JP2010084123A - Unsaturated alicyclic polycarbonate and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new polycarbonate and a method for producing the same. <P>SOLUTION: The unsaturated alicyclic polycarbonate is expressed by general formula (I) (wherein, R1 is independently selected from a substituted or unsubstituted alkyl, alkenyl, or aryl, respectively, x is an integer of 0-4, and n is an integer of 10-10,000). A halogen adduct of the unsaturated alicyclic polycarbonate is provided. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a polycarbonate obtained by a reaction of epoxide and carbon dioxide and a method for producing the same, and more particularly, an unsaturated alicyclic polycarbonate obtained by a reaction of unsaturated alicyclic epoxide and carbon dioxide. And a manufacturing method thereof.

  An aliphatic polycarbonate obtained by copolymerization of an aliphatic epoxide and carbon dioxide is interesting in that carbon dioxide is used as a raw material for a synthetic resin. In addition, since aliphatic polycarbonate has transparency and is completely decomposed when heated to a predetermined temperature or higher, it can be used for applications such as general moldings, films, fibers, and optical fibers such as optical fibers and optical disks. It can also be used as a material or a thermally decomposable material such as a ceramic binder or lost foam casting. Furthermore, since aliphatic polycarbonate can be decomposed in vivo, it can be applied as a medical material such as a sustained-release drug capsule, an additive of a biodegradable resin, or a main component of a biodegradable resin.

  Patent Document 1 describes an aliphatic polycarbonate obtained by reacting an aliphatic epoxide and carbon dioxide in the presence of a cobalt porphyrin chloride complex and a pyridine compound or an imidazole compound.

  Non-Patent Document 1 describes a saturated alicyclic polycarbonate obtained by alternating copolymerization of cyclohexene oxide and carbon dioxide with a manganese porphyrin complex.

JP 2006-241247 A

H. Sugimoto, H. Ohshima, and S. Inoue, J. Polym. Sci., Part A: Polym. Chem., Vol. 41, 3549-3555 (2003)

  An object of the present invention is to provide a novel polycarbonate and a method for producing the same.

又は下記一般式（II）：

（式中、Ｒ１はそれぞれ独立して、置換又は非置換の、アルキル基、アルケニル基又はアリール基から選択され、ｘは０〜４の整数であり、ｎは１０〜１００００の整数であり、ｌ及びｍはそれぞれ独立して０〜１００００の整数であってかつｌ＋ｍは１０〜１００００である。）で表される、不飽和脂環式ポリカルボナートである。本願における「不飽和脂環式ポリカルボナート」とは、ポリマー主鎖の少なくとも一部が環状炭化水素基及び炭酸基から構成され、当該環状炭化水素基に二重結合部位が含まれているものを指す。 One embodiment of the present invention is a compound represented by the following general formula (I):

Or the following general formula (II):

Wherein R1 is independently selected from a substituted or unsubstituted alkyl group, alkenyl group or aryl group, x is an integer of 0 to 4, n is an integer of 10 to 10,000, And m are each independently an integer of 0 to 10,000 and l + m is 10 to 10,000. “Unsaturated alicyclic polycarbonate” in the present application means that at least a part of a polymer main chain is composed of a cyclic hydrocarbon group and a carbonate group, and the cyclic hydrocarbon group contains a double bond site. Point to.

又は下記一般式（IV）：

（式中、Ｒ１はそれぞれ独立して、置換又は非置換の、アルキル基、アルケニル基又はアリール基から選択され、Ｒ２及びＲ３は、同一でも異なっていてもよく、水素原子、置換もしくは非置換のアルキル基、又は置換もしくは非置換の芳香族基であるか、又はＲ２とＲ３が互いに結合して置換もしくは非置換の環を形成してもよく、ｘは０〜４の整数であり、ｋ及びｎはそれぞれ独立して１〜１００００の整数であり、ｌ及びｍはそれぞれ独立して０〜１００００の整数であってかつｌ＋ｍは１〜１００００であり、ｋ＋ｎ及びｋ＋ｌ＋ｍは１０〜１００００である。）で表される、不飽和脂環式ポリカルボナートである。 Another embodiment of the present invention is the following general formula (III):

Or the following general formula (IV):

Wherein R1 is independently selected from a substituted or unsubstituted alkyl group, alkenyl group or aryl group, and R2 and R3 may be the same or different, and may be a hydrogen atom, substituted or unsubstituted An alkyl group, or a substituted or unsubstituted aromatic group, or R2 and R3 may be bonded to each other to form a substituted or unsubstituted ring, and x is an integer of 0 to 4, k and n is each independently an integer of 1 to 10,000, l and m are each independently an integer of 0 to 10,000, and l + m is 1 to 10,000, and k + n and k + l + m are 10 to 10,000.) It is unsaturated alicyclic polycarbonate represented by these.

又は下記一般式（VI）：

（式中、Ｒ１はそれぞれ独立して、置換又は非置換の、アルキル基、アルケニル基又はアリール基から選択され、ｘは０〜４の整数である。）で表される化合物と二酸化炭素とを共重合させる、不飽和脂環式ポリカルボナートの製造方法が提供される。 According to an embodiment of the present invention, in the presence of a cobalt porphyrin chloride complex and a pyridine compound or an imidazole compound, the following general formula (V):

Or the following general formula (VI):

(Wherein R1 is independently selected from a substituted or unsubstituted alkyl group, alkenyl group or aryl group, and x is an integer of 0 to 4) and carbon dioxide. A method for producing an unsaturated alicyclic polycarbonate to be copolymerized is provided.

（式中、Ｒ２及びＲ３は、同一でも異なっていてもよく、水素原子、置換もしくは非置換のアルキル基、又は置換もしくは非置換の芳香族基であるか、又はＲ２とＲ３が互いに結合して置換もしくは非置換の環を形成してもよい。）で表される化合物を、式（V）又は（VI）の化合物及び二酸化炭素と共重合させる、不飽和脂環式ポリカルボナートの製造方法が提供される。 Furthermore, according to another embodiment of the present invention, in the above-described method for producing an unsaturated alicyclic polycarbonate, the following general formula (VII):

(In the formula, R2 and R3 may be the same or different and are a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aromatic group, or R2 and R3 are bonded to each other. A compound represented by formula (V) or (VI) and carbon dioxide, and a method for producing an unsaturated alicyclic polycarbonate Is provided.

又は下記一般式（XI）：

（式中、Ｒ１はそれぞれ独立して、置換又は非置換の、アルキル基、アルケニル基又はアリール基から選択され、Ｘは、Ｃｌ、Ｂｒ又はＩから選択され、ｘは０〜４の整数であり、ｎ１は１〜１００００の整数、ｎ２は０〜１００００の整数であって、ｎ１＋ｎ２は１０〜１００００であり、ｌ１及びｍ１はそれぞれ独立して０〜１００００の整数であってｌ１＋ｍ１は１〜１００００、ｌ２及びｍ２はそれぞれ独立して０〜１００００の整数であってかつｌ１＋ｌ２＋ｍ１＋ｍ２は１０〜１００００である。）で表される、ハロゲン化脂環式ポリカルボナートである。 Another embodiment of the present invention is the following general formula (X):

Or the following general formula (XI):

Wherein R1 is independently selected from a substituted or unsubstituted alkyl group, alkenyl group or aryl group, X is selected from Cl, Br or I, and x is an integer of 0-4. , N1 is an integer from 1 to 10000, n2 is an integer from 0 to 10000, n1 + n2 is from 10 to 10000, l1 and m1 are each independently an integer from 0 to 10000, and l1 + m1 is from 1 to 10000, l2 and m2 are each independently an integer of 0 to 10,000, and l1 + l2 + m1 + m2 is 10 to 10,000.).

