KR20230024572A - Resin and preparation method thereof, resin composition and molded product - Google Patents

Abstract

The present application relates to a resin including a unit represented by chemical formula 1, a manufacturing method thereof, a resin composition including the same, and molded articles including the resin composition. The resin according to one embodiment of the present invention has a high refractive index and high transparency.

Description

Resin and its manufacturing method, resin composition and molded article {RESIN AND PREPARATION METHOD THEREOF, RESIN COMPOSITION AND MOLDED PRODUCT}

The present invention relates to resins and methods for their preparation. More specifically, the present invention relates to high refractive index and high transparency polyester or polycarbonate and a method for producing the same.

The higher the refractive index of the optical material, the thinner the optical lens required to achieve the same level of correction. Accordingly, the higher the refractive index of the optical material, the thinner and lighter the lens can be manufactured, and the miniaturization of various devices in which the lens is used is possible.

In general, when the refractive index of an optical material increases, there is a problem in that Abbe's number decreases, and transparency of a certain level or higher is required for use as an optical material.

Korean Patent Publication No. 10-2020-0034523

An exemplary embodiment of the present invention is to provide a resin having a novel structure and a manufacturing method thereof.

Another embodiment of the present invention is to provide a composition comprising a resin having a novel structure and a molded article made of the composition.

An exemplary embodiment of the present invention provides a resin including a unit represented by Formula 1 below.

[Formula 1]

In Formula 1,

Ar1 and Ar2 are the same as or different from each other, and each independently hydrogen; A substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

R1 is hydrogen; Or a substituted or unsubstituted alkyl group,

r1 is an integer from 0 to 4, and when r1 is 2 or more, 2 or more R1s are the same as or different from each other,

L1 and L2 are the same as or different from each other, and each independently represents a substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group,

l1 and l2 are the same as or different from each other, and are each independently an integer of 1 or 2, and when l1 and l2 are each 2, the structures in parentheses are the same as or different from each other,

L is a direct bond; or -CO-L'-;

L' is a substituted or unsubstituted arylene group,

X1 to X4 are the same as or different from each other, and are each independently O; or S,

Z1 and Z2 are the same as or different from each other, and each independently a substituted or unsubstituted alkylene group; Or a substituted or unsubstituted cycloalkylene group,

a and b are the same as or different from each other, and each independently represent an integer from 1 to 10, and when a and b are each 2 or more, the structures in parentheses are the same as or different from each other,

* means a site connected to the main chain of the resin.

An exemplary embodiment of the present invention is a compound represented by Formula 1a; and polymerizing a composition for preparing a resin including a polyester precursor or a polycarbonate precursor.

[Formula 1a]

In Formula 1a, the definitions of Ar1, Ar2, R1, r1, L1, L2, l1, l2, X1 to X4, Z1, Z2, a and b are as defined in Formula 1 above.

Another embodiment of the present invention provides a resin composition comprising the resin according to the above-described embodiment.

Another embodiment of the present invention provides a molded article comprising the resin composition according to the above-described embodiment.

Resin according to one embodiment of the present invention has a high refractive index and high transparency.

By using the resin according to the exemplary embodiments of the present invention, an excellent optical lens can be obtained.

Hereinafter, specific exemplary embodiments will be described in more detail.

The term "substitution" means that a hydrogen atom bonded to a carbon atom of a compound is replaced with another substituent, and the position to be substituted is not limited as long as the hydrogen atom is substituted, that is, a position where the substituent can be substituted, and when two or more are substituted , Two or more substituents may be the same as or different from each other.

As used herein, the term “substituted or unsubstituted” refers to halogen; nitro (NO ₂ ); nitrile (CN); alkyl; cycloalkyl; alkoxy; aryl; aryloxy group; arylthio groups; an alkylthio group; And it means that it is substituted with one or more substituents selected from the group consisting of heteroaryl, is substituted with a substituent in which two or more substituents among the above exemplified substituents are linked, or does not have any substituents.

In this specification, * means a binding site to another structure.

In this specification, cycloalkylene may be monocyclic or polycyclic cycloalkylene. Specifically, cycloalkylene is cycloalkylene having 3 to 20 carbon atoms; Monocyclic or polycyclic cycloalkylene having 6 to 18 carbon atoms; or monocyclic or polycyclic cycloalkylene having 6 to 12 carbon atoms. More specifically, the cycloalkylene may be a divalent group derived from an alicyclic hydrocarbon such as cyclopentylene, cyclohepsilene, or cycloheptylene as monocyclic cycloalkylene, and adamantane-diyl as polycyclic cycloalkylene , norbonane-diyl, and the like. However, it is not limited thereto. In addition, the cycloalkylene may be unsubstituted or substituted with one or more C1-C10 alkyl groups, C1-C10 alkoxy groups, or halogens.

In this specification, the description of cycloalkylene may be applied except that cycloalkyl is a monovalent group rather than a divalent group.

In the present specification, alkylene is a divalent group derived from an aliphatic hydrocarbon having 1 to 30 carbon atoms, 1 to 20 carbon atoms, 1 to 10 carbon atoms, or 1 to 5 carbon atoms, and may be straight-chain or branched-chain alkylene. Specific examples of alkylene include methylene, ethylene, propylene, n-propylene, isopropylene, butylene, n-butylene, isobutylene, tert-butylene, sec-butylene, 1-methyl-butylene, 1- Ethyl-butylene, pentylene, n-pentylene, isopentylene, neopentylene, tert-pentylene, hexylene, n-hexylene, 1-methylpentylene, 2-methylpentylene, 4-methyl- 2-pentylene, 3,3-dimethylbutylene, 2-ethylbutylene, heptylene, n-heptylene, 1-methylhexylene, octylene, n-octylene, tert-octylene, 1-methylheptylene Tylene, 2-ethylhexylene, 2-propylpentylene, n-nonylene, 2,2-dimethylheptylene, 1-ethyl-propylene, 1,1-dimethyl-propylene, isohexylene, 4-methylhexylene , 5-methylhexylene, etc., but is not limited thereto.

In this specification, the description of straight-chain or branched-chain alkylene may be applied except that the straight-chain or branched-chain alkyl is not divalent but monovalent.

In this specification, unless otherwise limited, alkyl includes straight chain alkyl, branched chain alkyl and cycloalkyl.

In the present specification, arylene may be monocyclic or polycyclic arylene, and the number of carbon atoms is not particularly limited, but preferably has 6 to 30 carbon atoms, and may have 6 to 20 carbon atoms. Specifically, the monocyclic arylene may be phenylene, biphenyllylene, terphenylylene, and the like, but is not limited thereto. When the arylene is polycyclic arylene, the number of carbon atoms is not particularly limited, but preferably has 10 to 30 carbon atoms, and may have 10 to 20 carbon atoms. Specifically, the polycyclic arylene may be naphthylene, anthracenylene, phenanthrenylene, triphenylenylene, pyrenylene, phenalenylene, perylenylene, chrysenylene, fluorenylene, and the like. It is not limited.

In this specification, the description of arylene may be applied except that aryl is a monovalent group rather than a divalent group.

In the present specification, heteroarylene includes at least one non-carbon atom or heteroatom, and specifically, the heteroarylene includes at least one atom selected from the group consisting of O, N, Se, and S. The number of carbon atoms of the heteroarylene is not particularly limited, but may be 1 to 30 carbon atoms, 3 to 30 carbon atoms, or 3 to 20 carbon atoms. The heteroarylene may be monocyclic or polycyclic. Examples of heteroarylene include thiophene group, furan group, dibenzofuran group, dibenzothiophene group, benzothiophene group, pyrrole group, imidazole group, thiazole group, oxazole group, oxadiazole group, pyridine group, bi Pyridine group, pyrimidine group, triazine group, triazole group, acridine group, pyridazine group, pyrazine group, quinoline group, quinazoline group, quinoxaline group, phthalazine group, pyridopyrimidine group, pyridopyrazine group, A pyrazino pyrazine group, an isoquinoline group, an indole group, a carbazole group, and the like, but are not limited thereto.

