CN100579995C - Copolymerization reaction method for styrene/maleic anhydride - Google Patents
Copolymerization reaction method for styrene/maleic anhydride Download PDFInfo
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Abstract
A copolymerization method of phenylethene/maleic anhydride belongs to polymer preparation technical field, for resolving the defect caused by stabilizer in traditional disperse polymerization system, which comprises under nitrogen gas protection, dissolving monomer Man and St, inducer organic hyperoxide or azocompound of suitable ratio in organic acid alkyl ester, the mixture of aromatics and organic acid alkyl ester or the mixture of ketone and alkane to react for 1/4-12h at 60-90 DEG C to obtain the disperse system of polymer microballoon, wherein the average particle diameter of microballoon in the disperse system is 90-1715mm, the disperse factor is 1.04-1.004 and the number average molecular weight is 80000-300000g/mol. The invention has the advantages of eliminated stabilizer, simple process, low cost, clean polymer microballoon or particle surface, controllable particle diameter, controllable shape and narrow granularity distribution.
Description
Technical field
The present invention relates to a kind of maleic anhydride (MAn) and the method that vinylbenzene (St) carries out copolyreaction, be specifically related to a kind of MAn and St obtain self stabilization alternating copolymer dispersion system after copolymerization method.
Background technology
Vinylbenzene (St), maleic anhydride (MAn) multipolymer are a kind of excellent property and cheap novel high polymer material, are widely used in the field such as emulsifying agent, curing agent for epoxy resin of emulsifying agent, the agricultural chemicals of properties-correcting agent, dispersing of pigments agent, the floor polishing of water conditioner, latex coating, glue paste.
In addition, preparation and application that a focus of present functional high polymer material field is a polymer microballoon, nano level to micron-sized polymer microballoon because of specific physique such as have that specific surface area is big, adsorptivity is strong, cohesion is big and the surface reaction ability is strong, be widely used for many high-technology fields such as analytical chemistry, biomedicine, standard metering, solid phase carrier, high performance liquid chromatography.
The preparation method of vinylbenzene (St), maleic anhydride (MAn) multipolymer mainly is solution polymerization at present, a spot of mass polymerization, precipitation polymerization, body-suspension polymerization and the letex polymerization of solution phase inversion.
Solution polymerization is the main method for preparing vinylbenzene (St), maleic anhydride (MAn) multipolymer at present, and the emphasis of research is the random multipolymer of preparation.As Tian Yong, Wang Xiufang at " R-SMA synthetic and performance study " (" Chinese leather ", 2007, the 3rd phase, pp.9-11) in the literary composition be with the pimelinketone solvent under higher temperature of reaction (greater than 90 ℃) by the monomeric technology of dropwise reaction, polymerization is finished after methanol extraction obtains pulverous irregular phenylethylene (St), maleic anhydride (MAn) multipolymer of white.Li Xiuqing, Song Yong is strong to be waited at " the synthetic and performance study of styrene-maleic anhydride copolymer " (" Inner Mongol University of Technology's journal ", 2006, the 3rd phase, pp.215-220) in the literary composition, be solvent, by the method for once feeding in raw material with acetone, react 4-5h at a certain temperature, the reaction products therefrom obtains the multipolymer of certain maleic anhydride content through ether sedimentation.And for example Li Huaming, Zhou Disheng etc. are at " solution polymerization process synthesizing styrene-maleic anhydride random copolymer " (" synthetic rubber and plastics ", 1998,15 (3), pp.64-65) in the literary composition, random maleic anhydride, styrol copolymer have been prepared by the method for in acetone solvent, adding polar solvent dimethyl sulfoxide (DMSO) and raising temperature of reaction.As seen a lot of solution polymerization process all concentrate on preparation random maleic anhydride, styrol copolymer with the emphasis of research.
