JP2003342342A - Ordered polyurethane-urea polymer having nonlinear optical characteristic - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a new ordered polyurethane-urea having the arrangement structure of its nonlinear optical component controlled for obtaining a greater nonlinear optical effect. <P>SOLUTION: The polyurethane-urea polymer contains diisocyanate structural units represented by formula (1), diamine structural units represented by formula (2), diol structural units represented by formula (3), and structural units represented by formula (I), wherein the numbers of those structural units respectively are k, l, m and x, satisfying the inequality: 0.7≤4x/(k+l+m)≤1. The polymer has a number-average molecular weight of 2,000 to 200,000. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an ordered polyurethane urea containing a non-linear optical component and having high non-linear optical properties. The polyurethaneurea of the present invention is a polymer nonlinear optical material applicable to various optical elements, for example, an optical switch utilizing nonlinear optical effects such as electro-optical effect, optical harmonic generation, and optical bistability. , Optical modulators, wavelength conversion elements, optical operation elements, and other optical elements.

[0002]

BACKGROUND OF THE INVENTION Polymers obtained by controlling the arrangement of monomers (hereinafter referred to as ordered polymers) have not only thermal and mechanical properties, but also liquid crystallinity and nonlinear optical properties (hereinafter referred to as NLO). It is also expected to have specific properties in terms of physical properties. However, polycondensation polymers such as polyurea, polyurethane, polyamide, and polyimide, which are industrially produced and widely used, have attracted a great deal of attention because of few synthetic examples to date because of difficulty in monomer design.

To date, the present inventors have found that by using asymmetric diisocyanates having different reactivities to nucleophiles, it is possible to synthesize polyurethane in which the sequence structure of monomers is controlled by a predetermined method. (JP-A-11
-171965, Japanese Patent Application 2000-230631). In addition to the above-mentioned asymmetric isocyanate, 4-aminophenethyl alcohol
(Has an aromatic amino group and an aliphatic hydroxyl group in the molecule)
It was also found that a polyurethane urea having a head-to-tail structure can be synthesized by using an asymmetric amino alcohol such as (Japanese Patent Application No. 2001-61191). Furthermore, in order to produce an ordered polymer from various raw materials and to facilitate functionalization, the ordered alcohol can be extended to two kinds of aromatic diamines and aliphatic diols as the asymmetric monomer. It was found that a polyurethane urea can be obtained (Japanese Patent Application No. 2002-4320).
3).

Therefore, we have introduced an NLO component as an aliphatic diol component for functionalization of an ordered polymer, and by controlling the array structure thereof, the NLO property is improved as compared with a conventional polymer without sequence control. I was careful.

Conventionally, in polymer nonlinear optical materials,
An NLO component in which at least one electron-donating group and an electron-withdrawing group are bonded to a π-electron conjugated system is known. There is known a polymer non-linear material in which this component is doped into a polymer component or randomly bonded to a polymer main chain, and an NLO component is oriented by an electric field orientation treatment to develop NLO characteristics. However, in the NLO component, the π-electron conjugated system has a planar structure, and the electron-donating group and the electron-withdrawing group are bonded to each other to spontaneously polarize. Therefore, when the NLO content in the polymer increases, the NLO components are separated from each other. , Tends to associate or aggregate to cancel this polarization. Moreover, when such a state where NLO components are associated with each other occurs, it is presumed that this association becomes difficult to dissolve even by an external electric field.

Therefore, in order to suppress the association of NLO components with each other, it is considered that a polymer non-linear material having a large NLO characteristic can be obtained by improving the dispersibility of NLO components in the polymer, and thus the dispersibility is improved. Therefore, an ordered polyurethane urea in which the arrangement structure of the NLO component was controlled was examined. Further, since such a polymer contains a urea bond, it is expected to have higher NLO characteristics than polyurethane. It should be noted that there has been no report up to now on the ordered polyurethane urea in which the arrangement structure (primary structure) of NLO in a polymer is controlled by using one kind of asymmetric monomer and two kinds of symmetrical monomer.

An object of the present invention is to produce a novel ordered polyurethane urea in which the arrangement structure of nonlinear optical components is controlled in order to obtain a large nonlinear optical effect.

