Method of producing copolymer

Abstract: The present invention provides a method of producing a maleimide-olefin copolymer having excellent transparency. The production method employs precipitation polymerization for producing a maleimide-olefin copolymer by radical polymerization of a maleimide and an olefin.

Description: Background of the Invention: Field of the Invention: The present invention relates to a method of producing a maleimide-olefin copolymer having excellent transparency. Description of the Related Art: A maleimide polymer, mainly phenyl maleimide, has been investigated as a polymer material having high heat resistance for many years. However, since the polymer product becomes remarkably brittle as the number of maleimide units is increased, the maleimide polymer is generally used only as a heat resistance modifier for ABS by adding in an amount of several tens %. In addition, the use of phenyl maleimide significantly causes coloring of the polymer product, thereby causing a critical problem according to the application. A copolymer of an alkyl maleimide and a specified olefin has practical mechanical strength in spite of its high maleimide content, and is an interesting material having excellent heat resistance. However, since the copolymer product is easily colored by the effects of remaining monomers, impurities and the like, a copolymer having excellent optical properties cannot be easily industrially produced. Generally known methods of radical polymerization of vinyl monomers include a suspension polymerization method, an emulsion polymerization method and a solution polymerization method. The suspension polymerization method and emulsion polymerization method are frequently used in the industrial field. However, when one of the above polymerization methods is employed for polymerizing a maleimide and an olefin, the problems below are produced. Since many maleimides are solid compounds at room temperature and are slightly soluble in olefins, it is difficult to employ a polymerization method such as the suspension polymerization method or the emulsion polymerization method, which is generally applied to liquid monomers. In addition, since the above polymerization methods use a dispersion stabilizer or an emulsifying agent, the methods are undesirable from the viewpoint of deterioration in the optical properties of the produced polymers. Further, in the case of a maleimide polymer, there is the problem that if maleimide or impurities remain in the produced polymer, as described above, the transparency and color tone of the polymer significantly deteriorate. From this point of view, the above polymerization methods are unsatisfactory production methods. Although a homogeneous solution polymerization method is a production method suitable for polymerization of solid monomers, the polymerization method also has the following problems. For example, the produced polymer can be purified by precipitating from the polymer solution produced by reaction using a poor solvent to obtain a copolymer having a relatively good color tone. However, this method is impractical because of the problems that the produced polymer cannot be easily industrially purified by the above reprecipitation method, and that the production process becomes complicated. In addition, although a method of removing the solvent from the obtained polymer solution by distillation or flushing is a relatively simple method, the method has the problem of significantly coloring the produced polymer. As described above, it has been so far difficult to industrially produce a maleimide-olefin copolymer having excellent transparency and color tone. EP-A-0055502 describes a process for producing copolymers of maleic acid acid anhydride and olefins by reaction in diisopropylketone or diisobutylketone in which the monomers are soluble but from which the copolymer precipitates. The precipitated copolymer is advocated for use as intermediates and epoxy hardeners. The precipitated copolymer is also identified as soluble in basic aqueous solutions and when dissolved can be used for sizing paper. Summary of the Invention: Accordingly, an object of the present invention is to provide an industrial method of producing a maleimide-olefin copolymer, and particularly to provide a method of producing a maleimide-olefin copolymer having excellent transparency and color tone. As a result of energetic investigation performed by the inventors in consideration of the above problems, it was found that the object is achieved by a production method using a specified polymerization solvent. This led