WO2017177813A1 - 一种乙烯基单体反应挤出共聚合的方法 - Google Patents

一种乙烯基单体反应挤出共聚合的方法 Download PDF

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WO2017177813A1
WO2017177813A1 PCT/CN2017/078308 CN2017078308W WO2017177813A1 WO 2017177813 A1 WO2017177813 A1 WO 2017177813A1 CN 2017078308 W CN2017078308 W CN 2017078308W WO 2017177813 A1 WO2017177813 A1 WO 2017177813A1
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screw
nano
vinyl
micro
polymerization
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French (fr)
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郑安呐
管涌
危大福
许祥
李军
刘伟兴
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华东理工大学
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    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
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    • C08L35/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
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    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
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Definitions

  • This invention relates to a process for the polymerization of copolymers, and more particularly to a process for reactive extrusion co-polymerization of vinyl monomers.
  • Polymers of vinyl monomers are commonly referred to as olefinic polymers, and their polymerization has become an extremely important part of the polymer synthesis reaction.
  • Monomer synthesis, and most of them are obtained by free radical polymerization, accounting for almost half of the polymer.
  • the removal of reaction heat, monomer diffusion and uniform distribution are difficult, making it difficult to implement such a polymer.
  • polymerization instead, polymerization methods such as solution, suspension, and emulsion are employed.
  • the solution polymerization method can avoid the difficulties of the above bulk polymerization method, the polymerization method is almost exclusively used for theoretical research except for the slow polymerization rate and the high energy consumption and environmental pollution caused by solvent removal in the post-treatment process. It has never been industrialized except when it is not possible.
  • the suspension polymerization method can also avoid the difficulty of heat dissipation and high viscosity, and the polymer can be separated from the water by simple separation, without removing the solvent as in the solution polymerization method, thereby avoiding unnecessary energy consumption. It is a more successful industrial polymerization method. However, during the separation and refining of the crude product, serious environmental pollution is also caused by the large amount of suspending agent and surfactant present on the surface of the bead polymer.
  • Emulsion polymerization is similar to suspension polymerization, but because the molecular weight can be made relatively high at higher polymerization rates, it is advantageous to improve product performance.
  • the polymer microbeads are finer, the emulsifiers and surfactants on the surface are more difficult to remove, and the environmental pollution problem is more serious. Fortunately, the emulsion polymerized polymer is beneficial for direct use as a coating, reducing some energy consumption, but The process used to prepare plastics has brought about a lot of pollution, such as the production of emulsion ABS.
  • the most popular polymerization method at present is continuous bulk thermal polymerization.
  • the polymerization method has no other impurities and is directly polymerized into a high polymer.
  • the transparency of the product is high and the environmental pollution is also reduced to a low level, so it is favored internationally.
  • this polymerization method has a problem that it is difficult to increase the molecular weight of the polymer, and the production efficiency greatly decreases as the molecular weight increases. If the weight average molecular weight is increased from 27 to 280,000 to only 400,000, the production efficiency will drop to 40% in the normal state.
  • the system is too viscous and the mass transfer process is severe, resulting in a wide molecular weight distribution. It can be seen that how to carry out the radical polymerization of the vinyl monomer has always been a defect in polymerization. Because of this, research on the polymerization of vinyl monomers by reactive extrusion has emerged.
  • the monomer was mainly polymerized in a second screw extruder, and the reactants flowed in a thin layer to obtain sufficient and effective kneading.
  • the pressure inside the barrel was maintained at 1.52 x 10 5 Pa, and the residence time of the reactant was controlled in the range of 1.5 to 18 minutes.
  • the reactants are then fed to a third twin screw extruder where the material is devolatilized and unreacted monomer is withdrawn from the two vacuum ports.
  • CN 1587292B, CN 1587288A, CN1644597, etc. disclose techniques for synthesizing plastics, rubbers, and thermoplastic elastomers by anionic polymerization using bulk polymerization.
  • CN101824151B discloses a technique for bulk anion ring-opening polymerization extrusion synthesis of a fluorosilicone polymer.
  • the number of vinyl monomers which can be subjected to anionic polymerization is too small, and the purification requirements of the monomers and all the raw materials are too high.
  • anionic ring-opening polymerization has expanded the application fields of some reactive extrusion polymerizations, it is widely used, and the channels for the extrusion polymerization of vinyl monomers by radicals must be opened.
  • the advantage is that the automatic acceleration effect in the free radical polymerization process is fully utilized, and only during the auto-acceleration effect, the radical polymerization can realize the possibility of simultaneous rapid growth of molecular weight and polymerization rate.
  • the auto-acceleration effect is a kind in the usual kettle polymerization. Deadly disasters must be avoided as much as possible, otherwise the reaction system will immediately collapse or even explode.
  • the twin-screw reaction extrusion it is its area of expertise. Because the working object of the twin-screw extruder is designed for high-viscosity melts, the extruder can fully mix the melt, so that heat transfer can be achieved well, and the temperature control is quite accurate and convenient.
  • CN103146105 B The acrylic resin monomer, the initiator and the modified resin are fed into the extruder from the first screw segment of the first-stage extruder of the double-stage screw extruder, and the viscosity of the system is changed by the modified resin, which is early Entering the auto-acceleration effect zone, the reaction extrusion polymerization is completed at a high speed.
  • the ratio of acrylic resin to modified resin is limited by viscosity.
  • the object of the present invention is to overcome the shortcomings of the prior art described above, and to provide a requirement that the reaction extrusion polymerization residence time can be completely satisfied, and at the same time, the polymer can meet the requirements of high molecular weight, and the functionalization and high concentration can be achieved. Performance-based copolymerization technology.
  • a method for reactive extrusion extrusion of a vinyl monomer by feeding a vinyl monomer or at least one vinyl comonomer and an initiator to a first screw segment of a twin-screw extruder, and The modified resin is added to the screw section; the corresponding monomer is continuously added to the screw section after the system enters the automatic acceleration zone, and the initiator corresponding to the temperature of the barrel is further added after the initiator half-life, and the micro-nano used for modification Inorganic modified material; and adding an antioxidant and an anti-ultraviolet agent at the end of the polymerization, and then removing the unpolymerized monomer and by-products through the devolatilization screw segment; by controlling the temperature of the different screw segments, the reaction extrusion polymerization is obtained.
  • a vinyl copolymer resin having a molecular weight of 5 ⁇ 10 2 to 6 ⁇ 10 5 .
  • a method for reactive extrusion extrusion of a vinyl monomer by feeding a vinyl monomer or at least one vinyl comonomer and an initiator to a first screw segment of a first-stage twin-screw extruder, and Adding a modified resin to the subsequent screw section; continuing to add the corresponding monomer in the screw section after the system enters the automatic acceleration zone, and continuing to supplement the initiator corresponding to the temperature of the barrel after the initiator half-life, and for modifying Micro-nano inorganically modified material, extruded to obtain a vinyl copolymer prepolymer; the vinyl copolymer prepolymer is fed into a second-stage twin-screw extruder, and the vinyl monomer and the initiator are further added, and The antioxidant and the anti-UV agent are added at the end of the polymerization, and then the unpolymerized monomer and the by-product are removed by the devolatilization screw; by controlling the temperature of the different screw segments, the reaction is extrusion-poly
  • the twin-screw extruder is a twin-screw power inlet with a pressure resistance of 0.3 MPa or more, or a tight-mesh twin-screw extruder having a reverse flow structure, and the twin-screw extruder is provided with an inert gas introduction unit. And the detaching screw section, the inert gas introduction unit introduces the inert gas into the detachment screw section.
  • the first-stage twin-screw extruder is a tight-mesh twin-screw extruder with a twin-screw power inlet pressure of 0.3 MPa or more, or a reverse-flowing structure
  • the second-stage twin-screw extruder is The co-rotating or counter-rotating twin-screw extruder; the second-stage twin-screw extruder is provided with an inert gas introduction unit and a detaching screw section, and the inert gas introduction unit introduces the inert gas into the detachment screw section.
  • the total mass ratio of the modified resin to the vinyl monomer and the vinyl comonomer is from 0 to 30: 100 to 70; the initiator is added in an amount of from 0 to 20% by weight based on the total of all the vinyl monomers;
  • the nano-micron inorganic modified material is added in an amount of 0-30% by weight of the total mass of the vinyl monomer and the vinyl comonomer;
  • the mass ratio of the antioxidant to the anti-UV agent is 2:1-1 : 2, the antioxidant and the anti-UV agent are added in an amount of 0.1 to 1% by weight based on the total amount of the reactants.
