TW399061B - Process for preparing methacrylic polymer - Google Patents

Abstract

A process for continuously preparing a methacrylic polymer is herein disclosed which comprises continuously polymerizing methyl methacrylate alone or a monomer mixture of methyl methacrylate and an alkyl acrylate in accordance with a solution polymerization using methanol as a solvent, directly feeding the resulting polymerization reaction product to an extruder having a plurality of vents, and extruding the polymer, while a volatile content is removed through the vents. According to the present invention, there can be provided a process for preparing a methacrylic polymer having an excellent quality with a high productivity.

Description

Printed by A7 B7, Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the Invention (l ·) Invention of (i) Hairpin Jaw City This invention is related to the method of making methacrylic acid polymer, and it is more detailed In other words, it is related to a method for producing a methacrylic polymer that can be used as an injection molding material and / or for extruding a rheological material β (i Π phase 鼸: > Motoyoshi 昍 methacrylic 糸 polymer has transparency Excellent weatherability and appearance, and therefore they have been used not only as signals, display and glazing materials as optical materials. To date, they can be used as injection molding materials and / or for extruded materials. The manufacturing method of acrylic acrylate polymer generally uses a suspension polymerization method, but in this method, the polymer is disturbed by a second material such as, and for this reason, it is difficult to obtain a high-purity polymer. The polymer prepared by this method is similar to the chemical bond. In addition, the post-processing steps of the polymer include filtration, washing and drying, and complicated operations that must treat a large amount of wastewater. Therefore, the suspension polymer The method is still not enough as an industrial method. As other manufacturing methods of the methacrylic strip polymer, there are a bulk polymerization method, a solution polymerization method, and the like. So far, the bulk polymerization method has been used for the manufacture of prepolymers that are polymerized, It has been indicated, for example, in Japanese Patent Publications 3392/1961, 19697/1961, 4794/1963, 1 3 5 3 6/1 9 6 3, 3 7 0 1/1 9 6 5 and 36 1 5 5/1 9 7 7, and the solution polymerization method has been used in the manufacture of polymers with relatively low molecular weight suitable for coating materials or the like, and it has been indicated, for example, that the Chinese national standard (CNS) A4 specification is applicable to the Japanese paper standard (210X297mm) (Please read the notes on the back before filling out this page) Order A7 ____B7 _ V. Description of the invention (2) Profit disclosure 1 ΗΠ 8 6/1 9 7 4, 1 2 8 0/1 9 7 8 And German patent DEP 2161909.0. In recent years, as a technology that can manufacture injection molding materials and / or materials for extrusion and can overcome the shortcomings of suspension polymerization methods, a lot of attention has been paid to the continuous polymer polymerization method. Itchy and tangled solution polymerization % Methods. These methods allow the manufacture of high-quality resins with excellent optical properties because no suspension dispersant or the like is used. Japanese Patent Publication 32665/1977 has proposed a flail bulk polymerization method in which polymerization is performed by using a tank Type reactor 'performs relatively low monomer conversion and then separates and removes unreacted monomers continuously. Furthermore, Japanese Patent Publication 111408/1991 has shown a continuous bulk polymerization method in which special reaction conditions are used to The ratio of the half-life of the radical polymerization initiator to the average residence time can be defined in a single entangled mixing tank reactor under agitation to provide a uniform reaction mass and so the concentration of the polymerization initiator in the reactor can be controlled. In addition, another bulk polymerization method has been disclosed in Japanese Patent Publication 1 8 6 9 4/1 9 8 5 and Japanese Patent Publication 1 35 7 0 2/1 9 89. ^ ϋ ·-^ sn- ^ 101 n ^ i I ml n ^ i, you 々In n nn --eJ (please read the precautions on the back before filling this page), and then the continuation of the French conglomerate should be applied .1 It is said that the printing of the consumer co-operatives of the Central Standards Bureau of the Ministry of Economic Affairs should be effective. .M and la should be anti-converged, and the stability of the system should be guaranteed. The system method is not necessary. The reason is that it is difficult to get together with this f 0 thing. It is often the most non-trivial way to concentrate the concentration of objects. In order to use as much as possible, it is necessary to use too much to consume and eliminate the necessary steps. The single gas should be reversed. The degree of concentration is concentrated. The large amount of heat is added to the receiver to gather. Due to the circumstances, it is not easy for this paper to be allowed to grow. This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm). A7 B7 V. Description of the invention (3) and degradation. On the other hand, as shown in Japanese Patent Publication No. 7845/1980 and the like, it has been known that according to a continuous solution polymerization method, for example, a solution polymerization method in which benzene or an alkylbenzene is used as a solvent, since the viscosity of the solvent reaction solution is reduced, The gel effect is suppressed and the stable polymerization reaction can be used for high monomer conversion. Moreover, Japanese Patent Publication 20830 8/1990 has shown a method for preparing a high-purity methacrylic strip resin by using a special inert solvent. Furthermore, Japanese Patent Laid-Open No. 20013/7; 1989 has shown a method in which solution polymerization of a monomer mixture containing methyl methacrylate as a main component is used by not less than 5% by weight and less than 30% It is carried out in a mixed solvent containing a monovalent alkyl alcohol and benzene or a noble benzene by weight. However, • In this method, the monovalent alkyl alcohol only accounts for 5 to 50% by weight of the mixed solvent, and therefore the method cannot be basically changed like the ordinary method using benzene or an alkylbenzene as a solvent. Another solution polymerization method has been shown in Japanese Patent Publication No. 2 2 0 0/19 6 5. And Japanese Patent Publication 28 7 00 2/1 9 9 3 0 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page) Even if you follow these continuous ore solution polymerization methods, if When polymers obtained by any of these methods are used as injection molding materials and / or materials for extruded sheets, volatile inclusions containing unreacted monomers, solvents and the like (which are polymerized It is unavoidable to remain in the polymer solution after the completion of the). As a technique for removing volatile contents from the polymerization product, a method has generally been used which includes heating the polymerization product to a high temperature and then guiding the heated product to a vacuum. The paper ruler applies the Chinese National Standard (CNS) Α4 Specifications (210X297 mm) A7 B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (4) 1 Evaporation / separation of volatile contents from it at atmospheric pressure This method is suitable for industrial-scale production of 1 1 cm. 0-please 1 first] For example, 1 Japanese Patent Publication 1 1 9 2 5 9/1 S 9 5 has been shown— > Method 1 Contains 40% by weight or more of selected white benzene 9 toluene and benzene benzene back! I 〆V of 1 solvent solution for continuous solution polymerization. That is to say 9 this side note 1 I method includes two consecutive entanglement Polymerization is carried out in the mixing tank reactor while the matter 1 |% is maintained under reduced pressure 9 and a portion of the obtained crude polymer is discharged. F Filling% hot crude polymer 9 is led to the rinse tank. 9 in which it is vented to make a page ___ " 1 I melt the polymer while avoiding the formation of foam scale > add some additives 1 1 'to 9 and then granulate the polymer 0 1 In addition 9 this patent publication 1 3 3 3 0 3/1 9 9 5 and 1333 11/19 95 have stated a method for conducting continuous solution polymerization in which a homogeneous system is maintained by using methanol as a solvent. However, this method is 9 With 1 there are many industrially-resolved problems 9 and 9 for example 9 have the resulting polymer 1 I after taking out the shape of the foam product once after the polymerization step. Question 1 1 Question 9 and then it is necessary to use an extruder to mold again in the step 0 'In the case of such a continuous solution polymerization method 9 there is a limit to reducing the amount of I of the solvent 9 and even if the Btt early body is transformed Increasing t The amount of volatile contents of the remaining 1 1 containing the solvent cannot be reduced, although 1 I is unreacted in the reaction solution. The amount of precursors may be reduced. Result 9 This method needs to be removed. The energy consumption of sexual contents is different from the overall polymerization method when it is 1 1 and it is different. In addition, this method also has, for example, the degradation of the polymer's heat resistance, the degradation of I and the recovery and reuse of monomer components. Question 1 1 1 1 1 1 This paper size is applicable to Chinese National Standard (CNS) A4 format (210X297 mm). Printed by A7 B7, Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. 5. Description of the invention (5). Regarding thermal decomposition resistance, it has been reported that in the thermal decomposition reaction of methacrylic strip polymers, the decomposition of the zipper (starting from the CC single bond adjacent to the terminal double bond) usually occurs at 23Q to 27Q ° C. Around temperature, and has also been reported to maintain extremely weak head-to-head bonds (cracking at 200 ° C or below) when using low polymerization temperatures such as less than 100 ° C [K. Hatada, T. Kitayama and E Masuda, Polyn, J., Vol. 1 (5), p. 395 (1986), and T. Kashiwagi, A. Inaba, E. Brown, K. Hatadafn E. Masuda, " Macromolecules " , Vol. 19, p. 2160 (1986) K In order to improve the thermal decomposition resistance of the methacrylic strip polymer, it is necessary to suppress the zipper decomposition and head-to-head bond cleavage reaction just described. In order to suppress the decomposition of zipper, the ratio of the terminal double bond of the polymer must be reduced, and in order to inhibit the cracking of the head-head bond, the temperature of the polymer must be set at 1QQ ° C or above to suppress the formation of the head-head bond. . The polymer having a double bond at the terminal and / or the polymer having a head-to-head bond is thermally weak, so the polymer is at least partially heated when it undergoes the thermal history of the extrusion step and during injection molding or the like. break down. As a result, some practical troubles occurred. For example, molding defects such as silver streaks and blistering occur, and unpleasant odors of the decomposition products occur. In view of these disadvantages, it is very important to control the thermal decomposition resistance of polymers that are not subjected to the extrusion step. For example, Japanese Patent Bulletin 72213/1995 has stated that a methacrylic paper with excellent thermal decomposition resistance (which can be expressed by the thermal decomposition index "") is applicable to the Chinese National Standard (CNS) A4 specification (210 × 297 mm) ( (Please read the notes on the back before filling out this page) Order A7 B7 Printed and Invented by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (6) Method for making enoic acid strip resin. In addition, Japanese Unexamined Patent Publication No. 2943〇t / 1991 has shown that the polymer terminal double can be prepared by the Jianao bulk polymerization method and wherein it is measured by the use of gel-dye chromatography (CPC) and nuclear magnetic resonance (NMR) measurements. The bond ratio is 2.5% by weight or less of methacrylate acrylic resin. However, in this announcement, nothing is described to control thermal decomposition.