又は下記一般式（XIII）：

（式中、Ｒ１はそれぞれ独立して、置換又は非置換の、アルキル基、アルケニル基又はアリール基から選択され、Ｒ２及びＲ３は、同一でも異なっていてもよく、水素原子、置換もしくは非置換のアルキル基、又は置換もしくは非置換の芳香族基であるか、又はＲ２とＲ３が互いに結合して置換もしくは非置換の環を形成してもよく、Ｘは、Ｃｌ、Ｂｒ又はＩから選択され、ｘは０〜４の整数であり、ｋは１〜１００００の整数であり、ｎ１は１〜１００００の整数、ｎ２は０〜１００００の整数であり、ｌ１及びｍ１はそれぞれ独立して０〜１００００の整数であってかつｌ１＋ｍ１は１〜１００００、ｌ２及びｍ２はそれぞれ独立して０〜１００００の整数であり、ｋ＋ｎ１＋ｎ２及びｋ＋ｌ１＋ｌ２＋ｍ１＋ｍ２は１０〜１００００である。）で表される、ハロゲン化脂環式ポリカルボナートである。 Another embodiment of the present invention is the following general formula (XII):

Or the following general formula (XIII):

Wherein R1 is independently selected from a substituted or unsubstituted alkyl group, alkenyl group or aryl group, and R2 and R3 may be the same or different, and may be a hydrogen atom, substituted or unsubstituted An alkyl group, or a substituted or unsubstituted aromatic group, or R2 and R3 may be bonded to each other to form a substituted or unsubstituted ring, and X is selected from Cl, Br, or I; x is an integer of 0 to 4, k is an integer of 1 to 10000, n1 is an integer of 1 to 10000, n2 is an integer of 0 to 10000, and l1 and m1 are each independently 0 to 10000. L1 + m1 is an integer of 1 to 10,000, l2 and m2 are each independently an integer of 0 to 10,000, and k + n1 + n2 and k + l1 + l2 + m1 + m2 are 10 to 10,000. That.) Represented by a halogen cycloaliphatic polycarbonate.

  In addition, another embodiment of the present invention includes addition of a halogen molecule selected from the group consisting of chlorine, bromine and iodine to the unsaturated alicyclic polycarbonate. It is a manufacturing method.

According to the present invention, by using an unsaturated cycloaliphatic epoxides having a double bond site on the cyclic moiety, high polycarbonate of T _g can be obtained by rigid. In addition, since various reactions can be further performed on the double bond site of the obtained polymer, the unsaturated alicyclic polycarbonate of the present invention is used as an intermediate raw material, so that a new suitable for a desired use can be obtained. Polycarbonates having various structures or functions can be synthesized.

  The above description should not be construed as disclosing all embodiments of the present invention and all advantages related to the present invention.

¹ is a ¹ H-NMR spectrum of a reaction mixture obtained by copolymerizing CHDO and carbon dioxide. ^{1 is} a ¹ H-NMR spectrum of a polycarbonate obtained by copolymerizing CHDO and carbon dioxide. FIG. 3 is a partially enlarged view of the ¹ H-NMR spectrum of FIG. 2. It is a ¹³ C-NMR spectrum of a polycarbonate obtained by copolymerizing CHDO and carbon dioxide. It is the elements on larger scale of the ¹³ C-NMR spectrum of FIG. It is IR spectrum of polycarbonate obtained by copolymerizing CHDO and carbon dioxide. It is a ¹ H-NMR spectrum of polycarbonate obtained by copolymerizing CHDO, PO and carbon dioxide. It is the elements on larger scale of the ¹ H-NMR spectrum of FIG. It is IR spectrum of polycarbonate obtained by copolymerizing CHDO, PO and carbon dioxide. It is a GPC chart (detection method: 90 ° light scattering) of polycarbonate obtained by copolymerizing CHDO and carbon dioxide. ^{1 is} a ¹ H-NMR spectrum of a polycarbonate obtained by adding bromine to a copolymer of CHDO and carbon dioxide. It is a ¹³ C-NMR spectrum of a polycarbonate obtained by adding bromine to a copolymer of CHDO and carbon dioxide. It is IR spectrum of the polycarbonate obtained by adding bromine to the copolymer of CHDO and carbon dioxide. It is a GPC chart (detection method: RI) of polycarbonate obtained by adding bromine to a copolymer of CHDO and carbon dioxide. It is a GPC chart (detection method: 90 ° light scattering) of polycarbonate obtained by adding bromine to a copolymer of CHDO and carbon dioxide. It is a DSC measurement result of a polycarbonate obtained by adding bromine to a copolymer of CHDO and carbon dioxide. It is a TG-DTA measurement result of a polycarbonate obtained by adding bromine to a copolymer of CHDO and carbon dioxide.

  Hereinafter, the present invention will be described in more detail for the purpose of illustrating representative embodiments of the present invention, but the present invention is not limited to these embodiments.

  The unsaturated alicyclic polycarbonate of the present invention is copolymerized alternately with carbon dioxide as the epoxide portion of the unsaturated alicyclic epoxide is opened, as represented by the following general formula (I) or (II) It has the structure.

  N in the formula (I) represents the number of copolymer units in one molecule of the polymer, and is generally an integer of 10 to 10,000. In addition, l and m in the formula (II) represent the numbers of two types of copolymer units having different unsaturated bond positions, respectively. Such two types of copolymerized units have a carbon atom capable of binding to carbon dioxide in one copolymerized unit even when one type of unsaturated alicyclic epoxide is copolymerized with carbon dioxide. It can occur because there are two in unsaturated alicyclic epoxides and they are not equivalent. Generally, l and m are each independently an integer of 0 to 10,000, and l + m is 10 to 10,000. Among these, since the double bond site is located farther from the polymer main chain, it is sterically advantageous when a reaction such as an addition reaction is further performed on the double bond site of the copolymer. Therefore, the unsaturated alicyclic polycarbonate of the formula (I) is preferable.

  R1 is a substituent that can be introduced at one or more positions on the unsaturated hydrocarbon ring, and x represents the number of substitutions therein. x is an integer of 0 to 4, and when x is 0, it means that the unsaturated hydrocarbon ring is not substituted. x is preferably an integer of 0 to 2, and more preferably 0 or 1. When x is 2 or more, the plurality of R1s may be different substituents or the same substituent. The position where R1 is introduced is preferably from the 3rd to 6th positions, that is, other than the 1st and 2nd carbon atoms bonded to the oxygen atom.

  R1 is selected from a substituted or unsubstituted alkyl group, alkenyl group or aryl group, preferably an alkyl group or an aryl group. Examples of such a group include a methyl group, an ethyl group, a propyl group, a butyl group, a vinyl group, an allyl group, a cyclopentyl group, a cyclohexyl group, and a phenyl group. A methyl group, an ethyl group, a cyclohexyl group, and a phenyl group include preferable.

