KR20200020441A - process for preparing cyclic carbonate using hyper crosslinked polymers and hyper crosslinked polymers for selective formation of cyclic carbonates - Google Patents

Abstract

The present invention relates to: a method for selectively manufacturing a cyclic carbonate in a high yield with a high conversion rate compared to a conventional catalyst by using an epoxide compound of various structures and carbon dioxide as raw materials, by using a hyper crosslinked biphenyl polymer as a catalyst; and the hyper crosslinked biphenyl polymer.

Description

Process for preparing cyclic carbonate using hyper crosslinked polymers and hyper crosslinked polymers for selective formation of cyclic carbonates

The present invention relates to a method for producing a cyclic carbonate by reacting an alkylene oxide compound with carbon dioxide using a supercrosslinked biphenyl polymer as a catalyst, and a supercrosslinked biphenyl polymer.

Cyclic carbonates are one of the important compounds used in a wide range of applications as organic solvents, synthetic fiber processing agents, pharmaceutical raw materials, cosmetic additives, electrolyte solutions for lithium batteries, and as intermediates in the synthesis of alkylene glycols and dialkyl carbonates.

Conventionally, this cyclic carbonate has been synthesized by reacting epoxide and carbon dioxide in the presence of a homogeneous catalyst under suitable pressurized conditions. As such a homogeneous catalyst, halides such as alkali metals and onium salts such as quaternary ammonium salts have been known for a long time and are also used industrially.

For example, in Chinese Patent No. 101921257, a 5-membered cyclic carbonate was synthesized using a catalyst composed of a strong base spherical styrene ion exchange resin having different halogen ions, and Japanese Patent Laid-Open No. 56-128778 describes an alkali metal compound and a crown. the final compound in a catalyst system consisting of a cyclic carbonate compound, Japanese Laid-Open Patent No. Sho 59-13776 was used as a quaternary ammonium alcohol, Japanese Laid-Open Patent Publication No. 2006-151891 arc in the presence of Bu ₂ SnI _2, and InCl ₃ epoxy compound Cyclic carbonate was prepared by reacting with CO 2, WO 2005/003113 used tetraalkyl phosphnium halide, and Korean Patent Laid-Open No. 2005-0115694 discloses a catalyst system composed of a metal salt and an alicyclic amine salt. I use it.

However, according to these synthesis methods, under mild reaction conditions, the reaction yield is low, so that a high temperature and a long reaction time are required to increase the yield, and there is a problem that the moisture content of carbon dioxide and alkylene oxide as raw materials is controlled to several hundred ppm or less. .

Chinese Patent No. 101921257 Japanese Patent Laid-Open No. 56-128778 Japanese Patent Laid-Open No. 59-13776 Japanese Laid-Open Patent No. 2006-151891 WO 2005/003113 Korean Patent Publication No. 2005-0115694

It is an object of the present invention to provide a method for producing cyclic carbonate with high efficiency and selectively by reacting alkylene oxide and carbon dioxide using a supercrosslinked biphenyl polymer as a catalyst.

It is another object of the present invention to provide a novel crosslinked biphenyl polymer.

The present invention provides a method for producing a cyclic carbonate by reacting carbon dioxide and alkylene oxide using a supercrosslinked biphenyl polymer including a structural unit represented by Formula 1 and Formula 2 simultaneously as a catalyst.

[Formula 1]

[Formula 2]

In Chemical Formulas 1 and 2,

R ₁ is -CH ₂ -R,

a and b are each independently an integer of 0 to 2,

,

,

또는

이고,R is halogen, ^{_{nitro, -NR 11 R 12, -N +}} R 13 R 14 R 15 X -,

,

,

or

ego,

R ₁₁ is hydrogen or-(CR ^a R ^b ) _m -Ar ₁ ,

m is an integer of 1 to 3,

R ^a and R ^b are, independently from each other, hydrogen or C1-C10 alkyl,

Ar ₁ is C6-C20aryl, said aryl may be further substituted with one or more selected from hydroxy and C1-C10alkoxy,

R ₁₂ is hydrogen,-(CR ^c R ^d ) _x -NH ₂ ,-(CR ^c R ^d ) _x -NH- (CR ^e R ^f ) _y -NH ₂ or-(CR ^c R ^d ) _z -Ar ₂ ego,

x, y and z are each independently an integer from 1 to 3,

R ^c to R ^g are each independently hydrogen or C 1 -C 10 alkyl,

Ar ₂ is C 6 -C 20 aryl, said aryl may be further substituted with one or more selected from hydroxy and C 1 -C 10 alkoxy,

R ₁₃ to R ₁₅ are each independently of the other hydrogen or C 1 -C 10 alkyl,

M is a divalent metal of Group 2, 6, 8, 9, 10, 11 or 12 of the periodic table,

L is acetoxy or halogen,

X ⁻ is a halogen anion.

In addition, the present invention provides a method for producing a cyclic carbonate by reacting carbon dioxide and alkylene oxide by using a crosslinked biphenyl polymer including a structural unit represented by the following Chemical Formulas 3 and 4 as a catalyst.

[Formula 3]

[Formula 4]

In Chemical Formulas 3 and 4,

이고; W is

ego;

M is a divalent metal of Group 2, 6, 8, 9, 10, 11 or 12 of the periodic table,

L is acetoxy or halogen,

는

또는

이고,

Is

or

ego,

는 M에 결합되는 부위를 나타내고,

Represents a site bound to M,

R ^g is hydrogen or C1-C10 alkyl,

X ⁻ is a halogen anion.

In addition, the present invention provides a supercrosslinked biphenyl polymer including the structural units represented by the following formula (1-1) and (2-1).

[Formula 1-1]

[Formula 2-1]

In Chemical Formulas 1-1 and 2-1,

R ₁ is hydrogen or —CH ₂ —R,

,

,

또는

이고,R is ^{_{-NR 11 R 12, -N + R}} 13 R 14 R 15 X -,

,

,

or

ego,

R ₁₁ is hydrogen or-(CR ^a R ^b ) _m -Ar ₁ ,

m is an integer of 1 to 3,

R ^a and R ^b are, independently from each other, hydrogen or C1-C10 alkyl,

Ar ₁ is C6-C20aryl, said aryl may be further substituted with one or more selected from hydroxy and C1-C10alkoxy,

R ₁₂ is hydrogen,-(CR ^c R ^d ) _x -NH ₂ ,-(CR ^c R ^d ) _x -NH- (CR ^e R ^f ) _y -NH ₂ or-(CR ^c R ^d ) _z -Ar ₂ ego,

x, y and z are each independently an integer from 1 to 3,

R ^c to R ^g are each independently hydrogen or C 1 -C 10 alkyl,

Ar ₂ is C 6 -C 20 aryl, said aryl may be further substituted with one or more selected from hydroxy and C 1 -C 10 alkoxy,

R ₁₃ to R ₁₅ are each independently of the other hydrogen or C 1 -C 10 alkyl,

M is a divalent metal of Group 2, 6, 8, 9, 10, 11 or 12 of the periodic table,

L is acetoxy or halogen,

X ⁻ is a halogen anion.