[0008]

DISCLOSURE OF THE INVENTION The inventors of the present invention filed in Japanese Patent Application No. 2002-43203 previously filed (i) having two isocyanate groups in the molecule and one of the isocyanate groups being an aromatic ring. Reactivity of (ii) aromatic diamines and aliphatic diols with asymmetric diisocyanate monomers that are directly bonded and the other isocyanate group is bonded to an aromatically bonded aliphatic carbon atom Was examined in detail. As a result, it has been found that such compounds have a clear difference in reactivity corresponding to each of the two isocyanate groups, and the amino group of the diamine and the hydroxyl group of the diol. Based on these results, when a similar method is applied to an aliphatic diol having an NLO component, an aromatic diamine, and an asymmetric diisocyanate, an ordered polymer in which the arrangement structure of the NLO component is controlled is obtained. It has been found.

That is, the first invention of the present application is represented by the following formula (1):

[Chemical 6] (In the formula, R ₁ and R ₂ are each independently hydrogen or a lower alkyl group, and n is an integer of 1 to 10.) A diisocyanate structural unit

Equation (2):

[Chemical 7] (In the formula, R ₃ represents a divalent aromatic group.), And

Formula (3):

[Chemical 8] (In the formula, R ₄ and R ₅ are each independently a lower alkyl group, R ₆
Is hydrogen or a lower alkyl group, X and Y are each independently C
H, N, and Z mean NO ₂ , CN, and CF ₃ . ), The structural unit of the formula (1) is k, the structural unit of the formula (2) is l, and the structural unit of the formula (3) is m.
Is a polyurethaneurea polymer having a number average molecular weight of 2,000 to 200,000 and containing the following formula (I):

[0012]

[Chemical 9] The present invention provides a polyurethaneurea containing x structural units represented by the following formula, wherein the relationship between k, l, m and x is 0.7 ≦ 4x / (k + l + m) ≦ 1.

The present invention also has the following formula (Ia):

[Chemical 10] (In the formula, p means an integer of 2 to 200.) A polyurethaneurea having a constitutional unit represented by the formula is provided. If the number average molecular weight is smaller than the above numerical range, a sufficient polymer compound cannot be obtained, while a polymer compound having a larger number average molecular weight is not practical. In addition, in the above-mentioned polyurethane polyurea, the formula (2) or the formula must be provided at both ends of the formula (1).
The structural units of (3) are bonded, and the structural units of formula (2) and formula (3) are not bonded continuously. Each of equations (1), (2), and (3) does not combine in series by themselves.

[0014]

DETAILED DESCRIPTION OF THE INVENTION The polyurethaneurea of the present invention has the formula
It has the structural units of (1), formula (2) and formula (3), and by selecting the reaction conditions of the monomer, 4x / (k +
A polyurethaneurea in which 1 + m) is 0.7 to 1 and the sequence unit of formula (I) is preferred is obtained.

Next, the monomer of the ordered polyurethane urea of the present invention and the polymerization method thereof will be described in detail.

(Diisocyanate Compound) The diisocyanate, which is a raw material for the ordered polyurethane urea of the present invention, is
The following formula:

[0017]

[Chemical 11] It is represented by. The characteristics of this diisocyanate monomer are:
It 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 a carbon atom bonded to the aromatic ring. Due to such a structure, the two isocyanate groups show a large difference in reactivity.

The isocyanate group on the aromatic ring and the isocyanate group bonded to the carbon atom may be in any of the ortho, meta and para positions. In formula (4), n = 1 to 10
Is. R ₁ and R ₂ are preferably a hydrogen atom or a lower alkyl group such as a methyl group and an ethyl group. Therefore, equation (4)
Typical examples of the compound (1) are diisocyanates such as isocyanatobenzyl isocyanate, isocyanatophenethyl isocyanate, and α- (isocyanatophenyl) -ethyl isocyanate. The molecular weight of the divalent asymmetric diisocyanate that can be used in the present invention is
It is usually 174 to 500, preferably 174 to 300.

(Aromatic Diamine) The aromatic diamine as a raw material for the ordered polyurethane urea of the present invention has the following formula:

[0020]

[Chemical 12] (R ₃ has the same meaning as described above) and is a divalent aromatic diamine. In the formula (5), R ₃ is specifically aromatic hydrocarbons such as phenylene, biphenylene and diphenyl ether, diphenylmethane, 2,2-
Hydrocarbons composed of aliphatic and aromatic groups such as bis [4- (4-aminophenoxy) phenyl] propane, including those having the following structural formulas.