V number or terminal double bond determination conditions. Japanese Patent Publications 206904/1995, 206905/1995 and 206906 / I " 5 and Japanese Patent Application No. 57362/1995 have described a polymerization method in which the amounts of a polymerization initiator and a chain transfer agent are thermally decomposed based on thermogravimetric analysis The ratio is adjusted to improve the thermal decomposition resistance in the polymerization step. However, this method has a problem that the resulting polymer is liable to be colored in the exhaust step. Examples of the technique for removing the remaining monomers, solvents, and the like from the polymer composition obtained by the above-mentioned polymerization reaction are described in Japanese Patent Publications 18393/1976, 30428/1979, 30670/1979, 3 6 1 8 2/1 9 7 9 and 5 0 4 4 1/1 9 8 0 There have been proposed volatile devices represented by flushing tanks; a type that uses a screw type evaporator to finally remove volatile contents through a screw tube evaporator The method is described in Japanese Patent Publication No. 43242/1981; and a method comprising heating a polymerized product, feeding it directly into an exhaust-type extruder or the like, and then collectively performing a series of post-treatments such as exhaust gas, mixing of additives And granulation methods. As an example of the exhausting method, for example, Japanese Patent Laid-Open No. 89710/1987 has shown a method which includes heating a methacrylic polymer product to a high temperature and putting it into a row having a space section at the upper part thereof-8 -This paper size is in accordance with Chinese National Standard (CNS) A4 scale (210X297 mm) (Please read the precautions on the back before filling in this page) ·-· Order-Μ B7 V. Description of the invention (7) To remove volatile content therefrom, and then feed the product into a vented extruder to reduce the remaining volatile content to 1% by weight or less. In addition, Japanese Patent Publications 17555/1977 and 29914/1976 and Japanese Patent Publications 17516/1993 and 148311/1993 have reported a method including heating a methacrylic acid strip polymer prepared by a bulk polymerization method or a solution polymerization method to a At high temperature, it is directly blow-molded, and through the fine orifice, the feed screw of the exhaust extruder maintained at a pressure less than atmospheric pressure to separate and recover most of the volatile content, and then maintain it in it At the temperature of 250 to 2 90 ° C and the decompression downstream exhaust port to separate the remaining volatile contents. Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) However, in this method, the inside of the exhaust tank needs to be heated to a high temperature of 200 ° C or more, and the polymer tends to be easily stagnated on the hot wall of the tank over a long period of time, so the quality of the polymer deteriorates. doubt. Because monomers, alkylbenzenes, and the like have a strong affinity for polymers, and their less volatility, the need for an extruder with a high exhaust force with multi-stage exhaust ports must facilitate direct processing. The exhaust of the extruder must be maintained at high temperature under high vacuum for the polymerization product of high concentration of volatile contents. In view of this operating environment, the use of this method in the industrial method also has the problem of increased equipment costs. Japanese Patent Laid-Open No. 194004/1990 has described a method including mixing a pressurized and melted polymerization product and a supercritical state extraction gas, and then reducing the pressure to remove that volatile content from the product. However, in order to apply this supercritical state to the industrial entanglement method, it is necessary to increase the paper size to apply the Chinese national standard (CNS > A4 size (210X 297 mm)), printed by the Central Standards Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperative, printed A7 B7 V. Description of the invention (8) The pressure resistance of the instrument, which leads to many problems such as increased equipment cost. On the other hand, Japanese Patent Publications 86492/1994 and 37482/1995 have shown a method including performing a method mainly including methyl methacrylate The radical polymerization of an ester in a solvent such as an aliphatic monovalent alcohol such as methanol or an aliphatic hydrocarbon such as hexane, followed by precipitation and separation such as

V The resulting polymer. However, this method has many problems that should be solved in industrial applications. For example, a large amount of solvent is used, such as 80 to 30 parts relative to 20 to 70 parts of single p component, and in order to separate the polymer, a precipitation step, a filtration step, and a drying step are necessary. The polymer slurry must be delivered and processed in a fixed composition. In addition, in Japanese Patent Laid-Open No. 1 3 3 3 1 2/1 9 9 5, another method is shown, which includes successive solution polymerization in a water-methanol mixed solvent system, and then cooling and pressing the polymer thus obtained. To separate from it. However, in this method, a step in which the polymer is further molded by extrusion is required, so that the method is complicated / the use thereof is an industrial method which raises a problem of increasing equipment cost. Therefore, the present invention has solved the problems of the conventional techniques described above, and an object of the present invention is to provide a method for economically and advantageously preparing a high-quality methacrylic acid strip polymer by controlling the polymerization reaction stably. Inventory stockings The inventors have discovered that most of the volatile content can be efficiently removed from the polymer component. The continuous feed contains a constant amount of methanol as a solvent, methyl methacrylate alone or Methyl acrylate and propylene-10- This paper ruler: Applicable to China National Standard (CNS) A4 scale (210X297 mm) (Please read the precautions on the back before filling this page) tr. Staff of the Central Bureau of Standards, Ministry of Economic Affairs Consumption cooperative printing bag A7 B7 V. Description of the invention (9) The monomer components composed of acid alkyl ester, the solution of the substance of the bond transfer agent and the polymerization agent are sent to the polymerization reactor for polymerization, and the polymer products are continuously discharged. In part, it is heated and then fed to the screw of the extruder through a feed port that is maintained at substantially atmospheric pressure. In addition, it has been found that high-quality polymers that can be used as forming materials can be used without trouble ( E.g.