In the present specification, the description of heteroarylene may be applied except that the heteroaryl is a monovalent group rather than a divalent group.

In this specification, the divalent aliphatic hydrocarbon group means the aforementioned alkylene, cycloalkylene, and the like.

In the present specification, alkoxy may be an alkoxy group having 1 to 10 carbon atoms or 1 to 5 carbon atoms. Specific examples of alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, 1-methyl-butoxy, 1-ethyl- butoxy, pentoxy, etc., but are not limited thereto.

In this specification, halogen is a fluoro, chloro, bromo, or iodo group.

In the present specification, the description of cycloalkylene or heterocycloalkylene described above may be applied to the aliphatic ring, and the description of arylene or heteroarylene may be applied to the aromatic ring.

In the present specification, the aliphatic heterocycle includes at least one atom or heteroatom other than carbon, and specifically, the heteroatom includes at least one atom selected from the group consisting of O, N, Se, and S. means

In the present specification, the aryloxy group may be represented by -ORo, and the description of the above-mentioned aryl applies to the Ro.

In the present specification, an arylthio group may be represented by -SRs1, and the description of the above-mentioned aryl applies to Rs1.

In the present specification, the alkylthio group may be represented by -SRs2, and the description of the above-described alkyl is applied to Rs2.

An exemplary embodiment of the present invention provides a resin including a unit represented by Formula 1 below.

[Formula 1]

In Formula 1,

Ar1 and Ar2 are the same as or different from each other, and each independently hydrogen; A substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

R1 is hydrogen; Or a substituted or unsubstituted alkyl group,

r1 is an integer from 0 to 4, and when r1 is 2 or more, 2 or more R1s are the same as or different from each other,

L1 and L2 are the same as or different from each other, and each independently represents a substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group,

l1 and l2 are the same as or different from each other, and are each independently an integer of 1 or 2, and when l1 and l2 are each 2, the structures in parentheses are the same as or different from each other,

L is a direct bond; or -CO-L'-;

L' is a substituted or unsubstituted arylene group,

X1 to X4 are the same as or different from each other, and are each independently O; or S,

Z1 and Z2 are the same as or different from each other, and each independently a substituted or unsubstituted alkylene group; Or a substituted or unsubstituted cycloalkylene group,

a and b are the same as or different from each other, and each independently represent an integer from 1 to 10, and when a and b are each 2 or more, the structures in parentheses are the same as or different from each other,

* means a site connected to the main chain of the resin.

From the relationship between the molecular structure and the refractive index known by Lorentz-Lorenz's formula, it can be seen that the refractive index of the material composed of molecules is increased by increasing the electron density of the molecule and reducing the molecular volume.

Since the core structure of the resin containing the unit represented by Formula 1 is a naphthalene group, the molecular volume is small and the packing ability is excellent, thereby improving the refractive index of the resin. In addition, an arylene group in which L1 and L2 are substituted or unsubstituted; Alternatively, in the case of an electron-rich substituent such as a substituted or unsubstituted heteroarylene group, the refractive index of the resin may be further improved by increasing the electron density of the structure represented by Formula 1.

In addition, when the resin including the unit represented by Chemical Formula 1 is applied to manufacturing a resin having a high refractive index, it must have a glass transition temperature (Tg) above a certain temperature for an injection process. Compared to the compound represented by Formula 1a constituting the unit represented by Formula 1, the monomer containing an acrylate group as an end group has a relatively low glass transition temperature (Tg) due to the nature of the terminal group, and therefore, according to the present invention It is not possible to prepare a resin that satisfies the desired physical properties. On the other hand, when preparing a resin containing a unit represented by the formula (1) of the present invention with a compound represented by the following formula (1a), the glass transition temperature (Tg) for preparing a resin having a high refractive index desired in the present invention easy to adjust

In one embodiment of the present invention, Ar1 and Ar2 are the same as or different from each other, and each independently hydrogen; A substituted or unsubstituted alkyl group having 1 to 30 carbon atoms; A substituted or unsubstituted aryl group having 6 to 30 carbon atoms; or a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms.

In one embodiment of the present invention, Ar1 and Ar2 are the same as or different from each other, and each independently hydrogen; A substituted or unsubstituted alkyl group having 1 to 25 carbon atoms; A substituted or unsubstituted aryl group having 6 to 25 carbon atoms; or a substituted or unsubstituted heteroaryl group having 3 to 25 carbon atoms.

In one embodiment of the present invention, Ar1 and Ar2 are the same as or different from each other, and each independently hydrogen; A substituted or unsubstituted alkyl group having 1 to 20 carbon atoms; A substituted or unsubstituted aryl group having 6 to 20 carbon atoms; or a substituted or unsubstituted heteroaryl group having 3 to 20 carbon atoms.

In one embodiment of the present invention, Ar1 and Ar2 are the same as or different from each other, and each independently hydrogen; A substituted or unsubstituted alkyl group having 1 to 10 carbon atoms; A substituted or unsubstituted aryl group having 6 to 12 carbon atoms; or a substituted or unsubstituted heteroaryl group having 3 to 12 carbon atoms.

In one embodiment of the present invention, Ar1 and Ar2 are the same as or different from each other, and each independently hydrogen; A substituted or unsubstituted propyl group; A substituted or unsubstituted hexyl group; A substituted or unsubstituted phenyl group; A substituted or unsubstituted naphthyl group; A substituted or unsubstituted carbazole group; A substituted or unsubstituted dibenzofuran group; or a substituted or unsubstituted dibenzothiophene group.

In one embodiment of the present invention, Ar1 and Ar2 are the same as or different from each other, and each independently hydrogen; n-propyl group; n-hexyl group; A phenyl group unsubstituted or substituted with a carbazole group; A naphthyl group unsubstituted or substituted with a phenyl group; A carbazole group substituted with a phenyl group; Dibenzofuran group; or a dibenzothiophene group.

In one embodiment of the present invention, R1 is hydrogen; or a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms.

In one embodiment of the present invention, R1 is hydrogen; or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms.

In one embodiment of the present invention, R1 is hydrogen; or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms.

In one embodiment of the present invention, R1 is hydrogen.

In one embodiment of the present invention, L1 and L2 are the same as or different from each other, and each independently represents a substituted or unsubstituted arylene group having 6 to 30 carbon atoms; or a substituted or unsubstituted heteroarylene group having 3 to 30 carbon atoms.

In one embodiment of the present invention, L1 and L2 are the same as or different from each other, and each independently represents a substituted or unsubstituted arylene group having 6 to 20 carbon atoms; or a substituted or unsubstituted heteroarylene group having 3 to 20 carbon atoms.

In one embodiment of the present invention, L1 and L2 are the same as or different from each other, and each independently represents a substituted or unsubstituted arylene group having 6 to 12 carbon atoms; or a substituted or unsubstituted heteroarylene group having 3 to 12 carbon atoms.

In one embodiment of the present invention, L1 and L2 are the same as or different from each other, and each independently represents a substituted or unsubstituted phenylene group; A substituted or unsubstituted biphenyl group; Or a substituted or unsubstituted naphthylene group.

In one embodiment of the present invention, l1 and l2 are 1.

In one embodiment of the present invention, l1 and l2 are 2.

In one embodiment of the present invention, L is a direct bond.