  R1 may be an alkyl group substituted with an alkoxy group or a siloxy group. For example, examples of the alkyl group having an alkoxy group as a substituent include a methoxymethyl group, a methoxyethyl group, a methoxypropyl group, an ethoxymethyl group, an ethoxyethyl group, an ethoxypropyl group, and an isopropoxymethyl group. Examples of the alkyl group having a siloxy group as a substituent include a trimethylsilyloxymethyl group, a trimethylsilyloxyethyl group, a triethylsilyloxymethyl group, and a triethylsilyloxyethyl group.

  R1 may be an aryl group or a cyclohexyl group having a substituent. For example, an aryl group or a cyclohexyl group substituted with a methyl group, an ethyl group or the like can be used. The substitution position and the number of substitutions in the aryl group or cyclohexyl group are not particularly limited.

  A part or all of the hydrogen atoms of R1 can be substituted with fluorine atoms. For example, when R1 is an alkyl group, it may be a fluoroalkyl group substituted at one or more fluorine atoms at any position including a perfluoroalkyl group. Examples of such a fluoroalkyl group include a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a perfluoroethyl group, and the like.

  In the unsaturated alicyclic polycarbonate of another embodiment of the present invention, the epoxide moiety of the unsaturated alicyclic epoxide and the second epoxide is opened as represented by the following general formula (III) or (IV). It has a structure in which the ring is copolymerized with carbon dioxide. The unsaturated alicyclic epoxide and the second epoxide each form a copolymer unit in pairs with carbon dioxide. These copolymerized units may be present randomly in the polymer, or may be present in at least a part of the polymer in a state where these copolymerized units are arranged as a block or arranged alternately.

  K and n in formula (III) represent the number of two types of copolymer units in the polymer, generally k and n are each independently an integer from 1 to 10,000 and k + n is from 10 to 10,000 . In addition, l and m in the formula (IV) respectively represent the number of two types of copolymer units having different unsaturated bond positions as described above for the unsaturated alicyclic polycarbonate of the formula (II), In general, l and m are each independently an integer of 0 to 10,000, l + m is 1 to 10,000, and k + m + l is 10 to 10,000. Among these, since the double bond site is located farther from the polymer main chain, it is sterically advantageous when a reaction such as an addition reaction is further performed on the double bond site of the copolymer. Therefore, the unsaturated alicyclic polycarbonate of the formula (III) is preferable.

  The substituent R1 and the number x in the formulas (III) and (IV) are as described above for the unsaturated alicyclic polycarbonates of the formulas (I) and (II).

  R2 and R3 may be the same or different and are a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aromatic group, or R2 and R3 are bonded to each other and substituted or unsubstituted. The ring may be formed.

  The alkyl group for R2 and R3 is preferably a linear or branched substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, n -Butyl group, sec-butyl group, tert-butyl group, n-pentyl group, 2-pentyl group, 3-pentyl group, iso-pentyl group, neopentyl group, tert-pentyl group, n-hexyl group, 2-hexyl Group, 3-hexyl group, 1-methyl-1-ethyl-n-pentyl group, 1,1,2-trimethyl-n-propyl group, 1,2,2-trimethyl-n-propyl group, 3,3- Dimethyl-n-butyl group, n-heptyl group, 2-heptyl group, 1-ethyl-1,2-dimethyl-n-propyl group, 1-ethyl-2,2-dimethyl-n-propyl group, n-octyl Group, - nonyl, n- decyl group, more preferably a methyl group. The alkyl group may be substituted with one or more substituents selected from, for example, a hydroxy group, an amino group, a carboxyl group, a sulfanyl group, a cyano group, a sulfo group, a formyl group, a halogen atom, and an aromatic group. Good.

  The substituted or unsubstituted aromatic group represented by R2 and R3 is preferably a substituted or unsubstituted aromatic group having 6 to 10 carbon atoms. For example, a substituted or unsubstituted aromatic group such as a phenyl group, an indenyl group, a naphthyl group, a tetrahydronaphthyl group, or the like. An unsubstituted aromatic hydrocarbon group is mentioned, More preferably, it is a phenyl group. Examples of the aromatic group include an alkyl group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group, and an aromatic group such as a phenyl group and a naphthyl group. It may be substituted with one or more substituents selected from the above.

R2 and R3 may be bonded to each other to form a substituted or unsubstituted ring, and may preferably form a substituted or unsubstituted aliphatic ring having 4 to 10 carbon atoms. For example, R2 and R3 are - _{(CH 2) 4} - when combined with one another through a form a cyclohexane ring. The ring thus formed is, for example, an alkyl group such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, phenyl group, naphthyl group, etc. It may be substituted with one or a plurality of substituents selected from the following aromatic groups.

  A part or all of the hydrogen atoms of R2 and / or R3 can be substituted with fluorine atoms. For example, when R2 and / or R3 is an alkyl group, it may be a fluoroalkyl group substituted at one or more fluorine atoms at any position including a perfluoroalkyl group. Examples of such a fluoroalkyl group include a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a perfluoroethyl group, and the like.

In particular, both R2 and R3 are hydrogen atoms, one of R2 and R3 is a methyl group and the other is a hydrogen atom, or one of R2 and R3 is a phenyl group and the other is a hydrogen atom, or R3 is preferably bonded to each other via — (CH ₂ ) ₄ — to form a cyclohexane ring.

  The unsaturated alicyclic polycarbonate of the present invention can be synthesized according to a conventionally known method for producing an aliphatic polycarbonate. Such production methods include, for example, zinc complexes (GW Coates, et al., J. Am. Chem. Soc. 2002, 124, 14284-14285), aluminum complexes (W. Kuran, et al., J. Macromol. Sci., Pure Appl. Chem., A35, 427-437 (1998)), porphyrin complex (JP 2006-241247 A) or salen complex (GW Coates, et al., Angew. Chem. Int. Ed. 2003, 42, 5484-5487), and a copolymerization reaction of epoxide and carbon dioxide. Among them, a method using a catalyst system in which a cobalt porphyrin chloride complex and a pyridine compound or an imidazole compound are combined as described in JP 2006-241247 A is an unsaturated alicyclic polycarbohydrate of the present invention. It can be advantageously used in the synthesis of nates and will be described in detail below.

  According to the production method of one embodiment of the present invention, an unsaturated alicyclic epoxide and carbon dioxide are copolymerized in the presence of a cobalt porphyrin chloride complex and a pyridine-based compound or an imidazole-based compound. An alicyclic polycarbonate is produced.

  The unsaturated alicyclic epoxide is a compound represented by the following general formula (V) or (VI), or a plurality of combinations thereof. The substituent R1 and the number x in the formulas (V) and (VI) are as described above for the unsaturated alicyclic polycarbonates of the formulas (I) to (IV).

  Compounds of formula (V) or (VI) can be synthesized utilizing various reactions and synthetic schemes known to those skilled in the art. Examples include substituted or unsubstituted alicyclic dienes such as 1,4-cyclohexadiene, 1,3-cyclohexadiene, 1-methyl-1,4-cyclohexadiene, 1-phenyl-1,4-cyclohexadiene, etc. The carbon-carbon double bond is epoxidized using an oxidizing agent such as meta-chloroperbenzoic acid. In this case, an unsaturated alicyclic epoxide having both a double bond site and an epoxy group in the molecule can be obtained by appropriately selecting reaction conditions, purification conditions, and the like.

