KR20210038240A - Preparation method of polyurethane copolymer - Google Patents

Abstract

According to the present invention, it is possible to prepare a high-strength polyurethane copolymer having excellent stability, causing little environmental hazard, and having excellent heat resistance and transparency. The method for preparing a polyurethane copolymer includes a step of polymerizing by adding a diol compound represented by chemical formula 1, a diisocyanate compound represented by chemical formula 2, and a capping agent.

Description

Manufacturing method of polyurethane copolymer {PREPARATION METHOD OF POLYURETHANE COPOLYMER}

The present invention relates to a method for producing a high-strength polyurethane copolymer having excellent stability and low environmental hazard, and excellent heat resistance and transparency.

Since polyurethane was synthesized by Otto Bayer in the late 1930s, it is used as an important additive in adhesives, coatings, and paints, and is a polymer compound widely used as a binder for inks and paints.

In general, polyurethanes are obtained by reaction of polyester glycols or polyether glycols with diisocyanates. As a typical polyester glycol, a polyester glycol having a molecular weight of about 1500 g/mol to about 3000 g/mol obtained from ethylene glycol, adipic acid, etc. is used, and as the diisocyanate, tolylene diisocyanate [TDI] or the like is used.

Polyurethane synthesizes a high molecular weight prepolymer having isocyanate groups at both ends of the molecule by reacting an excess of diisocyanate with polyester glycol or polyether glycol. In addition, diamine, amino alcohol, glycol, etc. are added to increase the chain length and at the same time It can also be produced by carrying out a crosslinking reaction.

In the polyurethane prepared in this way, the end of the polymer ends with -OH group or -NCO group. Polyurethane ending in -NCO group has several weaknesses. One is that it reacts with water _{to generate CO 2} , so it has low bonding strength and the other is that it is toxic. And, since the reaction between alcohol and diisocyanate proceeds even at room temperature, there is a risk that the reaction continues to proceed as long as the reactor is alive.

Therefore, the development of a process capable of providing a high-strength polyurethane copolymer with excellent heat resistance and transparency, as well as securing storage stability by blocking the terminal isocyanate groups of highly reactive polyurethanes so that they are not reactive, is continuing. Is being demanded.

The present invention is to provide a method for producing a high-strength polyurethane copolymer having excellent stability and low environmental hazard, and excellent heat resistance and transparency.

In addition, the present invention is to provide a polymer resin composition comprising a polyurethane copolymer prepared by the method as described above.

The present invention includes a step of polymerization reaction by introducing a diol compound represented by the following formula (1), a diisocyanate compound represented by the following formula (2), and a capping agent,

The capping agent is an alcohol compound or a polyhydric acid anhydride containing at least one from the group consisting _{of a C 6-60} aryl group, a C _6-60 cycloalkyl group, and a C _{7-60 aralkyl group, polyurethane} It provides a method for producing a copolymer.

[Formula 1]

In Formula 1,

R ₁ to R ₄ are each independently hydrogen, hydroxy, nitro, cyano, C _1-10 alkyl, C _1-10 alkoxy, C _1-10 haloalkyl, C _1-10 haloalkoxy, or C _6-20 Is one of the aryls,

L ₁ and L ₂ are each independently one of -S-, -O-, or -SO ₂ -,

L ₃ and L ₄ are each independently one of a single bond, C _1-10 alkylene, C _3-15 cycloalkylene, or C _6-30 arylene,

[Formula 2]

In Chemical Formula 2,

T ₁ is a divalent organic group.

In addition, the present invention provides a polymer resin composition comprising a polyurethane copolymer prepared by the above-described method.

In addition, the present invention provides an optical lens or optical article comprising the cured product of the polymer resin composition.

Hereinafter, a method for preparing a polyurethane copolymer according to a specific embodiment of the present invention, a polymer resin composition including a polyurethane copolymer prepared therefrom, and an optical lens will be described in more detail.

The terms used in the present specification are only used to describe exemplary embodiments, and are not intended to limit the present invention.

Singular expressions include plural expressions unless the context clearly indicates otherwise.

In the present specification, terms such as'include','have', or'have' are used to describe implemented features, numbers, steps, components, or combinations thereof, and one or more other features, numbers, or steps , Components, combinations thereof, or the possibility of addition are not excluded.

In addition, in the present specification, when each layer or element is referred to as being formed'on' or'on' of each layer or element, it means that each layer or element is formed directly on each layer or element, or It means that a layer or element may be additionally formed between each layer, on the object, or on the substrate.

The present invention will be described in detail below and exemplify specific embodiments, as various modifications can be made and various forms can be obtained. However, this does not limit the present invention to a specific form of disclosure, and it should be understood that all changes, equivalents, and substitutes included in the spirit and scope of the present invention are included.

In the present specification, terms including ordinal numbers such as'first' and'second' are used for the purpose of distinguishing one component from other components, and are not limited by the ordinal number. For example, within the scope of the present invention, a first element may be referred to as a second element, and similarly, a second element may be referred to as a first element.

In the present specification, the term “resin” refers to a polymer or a copolymer, wherein the polymer refers to a homopolymer composed of a single repeating unit, and the copolymer refers to a composite polymer containing two or more repeating units. In the specification, the copolymer refers to a composite polymer containing two or more kinds of repeating units.

In the present specification, the term'substitution' means that other functional groups are bonded instead of a hydrogen atom in the compound, and the position to be substituted is not limited as long as the position at which the hydrogen atom is substituted, that is, the position where the substituent can be substituted, , Two or more substituents may be the same or different from each other.

In the present specification, the term'substituted or unsubstituted' refers to deuterium; Halogen group; Cyano group; Nitro group; Hydroxy group; Carbonyl group; Ester group; Imide group; Amide group; Primary amino group; Carboxyl group; Sulfonic acid group; Sulfonamide group; Phosphine oxide group; Alkoxy group; Aryloxy group; Alkyl thioxy group; Arylthioxy group; Alkyl sulfoxy group; Arylsulfoxy group; Silyl group; Boron group; Alkyl group; Cycloalkyl group; Alkenyl group; Aryl group; Aralkyl group; Aralkenyl group; Alkylaryl group; Alkoxysilylalkyl group; Arylphosphine group; Or it means substituted or unsubstituted with one or more substituents selected from the group consisting of a heterocyclic group containing one or more of N, O, and S atoms, or substituted or unsubstituted with two or more substituents connected among the above-exemplified substituents. . For example, the'substituent to which two or more substituents are connected' may be a biphenyl group. That is, the biphenyl group may be an aryl group or may be interpreted as a substituent to which two phenyl groups are connected.

In the present specification, the alkyl group is a monovalent functional group derived from alkane and may be linear or branched, and the number of carbon atoms of the linear alkyl group is not particularly limited, but is preferably 1 to 20. Further, the branched chain alkyl group has 3 to 20 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, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 1-ethyl- Propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, 2,6-dimethylheptan-4-yl, and the like, but are not limited thereto. The alkyl group may be substituted or unsubstituted.

In the present specification, the haloalkyl group refers to a functional group in which a halogen group is substituted with the above-described alkyl group, and examples of the halogen group include fluorine, chlorine, bromine, or iodine. The haloalkyl group may be substituted or unsubstituted.

