CN101338008A - Process for preparing cross-linking maleic anhydride-styrene copolymer - Google Patents
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Abstract
A cross linking maleic anhydride-vinyl acetate copolymer preparation method belongs to the field of copolymers. At present, the research on maleic anhydride-vinyl acetate copolymers mostly focuses on the polymerization research of linear polymers. The invention introduces a monomer, cross linking agents and initiators into medium to dissolve under the condition of nitrogen protection, and reacts for 2 to 24 hours under the temperature of 60 DEG C to 90 DEG C; the monomer is maleic anhydride Man and styrene St, the mol ratio is 1:1, and the mass concentration in the polymerization system is 5 percent to 45 percent; the initiators are organic peroxides or azo compounds, and are 0.05 percent to 1 percent of the total mass of the monomers; the cross linking agents are polyfunctionality alkene organic compounds, and are 0.08 percent to 8.8 percent of the total mass of the reactions system, and the rest is the alkyl ester of medium organic acid. The invention does not use surface active agents or stabilizers, can realize the adjustment and control of crosslinking polymer particle size, appearance and chemical physical properties through the adjustment of the addition amount of the cross linking agents.
Description
Technical field
The present invention relates to the polymerization process of a kind of preparation cross-linked maleic anhydride (MAn)-vinylbenzene (St) polymer particle, form the polymerization process of self-stabilized crosslinked dispersion of polymer particle system after particularly relating to a kind of polyreaction and finishing.Utilize this method not only can prepare the cross-linking polymer particle of different-shape, can also keep the activity acid anhydride base of polymer beads sub-surface.
Background technology
The research of maleic anhydride (MAn)-vinylbenzene (St) multipolymer focuses mostly on the polymerization studies of linear polymer.Vinylbenzene (St)-maleic anhydride (MAn) multipolymer is a kind of excellent property and cheap novel high polymer material, is 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.
The preparation method of vinylbenzene (St)-maleic anhydride (MAn) linear copolymer mainly is solution polymerization at present, a spot of mass polymerization, precipitation polymerization, body-suspension polymerization and the letex polymerization of solution phase inversion.In these copolymerization process of 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.As 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.Li Chunsheng and for example, Zhang Shuxiang etc. are in " maleic anhydride and cinnamic polymerization in the supercritical CO 2 " (" polymer material science and engineering ", 2006, vol.22, No.5, pp95-97), in reaction pressure during greater than 16MPa, do not have polystyrene (PS) to generate, (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.Zhou Wen, multitude Paine are in " the synthetic and characterization research of the body-suspension method of SMA resin " (" modern plastics processed and applied " for another example, 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-styrene copolymers.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.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.Tian Yong, Wang Xiufang are at " the synthetic and performance study of R-SMA " (" Chinese leather " for another example, 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 Xiu is clear for another example, 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.
Randy etc. are at " Synthesis of Diviylbenzene-maleic AnhydrideMicrosphere Using Precipitation Polymerization " (J.Polym.Sci., Part A:Polym.Chem.1998 (36), 2223-2227) prepared the cross-linked polymer microsphere of maleic anhydride and Vinylstyrene in the literary composition by precipitation polymerization, its preparation method is that reaction medium can prepare the copolymer microsphere (ratio of maleic anhydride and vinyl double bond is 8.2: 8.6) than the polydivinylbenezene-maleic anhydride of high-crosslinking-degree based on the crosslinked precipitation polymerization of Vinylstyrene with the hexane of suitable composition and the mixed solvent of methylethylketone.Monomer feeding ratio is certain in the literary composition, and does not have the adding of styrene monomer.This method need add the monomer that higher Vinylstyrene is held concurrently reaction as linking agent, and the crosslinking degree of the higher and microballoon of the crosslinking degree of thus obtained microsphere is can not successive artificially adjustable.
Do not mention the method for preparing maleic anhydride-styrene linear copolymer particle dispersion system under any tensio-active agent or the stablizer condition not adding among the preparation method of the maleic anhydride-styrene copolymers that document is mentioned, more do not mention the preparation method of cross-linking maleic anhydride-styrene copolymer particle.
