KR102517520B1 - Polycarbonate and method for preparing same - Google Patents

Abstract

The present invention relates to polycarbonate and a method for producing the same.

Description

Polycarbonate and its manufacturing method {POLYCARBONATE AND METHOD FOR PREPARING SAME}

This application claims the benefit of the filing date of Korean Patent Application No. 10-2020-0134330 filed with the Korean Intellectual Property Office on October 16, 2020, the entire contents of which are incorporated herein.

The present invention relates to polycarbonate and a method for producing the same. More specifically, it relates to a polycarbonate having a novel structure with excellent mechanical properties, improved flame retardancy, heat resistance, transparency, hardness, and the like, and a manufacturing method thereof.

Polycarbonate resin is a polymer material that is widely used in fields such as exterior materials for electric and electronic products, automobile parts, building materials, and optical parts due to its physical properties such as excellent impact strength, dimensional stability, heat resistance, and transparency.

As the application fields of such polycarbonate resins have recently expanded, such as being applied to glass and lenses, there is a demand for the development of new polycarbonate structures with improved weather resistance and refractive index while maintaining the inherent properties of polycarbonate resins.

Accordingly, studies have been attempted to obtain desired physical properties by copolymerizing two or more aromatic diol compounds having different structures and introducing units having different structures into the main chain of polycarbonate. However, most technologies have limitations such as high production cost, increased chemical resistance or impact strength, and conversely, reduced transparency, and improved transparency, reduced chemical resistance or impact strength.

Accordingly, there is still a need for research and development on polycarbonates having excellent mechanical properties such as hardness and excellent flame retardancy, heat resistance, transparency, hardness and impact resistance as well.

International Patent Publication No. 99/028387

The present invention relates to a polycarbonate having excellent mechanical properties, flame retardancy, heat resistance, hardness and impact resistance, and a method for producing the same.

However, the problem to be solved by the present invention is not limited to the above-mentioned problem, and other problems not mentioned will be clearly understood by those skilled in the art from the following description.

The present invention provides a polycarbonate comprising a repeating unit derived from a diol compound represented by Formula 1 below and a carbonate precursor.

[Formula 1]

In Formula 1,

Z ₁ is CR ₁ R ₂ , O, S, SS, C=O, C=S, SO, SO ₂ , (CH ₂ ) _n -L ₁ -(CH ₂ ) _m or O-(C=O); ,

R ₁ and R ₂ are each independently hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted haloalkyl, OR ^a , SR ^b , NR ^c R ^d , COOR ^e , OCOR ^f , halogen, CN or NO ₂ ;

R ₁ and R ₂ are connected to form a substituted or unsubstituted aliphatic or aromatic ring with halogen, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;

L ₁ is O or S;

n and m are each independently an integer from 1 to 3;

Z ₂ and Z ₃ are each independently a single bond, a substituted or unsubstituted alkylene, a substituted or unsubstituted cycloalkylene, a substituted or unsubstituted arylene, or a substituted or unsubstituted heteroarylene, or a combination thereof. is,

X ₁ and X ₂ are each independently CR ₁₀₀ or N;

Y ₁ and Y ₂ are each independently CR ₁₀₁ R ₁₀₂ , O or S;

R ₁₀₀ , R _{101 ,} R _{102 ,} R ₃ and R ₄ are each independently hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted haloalkyl, OR ^a , SR ^b , NR ^c R ^d , COOR ^e , OCOR ^f , halogen, CN or NO ₂ ;

a and b are each independently an integer from 0 to 3,

R ^a to R ^f are each independently hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl.

The present invention is a polycarbonate containing a diol compound represented by Formula 1 and a repeating unit derived from a carbonate precursor, and the Izod room temperature impact strength measured at 23 ° C. in accordance with ASTM D256 (1/8 inch, Notched Izod) is 220 J / m or more.

The present invention provides a polycarbonate manufacturing method comprising the step of polymerizing a composition including the diol compound represented by Formula 1 and a carbonate precursor.

The present invention provides a molded article comprising the polycarbonate.

The polycarbonate according to the present invention has excellent mechanical properties, flame retardancy, heat resistance, hardness and impact resistance.

Effects of the present invention are not limited to the above-mentioned effects, and effects not mentioned will be clearly understood by those skilled in the art from the present specification and accompanying drawings.

1 is a ¹ H-NMR graph of a diol compound represented by Compound 1 prepared in Example 1. FIG.
2 is a ¹ H-NMR graph of a diol compound represented by Compound 2 prepared in Example 2;
3 is a ¹ H-NMR graph of a diol compound represented by Compound 3 prepared in Example 3;

Hereinafter, in order to aid understanding of the present invention, it will be described in more detail.

The polycarbonate and its manufacturing method according to the present invention are detailed below, but unless there is another definition in the technical and scientific terms used at this time, the meaning commonly understood by those of ordinary skill in the art to which this invention belongs In the following description, descriptions of known functions and configurations that may unnecessarily obscure the subject matter of the present invention will be omitted.

The terms or words used in the description and claims of the present invention should not be construed as being limited to ordinary or dictionary meanings, and the inventors use the concept of terms appropriately in order to explain their invention in the best way. Based on the principle that it can be defined, it should be interpreted as meaning and concept consistent with the technical spirit of the present invention.

Throughout the present specification, when a certain component is said to "include", it means that it may further include other components without excluding other components unless otherwise stated.

Throughout the present specification, when a member is said to be positioned “on” another member, this includes not only the case where a member is in contact with another member, but also the case where another member exists between the two members.

In the entire specification of the present application, "parts by weight" may mean a weight ratio between each component.

Throughout this specification, "molar ratio" refers to the ratio of the molar equivalent of X to the molar equivalent of Y, where X and Y may be, for example, each component in the reaction mixture.

Throughout this specification, "one or more" means, for example, "1, 2, 3, 4 or 5, particularly 1, 2, 3 or 4, more particularly 1, 2 or 3, even more particularly 1 or 2" means

Throughout the present specification, the weight average molecular weight (Mw), number average molecular weight (Mn), and Z average molecular weight (Mz+1) are standard polystyrene measured using gel permeation chromatography (GPC, manufactured by Water). is a conversion value for However, the weight average molecular weight (Mw), number average molecular weight (Mn), and Z average molecular weight (Mz+1) are not limited thereto and may be measured by other methods known in the art to which the present invention belongs.

In this specification, "*" means a bond connected to another substituent.

』이란, 다른 치환기 또는 연결부에 연결되는 결합을 의미한다.In this specification, "

』 means a bond connected to another substituent or linking part.

In this specification, the term "single bond" means a direct bond.

In the present specification, the term "derived repeating unit" means a repeating unit formed in the polymer by participating in the polymerization reaction of the input monomer during polymerization of the polymer.

