JPH11279251A - Polyurethane having fluorene skeleton - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polyurethane having thermal resistance (i.e., a high glass transition temperature), formability of film and a high refractive index. SOLUTION: This polyurethane has a repeating unit of the formula (A<1> and A<2> are each H or methyl; R is biphenyl or bicyclohexyl both able to have an alkyl or an alkoxy) and a weight-average molecular weight of 2,000-300,000. The polyurethane is obtained by reacting 9,9-bis(4-(2-hydroxyalcoxy)phenyl) fluorene with diisocyantes in the presence or absence of a solvent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a polyurethane and a method for producing the same.

[0002]

2. Description of the Related Art Polyurethane is used as a transparent conductive film, an organic semiconductor, an organic superconductor and a photosensitive material in the electric and electronic industries; optical lenses such as automobile lenses, CD pickup lenses and Fresnel lenses, and projection television screens. , As a material for a film such as a retardation film, plastic optical fiber, optical disc substrate, and the like; and in the fields of paints, fibers, synthetic leather, and the like, for example, tires, belts, packings, gears,
Widely used as a material for shoe soles.

[0003] Polyurethanes are obtained by the reaction of polyester or polyether glycols with diisocyanates. As typical polyester glycols, those having a molecular weight of about 1500 to 3000 obtained from ethylene glycol or the like and adipic acid are used.
Tolylene diisocyanate or the like is used as the diisocyanate.

In the reaction of polyester glycol or polyether glycol with diisocyanate, the diisocyanate is excessively reacted to synthesize a high molecular weight prepolymer having isocyanate groups at both ends, and furthermore, diamine, amino alcohol, Glycol is added to extend the chain length and to carry out an intermolecular crosslinking reaction.

[0005] Polyurethanes have different physical properties depending on the type of raw materials, crosslinking conditions, and the like. Generally, polyurethanes have excellent oil resistance and abrasion resistance, but have the disadvantage of low heat resistance.
What has a film forming ability and what has a high refractive index suitable as an optical material is not known very much.

The present inventor has proposed a polyurethane having a fluorene skeleton as a rigid and chemically stable polyurethane having heat resistance and film forming ability (Japanese Patent Laid-Open No. Hei 8 (1994)).
-3260 publication).

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel polyurethane having a fluorene skeleton which is rigid and chemically stable, has a film forming ability with further improved heat resistance. An object of the present invention is to provide a novel polyurethane having a high refractive index suitable as an optical material.

[0008]

The polyurethane of the present invention has a repeating unit represented by the following formula (1) and has a weight average molecular weight of 20,000 or more, preferably 30,000 or more, more preferably 40,000 or more, and usually, 40000
0 or less, further 300,000 or less, especially 100,000
Below, in some cases, it is in the range of 60000 or less. If the weight average molecular weight is too high, the film forming ability tends to decrease.

The polyurethane of the present invention is, for example, 90 to 1
About 80 ° C, usually about 110 to 160 ° C, especially 12
It has a glass transition point of about 0 to 150 ° C.

[0010]

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In the formula (1), A ¹ and A ² are the same or different and each represent a hydrogen atom or a methyl group, and R represents an alkyl group (for example, an alkyl group having 1 to 3 carbon atoms, particularly a methyl group) or an alkoxy group. (E.g., a biphenyl group or an alkyl group (e.g., an alkyl group having 1 to 3 carbon atoms, particularly a methyl group) or an alkoxy group (e.g., a carbon number of 1 to 3 carbon atoms, particularly a methoxy group). A bicyclohexyl group which can have 1 to 3 alkoxy groups, especially a methoxy group).

Examples of the biphenyl group which can have an alkyl group or an alkoxy group include a biphenyl group represented by the following formula (4), a 3,3′-dimethylbiphenyl group represented by the following formula (5), There is a 3,3′-dimethoxybiphenyl group represented by the following formula (6). Examples of the bicyclohexyl group that can have an alkyl group or an alkoxy group include a bicyclohexyl group represented by the following formula (7).