[0021]

[Chemical 13]

Therefore, typical diamines represented by the above formula (5) are, for example, 1,4-phenylenediamine, biphenylenediamine, 3,3-dimethyl-4,
4'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether,
1,3-bis (4-aminophenoxy) benzene, 1,4-
Bis (4-aminophenoxy) benzene, 4,4'-bis
(4-aminophenoxy) biphenyl, 4,4'-diaminodiphenyl sulfide, 9,9-bis (4-aminophenyl) fluorene, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4, 4'-diaminobenzophenone, 3,4-diaminobenzophenone, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, 4,4'-diaminodiphenylmethane, 3 , 4'-Diaminodiphenylmethane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 2,2'-dimethyl-4,4'-
Diaminobiphenyl, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, 2,2-bis (4-
Aminophenyl) propane, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2-bis [4- (4
-Aminophenoxy) phenyl] propane, 2,2-bis
[4- (4-Aminophenoxy) phenyl] hexafluoropropane, neopentyl glycol bis (4-aminophenyl) ether, propene bis (4-aminophenyl)
Ether, butene bis (4-aminophenyl) ether,
It is a divalent aromatic diamine that reacts with isocyanates such as heptene bis (4-aminophenyl) ether. The molecular weight of the divalent aromatic diamine used in the present invention is usually 108 to 600, preferably 108 to 400.

(Aliphatic diol) On the other hand, the aliphatic diol has the following formula:

[Chemical 14] (R ₄ , R ₅ , R ₆ , X, Y and Z have the same meanings as described above.), Which is a divalent aliphatic diol, and NLO
Contains ingredients. The NLO component is composed of an electron-withdrawing group and an electron-donating group bonded to a π-electron conjugated system. The formula
In (6), X and Y each independently represent CH or N,
Specifically, it is a π-electron conjugated system such as a stilbene group, an azobenzene group, and a benzylideneaniline group. Also,
R ₄ and R ₅ each independently represent a lower alkyl group such as a methyl group or an ethyl group, and are electron-donating groups such as a dialkylamino group. R ₆ means hydrogen or a lower alkyl group such as a methyl group. Z means an electron withdrawing group such as a nitro group, a cyano group and a trifluoromethyl group.

Therefore, a typical diol represented by the above formula (6) is, for example, 4-N, N'-bis (2-
Hydroxyethyl) amino-2,2'-dimethyl-4'nitroazobenzene, 4-N, N'-bis (2-hydroxyethyl) amino-2-methyl-4'-nitroazobenzene,
4-N, N'-bis (2-hydroxyethyl) amino-2 '
-Methyl-4'-nitroazobenzene, 4-N, N'-bis (2-hydroxyethyl) amino-4'-nitroazobenzene, 4-N, N'-bis (2-hydroxyethyl) amino-2,2 '-Dimethyl-4'-cyanoazobenzene, 4
-N, N'-bis (2-hydroxyethyl) amino-2-methyl-4'-cyanoazobenzene, 4-N, N'-bis (2
-Hydroxyethyl) amino-2'-methyl-4'-cyanoazobenzene, 4-N, N'-bis (2-hydroxyethyl) amino-4'-cyanoazobenzene, 4-N, N'-
Bis (2-hydroxyethyl) amino-2,2'-dimethyl-4'-trifluoromethylazobenzene, 4-N, N '
-Bis (2-hydroxyethyl) amino-2-methyl-
4'-trifluoromethylazobenzene, 4-N, N'-
Bis (2-hydroxyethyl) amino-2'-methyl-4 '
-Cyanoazobenzene, 4-N, N'-bis (2-hydroxyethyl) amino-4'-trifluoromethylazobenzene, 4-N, N'-bis (2-hydroxyethyl) amino-4'-nitrostilbene, N, N'-bis (2-hydroxyethyl) amino-2-dimethyl-4'-nitrostilbene, 4-N, N'-bis (2-hydroxyethyl) amino-
Any compound having a divalent hydroxyl group that reacts with an isocyanate such as 4′-cyanostilbene may be used. The molecular weight of dihydric alcohols that can be used is usually 280 to 6
00, preferably 280 to 400.

(Method for Producing Ordered Polyurethane Urea) Next, using the above-mentioned monomer, the sequence unit of the formula (4) has priority, that is, 4x / (k + l + m) is 0.7 to 1. The method for producing an ordered polyurethane urea with sequence control will be described in detail below.

