JP2002088135A - Urethane copolymer and optical material using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a urethane copolymer from a nonequivalent reactive diisocyanate monomer and two kinds of diol monomers to be effectively reacted with, and a polyurethane having various refractive indexes by carrying out a monomer sequence control. SOLUTION: This urethane copolymer is represented by formula (R1 and R2 are each independently a hydrogen atom or a 1-10C alkyl group; R3 and R4 are each independently a bifunctional alcohol residue; n is 1-10; l and m are each an integer of 1-10,000). This optical material is obtained by using the urethane copolymer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ordered or random urethane copolymer having a diisocyanate having a non-equivalent reactivity as a monomer and a method for producing the same. The copolymer of the present invention is used for paints, foams, elastomers and the like. Further, according to the present invention, polyurethanes having different optical characteristics such as a refractive index can be obtained from the same raw material monomer, which is useful as an optical material.

[0002]

BACKGROUND OF THE INVENTION Copolymers obtained by the polymerization of two or more types of monomers have a polymer molecular chain composed of a skeleton derived from each monomer, and are obtained by blending two or more types of polymer compounds having a single skeleton. It is important as a functional polymer because it shows properties different from those of the polymer.

For example, in the polymerization of two radically reactive monomers of A and B, not only a polymer consisting of A and B alone, but also a reaction based on Q and e values, which are indicators of the reactivity of the monomers. Block copolymers (-AAAAABBBBB-) and alternating copolymers (-ABABABA
BABA-) can be obtained (New Polymer Experimental Science 2: Synthesis and Reaction of Polymer (1) Polymer Society).

On the other hand, in the case of a sequential polymerization system such as polyurethanes and polyamides, a monomer (XAX, X is a polymerization point) and a monomer having a polymerization point that effectively reacts with the monomer (YBY, Y are (Polymerization point) to obtain an inevitable alternating copolymer, but still another type of monomer (YCY)
In general, an alternating copolymer cannot be obtained when is used.

That is, one kind of monomer (XAX) and two kinds of monomers (YBY and Y
When (CY) is used, the prepolymer is first prepared from XAX and YBY.
It is possible to obtain a block copolymer (-ABABABABACACACAC-) by a method of charging monomers, such as preparing (-XABABABAXAX-) and further adding monomers XAX and YCY.
(Chemical Extra 27, Copolymer Synthesis and Properties, Chemical Doujin).

However, in the case of the successive polymerization reactive monomer, the reactivity of the polymerization point cannot be controlled as in the case of the radically reactive monomer, and an alternating copolymer (-ABACABACABACA-) is obtained from three kinds of monomers. It is extremely difficult.

[0007]

OBJECTS AND SUMMARY OF THE INVENTION A first object of the present invention is to produce an ordered polyurethane such as the aforementioned alternating copolymer in a sequential polymerization system. The present inventors have found that an alternating copolymer can be obtained by using a monomer having unequal reactivity in a molecule and two or more suitable monomers that effectively react with the monomer, and completed the present invention. did. More specifically, a urethane alternating copolymer is obtained from a non-equivalent reactive diisocyanate monomer having aromatic and aliphatic isocyanates in the molecule and two diol monomers effectively reacting with the diisocyanate monomer. . The present invention also produces other ordered polyurethanes and randomly arranged polyurethanes.

Another object of the present invention is to obtain a urethane copolymer having a different refractive index by changing the monomer arrangement using the same monomer raw material, and obtaining an optical material therefrom. The present inventors have found that a monomer having non-equivalent reactivity in a molecule and an ordered polyurethane obtained by controlling the monomer arrangement using two or more suitable monomers effectively reacting with the monomer are the same. It was found that the polymer materials had different refractive indices while having different compositions. According to the present invention,
For example, an ordered polyurethane is synthesized and refracted from a non-equivalent reactive diisocyanate monomer having aromatic and aliphatic isocyanates in the molecule, and ethylene glycol and 1,3-benzenedimethanol that effectively react with the monomer. Various materials with a ratio of 1.59 to 1.61 can be obtained.

The present invention provides the following formula:

[0010]

Embedded image (Wherein, R ₁ and R ₂ are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; R ₃ and R ₄ are each independently a dihydric alcohol residue; n is 1 to 10, 1 and m each represent an integer of 1 to 10000), and the first invention of the present application is represented by the following formula:

[0011]

Embedded image (Wherein, R ₁ and R ₂ are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; R ₃ and R ₄ are different dihydric alcohol residues. N is an integer of 1 to 10, x is 1 to
It means an integer of 10,000. The present invention provides an alternately polymerized urethane copolymer having a structural unit represented by the formula (1):

The second invention of the present application provides the following formulas (1a), (1b),
(1c) and (1d):

[0013]

Embedded image

[0014]

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[0015]

Embedded image

[0016]

Embedded image (In formulas (1a) to (1d), R ₁ and R ₂ are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; R ₃ and R ₄ are different dihydric alcohol residues. N Is an integer of 1 to 10, and x _a , x _b , x _c and x _d are integers of 1 to 2500.)

According to a third aspect of the present invention, the following formula is used:

[0018]

Embedded image (Wherein, R ₁ and R ₂ are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; R ₃ and R ₄ are different dihydric alcohol residues. N is an integer of 1 to 10, l and m
Means an integer of 1 to 10,000. The present invention provides a random urethane copolymer having a structural unit represented by the formula: Another invention of the present application provides a method for producing these urethane copolymers, and has the following formula:

[0019]

Embedded image (Wherein, R ₁ and R ₂ are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and n represents an integer of 1 to 10). On the other hand, two diol compounds are reacted by a predetermined method. Still another invention of the present application is to provide an optical material combining these polyurethanes having different refractive indexes.

Conventionally, a material obtained by combining a plurality of polymers having different refractive indexes is expected to be used for a plastic optical fiber or the like. However, even if polymers having different refractive indices are simply combined, many other characteristics such as thermal expansion coefficient and hygroscopicity are also different, and when combined as a material, problems such as cracking and warpage are likely to occur.

Optical properties such as the refractive index are related to the density of the material, and the density is related to the crystallinity of the material. That is, if polymers having different monomer sequences are synthesized from the same monomer,
There is a possibility that a polymer for an optical material having almost the same properties such as a coefficient of thermal expansion and hygroscopicity and different in only optical properties such as a refractive index may be obtained. In the optical material of the present invention, the intermolecular interaction of the polymer chains is different due to the difference in the monomer arrangement,
Therefore, it is assumed that the polymer solid structure, that is, the crystallinity changes.

In the polyurethane of the present invention, a diisocyanate monomer having asymmetric reactivity and a plurality of ordered polyurethanes having different refractive indices even with the same monomer composition using two kinds of symmetric diol monomers. To manufacture. That is, the two types of symmetric diol monomers are represented by A and B, respectively, and the structure of an ordered polyurethane obtained by using the aromatic isocyanate group of the diisocyanate monomer as a Head site and the aliphatic isocyanate group as a Tail site. Considering the following, (1) HH-TT ordered polyurethane in which A is bonded to the Head site of the diisocyanate monomer and B is bonded to the Tail site, (2) A and B are bonded in reverse order to HH (A) HH-TT ordered polyurethane,
(3) Orientation of diisocyanate monomer is HH-TT sequence, but HH-TT ordered polyurethane having no regularity at positions A and B (denoted as HH (A, B)), (4) diisocyanate Polyurethanes having a total of four types of arrangement of three types of regular polyurethanes and random polyurethanes, which are random polyurethanes having no regularity in the orientations of the monomers and the positions of A and B, can be produced.

Since the polyurethanes thus obtained have different monomer sequences, they have different intermolecular interactions and different molecular packings. As a result, a difference occurs in the solid structure, and even if the composition is the same, a difference in the density of the polymer occurs, and a polyurethane having different optical properties such as a refractive index is obtained (Sefer).
is, JC Polymer Handbook 3rd Ed .; Brandrup, J .:
and Immergut, EH Ed .; Wiley-Interscience: New
York, 1989, p16., VI, p451).

[0024]

DETAILED DESCRIPTION OF THE INVENTION In the present invention, the formula (1)
In the urethane copolymers represented by (1a) to (1d) and the formula (2), R ₁ and R ₂ are each independently hydrogen or a carbon atom having 1 carbon atom.
10 to 10 alkyl groups. R ₃ and R ₄ are each a dihydric alcohol residue and are different from each other. n is an integer of 1 to 10, and preferably 1 to 3. Also, x is 1 to
It is 10,000, and about 30 to 100 is practical.
In the formula (2), l and m are 1 to 10,000, and about 30 to 100 is practical.

Specific examples of the dihydric alcohol residue include linear aliphatic hydrocarbons such as ethylene group, trimethylene group and tetramethylene group, and branched aliphatic hydrocarbon groups such as 2-methyltrimethylene group. , Heteroatom-containing hydrocarbons such as 3-oxapentamethylene group, cyclic aliphatic hydrocarbons such as cyclohexylene group and steroid skeleton,
Aromatic hydrocarbons such as phenylene and biphenylene, and aliphatic-aromatic hydrocarbons such as 2,2-diphenylenepropane; 1,1,1,3,3,3-hexafluoro-2, Examples thereof include hydrocarbons composed of aliphatic, aromatic and hetero atoms such as 2-diphenylenepropane, and skeletons derived from bifunctional alcohols used as monomers described below are preferable.