V color), and maintains high productivity stably. The remaining volatile content is removed from the polymer composition by an exhaust port on the downstream side, and then it is extruded. To conclude, the present invention is completed based on these findings. That is to say, the present invention is related to a method for preparing a polymer, which includes the following steps: (1) polymerization in a polymerization tank containing one or two consecutive links The reactor is stirred with methyl methacrylate alone or 0.1 to 160 millimoles / liter polymerization initiator with a half-life of 0.6 to 60 minutes at the polymerization temperature and 0.1 to 370 millimoles / liter bond The monomer mixture of the transfer agent in a homogeneous solution, based on 71 to 95 parts by weight of methyl methacrylate alone or containing 75% by weight or more of methyl methacrylate and 25% by weight or less of propylene alkyl esters and Continuous polymerization of 29 to 5 weights of a mixture of monomer mixtures containing methanol as a solvent (diluent) to provide a homogeneous solution reactant so that the monomer conversion rate can be from 1 QD to 1 8 G ° C. The polymerization temperature can be between 5 5 To 93% by mole, and (2) at a temperature of 130 to 27 (TC), the polymerization product discharged from the polymerization reactor is directly fed to a barrel having a setting of 170 to 27 Q ° C Extruder with several exhaust ports at temperature, and extruded polymer product from extruder At the same time, most of the volatile content is separated and recovered through the exhaust port of the extruder, and at the same time the remaining volatile content is passed through at least one other downstream exhaust port, which sets the exhaust port pressure of 1 to 400 mm Hg- 11- Paper rule: Applicable to Chinese National Standard (CNS) Α4ί! Grid (2 丨 OX297 mm) —: --- r ----- ^ 装 ----- ^ J ------ A (Please read the precautions on the back before filling out this page) Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs A7 B7 V. Description of the invention (10) Removal 'to prepare the content of the remaining volatile contents Polymers having a weight average molecular weight in the range of 80,000 to 200,000 and a thermal decomposition ratio of 3.0% by weight or less, as measured by GPC, at 1% by weight or less. The thermal decomposition ratio refers to the weight reduction of samples heated at 2 ° C / minute in the range of 30 to 300 eC, relative to the weight of the sample during thermogravimetric analysis (where the sample was dried at 80 ° C for 24 hours under 2% nitrogen). ° C / minute heating rate to the temperature of 30 to 450 ° C), the total weight of the sample, the percentage of weight. The description of the night hall Figure 1 is a view showing the outline of the device used in Example 1, and in this illustration, reference numeral 1 is a blend of substances, Shuyu 2 is a pipeline, and 3 is a fixed delivery Pump, 4 is the pipeline, 5 is the inlet, 6 is the reactor equipped with a jacket, 7 is the motor, 8 is the stirring shaft, 9 is the stirring forbidden piece, 10 is the steam exhaust line, 11 is the condenser, and 12 is the reflux The pipeline, 13 is a fixed delivery pump, 14 is a pipeline, 15 is a heater, 16 is a pipeline, 17 is a control valve, 18 is an extruder, 19 is a first exhaust port, and 20 is a polymerization. Product inlet, 21 is additive blending tank22 is pipeline, 23 is additive inlet, 24 is second exhaust port, 25 is die of extruder, 26 is ribbon polymer, 27 It is a water bath, 2δ is a pelletizer, 29 is a pellet, 30 is a pipeline, 31 is a pipeline, 32 is a distillation column, 33 is a valve, 34 is a pipeline, 35 is a pipeline, 36 is a condenser, 37 is a pipeline, 38 It is a receiving pipe, 39 is a pipeline, 4D is a fixed delivery pump, 41 is a pipeline, 42 is a heat exchanger, 43 is a pipeline, and 44 is a vacuum device. The second part is a view of the outline of the device used in Example 2, and this figure-12- This paper size applies the Chinese National Standard (CNS) Α4 grid (210X297 mm) (Please read the precautions on the back before filling On this page), Order A7 B7 printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs. 5. In the description of the invention (u), reference numeral 51 is a material joint groove, numeral 52 is a pipeline, 53 is a fixed delivery pump, and 54 is a pipeline. , 55 is the inlet, 56 is the first reactor equipped with a jacket, 57 is a motor, 58 is a search partner shaft, 58 is a pseudo-associated leaf M, 60 is a steam exhaust line, 61 is a condenser, and 62 is a reflux. Line '63 is a fixed delivery pump, 64 is a line, 65 is a side-feed material tank, 66 is a line, 67 is a fixed delivery mill '68 is a line, 69 is a valve, 70 is a line, 71 is The inlet, 72 is the second reactor equipped with a jacket, Ή is the motor, the stirring shaft · 7 5 · is the stirring blade '76 is the steam exhaust line, .7 7 is the condenser, and 78 is the return line' 7 9 fixed delivery springs, 80 is the pipeline, 81 is the pipeline, 82 is the control valve, 83 is the polymerization product Port, 84 is the extruder, 85 is the first exhaust port, 86 is the additive blending tank, 87 is the pipeline, 88 is the feed port of the additive '89 is the second exhaust port, 9Q is the die of the extruder Head, 91 is a ribbon polymer, 92 is a water bath, 93 is a granulator, 94 is a pellet, 95 and 96 are pipelines, 97 is a distillation column, 98 is a valve, 99 is a pipeline, 100 is a pipeline, It is a condenser, 102 is a pipeline, 103 is a receiver, 104 is a pipeline, 105 is a fixed delivery pump, 106 is a pipeline, 107 is a pipeline, a heat exchanger and 109 is a vacuum device. The description of M allows the methanol used as a solvent in the present invention to have the following characteristics. (1) Methanol can completely dissolve in the monomer components of formamidine methacrylate and / or alkyl acrylate, regardless of the temperature, and it also has a temperature of 100 ° C or above It has sufficient solubility and can maintain the homogeneity of the polymer solution in a wide concentration range. Therefore, methanol should be: -13- This paper size applies to the Chinese National Standard (CNS) A4 specification (2IOX297 mm) (Please read the precautions on the back before filling this page) V.-Order IK. Consumption cooperative prints A7 _____B7 _ 5. Description of the invention (12) The solvent used for solution polymer is desirable. (2) When methanol is used, the viscosity of the polymer solution is lower than that of a solvent such as an alkyl group when used in a methacrylic strip polymer of equivalent concentration. (3) When the polymerization product containing the flux is cooled, the solubility of the volatile v content in the polymer decreases rapidly. Therefore, the solvent is easily separated from the polymer, and the precipitation of the polymer on the inner wall of the device and the tube can be suppressed. (4) Because the boiling point of methanol is lower than that of the monomer component, the proportion of methanol in the polymerization reactor or in the weft of the reflux cooling pipe is higher than that in the liquid phase, so it can be suppressed in the reflux cooling line and the like. "Fouling on the wall". (5) Methanol has a low boiling point and is easily volatile, and it can further form an azeotropic mixture with a propylene monomer or propylene monomer with a boiling point β (6) at 80 ° At temperatures of C or below, methanol does not completely dissolve the methacrylic polymer. Π) Methanol is produced in large quantities on an industrial scale, so 'it is cheap and easy to obtain. With these special emblems, methanol is used as the solvent. The amount of solvent can be reduced, and stable operation can be performed in a polymer solution with an increased polymer concentration. In addition, because methanol can be easily separated from the polymer solution and an azeotrope can be formed to promote the evaporation of the monomer components, Methanol is not completely contained in the product, as compared to solution polymerization using alkylbenzene. As understood from the above, since it mainly contains methyl methacrylic acid mono--14- this paper 1_degree applies Chinese National Standard (CNS) A4 specification (210X297 mm) (Please read the notes on the back before filling this page) Order A7 printed by the Consumers Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs _B7_ V. Description of the invention (u) A solution polymerization method using a bulk mixture (which uses methanol as a solvent) can improve productivity and particularly simplify the exhaustion step and volatile content recovery step of a manufacturing plant, as compared to a conventional method using a solvent such as alkylbenzene. As a result, This solution polymerization method allows methyl methacrylate polymer to be economically and economically produced. The method of the present invention includes a material blending step, a polymerization step, an exhaust step, and a step of recovering volatile contents. This method will be described in the order of these steps. In the substance blending step, a predetermined amount of monomer components, methanol, a bond transfer agent and a polymerization initiator are combined, and the mixture is then continuously fed into a polymerization reactor. In the meantime, if older children's ingredients are needed, they can be mixed with the condensed solution delivered from the volatile content recovery step after composition analysis. Thus, the recycled material can be used in a recycling manner. The monomer components that can be used in the present invention can be methyl methacrylate alone or those containing 75% by weight or more of methyl methacrylate and 25 weight children or The monomer mixture of the following alkyl acrylate, and the monomer mixture of the present invention, does not substantially contain unsaturated aliphatic hydrocarbons such as ethylene, unsaturated aromatic hydrocarbons such as styrene, unsaturated acetic acids such as acrylic acid, methyl Acrylic acid, fluorene-butenedioic acid and its anhydrides, unsaturated chlorinated hydrocarbons such as ethylene gas and / or vinyl esters such as vinyl acetate. Alkyl acrylates are alcohols derived from alkyl groups having 1 to 8 moles Examples of acrylates include methyl acrylate, ethyl acrylate, n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, iso-butyl acrylate, tertiary-butyl acrylate, acrylic acid 2- -15- This paper size applies to Chinese National Standard (CNS) A4 (210X297 mm) (Please read the precautions on the back before filling this page)

、 A7 _B7 _____ printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (14) Ethylhexyl and n-octyl acrylate, and the preferred acrylic acid is selected from the group consisting of propylene methyl ester and ethyl acrylate And n-butyl acrylate. These acrylates may be used singly or in a combination of two or more thereof5 but a monomer mixture including 75% by weight or more of methyl methacrylate and 25% by weight or less of methyl acrylate is particularly preferably used. The polymerization activity of methyl methacrylate is different from that of alkyl acrylate, and therefore the monomer composition in the substance is not the same as the copolymer composition, but the relationship between these two components is determined by T akay uk i 〇tsu, " Chemistry of Polymer Synthesis ", Kagaku Doujin (1979) and similar techniques described by the like can be easily determined. a In the present invention, it is important that methanol is used in a monomer component of 29 to 5 parts by weight and 71 to 95 parts by weight, and preferably 25 to 7 parts by weight based on 75 to 93 parts by weight of the monomer component. If the amount of the monomer component is less than -71% by weight, the productivity is low, and the load of the exhaust step and the recovery step of the volatile content is high, which is a disadvantage from the viewpoint of energy consumption. Except that, the selectable molecular weight range is limited, and the thermal decomposition resistance of the obtained polymer is significantly deteriorated. On the contrary, when it is more than 95% by weight, the viscosity of the polymer solution increases, and it is not easy to control the polymerization stably when it is in bulk polymerization. In the present invention, a polymerization initiator that is decomposed at the polymerization temperature to produce a living ® is used, but this polymerization initiator needs to achieve the required polymerization ratio in the range of the average residence time, and it should conform to the polymerization at the polymerization temperature The half-life of the initiator is in the range of 0.6 to 6 minutes, preferably 1 'to 30 minutes. Examples of free radical polymerization initiators include over-gasification II-Third-1 6-This paper size is applicable to Chinese National Standard (CNS) A4 Tongge (210X297 mm) (Please read the precautions on the back before filling this page ) Order 4-1 1 ^ 02W ^ > ^ svy ^ ^

_8 stuffed 9¾¾ 聃, s S, 1-4 鼽 ®, 2 —called Qin 8,1- 卅 翦 0, HIIThupiss * Ν — flllMll ^ is »Nlfll—Μ ——τ 丨 筘 is, 2-fll-2— 3 翦 8, 3 —mis @ 却 8 * 3 丨 Tiefu 31S batch s, s Μ I i I N- ® s M s ο Ri — Φ ^-— Yaner_ 38 ® ^ s, m ^ s_5 $ ol 13TO ^^ w \ Half 3S Li 3 0 SW ^ ISISSISU ^ S 3S,, 3 Sweep 1 s ^ ®; SS18ISSISHS3S, Teng 荽 3__ 书 & Bing $ _ 令 ： & $: 000,000, 3 " & 1 ® i I 3- ϊ lw ii φ B e e * 口 卜; ^ 翊 22 2 stupid 3 8 8 选 选 3_ 占尽 薇 乡 乡 杂 | 3 3ii3 ^^? S ^-^ iss-SMWS — ^, Ί® Ning 1¾, 撖 咏 薜 乡, ISI®S8S si ^ l®elsw-8s ftsuMSVPSS '^^ ffl-, Room 笤, TathlayuKH · oc + su 地 -3ΚΦ Φ, Λ ^ υ: »wpg' ajku DOUa.incHST'too ^ aHmo'to T'atscysL • wnfoi Φ ^ s H i ft 2, z ± lcka.n Ko 5 ^ 0¾ Ϊ 5 甬 拎 3 (1S7G > 31 Migration. «IK * ylyl , I 1 3 UQ ® ^ as lettuce, ^ ® i Λ t 3 y ®, Ϊ o hang ttty swimsi ^ i, 3 ®s ^^ ιφ3β $ ο hang — cat sy road, e 18®iIel nint3SM 9 »; Si s Φ window bia & Φ ado vine i $ SJ River i miscellaneous. I 1 SI (SI) K |! H 'God!) Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Α7 Β7 V. Description of the invention (17) Dissolved oxygen in the substance makes the conversion of the monomer unstable and causes the color of the product, and therefore needs to be substantially removed. In the case of this method, a technique may be generally used which includes dispersing an inert gas such as nitrogen in a substance blending tank by a general air blowing, a disc decanter, or the like over a period of time, and continuously In the case of the method, a technique may be generally used, which includes mixing the solution with an inert gas by an in-line mixer installed on the pipeline, followed by gas-liquid separation. According to the techniques just described, the dissolved gas can be substantially removed. "After the insoluble matter is removed from the substance solution prepared by the above steps, it is fed into the polymerization reactor, preferably through a filter. Alternatively, the substance solution may be cooled and then fed, whereby the polymerization reaction may be further stably controlled. In the polymerization step, the polymerization temperature is (in the range of 100 to 18 ° C, preferably 130 to 170 ° C, and more preferably 135 to 165 ° C. If the polymerization temperature is less than 10 ° C The solubility deteriorates, so the homogeneity of the solution cannot be maintained, depending on the concentration of the polymer. B — On the one hand, if the polymerization temperature is greater than 180 ° C, the operating pressure increases, so the manufacturing cost of the reactor increases, which is economical Disadvantage. In addition, it has been reported that the formation of oligomers is increased, so it is easy to cause bleaching, which results in the deterioration of polymer quality [Fumio Ide, "Polymers", Vol. 27, p. 819, November issue ( (1978)]. In the present invention, the monomer conversion rate is 55 to 93 mole%, preferably 60 to 90 mole%, and more preferably 65 to 85 mole% β 'If the monomer conversion rate is less than 55 Mole%, exhaust step and volatile content recovery step -19- This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) --- Γ- I ----, ^ --- --Order (please read the notes on the back before filling this page) Α7 Β7 V. Description of the invention (18) Inconvenient load In order to increase the monomer conversion rate to 93 mole% or more, a long residence time is necessary, and if the unit conversion rate is 93 mole% or more, a polymerization reactor with a large capacity is required to enhance productivity. , And the viscosity of the obtained polymerization product increases. In the practical conversion range of this monomer, gel effect may occur, depending on the degree of the solvent. However, according to the method of the present invention, methanol as a solvent is reduced. The viscosity of the polymerization product and the polymerization ratio exhibiting a gel effect are increased, so that the gelling effect is suppressed and the polymerization reaction can be controlled to a stable state. The polymerization reactor includes a continuous mixing tank reactor or two-chain continuous entanglement The connected continuous-rotation mixing tank reactor is preferably a continuous mixing tank reactor. Regarding the shape of the polymerization reactor, any shape can be accepted as long as it can be completely mixed. A ring reactor can also be used, but it is more convenient. Good for a stirred tank reactor.. Printed by the Consumer Cooperatives of the Central Procurement Bureau of the Ministry of Economic Affairs