The amounts of the diamine monomer and the diol monomer are the sum of the number of amino groups of the diamine monomer and the number of hydroxyl groups of the diol monomer with respect to the number of isocyanate functional groups of the diisocyanate monomer in order to sufficiently increase the molecular weight of the copolymer. Are preferably used so as to be almost equal (equimolar amount), but the present invention is not limited thereto.
Here, the substantially equimolar amount means that the total amount of the diamine monomer and the diol monomer is 1 mole of diisocyanate.
It is 0.8 to 1.2 mol, preferably 0.9 to 1.1 mol, and more preferably 0.99 to 1.01 mol. At this time, the diamine monomer and the diol monomer are each 0.4 to 0.6 mol, preferably 0.4 per 1 mol of the total.
It is 5 to 0.55, and more preferably 0.49 to 0.51 mol.

In order to produce a polyurethaneurea containing a sequence unit represented by the formula (I) as a main component, polycondensation of the above-mentioned isocyanate compound with a diamine compound and a diol compound is carried out with respect to (i) diisocyanate. , Each about 1
/ 2 times the molar amount of aromatic diamine and aliphatic diol are reacted at substantially the same time. Or (b) First, only about 1/2 times the molar amount of the diamine monomer is dropped, and then about 1/2
Double moles of diol monomer may be added. Such a reaction operation means that substantially all of the diamine participates in the reaction at least at the start of the addition of the diol. In this way, the amino group of the diamine and the aromatic isocyanate group of the diisocyanate monomer react with each other ((1:
2) Select reaction conditions in which the adduct is preferentially produced.

On the other hand, for example, a mixture of a diamine monomer and a diol monomer is added dropwise to the diisocyanate monomer, or the diol monomer is added first and then the diol monomer is added. And the reaction conditions in which the addition of the diamine has not been completed at the time of adding the diol and substantially all of the diamine is not involved in the reaction, the content of the sequence unit of the formula (4) decreases.

As described above, in the present invention, substantially the entire amount of the diamine is added to the reaction system with the diisocyanate when the diol starts participating in the reaction. As such an operation, all of the monomers (diisocyanate, diamine and diol) are added at once to the reaction system,
Diisocyanate and a mixture of diamine and diol in about ½ times the molar amount of diisocyanate are added to the reaction system in equimolar amounts. Operations such as adding are included.

The reaction temperature of the polycondensation reaction is preferably as low as possible in order to improve the reaction selectivity of the diamine monomer and the diol monomer with respect to the diisocyanate monomer. In addition, side reactions such as the trimerization reaction of isocyanate that competes at the time of urethane bond formation can be suppressed by the reaction at low temperature. Therefore, the reaction temperature is -4.
It is 0 to 40 ° C., preferably −20 to 30 ° C., more preferably −10 to 0 ° C., and it is particularly preferable to react at around 0 ° C. The reaction temperature may be a constant temperature from the start to the end of the reaction, or may be low at the beginning and then raised.

The polymerization time is 5 to 48 hours, preferably 10 to 24, in consideration of the progress of polymerization.
It is good to do it in time.

As the solvent used in the reaction, it is necessary to use a highly polar solvent in order to make the target polymer highly polar and to allow the polymerization to proceed efficiently. For example, DMF (N, N-dimethylformamide), DMAc (N, N-dimethylacetamide), DMSO (dimethyl sulfoxide), NMP
Although it is preferable to select a highly polar aprotic solvent such as (N-methylpyrrolidone), aliphatic hydrocarbons such as cyclohexane, pentane and hexane, benzene and toluene, as long as the reaction substrate and the target substance are well dissolved. Aromatic hydrocarbons such as chlorobenzene, THF (tetrahydrofuran), diethyl ether, ethers such as ethylene glycol diethyl ether, acetone, methyl ethyl ketone, ketones such as 4-methyl-2-pentanone, methyl propionate, ethyl acetate, Solvents such as esters such as butyl acetate may be used, or these may be mixed and used. The amount of these solvents used is preferably such that the monomer substrate is diluted as much as possible from the viewpoint of improving the selectivity of the reaction, but if the reaction is proceeded efficiently and the reaction operation is taken into consideration, the amount of the monomer substrate is 0.1 to 2 mol. It is better to prepare it so that it becomes / L.

Since the reactivity of the amino group with respect to the isocyanate is higher than the reactivity of the hydroxyl group, a catalyst is generally not required to form the urea bond, but since the urethane bond formation proceeds efficiently, N , N, N ',
Tertiary alkylamines such as N'-tetramethyl-1,3-butanediamine, triethylamine and tributylamine, 1,4-diazabicyclo [2.2.2] octane, 1,
Known urethane bond-forming catalysts such as condensed amines such as 8-diazabicyclo [5.4.0] unde-7-ene, alkyltins such as DBTL, tetrabutyltin, and tributyltin acetate can be used.