[0013]

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The polyurethane of the present invention is, for example, 9,9-bis (4- (2-hydroxyalkoxy) phenyl) fluorene (hereinafter referred to as "BPAF") represented by the following formula (2).
And a diisocyanate represented by the formula (3): OCN-R-NCO.

[0015]

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As BPAF, for example, in the formula (2),
9,9-bis (4- (2- (2) wherein A ¹ and A ² are hydrogen atoms
(Hydroxyethoxy) phenyl) fluorene (hereinafter referred to as "B
9, 9 and 9, wherein A ¹ and A ² are methyl groups.
-Bis (4- (2-hydroxypropoxy) phenyl)
Fluorene (hereinafter referred to as "BPPF").

BPAF can be produced, for example, by reacting fluorenone with phenoxyethanol or phenoxypropanol. Fluorenone and phenoxyethanol or phenoxypropanol can be reacted, for example, by using sulfuric acid and thiol as catalysts.

In the formula (3), R represents an alkyl group (for example, an alkyl group having 1 to 3 carbon atoms, particularly a methyl group) or an alkoxy group (for example, an alkoxy group having 1 to 3 carbon atoms, particularly, a methoxy group). A biphenyl group or an alkyl group (for example, an alkyl group having 1 to 3 carbon atoms, in particular, a methyl group) or an alkoxy group (for example, having 1 to 3 carbon atoms)
A bicyclohexyl group which can have an alkoxy group, especially a methoxy group).

The biphenyl group which may have an alkyl group or an alkoxy group includes, for example, a compound represented by the formula (4)
A biphenyl group represented by the formula: 3,3 ′ represented by the formula (5)
A dimethylbiphenyl group, 3,3 ′ represented by the formula (6)
A dimethoxybiphenyl group. Examples of the bicyclohexyl group that can have an alkyl group or an alkoxy group include a bicyclohexyl group represented by the following formula (7).

Examples of the diisocyanates include 4,4'-biphenyl diisocyanate (BDI) represented by the following formula (8) and 3,3'-dimethylbiphenyl- represented by the following formula (9). 4,4'-diisocyanate (TOD
I), 3,3′-dimethoxybiphenyl-4,4′-diisocyanate (DAD) represented by the following formula (10)
I), 4,4′-bicyclohexyl diisocyanate (hydrogenated BDI) represented by the following formula (11) and the like can be used.

[0021]

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The polyurethane of the present invention can be efficiently produced, for example, by reacting about equimolar BPAF with diisocyanates. BPAF and diisocyanates can be reacted in the presence or absence of a solvent. The reaction is usually performed by mixing BPAF and diisocyanates, for example, by mixing 60 to 150.
It can be completed by stirring, if necessary, for 1 to 10 hours under a temperature condition of about ° C.

With regard to the reaction between BPAF and diisocyanates, a prepolymer having isocyanate groups at both ends is synthesized by reacting the diisocyanates in excess,
Furthermore, diamines, amino alcohols, glycols and the like can be added to extend the chain length and to carry out an intermolecular crosslinking reaction.

The solvent is not particularly restricted but includes, for example, benzene, toluene, chlorobenzene,
o-Dichlorobenzene, dimethylformamide, dimethylacetamide, dimethylsulfoxide and the like can be used.

By reacting BPAF with isocyanates in the absence of a solvent or in the presence of chlorobenzene, a polyurethane having higher heat resistance, for example, having a glass transition point of about 90 to 180 ° C., usually 110 to 160 ° C. ° C
Polyurethane having a temperature of about 120 to 150 ° C. can be produced.

Although it depends on the type of isocyanate, chlorobenzenes, particularly monochlorobenzene, can be used as a solvent to produce a polyurethane having a high molecular weight.

For example, when BDI is used as an isocyanate, a polyurethane having a weight average molecular weight of 30,000 or more, especially 40,000 or more, further 50,000 or more, usually 100,000 or less can be produced.

