CN101781387A - Method for copolymerization of maleic anhydride/conjugated diene - Google Patents
Method for copolymerization of maleic anhydride/conjugated diene Download PDFInfo
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Abstract
The invention discloses a method for copolymerization of maleic anhydride/conjugated diene, relating to the field of high polymer self-stable precipitation polymerization. The invention comprises the following steps: under the protection of nitrogen, adding the monomer maleic anhydride and initiators into medium to dissolve fully; after that, adding the monomer conjugated diene into the system, dissolving, and reacting for 0.5-73h at 50-90 DEG C to obtain a disperse system of copolymer microspheres of the maleic anhydride and the conjugated diene; then obtaining a white solid of the copolymer of the maleic anhydride and the conjugated diene through centrifugation and vacuum drying. The invention has the advantages of simple process, simple post-treatment to the synthesized copolymer, low cost, environmental friendliness, etc.
Description
Technical field
The present invention relates to a kind of maleic anhydride (MAn) and the method that conjugated diene carries out copolyreaction, be specifically related to the copolymerization process of a kind of maleic anhydride (MAn) and divinyl and maleic anhydride (MAn) and isoprene.The self stabilization monodisperse copolymerization thing microballoon that utilizes this method to prepare to have reactive group.
Background technology
Maleic anhydride (MAn), conjugated diene copolymer are a kind of important novel high polymer materials, are widely used in properties-correcting agent, the dispersing of pigments agent of latex coating, glue paste, the fields such as compatilizer of rubber plastic.
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 emphasis of conjugated diene, maleic anhydride research is the segmented copolymer grafted maleic anhydride poly-conjugated-diolefin or conjugated diene at present.As he stroke, Xu soldier is in " research of maleic anhydride graft liquid polybutadiene " (" Anhui chemical industry ", 1998, the 3 phases, pp.32-34) in the literary composition, cause method, at 180～200 ℃ with high temperature, react 4～5h, realized the graft reaction of polyhutadiene and maleic anhydride.Ni Hongbo, Li Xudong etc. are at " research of relative molecular polyhutadiene grafted maleic anhydride " (" elastomerics ", 2004, the 5th phase, pp.11-15) in the literary composition, with dimethylbenzene is that solvent, benzoyl peroxide are initiator, polyhutadiene has been carried out the graft modification of maleic anhydride with solution grafting.
And for example Li Chao, Cheng Xu etc. are at " different initiators cause the mechanism research of SBS grafted maleic anhydride " (" polymer journal ", 2002, the 6th phase, pp.813-817) in the literary composition, studied the influence of benzoyl peroxide and Diisopropyl azodicarboxylate p-poly-phenyl ethene-polyhutadiene-polystyrene (SBS) grafted maleic anhydride with infrared and nuclear-magnetism, and corresponding grafting mechanism has been discussed.Li Gu, wheat may become etc. in " styrene isoprene styrene block copolymer (SIS) and grafting thereof
Maleic anhydride enhancing touthness of polyphenylethylene by adding/nano calcium carbonate composite material " (" China Synthetic Rubber Industry "; 2005; the 6th phase; pp.441-445) in the literary composition; is initiator with the dicumyl peroxide melt extrudes by single screw extrusion machine and prepared the styrene-isoprene-phenylethene grafted maleic anhydride.
The preparation method of maleic anhydride (MAn), conjugated diene copolymer mainly is radical polymerization at present, a spot of polycoordination.
Radical polymerization is the main method for preparing maleic anhydride (MAn), conjugation isoprene copolymer at present.As B.C.Trivedi, B.M.Culbertson (" Maleic Anhydride ", PlenumPress, New York, 1982, be that solvent is in the time of 80 ℃ with the pimelinketone pp.344), obtained the alternating copolymer of maleic anhydride/isoprene, contained high-cis 1, the 4-structure.
(" SCI ", 2001, the 6 phases are pp.1049-1052) in the literary composition, with Nd (naph) at " rare earth catalyst isoprene-maleic anhydride alternate copolymerization " for Hu Zhiguo, Zhang Yifeng etc.
