JP2572129B2 - Polylactone - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a novel polylactone.

(Prior Art) Polylactone is useful as a raw material for polyurethane and polyester used for elastomers and synthetic leathers, or as a raw material for paints and adhesives.

Such a polylactone is obtained by ring-opening polymerization using a polymerization initiator such as ethylene glycol, diethylene glycol, neopentyl glycol or the like.

(Problems to be Solved by the Invention) All of the polylactones obtained as described above contain a soft segment in the skeleton. Therefore, for example, the polyurethane obtained by reacting a polylactone with a diisocyanate compound has an initial property. There were drawbacks of low modulus and insufficient toughness.

By the way, 4,4 ″ -dihydroxy-p-terphenyl and 4,4-dihydroxy-p-quarterphenyl are low molecular compounds exhibiting liquid crystallinity, and have a transition point from a crystalline state to a liquid crystal state of 250 ° C. or higher. Here, the liquid crystal state refers to a state in which the orientation of molecules is maintained during melting, and such liquid crystal molecules generally have high crystallinity, and the above-described dihydroxy compound is in a transition state. Since the point is high, incorporating this dihydroxy compound into the polymer chain effectively works as a physical cross-linking point and improves the heat resistance of the polymer.

However, such a dihydroxy compound is difficult to melt at a low temperature by itself, and is also difficult to dissolve in a solvent.
It has been difficult to use the dihydroxy compound as it is as a raw material for polyester or polyurethane.

The present invention has been made by paying attention to such a situation, and when used as a raw material for an elastomer, to obtain an elastomer which is excellent in meltability and solubility, easy to handle, and excellent in flexibility and toughness. It is an object of the present invention to provide a polylactone that can be used.

(Means for Solving the Problems) The polylactone of the present invention is obtained by ring-opening polymerization of a lactone using a dihydroxy compound represented by the following formula [I] as a polymerization initiator, and the following formula [ II] and having a molecular weight of 500 to 5,000, thereby achieving the above object.

(In the formula, l and m are 0 or 1, and n represents 3 or 4.) (Wherein l, m, and n are each defined as in Formula I, R represents a lactone residue, p and q are each a positive integer, and the sum of p and q Is 1 to 10
It is 0. The lactones used in the present invention have four or more carbon atoms in the ring. Preferred lactones are 5- to 8-membered lactones, such as ε-caprolactone, δ-valerolactone, and γ-butyrolactone. These may be used alone or in combination.

The dihydroxy compound represented by the general formula [I] is a low-molecular compound exhibiting liquid crystallinity, and l and m are preferably 0 or 1, and 4,4 ″-represented by the following formula [A] Dihydroxy-p-terphenyl, represented by the following formula (B):
4 "-di (2-hydroxyethoxy) -p-terphenyl; 4,4-dihydroxy-p- represented by the following formula [C]
Quarterphenyl and 4,4-di (2-hydroxyethoxy) -p-quarterphenyl represented by the following formula [D] are preferably used.

Note that the transition point of 4,4-dihydroxy-p-quarterphenyl [C] from the crystalline state to the liquid crystal state is 336 ° C.
That of 4,4-di (2-hydroxyethoxy) -p-quarterphenyl [D] is 403 ° C.

These dihydroxy compounds may be used alone or in combination.

4,4 "-dihydroxy-p-terphenyl [A] is
For example, preparing a Grignard reagent using 4-methoxy-4 ″ -bromobiphenyl in Mg in tetrahydrofuran,
This was used as a catalyst with 4-bromoanisole and Nicl ₂ (dpp
p) (dppp: 1,3-bis (diphenylphosphino) was coupled with propane) 4,4 '- dimethoxy biphenyl synthesized, then, can be obtained using the in methylene chloride PBr _3.

4,4 "-di (2-hydroxyethoxy) -p-terphenyl [B] is 4,4" -di (2-hydroxyethoxy)
It can be obtained by adding ethylene oxide to -p-terphenyl [A].

4,4-Dihydroxy-p-quarterphenyl [C] is described, for example, in Journal of Chemical Society, 1379.
-85 (1940) or 4-hydroxy-4 ″-
Bromobiphenyl can be synthesized by a method in which a dimer is synthesized by reacting by heating and pressurizing with a palladium catalyst in the presence of an alkali, followed by acid precipitation.