to the achievement of the present invention. The present invention relates to a method of producing a maleimide-olefin copolymer using a precipitation polymerization method in which a maleimide-olefin copolymer is produced by radical polymerization of a maleimide and an olefin using a polymerization solvent which dissolves the maleimide and does not dissolve the produced polymer to precipitate the produced polymer in a granular form. The use of the production method of the present invention enables the production of a polymer having very low yellowness and good transparency. It is thought that this is:caused by dissolution of remaining monomers or impurities such as denatured substances of the monomers, which seem to affect the color tone of the produced polymer, in the solvent and removal from the produced polymer. In addition, since the production method of the present invention does not use an emulsifying agent or a dispersant, which is used in the general emulsion polymerization method or suspension polymerization method, the method is excellent in the point that a polymer having excellent optical properties can be obtained. Further, since the production method of the present invention produces a granular polymer, the production process comprising a separation step, a drying step and so on can be simplified. In the production method of the present invention, a polymerization solvent which easily dissolves maleimides and olefins and which does not dissolve the produced polymer to precipitate the produced polymer in a granular form must be used as the polymerization solvent. The average grain size of the produced polymer grains is 50 to 2000 µm (micrometres), preferably 100 to 1000 µm (micrometres). An average grain size less than 50 µm (micrometres) is undesirable because the polymer grains are scattered or cause clogging of a filter during filtration separation and are thus difficult to handle. An average grain size over 2000 µm (micrometres) is also undesirable because the produced polymer tends to be colored. The bulk density of the produced polymer grains is 0.1 to 1.0 g/cm 3 , preferably 0.2 to 0.8 g/cm 3 . A bulk density less than 0.1 g/cm 3 is undesirable because the polymer grains are difficult to handle and are processed into pellets or a molded product with poor workability. A bulk density over 1.0 g/cm 3 is also undesirable because the produced polymer tends to be colored. The polymerization solvent preferable from the viewpoint of the production of a polymer decreases the amount of the polymer (scale) which adheres to the reactor or agitator used. An example of polymerization solvents which are preferably used in the production method of the present invention is a solvent mixture containing an aromatic solvent and at least one selected from the group consisting of alcohols, ketones, acetates and ethers. Examples of aromatic solvents include benzene, toluene, xylene, ethylbenzene, propylbenzene and butylbenzene. Examples of alcohols include methyl alcohol, ethyl alcohol, n-propyl alcohol, i-propyl alcohol, n-butyl alcohol, i-butyl alcohol, s-butyl alcohol, t-butyl alcohol, hexyl alcohol, cyclohexyl alcohol, lauryl alcohol and stearyl alcohol. Examples of ketones include acetone, diethyl ketone, methyl ethyl ketone and cylcohexanone. Examples of acetates include methyl acetate, ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, s-butyl acetate, t-butyl acetate and hexyl acetate. Examples of ethers include dimethyl ether, diethyl ether, tetrahydrofuran and dioxane. Of these solvents, mixed solvents containing alcohols and aromatic solvents are preferable from the viewpoint of occurrence of little scale. Particularly, a mixed solvent containing methanol and toluene is preferable. Although the ratio of an alcohol, ketone, acetate or ether to an aromatic solvent depends upon the composition of the monomers charged and the substituents of maleimide, the ratio is preferably 98/2 to 2/98 % by weight, more preferably 90/10 to 20/80 % by weight. Another example of polymerization solvents which are preferably used in the production method of the present invention is a mixed solvent containing an acetate and at least one selected from the group consisting of alcohols, ketones and ethers. The ratio of an alcohol, ketone or ether to an acetate is preferably 98/2 to 2/98 % by weight, more preferably 90/10 to 20/80 % by weight. A further preferable polymerization solvent is nitrile solvent. Examples of nitrile solvents used in the production method of the present invention include lower aliphatic nitriles such as acetonitrile, propionitrile, butyronitrile