JPH02311524A - 4-hydroxy-p-quaterphenyl derivative and aliphatic polyester - Google Patents

Abstract

PURPOSE:To obtain a thermoplastic elastomer excellent in heat resistance, mechanical properties and moldability by using a specified 4-hydroxy-p- quaterphenyl derivative as a component of a fatty acid polyester. CONSTITUTION:A 4-hydroxy-p-quaterphenyl derivative of formula I, wherein R<1> is an alkyl, an acyl or a group of formula II (wherein R'' is an alkylene, and (n) is 0 or >=1), which is a rigid low-molecular compound having an m.p. as high as about 300 deg.C or above in reflection of its characteristic structure. Therefore, when it is incorporated into the polymer chain, the heat resistance can be remarkably improved. Namely, when the above 4-hydroxy-p-quaterphenyl skeleton is introduced into the terminals of an aliphatic polyester obtained by the copolymerization of an aliphatic dicarboxylic acid with a diol, a thermoplastic elastomer excellent in heat resistance can be obtained.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention provides a p-quarterphenyl derivative and its ρ-
The present invention relates to an aliphatic polyester containing a quarterphenyl derivative as a constituent component, and the present invention can provide an aliphatic polyester that can be suitably used as a material for various molded products.

(Prior Art) Generally, in order for a material to exhibit rubber elasticity, it is necessary that an amorphous polymer whose two molecular chains easily rotate is partially crosslinked. For example, in rubber having an elasticity of 9, sulfur molecules bridge molecular chains through chemical bonds to form a network structure. In addition to rubber, materials have been proposed in which a variety of polymer compounds and crosslinking agents are combined. These materials require a crosslinking step to be molded, and once chemically crosslinked they do not exhibit thermoplastic properties.

Crosslinked materials cannot be formed by injection molding or extrusion.

In recent years, thermoplastic elastomers that exhibit rubber elasticity at room temperature and become plasticized at high temperatures have been developed, and various types of thermoplastic elastomers have been manufactured and marketed. This thermoplastic elastomer does not require a long crosslinking process unlike conventional rubber, and can be molded by injection molding or extrusion molding. What are the characteristics of the molecular structure of thermoplastic elastomers?

A typical thermoplastic elastomer is a crosslinking system that does not rely on strong chemical bonds, that is, a system that imposes some kind of inter-polymer restraint that is only effective at around room temperature, and is a polymer aggregate consisting of soft segments and hard segments. It has a unique structure. Soft segments and hard segments have different chemical structures9. In a hybrid composition of the two, the homogeneous parts aggregate and the heterogeneous parts form a microscopically unbalanced structure that is phase-separated from each other. The aggregation portion exhibits the constraining effect between the molecules.

Examples of thermoplastic elastomers include 1, styrene,
Olefin type, urethane type, ester type.

There are also amide types. In styrene-based materials, polystyrene forms a frozen phase as a hard segment, restraining molecular chains, and as a result exhibits rubber elasticity.

In olefin systems, the crystalline phase of polypropylene acts as a hard segment. Furthermore, in urethane systems, polyurethane segments create physical crosslinks between molecular chains through hydrogen bonds. In addition, the ester type has polybutylene terephthalate chains, and the amide type has 6-nylon, 6,6
- Nylon chains such as nylon act as hard segments.

(Problems to be Solved by the Invention) As described above, thermoplastic elastomers exhibit rubber elasticity at room temperature and can be molded, so they are widely used in automobile parts and various industrial products. but.

Compared to cross-linked rubber, conventional thermoplastic elastomers are cross-linked through physical restraint, which limits the softening and melting point of that part, resulting in lower heat resistance and inferior creep properties. Ta. For example, Toyobo's Perbrene S-9001 is known as an ester type with the highest heat resistance among thermoplastic elastomers.
Also, melting point 223℃, heat distortion temperature (low load) 14
6°C, and even for urethane, the softening point is at most 140°C.

The present invention was made in view of this situation, and has properties as a thermoplastic elastomer.

The object of the present invention is to provide a 4-hydroxy-p-quarterphenyl derivative as a constituent component of a polymer compound having excellent heat resistance and mechanical properties as well as excellent moldability. Another object of the present invention is to provide an aliphatic polyester that has properties as a thermoplastic elastomer, has excellent heat resistance and mechanical properties, and is also excellent in moldability.

(The following is a blank space) (Means for solving the problem) The 4-hydroxy-p-quarterphenyl derivative of the present invention is as follows.

General formula (1) The above objective is thereby achieved.

Furthermore, the aliphatic polyester of the present invention comprises a monohydroxy compound whose general formula is represented by the following formula (n), an aliphatic dicarboxylic acid whose general formula is represented by the following formula (I[I), and an aliphatic polyester of the present invention. diol as the main constituents, thereby achieving the above object.

(In the formula, R2 represents an alkylene group, and 2 represents O or an integer of 1 or more) HOOC-(CHz)m-COOH(I[[) (In the formula, 2
m is an integer of 0 to 10) The above-mentioned 4-hydroxy-p-quarterphenyl derivatives are a group of compounds represented by the above formula CI), and specifically,
4-Hydroxy-p-quarterphenyl.

Monohydroxy compounds such as 4-(2-hydroxyethoxy)-p-quarterphenyl, 4-(3-hydroxypropoxy)-p-quarterphenyl, 4-methoxy-p-quarterphenyl, 4-ethoxy-p-quarterphenyl , 4-butoxy-p-quarterphenyl and other monoalkoxy compounds and 4-acetoxy-p-
Examples include monoacyloxy compounds represented by quarterphenyl.

