was added under stirring to fully dissolve it. The temperature of the three-necked flask was raised to a reaction temperature of 120°C, and stirring was continued at this temperature for 8 hours. After the reaction was completed, the solvent was removed by vacuum drying, and the polymer was extracted with methanol for 10 hours to remove the unreacted raw material N-methylimidazole. Vacuum drying gave imidazole hydrochloride-supported microsphere heterogeneous catalyst (P-IM, 0.36g). Elemental analysis (%): imidazole hydrochloride loading (N content 2.68%) is 0.96mmol / g.

[0116] The supported heterogeneous catalyst P-IM ​​(0.25 mmol), 1,2-butylene oxide (50 mmol) and CH 2 Cl 2(4 mL) was added into the catalytic reactor, the reactor was closed, carbon dioxide was charged into it to a pressure of 2.0 MPa, and the reaction was continued at a reaction temperature of 120°C for 48 hours.

[0117] After the catalytic reaction is completed, the P-IM ​​catalyst is recovered from the material in the reactor, added back into the catalytic reactor, and the catalytic reaction is repeated again as described above. The P-IM ​​catalyst is not replaced or supplemented, and the recycling is repeated three times. The reaction product of the above catalytic reaction is used 1 The yield was characterized by H NMR. Figure 5 The product obtained in the first cycle of this embodiment is shown in 1 H NMR confirmed that butylene carbonate was synthesized. The yield characterization results are summarized in Table 1. Table 1 Catalytic reaction results

[0118] Catalytic reaction Catalyst cycle usage Yield (%) 1 Fresh Catalyst 95 2 1 94 3 2 92 4 3 92

[0119] As shown in Table 1, the imidazole hydrochloride-supported microsphere heterogeneous catalyst (P-IM) can effectively catalyze the cycloaddition reaction of butylene oxide and carbon dioxide, and selectively obtain cyclic butylene carbonate products. Under the same reaction conditions, the heterogeneous catalyst P-IM ​​was recycled three times, and the reaction activity did not decrease significantly.

Claims

1. A method for preparing haloalkyl functionalized microspheres, the method comprising: In a reaction kettle, a polymerization reaction mixture containing a modified comonomer, an aromatic monomer, a halogenated aromatic monomer, an aliphatic monomer, and a polyether is polymerized to generate the halogenated alkyl functionalized microspheres; The modified comonomer is a polyether polyol modified with a modifying compound, wherein the modifying compound is a C4-C12 ethylenically unsaturated polycarboxylic acid or anhydride thereof; The aromatic monomer is a C8-C18 aromatic compound containing at least one C2-C6 aliphatic alkenyl substituent; The halogenated aromatic monomer is a C9-C18 aromatic compound containing at least one C2-C6 aliphatic alkenyl substituent and at least one C1-C6 aliphatic haloalkyl substituent; The aliphatic monomer is a C3-C12 aliphatic ethylenically unsaturated compound and contains at least one functional group selected from the following: cyano group, carboxyl group, ester group, and acid anhydride group.

2. The method according to claim 1, characterized in that The modified comonomer is prepared by the following steps: modifying an unmodified polyether polyol with a modifying compound, and then capping it with a capping compound, wherein the capping compound is selected from: C2-C6 alkylene oxide, C2-C6 polyol, or a combination thereof; The unmodified polyether polyol has a functionality of 3-6 and a number average molecular weight of 6000-15000; The molar ratio of the modified compound to the unmodified polyether polyol is 0.8:1 to 2:1; The molar ratio of the modifying compound to the end-capping compound is 1:3 to 1:

7.

3. The method according to claim 2, characterized in that The modified comonomer is prepared by the following steps: i. activating a mixture of an unmodified polyether polyol and a catalyst at a temperature of 90-130° C., wherein the catalyst is an alkali metal hydroxide; ii. reacting a mixture containing a modified compound, an unmodified polyether polyol and a catalyst at a temperature of 65-80°C; iii. capping the product obtained in step ii with a capping compound at a temperature of 90-130 ° C; iv. Aging at a temperature of 90-130°C.

4. The method according to claim 2, characterized in that The modifying compound is selected from one or more of the following: maleic acid / anhydride, fumaric acid / anhydride, glutaconic acid / anhydride, hexamethylenediamine / anhydride, heptenedioic acid / anhydride, octenic acid / anhydride.

5. The method according to claim 1, characterized in that The functionality of the polyether is 2-3 and the number average molecular weight is 3000-6000; Based on the total weight of the polymerization reaction mixture being 100 weight %, the content of the polyether is 40-60 weight %.

6. The method according to claim 1, characterized in that The aromatic monomer is selected from at least one of the following: styrene, methyl styrene, dimethyl styrene, ethyl styrene, propyl styrene, butyl styrene, divinylbenzene, propenylbenzene, and butenylbenzene; The halogenated aromatic monomer is selected from at least one of the following: chloromethylstyrene, chloroethylstyrene, chloropropylstyrene, chlorobutylstyrene, chloromethylpropylenebenzene, and chloromethylbutylbenzene; The aliphatic monomer is selected from at least one of the following: acrylonitrile, methacrylonitrile, acrylic acid, and methacrylic acid.

7. The method according to claim 1, characterized in that Based on the weight of the polymerization reaction mixture as 100 wt%, the amount of the modified comonomer is 2-10 wt%, the amount of the aromatic monomer is 4-15 wt%, the amount of the halogenated aromatic monomer is 10-26 wt%, the amount of the aliphatic monomer is 9-20 wt%, and the mass ratio of the aromatic monomer to the halogenated aromatic monomer is 1:1 to 1:

3.

8. The method according to claim 1, characterized in that The polymerization reaction mixture further contains a chain transfer agent and a free radical initiator. Based on 100 wt % of the polymerization reaction mixture, the amount of the chain transfer agent is 3-8 wt %, and the amount of the free radical initiator is 0.1-1 wt %.

9. The method according to claim 1, characterized in that The method is carried out without the use of an emulsifier.

10. A haloalkyl functionalized microsphere, wherein the microsphere is synthesized by the method according to any one of claims 1 to 9.

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