Zhou Wen, multitude Paine are in " the synthetic and characterization research of the body-suspension method of SMA resin " (" modern plastics processed and applied ", 1999, the 4th phase, pp.5-9) in the literary composition, by continuous dropping monomer methods, carry out mass polymerization in 90 ℃, when transformation efficiency reaches 40%～50%, carry out the method for suspension polymerization, prepared random maleic anhydride, styrol copolymer.Because maleic anhydride facile hydrolysis in water medium becomes toxilic acid, reactive behavior reduces greatly, has influenced the composition and the distribution of copolymerization rate and product, must make acid be dehydrated into acid anhydride again during aftertreatment simultaneously, the processing condition complexity.
Li Chunsheng, Zhang Shuxiang etc. are at " supercritical CO
2In maleic anhydride and cinnamic polymerization " (" polymer material science and engineering "; 2006; vol.22; No.5; pp95-97); during greater than 16MPa, do not have polystyrene (PS) generation in reaction pressure, (number-average molecular weight can reach 4.6 * 10 can to obtain very high transformation efficiency and higher molecular weight
4G/mol) pure MAn and St alternating copolymer, product is the fine powdered solid.Reaction will be carried out under higher pressure, and is higher to the device and the processing requirement of polyreaction.
Li Xiaorui, Shen Yiding is in " research of SMA copolymerization and modification " (" polymer material science and engineering ", 2000,16 (3), pp.56-60) mention the mass polymerization of maleic anhydride (MAn) and vinylbenzene (St) in the literary composition, but be difficult to reach reaction in the polymerization process relatively steadily and good heat transfer, mass transfer condition arranged.Therefore the random SMA with the synthetic high molecular weight of substance law and its narrowly distributing has bigger difficulty.
Shen Yiding, Li Xiaorui is in " preparation of styrene-maleic anhydride random copolymers and performance " (" polymer material science and engineering ", 2000,13 (3), pp.32-35) in the literary composition, by solution phase inversion method of emulsion polymerization,, make Zelan 338 with random structure in 90～130 ℃ temperature and using under the condition of polar solvent as medium.Same because maleic anhydride facile hydrolysis in water medium becomes toxilic acid, and reactive behavior reduces greatly, has influenced the composition and the distribution of copolymerization rate and product, must make acid be dehydrated into acid anhydride again during aftertreatment simultaneously, the processing condition complexity.
In the copolymerization process of as seen above-mentioned maleic anhydride (MAn) and vinylbenzene (St), in the preparation that focuses on random copolymers that mostly will study, the purposes of multipolymer also generally concentrates on the chemical property of multipolymer itself and reaches in the follow-up modification.Though the preparation and the application that relate to dispersion system are arranged, also focus on the preparation of polymer material, with focusing on copolymer structure and the molecular weight of reaction control.And all need add some surfactant stabilisers in the preparation of relevant dispersion system and in using, increase difficulty for the purifying of follow-up polymkeric substance, also can increase economically cost and to the pollution of environment.
Nearest Willem Jan Soer etc. are at " Surfactant-free artificiallatexes from modified styrene-maleic anhydride (SMA) copolymers " (Polymer, 2006,47,7621-7627) in the literary composition, under the condition that does not add any stablizer, prepared colloid based on maleic anhydride (MAn) vinylbenzene (St) multipolymer.But the maleic anhydride-styrene polyreaction is the solution polymerization of carrying out in methylethylketone, the preparation of polymeric colloid relates to the amino-alkylation and the conversion of reacting the dispersion system medium of the molecular chain of maleic anhydride (MAn) vinylbenzene (St) multipolymer, no longer be simple maleic anhydride (MAn) vinylbenzene (St) multipolymer, and complex process.
As seen, the oyster white colloid and the colloidal disperse phase that prepare maleic anhydride (MAn) vinylbenzene (St) multipolymer by the self stabilization dispersion polymerization processes that does not add any stablizer are the polymerization process of monodisperse copolymerization thing particle, do not appear in the newspapers up to now.
Summary of the invention
The objective of the invention is to solve the drawback of using stablizer to bring in traditional dispersion polymerization system, and a kind of preparation method of phenylethylene/maleic anhydride copolymer colloidal dispersion system of self stabilization is provided.The colloidal disperse phase is monodispersed polymer microballoon, the monodisperse polymer micro-sphere surface cleaning, and pattern is controlled, and particle diameter is controlled, and narrow particle size distribution, and polymer microballoon is made up of the alternating copolymer of maleic anhydride-styrene.