and the like. Acetonitrile is particularly preferable. A still further preferable polymerization solvent is an aromatic solvent shown by the following formula (3), wherein R 4 to R 9 each denote a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxyl group or a halogen atom. Examples of aromatic solvents include benzene, xylene, ethylbenzene, propylbenzene and butylbenzene. Xylene and ethylbenzene are particularly preferable. Maleimides that are preferably used in the present invention are N-alkyl-substituted maleimides expressed by the following formula (1): wherein R 1 denotes a (cyclo)alkyl group having 1 to 6 carbon atoms. Examples of such maleimides include N-methylmaleimide, N-ethylmaleimide, N-n-propylmaleimide, N-i-propylmaleimide, N-n-butylmaleimide, N-i-butylmaleimide, N-s-butylmaleimide, N-t-butylmaleimide, M-n-hexylmaleimide, N-cyclopropylmaleimide, N-cylcobutylmaleimide, N-cyclohexylmaleimide and the like. These compounds may be used singly or in combination of two or more compounds. Of these compounds, N-methylmaleimide is preferably used from the viewpoints of the heat resistance, mechanical properties and so on of the produced polymer. Compounds expressed by the following formula (2) are preferably used as olefins in the present invention; wherein R 2 and R 3 each denote a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Preferable examples of such compounds include ethylene, isobutene, 2-methyl-1-butene, 2-methyl-1-pentene, 2-methyl-1-hexene, 1-methyl-1-heptene, 1-isooctene, 2-methyl-1-octene, 2-ethyl-1-pentene, 2-methyl-2-butene, 2-methyl-2-pentene and 2-methyl-2-hexene. These compounds may be used singly or in combination of two or more compounds. Particularly, isobutene is preferable from the viewpoints of reactivity, the mechanical properties of the produced polymer and so on. Although the ratio between the maleimide and the olefin used in the present invention is not limited, the ratio of the olefin used is preferably within the range of 0.1 to 50 mol, more preferably 1.0 to 20 mol, more particularly 2.0 to 15 mol, relative to 1 mol of maleimide, from the viewpoints of reactivity. Generally known radical polymerization catalysts can be used as a radical polymerization initiator in the production method of the present invention. Examples of such initiators include organic peroxides such as benzoyl peroxide, lauryl peroxide, octanoyl peroxide, acetyl peroxide, di-t-butyl peroxide, t-butylcumyl peroxide, dicumyl peroxide, t-butyl peroxyacetate, t-butyl peroxybenzoate and perbutyl neodecanoate; azo-type initiators such as 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2-butyronitrile), 2,2'-azobisisobutyronitrile, dimethyl-2,2'-azobisisobutyrate and 1,1'-azobis(cyclohexane-1-carbonitrile). These catalysts may be used singly or in combination of two or more compounds. The amount of the catalyst used is 0.0001 to 1.0 mol%, preferably 0.001 to 0.1 mol%, relative to the total amount of monomers. The total amount of catalyst may be added in an early stage of polymerization, or may be divided into several portions and added during polymerization. The polymerization temperature can be appropriately determined in accordance with the decomposition temperature of the initiator used. However, the polymerization temperature is preferably within the range of 40 to 150°C. The polymerization temperature may be constant throughout reaction or continuously or stepwisely increased and decreased. Although the polymerization time is not particularly limited, the time is 0.1 to 50 hours, preferably 1 to 20 hours. The production method of the present invention can be performed in a batch manner or continuous manner. The material of the reactor used is not limited, and it can be selected in view of the effects of the metals remaining in the produced polymer and scale. The reactor may be lined with glass in order to prevent the occurrence of scale. Agitation conditions are not limited, and a general anchor-type, spiral or bloomer gin-type agitating element can be used. The rate of agitation is generally 50 to 2000 rpm. In addition, if required, a chain transfer agent such as alkyl mercaptan may be added. A hindered phenol type or phosphorus type antioxidant may also be added in an early stage of polymerization, during polymerization or after polymerization. Further, a dispersion stabilizer may be added for stabilizing polymer grains within a range which does not cause deterioration in the characteristics of the produced polymer. If required, other vinyl monomers can be copolymerized. Examples of other vinyl monomers include