Jr— n III, ^ -II II (Please read the precautions on the back before filling this page) Connect the material solution. Continue to feed into the polymerization reactor, and when the substantially mixed state is reached, take it out immediately and continuously. Solution in the polymerization reactor》 In the case of using a stirred tank, ordinary 粲 blades and iron anchor blades can be used as the stirring blade κ, but preferably a double-spiral ribbon ribbon blade, which is manufactured by Shinko Pat6c Co., Ltd. Regional blades, Sunmeller blades and AR cymbals manufactured by Mitsubishi Heavy Industries, Ltd., and Ma xb lend leaves and Su p erb 1 e η d leaves manufactured by Sumitomo Heavy Industries Co., Ltd. The residence time is usually 2 to 7 hours per polymerization reactor, preferably 2.5 to 6 hours, and more preferably 3 to 5 hours. Small-20-This paper size applies to Chinese national standards (CNS > Α4 size ( 210X297 mm) Member of the Central Standards Bureau of the Ministry of Economic Affairs, M Consumer Cooperative, printed A7 ____ B7_ V. The scope of the invention description (l9). If the average residence time is less than 2 hours and the polymerization reaction proceeds until the monomer conversion rate of the present invention Since the heating value increases, it is difficult to control the reaction stably and the amount of polymerization initiator must be increased. In addition, if an attempt is made to obtain a desired molecular weight, the production ratio of a polymer having a terminal double bond is increased, so the thermal decomposition resistance is significantly deteriorated. If the average residence time is more than 7 hours, a large-capacity polymerization reactor is required, which is economically disadvantageous. ° In the case where the polymerization reaction proceeds in the case of a mixing tank reactor for the polymerization of two tandem connections, The intermediate polymerization product discharged from the first polymerization reactor may be fed directly into the second polymerization reactor, or it may include a polymer containing 0 to 100% by weight of methyl methacrylate and 100 to 0% by weight of an alkyl acrylate. The monomer mixture and / or the side-feeding material solution of the methanol may be simultaneously fed in. The side-feeding material solution may be the same as or different from the material solution fed into the first polymerization reactor. Furthermore, at least a portion The side feed material may be a recirculation material from the recovery step of the volatile contents, and in the case where the chain transfer agent and / or the polymerization initiator is contained in the side feed material solution, The material solution fed to the first polymerization reactor may be the same as or different from the side feed material solution. In addition, the weight ratio of the side feed material to the main material is not particularly limited, but the weight ratio is usually 30% by weight or less It is preferably 20% by weight or less. The polymer obtained from the polymerization reactor should have the required polymerization ratio, average molecular weight, copolymerization composition of the polymer, and resistance to thermal decomposition. 'For polymerization power There is no particular limitation, and the polymerization reaction can be carried out by inert gas pressure. However, when the pressure is too high, Bao-2 1- The X degree of this paper applies the Chinese National Standard (CNS) A4 specification (210X297 (Mm) (Please read the notes on the back before filling this page) Order A7 B7 V. Description of the invention (20) The amount of condensing steam containing methanol, which is the main component in the reflux condenser used to build each polymerization reactor, is reduced. It is disadvantageous from the viewpoint of heat removal. Therefore, the polymerization is usually carried out at a polymerization temperature near the vapor pressure of the polymerization product. Techniques that use the sensitive heat of a substance, techniques that use a heat medium to remove the heat transferred from the reaction solution, and use the evaporation potential of methanol and monomer components in the reaction solution. Heat techniques to remove the heat of polymerization, but together The use of these techniques is what Λ wants. Because the method of the present invention uses methanol as a solvent, the relatively large heat can be removed due to the latent heat of evaporation at a fixed solution weight concentration compared with bulk polymerization and solution polymerization using alkylbenzene as a solvent. In addition, the formazan methanol is contained in the gas phase, for example, the trouble of scale adhesion in a reflux reactor can be prevented, as opposed to polymerization. As a result, it is unnecessary to insert the heat exchanger into the polymerization reactor, and it is not necessary to install an external heat exchanger, and the reaction solution is circulated externally through a cycle pump. Therefore, the structure of the reactor can be simplified, and the cost of common units and equipment can be reduced, which is economically advantageous. The polymerization product in the present invention includes a polymer, a monomer, a solvent as a main component, a component derived from a polymerization initiator, a chain transfer agent, and an additive added during polymerization. The concentration of the polymer is 39 to 90% by weight, preferably 43 to 87% by weight, and more preferably 46 to 85% by weight. If the concentration of the polymer is more than 90% by weight, the polymerization product has a high viscosity, and therefore it is difficult to move / flow the product through the pipeline and the heater. If the concentration of the polymer is less than 39% by weight, the volatile content of the polymer increases, The load of the exhaust step and the volatiles-containing recovery step are also increased. -22 " This paper size r applies the Chinese National Standard (CNS) A4 specification (21〇 × 297 mm) (Please read the precautions on the back before filling (This page) Printed by the Consumer Cooperatives, Central Bureau of Standards, Ministry of Economic Affairs