In addition, the present invention provides a supercrosslinked biphenyl polymer including the structural units represented by the following formula (3) and (4).

[Formula 3]

[Formula 4]

In Chemical Formulas 3 and 4,

이고; W is

ego;

M is a divalent metal of Group 2, 6, 8, 9, 10, 11 or 12 of the periodic table,

L is acetoxy or halogen,

는

또는

이고,

Is

or

ego,

는 M에 결합되는 부위를 나타내고,

Represents a site bound to M,

R ^g is hydrogen or C1-C10 alkyl,

X ⁻ is a halogen anion.

According to the present invention, a method for preparing a cyclic carbonate using a supercrosslinked biphenyl polymer as a heterogeneous catalyst that does not dissolve in a reactant and a product in the reaction of carbon dioxide and an epoxide compound produces a cyclic carbonate at high conversion under milder conditions. can do.

In addition, since the catalyst of the present invention is a heterogeneous system, the product and the catalyst can be separated by simple precipitation and filtration after the reaction, and the separated catalyst can be reused without any separate treatment, and also during the reaction of the carbon dioxide and the epoxide compound. In spite of the reuse of the catalyst, it is still possible to produce cyclic carbonates with excellent conversion.

Figure 1-IR spectrum of Polymer A
Figure 2-IR spectrum of Polymer B
Figure 3-IR spectrum of Polymer D
Figure 4-IR spectrum of Polymer E
Figure 5-IR spectrum of Polymer F
Figure 6-IR spectrum of Polymer H
Figure 7-IR spectrum of Polymer I
8-IR spectrum of polymer Zn-H

Hereinafter, the present invention will be described in detail. At this time, if there is no other definition in the technical terms and scientific terms used, those having ordinary skill in the technical field to which the present invention has a meaning commonly understood, the following description may unnecessarily obscure the subject matter of the present invention. Descriptions of known functions and configurations are omitted.

As used herein, the term “alkyl” refers to a monovalent straight or crushed saturated hydrocarbon radical consisting solely of carbon and hydrogen atoms, examples of which alkyl radicals are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl , Pentyl, hexyl, octyl, dodecyl, and the like.

As used herein, the term “aryl” refers to an organic radical derived from an aromatic hydrocarbon by one hydrogen removal, wherein a single or fused ring contains 4 to 7, preferably 5 or 6 ring atoms, as appropriate for each ring. It includes a system, including a form where a plurality of aryl is connected by a single bond. Specific examples include, but are not limited to, phenyl, naphthyl, biphenyl, anthryl, indenyl, fluorenyl, and the like.

As used herein, the term "alkoxy" refers to a monovalent atomic group in which oxygen and alkyl are bonded, where "alkyl" is as defined above. Examples of such alkoxy atom groups include, but are not limited to, methoxy, ethoxy, isopropoxy, butoxy, isobutoxy, t-butoxy and the like.

The present invention provides a method for preparing a cyclic carbonate by reacting carbon dioxide and alkylene oxide using a supercrosslinked biphenyl polymer as a catalyst, wherein the reactant alkylene oxide includes one or more epoxides in the compound structure. When reacted with all epoxides can react to form cyclic carbonates.

The hypercrosslinked biphenyl polymer according to one embodiment of the present invention simultaneously includes the structural units represented by the following formula (1) and (2).

[Formula 1]

[Formula 2]

In Chemical Formulas 1 and 2,

R ₁ is -CH ₂ -R,

a and b are each independently an integer of 0 to 2,

,

,

또는

이고,R is halogen, ^{_{nitro, -NR 11 R 12, -N +}} R 13 R 14 R 15 X -,

,

,

or

ego,

R ₁₁ is hydrogen or-(CR ^a R ^b ) _m -Ar ₁ ,

m is an integer of 1 to 3,

R ^a and R ^b are, independently from each other, hydrogen or C1-C10 alkyl,

Ar ₁ is C6-C20aryl, said aryl may be further substituted with one or more selected from hydroxy and C1-C10alkoxy,

R ₁₂ is hydrogen,-(CR ^c R ^d ) _x -NH ₂ ,-(CR ^c R ^d ) _x -NH- (CR ^e R ^f ) _y -NH ₂ or-(CR ^c R ^d ) _z -Ar ₂ ego,

x, y and z are each independently an integer from 1 to 3,

R ^c to R ^g are each independently hydrogen or C 1 -C 10 alkyl,

Ar ₂ is C 6 -C 20 aryl, said aryl may be further substituted with one or more selected from hydroxy and C 1 -C 10 alkoxy,

R ₁₃ to R ₁₅ are each independently of the other hydrogen or C 1 -C 10 alkyl,

M is a divalent metal of Group 2, 6, 8, 9, 10, 11 or 12 of the periodic table,

L is acetoxy or halogen,

X ⁻ is a halogen anion.

The hypercrosslinked biphenyl polymer according to one embodiment of the present invention simultaneously includes structural units represented by the following Chemical Formulas 3 and 4.

[Formula 3]

[Formula 4]

In Chemical Formulas 3 and 4,

이고; W is

ego;

M is a divalent metal of Group 2, 6, 8, 9, 10, 11 or 12 of the periodic table,

L is acetoxy or halogen,

는

또는

이고,

Is

or

ego,

는 M에 결합되는 부위를 나타내고,

Represents a site bound to M,

R ^g is hydrogen or C1-C10 alkyl,

X ⁻ is a halogen anion.

,

,

또는

이고, R₁₁은 수소 또는 -(CR^aR^b)_m-Ar₁이고, m은 1 내지 3의 정수이고, R^a 및 R^b는 서로 독립적으로 수소 또는 C1-C3알킬이고, Ar₁은 C6-C12아릴이고, 상기 아릴은 하이드록시 및 C1-C3알콕시로부터 선택된 하나 이상으로 더 치환될 수 있고, R₁₂는 수소, -(CR^cR^d)_x-NH₂, -(CR^cR^d)_x-NH-(CR^eR^f)_y-NH₂ 또는 -(CR^cR^d)_z-Ar₂ 이고, x, y 및 z는 서로 독립적으로 1 내지 3의 정수이고, R^c 내지 R^g는 서로 독립적으로 수소 또는 C1-C3알킬이고, Ar₂은 C6-C12아릴이고, 상기 아릴은 하이드록시 및 C1-C3알콕시로부터 선택된 하나 이상으로 더 치환될 수 있고, R₁₃ 내지 R₁₅는 서로 독립적으로 C1-C3알킬이고, M은 주기율표상 2족, 6족, 8족, 9족, 10족, 11족 또는 12족의 2가 금속이고, L은 아세톡시 또는 할로겐이고, X^-는 할로겐 음이온일 수 있다.In the hypercrosslinked biphenyl polymer including Formula 1 and Formula 2 simultaneously according to one embodiment of the present invention, R ₁ is —CH ₂ —R, a and b are each independently an integer of 0 or 1, and R is halogen ^{_{, -NR 11 R 12, -N +}} R 13 R 14 R 15 X -,