4,4-Di (2-hydroxyethoxy) -p-quarterphenyl [D] can be obtained by adding ethylene oxide to a dihydroxy compound [C].

Since these liquid crystal molecules exhibit crystallinity and have a high transition point, when the dihydroxy compound [I] is incorporated into the polymer chain, a strong physical cross-link is formed even when the compounding amount is small. However, it is presumed that a thermoplastic elastomer having high heat resistance is produced without impairing the flexibility derived from the soft segment.

In order to start the polymerization of the lactones and to carry out the polymerization continuously, the lactones and the dihydroxy compound are mixed and heated to about 100 to 350 ° C, preferably 160 to 240 ° C. When the heating temperature exceeds 350 ° C., thermal decomposition of lactones occurs, which is not preferable. In the ring-opening polymerization of lactones, a catalyst for promoting the reaction is preferably present.
Examples of the catalyst include organic titanium compounds such as tetrabutyl titanate, tetrapropyl titanate, and tetraethyl titanate; organic tin compounds such as tin octylate, dibutyltin oxide, and dibutyltin laurate; stannous chloride; stannous bromide; Examples thereof include stannous halides such as stannous tin, and the like, and preferably 0.05 to 1000 ppm, more preferably 0.1 to 100 ppm.

The following formula shows a novel polylactone synthesized using the above dihydroxy compound [A] using ε-caprolactone as a lactone.

(In the formula, m and n are positive integers.) The polylactone obtained by the present invention is a linear polymer having hydroxyl groups at both ends, and usually has a molecular weight of 500 to 5,000.
And the sum of m and n is 1 to 100. The molecular weight of the obtained polylactone can be adjusted by changing the molar ratio between the dihydroxy compound and the lactone.

The novel polylactone thus obtained can be used as a raw material for various polymers such as polyurethane and polyester.For example, when preparing polyurethane using this polylactone, a thermoplastic urethane elastomer, urethane foam, adhesive Agent, paint, synthetic leather, etc., and when polyester is prepared using polylactone, it can be suitably used for thermoplastic ester elastomers, adhesives, paints, molded articles, etc. . The polymer containing this polylactone as a constituent component is excellent in heat resistance and toughness because it contains a high-temperature liquid crystalline segment based on a dihydroxy compound in the polymer chain.

(Examples) Hereinafter, the present invention will be described in detail based on examples.

<Synthesis of Dihydroxy Compound> (A) A Grignard reagent was prepared by using 4,4 ″ -dihydroxy-p-terphenyl (hereinafter, referred to as DHT) 4-methoxy-4 ″ -bromobiphenyl in Mg in tetrahydrofuran. Was coupled with 4-bromoanisole using NiCl ₂ (dppp) as a catalyst to synthesize 4,4 ″ -dimethoxybiphenyl, and then using PBr ₃ in methylene chloride.

(B) 4,4 ″ -di (2-hydroxyethoxy) -P-terphenyl (hereinafter referred to as DHET) The above DHT was synthesized by reacting it with ethylene oxide in the presence of sodium carbonate.

(C) 4,4-dihydroxy-p-quarterphenyl (hereinafter referred to as DHQ) 4-hydroxy-4'-bromobiphenyl
100 g of methanol, 300 g of 10 Wt% sodium hydroxide aqueous solution,
13 g of 5 wt% palladium / carbon was added, and the mixture was reacted at 120 ° C. and 5 atm for 4 hours to obtain a sodium salt of 4,4-dihydroxy-p-quarterphenyl. After adding N, N-dimethylformamide to the solid and filtering by heating to separate the catalyst, the filtrate was acid precipitated with dilute sulfuric acid and washed with methanol to obtain DHQ as white crystalline powder. The liquid crystal transition point of DHQ was 336 ° C.

(D) 4,4-di (2-hydroxyethoxy) -p-quarterphenyl (hereinafter referred to as DHEQ) By reacting DHQ obtained in the above section (C) with ethylene oxide in the presence of sodium carbonate, DHEQ was obtained. The liquid crystal transition point of DHEQ was 403 ° C.

In addition, the measuring method of the physical property of the obtained sample was as follows.