The method of a kind of phenylethylene/maleic anhydride copolyreaction provided by the present invention, under the condition of nitrogen protection, monomer and initiator joined in the medium dissolve, and in 60～90 ℃ of reaction 1/4～12h, obtain the dispersion system of phenylethylene/maleic anhydride polymer microballoon, obtain the white solid of phenylethylene/maleic anhydride alternate copolymer again through centrifugation; Wherein, described monomer is maleic anhydride Man and vinylbenzene St, and the mol ratio of the two is 6: 1～1: 6, and monomeric mass concentration is 1%～50% in the reaction system; Described initiator is organo-peroxide or azo-compound, and the mass concentration of initiator is 0.01%～1% in the reaction system; Described medium is the mixing solutions of organic acid alkyl ester or ketone and alkane, and wherein, the volume fraction of ketone is 5%～65% in the mixing solutions of ketone and alkane, preferred 10%～50%.
The mass concentration of described monomer in reaction system preferred 15%～36%.
The initiator that is adopted among the present invention is conventional thermolysis type initiator, comprise for known this compounds of professional and technical personnel: (1) organo-peroxide, for example: dibenzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, dilauroyl peroxide, the special butyl ester of peroxidation phenylformic acid, peroxy dicarbonate diisopropyl ester, di-cyclohexylperoxy dicarbonate etc.; (2) azo-compound, for example: Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile) etc.
The mass concentration of initiator in reaction system preferred 0.06%～0.6%.
The present invention is by selecting suitable media implementation MAn and the self stabilization dispersion polymerization of St, its characteristics are: need not to add any stablizer and co-stabilizer in (1) this dispersion polymerization system, can obtain having the colloidal dispersion system of self stabilization effect after polymerization is finished; (2) in the polymerization system be monodisperse polymer micro-sphere or lopsided particle, the microsphere surface cleaning, particle diameter is controlled, the controlled and narrow particle size distribution of pattern.(3) polymer microballoon is made up of the maleic anhydride-styrene alternating copolymer with certain molecular weight.
The selection of reaction medium is crucial unusually for the dispersion polymerization of the self stabilization of MAn and St among realization the present invention, its fundamental principle is: (1) medium all has good solvency action for MAn and two kinds of monomers of St and initiator, to guarantee that before the reaction be homogeneous system; (2) medium can not dissolve for the PMS multipolymer that is generated, after macromolecular chain reaches certain critical length just from medium precipitating come out; (3) polymkeric substance that comes out of precipitating precipitates down with Powdered or block can not be in precipitation polymerization, but stably is suspended in the medium with the microballoon or the form of particle, forms the stable dispersion that is similar to polymer emulsion.The medium that can be used as self stabilization dispersion polymerization system among the present invention has: the mixing solutions of organic acid alkyl ester or ketone and alkane.
Wherein, the general structure of described organic acid alkyl ester is:
In the formula, R
1For H, C atomicity are 1～8 alkyl, phenyl or benzyl, R
2It for the C atomicity 1～5 alkyl.This type of medium is that its toxicity is lower in the advantage aspect industrial operation and the environmental protection, and mostly has no irritating odor.
The organic acid alkyl ester that the present invention adopts is an ethyl formate, propyl formate, tetryl formate, pentyl formate, ethyl acetate, butylacetate, isobutyl acetate, sec-butyl acetate, pentyl acetate, Isoamyl Acetate FCC, jasmal, methyl propionate, ethyl propionate, butyl propionate, methyl-butyrate, ethyl butyrate, butyl butyrate, isoamyl butyrate, Ethylisovalerate, isoamyl isovalerate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, isoamyl benzoate, methyl phenylacetate or Phenylacetic acid ethylester etc.
Described ketone is selected from acetone, butanone, pimelinketone or hexone.
Described alkane is selected from hexanaphthene, normal hexane, normal heptane, Skellysolve A, octane or octane-iso.
