JPH08295645A - Liquid crystal compound - Google Patents

Abstract

PURPOSE: To obtain a new liquid crystal compound useful as an additive to thermoplastic resins and capable of improving their mechanical properties, thermal properties and molding processability. CONSTITUTION: This new liquid crystal compound is expressed by formula I ((m) is 6-10; (n) is 6-14), and is obtained by reaction of a tolan derivative of formula II with a straight-chain 6-10C 1,ω-dibromoalkane under basic conditions. The compound exhibits optical anisotropy while maintaining its molecular liquid crystal nature, i.e., partly retaining the orientation of its molecule within a certain temperature range when melting. Therefore, addition of this compound to a thermoplastic resin lowers the melt viscosity of the resin or facilitates its processing such as injection molding owing to the high orientation of the liquid crystal molecules in the resin. Besides, during melt processing of the resin, the liquid crystal molecules set to fibrous form exhibit self-reinforcing action, resulting in improving the mechanical properties and thermal properties of the resin and also preventing the thermoplastic resin from declining in performance in its recycling.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel bistolan derivative used as a liquid crystal compound and a method for producing the same. More specifically, the present invention relates to a bistolan derivative capable of improving the mechanical and thermal properties and processability of a thermoplastic resin by adding this liquid crystal compound to the thermoplastic resin, and a method for producing the same.

[0002]

Fillers are commonly added to improve the mechanical properties of polymeric materials. Examples of this type of filler include chopped glass fibers. This glass fiber is inexpensive and, when added to plastics, greatly improves its strength and elastic modulus.

[0003]

However, phase separation between the filler and the plastic, increase in product weight, poor appearance due to the filler appearing on the surface, abrasion of the molding machine due to friction with the filler, and its abrasion There are various problems such as contamination of molded products with metal powder, increase in melt viscosity, increase in energy consumption, and the like. In addition, recently, plastic recycling has been actively considered for environmental protection and effective use of resources, but glass fiber is damaged during recycling and its performance deteriorates, limiting reuse. There are also problems.

Therefore, in place of the conventional filler, it is possible to improve the physical properties such as strength and elastic modulus of the thermoplastic polymer, and at the same time, the workability during molding is excellent and the original performance is not deteriorated during recycling. Agents are desired.

The present invention has been made by paying attention to the problems existing in the prior art. The purpose is that it can be used as an additive for thermoplastic resins and can improve the mechanical properties, thermal properties and molding processability of the thermoplastic resin, and at the same time reduce the performance of the thermoplastic resin at the time of a recycle. It is intended to provide a novel bistouran derivative capable of preventing the above-mentioned problems and a method for producing the same.

[0006]

In order to achieve the above object, the invention of the bistolane derivative described in claim 1 is represented by the general formula (1).

In the invention of the method for producing a bis-tolan derivative according to claim 2, the tolan derivative represented by the general formula (2) and a linear 1, ω-dibromoalkane having 6 to 10 carbon atoms are used. , To react under basic conditions.

The present invention will be described in detail below. The novel bistourane derivative of the present invention is a compound represented by the general formula (1) in a specific range. This bistourane derivative exhibits liquid crystallinity, that is, optical anisotropy while partially maintaining the orientation of the molecule in a certain temperature range during melting. Therefore, in the thermoplastic resin to which the bistourane derivative is added, liquid crystal molecules are highly oriented in the resin, the melt viscosity becomes low, and the processing such as injection molding becomes easy.

Further, the fibrous liquid crystal molecules in the melt processing step exhibit a self-reinforcing action, and improve the mechanical and thermal physical properties of the thermoplastic resin. Further, it is possible to prevent the performance of the thermoplastic resin from being degraded at the time of the re-cile.
Since the phase transition temperature of this bistourane derivative differs depending on the number of n and m in the general formula (1), the optimum one is selected depending on the resin whose physical properties are desired to be improved and molding conditions.

This bis-Tolan derivative is prepared by
It is obtained by the manufacturing method according to 5. Step 1: p-iodophenol and 1-bromoalkane (C _n
H _{2n + 1} Br) is reacted in dimethylformamide (DMF) with potassium carbonate (K ₂ CO ₃ ) as a catalyst to obtain a compound represented by the following general formula (3).

