KR20140108200A - Block and graft copolymers of poly(alkylene carbonate) and various polymers - Google Patents

Abstract

The present invention relates to a method for producing poly(alkylene carbonate) by means of the alternating copolymerization of carbon dioxide and epoxide. In particular, the present invention relates to a method for producing a block or graft copolymer of a polymer compound and poly(alkylene carbonate) and to a block or graft copolymer produced by means of the method, wherein the block or graft copolymer is produced by performing alternating copolymerization on an epoxide compound and carbon dioxide by using a metal trivalent compound produced from a salen-type ligand including quartic ammonium salt under the presence of the polymer comound having functional groups of hydroxyl or carboxylic acid.

Description

BACKGROUND OF THE INVENTION [0002] Block and graft copolymers of poly (alkylene carbonate) and various polymers with poly (alkylene carbonate)

The present invention relates to the production of poly (alkylene carbonates) by alternating copolymerization of carbon dioxide and epoxide. Specifically, using a metal trivalent compound prepared from a Salen-type ligand containing a quaternary ammonium salt as a catalyst, in the presence of a polymer compound having a hydroxy or carboxylic acid functional group, an epoxide compound and carbon dioxide To a block or graft copolymer of the polymer compound and a poly (alkylene carbonate), and to a block or graft copolymer produced by the method.

Poly (alkylene carbonate) is a biodegradable polymer, and is useful as, for example, a packaging material or a coating material. The method of producing a poly (alkylene carbonate) from an epoxide compound and carbon dioxide is environmentally-friendly in that it does not use a poisonous compound, phosgene, and that carbon dioxide can be obtained at low cost.

Since the 1960s, many researchers have developed various types of catalysts to produce poly (alkylene carbonates) from epoxide compounds and carbon dioxide. Recently, we have found that salen containing quaternary ammonium salts [Salen: ([H₂Salen =N,N '-bis (3,5-dialkylsalicylidene) -1,2-ethylenediamine] -type ligand [Japanese Patent Publication 10-0853358 (Registered on August 23, 2008) ; This disruption, Sujith S, Noh, Eun Kyung, Min Jae Ki, Korean Patent Application No. 10-2008-0015454 (filed Feb. 20, 2008); This split, Sujith S, Noh, Eun Kyung, Min Jae Ki, PCT / KR2008 / 002453 (Filing date: 2008.04.30); Eun Kyung Noh, Sung Jae Na, Sujith S, Sang-Wook Kim, and Bun Yeoul Lee *J. Am. Chem. Soc. 2007,129, 8082-8083 (2007.07.04); Sujith S, Jae Ki Min, Jong Eon Seong, Sung Jea Na, and Bun Yeoul Lee,Angew. Chem. Int. Ed.,2008, 47, 7306-7309 (2008.09.08)]. The catalyst disclosed by the present inventors can exhibit high activity and high selectivity, can produce a copolymer having a high molecular weight, can be polymerized at a high temperature, and can be applied to commercial processes. Also, since the quaternary ammonium salt is contained in the ligand, the catalyst can be easily separated from the copolymer after the carbon dioxide / epoxide copolymerization reaction and reused.

Further, the present inventors have carefully analyzed the structure of a catalyst showing particularly high activity and high selectivity in comparison with the catalyst group of the above patent, and found that the structure of the catalyst does not coordinate the nitrogen atom of the Salen- (An Example, 1, Sung Jae Na, Sujith S, Anish Cyriac, Bo Eun Kim, Jina Yoo, Youn K. Kang, Su Jung Han, Chongmok Lee, and Bun Yeoul Lee * "Elucidation of the Structure of A Highly Active Catalytic System for CO 2 / Epoxide Copolymerization: A Salen-Cobaltate Complex of An Unusual Binding Mode" Inorg. Chem. 2009 , 48 , 10455-10465).

Also, a method for easily synthesizing a ligand of the compound of Example 1 has been developed (Min, J .; Seong, JE; Na, SJ; Cyriac, A .; Lee, BY Bull. Korean Chem. Soc. 2009 , 30 , 745-748).

Structure 1 of the high activity catalyst A high molecular weight poly (alkylene carbonate) can be produced economically using a compound. However, poly (alkylene carbonate) itself has certain limitations in development of applications.

The present invention relates to a process for producing a poly (alkyl (meth) acrylate) which is prepared by introducing a polymer compound having a functional group of hydroxy or carboxylic acid into an alternating copolymerization reaction of carbon dioxide / epoxide using a newly developed highly active catalyst, A method for producing a block or graft copolymer of a block copolymer or a graft copolymer and various block polymers or graft copolymers, and a block or graft copolymer prepared by the process. The block or graft copolymer according to the invention enables diversification in the use of copolymers of carbon dioxide and epoxide.

In order to achieve the object of the present invention,

Using a complex of the following formula (1) as a catalyst,

In the presence of a polymer compound containing a hydroxyl or carboxylic acid group in terminal or side chain,

(C2-C20) alkylene oxide substituted or unsubstituted with halogen, (C1-C20) alkyloxy, (C6-C20) aryloxy or (C6-C20) aryl (C1-C20) aralkyloxy; (C4-C20) cycloalkylene oxides unsubstituted or substituted with halogen, (C1-C20) alkyloxy, (C6-C20) aryloxy or (C6-C20) aryl (C1-C20) aralkyloxy; And (C8-C20) aralkyloxy which is unsubstituted or substituted by halogen, (C1-C20) alkyloxy, (C6-C20) aryloxy, (C6- (Alkylene carbonate) comprising alternating copolymerization of carbon dioxide with at least one epoxide compound selected from the group consisting of styrene oxide, .

[Chemical Formula 1]

[In the above formula (1)

M is a cobalt trivalent or chromium trivalent;

A is an oxygen or sulfur atom;

Q is a diradical linking two nitrogen atoms;

R ¹ - R ¹⁰ is independently from each other hydrogen; halogen; (C1-C20) alkyl; (C1-C20) alkyl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C2-C20) alkenyl; (C2-C20) alkenyl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C1-C20) alkyl (C6-C20) aryl; (C 1 -C 20) alkyl (C 6 -C 20) aryl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C6-C20) aryl (C1-C20) alkyl; (C6-C20) aryl (C1-C20) alkyl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C1-C20) alkoxy; (C6-C30) aryloxy; Formyl; (C1-C20) alkylcarbonyl; (C6-C20) arylcarbonyl; Or a metalloid radical of a Group 14 metal substituted with hydrocarbyl;

The R &^lt; ^{1 &} R ¹⁰ Two of which may be connected to each other to form a ring;

The R &^lt; ^{1 &} At least one of the hydrogen atoms contained in R ¹⁰ and Q is a proton residue selected from the group consisting of the following formulas a, b and c;

X ^- are independently of one another a halogen anion; HCO ₃ ^- ; BF ₄ ^- ; ClO ₄ ^-; NO ₃ ^- ; PF ₆ ^- ; (C6-C20) aryloxy anion; (C6-C20) aryloxy anion comprising at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C1-C20) alkylcarboxy anion; (C1-C20) alkylcarboxy anion comprising at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C6-C20) arylcarboxy anion; (C6-C20) arylcarboxy anion comprising at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C1-C20) alkoxy anion; (C1-C20) alkoxy anion containing at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C1-C20) alkylcarbonate anion; A (C1-C20) alkylcarbonate anion comprising at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C6-C20) aryl carbonate anion; (C6-C20) aryl carbonate anion comprising at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C1-C20) alkylsulfonate anion; (C1-C20) alkylsulfonate anion comprising at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C1-C20) alkyl amido anion; (C1-C20) alkyl amido anion comprising at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C6-C20) arylamido anion; (C6-C20) aryl amido anion containing at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C1-C20) alkylcarbamate anion; (C1-C20) alkylcarbamate anion containing at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C6-C20) aryl carbamate anion; (C6-C20) arylcarbamate anion containing at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom;

Z is a nitrogen or phosphorus atom;

R ²¹ , R ²² , R ²³ , R ³¹ , R ³² , R ³³ , R ³⁴ and R ³⁵ independently of one another are (C 1 -C 20) alkyl; (C1-C20) alkyl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C2-C20) alkenyl; (C2-C20) alkenyl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C1-C20) alkyl (C6-C20) aryl; (C 1 -C 20) alkyl (C 6 -C 20) aryl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C6-C20) aryl (C1-C20) alkyl; (C6-C20) aryl (C1-C20) alkyl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; Or a metalloid radical of a Group 14 metal substituted with hydrocarbyl; Two of R ²¹ , R ²² and R ²³ or two of R ³¹ , R ³² , R ³³ , R ³⁴ and R ³⁵ may be connected to each other to form a ring;

R ⁴¹ , R ⁴² and R ⁴³ independently of one another are hydrogen; (C1-C20) alkyl; (C1-C20) alkyl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C2-C20) alkenyl; (C2-C20) alkenyl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C1-C20) alkyl (C6-C20) aryl; (C 1 -C 20) alkyl (C 6 -C 20) aryl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C6-C20) aryl (C1-C20) alkyl; (C6-C20) aryl (C1-C20) alkyl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; Or a metalloid radical of a Group 14 metal substituted with hydrocarbyl; Two of R ⁴¹ , R ⁴² and R ⁴³ may be connected to each other to form a ring;

X 'is an oxygen atom, a sulfur atom or N-R wherein R is (C1-C20) alkyl;

n is from R &^lt; R < ¹⁰ > and Q plus 1 to the total number of protons included;

X ^- may coordinate to M;

The nitrogen atom of the imine can be decarboxylated to M.]

The carbon dioxide / epoxide copolymerization using the compound of Formula 1 as a catalyst was patented by the present inventor and was also disclosed in the journal (Korean Patent Registration No. 10-0853358; J. Am. Chem. Soc. 2007, 129 , 8082-8083 , Angew. Chem. Int. Ed. , 2008, 47, 7306-7309), the copolymerization of hydroxyl or carboxylic acid groups provided by the present invention in the presence of polymeric compounds comprising terminal or side chains has not been known. Carbon dioxide / epoxide copolymerization in the course of polymer chain growth in the presence of a polymer compound containing a hydroxyl or carboxylic acid group in a terminal or a side chain is carried out in such a manner that X ^- It starts by attacking the side with a nucleophile. When the polymerization catalyst is disclosed which X has ^- beginning to the growing polymer chain from the end and X ^- is a device that is carbonate or an alkoxy anion in the polymer chain. The carbonate or alkoxy anion is a compound in the form of an alcohol or a carboxylic acid in the form of a hydroxyl or carboxylic acid group proton possessed by a polymer compound containing a further introduced hydroxyl or carboxylic acid group in a terminal or a side chain, The polymer compound containing an acid group in the terminal or side chain is a carboxyl or alkoxy anion. Once the polymer compound containing a hydroxyl or carboxylic acid group in the terminal or side chain becomes a carbosyl or alkoxy anion, the polymer chain can grow from it. The proton exchange reaction is a reaction that can take place very quickly, and the polymeric material resulting from this proton exchange and chain growth reaction is the polymer chain from the X ^- containing initial catalyst and the additional hydroxyl or carboxyl A polymer chain grown from a polymer compound containing an acid group in a terminal or a side chain is obtained. Since the polymer compound containing the introduced hydroxyl or carboxylic acid group in the terminal or side chain is a polymer compound, the compound obtained by the copolymerization reaction is a block copolymer.

Preferably, in Formula 1, M is a cobalt trivalent; A is oxygen; Q is trans-1, 2-cyclohexylene, phenylene or ethylene; R ¹ and R ² is the same or different primary (C 1 -C 20) alkyl; R ³ - R ¹⁰ is independently from each other hydrogen or - [YR ⁵¹ _3-a {(CR ⁵² R ⁵³ ) _b N ⁺ R ⁵⁴ R ⁵⁵ R ⁵⁶ } _a ]; Y is C or Si; R ⁵¹ , R ⁵² , R ⁵³ , R ⁵⁴ , R ⁵⁵ and R ⁵⁶ independently of one another are hydrogen; halogen; (C1-C20) alkyl; (C1-C20) alkyl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C2-C20) alkenyl; (C2-C20) alkenyl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C1-C20) alkyl (C6-C20) aryl; (C 1 -C 20) alkyl (C 6 -C 20) aryl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C6-C20) aryl (C1-C20) alkyl; (C6-C20) aryl (C1-C20) alkyl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C1-C20) alkoxy; (C6-C30) aryloxy; Formyl; (C1-C20) alkylcarbonyl; (C6-C20) arylcarbonyl; Or a metalloid radical of a Group 14 metal substituted with hydrocarbyl, and R ⁵⁴ , Two of R ⁵⁵ and R ⁵⁶ may be connected to each other to form a ring; a is an integer from 1 to 3, b is an integer from 1 to 20; n is R < ³ > A total number of quaternary ammonium salts included in R < ¹⁰ > Provided that when a is 1, R < ³ > At least three or more of the R ¹⁰ is _{^{- [YR 51 3-a {}} (CR 52 R 53) b N + R 54 R 55 R 56} a] , and if a is 2 to ³ R At least two or more of R ¹⁰ is _{^{- [YR 51 3-a {}} (CR 52 R 53) b N + R 54 R 55 R 56} a] and, if a is 3 to R ³ R < ¹⁰ > is - [YR ⁵¹ _3-a {(CR ⁵² R ⁵³ ) _b N ⁺ R ⁵⁴ R ⁵⁵ R ⁵⁶ } _a ].