Adopt water-bath or oil bath heating among the present invention, according to technique known, polymeric reaction temperature is determined by the decomposition temperature of initiator, be suitable for 60～90 ℃ as dibenzoyl peroxide, and Diisopropyl azodicarboxylate is suitable for 45～80 ℃; According to the difference that reaction system is formed, the speed of polyreaction is different, approximately reacts 1/4～12h.
From the dispersion system of polymer microballoon, take a sample, observe the form of the prepared polymer microballoon of the present invention with scanning electronic microscope (SEM).The size of microballoon represents that with median size (Dn) size-grade distribution represents that with dispersion coefficient (U) formula is as follows:
U＝D
w/D
n (3)
Wherein, D
iBe the diameter (nm) of i particle, n is a size of a sample, D
wMathematic(al) mean particle diameter for definition.
The median size of the phenylethylene/maleic anhydride copolymer microballoon that the inventive method is prepared is 90～1715nm, and its particle diameter can be controlled by processing parameters such as reaction times, monomer concentration, reaction mediums; Dispersion coefficient is 1.04～1.004, for monodispersity or near monodispersity.Resulting polymers is the alternating copolymer of phenylethylene/maleic anhydride, and the number-average molecular weight scope of alternating copolymer is 80000～300000g/mol.
The present invention has following beneficial effect:
1) the present invention is owing to need not to add any stablizer and co-stabilizer, and reaction system is very simple, and technology controlling and process is easy, saves cost, reduces environmental pollution.
2) prepared polymer microballoon or the particle surface cleaning of the inventive method, and particle diameter is controlled, and pattern is controlled, narrow particle size distribution.
3) phenylethylene/maleic anhydride alternate copolymer of the inventive method preparation has higher molecular weight.
4) technology of the present invention is simple, and speed of reaction is fast, final transformation efficiency height, and the product separate easily, used reaction medium belongs to low toxicity chemical and recyclable utilization.
Description of drawings
The surface sweeping electron micrograph (magnification 10000) of the polymer microballoon of Fig. 1, embodiment 4 preparations.
The surface sweeping electron micrograph (magnification 10000) of the polymer microballoon of Fig. 2, embodiment 6 preparations.
The electron scanning micrograph (magnification 10000) of the polymer microballoon of Fig. 3, embodiment 7 preparations.
The electron scanning micrograph (magnification 10000) of the polymer microballoon of Fig. 4, embodiment 12 preparations.
The electron scanning micrograph (magnification 10000) of the polymer microballoon of Fig. 5, embodiment 15 preparations.
The electron scanning micrograph (magnification 10000) of the polymer microballoon of Fig. 6, embodiment 16 preparations.
The electron scanning micrograph (magnification 10000) of the polymer microballoon of Fig. 7, embodiment 17 preparations.
The electron scanning micrograph (magnification 10000) of the polymer microballoon of Fig. 8, embodiment 18 preparations.
The electron scanning micrograph (magnification 10000) of the polymer microballoon of Fig. 9, embodiment 19 preparations.
Figure 10 is the electron scanning micrograph (magnification 10000) of the polymer microballoon of embodiment 20 preparations.
Below in conjunction with the drawings and the specific embodiments the present invention is further described.
Embodiment
Embodiment 1
MAn and St mole proportioning 1: 1, MAn 0.3065g wherein, St 0.325g; Initiator is Diisopropyl azodicarboxylate AIBN, 0.05g; Medium is an Isoamyl Acetate FCC, 45mL.Adopt heating in water bath, reaction is 6 hours under 70 ℃ temperature, obtains maleic anhydride/cinnamic alternating copolymer PMS microballoon.Median size (Dn), dispersion coefficient (U) and polymerization yield (C
p), and the number-average molecular weight of polymkeric substance (
) the results are shown in Table 1.
Embodiment 2
MAn and St mole proportioning 1: 1, MAn 0.613g wherein, St 0.325g; Initiator is AIBN, 0.04g; Medium is an Isoamyl Acetate FCC, 45mL.Adopt heating in water bath, reaction is 6 hours under 70 ℃ temperature, obtains median size (Dn), dispersion coefficient (U) and the polymerization yield (C of PMS copolymer microsphere
p), and the number-average molecular weight of polymkeric substance (
) the results are shown in Table 1.