[0011]

Embedded image

Step 2: Compound represented by the general formula (3)
And palladium chloride (II, PdCl ₂), Cuprous iodide
(II, CuI), triphenylphosphine [P (C₆H
_Five) ₃], Diethylamine [(C₂H_Five)₂NH]
The reaction is carried out under an elementary air stream, and trimethylsilylacetylene is added there.
[[CH₃)₃SiC ≡ CH]
The compound represented by (4) is obtained.

[0013]

[Chemical 4]

Step 3: In tetrahydrofuran (THF), the compound represented by the above general formula (4) is hydrolyzed with potassium hydroxide (KOH) to give sodium hydrogen carbonate (Na).
HCO ₃ ) to obtain a compound represented by the following general formula (5).

[0015]

Embedded image

Step 4: The compound represented by the general formula (5) is reacted with p-iodophenol, palladium chloride, cuprous iodide, triphenylphosphine and diethylamine under a nitrogen stream to obtain the compound represented by the general formula (2). ) Is obtained.

Step 5: a compound represented by the general formula (2)
1,6-dibromohexane [Br (CH ₂)₆Br] and charcoal
The reaction was carried out in DMF using potassium acid as a catalyst,
A compound represented by formula (1) is obtained.

As described above, if the production is carried out according to the above steps, the bistouran derivative can be obtained efficiently and surely.

[0019]

EXAMPLES The present invention will be described in more detail below with reference to examples. Example 1 A bistouran derivative represented by the following chemical formula 6 (m = 6, n = 10 in the general formula (1)) was produced according to steps 1 to 5.

[0020]

[Chemical 6]

Step 1: p-iodophenol (6.16 g), 1-
Bromodecane (6.00g), potassium carbonate (12g), DMF (70m
l) in a flask equipped with a reflux condenser, 110 ~
The mixture was stirred at 120 ° C for 1.5 hours using a magnetic stirrer. The reaction mixture is then treated with 1N aqueous NaOH solution 1200
It was poured into ml and stirred vigorously for 30 minutes. And 100 ml
Column chromatography (S
purified by iO ₂ , hexane / ether = 5/1), 1-
n-Decyloxy-4-iodobenzene was obtained.

Step 2: 1-n-decyloxy-4-iodobenzene (8.64 g), palladium (II) chloride (48 mg), cuprous iodide (II) (24 mg), triphenylphosphine (290 mg),
Diethylamine (85 ml) was placed in a flask equipped with a reflux condenser and stirred under a nitrogen stream at 60 ° C. for 40 minutes using a magnetic stirrer.

Then, this was cooled to 45 ° C., trimethylsilylacetylene (2.94 g) was added dropwise, and the reaction mixture was added to 40-
Stir overnight at 45 ° C. Then, the solvent was distilled off, 200 ml of ether was added to the residue, and the diethylammonium salt was filtered off. After the ether was distilled off, column chromatography (Si
Purified with O ₂ , hexane / ether = 5/1), 1- (4
-n-decyloxyphenyl) -2- (trimethylsilyl) acetylene was obtained.

Step 3: 1- (4-n-decyloxyphenyl)-
2- (Trimethylsilyl) acetylene (6.73 g) was dissolved in 50 ml of THF in a flask under a nitrogen stream, to which 25 ml of 1.5N potassium hydroxide methanol solution was added dropwise. The reaction mixture was stirred at room temperature for 40 minutes using a magnetic stirrer. Then, the solvent was distilled off, and 300 ml of 10% aqueous sodium hydrogen carbonate solution was added to the residue, followed by 100 ml of ether.
It was extracted 4 times. After drying over sodium sulfate, the organic phase was concentrated under reduced pressure and purified by column chromatography (SiO ₂ , hexane / benzene = 4/1) to obtain 4-n-decyloxyphenylacetylene.

Step 4: 4-n-decyloxyphenylacetylene (5.28 g) was added to p-iodophenol (3.75 g), palladium (II) chloride (30 mg), cuprous iodide (II) (15 mg), tri Phenylphosphine (180 mg) and diethylamine (65 ml) were placed in a flask equipped with a reflux condenser and placed under a nitrogen stream.
The mixture was stirred at 60 ° C for 40 minutes using a magnetic stirrer. Then the reaction mixture was cooled to 40-45 ° C. and stirred overnight. After distilling off the solvent, 200 ml of ether was added to the residue, and the diethylammonium salt was filtered off. After the ether was distilled off, column chromatography (SiO ₂ , ether / benzene =
4/1) and purified by 4- (hydroxyphenyl) -4'-
(n-decyloxyphenyl) acetylene was obtained.