That is, as the catalyst, a complex compound of the following formula (2) can be used.

(2)

[In the formula (2)

Q is trans-1, 2-cyclohexylene, phenylene or ethylene;

R ¹ and R ² is the same or different primary (C 1 -C 20) alkyl;

R ³ - R ¹⁰ is independently from each other hydrogen or - [YR ⁵¹ _3-a {(CR ⁵² R ⁵³ ) _b N ⁺ R ⁵⁴ R ⁵⁵ R ⁵⁶ } _a ];

Y is C or Si;

R ⁵¹ , R ⁵² , R ⁵³ , R ⁵⁴ , R ⁵⁵ and R ⁵⁶ independently of one another are hydrogen; halogen; (C1-C20) alkyl; (C1-C20) alkyl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C2-C20) alkenyl; (C2-C20) alkenyl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C1-C20) alkyl (C6-C20) aryl; (C 1 -C 20) alkyl (C 6 -C 20) aryl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C6-C20) aryl (C1-C20) alkyl; (C6-C20) aryl (C1-C20) alkyl, including at least one of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; (C1-C20) alkoxy; (C6-C30) aryloxy; Formyl; (C1-C20) alkylcarbonyl; (C6-C20) arylcarbonyl; Or a metalloid radical of a Group 14 metal substituted with hydrocarbyl, and R ⁵⁴ , Two of R ⁵⁵ and R ⁵⁶ may be connected to each other to form a ring;

a is an integer from 1 to 3, b is an integer from 1 to 20;

X ^- are independently of one another a halogen anion; HCO ₃ ^- ; BF ₄ ^- ; ClO ₄ ^-; NO ₃ ^- ; PF ₆ ^- ; (C6-C20) aryloxy anion; (C6-C20) aryloxy anion comprising at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C1-C20) alkylcarboxy anion; (C1-C20) alkylcarboxy anion comprising at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C6-C20) arylcarboxy anion; (C6-C20) arylcarboxy anion comprising at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C1-C20) alkoxy anion; (C1-C20) alkoxy anion containing at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C1-C20) alkylcarbonate anion; A (C1-C20) alkylcarbonate anion comprising at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C6-C20) aryl carbonate anion; (C6-C20) aryl carbonate anion comprising at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C1-C20) alkylsulfonate anion; (C1-C20) alkylsulfonate anion comprising at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C1-C20) alkyl amido anion; (C1-C20) alkyl amido anion comprising at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C6-C20) arylamido anion; (C6-C20) aryl amido anion containing at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C1-C20) alkylcarbamate anion; (C1-C20) alkylcarbamate anion containing at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom; (C6-C20) aryl carbamate anion; (C6-C20) arylcarbamate anion containing at least one of a halogen atom, a nitrogen atom, an oxygen atom, a silicon atom, a sulfur atom and a phosphorus atom;

R ³ - The total number of quaternary ammonium salts included in R ¹⁰ is an integer of 3 or more;

n is R < ³ > And the sum of the total number of quaternary ammonium salts contained in R < ¹⁰ >

When R < ¹ > and R < ² > are primary alkyls and the number of quaternary ammonium salts contained in the compound is 3 or more as in Formula 2, a unique coordination structure in which the nitrogen of the imine of Structure 1 is not coordinated in the polymerization reaction is formed, ( Inorg. Chem., 2009 , 48 , 10455-10465; Bulletin of Korean Chemical Society 2010 , under publication; Korean patent application No. 10-2008-0074435 (July 30, 2008) ) Carbon dioxide / epoxide copolymerization, which utilizes this type of catalyst and is carried out in the presence of a polymeric compound containing a hydroxyl or carboxylic acid group in the terminal or side chain, is not known.

More preferably, a complex compound represented by the following formula (3) is used as the catalyst.

(3)

[Wherein R ⁶¹ and R ⁶² are independently of each other methyl or ethyl; X ^- are independently of each other nitrate or acetate anion; Nitrogen of imine can be coordinated or disubstituted to cobalt, and each anion can coordinate to cobalt.]

The complex of formula (3) is a compound which can be easily synthesized in a large amount and is most preferable compound to be applied to commercialization ( Bull. Korean Chem. Soc. 2009 , 30 , 745-748) And carbon dioxide / epoxide copolymerization in which a hydroxyl or carboxylic acid group is carried out in the presence of a polymer compound containing terminal or side chains has not been known.

The polymer compound containing the hydroxyl or carboxylic acid group in terminal or side chain is selected from the following formulas (4) to (12).

[Chemical Formula 4]

R ⁷⁰ - [OL] _m -OH

Wherein R ⁷⁰ is (C1-C30) hydrocarbyl or hydrogen, which may or may not contain an ether group, an ester group, or an amino group; L is a (C1-C30) hydrocarbyl radical and m Ls in a chain may be the same or different; The number average molecular weight of the polymer compound of formula (4) is 500 to 500000.]

[Chemical Formula 5]

HO ₂ C- [E-CO ₂ -FO ₂ C] _m -E-CO ₂ H

[Chemical Formula 6]

HO- [FO ₂ CE-CO ₂ ] _m -F-OH

(7)

HO ₂ C- [E-CO ₂ -FO ₂ C] _m -E-CO ₂ -F-OH

Wherein E is (C1-C30) hydrocarbyl radical and m E groups in one chain may be the same or different from each other; F is a (C2-C30) hydrocarbyl radical containing an ether group, an ester group, or an amino group, and m Fs in a chain may be the same or different from each other; The number average molecular weight of the polymer compound of formulas (5) to (7) is 500 to 500000.]

[Chemical Formula 8]

{HO- [G-CO ₂ ] _m } _f -R ⁹⁰

Wherein G is a (C1-C15) hydrocarbyl radical and m G's in one chain may be the same or different from each other; f is an integer of 1-4 and when f is 1, R ⁹⁰ is hydrogen, (C 1 -C 30) hydrocarbyl, (C 1 -C 30) alkylcarbonyl or (C 6 -C 30) arylcarbonyl, when R ⁹⁰ is (C1-C30) dihydro car bildayi radical, when f is 3 R ⁹⁰ is (C1-C30) is a hydrocarbyl tree radical, f is R is 4 ^{to 90} is (C1-C30) hydrocarbyl-tetra Radical; The number average molecular weight of the polymer compound of formula (8) is 500 to 500000.]

[Chemical Formula 9]

HO- [Q-OC (O) O] _m- Q-OH

Wherein Q is independently (C1-C30) hydrocarbyl radical and m Qs belonging to one chain may be the same or different from each other; The number average molecular weight of the polymer compound of formula (9) is 500 to 500000.

[Chemical formula 10]

HO - [(R ¹¹¹ ) (R ¹¹² ) Si-O] _m -R ¹¹³

Wherein R ¹¹¹ and R ¹¹² are, independently of each other, a (C1-C15) hydrocarbyl radical; R < ¹¹³ > is hydrogen or (C1-C30) hydrocarbyl; The number average molecular weight of the polymer compound of formula (10) is 500 to 500000.]

(11)

R ¹⁰⁰ - [T] _m -JH

[Chemical Formula 12]

- {[T] _x - [CH ₂ CR ¹²¹ (JH)] _y } _m -

[In Formula 11 and 12, T is _{-CH 2 CH 2 -, -CH 2} CH (CH 3) -, -CH 2 CH (CH 2 CH 3) -, -CH 2 CH (CH 2 CH 2 CH 2 _{CH 3) -, -CH 2 CH} (CH 2 CH 2 CH 2 CH 2 CH 2 CH 3) -, -CH 2 CH (C 6 H 5) -, -CH 2 CH (CO 2 Me) -, -CH _{2 CH (Cl) -, -CH} 2 C (Me) (CO 2 Me) -, -CH 2 CH (OC (O) CH 3) -, -CH 2 CH = CHCH 2 -, -CH (Me) CH = CHCH ₂ - or _{-CH (Cl) CH = CHCH 2} - , and each T belonging to the chain may be the same or different from each other; R ¹⁰⁰ is HJ-, hydrogen, (C1-C20) hydrocarbyl, (C1-C20) alkoxy, (C1-C20) alkylcarbonyloxy or (C6-C20) arylcarbonyloxy; R < ¹²¹ > is hydrogen or methyl; J is -O- or -CO ₂ - and; The number average molecular weight of the polymer compound of formulas (11) and (12) is 500 to 500000.

The compound of formula (4) can be easily prepared by the reaction of the following reaction formulas (1) and (2).

[Reaction Scheme 1]

[Reaction Scheme 2]

There is no restriction on the molecular weight of the polymer compound to be added, but in order to realize the physical properties of the obtained block copolymer, the molecular weight of the polymer to be added is preferably 500 or more. Further, when a polymer having a too large molecular weight is added, the molar number of the hydroxyl or carboxylic acid group contained in the added polymer is smaller than the number of moles of the anion X < ^- > The polymer chain grown from X < ^- > can be obtained and the above object can not be achieved. The limit of the TON that can be implemented with the catalyst of the above formula (1) is about 50,000. For example, R ⁷⁰ having a 50 molecular weight of only 1 mole (500 Kg) added the alkyl polymer other than hydrogen, and put the propylene oxide (5800 Kg) of 100,000 mol In the catalyst 1 mole (about 1.5 Kg) and The maximum amount of polymer that can be obtained when the polymerization reaction is carried out under the pressure of carbon dioxide is 5000 Kg (equivalent to 50000 TON, except for the input 500 Kg polymer). Among them, the amount of poly (propylene carbonate) grown from the introduced polymer chains is 1/6 of the total amount, and the remainder is the polymer chain grown from X ^- . When the same activity is achieved by injecting 5 moles of the polymer, the amount of the poly (propylene carbonate) grown from the polymer chain and the amount of the polymer chain grown from X ^- become the same amount. In this calculation, the maximum molecular weight of a polymer capable of producing a block copolymer is limited to 500,000.

The compounds of Formulas 5 to 7 can be prepared by the condensation reaction of HO ₂ CE-CO ₂ H and HO-F-OH.

The compound of formula (8) is prepared by ring-opening polymerization of the following reaction formula (3). A change in R ⁹⁰ is possible depending on the initiator used.

[Reaction Scheme 3]

The compound of formula (9) can be prepared by the condensation reaction of dimethyl carbonate or diethyl carbonate with HOQ-OH.

The compound of formula (10) can be prepared by ring-opening polymerization of the following reaction formula (4).

[Reaction Scheme 4]

The compound of formula (11) can be prepared by radical, anion, or cationic polymerization of an olefin compound corresponding to each T.

The compound of formula (12) may be prepared by copolymerizing an olefin compound corresponding to each T with CH ₂ ═C (Me) (CO ₂ H) or CH ₂ ═CH (CO ₂ H) using a suitable initiator, Olefin compound and a compound of CH ₂ ═C (Me) (CO ₂ Me), CH ₂ ═CH (CO ₂ Me), or CH ₂ ═CH (O (O) CMe) with a radical and an appropriate initiator Followed by hydrolysis. In this case, the amount of the hydroxyl or carboxylic acid group contained in the introduced polymer is not limited by the molecular weight of the input polymer, so there is no limitation on the molecular weight of the polymer to be added. It is also unaffected by the aspect of the terminal.

In Formula 4, R ⁷⁰ is preferably hydrogen or (C 1 -C 15) alkyl, and L is preferably -CH ₂ CH ₂ -, -CH ₂ CH (CH ₃ ) - or -CH ₂ CH ₂ CH ₂ CH ₂ - Do. In the above Formulas 5 to 7, E is _{-CH 2 CH 2 -, -CH 2} CH 2 CH 2 -, -CH 2 CH 2 CH 2 CH 2 -, p-phenylene, or 2,6-butylene di naphtha days and, F is _{-CH 2 CH 2 OCH 2 CH 2} -, -CH 2 CH 2 -, -CH 2 CH (CH 3) -, -CH 2 CH 2 CH 2 -, -CH 2 C (CH 3) 2 CH ₂ -, -CH ₂ CH (CH ₃ ) CH ₂ - or -CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ -.