Throughout the present specification, “substituted or unsubstituted” means deuterium; halogen group; cyano group; nitrile group; nitro group; hydroxy group; alkoxy group; cycloalkoxy group; aryloxy group; heterocyclyloxy group; haloalkyl group; an alkyl group; cycloalkyl group; alkenyl group; alkynyl group; aryl group; And means substituted or unsubstituted with one or more substituents selected from the group consisting of a heteroaryl group containing one or more of N, O, and S atoms, or substituted or unsubstituted with two or more substituents linked to each other among the substituents exemplified above. .

In the entire specification of the present application, “a substituent in which two or more substituents are linked” may be a biphenyl group. That is, the biphenyl group may be an aryl group or may be interpreted as a substituent in which two phenyl groups are connected.

As used herein, the term "deuterium" refers to a stable isotope of hydrogen having a mass approximately twice that of the most common isotope, i.e., a mass of about 2 atomic mass units.

Throughout the present specification, "halogen group" refers to a fluoro (F), chloro (Cl), bromo (Br) or iodine (I) atom.

In this specification, the term "cyano group" or "nitrile group" means a -C≡N group.

In the entire specification of this application, "isocyanate group" means -N≡C=O group.

Throughout the present specification, a "nitro group" refers to a -NO ₂ group.

Throughout the present specification, "hydroxy group" refers to an -OH group.

Throughout this specification, “alkoxy groups,” “cycloalkoxy groups,” “aryloxy groups,” and “heterocyclyloxy groups” refer to the above alkyl, cycloalkyl groups attached to the remainder of the molecule through an oxygen atom (-O-). Refers to either alkyl, aryl or heterocyclyl. At this time, the alkyl, cycloalkyl, aryl or heterocyclyl is substituted or unsubstituted.

Throughout this specification, "alkylthioxy group" and "arylthioxy group" refer to either the above alkyl or aryl attached to the remainder of the molecule via a sulfur atom (-S-).

Throughout the present specification, "aliphatic ring" refers to a saturated or unsaturated non-aromatic monocyclic, bicyclic, or tricyclic hydrocarbon moiety of 5 to 14, 5 to 10, or 5 to 6 carbon atoms, Examples include, but are not limited to, cycloalkane rings such as cyclopentane rings and cyclohexane rings, and cycloalkene rings such as cyclopentene rings, cyclohexene rings, and cyclooctene rings. The aliphatic ring is an aliphatic hydrocarbon ring or an aliphatic heterocyclic ring.

Throughout the present specification, "aromatic ring" refers to an aryl ring or a heteroaryl ring, and descriptions of the aryl and heteroaryl are as follows.

Throughout the present specification, "isosorbide" is a 100% natural biomaterial made from corn as a raw material, and stereochemistry is not particularly limited, and isomers of isosorbide may be included.

Throughout the present specification, "alkyl group" means a straight-chain or branched-chain saturated hydrocarbon. Specifically, the number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 to 40. According to one embodiment, the number of carbon atoms of the alkyl group is 1 to 20. According to another exemplary embodiment, the number of carbon atoms of the alkyl group is 1 to 10. According to another exemplary embodiment, the alkyl group has 1 to 6 carbon atoms. Specific examples of the alkyl group include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n -pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl , n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2 -Dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 4-methylhexyl, 5-methylhexyl, etc., but is not limited thereto.

Throughout the present specification, "haloalkyl group" means that the alkyl group is substituted with at least one halogen group.

Throughout the present specification, "cycloalkyl group" refers to fully saturated and partially unsaturated hydrocarbon rings of carbon atoms. Specifically, the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms, and according to an exemplary embodiment, the cycloalkyl group has 3 to 30 carbon atoms. According to another exemplary embodiment, the number of carbon atoms of the cycloalkyl group is 3 to 20. According to another exemplary embodiment, the number of carbon atoms of the cycloalkyl group is 3 to 6. Specifically, cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3, 4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, and the like, but are not limited thereto.

Throughout the present specification, "alkenyl group" refers to a straight-chain or branched unsaturated hydrocarbon containing at least one double bond. Specifically, the alkenyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. According to one embodiment, the alkenyl group has 2 to 20 carbon atoms. According to another exemplary embodiment, the alkenyl group has 2 to 10 carbon atoms. According to another exemplary embodiment, the alkenyl group has 2 to 6 carbon atoms. Specific examples include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 3-methyl-1- Butenyl, 1,3-butadienyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, 2,2-diphenylvinyl-1-yl, 2-phenyl-2-( naphthyl-1-yl)vinyl-1-yl, 2,2-bis(diphenyl-1-yl)vinyl-1-yl, stilbenyl group, styrenyl group, etc., but is not limited thereto.

Throughout the present specification, the term "alkynyl group" means a straight-chain or branched unsaturated hydrocarbon radical containing at least one triple bond. Specifically, the alkynyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. According to one embodiment, the number of carbon atoms of the alkynyl group is 2 to 20. According to another embodiment, the number of carbon atoms of the alkynyl group is 2 to 10. According to another exemplary embodiment, the number of carbon atoms of the alkynyl group is 2 to 6. Specific examples include ethynyl, prop-1-in-1-yl, prop-2-in-1-yl, but-1-in-1-yl, but-1-in-3-yl or but- It may be a short-chain hydrocarbon radical selected from 3-in-1-yl and the like, but is not limited thereto.

Throughout the present specification, "alkylene group" means a straight-chain or branched-chain divalent saturated aliphatic hydrocarbon. Specifically, it may mean divalent aliphatic saturated hydrocarbons such as methylene, ethylene, propylene, and butylene, but is not limited thereto.

Throughout the present specification, an "aryl group" is an organic radical derived from an aromatic hydrocarbon by removing one hydrogen, and means a monocyclic or polycyclic aromatic hydrocarbon radical. Specifically, the aryl group is not particularly limited, but preferably has 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to one embodiment, the number of carbon atoms of the aryl group is 6 to 30. According to one embodiment, the number of carbon atoms of the aryl group is 6 to 20. The aryl group may be a phenyl group, a biphenyl group, a terphenyl group, etc. as a monocyclic aryl group, but is not limited thereto. The polycyclic aryl group may be a naphthyl group, anthracenyl group, phenanthryl group, pyrenyl group, perylenyl group, chrysenyl group, fluorenyl group, and the like, but is not limited thereto.

Throughout the present specification, "fluorenyl group" means a 9-fluorenyl radical.

등이 될 수 있다. 다만, 이에 한정되는 것은 아니다.Specifically, the fluorenyl group may be substituted, and two substituents may be bonded to each other to form a spiro structure. When the fluorenyl group is substituted,

etc. However, it is not limited thereto.