3-AlEt
3Catalyst system, toluene/dioxane are mixed solvent, and polymerization 2h in the time of 5 ℃ has obtained maleic anhydride-isoprene alternating copolymer.And for example Jiang Hua, room, Yang Kefang are at " Fe (acac)
3-Al (i-Bu)
3Catalysis maleic anhydride and isoprene copolymer close research " (" polymer material science and engineering ", 2006, the 1 phases are pp.36-39) in the literary composition, with bimetal system Fe (acac)
3-Al (i-Bu)
3Be catalyzer, toluene/dioxane is a mixed solvent, and polymerization 2h has obtained maleic anhydride-isoprene copolymer in the time of 20 ℃.This method solvent toxicity is bigger, and catalyst system is complicated.
As seen in the above-mentioned copolymerization process, in the preparation that focuses on copolymer species that mostly will study, the purposes of multipolymer also generally concentrates on the chemical property of multipolymer itself and 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 the copolymer structure 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.
As seen, the oyster white colloid and the colloidal disperse phase that prepare maleic anhydride (MAn) conjugated diene copolymer 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 maleic anhydride/conjugated diene copolymer colloidal dispersion system of self stabilization is provided.Mono-dispersion microballoon that colloid is made up of maleic anhydride/conjugated diene copolymer and suitable organic medium are formed; 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 maleic anhydride/conjugated diene copolymer.
The method of a kind of maleic anhydride provided by the present invention/conjugated diolefin copolymer reaction, it is characterized in that, under the condition of nitrogen protection, after monomer maleic anhydride and initiator joined in the medium fully dissolving, add the monomer conjugated diene again and in system, dissolve, and, obtain the dispersion system of maleic anhydride and conjugated diene copolymer microballoon in 50～90 ℃ of reaction 0.5～73h, through centrifugation, vacuum-drying, obtain the white solid of maleic anhydride and conjugated diene copolymer again; Wherein, the mol ratio of described maleic anhydride MAn and conjugated diene is 5: 1～1: 5, and the mass concentration sum of monomer maleic anhydride MAn and conjugated diene is 0.6%～37% 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, aromatic hydrocarbon or organic acid alkyl ester and alkane, and wherein, the volume fraction of alkane is 25%～75% in the mixing solutions of organic acid alkyl ester and alkane.
The conjugated diene that is adopted among the present invention is as divinyl, isoprene etc.
Described maleic anhydride MAn and the conjugated diene mass concentration sum preferred 0.6%～26% in reaction system.
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 0.04%～0.5%.
The present invention is by selecting the suitable media implementation MAn and the self stabilization dispersion polymerization of conjugated diene, 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 flower type 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 maleic anhydride/conjugated diene copolymer.
The selection of reaction medium is crucial unusually for the dispersion polymerization of the self stabilization of maleic anhydride and conjugated diene among realization the present invention, its fundamental principle is: (1) medium all has good solvency action for maleic anhydride and two kinds of monomers of conjugated diene and initiator, to guarantee that before the reaction be homogeneous system; (2) medium can not dissolve for the 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, aromatic hydrocarbon or organic acid alkyl ester and alkane.
Wherein, the general structure of described organic acid alkyl ester is:
In the formula, R
1Be hydrogen atom, C
1～C
5Alkyl, phenyl or benzyl, R
2It for the C atomicity 1～5 alkyl; Consider that medium need have polarity, solubility parameter and the viscosity of appropriateness, R
1Preferred C atomicity is 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 aromatic hydrocarbon is selected from benzene,toluene,xylene, chlorobenzene or bromobenzene.
Described alkane is selected from hexanaphthene, normal hexane, normal heptane, Skellysolve A, octane or octane-iso.
Dispersion polymerization system of the present invention is fairly simple, except several components of monomer, initiator and medium, does not need traditional dispersion polymerization system must add a large amount of stablizer and co-stabilizer like that.
The technological operation of dispersion polymerization of the present invention is as follows.Monomer, initiator and medium are dosed in the reactor that nitrogen protection, agitator, prolong and thermometer are housed by preset proportion is disposable.Monomer and initiator are dissolved in the medium fully, form the homogeneous phase solution of clear.Logical nitrogen uses water-bath (or oil bath) heating to react with the oxygen in the system of removing then.Obtain the copolymer dispersion system of white emulsion shape, obtain the solid product of multipolymer again by centrifugation.
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 0.5～73h.