  Specific examples of the compound of formula (V) include 1,4-cyclohexadiene-1,2-oxide, 4-methyl-1,4-cyclohexadiene-1,2-oxide, 4-vinyl-1,4-cyclo Hexadiene-1,2-oxide, 4-trifluoromethyl-1,4-cyclohexadiene-1,2-oxide, 4-ethyl-1,4-cyclohexadiene-1,2-oxide, 4- (2,2 , 2-trifluoroethyl) -1,4-cyclohexadiene-1,2-oxide, 4,5-dimethyl-1,4-cyclohexadiene-1,2-oxide, 4-cyclohexyl-1,4-cyclohexadiene -1,2-oxide, 4-methoxymethyl-1,4-cyclohexadiene-1,2-oxide, 4- (trimethylsilyloxymethyl) -5-methyl-1,4-cyclo Hexadiene-1,2-oxide, 4- (3-methylcyclohexyl) -1,4-cyclohexadiene-1,2-oxide, 4-phenyl-1,4-cyclohexadiene-1,2-oxide, 4- ( p-methylphenyl) -1,4-cyclohexadiene-1,2-oxide, 4- (2,4-dimethylcyclohexyl) -1,4-cyclohexadiene-1,2-oxide, 3-methyl-1,4 -Cyclohexadiene-1,2-oxide, 3,4-dimethyl-1,4-cyclohexadiene-1,2-oxide, 3-ethyl-1,4-cyclohexadiene-1,2-oxide, 3-phenyl- Examples include 1,4-cyclohexadiene-1,2-oxide and 3-cyclohexyl-1,4-cyclohexadiene-1,2-oxide. It is not. Among these, 1,4-cyclohexadiene-1,2-oxide is preferable.

  Specific examples of the compound of formula (VI) include 1,3-cyclohexadiene-1,2-oxide, 4-methyl-1,3-cyclohexadiene-1,2-oxide, 4-vinyl-1,3-cyclo Hexadiene-1,2-oxide, 4-trifluoromethyl-1,3-cyclohexadiene-1,2-oxide, 4-ethyl-1,3-cyclohexadiene-1,2-oxide, 4- (2,2 , 2-trifluoroethyl) -1,3-cyclohexadiene-1,2-oxide, 4,5-dimethyl-1,3-cyclohexadiene-1,2-oxide, 4-cyclohexyl-1,3-cyclohexadiene -1,2-oxide, 4-methoxymethyl-1,3-cyclohexadiene-1,2-oxide, 4- (trimethylsilyloxymethyl) -5-methyl-1,3-cycl Hexadiene-1,2-oxide, 4- (3-methylcyclohexyl) -1,3-cyclohexadiene-1,2-oxide, 4-phenyl-1,3-cyclohexadiene-1,2-oxide, 4- ( p-methylphenyl) -1,3-cyclohexadiene-1,2-oxide, 4- (2,4-dimethylcyclohexyl) -1,3-cyclohexadiene-1,2-oxide, 3-methyl-1,3 -Cyclohexadiene-1,2-oxide, 3,4-dimethyl-1,3-cyclohexadiene-1,2-oxide, 3-ethyl-1,3-cyclohexadiene-1,2-oxide, 3-phenyl- In addition to 1,3-cyclohexadiene-1,2-oxide, 3-cyclohexyl-1,3-cyclohexadiene-1,2-oxide, etc., an unsaturated hydrocarbon ring Examples include, but are not limited to, isomers of the above-mentioned compounds in which the positions of substituents are different. Among these, 1,3-cyclohexadiene-1,2-oxide is preferable.

  In the cobalt porphyrin chloride complex used in the production method of the present invention, four nitrogen atoms of tetraphenylporphyrin (TPP) are coordinated to the central metal cobalt in a planar four-coordinate, and a chlorine atom is coordinated to an axial position. (5,10,15,20-tetraphenylporfinato) cobalt chloride [(TPP) CoCl] is preferred.

  The amount of the cobalt porphyrin chloride complex used is generally 0.05 mol% to 1 mol%, preferably 0.1 mol% to 0.5 mol%, based on the total amount of epoxide to be reacted.

  As the pyridine-based compound, a compound represented by the following general formula (VIII) can be used.

  R4 is a substituent that can be introduced at one or more positions on the pyridine ring, and is selected from a substituted or unsubstituted methyl group, formyl group, or amino group, and is a methyl group, formyl group, or dimethylamino group. It is preferable that it is a dimethylamino group. In the above formula (VIII), y representing the number of substitutions is an integer of 0 to 5, and is preferably 0 or 1. When y is 2 or more, the plurality of R4s may be different substituents or the same substituent. The substitution position of R4 is preferably the 3-position or 4-position of the pyridine ring, and more preferably the 4-position.

  Examples of such pyridine compounds generally include pyridine, 4-methylpyridine, 4-formylpyridine, 4- (N, N-dimethylamino) pyridine, and the like, such as pyridine, 4-methylpyridine, 4- (N, N-dimethylamino) pyridine is preferred, and 4- (N, N-dimethylamino) pyridine is more preferred.

  As the imidazole compound, a compound represented by the following general formula (IX) can be used.

  R5 is a substituted or unsubstituted alkyl group such as a methyl group, an ethyl group, or a propyl group. Examples of such an imidazole compound include N-methylimidazole, N-ethylimidazole, N-propylimidazole and the like, and N-methylimidazole is preferable.

  The ratio of the cobalt porphyrin chloride complex and the pyridine compound is generally 0.3 to 5 mol of the pyridine compound with respect to 1 mol of the complex, preferably 0.3 to 2 mol. More preferably, it is 3 to 1 mol. If it exceeds 5 moles, the reaction rate becomes slow, the yield decreases, and cyclic carbonate (compound obtained by reaction of one epoxide molecule and one carbon dioxide molecule) is likely to be produced. On the other hand, when it is lower than 0.3 mol, the reaction rate becomes slow, carbon dioxide is not taken in, and a polyether in which only the epoxide is reacted is easily generated.

  The ratio of the cobalt porphyrin chloride complex and the imidazole compound is generally 0.3 to 1 mol of the imidazole compound with respect to 1 mol of the complex, and preferably 0.4 to 0.6 mol. .

  Copolymerization of epoxide and carbon dioxide may be performed without a solvent or in a solvent. When using a solvent, aromatic hydrocarbons such as benzene and toluene, halogenated hydrocarbons such as dichloromethane and chloroform, amides such as dimethylformamide, ethers such as tetrahydrofuran, and combinations thereof can be used. , Dimethylformamide and tetrahydrofuran are preferred, and dichloromethane and tetrahydrofuran are more preferred. When the reaction is performed using a solvent, the solvent is preferably 9 parts by volume or less and more preferably 3 parts by volume or less with respect to 1 part by volume of the epoxide.

  Regarding the cobalt porphyrin chloride complex, epoxide, pyridine compound or imidazole compound, and the solvent used as necessary, there is no particular limitation on the order of addition to the reaction vessel, but when using a solvent, the complex is previously added to the solvent. It is preferable to prepare a dissolved solution.

  The carbon dioxide pressure required for the progress of the reaction can generally be 1 to 100 atm, and can be reacted at a lower pressure as 1 to 50 atm. The carbon dioxide pressure may be adjusted by charging only carbon dioxide, or may be adjusted so that the carbon dioxide partial pressure is within the above range in the presence of nitrogen.

  Generally reaction temperature can be 100 degrees C or less, It is preferable that it is room temperature-80 degreeC, and it is more preferable that it is 30-60 degreeC.