,

,

or

R ₁₁ is hydrogen or-(CR ^a R ^b ) _m -Ar ₁ , m is an integer from 1 to 3, R ^a and R ^b are independently of each other hydrogen or C1-C3 alkyl, and Ar ₁ is C6 -C 12 aryl, wherein the aryl may be further substituted with one or more selected from hydroxy and C 1 -C 3 alkoxy, R ₁₂ is hydrogen,-(CR ^c R ^d ) _x -NH ₂ ,-(CR ^c R ^d ) _x -NH- (CR ^e R ^f ) _y -NH ₂ or-(CR ^c R ^d ) _z -Ar ₂ , x, y and z are each independently an integer from 1 to 3, R ^c to R ^g is Independently from each other hydrogen or C1-C3 alkyl, Ar ₂ is C6-C12 aryl, said aryl may be further substituted with one or more selected from hydroxy and C1-C3 alkoxy, R ₁₃ to R ₁₅ are independently of one another C 1 -C 3 alkyl, M is a divalent metal of Groups 2, 6, 8, 9, 10, 11 or 12 of the periodic table, L is acetoxy or halogen and X ⁻ is halogen anion Can be.

,

,

,

,

또는

이고, M은 Mg^{2 +}, Cr^{2 +}, Fe^{2 +}, Co^{2 +}, Ni^{2 +}, Cu^{2 +} 또는 Zn^{2 +}이고, L은 아세톡시 또는 할로겐이고, X^-는 할로겐 음이온일 수 있다.More preferably, the R ₁ is hydrogen, halo, _{methyl, -CH 2 NH 2, -CH 2} NHCH 2 CH 2 NH 2, -CH 2 -N + Me 3 X -, -CH 2 -N + Et 3 X - , -CH ₂ NHCH ₂ C (Me) ₂ CH ₂ NH ₂ , -CH ₂ NHCH ₂ CH ₂ NHCH ₂ CH ₂ NH ₂ ,

,

,

,

,

or

And, M is a ^{Mg 2 +, Cr 2 +,} Fe 2 +, Co 2 +, Ni 2 +, Cu 2 + or Zn ^{2 +,} L is acetoxy or halogen, X ^- may be a halogen anion.

이고; M은 주기율표상 2족, 6족, 8족, 9족, 10족, 11족 또는 12족의 2가 금속이고, L은 아세톡시 또는 할로겐이고,

는

또는

이고,

는 M에 결합되는 부위를 나타내고, R^g는 수소 또는 C1-C3알킬이고, X^-는 할로겐 음이온일 수 있다.In the supercrosslinked biphenyl polymer simultaneously containing Formula 3 and Formula 4 according to an embodiment of the present invention W is

ego; M is a divalent metal of Groups 2, 6, 8, 9, 10, 11 or 12 of the periodic table, L is acetoxy or halogen,

Is

or

ego,

Represents a moiety bonded to M, R ^g is hydrogen or C 1 -C 3 alkyl and X ⁻ may be a halogen anion.

는

또는

이고, M은 Mg^{2 +}, Cr^{2 +}, Fe^{2 +}, Co^{2 +}, Ni^{2 +}, Cu^{2 +} 또는 Zn^{2 +}이고, R^g는 수소 또는 C1-C3알킬이고, X^-는 할로겐 음이온일 수 있다.More preferably

Is

or

And, M is ^{Mg 2 +, Cr 2 +,} Fe 2 +, Co 2 +, Ni 2 +, Cu 2 + or Zn ^{2 +} a, R ^g is hydrogen or C1-C3 alkyl, X ^- is a halogen anion days Can be.

More specifically, the present invention provides a method of preparing a cyclic carbonate represented by the following Chemical Formula 6 by reacting carbon dioxide with an alkylene oxide represented by the following Chemical Formula 5 using the supercrosslinked biphenyl polymer as a catalyst.

[Formula 5]

[Formula 6]

(In Chemical Formulas 5 and 6,

R ₁₀₀ and R ₁₀₁ are each independently hydrogen, C 1 -C 10 alkyl or C 6 -C 20 aryl, or R _a and R _b may be linked to a C 3 -C 7 alkylene with or without a fused ring to form a ring .)

In the method for producing a cyclic carbonate according to an embodiment of the present invention, the alkylene oxide represented by Formula 5 may be specifically selected from the following structures, but is not limited thereto.

(R ₁₀₁ is C 1 -C 7 alkyl or C 6 -C 12 aryl.)

In the manufacturing method of the cyclic carbonate according to an embodiment of the present invention, the amount of the supercrosslinked biphenyl polymer is not particularly limited, but 0.5 to 5 weight parts based on 100 parts by weight based on the alkylene oxide of Formula 5 Parts, more preferably 0.5 to 2.5 parts by weight. Appropriate reaction rates and selectivity can be exhibited within this range.

In the manufacturing method of the cyclic carbonate according to an embodiment of the present invention, it may further include an ammonium-based or amine-based promoter for improved reaction rate and high yield, the ammonium-based or amine-based promoter is 0.01 to 5.0 mol%, preferably 0.05 to 1.0 mol%, more preferably 0.05 to 0.5 mol%, relative to the alkylene oxide of 5. Aliphatic amine salts, aromatic amine salts or heteroaromatic amine salts may be used as the ammonium promoter, and specifically, tetrabutylammonium bromide (NBu ₄ Br), tetramethylammonium bromide (NMe ₄ Br), and tetraethylammonium Tetrafluoroborate (NEt ₄ BF4), tetrapropylammonium bromide (NPr ₄ Br), tetrahexylammonium chloride (N [(CH ₂ ) ₅ CH ₃ ] ₄ Cl), tetrapentylammonium bromide (N [(CH ₂ ) ₄ CH ₃ ] ₄ Br), tetraheptylammonium bromide (N [(CH ₂ ) ₆ CH ₃ ] ₄ Br), tetraoctylammonium bromide (N [CH ₂ ) ₇ CH ₃ ] ₄ Br), trimethyldodecylammonium chloride (CH ₃ (CH ₂ ) ₁₁ N (CH ₃ ) ₃ Cl), trimethyltetradecylammonium bromide (CH ₃ (CH ₂ ) ₁₃ N (CH ₃ ) ₃ Br), trimethylhexadecylammonium chloride (CH ₃ (CH _{2) ) 15 N (CH 3) 3} Cl), methyl trioctyl ammonium chloride _{(CH 3 N [(CH 2} ) 7 CH 3] 3 Cl), tetrabutyl ammonium Fluoride (NBu ₄ F), tetrabutylammonium chloride (NBu ₄ Cl), tetrabutylammonium iodide (NBu ₄ I), 1- butyl-3-methylimidazolium bromide ([bmim] Br), 1- Butyl-3-methylimidazolium chloride ([bmim] Cl), bis (triphenylphosphine) imium chloride ([((C ₆ H ₅ ) ₃ P) ₂ N] Cl, PPNCl) The amine-based promoter may be specifically triethylamine (Et ₃ N), 1,8-diazabicycloun-7-kin (DBU), pyridine (C ₅ H ₅ N) and 4-dimethylamino It may be selected from the group consisting of pyridine (C ₇ H ₁₀ N ₂ , DMAP), it is preferable to use tetrabutylammonium bromide (NBu ₄ Br) as the cocatalyst.