Embodiment 3
MAn and St mole proportioning 1: 1, MAn 1.226g wherein, St 1.3g; Initiator is AIBN, 0.04g; Medium is an Isoamyl Acetate FCC, 45mL.Adopt heating in water bath, reaction is 6 hours under 70 ℃ temperature, obtains median size (Dn), dispersion coefficient (U) and the polymerization yield (C of PMS copolymer microsphere
p), and the number-average molecular weight of polymkeric substance (
) the results are shown in Table 1.
Embodiment 4
MAn and St mole proportioning 1: 1, MAn 2.452g wherein, St 2.6g; Initiator is AIBN, 0.03g; Medium is an Isoamyl Acetate FCC, 45mL.Adopt heating in water bath, reaction is 6 hours under 70 ℃ temperature, obtains median size (Dn), dispersion coefficient (U) and the polymerization yield (C of PMS copolymer microsphere
p), and the number-average molecular weight of polymkeric substance (
) the results are shown in Table 1, the electron scanning micrograph of polymer microballoon is seen Fig. 1.
Embodiment 5
MAn and St mole proportioning 1: 1, MAn 4.904g wherein, St 5.2g; Initiator is AIBN, 0.03g; Medium is an Isoamyl Acetate FCC, 45mL.Adopt heating in water bath, reaction is 6 hours under 70 ℃ temperature, obtains median size (Dn), dispersion coefficient (U) and the polymerization yield (C of PMS copolymer microsphere
p), and the number-average molecular weight of polymkeric substance (
) the results are shown in Table 1.
Embodiment 6
MAn and St mole proportioning 1: 1, MAn 7.356g wherein, St 7.8g; Initiator is AIBN, 0.03g; Medium is an Isoamyl Acetate FCC, 45mL.Adopt heating in water bath, reaction is 6 hours under 70 ℃ temperature, obtains median size (Dn), dispersion coefficient (U) and the polymerization yield (C of PMS copolymer microsphere
p), and the number-average molecular weight of polymkeric substance (
) the results are shown in Table 1, the electron scanning micrograph of polymer microballoon is seen Fig. 2.
Embodiment 7
MAn and St mole proportioning 4: 1, MAn 9.806g wherein, St 2.6g; Initiator is AIBN, 0.03g; Medium is an Isoamyl Acetate FCC, 45mL.Adopt heating in water bath, reaction is 6 hours under 70 ℃ temperature, obtains median size (Dn), dispersion coefficient (U) and the polymerization yield (C of PMS copolymer microsphere
p), and the number-average molecular weight of polymkeric substance (
) the results are shown in Table 1, the electron scanning micrograph of polymer microballoon is seen Fig. 3.
Embodiment 8
MAn and St mole proportioning 3: 1, MAn 7.356g wherein, St 2.6g; Initiator is AIBN, 0.03g; Medium is an Isoamyl Acetate FCC, 45mL.Adopt heating in water bath, reaction is 6 hours under 70 ℃ temperature, obtains median size (Dn), dispersion coefficient (U) and the polymerization yield (C of PMS copolymer microsphere
p), and the number-average molecular weight of polymkeric substance (
) the results are shown in Table 1.
Embodiment 9
MAn and St mole proportioning 2: 1, MAn 4.904g wherein, St 2.6g; Initiator is AIBN, 0.03g; Medium is an Isoamyl Acetate FCC, 45mL.Adopt heating in water bath, reaction is 6 hours under 70 ℃ temperature, obtains median size (Dn), dispersion coefficient (U) and the polymerization yield (C of PMS copolymer microsphere
p), and the number-average molecular weight of polymkeric substance (
) the results are shown in Table 1.
Embodiment 10
MAn and St mole proportioning 1: 1, MAn 2.452g wherein, St 2.6g; Initiator is AIBN, 0.03g; Medium is an Isoamyl Acetate FCC, 45mL.Adopt heating in water bath, reaction is 6 hours under 70 ℃ temperature, obtains median size (Dn), dispersion coefficient (U) and the polymerization yield (C of PMS copolymer microsphere
p), and the number-average molecular weight of polymkeric substance (
) the results are shown in Table 1.