In the first invention of the present application, among the copolymers of the formula (1), a preferred polymer is the following formula (4):

[0027]

Embedded image (Wherein, R ₃ , R ₄ and x are the same as described above). Such alternating polymers are preferred as paints, foams, elastomers and the like.

The formula (1a) of the second and third aspects of the present invention
In the copolymers of the formulas (1d) and (2), R ₁ and R ₂ are preferably hydrogen, and R ₃ and R ₄ are an ethylene glycol residue or a 1,3-benzenedimethanol residue. Is preferred. Thus, preferred polymers are of the formula:

[0029]

Embedded image (Wherein, l and m are the same as above).

In order to produce the alternating copolymer and the ordered urethane copolymer according to the first to third aspects of the present invention, a more reactive aromatic isocyanate group is first added to the diisocyanate monomer. Reaction with a diol monomer is performed, followed by a sequential reaction of reacting the aliphatic isocyanate group with another diol monomer.

On the other hand, to produce a random copolymer,
The diisocyanate and the diol compound are reacted at once.

(Diisocyanate monomer) The diisocyanate monomer used in the present invention is represented by the following formula:

[0033]

Embedded image It is represented by This diisocyanate monomer has two isocyanate groups in the molecule, one of which is directly bonded to an aromatic ring, and the other of which is bonded to an aromatically bonded carbon atom. Therefore, there is a difference in reactivity in the nucleophilic addition reaction of alcohol.
Here, R ₁ , R ₂ and n are the same as described above. The position of the isocyanate group may be any of the ortho, meta and para positions. Here, n is 1 or more, preferably an integer of 1 to 10. R ₁ and R ₂ are a hydrogen atom or an alkyl group, preferably an alkyl group having 1 to 10 carbon atoms such as a methyl group and an ethyl group. Accordingly, as the diisocyanate monomer, for example, diisocyanates such as isocyanatobenzyl isocyanate, isocyanatophenethyl isocyanate, α- (isocyanatophenyl) -ethyl isocyanate, and the like, and particularly isocyanate benzyl isocyanate ( The following formula (3a) is preferred.

[0034]

Embedded image

(Diols) In order to obtain an ordered polyurethane or a random polyurethane from the above-mentioned diisocyanate, two appropriate diols which effectively react with an isocyanate group are used. Examples of such diols include aliphatic diols such as ethylene glycol, diethylene glycol, pentanediol, heptanediol, dihydroxycyclohexane, isomannide, and 2,3-dihydroxybutane, and hydroquinones, bisphenol A, 4,4′-isopropylidene- Bis (2,6-methylphenol), 4,4 ′-(hexafluoroisopropylidene) diphenol, 4,4 ′-(hexafluoroisopropylidene) -bis (2,6-methylphenol),

4,4'-dihydroxybiphenyl, 4'-
[(N, N-dihydroxyethyl) amino] -4-nitroazobenzene, 4 '-[(N, N-dihydroxyethyl) amino] -4-methoxyazobenzene, 4'-[(N, N-dihydroxyethyl) amino ] -4-cyanoazobenzene, 4
-N, N-bis (2-hydroxyethyl) amino-2,2 '
Diols having a non-linear optical property functional group such as -dimethyl-4'-nitroazobenzene, 3,6-hydroxymethyl-9-heptylcarbazole, 2-hydroxymethyl-3- (N-benzyl-3-carbazolyl) propanol, 2-hydroxymethyl-3- (N-ethyl-3-
Carbazolyl) propanol, 2-hydroxymethyl-
Diols having a photocharge generating function such as 3- (N-heptyl-3-carbazolyl) propanol, 2,2 ′-[N
-[6-[(4-nitrophenylazo] phenyloxy] hexyl] iminodiethanol, 4-N, N-bis (2-hydroxyethyl) amino-4′-octylazobenzene,
4-N, N-bis (2-hydroxyethyl) amino-4'-
Hexylazobenzene, 4-N, N-bis (2-hydroxyethyl) amino-4′-octyloxyazobenzene,
4-N, N-bis (2-hydroxyethyl) amino-4'-
Butylazobenzene, 2- [6- [4'-methoxy-4-
Biphenyloxy) hexyl] propane-1,3-diol, 2- [6- [4'-butoxy-4-biphenyloxy)
Hexyl] propane-1,3-diol, 2- [6- [4 '
-Methoxy-4-biphenyloxy) butyl] propane-
Diols having a mesogen such as 1,3-diol, 2- [6- [4'-butoxy-4-biphenyloxy) butyl] propane-1,3-diol, N, N-dihydroxyethylisonicotinamide, N -Diols having an amino group capable of hydrogen bonding such as -phenyldiethanolamine, aromatic-containing diols such as 4,4 '-(1,3-adamantendiyl) diphenol, 2,6-pyridinedimethanol, and isosorbide And asymmetric diols such as hyodeoxycholic acid, chenodeoxycholic acid, dihydroxytetrahydronaphthalene and hydroxybenzyl alcohol.

In the present invention, two kinds may be selected from these diol compounds, but these may be aliphatic diol compounds, aromatic diol compounds or different. Among these, particularly preferred combinations include ethylene glycol and 1,3-benzenedimethanol, and ethylene glycol and 4 ′-[N, N-
(Dihydroxyethyl) amino] -4-nitroazobenzene, 4 '-[N, N- (dihydroxyethyl) amino]-
4-nitroazobenzene and 4 '-[N, N- (dihydroxyethyl) amino] -4-methoxyazobenzene are exemplified.

(Method for Producing an Orderly Urethane Copolymer) Next, a method for producing a urethane copolymer will be described. In the polymerization, in order to sufficiently elongate the molecular weight, it is preferable that the number of isocyanate functional groups and the number of hydroxyl groups of the diol monomer be substantially equal (equimolar amount), but it is not limited thereto. Here, the substantially equimolar amount refers to 0.8 to 1.2 moles, preferably 0.9 to 1.1 moles, more preferably 0.99 to 1.0 moles of diol per mole of diisocyanate.
Is a mole.

In order to produce an orderly polyurethane, a diisocyanate monomer having asymmetric reactivity and two kinds of symmetric diol monomers are used. First, an aromatic isocyanate group having higher reactivity is combined with a diol monomer. Let react. Then, the less reactive aliphatic isocyanate is reacted with the diol to select sequential reaction conditions.

In the initial stage of the reaction, the first step of reacting about 0.5 mole equivalent of the diol monomer with respect to the diisocyanate monomer is used, and further, about 0.5 mole equivalent of the diol monomer with respect to the diisocyanate monomer is used. The polymerization is completed in the second step of reacting with the addition of the compound to produce the desired copolymer.

In order to carry out such a reaction, in the first step, it is necessary to add the above-mentioned specified amount of the diol monomer to the isocyanate monomer. Various methods can be adopted for adding the diol monomer. For example, it may be added at one time, or may be added stepwise in several steps. Further, it may be continuously added by dropping, or may be diluted with a solvent and gradually added. Depending on the form, such as whether the diol monomer used is a powder or a liquid, it may be slowly added by an appropriate method. As an operation to add slowly, it may be added over a long period of several days,
From the viewpoint of efficiency, the addition is preferably performed over 0 to 48 hours, more preferably 0 to 5 hours, particularly preferably about 3 hours.

As described above, by the operation of slowly adding the diol monomer in the first step, the reaction conditions in which the diisocyanate monomer is present in an excessive amount with respect to the diol monomer are selected, so that the aromatic diamine having high reactivity is selected. Isocyanate groups react preferentially with diol monomers.

Therefore, the total amount of the diol monomer used in the first-stage reaction is preferably 0.5 mol with respect to the diisocyanate monomer, and it is difficult to complete the first-stage reaction with any other amount. -May interfere with elongation of the head binding portion.

In the first step, the diol monomer is added as slowly as possible in the above-mentioned prescribed amount, whereby only the head-to-head binding unit portion is more reliably extended. Furthermore, in order to improve the reaction selectivity at the beginning of the reaction, the reaction temperature may be lowered as much as possible, and the reaction may proceed slowly. However, if the reaction temperature is too low, the reaction efficiency is reduced, and a side reaction such as an isocyanate trimerization reaction competing at the time of urethane bond formation is also likely to proceed.
The temperature is preferably −10 to 30 ° C., and it is particularly preferable to drop the diol monomer around 0 ° C.

Since the obtained polymer is expected to be highly polar, a highly polar solvent is used for efficient polymerization. However, these solvents are known to reduce the rate of urethane bond formation by solvation of the monomer (Adolf E. Oberth and Rolf S. Bruenner, J. Phys.
hem., Vol 72, 845-855 (1968)), resulting in reduced reaction selectivity.