styrene, α-methylstyrene, vinyltoluene, 1,3-butadiene, isoprene, 2-butene and halogen-substituted derivatives thereof; methacrylates such as methyl methacrylate, ethyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate and benzyl methacrylate; acrylates such as methyl acrylate, ethyl acrylate, butyl acrylate, cyclohexyl acrylate, phenyl acrylate and benzyl acrylate; vinyl vinyl esters such as vinyl acetate and vinyl benzoate; vinyl ethers such as methyl vinyl ether; ethyl vinyl ether, propyl vinyl ether and butyl vinyl ether: vinyl chloride, vinylidene chloride and acrylonitrile. At least one of these compounds is selected as a vinyl monomer. Although such a monomer can be added within a range which does not result in a failure of achievement of the object of the present invention, the amount of the monomer added is preferably 15 mol% or less, more preferably 5 mol% or less, particularly preferably 3 mol% or less, relative to the amount of maleimide. The addition of a vinyl monomer in an amount over the above value is undesirable because it has the tendency to decrease the transparency, color tone, thermal stability and mechanical strength of the produced polymer, and the tendencies to increase the scale and cause blocking. The polymer grains obtained by the aforementioned method are washed by a solvent which will dissolve maleimides and olefins and which will not dissolve the produced polymer grains so that the transparency of the produced polymer can be improved. Examples of washing solvents include aromatic solvents such as toluene and xylene; alcohols such as methanol and ethanol; ketones such as methyl ethyl ketone and cyclohexanone; ethers such as diethyl ether; acetates such as methyl acetate, ethyl acetate propyl acetate and butyl acetate. The maleimide-olefin copolymer obtained by the production method of the present invention comprises a maleimide repeating unit [formula (4)] wherein R 1 denotes a (cyclo) alkyl group having 1 to 6 carbon atoms and an olefin repeating unit [formula (5)] wherein R 2 and R 3 each denote a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. The ratio of the maleimide unit is preferably 30 to 98 mol%, more preferably 40 to 75 mol%, particularly preferably 50 to 70 mol%, of the total amount. The weight average molecular weight of the copolymer, which is determined by gel permeation chromatography (GPC), is preferably 1 x 10 3 to 1 x 10 7 , more preferably 1 x 10 4 to 1 x 10 6 . The maleimide-olefin copolymer obtained by the above method has a very low degree of yellowness and excellent transparency, and can thus be used as various optical materials, illumination parts, sheets and films. Description of the Preferred Embodiments. Although the present invention is described below with reference to examples, the present invention is not limited to the examples. The molecular weight of the produced polymer was measured by GPC (manufactured by Tosoh Corporation, HLC-802A) and was determined in terms of polystyrene. The light transmittance was measured by using a specimen which was formed by the small precision injection molding machine sold under the mark Minimat (manufactured by Sumitomo Jukikikai-kogyo K. K.) using pellets formed by a device sold under the mark Laboplastmill (Toyo-seiki K. K.) in accordance with ASTM 1746. The yellowness of the polymers was evaluated by a color computer (manufactured by Suga Shikenki K. K.) using a pressed piece of 50 x 25 x 0.8 mm in accordance with JIS K710 (reflection method: three stimulus values of a reflecting plate, X; 97.44; Y; 82.22, Z; 94.51). Example 1 117.7 g of N-methylmaleimide and 1.9 g of 2,2'-azobisisobutyronitrile (AIBN) were dissolved in a mixed solvent of toluene and methanol (weight ratio 5/5), and 1.5 l of the thus-formed solution was charged into a 3 litre autoclave provided with an anchor-type agitator, a nitrogen inlet tube, a thermometer and a deairing tube. After the solution was purged with nitrogen several times, 854 ml of isobutene was charged into the autoclave, followed by reaction at an agitation rate of 500 rpm and at 60°C for 10 hours. The precipitated polymer grains were filtered off and then dried under reduced pressure at 60°C for 24 hours. The yield was 175 g. The produced polymer grains had an average grain size of 250 µm (micrometres), a bulk density of 0.35 g/cm 3 and a scale content of 1% or less. The amount of the monomers remaining in the polymer obtained was 0.1 % by weight or less. The results (C; 64.7 % by weight, H; 7.8 % by weight, N; 8.4 % by weight) on elemental analysis of the polymer obtained showed that the amount of