Step 5: 4- (hydroxyphenyl) -4 '-(n-
Decyloxyphenyl) acetylene (388 mg), 1,6-dibromohexane (122 mg), potassium carbonate (0.5 g), DMF (4 ml)
In a test tube fitted with a reflux condenser, 120-125 ° C
The mixture was stirred for 3 hours using a magnetic stirrer.
The reaction mixture was poured into 100 ml of 1N aqueous sodium hydroxide solution, and stirred vigorously for 30 minutes. Filter the precipitate, 20
Wash with 0 ml water, 50 ml methanol, 20 ml ether. This was recrystallized from chloroform and purified, and the bistourane derivative represented by the above chemical formula 6 (compound 1; m =
6, n = 10) was obtained.

Spectral data of this bistourane derivative (m = 6, n = 10): 1H NMR (δppm): 0.88 (t, -CH ₃ , 6H), 1.30 (m, -CH)
_2- , 40H), 3.95 (t, -O-CH _2- , 8H), 6.75-7.50 (m, C ₆ H
₄ and 16H).

IR (KBr, cm ^-1 ): 2938, 2922, 2853 (aliphatic CH); 1609, 1516 (benzene ring); 1476 (HCH bending); 1285, 1250 (CO); 1175, 1111, 1022 (Benzene ring); 839, 828, 806, 785 (= CH out-of-plane); 721 (-CH ₂ -pitch); 556, 534 (benzene ring skeleton). (Example 2) 1,10-dibromohexane in Example 1 was replaced with 1,10
-By the same method as in place of dibromodecane, the bistourane derivative represented by the following chemical formula (7) (m = 10, n = 10
) Was manufactured.

[0029]

[Chemical 7]

This bistourane derivative (m = 10, n = 10)
Spectral data for: 1H NMR (δppm): 0.88 (t, -CH ₃ , 6H), 1.30 (m, -CH _2- ,
48H), 3.95 (t, -O-CH _2- , 8H), 6.75-7.50 (m, C ₆ H ₄ ,
16H).

IR (KBr, cm ^-1 ): 2955, 2922, 2853 (aliphatic CH); 1609, 1518 (benzene ring); 1476 (HCH bending); 1285, 1250 (CO); 1175, 1109, 1047 , 1020 (benzene ring); 839, 826, 801, 785 (= CH out of plane); 721 (-C
H ₂ -pitch); 559, 534 (benzene ring skeleton). (Example 3) 1,6-dibromohexane in Example 1 was replaced with 1,9-
By the same method as in place of dibromononane, the bistorane derivative represented by the following chemical formula (8) (m = 9, n = 10)
Was manufactured.

[0032]

Embedded image

Spectral data of this bistourane derivative (m = 9, n = 10): 1H NMR (δppm): 0.88 (t, -CH ₃ , 6H), 1.30 (m, -CH)
_2- , 46H), 3.95 (t, -O-CH _2- , 8H), 6.75-7.50 (m, C ₆ H
₄ and 16H).

IR (KBr, cm ^-1 ): 2955, 2922, 2874,2853
(Aliphatic CH); 1611, 1518 (Benzene ring); 1472 (HC-
H bending angle); 1285, 1252 (CO); 1175, 1111, 1073, 1047,
1022 (benzene ring); 839, 826 (= CH out of plane); 725 (-C
H ₂ -pitch); 565, 534 (benzene ring skeleton). (Example 4) 1-bromodecane in Example 1 was replaced with 1-bromohexane, and the following chemical formula (9) was used.
A bistouran derivative represented by (m = 6, n = 6) was produced.

[0035]

[Chemical 9]

Spectral data of this bistourane derivative (m = 6, n = 6): 1H NMR (δppm): 0.88 (t, -CH ₃ , 6H), 1.30 (m, -CH)
_2- , 24H), 3.95 (t, -O-CH _2- , 8H), 6.75-7.50 (m, C ₆ H
₄ and 16H).