Therefore, when the diol monomer is added at the beginning of the reaction, aliphatic hydrocarbons such as cyclohexane, pentane and hexane, aromatic hydrocarbons such as benzene, toluene and chlorobenzene, THF (tetrahydrofuran), diethyl ether, Reaction selectivity using low polar solvents such as ethers such as ethylene glycol diethyl ether, ketones such as acetone, methyl ethyl ketone and 4-methyl-2-pentanone, and esters such as methyl propionate, ethyl acetate and butyl acetate. Improve.

Thereafter, in order to complete the polymerization reaction, it is preferable to add a highly polar solvent or to remove the less polar solvent by distilling it off and then add a highly polar solvent.
As the low polarity solvent, ethers such as THF are particularly preferable in consideration of reaction operability and solubility of the monomer substrate.
The amount of the solvent used at this time is preferably used so as to dilute the monomer substrate as much as possible in order to enhance the selectivity. However, in consideration of the efficient progress of the reaction and the reaction operation, the amount of the monomer substrate is 0.1 to 0.3 mol / It is desirable to use it to be 1.

At this time, a catalyst may be added to carry out the reaction efficiently. Specific catalysts include tertiary alkylamines such as N, N, N ′, N′-tetramethyl-1,3-butanediamine, triethylamine and tributylamine in order to efficiently progress urethane bond formation; 4-
Condensed amines such as diazabicyclo [2.2.2] octane, 1,8-diazabicyclo [5.4.0] undec-7-ene; DBTL (dibutyltin dilaurate);
Alkyl tins such as tetrabutyltin and tributyltin acetate are used. Alkyl tins and condensed amines are more active catalysts for urethane bond formation reaction than alkyl amines (F. Hostettler and
EFCox, Ind.Eng.Chem., Vol. 52, 609-610, (1960)),
As a result, the required reaction selectivity in the initial stage of the reaction decreases.

Therefore, in the early stage of the reaction, it is desirable to use a trialkylamine, particularly triethylamine in consideration of the reaction operability, and then it is preferable to use a more active catalyst in order to carry out the reaction efficiently.
For example, in the case of trialkylamines, the catalyst amount is
Considering the reaction selectivity, allowing the reaction to proceed efficiently, and taking into account the reaction operation,
It is desirable to use 1 mol% to 30 mol%.

Thereafter, in order to complete the polymerization operation in the second step, the remaining diol monomer having an R ₄ skeleton is added. As the diol monomer to be added at this time, approximately 0.5 mole equivalent of the diol monomer equivalent to the unreacted isocyanate group may be added, calculated backward from the amount of the diol monomer added at the beginning of the reaction. The amount may be changed accordingly. In this way, a polyurethane in which the R ₃ skeleton and the R ₄ skeleton are alternately arranged is obtained.

At this time, as the solvent, since it is expected that the obtained polymer is highly polar as described above, N, N-dimethylformamide, N, N It is desirable to use a highly polar aprotic solvent such as N-dimethylacetamide, dimethylsulfoxide, and sulfolane. The solvent may be added to the solvent at the beginning of the reaction as it is, or may be added after the solvent at the beginning of the reaction is once distilled off. The amount of solvent added
The reaction may be added to increase the concentration so as to complete the reaction promptly. However, if the concentration is too high, an undesired side reaction such as allophanation may occur, so that the concentration is preferably 0.1 to 0.5 mol / l. It is better to add

At this time, a catalyst may be used. Specifically, the above-mentioned tertiary amines and alkyltins are desirable, and in order to carry out the reaction quickly, alkyltins having high catalytic activity for urethane bond formation, such as DBTL and stannoxane, are desirable. The addition amount is preferably 1 to 30 mol% with respect to the monomer substrate in consideration of efficient progress of the reaction and reaction operability.

Further, by using a mixture of a diol monomer having an R ₃ skeleton and a diol monomer having an R ₄ skeleton with respect to the diisocyanate monomer in the same manner as described above, only the diisocyanate monomer is obtained. An ordered polyurethane having sequence regularity is obtained.

(Method for producing random copolymer) On the other hand, when two kinds of diol monomers and a diisocyanate monomer are simultaneously reacted, a polyurethane having no sequence regularity can be obtained. Here, the amount of the diol monomer is preferably used so as to be substantially equal (equimolar amount) to the diisocyanate monomer for the same purpose as described above.

In the method for producing a random polyurethane, the diol compound is substantially reacted with the diisocyanate compound at a time, that is, the polymerization is carried out under conditions that cancel the difference in the reactivity of the isocyanate group of the diisocyanate compound. Perform the reaction. That is, as a method of adding the monomer, it is preferable to add the diol in an equimolar amount to the diisocyanate monomer at once as soon as possible in consideration of the stoichiometric ratio.

On the other hand, if the diisocyanate monomer is added dropwise to ethylene glycol, the content of the desired structural unit decreases. "Reacting the diol compound substantially at once" means that all diisocyanates and all diols are present in the reaction system over substantially all of the reaction time from the start to the completion of the reaction. I do. That is, it is intended to eliminate a means for dividing the diol to be reacted with one of the diisocyanates and adding the diol to the reaction system step by step. Therefore, the following operations are included. All monomers are simultaneously added to the reaction system. Equimolar amounts of monomers are added simultaneously. In the presence of one monomer, the other is added quickly.

The catalyst is preferably added after the diisocyanate and the diol have been added. For example, when a monomer is added in the presence of a catalyst, the reaction starts before the completion of the addition of the monomer, and even when the monomer is added in a short time, the condition that the reaction is started in a reaction system in which diisocyanate and diol are present in equimolar amounts is required. I can't get it. In the absence of a catalyst, the spontaneous reaction between diisocyanate and diol is extremely slow, making it possible to approach the ideal reaction conditions of starting the reaction in the presence of equimolar amounts of diisocyanate and diol. Become.

Preferred catalysts for this purpose include organotin catalysts such as dibutyltin dilaurate (DBTL) and tetraalkyldistannoxanes, and condensed amines such as triethylamine and diazabicyclo [2.2.2] octane. Any catalyst can be used as long as it can efficiently perform a urethanization reaction.

As a reaction solvent, since polyurethane is generally highly polar, it is necessary to use D to make the reaction proceed efficiently.
Highly polar aprotic solvents such as MF, DMAc, NMP, DMSO, and sulfolane are preferred, but other solvents may be used as long as they dissolve the substrate.

The reaction temperature is desirably −60 to 80 ° C., and the difference in reactivity of the isocyanate monomer, the substrate selectivity of the catalyst,
In consideration of the reaction efficiency and the like, the temperature is preferably set to about 30 to 80 ° C. in order to complete the reaction quickly.
It is thought that the longer the reaction time is, the higher the growth of the polymer chain becomes. However, considering the actual reaction operation, 3 to 4
Preferably, the reaction is continued for about 8 hours.

[0061]

Next, the present invention will be described in more detail with reference to Examples and Comparative Examples.

(In the case of using ethylene glycol and pyridine dimethanol) A quantitative study on the sequence isomerism of the urethane copolymer thus obtained was carried out by examining ethylene glycol and aromatic isocyanate in the polymer main chain. A skeleton derived from a binding site and a skeleton derived from an ethylene glycol and aliphatic isocyanate binding site, and a total of four similar model compounds using pyridine dimethanol as a diol, a total of four model compounds corresponding to each, were previously synthesized, It was performed by comparing the ¹³ C-NMR spectrum of the polymer obtained and their ¹³ C-NMR spectra.

Specifically, in a deuterated DMF solvent, 80
Using ¹³ C-NMR at 150 MHz in degree, 2
The peak of the methylene group derived from ethylene glycol of the species model compound appears at 64.3 ppm when it is bonded to the aromatic isocyanate site, whereas it appears at 64.3 ppm for the aliphatic isocyanate, and can be distinguished by the difference in structure. That was confirmed.

Next, in the obtained polymer, ¹³ C
As a result of -NMR spectrum analysis, it was confirmed that the peak of the methylene group derived from ethylene glycol changed depending on the polymerization conditions, and the peak position corresponded to the value observed for the model compound.