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 maleic anhydride that the inventive method is prepared/conjugated diene copolymer microballoon is 321～1251nm, and its particle diameter can be controlled by processing parameters such as reaction times, monomer concentration, reaction mediums; Dispersion coefficient is 1.017～1.001, for monodispersity or near monodispersity.
Self stabilization dispersion polymerization of the present invention, the stable of system is due to the solvation special between resulting polymers and reaction medium, this special solvation between particle surface polymer molecular chain and reaction medium does not just keep the dispersive state thereby cohesion just can not take place the polymer particle that is precipitated out in the reaction.
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) maleic anhydride/conjugated diene copolymer of the inventive method preparation is a cross-linking copolymer, is insoluble to acetone, tetrahydrofuran (THF), N, dinethylformamide;
4) technology of the present invention is simple, and speed of reaction is fast, the product separate easily, and 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 7 preparations.
The electron scanning micrograph (magnification 10000) of the polymer microballoon of Fig. 3, embodiment 8 preparations.
The electron scanning micrograph (magnification 10000) of the polymer microballoon of Fig. 4, embodiment 10 preparations.
The electron scanning micrograph (magnification 10000) of the polymer microballoon of Fig. 5, embodiment 11 preparations.
The electron scanning micrograph (magnification 10000) of the polymer microballoon of Fig. 6, embodiment 12 preparations.
The electron scanning micrograph (magnification 10000) of the polymer microballoon of Fig. 7, embodiment 14 preparations.
The electron scanning micrograph (magnification 10000) of the polymer microballoon of Fig. 8, embodiment 22 preparations.
The electron scanning micrograph (magnification 10000) of the polymer microballoon of Fig. 9, embodiment 24 preparations.
The electron scanning micrograph (magnification 10000) of the polymer microballoon of Figure 10, embodiment 29 preparations.
The electron scanning micrograph (magnification 10000) of the polymer microballoon of Figure 11, embodiment 31 preparations.
Figure 12 is the electron scanning micrograph (magnification 10000) of the polymer microballoon of embodiment 32 preparations.
Below in conjunction with the drawings and the specific embodiments the present invention is further described.
Embodiment
Below the present invention will be described in more detail by specific embodiment.Embodiment only is to a kind of explanation of the present invention, and is not construed as limiting the invention.Embodiment is the practical application example, is easy to grasp and checking for those skilled in the art.If make certain change on basis of the present invention, its essence does not exceed scope of the present invention so.
Embodiment 1
Under the condition of nitrogen protection, monomer maleic anhydride and initiator joined in the medium fully dissolving after, add the monomer conjugated diene again and in system, dissolve, MAn and divinyl mole proportioning 1: 1, MAn 4.903g wherein, divinyl 2.84g; Initiator is Diisopropyl azodicarboxylate AIBN, 0.03g; Medium is an Isoamyl Acetate FCC, 102mL.Adopt heating in water bath, reaction is 6 hours under 60 ℃ temperature, obtains the dispersion system of maleic anhydride and conjugated diene copolymer microballoon, again through centrifugation, vacuum-drying, obtains the white microsphere solid of maleic anhydride and conjugated diene copolymer.Median size (Dn), dispersion coefficient (U) see Table 1.
Embodiment 2
Implementation step is as embodiment 1.MAn and divinyl mole proportioning 1: 2, MAn 4.903g wherein, divinyl 5.55g; Initiator is AIBN, 0.03g; Medium is an Isoamyl Acetate FCC, 98mL.Adopt heating in water bath, reaction is 6 hours under 60 ℃ temperature, and the median size (Dn), the dispersion coefficient (U) that obtain copolymer microsphere see Table 1.
Embodiment 3
Implementation step is as embodiment 1.MAn and divinyl mole proportioning 1: 5, MAn 4.903g wherein, divinyl 14.73g; Initiator is AIBN, 0.04g; Medium is an Isoamyl Acetate FCC, 86mL.Adopt heating in water bath, reaction is 6 hours under 60 ℃ temperature, and the median size (Dn), the dispersion coefficient (U) that obtain copolymer microsphere see Table 1.