In Formula 8, G represents -CH ₂ -, -CH (CH ₃ ) -, -CH (CH ₃ ) CH ₂ -, -CH (CH ₂ CH ₃ ) CH ₂ - or -CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ - and R ⁹⁰ is hydrogen, (C 1 -C 8) alkyl or (C 2 -C 8) alkylcarbonyl.

In Formula 9, Q is preferably -CH ₂ CH ₂ CH ₂ CH ₂ - or -CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ -.

In Formula 10, R ¹¹¹ and R ¹¹² are independently methyl or phenyl, and R ¹¹³ is preferably hydrogen or (C 1 -C 8) alkyl.

In Formula 11 and T 12 are _{-CH 2 CH 2 -, -CH 2} CH (CH 3) -, -CH 2 CH (CH 2 CH 3) -, -CH 2 CH (CH 2 CH 2 CH 2 CH 3 _{) -, -CH 2 CH (CH} 2 CH 2 CH 2 CH 2 CH 2 CH 3) -, -CH 2 CH (C 6 H 5) -, -CH 2 CH (CO 2 Me) -, -CH 2 CH _{(Cl) -, -CH 2 C} (Me) (CO 2 Me) -, -CH 2 CH (OC (O) CH 3) -, -CH 2 CH = CHCH 2 -, -CH (Me) CH = CHCH _2, or may be selected from _{-CH (Cl) CH = CHCH 2} .

Wherein J is -O-, T is -CH ₂ CH ₂ - or -CH ₂ CH (CH ₂ CH ₃ ) -, R ¹⁰⁰ is hydrogen or HO-, or J is -CO ₂ - , T is -CH ₂ CH (C ₆ H ₅ ) -, R ¹⁰⁰ is preferably HO ₂ C- or butyl, J is -CO ₂ -, T is -CH ₂ CH (C ₆ H ₅ ) - and R ¹⁰⁰ is HO ₂ C- or butyl can be prepared by anionic polymerization of styrene and terminating the reaction with CO ₂ .

In Formula 12, T is _{-CH 2 CH 2 -, -CH 2} CH (C 6 H 5) -, -CH 2 CH (CO 2 Me) -, -CH 2 CH (Cl) - or -CH ₂ C (Me) (CO ₂ Me) -, R ¹²¹ is hydrogen or methyl, and J is -CO ₂ -.

The above-mentioned macromolecular compounds are general-purpose macromolecular compounds that can be purchased from companies such as Aldrich.

Specific examples of the epoxide compound in the above-described production process include ethylene oxide, propylene oxide, butene oxide, pentene oxide, hexene oxide, octene oxide, decene oxide, dodecene oxide, tetradecene oxide, hexadecene oxide, Butadiene glycidyl ether, t-butyl glycidyl ether, isobutyl glycidyl ether, isopropyl glycidyl ether, butyl glycidyl ether, t-butyl glycidyl ether, Ethylhexyl glycidyl ether, allyl glycidyl ether, cyclopentene oxide, cyclohexene oxide, cyclooctene oxide, cyclododecene oxide, alpha-pinene oxide, 2,3-epoxide norbornene, Limonene oxide, dieldrin, 2,3-epoxide propylbenzene, styrene oxide, phenylpropylene oxide 1,3-phenoxypropane, benzyloxymethyloxirane, glycidyl-methylphenyl ether, chlorophenyl-2,3-epoxide, chlorophenyl-2,3-epoxide Propyl ether, epoxypropyl methoxyphenyl ether, biphenyl glycidyl ether, glycidyl naphthyl ether, and the like.

Examples of the solvent include aliphatic hydrocarbons such as pentane, octane, decane and cyclohexane, aromatic hydrocarbons such as benzene, toluene and xylene, aromatic hydrocarbons such as chloromethane, methylene chloride , Chloroform, carbon tetrachloride, 1,1-dichloroethane, 1,2-dichloroethane, ethyl chloride, trichloroethane, 1- chloropropane, 2- chloropropane, 1- chlorobutane, 2- -Chloro-2-methylpropane, halogenated hydrocarbons such as chlorobenzene and bromobenzene, or a combination of two or more of them. More preferably, bulk polymerization can be carried out using the monomer itself as a solvent.

The molar ratio of the epoxide compound to the catalyst, that is, the epoxide compound: catalyst molar ratio is 1,000 to 1,000,000, preferably 50,000 to 200,000. In the copolymerization step, the pressure of the carbon dioxide can be from normal pressure to 100 atm, preferably at 5 atm and 30 atm. In the copolymerization step, the polymerization temperature may range from 20 占 폚 to 120 占 폚, preferably from 50 占 폚 to 90 占 폚.

The polymerization of the poly (alkylene carbonate) can be carried out by a batch polymerization method, a semi-batch polymerization method or a continuous polymerization method. In the case of using the batch or semi-batch polymerization method, the reaction time may be 0.5 to 24 hours, preferably 0.5 to 4 hours. The average residence time of the catalyst in the case of using the continuous polymerization method is also preferably 0.5 to 4 hours.

In another aspect of the present invention, there is provided a process for producing a block or graft copolymer of a poly (alkylene carbonate) and a polymer compound containing a hydroxyl or carboxylic acid group in a terminal or a side chain, And a solution in which the prepared block or graft copolymer and the catalyst are dissolved is contacted with a solid inorganic material, a polymer substance or a mixture thereof, which is not soluble in the solution, to form a complex of the solid inorganic material or the polymer substance with the catalyst And separating the prepared block or graft copolymer from the catalyst. The present invention also provides a method for producing a poly (alkylene carbonate).

Although a method for separating a catalyst after carrying out carbon dioxide / epoxide copolymerization using the same catalyst has already been known by the inventors (Korean Patent Application 10-2008-0015454; Angew. Chem. Int. Ed. , 2008 , 47, 7306-7309), a method of introducing a polymer compound containing a hydroxyl or carboxylic acid group selected from the formulas (4) to (12) into a terminal or a side chain to copolymerize and then separating the catalyst has not been known.

The solid inorganic material may be silica or alumina that is not surface-modified or surface-modified, and the polymer material may be a polymer material having a functional group capable of causing a deprotonation reaction by an alkoxy anion. The alkoxy anion may cause a deprotonation reaction The functional group that can occur is a sulfonic acid group, a carboxylic acid group, a phenol group or an alcohol group. Specific examples of the solid inorganic material containing silicon or aluminum as a main component including a brent acid acid point capable of providing a proton to an alkoxy anion or carbonate anion include silica, alumina, aluminosilicate (zeolite), aluminophosphate, Titanium silicate, clay, or the like, and it is more preferable to use silica or alumina that is not surface-modified or surface-modified.

It is preferable that the polymer material is crosslinked with a number average molecular weight of 500 to 10,000,000, but it is possible that it is not dissolved in a solution containing a copolymer and a catalyst even if it is not crosslinked. More specific examples of the "polymer substance having a functional group capable of causing a deprotonation reaction by an alkoxy anion" include a copolymer containing a monomer unit represented by the following formulas (I) to (V) in a polymer chain or a homopolymer composed of such a monomer unit . The polymer substance serving as such a support may be not crosslinked unless dissolved in the above-mentioned solution, but it is preferable that the polymer substance is crosslinked appropriately in order to lower the solubility.

In still another embodiment of the present invention, there is provided a block copolymer compound selected from the following formulas (13) to (15). There are no reported examples of such block copolymers of poly (alkylene carbonate) and other polymers.

[Chemical Formula 13]

W- {CR ^e1 R ^e2 -CR ^e3 R ^e4 -OC (O) O} _d -CR ^e1 R ^e2 -CR ^e3 R ^e4 -OH

[Wherein, W is _{^{R 70 - [OL] m -O-}} ( formula ^{d), HO-CR e3 R} e4 -CR e1 R e2 - {OC (O) O-CR e3 R e4 -CR e1 R e2} _d - [OL] _m -O- (formula ^{e), HO-CR e3 R} e4 -CR e1 R e2 - {OC (O) O-CR e3 R e4 -CR e1 R e2} d -O 2 C- [ _{E-CO 2 -FO 2 C]} m -E-CO 2 - ( formula ^{f), HO-CR e3 R} e4 -CR e1 R e2 - {OC (O) O-CR e3 R e4 -CR e1 R e2} _{d -O- [FO 2 CE-CO} 2] m -FO- ( formula ^{g), HO-CR e3 R} e4 -CR e1 R e2 - {OC (O) O-CR e3 R e4 -CR e1 R e2} _{d -O 2 C- [E-CO} 2 -FO 2 C] m -E-CO 2 -FO- ( formula ^{h), HO-CR e3 R} e4 -CR e1 R e2 - {OC (O) O-CR ^{e3 R e4 -CR e1 R e2}} d -O- [G-CO 2] m - ( formula ^{i), HO-CR e3 R} e4 -CR e1 R e2 - {OC (O) O-CR e3 R e4 - _{^{CR e1 R e2} d -O- [}} Q-OC (O) O] m -QO- ( formula j), -O - [(R 111) (R 112) Si-O] m -R 113 ( formula k ^{), HO-CR e3 R e4} -CR e1 R e2 - {OC (O) O-CR e3 R e4 -CR e1 R e2} d -O - [(R 111) (R 112) Si-O] m - (formula ^{l), R 100 - [T} ] m -J- ( formula m) and ^{HO-CR e3 R e4 -CR e1} R e2 - {OC (O) O-CR e3 R e4 -CR e1 R e2} d -J- [T] _m- J- (formula n);

R ^e1 to R ^e4 independently of one another are hydrogen; (C1-C10) alkyl unsubstituted or substituted with halogen or (C1-C20) alkoxy; (C6-C10) aryl which is unsubstituted or substituted by halogen or (C1-C20) alkoxy, and R ^e1 to R ^e4 may be linked to form a ring, and d is an integer of 10 to 5000;

R ⁷⁰ is a (C1-C30) hydrocarbyl containing or not having an ether group, an ester group or an amino group;

L is a (C1-C30) hydrocarbyl radical and m Ls in a chain may be the same or different;

E is a (C1-C30) hydrocarbyl radical and the m E groups in a chain may be the same or different;

F is a (C2-C30) hydrocarbyl radical containing an ether group, an ester group, or an amino group, and m Fs in a chain may be the same or different from each other; G is a (C1-C15) hydrocarbyl radical and m G's in one chain may be the same or different from each other;

Q is independently (C1-C30) hydrocarbyl radical and the m Qs in a chain may be the same or different;

R ¹¹¹ and R ¹¹² are independently of each other a (C 1 -C 15) hydrocarbyl radical; R < ¹¹³ > is hydrogen or (C1-C30) hydrocarbyl;

J is -O- or -CO ₂ - and;

T is _{-CH 2 CH 2 -, -CH 2} CH (CH 3) -, -CH 2 CH (CH 2 CH 3) -, -CH 2 CH (CH 2 CH 2 CH 2 CH 3) -, -CH 2 _{CH (CH 2 CH 2 CH 2} CH 2 CH 2 CH 3) -, -CH 2 CH (C 6 H 5) -, -CH 2 CH (CO 2 Me) -, -CH 2 CH (Cl) -, - _{CH 2 C (Me) (CO} 2 Me) -, -CH 2 CH (OC (O) CH 3) -, -CH 2 CH = CHCH 2 -, -CH (Me) CH = CHCH 2 - or -CH ( Cl) CH = CHCH ₂ -, and m number of T belonging to the chain may be the same or different from each other;

R ¹⁰⁰ is hydrogen, (C1-C20) hydrocarbyl, (C1-C20) alkoxy, (C1-C20) alkylcarbonyloxy or (C6-C20) arylcarbonyloxy;

R ⁷⁰ - [OL] _m -, - [OL] _m -, - O ₂ C- [E-CO ₂ -FO ₂ C] _m -E-CO ₂ -, -O- [FO _2- CE-CO ₂ ] _m -FO-, -O ₂ C- [E-CO ₂ -FO ₂ C] _m -E-CO ₂ -FO-, -O- [G-CO ₂ ] _m -, -O - [Q-OC (O) O] m -QO-, -O - [(R 111) (R 112) Si-O] m -R 113, -O - [(R 111) (R 112) Si- O] _m -, R ¹⁰⁰ - [T] _m -J- and -J- [T] _m -J-blocks have a number average molecular weight of 500 to 500000.