Throughout the present specification, a "heteroaryl group" is an organic radical derived from an aromatic hydrocarbon by removing one hydrogen, and includes one or more heteroatoms selected from B, N, O, S, P(=O), Si, and P. It means a heteroaryl containing. Specifically, the number of carbon atoms of the heteroaryl group is not particularly limited, but preferably has 3 to 60 carbon atoms. Examples of the heteroaryl group include a thiophene group, a furan group, a pyrrole group, an imidazole group, a thiazole group, an oxazole group, an oxadiazole group, a triazole group, a pyridyl group, a bipyridyl group, a pyrimidyl group, a triazine group, a triazole group, Acridyl group, pyridazine group, pyrazinyl group, quinolinyl group, quinazoline group, quinoxalinyl group, phthalazinyl group, pyridopyrimidinyl group, pyridopyrazinyl group, pyrazinopyrazinyl group, isoquinoline group , Indole group, carbazole group, benzoxazole group, benzoimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuranyl group, phenanthroline group, thiazolyl group, An isoxazolyl group, an oxadiazolyl group, a thiadiazolyl group, a benzothiazolyl group, a phenothiazinyl group, and a dibenzofuranyl group, but are not limited thereto.

In the present specification, the description of the aryl group described above may be applied except that the arylene is a divalent group.

In the present specification, the description of heteroaryl described above may be applied except that the heteroarylene is a divalent group.

polycarbonate

The diol compound-derived repeating unit represented by Chemical Formula 1 has excellent hardness, so that polycarbonate having excellent mechanical properties can be prepared.

The present invention provides a polycarbonate comprising a repeating unit derived from a diol compound represented by Formula 1 below and a carbonate precursor.

[Formula 1]

In Formula 1,

Z ₁ is CR ₁ R ₂ , O, S, SS, C=O, C=S, SO, SO ₂ , (CH ₂ ) _n -L ₁ -(CH ₂ ) _m or O-(C=O); ,

R ₁ and R ₂ are each independently hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted haloalkyl, OR ^a , SR ^b , NR ^c R ^d , COOR ^e , OCOR ^f , halogen, CN or NO ₂ ;

R ₁ and R ₂ are connected to form a substituted or unsubstituted aliphatic or aromatic ring with halogen, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;

L ₁ is O or S;

n and m are each independently an integer from 1 to 3;

Z ₂ and Z ₃ are each independently a single bond, a substituted or unsubstituted alkylene, a substituted or unsubstituted cycloalkylene, a substituted or unsubstituted arylene, or a substituted or unsubstituted heteroarylene, or a combination thereof. is,

X ₁ and X ₂ are each independently CR ₁₀₀ or N;

Y ₁ and Y ₂ are each independently CR ₁₀₁ R ₁₀₂ , O or S;

R ₁₀₀ , R _{101 ,} R _{102 ,} R ₃ and R ₄ are each independently hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted haloalkyl, OR ^a , SR ^b , NR ^c R ^d , COOR ^e , OCOR ^f , halogen, CN or NO ₂ ;

a and b are each independently an integer from 0 to 3,

R ^a to R ^f are each independently hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl.

In the present invention, in Formula 1,

Z ₁ is CR ₁ R ₂ , O, S, SS, C=O, C=S, SO, SO ₂ , (CH ₂ ) _n -L ₁ -(CH ₂ ) _m or O-(C=O); ,

R ₁ and R ₂ are each independently hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted haloalkyl, OR ^a , SR ^b , NR ^c R ^d , COOR ^e , OCOR ^f , halogen, CN or NO ₂ ;

또는

의 지방족 고리를 형성하고, R ₁ and R ₂ are connected

or

form an aliphatic ring of

* means a part connected to Formula 1,

L ₁ is O or S;

n and m are each independently an integer from 1 to 3;

Z ₄ and Z ₅ are each independently CR ₁₀₃ R ₁₀₄ , NR ₁₀₅ , O or S;

R ₁₀₃ to R _105, R ₉ and R ₁₀ are each independently hydrogen, halogen, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;

c is an integer from 0 to 8, and d is an integer from 0 to 6.

In one embodiment of the present invention, Z ₄ and Z ₅ are O or S.

,

또는

이며,In the present invention, Z ₂ and Z ₃ are each independently

,

or

is,

* means a part connected to Formula 1,

Wherein R ₁₁ to R ₁₃ are each independently hydrogen, substituted or unsubstituted alkoxy, substituted or unsubstituted alkyl or OH;

Z ₆ is NRn, O or S;

Rn is hydrogen or a substituted or unsubstituted alkyl group,

e and j are each independently an integer from 0 to 4,

g is an integer from 0 to 10;

f, h and i are each independently an integer of 0 to 10.

In the present invention, R ₁₁ to R ₁₃ are each independently hydrogen, substituted or unsubstituted alkoxy having 1 to 30 carbon atoms, substituted or unsubstituted alkyl having 1 to 30 carbon atoms, or OH.

In the present invention, R ₁₁ to R ₁₃ are each independently hydrogen, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, or OH.

In the present invention, R ₁₁ to R ₁₃ are each independently hydrogen, substituted or unsubstituted alkoxy having 1 to 10 carbon atoms, substituted or unsubstituted alkyl having 1 to 10 carbon atoms, or OH.

In the present invention, the R ₁₁ to R ₁₃ are each independently hydrogen, methoxy, substituted or unsubstituted methyl or OH.

In one embodiment of the present invention, R ₁₁ to R ₁₃ are each independently hydrogen, a substituted or unsubstituted methoxy group, a substituted or unsubstituted methyl group, or OH.

In one embodiment of the present invention, R ₁₁ to R ₁₃ are each independently hydrogen, a methoxy group, a methyl group or OH.

In one embodiment of the present invention, Z ₆ is O.

In the present invention, when X ₁ and X ₂ are N, Y ₁ and Y ₂ are each independently O or S, and when X ₁ and X ₂ are CR ₁₀₀ , Y ₁ and Y ₂ are each independently CR ₁₀₁ R ₁₀₂ or O.

In the present invention, Z ₁ is CR ₁ R ₂ , O, S, SS, C=O, C=S, SO ₂ , (CH ₂ ) _n -L ₁ -(CH ₂ ) _m .

In the present invention, Z ₁ is CR ₁ R ₂ or SO ₂ .

In the present invention, Z ₁ is C=O.

In the present invention, Z ₁ is SO ₂ .

In the present invention, R ₁ and R ₂ are each independently hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted haloalkyl, OR ^a , SR ^b , COOR ^f , halogen, CN or NO ₂ , or R ₁ and R ₂ are connected to form an aliphatic ring.

In the present invention, R ₁ and R ₂ are each independently hydrogen, substituted or unsubstituted alkyl having 1 to 30 carbon atoms, substituted or unsubstituted haloalkyl having 1 to 30 carbon atoms, OR ^a , SR ^b , COOR ^f , Halogen, CN or NO ₂ , or R ₁ and R ₂ are connected to form an aliphatic ring having 1 to 30 carbon atoms.

In the present invention, R ₁ and R ₂ are each independently hydrogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted haloalkyl having 1 to 20 carbon atoms, OR ^a , SR ^b , COOR ^f , halogen, CN or NO ₂ , or R ₁ and R ₂ are connected to form an aliphatic ring having 1 to 20 carbon atoms.