Embodiment 4
Implementation step is as embodiment 1.MAn and divinyl mole proportioning 1: 1, MAn 4.903g wherein, divinyl 2.7g; Initiator is AIBN, 0.03g; Medium is an Isoamyl Acetate FCC, 80mL.Adopt heating in water bath, reaction is 6 hours under 70 ℃ temperature, and the median size (Dn), the dispersion coefficient (U) that obtain copolymer microsphere see Table 1, and the electron scanning micrograph of polymer microballoon is seen Fig. 1.
Embodiment 5
Implementation step is as embodiment 1.MAn and divinyl mole proportioning 2: 1, MAn 9.806g wherein, divinyl 2.7g; Initiator is AIBN, 0.03g; Medium is an Isoamyl Acetate FCC, 80mL.Adopt heating in water bath, reaction is 6 hours under 70 ℃ temperature, and the median size (Dn), the dispersion coefficient (U) that obtain copolymer microsphere see Table 1.
Embodiment 6
Implementation step is as embodiment 1.MAn and divinyl mole proportioning 1: 2, MAn 4.903g wherein, divinyl 5.4g; Initiator is AIBN, 0.03g; Medium is an Isoamyl Acetate FCC, 100mL.Adopt heating in water bath, reaction is 6 hours under 60 ℃ temperature, and the median size (Dn), the dispersion coefficient (U) that obtain copolymer microsphere see Table 1.
Embodiment 7
Implementation step is as embodiment 1.MAn and divinyl mole proportioning 2: 3, MAn 4.903g wherein, divinyl 3.95g; Initiator is AIBN, 0.03g; Medium is a butylacetate, 100mL.Adopt heating in water bath, reaction is 7 hours under 60 ℃ temperature, and the median size (Dn), the dispersion coefficient (U) that obtain copolymer microsphere see Table 1, and the electron scanning micrograph of polymer microballoon is seen Fig. 2.
Implementation step is as embodiment 1.MAn and divinyl mole proportioning 1: 1, MAn 1.226g wherein, divinyl 0.675g; Initiator is AIBN, 0.03g; Medium is a benzene, 100mL.Adopt heating in water bath, reaction is 6 hours under 70 ℃ temperature, and the median size (Dn), the dispersion coefficient (U) that obtain copolymer microsphere see Table 1, and the electron scanning micrograph of polymer microballoon is seen Fig. 3.
Embodiment 9
Implementation step is as embodiment 1.MAn and divinyl mole proportioning 2: 5, MAn 4.903g wherein, divinyl 6.47g; Initiator is benzoyl peroxide BPO, 0.1g; Medium is Isoamyl Acetate FCC 60mL, normal hexane 140mL.Adopt heating in water bath, reaction is 73 hours under 50 ℃ temperature, and the median size (Dn), the dispersion coefficient (U) that obtain copolymer microsphere see Table 1.
Embodiment 10
Implementation step is as embodiment 1.MAn and divinyl mole proportioning 1: 2, MAn 4.903g wherein, divinyl 5.4g; Initiator is AIBN, 0.03g; Medium is Isoamyl Acetate FCC 75mL, hexanaphthene 25mL.Adopt heating in water bath, reaction is 72 hours under 50 ℃ temperature, and the median size (Dn), the dispersion coefficient (U) that obtain copolymer microsphere see Table 1, and the electron scanning micrograph of polymer microballoon is seen Fig. 4.
Embodiment 11
Implementation step is as embodiment 1.MAn and divinyl mole proportioning 1: 2, MAn 4.903g wherein, divinyl 5.4g; Initiator is AIBN, 0.03g; Medium is Isoamyl Acetate FCC 67mL, hexanaphthene 33mL.Adopt heating in water bath, reaction is 72 hours under 50 ℃ temperature, and the median size (Dn), the dispersion coefficient (U) that obtain copolymer microsphere see Table 1, and the electron scanning micrograph of polymer microballoon is seen Fig. 5.
Embodiment 12
Implementation step is as embodiment 1.MAn and divinyl mole proportioning 1: 2, MAn 4.903g wherein, divinyl 5.4g; Initiator is AIBN, 0.03g; Medium is Isoamyl Acetate FCC 50mL, hexanaphthene 50mL.Adopt heating in water bath, reaction is 72 hours under 50 ℃ temperature, and the median size (Dn), the dispersion coefficient (U) that obtain copolymer microsphere see Table 1, and the electron scanning micrograph of polymer microballoon is seen Fig. 6.