Embodiment 11
MAn and St mole proportioning 1: 2, MAn 2.452g wherein, St 5.2g; Initiator is AIBN, 0.03g; Medium is an Isoamyl Acetate FCC, 45mL.Adopt heating in water bath, reaction is 6 hours under 70 ℃ temperature, obtains median size (Dn), dispersion coefficient (U) and the polymerization yield (C of PMS copolymer microsphere
p), and the number-average molecular weight of polymkeric substance (
) the results are shown in Table 1.
Embodiment 12
MAn and St mole proportioning 1: 3, MAn 2.452g wherein, St 7.8g; Initiator is AIBN, 0.03g; Medium is an Isoamyl Acetate FCC, 45mL.Adopt heating in water bath, reaction is 6 hours under 70 ℃ temperature, obtains median size (Dn), dispersion coefficient (U) and the polymerization yield (C of PMS copolymer microsphere
p), and the number-average molecular weight of polymkeric substance (
) the results are shown in Table 1, the electron scanning micrograph of polymer microballoon is seen Fig. 4.
Embodiment 13
MAn and St mole proportioning 1: 4, MAn 2.452g wherein, St10.4g; Initiator is AIBN, 0.03g; Medium is an Isoamyl Acetate FCC, 45mL.Adopt heating in water bath, reaction is 6 hours under 70 ℃ temperature, obtains median size (Dn), dispersion coefficient (U) and the polymerization yield (C of PMS copolymer microsphere
p), and the number-average molecular weight of polymkeric substance (
) the results are shown in Table 1.
Embodiment 14
MAn and St mole proportioning 1: 1, MAn 2.452g wherein, St 2.6g; Initiator is AIBN, 0.03g; Medium is a pentyl acetate, 45mL.Adopt heating in water bath, reaction is 6 hours under 70 ℃ temperature, obtains median size (Dn), dispersion coefficient (U) and the polymerization yield (C of PMS copolymer microsphere
p), and the number-average molecular weight of polymkeric substance (
) the results are shown in Table 2.
Embodiment 15
MAn and St mole proportioning 1: 1, MAn 2.452g wherein, St 2.6g; Initiator is AIBN, 0.03g; Medium is an ethyl butyrate, 45mL.Adopt heating in water bath, reaction is 6 hours under 70 ℃ temperature, obtains median size (Dn), dispersion coefficient (U) and the polymerization yield (C of PMS copolymer microsphere
p), and the number-average molecular weight of polymkeric substance (
) the results are shown in Table 2, the electron scanning micrograph of polymer microballoon is seen Fig. 5.
Embodiment 16
MAn and St mole proportioning 1: 1, MAn 2.452g wherein, St 2.6g; Initiator is AIBN, 0.03g; Medium is an ethyl benzoate, 45mL.Adopt heating in water bath, reaction is 6 hours under 70 ℃ temperature, obtains median size (Dn), dispersion coefficient (U) and the polymerization yield (C of PMS copolymer microsphere
p), and the number-average molecular weight of polymkeric substance (
) the results are shown in Table 2, the electron scanning micrograph of polymer microballoon is seen Fig. 6.
Embodiment 17
MAn and St mole proportioning 1: 1, MAn 2.452g wherein, St 2.6g; Initiator is AIBN, 0.03g; Medium is butanone 4mL, hexanaphthene 41mL.Adopt heating in water bath, reaction is 6 hours under 70 ℃ temperature, obtains median size (Dn), dispersion coefficient (U) and the polymerization yield (C of PMS copolymer microsphere
p), and the number-average molecular weight of polymkeric substance (
) the results are shown in Table 2, the electron scanning micrograph of polymer microballoon is seen Fig. 7.