In one embodiment of the present invention, L is -CO-L'-.

In one embodiment of the present invention, L' is a substituted or unsubstituted arylene group having 6 to 30 carbon atoms.

In one embodiment of the present invention, L' is a substituted or unsubstituted arylene group having 6 to 20 carbon atoms.

In one embodiment of the present invention, L' is a substituted or unsubstituted arylene group having 6 to 12 carbon atoms.

In one embodiment of the present invention, L' is a substituted or unsubstituted phenylene group.

In one embodiment of the present invention, L' is a phenylene group.

In one embodiment of the present invention, X1 to X4 are O.

In one embodiment of the present invention, X1 to X4 are S.

In one embodiment of the present invention, Z1 and Z2 are the same as or different from each other, and each independently a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms; or a substituted or unsubstituted cycloalkylene group having 3 to 30 carbon atoms.

In one embodiment of the present invention, Z1 and Z2 are the same as or different from each other, and each independently a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms; or a substituted or unsubstituted cycloalkylene group having 3 to 20 carbon atoms.

In one embodiment of the present invention, Z1 and Z2 are the same as or different from each other, and each independently a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms; or a substituted or unsubstituted cycloalkylene group having 3 to 10 carbon atoms.

In one embodiment of the present invention, Z1 and Z2 are the same as or different from each other, and each independently represents a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms.

In one embodiment of the present invention, Z1 and Z2 are the same as or different from each other, and each independently a substituted or unsubstituted methylene group; A substituted or unsubstituted ethylene group; A substituted or unsubstituted propylene group; Or a substituted or unsubstituted hexylene group.

In one embodiment of the present invention, Z1 and Z2 are the same as or different from each other, and each independently a methylene group; ethylene group; propylene group; or a hexylene group.

In one embodiment of the present invention, Z1 and Z2 are ethylene groups.

According to an exemplary embodiment of the present invention, the resin has a terminal group of -OH; -SH; -CO ₂ CH ₃ ; or -OC ₆ H ₅ .

In one embodiment of the present invention, the resin may further include a unit represented by Formula C below.

[Formula C]

In the above formula (C), the definition of L is the same as the definition in the above formula (1).

In one embodiment of the present invention, the weight average molecular weight of the resin is 19,000 g / mol to 200,000 g / mol, preferably 20,000 g / mol to 100,000 g / mol or 20,000 g / mol to 50,000 g / mol . More preferably, it is 20,000 g/mol to 30,000 g/mol or 20,000 g/mol to 26,000 g/mol.

In one embodiment of the present invention, the number average molecular weight of the resin is 14,000 g / mol to 19,000 g / mol, preferably 14,000 g / mol to 18,500 g / mol, more preferably 14,000 g / mol to 18,000 g/mol.

When the resin satisfies the weight average molecular weight and number average molecular weight ranges described above, the resin may have optimal fluidity and processability.

In the present invention, the weight average molecular weight (Mw) or number average molecular weight (Mn) of the resin and the oligomer used for its preparation was determined by gel permeation chromatography (gel permeation chromatography) using a polystyrene standard (PS standard) using an Agilent 1200 series. It can be measured by chromatograph; GPC). Specifically, it can be measured using an Agilent 1200 series instrument using a Polymer Laboratories PLgel MIX-B 300 mm length column, at which time the measurement temperature is 40 ° C, the solvent used is tetrahydrofuran (THF), and the flow rate is 1 mL / is min. A sample of the resin or oligomer is prepared at a concentration of 1.0 mg/1 mL, respectively, and then supplied in an amount of 10 µL, and a weight average molecular weight or number average molecular weight value is derived using a calibration curve formed using polystyrene standards. At this time, the molecular weight (g / mol) of the polystyrene standard is 2,000 / 10,000 / 30,000 / 70,000 / 200,000 / 700,000 / 2,000,000 / 4,000,000 / 10,000,000.

In one embodiment of the present invention, the glass transition temperature (Tg) of the resin may be 135 ℃ to 150 ℃. Preferably it may be 135 ℃ to 145 ℃, more preferably 138 ℃ to 144 ℃. When the resin satisfies the glass transition temperature range, it has excellent heat resistance and injection properties, and is easy to adjust to the glass transition temperature value required to manufacture a resin having a high refractive index intended in the present invention, and has excellent processability. Thus, a molded article having desired properties in the present invention can be manufactured. When the glass transition temperature of the resin exceeds 150° C., the fluidity of the resin is reduced, and processing may be difficult when a molded product is manufactured with the resin.

The glass transition temperature (Tg) can be measured by differential scanning calorimetry (DSC). Specifically, the glass transition temperature can be measured from a graph obtained by heating 5.5 mg to 8.5 mg of the resin sample to 270 ° C. under a nitrogen atmosphere, then heating at a heating rate of 10 ° C. during the second heating after cooling, and scanning. .

In one embodiment of the present invention, the refractive index of the resin measured at a wavelength of 589 nm is 1.67 to 1.75. The refractive index may be preferably 1.68 to 1.73, more preferably 1.691 to 1.721. When the resin satisfies the refractive index, it is possible to manufacture a thin and lightweight optical lens when applied to a molded article such as an optical lens.

In one embodiment of the present invention, the Abbe number measured and calculated at wavelengths of 589 nm, 486 nm, and 656 nm of the resin may be 17.5 to 20. It may be preferably 17.6 to 19. When the resin satisfies the Abbe number range, dispersion is reduced and sharpness is increased when the resin is applied to a molded product such as an optical lens while maintaining a high refractive index. The Abbe number is specifically measured at the D (589 nm), F (486 nm), and C (656 nm) wavelengths (n _D , n _F , n _C ) at 20 ° C. Abbe number can be obtained.

Abbe number=(n _D -1)/(n _F - n _C )

The refractive index and Abbe number measurement may be performed from a film prepared by applying a solution prepared by dissolving the resin in a solvent to a silicon wafer by spin-coating, and the coated film may be measured using an ellipsometer at 20 ° C. ) can be used to obtain the result value according to the wavelength of light and measure it. The coating by spin coating may be performed at a rotation speed of 150 rpm to 300 rpm, and the thickness of the coated film may be 5 μm to 20 μm. The silicon wafer is not particularly limited, and any one capable of measuring the refractive index and Abbe number of the resin composition according to the present invention may be appropriately employed. The solvent may be dimethylacetamide or 1,2-dichlorobenzene, and the solution may be prepared by dissolving the resin sample at 10% by weight based on the total weight of the solution.

An exemplary embodiment of the present invention is a compound represented by Formula 1a; and polymerizing a composition for preparing a resin including a polyester precursor or a polycarbonate precursor.

[Formula 1a]

In Formula 1a, the definitions of Ar1, Ar2, R1, r1, L1, L2, l1, l2, X1 to X4, Z1, Z2, a and b are as defined in Formula 1 above.

An exemplary embodiment of the present invention preferably provides a method for preparing the resin comprising the step of polymerizing a composition for preparing a resin including the compound represented by Formula 1a and the polyester precursor.

An exemplary embodiment of the present invention is a compound represented by Formula 1a; And it provides a composition for preparing a resin comprising a polyester precursor or a polycarbonate precursor.

In one embodiment of the present invention, 2,2'-(((9H-fluorene-9,9-diyl)bis(4,1-phenylene))bis(oxy))bis( Requires ethane-1-ol)(2,2'-(((9H-fluorene-9,9-diyl)bis(4,1-phenylene))bis(oxy))bis(ethan-1-ol)) Depending on, more may be included.