For example, TODI isocyanates
When using, more than 10,000, especially 20,000
As described above, a polyurethane having a weight average molecular weight of 30,000 or more, usually 100,000 or less, particularly 50,000 or less can be produced.

For example, DADI isocyanates
When using 20,000 or more, especially 30,000
As described above, a polyurethane having a weight average molecular weight of 40,000 or more, usually 100,000 or less, particularly 70,000 or less can be produced.

For example, hydrogenated M as isocyanates
If DI is used, it should be 20,000 or more, especially 300
00 or more, further 40000 or more, usually 100,000
A polyurethane having a weight average molecular weight of 60,000 or less can be produced.

After reacting the BPAF with the diisocyanates, the resulting polyurethane can be recovered by conventional means, for example, by removing the solvent and the like as necessary, and by filtration and the like.

The recovered polyurethane is isolated and purified by conventional means, for example, by washing with a hydrocarbon solvent such as hexane, an ether solvent such as diethyl ether, and a lower aliphatic alcohol solvent such as methanol. be able to.

The polyurethane of the present invention can be dissolved in various solvents, for example, N, N-dimethylformamide (DMF), tetrahydrofuran (THF), acetone and the like.

A film made of the polyurethane of the present invention can be formed by applying a solution of the polyurethane of the present invention in a solvent to the surface of a substrate and removing the solvent. According to the polyurethane of the present invention,
A film having a refractive index of 50 or more, preferably 1.55 or more, more preferably 1.6 or more can be formed.

[0035]

The novel polyurethane having a fluorene skeleton according to the present invention has heat resistance (specifically, a high glass transition point) and film-forming ability, and is rigid and chemically stable.

[0036]

(1) Production of polyurethane Example 1 (BPEF-BDI / without solvent) 87.6 g of BPEF in a 2 L round bottom flask under a nitrogen atmosphere.
(0.2 mol), and heated to 130 ° C. while stirring to make a liquid. In this state, 47.2 g of BDI (0.
2 mol) was added dropwise from a dropping funnel and stirred. After a uniform and transparent solution was obtained, the reaction was performed at 130 ° C. for 4 hours. After cooling the reaction mixture to room temperature, the obtained crude product was washed three times with 5 L of hexane to obtain a product 128.0.
g (95.0% yield).

The product obtained was analyzed by IR for BPEF-
Identified as BDI polyurethane. The results are shown below.
The weight-average molecular weight (Mw) of the obtained polyurethane measured by gel permeation chromatography (GPC) was 55000, and it was measured by differential scanning calorimetry (DS).
The glass transition point (Tg) measured according to C) is 139.2
° C.

IR (KBr): 3402 (NH; urethane), 3030 (aromatic ring νCH), 2920 (νa)
s-CH _2- ), 2845 (vs-CH _2- ), 1450 (-
CH ₂ -scissors), 1725 (-NHCOO-urethane),
1215 and 1060 (Ar-O-CH _2- ; aromatic ether), 1890 and 830 (aromatic ring δC-H; 1,4-2 substituted), 750 (aromatic ring δC-H; 1,2-2 substituted)

Example 2 (BPEF-BDI / with Solvent) 87.6 g of BPEF in a 2 L round bottom flask under a nitrogen atmosphere
(0.2 mol) and 400 mL of monochlorobenzene were charged and heated to 130 ° C. with stirring to form a uniform solution. In this state, 47.2 g (0.2 mol) of BDI was dropped from the dropping funnel and stirred. After a uniform and transparent solution was obtained, the reaction was performed at 130 ° C. for 4 hours. After cooling the reaction mixture to room temperature, the obtained crude product was washed three times with 5 L of hexane to obtain 130.5 g of a product (yield: 96.8).
%).

The product obtained was analyzed by IR for BPEF-
Identified as BDI polyurethane. The results are shown below.
The weight average molecular weight of the obtained polyurethane measured by GPC was 58,000, and the glass transition point measured by DSC was 139.5 ° C.