[Chemical Formula 14]

^{{HO-CR e3 R e4 -CR} e1 R e2 - {OC (O) O-CR e3 R e4 -CR e1 R e2} d -O- [G-CO 2] m} f -R 90

Wherein G is a (C1-C15) hydrocarbyl radical and m G's in one chain may be the same or different from each other; f is an integer of 1-4 and when f is 1, R ⁹⁰ is hydrogen, (C 1 -C 30) hydrocarbyl, (C 1 -C 30) alkylcarbonyl or (C 6 -C 30) arylcarbonyl, when R ⁹⁰ is (C1-C30) dihydro car bildayi radical, when f is 3 R ⁹⁰ is (C1-C30) is a hydrocarbyl tree radical, f is R is 4 ^{to 90} is (C1-C30) hydrocarbyl-tetra Radical; - {O- [G-CO ₂ ] _m } _f -R ⁹⁰ block has a number average molecular weight of 500 to 500000, and R ^e1 to R ^e4 independently of one another are hydrogen; (C1-C10) alkyl unsubstituted or substituted with halogen or (C1-C20) alkoxy; (C6-C10) aryl which is unsubstituted or substituted by halogen or (C1-C20) alkoxy, and R ^e1 to R ^e4 may be linked together to form a ring, and d is an integer of 10 to 5000.

[Chemical Formula 15]

_{- {[T] x - [} CH 2 CR 121 (J- {CR e1 R e2 -CR e3 R e4 -OC (O) O} d -CR e1 R e2 -CR e3 R e4 -OH)] y} m -

[In the formula 15, J is -O- or -CO ₂ - and; T is _{-CH 2 CH 2 -, -CH 2} CH (CH 3) -, -CH 2 CH (CH 2 CH 3) -, -CH 2 CH (CH 2 CH 2 CH 2 CH 3) -, -CH 2 _{CH (CH 2 CH 2 CH 2} CH 2 CH 2 CH 3) -, -CH 2 CH (C 6 H 5) -, -CH 2 CH (CO 2 Me) -, -CH 2 CH (Cl) -, - _{CH 2 C (Me) (CO} 2 Me) -, -CH 2 CH (OC (O) CH 3) -, -CH 2 CH = CHCH 2 -, -CH (Me) CH = CHCH 2 - or -CH ( Cl) CH = CHCH ₂ -, and each T belonging to the chain may be the same or different from each other; R < ¹²¹ > is hydrogen or methyl; The number-average molecular weight of the main chain of the polymer is 500 to 500000, and R ^e1 to R ^e4 independently of one another are hydrogen; (C1-C10) alkyl unsubstituted or substituted with halogen or (C1-C20) alkoxy; (C6-C10) aryl which is unsubstituted or substituted by halogen or (C1-C20) alkoxy, and R ^e1 to R ^e4 may be linked together to form a ring, and d is an integer of 10 to 50000.

The maximum turnover number (TON) that can be implemented with the catalyst used in the present invention is about 50,000. If d is 5000, the number of chains grown is 10. Five chains were grown from the catalyst X ^- and the remaining five were grown from the polymer. That is, it can be said that half of the poly (alkylene carbonate) is a pure poly (alkylene carbonate) and half of the block copolymer gives physical properties of the block copolymer.

In the above formula (13), when W is R ⁷⁰ - [OL] _m -O- (formula d), it is represented by the following formula 13-d.

[Chemical Formula 13-d]

R ⁷⁰ - [OL] _m -O- {CR ^e1 R ^e2 -CR ^e3 R ^e4 -OC (O) O} _d -CR ^e1 R ^e2 -CR ^e3 R ^e4 -OH

[In the formula 13-d, R ⁷⁰ is (C1-C30) hydrocarbyl with or without an ether group, an ester group, or an amino group; L is a (C1-C30) hydrocarbyl radical and m Ls in a chain may be the same or different; The number average molecular weight of the R ⁷⁰ - [OL] _m block is 500 to 500000, and R ^e1 to R ^e4 independently of one another are hydrogen; (C1-C10) alkyl unsubstituted or substituted with halogen or (C1-C20) alkoxy; (C6-C10) aryl which is unsubstituted or substituted by halogen or (C1-C20) alkoxy, and R ^e1 to R ^e4 may be linked together to form a ring, and d is an integer of 10 to 5000.

Specifically, R ⁷⁰ of the polymer compound of the above formula (13-d) is (C 1 -C 15) alkyl; L is _{-CH 2 CH 2 -, -CH 2} CH (CH 3) - or _{-CH 2 CH 2 CH 2 CH 2} - , and; R ^e1 to R ^e4 are each independently hydrogen or methyl, preferably all of R ^e1 to R ^e4 are hydrogen, or R ^e1 to R ^e3 are all hydrogen and R ^e4 is methyl (R ^e1 is methyl And all of R ^e2 to R ^e4 are hydrogen).

In formula (13), W represents a group represented by HO-CR ^{e3R e4} -CR ^e1 R ^e2 - {OC (O) O-CR ^e3 R ^e4 -CR ^e1 R ^e2 _d- [OL] _m- Is represented by the following formula (13-e).

[Formula 13-e]

^{HO-CR e3 R e4 -CR e1} R e2 - {OC (O) O-CR e3 R e4 -CR e1 R e2} d - [OL] m -O- {CR e1 R e2 -CR e3 R e4 -OC (O) O} _d -CR ^e1 R ^e2 -CR ^e3 R ^e4 -OH

[In the above formula (13-e), L is a (C1-C30) hydrocarbyl radical and m Ls belonging to one chain may be the same or different from each other; - [OL] _m blocks have a number average molecular weight of 500 to 500000, and R ^e1 to R ^e4 independently of one another are hydrogen; (C1-C10) alkyl unsubstituted or substituted with halogen or (C1-C20) alkoxy; (C6-C10) aryl which is unsubstituted or substituted by halogen or (C1-C20) alkoxy, and R ^e1 to R ^e4 may be linked together to form a ring, and d is an integer of 10 to 5000.

Specifically, L of the polymer compound of Formula 13-e is -CH ₂ CH ₂ -, -CH ₂ CH (CH ₃ ) - or -CH ₂ CH ₂ CH ₂ CH ₂ -; R ^e1 to R ^e4 are each independently hydrogen or methyl, preferably all of R ^e1 to R ^e4 are hydrogen, or R ^e1 to R ^e3 are all hydrogen and R ^e4 is methyl (R ^e1 is methyl And all of R ^e2 to R ^e4 are hydrogen).

In Formula 13, the W ^{HO-CR e3 R e4 -CR e1} R e2 - {OC (O) O-CR e3 R e4 -CR e1 R e2} d -O 2 C- [E-CO 2 -FO 2 _{C] m -E-CO 2 -} ( formula ^{f), HO-CR e3 R} e4 -CR e1 R e2 - {OC (O) O-CR e3 R e4 -CR e1 R e2} d -O- [FO 2 CE-CO _{2] m} -FO- (formula g) or ^{HO-CR e3 R e4 -CR e1} R e2 - {OC (O) O-CR e3 R e4 -CR e1 R e2} d -O 2 C- [ E-CO ₂ -FO ₂ C] _m -E-CO ₂ -FO- (formula h), the compound is represented by the following formula 13-f, 13-g or 13-h.

[Chemical Formula 13-f]

^{HO-CR e3 R e4 -CR e1} R e2 - {OC (O) O-CR e3 R e4 -CR e1 R e2} d -O 2 C- [E-CO 2 -FO 2 C] m -E-CO ₂ - {CR ^e1 R ^e2 -CR ^e3 R ^e4 -OC (O) O} _d -CR ^e1 R ^e2 -CR ^e3 R ^e4 -OH

[Chemical Formula 13-g]

^{HO-CR e3 R e4 -CR e1} R e2 - {OC (O) O-CR e3 R e4 -CR e1 R e2} d -O- [FO 2 CE-CO 2] m -FO- {CR e1 R e2 -CR ^e R ^e4 -OC (O) O} _d -CR ^e1 R ^e2 -CR ^e3 R ^e4 -OH

[Chemical Formula 13-h]

^{HO-CR e3 R e4 -CR e1} R e2 - {OC (O) O-CR e3 R e4 -CR e1 R e2} d -O 2 C- [E-CO 2 -FO 2 C] m -E-CO ₂ -FO- {CR ^e1 R ^e2 -CR ^e3 R ^e4 -OC (O) O} _d -CR ^e1 R ^e2 -CR ^e3 R ^e4 -OH

[Eq. 13-f to 13-h, E is a (C1-C30) hydrocarbyl radical and m E groups in a chain may be the same or different from each other; F is a (C2-C30) hydrocarbyl radical containing an ether group, an ester group, or an amino group, and m Fs in a chain may be the same or different from each other; -O ₂ C- [E-CO ₂ -FO ₂ C] _m -E-CO ₂ -, -O- [FO ₂ CE-CO ₂ ] _m -FO-, or -O ₂ C- [E-CO ₂ -FO ₂ C] _m -E-CO ₂ -FO- block has a number average molecular weight of 500 to 500000, and R ^e1 to R ^e4 independently of one another are hydrogen; (C1-C10) alkyl unsubstituted or substituted with halogen or (C1-C20) alkoxy; (C6-C10) aryl which is unsubstituted or substituted by halogen or (C1-C20) alkoxy, and R ^e1 to R ^e4 may be linked together to form a ring, and d is an integer of 10 to 5000.

Specifically, E of the polymer compound of the formulas 13-g to 13-h is -CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ CH ₂ -, para- and 2,6-naphtha len die work, F is _{-CH 2 CH 2 OCH 2 CH 2} -, -CH 2 CH 2 -, -CH 2 CH (CH 3) -, -CH 2 CH 2 CH 2 -, - _{CH 2 C (CH 3) 2} CH 2 -, -CH 2 CH (CH 3) CH 2 - or _{-CH 2 CH 2 CH 2 CH 2} CH 2 CH 2 - , and, R ^e1 to R ^e4 are independently from each other hydrogen Or methyl, preferably R ^e1 to R ^e4 are all hydrogen, or R ^e1 to R ^e3 are all hydrogen and R ^e4 is methyl (in some repeat units, R ^e1 is methyl and the remaining R ^e2 to R ^e4 are both hydrogen ).

In Formula 13, the W ^{HO-CR e3 R e4 -CR e1} R e2 - {OC (O) O-CR e3 R e4 -CR e1 R e2} d -O- [G-CO 2] m - ( formula i), it is represented by the following formula (13-i).

[Chemical Formula 13-i]

CR ^e R ^e4 -CR ^e1 R ^e2 - {OC (O) O-CR ^e3 R ^e4 -CR ^e1 R ^e2 } _d -O- [G-CO ₂ ] _m - {CR ^e1 R ^e2 -CR ^e3 R ^e4- OC (O) O} _d -CR ^e1 R ^e2 -CR ^e3 R ^e4 -OH

[Wherein, in the above formula (13-i), G is a (C1-C15) hydrocarbyl radical and m G's in one chain may be the same or different from each other; -O- [G-CO ₂ ] _m - block has a number average molecular weight of 500 to 500000, and R ^e1 to R ^e4 independently of one another are hydrogen; (C1-C10) alkyl unsubstituted or substituted with halogen or (C1-C20) alkoxy; (C6-C10) aryl which is unsubstituted or substituted by halogen or (C1-C20) alkoxy, and R ^e1 to R ^e4 may be linked together to form a ring, and d is an integer of 10 to 5000.

Specifically, G of the polymer compound of Formula 13-i is _{-CH 2 -, -CH (CH 3} ) -, -CH (CH 3) CH 2 -, -CH (CH 2 CH 3) CH 2 - or -CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ -; R ^e1 to R ^e4 are each independently hydrogen or methyl, preferably all of R ^e1 to R ^e4 are hydrogen, or R ^e1 to R ^e3 are all hydrogen and R ^e4 is methyl (R ^e1 is methyl And all of R ^e2 to R ^e4 are hydrogen).

In Formula 13, the W ^{HO-CR e3 R e4 -CR e1} R e2 - {OC (O) O-CR e3 R e4 -CR e1 R e2} d -O- [Q-OC (O) O] m -QO- (formula j), it is represented by the following formula 13-j.