Embodiment 13
Implementation step is as embodiment 1.MAn and divinyl mole proportioning 1: 2, MAn 4.903g wherein, divinyl 5.4g; Initiator is AIBN, 0.03g; Medium is Isoamyl Acetate FCC 33mL, hexanaphthene 67mL.Adopt heating in water bath, reaction is 72 hours under 50 ℃ temperature, and the median size (Dn), the dispersion coefficient (U) that obtain copolymer microsphere see Table 1.
Embodiment 14
Implementation step is as embodiment 1.MAn and divinyl mole proportioning 1: 2, MAn 4.903g wherein, divinyl 5.4g; Initiator is AIBN, 0.03g; Medium is Isoamyl Acetate FCC 25mL, hexanaphthene 75mL.Adopt heating in water bath, reaction is 72 hours under 50 ℃ temperature, and the median size (Dn), the dispersion coefficient (U) that obtain copolymer microsphere see Table 1, and the electron scanning micrograph of polymer microballoon is seen Fig. 7.
Embodiment 15
Implementation step is as embodiment 1.MAn and divinyl mole proportioning 1: 1, MAn 9.806g wherein, divinyl 5.4g; Initiator is AIBN, 0.07g; Medium is an Isoamyl Acetate FCC, 160mL.Adopt heating in water bath, reaction is 1 hour under 70 ℃ temperature, and the median size (Dn), the dispersion coefficient (U) that obtain copolymer microsphere see Table 2.
Embodiment 16
Implementation step is as embodiment 1.MAn and divinyl mole proportioning 1: 1, MAn 9.806g wherein, divinyl 5.4g; Initiator is AIBN, 0.07g; Medium is an Isoamyl Acetate FCC, 160mL.Adopt heating in water bath, reaction is 2 hours under 70 ℃ temperature, and the median size (Dn), the dispersion coefficient (U) that obtain copolymer microsphere see Table 2.
Embodiment 17
Implementation step is as embodiment 1.MAn and divinyl mole proportioning 1: 1, MAn 9.806g wherein, divinyl 5.4g; Initiator is AIBN, 0.07g; Medium is an Isoamyl Acetate FCC, 160mL.Adopt heating in water bath, reaction is 3 hours under 70 ℃ temperature, and the median size (Dn), the dispersion coefficient (U) that obtain copolymer microsphere see Table 2.
Embodiment 18
Implementation step is as embodiment 1.MAn and divinyl mole proportioning 1: 1, MAn 9.806g wherein, divinyl 5.4g; Initiator is AIBN, 0.07g; Medium is an Isoamyl Acetate FCC, 160mL.Adopt heating in water bath, reaction is 5 hours under 70 ℃ temperature, and the median size (Dn), the dispersion coefficient (U) that obtain copolymer microsphere see Table 2.
Embodiment 19
Implementation step is as embodiment 1.MAn and divinyl mole proportioning 1: 1, MAn 9.806g wherein, divinyl 5.4g; Initiator is AIBN, 0.07g; Medium is an Isoamyl Acetate FCC, 160mL.Adopt heating in water bath, reaction is 7 hours under 70 ℃ temperature, and the median size (Dn), the dispersion coefficient (U) that obtain copolymer microsphere see Table 2.
Embodiment 20
Implementation step is as embodiment 1.MAn and divinyl mole proportioning 1: 1, MAn 9.806g wherein, divinyl 5.4g; Initiator is AIBN, 0.07g; Medium is an Isoamyl Acetate FCC, 160mL.Adopt heating in water bath, reaction is 15 hours under 70 ℃ temperature, and the median size (Dn), the dispersion coefficient (U) that obtain copolymer microsphere see Table 2.
Embodiment 21
Implementation step is as embodiment 1.MAn and divinyl mole proportioning 1: 1, MAn 9.806g wherein, divinyl 5.4g; Initiator is AIBN, 0.07g; Medium is an Isoamyl Acetate FCC, 160mL.Adopt heating in water bath, reaction is 23 hours under 70 ℃ temperature, and the median size (Dn), the dispersion coefficient (U) that obtain copolymer microsphere see Table 2.