Test Example I-1 Synthesis of a Model Compound for NMR Measurement (Structural Formula I-1) Corresponding to the Bonding Site between Ethylene Glycol and Aromatic Isocyanate

[0066]

Embedded image

DBTL 0.1 in 50 ml of 1,4-dioxane.
55 g (0.87 mmol), ethylene glycol 1.28
g (20.6 mmol), phenyl isocyanate 4.96
g (41.6 mmol) was added, and the mixture was stirred at 60 ° C. for 1 day. After evaporating the solvent, the residue was purified by recrystallization with ethyl acetate to obtain a crystalline solid. ¹³ C of the product obtained here
-NMR measurement was performed (FIG. I-1). The result is 154.9.
A carbonyl group (b) peak was observed at
A peak of the aromatic ring (a) was observed at 0.8, 130.0, 123.8, and 119.6 ppm, and methylene was observed at 64.3 ppm.
From the observation of the peak (c), it was confirmed that the compound corresponded to the expected binding site structure of ethylene glycol and aromatic isocyanate. 4.76 g (76.3% yield)

Test Example I-2 Synthesis of a Model Compound for NMR Measurement (Structural Formula I-2) Corresponding to Ethylene Glycol and Aliphatic Isocyanate Bonding Site

[0069]

Embedded image

DBTL 0.1 in 50 ml of 1,4-dioxane.
55 g (0.87 mmol), ethylene glycol 1.10
g (17.7 mmol), benzyl isocyanate 4.74
g (35.6 mmol) was added, and the mixture was stirred at 60 ° C. for 1 day. After evaporating the solvent, the residue was purified by recrystallization with ethyl acetate to obtain a crystalline solid. ¹³ C of the product obtained here
-NMR measurement was performed (FIG. I-2). The result is 158.0
A carbonyl group (c) peak was observed at
A peak of the aromatic ring (a) was observed at 1.4, 129.6, 128.6, and 128.2 ppm, and methylene was observed at 64.2 ppm.
The peak of (d) was observed and the peak of benzylic methylene (b) was observed at 45.7 ppm, confirming that the compound corresponds to the expected ethylene glycol and aliphatic isocyanate binding site structure. . Yield 4.7
2g (80.8% yield)

Test Example I-3 Synthesis of a Model Compound for NMR Measurement (Structural Formula I-3) Corresponding to the Binding Site between 2,6-pyridinedimethanol and Aromatic Isocyanate

[0072]

Embedded image

DBTL 0.1 in 70 ml of 1,4-dioxane.
29 g (0.46 mmol), 1.34 g (9.63 mmol) of 2,6-pyridinedimethanol and 2.31 g (21.0 mmol) of phenyl isocyanate were added, and the mixture was stirred at 60 ° C. for 1 day. After evaporating the solvent, the residue was purified by recrystallization with ethyl acetate to obtain a crystalline solid. Of the product obtained here
^{A 13} C-NMR measurement was performed (FIG. I-3). Result 15
A peak of the carbonyl group (b) was observed at 8.1 ppm,
119.6, 121.8, 124.1, 130.4, 13
The peak of the aromatic ring (a) was observed at 9.3, 141.1, and 155.1 ppm, and the peak of methylene (c) was observed at 68.0 ppm. It was confirmed that the compound corresponded to the structure of the aromatic isocyanate binding site. Yield 1.03 g (28.1% yield)

[Test Example I-4] N corresponding to the binding site between 2,6-pyridinedimethanol and aliphatic isocyanate
Synthesis of Model Compound for MR Measurement (Structural Formula I-4)

[0075]

Embedded image

DBTL 0.1 in 70 ml of 1,4-dioxane.
34 g (0.54 mmol), 2.45 g (10.4 mmol) of 2,6-pyridinedimethanol and 2.80 g (19.4 mmol) of benzyl isocyanate were added, and the mixture was stirred at 60 ° C. for 1 day. After evaporating the solvent, the residue was purified by recrystallization with ethyl acetate to obtain a crystalline solid. Of the product obtained here
^{A 13} C-NMR measurement was performed (FIG. I-4).

As a result, a carbonyl group was added to 158.5 ppm.
The peak of (c) was observed, and 121.3, 128.4, 12
8.7, 129.8, 139.1, 141.5, 158.p
pm, an aromatic ring (a) peak was observed at 67.9 ppm.
The peak of methylene (d) was observed at 45.9 ppm, and the peak of methylene (b) at the benzyl position was observed at 45.9 ppm, which corresponded to the expected 2,6-pyridinedimethanol and aromatic isocyanate binding site structure. It was confirmed to be a compound. 3.59 g (84.4% yield)

Example I-1 Urethane Alternating Copolymer
Synthesis of (Structural Formula I-5)

[0079]

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0.187 g (1.7 g) of ethylene glycol
51 mmol), 0.0338 g of triethylamine (0.3
A solution (34 mmol) of tetrahydrofuran (20 ml) was prepared and added dropwise to 0.6100 g (3.502 mmol) of 4-isocyanatobenzyl isocyanate over 90 minutes under ice-cooling. After stirring at 30 ° C. for 1 hour as it was, the solvent was completely distilled off from the reaction system.

15 ml of DMF was added to the reaction vessel, and 0.0473 g of dibutyltin dilaurate (0.0473 g) was added thereto.
075 mmol) and 0.23737 g of pyridinedimethanol
(1.751 mmol), heated to 30 ° C.,
Stirred for hours. The solvent was distilled off, and the reaction solution was concentrated. This was reprecipitated with methanol, and dried at 80 ° C. under vacuum for 2 days to obtain a compound. 0.7844g (81.5% yield)

¹³ C-NMR of the compound thus obtained
(Fig. I-5, Fig. I-6) From the ethylene glycol-derived methylene peak that appeared at 64.3 ppm, this polymer is expected to have an alternating copolymer polyurethane having a structure in which an aromatic isocyanate moiety is bonded to ethylene glycol. It turned out that it was obtained. The molecular weight was determined by gel permeation chromatography (hereinafter abbreviated as GPC) using polystyrene as a reference substance. The weight average molecular weight was 62,000 and the molecular weight distribution was 2.8.

Example I-2 Urethane Alternating Copolymer
Synthesis of (Structural Formula I-6)

[0084]

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0.2440 g of pyridinedimethanol (1.
753 mmol), 0.0405 g of triethylamine (0.04 g).
A solution (400 mmol) of tetrahydrofuran (50 ml) was prepared and added dropwise to 0.6106 g (3.506 mmol) of 4-isocyanatobenzyl isocyanate over 90 minutes under ice-cooling. After stirring at 30 ° C. for 1 hour as it was, the solvent was completely distilled off from the reaction system.

15 ml of DMF was added to the reaction vessel, and 0.0428 g (0.0428 g) of dibutyltin dilaurate was added thereto.
068 mmol) and 0.188 g of ethylene glycol
(1.753 mmol) and heated to 60 ° C., followed by another 16
Stirred for hours. The solvent was distilled off, and the reaction solution was concentrated. This was reprecipitated with methanol, and dried at 80 ° C. under vacuum for 2 days to obtain a compound. 0.7809 g (83.2% yield)

¹³ C-NMR of the compound thus obtained
(Fig. I-7, Fig. I-8) From the peak derived from methylene of ethylene glycol which appeared at 64.2 ppm in this polymer, this polymer is an alternating copolymer having an expected structure in which an aliphatic isocyanate moiety is bonded to ethylene glycol. It was found that a united polyurethane was obtained. Gel permeation chromatography (hereinafter abbreviated as GPC)
As a result, the weight average molecular weight was 17000 and the molecular weight distribution was 2.4.

Comparative Example I-1 Synthesis of Urethane Random Copolymer (Structural Formula I-7)

[0089]

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To 0.1580 g (1.889 mmol) of ethylene glycol, 0.2629 g (1.889 mmol) of 2,6-pyridinedimethanol and 0.0390 g of triethylamine were added to 0.6580 g (3.778 mmol) of 4-isocyanatobenzyl isocyanate. (0.385 mmol) in D
It was added to 15 ml of MF at a time. After stirring at 60 ° C. for 2.5 hours, 0.0421 g (0.067 mmol) of DBTL was added, and the mixture was further stirred at 60 ° C. for one day. The obtained polymer was purified and treated in the same manner as in Example I-1. 0.9000 g (86.7% yield)

¹³ C-NMR of the compound thus obtained
(Figures I-9 and I-10) show 64.2 ppm and 64.
Since a methylene peak derived from ethylene glycol was present at 3 ppm and the integrated amounts of the respective peaks were substantially equal, it was found that this polymer was a random copolymer polyurethane having substantially equal values of x and y.

The molecular weight was determined by GPC using polystyrene as a reference substance.
The molecular weight distribution was 3.3.

(When ethylene glycol and 1,3-benzenedimethanol are used) The following quantitative study on the sequence isomerism of the urethane copolymer was carried out by examining the binding of ethylene glycol and aromatic isocyanate in the polymer main chain. A skeleton derived from a site and a skeleton derived from an ethylene glycol-aliphatic isocyanate binding site, and a skeleton bonded to both ethylene glycol, an aromatic isocyanate and an aliphatic isocyanate, and 1,3-benzenedimethanol as a diol Model compounds corresponding to each of the three same model compounds were synthesized in advance, and the corresponding model compounds were synthesized in advance.
¹³ C-NMR spectrum and ¹³ C-
The comparison was performed with the NMR spectrum.

Specifically, in deuterated DMF solvent, 15
Using 0 MHz and ¹³ C-NMR, the peak of the methylene group derived from ethylene glycol of the model compound derived from ethylene glycol was 64.3 ppm when the peak was bonded to the aromatic isocyanate site, and 64 ppm when the aliphatic isocyanate was used. 0.4 ppm, and 64.2 ppm and 64.4 ppm when combined with aromatic and aliphatic isocyanates.
Appeared at 6 ppm. The peak of the methylene group derived from ethylene glycol of the model compound derived from 1,3-benzenedimethanol is 67.0 ppm when the peak is bonded to the aromatic isocyanate site, 67.3 ppm for the aliphatic isocyanate, and 67.3 ppm and 67.0 ppm when combined with aromatic and aliphatic isocyanates
And it was confirmed that it was possible to distinguish by differences in structure.