In the present invention, R ₁ and R ₂ are each independently hydrogen, substituted or unsubstituted alkyl having 1 to 10 carbon atoms, substituted or unsubstituted haloalkyl having 1 to 10 carbon atoms, OR ^a , SR ^b , COOR ^f , Halogen, CN or NO ₂ , or R ₁ and R ₂ are connected to form an aliphatic ring having 1 to 10 carbon atoms.

또는

의 지방족 고리를 형성한다. In the present invention, R ₁ and R ₂ are each independently hydrogen, methyl, trifluoromethyl, tert-butyl, OR ^a , SR ^b , COOR ^f , chlorine, CN or NO ₂ , or R ₁ and R ₂ is connected

or

form an aliphatic ring of

In the present invention, R ₁ and R ₂ are a trifluoromethyl group or a methyl group.

In the present invention, R ^a to R ^f are each independently hydrogen, substituted or unsubstituted alkyl having 1 to 30 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 30 carbon atoms, substituted or unsubstituted cycloalkyl having 6 to 30 carbon atoms of aryl or substituted or unsubstituted heteroaryl having 2 to 30 carbon atoms.

In the present invention, R ^a to R ^f are each independently hydrogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 6 to 20 carbon atoms aryl or substituted or unsubstituted heteroaryl having 2 to 20 carbon atoms.

In the present invention, R ^a to R ^f are each independently hydrogen, substituted or unsubstituted alkyl having 1 to 10 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 10 carbon atoms, substituted or unsubstituted cycloalkyl having 6 to 10 carbon atoms aryl or substituted or unsubstituted heteroaryl having 2 to 10 carbon atoms.

In the present invention, R ^a , R ^b or R ^f are each independently hydrogen or substituted or unsubstituted alkyl.

In the present invention, R ^a , R ^b or R ^f are each independently hydrogen or substituted or unsubstituted alkyl having 1 to 30 carbon atoms.

In the present invention, R ^a , R ^b or R ^f are each independently hydrogen or substituted or unsubstituted alkyl having 1 to 20 carbon atoms.

In the present invention, R ^a , R ^b or R ^f are each independently hydrogen or substituted or unsubstituted alkyl having 1 to 10 carbon atoms.

In the present invention, R ^a , R ^b or R ^f are each independently hydrogen or a substituted or unsubstituted methyl group.

In the present invention, R ^a , R ^b or R ^f is each independently hydrogen or a methyl group.

In the present invention, L ₁ is O.

In the present invention, L ₁ is S.

In the present invention, n and m are 1.

In the present invention, Z ₂ and Z ₃ are each independently a single bond, substituted or unsubstituted alkylene having 1 to 30 carbon atoms, substituted or unsubstituted cycloalkylene having 3 to 30 carbon atoms, substituted or unsubstituted carbon atoms 6 to 30 arylene or substituted or unsubstituted heteroarylene having 2 to 30 carbon atoms, or a combination thereof.

In the present invention, Z ₂ and Z ₃ are each independently a single bond, substituted or unsubstituted alkylene having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkylene having 3 to 20 carbon atoms, substituted or unsubstituted carbon atoms 6 to 20 arylene or substituted or unsubstituted heteroarylene having 2 to 20 carbon atoms, or a combination thereof.

In the present invention, Z ₂ and Z ₃ are each independently a single bond, substituted or unsubstituted alkylene having 1 to 10 carbon atoms, substituted or unsubstituted cycloalkylene having 3 to 10 carbon atoms, substituted or unsubstituted carbon atoms 6 to 10 arylene or substituted or unsubstituted heteroarylene having 2 to 10 carbon atoms, or a combination thereof.

In the present invention, Z ₂ and Z ₃ are each independently substituted or unsubstituted cyclohexylene, substituted or unsubstituted cyclohexylene-substituted or unsubstituted methylene, substituted or unsubstituted phenylene, substituted or unsubstituted substituted or unsubstituted phenylene-substituted or unsubstituted methylene, or substituted or unsubstituted phenylene-substituted or unsubstituted divalent thiophene-substituted or unsubstituted methylene.

In the present invention, Z ₂ and Z ₃ are each independently cyclohexylene; cyclohexylene-methylene; phenylene unsubstituted or substituted with a methyl group, a methoxy group or a hydroxy group; phenylene-methylene; or phenylene-divalent thiophene-methylene.

In the present invention, X ₁ and X ₂ are CR ₁₀₀ and R ₁₀₀ is hydrogen.

In the present invention, X ₁ and X ₂ are N.

In the present invention, Y ₁ and Y ₂ are CR ₁₀₁ R ₁₀₂ , and R ₁₀₁ and R ₁₀₂ are hydrogen.

In the present invention, Y ₁ and Y ₂ are O.

In the present invention, Y ₁ and Y ₂ are S.

In the present invention, R ₁₀₀ , R _{101 ,} R _{102 ,} R ₃ and R ₄ are each independently hydrogen, substituted or unsubstituted alkyl having 1 to 30 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 30 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 2 to 30 carbon atoms; substituted or unsubstituted haloalkyl having 1 to 30 carbon atoms, OR ^a , SR ^b , NR ^c R ^d , COOR ^e , OCOR ^f , halogen, CN, COOH or NO ₂ .

In the present invention, R ₁₀₀ , R _{101 ,} R _{102 ,} R ₃ and R ₄ are each independently hydrogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 20 carbon atoms, substituted or unsubstituted heteroaryl having 2 to 20 carbon atoms; substituted or unsubstituted haloalkyl having 1 to 20 carbon atoms, OR ^a , SR ^b , NR ^c R ^d , COOR ^e , OCOR ^f , halogen, CN, COOH or NO ₂ .

In the present invention, R ₁₀₀ , R _{101 ,} R _{102 ,} R ₃ and R ₄ are each independently hydrogen, substituted or unsubstituted alkyl having 1 to 10 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 10 carbon atoms, substituted or unsubstituted aryl having 6 to 10 carbon atoms, substituted or unsubstituted heteroaryl having 2 to 10 carbon atoms; substituted or unsubstituted haloalkyl having 1 to 10 carbon atoms, OR ^a , SR ^b , NR ^c R ^d , COOR ^e , OCOR ^f , halogen, CN, COOH or NO ₂ .

In the present invention, R ₁₀₀ is hydrogen.

In the present invention, R ₁₀₁ and R ₁₀₂ are hydrogen.

In one embodiment of the present invention, R ₃ and R ₄ are each independently hydrogen, substituted or unsubstituted alkyl, halogen, CN or NO ₂ .

In the present invention, R ₃ and R ₄ are each independently hydrogen, halogen, CN, NO ₂ or substituted or unsubstituted alkyl having 1 to 30 carbon atoms.