  • the vinyl monomer or vinyl comonomer is selected from the group consisting of styrene, ⁇ -methyl styrene, divinyl benzene, acrylonitrile, butadiene, isoprene, methacrylic acid, methacrylic acid Ester, ethyl methacrylate, butyl methacrylate, amyl methacrylate, hydroxyethyl methacrylate, ⁇ -hydroxypropyl methacrylate, cyclohexyl methacrylate, glycidyl methacrylate , acrylic acid, ethyl acrylate, butyl acrylate, amyl acrylate, hydroxyethyl acrylate, ⁇ -hydroxypropyl acrylate, cyclohexyl acrylate, glycidyl acrylate, polycyclonorbornyl methacrylate, methyl Dicyclopentyl acrylate, phenyl methacrylate, p-ch
  • N-phenylmaleimide, biscyclopentenyl methacrylate, phenyl methacrylate, p-chlorophenyl methacrylate, adamantyl methacrylate, etc. can significantly improve the glass transition temperature and modulus of the polymer to achieve high performance; and methacrylic acid, acrylic acid, maleic anhydride, maleic acid, fumaric acid, glycidyl methacrylate, etc. After the copolymerization, various functions can be further introduced to achieve functionalization.
  • the amount and distribution of the copolymers they enter are affected by their reactivity ratios r 1 , r 2 , r 3 , etc., if all the reactivity ratios are much less than 1, then directly pass through the monomers.
  • the amount added can determine the amount and distribution of each monomer entering the copolymer.
  • the proportion of the monomer added to the screw barrel in the front section of the extruder is as small as possible, and is mainly added to the screw barrel in the latter stage. It is possible to have more monomer in the copolymer into the copolymer and achieve a uniform distribution.
  • the content and distribution of the components of the vinyl copolymer can be detected by conventional infrared spectroscopy and nuclear magnetic resonance spectroscopy according to the structure of each constituent monomer.
  • the initiator is selected from one or more of an inorganic peroxide, an organic peroxide, an azo initiator or a redox initiator;
  • the inorganic peroxide comprises potassium persulfate, sodium persulfate or ammonium persulfate;
  • the organic peroxide has the formula: R-O-O-R', wherein R, R' may be H, alkyl, acyl or carbonate, and R, R' may be the same or different;
  • the azo initiator includes azobisisobutyronitrile or azobisisoheptonitrile;
  • the redox initiator comprises a cumene hydroperoxide-ferrous salt or an organic peroxide-aromatic tertiary amine system.
  • the initiators it is preferred to be able to dissolve in the monomer, at least to dissolve in some solvent, which is convenient for the dose addition of the twin screw and for the formation of homogeneous polymerization.
  • the viscosity of the system is also continuously increased, and it is necessary to increase the temperature of the barrel differently depending on the polymer. It can be seen that a single initiator can not meet the polymerization concentration of the active species.
  • the initiator added in the front part of the extruder has a lower decomposition temperature requirement. After the half-life is reached, the decomposition temperature of the added initiator is higher as the temperature of the barrel increases, so that the decomposition is gradually added. A higher temperature initiator to achieve polymerization of the same active species concentration. The resulting copolymer is more uniform and stable.
  • the modified resin is selected from the group consisting of styrene-butadiene rubber, nitrile rubber, natural rubber, styrene-butadiene-styrene triblock copolymer, styrene-isoprene-styrene triblock copolymer, Hydrogenated styrene-butadiene-styrene triblock copolymer, hydrogenated styrene-isoprene-styrene triblock copolymer, styrene/butadiene random copolymer thermoplastic elastomer, methyl Methyl acrylate-butyl methacrylate micro-nano-sized diblock copolymer, methyl acrylate-butyl acrylate micro-nano-sized diblock copolymer, methyl methacrylate-butyl acrylate micro-nano-sized diblock copolymer , methyl methacrylate-buty
  • the addition of the modified resin into the reaction extrusion polymerization system not only improves the viscosity of the system, accelerates the entry into the auto-acceleration effect zone, accelerates the polymerization reaction, but also adds the polymerization system when the modified resin is a rubber or a thermoplastic elastomer. Improve the impact resistance of the copolymer; if it is a block copolymer, when added to the polymerization system, the copolymer can also be used as an excellent polymer compatibilizer.
  • the nano-nano inorganic modified material is selected from the group consisting of micro-nano-sized silica, micro-nano-sized calcium carbonate, micro-nano-sized aluminum oxide, micro-nano-sized aluminum hydroxide, micro-nano-sized magnesium hydroxide, and micro-nano-scale five.
  • Nano micron inorganic modified materials are added to the system in a very small amount, which not only can improve the rigidity of the copolymer, but also can improve the toughness of the copolymer to a certain extent, and the performance thereof can be improved.
  • such as the addition of micro-nano whiskers, micro-nano-sized zirconia can improve the surface scratch resistance of the copolymer; such as the addition of micro-nano-sized cerium oxide, micro-nano-sized cerium oxide, micro-nano-sized cerium oxide or micro-nano Grade yttrium oxide can increase the thermal oxidative degradation of the copolymer, and has functions such as fluorescence, light scattering, luminescence, and piezoelectric.
  • the antioxidant is selected from the group consisting of a commercially available antioxidant 168, an antioxidant 1076, an antioxidant bht, an antioxidant B215, an antioxidant 245 or an antioxidant 1010, and a bis(octadecyl ester) thiodipropionate.
  • diphenyl isooctyl phosphite diphenyl isooctyl phosphite, tetrakis[methyl- ⁇ -(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] pentaerythritol ester, 1,3-tris(2-methyl) 4-hydroxy-5-tert-butylphenyl)butane, 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenol), 3,5-di-tert-butyl- Octadecyl 4-hydroxyphenylpropionate, 2,2'-methylenebis(4-methyl-6-tert-butyl)phenol, 4'4-thiobis(6-tert-butyl-o-cresol), 4 Any one of 4'-thiobis(3-methyl-6-tert-butyl)phenol and 4'4-(dihydroxy-3,3',5,5'-tetra-tert-butyl
  • the twin-screw extruder has an aspect ratio of 48/1 or more and a screw rotation speed of 2-300 rpm.
  • the inert gas includes carbon dioxide, nitrogen, helium, argon, butanol, alcohol or water vapor.
  • the choice of inert gas is very important, the principle is that its polarity is as close as possible to the polymer, so that the unpolymerized monomers and by-products are removed from the polymer more efficiently, and the inertness with phase transition is avoided as much as possible. gas.
  • water is often used as an auxiliary gas for removal, although equipment manufacturing is convenient.
  • the reactivity ratio of the vinyl monomer to the vinyl comonomer is less than or equal to 1, otherwise, the monomer having a low reactivity ratio must be added to different screw segments according to the content of the copolymer.
  • the absolute molecular weight of the vinyl copolymer obtained by the above reaction extrusion polymerization can be measured by a gel permeation chromatography (GPC) method:
  • the absolute molecular weight and molecular weight distribution of the polymer must be determined using two sets of detection systems with multiple angle laser detection (LS) and refractive index differential scanning (RI).
  • LS multiple angle laser detection
  • RI refractive index differential scanning
  • Tetrahydrofuran (THF), dimethylformamide (DMF), dimethyl sulfoxide or the like can be used as the mobile phase, the flow rate is set to 1.0 ml/min, and the detection temperature is 25 °C.
  • the column is packed with a styrene-divinylbenzene copolymer gel, and the sample solution has a mass concentration of 0.002 to 0.004 g/ml.
  • the structural principle of the above-mentioned co-rotating tight meshing twin-screw extruder having a reverse flow structure is shown in FIG. It is actually a twin screw puller. Therefore, the bearing direction of the thrust bearing in the gearbox is completely opposite to that of the conventional extruder.
  • the raw material enters the extruder from the screw end, and the output material is close to one end of the gear box.
  • the aspect ratio is 48/1 or more, preferably 60/1 or more, and the screw rotation speed is 2-300 rpm.
  • the temperature of each screw section is sequentially increased to a temperature of 100-300 ° C at the end of the extruder, which is higher than the flow temperature of the copolymer.
  • Twin-screw extruders have a high transport capacity for viscous melts, but for water-like monomers, the transport capacity is low. For this reason, the pressure of the metering pump must be used to not only transport the monomer into the screw, but also to promote the rotation of the monomer with the screw, so that the extruder is resistant to the power inlet. The pressure must be above 0.3 MPa and must be stable for long-term operation. With a reverse flow-oriented extruder, since the monomer feedstock enters the extruder from the end of the screw, it is completely closed here and there is no problem of sealing. Although the output end is turned to the end of the gear box, there are also two screws rotating, but at this time the material has become a high-concentration melt, and there is almost no leakage problem.
  • the inert gas introduction unit used in the present invention is as shown in Figs. 2 and 3, and as shown in the drawing, 1 is a vacuum detachment screw section, 2 is an inert gas inlet port, and 3 is a one-way needle valve.
  • Figure 1 is a structural schematic view of a co-rotating tight-engagement twin-screw extruder having a reverse flow structure
  • Figure 2 is a structural schematic diagram of the inert gas introduction unit before the detachment screw section;
  • Figure 4 is an infrared absorption spectrum of MMA/MAH copolymer, in which: a. MMA/MAH copolymer b. MMA commercial homopolymer;
  • Figure 5 is a 1 H-NMR spectrum of the MMA/MAH copolymer
  • Figure 6 is a dynamic mechanical curve of a homopolymer of MMA/MAH copolymer and MMA
  • Example 7 is a GPC chart of the samples of Example 1 and Comparative Example 1, in which: A. Comparative Example 1; B. Example 1;
  • Figure 8 is a GPC curve of the copolymer of Example 2.