In the present specification, the alkylene group is a divalent functional group derived from alkane, and the description of the above alkyl group may be applied except that these are divalent functional groups. For example, as a linear or branched type, it may be a methylene group, an ethylene group, a propylene group, an isobutylene group, a sec-butylene group, a tert-butylene group, a pentylene group, a hexylene group, and the like. The alkylene group may be substituted or unsubstituted.

In the present specification, the cycloalkylene group is a divalent functional group derived from cycloalkane, and may be monocyclic or polycyclic, and is not particularly limited, but the number of carbon atoms is 3 to 20. According to another exemplary embodiment, the cycloalkylene group has 3 to 10 carbon atoms. Specifically, cyclopropylene, cyclobutylene, cyclopentylene, 3-methylcyclopentylene, 2,3-dimethylcyclopentylene, cyclohexylene, 3-methylcyclohexylene, 4-methylcyclohexylene, 2,3 -Dimethylcyclohexylene, 3,4,5-trimethylcyclohexylene, 4-tert-butylcyclohexylene, cycloheptylene, cyclooctylene, bicyclo[2,2,1]heptylene, etc. Not limited. The cycloalkylene group may be substituted or unsubstituted.

In the present specification, the alkoxy group may be a straight chain, branched chain, or cyclic chain. Although the number of carbon atoms of the alkoxy group is not particularly limited, it is preferably 1 to 30 carbon atoms. Specifically, methoxy, ethoxy, n-propoxy, isopropoxy, i-propyloxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentyloxy, neopentyloxy, Isopentyloxy, n-hexyloxy, 3,3-dimethylbutyloxy, 2-ethylbutyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, benzyloxy, p-methylbenzyloxy, etc. May be, but is not limited thereto.

In the present specification, the halo alkoxy group refers to a functional group in which a halogen group is substituted with the alkoxy group described above, and examples of the halogen group include fluorine, chlorine, bromine, or iodine. The haloalkoxy group may be substituted or unsubstituted.

In the present specification, the aryl group is a monovalent functional group derived from arene, is not particularly limited, but preferably has 6 to 30 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. The aryl group may be a phenyl group, a biphenyl group, or a terphenyl group, but the monocyclic aryl group is not limited thereto. The polycyclic aryl group may be a naphthyl group, an anthracenyl group, a phenanthryl group, a pyrenyl group, a perylenyl group, a chrysenyl group, a fluorenyl group, and the like, but is not limited thereto. The aryl group may be substituted or unsubstituted.

In the present specification, the arylene group is a divalent functional group derived from arene, and the description of the aryl group described above may be applied except that these are divalent functional groups. For example, it may be a phenylene group, a biphenylene group, a terphenylene group, a naphthalene group, a fluorenyl group, a pyrenyl group, a phenanthrenyl group, a perylene group, a tetracenyl group, an anthracenyl group, and the like. The arylene group may be substituted or unsubstituted.

, 또는

는 다른 치환기에 연결되는 결합을 의미한다. In this specification,

, or

Means a bond connected to another substituent.

In the present specification, a multivalent organic group is a residue in which a plurality of hydrogen atoms bonded to an arbitrary compound has been removed, and examples thereof include a divalent organic group, a trivalent organic group, and a tetravalent organic group. . As an example, a tetravalent organic group derived from cyclobutane refers to a residue in which any 4 hydrogen atoms bonded to cyclobutane have been removed.

In the present specification, a direct bond or a single bond means that no atom or group of atoms exists at the corresponding position and is connected by a bonding line.

In this specification, the weight average molecular weight means the weight average molecular weight in terms of polystyrene measured by the GPC method. In the process of measuring the weight average molecular weight in terms of polystyrene measured by the GPC method, a commonly known analysis device, a detector such as a differential refractive index detector, and a column for analysis can be used, and the commonly applied temperature Conditions, solvents, and flow rates can be applied. For a specific example of the measurement conditions, an Agilent mixed B column was used and a Waters alliance 2695 instrument was used, the evaluation temperature was 40° C., Tetrahydrofuran was used as a solvent, the flow rate was 1.0 mL/min, and the sample was It is prepared at a concentration of 1 mg/1 mL, and then supplied in an amount of 100 μL, and the value of Mw can be calculated using a calibration curve formed using a polystyrene standard. The molecular weight of polystyrene standards is 2000 g/mol, 10000 g/mol, 30000 g/mol, 70000 g/mol, 200000 g/mol, 700000 g/mol, 2000000 g/mol, 4000000 g/mol, 10000000 g/mol. 9 types were used.

According to an embodiment of the present invention, a method for producing a polyurethane copolymer comprising the step of polymerizing a diol compound represented by Formula 1, a diisocyanate compound represented by Formula 2, and a capping agent. Can be provided.

As a result of continuous research, the present inventors reacted by adding a specific diol compound, a diisocyanate compound, and a specific capping agent together in the polyurethane copolymerization reaction, thereby reacting at the maximum ratio of terminal isocyanate groups of the highly reactive polyurethane. It was confirmed that it was possible to manufacture a high-strength polyurethane copolymer having excellent heat resistance and transparency, while minimizing damage due to environmental hazards, as well as securing storage stability by blocking the terminal group without this.

In more detail, looking at the manufacturing method of the polyurethane copolymer of the embodiment, as much as possible by minimizing the molar ratio of the capping agent to the urethane monomer including the diol compound represented by Formula 1 and the diisocyanate compound represented by Formula 2 Blocking can be made so that there is no reactivity in proportion, and accordingly, deterioration of physical properties such as heat resistance and transparency due to the capping agent Tui can be minimized.

In general, it is known to react urethane-forming monomers first to prepare a prepolymer, and then add a capping agent to block the ends.However, the end capping agent reacts less than the addition due to the long chain of the prepolymer during end capping after preparing the prepolymer. Thus, there is a problem in that more end capping agents must be added, and accordingly, the phenomenon of deteriorating physical properties due to the capping agent input increases.

Accordingly, in the present invention, a capping agent is simultaneously added with a monomer constituting a polymer basic structure, that is, a diol compound represented by Formula 1 and a diisocyanate compound represented by Formula 2, without a separate prepolymer production process, It is possible to prepare a high-strength polyurethane copolymer having excellent heat resistance and transparency with maximum terminal blocking effect with minimum input.

Specifically, the diol compound represented by Formula 1 is in a molar ratio of about 0.98 to about 1, or a molar ratio of about 0.985 to about 0.995, or a molar ratio of 0.99 based on 1 mole of the diisocyanate compound represented by Formula 2. You can put it in. In addition, the capping agent may be added in a molar ratio of about 0.01 to about 0.22 molar ratio, or about 0.015 to about 0.21 molar ratio, about 0.02 to about 0.2 molar ratio, or 0.2 based on 1 mol of the diisocyanate compound represented by Formula 2. I can. In particular, in the case of manufacturing by simultaneously adding a capping agent and a urethane monomer without going through the prepolymer step, the molar ratio of the capping agent based on 1 mol of the diisocyanate compound is about 0.01 mol or more or about 0.015 mol or more, or More than about 0.02 mol may be added. However, if the capping agent is added in excess of about 0.22 mol, the polymer reaction is quickly terminated, and the molecular weight may be produced short so that it cannot have the properties of the polymer, and thus about 0.22 mol or less, or about 0.21 mol or less, or about 0.2 It can be put in mol or less.