In order to preferentially cause the reaction between the aromatic isocyanate and the amino group and suppress the reactivity between the aromatic isocyanate and the hydroxyl group, the initial polymerization is carried out without a catalyst, and thereafter,
It is preferable to use a catalyst having higher activity such as alkyl tins and condensed amines so that the urethane bond can be efficiently generated.

The amount of the catalyst used is 0.1 to 30 mo with respect to the monomer substrate in consideration of efficient reaction and reaction operation.
It is preferable to use 1%.

As described above, in order to preferentially generate the structural unit of the formula (I), the reactivity of the diamine monomer and the diol monomer with respect to each isocyanate group must be different, and at least the addition of the diol should be started. At this point, substantially all of the diamine is added, the amino groups of the diamine monomer react preferentially with the aromatic isocyanate in the diisocyanate monomer, and the hydroxyl groups of the diol monomer preferentially react with the aliphatic isocyanate groups. It is important to select the reaction conditions.

Quantitative studies on the ordering property of the thus obtained polymer are carried out by ¹³ C-derived from the diol monomer in the polymer main chain as disclosed in JP-A No. 11-171965.
It was used that the peak of the NMR methylene group differs depending on the head-to-head structure, the tail-to-tail structure, and the head-to-tail structure. That is, three kinds of model compounds corresponding to the respective sequences were synthesized, and this was compared with the monomers obtained in the examples. In the obtained polymer, if the signal of the methylene group derived from the diol monomer is a tail-to-tail structure, the arrangement structure of the other diamine monomer is a head-to-head structure, and it has a desired arrangement structure. I can judge.

Here, among the arrangement units of the polymer obtained by reacting the asymmetric diisocyanate compound and the diol, the following formula:

[0039]

[Chemical 15] Is defined as a head-to-head sequence unit (an aromatic isocyanate group having high reactivity with the central diol unit is bound to both ends).

The following equation:

[0041]

[Chemical 16] The sequence represented by is defined as a tail-to-tail sequence unit.

Further, the following formula:

[Chemical 17] The sequence represented by is defined as a head-to-tail sequence unit.

[0043]

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

Reference Example 1 Synthesis of Model Compound Corresponding to Head-to-Head Structure 0.55 g (0.8) of DBTL in 50 mL of 1,4-dioxane.
7 mmol), ethylene glycol 1.28 g (20.6 m)
mol), 4.96 g of phenyl isocyanate (41.6 m)
mol) was added and the mixture was stirred at 60 ° C. for 1 day. After distilling off the solvent, the residue was purified by recrystallization with ethyl acetate to obtain a crystalline solid. The ¹³ C-NMR measurement of the product obtained here was performed (FIG. 1). As a result, a peak of the carbonyl group (b) was observed at 154.9 ppm, which was 140.8, 130.0, 123.8,
A peak of the aromatic ring (a) was observed at 119.6 ppm.
Since a peak of methylene (c) was observed at 4.2 ppm, it was confirmed that the compound corresponds to the expected head-to-head structure. Yield 4.76g (76% yield)

[Reference Example 2] Synthesis of model compound corresponding to tail-to-tail structure 0.55 g (0.8) of DBTL was added to 50 mL of 1,4-dioxane.
7 mmol), ethylene glycol 1.10 g (17.7 m)
mol), benzyl isocyanate 4.74 g (35.6 m)
mol) was added and the mixture was stirred at 60 ° C. for 1 day. After distilling off the solvent, the residue was purified by recrystallization with ethyl acetate to obtain a crystalline solid. ¹³ C-NMR measurement of the product obtained here was performed (FIG. 2). As a result, a peak of carbonyl group (c) was observed at 158.0 ppm, which was 141.4, 129.6, 128.6,
A peak of the aromatic ring (a) was observed at 128.2 ppm.
A methylene (d) peak was observed at 4.3 ppm and 45.
Since a peak of benzylic methylene (b) was observed at 7 ppm, it was confirmed that the compound corresponds to the expected tail-to-tail structure. Yield 4.72 g (81% yield)