  • Methyl methacrylate (MMA) was selected as the vinyl monomer
  • maleic anhydride (MAH) was selected as the vinyl comonomer
  • the mass ratio of the two was 95.2:4.8.
  • the reactivity ratios r MMA and r MAH of the two are 6.7 and 0.02, respectively, indicating that MMA is more prone to self-polymerization, while MAH is more prone to copolymerization, which is obviously not conducive to the appearance of MAH on the molecular chain of the copolymer, so it is necessary to be in the initial stage of polymerization. To strengthen the content of MAH raw materials.
  • BPO benzoyl peroxide
  • An inert gas introduction unit shown in Fig. 2 is attached in front of the fifth-stage barrel of the 18-stage barrel, and a carbon dioxide inert gas is connected.
  • the 5-stage screw barrel after the inert gas introduction unit is a detachment screw section, and a pressure reduction system having an absolute air pressure of 0.0012 MPa is disposed.
  • the vibration absorption peak of the saturated ester group indicates that MAH has successfully copolymerized with MMA.
  • Figure 6 is a dynamic mechanical curve of the MMA/MAH copolymer and the commercial MMA homopolymer. It can be seen that the glass transition temperature Tg of the MMA/MAH copolymer prepared by reactive extrusion is 144 ° C, which is 12 ° C higher than the Tg of the MMA commercial homopolymer. This is due to the introduction of a rigid maleic anhydride five-membered ring into the copolymer. The Tg of the MMA/MAH copolymer is significantly improved. At the same time, it is further proved from another angle that maleic anhydride is uniformly distributed in the copolymer. Its rigidity is also significantly better than the pure homopolymer of MMA. The temperature at which the storage modulus begins to drop sharply is 20 °C higher than the latter, effectively increasing the temperature at which it is used.
  • MMA methyl methacrylate
  • MAH maleic anhydride
  • MAH was dissolved in MMA, and the mass ratio of the two was also 95.2:4.8.
  • BPO in which the total amount of the two is 0.4% by mass, IPBP of 0.1% by mass, and then the same two-stage double of the diaphragm pump with a limit pressure of 15 MPa at a metering rate of 3.6 kg/h. In the screw extruder, the temperature setting is also the same. Use the same devolatilization system. The final polymer of the reaction extrusion polymerization was obtained after sufficient devolatilization, and the polymerization conversion ratio was only 85.7%.
  • the sample had a number average molecular weight of 6.4 ⁇ 10 4 , a weight average molecular weight of 1.3 ⁇ 10 5 and a PDI of 2.21. by GPC.
  • the GPC spectrum and the GPC spectrum of the sample of Comparative Example 1 are shown in Fig. 7, and DRI and LS are detection signals of both the refractive index and the laser light scattering detectors.
  • Example 1 When the conversion rate was extremely increased after the automatic acceleration effect region was reached, it was not fully utilized. In contrast, a considerable portion of the monomers in Example 1 are added to the system after the system enters the auto-acceleration effect region, thereby fully utilizing the advantages of high polymerization rate and large molecular weight when the auto-acceleration effect occurs, and the polymerization is rapidly completed, and the polymerization is converted. The rate is almost 100%, while Comparative Example 1 is only 85.7%, which is obviously not suitable for industrialization.
  • Styrene (St) was selected as the vinyl monomer, and maleic anhydride (MAH) was selected as the vinyl comonomer.
  • the mass ratio of the two was 97.09:2.91. Since the reactivity ratio of the two is an ideal alternating copolymerization, the composition ratio of the copolymer is the same as the ratio of the raw materials, so there is no need to consider strengthening the raw material to strengthen the reaction in advance. Then, a styrene-butadiene-styrene triblock thermoplastic elastomer (SBS) having a molecular weight of 1.5 ⁇ 10 5 was dissolved and dissolved in the above two mixed monomers, and the mass ratio of the mixed monomer to the SBS was 7.5:2.5. .
  • SBS thermoplastic elastomer
  • the polymerization Since the molecular weight of the polymerization is not designed to be large, and since the SBS thermoplastic elastomer having a mass of 25% is preliminarily dissolved in the mixed monomer, the polymerization is directly in the auto-acceleration effect region, and thus the polymerization rate is high, so that the polymerization can be completed by a single extruder.
  • the inert gas introduction unit shown in Fig. 2 and Fig. 3 is installed in front of the fourth stage of the 19th stage of the barrel, and the carbon dioxide inert gas is connected. A pressure reduction system with an absolute air pressure of 0.0012 MPa was placed after the last fourth stage of the barrel.
  • the final polymer of the reaction extrusion polymerization was obtained after sufficient devolatilization, and the polymerization conversion ratio was 99.999%.
  • the purified GPC analysis showed a number average molecular weight of 4,920 and a molecular weight distribution of 1.54. The molecular weight of the polymer and its GPC curve are shown in Figure 8.
  • Example 2 is extremely effective in improving the impact resistance of nylon 66 resin and has no significant effect on other mechanical properties.
  • the material also showed no obvious phase separation, which is a very good modified resin of nylon.
  • Styrene (St) was selected as the vinyl monomer, and acrylonitrile (AN) and glycidyl methacrylate (GMA) were selected as the vinyl comonomer.
  • the mass ratio of the three was 69.9:30:0.1. Since the reactivity ratio of AN and GMA and St is less than 1, the composition ratio of the copolymer can be regarded as the same as the raw material ratio, so it is not necessary to consider strengthening the raw material to strengthen the reaction in advance.
  • the inert gas guide shown in Figure 2 and Figure 3 is installed in front of the sixth stage of the 19-stage screw barrel. Enter the unit and connect the carbon dioxide inert gas.
  • the 6-stage barrel after the inert gas introduction unit is followed by a detachment screw section, and a pressure reduction system having an absolute gas pressure of 0.0012 MPa is disposed.
  • the copolymer of Example 3 was used as a compatibility of ABS plastic with plastic alloys such as nylon, polycarbonate (PC), poly(p-butylene dicarboxylate) (PBT), and polyethylene terephthalate (PET). Very good results can be obtained. The addition amount is only 5-10% in total to obtain an alloy in which no macroscopic phase separation exists.
  • Styrene was selected as the vinyl monomer, and glycidyl methacrylate was selected as the vinyl comonomer, and the mass ratio of the two was 99.99:0.01. Since the reactivity ratio of St and GMA is much less than 1, the composition ratio of the copolymer can be regarded as the same as the raw material ratio, so it is not necessary to consider strengthening the raw material to strengthen the reaction in advance. A total of 0.75% by mass of azobisisobutyronitrile was added thereto. Nano-sized silica with a diameter of 80 nm was selected as a functional auxiliaries, and the surface thereof was treated with a KH550 silane coupling agent.
  • the temperature of the barrel is set to 70 to 100 ° C according to the polymerization molecular weight.
  • the inert gas introduction unit shown in Fig. 2 and Fig. 3 is installed in front of the fifth stage of the screw barrel, and the carbon dioxide inert gas is connected. After the inert gas introduction unit, the five-stage screw barrel is followed by a detachment screw section, and a pressure reduction system having an absolute gas pressure of 0.0012 MPa is disposed.
  • Example 4 All the implementation measures were the same as those in Example 4. The only difference was that no nano silica was added to the mixed monomer, and the obtained copolymer was purified and its number average molecular weight was 2.92 ⁇ 10 5 by GPC. The molecular weight was 4.44 ⁇ 10 5 and the PDI was 1.52.
  • the polystyrene copolymer obtained in Example 4 containing nano silica is not only completely transparent, but also has tensile, bending and impact strength ratios than those without nanometers.
  • the polystyrene copolymer obtained in Comparative Example 2 of silica copolymerization was high, and the surface hardness was particularly improved, so that the scratch resistance of the surface of the material was remarkably improved.