[Chemical Formula 13-j]

^{HO-CR e3 R e4 -CR e1} R e2 - {OC (O) O-CR e3 R e4 -CR e1 R e2} d -O- [Q-OC (O) O] m -QO- {CR e1 R ^{e2 -CR e3 R e4 -OC (O} ) O} d -CR e1 R e2 -CR e3 R e4 -OH

Wherein Q is independently (C1-C30) hydrocarbyl radical and m Qs belonging to one chain may be the same or different from each other; -O- [Q-OC (O) O] _m -QO- block has a number average molecular weight of 500 to 500000, and R ^e1 to R ^e4 independently of one another are hydrogen; (C1-C10) alkyl unsubstituted or substituted with halogen or (C1-C20) alkoxy; (C6-C10) aryl which is unsubstituted or substituted by halogen or (C1-C20) alkoxy, and R ^e1 to R ^e4 may be linked together to form a ring, and d is an integer of 10 to 5000.

Specifically, Q of the polymer compound of Formula 13-j is -CH ₂ CH ₂ CH ₂ CH ₂ - or -CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ -; R ^e1 to R ^e4 are each independently hydrogen or methyl, preferably all of R ^e1 to R ^e4 are hydrogen, or R ^e1 to R ^e3 are all hydrogen and R ^e4 is methyl (R ^e1 is methyl And all of R ^e2 to R ^e4 are hydrogen).

In the formula (13), when W is -O- [(R ¹¹¹ ) (R ¹¹² ) Si-O] _m -R ¹¹³ (formula k), it is represented by the following formula 13-k.

[Chemical Formula 13-k]

^{HO-CR e3 R e4 -CR e1} R e2 - {OC (O) O-CR e3 R e4 -CR e1 R e2} d -O - [(R 111) (R 112) Si-O] m -R 113

[Wherein R ¹¹¹ and R ¹¹² are, independently of each other, a (C1-C15) hydrocarbyl radical; R < ¹¹³ > is hydrogen or (C1-C30) hydrocarbyl; The number average molecular weight of the -O - [(R ¹¹¹ ) (R ¹¹² ) Si-O] _m -R ¹¹³ block is 500 to 500000, and R ^e1 to R ^e4 independently of one another are hydrogen; (C1-C10) alkyl unsubstituted or substituted with halogen or (C1-C20) alkoxy; (C6-C10) aryl which is unsubstituted or substituted by halogen or (C1-C20) alkoxy, and R ^e1 to R ^e4 may be linked together to form a ring, and d is an integer of 10 to 5000.

Specifically, R ¹¹¹ and R ¹¹² of the polymer compound of Formula 13-k are, independently of each other, methyl or phenyl; R < ¹¹³ > is hydrogen or (C1-C8) alkyl; R ^e1 to R ^e4 are each independently hydrogen or methyl, preferably all of R ^e1 to R ^e4 are hydrogen, or R ^e1 to R ^e3 are all hydrogen and R ^e4 is methyl (R ^e1 is methyl And all of R ^e2 to R ^e4 are hydrogen).

In Formula 13, the W ^{HO-CR e3 R e4 -CR e1} R e2 - {OC (O) O-CR e3 R e4 -CR e1 R e2} d -O - [(R 111) (R 112) Si -O] _m - (formula (1)).

[Chemical Formula 13-1]

^{HO-CR e3 R e4 -CR e1} R e2 - {OC (O) O-CR e3 R e4 -CR e1 R e2} d -O - [(R 111) (R 112) Si-O] m - {CR ^e1 R ^e2 -CR ^e3 R ^e4 -OC (O) O} _d -CR ^e1 R ^e2 -CR ^e3 R ^e4 -OH

[Wherein R ¹¹¹ and R ¹¹² are, independently of each other, a (C1-C15) hydrocarbyl radical; The number average molecular weight of the -O - [(R ¹¹¹ ) (R ¹¹² ) Si-O] _m -block is 500 to 500000, and R ^e1 to R ^e4 are independently of each other hydrogen; (C1-C10) alkyl unsubstituted or substituted with halogen or (C1-C20) alkoxy; (C6-C10) aryl which is unsubstituted or substituted by halogen or (C1-C20) alkoxy, and R ^e1 to R ^e4 may be linked together to form a ring, and d is an integer of 10 to 5000.

Specifically, R ¹¹¹ and R ¹¹² of the polymer compound of Formula 13-l are independently of each other methyl or phenyl; R ^e1 to R ^e4 are each independently hydrogen or methyl, preferably all of R ^e1 to R ^e4 are hydrogen, or R ^e1 to R ^e3 are all hydrogen and R ^e4 is methyl (R ^e1 is methyl And all of R ^e2 to R ^e4 are hydrogen).

In the above formula (13), when W is R ¹⁰⁰ - [T] _m -J- (formula m), it is represented by the following formula 13-m.

[Formula 13-m]

R ¹⁰⁰ - [T] _m -J- {CR ^e1 R ^e2 -CR ^e3 R ^e4 -OC (O) O} _d -CR ^e1 R ^e2 -CR ^e3 R ^e4 -OH

[In the formula 13-m, J is -O- or -CO ₂ - and; T is _{-CH 2 CH 2 -, -CH 2} CH (CH 3) -, -CH 2 CH (CH 2 CH 3) -, -CH 2 CH (CH 2 CH 2 CH 2 CH 3) -, -CH 2 _{CH (CH 2 CH 2 CH 2} CH 2 CH 2 CH 3) -, -CH 2 CH (C 6 H 5) -, -CH 2 CH (CO 2 Me) -, -CH 2 CH (Cl) -, - _{CH 2 C (Me) (CO} 2 Me) -, -CH 2 CH (OC (O) CH 3) -, -CH 2 CH = CHCH 2 -, -CH (Me) CH = CHCH 2 - or -CH ( Cl) CH = CHCH ₂ -, and m number of T belonging to the chain may be the same or different from each other; R ¹⁰⁰ is hydrogen, (C1-C20) hydrocarbyl, (C1-C20) alkoxy, (C1-C20) alkylcarbonyloxy or (C6-C20) arylcarbonyloxy; R ¹⁰⁰ - [T] _m -J- block has a number average molecular weight of 500 to 500000, and R ^e1 to R ^e4 independently of one another are hydrogen; (C1-C10) alkyl unsubstituted or substituted with halogen or (C1-C20) alkoxy; (C6-C10) aryl which is unsubstituted or substituted by halogen or (C1-C20) alkoxy, and R ^e1 to R ^e4 may be linked together to form a ring, and d is an integer of 10 to 50000.

T of the formula 13-m is _{-CH 2 CH 2 -, -CH 2} CH (CH 3) -, -CH 2 CH (CH 2 CH 3) -, -CH 2 CH (CH 2 CH 2 CH 2 CH 3 _{) -, -CH 2 CH (CH} 2 CH 2 CH 2 CH 2 CH 2 CH 3) -, -CH 2 CH (C 6 H 5) -, -CH 2 CH (CO 2 Me) -, -CH 2 CH _{(Cl) -, -CH 2 C} (Me) (CO 2 Me) -, -CH 2 CH (OC (O) CH 3) -, -CH 2 CH = CHCH 2 -, -CH (Me) CH = CHCH ₂ - or _{-CH (Cl) CH = CHCH 2} - may be selected from.

Specifically, J of the polymer compound of Formula 13-m is -O-; T is -CH ₂ CH ₂ - or _{-CH 2 CH (CH 2 CH 3} ) - is; R ¹⁰⁰ is hydrogen; R ^e1 to R ^e4 are each independently hydrogen or methyl, preferably all of R ^e1 to R ^e4 are hydrogen, or R ^e1 to R ^e3 are all hydrogen and R ^e4 is methyl (R ^e1 is methyl And all of R ^e2 to R ^e4 are hydrogen). In addition, J of the polymer compound of the general formula 13-m is -CO ₂ - and; T is _{-CH 2 CH (C 6 H 5} ) - and; R ¹⁰⁰ is butyl; R ^e1 to R ^e4 are each independently hydrogen or methyl, preferably all of R ^e1 to R ^e4 are hydrogen, or R ^e1 to R ^e3 are all hydrogen and R ^e4 is methyl (R ^e1 is methyl And all of R ^e2 to R ^e4 are hydrogen).

In Formula 13, the W ^{HO-CR e3 R e4 -CR e1} R e2 - {OC (O) O-CR e3 R e4 -CR e1 R e2} d -J- [T] m -J- ( formula n ) Is represented by the following formula (13-n).

[Formula 13-n]

^{HO-CR e3 R e4 -CR e1} R e2 - {OC (O) O-CR e3 R e4 -CR e1 R e2} d -J- [T] m -J- {CR e1 R e2 -CR e3 R e4 -OC (O) O} _d -CR ^e1 R ^e2 -CR ^e3 R ^e4 -OH

[In the formula 13-n, J represents -O- or -CO ₂ - and; T is _{-CH 2 CH 2 -, -CH 2} CH (CH 3) -, -CH 2 CH (CH 2 CH 3) -, -CH 2 CH (CH 2 CH 2 CH 2 CH 3) -, -CH 2 _{CH (CH 2 CH 2 CH 2} CH 2 CH 2 CH 3) -, -CH 2 CH (C 6 H 5) -, -CH 2 CH (CO 2 Me) -, -CH 2 CH (Cl) -, - _{CH 2 C (Me) (CO} 2 Me) -, -CH 2 CH (OC (O) CH 3) -, -CH 2 CH = CHCH 2 -, -CH (Me) CH = CHCH 2 - or -CH ( Cl) CH = CHCH ₂ -, and m number of T belonging to the chain may be the same or different from each other; R ¹⁰⁰ is hydrogen, (C1-C20) hydrocarbyl, (C1-C20) alkoxy, (C1-C20) alkylcarbonyloxy or (C6-C20) arylcarbonyloxy; The number average molecular weight of the -J- [T] _m- J-block is 500 to 500000, and R ^e1 to R ^e4 are independently of each other hydrogen; (C1-C10) alkyl unsubstituted or substituted with halogen or (C1-C20) alkoxy; (C6-C10) aryl which is unsubstituted or substituted by halogen or (C1-C20) alkoxy, and R ^e1 to R ^e4 may be linked together to form a ring, and d is an integer of 10 to 50000.

T is of the formula 13-n _{-CH 2 CH 2 -, -CH 2} CH (CH 3) -, -CH 2 CH (CH 2 CH 3) -, -CH 2 CH (CH 2 CH 2 CH 2 CH 3 _{) -, -CH 2 CH (CH} 2 CH 2 CH 2 CH 2 CH 2 CH 3) -, -CH 2 CH (C 6 H 5) -, -CH 2 CH (CO 2 Me) -, -CH 2 CH _{(Cl) -, -CH 2 C} (Me) (CO 2 Me) -, -CH 2 CH (OC (O) CH 3) -, -CH 2 CH = CHCH 2 -, -CH (Me) CH = CHCH ₂ - or _{-CH (Cl) CH = CHCH 2} - may be selected from.

Specifically, J of the polymer compound of Formula 13-n is -O-; T is -CH ₂ CH ₂ - or _{-CH 2 CH (CH 2 CH 3} ) - is; R ^e1 to R ^e4 are each independently hydrogen or methyl, preferably all of R ^e1 to R ^e4 are hydrogen, or R ^e1 to R ^e3 are all hydrogen and R ^e4 is methyl (R ^e1 is methyl And all of R ^e2 to R ^e4 are hydrogen). Further, J of the polymer compound of Formula 13-n is -CO ₂ -; T is _{-CH 2 CH (C 6 H 5} ) - and; R ^e1 to R ^e4 are each independently hydrogen or methyl, preferably all of R ^e1 to R ^e4 are hydrogen, or R ^e1 to R ^e3 are all hydrogen and R ^e4 is methyl (R ^e1 is methyl And all of R ^e2 to R ^e4 are hydrogen).

The polymer compound of the Formula 14, G is _{-CH 2 -, -CH (CH 3} ) -, -CH (CH 3) CH 2 -, -CH (CH 2 CH 3) CH 2 - or -CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ -, and, R ⁹⁰ is hydrogen, (C1-C8) alkyl or (C2-C8) alkylcarbonyl, R ^e1 to R ^e4 are hydrogen or methyl, independently of each other, preferably R ^e1 to R ^e4 are all hydrogen, or R ^e1 to R ^e3 are all hydrogen and R ^e4 is methyl (in some repeat units, R ^e1 is methyl and all of R ^e2 to R ^e4 are hydrogen).