In the manufacturing method of the cyclic carbonate according to an embodiment of the present invention, the reaction temperature is preferably 40 to 100 ℃, if the reaction temperature is too low the reaction rate is slow, if the reaction temperature is too high alkylene oxide raw material May be decomposed to lower the final yield. In addition, the carbon dioxide in the reaction is supplied to the reactor at a pressure of 1 to 10 bar. If the reaction pressure is less than 1 bar, the reaction rate is significantly slowed, and if it exceeds 10 bar it is uneconomical because there is no effect of improving the reaction rate.

In the method for producing a cyclic carbonate according to an embodiment of the present invention, the reaction may be performed under an organic solvent or even neat. Neat is the reaction of carbon dioxide and alkylene carbonate without using an organic solvent. In some cases, an organic solvent may be used to prevent rapid exotherm. As the organic solvent usable, any solvent commonly used in the art may be employed. For example, organic solvents such as methylene chloride, chloroform, ethyl acetate, tert-methylbutyl ether, toluene, isopropyl alcohol, dioxane, acetonitrile, alkylene carbonate can be used, but are not limited thereto.

The present invention also provides a novel crosslinked biphenyl polymer.

The supercrosslinked biphenyl polymer according to an embodiment of the present invention may be a supercrosslinked biphenyl polymer simultaneously containing the structural units represented by the following Chemical Formulas 1-1 and 2-1.

[Formula 1-1]

[Formula 2-1]

In Chemical Formulas 1-1 and 2-1,

R ₁ is hydrogen or —CH ₂ —R,

,

,

또는

이고,R is ^{_{-NR 11 R 12, -N + R}} 13 R 14 R 15 X -,

,

,

or

ego,

R ₁₁ is hydrogen or-(CR ^a R ^b ) _m -Ar ₁ ,

m is an integer of 1 to 3,

R ^a and R ^b are, independently from each other, hydrogen or C1-C10 alkyl,

Ar ₁ is C6-C20aryl, said aryl may be further substituted with one or more selected from hydroxy and C1-C10alkoxy,

R ₁₂ is hydrogen,-(CR ^c R ^d ) _x -NH ₂ ,-(CR ^c R ^d ) _x -NH- (CR ^e R ^f ) _y -NH ₂ or-(CR ^c R ^d ) _z -Ar ₂ ego,

x, y and z are each independently an integer from 1 to 3,

R ^c to R ^g are each independently hydrogen or C 1 -C 10 alkyl,

Ar ₂ is C 6 -C 20 aryl, said aryl may be further substituted with one or more selected from hydroxy and C 1 -C 10 alkoxy,

R ₁₃ to R ₁₅ are each independently of the other hydrogen or C 1 -C 10 alkyl,

M is a divalent metal of Group 2, 6, 8, 9, 10, 11 or 12 of the periodic table,

L is acetoxy or halogen,

X ⁻ is a halogen anion.

,

,

또는

이고, R₁₁은 수소 또는 -(CR^aR^b)_m-Ar₁이고, m은 1 내지 3의 정수이고, R^a 및 R^b는 서로 독립적으로 수소 또는 C1-C3알킬이고, Ar₁은 C6-C12아릴이고, 상기 아릴은 하이드록시 및 C1-C3알콕시로부터 선택된 하나 이상으로 더 치환될 수 있고, R₁₂는 수소, -(CR^cR^d)_x-NH₂, -(CR^cR^d)_x-NH-(CR^eR^f)_y-NH₂ 또는 -(CR^cR^d)_z-Ar₂ 이고, x, y 및 z는 서로 독립적으로 1 내지 3의 정수이고, R^c 내지 R^g는 서로 독립적으로 수소 또는 C1-C3알킬이고, Ar₂은 C6-C12아릴이고, 상기 아릴은 하이드록시 및 C1-C3알콕시로부터 선택된 하나 이상으로 더 치환될 수 있고, R₁₃ 내지 R₁₅는 서로 독립적으로 C1-C3알킬이고, M은 주기율표상 2족, 6족, 8족, 9족, 10족, 11족 또는 12족의 2가 금속이고, L은 아세톡시 또는 할로겐이고, X^-는 할로겐 음이온일 수 있다.In the crosslinked biphenyl polymer including Formula 1-1 and Formula 2-1 simultaneously according to one embodiment of the present invention, R ₁ is hydrogen or -CH ₂ -R, R is halogen, -NR ₁₁ R ₁₂ ,- ^{_{N + R 13 R 14 R 15}} X -,

,

,

or

R ₁₁ is hydrogen or-(CR ^a R ^b ) _m -Ar ₁ , m is an integer from 1 to 3, R ^a and R ^b are independently of each other hydrogen or C1-C3 alkyl, and Ar ₁ is C6 -C 12 aryl, wherein the aryl may be further substituted with one or more selected from hydroxy and C 1 -C 3 alkoxy, R ₁₂ is hydrogen,-(CR ^c R ^d ) _x -NH ₂ ,-(CR ^c R ^d ) _x -NH- (CR ^e R ^f ) _y -NH ₂ or-(CR ^c R ^d ) _z -Ar ₂ , x, y and z are each independently an integer from 1 to 3, R ^c to R ^g is Independently from each other hydrogen or C1-C3 alkyl, Ar ₂ is C6-C12 aryl, said aryl may be further substituted with one or more selected from hydroxy and C1-C3 alkoxy, R ₁₃ to R ₁₅ are independently of one another C 1 -C 3 alkyl, M is a divalent metal of Groups 2, 6, 8, 9, 10, 11 or 12 of the periodic table, L is acetoxy or halogen and X ⁻ is halogen anion Can be.