[Reference Example 3] Synthesis of model compound corresponding to head-to-tail structure N-benzyl- (2-hydroxy) ethylcarbamic acid ester 2.93g to DBTL 0.73g (1.16mmo)
l) and phenyl isocyanate 1.81 (15.2 mmo)
1) was added, and the mixture was stirred in 90 mL of 1,4-dioxane at 60 ° C. for 1 day. The solvent was distilled off, and recrystallized and purified with a mixed solvent of n-hexane / ethyl acetate to obtain a crystalline solid. The ¹³ C-NMR measurement of the product obtained here was performed (FIG. 3). As a result, the peak of the carbonyl group (e) was observed at 158.0 ppm, the peak of the carbonyl group (b) was observed at 155.0 ppm, and 141.0, 130.1, 123.8, 1
A peak of the aromatic ring (a) was observed at 19.7 ppm.
Aromatic ring (g) peaks were observed at 1.4, 129.6, 128.6 and 128.2 ppm, and methylene at 64.5 ppm.
The peak of (d) was observed, and methylene was detected at 64.1 ppm.
Since the peak of (c) was observed and the peak of methylene (f) at the benzyl position was confirmed at 45.8 ppm, the compound was confirmed to correspond to the expected head-to-tail structure. Yield 2.84g (60% yield)

Reference Example 4 Synthesis of Model Polymer of Ordered Polyurethane Urea p-Isocyanatobenzylisocyanate (PIBI) (1.742 g, 10.0 mmo) was placed in a 50 mL three-necked flask.
l), 5 mL of DMF was charged, and dimethyl-
4,4'-diaminobiphenyl (hereinafter m-TB) (1.601)
g, 5.0 mmol) in a DMF solution (15 mL) under an ice bath for 3
The mixture was slowly added dropwise over 0 minutes, and the mixture was further stirred at 0 ° C for 1 hour. After returning the solution to room temperature, ethylene glycol
(Hereinafter EG) (0.310 g, 5.0 mmol), DBTL
(0.316g, 0.25mmol) was added and the mixture was stirred at room temperature for 20
Stir for hours. The polymerization solution was poured into methanol, and the obtained precipitate was separated by filtration. Dried under vacuum at 70 ° C overnight,
2.89 g of white powder (yield 93%) was obtained.

In the ¹³ C-NMR spectrum (FIGS. 4 and 5) of the obtained polymer, the peak of the methylene group was 62.6.
Only ppm was observed, and it was found that a polyurethane urea having a tail-tail structure of the diol component and a head-head structure of the diamine component was obtained (4a / (k + l + m)).
= 1). At this time, the peak of the carbonyl carbon of the urethane bond obtained from the diol component having a tail-to-tail structure and the benzyl isocyanate site of PIBI is 156.2 p.
and a diamine component having a head-to-head structure observed in pm and P
It was confirmed that the carbonyl carbon of the urea bond obtained from the phenyl isocyanate site of IBI was observed at 152.6 ppm.

When the molecular weight was determined by GPC using polystyrene as a reference substance, the number average molecular weight was 10,000.
The molecular weight distribution was 2.3.

Reference Example 5 Synthesis of Model Polymer of Random Polyurethane Urea m-TB (1.133 g, 5.3 m) in a 50 mL three-necked flask.
mol), EG (0.331 g, 5.3 mmol), DBTL
(0.158 g, 0.25 mmol), 5 mL of DMF was charged, and PIBI (1.858 g, 10.6 mmo)
10 mL of the DMF solution of 1) was slowly added dropwise to the solution in 50 ° C. over 30 minutes, and the mixture was further reacted for 1 hour. After cooling to room temperature, the mixture was stirred for 20 hours. This polymerization solution was poured into methanol, and the obtained precipitate was separated by filtration. Under reduced pressure,
After drying overnight at 70 ° C, 3.15 g of white powder (94% yield)
Got

In the ¹³ C-NMR spectrum (FIGS. 6 and 7) of the obtained polymer, the peak of the methylene group was 62.
It was observed at 4, 62.6 and 62.8 ppm, and the diol component and the diamine component were a head-head structure, a head-tail structure, a tail-
It was found that a polyurethane urea having a tail structure sequence was obtained. At this time, the peak of the carbonyl carbon of the urethane bond obtained from PIBI with a diol component having a head-to-head structure, a head-to-tail structure, and a tail-to-tail structure is 15
Observed at 6.2 and 153.3 ppm, head-head structure, head-
The carbonyl carbon of the urea bond obtained from the PIBI having a tail structure, a diamine component having a tail-tail structure is 155.
It was confirmed that it was observed at 3,152.6 ppm.