The polymer compound of the general formula (15) is T is _{-CH 2 CH 2 -, -CH 2} CH (C 6 H 5) -, -CH 2 (CO 2 Me) CH -, -CH 2 CH (Cl) - or -CH _{2 C (Me) (CO 2} Me) - , and, R ¹²¹ is hydrogen or methyl, J is -CO ₂ -, R ^e1 to R ^e4 are independently from each other hydrogen or methyl, preferably R ^e1 to ^e4 R Are all hydrogen, or R ^e1 to R ^e3 are all hydrogen and R ^e4 is methyl (in some repeat units, R ^e1 is methyl and the remaining R ^e2 to R ^e4 are all hydrogen).

By the production process according to the present invention, a block or graft copolymer of a poly (alkylene carbonate) and a polymer compound having a functional group of a hydroxy or carboxylic acid can be prepared to produce a poly (alkylene carbonate) itself Can be used to complement the physical properties of the product. Further, the obtained block or graft copolymer may be used for facilitating blending of poly (alkylene carbonate) with various polymers.

Figure 1 is a polystyrene-poly (propylene carbonate) block copolymer GPC curve (Example 13).
2 is a polystyrene-poly (propylene carbonate) block copolymer DSC data (Example 13).

The following Examples and Comparative Examples illustrate the effects of the present invention in detail. However, the following examples are intended to illustrate the present invention and are not intended to limit the scope of the present invention.

[Preparation Example 1] Catalyst synthesis

The catalysts used in the present invention were prepared as shown below. The starting compound A was synthesized by a known method ( Bull. Korean Chem. Soc. 2009 , 30 , 745-748).

compound B Synthesis of

Compound A (100 mg, 0.054 mmol) and AgNO ₃ (37.3 mg, 0.219 mmol) were dissolved in ethanol (3 mL) and stirred overnight. The AgI was removed by filtration using celite. The solvent was removed in vacuo to give Compound B in the form of a yellow solid powder (0.80 g, 94%). _{^{1 H NMR (CDCl 3):}} δ 3.51 (s, 2H, OH), 8.48 (s, 2H, CH = N), 7.15 (s, 4H, m -H), 3.44 (br, 2H, cyclohexyl-CH) , 3.19 (br, 32H, NCH 2), 2.24 (s, 6H, CH 3), 1.57-1.52 (br, 4H, cyclohexyl-CH 2), 1.43-1.26 (br, 74H), 0.90-070. _{(br, 36H, CH 3)} ppm.

compound C Synthesis of

Compound ( B) (95 mg, 0.061 mmol) and Co (OAc) ₂ (10.7 mg, 0.061 mmol) were added to the flask and dissolved in methylene chloride (3 mL). After stirring at room temperature for 3 hours under an oxygen atmosphere, the solvent was removed under reduced pressure to obtain Compound C in the form of a brown solid powder (85 mg, 83%). _{^{1 H NMR (DMSO-d 6}} , 38 ℃): major signal set, δ 7.83 (s, 2H, CH = N) 7.27 (br s, 2H, mH), 7.22, 7.19 (brs, 2H, m -H) , 3.88 (br, 1H, cyclohexyl -CH), 3.55 (br, 1H, cyclohexyl-CH), 3.30-2.90 (br, 32H, NCH 2), 2.58 (s, 3H, CH 3), 2.55 (s, 3H , CH ₃ ), 2.10-1.80 (br, 4H, cyclohexyl-CH ₂ ), 1.70-1.15 (br m, 74H), 1.0-0.80 (br, 36H, CH ₃ ) ppm; (S, 2H, m- H), 3.60 (br, 2H, cyclohexyl-CH), 3.30-2.90 (s, 2H, _{br, 32H, NCH 2),} 2.66 (s, 6H, CH 3), 2.10-1.80 (br, 4H, cyclohexyl-CH 2), 1.70-1.15 (br m, 74H), 1.0-0.80 (br, 36H, CH ₃₎ ppm. ^{_{1 H NMR (CD 2 Cl 2}} ): δ 7.65 (br, 2H, CH = N) 7.34 (br, 2H, mH), 7.16 (br, 2H, m -H), 3.40-2.00 (br, 32H, NCH _{2), 2.93 (br s,} 6H, CH 3), 2.10-1.80 (br m, 4H, cyclohexyl-CH 2), 1.70-1.15 (br m, 74H), 1.1-0.80 (br, 36H, CH 3) ppm.

Two sets of signals were observed at a ratio of 6: 4 in the ¹ H NMR spectrum obtained by dissolving in DMSO-d ₆ . The major signal set shows that the two phenoxy ligands of the Salen-units are different, and the minor signal set shows that the two phenoxy ligands are the same. This can be interpreted as the equilibrium state described below in the dmso solvent of the compound C. It has been found that when a substituent having a small steric hindrance such as methyl is present at the o-position of the two phenoxy ligands of the Salen-unit, the structure of the imine nitrogen is not coordinated in a polar solvent like DMSO ( Inorg. Chem. 2009 , 48 , 10455-10465). In the non-polar solvent methylene chloride an overall broad set of signals was observed. Considering the fact that NO ₃ ^- anion is weak in ionization power, it is expected that the nitrogen atom is coordinated with imine and the nitrate anion and acetate anion are exchanged with each other, .

<Expected structure in DMSO of Compound C >

<화합물 C의 CH₂Cl₂에서의 예상 구조>

<Expected structure of CH ₂ Cl ₂ of Compound C >

[Example 1] Carbon dioxide / propylene oxide copolymerization and catalyst separation in the presence of poly (ethylene glycol)

Copolymerization reaction

The compound C (3.0 mg, monomer / catalyst = 100,000) and propylene oxide (10.0 g, 172 mmol) prepared in Preparation Example 1 were fed into a 50 mL bomb reactor and charged with poly (ethylene glycol) R ⁷⁰ of formula (4) is hydrogen, L is -CH ₂ CH ₂ -, Mn is 8500-11500, 200 mg, [OH] / [Co] = 22) and the reactor is assembled. After the carbon dioxide gas pressure of 15 bar was applied, the reactor was immersed in an oil bath whose temperature had been previously adjusted to 73 DEG C and stirring was started. After 35 minutes, the internal temperature of the reactor reached 70 DEG C and from this point the reactor pressure was observed to decrease. The polymerization reaction was carried out for 1 hour from the start of the reaction when the internal temperature of the reactor reached 70 ° C. The reactor was immersed in a cold bath, cooled, and the reaction was terminated by removing the carbon dioxide gas. A pale yellow mucilage solution was obtained.

Catalyst separation

10 g of propylene oxide was added to the prepared mucous solution to lower the viscosity of the solution. The solution was passed through a pad of silica gel (400 mg, manufactured by Merck, 0.040-0.063 mm particle diameter (230-400 mesh) to give a colorless solution Propylene carbonate by-product was produced in an amount of 1 to 10% in some cases, and the resulting byproduct, propylene carbonate, was removed by keeping the sample overnight in a vacuum oven at 150 ° C. 1.65 g of pure The polymer had a TON value of 7600 and a molecular weight (Mn) of 68300 and a molecular weight distribution (Mw / Mn) of 1.48 as measured by GPC using polystyrene as a standard. The GPC curve showed that the nitrate or acetate The polymer chain was observed at around 47000, and it was found that the polymer chains grown in the input polymer chains were relatively broad distributed at 105,000 The glass transition temperature (Tg) measured by DSC was 26 ° C. The poly (propylene carbonate) signal was observed at 5.01, 4.32-4.10, and 1.36 ppm in the ¹ H NMR spectrum and the input poly (ethylene glycol) ppm.

(TOF, 12200 h ^-1 ) was obtained by carrying out polymerization reaction in the same manner as above except that 200 mg ([OH] / [Co] = 108) of the polymer having Mn of 1950-2050 was substituted. The obtained polymer had a Mn of 19900 and a molecular weight distribution (Mw / Mn) of 1.30. A glass transition signal was observed at -27 ° C in the DSC.

(TOF, 15100 h ^-1 ) was obtained by carrying out polymerization reaction in the same manner as in Example 1, except that 250 mg ([OH] / [Co] = 8) The obtained polymer had a Mn of 111000 and a molecular weight distribution (Mw / Mn) of 1.57. In the DSC, a glass transition signal was observed at 39 ° C and a further melting signal was observed at 53 ° C.

500 mg ([OH] / [Co] = 16) of the polymer having Mn of 35000 was charged in place of the polymer and polymerization reaction was carried out in the same manner to obtain 2.17 g of a block copolymer (TOF, 9100 h ^-1 ). The obtained polymer had Mn of 54900 and a molecular weight distribution (Mw / Mn) of 1.19. A glass transition signal was observed at 27 ° C in the DSC and a further melting signal was observed at 55 ° C.

[Example 2] Carbon dioxide / propylene oxide copolymerization and catalyst separation in the presence of poly (propylene glycol)

(R ⁷⁰ in Formula 4 is hydrogen, L is -CH ₂ CH (CH ₃ ) -, Mn is 3500, 350 mg, [OH] / [Co] = 112) in place of poly (ethylene glycol) And the polymerization reaction was carried out in the same manner as in Example 1, and the catalyst was removed by the same method. 2.82 g of a pure polymer was obtained, which had a TON value of 13,600 and a molecular weight (Mn) of 22800 and a molecular weight distribution (Mw / Mn) of 1.27 as measured by GPC using polystyrene as a standard. The glass transition temperature (Tg) measured by DSC was 36 ° C. ^The poly (propylene glycol) signal input at ¹ H NMR spectrum was shown at 3.55, 3.42, and 1.56 ppm.

[Example 3] Carbon dioxide / propylene oxide copolymerization and catalyst separation using poly (tetrahydrofuran)

(R ⁷⁰ in formula (4) is hydrogen, L is -CH ₂ CH ₂ CH ₂ CH ₂ -, Mn is 2900, 260 mg, [OH] / [Co] 100) were charged, and the polymerization reaction was carried out in the same manner as in Example 1, and the catalyst was removed by the same method. 3.13 g of a pure polymer was obtained, which had a TON value of 15,700 and a molecular weight (Mn) of 33,800 and a molecular weight distribution (Mw / Mn) of 1.13 as determined by GPC using polystyrene as a standard. It was observed that 28100 was grown in the polymer chain injected from the GPC curve. The glass transition temperature (Tg) measured by DSC was 37 ° C. ^The poly (tetrahydrofuran) signal input at ¹ H NMR spectrum was observed at 3.42, 1.64 ppm.

Example 4: Carbon dioxide / propylene oxide copolymerization and catalyst separation in the presence of poly (di (ethylene glycol) adipic acid)) (poly (di (ethylene glycol) adipate)

Poly (ethylene glycol) adipic acid (E in the formula 5-7 is -CH ₂ CH ₂ CH ₂ CH ₂ -, F is -CH ₂ CH ₂ OCH ₂ CH ₂ -, Mn is 2500, 200 mg, and [OH] / [Co] = 90) were charged in the same manner as in Example 1. The catalyst was removed in the same manner as in Example 1. 2.18 g of a pure polymer was obtained, (Mw / Mn) of 1.09. The glass transition temperature (Tg) measured by DSC was 35 ° C. ¹ H NMR The poly (di (ethylene glycol) adipic acid) signal input in the spectrum was observed at 3.71, 2.38, and 1.68 ppm.

Example 5 Copolymerization and Catalytic Separation of Carbon Dioxide / Propylene Oxide in the Presence of Poly (3-hydroxybutyric acid)

Poly (ethylene glycol) instead of poly (3-hydroxy-butanoic acid) to (G in formula (8) is _{-CH (CH 3) CH 2 -} , f is 1, R ⁹⁰ is hydrogen, 200 mg) of Example 1 by introducing the And the catalyst was removed by the same method. 1.27 g of a pure polymer was obtained, which had a TON value of 6900 and a molecular weight (Mn) of 107,100 and a molecular weight distribution (Mw / Mn) of 1.32 as determined by GPC using polystyrene as a standard. In the GPC curve, the catalyst chain of nitrate or acetate - grown polymer chain was observed at around 84600 and the growth in the introduced polymer chain was observed at 199500. The glass transition temperature (Tg) measured by DSC was 25 占 폚. The methyl signal of the poly (3-hydroxybutanoic acid) charged in the ¹ H NMR spectrum was observed at 1.30 ppm and the remaining signal was not observed to be broad.

[Example 6] Carbon dioxide / propylene oxide copolymerization and catalyst separation in the presence of poly (caprolactone diol)

(G is -CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ -, f is 2, aldrich yarn, Mn is 2000, 250 mg, [OH]), poly (caprolactone diol) / [Co] = 139) were charged in the same manner as in Example 1, and the catalyst was removed by the same method. 3.29 g of a pure polymer was obtained, which had a TON value of 15900 and had a molecular weight (Mn) of 32000 and a molecular weight distribution (Mw / Mn) of 1.07 as determined by GPC using polystyrene as a standard. The glass transition temperature (Tg) measured by DSC was 33 ° C. ^The poly (caprolactone diol) signal input at ¹ H NMR spectrum was observed at 4.07, 2.33, and 1.68 ppm.