Embodiment 22
Implementation step is as embodiment 1.MAn and isoprene mole proportioning 1: 1, MAn 0.3064g wherein, isoprene 0.204g; Initiator is AIBN, 0.03g; Medium is an Isoamyl Acetate FCC, 90mL.Adopt heating in water bath, reaction is 8 hours under 70 ℃ temperature, and the median size (Dn), the dispersion coefficient (U) that obtain copolymer microsphere see Table 3, and the electron scanning micrograph of polymer microballoon is seen Fig. 8.
Embodiment 23
Implementation step is as embodiment 1.MAn and isoprene mole proportioning 1: 1, MAn 4.903g wherein, isoprene 3.4g; Initiator is AIBN, 0.03g; Medium is an Isoamyl Acetate FCC, 100mL.Adopt heating in water bath, reaction is 6 hours under 70 ℃ temperature, and the median size (Dn), the dispersion coefficient (U) that obtain copolymer microsphere see Table 3.
Embodiment 24
Implementation step is as embodiment 1.MAn and isoprene mole proportioning 1: 1, MAn 9.806g wherein, isoprene 6.8g; Initiator is AIBN, 0.10g; Medium is an Isoamyl Acetate FCC, 100mL.Adopt heating in water bath, reaction is 4 hours under 70 ℃ temperature, and the median size (Dn), the dispersion coefficient (U) that obtain copolymer microsphere see Table 3, and the electron scanning micrograph of polymer microballoon is seen Fig. 9.
Embodiment 25
Implementation step is as embodiment 1.MAn and isoprene mole proportioning 1: 1, MAn 4.903g wherein, isoprene 3.4g; Initiator is AIBN, 0.16g; Medium is an Isoamyl Acetate FCC, 90mL.Adopt heating in water bath, reaction is 6 hours under 70 ℃ temperature, and the median size (Dn), the dispersion coefficient (U) that obtain copolymer microsphere see Table 3.
Embodiment 26
Implementation step is as embodiment 1.MAn and isoprene mole proportioning 1: 2, MAn 4.903g wherein, isoprene 6.8g; Initiator is AIBN, 0.03g; Medium is an Isoamyl Acetate FCC, 90mL.Adopt heating in water bath, reaction is 6 hours under 70 ℃ temperature, and the median size (Dn), the dispersion coefficient (U) that obtain copolymer microsphere see Table 3.
Embodiment 27
Implementation step is as embodiment 1.MAn and isoprene mole proportioning 1: 1, MAn 4.903g wherein, isoprene 3.4g; Initiator is BPO, 0.03g; Medium is an Isoamyl Acetate FCC, 90mL.Adopt heating in water bath, reaction is 6 hours under 70 ℃ temperature, and the median size (Dn), the dispersion coefficient (U) that obtain copolymer microsphere see Table 3.
Embodiment 28
Implementation step is as embodiment 1.MAn and isoprene mole proportioning 1: 1, MAn 4.903g wherein, isoprene 3.4g; Initiator is AIBN, 0.03g; Medium is an Isoamyl Acetate FCC, 100mL.Adopt heating in water bath, reaction is 6 hours under 90 ℃ temperature, and the median size (Dn), the dispersion coefficient (U) that obtain copolymer microsphere see Table 3.
Embodiment 29
Implementation step is as embodiment 1.MAn and isoprene mole proportioning 1: 1, MAn 4.903g wherein, isoprene 3.4g; Initiator is AIBN, 0.03g; Medium is a dimethylbenzene, 90mL.Adopt heating in water bath, reaction is 6 hours under 70 ℃ temperature, and the median size (Dn), the dispersion coefficient (U) that obtain copolymer microsphere see Table 3, and the electron scanning micrograph of polymer microballoon is seen Figure 10.
Embodiment 30
Implementation step is as embodiment 1.MAn and isoprene mole proportioning 1: 1, MAn 4.903g wherein, isoprene 3.4g; Initiator is AIBN, 0.03g; Medium is an oil of cognac, 90mL.Adopt heating in water bath, reaction is 6 hours under 70 ℃ temperature, and the median size (Dn), the dispersion coefficient (U) that obtain copolymer microsphere see Table 3.