Abstract

一种乙烯基单体反应挤出共聚合的方法，是将乙烯基单体或和至少一种乙烯基共聚单体以及引发剂送入双螺杆挤出机的第一螺段，并在后面的螺段添加改性树脂；在系统进入自动加速区后的螺段继续补加相应单体，在引发剂过半衰期后继续补加与螺筒温度相应的引发剂，以及用于改性的微纳米无机改性材料；并在聚合终止时加入抗氧剂与抗紫外剂，然后通过脱挥螺段脱除未聚合的单体以及副产物；通过控制不同螺段的温度，反应挤出聚合得到预定分子量为5×102至6×105的乙烯基共聚树脂。本发明克服了现有用于自由基反应挤出聚合技术存在的缺陷，既可以完全满足反应挤出聚合停留时间短的要求，集功能化与高性能化于一身，同时又可以满足聚合物达到高分子量的要求。

Description

一种乙烯基单体反应挤出共聚合的方法 技术领域
本发明涉及共聚物的聚合方法，尤其是涉及一种乙烯基单体反应挤出共聚合的方法。
背景技术
乙烯基单体的聚合物通常称为烯类聚合物，它们的聚合反应已成为高聚物合成反应极为重要的一部分。例如聚苯乙烯、聚氯乙烯、聚(甲基)丙烯酸酯、聚醋酸乙烯酯、ABS树脂以及与其相关的，应用极广的各类塑料、橡胶、热塑性弹性体、涂料等都是由这类单体合成，而其中绝大部分均是采用自由基聚合得到，差不多占了聚合物的一大半份额。然而由于这类聚合物的聚合反应速度快、放热量大、物料黏度在瞬间迅速增加，致使反应热的撤移、单体的扩散与均布都比较困难，致使这类聚合物很难实施本体聚合。取而代之的是采用溶液、悬浮、乳液等聚合方法。
溶液聚合法虽可避免上述本体聚合法的难点，但由于聚合速度缓慢以及在后处理过程中脱除溶剂产生的高能耗和环境污染，使这种聚合法几乎只用于理论研究，除阴离子聚合非采用不可的场合外，从未进行过工业化。悬浮聚合法同样也可以避免散热和高黏度的困难，而且只需简单的分离就可以将聚合物与水分开，无须像溶液聚合法那样进行溶剂的脱除，避免了不必要的能耗，因此是较为成功的一种工业化聚合法。但在聚合粗产品的分离和精制过程中，由于要清洗掉在珠粒状聚合物表面存在的大量悬浮剂和表面活性剂，同样也造成了严重的环境污染。进行干燥时又需耗用相当大的能量。此外由于表面活性剂与悬浮剂的残留，使产品的纯净度及力学性能下降，所以这种聚合方法只用在对聚合物性能要求不高，而且又希望直接采用聚合物微珠的可发性聚苯乙烯(EPS)工艺之中。乳液聚合与悬浮聚合相类似，但由于在较高聚合速率下分子量可以做得相当高，对提高产品性能较为有利。但另一方面，由于聚合物微珠更细小，使其表面的乳化剂和表面活性剂更难以去除，环境污染问也就题更为严重。好在乳液聚合成的聚合物有利于直接用做涂料，减少了一些能耗，但 用于制备塑料的工艺却带来了很大的污染，如乳液法ABS的生产。
目前最为流行的聚合法是连续本体热聚合法。该聚合法无其它杂质，直接由单体聚合成高聚物，产品的透明度高，环境污染也降到较低的程度，所以在国际上很受青睐。然而该聚合法又存在着很难提高聚合物的分子量的问题，生产效率几乎随分子量上升而大幅下降。如将重均分子量由27～28万仅仅提高到40万，生产效率将下降至通常状态下的40％。而且在反应后期由于体系过黏严重缺乏传质过程，导致分子量分布过宽的弊病。可见，如何实施乙烯基单体的自由基聚合，一直存在着聚合上的缺陷。也正因为如此，通过反应挤出来实施乙烯基单体聚合的研究相继涌现。
Stuber等利用一台
Figure PCTCN2017078308-appb-000001
反向自洁净紧啮合双螺杆挤出机，研究了甲基丙烯酸甲酯的本体聚合，并通过在第一螺段上注入固体染料来测定物料的停留时间及其分布(Stuber N P,Tirrell M.Polym Process Eng,1985,3:71)。
Lee(Lee R W,Miloscia W J.Standard Oil,US 4,410,659,1983)与Bodolus等(Bodolus C L,Woodhead D A,Standard Oil,US 4,542,189,1985)采用同向双螺杆挤出机研究了对甲基丙烯酸甲酯与丙烯腈以及溶解于单体的丁腈橡胶的本体聚合。聚合条件为：每分钟输入液态单体27g(丙烯腈占75份)，丁腈橡胶2.45g，料筒温度为110～177℃，螺杆转速为75rpm，物料在螺杆中的停留时间为4分钟，未反应的单体由挤出机上的脱挥口脱出。得到的产物的转化率为77％，其抗冲击性能比不添加丁腈橡胶橡胶时高10倍以上。
就苯乙烯与其相应单体的共聚反应而言，Stober和Amos(US 2,530,409,1950)早在1950年就报道了他们的研究，将苯乙烯预聚体加入单螺杆挤出机中，在沿螺杆方向的温度梯度为120～200℃，螺杆转速为1rpm，物料的平均停留时间为18h。
Illing(US 3,536,680,1970)研究了苯乙烯与丙烯腈、甲基丙烯酸甲酯或丙烯酰胺的本体共聚合。为了能提供较长的停留时间，设计了一个3级串联的紧啮合双螺杆挤出反应器。将5℃的含有引发剂的苯乙烯与丙烯腈单体的混合物从第一个双螺杆挤出机的进料口加入，物料在该挤出机中被加热至130～180℃、停留20～40秒后送入第二个双螺杆挤出机，螺杆的直径大约为60～200mm。单体主要在第二个螺杆挤出机中聚合，反应物呈薄层状流动，以得到 充分、有效的揑合。螺筒内保持1.52×105Pa压力，反应物停留时间控制在1.5～18分钟范围内。然后再将反应物送入第三个双螺杆挤出机，物料在挤出机中脱挥，未反应单体从两个抽真空口脱出。
然而正如在上述连续本体热聚合法中所指出的那样，由于自由基引发的乙烯基单体的聚合。总是必然存在着聚合速率与聚合分子量的一对矛盾，要达到足够高的分子量，聚合时间就太长，这对于靠连续化快速生产的反应挤出过程而言是无法被接受的。反之，若要提高聚合速率则分子量以及转化率都会很低，因而迄今为止采用自由基引发的反应挤出聚合，很少有真正实现工业化生产的。
为了使乙烯基单体的本体反应挤出聚合得以应用，CN 1587292B、CN 1587288A、CN1644597等公开了采用阴离子聚合方式，本体反应挤出聚合合成了塑料、橡胶以及热塑性弹性体的技术。CN101824151B则公开了一项氟硅氧聚合物本体阴离子开环聚合反应挤出合成的技术。然而由于可以实施阴离子聚合的乙烯基单体的种类过少，且单体及所有原料精制要求过高。而阴离子开环聚合虽然扩大了一些反应挤出聚合的应用领域，但应用极广的，利用自由基引发乙烯基单体反应挤出聚合的渠道必须打通。
如上所述，早期的自由基引发反应挤出聚合，由于在技术上存在较大的缺陷，难以实用。于是，陈继新等人(化工科技，2012,20(2):80-84)公开了一种先将MMA单体在聚合反应釜中预聚合，然后再输入螺杆挤出机进行最终高黏度体系的聚合。方案似乎很合理，但事实上无法实施。因为将MMA单体在聚合反应釜中预聚合，对于具有较高黏度的反应体系是无法迅速冷却并终止聚合的，存在着极大的暴聚风险。即便侥幸没有发生暴聚，也不可能得到稳定的工业化产品。