The copolymer particle for preparing cross-linking maleic anhydride-styrene by the self stabilization precipitation polymerization process not only can avoid the tensio-active agent or the use of stablizer reduce economically cost and to the impact of environment, also can realize the stepless control of polymer particle crosslinking degree (realizing) in a big way, thereby realization is to the regulation and control of cross-linking polymer particle size, pattern and chemical physical property by the add-on of regulating linking agent.
Summary of the invention
The objective of the invention is to propose the novel method of a kind of preparation cross-linked maleic anhydride (MAn)-vinylbenzene (St) copolymer particle, need not to add any stablizer.In the dispersion system of polymer particle, the polymer particle surface cleaning, the polymer particle pattern is controlled, the controllable size of polymer particle.
The technical characterictic that the self stabilization precipitation polymerization prepares cross-linked maleic anhydride (MAn)-vinylbenzene (St) polymer microballoon is: need not to add under the condition of any stablizer and co-stabilizer in polymerization system, copolyreaction 2～24h obtains the dispersion system of polymer microballoon; Reaction monomers maleic anhydride and vinylbenzene, two monomeric mol ratios are 1: 1; The mass concentration of two monomers in polymerization reaction system is 5%～45%; Initiator is organo-peroxide or azo-compound, and the amount of initiator is 0.05%～1% of the reaction total monomer quality; Used linking agent is the olefines organic compound of polyfunctionality, as aliphatic divinyl ester, as Diethylene Glycol base dimethacrylate (EGDMA), Diethylene Glycol base diethyl acrylate, trimethylolpropane trimethacrylate (TMPTMA) etc., aromatic Vinylstyrene etc.; The mass concentration of linking agent is 0.08%～8.8% of a polymerization reaction system total mass; All the other are medium, and medium is the organic acid alkyl ester, and chemical structural formula is:
Wherein, R
1Be hydrogen atom, C
1～C
5Alkyl, phenyl or benzyl, R
2Be C
1～C
5Alkyl.
R preferably in the chemical structural formula of organic acid alkyl ester
1Be C
1～C
5Alkyl, R
2Be C
1～C
5Alkyl.The organic acid alkyl ester that the present invention adopts, for example: 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.
The initiator that can be used for polymerization system of 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.Initiator for add as 0.05%～1% of monomer total mass, reasonable is between 0.06%～0.6%.
The consumption difference of linking agent can obtain the cross-linking polymer particle of different-shape, for example when the mass concentration of Vinylstyrene 0.08%～0.32% the time, in the organic acid alkyl ester solvents, can realize the preparation of microsphere particles; Be equally in the solvent of organic acid alkyl ester, when the mass concentration of linking agent 0.52%～0.77% the time, can obtain the polymer microballoon particle of bunchiness.
The present invention is in the dispersion system of polymer microballoon, and the median size of polymer microballoon is at 249～1000nm; Dispersion coefficient is 1.004～1.07.
The present invention realizes the self stabilization precipitation cross-linking polymerization of MAn and St by selecting suitable medium and dosage of crosslinking agent, and its characteristics are: need not to add any stablizer and co-stabilizer in (1) this dispersion polymerization system, have the dispersion effect of self stabilization; (2) in the polymerization system be monodisperse cross-linked polymer microspheres or bunchiness particle, particle surface cleaning, controllable size, the controlled and narrow size distribution of pattern.
Dispersion polymerization system of the present invention is fairly simple, except several components of monomer, initiator, linking agent 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 polyreaction of the present invention is as follows.Monomer, linking agent initiator and medium are dosed in the reactor that nitrogen protection, agitator, prolong and thermometer are housed by preset proportion is disposable.Monomer, linking agent 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.The whole process of reaction has nitrogen protection.The crosslinked PMS copolymer dispersion that obtains the white emulsion shape is can obtain the solid product of crosslinked PMS multipolymer again by centrifugation, calculating polymerization yield (C
p).
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 ℃, and so on.According to the difference that reaction system is formed, the speed of polyreaction is different, approximately reacts 2～24h.
From polymerization system, take a sample, observe the form of polymer microballoon 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.