  When the desired amount of epoxide has reacted, acetic anhydride, methanol or the like can be added to the reaction mixture as a reaction terminator, and the reaction can be terminated by raising the temperature and / or stirring as necessary. After completion of the reaction, the cobalt porphyrin chloride complex incorporated into the polymer may be removed by a method in which only one is precipitated from the complex and polymer solution, or a method in which only one is extracted from the solid mixture of the complex and polymer. it can. Specifically, it can react with a solvent that can dissolve the complex but is a poor solvent for the polymer, a solvent that can dissolve the polymer but is a poor solvent for the complex, or a basic site of the complex. It is possible to separate the complex from the polymer using an acidic substance that can form a salt. For example, the polymer may be reprecipitated using methanol, chloroform, dichloromethane or the like as a poor solvent, and the complex may be extracted from the solid mixture using a Soxhlet extractor. In addition, the polymer may be further purified using a known means such as column chromatography.

  In another embodiment of the invention, the second epoxide can be copolymerized with an unsaturated alicyclic epoxide and carbon dioxide.

  The second epoxide is a compound represented by the following general formula (VII), or a plurality of combinations thereof. The substituents R2 and R3 are as described above for the unsaturated alicyclic polycarbonates of formula (III) and formula (IV).

In particular, as the compound of formula (VII), ethylene oxide in which both R2 and R3 are hydrogen atoms, propylene oxide in which one of R2 and R3 is a methyl group and the other is a hydrogen atom, or one of R2 and R3 Is a phenyl group and the other is a hydrogen atom, and cyclohexene oxide in which R 2 and R ₃ are bonded to each other via — (CH ₂ ) ₄ — to form a cyclohexane ring.

  The second epoxide may be added in admixture with the unsaturated alicyclic epoxide, or may be added separately at any stage before the start of the reaction or during the reaction. The second epoxide is generally more reactive than the unsaturated alicyclic epoxide, and in this case, as the reaction proceeds, the second epoxide in the system is consumed relatively quickly and the unreacted second epoxide is consumed. The ratio of 2 epoxides to unsaturated alicyclic epoxides changes over time. In such a case, the ratio of the second epoxide and the unsaturated alicyclic epoxide incorporated into the growing part of the polymer (the part where the copolymerization is in progress) by adding an appropriate amount of the second epoxide during the reaction. Can be maintained within a certain range as required. Alternatively, only the unsaturated alicyclic epoxide is used at the start of the reaction, and the second epoxide is added after they are completely consumed, whereby the unsaturated alicyclic epoxide and carbon dioxide are alternately copolymerized and A block in which the second epoxide and carbon dioxide are alternately copolymerized can be formed in the polymer chain. Or the arrangement | positioning of a block can also be reversed by changing the injection | throwing-in order of an unsaturated alicyclic epoxide and a 2nd epoxide.

The unsaturated alicyclic polycarbonate of the present invention has various uses. Since unsaturated alicyclic polycarbonates of the present invention, including part of an alicyclic structure in the polymer chain, the motion of the molecular chain is limited, a higher T _g as compared to common aliphatic polycarbonates It has more rigidity. Therefore, handling property and workability in the vicinity of room temperature, which has often been a problem with aliphatic polycarbonates, can be improved. Furthermore, various reactions can be further performed using the double bond site of the obtained polymer. For example, by adding a halogen atom such as bromine to the double bond site of the polymer, an alicyclic polycarbonate having a high specific gravity and a high refractive index can be obtained. In addition, by performing Diels-Alder reaction using 1,3-butadiene or 1,3-cyclopentadiene or the like at the double bond site of the polymer, an aliphatic condensed ring or a bridged condensed ring having a double bond is included. , An alicyclic polycarbonate having a low birefringence can be obtained. These alicyclic polycarbonates are considered to be applicable to optical applications in combination with the high transparency generally possessed by aliphatic polycarbonates. In addition, various functional groups can be imparted using a conventionally known organic synthesis reaction for a carbon-carbon double bond.

又は下記一般式（XI）：

（式中、Ｒ１はそれぞれ独立して、置換又は非置換の、アルキル基、アルケニル基又はアリール基から選択され、Ｘは、Ｃｌ、Ｂｒ又はＩから選択され、ｘは０〜４の整数であり、ｎ１は１〜１００００の整数、ｎ２は０〜１００００の整数であって、ｎ１＋ｎ２は１０〜１００００であり、ｌ１及びｍ１はそれぞれ独立して０〜１００００の整数であってｌ１＋ｍ１は１〜１００００、ｌ２及びｍ２はそれぞれ独立して０〜１００００の整数であってかつｌ１＋ｌ２＋ｍ１＋ｍ２は１０〜１００００である。）で表される、ハロゲン化脂環式ポリカルボナートが挙げられる。 For example, as the halogenated alicyclic polycarbonate obtained by adding halogen to the unsaturated alicyclic polycarbonate, the following general formula (X):

Or the following general formula (XI):

Wherein R1 is independently selected from a substituted or unsubstituted alkyl group, alkenyl group or aryl group, X is selected from Cl, Br or I, and x is an integer of 0-4. , N1 is an integer from 1 to 10000, n2 is an integer from 0 to 10000, n1 + n2 is from 10 to 10000, l1 and m1 are each independently an integer from 0 to 10000, and l1 + m1 is from 1 to 10000, l2 and m2 are each independently an integer of 0 to 10,000, and l1 + l2 + m1 + m2 is 10 to 10,000.).

又は下記一般式（XIII）：

（式中、Ｒ１はそれぞれ独立して、置換又は非置換の、アルキル基、アルケニル基又はアリール基から選択され、Ｒ２及びＲ３は、同一でも異なっていてもよく、水素原子、置換もしくは非置換のアルキル基、又は置換もしくは非置換の芳香族基であるか、又はＲ２とＲ３が互いに結合して置換もしくは非置換の環を形成してもよく、Ｘは、Ｃｌ、Ｂｒ又はＩから選択され、ｘは０〜４の整数であり、ｋは１〜１００００の整数であり、ｎ１は１〜１００００の整数、ｎ２は０〜１００００の整数であり、ｌ１及びｍ１はそれぞれ独立して０〜１００００の整数であってかつｌ１＋ｍ１は１〜１００００、ｌ２及びｍ２はそれぞれ独立して０〜１００００の整数であり、ｋ＋ｎ１＋ｎ２及びｋ＋ｌ１＋ｌ２＋ｍ１＋ｍ２は１０〜１００００である。）で表される、ハロゲン化脂環式ポリカルボナートも挙げられる。 In addition, the following general formula (XII):

Or the following general formula (XIII):

Wherein R1 is independently selected from a substituted or unsubstituted alkyl group, alkenyl group or aryl group, and R2 and R3 may be the same or different, and may be a hydrogen atom, substituted or unsubstituted An alkyl group, or a substituted or unsubstituted aromatic group, or R2 and R3 may be bonded to each other to form a substituted or unsubstituted ring, and X is selected from Cl, Br, or I; x is an integer of 0 to 4, k is an integer of 1 to 10000, n1 is an integer of 1 to 10000, n2 is an integer of 0 to 10000, and l1 and m1 are each independently 0 to 10000. L1 + m1 is an integer of 1 to 10,000, l2 and m2 are each independently an integer of 0 to 10,000, and k + n1 + n2 and k + l1 + l2 + m1 + m2 are 10 to 10,000. That.) Represented by, and also halogen cycloaliphatic polycarbonate.