,

,

,

,

또는

이고, M은 Mg^{2 +}, Cr^{2 +}, Fe^{2 +}, Co^{2 +}, Ni^{2 +}, Cu^{2 +} 또는 Zn²⁺이고, L은 아세톡시 또는 할로겐이고, X^-는 할로겐 음이온일 수 있다.More preferably, the R ₁ is hydrogen, halo, _{methyl, -CH 2 NH 2, -CH 2} NHCH 2 CH 2 NH 2, -CH 2 -N + Me 3 X -, -CH 2 -N + Et 3 X - , -CH ₂ NHCH ₂ C (Me) ₂ CH ₂ NH ₂ , -CH ₂ NHCH ₂ CH ₂ NHCH ₂ CH ₂ NH ₂ ,

,

,

,

,

or

And, M is a ^{Mg 2 +, Cr 2 +,} Fe 2 +, Co 2 +, Ni 2 +, Cu 2 + or Zn ^2+, L is acetoxy or halogen, X ^- may be a halogen anion.

The supercrosslinked biphenyl polymer according to an embodiment of the present invention may be a supercrosslinked biphenyl polymer simultaneously containing structural units represented by the following Chemical Formulas 3 and 4.

[Formula 3]

[Formula 4]

In Chemical Formulas 3 and 4,

이고; W is

ego;

M is a divalent metal of Group 2, 6, 8, 9, 10, 11 or 12 of the periodic table,

L is acetoxy or halogen,

는

또는

이고,

Is

or

ego,

는 M에 결합되는 부위를 나타내고,

Represents a site bound to M,

R ^g is hydrogen or C1-C10 alkyl,

X ⁻ is a halogen anion.

이고; M은 주기율표상 2족, 6족, 8족, 9족, 10족, 11족 또는 12족의 2가 금속이고, L은 아세톡시 또는 할로겐이고,

는

또는

이고,

는 M에 결합되는 부위를 나타내고, R^g는 수소 또는 C1-C3알킬이고, X^-는 할로겐 음이온일 수 있다.In the supercrosslinked biphenyl polymer simultaneously containing Formula 3 and Formula 4 according to an embodiment of the present invention W is

ego; M is a divalent metal of Groups 2, 6, 8, 9, 10, 11 or 12 of the periodic table, L is acetoxy or halogen,

Is

or

ego,

Represents a moiety bonded to M, R ^g is hydrogen or C 1 -C 3 alkyl and X ⁻ may be a halogen anion.

는

또는

이고, M은 Mg^{2 +}, Cr^{2 +}, Fe^{2 +}, Co^{2 +}, Ni^{2 +}, Cu^{2 +} 또는 Zn^{2 +}이고, R^g는 수소 또는 C1-C3알킬이고, X^-는 할로겐 음이온일 수 있다.More preferably

Is

or

And, M is ^{Mg 2 +, Cr 2 +,} Fe 2 +, Co 2 +, Ni 2 +, Cu 2 + or Zn ^{2 +} a, R ^g is hydrogen or C1-C3 alkyl, X ^- is a halogen anion days Can be.

Supercrosslinked biphenyl polymer according to an embodiment of the present invention can be efficiently produced through the Friedel-Crafts reaction of biphenyl and dichloromethane, benzene of biphenyl to introduce various substituents The chloromethyl group may be introduced into the ring and then reacted with various amine compounds. The aminated hypercrosslinked biphenyl polymer can also be reacted with a divalent metal complex to produce the complexed supercrosslinked biphenyl polymer.

More specifically, the Friedel-Crafts reaction of biphenyl and dichloromethane is carried out under a Lewis acid catalyst, and usable Lewis acid catalysts include ferric chloride (FeCl ₃ ), aluminum chloride (AlCl ₃ ), and tin tin chloride. (SnCl ₄ ), boron trifluoride (BF ₃ ), hydrofluoric acid (HF) is preferably selected from the group consisting of, aluminum chloride, tin dichloride and ferric chloride is more reactive and easy to handle. desirable. In addition, in the Friedel-Craft reaction, dichloromethane may be used as a reaction solvent while simultaneously crosslinking biphenyl and biphenyl with methylene bridge.

The hypercrosslinked biphenyl polymer prepared through the Friedel-Craft reaction can be reacted with an alkylhalide material to introduce a haloalkyl group into the benzene ring of the hypercrosslinked biphenyl polymer.

For example, a supercrosslinked biphenyl polymer obtained by reacting biphenyl and dichloromethane with Friedel-Crafts is subjected to a nucleophilic chloromethylating agent such as paraformaldehyde hydrochloride or formalin hydrochloric acid and phosphoric acid, sulfuric acid or aluminum chloride (AlCl ₃ ). , In the presence of a metal chloride catalyst such as iron chloride (FeCl ₃ ) and zinc chloride (ZnCl ₂ ), an appropriate choice of reaction temperature and reaction time in an organic solvent such as acetic acid, dichloromethane, carbon tetrachloride, or chloroform can be achieved. The supercrosslinked biphenyl polymer introduced can be obtained.

The supercrosslinked biphenyl polymer introduced with the haloalkyl group obtained above may be reacted with an aminizing agent, that is, various amine compounds, to obtain aminated crosslinked biphenyl polymer. Through the amination reaction, the halogen group of the halomethyl group of the hypercrosslinked biphenyl polymer may be substituted with an amine group or may form a weak bond with the amine group to exist as a salt.

In addition, the aminated supercrosslinked biphenyl polymer is a supercrosslinked biphenyl polymer complexed by coordinating with a divalent metal complex of Group 2, 6, 8, 9, 10, 11 or 12 of the periodic table. It may be prepared.

Hereinafter, the structure of the present invention will be described in more detail with reference to Examples, but the following Examples are provided to assist in understanding the present invention, and the scope of the present invention is not limited thereto.

Commercially available reagents and carbon dioxide (99.99%) were used without further purification or drying. All reactions were performed in a 150 ml stainless steel reactor.

The yield (%) of polymer A in Example 1 was calculated as [weight of biphenyl, the weight of polymer A / monomer] * 100. The yield (%) of the polymer prepared in the remaining examples was calculated as [weight of polymer obtained / weight of polymer that is starting material] * 100.

¹ H NMR was recorded using a Varian 300 spectrometer and all chemical mobility was reported in ppm relative to the internal standard tetramethyl silane. IR spectra were measured directly on the samples using FT-IR (surface reflection infrared spectroscopy).

The metal content in the polymer was measured by ICP analysis using an Inductively Coupled Plasma Atomic Emission Spectrometer.

Model: OPTIMA 7300 DV

-Manufacturer: Perkin-Elmer (USA)

RF generator frequency: 40 MHz

-Optical system: Echelle polychromator

Plasma viewing: Dual (Axial and Radial) viewing

Wavelength range: 163-782 nm

-Detector system: 2 sets of SCD (Segmented-array Charge-coupled Device)

-Automatic On-line Hydride Generation System

Example 1 Preparation of Polymer B

Preparation of Polymer A

Polymer A is described in Sci. Adv. 2017; 3: can be prepared by the method described in e1602610.