Liquid crystal transition point: The sample was heated at a heating rate of 5 ° C./min, and expressed as a transition point from a crystal phase to a liquid crystal phase by observation with a polarizing microscope.

Melting point: The sample was heated at a heating rate of 5 ° C./min, and the point at which the sample became isotropic by polarization microscope observation was defined as the melting point.

Intrinsic viscosity [η]: Measured at 30 ° C. in o-chlorophenol using an ubelope type viscosity tube.

Solubility: Expressed as solubility in dimethylformamide at 25 ° C (g / 100g).

Example 1 A four-necked flask equipped with a stirrer, a thermometer, a nitrogen gas inlet tube and a condenser was charged with 300 parts by weight of DHT (hereinafter referred to as "parts"), 700 parts of ε-caprolactone, and 0.01 part of tetrabutyl titanate. At 200 ° C. for 4 hours to obtain polylactone. The intrinsic viscosity [η] of the obtained polylactone was 0.11, and the melting point was 38 to 41 ° C. The solubility of polylactone was 59 (g / 100 g).

Example 2 In the same four-necked flask as in Example 1, the above DHET300
Parts, 1400 parts of ε-caprolactone and 0.02 part of tetrabutyl titanate were charged and reacted at 180 ° C for 7 hours to obtain polylactone. The intrinsic viscosity [η] of the obtained polylactone is
0.17, melting point 35-40 ° C. The solubility of polylactone was 77 (g / 100 g).

Example 3 A polylactone was obtained in the same manner as in Example 1 except that DHQ was used instead of DHT. The resulting polylactone had an intrinsic viscosity [η] of 0.12 and a melting point of 38 to 42 ° C. Also,
The solubility of the polylactone was 52 (g / 100 g).

Example 4 A polylactone was obtained in the same manner as in Example 1 except that DHEQ was used instead of DHET. The intrinsic viscosity [η] of the obtained polylactone was 0.18, and the melting point was 37 to 40 ° C. The solubility of polylactone was 68 (g / 100 g).

Comparative Example 1 The liquid crystal transition point and solubility of only DHT were measured. As a result, the liquid crystal transition point was 270 ° C., and the solubility was 7 (g / 100 g).

Comparative Example 2 The liquid crystal transition point and solubility of DHET alone were measured. As a result, the liquid crystal transition point was 300 ° C., and the solubility was 4 (g / 100 g).

Comparative Example 3 The liquid crystal transition point and solubility of DHQ alone were measured. As a result, the liquid crystal transition point was 336 ° C., and the solubility was 5 (g / 100 g).

Comparative Example 4 The liquid crystal transition point and solubility of only DHEQ were measured. As a result, the liquid crystal transition point was 403 ° C., and the solubility was 2 (g / 100 g).

From the above examples, it was confirmed that by polymerizing lactones in the presence of the dihydroxy compound [1], a polylactone having excellent meltability and solubility was obtained.
This polylactone has good workability during polymerization and the like.

(Effect of the Invention) The constitution of the polylactone of the present invention is as described above, and an elastomer excellent in meltability and solubility, easy to handle, and excellent in flexibility and toughness can be obtained.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Toranosuke Saito 5-17-21 Yamatedai, Ibaraki-shi, Osaka (72) Inventor Hiroki Kadomachi 7-20, Otemachi, Ibaraki-shi, Osaka (72) Inventor Daishiro Kishimoto 2-11-20 Mishimaoka, Ibaraki-shi, Osaka Umeyama Mansion 102 (56) References JP-A-2-276817 (JP, A) JP-A-2-196820 (JP, A) JP-A Sho-59 -135218 (JP, A) Japanese Patent Publication 35-189 (JP, B1) Japanese Patent Publication 34-5293 (JP, B1) USSR Patent 186124 (SU, A)

Claims (1)

(57) [Claims] 1. A compound represented by the general formula: obtained by ring-opening polymerization of a lactone using a dihydroxy compound represented by the following formula [I] as a polymerization initiator, and having a molecular weight of 500 to 500 represented by the following formula [II]: 500
Polylactone of 0. (In the formula, l and m are 0 or 1, and n represents 3 or 4.) (Wherein l, m, and n are each defined as in Formula I, R represents a lactone residue, p and q are each a positive integer, and the sum of p and q Is 1 to 10
It is 0. )