maleimide units in the product polymer was 50 mol%. The polymer obtained had a molecular weight (Mw) of 250,000, a glass transition temperature (Tg) of 152°C and a decomposition temperature (Td) of 397°C. The optical characteristics of the polymer obtained are shown in Table 1. Example 2 117.7 g of N-methylmaleimide and 0.8 g of perbutyl neodecanoate were dissolved in a mixed solvent of toluene and methanol (weight ratio 7/3), and 1.5 l of the thus-formed solution was charged into a 3 litre autoclave provided with a bloomer gin-type agitator, a nitrogen inlet tube, a thermometer and a deairing tube. After the solution was purged with nitrogen several times, 854 ml of isobutene was charged in the autoclave, followed by reaction at an agitation rate of 500 rpm and at 60°C for 5 hours. The precipitated polymer grains were filtered off and then dried under reduced pressure at 60°C for 24 hours. The yield was 174 g. The produced polymer grains had an average grain size of 200 µm (micrometres), a bulk density of 0.37 g/cm 3 and a scale content of 1% or less. The amount of the monomers remaining in the polymer obtained was 0.1 % by weight or less. The results of elemental analysis of the polymer obtained showed that the amount of maleimide units in the product polymer was 50 mol%. The polymer obtained had a molecular weight (Mw) of 180,000, glass transition temperature (Tg) of 153°C and a decomposition temperature (Td) of 397°C. The optical characteristics of the polymer obtained are shown in Table 1. Example 3 Part of the polymer grains obtained in Example 1 were transferred is form the reaction vessel and then agitated in 2 l of toluene at 60°C for 1 hour. The polymer was filtered off and then dried under reduced pressure at 60°C for 24 hours. The optical characteristics of the polymer obtained are shown in Table 1. Example 4 117.7 g of N-methylmaleimide and 0.94 g of lauryl peroxide were dissolved in a mixed solvent of butyl acetate and methyl ethyl ketone (weight ratio 7/3), and 1.5 l of the thus-formed solution was charged into a 3 litre autoclave provided with an anchor-type agitator, a nitrogen inlet tube, a thermometer and a deairing tube. After the solution was purged with nitrogen several times, 854 ml of isobutene was charged in the autoclave, followed by reaction at an agitation rate of 600 rpm and at 70°C for 8 hours. The precipitated polymer grains were filtered off and then dried under reduced pressure at 60°C for 24 hours. The yield was 174 g. The produced polymer grains had an average grain size of 470 µm (micrometres) and a scale content of 3.5 %. The amount of the monomers remaining in the polymer obtained was 0.1 % by weight or less. The results (C; 64.7 % by weight, H; 7.8 % by weight, N; 8.4 % by weight) of elemental analysis of the polymer obtained showed that the amount of N-alkylmaleimide units in the product polymer was 50 mol%. The polymer obtained had a molecular weight (Mw) of 220,000, a glass transition temperature (Tg) of 155°C and a decomposition temperature (Td) of 397°C. The optical characteristics of the polymer obtained are shown in Table 1. Example 5 117.7 g of N-methylmaleimide and 0.8 g of perbutyl neodecanoate were dissolved in a mixed solvent of ethyl acetate and butanol (weight ratio 6/4), and 1.5 l of the thus-formed solution was charged into a 3 litre autoclave provided with a bloomer gin-type agitator, a nitrogen inlet tube, a thermometer and a deairing tube. After the solution was purged with nitrogen several times, 767 ml of isobutene was charged in the autoclave, followed by reaction at an agitation rate of 800 rpm and at 60°C for 5 hours. The precipitated grains were filtered off, transferred to the reactor, and then agitated in 1.5 l methanol at 60°C for 30 minutes. The polymer was filtered off and then dried under reduced pressure at 60°C for 24 hours. The yield was 174 g. The produced polymer grains had an average grain size of 830 µm (micrometres) and a scale content of 8.4 %. The amount of the monomers remaining in the polymer obtained was 0.1 % by weight or less. The results of elemental analysis of the polymer obtained showed that the amount of N-alkylmaleimide units in the product polymer was 50 mol%. The polymer obtained had a molecular weight (Mw) of 180,000, a glass transition temperature (Tg) of 154°C and a decomposition temperature (Td) of 397°C. The optical characteristics of the polymer obtained are shown in Table 1. Example 6 32.8 g of N-methylmaleimide and 0.26 g of perbutyl neodecanoate were dissolved in xylene, and 0.5 l of the thus-formed solution was charged into a 1 litre autoclave