The 2,2'-(((9H-fluorene-9,9-diyl)bis(4,1-phenylene))bis(oxy))bis(ethane-1-ol) is the composition for preparing the resin, 100 weight It may be included in 20 parts by weight to 80 parts by weight per part. Specifically, the 2,2'-(((9H-fluorene-9,9-diyl)bis(4,1-phenylene))bis(oxy))bis(ethane-1-ol) is 30 parts by weight to 70 parts by weight, 30 parts by weight to 60 parts by weight, or 30 parts by weight to 50 parts by weight may be included.

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

In one embodiment of the present invention, the compound represented by Formula 1a may be included in 1 part by weight to 99 parts by weight based on 100 parts by weight of the composition for preparing a resin.

The compound represented by Formula 1a may be included in an amount of preferably 1 to 60 parts by weight, 1 to 50 parts by weight, 1 to 40 parts by weight, 10 to 40 parts by weight, or 20 to 35 parts by weight based on 100 parts by weight of the composition for preparing the resin. there is.

In one embodiment of the present invention, the polyester precursor or polycarbonate precursor may be included in 1 part by weight to 30 parts by weight based on 100 parts by weight of the composition for preparing the resin.

The polyester precursor or polycarbonate precursor may be preferably included in an amount of 1 to 30 parts by weight, 10 to 30 parts by weight, or 20 to 30 parts by weight based on 100 parts by weight of the resin preparation composition.

The compound represented by Formula 1a may be prepared according to Reaction Scheme 1 or 2 below.

[Scheme 1]

[Scheme 2]

In Schemes 1 and 2, R ^* is hydrogen, or adjacent R ^* are bonded to each other to form a substituted or unsubstituted aliphatic heterocycle, and the definitions of the remaining substituents are as defined in Formula 1a above.

In Reaction Schemes 1 and 2, the process of synthesizing a compound having a specific substituent bonded to a specific position is exemplified, but is not limited thereto. A unit corresponding to the scope of Formula 1a may be synthesized by a synthetic method.

According to an exemplary embodiment of the present invention, the polyester precursor may be represented by the following formula A, and the polycarbonate precursor may be represented by the following formula B.

[Formula A]

[Formula B]

In the formulas A and B,

Ra1, Ra2, Rb1 and Rb2 are the same as or different from each other, and each independently a substituted or unsubstituted alkyl group; Or a substituted or unsubstituted aryl group,

L' is a substituted or unsubstituted arylene group.

In one embodiment of the present invention, Ra1, Ra2, Rb1 and Rb2 are the same as or different from each other, and each independently a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms; or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms.

In one embodiment of the present invention, Ra1, Ra2, Rb1 and Rb2 are the same as or different from each other, and each independently a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms; or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms.

In one embodiment of the present invention, Ra1, Ra2, Rb1 and Rb2 are the same as or different from each other, and each independently a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms; or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms.

In one embodiment of the present invention, Ra1, Ra2, Rb1 and Rb2 are the same as or different from each other, and each independently a substituted or unsubstituted methyl group; A substituted or unsubstituted ethyl group; Or a substituted or unsubstituted phenyl group.

In one embodiment of the present invention, Ra1, Ra2, Rb1 and Rb2 are the same as or different from each other, and each independently a methyl group; an ethyl group substituted with a hydroxyl group; or a phenyl group.

In one embodiment of the present invention, Ra1 and Ra2 are ethyl groups substituted with hydroxyl groups.

In one embodiment of the present invention, Rb1 and Rb2 are phenyl groups.

In one embodiment of the present invention, L' is a substituted or unsubstituted arylene group having 6 to 30 carbon atoms.

In one embodiment of the present invention, L' is a substituted or unsubstituted arylene group having 6 to 20 carbon atoms.

In one embodiment of the present invention, L' is a substituted or unsubstituted arylene group having 6 to 12 carbon atoms.

In one embodiment of the present invention, L' is a substituted or unsubstituted phenylene group.

In one embodiment of the present invention, L' is a phenylene group.

The polyester precursor may specifically be bis(2-hydroxyethyl)terephthalate. The bis(2-hydroxyethyl)terephthalate (Bis(2-hydroxyethyl)terephthalate) can be obtained from Sigma-Aldrich.

The polycarbonate precursor serves to connect additional comonomers as necessary, and other specific examples that can be applied as the compound represented by Formula B or other examples include phosgene, triphosgene, diphosgene, bromophosgene , dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, ditoryl carbonate, bis(chlorophenyl) carbonate, m-cresyl carbonate, dinaphthylcarbonate, bis(diphenyl) carbonate or bishalophor mates, etc., and any one or a mixture of two or more of these may be used.

The unit of Formula 1 may be formed by polymerization of the compound represented by Formula 1a and the polyester precursor of Formula A or the polycarbonate precursor of Formula B.

In one embodiment of the present invention, the resin is preferably polymerized from the compound represented by Chemical Formula 1a and the polyester precursor represented by Chemical Formula A.

The compound represented by Formula 1a may be used in an amount of 1 to 60 parts by mole based on 100 parts by mole of the total monomers constituting the resin including the unit represented by Formula 1.

The polyester precursor represented by Formula A or the polycarbonate precursor represented by Formula B may be used in an amount of 50 to 150 parts by mole based on 100 parts by mole of the total monomers of the compound represented by Formula 1a constituting the resin.

For the polymerization of the resin according to the present invention, a method known in the art may be used.

The polymerization is preferably carried out by melt polycondensation.

The melt polycondensation method uses the composition for preparing a resin, can further apply a catalyst if necessary, and performs melt polycondensation while removing by-products by a transesterification reaction under heating and further under normal pressure or reduced pressure. it could be The catalyst may be a material generally applied in the art, but for example, titanium (IV) butoxide, titanium (IV) tertbutoxide, titanium ( IV) Tetrabutoxide (Titanium(IV) tetrabutoxide), Chloroisopropoxy titanium(IV), or Tetrakis (diethylamino)titanium(IV) )) can be used.

The catalyst may be included in an amount of 0.05 parts by weight to 5 parts by weight based on 100 parts by weight of the composition for preparing the resin. Specifically, the catalyst may be included in an amount of 0.05 parts by weight to 1 part by weight based on 100 parts by weight of the composition for preparing the resin.

Specifically, the melt polycondensation method is a compound represented by Formula 1a; And after the polyester precursor or the polycarbonate precursor is melted in a reaction vessel, it is preferable to carry out the reaction in a state in which by-produced compounds are retained.

In order to retain the by-produced compound, the pressure can be controlled by closing the reactor, reducing the pressure, or pressurizing the reactor.

The reaction time of this step is 20 minutes or more and 600 minutes or less, preferably 40 minutes or more and 450 minutes or less, and more preferably 60 minutes or more and 300 minutes or less.

At this time, if the by-produced compound is distilled off immediately after generation, the finally obtained resin has a small content of high molecular weight body. However, when the by-produced monohydroxy compound is allowed to remain in the reaction vessel for a certain period of time, a resin finally obtained having a high content of a high molecular weight body is obtained.

In one embodiment of the present invention, the melt polycondensation method is performed by maintaining nitrogen purging of the composition for preparing a resin at normal pressure and room temperature for 30 minutes, and then gradually raising the temperature while stirring at 30 rpm to 120 rpm. It can be done by heating. Then, when the temperature reaches 200℃, stop the flow of nitrogen, close the inlet, connect the vacuum pump, and gradually lower the pressure inside the reactor to remove by-products. A polymerization reaction may be performed until the stirring torque rises.