Embodiment 31
Implementation step is as embodiment 1.MAn and isoprene mole proportioning 1: 1, MAn 4.903g wherein, isoprene 3.4g; Initiator is AIBN, 0.03g; Medium is a Valeric acid ethylester, 90mL.Adopt heating in water bath, reaction is 6 hours under 70 ℃ temperature, and the median size (Dn), the dispersion coefficient (U) that obtain copolymer microsphere see Table 3, and the electron scanning micrograph of polymer microballoon is seen Figure 11.
Embodiment 32
Implementation step is as embodiment 1.MAn and isoprene mole proportioning 1: 1, MAn 4.903g wherein, isoprene 3.4g; Initiator is AIBN, 0.03g; Medium is an ethyl butyrate, 90mL.Adopt heating in water bath, reaction is 6 hours under 70 ℃ temperature, and the median size (Dn), the dispersion coefficient (U) that obtain copolymer microsphere see Table 3, and the electron scanning micrograph of polymer microballoon is seen Figure 12.
Embodiment 33
Implementation step is as embodiment 1.MAn and isoprene mole proportioning 1: 1, MAn 4.903g wherein, isoprene 3.4g; Initiator is AIBN, 0.03g; Medium is an ethyl benzoate, 90mL.Adopt heating in water bath, reaction is 6 hours under 70 ℃ temperature, and the median size (Dn), the dispersion coefficient (U) that obtain copolymer microsphere see Table 3.
Embodiment 34
Implementation step is as embodiment 1.MAn and isoprene mole proportioning 1: 1, MAn 4.903g wherein, isoprene 3.4g; Initiator is AIBN, 0.03g; Medium is a butylacetate, 90mL.Adopt heating in water bath, reaction is 6 hours under 70 ℃ temperature, and the median size (Dn), the dispersion coefficient (U) that obtain copolymer microsphere see Table 3.
Embodiment system outward appearance polymer particle particle diameter/nm polymer particle dispersion coefficient U
Embodiment 1 oyster white dispersion system 518 1.003
Embodiment 2 oyster white dispersion systems 534 1.004
Embodiment 3 oyster white dispersion systems 516 1.004
Embodiment 4 oyster white dispersion systems 521 1.004
Embodiment 5 oyster white dispersion systems 371 1.017
Embodiment 6 oyster white dispersion systems 588 1.004
Embodiment 7 oyster white dispersion systems 747 1.003
Embodiment 9 oyster white dispersion systems 946 1.002
Embodiment 10 oyster white dispersion systems 884 1.010
Embodiment 11 oyster white dispersion systems 950 1.006
Embodiment 12 oyster white dispersion systems 998 1.006
Embodiment 13 oyster white dispersion systems 1,113 1.004
Embodiment 14 oyster white dispersion systems 1,251 1.004
Gained copolymer dispersion system under table 1 different condition
Reaction times/min system outward appearance polymer particle particle diameter/nm polymer particle dispersion coefficient U
Embodiment 15 oyster white dispersion systems 321 1.014
Embodiment 16 oyster white dispersion systems 432 1.005
Embodiment 17 oyster white dispersion systems 461 1.002
Embodiment 18 oyster white dispersion systems 488 1.003
Embodiment 19 oyster white dispersion systems 517 1.004
Embodiment 20 oyster white dispersion systems 591 1.002
Embodiment 21 oyster white dispersion systems 591 1.002
Table 2 differential responses time gained copolymer dispersion system
Implementation example system outward appearance polymer particle particle diameter/nm polymer particle dispersion coefficient U
Embodiment 22 oyster white dispersion systems 571 1.005
Embodiment 23 oyster white dispersion systems 504 1.002
Embodiment 24 oyster white dispersion systems 515 1.002
Embodiment 25 oyster white dispersion systems 637 1.002
Embodiment 26 oyster white dispersion systems 493 1.003
Embodiment 27 oyster white dispersion systems 478 1.008
Embodiment 28 oyster white dispersion systems 616 1.001
Embodiment 29 oyster white dispersion systems 592 1.001
Embodiment 30 oyster white dispersion systems 531 1.004
Embodiment 31 oyster white dispersion systems 572 1.002
Embodiment 32 oyster white dispersion systems 613 1.002
Embodiment 33 oyster white dispersion systems 609 1.003
Embodiment 34 oyster white dispersion systems 764 1.002
Gained copolymer dispersion system under table 3 different condition
Claims (5)
1. the method for a maleic anhydride/conjugated diolefin copolymer reaction, it is characterized in that, under the condition of nitrogen protection, after monomer maleic anhydride and initiator joined in the medium fully dissolving, add the monomer conjugated diene again and in system, dissolve, and, obtain the dispersion system of maleic anhydride and conjugated diene copolymer microballoon in 50～90 ℃ of reaction 0.5～73h, through centrifugation, vacuum-drying, obtain the white solid of maleic anhydride and conjugated diene copolymer again;
Wherein, the mol ratio of described maleic anhydride MAn and conjugated diene is 5: 1～1: 5, the mass concentration sum of monomer maleic anhydride MAn and conjugated diene is 0.6%～37% 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, aromatic hydrocarbon or organic acid alkyl ester and alkane, and wherein, the volume fraction of alkane is 25%～75% in the mixing solutions of organic acid alkyl ester and alkane, and the general structure of described organic acid alkyl ester is:
In the formula, R
1Be hydrogen atom, C
1～C
5Alkyl, phenyl or benzyl, R
2It for the C atomicity 1～5 alkyl.