V. Description of the invention (21) Therefore, the production efficiency is reduced. For these reasons, this low polymer concentration is impractical. The polymerization product usually contains 5 to 43% by weight, preferably 8 to 38% by weight, and more preferably 10 to 33% by weight of monomer components. "It is practically difficult to obtain monomer components in an amount of less than 5% by weight, and If the amount of the monomer component exceeds 43% by weight, the productivity of the polymer to be obtained deteriorates, which is impractical. In the exhaust step, it is necessary to maintain the polymerization product until the practice of exhaust is at a temperature of not less than one temperature (at At this time, the product has a homogeneous and flowable viscosity), and in a composition that complies with the volatile content content, the product is maintained at a temperature at which the most appropriate exhaust effect can be obtained. This temperature is usually s. 'Is in the range of 130 to 270 ° C, preferably 135 to 25 (3 ° C, more preferably the polymerization temperature. If the temperature is less than 130 ° C, The viscosity of the solution increases, so it is difficult to quantitatively feed the polymerized product to the extruder. If the temperature is greater than 270 ° C, the manufacture of high-boiling substances such as dimers and trimers undesirably increases. Central Standards of the Ministry of Economic Affairs Printed by the Bureau's Consumer Cooperative. In addition, the pressure in the heater depends on the composition of the volatile content in the polymerization product, the temperature and feed rate of the polymerization product, due to the pressure of the tubes, heaters and nozzles, and the like. Depending on the loss, but any pressure is acceptable as long as it does not exceed the pressure resistance limits of the tubes, heaters, and the like. Before heating the polymerization reaction product to the polymerization temperature or above, use a heat exchanger, and a shell and Tube type heat exchangers, static mixer type heat exchangers and the like are suitable. In order to avoid thermal degradation of the polymerization products and increase in the production of by-products such as dimers and trimers, the polymerization products 霈 -23- paper ruler Applicable to China National Standard (CNS) A4g (210X297mm) A7 B7 V. Description of the invention (22) It should be heated to the predetermined temperature in the shortest possible time, and the heat exchanger is suitable to have heat exchange in it to be carried out efficiently. As a result, in order to quickly feed the thermal polymerization product into the extruder, it is desirable that the heater be arranged near the feed port of the extruder whenever possible. The polymerization product is directly from the tube and / or heated The device is fed into an extruder with most exhaust ports through a control valve for adjusting pressure and flow rate, wherein the barrel temperature is set at 170 to 270 ° C, preferably 180 to 260 ° C, more preferably 190 to 250 ° C. Depending on the use of the control valve, a pressure difference is generated in the range from the tube and / or heater to the extruder to keep the tube and / or heater under pressure. As a result, it can prevent sudden bubbling and volatilization up to the tube and the heater. The heat exchange force of the heater can be improved, it can promote the evaporation / separation of volatile contents, and it can reduce the common unit because Can suppress sudden foaming and volatilization in the tube, so the polymerization product can Constant flow rate and fixed composition feed to the feed of the extruder. The mouth can suppress the pulsations that cause trouble in the extruder. Any control valve can be used as long as it has the function of adjusting pressure and flow rate, and it is better Needle valve can be used. Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) The pressure in the inlet of the pipeline and / or heater is maintained at 3 to 80 kg / sq. In the range of cm, preferably 7 to 60 kg / cm2, and under these conditions, the polymerization product can be efficiently vented. If the pressure at the feed port is less than 3 kg / cm2, the pipeline and / or The heat exchange capacity in the heater is reduced, and if it is greater than kg / cm2, the pressure resistance of the pipeline and / or the heater must be increased, which leads to an increase in manufacturing costs. Therefore, the use of such a high pressure is economically disadvantageous. -24-The bottom of this paper is in accordance with Chinese National Standard (CNS) A4 (210X297mm) Α7 Β7 Printing by Zhengong Consumer Cooperative, Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (23) The polymerization product is arranged on the extruder The first exhaust port, or the feed port of the barrel adjacent to the row * 1 port, is fed to the screw of the extruder, and most of the volatile content is separated and recovered through the first exhaust port, and polymerized. It is carried out downstream by a screw. The feed port can be placed on the first exhaust port of the extruder or anywhere on the barrel near the exhaust port, but the temperature of the feed port needs to be fully maintained. In the case where the feed port is connected to the first exhaust port, it is arranged close to the screw of the extruder, whereby the polymerization product can be directly injected. Alternatively, in the case where the feed port is built near the barrel near the first exhaust port, it is usually arranged on the downstream side of the first exhaust port. In this case, the polymerization product can be fed from any direction on the vertical section of the screw of the extruder to the barrel of the extruder. At the first exhaust port of the extruder, it is maintained close to 2 3 0 to 2 2 Atmospheric pressure in the range of 80 mm Hg, preferably 300 to 1520 mm Hg, more preferably 380 to 1 140 mm Hg. Because methanol has a low boiling point, volatile contents can be recovered smoothly, even if the pressure in the exhaust port of the first pump is close to atmospheric pressure. The concentration of the remaining volatile contents of the polymer composition adjacent to the first exhaust port is maintained at 1 to 1% by weight, preferably 1 to 6% by weight. Extruders that can be used to remove volatile contents from the polymerization product should be provided with an exhaust port to discharge the volatile contents, and should have the function of kneading and melting the polymer composition from most of the volatile contents The function of extruding the polymer composition forward through the first exhaust port and through the die has since been removed from the remaining volatile content through the exhaust port on the downstream side. Generally, a twin-screw extruder having such a conventional exhaust port can be used. In addition, -25 which can be set from the feeding part to the die head can be used. This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) m ·-· 11 ^ — ^ 1 f ^ n — ^ 1 —ϋ m · 1 ^ 1 nn In (Please read the notes on the back before filling in this page.) A7 B7 V. Description of the invention (24) Extruder for barrel temperature of each component. The temperature of each part of the extruder can be set according to the type and brand of the polymer composition to be manufactured, and the temperature of the barrel is maintained at 18 Q to 270 ° C, preferably 19 Q to 250 ° C. bBecause most of the volatile contents can be separated and removed at the first exhaust port, the downstream exhaust port does not need to be kept in a state of high pull, but the pressure in the downstream exhaust port is maintained at 1 to 4.0 mm Hg, preferably 5 to 2.0 mm Hg. In the case of arranging most downstream exhaust ports, for example, in the case of two downstream exhaust ports, the second and third exhaust ports can be maintained at the same pressure or at different pressures, but the downstream side The exhaust port is preferably maintained at a pressure lower than that of the exhaust port near the first exhaust port. " If necessary, some additives can be added to the polymer composition by using an extruder, and examples of the additives include ultraviolet absorbers, lubricants, antioxidants, dyes, pigments, antistatic agents, light diffusers Propellants, impact modifiers and flame retardants. Additives may be added through the feed port of the polymerization product and / or on the downstream side of the first exhaust port. Printed by the Consumers' Cooperative of the China Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) The polymer thus extruded is finely cut with a granulator or similar to obtain a polymer that can be used as an injection molding material And this polymer generally contains 1% by weight or less, preferably 0.5% by weight or less, more preferably 0.4% by weight or less, and the following includes unreacted monomers, solvents, unreacted polymerization initiators, and Reactive chain transfer agent and / or the remaining volatile content of the dimer or trimer derived from the monomer. Because the obtained polymer is used as an injection molding material or a material for extruding tablets, the weight average molecular weight of the polymer preferably measured by G PC is usually 80, 0GG to 200,000, preferably 90, Q00 to 160, The scope of OQQ. If the weight average molecular weight is small -2 6-this paper rule; using Chinese National Standard (CNS) A4 specifications (210X297 mm) A 7 B7 V. Description of the invention (25) at 80,000, the necessary mechanical properties cannot be obtained, and If it is more than 200,000, the polymer melt viscosity is high, so injection molding or extrusion is difficult. The thermal decomposition ratio of the obtained polymer needs to be 3.0% by weight or less, and more preferably 1.0% by weight or less. Here, the thermal decomposition ratio is the weight loss of the sample heated at 2 ° C / min in the range of 30 to 300 ° C relative to the weight of the sample during thermogravimetric analysis (wherein the sample dried at 80 ° C for 24 hours under the nitrogen flow at 2 ° C / min heating rate to a temperature of 30 to 450 ° C). If the thermal decomposition ratio is more than 3.0% by weight, heating deterioration occurs during injection molding or extrusion, and coloring and bad taste emission also occur. Except that polymers having terminal double bonds are present in large amounts, which causes molding disadvantages such as silver streaks and blistering. As a result, products with desirable qualities cannot be obtained. Printed by the Consumer Standards Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) In the volatile content recovery step, the volatile content evaporated and separated from the polymer product in the exhaust step is usually An exhaust device such as a jack, a blower or a vacuum pump is led into the condenser, where it is cooled and condensed to recover itself. By-products such as dimers, trimers and oligomers derived from monomers and high boiling point materials such as unreacted chain transfer agents need to be removed. For this removal, a method may be used which comprises introducing volatile contents into a condenser, cooling / condensing it, and then separating / removing high-boiling substances by a separator, or another method, which comprises High-boiling substances are separated / removed by a separator before the volatile contents are condensed, the volatile contents are led to a condenser, where they are then cooled / condensed. _ 2 7-This paper size applies to Chinese National Standard (CNS) A4 (2 丨 0X297 mm) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (26) As a high boiling point material separator, Use simple flushing towers, demisters or ordinary distillation towers. It is preferred that a very small amount of air is introduced into the tower to avoid polymerization in the tower and then discharged through a condenser at the top of the tower. The recovered solution from which the high-boiling point substance has been separated / removed is advanced to a storage tank, but this storage tank preferably has an air pressure therein. The above-mentioned recovered solution is subjected to component analysis and then delivered to the material blending step and / or the side 1 feed material blending tank ^ As described above, the method of the present invention can stably control operation, simplify equipment, and reduce polymer suffering Thermal history, and can reduce the area of contact with the equipment causing the pollution "· Disgrace, can save the energy consumption of volatile content recovery under reduced pressure, maintenance of vacuum in the flushing tank and maintenance of the polymerization product fluidity And the capacity of equipment such as vacuum devices, condensers and extruders can be reduced. In addition, polymers that should be protected from thermal degradation and contamination can be advantageously processed without any coloration and damage to the appearance. As a result, public unit and equipment costs can be reduced, and thus high-quality polymers can be economically and advantageously produced. According to the method for polymerizing a continuous ore solution containing methyl methacrylate as a main component of the present invention in methanol as a monomer in a solvent, a methacrylic acid strip polymer having excellent quality can be prepared with high productivity under stable operating conditions And this has a lot of industrial significance. Next, the present invention will be explained in more detail with reference to the following implementations. In these examples, the catalytic activity and the like depend on the components of the catalyst and its manufacturing method. Incidentally, the scope of the present invention should not be limited to these * 2 8 _ This paper rule applies to China National Standard (CNS) A4 unified grid (210X297 mm) (Please read the precautions on the back before filling this page) Printed by the Consumers Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs, printed A7 B7 V. Description of Invention (27) In the embodiment. Examination Example 1 Fig. 1 is a flowchart showing the outline of an apparatus equipped with a stirring tank, and a specific embodiment of the present invention will be described based on this flowchart. A solution of fresh matter including methyl methacrylate, methyl acrylate, methanol, 1-dodecanethiol and di-% tertiary-butyl pergassing (whose half-life is about 16 () ° C for about 12 minutes) and The recycled substance solution in the substance blending tank 1 is blended. The resulting blend was composed of 85% by weight of a monomer mixture containing 96 parts by weight of methyl methacrylate and 4 parts by weight of methyl acrylate, 15% by weight of methanol, 0.25% by weight (10.8 millimoles / liter). Π-dodecanethiol and " 0.01% by weight (Q. 5 mmol / L) di-third-butyl peroxide, the blending substance is formed by a circle in the substance blending tank The disc atomizer blows nitrogen for 30 minutes to remove oxygen, and then the material is fed to the equipment jacket via line 2 and the fixed delivery pump 3, line 4 and reactor 6 in the feed port 5 are at a predetermined flow rate to make the average residence time 5 hours. Jacketed reactor