The melt polycondensation method may be carried out continuously or batchwise. The reaction apparatus used in carrying out the reaction may be a vertical type equipped with an anchor type stirring blade, a max blend stirring blade, a helical ribbon type stirring blade, etc., or a horizontal type equipped with a paddle blade, a lattice blade, a glass blade, etc. It may be, and may be an extruder type equipped with a screw. In addition, in view of the viscosity of the polymer, it is preferable to use a reaction device in which these reaction devices are appropriately combined.

In the method for producing the resin used in the present invention, the catalyst may be removed or deactivated in order to maintain thermal stability and hydrolysis stability after the polymerization reaction is completed. A method of deactivating the catalyst by adding an acidic material known in the art can be preferably carried out.

Examples of the acidic substance include esters such as butyl benzoate and aromatic sulfonic acids such as p-toluenesulfonic acid; aromatic sulfonic acid esters such as butyl p-toluenesulfonate and hexyl p-toluenesulfonate; phosphoric acids such as phosphorous acid, phosphoric acid, and phosphonic acid; phosphite esters such as triphenyl phosphite, monophenyl phosphite, diphenyl phosphite, diethyl phosphite, di n-propyl phosphite, di n-butyl phosphite, di n-hexyl phosphite, dioctyl phosphite, and monooctyl phosphite; phosphoric acid esters such as triphenyl phosphate, diphenyl phosphate, monophenyl phosphate, dibutyl phosphate, dioctyl phosphate, and monooctyl phosphate; phosphonic acids such as diphenylphosphonic acid, dioctylphosphonic acid, and dibutylphosphonic acid; phosphonic acid esters such as diethyl phenylphosphonate; phosphines such as triphenylphosphine and bis(diphenylphosphino)ethane; boric acids such as boric acid and phenylboric acid; aromatic sulfonic acid salts such as tetrabutylphosphonium salt of dodecylbenzenesulfonic acid; organic halides such as stearic acid chloride, benzoyl chloride, and p-toluenesulfonic acid chloride; Alkyl sulfuric acid, such as dimethyl sulfuric acid; Organic halides, such as benzyl chloride, etc. are used preferably.

The acidic material may be used in an amount of 0.1 to 5 parts by mole, preferably 0.1 to 1 part by mole, based on 100 parts by mole of the catalyst.

When the amount of the acidic substance is less than 0.1 part by mole, the deactivation effect becomes insufficient, which is not preferable. Moreover, when it exceeds 5 mol parts, since the heat resistance of resin will fall and a molded article will become easily colored, it is unpreferable.

After deactivation of the catalyst, a step of devolatilizing and removing the low boiling point compound in the resin at a pressure of 0.1 mmHg to 1 mmHg and a temperature of 200°C to 350°C may be further performed. In this step, a horizontal device equipped with stirring blades excellent in surface renewability, such as paddle blades, lattice blades, spectacle blades, or the like, or a thin film evaporator is preferably used.

The resin of the present invention preferably has as little foreign material content as possible, and filtration of molten raw materials, filtration of catalyst liquid, and the like are preferably performed.

It is preferable that the mesh of the filter used for the said filtration is 5 micrometers or less, More preferably, it is 1 micrometer or less. Further, filtration of the resulting resin with a polymer filter is preferably performed. The mesh of the polymer filter is preferably 100 μm or less, and more preferably 30 μm or less. In addition, the process of collecting resin pellets must be in a low dust environment, preferably class 6 or less, more preferably class 5 or less.

Another embodiment of the present invention provides a resin composition comprising a resin according to the above-described embodiment.

In one embodiment of the present invention, the resin may be included in 1 part by weight to 80 parts by weight based on 100 parts by weight of the resin composition.

In one embodiment of the present invention, the resin composition may further include a solvent. The solvent may be, for example, dimethylacetamide or 1,2-dichlorobenzene.

The solvent may be included in an amount of 20 parts by weight to 99 parts by weight based on 100 parts by weight of the resin composition.

The resin composition may include the resin in which an additional monomer is further polymerized in addition to the compound represented by Formula 1a. The additional monomer is not particularly limited, and monomers generally applied in the art related to polyester or polycarbonate may be appropriately employed within a range that does not change the main physical properties of the resin composition. The additional monomer may be used in an amount of 1 to 50 parts by mole based on 100 parts by mole of the total monomers constituting the resin including the unit represented by Formula 1.

In addition to the resin containing the unit represented by Formula 1, the resin composition may optionally contain additives such as antioxidants, plasticizers, antistatic agents, nucleating agents, flame retardants, lubricants, impact modifiers, optical brighteners, ultraviolet absorbers, pigments and dyes. It may further include one or more selected from the group consisting of.

The additive may be included in an amount of 1 to 99 parts by weight based on 100 parts by weight of the resin composition.

Types of the antioxidant, plasticizer, antistatic agent, nucleating agent, flame retardant, lubricant, impact modifier, optical whitening agent, ultraviolet absorber, pigment or dye are not particularly limited, and those applied in the art may be appropriately employed.

Another embodiment of the present invention provides a molded article including the resin composition according to the above-described embodiment.

In one embodiment of the present invention, the molded article may be manufactured from the resin composition or a cured product thereof.

As an example of the method for producing the molded article, after mixing the resin containing the unit represented by the above-mentioned formula (1) and the additives well using a mixer, extruding them with an extruder to produce pellets, drying the pellets, and then It may include injecting with an injection molding machine.

In addition, as a molding method of a molded article containing the resin, compression molding, casting, roll processing, extrusion molding, stretching, etc. are exemplified in addition to injection molding, but are not limited thereto.

In one embodiment of the present invention, the molded article is an optical lens.

The optical lens is manufactured using the resin, has a high refractive index and high transparency, and may be preferably applied to a camera.

Hereinafter, the present invention is illustrated in more detail through examples.

Examples and Comparative Examples.

1. Synthesis of Monomer 1

Synthesis of Intermediate 1-1

10 g of 2,6-dibromonaphthalene, 6-(4,4,5,5-tetramethyl-1,3,2-dioxabolane-2 in a 250 ml round bottom flask (RBF) -yl)naphthalen-2-ol (6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)naphthalen-2-ol) 19.1g tetrahydrofuran (THF) 60ml and heated and stirred at 45°C. After 10 minutes, 19.3 g of K ₂ CO ₃ was dissolved in 40 ml of H ₂ O and put into a round bottom flask (RBF). Then, 179 mg of BTP (Pd(t-Bu ₃ P) ₂ ) catalyst was added. The temperature was raised to 75° C. and the reaction proceeded for about 5 hours. After cooling to room temperature, the organic layer was separated, and ethyl acetate (EA)/distilled water extraction was performed twice. Thereafter, the separated organic layer was treated with activated carbon and MgSO ₄ , stirred for 15 minutes or longer, and filtered on a Celite layer. After adsorbing the obtained crude material to silica, it is purified by medium pressure liquid chromatography (mplc) with dichloromethane (DCM) / ethyl acetate (EA). The separated product was dissolved in dichloromethane (DCM), crystallized by precipitation by dropwise addition to hexane (HEX), and then dried to obtain intermediate 1-1 as a white solid.

Synthesis of monomer 1

After dissolving 10 g of Intermediate 1-1, 5.3 g of ethylene carbonate, and 670 mg of K ₂ CO ₃ in 50 ml of dimethylacetamide (DMAc) in a 250 ml round bottom flask (RBF), the temperature was raised to 130 ° C and stirred to react. . After 3 hours, 0.1 g of NaOH and 4.0 ml of ethylene glycol were added, followed by additional stirring for 1 hour. After cooling to room temperature, when H ₂ O was added, crystallization proceeded. After filtering, it was dissolved in tetrahydrofuran (THF), adsorbed on silica, stirred for 30 minutes, and then filtered through a Celite layer. The filtered material is crystallized by adding it to dichloromethane (DCM) and tetrahydrofuran (THF), and then crystallized by adding it to dichloromethane (DCM) and tetrahydrofuran (THF), followed by recrystallization. Monomer 1 as a solid was obtained.