IR (KBr): 3405 (NH; urethane), 3032 (aromatic ring νCH), 2921 (νa)
s-CH _2- ), 2848 (vs-CH _2- ), 1449 (-
CH ₂ -scissors), 1725 (-NHCOO-urethane),
1216 and 1063 (Ar-O-CH _2- ; aromatic ether), 1882 and 830 (aromatic ring δC-H; 1,4-2 substituted), 749 (aromatic ring δC-H; 1,2-2 substituted)

Example 3 (BPEF-hydrogenated BDI / solvent)
None) BPEF 87.6g in a 5L round bottom flask under nitrogen atmosphere
(0.2 mol), and heated to 130 ° C. while stirring to make a liquid. In this state, 49.6 g of hydrogenated BDI
(0.2 mol) was added dropwise from a dropping funnel and stirred. After a uniform and transparent solution was obtained, the reaction was performed at 130 ° C. for 4 hours. After cooling the reaction mixture to room temperature, the obtained crude product was washed three times with 5 L of hexane to obtain product 13
3.2 g (94.9% yield) was obtained.

The product obtained was identified by IR as BPEF-hydrogenated BDI polyurethane. The results are shown below. The weight average molecular weight of the obtained polyurethane measured by GPC was 41,000, and the glass transition point measured by DSC was 123.8 ° C.

IR (KBr): 3418 (NH; urethane), 3075 and 3035 (aromatic ring νCH), 29
25 (νas-CH _2- ), 2858 (νs-CH _2- ), 1
450 (-CH ₂ -scissors), 1720 (-NHCOO-urethane), 1219 and 1055 (Ar-O-CH _2- ; aromatic ether), 826 (aromatic ring δC-H; 1,4-substituted), 749 (aromatic ring δC-H; 1,2-substituted)

Example 4 (BPEF-hydrogenated BDI / solvent)
Yes ) BPEF 87.6g in 2L round bottom flask under nitrogen atmosphere
(0.2 mol) and 400 mL of monochlorobenzene were charged and heated to 130 ° C. with stirring to form a uniform solution. In this state, 49.6 g of hydrogenated BDI (0.2 mol
l) was added dropwise from a dropping funnel and stirred. After a uniform and transparent solution was obtained, the reaction was performed at 130 ° C. for 4 hours.
After cooling the reaction mixture to room temperature, the obtained crude product was washed three times with 5 L of hexane to obtain 133.6 g of a product (yield 97.4%).

The obtained product was analyzed by IR for BPEF-
It was identified as a hydrogenated BDI polyurethane. The results are shown below. The weight average molecular weight of the obtained polyurethane measured by GPC was 43000, and the glass transition point measured by DSC was 124.0 ° C.

IR (KBr): 3420 (NH; urethane), 3078 and 3032 (aromatic ring νCH), 29
25 (νas-CH _2- ), 2855 (νs-CH _2- ), 1
454 (-CH ₂ -scissors), 1722 (-NHCOO-urethane), 1220 and 1057 (Ar-O-CH _2- ; aromatic ether), 828 (aromatic ring δC-H; 1,4-2 substituted), 747 (aromatic ring δC-H; 1,2-substituted)

Example 5 (BPEF-TODI / solvent
B) 87.6 g of BPEF in a 2 L round bottom flask under a nitrogen atmosphere
(0.2 mol) and 400 mL of monochlorobenzene were charged and heated to 130 ° C. with stirring to make a liquid. In this state, 52.8 g (0.2 mol) of TODI was dropped from the dropping funnel and stirred. After a uniform and transparent solution was obtained, the reaction was performed at 130 ° C. for 4 hours. After cooling the reaction mixture to room temperature, the obtained crude product was washed three times with 5 L of hexane to obtain 133.2 g of a product (yield 94.9%).
I got

The product obtained was analyzed by IR for BPEF-
Identified as TODI polyurethane. The results are shown below. The weight average molecular weight of the obtained polyurethane measured by GPC was 32,000, and the glass transition point measured by DSC was 141.4 ° C.