In a 100 mL round-bottom flask, add biphenyl (0.77 g, 0.005 mol), aluminum chloride (AlCl ₃ , 2.67 g, 0.02 mol), dichloromethane (DCM, 8 mL) for 4 hours at 0 ° C under nitrogen atmosphere. Stirred and stirred at 30 ° C. for 8 hours and then at 40 ° C. for 8 hours. Then, the mixture was stirred at 60 ° C. for 24 hours and then at 80 ° C. for 24 hours. Then, an aqueous hydrochloric acid solution (100 mL) prepared by mixing hydrochloric acid and water in a volume ratio of 2: 1 was added thereto, stirred for 30 minutes, and the resulting black precipitate was filtered and washed with water and methanol. The resulting black precipitate was stirred for 48 h again in methanol (200 mL), filtered and dried in an oven at 60 ° C. to give the title compound Polymer A as a dark brown solid (yield: 1.07 g, yield: 140%). ).

FT-IR ( ν _max / cm ^-1 ): 2980 (CH stretch), 1452 (CH2 bending), 1600 (phenyl C = C ring stretch)

Preparation of Polymer B

Polymer A (400 mg), paraformaldehyde (PFA, 2.0 g), acetic acid (12 mL), hydrochloric acid (40 mL) and phosphoric acid (6.0 mL) were placed in a 100 mL round bottom flask for 3 days at 90 ° C. under nitrogen atmosphere. Was stirred. After stirring was complete, the reaction mixture was washed with water and methanol to obtain the title compound (B) as a black solid (yield: 446 mg, yield: 107.8%).

FT-IR ( ν _max / cm ^-1 ): 2934 (CH stretch), 1452 (CH2 bending), 1600 (phenyl C = C ring stretch), 1230 (CH2-Cl bending)

Example 2 Preparation of Polymer C

Polymer B (200 mg) and ammonia water (20 mL) were placed in a round bottom flask and stirred under reflux at 90 ° C. for 3 days. When the reaction was completed, the product was filtered with washing with water and methanol to obtain the title compound Polymer C as a black solid (yield: 189 mg, yield: 94.5%).

Example 3 Preparation of Polymer D

The reaction was carried out in the same manner as in Example 2, except that 1,2-diaminoethane (10 mL) was used instead of ammonia water to obtain the title compound Polymer D as a black solid (amount: 212 mg, yield: 106). %).

FT-IR ( ν _max / cm ^-1 ): 2956 (CH stretch), 1452 (CH2 bending), 1600 (phenyl C = C ring stretch), 1620 (NH bending)

Example 4 Preparation of Polymer E

Polymer B (200 mg), pyridine (1 mL) and methanol (10 mL) were placed in a round bottom flask and stirred under reflux for 3 days at 90 ° C. When the reaction was completed, the product was filtered with washing with water and methanol to give the title compound Polymer E as a black solid (yield: 202 mg, yield: 101%).

FT-IR ( ν _max / cm ^-1 ): 2947 (CH stretch), 1452 (CH2 bending), 1600 (phenyl C = C ring stretch)

Example 5 Preparation of Polymer F

The reaction was carried out in the same manner as in Example 4, except that triethylamine (1 mL) was used instead of pyridine to obtain the title compound Polymer F as a black solid (yield: 209 mg, yield: 104.5%).

FT-IR ( ν _max / cm ^-1 ): 2938 (CH stretch), 1452 (CH2 bending), 1610 (phenyl C = C ring stretch), 1615 (NH bending)

Example 6 Preparation of Polymer G

The reaction was carried out in the same manner as in Example 2, except that 2,2-dimethyl-1,3-propanediamine (10 mL) was used instead of ammonia water to obtain the title compound Polymer G as a black solid (yield) : 216 mg, yield: 108%).

Example 7 Preparation of Polymer H

The reaction was carried out in the same manner as in Example 2, except that diethylenetriamine (10 mL) was used instead of ammonia water to obtain the title compound Polymer H as a black solid (amount: 217 g, yield: 108.5%).

FT-IR ( ν _max / cm ^-1 ): 2943 (CH stretch), 1456 (CH2 bending), 1596 (phenyl C = C ring stretch), 1655 (NH bending)

Example 8 Preparation of Polymer I

Preparation of Compound J

Ortho-vanillin (ortho -Vanillin, 5 g) and 2,2-dimethyl-put-1, 3-propane-diamine (1.67 g) at room temperature after which sodium beam stirred for one day hydride (NaBH ₄₎ ( 3.5 equivalents) was added, stirred and filtered to yield compound J.

¹ H NMR (300 MHz, CDCl ₃ , 298 K) -δ6.79 (dd, 2H, m-Ph), 6.74 (t, 2H, p-Ph), 6.66 (dd, 2H, m-Ph), 3.96 (s, 4H, NH-CH2-Ph), 3.86 (s, 6H, O-CH3), 2.56 (s, 4H, NH-CH2-C), 0.99 (s, 6H, C- (CH3)).

Preparation of Polymer I

The reaction was carried out in the same manner as in Example 2, except that Compound J (1 g) was used instead of ammonia water to obtain the title compound Polymer I as a black solid (amount: 207 mg, yield: 103.5%).

FT-IR ( ν _max / cm ^-1 ): 2947 (CH stretch), 2825 (OCH3 strech) 1475 (CH2 bending), 1569 (phenyl C = C ring stretch)

Example 9 Preparation of Polymer K

The reaction was carried out in the same manner as in Example 2, except that imidazole (1 g) was used instead of ammonia water to obtain the title compound Polymer K as a black solid (yield: 205 mg, yield: 102.5%).

Example 10 Preparation of Polymer L

The reaction was carried out in the same manner as in Example 2, except that 1-methylimidazole (10 mL) was used instead of ammonia water to obtain the title compound Polymer L as a black solid (amount: 208 g, yield: 104%). ).

Example 11 Preparation of Metal Complex Zn-C

Polymer C (200 mg) and zinc acetate (50 mg) were added to methanol (10 mL), stirred at room temperature for 1 day, and the product was filtered with washing with methanol to give the title compound metal complex Zn-C as a black solid. Obtained (yield: 205 mg, yield: 102.5%). The Zn content was 21849 ppm as a result of nCP-MS (nductively coupled plasma-mass spectometry) analysis of the polymer Zn-C.

Example 12 Preparation of Metal Complex Zn-K

The reaction was carried out in the same manner as in Example 11, except that Polymer K (200 mg) was used instead of Polymer C to obtain the title compound, the metal complex, Zn-K, as a black solid (amount: 205 g, yield: 102.5%). ). The Zn content was 40397 ppm as a result of nCP-MS (nductively coupled plasma-mass spectometry) analysis of the polymer Zn-K.

Example 13 Preparation of Metal Complex Zn-L

The reaction was carried out in the same manner as in Example 11, except that Polymer L (200 mg) was used instead of Polymer C to obtain the title compound, the metal complex, Zn-L, as a black solid (amount: 205 g, yield: 102.5%). ). The Zn content of the polymer Zn-L was 35198 ppm as measured by inductively coupled plasma-mass spectometry (ICP-MS).