Embodiment 18
MAn and St mole proportioning 1: 1, MAn 2.452g wherein, St 2.6g; Initiator is AIBN, 0.03g; Medium is butanone 8mL, hexanaphthene 37mL.Adopt heating in water bath, reaction is 6 hours under 70 ℃ temperature, obtains median size (Dn), dispersion coefficient (U) and the polymerization yield (C of PMS copolymer microsphere
p), and the number-average molecular weight of polymkeric substance (
) the results are shown in Table 2, the electron scanning micrograph of polymer microballoon is seen Fig. 8.
Embodiment 19
MAn and St mole proportioning 1: 1, MAn 2.452g wherein, St 2.6g; Initiator is AIBN, 0.03g; Medium is butanone 25mL, hexanaphthene 20mL.Adopt heating in water bath, reaction is 6 hours under 70 ℃ temperature, obtains median size (Dn), dispersion coefficient (U) and the polymerization yield (C of PMS copolymer microsphere
p), and the number-average molecular weight of polymkeric substance (
) the results are shown in Table 2, the electron scanning micrograph of polymer microballoon is seen Fig. 9.
Embodiment 20
MAn and St mole proportioning 1: 1, MAn 2.452g wherein, St 2.6g; Initiator is AIBN, 0.03g; Medium is butanone 33mL, hexanaphthene 12mL.Adopt heating in water bath, reaction is 6 hours under 70 ℃ temperature, obtains median size (Dn), dispersion coefficient (U) and the polymerization yield (C of PMS copolymer microsphere
p), and the number-average molecular weight of polymkeric substance (
) the results are shown in Table 2, the electron scanning micrograph of polymer microballoon is seen Figure 10.
Embodiment 21
MAn and St mole proportioning 1: 1, MAn 2.452g wherein, St 2.6g; Initiator is AIBN, 0.03g; Medium is butanone 37mL, hexanaphthene 8mL.Adopt heating in water bath, reaction is 6 hours under 70 ℃ temperature, obtains median size (Dn), dispersion coefficient (U) and the polymerization yield (C of PMS copolymer microsphere
p), and the number-average molecular weight of polymkeric substance (
) the results are shown in Table 2.
Embodiment 22
MAn and St mole proportioning 1: 1, MAn 2.452g wherein, St 2.6g; Initiator is AIBN, 0.03g; Medium is an Isoamyl Acetate FCC, 45mL.Adopt heating in water bath, under 70 ℃ temperature, react 15min, obtain median size (Dn), dispersion coefficient (U), the polymerization yield (C of PMS copolymer microsphere
p), the number-average molecular weight of polymkeric substance (
) the results are shown in Table 3.
Embodiment 23
MAn and St mole proportioning 1: 1, MAn 2.452g wherein, St 2.6g; Initiator is AIBN, 0.03g; Medium is an Isoamyl Acetate FCC, 45mL.Adopt heating in water bath, under 70 ℃ temperature, react 25min, obtain median size (Dn), dispersion coefficient (U), the polymerization yield (C of PMS copolymer microsphere
p), the number-average molecular weight of polymkeric substance (
) the results are shown in Table 3.
Embodiment 24
MAn and St mole proportioning 1: 1, MAn 2.452g wherein, St 2.6g; Initiator is AIBN, 0.03g; Medium is an Isoamyl Acetate FCC, 45mL.Adopt heating in water bath, under 70 ℃ temperature, react 35min, obtain median size (Dn), dispersion coefficient (U), the polymerization yield (C of PMS copolymer microsphere
p), the number-average molecular weight of polymkeric substance (
) the results are shown in Table 3.
Embodiment 25
MAn and St mole proportioning 1: 1, MAn 2.452g wherein, St 2.6g; Initiator is AIBN, 0.03g; Medium is an Isoamyl Acetate FCC, 45mL.Adopt heating in water bath, under 70 ℃ temperature, react 50min, obtain median size (Dn), dispersion coefficient (U), the polymerization yield (C of PMS copolymer microsphere
p), the number-average molecular weight of polymkeric substance (
) the results are shown in Table 3.
Embodiment 26
MAn and St mole proportioning 1: 1, MAn 2.452g wherein, St 2.6g; Initiator is AIBN, 0.03g; Medium is an Isoamyl Acetate FCC, 45mL.Adopt heating in water bath, under 70 ℃ temperature, react 60min, obtain median size (Dn), dispersion coefficient (U), the polymerization yield (C of PMS copolymer microsphere
p), the number-average molecular weight of polymkeric substance (
) the results are shown in Table 3.