可见自由基引发聚合的关键障碍在于自由基引发体系中，总是必然存在着聚合速率与聚合分子量的一对矛盾。要达到足够高的分子量，聚合时间就太长，这对于靠连续化快速生产的反应挤出过程而言是无法被接受的。反之，若要提高聚合速率则分子量会很低。为突破这一瓶颈，CN103146105B公开了一项(甲基)丙烯酸类单体反应挤出聚合的技术。其优势在于充分利用自由基聚合过程中的自动加速效应，只有在自动加速效应期间，自由基聚合才可能实现分子量与聚合速率同时快速增长的可能。但自动加速效应在通常釜式聚合中却是一种 致命的灾害，必须尽可能避免，否则反应体系马上发生暴聚甚至爆炸。但在双螺杆的反应挤出中，却是其擅长领域。因为双螺杆挤出机的工作对象就是针对高黏度熔体而设计的，所以挤出机能够使熔体充分混合，从而能良好地实现热量传递，温度控制相当准确、方便。能够提供良好的分散混合和分布混合，将少量的催化剂和反应物混合均一。而且由于聚合物熔体在螺杆挤出机中获得极为良好的表面更新作用，更有利于小分子副产物的脱除。可见在反应挤出聚合过程中充分利用自由基聚合中的自动加速效应，是实现自由基引发反应挤出聚合的关键。CN103146105 B将丙烯酸树脂类单体、引发剂、改性树脂从双阶式螺杆挤出机第一阶挤出机的第一螺段送入挤出机，通过改性树脂改变体系的黏度，提早进入自动加速效应区，从而高速完成反应挤出聚合。然而该技术依然存在一些不足，如丙烯酸树脂类单体与改性树脂的比例受到黏度的制约；其二，虽然进入了自动加速效应区聚合会很快，但单体的总量仅局限于初始加入量，没能很好地利用自动加速效应在后面的螺杆段继续补加单体，制约了生产效率；其三，未能在引发剂过了半衰期后及时补加，结果延缓了聚合速率，从而导致产能受到制约。
发明内容
本发明的目的就是为了克服上述现有技术存在的缺陷，而提供一种既可以完全满足反应挤出聚合停留时间短的要求，同时又可以满足聚合物达到高分子量的要求，集功能化与高性能化于一身的共聚合技术。
本发明的目的可以通过以下技术方案来实现：
一种乙烯基单体反应挤出共聚合的方法，是将乙烯基单体或和至少一种乙烯基共聚单体以及引发剂送入双螺杆挤出机的第一螺段，并在后面的螺段添加改性树脂；在系统进入自动加速区后的螺段继续补加相应单体，在引发剂过半衰期后继续补加与螺筒温度相应的引发剂，以及用于改性的微纳米无机改性材料；并在聚合终止时加入抗氧剂与抗紫外剂，然后通过脱挥螺段脱除未聚合的单体以及副产物；通过控制不同螺段的温度，反应挤出聚合得到预定分子量为5×102至6×105的乙烯基共聚树脂。
一种乙烯基单体反应挤出共聚合的方法，是将乙烯基单体或和至少一种乙 烯基共聚单体以及引发剂送入第一阶双螺杆挤出机的第一螺段，并在后面的螺段添加改性树脂；在系统进入自动加速区后的螺段继续补加相应单体，在引发剂过半衰期后继续补加与螺筒温度相应的引发剂，以及用于改性的微纳米无机改性材料，挤出得到乙烯基共聚物预聚体；将乙烯基共聚物预聚体送入第二阶双螺杆挤出机，继续补加乙烯基单体与引发剂，并在聚合终止时加入抗氧剂与抗紫外剂，然后通过脱挥螺段脱除未聚合的单体以及副产物；通过控制不同螺段的温度，反应挤出聚合得到预定分子量为5×102至6×105的乙烯基共聚树脂。
所述的双螺杆挤出机为双螺杆动力入口耐压0.3MPa以上不泄漏的，或者为具有反流向结构的紧啮合双螺杆挤出机，该双螺杆挤出机设有惰性气体导入单元和脱挥螺段，惰性气体导入单元将惰性气体导入脱挥螺段。
所述第一阶双螺杆挤出机为双螺杆动力入口耐压0.3MPa以上不泄漏的，或者为反流向结构的紧啮合双螺杆挤出机，所述第二阶双螺杆挤出机为同向或异向旋转双螺杆挤出机；第二阶双螺杆挤出机设有惰性气体导入单元和脱挥螺段，惰性气体导入单元将惰性气体导入脱挥螺段。
所述改性树脂与乙烯基单体及乙烯基共聚单体的总质量比为0-30:100-70；所述引发剂的加入量为所有乙烯基单体总量的0-20wt％；所述纳微米无机改性材料的加入量为乙烯基单体及乙烯基共聚单体总质量的0-30wt％；所述抗氧剂与抗紫外剂两者的质量比为2:1-1:2，抗氧剂与抗紫外剂的加入量为反应物总量的0.1-1wt％。
所述的乙烯基单体或乙烯基共聚单体选自苯乙烯、α-甲基苯乙烯、二乙烯基苯、丙烯腈、丁二烯、异戊二烯、甲基丙烯酸、甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丁酯、甲基丙烯酸戊酯、甲基丙烯酸羟乙酯、甲基丙烯酸β-羟丙酯、甲基丙烯酸环己酯、甲基丙烯酸环氧丙酯、丙烯酸、丙烯酸乙酯、丙烯酸丁酯、丙烯酸戊酯、丙烯酸羟乙酯、丙烯酸β-羟丙酯、丙烯酸环己酯、丙烯酸环氧丙酯、甲基丙烯酸多环降冰片烯酯、甲基丙烯酸双环戊烯酯、甲基丙烯酸苯酯、甲基丙烯酸对氯苯酯、甲基丙烯酸金刚烷酯、甲基丙烯酸异冰片酯、乙烯基吡啶、马来酸酐、顺丁烯二酸、富马酸、顺丁烯二酸单酯、顺丁烯二酸二酯、富马酸单酯、富马酸二酯、N-甲基马来酰亚胺、N-环己基马来酰亚胺、N-苯基马来酰亚胺、N-甲苯基马来酰亚胺、N-邻氯苯马来酰亚胺、十一碳 烯酸、衣康酸、衣康酸酯、山梨酸、山梨酸酯、四氟乙烯、六氟乙烯、偏氟乙烯、氯乙烯、偏氯乙烯、乙烯基异氰酸酯或丙烯酰氯中的一种或几种。在这些乙烯基单体中，N-苯基马来酰亚胺、甲基丙烯酸双环戊烯酯、甲基丙烯酸苯酯、甲基丙烯酸对氯苯酯、甲基丙烯酸金刚烷酯等参与共聚后，可以明显提高聚合物的玻璃化温度及模量，从而实现高性能化；而甲基丙烯酸、丙烯酸、马来酸酐、顺丁烯二酸、富马酸、甲基丙烯酸环氧丙酯等参与共聚后，可以进一步导入各种功能，从而实现功能化。它们进入共聚物的多寡以及分布情况受它们的竞聚率r1、r2、r3......的影响，如果所有的竞聚率都远小于1，那么直接通过各单体的加入量，即可决定各单体进入共聚物的多寡以及分布。但如果由某单体的竞聚率较大，甚至远大于1，那么该单体在挤出机前段螺筒中加入的比例尽可能少，主要补加至后段的螺筒内。才可能使其他单体有较多的量进入共聚物中，而且实现均匀分布。
乙烯基共聚物的各组份的含量与分布，可以依据各组成单体的结构，通过常用的红外光谱及核磁共振光谱进行检测。
所述的引发剂选自无机过氧化物、有机过氧化物、偶氮类引发剂或氧化还原引发剂中的一种或几种；
所述的无机过氧化物包括过硫酸钾、过硫酸钠或过硫酸铵；
所述的有机过氧化物的通式为：R-O-O-R’，其中R，R’可以是H，烷基，酰基或碳酸酯，R，R’可以相同，也可以不同；
所述的偶氮类引发剂包括偶氮二异丁腈或偶氮二异庚腈；
所述的氧化还原引发剂包括异丙苯过氧化氢-亚铁盐或有机过氧化物-芳叔胺体系。
在这些引发剂中，优选能够溶解于单体，至少能够溶解于某些溶剂，这样既便于剂量加入双螺杆，又有利于形成均相聚合。此外，随着聚合转化率的上升，体系的黏度也在不断地提高，就必须根据聚合物的不同而不同幅度地提高螺筒温度。可见单一引发剂是满足不了等活性种浓度聚合的。挤出机前段加入的引发剂其分解温度要求较低，待其达到半衰期后，后面补加的引发剂的分解温度随着螺筒温度的升高而要求更高一些，如此循序渐进地补加分解温度高一点的引发剂，从而实现等活性种浓度的聚合。得到的共聚物更为均一与稳定。
所述的改性树脂选自丁苯橡胶、丁腈橡胶、天然橡胶、苯乙烯-丁二烯-苯乙烯三嵌段共聚物、苯乙烯-异戊二烯-苯乙烯三嵌段共聚物、氢化苯乙烯-丁二烯-苯乙烯三嵌段共聚物、氢化苯乙烯-异戊二烯-苯乙烯三嵌段共聚物、苯乙烯/丁二烯无规共聚物类热塑性弹性体、甲基丙烯酸甲酯-甲基丙烯酸丁酯微纳米级二嵌段共聚物、丙烯酸甲酯-丙烯酸丁酯微纳米级二嵌段共聚物、甲基丙烯酸甲酯-丙烯酸丁酯微纳米级二嵌段共聚物、甲基丙烯酸甲酯/甲基丙烯酸丁酯无规共聚物、甲基丙烯酸甲酯/丙烯酸丁酯无规共聚物、苯乙烯-丁二烯-甲基丙烯酸甲酯微纳米级三嵌段共聚物、苯乙烯-异戊二烯-甲基丙烯酸甲酯微纳米级三嵌段共聚物、热塑性聚氨酯，以及乙烯基单体及乙烯基共聚单体共聚物自身中的一种或几种。改性树脂添加入反应挤出聚合体系，不仅可以提高体系的黏度，加快进入自动加速效应区，加速聚合反应，而且当改性树脂属于橡胶或是热塑性弹性体时，加入聚合体系，还可以大大提高共聚物的抗冲击性能；如果是嵌段共聚物，加入聚合体系，则共聚物还可以作为优秀的高分子相容剂使用。