IR (KBr): 3420 (NH; urethane), 3030 (aromatic ring νCH), 2970 (νa)
sCH _3- ), 2885 (νs CH _3- ), 2925 (νa
s-CH _2- ), 2855 (vs-CH _2- ), 1455 (-
CH ₂ -scissors), 1729 (-NHCOO-urethane),
1215 and 1067 (Ar-O-CH _2- ; aromatic ether), 1900, 1761 and 820 (aromatic ring δC-H;
1,2,4-3 substitution), 825 (aromatic ring δC-H; 1,4
-2 substitution)

Example 6 (BPEF-DADI / solvent
B) 87.6 g of BPEF in a 2 L round bottom flask under a nitrogen atmosphere
(0.2 mol) and 400 mL of monochlorobenzene were charged and heated to 130 ° C. with stirring to make a liquid. In this state, 59.2 g (0.2 mol) of TODI was dropped from the dropping funnel and stirred. After a uniform and transparent solution was obtained, the reaction was performed at 130 ° C. for 4 hours. After cooling the reaction mixture to room temperature, the obtained crude product was washed three times with 5 L of hexane to obtain 140.1 g of a product (yield: 95.4%).
I got

The product obtained was analyzed by IR for BPEF-
Identified as DADI polyurethane. The results are shown below. The weight average molecular weight of the obtained polyurethane measured by GPC was 48,000, and the glass transition point measured by DSC was 143.6 ° C.

IR (KBr): 3420 (NH; urethane), 3030 (aromatic ring νCH), 2825 (νs
CH ₃ —O—), 2925 (νas-CH ₂ —), 2850
_{(Νs-CH 2 -),} 1454 (-CH 2 - Scissors), 173
1 (-NHCOO-urethane), 1215 and 1067 (A
r-O-CH ₂ -; aromatic ethers), 1906 and 1764
And 822 (aromatic ring δC-H; 1,2,4-3 substitution), 82
8 (aromatic ring δC-H; 1,4-2 substituted)

Example 7 (BPPF-BDI / with solvent) 93.4 g of BPPF in a 2 L round bottom flask under a nitrogen atmosphere
(0.2 mol) and 400 mL of monochlorobenzene were charged and heated to 130 ° C. with stirring to form a uniform solution. In this state, 47.2 g (0.2 mol) of BDI was dropped from the dropping funnel and stirred. After a uniform and transparent solution was obtained, the reaction was performed at 130 ° C. for 4 hours. After the reaction mixture was cooled to room temperature, the obtained crude product was washed three times with 5 L of hexane, and 133.2 g of a product was obtained (yield: 94.0 g).
7%).

The obtained product was analyzed by IR for BPPF-
Identified as BDI polyurethane. The results are shown below.
The weight average molecular weight of the obtained polyurethane measured by GPC was 60000, and the glass transition point measured by DSC was 141.8 ° C.

IR (KBr): 3403 (NH; urethane), 3032 (aromatic ring νCH), 2962 (νa)
sCH _3- ), 2921 (νas-CH _2- ), 2871
_{(Νs-CH 3 -),} 2848 (νs-CH 2 -), 1460
(Δas-CH ₃ ), 1449 (-CH ₂ -scissors), 13
81 (δs-CH ₃ ), 1725 (-NHCOO-urethane), 1216 and 1063 (Ar-O-CH _2- ; aromatic ether), 1881 and 832 (aromatic ring δC-H; 1,4-
Disubstituted), 751 (aromatic ring δC-H; 1,2-disubstituted)

COMPARATIVE EXAMPLE 1 87.6 g of BPEF was placed in a 2 L round bottom flask under a nitrogen atmosphere.
(0.2 mol) and 400 mL of monochlorobenzene were charged and heated to 130 ° C. with stirring to make a liquid. In this state, hexamethylene diisocyanate (HDI) 3
3.6 g (0.2 mol) was dropped from the dropping funnel and stirred. After a uniform and transparent solution was obtained, the reaction was performed at 130 ° C. for 4 hours. After cooling the reaction mixture to room temperature, the obtained crude product was washed three times with 5 L of hexane to obtain 117.3 g (yield: 96.8%) of a product.