Embodiment 27
MAn and St mole proportioning 1: 1, MAn 2.452g wherein, St 2.6g; Initiator is AIBN, 0.03g; Medium is an Isoamyl Acetate FCC, 45mL.Adopt heating in water bath, under 70 ℃ temperature, react 90min, obtain median size (Dn), dispersion coefficient (U), the polymerization yield (C of PMS copolymer microsphere
p), the number-average molecular weight of polymkeric substance (
) the results are shown in Table 3.
Gained copolymer dispersion system under table 1 different condition
The copolymer dispersion of diverse microcosmic appearance system under table 2 different condition
The copolymer dispersion system of table 3 differential responses during the time
Claims (5)
1, a kind of method of phenylethylene/maleic anhydride copolyreaction, it is characterized in that, under the condition of nitrogen protection, monomer and initiator joined in the medium dissolve, and in 60～90 ℃ of reaction 1/4～12h, obtain the dispersion system of phenylethylene/maleic anhydride polymer microballoon, obtain the white solid of phenylethylene/maleic anhydride alternate copolymer again through centrifugation; Wherein, described monomer is maleic anhydride Man and vinylbenzene S t, and the mol ratio of the two is 6: 1～1: 6, and monomeric mass concentration is 1%～50% in the reaction system; Described initiator is organo-peroxide or azo-compound, and the mass concentration of initiator is 0.01%～1% in the reaction system; Described medium is the mixing solutions of organic acid alkyl ester or ketone and alkane; Wherein, the general structure of described organic acid alkyl ester is:
In the formula, R
1For H, C atomicity are 1～8 alkyl, phenyl or benzyl, R
2It for the C atomicity 1～5 alkyl; The volume fraction of ketone is 5%～65% in the mixing solutions of ketone and alkane, and described ketone is selected from acetone, butanone, pimelinketone or hexone, and described alkane is selected from hexanaphthene, normal hexane, normal heptane, Skellysolve A, octane or octane-iso.
2, method according to claim 1 is characterized in that, the mass concentration of described monomer in reaction system is 15%～36%.
3, method according to claim 1 is characterized in that, the mass concentration of described initiator in reaction system is 0.06%～0.6%.
4, method according to claim 1 is characterized in that, the volume fraction of ketone is 10%～50% in the mixing solutions of described ketone and alkane.
5, method according to claim 1, it is characterized in that, the median size of microballoon is 90～1715nm in the dispersion system of described phenylethylene/maleic anhydride polymer microballoon, dispersion coefficient is 1.04～1.004, and the number-average molecular weight scope of phenylethylene/maleic anhydride alternate copolymer is 80000～300000g/mol.
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| CN101781387B (en) * | 2010-03-22 | 2012-06-20 | 北京化工大学 | Method for copolymerization of maleic anhydride/conjugated diene |
| CN101979417B (en) * | 2010-10-22 | 2013-01-02 | 北京化工大学 | Novel method for preparing itaconic anhydride-styrene monomer alternating copolymer |
| CN102250273B (en) * | 2011-06-02 | 2012-10-17 | 北京化工大学 | Preparation method of styrene-maleic anhydride random copolymer |
| CN103193932B (en) * | 2012-01-09 | 2015-09-16 | 上海飞凯光电材料股份有限公司 | The synthetic method of low molecular weight phenylethylene-maleic anhydride alternate copolymer |
| CN107417840B (en) * | 2017-08-04 | 2020-04-17 | 北京化工大学 | Multi-copolymer micro-nano particles and preparation method thereof |
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| CN114426617B (en) * | 2020-10-14 | 2024-07-02 | 中国石油化工股份有限公司 | Maleic anhydride-styrene copolymer microsphere, and preparation method and application thereof |
| CN114437279B (en) * | 2020-10-16 | 2024-07-02 | 中国石油化工股份有限公司 | Maleic anhydride copolymer and preparation method and application thereof |
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