In the present invention, R ₃ and R ₄ are each independently hydrogen, halogen, CN, NO ₂ or substituted or unsubstituted alkyl having 1 to 20 carbon atoms.

In the present invention, R ₃ and R ₄ are each independently hydrogen, halogen, CN, NO ₂ or substituted or unsubstituted alkyl having 1 to 10 carbon atoms.

In the present invention, R ₃ and R ₄ are each independently hydrogen, bromine, CN, NO ₂ or a substituted or unsubstituted methyl group.

In the present invention, R ₃ and R ₄ are each independently hydrogen, bromine, CN, NO ₂ or a methyl group.

In the present invention, the diol compound represented by Formula 1 may be any one of the following compounds, but is not limited thereto.

In the present invention, the repeating unit derived from the diol compound represented by Formula 1 and the carbonate precursor is represented by Formula 2 below.

[Formula 2]

In Formula 2,

Z ₁ , to Z ₃ , R ₃ , R ₄ , X ₁ , X ₂ , Y ₁ , Y ₂ , a and b are as defined in Formula 1 above.

In the present invention, the weight average molecular weight (Mw) of polycarbonate can be properly adjusted according to the purpose and use, and the weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) using PC standards (Standard) is 1,000 g/mol to 10,000 g/mol, preferably 10,000 g/mol to 100,000 g/mol, more preferably 10,000 g/mol to 50,000 g/mol, 48,000 g/mol to 49,000 g/mol or 48,100 g/mol mol to 48,900 g/mol. In a specific embodiment, when the weight average molecular weight (Mw) of the polycarbonate according to the present invention satisfies the above range, mechanical properties and productivity of the polycarbonate are excellent.

In the present invention, the melt index (melt index) measured in accordance with ASTM D1238 (300 ℃, 1.2kg conditions) of the polycarbonate can be properly adjusted according to the purpose and use, 1 g / 10min or more, or 3 g / 10 min or more, or 8 g / 10 min or more, and may be 100 g / 10 min or less, or 30 g / 10 min or less, or 15 g / 10 min or less.

An exemplary embodiment of the present invention is a polycarbonate comprising a diol compound represented by Formula 1 and a repeating unit derived from a carbonate precursor, and Izod room temperature measured at 23 ° C. in accordance with ASTM D256 (1/8 inch, Notched Izod) Provided is a polycarbonate having an impact strength of 220 Kgf/m ² or more.

Specifically, the Izod room temperature impact strength is 230 Kgf/m ² or more, or 240 Kgf/m ² or more, or 250 Kgf/m ^{2 or more, and 1,000 Kgf/m 2 or} less, or 500 Kgf/m ² or less, or 400 It has excellent physical strength of Kgf/m ² or less, or 300 Kgf/m ² or less.

In the present invention, the glass transition temperature (Tg) of the polycarbonate is 150 ° C. or more and 190 ° C. or less. Specifically, it may exhibit high heat resistance of 150 ° C. or more, 180 ° C. or less, or 170 ° C. or less.

In the present invention, the pencil hardness of the polycarbonate may indicate a high hardness of 2B or HB when measured at an angle of 45 degrees under a load of 50 g in accordance with ASTM D3363.

In the present invention, the transmittance of the polycarbonate is 80% or more. Specifically, it is 80% or more and 90% or less. The permeability of the polycarbonate can be measured according to ASTM test method D1003. When the transmittance of the polycarbonate satisfies the aforementioned range, it has excellent optical properties.

Polycarbonate manufacturing method

The present invention provides a polycarbonate manufacturing method comprising the step of polymerizing a composition including a diol compound represented by Formula 1 below and a carbonate precursor.

[Formula 1]

In Formula 1,

Z ₁ is CR ₁ R ₂ , O, S, SS, C=O, C=S, SO, SO ₂ , (CH ₂ ) _n -L ₁ -(CH ₂ ) _m or O-(C=O); ,

R ₁ and R ₂ are each independently hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted haloalkyl, OR ^a , SR ^b , NR ^c R ^d , COOR ^e , OCOR ^f , halogen, CN or NO ₂ ;

R ₁ and R ₂ are connected to form a substituted or unsubstituted aliphatic or aromatic ring with halogen, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;

L ₁ is O or S;

n and m are each independently an integer from 1 to 3;

Z ₂ and Z ₃ are each independently a single bond, a substituted or unsubstituted alkylene, a substituted or unsubstituted cycloalkylene, a substituted or unsubstituted arylene, or a substituted or unsubstituted heteroarylene, or a combination thereof. is,

X ₁ and X ₂ are each independently CR ₁₀₀ or N;

Y ₁ and Y ₂ are each independently CR ₁₀₁ R ₁₀₂ , O or S;

R ₁₀₀ , R _{101 ,} R _{102 ,} R ₃ and R ₄ are each independently hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted haloalkyl, OR ^a , SR ^b , NR ^c R ^d , COOR ^e , OCOR ^f , halogen, CN or NO ₂ ;

a and b are each independently an integer from 0 to 3,

R ^a to R ^f are each independently hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl.

In the present invention, the carbonate precursor serves to prepare polycarbonate from the compound represented by Formula 1, and specific examples thereof include phosgene, triphosgene, diphosgene, bromophosgene, dimethyl carbonate, diethyl carbonate, di butyl carbonate, dicyclohexyl carbonate, diphenyl carbonate, ditoryl carbonate, bis(chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis(diphenyl) carbonate or bishaloformate; , but is not limited thereto.

Preferably the carbonate precursor is triphosgene.

In an exemplary embodiment of the present invention, the composition including the diol compound represented by Chemical Formula 1 and the carbonate precursor may further include a compound represented by Chemical Formula 3 below.

[Formula 3]

In Formula 3,

A ₂ is substituted or unsubstituted alkylene, substituted or unsubstituted cycloalkylene, substituted or unsubstituted arylene, substituted or unsubstituted heteroarylene, O, S, SO, SO ₂ or C=O; ,

R ₅ and R ₆ are each independently hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, alkoxy or halogen;

r ₅ and r ₆ are each independently an integer of 0 to 4;

In the present invention, A ₂ is substituted or unsubstituted alkylene having 1 to 30 carbon atoms, substituted or unsubstituted cycloalkylene having 3 to 30 carbon atoms, substituted or unsubstituted arylene having 6 to 30 carbon atoms, substituted or It is an unsubstituted heteroarylene having 2 to 30 carbon atoms, O, S, SO, SO ₂ or C=O.

In the present invention, A ₂ is substituted or unsubstituted alkylene having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkylene having 3 to 20 carbon atoms, substituted or unsubstituted arylene having 6 to 20 carbon atoms, substituted or unsubstituted It is unsubstituted heteroarylene having 2 to 20 carbon atoms, O, S, SO, SO ₂ or C=O.