I 6 is provided with a stirring shaft 8 extending from the motor 7, a stirring blade 9 connected to the stirring shaft 8, and a line for reflux condensation. This line for reaction control configured for reflux condensation includes a steam discharge line 10, a condenser 11 and a reflux line 12, and a reflux liquid fed into the condenser 11 via the steam discharge line 10 and then condensed therein is fed into the reflux 12 line Feed into the reactor 6 equipped with a jacket. The condenser 11 is provided with a pressure regulating valve, and the pressure of the jacketed reactor 6 is controlled by an appropriate pressure controller to maintain the pressure at about 15 kg / cm2. By controlling the jacket temperature of the reactor 6 equipped with the jacket, the material to be fed is to be charged to the material of the reactor 6 equipped with the jacket-29- This paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) ) (Please read the precautions on the back before filling this page.) Ordering printed A7 B7_. Consumers' Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs. 5. Description of the invention (26) The temperature of the solution, the amount of reflux condensate and the condenser 11 Moderate pressure, the temperature of the reactor 6 equipped with the jacket was adjusted to 160 ° C, and the polymerization ratio was adjusted to 70 mol%, and as a result, the molecular weight and molecular distribution of the polymer prepared in the reactor could also be accurately Adjustment. At this time, the composition of the polymerization product was composed of 59.4% by weight of polymer, 2.4.9% by weight of methyl methacrylate, 0.7% by weight of methyl acrylate, and 15% by weight of methanol. A part of the polymer solution in the jacketed reactor 6 is fed through the 14 line at a fixed flow rate in the jacketed reactor 6 equipped with the liquid level by a fixed delivery pump 13 In heater 15, then heat up to 20 ° C. In order to avoid thermal degradation of the polymerization product, the solution is uniformly heated up to 200 ° C in the shortest possible time. For the thermal polymerization product can be quickly fed to the extrusion In the machine, the heater 15 is arranged as close as possible to the feed port 19 in the extruder. The outlet of the heater 15 is connected to the first exhaust port of the exhaust extruder 18 through a line 16 and a control valve 17. The feed port 20, which is slightly downstream of 19, is controlled by the control valve 17, the pressure of the heater 15 and the pressure of the line 16 and the flow rate at the feed port 2G to be constant, and the thermal polymerization product is injected to have a pressure of 2 3 0 ° C barrel temperature in the exhaust-type extruder 18. The pressure in the first exhaust port 19 is maintained at 840 mmHg.. When the screw is forwarded, feed to the exhaust-type extruder. The polymerized ingredients in the machine 18 are heated and melted, and TIN UV IN P (2- (manufactured by Ciba-Geigy) 5-methyl-2-hydroxyphenyl) benzotriazole] is fed from the additive blending tank 21 into the vented extruder 18 through the line 22 and the addition feed port 23. The polymer is melted and kneaded forward To the second exhaust port maintained at 20D mmHg-30- (Please read the precautions on the back before filling out this page) This paper ruler applies the Chinese National Standard (CNS) A4 standard grid (210X297 mm) Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7____ V. Invention Description (29) 24 and the volatile contents are removed at this second exhaust port 24, and then the polymer is extruded continuously through the die 25. Then, The polymer ribbon strip 26 extruded through the die 25 is cooled in a water bath 27 and then molded into pellets 29 by a pelletizer 28. When the polymerized product is injected into the extruder 18, the volatile content passes through the pipeline 30 is discharged from the first exhaust port 19, and the volatile contents separated in the extruder 18 are discharged through the second exhaust port 24 of the line 25, and the individual volatile contents are fed into the distillation column 32. High After the boiling point material has been removed by valve 33 and line 34, it contains methanol and unreacted monomer as the main components. The fraction of the steam passes through the line 35 to the condenser 36 and condenses therein. Thus the condensed liquid passes through the line 37 to the receiver 38 and then is recovered therein. The condensed liquid collected in the receiver 38 is fixedly delivered via the line 39 The pump 40 and the line 43 are circulated to the material step, and the remaining components are forwarded to the vacuum device via the line 41 and the heat exchanger 42 in this way, establishing a program failure (1 ο ο P). The resulting polymer is colorless and transparent , And from the results measured by Gas Chromatography (GC), the remaining volatile contents consisted of 0.20% by weight of methyl methacrylate, 0.01% by weight of methyl acrylate, and 50 PP® or Composed of the following methanol. In order to obtain the polymer, the melt flow rate (MFR) was measured in accordance with American Institute of Material Testing D1238 at a load of 3.80 kg at 230 ° C, and the result was 1.7 g / 1 G minutes. The molecular weight distribution of the polymer was measured by G PC, and from the results obtained, the average molecular weight of the polymer was 100,000. Except that, the polymer was subjected to thermogravimetric analysis using a thermogravimetric analyzer RTG 22D manufactured by Seiko Instruments Corporation under a krypton gas flow, and as a result, the thermal decomposition ratio of the polymer was% by weight. -31- This paper size applies Chinese National Standard (CNS) Λ4 specification (210X297 mm) (Please read the notes on the back before filling out this page) Order printed by the Consumers Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Α7 Β7 V. Invention Explanation (30): The obtained polymer was injection-molded into a disc having a diameter of 100 mm and a thickness of 3 mm by using an injection molding machine Arburg 75t. In this case, injection molding was performed as many as 100 rounds, and at this time, molding defects such as silver streaks and foaming did not occur. The total transmittance and result of this molded disc were measured by a color difference meter manufactured by Nippon Denskoku Co., Ltd., which was 93%, and the Η of the disc was 1.8 according to the penetration method. Example 2 of Honey Trip Example 2 is a schematic flow chart of a device equipped with a stirring tank connected in succession, and another specific embodiment of the present invention will be described based on this flow. Fresh substance solution and substance mixing tank consisting of methyl methacrylate, ethyl acrylate, methanol, dodecanethiol and di-third-butyl peroxide (its half-life is about 16 minutes at T) 51 The recycled substance solution in the blend. The composition of the obtained blend was composed of 93% by weight of 90% by weight of methyl methacrylate and 10% by weight of ethyl acrylate, 7% by weight of methanol, 0.09% by weight (5.3 millimolars / liter) 1-10 A monomer mixture of a dioxanethiol alcohol and 0.03% by weight (1.0 millimolars / liter) of a di-third-butyl pergas. The blended material is degassed by nitrogen substitution in the metering flow line 52, and then the material is entangled through the line 52, the fixed delivery pump 53, the line 54 and the feed port 55 so that the average residence time can be a predetermined flow rate of 3 hours. It is fed into a jacketed first reactor 56. The jacketed first reactor 56 provides a stirring shaft 58 extending from the motor 5 * 7, a stirring blade 59 connected to the stirring shaft 58 and a line for reflux condensation. This reaction-controlling line for reflux condensation includes a steam exhaust line 60, a condenser 61 and a reflux line 62, and via a steam exhaust pipe -32- This paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 (Mm) (Please read the notes on the back before filling in this page)-Order A7 B7____ V. Invention Description (3L) / Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (Please read the notes on the back before filling in this page -Spring. Line 60 is fed to the condenser 61 and the reflux liquid condensed therein is fed via the return 62 line to the first reactor 56 equipped with a jacket. The condenser 61 is provided with a pressure-regulating valve and the power in the jacketed first reactor 56 is controlled by an appropriate pressure controller to maintain the pressure at about 9 kg / cm2. By controlling the jacket temperature of the first reactor 56 provided with the jacket, the temperature of the substance solution to be fed to the first reactor 56 provided with the jacket, the amount of the reflux condensed liquid and the temperature in the condenser 61 Pressure, the temperature of the first reactor 56 equipped with a jacket was adjusted to 150 ° F, and the polymerization ratio was adjusted to 65 mol%, and as a result, the polymerization ratio, molecular weight and molecular distribution of the polymer prepared in the first reactor It can also be adjusted precisely. The intermediate product polymerization reaction solution is discharged from the jacketed first reaction reactor 56 by using a pump 63 at a liquid surface level 56 in the jacketed first reactor 56 at a fixed flow rate. In the valve 69, it is mixed with the side feed material which has been prepared in the side feed material blending tank 65, deoxidized, and then fed to β through line 66. Then, the mixture passes through the inlet 71 and line 70 at a fixed flow rate. The second reactor 72 is continuously fed with a jacket. The composition of the side-feeding material is 95% by weight of a monomer mixture containing 80 parts by weight of methyl methacrylate and 20 parts by weight of ethyl acrylate, 5% by weight of methanol, 0.005% by weight (0.3 millimoles / liter ) 1-octanethiol and 0.05% by weight (2.0 millimolars / liter) of di-third-pentyl pergassers, and an intermediate polymerization reaction solution discharged from the first reactor 56 equipped with a jacket The weight-to-child ratio of the side-feed material is 10: 1. The jacketed second reactor 72 is provided with a stirrer 74 extending from the motor 73, a search blade 75 connected to the stirring shaft 74, and a line for reflux condensation. _ 3 3 _ This paper size applies to Chinese National Standards (CNS) Α4 grid (210 × 297 mm) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (32) This configuration is for reaction control for reflow The condensing line includes a steam exhaust line, an outlet line 76, a condenser 77, and a return line 78, and the reflux liquid fed into the condenser 77 via the vapor discharge line 76 and then condensed therein is fed through the return line 7 to the equipment equipped with a clamp Nested in the second reactor 72. The condenser 77 is provided with a pressure regulating valve, and the pressure in the jacketed second reactor 72 is controlled by a suitable pressure controller to a holding pressure of about 10 kg / cm2 (gauge pressure). By controlling the jacket temperature of the second reactor 72 equipped with the jacket, the temperature of the intermediate polymerization reaction solution to be fed to the second reactor 72 equipped with the jacket, the amount of reflux condensed liquid and the condenser 77 The temperature of the second reactor 72 equipped with a jacket was adjusted to 15 ITC, and the total polymerization ratio j was adjusted to 90 mol%, and as a result, the polymer prepared in the reactor, the polymerization ratio, the molecular weight and The molecular distribution can also be precisely adjusted. At this time, the composition of the polymerization product was composed of 83.9% by weight of polymer, 8.7% by weight of methyl methacrylate, 0.6% by weight of methyl acrylate, and 6.8% by weight of methanol. A part of the polymerization reaction solution in the jacketed second reactor 72 was continuously discharged to the line 81 by using a fixed delivery pump 79 through the line 80 at an average residence time of 4 hours and maintaining the liquid level, and then This solution was maintained at 150 ° Ce. The outlet of the second reactor 72 was directly connected to the inlet 83, which is located slightly downstream of the first exhaust port 85 of the extruder 84, via a line 81 and a control valve 82. The pressure of the control valve 82, the line 81 and the flow rate at the feed port 83 are controlled so as to be constant, and the thermal polymerization product is injected into a vented extruder maintained at a barrel temperature of 2 4 G ° C 8 4 . The pressure in the first exhaust port was maintained at 610 mmHg. When the screw is forward, -34- This paper size applies to China National Standard (CNS) A4 specification (210 × 297 mm) J, ---------- ^ Loading ----,-Order > --- I · ----... ^. (Please read the notes on the back before filling out this page) Printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A 7 __B7_ V. Description of Invention (33) The polymer composition injected into the exhaust-type extruder 84 is heated and melted, and monoglyceryl stearate is fed from the additive blending tank 86 via the line 87 and the additive feed port 88 to the exhaust-type extruder 84. . The molten and kneaded polymer is forwarded to the second exhaust port 89 and the volatile contents are removed at this second exhaust port, and then the polymer is extruded through the die 90 continuously. Then, the polymer ribbon tape 91 extruded through the die 90 is cooled in a water bath 92, and then molded into pellets 94 by a pelletizer 93. When the polymerized product is injected into the extruder 84, the volatile contents are discharged from the first exhaust port 85 through the line 95, and the volatile contents are discharged from the second exhaust port 89 through the line 96 (where the pressure is maintained at 10 mm Hg) ) Is discharged, and other volatile contents are fed to the distillation column 97. After the high boiling point substance has been removed by the valve 98 and the line 99, the vapor containing the solvent and unreacted monomers as the main components is forwarded to the condenser 101 via the line 100 and condensed therein. After such a condensed liquid is advanced through the line 102 to the receiver 103 and then recovered therein. The condensed liquid collected in the receiver 1 fl 3 is circulated to the material step via line 10 彳, the fixed delivery pump 1D5 and line 106, and the remaining components are forwarded to the vacuum device 109 via line 107 and heat exchanger 108. In this way, The polymer obtained by establishing the procedural ring (1〇ορ) β was colorless and transparent, and from the results measured by gas chromatography (GC), the remaining volatile content was 0.14% by weight of methyl methacrylate Ester, 0.11% by weight of ethyl acrylate and 50 ppm or less of methanol. In order to obtain the polymer, MFR was measured according to the American Society for Testing and Materials D 1 2 3 8 under a load of 3.8 G kg at 2 3 Q ° C, and as a result, it was 11.0 g / 10 minutes β polymerization was measured by GPC Molecular weight distribution of polymers, and from the results obtained, the average weight molecular weight of the polymer is -35- This paper size is applicable to the Chinese National Standard (CNS) A4 specification (2 丨 〇'χ297 mm) (Please read the precautions on the back first Fill out this page again) Order A7 B7 V. Description of Invention (34) 110,000. Except that, the polymer was subjected to thermogravimetric analysis under a nitrogen stream using a thermogravimetric analysis device RTG 220 manufactured by Seiko Instruments Corporation. As a result, the polymer had a thermal decomposition ratio of 0.9% by weight. By using the injection molding machine Arburg 75t, the obtained polymer was injected to form a disk having a diameter of 100 mm and a thickness of 3 mm. In this case, injection molding was performed as many as 100 rounds, and at this time, no mold occurred. Plastic defects such as silver streaks and foaming. The total transmittance of this molded disc was measured by a fe meter made by Nippon Denskoku Co., Ltd., which was 93%, and the YI of the disc was 1.2 according to the penetration method. Fenyu Example 3 Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page) Use the device shown in Figure 1 and place 4.5 kg with 60.0 parts by weight. Methyl methacrylate, 25.6 parts by weight of methyl methacrylate, 1.1 parts by replacement of methyl acrylate and 13.3 parts of methanol are placed in a jacketed reactor 6 and then heated to a high temperature 150. 〇 in order to dissolve the other ingredients evenly. This mixture was passed through the fixed delivery pump 13 at 1 kg / hr. Line 14 was continuously discharged from the reactor / forward to the heater 15 and then fed through line 16 and control valve 17 to have a temperature of 22 (rc barrel temperature). The exhaust-type extruder 18 is simultaneously maintained at i5 (rc. By controlling the valve 17, the fly force in the insert portion of the heater 15 is maintained at 25 kg / cm2 (mine pressure). The pressure and the flow rate of the mixture at the feed port 21 are fixedly controlled, and the pressure in the first exhaust port 19 is maintained at 84 mm Hg. When the screw enters, heating and melting have been injected into the exhaust type I. Extrusion Xiao Xiao 18 towels from the polymer composition obtained, with this volatile content-further from Xiongzhi-3 6-This paper size applies Chinese National Standard (CNS) A4 specifications (210X297 mm). Printed 5. Description of the invention (35 A7 B7 molds are grouped and then 0 2 4 P gas exhaust column second column mercury meter is removed from the form of 9 2 pellets but cold 7 2 bath water in the system Squeeze 5 2 Nodene 0 Propyl radicals Intravenous% Sex 2 ί -〇0 eIHt 3 0 Contains the residues of the formic acid of the polyester and the emission of propylene gas from the propylene gas% 113 No. 0. Nearly. The o-ester is produced from the formic acid formic acid%% 21 21 ο Has physical storage In the case of poly-and-intermediate, the granular esters are in the acidic allyl group. The properties are 01. The volatile esters of the methyl ester are acidic, and the allyl groups are good. Αα Clear examples and black hh None 1 degree of homo-acid mixed with allylic acid liquid acrylate I or acetic acid with ethylene acid to prepare propylene, and the first ester allylic acid acrylate containing all the substances included in the body When the ester gas was lined up, the material method showed the same apparent phase for each of 3 4 cases to 1 after the actual table was shown as 0, and then the materials were aggregated and aggregated. Send it to i, choose 1 and the table shows its presence and 〇, the light strips indicate the permeation sum of the gas particles, the rate and speed of the polymer material, the temperature and the heat capacity of the material plus the internal method .¾¾ mechanism squeezed air exhaust to the feed into the table and wash the wash table) / B (0 and the production of raw materials into the machine Production extrusion extrusion nozzle to the mouth of the spray material compounding machine injection molding injection extrusion connection in line (please read the precautions on the back before filling this page)