所述的纳微米无机改性材料选自微纳米级二氧化硅、微纳米级碳酸钙、微纳米级三氧化二铝、微纳米级氢氧化铝、微纳米级氢氧化镁、微纳米级五氧化二钽、微纳米级晶须、微纳米级石英、微纳米级氧化鈰、微纳米级氧化銪、微纳米级氧化锆、微纳米级氧化钡或微纳米级氧化镧中的一种或几种。纳微米无机改性材料极少量地加入体系，不仅可以提高共聚物的刚性，而且还可以在一定程度上提高共聚物的韧性，使其性能得以提高。此外，如添加微纳米级晶须、微纳米级氧化锆，又可以提高共聚物的耐表面划伤性能；如添加微纳米级氧化鈰，微纳米级氧化銪，微纳米级氧化钡或微纳米级氧化镧，可以增加共聚物的抗热氧化降解、具备荧光、光散射、发光、压电等功能。
所述的抗氧剂选自市售抗氧剂168、抗氧剂1076、抗氧剂bht、抗氧剂B215、抗氧剂245或抗氧剂1010，硫代二丙酸二(十八酯)、亚磷酸二苯异辛酯、四[甲基-β-(3,5-二叔丁基-4-羟基苯基)丙酸酯]季戊四醇酯、1,3-三(2-甲基-4-羟基-5-特丁基苯基)丁烷、1,1,3-三(2-甲基-4-羟基-5-叔丁基苯酚)、3,5-二特丁基-4-羟基苯丙酸十八酯、2,2’-亚甲基双(4-甲基-6-特丁基)苯酚、4’4-硫代双(6-叔丁基邻甲酚)、4,4’-硫代双(3-甲基-6-叔丁基)苯酚、4’4-(二羟基-3,3’,5,5’-四叔丁基联苯)中的任意一种或数种复配；所述的抗紫外剂选自UV-531、UV-9、UV-326、 UV-327、UV-328、UV-329、邻羟基苯甲酸苯酯、邻硝基苯胺或对甲苯酚中的任意一种或数种复配。
所述的双螺杆挤出机的长径比为48/1以上，螺杆转速为2-300rpm。
所述惰性气体包括二氧化碳、氮气、氦气、氩气、丁醇、酒精或水蒸气。惰性气体的选择非常重要，其原则是其极性尽可能与聚合物相近，这样才更有效地从该聚合物中脱除未聚合单体及副产物，而且尽可能避免使用具有相转变的惰性气体。现在技术中常会出现采用水作为脱除用辅助气体的，虽然设备制造会很方便。但由于水的沸点常压下为100℃，加入通常在200℃左右温度的挤出机中时，不仅水的汽化热大大消耗了能量，而且会使聚合物变成固体，更加难以脱出副产物。所以二氧化碳应该最被优选。
所述乙烯基单体与乙烯基共聚单体的竞聚率均要小于等于1，否则，必须按照在共聚物中含量的要求，在不同螺段添加竞聚率低的单体。
上述反应挤出聚合得到的乙烯基共聚物的绝对分子量可以通过凝胶渗透色谱(GPC)法进行测定：
为了测定聚合物的绝对分子量，必须采用配有多个角度激光检测(LS)和折光率示差扫描(RI)2套检测体系，对聚合物绝对分子量和分子量分布进行测定。如美国Wyatt技术公司Water 1515型多检测凝胶渗透色谱仪。可使用四氢呋喃(THF)、二甲基甲酰胺(DMF)、二甲基亚砜等为流动相，流速设定为1.0ml/min，检测温度为25℃。采用苯乙烯-二乙烯基苯共聚物凝胶填充色谱柱，样品溶液质量浓度为0.002～0.004g/ml。
上述具有反流向结构的同向旋转紧啮合双螺杆挤出机的结构原理如图1所示。其实际上是一台双螺杆拉出机。因此其齿轮箱中的止推轴承的承力方向与通常挤出机完全相反，原料由螺杆端头进入挤出机，而输出物料在紧靠齿轮箱一端。其长径比为48/1以上，优选60/1以上，螺杆转速为2-300rpm。各螺段的温度依次升高，至挤出机的末段时，温度为100-300℃，高于共聚物的流动温度。
双螺杆挤出机对于黏性熔体具有很高的输送能力，但对于如同水一样的单体而言，输送能力就很低。为此，须借助计量泵的压力，不仅将单体输送进入螺杆，而且还负有推动单体随螺杆转动前进的作用，因而挤出机动力入口处耐 压必须在0.3MPa以上，而且须保证能够长期稳定运行。采用反流向结构的挤出机，由于单体原料由螺杆端头进入挤出机，此处是完全封闭的，不存在密封的问题。输出端虽转至紧靠齿轮箱一端同样有两根螺杆在转动，但此时物料已经成为高浓度熔体，也几乎不存在泄漏问题。
本发明所采用的惰性气体导入单元如图2、图3所示，图中所示，1为真空脱挥螺段，2为惰性气体进入口，3为单向针形阀。通过导入惰性气体降低分压以及携带的作用，可以事半功倍地提升脱挥的效果。
附图说明
图1具有反流向结构的同向旋转紧啮合双螺杆挤出机的结构原理图；
图2、图3脱挥螺段前惰性气体导入单元的结构原理图；
图4为MMA/MAH共聚物红外吸收光谱，图中：a.MMA/MAH共聚物b.MMA的商品均聚物；
图5为MMA/MAH共聚物的1H-NMR谱；
图6为MMA/MAH共聚物与MMA商品均聚物的动态力学曲线；
图7为实施例1与比较例1试样的GPC图谱，图中：A.比较例1；B.实施例1；
图8为实施例2共聚物的GPC曲线。
具体实施方式
下面结合附图和具体实施例对本发明进行详细说明。
实施例1:
选取甲基丙烯酸甲酯(MMA)作为乙烯基单体，选取马来酸酐(MAH)作为乙烯基共聚单体，两者的质量比为95.2:4.8。两者的竞聚率rMMA和rMAH分别为6.7和0.02，从而表明MMA更容易自聚，而MAH更倾向于共聚，明显不利于MAH出现在共聚物分子链上，因而有必要在聚合初期就强化MAH原料的含量。将MAH溶解于溶于MMA中，两者的质量比为88.9:11.1，并于其中加入该二者总量0.93％质量分数的过氧化苯甲酰(BPO)，然后以1.54kg/h的计量速率，采用极限压力为15MPa的隔膜泵输入一台Ф35，长径比：L/D＝60， 如图1所示反流向结构的，同向旋转紧啮合双螺杆挤出机的第一螺段，螺筒的温度根据聚合分子量的要求设定为70～100℃。经第一阶双螺杆聚合后的乙烯基共聚物预聚体，通过一个熔体泵连接至第二阶双螺杆挤出机上，其为一台长径比：L/D＝70，异向旋转双螺杆挤出机。在其18段螺筒的倒数第5段螺筒前加装了图2所示的惰性气体导入单元，并连接二氧化碳惰性气体。惰性气体导入单元后的5段螺筒为脱挥螺段，配置了绝对气压为0.0012MPa的减压系统。选取MMA与异丙苯过氧化氢(IPBP)配成质量比为99.82:0.18溶液，以两台极限压力为15MPa的隔膜泵，以1.032kg/h的计量速率，分别输入第二阶挤出机的第2以及第5段螺筒。挤出机螺筒温度控制在100～200℃，反应挤出聚合的最终聚合物经充分脱挥以后得到，聚合转化率为99.999％。其经过精制后的红外光谱以及核磁共振图谱分别如图4及图5所示，图4中，a.MMA/MAH共聚物，b.MMA的商品均聚物。经GPC检测其数均分子量为6.7×104，重均分子量为1.0×105，PDI为1.54。
与纯商品MMA均聚物相比，由红外光谱可见1853cm-1和1783cm-1处为共聚物中MAH单元上C＝O的对称和非对称伸缩振动峰，1730cm-1为共聚物中MMA单元饱和酯基的振动吸收峰，表明MAH成功与MMA实现了共聚。在核磁共振图谱中，由共聚物中MMA酯基上的甲基氢(δ＝3.42～3.67)和MAH上的次甲基氢(δ＝2.6～3.1)峰面积的比值计算得知，共聚物中n(MAH)：n(MMA)＝0.051，与加入单体的摩尔比相等。从而表明尽管两者的竞聚率相差很大，极其不利于MAH参与共聚，但通过反应挤出过程的控制，还是得到了理想的共聚物。
图6为MMA/MAH共聚物与商品MMA均聚物的动态力学曲线。可以看到，反应挤出制备的MMA/MAH共聚物的玻璃化温度Tg＝144℃，比MMA商品纯均聚物的Tg高12℃。这是由于共聚物中引入了刚性的马来酸酐五元环。使得MMA/MAH共聚物的Tg得到明显地提高。同时从另一角度进一步证明马来酸酐在共聚物中得到了均匀地分布。其刚性也明显优于MMA商品纯均聚物。储能模量开始大幅下降的温度较后者提高20℃，有效地提高了其使用温度。