Example 14 Preparation of Metal Complex Zn-C-1

The reaction was carried out in the same manner as in Example 11, except that zinc bromide (50 mg) was used instead of zinc acetate to obtain the title compound, the metal complex, Zn-C-1, as a black solid (amount: 201 mg, yield: 100.5%). The Zn content was 18653 ppm as a result of inductively coupled plasma-mass spectometry (ICP-MS) analysis of the polymer Zn-C-1.

Example 15 Preparation of Metal Complex Zn-D

The reaction was carried out in the same manner as in Example 14, except that Polymer D (200 mg) was used instead of Polymer C to obtain the title compound, the metal complex, Zn-D, as a black solid (amount: 204 mg, yield: 102%). ). The Zn content was 28624 ppm as a result of inductively coupled plasma-mass spectometry (ICP-MS) analysis of the polymer Zn-D.

Example 16 Preparation of Metal Complex Zn-H

The reaction was carried out in the same manner as in Example 14, except that Polymer H (200 mg) was used instead of Polymer C to obtain the title compound, the metal complex, Zn-H, as a black solid (amount: 211 mg, yield: 105.5%). ). The Zn content was 452487 ppm as a result of inductively coupled plasma-mass spectometry (ICP-MS) analysis of the polymer Zn-H.

FT-IR ( ν _max / cm ^-1 ): 2943 (CH stretch), 1456 (CH2 bending), 1615 (phenyl C = C ring stretch), 1646 (NH bending)

Example 17 Preparation of Cyclic Carbonate Using Carbon Dioxide and Propylene Oxide

In a 150 mL Teflon vessel, a catalyst and a promoter, tetrabutylammonium bromide (NBu ₄ Br, TBAB) and propylene oxide (10 mL), were added, and then the Teflon vessel was placed in a stainless steel bomb reactor. If necessary, add zinc acetate. After filling and emptying the reactor with 2 bar of CO ₂ , finally, 10 bar of CO ₂ is filled. Thereafter, the reactor was locked and the reaction proceeded for 24 hours while stirring at 60 ° C. After the reaction was completed, a part of the reaction mixture was dissolved in CDCl ₃ and analyzed using ¹ H-NMR.

The type and amount of the catalyst used in Table 1, the amount of the cocatalyst, the amount of zinc acetate, the amount of propylene oxide and the conversion rate of the product were described.

catalyst Catalyst usage (mg) Promoter Usage (mg) Zinc Acetate (mg) Amount of propylene oxide (mL) % Conversion One A 200 35 20 10 73.0 2 C 200 35 20 10 93.0 3 Zn-C 200 35 - 10 77.52 ¹ H NMR of cyclic carbonate I (300 MHz, CDCl ₃ -d ₁ ): δ1.51 (d, 3H), 4.05 (m, 1H), 4.60 (m, 1H), 4.90 (m, 1H)

Example 18 Reuse of Catalysts for Preparation of Cyclic Carbonate Using Carbon Dioxide and Propylene Oxide

In a 150 mL Teflon vessel, a catalyst and a promoter, tetrabutylammonium bromide (NBu ₄ Br, TBAB) and propylene oxide (10 mL), were added, and then the Teflon vessel was placed in a stainless steel bomb reactor. After filling and emptying the reactor with 2 bar of CO ₂ , finally, 10 bar of CO ₂ is filled. Thereafter, the reactor was locked and the reaction proceeded for 24 hours while stirring at 60 ° C. After the reaction was completed, a part of the reaction mixture was dissolved in CDCl ₃ and analyzed using ¹ H-NMR.

In addition, the catalyst was separated and recovered by filtration of the reaction mixture, and the catalyst was repeatedly reused up to four times by washing the separated and recovered catalyst with methanol and drying it in an oven at 80 ° C. for 10 hours.

The type and amount of the catalyst used in Table 2, the amount of the cocatalyst, the amount of propylene oxide, the number of reuse and the conversion rate of the product were described.

catalyst Catalyst usage (mg) Promoter Usage (mg) Amount of propylene oxide (mL) Reuse count % Conversion One Zn-K 100 46 10 One 53 2 Zn-K 96 35 10 2 58 3 Zn-K 84 35 10 3 58 4 Zn-K 64 35 10 4 49 5 Zn-H 180 - 10 One 88.5 6 Zn-H 173 - 10 2 86.8 7 Zn-H 165 - 10 3 85 8 Zn-H 150 - 10 4 82.6 ¹ H NMR of cyclic carbonate I (300 MHz, CDCl ₃ -d ₁ ): δ1.51 (d, 3H), 4.05 (m, 1H), 4.60 (m, 1H), 4.90 (m, 1H)

From the above results, it can be seen that when the cyclic carbonate using carbon dioxide and the epoxide compound having various structures, the cyclic carbonate is produced at a high conversion rate of 50% or more when the supercrosslinked biphenyl polymer of the present invention is used as a catalyst. have. In addition, it can be seen that the supercrosslinked biphenyl polymer of the present invention can be reused up to four times without losing catalytic activity.

Claims (13)

A method of preparing a cyclic carbonate by reacting carbon dioxide and alkylene oxide using a supercrosslinked biphenyl polymer including a structural unit represented by Formula 1 and Formula 2 simultaneously as a catalyst.
[Formula 1]

[Formula 2]

In Chemical Formulas 1 and 2,
R ₁ is -CH ₂ -R,
a and b are each independently an integer of 0 to 2,
R is halogen, ^{_{nitro, -NR 11 R 12, -N +}} R 13 R 14 R 15 X -,

,

,

or

ego,
R ₁₁ is hydrogen or-(CR ^a R ^b ) _m -Ar ₁ ,
m is an integer of 1 to 3,
R ^a and R ^b are, independently from each other, hydrogen or C1-C10 alkyl,
Ar ₁ is C6-C20aryl, said aryl may be further substituted with one or more selected from hydroxy and C1-C10alkoxy,
R ₁₂ is hydrogen,-(CR ^c R ^d ) _x -NH ₂ ,-(CR ^c R ^d ) _x -NH- (CR ^e R ^f ) _y -NH ₂ or-(CR ^c R ^d ) _z -Ar ₂ ego,
x, y and z are each independently an integer from 1 to 3,
R ^c to R ^g are each independently hydrogen or C 1 -C 10 alkyl,
Ar ₂ is C 6 -C 20 aryl, said aryl may be further substituted with one or more selected from hydroxy and C 1 -C 10 alkoxy,
R ₁₃ to R ₁₅ are each independently of the other hydrogen or C 1 -C 10 alkyl,
M is a divalent metal of Group 2, 6, 8, 9, 10, 11 or 12 of the periodic table,
L is acetoxy or halogen,
X ⁻ is a halogen anion. A method of preparing a cyclic carbonate by reacting carbon dioxide and alkylene oxide using a supercrosslinked biphenyl polymer simultaneously containing structural units represented by the following Chemical Formulas 3 and 4 as a catalyst.
[Formula 3]