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A7 B7 V. Description of the invention (39) Table 2 (wrapping) Example 10 11 12 13 14 15 Employees' cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs print the remaining volatile contents in the inlet of the extruder (%) MMA 4.10 4.60 2.30 3.60 5.20 2.10 Co-monomer 0.12 0.13 0.07 0.1.1 0.15 0.06 Solvent 0.04 0.05 0.04 0.05 0.04 0.05 Extruder barrel temperature (° c) 230 230 230 230 230 230 Vacuum degree of the second exhaust port (mmHg) 150 150 150 150 150 150 Extruded pellets remaining volatile content (%). MMA 0.33 0.36 0.23 0.30 0.39 0.22 comonomer 0.01 0.01 0.01 0.01 0.01 0.01 solvent ND ND ND ND ND ND total light transmittance (%) 93 93 93 93 93 93 MA: Methyl acrylate Me: Methanol ND: Not measured by GC (0.01% or below) -41- (Please read the precautions on the back before filling this page) The paper size of the paper is applicable to Chinese national standards (CNS ) A4 specification (210X297 mm) A7 B7 V. Description of invention (40) Table 3 Example 16 17 18 19 20 21. Co-monomers printed by employees' cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs _ HA ΜΑ MA EA BA ^ Child in MA polymer (%) 4 9 4 4 4 4 Composition of solvent Me Me Me Me Me Me Polymerization product (%) Polymer 40.6 60.0 60.0 60.0 60.0 60.0 MMA 28.2 24.3 25.6 25.6 25.6 25.6 Co-monomer 1.2 2.4 1.1 1.1 1.1 1.1 Solvent 28.0 13.3 13.3 13.3 13.3 13.3 Feed temperature of polymerization product (° c) 150 150 150 150 150 150 Feed rate (kg / hr) 1.0 1.0 '1.0 1.0 1.0 1.0 Heater outlet temperature (° C) 190 190 150 190 190 190 Heater inlet pressure 30 25 20 25 25 25 (kg / cm2) Method of feeding to the exhaust extruder (A) (A) (A) (A) (A) (A) ) Pressure of the first exhaust port (mmHg) 680 760 460 760 760 760 -42- (Please read the notes on the back before filling this page) The printed paper is also applicable to the Chinese National Standard (CNS) A4 specification (2 丨0X297 mm) A7 B7 V. Description of the invention (41) Table 3 (setting) Example 16 17 18 19 20 21 The Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs prints the remaining volatile contents in the feed port of the extruder ( %) MMA 2.50 3.40 3.60 4.10 4.20 4.10 Co-monomer 0.04 0 .24 0.11 0.14 0.18 0.12 Solvent 0.04 0.05 0.04 0.04 0.05 0.04 Extruder barrel temperature (° c) 230 230 230 230 230 230 Vacuum degree of the second exhaust port (BimHg) 100 150 150 150 150 150 Extruded pellets · others Volatile content (%). MMA 0.18 0.29 0.40 0.33 0.33 0.33 Comonomer 0.01 0.02 0.01 0.01 0.01 0.01 0.01 Solvent ND ND ND ND ND ND Total light transmittance (%) 93 93 93 93 93 93 (Please read the back Note: Please fill in this page again.) V, Order M: Methyl acrylate ΕΑ: Ethyl acrylate ΒΑ: N-butyl acrylate Me: Methanol ND: Not measured by GC (0.01% or less) -43- This paper size applies to China National Standard (CNS) A4 (210X297 mm) Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs * A7 B7 V. Description of the invention (42) Table 4 Example 22 Comparative Example 1 Comparative Example 2 Comonomer MA ΜΑ ΜΑ Polymerization Amount (%) 4 4 4 Solvent Me TOL None Composition (%) of the polymerization product. 'Polymer 60.0 60.0 71.0 MMA 25.6 25.6 27.8 Comonomer 1.1 1.1 1.2 Solvent' 13.3 13.3 0.0 Feed of the polymerization product Degree (° c) 150 150 150 Feed rate (kg / hr) 1.0 1.0 1.0 Heater outlet temperature (° c) 190 190 190 Heater inlet pressure 24 8 7 (kg / cm2) Feed to exhaust extrusion Control method (A) (A) (A) Pressure of the first exhaust port (mmHg) 760 760 760 -44- I ： ------------------ Order (Please read the notes on the back before filling this page) This paper ruler applies the Chinese National Standard (CNS) A4 specification (210X297 mm) A7 B7 V. Description of the invention (43) Table 4 (achievement) Example 22 Comparative Example 1 Comparative Example 2 The rest of the content in the feed of the extruder (%) MMA 4.20 9.50 9.70 Co-monomer 0.12 0.28 0.28 Solvent '0.05 4.93 ND Extruder barrel temperature (° c) 230 230 230 Second Vacuum degree of exhaust port UmHg) 150 150 150 Extruded pellet remaining volatile content (%) MMA 0.33 1.16 1.18 comonomer 0.01 0.03 0.03 solvent ND 0.60 ND total light transmittance (%) 93 93 93 (Please read first (Notes on the back, please fill out this page) Order MA printed by the Consumers Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Ester Me: methanol TOL: Toluene o: not determined by GC (0.01% or less) -45- applies the present paper China National Standard Scale (CNS) A4 size (Shu 0X297 mm 2)