比较例1:
同样采用甲基丙烯酸甲酯(MMA)作为乙烯基单体，选取马来酸酐(MAH) 作为乙烯基共聚单体，将MAH溶解于溶于MMA中，两者的质量比也为95.2:4.8，于其中溶入该二者总量0.4％质量分数的BPO，0.1％质量分数的IPBP，然后以3.6kg/h的计量速率，采用极限压力为15MPa的隔膜泵输入与实施例相同的两阶双螺杆挤出机中，温度设定也完全相同。使用同样的脱挥体系。反应挤出聚合的最终聚合物经充分脱挥以后得到，聚合转化率仅为85.7％。经GPC检测试样的数均分子量为6.4×104，重均分子量为1.3×105，PDI为2.21。该GPC图谱以及作为对比的实施例1样品的GPC图谱共示于图7之中，DRI及LS分别为折光率以及激光光散射两种检测器的检测信号。
可以看到，尽管比较例1所采用的乙烯基单体、共聚单体、引发剂的种类及加入量、螺杆聚合的温度等都与实施例1完全相同，然而在关键两点上不同于实施例1。其一，由于没有考虑到引发剂的半衰期，因此后期未能补加，从而导致聚合速率的下降，但分子量增加较大，分布较宽。相比之下，实施例1整个聚合过程均匀，快速平稳，分子量分布窄。更重要的是比较例1没能利用自动加速效应，前期引发剂大量消耗，达到自动加速效应区后转化率极速提升时又未能充分利用。相比之下，实施例1中相当部分单体在体系进入自动加速效应区后再行加入体系，从而充分利用了自动加速效应发生时聚合速率高，分子量大的优势，迅速完成聚合，聚合转化率几乎达到100％，而比较例1仅为85.7％，显然不适合工业化。
实施例2:
选取苯乙烯(St)作为乙烯基单体，选取马来酸酐(MAH)作为乙烯基共聚单体，两者的质量比为97.09:2.91。由于两者的竞聚率属于理想的交替共聚，因此共聚物的组分比与原料比相同，故而没有必要考虑强化那种原料须先期强化反应。然后选取苯乙烯-丁二烯-苯乙烯三嵌段热塑性弹性体(SBS)，分子量为1.5×105，溶解在上述二混合单体之中，混合单体与SBS的质量比为7.5:2.5。选择偶氮二异丁腈作为引发剂，加入量为二混合单体总量的1.2％质量分数。然后以3.6kg/h的计量速率，采用极限压力为15MPa的隔膜泵输入一台双螺杆动力入口耐压1MPa不泄漏的Ф35，长径比L/D＝76，同向旋转紧啮合双螺杆挤出机的第一螺段。螺筒的温度根据聚合分子量的要求设定为70～175℃。由于聚合分子量设计不大，且由于混合单体中预先溶解了质量达25％的SBS热塑性弹性 体，所以聚合直接处于自动加速效应区，因而聚合速率很高，因而单一挤出机即可完成聚合。且在其19段螺筒的倒数第4段螺筒前加装了图2、图3所示的惰性气体导入单元，并连接二氧化碳惰性气体。并在倒数第4段螺筒后配置了绝对气压为0.0012MPa的减压系统。反应挤出聚合的最终聚合物经充分脱挥以后得到，聚合转化率为99.999％。其经过精制后的经GPC分析，其数均分子量为4920，分子量分布为1.54。聚合物的分子量及其GPC曲线如图8所示。
采用实施例2的共聚物改性河南神马公司的尼龙66，其结果如表1所示。
表1 实施例2改性尼龙66的配比与性能
Figure PCTCN2017078308-appb-000002
可以看到，实施例2对于尼龙66树脂抗冲击性能有着极为有效地改善，而且对其他力学性能并没有明显的影响。材料也没有出现明显的相分离，可见是尼龙极好的一种改性树脂。
实施例3:
选取苯乙烯(St)作为乙烯基单体，选取丙烯腈(AN)以及甲基丙烯酸环氧丙酯(GMA)作为乙烯基共聚单体，三者的质量比为69.9:30:0.1。由于AN以及GMA与St的竞聚率均小于1，因此共聚物的组分比可以视为与原料比相同，故而没有必要考虑强化那种原料须先期强化反应。
将St、AN以及GMA三者均匀混合在一起，并于其中加入该三者总量0.80％质量分数的过氧化苯甲酰(BPO)，然后以1.54kg/h的计量速率，采用极限压力为15MPa的隔膜泵输入一台Ф40，长径比：L/D＝65，如图1所示具有反流向结构的同向旋转紧啮合双螺杆挤出机的第一螺段，螺筒的温度根据聚合分子量的要求设定为70～110℃。经第一阶双螺杆聚合后的乙烯基共聚物预聚体，直连接至第二阶双螺杆挤出机上，其为一台长径比：L/D＝75，异向旋转双螺杆挤出机。其共计19段螺筒的倒数第6段螺筒前加装了图2、图3所示的惰性气体导 入单元，并连接二氧化碳惰性气体。惰性气体导入单元后的6段螺筒后为脱挥螺段，配置了绝对气压为0.0012MPa的减压系统。选取与第一阶挤出机输入相同质量比的单体St:AN:GMA＝69.9:30:0.1与异丙苯过氧化氢(IPBP)配成质量比为99.23:0.77溶液，以两台极限压力为15MPa的隔膜泵，以1.038kg/h的计量速率，分别输入第二阶挤出机的第2以及第5段螺筒。挤出机螺筒温度控制在100～200℃，反应挤出聚合的最终聚合物经充分脱挥以后得到，聚合转化率为99.999％。其经过精制后的试样经GPC检测其数均分子量为3.2×104，重均分子量为4.6×104，PDI为1.44。
采用实施例3共聚物作为ABS塑料与尼龙、聚碳酸酯(PC)、聚对笨二甲酸丁二醇酯(PBT)、聚对笨二甲酸乙二醇酯(PET)等塑料合金的相容剂，可以得到十分理想的结果。加入量仅需总量5-10％即可得到不存在宏观相分离的合金。
实施例4:
选取苯乙烯作为乙烯基单体，选取甲基丙烯酸环氧丙酯作为乙烯基共聚单体，两者的质量比为99.99:0.01。由于St与GMA的竞聚率均远小于1，因此共聚物的组分比可以视为与原料比相同，故而没有必要考虑强化那种原料须先期强化反应。于其中加入该二者总量0.75％质量分数的偶氮二异丁腈。选取直径为80nm的纳米级二氧化硅作为功能化助剂，其表面经过KH550硅烷偶联剂的处理。选取上述两种混合单体与纳米二氧化硅的质量比为90.25:9.75，充分混合成悬浮液。然后以1.82kg/h的计量速率，采用极限压力为16MPa的齿轮泵输入一台Ф40，长径比：L/D＝75，如图1所示具有反流向结构的同向旋转紧啮合双螺杆挤出机的第一螺段，螺筒的温度根据聚合分子量的要求设定为70～100℃。经第一阶双螺杆聚合后的乙烯基共聚物预聚体，通过一个熔体泵连接至第二阶双螺杆挤出机上，其为一台长径比：L/D＝75，19段螺筒的异向旋转双螺杆挤出机。其倒数第5段螺筒前加装了图2、图3所示的惰性气体导入单元，并连接二氧化碳惰性气体。惰性气体导入单元后的5段螺筒后为脱挥螺段，配置了绝对气压为0.0012MPa的减压系统。选取与第一阶挤出机输入相同质量比的单体St:GMA＝99.99:0.01与异丙苯过氧化氢(IPBP)配成质量比为99.23:0.77溶液，以两台极限压力为15MPa的隔膜泵，以1.038kg/h的计量速率， 分别输入第二阶挤出机的第2以及第5段螺筒。挤出机螺筒温度控制在100～200℃，反应挤出聚合的最终聚合物经充分脱挥以后得到，聚合转化率为99.999％，试样完全透明。其经过精制后经GPC检测其数均分子量为2.98×105，重均分子量为4.68×105，PDI为1.57。
比较例2:
所有实施措施均与实施例4相同，唯独有的区别是在混合单体中不添加纳米二氧化硅，得到的共聚物经过精制后经GPC检测其数均分子量为2.92×105，重均分子量为4.44×105，PDI为1.52。
表2 聚苯乙烯物理性能对比
Figure PCTCN2017078308-appb-000003