IR (KBr, cm ^-1 ): 2940, 2866 (aliphatic C-
H); 1609, 1518 (benzene ring); 1476 (HCH bending); 12
85, 1248 (CO); 1175, 1111, 1026, 997 (benzene ring); 839, 828, 806, 785 (= CH out of plane); 731 (-CH ₂ -pitch); 554, 532 (benzene ring skeleton) ). (Example 5) In the same manner as in Example 1 except that 1-bromodecane was replaced with 1-bromohexane and 1,6-dibromohexane was replaced with 1,10-dibromodecane, a bistolane derivative represented by the following chemical formula (10) was used. (M = 10, n = 6) was produced.

[0038]

[Chemical 10]

Spectral data of this bistourane derivative (m = 10, n = 6): 1H NMR (δppm): 0.88 (t, -CH ₃ , 6H), 1.30 (m, -CH)
_2- , 32H), 3.95 (t, -O-CH _2- , 8H), 6.75-7.50 (m, C6H
4, 16H).

IR (KBr, cm ^-1 ): 2955, 2925, 2859 (aliphatic CH); 1609, 1518 (benzene ring); 1474 (HCH bending); 1283, 1248 (CO); 1175, 1111, 1047 , 1019 (benzene ring); 839, 826, 785 (= CH out-of-plane); 729 (-CH2- pitching); 561, 534 (benzene ring skeleton). Example 6 By replacing 1-bromodecane in Example 1 with 1-bromohexane and replacing 1,6-dibromohexane with 1,9-dibromononane in the same manner as in Example 1, the bistourane derivative represented by the following chemical formula (11) was used. (M = 9, n = 6) was produced.

[0041]

[Chemical 11]

Spectral data of this bistourane derivative (m = 9, n = 6) 1H NMR (δppm): 0.88 (t, -CH ₃ , 6H), 1.30 (m, -CH)
_2- , 30H), 3.95 (t, -O-CH _2- , 8H), 6.75-7.50 (m, C ₆ H
₄ and 16H).

IR (KBr, cm ^-1 ): 2955, 2926, 2874, 2853
(Aliphatic CH); 1609, 1518 (Benzene ring); 1470 (HC
-H bending angle); 1285, 1250 (CO); 1177, 1113, 1073, 1046,
1028, 1017, 997 (benzene ring); 839, 824 (= CH out-of-plane); 725 (-CH ₂ -pitch); 569, 534 (benzene ring skeleton). (Example 7) By replacing 1-bromodecane in Example 1 with 1-bromotetradecane, a bistourane derivative (m = 6, n = 14) represented by the following chemical formula (12) was produced by the same method.

[0044]

[Chemical 12]

Spectral data of this bistourane derivative (m = 6, n = 14): 1H NMR (δppm): 0.88 (t, -CH ₃ , 6H), 1.30 (m, -CH)
_2- , 56H), 3.95 (t, -O-CH _2- , 8H), 6.75-7.50 (m, C ₆ H
₄ and 16H).

IR (KBr, cm ^-1 ): 2920, 2851 (aliphatic C-
H); 1609, 1518 (benzene ring); 1476 (HCH bending); 12
85, 1250 (CO); 1175, 1109, 1022 (benzene ring); 83
9, 826, 806, 785 (= CH out-of-plane); 727, 721 (-CH ₂ -pitch); 556, 534 (benzene ring skeleton). Example 8 In the same manner as in Example 1 except that 1-bromodecane was replaced with 1-bromotetradecane and 1,6-dibromohexane was replaced with 1,10-dibromodecane, the following chemical formula (1
The bistourane derivative (3) (m = 10, n = 14) was produced.

[0047]

[Chemical 13]

This bistourane derivative (m = 10, n = 14)
Spectral data for: 1H NMR (δppm): 0.88 (t, -CH ₃ , 6H), 1.30 (m, -CH _2- ,
64H), 3.95 (t, -O-CH _2- , 8H), 6.75-7.50 (m, C ₆ H ₄ ,
16H).

IR (KBr, cm ^-1 ): 2955, 2920, 2851 (aliphatic CH); 1609, 1518 (benzene ring); 1476 (HCH bending); 1285, 1250 (CO); 1175, 1109, 1047 , 1020 (benzene ring); 839, 826, 785 (= CH out of plane); 727, 721 (-CH
_2- Pitch); 561, 534 (benzene ring skeleton). (Example 9) In the same manner as in Example 1 except that 1-bromodecane was replaced with 1-bromotetradecane and 1,6-dibromohexane was replaced with 1,9-dibrononane, a bistourane derivative represented by the following chemical formula (14) ( m = 9, n = 14) was produced.