  Specific examples of R1, R2 and R3 in formulas (X) to (XIII), general values of x, and preferred types and numerical ranges thereof are those described above for unsaturated alicyclic polycarbonates. It is the same. N1 in formula (X) represents the number of halogenated copolymer units in one molecule of the polymer, and n2 represents the number of copolymer units that are not halogenated. In general, n1 is an integer of 1 to 10,000, n2 is an integer of 0 to 10,000, and n1 + n2 is 10 to 10,000. Here, when n2 is 0, it means that all the copolymer units having an aliphatic ring in one molecule of the polymer are halogenated. In the formula (XI), l1 and m1 represent the number of two types of copolymer units having different halogen substituent positions, respectively, and l2 and m2 represent two types of unhalogenated unsaturated bond positions. Each represents the number of copolymerized units. In general, l1 and m1 are each independently an integer of 0 to 10,000, l1 + m1 is 1 to 10,000, l2 and m2 are each independently an integer of 0 to 10,000, and l1 + l2 + m1 + m2 is 10 to 10,000. Here, when l2 and m2 are 0, it means that all copolymer units having an aliphatic ring in one polymer molecule are halogenated. In formulas (XII) and (XIII), k represents the number of different types of copolymer units, and k is an integer of 1 to 10,000. Except for k + n1 + n2 and k + l1 + l2 + m1 + m2 being 10 to 10,000, n1, n2, l1, l2, m1, and m2 in formulas (XII) and (XIII) are halogenated cycloaliphatic polymorphs of formulas (X) and (XI). The numerical value explaining the carbonate is taken. When an alicyclic polycarbonate having a high specific gravity and / or a high refractive index is desired, X is preferably Br or I.

The halogen addition reaction for the unsaturated alicyclic polycarbonate can be performed by a general method known to those skilled in the art. For example, by dissolving unsaturated alicyclic polycarbonate in a suitable solvent such as methylene chloride and adding chlorine (Cl ₂ ), bromine (Br ₂ ) or iodine (I ₂ ) thereto, the halogenated alicyclic ring The formula polycarbonate can be obtained. Chlorine is generally introduced in the gaseous state. Bromine and iodine can be added as such or dissolved in a suitable solvent. Chlorine, bromine or iodine may be used in stoichiometric amounts or in excess to completely halogenate the carbon-carbon double bonds, and these amounts may be adjusted as appropriate to leave the carbon-carbon double bonds. May be. From the viewpoint of reactivity to the carbon-carbon double bond, bromine or iodine can be advantageously used.

  Since the molecular weight increases with respect to the excluded volume of the polymer chain by the halogen addition, an alicyclic polycarbonate having a large specific gravity can be obtained. Further, since halogen atoms having a large atomic refraction are introduced by halogen addition, an alicyclic polycarbonate having a high refractive index can be obtained. In addition, a halogenated alicyclic polycarbonate having a double bond site that is not halogenated in the molecule, that is, a halogenated alicyclic poly (N2), l2 or m2 in formulas (X) to (XIII) is 1 or more. With respect to the carbonate, the organic synthesis reaction as described above can be further performed using the remaining double bond site.

  EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples.

Synthesis of unsaturated alicyclic epoxide 1,4-cyclohexadiene-1,2-oxide (CHDO) used as an unsaturated alicyclic epoxide in this example was synthesized as follows. 25 mL of 1,4-cyclohexadiene (254 mmol, used from Acros without purification) was dissolved in 100 mL of dichloromethane and cooled to 0 ° C. A mixed solution of meta-chloroperbenzoic acid 62.5 g (m-CPBA, 279 mmol, obtained from Sigma-Aldrich without purification), sodium hydrogen carbonate 23.4 g, dichloromethane 750 mL, and water 5 mL was added. It was added dropwise over 30 minutes while maintaining the temperature. After maintaining at 0 ° C. for 3 hours, the mixture was slowly returned to room temperature and stirred as it was overnight. Then, it wash | cleaned 3 times by turns with saturated sodium hydrogen carbonate solution and 5% sodium sulfite aqueous solution, and was finally washed with the saturated salt solution. After drying the organic layer with magnesium sulfate, the solvent was distilled off under reduced pressure to obtain a pale yellow liquid. The resulting liquid was distilled under reduced pressure over calcium hydride under nitrogen to give a colorless liquid (10.48 g, 42.9%). ^The identification result by ¹ H-NMR is shown below.

¹ H-NMR (400 MHz, CDCl ₃ ): δ 5.44 (2H, s, C═CH), 3.30 (2H, s, CH—O—), 2.58-2.53 (2H, CH ₂ ), 2.46-2.41 (2H, CH ₂ )

Synthesis of cobalt porphyrin chloride complex The cobalt porphyrin chloride complex [(TPP) CoCl] used in this example was synthesized as follows.

Propionic acid (2 L) was placed in a 2 L two-necked eggplant flask and refluxed. After stopping the heating, benzaldehyde (60 mL, 0.6 mol) and pyrrole (40 mL, 0.6 mol) were added thereto, and the reaction solution was stirred until it reached room temperature and left overnight. Thereafter, suction filtration was performed, and the resulting purple solid was repeatedly washed with warm water and methanol. The purple solid was recrystallized from chloroform (800 mL) / methanol (1200 mL) to obtain needle-like purple crystals (tetraphenylporphyrin, TPPH ₂ ) (yield 8.6 g, yield 9.6%).

Next, acetic acid (1500 mL) was put into a 2000 mL two-necked eggplant flask and refluxed. TPPH ₂ (2.4 mmol, 1.5 g), cobalt chloride (11.9 mmol, 2.85 g) and sodium acetate (2.0 g) were added to this, and the mixture was refluxed at 120 ° C. for 5 minutes. Left overnight. Thereafter, suction filtration was performed, and the residue was repeatedly washed with water, sodium bicarbonate water, and water in this order and dried to obtain a red solid (tetraphenylporfinatocobalt, TPPCo) (yield 1.13 g, yield 69%). Obtained.

  TPPCo (1.0 g, 1.46 mmol), methanol (1000 mL) and hydrochloric acid (10 mL) were placed in a 1000 mL one-necked eggplant flask and stirred overnight at room temperature. This was distilled off under reduced pressure, recrystallized from chloroform / hexane, and then dried to obtain a purple solid (tetraphenylporfinato) cobalt chloride complex [(TPP) CoCl] (yield 0.98 g, yield 93%). Got. Each UV-vis spectrum in methanol was in good agreement with literature values.

Evaluation apparatus and method
¹ H-NMR and ¹³ C-NMR measurements were performed at 27 ° C. in a Bruker DPX-400 spectrometer using CDCl ₃ as a solvent and tetramethylsilane (δ = 0.00 ppm) as an internal standard. The IR measurement was performed using either a KBr method or a film method using a Horiba FT-210 spectrometer. GPC measurement was performed with a calibration curve created with THF and standard polystyrene (TSK standard polystyrene, Tosoh) as an eluent in a Tosoh 8020 high-performance liquid chromatograph equipped with a differential refractive index detector and a tunable UV-visible light detector. At 40 ° C. and a flow rate of 0.8 mL / min. DSC measurement was performed in SII Nanotechnology Co., Ltd. DSC7020 under nitrogen at a measurement temperature range of −30 ° C. to 160 ° C. and a temperature increase rate of 10 ° C./min. The TG-TDA measurement was performed in SII Nano Technology Co., Ltd. TG / DTA6200 under nitrogen at a measurement range of 25 ° C. to 450 ° C. and a heating rate of 20 ° C./min.