Next, the obtained polymer was similarly treated with ¹³ C
As a result of performing -NMR spectrum analysis, the peaks of the methylene groups derived from ethylene glycol and 1,3-benzenedimethanol changed depending on the polymerization conditions, and the peak positions corresponded to the values observed for the model compound. It was confirmed that there was. Furthermore, by assigning a structure based on the area of these peaks, it was confirmed that the polyurethane was an ordered polyurethane having a target monomer sequence.

The fact that the obtained polymers were composed of the same composition and had different solid structures was determined by comparing the structural assignments and the elemental analysis values obtained by the NMR measurement, and further by the DSC.
It was confirmed from the presence or absence of an endothermic peak in the measurement, the endothermic temperature and the amount of endothermic peak. The measurement of the refractive index was confirmed by forming a polyurethane film on a high refractive index glass plate and measuring with an Atago 1T refractometer.

Test Example II-1 Synthesis of a Model Compound for NMR Measurement (Structural Formula II-1) Corresponding to the Bonding Site between Ethylene Glycol and Aromatic Isocyanate

[0098]

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1.28 g (20.6 m) of ethylene glycol
mol) and 4.91 g (41.2 m) of phenyl isocyanate
mol) and 0.55 g of dibutyltin dilaurate
(0.87 mmol) of 1,4-dioxane (50 mL) was added and the mixture was stirred at 60 ° C. for 24 hours, and then the solvent was distilled off. The reaction mixture was recrystallized and purified from a mixed solvent of ethyl acetate and n-hexane to recover colorless and transparent plate-like crystals. 4.76 g (76% yield). Mp: 154-15
5 ° C. (decomp.). IR (KBr, cm ⁻¹ ): 3346 (s),
3061 (w), 2974 (w), 2910 (w), 1711
(s), 1599 (s),

1531 (s), 1448 (s), 1336
(m), 1315 (m), 1219 (s), 1090 (s), 107
5 (s), 1032 (w), 904 (w), 775 (m), 739
(m). ¹ H-NMR (600 MHz, DMF-d ₇ ): δ
_{4.40 (s, 4H, -CH 2} -), 7.00-7.66 (m, 1
^{_{0H, C 6 H 5 -.}} ), 9.79 (br, 2H, -NH-) 13
C-NMR (150 MHz, DMF-d ₇ ): δ 64.3,
119.8, 123.9, 130.1, 140.9, 155.1.
(Figure II-1) Anal.Calcd for C ₁₆ H ₁₆ N ₂ O ₄ :
C, 63.99; H, 5.37; N, 9.33. Found:
C, 63.79; H, 5.31; N, 9.20.

Test Example II-2 Synthesis of a Model Compound for NMR Measurement (Structural Formula II-2) Corresponding to a Bonding Site between Ethylene Glycol and Aliphatic Isocyanate

[0102]

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1.10 g (17.7 m) of ethylene glycol
mol) to 4.71 g (35.4 m) of benzyl isocyanate
mol) and 0.55 g of dibutyltin dilaurate
(0.87 mmol) was added to 50 ml of 1,4-dioxane, and the mixture was stirred at 60 ° C. for 24 hours. The reaction mixture was recrystallized and purified from a mixed solvent of ethyl acetate and n-hexane to recover colorless and transparent plate-like crystals. Yield 4.72 g (81% yield) .mp: 158-159 ° C.I
R (KBr, cm ^-1 ): 3311 (s), 3086 (w), 3
033 (w), 2957 (w), 2929 (w), 1687 (s),
1553 (s), 1454 (m), 1261 (m), 1150
(m), 1051 (m), 1025 (w), 950 (w), 696
(s). ¹ H-NMR (600 MHz, DMF-d ₇ ): δ
_{4.21-4.31 (m, 8H, -CH 2} -), 7.22-7.
_{33 (m, 10H, C 6} H 5 -), 7.66 (br, 2H, -N
H-). ¹³ C-NMR (150 MHz, DMF-d ₇ ): δ
45.8, 64.4,

128.3, 128.8, 129.8, 14
1.6, 158.2. (Fig. II-2) Anal Calcd for _{C18
H 20 N 2 O 4: C} , 65.84; H, 6.14; N, 8.5
3. Found: C, 65.87; H, 6.11; N, 8.5.
0.

Test Example II-3 A model compound for NMR measurement corresponding to the binding site between ethylene glycol and an aromatic isocyanate or an aliphatic isocyanate (structural formula II-
Synthesis of 3)

[0106]

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A mixture of 7.18 g (39.6 mmol) of N-phenyl- (2-hydroxyethyl) urethane and 1.11 g (1.76 mmol) of dibutyltin dilaurate in 1,4
5.27 g (39.6 mmol) of benzyl isocyanate was added to a dioxane solution (50 ml), and the mixture was stirred at 80 ° C. for 16 hours. Reaction mixture column chromatography obtained by distilling off the solvent (filler: Wako Pure Chemical Industries, Ltd.
LC-300, developing solvent: ethyl acetate / n-hexane mixed solvent) to recover colorless and transparent plate-like crystals. 5.15 g (41% yield) .mp 113 ° C. (decom)
p.). IR (KBr, cm ^-1 ): 3308 (s), 3138
(w), 3064 (w), 2955 (w), 1694 (s), 16
02 (m), 1549 (m), 1500 (w), 1446 (m), 1
317 (m),

1255 (s), 1234 (s), 1152 (m),
1090 (m), 1074 (m), 1024 (w), 950 (w),
772 (m), 747 (m), 693 (m). ¹ H-NMR (60
0 MHz, DMF-d ₇ ): δ 4.23-4.32 (m, 6H,
_{-CH 2 -), 6.98-7.72 (m} , 10H, C 6 H 5 -)
_{7.56 (br, 1H, C 6} H 5 -CH 2 -NH-) 9.67
_{(br, 1H, C 6 H} 5 -NH-). 13 C-NMR (15
0 MHz, DMF-d ₇ ): δ 45.8, 64.2, 64.5,
119.8, 124.0, 128.3, 128.8, 129.8,
130.3, 141.2, 141.6, 155.2, 158.2.
(Figure II-3) Anal Calcd for C ₁₇ H ₁₈ N ₂ O ₄ : C,
H, 5.77; N, 8.91. Found:
C, 64.74; H, 5.94; N, 8.85.

[Test Example II-4] N corresponding to the binding site between 1,3-benzenedimethanol and aromatic isocyanate
Synthesis of model compound for MR measurement (Structural formula II-4)

[0110]

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0.49 g of 1,3-benzenedimethanol
(3.55 mmol), 0.84 g of phenyl isocyanate
(7.10 mmol) and 0.09 g (0.14 mmol) of dibutyltin dilaurate in 1,4-dioxane 2
The mixture was added to 6 ml and stirred at 60 ° C. for 19 hours. The reaction mixture obtained by distilling off the solvent was purified by recrystallization from a mixed solvent of ethyl acetate and n-hexane to obtain colorless and transparent needle-like crystals. 0.99 g (75% yield). mp: 133.5
-135.0 ° C. IR (KBr, cm ^-1 ): 3349 (s),
3126 (w), 3045 (m), 3016 (w), 2973
(m), 2938 (m), 2887 (w), 1711 (s), 160
2 (s), 1536 (s), 1500 (s), 1461 (m), 14
46 (s), 1376 (m), 1366 (m), 1316 (s), 1
300 (s), 1248 (s), 1177 (s), 1165 (m),
1083 (s), 1064 (s),

1028 (s), 979 (m), 901 (w), 8
46 (w), 825 (w), 788 (s), 768 (s), 748
(s), 719 (s), 689 (s), 631 (s), 618 (s).
¹ H-NMR (600 MHz, DMF-d ₇ ): δ 5.2
_{6 (s, 2H, -CH 2} -), 7.04 (m, 7H, -C 6 H 4
^{_{-, C 6 H 5 -.}} ), 9.80 (br, 1H, -NH-) 13
C-NMR (150 MHz, DMF-d ₇ ): δ 65.1, 1
17.6,121.8,126.8,126.9,127.0,1
28.0, 128.1, 136.8, 138.9, 153.0.
(Figure II-4) Anal Calcd for C 22 H 20 N 2 O 4:
C, 70.20; H, 5.36; N, 7.44. Found:
C, 69.89; H, 5.23; N, 7.40.