由表2中聚苯乙烯共聚物性能的对比可以看到，含有纳米二氧化硅的实施例4得到的聚苯乙烯共聚物不仅完全透明，而且抗拉、弯曲以及抗冲击强度均比不含纳米二氧化硅共聚的比较例2得到的聚苯乙烯共聚物要高，尤为突出的是表面硬度提高较大，致使材料表面的耐划伤性能有明显提高。

Claims (13)

  1. 一种乙烯基单体反应挤出共聚合的方法，其特征在于：将乙烯基单体或和至少一种乙烯基共聚单体以及引发剂送入双螺杆挤出机的第一螺段，并在后面的螺段添加改性树脂；在系统进入自动加速区后的螺段继续补加相应单体，在引发剂过半衰期后继续补加与螺筒温度相应的引发剂，以及用于改性的微纳米无机改性材料；并在聚合终止时加入抗氧剂与抗紫外剂，然后通过脱挥螺段脱除未聚合的单体以及副产物；通过控制不同螺段的温度，反应挤出聚合得到预定分子量为5×102至6×105的乙烯基共聚树脂。
  2. 一种乙烯基单体反应挤出共聚合的方法，其特征在于：将乙烯基单体或和至少一种乙烯基共聚单体以及引发剂送入第一阶双螺杆挤出机的第一螺段，并在后面的螺段添加改性树脂；在系统进入自动加速区后的螺段继续补加相应单体，在引发剂过半衰期后继续补加与螺筒温度相应的引发剂，以及用于改性的微纳米无机改性材料，挤出得到乙烯基共聚物预聚体；将乙烯基共聚物预聚体送入第二阶双螺杆挤出机，继续补加乙烯基单体与引发剂，并在聚合终止时加入抗氧剂与抗紫外剂，然后通过脱挥螺段脱除未聚合的单体以及副产物；通过控制不同螺段的温度，反应挤出聚合得到预定分子量为5×102至6×105的乙烯基共聚树脂。
  3. 根据权利要求1所述的乙烯基单体反应挤出共聚合的方法，其特征在于：所述的双螺杆挤出机为双螺杆动力入口耐压0.3MPa以上不泄漏的，或者为反流向结构的紧啮合双螺杆挤出机，该双螺杆挤出机设有惰性气体导入单元和脱挥螺段，惰性气体导入单元将惰性气体导入脱挥螺段。
  4. 根据权利要求2所述的乙烯基单体反应挤出共聚合的方法，其特征在于：所述第一阶双螺杆挤出机为双螺杆动力入口耐压0.3MPa以上不泄漏的，或者为反流向结构的紧啮合双螺杆挤出机，所述第二阶双螺杆挤出机为同向或异向旋转双螺杆挤出机；第二阶双螺杆挤出机设有惰性气体导入单元和脱挥螺段，惰性气体导入单元将惰性气体导入脱挥螺段。
  5. 根据权利要求1或2所述的乙烯基单体反应挤出共聚合的方法，其特征在于：所述改性树脂与乙烯基单体及乙烯基共聚单体的总质量比为 0-30:100-70；所述引发剂的加入量为所有乙烯基单体总量的0-20wt％；所述纳微米无机改性材料的加入量为乙烯基单体及乙烯基共聚单体总质量的0-30wt％；所述抗氧剂与抗紫外剂两者的质量比为2:1-1:2，抗氧剂与抗紫外剂的加入量为反应物总量的0.1-1wt％。
  6. 根据权利要求1或2所述的乙烯基单体反应挤出共聚合的方法，其特征在于：所述的乙烯基单体或乙烯基共聚单体选自苯乙烯、α-甲基苯乙烯、二乙烯基苯、丙烯腈、丁二烯、异戊二烯、甲基丙烯酸、甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丁酯、甲基丙烯酸戊酯、甲基丙烯酸羟乙酯、甲基丙烯酸β-羟丙酯、甲基丙烯酸环己酯、甲基丙烯酸环氧丙酯、丙烯酸、丙烯酸乙酯、丙烯酸丁酯、丙烯酸戊酯、丙烯酸羟乙酯、丙烯酸β-羟丙酯、丙烯酸环己酯、丙烯酸环氧丙酯、甲基丙烯酸多环降冰片烯酯、甲基丙烯酸双环戊烯酯、甲基丙烯酸苯酯、甲基丙烯酸对氯苯酯、甲基丙烯酸金刚烷酯、甲基丙烯酸异冰片酯、乙烯基吡啶、马来酸酐、顺丁烯二酸、富马酸、顺丁烯二酸单酯、顺丁烯二酸二酯、富马酸单酯、富马酸二酯、N-甲基马来酰亚胺、N-环己基马来酰亚胺、N-苯基马来酰亚胺、N-甲苯基马来酰亚胺、N-邻氯苯马来酰亚胺、十一碳烯酸、衣康酸、衣康酸酯、山梨酸、山梨酸酯、四氟乙烯、六氟乙烯、偏氟乙烯、氯乙烯、偏氯乙烯、乙烯基异氰酸酯或丙烯酰氯中的一种或几种。
  7. 根据权利要求1或2所述的乙烯基单体反应挤出共聚合的方法，其特征在于：所述的引发剂选自无机过氧化物、有机过氧化物、偶氮类引发剂或氧化还原引发剂中的一种或几种；
    所述的无机过氧化物包括过硫酸钾、过硫酸钠或过硫酸铵；
    所述的有机过氧化物的通式为：R-O-O-R’，其中R，R’可以是H，烷基，酰基或碳酸酯，R，R’可以相同，也可以不同；
    所述的偶氮类引发剂包括偶氮二异丁腈或偶氮二异庚腈；
    所述的氧化还原引发剂包括异丙苯过氧化氢-亚铁盐或有机过氧化物-芳叔胺体系。
  8. 根据权利要求1或2所述的乙烯基单体反应挤出共聚合的方法，其特征在于：所述的改性树脂选自丁苯橡胶、丁腈橡胶、天然橡胶、苯乙烯-丁二烯-苯乙烯三嵌段共聚物、苯乙烯-异戊二烯-苯乙烯三嵌段共聚物、氢化苯乙烯-丁 二烯-苯乙烯三嵌段共聚物、氢化苯乙烯-异戊二烯-苯乙烯三嵌段共聚物、苯乙烯/丁二烯无规共聚物类热塑性弹性体、甲基丙烯酸甲酯-甲基丙烯酸丁酯微纳米级二嵌段共聚物、丙烯酸甲酯-丙烯酸丁酯微纳米级二嵌段共聚物、甲基丙烯酸甲酯-丙烯酸丁酯微纳米级二嵌段共聚物、甲基丙烯酸甲酯/甲基丙烯酸丁酯无规共聚物、甲基丙烯酸甲酯/丙烯酸丁酯无规共聚物、苯乙烯-丁二烯-甲基丙烯酸甲酯微纳米级三嵌段共聚物、苯乙烯-异戊二烯-甲基丙烯酸甲酯微纳米级三嵌段共聚物、热塑性聚氨酯，以及乙烯基单体及乙烯基共聚单体共聚物自身中的一种或几种。
  9. 根据权利要求1或2所述的乙烯基单体反应挤出共聚合的方法，其特征在于：所述的纳微米无机改性材料选自微纳米级二氧化硅、微纳米级碳酸钙、微纳米级三氧化二铝、微纳米级氢氧化铝、微纳米级氢氧化镁、微纳米级五氧化二钽、微纳米级晶须、微纳米级石英、微纳米级氧化鈰、微纳米级氧化銪、微纳米级氧化锆、微纳米级氧化钡或微纳米级氧化镧中的一种或几种。
  10. 根据权利要求1或2所述的乙烯基单体反应挤出共聚合的方法，其特征在于：所述的抗氧剂选自市售抗氧剂168、抗氧剂1076、抗氧剂bht、抗氧剂B215、抗氧剂245或抗氧剂1010，硫代二丙酸二(十八酯)、亚磷酸二苯异辛酯、四[甲基-β-(3,5-二叔丁基-4-羟基苯基)丙酸酯]季戊四醇酯、1,3-三(2-甲基-4-羟基-5-特丁基苯基)丁烷、1,1,3-三(2-甲基-4-羟基-5-叔丁基苯酚)、3,5-二特丁基-4-羟基苯丙酸十八酯、2,2’-亚甲基双(4-甲基-6-特丁基)苯酚、4’4-硫代双(6-叔丁基邻甲酚)、4,4’-硫代双(3-甲基-6-叔丁基)苯酚、4’4-(二羟基-3,3’,5,5’-四叔丁基联苯)中的任意一种或数种复配；所述的抗紫外剂选自UV-531、UV-9、UV-326、UV-327、UV-328、UV-329、邻羟基苯甲酸苯酯、邻硝基苯胺或对甲苯酚中的任意一种或数种复配。
  11. 根据权利要求3或4所述的乙烯基单体反应挤出共聚合的方法，其特征在于：所述的双螺杆挤出机的长径比为48/1以上，螺杆转速为2-300rpm。
  12. 根据权利要求3或4所述的乙烯基单体反应挤出共聚合的方法，其特征在于：所述惰性气体包括二氧化碳、氮气、氦气、氩气、丁醇、酒精或水蒸气。
  13. 根据权利要求1或2所述的乙烯基单体反应挤出共聚合的方法，其特 征在于：所述乙烯基单体与乙烯基共聚单体的竞聚率均要小于等于1，否则，必须按照在共聚物中含量的要求，在不同螺段添加竞聚率低的单体。
PCT/CN2017/078308 2016-04-11 2017-03-27 一种乙烯基单体反应挤出共聚合的方法 WO2017177813A1 (zh)

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