[Example 7] Carbon dioxide / propylene oxide copolymerization and catalyst separation in the presence of poly (caprolactone triol)

Instead of poly (ethylene glycol), poly (caprolactone triol lactone) (G of the formula (VIII) are _{-CH 2 CH 2 CH 2 CH 2} CH 2 -, f is 3, R ⁹⁰ is _{CH 3 CH 2 C {CH 2} -} ₃ , Mn was 900, 200 mg, and [OH] / [Co] = 374) were charged in the same manner as in Example 1, and the catalyst was removed by the same method. 1.21 g of a pure polymer was obtained, which had a TON value of 6600 and a molecular weight (Mn) of 8300 and a molecular weight distribution (Mw / Mn) of 1.04 as determined by GPC using polystyrene as a standard. The glass transition temperature (Tg) measured by DSC was 20 占 폚. ^The poly (caprolactone triol) signal input at ¹ H NMR spectrum was observed at 3.99, 2.33, 1.67, and 1.23 ppm.

[Example 8] Carbon dioxide / propylene oxide copolymerization and catalyst separation in the presence of a poly (hexamethylene carbonate)

(Q of the formula 9 is -CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ -, Mn is 2000, 200 mg, [OH] / [Co]) instead of poly (ethylene glycol) = 112) were charged in the same manner as in Example 1, and the catalyst was removed by the same method. 2.18 g of a pure polymer was obtained, which had a TON value of 11,900 and had a molecular weight (Mn) of 24000 and a molecular weight distribution (Mw / Mn) of 1.07 as determined by GPC using polystyrene as a standard. The glass transition temperature (Tg) measured by DSC was 31 ° C. ^The poly (hexamethylene carbonate) diol signal added in the ¹ H NMR spectrum was observed at 3.67, 1.70, and 1.43 ppm.

[Example 9] Carbon dioxide / propylene oxide copolymerization and catalyst separation in the presence of poly (dimethylsiloxane)

Instead of poly (ethylene glycol), poly (dimethylsiloxane) (R &lt; ¹¹¹ &^gt; R ¹¹² was methyl, R ¹¹³ was hydrogen, Viscosity 1,800-2,200 cSt, 200 mg), and the polymerization reaction was carried out in the same manner as in Example 1, and the catalyst was removed by the same method. 1.90 g of a pure polymer was obtained, which had a TON value of 10,000 and a molecular weight (Mn) of 148000 and a molecular weight distribution (Mw / Mn) of 1.39 as measured by GPC using polystyrene as a standard. The glass transition temperature (Tg) measured by DSC was 42 占 폚. ^The poly (dimethylsiloxane) signal input at ¹ H NMR spectrum was observed at 0.09 ppm.

[Example 10] Carbon dioxide / propylene oxide copolymerization and catalyst separation in the presence of polyethylene monoalcohol

Poly J in place of poly (ethylene glycol), polyethylene monoalcohol (Formula 11 is -O-, T is -CH ₂ CH ₂ -, R ¹⁰⁰ is hydrogen, Mn was 700, 100 mg, [OH] / [Co] = 80 ) Was added thereto, and the polymerization reaction was carried out in the same manner as in Example 1, and the catalyst was removed by the same method. 1.80 g of a pure polymer was obtained, which had a TON value of 9900 and had a molecular weight (Mn) of 18800 and a molecular weight distribution (Mw / Mn) of 1.18 as determined by GPC using polystyrene as a standard. In the DSC curve, the glass transition temperature (Tg) of poly (propylene carbonate) was observed at 37.2 ° C and the melting (Tm) signal of PE was observed at 92 ° C. ^The polyethylene signal added in the ¹ H NMR spectrum was observed at 1.27 ppm.

500 mg ([OH] / [Co] = 397) of the same polyethylene alcohol was charged in place and polymerization reaction was carried out in the same manner to obtain 2.94 g of a block copolymer (TOF, 13500 h ^-1 ). The obtained polymer had a Mn of 7800 and a molecular weight distribution (Mw / Mn) of 1.18. In the DSC, a glass transition signal was observed at 34 ° C and a further melting signal was observed at 96 ° C.

(TOF, 8600 h &lt; ^-1 &gt;) was obtained by charging the same polyethylene alcohol (1.00 g, [OH] / [Co] = 794) instead of the same polyethylene glycol. The obtained polymer had Mn of 3500 and a molecular weight distribution (Mw / Mn) of 1.45. A glass transition signal was observed at 26 ° C in the DSC and a further melting signal was observed at 103 ° C.

[Example 11] Carbon dioxide / propylene oxide copolymerization and catalyst separation in the presence of poly (ethylene-co-acrylic acid)

Poly (ethylene glycol) in place of poly (ethylene acrylic acid -co-) (T in the formula (12) is -CH ₂ CH ₂ -, R ¹²¹ is hydrogen, J is _{-CO 2 -, Brookfield viscosity 575 cps} (145 ℃), 100 [COOH] / [Co] = 39) as a catalyst were added in the same manner as in Example 1, and the catalyst was removed by the same method. 2.23 g of a pure polymer was obtained, which had a TON value of 12,200 and a molecular weight (Mn) of 64,500 and a molecular weight distribution (Mw / Mn) of 2.01 as determined by GPC using polystyrene as a standard. In the GPC curve, the chain of the nitrate or acetate grown in the catalyst was observed to be small at around 30000, the chain grown at the water was observed to be small at around 63000, and the growth at the polymer chain introduced was relatively broad at 106900 Respectively. In the DSC curve, the glass transition temperature (Tg) of poly (propylene carbonate) was observed at 38.9 ° C and the melting (Tm) signal of PE was observed at 65 ° C and 95 ° C. A poly (ethylene-co-acrylic acid) signal input at ¹ H NMR spectrum was observed at 1.27 ppm.

2.00 g of a block copolymer (TOF, 10700 h ^-1 ) was obtained by carrying out the polymerization reaction in the same manner as above except that 200 mg ([OH] / [Co] = 78) of the same poly (ethylene- . The obtained polymer had an Mn of 37900 and a molecular weight distribution (Mw / Mn) of 1.79. A glass transition signal was observed in DSC at 37 ° C and a further melting signal was observed at 98 ° C.

(TOF, 13800 h ^-1 ) was obtained by charging the same poly (ethylene-co-acrylic acid) in an amount of 400 mg ([OH] / [Co] = 154) . The obtained polymer had Mn of 34000 and a molecular weight distribution (Mw / Mn) of 1.54. A glass transition signal was observed at 36 ° C in DSC and a further melting signal was observed at 102 ° C.

(TOF, 11500 h ^-1 ) was obtained by charging the same poly (ethylene-co-acrylic acid) 600 mg ([OH] / [Co] = 231) . The obtained polymer had Mn of 22500 and a molecular weight distribution (Mw / Mn) of 1.58. A glass transition signal was observed at 33 ° C in DSC and a further melting signal was observed at 102 ° C.

[Example 12] Carbon dioxide / propylene oxide copolymerization and catalyst separation in the presence of poly (methyl methacrylate- co -methacrylic acid)

(Methyl methacrylate- co -methacrylic acid) (T in the formula (12) is -CH ₂ C (Me) (CO ₂ Me) -, R ¹²¹ is methyl, J is -CO ₂ -, x: y = 1: 0.016, Mn: 15,000, 200 mg, and [COOH] / [Co] = 18) were charged and the catalyst was removed by the same method . 2.06 g of a pure polymer was obtained, which had a TON value of 11200 and a molecular weight (Mn) of 118500 and a molecular weight distribution (Mw / Mn) of 2.23 as measured by GPC using polystyrene as a standard. In the GPC curve, the catalyst chain of nitrate or acetate-grown polymer chains was observed at about 55400, and the chains grown in water were observed at about 115400, and the growth in the introduced polymer chain was found to be relatively widespread at 483500 . The glass transition temperature (Tg) measured by DSC was 37 ° C. ^The poly (methyl methacrylate - co - methacrylic acid) signal input at ¹ H NMR spectrum was observed at 3.62, 1.04 and 0.86 ppm.

400 mg ([OH] / [Co] = 36) of the same poly (methyl methacrylate- co -methacrylic acid) was charged in place and polymerization reaction was carried out in the same manner to obtain 1.94 g of a block copolymer (TOF, 8500 h ^-1 ). The obtained polymer had an Mn of 71000 and a molecular weight distribution (Mw / Mn) of 1.93. A glass transition signal was observed in DSC at 34 &lt; 0 &gt; C.

[Example 13] Carbon dioxide / propylene oxide copolymerization and catalyst separation in the presence of polystyrene carboxylic acid

Poly (ethylene glycol) J in place of the polystyrene carboxylic acid (Formula 11 is -C (O) O-, T is _{-CH 2 CH (Ph) -,} R 100 is a butyl, Mn is 44000, 250 mg, [OH] / [Co] = 3) were charged in the same manner as in Example 1, and the catalyst was removed by the same method. 2.34 g of a pure polymer was obtained, which had a TON value of 11,500 and had a molecular weight (Mn) of 123000 and a molecular weight distribution (Mw / Mn) of 1.43 measured by GPC using polystyrene as a standard. In the DSC curve, the glass transition temperature (Tg) of poly (propylene carbonate) was observed at 41 ° C and the glass transition temperature (Tg) of polystyrene was weakly observed at 107 ° C. ^The polystyrene signal input in the ¹ H NMR spectrum was observed broadly at 7.20-6.40.

500.0 mg of the same polystyrene carboxylic acid ([OH] / [Co] = 6) was charged in place and the polymerization reaction was carried out in the same manner to obtain 2.50 g of a block copolymer (TOF, 9700 h ^-1 ). The obtained polymer had an Mn of 113500 and a molecular weight distribution (Mw / Mn) of 1.50 (Fig. 1). A glass transition signal was observed at 43 ° C in DSC and a glass transition signal was observed at 108 ° C (FIG. 2).

Claims (15)