In addition, the capping agent uses an alcohol compound or a polyhydric acid anhydride containing at least one type from the group consisting _{of a C 6-60} aryl group, a C _6-60 cycloalkyl group, and a C _{7-60 aralkyl group.} Characterized in that. Specifically, the capping agent is benzyl alcohol, phthalic anhydride, and 5-norbornene-exo-2,3 dicarboxylic anhydride. ) And one or more selected from the group consisting of.

In particular, in the case of capping the end by using a urethane bond as the capping agent, alcohol, such as benzyl alcohol, in which alcohol is not directly attached to the benzene ring, is added to the capping agent in which the alcohol is directly attached to the benzene ring, such as phenol. Compared with the thermal stability after bonding, it is suitable as a capping agent, and alkyl alcohol is more suitable than aryl alcohol. In addition, when capping the end using an imide bond, phthalic anhydride, and 5-norbornene-exo-2,3 dicarboxylic anhydride (5-norbornene-exo-2,3-dicarboxylic anhydride) ), an acid anhydride having two or more rings may be used, and these compounds may be used in various isomeric forms such as cis or trans (tarns).

Hereinafter, a method for preparing a polyurethane copolymer of one embodiment will be described in detail for each step.

First, in the manufacturing method of one embodiment, the diol compound that generates the prepolymer is represented by the following formula (1).

[Formula 1]

In Formula 1,

R ₁ to R ₄ are each independently hydrogen, hydroxy, nitro, cyano, C _1-10 alkyl, C _1-10 alkoxy, C _1-10 haloalkyl, C _1-10 haloalkoxy, or C _6-20 Is one of the aryls,

L ₁ and L ₂ are each independently one of -S-, -O-, or -SO ₂ -,

L ₃ and L ₄ are each independently one of a single bond, a C _1-10 alkylene group, a C _3-15 cycloalkylene group, or a C _6-30 arylene group,

Specifically, in Formula 1, each of R ₁ to R ₄ may be hydrogen, methyl, or phenyl, and preferably hydrogen.

Specifically, in Formula 1, L ₁ and L ₂ may each independently be one of -O- or -S-, preferably -O-.

Specifically, in Formula 1, L ₃ and L ₄ may each be C _2-6 alkylene. For example, L ₃ and L ₄ may each be ethylene, propylene, butylene, pentylene, or hexylene, and preferably, L ₃ and L ₄ may be ethylene (-CH ₂ -CH ₂ -). .

The diol compound represented by Chemical Formula 1 is not greatly limited, but may be, for example, represented by Chemical Formula 1-1.

[Formula 1-1]

In addition, the diisocyanate compound that reacts with the above-described diol compound to produce urethane is represented by the following formula (2).

[Formula 2]

In Chemical Formula 2,

T ₁ is a divalent organic group.

In the diisocyanate compound represented by Formula 2, T ₁ may be a divalent organic group, and specifically, may be a divalent organic group represented by Formula 3 below.

[Formula 3]

In Chemical Formula 3,

R ₅ and R ₆ are each independently halogen, cyano, C _1-10 alkyl, C _2-10 alkenyl, C _1-10 alkoxy, C _1-10 fluoroalkyl, or C _1-10 fluoroalkoxy. Is one,

p and q are each independently an integer of 0 to 4,

L ₅ , L ₆ , and L ₇ are each independently a single bond, -S-, -O-, -SO ₂ -, C _1-10 alkylene, C _3-15 cycloalkylene, or C _6-30 aryl Is one of the ren,

k, m, and n are each independently an integer of 0 to 3, provided that at least one of k, m, and n is not 0.

Specifically, T ₁ may be a divalent organic group represented by Formula 3-1 or Formula 3-2 below.

[Chemical Formula 3-1]

[Chemical Formula 3-2]

,

Preferably, the diisocyanate compound is methylene diphenyl diisocyanate (MDI), p-phenylene diisocyanate (PPDI), tolylene-2,4-diisocyanate (2,4-TDI), tolylene-2 ,6-diisocyanate (2,6-TDI), xylylene diisocyanate (XDI), 1,5-naphthalene diisocyanate (NDI), hexamethylene diisocyanate (HDI), 4,4'-methylene dicyclohexyl di Any selected from the group consisting of isocyanate (H12MDI), 1,4-cyclohexane diisocyanate (CHDI), isophorone diisocyanate (IPDI), and 1,3-bis(isocyanatomethyl)cyclohexane (H6XDI) You can use more than one. Specifically, methylene diphenyl diisocyanate (MDI) or xylylene diisocyanate (XDI) can be mentioned.

The polymerization reaction may be carried out under atmospheric pressure, pressure, or reduced pressure conditions, but is preferably carried out at atmospheric pressure from the viewpoint of securing process efficiency and stability. In addition, the polymerization reaction temperature may be about 50 ^o C to about 200 ^o C, preferably about 65 ^o C to about 180 ^o C, or about 80 ^o C to about 170 ^o C, or about 85 ^o C From about 165 ^o C or about 100 ^o C to 150 ^o C, the polymerization process may be performed. In addition, the polymerization reaction may be stirred for about 10 minutes or more or about 10 minutes to about 100 hours, or about 20 minutes or more or about 20 minutes to about 24 hours while maintaining the reaction temperature as described above.

As an example, the polymerization reaction may be performed without a separate catalyst component or by adding a catalyst component. For example, when performing the reaction by adding a catalyst component, an amidine-based catalyst, a tin-based catalyst, or a bismuth-based catalyst may be used. Examples of the amidine-based catalyst include 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU, 1,8-Diazabicyclo[5.4.0]undec-7-ene), and the like. Tin-based catalysts include dibutyltin dilaurate, dibutyltin diacetate, and dibutyltin oxide, and bismuth-based catalysts include dibutylbismuth dilaurate, dibutylbismuth diacetate, and dibutylbismuth. Oxide, bismuth carboxylate, and the like. In addition, various metal catalysts known to effectively perform urethane reactions may be used without any limitation, but preferably 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU, 1,8- Amidine catalysts such as Diazabicyclo[5.4.0]undec-7-ene) can be used.

When the catalyst is added in this way, the molar ratio of about 0.01 to about 0.5, or about 0.015 to about 0.3, or about 0.02 to about 0.1 molar ratio based on the number of moles of the diol compound represented by Formula 1 You can put it in.

The method for producing a polyurethane copolymer according to the present invention, except for the above-described process conditions, is a method for producing a polyurethane copolymer, and any method well known in the art pertaining to the present invention can be applied without limitation. For example, any suitable method such as a solid-phase polymerization method or a solution polymerization method can be applied.

As an example, the method of preparing the polyurethane copolymer is diphenyl ether, 1-methyl-2-pyrrolidinone (NMP, 1-methyl-2-pyrrolidinone), dimethylformamide (DMF, dimethylformamide) , Dimethylacetamide (DMAC, dimethylacetamide) can be carried out using one or more kinds of organic solvents.

As an example, the method of preparing the polyurethane copolymer may perform a urethane reaction under an inert gas atmosphere, and specifically, may be performed under a nitrogen or argon atmosphere.

The polyurethane copolymer obtained through the capping process as described above is not greatly limited, but may be, for example, represented by Formula 5 below.

[Formula 5]

In Formula 5, n is a value that satisfies the range of 10≦n≦100, and preferably may have a range of 15≦n≦90 or 20≦n≦80 or 25≦n≦75.

Meanwhile, according to another embodiment of the present invention, a polymer resin composition including the polyurethane copolymer is provided.