1H NMR (500 MHz): δ = 8.00 (d, 2H), 7.79-7.75 (m, 4H), 7.64 (s, 2H), 7.43-7.40 (m, 6H), 7.25 (d, 2H), 7.16 ( d, 2H), 4.90 (s, 2H), 4.44 (t, 4H), 3.67 (t, 4H)

2. Synthesis of Monomer 2

Synthesis of Intermediate 2-1

10 g of 2,6-dibromo-3,7-dichloronaphthalene, naphthalen-2-ylboronic acid in a 250 ml round bottom flask (RBF) ) 9.8 g was dissolved in 40 ml of tetrahydrofuran (THF) and heated and stirred at 45 ° C. After 10 minutes, 15.6 g of K ₂ CO ₃ was dissolved in 30 ml of H ₂ O and put into a round bottom flask (RBF). Thereafter, 144 mg of BTP (Pd(t-Bu ₃ P) ₂ ) catalyst was added. The temperature was raised to 80 °C and the reaction proceeded for about 7 hours. After cooling to room temperature, the organic layer was separated, and ethyl acetate (EA)/distilled water extraction was performed twice. Thereafter, the separated organic layer was treated with activated carbon and MgSO ₄ , stirred for 15 minutes or more, and then filtered through a Celite layer. The obtained crude material was adsorbed onto silica, and then purified by medium pressure liquid chromatography (MPLC) using dichloromethane (DCM)/ethyl acetate (EA). The separated product was dissolved in dichloromethane (DCM), crystallized by a precipitation method in which it was added dropwise to hexane (HEX), and then dried to obtain intermediate 2-1 as a white solid.

Synthesis of Intermediate 2-2

Intermediate 2-1 in a 250 ml round bottom flask (RBF) 10 g, 6-(4,4,5,5-tetramethyl-1,3,2-dioxabolan-2-yl)naphthalen-2-ol (6-(4,4,5,5-tetramethyl-1 12.1 g of ,3,2-dioxaborolan-2-yl) naphthalen-2-ol) was dissolved in 35 ml of tetrahydrofuran (THF) and heated and stirred at 40°C. After 10 minutes, 12.3 g of K ₂ CO ₃ was dissolved in 25 ml of H ₂ O and put into a round bottom flask (RBF). Then, 114 mg of BTP (Pd(t-Bu ₃ P) ₂ ) catalyst was added. The temperature was raised to 85 °C and the reaction proceeded for 10 hours. After cooling to room temperature, the organic layer was separated, and ethyl acetate (EA)/distilled water extraction was performed twice. Thereafter, the separated organic layer was treated with activated carbon and MgSO ₄ , stirred for 15 minutes or more, and then filtered through a Celite layer. The obtained crude material was dissolved in tetrahydrofuran (THF), silica was added, stirred for 30 minutes, and filtered through a Celite layer. After removing the solvent, the filtered solution was crystallized by adding tetrahydrofuran (THF) and hexane, stirring for 15 minutes, and filtering to obtain intermediate 2-2.

Synthesis of monomer 2

After dissolving 10 g of intermediate 2-2, 3.3 g of ethylene carbonate, and 416 mg of K ₂ CO ₃ in 30 ml of dimethylacetamide (DMAc) in a 250 ml round bottom flask (RBF), the external temperature was raised to 130 ^o C and stirred to react made it After 3 hours, 0.06 g of NaOH and 2.5 ml of ethylene glycol were added and further stirred for 1 hour. After cooling to room temperature, when H ₂ O was added, crystallization proceeded. After filtering, it was dissolved in tetrahydrofuran (THF), adsorbed on silica, stirred for 30 minutes, and then filtered on a Celite layer. Methanol (MeOH) was added to the filtered solution to crystallize it, and then dried to obtain monomer 2.

1H NMR (500 MHz): δ = 8.65 (s, 4H), 8.04-7.99 (m, 6H), 7.80-7.78 (m, 4H), 7.60-7.55 (m, 6H), 7.40-7.38 (m, 6H) ), 7.22 (d, 2H), 7.16 (d, 2H), 4.89 (s, 2H), 4.38 (t, 4H), 3.69 (t, 4H)

3. Synthesis of Monomer 3

Synthesis of Intermediate 3-1

10 g of 2,6-dibromo-3,7-dichloronaphthalene in a 250 ml round bottom flask (RBF), (9-phenyl-9H-carbazol-3-yl ) 16.3 g of boronic acid ((9-phenyl-9H-carbazol-3-yl) boronic acid) was dissolved in 40 ml of tetrahydrofuran (THF) and heated and stirred at 45 ° C. After 10 minutes, 15.6 g of K ₂ CO ₃ was dissolved in 30 ml of H ₂ O and put into a round bottom flask (RBF). Then, 144 mg of BTP (Pd(t-Bu ₃ P) ₂ ) catalyst is added. The temperature was raised to 80 °C and the reaction proceeded for about 7 hours. After cooling to room temperature, the organic layer was separated, and ethyl acetate (EA)/distilled water extraction was performed twice. Thereafter, the separated organic layer was treated with activated carbon and MgSO ₄ , stirred for 15 minutes or more, and then filtered through a Celite layer. The obtained crude material was adsorbed onto silica, and then purified by medium pressure liquid chromatography (MPLC) using dichloromethane (DCM)/ethyl acetate (EA). The separated product was dissolved in dichloromethane (DCM), crystallized by a precipitation method in which it was added dropwise to hexane (HEX), and then dried to obtain intermediate 3-1 as a white solid.

Synthesis of Intermediate 3-2

Intermediate 3-1 in a 250 ml round bottom flask (RBF) 10g, 4-(4,4,5,5-tetramethyl-1,3,2-dioxabolan-2-yl)phenol (4-(4,4,5,5-tetramethyl-1,3,2 -dioxaborolan-2-yl)phenol) 6.5 g was dissolved in 25 ml of tetrahydrofuran (THF) and heated and stirred at 40 ° C. After 10 minutes, 8.1 g of K ₂ CO ₃ was dissolved in 15 ml of H ₂ O and put into a round bottom flask (RBF). Then, 75 mg of BTP (Pd(t-Bu ₃ P) ₂ ) catalyst was added. The temperature was raised to 85 °C and the reaction proceeded for 10 hours. After cooling to room temperature, the organic layer was separated, and ethyl acetate (EA)/distilled water extraction was performed twice. Thereafter, the separated organic layer was treated with activated carbon and MgSO ₄ , stirred for 15 minutes or longer, and then filtered through a celite layer. The obtained raw material was dissolved in tetrahydrofuran, silica was added, stirred for 30 minutes, and filtered through a layer of celite. After removing the solvent, the filtered solution was crystallized by adding tetrahydrofuran (THF) and hexane, stirring for 15 minutes, and filtering to obtain a solid intermediate 3-2.

Synthesis of monomer 3

After dissolving 10 g of intermediate 3-2, 2.8 g of ethylene carbonate, and 348 mg of K ₂ CO ₃ in 25 ml of dimethylacetamide (DMAc) in a 250 ml round bottom flask (RBF), the temperature was raised to 130 ° C and reacted by stirring. . After 3 hours, 0.05 g of NaOH and 2.1 ml of ethylene glycol were added and further stirred for 1 hour. After cooling to room temperature, when H ₂ O was added, crystallization proceeded. After filtering, it was dissolved in tetrahydrofuran (THF) and adsorbed on silica, stirred for 30 minutes, and then filtered through a celite layer. Methanol was added to the filtered solution to crystallize and then dried to obtain monomer 3.