The number average molecular weight was determined to be 30,000 by GPC using polystyrene as a reference substance.
The molecular weight distribution was 3.0.

Example 1 Synthesis of Ordered Polyurethane Urea PIBI (1.742 g, 10.
0 mmol) and 5 mL of DMF were charged, and m
-TB (1.062 g, 5.0 mmol) in DMF solution 15
mL was slowly added dropwise in an ice bath over 1 hour, and the mixture was further stirred at 0 ° C. for 1 hour. After returning the solution to room temperature, 4
-N, N'-bis (2-hydroxyethyl) amino-2,2 '
-Dimethyl-4'nitroazobenzene (1.792 g, 5.
0 mmol), DBTL (0.158 g, 0.25 mmol)
Was added, 15 mL of DMF was added, and the mixture was stirred at room temperature for 20 hours. The polymerization solution was poured into methanol, and the obtained precipitate was separated by filtration. After drying under reduced pressure at 70 ° C. overnight, 4.256 g (yield 93%) of red powder was obtained.

In the ¹³ C-NMR spectrum (FIGS. 8 and 9) of the obtained polymer, the peak of the carbonyl group of the urethane bond was found at 156.3 ppm and the peak of the carbonyl group of the urea bond was found at 152.5 ppm. From the knowledge of Reference Example 4, it was found that the diamine component was a polyurethane urea having a head-to-head structure and the NLO component was a tail-to-tail structure (4x / (k + l + m) = 1).

When the molecular weight of the obtained polymer was determined by GPC using polystyrene as a reference substance, the number average molecular weight was 35,000 and the molecular weight distribution was 3.0.

Further, it was found that the maximum absorption wavelength (in DMF solvent) of the polymer of the obtained polymer was 492 nm.

The polymer obtained in Example 1 was analyzed by differential scanning calorimetry (DSC) under a nitrogen stream at room temperature to 250 ° C.
When the glass transition temperature (Tg) was examined by heating up to 10 ° C./min, Tg was found to be 174 ° C.

Comparative Example 1 Synthesis of Random Polyurethane Urea m-TB (1.062 g, 5.0) dissolved in 10 mL of DMF.
mmol), 4-N, N'-bis (2-hydroxyethyl)
Amino-2,2'-dimethyl-4'-nitroazobenzene
(1.792 g, 5.0 mmol), DBTL (0.158 g,
0.25 mmol) to P dissolved in 15 mL of DMF
IBI (1.744 g, 5.0 mmol) was slowly added dropwise at room temperature over 1 hour, and the mixture was stirred for 20 hours. The polymerization solution was poured into methanol, and the obtained precipitate was separated by filtration. After drying at 70 ° C. under reduced pressure overnight, 4.190 g of red powder (yield 9
1%).

In the ¹³ C-NMR spectrum (FIGS. 10 and 11) of the obtained polymer, the peaks of the carbonyl group of the urethane bond were 156.3 and 153.4 ppm and the peaks of the carbonyl group of the urea bond were 155. 3, 152.
It was observed at 5 ppm, and from the findings of Reference Example 5, the diamine component and the NLO component were respectively a head-head structure, a head-tail structure, and a tail-
It was found to be a random polyurethaneurea containing all sequences of the tail structure.

When the molecular weight of the obtained polymer was determined by GPC using polystyrene as a reference substance, the number average molecular weight was 20,000 and the molecular weight distribution was 3.5.

Further, it was found that the absorption maximum wavelength (in DMF solvent) of the polymer of the obtained polymer was 492 nm.

The polymer obtained in Example 1 was analyzed by differential scanning calorimetry (DSC) under a nitrogen stream at room temperature to 250 ° C.
When the glass transition temperature (Tg) was examined by heating up to 10 ° C./min, Tg was found to be 170 ° C.

(Evaluation of Nonlinear Optical Properties) Next, the nonlinear optical properties of the ordered polyurethane urea obtained in Example 1 were evaluated by the d constant obtained by the second harmonic generation (SHG). A pulse of Nd: YAG laser (wavelength; 1064 nm, pulse width; 7 ns) was used as the incident fundamental wave. Quartz crystal (d ₃₃ = 0.5 pm / V) was used as the standard sample.
It was used. The refractive index of the polymer was measured with a prism coupler.