Example 1 (Binary copolymer of CHDO and carbon dioxide)
A magnetic stirrer was placed in an autoclave purged with nitrogen, and (TPP) CoCl 50 μmol (35.3 mg) and 4- (N, N-dimethylamino) pyridine (obtained from Sigma-Aldrich) 37.5 μmol (4.6 mg) [0.75 equivalent to 1 equivalent of (TPP) CoCl] was added thereto, and 1.8 mL of dichloromethane was added thereto as a solvent, and then 25 mmol (2.4 g) of 1,4-cyclohexadiene-1,2-oxide (CHDO) was added. ) [500 times equivalent to (TPP) CoCl]. Carbon dioxide was injected under pressure, and the total pressure was adjusted to 50 atm (equivalent to 300 mmol of carbon dioxide). After reacting at 40 ° C. for 21 days, the reaction mixture was cooled to room temperature, and the reaction mixture was sampled and analyzed by ¹ H-NMR and IR.

FIG. 1 shows the ¹ H-NMR spectrum of the reaction mixture. From the integrated value of the remaining CHDO peak in this ¹ H-NMR spectrum, it was found that the reaction conversion rate of CHDO was 79%. The hydrogen atoms of the cyclohexene ring contained in the polycarbonate shown by a to d in the chemical structural formula of FIG. 1 are assigned to signals ^{1 to} d of ¹ H-NMR in FIG. Moreover, the signal which attached | subjected the black circle in FIG. 1 originates in the hydrogen atom of unreacted CHDO.

Also, the IR spectrum, an absorption due to C = O stretching vibration derived from a chain-like polycarbonate (1751cm ^-1) was observed, confirming the absorption (1780 cm ^-1) by a C = O stretching vibration derived from cyclic carbonate Was not.

Next, acetic anhydride was added to the autoclave as a terminator, the temperature was raised to 80 ° C., and the reaction was stopped at that temperature for 24 hours. Then, the contents were taken out and reprecipitated from chloroform / methanol. The obtained crude product was purified by silica gel column chromatography to obtain 2.17 g (yield 62%) of the product. About the obtained product, the result of having measured < ¹ > H-NMR, < ¹³ > C-NMR, IR, GPC, DSC, and TG-TDA is shown below. 2 and 3 show a ¹ H-NMR spectrum and a partially enlarged view thereof, respectively. FIGS. 4 and 5 show a ¹³ C-NMR spectrum and a partially enlarged view thereof, respectively. FIG. 6 shows the IR spectrum.

¹ H-NMR (400 MHz, CDCl ₃ ): δ 5.58 (a: 2H, s, C═CH), 5.02-4.88 (b: 2H, m, CH—O— (C═O) — _{), 2.76-2.53 (c: 2H,} m, CH 2), 2.35-2.15 (d: 2H, m, CH 2)
¹³ C-NMR (400 MHz, CDCl ₃ ): δ 153.9 (C═O), 153.6 (C═O), 123.2 (CH), 73.9-72.2 (CH—O—), 29.9-28.2 _(CH 2)
IR (KBr): 1751 cm ⁻¹ (C═O)
GPC (THF): Mn = 12,100, Mn / Mw = 1.09
DSC: T _g = 112 ° C
TG-DTA: T _d = 289 ° C.

^{From a 1} H-NMR spectrum, a signal d (5.0 ppm) derived from a methine proton of a chain carbonate was confirmed, but a signal derived from a methine proton of a polyether (around 3 to 4 ppm) was not confirmed. Therefore, the obtained product was a polycarbonate in which CHDO and carbon dioxide were alternately copolymerized. Further, since signal a was observed at 5.6 ppm with a signal d of 5.0 ppm and an integration ratio of 1: 1, it was also confirmed that a double bond site of an unsaturated six-membered ring was present in the polycarbonate. ^{From the 13} C-NMR spectrum, two signals were observed in the region of 150 to 155 ppm.

From the measurement results of GPC, it was found that the obtained polycarbonate was copolymerized with a narrow molecular weight distribution. From the results of DSC and TG-DTA, the glass transition temperature _{T g} of the polycarbonate containing an unsaturated hydrocarbon ring structure 112 ° C., the thermal decomposition temperature _{T d} was 289 ° C.. These values obtained by copolymerizing cyclohexene oxide and (CHO) and carbon dioxide for the poly (cyclohexene _{carbonate) (PCHC) (T g =} 115 ℃, T d = 280 ℃) compared with, _{T g} is approximately equal , _Td was about 10 ° C. higher.

Example 2 (CHDO, PO and carbon dioxide terpolymer)
A magnetic stirrer was added and the inside of the autoclave purged with nitrogen was charged with 0.1 mmol (70.7 mg) of (TPP) CoCl and 0.075 mmol (9.2 mg) of 4- (N, N-dimethylamino) pyridine [(TPP) CoCl1. 0.75 equivalent to the equivalent] was added, and 3.5 mL of dichloromethane was added thereto as a solvent, and then 30 mmol (2.5 mL) of CHDO [300 times equivalent to (TPP) CoCl] and propylene oxide (PO) ( Obtained from Tokyo Chemical Industry Co., Ltd.) 25 mmol (1.8 mL) [250 times equivalent to (TPP) CoCl] was added. Carbon dioxide was injected under pressure, and the total pressure was adjusted to 50 atm (equivalent to 300 mmol of carbon dioxide). When the reaction mixture was sampled to confirm the reaction conversion rate of each epoxide at the time of reaction for one week, CHDO was 38.5% and PO was 99%. The reaction was carried out at 40 ° C. for a total of 13 days, and then the reaction was stopped with methanol. The contents were taken out and reprecipitated twice using dichloromethane and methanol. The obtained crude product was purified by silica gel column chromatography (ethyl acetate: hexane = 3: 2) to obtain 5.21 g (yield: 85.1%, calculated from the amount of product) of the product. About the obtained product, the result of having measured < ¹ > H-NMR, IR, and GPC is shown below. 7 and 8 show the ¹ H-NMR spectrum and its partially enlarged view, respectively, and FIG. 9 shows the IR spectrum.

Hereinafter, “PCHDC” and “PPC” mean copolymerized units derived from polycyclohexadiene carbonate and polypropylene carbonate, respectively.
¹ H-NMR (400 MHz, CDCl ₃ ): δ 5.58 (s, PCHDC-CH), 4.97 (br, PCHDC-CHO, PPC-CHO), 4.33-4.05 (m, PPC-CH) _{2 O), 2.74-2.56 (d,} PCHDC-CH 2), 2.35-2.16 (d, PCHDC-CH 2), 1.38-1.29 (d, PPC-CH 3 )
IR (film): 1747 cm ⁻¹ (C═O)
GPC (THF): Mn = 16,000, Mn / Mw = 1.13

^From the integrated value of the signal of the ¹ H-NMR spectrum, it was found that the obtained product was a copolymer composed of PCHDC: PPC = 47: 53. Further, a signal (5.0 ppm) derived from a methine proton of a chain carbonate was confirmed, but a signal derived from a methine proton of a polyether (around 3 to 4 ppm) was not confirmed. Therefore, the obtained polymer was a polycarbonate in which epoxide (CHDO or PO) and carbon dioxide were alternately copolymerized. In addition, since a signal was observed at 5.5 ppm, it was also confirmed that a double bond site of an unsaturated six-membered ring was present in the polycarbonate. In the IR spectrum, a broad peak due to the terminal OH group was observed in the vicinity of 2800 to 3700 cm ⁻¹ . Since the obtained polycarbonate exhibits the same GPC peak shape as that of the polycarbonate obtained in Example 1, it is a terpolymer of CHDO, PO and carbon dioxide copolymerized with a narrow molecular weight distribution. I found out.