The polyurethane copolymer has a molar ratio of a terminal group derived from the diol compound and a terminal group derived from the capping agent of about 1: 0.019 to about 1:0.8, or about 1: 0.05 to about 1:0.75 , Or about 1: 0.11 to about 1:0.7, or about 1: 0.115 to about 1:0.69 or about 1:0.117 to about 1:0.68, preferably about 1:0.22 to about 1:0.67. have.

Specifically, the molar ratio of terminal groups of the polyurethane copolymer can be measured through nuclear magnetic resonance spectroscopy (NMR) analysis. ^{For example, 1} H-NMR can be measured using an NMR device (Bruker 700 MHz). At this time, after preparing a sample by dissolving the polyurethane copolymer in an organic solvent such as dimethyl sulfoxide-d ₆ (DMSO-d ₆ ), the NMR spectrum may be measured. By integrating the NMR peak obtained as a result of the NMR measurement in this way, the equivalent ratio of the repeating unit from a diol compound (e.g., BPEF) and a repeating unit derived from a diisonate compound (e.g., MDI) and a diol compound present at the terminal (e.g., BPEF) It is possible to calculate the molar ratio of the alcohol end group derived from and the end group derived from the capping agent. For a more specific measurement method, reference may be made to Test Example 2 to be described later.

In addition, in the polyurethane copolymer, the terminal isocyanate group of the polyurethane copolymer is end-capping by a urethane reaction or imidation reaction, and the transmittance (480 nm) of the 20 wt% polymer solution is 60% or more, or The weight average molecular weight (Mw) is 5000 g/mol to 100000 g/mol, or the refractive index (n _D ) is 1.6 or more or 1.6 to 1.75, or the Abbe number (V _D ) is about 20 or more Or, or the glass transition temperature (Tg) may be at least 120 ℃ or 120 ℃ to 180 ℃.

For example, the polyurethane copolymer may have a transmittance (480nm) of a 20wt% polymer solution of about 60% or more, or about 70% or more, or about 75% or more, or about 80% or more. Specifically, the transmittance of the polyurethane copolymer can be measured using ultraviolet visible light spectroscopy (UV-VIS spectroscopy, Cary 8454 manufactured by Agilent Technologies). Specifically, after dissolving the polyurethane copolymer at a concentration of 20 wt% in an organic solvent such as NMP, transmittance can be measured at a wavelength of 480 nm by UV-VIS spectroscopy (Cary 8454 manufactured by Agilent Technologies).

In addition, the weight average molecular weight of the polyurethane copolymer is about 5000 g/mol to about 100000 g/mol, or about 7000 g/mol to about 80000 g/mol, or about 9000 g/mol to about 65000 g/mol, Or from about 10000 g/mol to about 55000 g/mol. When the molecular weight of the polyurethane copolymer is less than about 5000 g/mol, optical transmittance and heat resistance may decrease, and when the molecular weight exceeds about 100000 g/mol, a problem may occur due to a decrease in fluidity.

In addition, the polyurethane copolymer has a glass transition temperature (Tg) of about 120 ^o C to about 180 ^o C, or about 130 ^o C to about 175 ^o C, or about 145 ^o C to about 172 ^o C, or about 160 ^o C to about 170 ^o C. When the glass transition temperature (Tg) of the polyurethane copolymer is ^{less than about 120 o} C, heat resistance may be poor, making it unsuitable for use as an optical lens, and ^{when it exceeds about 180 o} C, the flow characteristics are poor and extrusion As the temperature rises, there may be a problem that the extrusion and injection conditions become difficult.

For example, the glass transition temperature (Tg) of the polyurethane copolymer may be measured using a Differential Scanning Calorimeter (DSC, METTLER TOLEDO, DSC 3+). Specifically, by increasing the temperature of the polyurethane copolymer sample at a ^{rate of 10 o} C/min from a temperature below room temperature, a part where the heat flow changes in the DSC (Differential Scanning Calorimeter, manufactured by Mettler) curve appears. The intermediate value between the temperature at which the change starts and the temperature at which the change ends is taken as the glass transition temperature (Tg). ^{For example, in a nitrogen gas atmosphere, the polyurethane copolymer was heated at 10 o} C/min in the range ^{of 50 o} C to 230 ^o C by raising the temperature for a polyurethane copolymer sample of 1 mg to 10 mg, ^{and then 230 o} C. In the section of heating ^{at 10 o C/min to 230 o} C after holding for 10 minutes at 10 ^o C/min after cooling at 10 ^{o C/min from 230 o} C to 50 ^{o C, keeping it at 50 o} C for 10 minutes and then heating again to 230 o C at 10 o C/min. Measure the glass transition temperature (Tg) shown. For a specific method of measuring the glass transition temperature, Test Example 1 described below may be referred to.

In addition, the refractive index (n _D ) of the polyurethane copolymer is about 1.6 or more or about 1.6 to about 2.0, or about 1.62 or more or about 1.62 to about 1.75, or about 1.64 or more or about 1.64 to about 1.72, or It may be greater than or equal to about 1.646 or from about 1.646 to about 1.70. In particular, the refractive index of the polyurethane copolymer represents _{a value (n D) measured at a wavelength of 590.2 nm.} When the refractive index of the polyurethane copolymer is less than 1.60, the refractive index is poor and thus it is inappropriate for use as an optical lens, or a technical problem in which miniaturization of a camera is impossible may occur. The higher the refractive index is, the better it is, but in general, the Abbe number tends to decrease as the refractive index increases. Thus, the Abbe number of the polyurethane copolymer is about 20 or more, or about 20 to about 40, or about 21 or more, or about 21 to about 38, or about 22 or more, or about 22 to about 36, or about 22.5 or more or about 22.5 To about 34, or about 22.9 or more, or about 22.9 to about 32, or about 23 or more, or about 23 to about 30.

Preferably, the polyurethane copolymer has a refractive index (n _D ) of about 1.6 or more, and an Abbe number (V _D ) of about 20 or more.

As an example, the refractive index (n _D ) and Abbe number (V _D ) of the polyurethane copolymer can be measured using Spectroscopy Ellipsometry (Ellipsometer M-2000, JA Woollam). I can. Specifically, the refractive index and Abbe number were measured psi and delta values for samples having a thickness of 0.5 µm to 1 µm at room temperature (about 24.8 °C to about 25.2 °C) using JAWoolam's Spectroscopic ellipsometry (M-2000), and Gen Using the -Osc model, psi and delta values for a region of 245 nm to 1700 nm are measured through fitting, and the Abbe number can be calculated as the result. For example, the copolymer of the polyurethane copolymer is dissolved in an organic solvent (eg, 1-methyl-2-pyrrolidinone, NMP) to prepare a solution having a concentration of about 10 wt%, and the solution is applied to a glass substrate using a spin coating machine. After pouring, spin for 30 seconds at a speed of 1000 rpm to obtain a sample and ^{dry it at 80 o} C for 10 minutes, 120 ^o C for 10 minutes, 170 ^o C for 10 minutes, and 210 ^o C for 10 minutes to obtain a thickness of 0.2 μm. After preparing a 1.0 μm film as a sample, the refractive index and Abbe number may be measured using the ellipsometer (M-2000). _{In particular, the refractive index is a value (n D} ) measured at a wavelength D (590.2 nm) at about 24.8° C. to about 25.2° C., and specifically at a temperature of about 25° C. _{In addition, by measuring the refractive index (n D} , n _F , n _C ) at the wavelengths D (590.2 nm), F (485.5 nm), and C (656.7 nm), respectively, the Abbe number (V _D ) was calculated by the following equation 1 You can get it.