provided with an anchor-type agitator, an isobutene inlet tube, a nitrogen inlet tube, a thermometer and a deairing tube. After the solution was purged with nitrogen several times, 240 ml of liquefied isobutene was charged into the autoclave, followed by reaction at an agitation rate of 600 rpm and at 60°C for 8 hours. The precipitated grains were filtered off, and then dried under reduced pressure at 60°C for 24 hours. The yield was 45 g. The produced polymer grains had an average grain size of 130 µm (micrometres) and a scale content of 6.5 %. The amount of the monomers remaining in the polymer obtained was 0.1 % by weight or less. The results of elemental analysis of the polymer obtained showed that the amount of N-methylmaleimide units in the product polymer was 50 mol%. The polymer obtained had a molecular weight (Mw) of 120,000, a glass transition temperature (Tg) of 155°C and a decomposition temperature (Td) of 397°C. The optical characteristics of the polymer obtained are shown in Table 1. Example 7 32.8 g of N-methylmaleimide and 0.8 g of perbutyl neodecanoate were dissolved in ethylbenzene, and 0.5 l of the thus-formed solution was charged into a 1 litre autoclave provided with a bloomer gin-type agitator, an isobutere inlet tube, a nitrogen inlet tube, a thermometer and a deairing tube. After the solution was purged with nitrogen several times, 240 ml of liquefied isobutene was charged into the autoclave, followed by reaction at an agitation rate of 500 rpm and at 60°C for 5 hours. The precipitated grains were filtered off, transferred to the reactor and then agitated in 0.5 l of methanol at 60°C for 30 minutes. The polymer obtained was filtered off and then dried under reduced pressure at 60°C for 24 hours. The yield was 44 g. The produced polymer grains had an average grain size of 630 µm (micrometres) and a scale content of 8.0 %. The amount of the monomers remaining in the polymer obtained was 0.1 % by weight or less. The results of elemental analysis of the polymer obtained showed that the amount of N-methylmaleimide units in the product polymer was 50 mol%. The polymer obtained had a molecular weight (Mw) of 90,000, a glass transition temperature (Tg) of 154°C and a decomposition temperature (Td) of 397°C. The optical characteristics of the polymer obtained are shown in Table 1. Example 8 38.72 g of N-methylmaleimide and 0.27 g of perbutyl neodecanoate were dissolved in acetonitrile, and 0.5 l of the thus-formed solution was charged into a 1 litre autoclave provided with an anchor-type agitator, an isobutene inlet tube, a nitrogen inlet tube, a thermometer and a deairing tube. After the solution was purged with nitrogen several times, 375 ml of liquefied isobutene was charged in the autoclave, followed by reaction at an agitation rate of 600 rpm and at 60°C for 5 hours. The precipitated grains were filtered off and then dried under reduced pressure at 60°C for 24 hours. The yield was 57 g. The produced polymer grains had an average grain size of 240 µm (micrometres) and a scale content of 9.5 %. The amount of the monomers remaining in the polymer obtained was 0.1 % by weight or less. The results of elemental analysis of the polymer obtained showed that the amount of N-methylmaleimide units in the product polymer was 50 mol%. The polymer obtained had a molecular weight (Mw) of 220,000, a glass transition temperature (Tg) of 155°C and a decomposition temperature (Td) of 397°C. The optical characteristics of the polymer obtained are shown in Table 1. Example 9 Part of the polymer grains obtained in Example 8 were transferred to the reactor, and then agitated in 0.5 l of methanol at 60°C for 30 minutes. The polymer was filtered off and then dried under reduced pressure at 60°C for 24 hours. The optical characteristics of the polymer obtained are shown in Table 1. Comparative Example 1 117.7 g of N-methylmaleimide and 0.94 g of lauryl peroxide were dissolved in dioxane, and 1.5 l of the thus-formed solution was charged into a 3 litre autoclave provided with an anchor-type agitator, a nitrogen inlet tube, a thermometer and a deairing tube. After the solution was purged with nitrogen several times, 854 ml of isobutene was charged in the autoclave, followed by reaction at an agitation rate of 500 rpm and at 60°C for 10 hours. After the reaction was completed, the polymerization system was homogeneous. The polymer solution obtained was poured into ethanol to precipitate the polymer, and the produced polymer was filtered off and then dried under reduced pressure at 60°C for 24 hours. The yield was 170 g. The amount of the monomers remaining