[0050]

Embedded image

Spectral data of this bistourane derivative (m = 9, n = 14): 1H NMR (δppm): 0.88 (t, -CH ₃ , 6H), 1.30 (m, -CH)
_2- , 62H), 3.95 (t, -O-CH _2- , 8H), 6.75-7.50 (m, C ₆ H
₄ and 16H).

IR (KBr, cm ^-1 ): 2955, 2920, 2851 (aliphatic CH); 1611, 1518 (benzene ring); 1472 (HCH bending); 1285, 1254 (CO); 1175, 1111, 1073 , 1038, 102
2 (benzene ring); 841, 826 (= CH out of plane); 721 (-CH _2-
Pitching); 565, 534 (benzene ring skeleton).

With respect to each of the bistourane derivatives of Examples 1 to 9, the phase transition temperature, the phase transition enthalpy, and the phase transition entropy were measured as thermodynamic data in the phase transition by the differential scanning calorimetry (DSC). The results are summarized in Tables 1 and 2. In Tables 1 and 2, T is the phase transition temperature (° C), ΔH is the phase transition enthalpy (KJ / mol), and ΔS is the phase transition entropy (J / m).
ol · K).

[0054]

[Table 1]

[0055]

[Table 2]

As shown in Tables 1 and 2, the phase transition temperature of the bistourane derivative represented by the general formula (1) changes depending on the numbers of n and m. Therefore, by appropriately selecting the bistourane derivative to be added to the thermoplastic resin based on the resin whose molding properties are desired to be improved, molding conditions, etc., it is possible to improve the mechanical properties of the thermoplastic resin or to facilitate the molding. it can. In addition, each of the bistourane derivatives,
In both cases, a change from the crystal phase to the liquid crystal phase was observed, and the liquid crystal exhibited the properties. In addition, each of the bistourane derivatives is
It shows the phase transition enthalpy and phase transition entropy depending on the number of n and m, the crystal phase, and the liquid crystal phase.

The technical idea understood from the above embodiment will be described below. (1) An additive for a thermoplastic resin containing, as a main component, the bistouran derivative represented by the general formula (1). By adding this additive to the thermoplastic resin, the mechanical and thermal properties and processability of the thermoplastic resin can be improved. (2) The method for producing a bistorane derivative according to claim 2, wherein the 1, ω-dibromoalkane has 6 to 10 carbon atoms. According to this production method, the bistourane derivative represented by the general formula (1) can be efficiently produced. (3) The tolan derivative represented by the general formula (2) is
a first step of reacting p-iodophenol with 1-bromodecane to obtain p-alkoxyiodobenzene,
A second step of reacting p-alkoxyiodobenzene with trimethylsilylacetylene to obtain 4-alkoxyphenyltrimethylsilylacetylene, and a third step of decomposing 4-alkoxyphenyltrimethylsilylacetylene to obtain 4-alkoxyphenylacetylene. The method for producing a bistouran derivative according to claim 2, which is obtained by the fourth step of reacting 4-alkoxyphenylacetylene with p-iodophenol. According to this structure, the desired tolan derivative can be reliably obtained.

[0058]

As described in detail above, according to the invention described in claim 1, it can be used as an additive for a thermoplastic resin,
It is possible to improve the mechanical properties, thermal properties and molding processability of the thermoplastic resin, and at the same time, it is possible to prevent the performance of the thermoplastic resin from deteriorating during a recycle.

According to the second aspect of the invention, the bistouran derivative can be efficiently and reliably obtained.

Claims (2)

[Claims] 1. A bistourane derivative represented by the following general formula (1): Embedded image (In the formula, m represents an integer of 6 to 10, and n represents an integer of 6 to 14.) 2. The method according to claim 1, wherein the tolan derivative represented by the following general formula (2) is reacted with a linear 1, ω-dibromoalkane having 6 to 10 carbon atoms under basic conditions. A method for producing the bistouran derivative represented by the general formula (1). Embedded image (In the formula, n represents an integer of 6 to 14.)