In the present invention, A ₂ is substituted or unsubstituted alkylene having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkylene having 3 to 10 carbon atoms, substituted or unsubstituted arylene having 6 to 10 carbon atoms, substituted or It is an unsubstituted heteroarylene having 2 to 10 carbon atoms, O, S, SO, SO ₂ or C=O.

In the present invention, A ₂ is a substituted or unsubstituted methylene.

In the present invention, A ₂ is methylene substituted with a methyl group.

In the present invention, R ₅ and R ₆ are each independently hydrogen, substituted or unsubstituted alkyl having 1 to 30 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 30 carbon atoms, substituted or unsubstituted 6 to 30 carbon atoms aryl, substituted or unsubstituted heteroaryl of 2 to 30 carbon atoms, alkoxy or halogen.

In the present invention, R ₅ and R ₆ are each independently hydrogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 6 to 20 carbon atoms aryl, substituted or unsubstituted heteroaryl of 2 to 20 carbon atoms, alkoxy or halogen.

In the present invention, R ₅ and R ₆ are each independently hydrogen, substituted or unsubstituted alkyl having 1 to 10 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 10 carbon atoms, substituted or unsubstituted cycloalkyl having 6 to 10 carbon atoms aryl, substituted or unsubstituted heteroaryl of 2 to 10 carbon atoms, alkoxy or halogen.

In the present invention, R ₅ and R ₆ are hydrogen.

As a method of polymerizing polycarbonate using a composition containing the compound represented by Formula 1 and a carbonate precursor, according to an embodiment, the polymerization process may be performed on a composition containing the two precursor compounds at once. .

In the present invention, the diol compound represented by Formula 1 is used in an amount of 1 wt% or more, 2 wt% or more, or 3 wt% or more, and 25 wt% or less or 20 wt% or less, based on 100 wt% of the composition. can

In the present invention, the carbonate precursor is 10% by weight or more, 15% by weight or more, or 20% by weight or more, and 80% by weight or less, 40% by weight or less, or 35% by weight or less with respect to 100% by weight of the composition can be used

When the diol compound represented by Chemical Formula 1 and the carbonate precursor are used in the above amounts, mechanical properties of the polycarbonate are improved.

In the present invention, the polymerization may be performed by interfacial polymerization or melt polymerization, but is not limited thereto.

Specifically, during interfacial polymerization, the polymerization temperature is preferably 0 °C to 40 °C and the reaction time is 10 minutes to 5 hours. Also, during the reaction, the pH is preferably maintained at 9 or higher or 11 or higher.

The solvent that can be used for the polymerization is not particularly limited as long as it is a solvent used for polymerization of polycarbonate in the art, and for example, halogenated hydrocarbons such as methylene chloride and chlorobenzene can be used.

In addition, the polymerization is preferably performed in the presence of an acid binder, and an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide or an amine compound such as pyridine may be used as the acid binder.

In the present invention, carbonic acid diester compounds that can be used as a starting raw material used in the transesterification reaction include carbonates of diaryl compounds, carbonates of dialkyl compounds, or carbonates of alkylaryl compounds. This is not limited to this.

In the production of the polycarbonate resin through the transesterification reaction of the present invention, additives such as end-stoppers, branching agents, and antioxidants may be additionally used as necessary.

The terminal terminator, branching agent, antioxidant, etc. may be added in the form of powder, liquid, gas, etc., and they serve to improve the quality of the obtained polycarbonate resin.

The reaction pressure during the transesterification reaction is not particularly limited and can be adjusted according to the vapor pressure of the monomers used and the reaction temperature, but in general, at the beginning of the reaction, a pressurized state of 1 to 10 atmospheres of atmospheric pressure (atmospheric pressure) is required, and the reaction In the latter stage, the pressure is reduced so that it is finally 0.1 to 100 mbar.

In addition, the reaction time during the transesterification reaction may be carried out until the target molecular weight is reached, and is usually carried out for 0.2 to 10 hours.

The transesterification reaction is usually carried out in the absence of an inert solvent, but may be carried out in the presence of 1 to 150% by weight of an inert solvent of the obtained polycarbonate resin, if necessary. Examples of the inert solvent include aromatic compounds such as diphenyl ether, halogenated diphenyl ether, benzophenone, polyphenylene ether, dichlorobenzene, and methylnaphthalene; Alternatively, cycloalkanes such as tricyclo(5,2,10)decane, cyclooctane, and cyclodecane may be used.

In addition, it may be carried out under an inert gas atmosphere if necessary, and examples of the inert gas include gases such as argon, carbon dioxide, dinitrogen monoxide, and nitrogen; chlorofluoro hydrocarbons, alkanes such as ethane or propane, or alkenes such as ethylene or propylene; and the like.

Phenols, alcohols, or esters thereof corresponding to the carbonic acid diester used as the transesterification reaction proceeds under the above conditions; and an inert solvent is released from the reactor. This effluent can be separated, purified, and regenerated. The transesterification reaction can be carried out either batchwise or continuously using any equipment.

At this time, any reaction device for the transesterification reaction can be used as long as it has a normal stirring function, and it is preferable to have a high viscosity type stirring function because the viscosity increases in the later stage of the reaction.

Also, a preferred type of reactor is a vessel type or an extruder type.

In addition, the reaction pressure during the prepolymerization is preferably carried out at 0.1 mbar to 100 mbar, more preferably at 1 mbar to 10 mbar. When the reaction pressure is in the range of 0.1 to 100 mbar, the carbonic acid diester, which is the starting raw material, is not distilled off, so the composition in the transesterification system does not change, and the by-product monohydroxy compound is distilled off, so that the reaction proceeds smoothly. It is even better in that it is done.

molding

The present invention provides a molded article comprising the polycarbonate.

As described above, polycarbonate including a repeating unit derived from the diol compound represented by Chemical Formula 1 has improved surface hardness, and thus has a wider range of applications than conventionally used molded articles made of polycarbonate.

In the present invention, the molded article is selected from the group consisting of an antioxidant, a plasticizer, an antistatic agent, a nucleating agent, a flame retardant, a lubricant, an impact modifier, a fluorescent whitening agent, an ultraviolet absorber, a pigment and a dye, as needed, in addition to the polycarbonate according to the present invention. One or more selected species may be further included.

In the present invention, as an example of the method for manufacturing the molded article, after mixing the polycarbonate and other additives according to the present invention well using a mixer, extruding with an extruder to produce pellets, drying the pellets, and then injection It may include the step of injecting into a molding machine.

In the present invention, in order to control the molecular weight of the polycarbonate during the polymerization, it is preferable to polymerize in the presence of a molecular weight regulator. C1-20 alkylphenols may be used as the molecular weight modifier, and specific examples thereof include p-tert-butylphenol, p-cumylphenol, decylphenol, dodecylphenol, tetradecylphenol, hexadecylphenol, octadecylphenol, eicosyl phenol, docosylphenol or triacontylphenol. The molecular weight modifier may be added before polymerization, during polymerization, or after polymerization. The molecular weight modifier may be used in an amount of 0.01 to 10 parts by weight, preferably 0.1 to 6 parts by weight, based on 100 parts by weight of the repeating unit of the compound represented by Formula 1, and a desired molecular weight can be obtained within this range.