1H NMR (500 MHz): δ = 8.63 (s, 4H), 8.32 (d, 2H), 8.16-8.13 (m, 4H), 7.80 (s, 2H), 7.71 (d, 4H), 7.65-7.50 ( m, 14H), 7.21 (t, 2H), 7.00 (d, 4H), 4.90 (s, 2H), 4.42 (t, 4H), 3.70 (t, 4H)

4. Synthesis of Monomer 4

Synthesis of Intermediate 4-1

2,6-dibromo-3,7-dichloronaphthalene (2,6-dibromo-3,7-dichloronaphthalene) 10g, dibenzo[b,d]thiophene-2-ylbo 13.0 g of ronic acid (dibenzo[b,d]thiophen-2-ylboronic acid) was dissolved in 40ml of tetrahydrofuran and heated and stirred at 45°C. After 10 minutes, 15.6 g of K ₂ CO ₃ was dissolved in 30 ml of H ₂ O and put into a round bottom flask (RBF). Thereafter, 144 mg of BTP (Pd(t-Bu ₃ P) ₂ ) catalyst was added. The temperature was raised to 80 °C and the reaction proceeded for about 7 hours. After cooling to room temperature, the organic layer was separated, and ethyl acetate/distilled water extraction was performed twice. Thereafter, the separated organic layer was treated with activated carbon and MgSO ₄ , stirred for 15 minutes or longer, and then filtered through a celite layer. After the obtained crude material was adsorbed on silica, medium pressure liquid chromatography (mplc) purification was performed with dichloromethane (DCM)/ethyl acetate (EA). The separated product was dissolved in dichloromethane (DCM), crystallized by precipitation by dropwise addition to hexane, and then dried to obtain intermediate 4-1 as a white solid.

Synthesis of Intermediate 4-2

Intermediate 4-1 in a 250 ml round bottom flask (RBF) 10g, 4-(4,4,5,5-tetramethyl-1,3,2-dioxabolan-2-yl)phenol (4-(4,4,5,5-tetramethyl-1,3,2 -dioxaborolan-2-yl)phenol) 8.2 g was dissolved in 25 ml of tetrahydrofuran (THF) and heated and stirred at 40 ° C. After 10 minutes, 9.8 g of K ₂ CO ₃ was dissolved in 15 ml of H ₂ O, and this was put into a round bottom flask (RBF). Then, 91 mg of BTP (Pd(t-Bu ₃ P) ₂ ) catalyst was added. The temperature was raised to 85 °C and the reaction proceeded for 10 hours. After cooling to room temperature, the organic layer was separated, and ethyl acetate/distilled water extraction was performed twice. Thereafter, the separated organic layer was treated with activated carbon and MgSO ₄ , stirred for 15 minutes or longer, and then filtered through a celite layer. The obtained raw material was dissolved in tetrahydrofuran, silica was added, stirred for 30 minutes, and filtered through a layer of celite. After removing the solvent, the filtered solution was crystallized by adding tetrahydrofuran and hexane, stirred for 15 minutes, and filtered to obtain a solid intermediate 4-2.

Synthesis of monomer 4

After dissolving 10 g of intermediate 4-2, 3.3 g of ethylene carbonate, and 408 mg of K ₂ CO ₃ in 30 ml of dimethylacetamide (DMAc) in a 250 ml round bottom flask (RBF), the temperature was raised to 130 ° C and reacted by stirring. . After 3 hours, 0.06 g of NaOH and 2.5 ml of ethylene glycol were added and further stirred for 1 hour. After cooling to room temperature, when H ₂ O was added, crystallization proceeded. After filtering, it was dissolved in tetrahydrofuran, adsorbed on silica, stirred for 30 minutes, and then filtered through a celite layer. Methanol was added to the filtered solution to crystallize and then dried to obtain monomer 4.

1H NMR (500 MHz): δ = 8.62 (s, 4H), 8.47 (d, 2H), 8.33 (s, 2H), 8.14-8.12 (m, 4H), 7.99-7.95 (m, 4H), 7.70 ( d, 4H), 7.55-7.45 (m, 4H), 7.00 (d, 4H), 4.92 (s, 2H), 4.34 (t, 4H), 3.69 (t, 4H)

Monomer Synthesis of Comparative Example 1

3,3′-((naphthalene-2,6-diylbis(4,1-phenylene))bis(oxy))bis(propan-1-ol)(3,3 30g of '-((naphthalene-2,6-diylbis(4,1-phenylene))bis(oxy))bis(propan-1-ol)) and 15g of triethylamine were added to 200ml of dichloromethane. melted After replacing with a nitrogen atmosphere, it was cooled to 0°C in an ice bath. After dissolving 15.8 g of acryloyl chloride in 100 ml of dichloromethane, it was slowly added dropwise to the reaction solution. After stirring overnight, the solvent was removed using a rotary evaporator, and the resulting crude was extracted once using water and dichloromethane. The extracted organic solvent was extracted twice using 1% aqueous hydrochloric acid solution and saturated NaCl aqueous solution. After adding Na ₂ SO ₄ and stirring for 10 minutes to remove moisture, the mixture was dried using a rotary vacuum evaporator. The dried material was recrystallized using dichloromethane and hexane to obtain a solid.

1H NMR (500 MHz): δ = 7.99 (d, 2H), 7.64-7.61 (m, 6H), 7.42 (d, 2H), 7.01 (d, 2H), 6.42 (dd, 2H), 6.14 (dd, 2H), 5.38 (dd, 2H), 4.28 (t, 4H), 4.18 (t, 4H), 2.12 (m, 4H)

Preparation of Resin 1

250ml beaker-type reactor (3-hole top/beaker-type bottom) and a heating mantle (heating mantle) first bind a magnetic drive and a stirring bar to adjust the height, and then 11.82g of the monomer 1 and bis(2-hydroxy Ethyl)terephthalate (Bis(2-hydroxyethyl)terephthalate) 15g, 2,2'-(((9H-fluorene-9,9-diyl)bis(4,1-phenylene))bis(oxy))bis (ethane-1-ol)(2,2'-(((9H-fluorene-9,9-diyl)bis(4,1-phenylene))bis(oxy))bis(ethan-1-ol)) 25.88 g and catalyst titanium (IV) butoxide (Titanium (IV) butoxide) 0.044g were added while measuring each mass to prepare a composition for preparing a resin.

Again, the height-adjusted magnetic drive and stirrer rod were attached to the reactor, the overhead mechanical stirrer was installed vertically, and the _N2 tube and condenser were installed, and the silicon tube and 3-way A glass cock and an oil bubbler were connected. In order to reduce the formation of by-products due to the temperature difference at the top of the reactor, the temperature was raised to 260 ° C using a heating band. Polymer polymerization was carried out by first maintaining the composition for preparing the resin under normal pressure and room temperature under nitrogen purging for 30 minutes, and then gradually raising and heating the composition while stirring at 100 rpm. After the temperature reached 200℃, the flow of nitrogen was stopped, the inlet was closed, and a vacuum pump was connected to gradually lower the pressure inside the reactor to remove by-products. The final temperature was 260℃~270℃ and the pressure was 1 Torr or less. Resin 1 was prepared by proceeding a polymerization reaction until the torque increased.

Preparation of Resin 2

Resin 2 was prepared in the same manner as in Resin 1, except that 11.82 g of Monomer 1 was changed to 17.77 g of Monomer 2 in the preparation of Resin 1.

Preparation of Resin 3

Resin 3 was prepared in the same manner as in Resin 1, except that 11.82 g of the monomer 1 was changed to 20.85 g of the monomer 3 in the preparation of the resin 1.