Claims (1)

3990 ^ 1 A8 B8 C8 D8 Patent application date and month • «eertgr Supplement No. 85110 72 7" Method for the Production of Methacrylic Polymers "Patent (Amended on December 24, 88) (Please read the precautions on the back first (Fill in this page again) 6. Scope of patent application: Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 1. A method of polymer production, which includes the following steps: (1) In a polymerization reactor containing one or two continuous connected polymerization tanks A homogeneous solution state of methyl methacrylate alone or 0.1 to 160 millimoles / liter of a polymerization initiator having a half-life of 0.6 to 60 minutes at a polymerization temperature and 0.1 to 370 millimoles / liter of a chain transfer agent is performed. Based on a mixture of 71 to 95 parts by weight of a monomer mixture containing 75 to 100% by weight of methyl methacrylate and 0 to 25% by weight of alkyl acrylate and 29 to 5 parts by weight of methanol as a solvent Continuous polymerization reaction so that the monomer conversion rate is from 100 to 180 ° C, the polymerization temperature may be in the range of 55 to 93 mole%, and (2) at a temperature of 130 to 270 ° C, it is discharged from the polymerization reactor. Polymerization product feed directly In an extruder with several exhaust ports set at a barrel temperature of 170 to 270 °, most of the volatile content passes through the first row of the extruder. The air ports are separated and recovered while the rest are volatile The content is removed through at least one other downstream exhaust port set at an exhaust port pressure of 1 to 400 mm Hg *, thereby preparing a remaining volatile content of 0 to 1% by weight, which is penetrated by the gel A polymer having a weight average molecular weight in the range of 80,000 to 200,000, and a thermal decomposition ratio of 0 to 3.0% by weight, as measured by color layer analysis (GPC). 2. The polymer manufacturing method according to item 1 of the scope of the patent application, in which the size of the paper used in the polymerization tank is in accordance with Chinese National Standard (CNS) A4 (210X297 mm) 3990 ^ 1 A8 B8 C8 D8 Patent application date and month • «eertgr Supplement No. 85110 72 7" Method for the Production of Methacrylic Polymers "Patent (Amended on December 24, 88) (Please read the precautions on the back first (Fill in this page again) 6. Scope of patent application: Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 1. A method of polymer production, which includes the following steps: (1) In a polymerization reactor containing one or two continuous connected polymerization tanks A homogeneous solution state of methyl methacrylate alone or 0.1 to 160 millimoles / liter of a polymerization initiator having a half-life of 0.6 to 60 minutes at a polymerization temperature and 0.1 to 370 millimoles / liter of a chain transfer agent is performed. Based on a mixture of 71 to 95 parts by weight of a monomer mixture containing 75 to 100% by weight of methyl methacrylate and 0 to 25% by weight of alkyl acrylate and 29 to 5 parts by weight of methanol as a solvent Continuous polymerization reaction so that the monomer conversion rate is from 100 to 180 ° C, the polymerization temperature may be in the range of 55 to 93 mole%, and (2) at a temperature of 130 to 270 ° C, it is discharged from the polymerization reactor. Polymerization product feed directly In an extruder with several exhaust ports set at a barrel temperature of 170 to 270 °, most of the volatile content passes through the first row of the extruder. The air ports are separated and recovered while the rest are volatile The content is removed through at least one other downstream exhaust port set at an exhaust port pressure of 1 to 400 mm Hg *, thereby preparing a remaining volatile content of 0 to 1% by weight, which is penetrated by the gel A polymer having a weight average molecular weight in the range of 80,000 to 200,000, and a thermal decomposition ratio of 0 to 3.0% by weight, as measured by color layer analysis (GPC). 2. As for the method for preparing polymer in item 1 of the scope of patent application, in which the paper size of the polymerization tank adopts the Chinese National Standard (CNS) A4 specification (210X297 mm) A8 S990S1 cl D8 6. The polymerization temperature in the scope of patent application is In the range of 130 to 170 ° C. (Please read the note on the back before filling this page.) 3. For the method of polymer preparation in item 1 of the patent application, the average residence time in the polymerization tank is in the range of 2 to 7 hours. 4. For the method for producing a polymer according to item 1 of the patent application scope, the number of polymerization tanks is one. 5. The method for producing a polymer according to item 1 of the patent application, wherein the polymerized product is fed onto the screw of the extruder through the inlet of the extruder at a temperature of 135 to 250 ° C. 6. The method for producing a polymer according to item 1 of the application, wherein the alkyl acrylate is at least one selected from the group consisting of methyl acrylate, ethyl acrylate, and n-butyl acrylate. 7. The method for producing a polymer according to item 1 of the patent application, wherein the half-life of the radical polymerization initiator at the polymerization temperature is in the range of 1 to 30 minutes, and the concentration of the radical polymerization initiator is in the range of 0.1 to 100. Range of millimolars per liter "8. The method for producing a polymer according to item 1 of the patent application range, wherein the thermal decomposition ratio of the obtained polymer is 0 to 1.0% by weight. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 9. For the method of polymer production under the scope of patent application No. 5, the polymer product is fed into the extruder through the control valve. 10. The method for producing a polymer according to item 1 of the patent application scope, wherein the exhaust gas from the polymerization reaction product is completed by the following steps (a) using a heater such as a heat exchanger to heat the polymerization product to 120 to 270 ° C, And -2- This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) A8 S990S1 cl D8 6. The polymerization temperature in the patent application range is in the range of 130 to 170 ° C. (Please read the note on the back before filling this page.) 3. For the method of polymer preparation in item 1 of the patent application, the average residence time in the polymerization tank is in the range of 2 to 7 hours. 4. For the method for producing a polymer according to item 1 of the patent application scope, the number of polymerization tanks is one. 5. The method for producing a polymer according to item 1 of the patent application, wherein the polymerized product is fed onto the screw of the extruder through the inlet of the extruder at a temperature of 135 to 250 ° C. 6. The method for producing a polymer according to item 1 of the application, wherein the alkyl acrylate is at least one selected from the group consisting of methyl acrylate, ethyl acrylate, and n-butyl acrylate. 7. The method for producing a polymer according to item 1 of the patent application, wherein the half-life of the radical polymerization initiator at the polymerization temperature is in the range of 1 to 30 minutes, and the concentration of the radical polymerization initiator is in the range of 0.1 to 100. Range of millimolars per liter "8. The method for producing a polymer according to item 1 of the patent application range, wherein the thermal decomposition ratio of the obtained polymer is 0 to 1.0% by weight. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 9. For the method of polymer production under the scope of patent application No. 5, the polymer product is fed into the extruder through the control valve. 10. The method for producing a polymer according to item 1 of the patent application scope, wherein the exhaust gas from the polymerization reaction product is completed by the following steps (a) using a heater such as a heat exchanger to heat the polymerization product to 120 to 270 ° C, And -2- This paper size applies to Chinese National Standard (CNS) A4 specification (210X297 mm) A8 B8 3㈣ 061. g88 6. Application scope of patent (b) The polymerized product is fed through the feed port formed by the nearby barrel. Feed to the first exhaust port of the extruder with a pressure maintained at 2 30 to 2280 mm Hg or on the extruder screw. 11. The method for producing a polymer according to item 1 of the patent application, wherein the polymerization product contains 5 to 55% by weight of a monomer and 5 to 65% by weight of a solvent. 12. The method for producing a polymer according to item 1 of the patent application, wherein the polymerization product is fed through a feed opening formed by a nearby barrel to an extruder having a pressure maintained at 380 to 11 40 mm Hg The first exhaust port is on the screw of the extruder. 13. The method for producing a polymer according to item 1 of the patent application, wherein the polymer product is fed onto the screw of the extruder by using a nozzle selected from a needle valve, a curved stopper, and a wire extrusion die. 14. The method for producing a polymer according to item 1 of the patent application, wherein the polymerized product is fed into the extruder through a feed port formed in a barrel adjacent to the first exhaust port of the extruder. 15. For example, the method for producing a polymer under the scope of patent application, wherein the polymerization product is blown to the screw of the extruder through a nozzle arranged at the inlet of the extruder (please read the precautions on the back before filling this page) • The paper size printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs adopts the Chinese National Standard (CNS) Α4 specification (2.10X297 mm)