In the present invention, in order to promote the polymerization reaction, tertiary amine compounds such as triethylamine, tetra-n-butylammonium bromide, and tetra-n-butylphosphonium bromide, quaternary ammonium compounds, and quaternary phosphonium compounds Reaction accelerators such as the like can be additionally used.

1 to 3 are ¹ H-NMR graphs of compounds 1 to 3 prepared in Examples 1 to 3, respectively.

Specifically, by showing a peak at 9.8 ppm in FIG. 1 , it can be confirmed that the diol compound 1 includes a structure of —OH.

Figure 2 shows a peak at 1.8 ppm, thereby confirming that the diol compound contains a structure of a dimethyl group, and showing a peak at 9.8 ppm, thereby confirming that the compound 2 contains a structure of -OH. .

Figure 3 shows a peak at 9.8 ppm, it can be confirmed that the compound 3 contains a structure of -OH.

The invention is explained in more detail in the following examples. However, the following examples are merely illustrative of the present invention, and the contents of the present invention are not limited by the following examples.

Example 1

(1) Preparation of compound 1 4,4'-((perfluoropropane-2,2-diyl)bis(benzo[d]oxazole-5,2-diyl))diphenol

4,4'-(perfluoropropane-2,2-diyl)bis(2-aminophenol) in a two-necked flask 50 g, 48 g of 4-hydroxybenzoic acid, and 71 g of p-Toluenesulfonic acid were added, 1,000 ml of toluene was added, and a Dean-Stark apparatus was used. installed. Then, it was refluxed and stirred for 24 hours. After completion of the reaction, extraction was performed once each with EA (ethyl acetate)/H ₂ O and EA/Sat.K ₂ CO ₃ solutions, and compound 1 was obtained through ethyl acetate/toluene recrystallization.

¹ H-NMR of the compound 1 is shown in FIG. 1 .

(2) Manufacture of polycarbonate

2,044 g of water, 140 g of NaOH, and 220.4 g of bisphenol A (BPA) were put into a polymerization reactor, and mixed and dissolved under an N ₂ atmosphere.

Here, 4.6 g of para-tert butylphenol (PTBP) and 11.6 g of the previously prepared compound 1 were dissolved in methylene chloride (MC, methylene chloride) and added thereto. Then, 128g of triphosgene (TPG) was dissolved in methylene chloride (MC) and reacted by adding it for 1 hour while maintaining the pH at 11 or higher. After 10 minutes, 46g of triethylamine (TEA) was added and coupled (coupling) reaction was performed. After a total reaction time of 1 hour and 20 minutes, the pH was lowered to 4 to remove triethylamine, and the resulting polymer was washed three times with distilled water to adjust the pH to 6-7 neutral. The polymer thus obtained was mixed with methanol and hexane. It was obtained by reprecipitation and then dried at 120 °C to obtain polycarbonate.

The obtained polycarbonate was confirmed to have a weight average molecular weight of 48,900 g/mol by measuring molecular weight by gel permeation chromatography (GPC) using a PC standard (Standard).

Example 2

(1) Preparation of compound 2 4,4'-(propane-2,2-diylbis(benzo[d]oxazole-5,2-diyl))diphenol

In Example 1, 4,4'-(perfluoropropane-2,2-diyl)bis(2-aminophenol)(4,4'-(perfluoropropane-2,2-diyl)bis(2-aminophenol) ) 50 g of 4,4'-(propane-2,2-diyl)bis(2-aminophenol) (4,4'-(propane-2,2-diyl)bis(2-aminophenol)) Compound 2 was synthesized in the same manner as in Example 1, except that it was used instead.

¹ H-NMR of the compound 2 is shown in FIG. 2 .

(2) Manufacture of polycarbonate

Polycarbonate was synthesized in the same manner as in Example 1, except that Compound 2 was used instead of Compound 1 in Example 1.

The obtained polycarbonate was confirmed to have a weight average molecular weight of 48,000 g/mol by measuring molecular weight by GPC using a PC standard.

Example 3

(1) Preparation of monomer 4,4'-(sulfonylbis(benzo[d]oxazole-5,2-diyl))diphenol

Except for using 50 g of 4,4'-(perfluoropropane-2,2-diyl)bis(2-aminophenol) in Example 1 instead of 38.2 g of 4,4'-sulfonylbis(2-aminophenol), the above Compound 3 was synthesized in the same manner as in Example 1.

¹ H-NMR of the compound 3 is shown in FIG. 3 .

(2) Manufacture of polycarbonate

Polycarbonate was synthesized in the same manner as in Example 1, except that Compound 3 was used instead of Compound 1 in Example 1.

The obtained polycarbonate was confirmed to have a weight average molecular weight of 48,100 g/mol by measuring the molecular weight by GPC using PC Standard.

comparative example

Comparative Example 1

Polycarbonate and its injection specimen were prepared in the same manner as in Example 1, except that Compound 1 was not used in Example 1.

The obtained polycarbonate was confirmed to have a weight average molecular weight of 49,700 g/mol by measuring molecular weight by GPC using PC Standard.

Comparative Example 2

Polycarbonate and its injection specimen were prepared in the same manner as in Comparative Example 1, except that bisphenol C was used instead of bisphenol A in Comparative Example 1.

The obtained polycarbonate resin was confirmed to have a weight average molecular weight of 48,300 g/mol by measuring molecular weight by GPC using PC Standard.

Experimental Example: Evaluation of physical properties of polycarbonate

Based on 100 parts by weight of each of the polycarbonate resins prepared in the above Examples and Comparative Examples, 0.050 parts by weight of tris (2,4-di-tert-butylphenyl) phosphite, octadecyl-3- (3,5-di 0.010 part by weight of -tert-butyl-4-hydroxyphenyl)propionate and 0.030 part by weight of pentaerythritol tetrastearate were added, pelletized using a HAAKE Mini CTW with a vent, and then pelletized using a HAAKE Minijet injection molding machine into a cylinder. Specimens were prepared by injection molding at a temperature of 300 ° C and a mold temperature of 120 ° C.

The properties of these injection specimens or polycarbonate were measured by the following method, and the results are shown in Table 1.

measurement method

-Repetition unit: Measured by ¹ H-NMR using Varian 500 MHz.

-Weight average molecular weight (g/mol): measured by calibration with PC standard using Agilent 1200 series.

-Izod impact strength at room temperature (Kgf/m ² ): Measured at 23°C in accordance with ASTM D256 (1/8 inch, Notched Izod).

-Glass transition temperature (Tg, ℃): The glass transition temperature was measured using DSC (TA Instrument) equipment.