[Formula 4]

In Chemical Formulas 3 and 4,
W is

ego;
M is a divalent metal of Group 2, 6, 8, 9, 10, 11 or 12 of the periodic table,
L is acetoxy or halogen,

Is

or

ego,

Represents a site bound to M,
R ^g is hydrogen or C1-C10 alkyl,
X ⁻ is a halogen anion. The method of claim 1,
Wherein R ₁ is hydrogen, halo, _{methyl, -CH 2 NH 2, -CH 2} NHCH 2 CH 2 NH 2, -CH 2 -N + Me 3 X -, -CH 2 -N + Et 3 X -, -CH 2 NHCH ₂ C (Me) ₂ CH ₂ NH ₂ , -CH ₂ NHCH ₂ CH ₂ NHCH ₂ CH ₂ NH ₂ ,

,

,

,

,

or

And, M is Mg ^{2 +,} Cr ^{2 +,} Fe ^{2 +,} Co ^{2 +,} Ni ^{2 +,} Cu ^{2 +} or Zn ^{2 +} and, L is acetoxy or halogen, X ^- is the method the halogen anion. The method of claim 2,
remind

Is

or

And, M is ^{Mg 2+, Cr 2 +, Fe} 2 +, Co 2 +, Ni 2 +, Cu 2 + or Zn ^{2 +} a, R ^g is hydrogen or C1-C3 alkyl, X ^- is a halogen anion Way. The method according to claim 1 or 2,
The alkylene oxide is represented by the following formula (5), wherein the cyclic carbonate is represented by the formula (6).
[Formula 5]

[Formula 6]

(In Chemical Formulas 5 and 6,
R ₁₀₀ and R ₁₀₁ are each independently hydrogen, C 1 -C 10 alkyl or C 6 -C 20 aryl, or R _a and R _b may be linked to a C 3 -C 7 alkylene with or without a fused ring to form a ring .) The method according to claim 1 or 2,
The catalyst is characterized in that it is used in 0.5 to 5 parts by weight based on 100 parts by weight of the alkylene oxide. The method according to claim 1 or 2,
An ammonium-based promoter or an amine-based promoter further comprising the production method. The method of claim 7, wherein
The ammonium co-catalyst or the amine co-catalyst is characterized in that used in 0.01 to 5.0 mol% based on the alkylene oxide. The method of claim 8,
The ammonium promoter is tetrabutylammonium bromide (NBu ₄ Br), tetramethylammonium bromide (NMe ₄ Br), tetraethylammonium tetrafluoroborate (NEt ₄ BF4), tetrapropylammonium bromide (NPr ₄ Br), tetra Hexylammonium chloride (N [(CH ₂ ) ₅ CH ₃ ] ₄ Cl), tetrapentylammonium bromide (N [(CH ₂ ) ₄ CH ₃ ] ₄ Br), tetraheptylammonium bromide (N [(CH ₂ ) ₆ CH ₃ ] ₄ Br), tetraoctylammonium bromide (N [CH ₂ ) ₇ CH ₃ ] ₄ Br), trimethyldodecylammonium chloride (CH ₃ (CH ₂ ) ₁₁ N (CH ₃ ) ₃ Cl), trimethyltetradecylammonium Bromide (CH ₃ (CH ₂ ) ₁₃ N (CH ₃ ) ₃ Br), trimethylhexadecylammonium chloride (CH ₃ (CH ₂ ) ₁₅ N (CH ₃ ) ₃ Cl), methyltrioctylammonium chloride (CH ₃ N [ (CH ₂ ) ₇ CH ₃ ] ₃ Cl), tetrabutylammonium fluoride (NBu ₄ F), tetrabutylammonium chloride (NBu ₄ Cl), tetrabutylammonium iodide (NBu ₄ I), 1-butyl-3-methylimidazolium bromide ([bmim] Br), 1-butyl-3-methylimidazolium chloride ([bmim] Cl), bis (triphenylphosphine) One or two or more mixtures selected from the group consisting of nium chloride ([((C ₆ H ₅ ) ₃ P) ₂ N] Cl, PPNCl), wherein the amine promoter is triethylamine (Et ₃ N), 1 One, two or more mixtures selected from the group consisting of, 8-diazabicycloun-7-kin (DBU), pyridine (C ₅ H ₅ N) and 4-dimethylaminopyridine (C ₇ H ₁₀ N ₂ , DMAP) Production method characterized in that. The method according to claim 1 or 2,
The reaction temperature is 40 to 100 ℃, the production pressure, characterized in that 1 to 10 bar. The method according to claim 1 or 2,
The reaction is a manufacturing method characterized in that the neat (neat) reaction. A hypercrosslinked biphenyl polymer comprising simultaneously the structural units represented by the following formulas (1-1) and (2-1).
[Formula 1-1]

[Formula 2-1]

In Chemical Formulas 1-1 and 2-1,
R ₁ is hydrogen or —CH ₂ —R,
R is ^{_{-NR 11 R 12, -N + R}} 13 R 14 R 15 X -,

,

,

or

ego,
R ₁₁ is hydrogen or-(CR ^a R ^b ) _m -Ar ₁ ,
m is an integer of 1 to 3,
R ^a and R ^b are, independently from each other, hydrogen or C1-C10 alkyl,
Ar ₁ is C6-C20aryl, said aryl may be further substituted with one or more selected from hydroxy and C1-C10alkoxy,
R ₁₂ is hydrogen,-(CR ^c R ^d ) _x -NH ₂ ,-(CR ^c R ^d ) _x -NH- (CR ^e R ^f ) _y -NH ₂ or-(CR ^c R ^d ) _z -Ar ₂ ego,
x, y and z are each independently an integer from 1 to 3,
R ^c to R ^g are each independently hydrogen or C 1 -C 10 alkyl,
Ar ₂ is C 6 -C 20 aryl, said aryl may be further substituted with one or more selected from hydroxy and C 1 -C 10 alkoxy,
R ₁₃ to R ₁₅ are each independently of the other hydrogen or C 1 -C 10 alkyl,
M is a divalent metal of Group 2, 6, 8, 9, 10, 11 or 12 of the periodic table,
L is acetoxy or halogen,
X ⁻ is a halogen anion. A hypercrosslinked biphenyl polymer comprising simultaneously the structural units represented by the following formula (3) and formula (4).
[Formula 3]

[Formula 4]

In Chemical Formulas 3 and 4,
W is

ego;
M is a divalent metal of Group 2, 6, 8, 9, 10, 11 or 12 of the periodic table,
L is acetoxy or halogen,

Is

or

ego,

Represents a site bound to M,
R ^g is hydrogen or C1-C10 alkyl,
X ⁻ is a halogen anion.

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