Preparation of Resin 4

Resin 4 was prepared in the same manner as in Resin 1, except that 11.82 g of Monomer 1 was changed to 18.06 g of Monomer 4 in the preparation of Resin 1.

Preparation of Comparative Example Resin 1

Comparative Example Resin 1 was prepared in the same manner as in Resin 1, except that 11.82 g of the monomer 1 was changed to 12.67 g of the monomer of Comparative Example 1 in the preparation of the resin 1.

Preparation of Comparative Example Resin 2

Comparative Example Resin 2 was prepared by the same manufacturing method as Resin 1, except that the monomer 1 was not applied in the preparation of Resin 1.

experimental example.

The molecular weight and molecular weight distribution of the polymerized resin sample were confirmed through gel permeation chromatography (GPC), and a thermogram was obtained using differential scanning calorimetry (DSC) to determine thermal characteristics. In order to measure the refractive index and the Abbe number, a result value according to the wavelength of light was obtained using an ellipsometer after film formation.

For the molecular weight through gel permeation chromatography (GPC), tetrahydrofuran (THF, stabilized with BHT (butylated hydroxytoluene)) was used as a solvent, and the resin sample was dissolved in tetrahydrofuran at a concentration of 1.0 mg/1 ml, and the syringe The result was obtained by injecting a solution prepared by filtering with a syringe filter and measuring at 40 ° C., which is shown in Table 1 below. A Waters RI detector was used and two columns of Agilent PLgel MIXED-B were used.

Differential scanning calorimetry (DSC) was measured to determine the glass transition temperature (Tg) of the resin. A resin sample of 5.5 mg to 8.5 mg was heated to 270 ° C under N ₂ flow, cooled, and then heated at a heating rate of 10 ° C for the second heating, and the glass transition temperature (Tg) was obtained on the graph obtained by scanning. It is listed in Table 1.

To measure the refractive index and Abbe number of the resin, a polymer solution prepared by dissolving a sample of the resin powder obtained by polymerization in dimethylacetamide in a solvent of 10% by weight based on the total weight of the polymer solution was spin-coated on a silicon wafer at 220 After coating at a rotational speed of rpm and forming a film with a thickness of 20 μm, the result values according to the wavelength of light were obtained using an ellipsometer at 20 ° C., which are shown in Table 1 below. Specifically, the refractive index is measured at a wavelength of 589 nm, and the Abbe number is measured by measuring the refractive index (n _D , n _F , n _C ) at D (589 nm), F (486 nm), and C (656 nm) wavelengths, respectively. The Abbe number was obtained by the following formula.

Abbe number=(n _D -1)/(n _F - n _C )

profit Mn (g/mol) Mw
(g/mol) Tg(℃) refractive index
(589 nm) Abe number Example 1 One 18,000 26,000 139.9 1.691 18.5 Example 2 2 15,000 23,000 140.7 1.701 18.9 Example 3 3 14,000 20,000 144.0 1.721 19.0 Example 4 4 18,000 22,000 141.6 1.719 17.6 Comparative Example 1 Comparative Example Resin 1 12,000 18,000 130.1 1.660 17.0 Comparative Example 2 Comparative Example Resin 2 4,000 8,000 152 1.650 16.0

In Table 1, Mn means a number average molecular weight, Mw means a weight average molecular weight, Tg is a glass transition temperature, and a refractive index is a value measured at a wavelength of 589 nm.

According to Table 1, it can be confirmed that the refractive indices of Examples 1 to 4 are higher than those of Comparative Examples 1 and 2.

Thus, the resin according to the present invention includes the unit represented by Formula 1, and since the core structure of Formula 1 is a naphthalene group, the molecular volume is small and the packing ability is excellent, so the refractive index of the resin is excellent. was able to confirm In addition, an arylene group in which L1 and L2 are substituted or unsubstituted; Alternatively, in the case of an electron-rich substituent such as a substituted or unsubstituted heteroarylene group, it was confirmed that the refractive index of the resin can be further improved by increasing the electron density of the structure represented by Formula 1.

According to Table 1, the number average molecular weight and weight average molecular weight of Examples 1 to 4 were higher than those of Comparative Examples 1 and 2, confirming that the processability of the resin according to the present invention was excellent.

In addition, the glass transition temperature (Tg) of Examples 1 to 4 satisfies 150 ° C or less, preferably 135 ° C or more and 145 ° C or less, thereby satisfying the physical properties for producing a resin having a high refractive index desired in the present invention. confirmed that it can.

Claims (13)

A resin comprising a unit represented by Formula 1 below:
[Formula 1]

In Formula 1,
Ar1 and Ar2 are the same as or different from each other, and each independently hydrogen; A substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,
R1 is hydrogen; Or a substituted or unsubstituted alkyl group,
r1 is an integer from 0 to 4, and when r1 is 2 or more, 2 or more R1s are the same as or different from each other,
L1 and L2 are the same as or different from each other, and each independently represents a substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group,
l1 and l2 are the same as or different from each other, and are each independently an integer of 1 or 2, and when l1 and l2 are each 2, the structures in parentheses are the same as or different from each other,
L is a direct bond; or -CO-L'-;
L' is a substituted or unsubstituted arylene group,
X1 to X4 are the same as or different from each other, and are each independently O; or S,
Z1 and Z2 are the same as or different from each other, and each independently a substituted or unsubstituted alkylene group; Or a substituted or unsubstituted cycloalkylene group,
a and b are the same as or different from each other, and each independently represent an integer from 1 to 10, and when a and b are each 2 or more, the structures in parentheses are the same as or different from each other,
* means a site connected to the main chain of the resin. The method according to claim 1, L1 and L2 are the same as or different from each other, each independently a substituted or unsubstituted arylene group having 6 to 30 carbon atoms; Or a resin that is a substituted or unsubstituted heteroarylene group having 3 to 30 carbon atoms. The method according to claim 1, Ar1 and Ar2 are the same as or different from each other, and each independently hydrogen; A substituted or unsubstituted alkyl group having 1 to 30 carbon atoms; A substituted or unsubstituted aryl group having 6 to 30 carbon atoms; Or a resin that is a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms. The resin according to claim 1, wherein Z1 and Z2 are the same as or different from each other, and are each independently a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms. The resin according to claim 1, wherein X1 to X4 are O. The resin according to claim 1, wherein the resin has a weight average molecular weight of 19,000 g/mol to 200,000 g/mol. The resin according to claim 1, wherein the resin has a glass transition temperature (Tg) of 135 °C to 150 °C. The resin according to claim 1, wherein the resin has a refractive index of 1.67 to 1.75 measured at a wavelength of 589 nm. A compound represented by Formula 1a; and
A method for producing a resin according to any one of claims 1 to 8, comprising the step of polymerizing a composition for preparing a resin comprising a polyester precursor or a polycarbonate precursor:
[Formula 1a]

In Formula 1a, the definitions of Ar1, Ar2, R1, r1, L1, L2, l1, l2, X1 to X4, Z1, Z2, a and b are as defined in Formula 1 above. The method according to claim 9, wherein the polyester precursor is represented by the following formula A, and the polycarbonate precursor is represented by the following formula B:
[Formula A]

[Formula B]

In the formulas A and B,
Ra1, Ra2, Rb1 and Rb2 are the same as or different from each other, and each independently a substituted or unsubstituted alkyl group; Or a substituted or unsubstituted aryl group,
L' is a substituted or unsubstituted arylene group. A resin composition comprising the resin according to any one of claims 1 to 8. A molded article comprising the resin composition according to claim 11. The molded article according to claim 12, wherein the molded article is an optical lens.