-Pencil hardness: Measured with a pencil of 3B, B, HB, H strength at an angle of 45 degrees under a load of 50 g in accordance with ASTM D3363 using a pencil hardness tester (Cometech).

- Permeability: measured according to ASTM test method D1003.

Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Impact strength (Kgf/m ² ) 280 230 260 210 120 Glass transition temperature (℃) 154 152 165 154 120 Permeability (%) 84 88 84 87 80 pencil hardness HB 2B 2B 3B H

According to Table 1, compared to Comparative Examples 1 and 2, it can be confirmed that the mechanical properties of Examples 1 and 3 are high in impact strength and excellent.

In addition, Examples 1 and 2 have higher glass transition temperatures than Comparative Examples 1 and 2, so it can be confirmed that the polycarbonate of the present invention has high heat resistance.

On the other hand, it can be seen that Comparative Example 2, although superior in pencil hardness to Examples 1 to 3, has very low impact strength and glass transition temperature, and does not satisfy the physical properties of the polycarbonate intended in the present invention.

Claims (11)

A polycarbonate comprising a repeating unit derived from a diol compound represented by Formula 1 below and a carbonate precursor:
[Formula 1]

In Formula 1,
Z ₁ is CR ₁ R ₂ , O, S, SS, C=O, C=S, SO, SO ₂ , (CH ₂ ) _n -L ₁ -(CH ₂ ) _m or O-(C=O); ,
R ₁ and R ₂ are each independently hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted haloalkyl, OR ^a , SR ^b , NR ^c R ^d , COOR ^e , OCOR ^f , halogen, CN or NO ₂ ;
R ₁ and R ₂ are connected to form a substituted or unsubstituted aliphatic or aromatic ring with halogen, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;
L ₁ is O or S;
n and m are each independently an integer from 1 to 3;
Z ₂ and Z ₃ are each independently a single bond, a substituted or unsubstituted alkylene, a substituted or unsubstituted cycloalkylene, a substituted or unsubstituted arylene, or a substituted or unsubstituted heteroarylene, or a combination thereof. is,
X ₁ and X ₂ are each independently CR ₁₀₀ or N;
Y ₁ and Y ₂ are each independently CR ₁₀₁ R ₁₀₂ , O or S;
R ₁₀₀ , R _{101 ,} R _{102 ,} R ₃ and R ₄ are each independently hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted haloalkyl, OR ^a , SR ^b , NR ^c R ^d , COOR ^e , OCOR ^f , halogen, CN or NO ₂ ;
a and b are each independently an integer from 0 to 3,
R ^a to R ^f are each independently hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl. According to claim 1,
In Formula 1,
Z ₁ is CR ₁ R ₂ , O, S, SS, C=O, C=S, SO, SO ₂ , (CH ₂ ) _n -L ₁ -(CH ₂ ) _m or O-(C=O); ,
R ₁ and R ₂ are each independently hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted haloalkyl, OR ^a , SR ^b , NR ^c R ^d , COOR ^e , OCOR ^f , halogen, CN or NO ₂ ;
R ₁ and R ₂ are connected

or

form an aliphatic ring of
* means a part connected to Formula 1,
L ₁ is O or S;
n and m are each independently an integer from 1 to 3;
Z ₄ and Z ₅ are each independently CR ₁₀₃ R ₁₀₄ , NR ₁₀₅ , O or S;
R ₁₀₃ to R _105, R ₉ and R ₁₀ are each independently hydrogen, halogen, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;
c is an integer from 0 to 8, d is an integer from 0 to 6, and the definitions of the remaining substituents are the same as in Formula 1 above. According to claim 1,
Z ₂ and Z ₃ are each independently

,

or

is,
* means a part connected to Formula 1,
Wherein R ₁₁ to R ₁₃ are each independently hydrogen, substituted or unsubstituted alkoxy, substituted or unsubstituted alkyl or OH;
Z ₆ is NRn, O or S;
Rn is hydrogen or a substituted or unsubstituted alkyl group,
e and j are each independently an integer from 0 to 4,
g is an integer from 0 to 10;
f, h and i are each independently an integer of 0 to 10 polycarbonate. According to claim 1,
When X ₁ and X ₂ are N, Y ₁ and Y ₂ are each independently O or S;
When X ₁ and X ₂ are CR ₁₀₀ , Y ₁ and Y ₂ are each independently CR ₁₀₁ R ₁₀₂ or O, which is a polycarbonate. According to claim 1,
R ₃ and R ₄ are each independently hydrogen, substituted or unsubstituted alkyl, halogen, CN or NO ₂ independently of one another. According to claim 1,
Polycarbonate wherein the diol compound represented by Formula 1 is any one of the following compounds:

. According to claim 1,
A polycarbonate wherein the diol compound represented by Formula 1 and the repeating unit derived from the carbonate precursor are represented by Formula 2 below:
[Formula 2]

In Formula 2,
Z ₁ , to Z ₃ , R ₃ , R ₄ , X ₁ , X ₂ , Y ₁ , Y ₂ , a and b are as defined in Formula 1 above. The polycarbonate according to any one of claims 1 to 7, wherein the Izod room temperature impact strength measured at 23 °C according to ASTM D256 (1/8 inch, Notched Izod) is 220 Kgf/m ² or more. Polycarbonate production method comprising the step of polymerizing a composition comprising a diol compound represented by the following formula (1) and a carbonate precursor:
[Formula 1]

In Formula 1,
Z ₁ is CR ₁ R ₂ , O, S, SS, C=O, C=S, SO, SO ₂ , (CH ₂ ) _n -L ₁ -(CH ₂ ) _m or O-(C=O); ,
R ₁ and R ₂ are each independently hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted haloalkyl, OR ^a , SR ^b , NR ^c R ^d , COOR ^e , OCOR ^f , halogen, CN or NO ₂ ;
R ₁ and R ₂ are connected to form a substituted or unsubstituted aliphatic or aromatic ring with halogen, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl;
L ₁ is O or S;
n and m are each independently an integer from 1 to 3;
Z ₂ and Z ₃ are each independently a single bond, a substituted or unsubstituted alkylene, a substituted or unsubstituted cycloalkylene, a substituted or unsubstituted arylene, or a substituted or unsubstituted heteroarylene, or a combination thereof. is,
X ₁ and X ₂ are each independently CR ₁₀₀ or N;
Y ₁ and Y ₂ are each independently CR ₁₀₁ R ₁₀₂ , O or S;
R ₁₀₀ , R _{101 ,} R _{102 ,} R ₃ and R ₄ are each independently hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted haloalkyl, OR ^a , SR ^b , NR ^c R ^d , COOR ^e , OCOR ^f , halogen, CN or NO ₂ ;
a and b are each independently an integer from 0 to 3,
R ^a to R ^f are each independently hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl. According to claim 9,
The polymerization is carried out by a melt polymerization method, polycarbonate production method. A molded article comprising the polycarbonate of any one of claims 1 to 7.

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