[Equation 1]

V _D = (n _D -1)/(n _F -n _C )

The polyurethane copolymer prepared according to the present invention is a high refractive material having a refractive index of 1.6 or more, and has a Tg of 120° C. or more, so that there is no deformation of the lens even at room temperature and high temperature, and it can be said to be a useful transparent resin as a camera lens material.

In addition, the polyurethane copolymer has a yellowness of 2.0 or less, 1.0 or more to 2.0 or less, 1.5 or more to 2.0 or less, 1.5 or more, as measured according to the measurement method of ASTM E313 (D1925) using Color-Eye 7000A (Xrite). To 1.9 or less. If the polyurethane copolymer has a yellowness of more than 2.0, transparency may be poor, and thus it may be inappropriate for use as an optical lens. Here, the yellowness of the polyurethane copolymer may be a value measured based on a thickness of 10 μm to 20 μm of a sample, and specifically, may be a value measured based on a thickness of 15 μm of a sample.

Meanwhile, the polymer resin composition of the embodiment includes the polyurethane copolymer, and the polyurethane copolymer may be included alone in powder form, or an organic solvent may be included together with the polyurethane copolymer.

Specifically, when the polyurethane copolymer is included alone, the polymer resin composition may be used in the form of a pallet.

Alternatively, in the case where the polymer resin composition includes a polyurethane copolymer and an organic solvent, the organic solvent is not largely limited, but 1-methyl-2-pyrrolidinone (NMP, 1-methyl-2-pyrrolidinone), It may contain at least one of dimethylformamide (DMF), dimethylacetamide (DMAC), and tetrahydrofuran (THF). In this case, the content of the organic solvent may be 30 parts by weight or more and 80 parts by weight or less based on 100 parts by weight of the polyurethane copolymer. By adjusting the content of the organic solvent within the above-described range, the solid content of the polymer resin composition can be controlled.

The polymer resin composition of the embodiment may further include additives such as a catalyst, a crosslinking agent, a UV absorber, and a filler.

Meanwhile, according to another embodiment of the present invention, an optical lens including a cured product of the polymer resin composition is provided.

The cured product refers to a material obtained through the curing process of the polymer resin composition of the embodiment.

As the optical lens includes the cured product of the polymer resin composition of the above-described embodiment, it may exhibit excellent optical properties and properties capable of realizing heat resistance.

The optical lens can be produced by injecting the above-described polyurethane copolymer into a desired shape, and other processing methods other than injection can be applied.

As described above, since the polyurethane copolymer according to the present invention has a high refractive index and a high Abbe number, it is possible to manufacture a lens with a thinner thickness compared to the conventional optical lens material.

Meanwhile, according to another embodiment of the present invention, an optical article including a cured product of the polymer resin composition is provided.

The cured product refers to a material obtained through the curing process of the polymer resin composition of the embodiment.

As the optical article includes the cured product of the polymer resin composition of the above-described embodiment, it may exhibit characteristics capable of implementing excellent optical properties and heat resistance.

As described above, according to the present invention, a high-strength polyurethane copolymer having excellent heat resistance and transparency while securing storage stability by blocking the terminal isocyanate groups of the highly reactive polyurethane so that they are not reactive, minimizing damage due to environmental hazards, is provided. Can be manufactured.

^{1 is a graph showing a comparison of 1} H-NMR spectrum measurement results for polyurethane copolymers prepared according to Example 1, Comparative Example 2, and Comparative Example 3 as in Test Example 2 to be described later.
^{2 is a graph showing comparison of 1} H-NMR spectrum measurement results for the polyurethane copolymers prepared according to Example 4 and Comparative Example 3 as in Test Example 2 to be described later.

Hereinafter, a preferred embodiment is presented to aid the understanding of the present invention. However, the following examples are provided for easier understanding of the present invention, and the contents of the present invention are not limited thereto.

[Example]

Example 1: Preparation of polyurethane copolymer (BPEF-MDI-BzO)

In Example 1, a polyurethane copolymer (BPEF-MDI-BzO) in which a benzyl alcohol-derived substituent group was bonded to a BPEF-MDI polyurethane terminal was prepared.

First, connect the mechanical stirrer and the condenser to a 250 mL 3-neck round bottom flask (rbf), add nitrogen to create a nitrogen atmosphere, and use 9,9-bis 4-(2-hydroxyethoxy)phenyl as the first monomer. Reaction by adding fluorine (BPEF) and 4,4'-methylene diphenyl diisocyanate (MDI) as a second monomer, and benzyl alcohol (BzO) as a capping agent together with a solvent of N-methyl-2-pyrrolidin-2-one (NMP) Made it. In this case, the solid content was 35% by weight (wt%), and the total amount of the solution was about 80 g. The input ratio of the first monomer, the second monomer, and the capping agent was BPEF:MDI:BzO=0.99:1:0.02 in a molar ratio, and the mechanical stirrer ^{was reacted at 100°} C for 2 hours at 150 rpm for 2 hours, and the polyurethane copolymer (BPEF-MDI-BzO) was prepared.

After completion of the urethane polymerization reaction, the solid content of the polyurethane copolymer produced with the tetrahydrofuran (THF) solvent was diluted to 10 wt% or less, and then methanol was added from about 5 times to about 10 times the volume of the mixed solution including the total polyurethane copolymer. After the pear was added to precipitate and filtered under reduced pressure, the polyurethane copolymer thus obtained was dissolved again in THF, precipitated with methanol, filtered under reduced pressure, and dried overnight in a vacuum oven at ^{about 90 o} C to about 180 ^{o C.} A urethane copolymer (BPEF-MDI-BzO) powder was obtained.

Example 2: Preparation of polyurethane copolymer (BPEF-MDI-BzO)

As shown in Table 1 below, the first monomer 9,9-bis 4-(2-hydroxyethoxy)phenyl fluorine (BPEF) and the second monomer 4,4'-methylene diphenyl diisocyanate (MDI), and the capping agent benzyl alcohol ( A polyurethane copolymer (BPEF-MDI-BzO) was prepared in the same manner as in Example 1, except that the input ratio of BzO) was changed to the molar ratio BPEF:MDI:BzO=0.99:1:0.2.

Example 3: Preparation of polyurethane copolymer (BPEF-MDI-NDA)

In Example 3, a polyurethane copolymer (BPEF-MDI-NDA) was prepared in which a substituent derived from cis-5-norbornene-exo-2,3-dicarboxylic anhydride was bonded to the end of BPEF-MDI polyurethane.

First, connect the mechanical stirrer and the condenser to a 250 mL 3-neck round bottom flask (rbf), add nitrogen to create a nitrogen atmosphere, and use 9,9-bis 4-(2-hydroxyethoxy)phenyl as the first monomer. N-methyl-2-pyrrolidin- fluorine (BPEF) and 4,4'-methylene diphenyl diisocyanate (MDI) as a second monomer, and cis-5-norbornene-exo-2,3-dicarboxylic anhydride (NDA) as a capping agent. It was introduced and reacted with a 2-one solvent. In this case, the solid content was 35 wt%, and the total solution amount was about 80 g. The input ratio of the first monomer, the second monomer, and the capping agent was BPEF:MDI:NDA =0.99:1:0.02 in a molar ratio, and the mechanical stirrer speed was ^{reacted at 100 o} C at 150 rpm for 1 hour and then at 150 ^o C. By reacting for 15 minutes, a polyurethane copolymer (BPEF-MDI-NDA) was prepared.