The product obtained was analyzed by IR for BPEF-
It was identified as HDI polyurethane. The results are shown below.
The weight average molecular weight of the obtained polyurethane measured by GPC was 21,800, and the glass transition point measured by DSC was 104.7 ° C.

IR (KBr): 3426, 3350 (N
-H; urethane), 3063 (aromatic ring νC-H), 293
5 (νas-CH _2- ), 2848 (νs-CH _2- ), 14
50 (-CH ₂ -scissors), 1724 (-NHCOO-),
1236 and 1055 (Ar-O-CH _2- ; aromatic ether), 1881 and 824 (aromatic ring δC-H; 1,4-2 substitution), 747 (aromatic ring δC-H; 1,2-2 substitution)

Comparative Example 2 93.4 g of BPPF was placed in a 2 L round bottom flask under a nitrogen atmosphere.
(0.2 mol) and 400 mL of monochlorobenzene were charged and heated to 130 ° C. with stirring to make a liquid. In this state, 33.6 g (0.2 mol) of HDI was dropped from the dropping funnel and stirred. After a uniform and transparent solution was obtained, the reaction was performed at 130 ° C. for 4 hours. After cooling the reaction mixture to room temperature, the obtained crude product was washed three times with 5 L of hexane to obtain 120.4 g (yield: 94.8%) of a product.

The product obtained was analyzed by IR for BPPF-
It was identified as HDI polyurethane. The results are shown below.
The weight average molecular weight of the obtained polyurethane measured by GPC was 21,800, and the glass transition point measured by DSC was 104.7 ° C.

IR (KBr): 3421, 3352 (N
-H; urethane), 3060 (aromatic ring νC-H), 296
2 (νas-CH ₃ ), 2929 (νas-CH _2- ), 2
_{871 (νs-CH 3),} 2858 (νs-CH 2 -), 1
460 (δas-CH ₃ ), 1450 (-CH ₂ -scissors), 1381 (δs-CH ₃ ), 1721 (-NHCO
O-), 1240 and 1045 (Ar-O-CH _2- ; aromatic ether), 1882 and 825 (aromatic ring δC-H; 1,
4-2 (substituted), 748 (aromatic ring δC-H; 1,2-substituted)

(2) Preparation of Film 2 g of the polyurethane obtained in each of Examples and Comparative Examples was
After dissolving the solution in 10 ml of F and uniformly flowing this solution on a glass board, the THF was removed. As a result, a transparent film was formed in each case.

(3) Measurement of Refractive Index The refractive index was measured using the film obtained above.
That is, a wavelength of 5 using an Abago refractometer 4T manufactured by Atago Co., Ltd.
The measurement was carried out by using sodium iodine line of 89.3 nm with diiodomethane as a contact liquid. Table 1 shows the results.

[0065]

[Table 1]

Claims (3)

[Claims] 1. Polyurethane having a repeating unit represented by the following formula (1) and having a weight average molecular weight in the range of 2,000 to 300,000 [in the formula (1), A ¹ and A ² are the same or different and are different from hydrogen R represents a biphenyl group which can have an alkyl group or an alkoxy group or a bicyclohexyl group which can have an alkyl group or an alkoxy group]. Embedded image 2. 9,9-bis (4- (2-hydroxyalkoxy) phenyl) fluorene represented by the following formula (2) and diisocyanates represented by formula (3): OCN-R-NCO Is reacted in the presence or absence of a solvent, wherein A ¹ and A ² are the same or different from each other in the formula (2). And in the formula (3), R represents a biphenyl group which can have an alkyl group or an alkoxy group, or a bicyclohexyl group which can have an alkyl group or an alkoxy group]. Embedded image 3. The method for producing a polyurethane according to claim 2, wherein 9,9-bis (4- (2-hydroxyalkoxy) phenyl) fluorene is reacted with diisocyanates in the absence of a solvent.