[Test Example II-5] N corresponding to the binding site between 1,3-benzenedimethanol and aliphatic isocyanate
Synthesis of model compound for MR measurement (Structural formula II-5)

[0114]

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0.49 g of 1,3-benzenedimethanol
(3.55 mmol), 0.94 g of benzyl isocyanate
(7.10 mmol) and 0.09 g (0.14 mmol) of dibutyltin dilaurate in 1,4-dioxane 2
The mixture was added to 6 ml and stirred at 60 ° C. for 19 hours. The reaction mixture obtained by distilling off the solvent was recrystallized and purified from a mixed solvent of ethyl acetate and n-hexane to obtain colorless transparent plate-like crystals. Yield 1.28 g (90% yield). MP: 144.0
-145.5 ° C. IR (KBr, cm ^-1 ): 3336
(s), 3087 (w), 3028 (w), 2925 (w), 16
92 (s), 1655 (m), 1595 (m), 1537 (w),
1495 (m), 1455 (m), 1431 (m),

1365 (m), 1276 (s), 1253
(s), 1204 (m), 1175 (w), 1137 (m), 107
9 (m), 1035 (m), 1003 (m), 983 (m), 93
8 (m), 813 (m), 738 (s), 670 (m), 615
(m). ¹ H-NMR (600 NHz, DMF-d ₇ ): δ
_{4.40 (d, 2H, -C H} 2 -NH -), 5.17 (s, 2H,
_{-C H 2 -C 6 H 4 -} ), 7.28-7.46 (m, 7H, -
_{C 6 H 4 -, C 6} H 5 -), 7.78 (br, 1H, -NH
−). ¹³ C-NMR (150 MHz, DMF-d ₇ ): δ
45.9,67.1,128.4,128.7,129.8,13
0.0, 139.3, 141.6, 158.3. (Figure II-5)
_{Calcd for C 24 H 24 N 2} O 4: C, 71.27; H,
5.98; N, 6.93. Found: C, 71.06; H, 5.9
6; N, 6.89.

Test Example II-6 Synthesis of a model compound for NMR measurement (structural formula II-6) corresponding to the binding site between 1,3-benzenedimethanol and aromatic isocyanate and aliphatic isocyanate

[0118]

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1- (N-phenylmethylcarbamate)-
0.45 g (1.74 mm) of 3-hydroxymethylbenzene
ol, benzyl isocyanate 0.23 g (1.74 mm
ol) and 0.04 g of dibutyltin dilaurate
(0.06 mmol) was added to 25 ml of 1,4-dioxane, and the mixture was stirred at 60 ° C. for 19 hours. The reaction mixture obtained by distilling off the solvent was purified by recrystallization from a mixed solvent of ethyl acetate and n-hexane to obtain colorless and transparent needle-like crystals. Yield 0.27 g (40% yield). mp: 118.0-120.0
° C. IR (KBr, cm ^-1 ): 3313 (s), 3037
(w), 2926 (w, 1701 (s), 1654 (w), 163
7 (w), 1602 (m), 1539 (s), 1498 (w), 14
46 (m), 1364 (w), 1315 (m), 1279 (s), 1
246 (s),

1177 (w), 1135 (w), 1080
(m), 1064 (m), 1027 (w), 983 (w), 900
(w), 818 (w), 782 (m), 755 (m), 737 (m),
693 (w), 669 (m), 623 (m).¹H-NMR (6
00MHz, DMF-d₇): δ 4.38 (d, 1H, -CH
₂ -NH-), 5.18-5.24 (m, 2H, -CH₂-C
₆H₄-CH₂−), 7.05-7.67 (m, 7H, −C₆
H₄−, C₆H₅-), 9.80 (br, 1H, -NH-).
¹³C-NMR (150 MHz, DMF-d₇): Δ45.
9,67.0,67.3,119.8,124.0,128.4,
128.7, 128.8, 128.9, 129.0, 129.8,
130.1, 130.3, 138.9, 139.5, 141.1,
141.6, 155.2, 158.3. (Fig. II-6) Anal.Calc
d for C₂₃H₂₂N ₂O₄: C, 70.75; H, 5.6
8; N, 7.17. Found: C, 70.52; H, 5.64;
N, 7.14.

Example II-1 Synthesis of Ordered Polyurethane (Structural Formula II-7) in which the aromatic portion of diisocyanate monomer is bonded to ethylene glycol

[0122]

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1.87 g (10.74 mmol) of p-isocyanatobenzyl isocyanate, 0.33 g (5.37 mmol) of ethylene glycol and 0.1% of triethylamine
0 g (1.00 mmol) of a THF solution (42 ml) was added over 1.5 hours under ice-cooling, and the mixture was stirred for 30 minutes.
After further stirring at room temperature for 30 minutes, the THF solvent was distilled off under reduced pressure. 0.74 g (5.37 m) of 1,3-benzenedimethanol
mol) and 0.13 g of dibutyltin dilaurate
(0.21 mmol) in DMF (42 ml) was added and 30
Stirred at C for 16 hours. The reaction solution was added to methanol for reprecipitation, and then dried under reduced pressure at 130 ° C. for 2 hours.

2.33 g (89% yield) IR (KBr,
cm ^-1 ): 3325 (s), 3051 (m), 2953
(m), 1700 (s), 1600 (s), 1536 (s), 1
415 (s), 1317 (s), 1241 (s), 1133
(s), 1063 (s), 981 (m), 897 (m), 826
(m), 769 (s), 653 (m). ¹ H-NMR (600
MHz, DMF-d ₇ ): δ 4.22-4.44 (m, 4H,
_{-O-CH 2 -CH 2 -O -} , - NH-CH 2 -C 6 H
_{4 -), 5.23 (s,} 2H, -C H 2 -C6H4-C H 2
-) 7.29-7.58 (m, 6H, -C 6 H 4 -), 7.69
(m, 1H, -CH2-N H -CO 2 -), 9.41 (br, 1
_{H, -C 6 H 4 -N H} -CO 2 -.) 13 C-NMR (15
0 MHz, DMF-d ₇ ): δ 45.4, 64.2, 64.4,
64.6,119.8,129.3,135.7,139.8,1
55.2, 158.1. (FIG. II-7) Mw (Mw / Mn) = 63
000 (3.3) .Anal.Calcd for (C ₂₈ H ₂₈ N ₄ O ₈ )
_n : C, 61.31; H, 5.14; N, 10.21. Found:
C, 61.24; H, 5.11; N, 10.13.

Example II-2 Synthesis of an ordered polyurethane (structural formula II-8) in which the aromatic moiety of a diisocyanate monomer is bonded to 1,3-benzenedimethanol

[0126]

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A THF solution (42 ml) of 1.84 g (10.56 mmol) of p-isocyanatobenzyl isocyanate, 0.73 g (5.28 mmol) of 1,3-benzenedimethanol and 0.10 g (1.00 mmol) of triethylamine was used.
Was added over 1.5 hours under ice-cooling, and the mixture was stirred as it was for 30 minutes. After further stirring at room temperature for 30 minutes, the THF solvent was distilled off under reduced pressure. 0.32 g of ethylene glycol (5.28 mmo
l) and 0.14 g (0.22 mmol) of DBTL in DMF (42 ml) were added, and the mixture was stirred at 30 ° C for 16 hours. The target product was obtained by performing the same operation as described above. Yield 2.48 g (86% yield). IR (KBr, cm ^-1 ): 3316 (m), 2
929 (m), 1701 (s), 1601 (s), 1541 (m),
1458 (w), 1415 (w), 1316 (m), 1225
(m), 1051 (m), 770 (w), 687 (w), 670
(m), 604 (m). ¹ H-NMR (600 MHz, DMF-
d ₇ ): δ 4.22-4.44 (m, 4H, -O-CH ₂ -C
H ₂ —O—, —NH—CH ₂ —C ₆ H ₄ —), 5.23 (s,
_{2H, -CH 2 -C 6 H 4} -CH 2 -) 7.29-7.58
_{(m, 6H, -C 6 H} 4 -), 7.69 (m, 1H, -CH 2 -
N H -CO ₂ -),

[0128] _{9.41 (br, 1H, -C 6} H 4 -N H -C
O ₂ −). ¹³ C-NMR (150 MHz, DMF-
d ₇ ): δ 45.4, 64.2, 64.4, 64.6, 67.0,
67.3, 119.8, 129.0, 129.1, 129.3, 1
30.2, 135.7, 138.9, 139.0, 139.5, 1
39.8, 155.2, 158.2. (Fig. II-8) Mw (Mw /
Mn) = 58,000 (3.0). Anal.Calcd for (C ₂₈ H
₂₈ N ₄ O ₈ ) _n : C, 61.31; H, 5.14; N, 1
0.21.Found: C, 61.39; H, 5.12; N, 10.
06.