By the prepared crosslinked PMS polymer microballoon of technology of the present invention, processing parameter such as the add-on that its particle diameter can be by reaction times, monomer concentration, linking agent and reaction medium is controlled, and scope is between 249～1000nm; And very even with the granularity of the polymer microballoon of this method preparation, its dispersion coefficient is between 1.004～1.07, for monodispersity or near monodispersity.In addition, the dispersion polymerization process system of self stabilization 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
Fig. 1 is the surface sweeping electron micrograph (magnification 10000) of the crosslinked PMS polymer microballoon of embodiment 1.
Fig. 2 is the surface sweeping electron micrograph (magnification 10000) of the crosslinked PMS polymer microballoon of embodiment 4.
Fig. 3 is the surface sweeping electron micrograph (magnification 15000) of the crosslinked PMS polymer microballoon of embodiment 5
Fig. 4 is the surface sweeping electron micrograph (magnification 15000) of the crosslinked PMS polymer microballoon of embodiment 6
Fig. 5 is the surface sweeping electron micrograph (magnification 10000) of the crosslinked PMS polymer microballoon of embodiment 7
Fig. 6 is the surface sweeping electron micrograph (magnification 10000) of the crosslinked PMS polymer microballoon of embodiment 8
Fig. 7 is the surface sweeping electron micrograph (magnification 10000) of the crosslinked PMS polymer microballoon of embodiment 9
Fig. 8 is the surface sweeping electron micrograph (magnification 10000) of the crosslinked PMS polymer microballoon of embodiment 10
Embodiment
Embodiment 1
MAn 2.452g, St 2.6g; Initiator is Diisopropyl azodicarboxylate (AINN), 0.02529g; Linking agent DVB, 0.04g; Medium is an Isoamyl Acetate FCC, 45mL.Adopt heating in water bath, reaction is 2 hours under 70 ℃ temperature, obtains median size (Dn), dispersion coefficient (U) and the polymerization yield (C of crosslinked PMS copolymer microsphere
p), the results are shown in Table 1, the electron scanning micrograph of cross-linked polymer is as shown in Figure 1.
Embodiment 2
MAn 2.452g, St 2.6g; Initiator is a 2,2'-Azobis(2,4-dimethylvaleronitrile), 0.0329g; Linking agent DVB, 0.06g; Medium is a butylacetate, 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 crosslinked PMS copolymer microsphere
p), the results are shown in Table 1
Embodiment 3
MAn 2.452g, St 2.6g; Initiator is a dibenzoyl peroxide, 0.05052g; Linking agent DVB, 0.0975g; Medium is an ethyl butyrate, 45mL.Adopt heating in water bath, reaction is 24 hours under 70 ℃ temperature, obtains median size (Dn), dispersion coefficient (U) and the polymerization yield (C of crosslinked PMS copolymer microsphere
p), the results are shown in Table 1
Embodiment 4
MAn 2.452g, St 2.6g; Initiator is AINN, 0.0329g; Linking agent DVB, 0.1625g; 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 crosslinked PMS copolymer microsphere
p), the results are shown in Table 1, the electron scanning micrograph of cross-linked polymer is as shown in Figure 2.
Embodiment 5
MAn 2.452g, St 2.6g; Initiator is a di-tert-butyl peroxide, 0.0303g; Linking agent DVB, 0.26g; Medium is an Isoamyl Acetate FCC, 45mL.Adopt heating in water bath, reaction is 18 hours under 70 ℃ temperature, obtains median size (Dn), dispersion coefficient (U) and the polymerization yield (C of crosslinked PMS copolymer microsphere
p), the results are shown in Table 1, the electron scanning micrograph of cross-linked polymer is as shown in Figure 3.
Embodiment 6
MAn 2.452g, St 2.6g; Initiator is a di-cyclohexylperoxy dicarbonate, 0.0329g; Linking agent DVB, 0.39g; Medium is a propyl benzoate, 45mL.Adopt heating in water bath, reaction is 12 hours under 70 ℃ temperature, obtains median size (Dn), dispersion coefficient (U) and the polymerization yield (C of crosslinked PMS copolymer microsphere
p), the results are shown in Table 1, the electron scanning micrograph of cross-linked polymer is as shown in Figure 4.