A block copolymer compound selected from the following formulas (13) to (15).
[Chemical Formula 13]
W- {CR ^e1 R ^e2 -CR ^e3 R ^e4 -OC (O) O} _d -CR ^e1 R ^e2 -CR ^e3 R ^e4 -OH
[Wherein, W is _{^{R 70 - [OL] m -O-}} ( formula ^{d), HO-CR e3 R} e4 -CR e1 R e2 - {OC (O) O-CR e3 R e4 -CR e1 R e2} _d - [OL] _m -O- (formula ^{e), HO-CR e3 R} e4 -CR e1 R e2 - {OC (O) O-CR e3 R e4 -CR e1 R e2} d -O 2 C- [ _{E-CO 2 -FO 2 C]} m -E-CO 2 - ( formula ^{f), HO-CR e3 R} e4 -CR e1 R e2 - {OC (O) O-CR e3 R e4 -CR e1 R e2} _{d -O- [FO 2 CE-CO} 2] m -FO- ( formula ^{g), HO-CR e3 R} e4 -CR e1 R e2 - {OC (O) O-CR e3 R e4 -CR e1 R e2} _{d -O 2 C- [E-CO} 2 -FO 2 C] m -E-CO 2 -FO- ( formula ^{h), HO-CR e3 R} e4 -CR e1 R e2 - {OC (O) O-CR ^{e3 R e4 -CR e1 R e2}} d -O- [G-CO 2] m - ( formula ^{i), HO-CR e3 R} e4 -CR e1 R e2 - {OC (O) O-CR e3 R e4 - _{^{CR e1 R e2} d -O- [}} Q-OC (O) O] m -QO- ( formula j), -O - [(R 111) (R 112) Si-O] m -R 113 ( formula k ^{), HO-CR e3 R e4} -CR e1 R e2 - {OC (O) O-CR e3 R e4 -CR e1 R e2} d -O - [(R 111) (R 112) Si-O] m - (formula ^{l), R 100 - [T} ] m -J- ( formula m) and ^{HO-CR e3 R e4 -CR e1} R e2 - {OC (O) O-CR e3 R e4 -CR e1 R e2} d -J- [T] _m- J- (formula n);
R ^e1 to R ^e4 independently of one another are hydrogen; (C1-C10) alkyl unsubstituted or substituted with halogen or (C1-C20) alkoxy; (C6-C10) aryl which is unsubstituted or substituted by halogen or (C1-C20) alkoxy, and R ^e1 to R ^e4 may be linked to form a ring, and d is an integer of 10 to 5000;
R ⁷⁰ is a (C1-C30) hydrocarbyl containing or not having an ether group, an ester group or an amino group;
L is a (C1-C30) hydrocarbyl radical and m Ls in a chain may be the same or different;
E is a (C1-C30) hydrocarbyl radical and the m E groups in a chain may be the same or different;
F is a (C2-C30) hydrocarbyl radical containing an ether group, an ester group, or an amino group, and m Fs in a chain may be the same or different from each other; G is a (C1-C15) hydrocarbyl radical and m G's in one chain may be the same or different from each other;
Q is independently (C1-C30) hydrocarbyl radical and the m Qs in a chain may be the same or different;
R ¹¹¹ and R ¹¹² are independently of each other a (C 1 -C 15) hydrocarbyl radical; R &lt; ¹¹³ &gt; is hydrogen or (C1-C30) hydrocarbyl;
J is -O- or -CO ₂ - and;
T is _{-CH 2 CH 2 -, -CH 2} CH (CH 3) -, -CH 2 CH (CH 2 CH 3) -, -CH 2 CH (CH 2 CH 2 CH 2 CH 3) -, -CH 2 _{CH (CH 2 CH 2 CH 2} CH 2 CH 2 CH 3) -, -CH 2 CH (C 6 H 5) -, -CH 2 CH (CO 2 Me) -, -CH 2 CH (Cl) -, - _{CH 2 C (Me) (CO} 2 Me) -, -CH 2 CH (OC (O) CH 3) -, -CH 2 CH = CHCH 2 -, -CH (Me) CH = CHCH 2 - or -CH ( Cl) CH = CHCH ₂ -, and m number of T belonging to the chain may be the same or different from each other;
R ¹⁰⁰ is hydrogen, (C1-C20) hydrocarbyl, (C1-C20) alkoxy, (C1-C20) alkylcarbonyloxy or (C6-C20) arylcarbonyloxy;
R ⁷⁰ - [OL] _m -, - [OL] _m -, - O ₂ C- [E-CO ₂ -FO ₂ C] _m -E-CO ₂ -, -O- [FO _2- CE-CO ₂ ] _m -FO-, -O ₂ C- [E-CO ₂ -FO ₂ C] _m -E-CO ₂ -FO-, -O- [G-CO ₂ ] _m -, -O - [Q-OC (O) O] m -QO-, -O - [(R 111) (R 112) Si-O] m -R 113, -O - [(R 111) (R 112) Si- O] _m -, R ¹⁰⁰ - [T] _m -J- and -J- [T] _m -J-blocks have a number average molecular weight of 500 to 500000.

[Chemical Formula 14]
^{{HO-CR e3 R e4 -CR} e1 R e2 - {OC (O) O-CR e3 R e4 -CR e1 R e2} d -O- [G-CO 2] m} f -R 90
Wherein G is a (C1-C15) hydrocarbyl radical and m G's in one chain may be the same or different from each other; f is an integer of 1-4 and when f is 1, R ⁹⁰ is hydrogen, (C 1 -C 30) hydrocarbyl, (C 1 -C 30) alkylcarbonyl or (C 6 -C 30) arylcarbonyl, when R ⁹⁰ is (C1-C30) dihydro car bildayi radical, when f is 3 R ⁹⁰ is (C1-C30) is a hydrocarbyl tree radical, f is R is 4 ^{to 90} is (C1-C30) hydrocarbyl-tetra Radical; - {O- [G-CO ₂ ] _m } _f -R ⁹⁰ block has a number average molecular weight of 500 to 500000, and R ^e1 to R ^e4 independently of one another are hydrogen; (C1-C10) alkyl unsubstituted or substituted with halogen or (C1-C20) alkoxy; (C6-C10) aryl which is unsubstituted or substituted by halogen or (C1-C20) alkoxy, and R ^e1 to R ^e4 may be linked together to form a ring, and d is an integer of 10 to 5000.

[Chemical Formula 15]
_{- {[T] x - [} CH 2 CR 121 (J- {CR e1 R e2 -CR e3 R e4 -OC (O) O} d -CR e1 R e2 -CR e3 R e4 -OH)] y} m -
[In the formula 15, J is -O- or -CO ₂ - and; T is _{-CH 2 CH 2 -, -CH 2} CH (CH 3) -, -CH 2 CH (CH 2 CH 3) -, -CH 2 CH (CH 2 CH 2 CH 2 CH 3) -, -CH 2 _{CH (CH 2 CH 2 CH 2} CH 2 CH 2 CH 3) -, -CH 2 CH (C 6 H 5) -, -CH 2 CH (CO 2 Me) -, -CH 2 CH (Cl) -, - _{CH 2 C (Me) (CO} 2 Me) -, -CH 2 CH (OC (O) CH 3) -, -CH 2 CH = CHCH 2 -, -CH (Me) CH = CHCH 2 - or -CH ( Cl) CH = CHCH ₂ -, and each T belonging to the chain may be the same or different from each other; R &lt; ¹²¹ &gt; is hydrogen or methyl; ^{- {CR e1 R e2 -CR e3} R e4 -OC (O) O} d -CR e1 R e2 -CR e3 R ^e4 and a number average molecular weight of the remaining blocks except for the -OH is from 500 to 500000, R ^e1 to ^e4 R Are independently selected from the group consisting of hydrogen; (C1-C10) alkyl unsubstituted or substituted with halogen or (C1-C20) alkoxy; (C6-C10) aryl which is unsubstituted or substituted by halogen or (C1-C20) alkoxy, and R ^e1 to R ^e4 may be linked together to form a ring, and d is an integer of 10 to 50000. The method according to claim 1,
W is R &lt; ⁷⁰ &gt; - [OL] _m- O- (formula d); R &lt; ⁷⁰ &gt; is (C1-C15) alkyl; L is _{-CH 2 CH 2 -, -CH 2} CH (CH 3) - or _{-CH 2 CH 2 CH 2 CH 2} - , and; And R ^e1 to R ^e4 independently of each other are hydrogen or methyl. The method according to claim 1,
Wherein W represents ^{HO-CR e3 R e4 -CR e1} R e2 - {OC (O) O-CR e3 R e4 -CR e1 R e2} d - [OL] m -O- ( formula e) and; L is _{-CH 2 CH 2 -, -CH 2} CH (CH 3) - or _{-CH 2 CH 2 CH 2 CH 2} - , and; And R ^e1 to R ^e4 independently of each other are hydrogen or methyl. The method according to claim 1,
Wherein W represents ^{HO-CR e3 R e4 -CR e1} R e2 - {OC (O) O-CR e3 R e4 -CR e1 R e2} d -O 2 C- [E-CO 2 -FO 2 C] m - E-CO ₂ - (formula ^{f), HO-CR e3 R} e4 -CR e1 R e2 - {OC (O) O-CR e3 R e4 -CR e1 R e2} d -O- [FO 2 CE-CO 2 ] _m -FO- (formula g) or ^{HO-CR e3 R e4 -CR e1} R e2 - {OC (O) O-CR e3 R e4 -CR e1 R e2} d -O 2 C- [E-CO 2 -FO ₂ C] _m -E-CO ₂ -FO- (formula h); E is _{-CH 2 CH 2 -, -CH 2} CH 2 CH 2 -, -CH 2 CH 2 CH 2 CH 2 -, p-phenylene, or 2,6-naphtha len die and one; F is _{-CH 2 CH 2 OCH 2 CH 2} -, -CH 2 CH 2 -, -CH 2 CH (CH 3) -, -CH 2 CH 2 CH 2 -, -CH 2 C (CH 3) 2 CH 2 -, -CH ₂ CH (CH ₃ ) CH ₂ - or -CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ -; And R ^e1 to R ^e4 independently of each other are hydrogen or methyl. The method according to claim 1,
Wherein W is HO-CR ^e R ^e4 -CR ^e1 R ^e2 - {OC (O) O-CR ^e3 R ^e4 -CR ^e1 R ^e2 } _d -O- [G-CO ₂ ] _m - G is _{-CH 2 -, -CH (CH 3} ) -, -CH (CH 3) CH 2 -, -CH (CH 2 CH 3) CH 2 - or _{-CH 2 CH 2 CH 2 CH 2} CH 2 - and ; And R ^e1 to R ^e4 independently of each other are hydrogen or methyl. The method according to claim 1,
Wherein W represents ^{HO-CR e3 R e4 -CR e1} R e2 - {OC (O) O-CR e3 R e4 -CR e1 R e2} d -O- [Q-OC (O) O] m -QO- ( (J); Q is _{-CH 2 CH 2 CH 2 CH 2} - or _{-CH 2 CH 2 CH 2 CH 2} CH 2 CH 2 - , and; And R ^e1 to R ^e4 independently of each other are hydrogen or methyl. The method according to claim 1,
W is -O- [(R ¹¹¹ ) (R ¹¹² ) Si-O] _m -R ¹¹³ (formula k); R ¹¹¹ and R ¹¹² are independently of each other methyl or phenyl; R &lt; ¹¹³ &gt; is hydrogen or (C1-C8) alkyl; And R ^e1 to R ^e4 independently of each other are hydrogen or methyl. The method according to claim 1,
Wherein W represents ^{HO-CR e3 R e4 -CR e1} R e2 - {OC (O) O-CR e3 R e4 -CR e1 R e2} d -O - [(R 111) (R 112) Si-O] m - (Formula I); R ¹¹¹ and R ¹¹² are independently of each other methyl or phenyl; And R ^e1 to R ^e4 independently of each other are hydrogen or methyl. The method according to claim 1,
Wherein T is _{-CH 2 CH 2 -, -CH 2} CH (CH 3) -, -CH 2 CH (CH 2 CH 3) -, -CH 2 CH (CH 2 CH 2 CH 2 CH 3) -, -CH _{2 CH (CH 2 CH 2 CH} 2 CH 2 CH 2 CH 3) -, -CH 2 CH (C 6 H 5) -, -CH 2 CH (CO 2 Me) -, -CH 2 CH (Cl) -, _{-CH 2 C (Me) (CO} 2 Me) -, -CH 2 CH (OC (O) CH 3) -, -CH 2 CH = CHCH 2 -, -CH (Me) CH = CHCH 2 - or -CH (Cl) CH = CHCH ₂ - a block copolymer compound. The method according to claim 1,
W is R ¹⁰⁰ - [T] _m -J- (formula m); J is -O-; T is -CH ₂ CH ₂ - or _{-CH 2 CH (CH 2 CH 3} ) - is; R ¹⁰⁰ is hydrogen; And R ^e1 to R ^e4 independently of each other are hydrogen or methyl. The method according to claim 1,
W is R ¹⁰⁰ - [T] _m -J- (formula m); J is -CO ₂ -, and; T is _{-CH 2 CH (C 6 H 5} ) - and; R ¹⁰⁰ is butyl; And R ^e1 to R ^e4 independently of each other are hydrogen or methyl. The method according to claim 1,
Wherein W represents ^{HO-CR e3 R e4 -CR e1} R e2 - {OC (O) O-CR e3 R e4 -CR e1 R e2} d -J- [T] m -J- ( formula n) and; J is -O-; T is -CH ₂ CH ₂ - or _{-CH 2 CH (CH 2 CH 3} ) - is; And R ^e1 to R ^e4 independently of each other are hydrogen or methyl. The method according to claim 1,
Wherein W represents ^{HO-CR e3 R e4 -CR e1} R e2 - {OC (O) O-CR e3 R e4 -CR e1 R e2} d -J- [T] m -J- ( formula n) and; J is -CO ₂ -, and; T is _{-CH 2 CH (C 6 H 5} ) - and; And R ^e1 to R ^e4 independently of each other are hydrogen or methyl. The method according to claim 1,
In Formula 14 G is _{-CH 2 -, -CH (CH 3} ) -, -CH (CH 3) CH 2 -, -CH (CH 2 CH 3) CH 2 - or -CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ -, R ⁹⁰ is hydrogen, (C 1 -C 8) alkyl or (C 2 -C 8) alkylcarbonyl, and R ^e1 to R ^e4 are independently of each other hydrogen or methyl. The method according to claim 1,
In Formula 15 T is _{-CH 2 CH 2 -, -CH 2} CH (C 6 H 5) -, -CH 2 CH (CO 2 Me) -, -CH 2 CH (Cl) - or -CH ₂ C ( Me) (CO ₂ Me) -; R &lt; ¹²¹ &gt; is hydrogen or methyl; J is -CO ₂ -, R ^e1 to ^e4 R is a block copolymer hydrogen or methyl, independently of each other.

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