The SHG measurement sample was prepared as follows. A 10 wt% DMF solution of the obtained polymer was prepared,
A film having a thickness of 2 μm was produced on the ITO electrode by spin coating. This electrode was placed on a hot stage heated to 190 ° C., and a voltage of 7.5 kV was applied between the electrode and a corona wire placed vertically at a distance of 14 nm from the sample. In this state, it was left for 1 hour and cooled to room temperature while applying voltage. When the SHG characteristics immediately after polling were evaluated, a high value of 100 pm / V was obtained as the nonlinear optical constant d ₃₃ value. It is considered that the NLO association could be suppressed by controlling the sequence structure of NLO.

Similarly, the non-linear optical characteristics of the random polyurethane obtained in Comparative Example 1 were subjected to corona poling treatment as in the case of the polyurethane of Example 1 to evaluate the non-linear optical characteristics. This nonlinear optical constant d ₃₃ value is 30
pm / V, which was lower than that of the ordered polyurethane urea obtained in Example 1. It is considered that some NLOs were associated because the sequence structure of NLOs was not controlled.

[0066]

EFFECT OF THE INVENTION An ordered polyurethane urea in which the NLO array structure is regulated can be easily obtained, and NL in the polymer can be obtained.
Since the O association is suppressed, high nonlinear optical characteristics can be obtained.

[Brief description of drawings]

FIG. 1 shows ¹³ C-of the model compound obtained in Reference Example 1.
It is an NMR spectrum.

FIG. 2 shows ¹³ C-of the model compound obtained in Reference Example 2.
It is an NMR spectrum.

FIG. 3 shows ¹³ C-of the model compound obtained in Reference Example 3.
It is an NMR spectrum.

FIG. 4 Ordered polyurethane urea obtained in Reference Example 4
Amodel polymer ^ThirteenIt is a C-NMR spectrum.

FIG. 5: ¹³ C of the model polymer obtained in Reference Example 4
-An enlarged view of the methylene carbon and carbonyl carbon regions of the NMR spectrum.

FIG. 6 is a ¹³ C-NMR spectrum of the random polyurethane urea model polymer obtained in Reference Example 5.

FIG. 7: ¹³ C of the model polymer obtained in Reference Example 5
-An enlarged view of the methylene carbon and carbonyl carbon regions of the NMR spectrum.

FIG. 8 is a ¹³ C-NMR spectrum of the ordered polyurethane urea obtained in Example 1.

FIG. 9 is an enlarged view of a carbonyl carbon region in a ¹³ C-NMR spectrum of the ordered polyurethane urea obtained in Example 1.

FIG. 10 is a ¹³ C-NMR spectrum of the random polyurethane urea obtained in Comparative Example 1.

FIG. 11 is an enlarged view of a carbonyl carbon region in the ¹³ C-NMR spectrum of the random polyurethane urea obtained in Comparative Example 1.

   ─────────────────────────────────────────────────── ─── Continued front page    F term (reference) 2K002 AB12 BA03 CA05 FA10 HA20                 4J034 BA06 CA04 CA15 CB02 CC05                       CC12 CC22 CC45 CC52 CC61                       CC62 CC67 CD01 HA01 HA07                       HC12 HC22 HC46 HC52 HC61                       HC71 HC73 JA02 JA14 JA32                       KA01 KB02 KD12 QB08 RA13                       RA14

Claims (2)

[Claims] 1. The following formula (1): (In the formula, R ₁ and R ₂ are each independently hydrogen or a lower alkyl group, and n is an integer of 1 to 10.) A diisocyanate structural unit represented by the following formula (2): ] (In the formula, R ₃ means a divalent aromatic group), and a diamine structural unit represented by the following formula (3): (In the formula, R ₄ and R ₅ are each independently a lower alkyl group, R ₆
Represents hydrogen or a lower alkyl group, X and Y each independently represent CH, N and Z represent NO ₂ , CN and CF ₃ . )
A number-average molecular weight of 2,000 containing a diol structural unit represented by the formula (1), including k structural units of the formula (1), l structural units of the formula (2), and m structural units of the formula (3). To 200,000 polyurethaneurea polymers having the following formula (I): A polyurethaneurea containing x structural units represented by the following formula, wherein the relationship between k, l, m and x is 0.7 ≦ 4x / (k + 1 + m) ≦ 1. 2. The following formula (Ia): The polyurethane urea according to claim 1, which has a structural unit represented by the formula (wherein p represents an integer of 2 to 200).