Example II-3 Synthesis of Ordered Polyurethane (Structural Formula II-9) Having Regularity Only in Diisocyanate Monomer Sequence

[0130]

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To 1.88 g (10.80 mmol) of p-isocyanatobenzyl isocyanate 0.16 g (2.70 mmol) of ethylene glycol, 0.37 g (2.70 mmol) of 1,3-benzenedimethanol and 0.10 g of triethylamine (1.00 mmol) of a THF solution (42 ml) was added over 1.5 hours under ice cooling, and the mixture was stirred for 30 minutes. After further stirring at room temperature for 30 minutes, the THF solvent was distilled off under reduced pressure. 0.16 g of ethylene glycol (2.70 mmo
l) 0.37 g of 1,3-benzenedimethanol (2.70 g)
mmol) and dibutyltin dilaurate 0.13
g (0.21 mmol) in DMF (42 ml) was added and 3
Stirred at 0 ° C. for 16 hours. The target product was obtained by performing the same operation as described above. Yield 2.53 g (86% yield). IR (KB
r, cm ^-1 ): 3666 (s), 3317 (s), 3054
(w), 2949 (w), 1719 (s),

1654 (s), 1601 (m), 15141
(m), 1458 (w), 1437 (w), 1415 (m), 131
5 (m), 1221 (s), 1050 (m), 821 (w), 767
(m), 654 (m), 607 (m).¹H-NMR (600MH
z, DMF-d₇): Δ 4.22-4.44 (m, 4H, -O
-CH₂-CH₂-O-,-NH-CH ₂ -C₆H
₄−), 5.23 (s, 2H, −CH ₂ -C₆H₄-CH
₂ −) 7.29-7.58 (m, 6H, -C₆H₄−), 7.6
9 (m, 1H, -CH₂-NH-CO₂−), 9.41 (br,
1H, -C₆H₄-NH-CO₂−).¹³C-NMR (1
50MHz, DMF-d₇): Δ45.4, 64.2, 64.
4,64.6,67.0,67.3,119.8,128.7,1
28.8, 129.0, 129.1, 129.3, 129.7,
130.0, 130.1, 130.2, 135.7, 138.9,
139.0, 139.5, 139.9, 155.3, 158.2.
(Figure II-9) Mw (Mw / Mn) = 34,000 (2.4). An
al.Calcd for (C ₂₈H₂₈N₄O₈)_n: C, 61.3
1; H, 5.14; N, 10.21. Found: C, 61.32;
H, 5.18; N, 10.16.

[Example II-4] Random polyurethane
Synthesis of (Structural Formula II-10)

[0134]

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0.32 g of ethylene glycol (5.28 g)
mmol) 0.72 g of 1,3-benzenedimethanol
(5.28 mmol) and 0.10 g of triethylamine (1.
00 mmol) in DMF solution (42 ml) was added 1.84 g (10.56 mm) of p-isocyanatobenzyl isocyanate.
ol) at 60 ° C. all at once and stirred for 16 hours. The target product was obtained by performing the same operation as described above. Yield 2.65 g (92% yield). IR (KBr, cm ^-1 ): 33
19 (s), 3112 (m), 3050 (m), 2951 (w), 1
701 (s), 1601 (s), 1528 (s), 1458 (m),
1415 (s), 1315 (m), 1219 (s), 1133
(m), 1051 (s), 830 (w), 767 (m),

700 (m), 661 (m).¹H-NMR (6
00MHz, DMF-d₇): Δ 4.22-4.44 (m, 4
H, -O-CH₂-CH₂-O-,-NH-CH₂-C₆
H₄-), 5.06-5.23 (m, 2H, -CH₂-C₆H
₄-CH₂−) 7.23-7.68 (m, 7H, −C₆H
₄-,-CH₂-NH-CO₂−) 9.76 (br, 1H, −
C₆H ₄-NH-CO₂−).¹³C-NMR (150M
Hz, DMF-d₇): Δ45.4, 64.2, 64.4, 6
4.6, 67.0, 67.3, 119.8, 128.7, 128.
8,129.0,129.1,129.3,130.1,130.
2, 135.7, 138.9, 139.0, 139.3, 139.
5,139.8,155.2,158.2. (FIG. II-10) Mw
(Mw / Mn) = 43,000 (2.4). Anal.Calcd for
(C₂₈H₂₈N₄O₈) _n: C, 61.31; H, 5.1
4; N, 10.21. Found: C, 61.33; H, 5.18;
N, 10.08.

(4-N, N-bis (2-hydroxyethyl)
(When amino-2,2'-dimethyl-4'-nitroazobenzene and 3,6-hydroxymethyl-9-heptylcarbazole are used.) 4-N, N-bis in chain
(2-hydroxyethyl) amino-2,2′-dimethyl-
Urethane ester derived from 4'-nitroazobenzene and 3,6-hydroxymethyl-9-heptylcarbazole ¹³ C-NMR spectrum of methylene group adjacent to oxygen bond and synthesized from ethylene glycol and 1,3-benzenedimethanol described above. ¹³ C- of six model compounds
The comparison was performed based on NMR spectra.

Specifically, in deuterated DMF solvent, 15
Using 0 MHz and ¹³ C-NMR, the peak of the methylene group derived from ethylene glycol of the model compound derived from ethylene glycol was 64.3 ppm when the peak was bonded to the aromatic isocyanate site, and 64 ppm when the aliphatic isocyanate was used. 0.4 ppm, and 64.2 ppm and 64.4 ppm when combined with aromatic and aliphatic isocyanates.
Appeared at 6 ppm. The peak of the methylene group derived from ethylene glycol of the model compound derived from 1,3-benzenedimethanol is 67.0 ppm when the peak is bonded to the aromatic isocyanate site, 67.3 ppm for the aliphatic isocyanate, and 67.3 ppm and 67.0 ppm when combined with aromatic and aliphatic isocyanates
And it was confirmed that it was possible to distinguish by differences in structure.

Next, the obtained polymer was similarly treated with ¹³ C
Performing a spectrum analysis by -NMR, 4-N,
The peak of the methylene group adjacent to the oxygen bond of the urethane ester derived from N-bis (2-hydroxyethyl) amino-2,2'-dimethyl-4'-nitroazobenzene and 3,6-hydroxymethyl-9-heptylcarbazole is polymerized. It changed depending on the conditions, and it was confirmed that the peak position corresponds to the value observed for the model compound. Specifically, in the ¹³ C-NMR spectrum of the polymer, 6
The peaks at 2.9, 63.3, 68.1 and 68.3 ppm changed according to the polymerization conditions. Furthermore, by assigning a structure based on the area of these peaks, it was confirmed that the polyurethane was an ordered polyurethane having a target monomer sequence.

Example III-1 A diisocyanate monomer having an aromatic moiety bonded to 4-N, N-bis (2-hydroxyethyl) amino-2,2′-dimethyl-4′-nitroazobenzene Synthesis of ordinal polyurethane (structural formula III-1)

Embedded image 2.50 g of p-isocyanatobenzyl isocyanate (1
4.4 mmol), 4-N, N-bis (2-hydroxyethyl) amino-2,2'-dimethyl-4'-nitroazobenzene 2.59 g (7.2 mmol), 3,6-hydroxymethyl-9- 2.34 g of heptylcarbazole (7.2 mmo
1) was synthesized in the same manner as in Example II-2. Yield 6.
61 g (89% yield)

IR (KBr, cm ^-1 ) 3394, 331
3,2924,2849,1714,1598,1518,
1416,1336,1221,1105,1080,80
8,767,725,707,678 ¹³ C-NMR (150 MHz, DMF-d ₇ ) 15.1,
18.5,19.1,23.9,28.4,33.1,44.2,4
5.5,50.4,51.4,63.2,68.1,110.8,1
12.1, 114.4, 118.1, 119.4, 119.9,
122.0, 123.6, 123.9, 127.7, 128.1,
129.4, 129.5, 135.9, 139.0, 139.8,
142.1, 144.2, 144.4, 148.6, 153.
4,155.4,156.6,158.5.

Example III-2 The aromatic moiety of the diisocyanate monomer was 3,6-hydroxymethyl-9-
Ordered polyurethane combined with heptylcarbazole
Synthesis of (Structural Formula III-2)

Embedded image 2.13 g of p-isocyanatobenzyl isocyanate (1
2.2 mmol), 1.99 g (6.1 mmol) of 3,6-hydroxymethyl-9-heptylcarbazole, 4-N,
2.21 g (6.1 mmol) of N-bis (2-hydroxyethyl) amino-2,2'-dimethyl-4'-nitroazobenzene
1) was synthesized in the same manner as in Example II-2. Yield 5.
55 g (88% yield)

IR (KBr, cm ^-1 ) 3394,331
3,2924,2849,1714,1598,1518,
1416,1336,1221,1105,1080,80
8,767,725,707,678 Mw (Mw / Mn)
¹³ C-NMR ¹³ C-NMR (150 MHz, DMF-d ₇ ) 15.1,
18.5,19.1,23.9,28.4,33.1,44.2,4
5.5,50.4,51.4,62.9,68.3,110.8,1
12.1, 114.4, 118.1, 119.4, 119.9,
122.0, 123.6, 123.9, 127.7, 128.1,
129.4, 129.5, 135.9, 139.0, 139.8,
142.1, 144.2, 144.4, 148.6, 153.
4,155.4,156.6,158.5.