Example 3 (bromine adduct of binary copolymer of CHDO and carbon dioxide)
After dissolving 0.65 g of the unsaturated alicyclic polycarbonate of Example 1 in 2.5 mL of methylene chloride and cooling to 0 ° C., the bromine / methylene chloride solution (2.9 mol / L) disappeared from the bromine color. It was dripped until it disappeared. Then, 1.13 g (yield 81%) of a bromine adduct was obtained as a product by reprecipitation using chloroform / methanol. About the obtained product, the result of having measured < ¹ > H-NMR, < ¹³ > C-NMR, IR, GPC, DSC, and TG-TDA is shown below. In addition, FIGS. 11, 12 and 13 show a ¹ H-NMR spectrum, a ¹³ C-NMR spectrum and an IR spectrum, respectively. 14 and 15 are charts of GPC measurement using an RI detector and a 90 ° light scattering (LS) detector, respectively, and FIGS. 16 and 17 are charts of DSC and TG-DTA, respectively. . FIG. 10 is a chart of GPC measurement using an 90 ° light scattering (LS) detector of unsaturated alicyclic polycarbonate before addition of bromine, and the results are also shown below.

¹ H-NMR (400 MHz, CDCl ₃ ): δ 5.16 (2H, br, CHBr), 4.54 (2H, br, CHBr), 2.74 (2H, br, CH ₂ ), 2.52 (2H , Br, CH ₂ )
¹³ C-NMR (400 MHz, CDCl ₃ ): δ 153.3 (C═O), 74.4 (CHO), 49.8 (CHBr), 34.5 (CH ₂ )
IR (film): 1756 cm ⁻¹ (C═O), 736 cm ⁻¹ (C—Br)
GPC (RI, THF) _Mn = 12,000, _Mw = 13,600, _Mn / _Mw = 1.13
(Before LS, THF, bromine addition) M _w = 23,000
(LS, THF, bromine adduct) M _w = 45,000
DSC: T _g = 36 ° C.
TG-DTA: T _d = 297 ° C.

From the IR spectrum of the obtained product, it was confirmed that the carbonate bond was retained. In addition, from ¹ H-NMR, the disappearance of a signal around 5.6 ppm indicating the double bond observed in the unsaturated alicyclic polycarbonate of Example 1 and a signal of 4.5 ppm indicating the presence of bromomethine were confirmed. It was done. When the molecular weight was measured by GPC, Mn = 12000 and Mw = 13600 in the RI detector, which were almost the same as the copolymer before addition of bromine. However, when the molecular weight was measured with a 90 ° light scattering detector for the copolymer before and after addition of bromine, Mw _(LS) = 23000 before addition and Mw _(LS) = 45000 after addition, so that addition of bromine Increase in molecular weight was confirmed. Further, in 90 ° light scattering, a difference in molecular weight was observed before and after addition of bromine, while no change was observed in RI, suggesting an increase in molecular weight with respect to the excluded volume of the polymer chain due to addition of bromine. DSC, from the measurement of TG-DTA, T _d bromine adduct showed a higher value than the copolymer of Example 1, T _g was significantly lower.

Claims (12)

The following general formula (I):

Or the following general formula (II):

Wherein R1 is independently selected from a substituted or unsubstituted alkyl group, alkenyl group or aryl group, x is an integer of 0 to 4, n is an integer of 10 to 10,000, And m are each independently an integer of 0 to 10,000, and l + m is 10 to 10,000.)   The unsaturated alicyclic polycarbonate according to claim 1, which is represented by the formula (I). The following general formula (III):

Or the following general formula (IV):

Wherein R1 is independently selected from a substituted or unsubstituted alkyl group, alkenyl group or aryl group, and R2 and R3 may be the same or different, and may be a hydrogen atom, substituted or unsubstituted An alkyl group, or a substituted or unsubstituted aromatic group, or R2 and R3 may be bonded to each other to form a substituted or unsubstituted ring, and x is an integer of 0 to 4, k and n is each independently an integer of 1 to 10,000, l and m are each independently an integer of 0 to 10,000, and l + m is 1 to 10,000, and k + n and k + l + m are 10 to 10,000.) An unsaturated alicyclic polycarbonate represented by:   The unsaturated alicyclic polycarbonate according to claim 3, which is represented by the formula (III). In the presence of a cobalt porphyrin chloride complex and a pyridine or imidazole compound, the following general formula (V):

Or the following general formula (VI):

(Wherein R1 is independently selected from a substituted or unsubstituted alkyl group, alkenyl group or aryl group, and x is an integer of 0 to 4) and carbon dioxide. A method for producing an unsaturated alicyclic polycarbonate to be copolymerized. Furthermore, the following general formula (VII):

(In the formula, R2 and R3 may be the same or different and are a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aromatic group, or R2 and R3 are bonded to each other. 6. The method according to claim 5, wherein the compound represented by formula (V) may be copolymerized with the compound of the formula (V) or (VI) and carbon dioxide.   The method according to claim 5 or 6, wherein the cobalt porphyrin chloride complex is (5,10,15,20-tetraphenylporfinato) cobalt chloride. The pyridine compound is represented by the following general formula (VIII):

(Wherein, R4 is selected from a substituted or unsubstituted methyl group, formyl group, or amino group, and y is an integer of 0 to 5). The method described in one. The imidazole compound is represented by the following general formula (IX):

(Wherein R5 is a substituted or unsubstituted alkyl group). The following general formula (X):

Or the following general formula (XI):

Wherein R1 is independently selected from a substituted or unsubstituted alkyl group, alkenyl group or aryl group, X is selected from Cl, Br or I, and x is an integer of 0-4. , N1 is an integer from 1 to 10000, n2 is an integer from 0 to 10000, n1 + n2 is from 10 to 10000, l1 and m1 are each independently an integer from 0 to 10000, and l1 + m1 is from 1 to 10000, l2 and m2 are each independently an integer of 0 to 10,000, and l1 + l2 + m1 + m2 is 10 to 10,000. The following general formula (XII):

Or the following general formula (XIII):

Wherein R1 is independently selected from a substituted or unsubstituted alkyl group, alkenyl group or aryl group, and R2 and R3 may be the same or different, and may be a hydrogen atom, substituted or unsubstituted An alkyl group, or a substituted or unsubstituted aromatic group, or R2 and R3 may be bonded to each other to form a substituted or unsubstituted ring, and X is selected from Cl, Br, or I; x is an integer of 0 to 4, k is an integer of 1 to 10000, n1 is an integer of 1 to 10000, n2 is an integer of 0 to 10000, and l1 and m1 are each independently 0 to 10000. L1 + m1 is an integer of 1 to 10,000, l2 and m2 are each independently an integer of 0 to 10,000, and k + n1 + n2 and k + l1 + l2 + m1 + m2 are 10 to 10,000. That.) Represented by halogen cycloaliphatic polycarbonate.   A halogenated alicyclic polycarbohydrate comprising adding a halogen molecule selected from the group consisting of chlorine, bromine and iodine to the unsaturated alicyclic polycarbonate according to any one of claims 1 to 4. Nart manufacturing method.

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