in the polymer obtained was 0.5 % by weight. The optical characteristics of the polymer obtained are shown in Table 1. Comparative Example 2 117.7 g of N-methylmaleimide and 0.94 g of lauryl peroxide were dissolved in dioxane, and 1.5 l of the thus-formed solution was charged into a 3 litre autoclave provided with an anchor-type agitator, a nitrogen inlet tube, a thermometer and a deairing tube. After the solution was purged with nitrogen several times, 854 ml of isobutene was charged in the autoclave, followed by reaction at an agitation rate of 500 rpm and at 60°C for 10 hours. After the reaction was completed, the polymerization system was homogeneous. The sample obtained by removing the solvent from the polymer solution obtained using an evaporator was dried under reduced pressure at 60°C for 24 hours. The optical characteristics of the polymer obtained are shown in Table 1. Sample Light transmittance (%) Yellowness Example 1 92 3.3 Example 2 92 3.2 Example 3 92 3.0 Example 4 91 3.7 Example 5 92 3.3 Example 6 91 3.5 Example 7 92 3.1 Example 8 92 3.2 Example 9 92 2.9 Comparative Example 1 84 8.5 Comparative Example 2 77 23.7 The production method of the present invention is capable of efficiently producing a maleimide-olefin copolymer having very low yellowness and excellent optical characteristics such as transparency and the like. The polymer produced by the method can thus be applied to various optical elements and illumination parts.

Claims: A method of producing a copolymer comprising polymerization in a polymerization solvent characterised in that the copolymer is a maleimide-olefin copolymer and in that the polymerization solvent will dissolve maleimides and olefins and will not dissolve the polymer which is produced whereby the product polymer is precipitated in a granular form, and in that the polymerization is radical copolymerization of a maleimide and an olefin. A production method as claimed in Claim 1, characterised in that the maleimides are compounds expressed by formula (1); wherein R 1 denotes a (cyclo)alkyl group having 1 to 6 carbon atoms, and the olefins are compounds expressed by formula (2); wherein R 2 and R 3 each denote a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. A production method as claimed in Claim 1 or Claim 2, characterised in that a maleimide is methylmaleimide, and an olefin is isobutene. A production method as claimed in any one of Claims 1 to 3, characterised in that the polymerization solvent which produces polymer grains having an average grain size of 50 to 2000 µm (micrometres) and a bulk density of 0.1 to 1.0 g/cm 3 is used. A production method as claimed in any one of Claims 1 to 3, characterised in that the polymerization solvent which produces polymer grains having an average grain size of 100 to 1000 µm (micrometres) and a bulk density of 0.2 to 0.8 g/cm 3 is used. A production method as claimed in any one of Claims 1 to 5, characterised in that the said polymerization solvent is a mixed solvent containing an aromatic solvent and at least one solvent selected from the group consisting of alcohols, ketones, ethers and acetates. A production method as claimed in Claim 6, characterised in that the said polymerization solvent is a mixed solvent containing an alcohol and an aromatic solvent. A production method as claimed in claim 7, characterised in that the alcohol is methanol, and the aromatic solvent is toluene. A production method as claimed in any one of Claims 1 to 5, characterised in that the said polymerization solvent is a mixed solvent containing an acetate and at least one solvent selected from the group consisting of alcohols, ketones and ethers. A production method as claimed in any one of Claims 1 to 5, characterised in that the said polymerization solvent is a nitrile solvent. A production method as claimed in Claim 10, characterised in that the said nitrile solvent is acetonitrile. A production method as claimed in any one of Claims 1 to 5, characterised in that the said polymerization solvent is an aromatic solvent expressed by following formula (3); wherein R 4 to R 9 each denote a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxyl group or a halogen atom. A production method as claimed in any one of Claims 1 to 12, characterised in that the precipitated polymer is separated and then washed with a solvent which will dissolve maleimides and olefins and which will not dissolve the polymer.

Inventors: DOI TORU, SUGIURA YOSHIHIKO, DOI, TORU, SUGIURA, YOSHIHIKO
Applicants: TOSOH CORP, TOSOH CORPORATION
Application year: 1992
Main classification: C08F222
IPC codes: C08F220