After completion of the urethane polymerization reaction, precipitation, filtration under reduced pressure, and drying were performed in the same manner as in Example 1, and a final polyurethane copolymer (BPEF-MDI-NDA) powder was obtained.

Example 4: Preparation of polyurethane copolymer (BPEF-MDI-NDA)

As shown in Table 1 below, the first monomer 9,9-bis 4-(2-hydroxyethoxy)phenyl fluorine (BPEF) and the second monomer as 4,4'-methylene diphenyl diisocyanate (MDI), and the capping agent cis- Polyurethane copolymer in the same manner as in Example 3, except that the addition ratio of 5-norbornene-exo-2,3-dicarboxylic anhydride (NDA) was changed to the molar ratio BPEF:MDI:NDA=0.99:1:0.2. BPEF-MDI-NDA) was prepared.

Example 5: Preparation of polyurethane copolymer (BPEF-MDI-PA)

In Example 5, a polyurethane copolymer (BPEF-MDI-PA) in which a phthalic anhydride-derived substituent group was bonded to a BPEF-MDI polyurethane terminal was prepared.

First, connect the mechanical stirrer and the condenser to a 250 mL 3-neck round bottom flask (rbf), add nitrogen to create a nitrogen atmosphere, and use 9,9-bis 4-(2-hydroxyethoxy)phenyl as the first monomer. Fluorine (BPEF) and 4,4'-methylene diphenyl diisocyanate (MDI) as a second monomer, and phthalic anhydride (PA) as a capping agent were added together with a -methyl-2-pyrrolidin-2-one (NMP) solvent to react. . In this case, the solid content was 35 wt%, and the total solution amount was about 80 g. The input ratio of the first monomer, the second monomer, and the capping agent was BPEF:MDI:PA =0.99:1:0.02 in molar ratio, and the mechanical stirrer speed was ^{reacted at 100 o} C for 5 minutes at ^{150 rpm and then at 150 o} C. By reacting for 15 minutes, a polyurethane copolymer (BPEF-MDI-PA) was prepared.

After completion of the urethane polymerization reaction, precipitation, filtration under reduced pressure, and drying were performed in the same manner as in Example 1, and a final polyurethane copolymer (BPEF-MDI-PA) powder was obtained.

Comparative Example 1: Preparation of polyurethane copolymer (BPEF-MDI-MA)

Comparative Example 1 was prepared a polyurethane copolymer (BPEF-MDI-MA) in which a maleic anhydride-derived substituent was bonded to the BPEF-MDI polyurethane terminal.

First, connect the mechanical stirrer and the condenser to a 250 mL 3-neck round bottom flask (rbf), add nitrogen to create a nitrogen atmosphere, and use 9,9-bis 4-(2-hydroxyethoxy)phenyl as the first monomer. Fluorine (BPEF) and 4,4'-methylene diphenyl diisocyanate (MDI) as a second monomer, and maleic anhydride (MA) as a capping agent were added together with an N-methyl-2-pyrrolidin-2-one solvent to react. At this time, the solid content was 40 wt%, and the total amount of solution was about 80 g. The input ratio of the first monomer, the second monomer, and the capping agent was BPEF:MDI:MA =0.99:1:0.02 in a molar ratio, and the mechanical stirrer speed was ^{reacted at 100 o} C for 15 minutes at ^{150 rpm and then at 150 o} C. By reacting for 15 minutes, a polyurethane copolymer (BPEF-MDI-MA) was prepared.

After completion of the urethane polymerization reaction, precipitation, filtration under reduced pressure, and drying were performed in the same manner as in Example 1, and a final polyurethane copolymer (BPEF-MDI-MA) powder was obtained.

Comparative Example 2: Preparation of polyurethane copolymer (BPEF-MDI-BzO)

Comparative Example 2 is to prepare a polyurethane copolymer (BPEF-MDI-BzO) in which a substituent derived from benzyl alcohol is bonded to a BPEF-MDI polyurethane terminal. A polyurethane copolymer (BPEF-MDI-BzO) was prepared after a long period of time by adding a pinting agent.

First, connect the mechanical stirrer and the condenser to a 250 mL 3-neck round bottom flask (rbf), add nitrogen to create a nitrogen atmosphere, and use 9,9-bis 4-(2-hydroxyethoxy)phenyl as the first monomer. Fluorine (BPEF) and 4,4'-methylene diphenyl diisocyanate (MDI) as a second monomer were added together with an N-methyl-2-pyrrolidin-2-one solvent to react. At this time, the solid content was 35% by weight (wt%), the total amount of the solution was about 80g, and the input ratio of the first monomer and the second monomer was BPEF:MDI=0.99:1 in molar ratio. After reacting the mechanical stirrer at 150 rpm for ^{25 minutes at 100 o} C, the capping agent, benzyl alcohol (BzO), was used as a second monomer to a 0.02 molar ratio based on the number of moles of 4,4'-methylene diphenyl diisocyanate (MDI). After ^{soaking, it was reacted at 100°} C. for 2 hours to prepare a polyurethane copolymer (BPEF-MDI-BzO).

After completion of the urethane polymerization reaction, precipitation, filtration under reduced pressure, and drying were performed in the same manner as in Example 1, and a final polyurethane copolymer (BPEF-MDI-BzO) powder was obtained.

Comparative Example 3: Preparation of polyurethane copolymer (BPEF-MDI)

In Comparative Example 3, a polyurethane copolymer (BPEF-MDI) was prepared without using a separate capping agent.

First, connect the mechanical stirrer and the condenser to a 250 mL 3-neck round bottom flask (rbf), add nitrogen to create a nitrogen atmosphere, and use 9,9-bis 4-(2-hydroxyethoxy)phenyl as the first monomer. Fluorine (BPEF) and 4,4'-methylene diphenyl diisocyanate (MDI) as a second monomer were added together with an N-methyl-2-pyrrolidin-2-one solvent to react. At this time, the solid content was 35 wt%, and the total amount of the solution was about 80 g. The input ratio of the first and second monomers was BPEF:MDI=1:1 in molar ratio, and the mechanical stirrer speed was ^{reacted at 100 o} C at 150 rpm for 2 hours to prepare a polyurethane copolymer (BPEF-MDI). I did.

After completion of the urethane polymerization reaction, precipitation, filtration under reduced pressure, and drying were performed in the same manner as in Example 1, and a final polyurethane copolymer (BPEF-MDI) powder was obtained.

When preparing the polyurethane copolymer prepared according to the above Examples and Comparative Examples, the molar ratio of the reactants, the type of the capping agent, and the order of addition are as shown in Table 1 below.

First monomer Second monomer Capping agent Time of capping agent input Input molar ratio of monomer and camping agent* Example 1 BPEF MDI BzO At the same time as the monomer 0.99:1:0.02 Example 2 BPEF MDI BzO At the same time as the monomer 0.99:1:0.2 Example 3 BPEF MDI NDA At the same time as the monomer 0.99:1:0.02 Example 4 BPEF MDI NDA At the same time as the monomer 0.99:1:0.2 Example 5 BPEF MDI PA At the same time as the monomer 0.99:1:0.02 Comparative Example 1 BPEF MDI MA At the same time as the monomer 0.99:1:0.02 Comparative Example 2 BPEF MDI BzO After monomer reaction 0.99:1:0.02 Comparative Example 3 BPEF MDI none none 1:1:0 * The input molar ratio of the monomer and the camping agent is expressed as the input molar ratio of the first monomer: the second monomer: the capping agent.