2. according to the method for claim 1 copolyreaction, it is characterized in that the mass concentration of described initiator in reaction system preferred 0.04%～0.5%.
3. according to the method for claim 1 copolyreaction, it is characterized in that described R
1Preferred C atomicity is 1～5 alkyl.
4. according to the method for claim 1 copolyreaction, it is characterized in that described aromatic hydrocarbon is selected from benzene,toluene,xylene, chlorobenzene or bromobenzene.
5. according to the method for claim 1 copolyreaction, it is characterized in that described alkane is selected from hexanaphthene, normal hexane, normal heptane, Skellysolve A, octane or octane-iso.
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| CN111484579A (en) * | 2020-04-16 | 2020-08-04 | 陕西科技大学 | High-temperature soluble bridge plug and preparation method thereof |
| CN111849063A (en) * | 2019-04-25 | 2020-10-30 | 中国石油化工股份有限公司 | Flame-retardant photodiffusion polypropylene composition and flame-retardant photodiffusion polypropylene |
| CN115353586A (en) * | 2022-09-26 | 2022-11-18 | 清华大学 | Preparation method of linear copolymer |
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| CN106046735B (en) | 2015-04-10 | 2018-12-28 | 中国石油化工股份有限公司 | It is a kind of with haze, the poly carbonate resin composition of high transparency and preparation method thereof |
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| JPH0465408A (en) * | 1990-07-06 | 1992-03-02 | Tosoh Corp | Production of aqueous solution of maleic anhydride copolymer or copolymer salt |
| CN1618826A (en) * | 2003-11-19 | 2005-05-25 | 北京化工大学 | Method of copolymerization of maleic anhydride and vinyl acetate |
| CN101235117A (en) * | 2008-03-14 | 2008-08-06 | 北京化工大学 | Copolymerization reaction method for styrene/maleic anhydride |
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| FR2821674B1 (en) * | 2001-03-01 | 2003-05-30 | Total Raffinage Distribution | METHOD FOR DETERMINING DIETHANOLAMINE IN AQUEOUS SOLUTION |
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| GB1219256A (en) * | 1968-04-26 | 1971-01-13 | Borg Warner | Method of copolymerizing unhindered conjugated dienes with maleic anhydride |
| JPH0465408A (en) * | 1990-07-06 | 1992-03-02 | Tosoh Corp | Production of aqueous solution of maleic anhydride copolymer or copolymer salt |
| CN1618826A (en) * | 2003-11-19 | 2005-05-25 | 北京化工大学 | Method of copolymerization of maleic anhydride and vinyl acetate |
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| CN111849063A (en) * | 2019-04-25 | 2020-10-30 | 中国石油化工股份有限公司 | Flame-retardant photodiffusion polypropylene composition and flame-retardant photodiffusion polypropylene |
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| CN111484579A (en) * | 2020-04-16 | 2020-08-04 | 陕西科技大学 | High-temperature soluble bridge plug and preparation method thereof |
| CN115353586A (en) * | 2022-09-26 | 2022-11-18 | 清华大学 | Preparation method of linear copolymer |
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