Example III-3 Synthesis of Random Polyurethane (Structural Formula III-3)

Embedded image 2.46 g of p-isocyanatobenzyl isocyanate (1
4.1 mmol), 2.54 g (7.0 mmol) of 4-N, N-bis (2-hydroxyethyl) amino-2,2'-dimethyl-4'-nitroazobenzene, 3,6-hydroxymethyl-9- 2.30 g of heptylcarbazole (7.1 mmo
1) was synthesized in the same manner as in Example II-4. Yield 6.
57 g (90% yield)

IR (KBr, cm ^-1 ) 3394, 331
3,2924,2849,1714,1598,1518,
1416,1336,1221,1105,1080,80
8,767,725,707,678 Mw (Mw / Mn) ¹³ C-NMR (150 MHz, DMF-d ₇ ) 15.1,
18.5,19.1,23.9,28.4,33.1,44.2,4
5.5,50.4,51.4,62.9,63.3,68.1,6
8.3, 110.8, 112.1, 114.4, 118.1, 1
19.4, 119.9, 122.0, 123.6, 123.9,
127.7, 128.1, 129.4, 129.5, 135.9,
139.0, 139.8, 142.1, 144.2, 144.4,
148.6, 153.4, 155.4, 156.6, 158.
5.

The obtained polyurethane (Structural formulas II-7 to II
-10) is due to differential scanning calorimetry (DS
C) It was confirmed by performing measurement. As a result, Example (II-
The DSC curves of polyurethanes 1) to (II-3) are crystalline polymers due to the presence of endothermic peaks, and are polymers having different crystal structures due to different endothermic peak temperatures and endothermic amounts. It was confirmed. Example II
No endothermic peak was found in DSC of polyurethane of No.-4, which confirmed that it was an amorphous polymer (FIG. II-
15).

The 15 wt% DMF solutions of the four polyurethanes obtained in Examples (II-1) to (II-4) were spin-coated on a high refractive index glass plate (n = 1.740).
After drying on a hot plate at 0 ° C x 10 minutes, 40 ° C x 5
It was dried under reduced pressure for a day. The refractive index of the obtained sample was measured with a Na light source lamp (light source wavelength = 5) using a 1T refractometer manufactured by Atago Co., Ltd.
89 nm) at room temperature. The results are shown in Table 1 below. Each of the four polyurethanes has a different refractive index, and the refractive index varies from 1.59 to 1.61 according to the order of crystallinity expected from DSC measurement.

[Table 1] Sample name Refractive index ━━━━━━━━━━━━━━━━━━━━━━━━━━ Example II-1 Orderly polyurethane 1.598 Example II-2 Ordered Polyurethane 1.605 Example II-3 Ordered Polyurethane 1.596 Example II-4 Random Polyurethane 1.596 ━━━━━━━━━

[0149]

According to the present invention, a non-equivalent reactive diisocyanate monomer having an aromatic and an aliphatic isocyanate in a molecule and two kinds of diol monomers effectively reacting with the monomer are an orderly polyurethane such as a urethane alternating copolymer. Can be synthesized. In addition, polymers having various refractive indexes can be obtained from such various polyurethanes.

[Brief description of the drawings]

FIG. I-1 shows the results of the model compound obtained in Test Example I-1.
^{It is a 13} C-NMR spectrum.

FIG. I-2 shows the results of the model compound obtained in Test Example I-2.
^{It is a 13} C-NMR spectrum.

FIG. I-3 shows the results of the model compound obtained in Test Example I-3.
^{It is a 13} C-NMR spectrum.

FIG. I-4 shows the results of the model compound obtained in Test Example I-4.
^{It is a 13} C-NMR spectrum.

FIG. I-5 is a ¹³ C-NMR spectrum of the urethane alternating copolymer obtained in Example I-1.

FIG. I-6 is an enlarged view of a ¹³ C-NMR spectrum of the urethane alternating copolymer obtained in Example I-1.

FIG. I-7 is a ¹³ C-NMR spectrum of the urethane alternating copolymer obtained in Example I-2.

FIG. I-8 is an enlarged view of a ¹³ C-NMR spectrum of the urethane alternating copolymer obtained in Example I-2.

FIG. I-9 is a ¹³ C-NMR spectrum of the urethane alternating copolymer obtained in Comparative Example I-1.

FIG. I-10 is an enlarged view of the ¹³ C-NMR spectrum of the urethane alternating copolymer obtained in Comparative Example I-1.

FIG. II-1 shows the relationship between the model compound obtained in Test Example II-1.
^{It is a 13} C-NMR spectrum.

FIG. II-2: The model compound obtained in Test Example II-2
^{It is a 13} C-NMR spectrum.

FIG. II-3: The model compound obtained in Test Example II-3
^{It is a 13} C-NMR spectrum.

FIG. II-4: The model compound obtained in Test Example II-4
^{It is a 13} C-NMR spectrum.

FIG. II-5: The model compound obtained in Test Example II-5
^{It is a 13} C-NMR spectrum.

FIG. II-6: The model compound obtained in Test Example II-6
^{It is a 13} C-NMR spectrum.

Fig. II-7. The polyurethane obtained in Example II-1
^{It is a 13} C-NMR spectrum.

Fig. II-8. Polyurethane obtained in Example II-1
It is an enlarged view of a ¹³ C-NMR spectrum.

Fig. II-9. Polyurethane obtained in Example II-2
^{It is a 13} C-NMR spectrum.

FIG. II-10 is an enlarged view of the ¹³ C-NMR spectrum of the polyurethane obtained in Example II-2.

FIG. II-11 is a ¹³ C-NMR spectrum of the polyurethane obtained in Example II-3.

FIG. II-12 is an enlarged view of the ¹³ C-NMR spectrum of the polyurethane obtained in Example II-3.

FIG. II-13 is a ¹³ C-NMR spectrum of the polyurethane obtained in Example II-4.

FIG. II-14 is an enlarged view of the ¹³ C-NMR spectrum of the polyurethane obtained in Example II-4.

FIG. II-15 is a DSC curve of the polyurethane obtained in Examples (II-1) to (II-4).

 ──────────────────────────────────────────────────の Continued on the front page F term (reference) 4J034 BA06 CA01 CA04 CB03 CB07 CC03 CC12 CC28 CC33 CC45 CC52 CC62 CC65 HA01 HA07 HA11 HC12 HC61 HC71 HC73 JA25 QA03 QA05 QB08 RA13

Claims (10)

[Claims] 1. The following formula: (Wherein, R ₁ and R ₂ are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; R ₃ and R ₄ are different dihydric alcohol residues. N is an integer of 1 to 10, x is 1 to
It means an integer of 10,000. An alternately polymerized urethane copolymer having a structural unit represented by the formula: 2. The following formulas (1a), (1b), (1c) and (1d): Embedded image Embedded image Embedded image (In formulas (1a) to (1d), R ₁ and R ₂ are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; R ₃ and R ₄ are different dihydric alcohol residues. N Is an integer of 1 to 10, and x _a , x _b , x _c and x _d are integers of 1 to 2500.) 3. The following formula: (Wherein, R ₁ and R ₂ are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; R ₃ and R ₄ are different dihydric alcohol residues. N is an integer of 1 to 10, l and m
Means an integer of 1 to 10,000. A) a random urethane copolymer having a structural unit represented by the formula: 4. R ₁ and R ₂ are hydrogen and R ₃ and R
_4. The urethane copolymer according to claim 1, wherein ₄ is an aliphatic diol residue or an aromatic-containing diol residue, each being a different substituent. 5. The method according to claim 1, wherein one of R ₃ and R ₄ is an ethylene glycol residue, and the other is a 2,6-pyridine dimethanol residue or a 1,3-benzene dimethanol residue. Any urethane copolymer. 6. The following formula: (Wherein, R ₁ and R ₂ are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and n represents an integer of 1 to 10). A method for producing a urethane copolymer in which two kinds of diol compounds are reacted, wherein a first step of reacting approximately 1/2 mole amount of a diol compound, and a second step in which polymerization is completed by further adding a diol compound. A process for producing a urethane copolymer comprising the steps of: 7. In a first step, a diol compound represented by the following formula: HO—R ₃ —OH (where R ₃ is a dihydric alcohol residue) is reacted, In the step, a diol compound represented by the following formula: HO—R ₄ —OH (wherein R ₄ represents a divalent alcohol residue different from R ₃ ), which is substantially equimolar to the diol in the step, is reacted. The method for producing a urethane copolymer according to claim 1, wherein 8. In each of the first step and the second step,
Following formula: HO-R 3 _-OH (. Wherein, R ₃ is a divalent alcohol residue) diol represented by compounds and the diol compounds with approximately equimolar amounts of the formula: HO-R ₄ - The method for producing a urethane copolymer according to claim 2, wherein a mixed diol compound comprising a diol compound represented by OH (wherein R ₄ represents a dihydric alcohol residue different from R ₃ ) is reacted. 9. The following formula: (Wherein, R ₁ and R ₂ are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and n represents an integer of 1 to 10). the following formula: _HO-R 3 -OH (wherein, _{R 3} is a divalent an alcohol residue.) diol represented by compound and the diol compound and approximately equimolar of the formula: _{HO-R 4} - OH (wherein R ₄ represents a dihydric alcohol residue different from R ₃ ), substantially simultaneously reacting a mixed diol comprising a diol compound represented by R ₃ to complete the polymerization reaction. The method for producing a urethane copolymer according to claim 3, characterized in that: 10. An optical material comprising at least one urethane copolymer selected from claims 1, 2 and 3.