[Test Example]

Test Example 1

With respect to the polyurethane copolymer powder (powder) prepared according to Examples 1-5 and Comparative Example 1, physical properties were evaluated in the following manner. The results are shown in Table 2 below.

1) Weight average molecular weight (Mw) and molecular weight distribution (PDI, Mw/Mn)

The weight average molecular weight (Mw) and number average molecular weight (Mn) of the polymer were measured using gel permeation chromatography (GPC, gel permeation chromatography, manufactured by Water), and the weight average molecular weight was divided by the number average molecular weight to obtain a molecular weight distribution (PDI). , polydispersity index, Mw/Mn) was calculated.

Specifically, a Waters alliance 2695 instrument was used using an Agilent mixed B column, the evaluation temperature was 40°C, Tetrahydrofuran was used as a solvent, the flow rate was 1.0 mL/min, and the sample was at a concentration of 1 mg/1 mL. After preparation, it was supplied in an amount of 100 µl, and the values of Mw and Mn were calculated using a calibration curve formed using a polystyrene standard. The weight average molecular weight of the polystyrene standard specimen is 2000 g/mol, 10000 g/mol, 30000 g/mol, 70000 g/mol, 200000 g/mol, 700000 g/mol, 2000000 g/mol, 4000000 g/mol, 10000000 g 9 types of /mol were used.

2) Glass transition temperature (Tg)

The glass transition temperature of the polyurethane copolymers prepared in Examples 1-5 and Comparative Example 1 was measured. Specifically, DSC3+ equipment of Mettler Toledo was used to obtain a DSC curve (Differential Scanning Calorimetry Thermogram) under the following thermal history conditions for a sample of 1 mg to 10 mg in a nitrogen gas atmosphere.

-Primary heating: heating from 30 ^o C to 230 ^o C at ^{a heating rate of 10 o} C/min, then maintaining at 230 °C for 10 minutes

-Cooling: from 230 ^o C to 50 ^o C at a ^{rate of 10 o} C/min, then maintained for 10 minutes

-Secondary heating: from 50 ^o C to 230 ^o C at a ^{rate of 10 o} C/min.

The glass transition temperature (Tg) was measured from the middle point in the stepped curve indicating the glass transition phenomenon among the DSC curves.

3) Refractive index/ Abbe number

The refractive index (n _D ) and Abbe number (V _D ) of the polyurethane copolymer were measured using Spectroscopy Ellipsometry (Ellipsometer M-2000, JA Woollam).

Specifically, the refractive index and Abbe number were measured at psi and delta values for samples having a thickness of 0.5 μm to 1 μm at about 25° C. using JAWoolam's Spectroscopic ellipsometry (M-2000), and 245 using the Gen-Osc model. Optical constants (n, k) were measured through fitting for psi and delta values in the nm to 1700 nm region, and the Abbe number was calculated as the result. In particular, the refractive index of the polyurethane copolymer represents _{a value (n D) measured at a wavelength of 590.2 nm.}

First, the polyurethane copolymer is dissolved in an organic solvent (e.g., NMP, 1-methyl-2-pyrrolidinone) to prepare a concentration of about 10 wt%, and after pouring the solution on a glass substrate using a spin coating machine, A sample was obtained by spinning at a speed for 30 seconds to obtain a sample, followed by ^{drying at 80 o} C for 10 minutes, 120 ^o C for 10 minutes, 170 ^o C for 10 minutes, and 210 ^o C for 10 minutes to form a film with a thickness of 0.2 µm to 1.0 µm. After preparing a sample, the refractive index and Abbe number were measured using the ellipsometer (M-2000). In particular, the refractive index is a value measured at a wavelength D (590.2 nm) under the condition of a temperature of 25°C. _{In addition, by measuring the refractive index (n D} , n _F , n _C ) at the wavelengths D (590.2 nm), F (485.5 nm), and C (656.7 nm), respectively, the Abbe number (V _D ) was calculated by the following equation 1 Obtained.

[Equation 1]

V _D = (n _D -1)/(n _F -n _C )

4) transmittance (%)

The transmittance of the polyurethane copolymer was measured using ultraviolet visible light spectroscopy (UV-VIS spectroscopy, Cary 8454 manufactured by Agilent Technologies).

Specifically, the polyurethane copolymer was dissolved in an organic solvent (NMP) at a concentration of 20 wt%, and the transmittance was measured at a wavelength of 480 nm by UV-VIS spectroscopy (Cary 8454 manufactured by Agilent Technologies).

Mw
(g/mol) Mw/Mn Tg
( ^o C) Refractive index* Abbesu
(V _D ) Transmittance (%, at 480nm) n _C n _D n _F Example 1 25000 1.75 162 1.642 1.649 1.67 23 83 Example 2 22000 1.86 163 1.640 1.648 1.668 23.9 87 Example 3 34000 1.57 164 1.640 1.647 1.668 23.4 80 Example 4 27000 1.89 167 1.641 1.648 1.669 23.1 96 Example 5 51000 1.89 168 1.638 1.646 1.666 23.2 80 Comparative Example 1 44000 1.98 168 1.638 1.645 1.666 22.8 36 * Refractive indexes n _D , n _F , and n _C are values measured at wavelengths D (590.2 nm), F (485.5 nm), and C (656.7 nm), respectively.

As shown in Table 2, it was confirmed that the polyurethane copolymers according to Examples 1 to 5 of the present invention exhibited excellent end capping so that the refractive index was high and the Abbe number was minimized to be high, and the transmittance was also excellent at 80% or more. I can. On the other hand, in Comparative Example 1, maleic anhydride (MA) was used as the capping agent, but the capping agent blocked the ends and displayed color, resulting in a problem that the transmittance was significantly lowered to 36%, and was not suitable as a transparent material. Able to know.

Test Example 2

For the polyurethane copolymer powders prepared according to Examples 1, 2 and 4 and Comparative Examples 2 and 3, additionally, through nuclear magnetic resonance spectroscopy (NMR) analysis in the following manner. The molar ratio of the terminal groups was measured, and the results are shown in Table 3 below.

Specifically, NMR was measured using an NMR device (Bruker 700 MHz), and as a sample, the polyurethane copolymer _{was dissolved in a solvent of Dimethyl sulfoxide-d 6} (DDMSO-d ₆ ), and an NMR spectrum was measured. In the case of Example 4, since the sample was not dissolved in a solvent at room temperature, the sample was dissolved at a high temperature, and an NMR spectrum was measured at 100°C.

By integrating the NMR peak obtained as a result of the NMR measurement in this way, the equivalent ratio of the repeating unit from the diol compound (e.g., BPEF) to the repeating unit derived from the diisocyanate compound (e.g., MDI) and the diol compound (e.g., BPEF) present at the terminal The molar ratio of the alcohol end group derived from and the end group derived from the capping agent was calculated, and the results are shown in Table 3 below. Here, the'molar ratio of the equivalence ratio of BPEF and MDI' is a value calculated by the molar ratio of the NMR peak of MDI when the NMR peak of BPEF is set to 100 on a molar basis.As a specific example, the BPEF molar ratio by integrating peak 1 in FIG. Is converted to 100, and in the case of MDI, the molar ratio of MDI was calculated by integrating peak 11. The'molar ratio of the BPEF present at the end and the end group derived from the capping agent' is a value obtained by calculating the integral values of each peak of b and a in FIG. It is expressed as a relative value when converted to.