Embodiment 7
MAn 2.452g, St 2.6g; Initiator is AINN, 0.0329g; Linking agent EGDMA, 0.099g; Medium is an isoamyl isovalerate, 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 crosslinked PMS copolymer microsphere
p), the results are shown in Table 1, the electron scanning micrograph of cross-linked polymer is as shown in Figure 5.
MAn 2.452g, St 2.6g; Initiator is the peroxy dicarbonate diisopropyl ester, 0.0329g; Linking agent EGDMA, 3.168g; Medium is an isoamyl 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 crosslinked PMS copolymer microsphere
p), the results are shown in Table 1, the electron scanning micrograph of cross-linked polymer is as shown in Figure 6.
Embodiment 9
MAn 2.452g, St 2.6g; Initiator is a dicumyl peroxide, 0.0329g; Linking agent TMPTMA, 0.423g; Medium is a methyl phenylacetate, 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 crosslinked PMS copolymer microsphere
p), the results are shown in Table 1, the electron scanning micrograph of cross-linked polymer is as shown in Figure 7.
Embodiment 10
MAn 2.452g, St 2.6g; Initiator is the special butyl ester of peroxidation phenylformic acid, 0.0329g; Linking agent TMPTMA, 4.23g; Medium is a jasmal, 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 crosslinked PMS copolymer microsphere
p), the results are shown in Table 1, the electron scanning micrograph of cross-linked polymer is as shown in Figure 8.
Detect as can be known by infrared spectra in all embodiments, kept activity in the resulting polymers and got the acid anhydride base.And the oyster white dispersion system of resulting polymers kept stable and sedimentation does not take place in 2～90 days.
Table 1
The average dispersed polymeres of polymerization produces
Implementation example system outward appearance
Method particle diameter/nm coefficient U leads Cp/%
The self stabilization branch
Embodiment 1 oyster white dispersion system 545 1.005 83
Diffusing polymerization
The self stabilization branch
Embodiment 2 oyster white dispersion systems 615 1.015 84
Diffusing polymerization
The self stabilization branch
Embodiment 3 oyster white dispersion systems 570 1.065 86
Diffusing polymerization
The self stabilization branch
Embodiment 4 oyster white dispersion systems 447 1.025 85
Diffusing polymerization
The self stabilization branch
Embodiment 5 oyster white dispersion systems 310 1.029 83
Diffusing polymerization
The self stabilization branch
Embodiment 6 oyster white dispersion systems 249 1.044 85
Diffusing polymerization
The self stabilization branch
Embodiment 7 oyster white dispersion systems 709 1.004 83
Diffusing polymerization
The self stabilization branch
Diffusing polymerization
The self stabilization branch
Embodiment 9 oyster white dispersion systems 610 1.005 82
Diffusing polymerization
The self stabilization branch
Embodiment 10 oyster white dispersion systems 1,000 1.017 85
Diffusing polymerization
Claims (2)
1, a kind of preparation method of cross-linking maleic anhydride-styrene copolymer, it is characterized in that, under the condition of nitrogen protection, monomer, linking agent and initiator joined in the medium dissolve, and in 60～90 ℃ of reaction 2～24h, obtain the dispersion system of cross-linked styrene-maleic anhydride polymer microballoon, obtain the white solid of cross-linked styrene-copolymer-maleic anhydride again through centrifugation; Wherein, described monomer is maleic anhydride and vinylbenzene, and the mol ratio of the two is 1: 1, and the mass concentration of two monomers in polymerization reaction system is 5%～45%; Initiator is organo-peroxide or azo-compound, and the amount of initiator is 0.05%～1% of a reaction monomers total mass; Used linking agent is the olefines organic compound of polyfunctionality, and the mass concentration of linking agent is 0.08%～8.8% of a reaction system total mass; Medium is the organic acid alkyl ester, and the general structure of described organic acid alkyl ester is:
In the formula, R1 is that H, C atomicity are 1～8 alkyl, phenyl or benzyl, and R2 is 1～5 alkyl for the C atomicity.
2, method according to claim 1 is characterized in that, the olefines organic compound of described polyfunctionality is aliphatic divinyl ester or aromatic Vinylstyrene.
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