^{Specifically, 1} H-NMR spectrum measurement results of the polyurethane copolymers prepared according to Example 1, Comparative Example 2, and Comparative Example 3 were compared to FIG. 1, and prepared according to Example 4 and Comparative Example 3 ^{The results of the 1} H-NMR spectrum measurement of the polyurethane copolymer were compared to FIG. 2 and shown.

Example 1, Comparative Example 2, and Comparative Example 3 are ^{the methods described above based on the 1} H-NMR data of FIG. 1, and'molar ratio of the equivalent ratio of BPEF and MDI'and'BPEF present at the terminal and the terminal group derived from the capping agent. The molar ratio' was measured, and in Example 4 and Comparative Example 3 ^{, based on the 1} H-NMR data of FIG. 2, the'molar ratio of the equivalent ratio of BPEF and MDI'and'terminal there BPEF and capping agent mole ratio of the resulting end groups, a was measured in example 2, also in example 1 in the same manner as NMR spectrum measurement, and measuring the ^first from the H-NMR data, the molar ratio of the equivalent ratio of BPEF and MDI to the "And'molar ratio of the BPEF present at the terminal and the terminal group derived from the capping agent' were measured.

Molar ratio of equivalent ratio of BREF and MDI
(Based on ¹ H-NMR data) Molar ratio of the BPEF present at the terminal and the terminal group derived from the capping agent
(Based on ¹ H-NMR data) BPEF MDI BPEF Terminal substituent derived from capping agent Example 1 100 101.8 6.8 0.8 Example 2 100 101.6 5.9 3.9 Example 4 100 104 5.7 1.5 Comparative Example 2 100 100.1 5.5 0.1 Comparative Example 3 100 100 6 -

As shown in Table 3, it can be seen that the polyurethane copolymers according to Examples 1, 2, and 4 of the present invention have better end capping compared to Comparative Examples 2 and 3. Specifically, from the data in Table 3, the ratio of the diol and diisocyanate that actually constitutes the polymer and the ratio of the alcohol and the terminal capping agent ending in the terminal can be known, through which Examples 1, 2, and 4 are compared. When compared with Examples 2 and 3, it was confirmed that the end capping agent was well bonded to the polymer to block the end.

Particularly, when comparing Comparative Example 2 and Example 1, when the terminal is blocked after making a prepolymer as in Comparative Example 2, the molar ratio of BPEF present at the terminal is 5.5 based on the NMR peak of BPEF and derived from the capping agent. While the molar ratio of the terminal groups was only 0.1, in the case of manufacturing by simultaneous injection according to Example 1, the molar ratio of the BPEF present at the terminal was 6.8 and the molar ratio of the terminal groups derived from the capping agent was 0.8. Compared to Comparative Example 2, it can be seen that the terminal blockade is significantly increased by about 6.47 times.

Moreover, in the case of Comparative Example 2, after producing the prepolymer, an additional step of administering a capping agent was performed, whereas in the case of Example 1, terminal blockade can be achieved along with polymerization without such a prepolymer production step, so the overall process efficiency Can be significantly improved.

Claims (12)

Including a polymerization reaction by introducing a diol compound represented by the following Formula 1, a diisocyanate compound represented by the following Formula 2, and a capping agent
The capping agent is an alcohol compound or a polyhydric acid anhydride containing at least one type from the group consisting _{of a C 6-60} aryl group, a C _6-60 cycloalkyl group, and a C _{7-60 aralkyl group,}
Method for producing polyurethane copolymer:
[Formula 1]

In Formula 1,
R ₁ to R ₄ are each independently hydrogen, hydroxy, nitro, cyano, C _1-10 alkyl, C _1-10 alkoxy, C _1-10 haloalkyl, C _1-10 haloalkoxy, or C _6-20 Is one of the aryls,
L ₁ and L ₂ are each independently one of -S-, -O-, or -SO ₂ -,
L ₃ and L ₄ are each independently one of a single bond, C _1-10 alkylene, C _3-15 cycloalkylene, or C _6-30 arylene,
[Formula 2]

In Chemical Formula 2,
T ₁ is a divalent organic group.
The method of claim 1,
The diol compound is added in a molar ratio of 0.98 to 1 based on 1 mol of the diisocyanate compound, and the capping agent is added in a molar ratio of 0.01 to 0.22 based on 1 mol of the diisocyanate compound to react,
Method for producing a polyurethane copolymer.
The method of claim 1,
In the second step, the capping agent is at least one selected from the group consisting of benzyl alcohol, phthalic anhydride, and 5-norborene-exo-2,3 dicarboxylic anhydride,
Method for producing a polyurethane copolymer.
The method of claim 1,
Wherein L ₁ and L ₂ are -O- or -S-,
Wherein L ₃ and L ₄ are each C _2-6 alkylene,
Method for producing a polyurethane copolymer.
The method of claim 1,
The diol compound represented by Formula 1 is represented by the following Formula 1-1,
Method for producing a polyurethane copolymer.
[Formula 1-1]

.
The method of claim 1,
The T ₁ is a divalent organic group represented by the following formula (3),
Method for producing polyurethane copolymer:
[Formula 3]

In Chemical Formula 3,
R ₅ and R ₆ are each independently halogen, cyano, C _1-10 alkyl, C _2-10 alkenyl, C _1-10 alkoxy, C _1-10 fluoroalkyl, or C _1-10 fluoroalkoxy. Is one,
p and q are each independently an integer of 0 to 4,
L ₅ , L ₆ , and L ₇ are each independently a single bond, -S-, -O-, -SO ₂ -, C _1-10 alkylene, C _3-15 cycloalkylene, or C _6-30 aryl Is one of the ren,
k, m, and n are each independently an integer of 0 to 3, provided that at least one of k, m, and n is not 0.
The method of claim 1,
The diisocyanate compound represented by Formula 2 is methylene diphenyl diisocyanate, p-phenylene diisocyanate, tolylene-2,4-diisocyanate, tolylene-2,6-diisocyanate, xylylene diisocyanate, 1 ,5-naphthalene diisocyanate, hexamethylene diisocyanate, 4,4'-methylene dicyclohexyl diisocyanate, 1,4-cyclohexane diisocyanate, isophorone diisocyanate, and 1,3-bis(isocyanatomethyl) Any one or more selected from the group consisting of cyclohexane,
Method for producing a polyurethane copolymer.
The method of claim 1,
The polymerization reaction is carried out at 50 ^o C to 200 ^o C,
Method for producing a polyurethane copolymer.
A polymer resin composition comprising a polyurethane copolymer prepared by the method according to claim 1.
The method of claim 9,
In the polyurethane copolymer, the molar ratio of the terminal group derived from the diol compound and the terminal group derived from the capping agent is 1: 0.019 to 1: 0.8,
Polymer resin composition.
An optical lens comprising a cured product of the polymer resin composition of claim 9.
An optical article comprising a cured product of the polymer resin composition of claim 9.

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