A method for synthesizing a 4-hydroxy-p-quarterphenyl derivative is shown below.

(1) 4-hydroxy-p-quarterphenyl (formula [
■] Synthesis of R', H) (R', CH3 in formula (I)) Reaction formula (1) (R'=H in formula (I)) Mas, 4-bromo 4'- The corresponding methoxy compound is synthesized by reacting hydroxybiphenyl with a methylating agent such as dimethyl sulfate. This methoxy form was dissolved in anhydrous TH.
Reaction with 1.1 equivalents of metallic magnesium in F (tetrahydrofuran) leads to the corresponding Grignard reagent, which is converted into NiClz(dl)I)l))(dp
4-methoxy-p-
You can get quarter phenyl. This methoxy form can be demethylated by the action of boron tribromide to obtain the corresponding monohydroxy form.

(2) Synthesis of monoalkoxy compound Using 4-hydroxy-p-quarterphenyl obtained by reaction formula (1) as a starting material, DMSO (dimethyl sulfoxide), DMF (dimethylformamide)
2CO3, NazC in abrotic polar solvents such as
It can be easily obtained by reacting with an alkyl halide in the presence of an inorganic base such as O= (reaction formula (2)
) 1) After generating a ferulate anion in advance using NaH instead of an inorganic base such as KzCOs or NazCOs, an alkyl halide may be applied (reaction formula (2) -2>. Each reaction formula is shown below.

Inorganic base/DMF, DMSO, etc. (3) Synthesis of monoacyloxy compound Using 4-hydroxyl p-quarterphenyl obtained by reaction formula (1) as a starting material, react an acid halide in a basic solvent such as pyridine or picoline. It can be easily obtained by

It can also be obtained by reaction with acid anhydrides, for example,
Reaction with acetic anhydride produces 4-acetoxy-p-quarterphenyl.

(4) Synthesis of monohydroxy compound By using 4-hydroxy-p-quarterphenyl obtained by reaction formula (1) as a starting material and reacting it with a hydroxyalkylating agent in the presence of an appropriate catalyst or acid scavenger. 4-(hydroxyalkyl)-p-quarterphenyl can be obtained.

For example, there are the following methods for hydroxyethylation.

(Left below) ■ 0
j CH2-CH2 (ethylene carbonate) When hydroxyethylation reactions ① to ① are compared, each has the following characteristics.

(2) It is carried out by heating 4-hydroxy-p-quarterphenyl and 2-haloethanol in an amount equal to or more than the same mole in an inert solvent in the presence of an acid scavenger (organic or inorganic base). Since this reaction involves side reactions such as ring closure or self-polymerization of X-CH2CH2-OH, the following reaction using halogenated acetaldehyde is more preferable.

(2) 4-hydroxy-p-quarterphenyl and ethylene oxide are reacted in the presence of a base in an inert solvent. Although the number of moles added can be controlled by changing the amount of ethylene oxide, since the number of moles added has a distribution, it is difficult to obtain only the desired hydroxyethoxy compound.

(2) 4-hydroxy-p-quarterphenyl and ethylene carbonate are reacted in the presence of a base in an inert solvent. Since the reaction rate is high and the number of moles added is easy to control, it is the most suitable method for one purpose.

In this way, the above hydroxyethylation reactions from ■ to ■ are as follows:
Although each method has its advantages and disadvantages, 4-(2-hydroxyethoxy>-p-quarterphenyl can be obtained by either method.

Similarly, by reacting with a hydroxypropylating agent, the corresponding 4-(2-hydroxypropoxy)-
p-quarterphenyl can be obtained.

In addition, in the reaction between 4-hydroxy-p-quarterphenyl and ethylene oxide, it is possible to lengthen the chain consisting of ethylene glycol units by introducing an excessive amount of ethylene oxide. (Formula below) %Formula %) The 4-hydroxy-p-quarterphenyl derivative (1) obtained by the present invention is a low molecular weight compound having rigidity, reflecting its characteristic structure.

The melting points of these compounds are extremely high, around 300"C or above. Therefore, when they are incorporated into polymer chains, heat resistance is significantly improved.

4 obtained by the present invention at the terminal of an aliphatic polyester obtained by copolymerization with an aliphatic dicarboxylic acid and a diol.
When a -hydroxy-p-quarterphenyl skeleton is introduced, a thermoplastic elastomer with excellent heat resistance can be obtained.

In other words, the single skeleton provides physical crosslinking that is extremely strong and highly heat resistant, making it possible to synthesize a highly heat resistant elastomer that is difficult to obtain using conventional methods.

When aromatic dicarboxylic acids and diols are used as copolymerization components, it is possible to synthesize polymers with high heat resistance and high strength.

For example, aromatic rigid liquid crystal polymers are one application example.

In addition, two 4-hydroxy-p-quarterphenyl derivatives CI) obtained according to the present invention are PES, PEEK
.

By adding a small amount to engineering plastics such as polyarylates, the fluidity can be significantly improved, so it can be used as an agent for making engineering plastics easier to mold.

Next, the aliphatic polyester of the present invention will be explained.

The monohydroxy compounds represented by the above formula (II) are rigid, low-molecular compounds having a paraphenylene skeleton, and reflecting their characteristic molecular structure, the melting points of these compounds are extremely high, at 250° C. or higher. Furthermore, the paraphenylene skeleton is known to be effective as a mesogen for low-molecular liquid crystal compounds, and this is because the skeleton has strong cohesive force not only in the solid state but also in the high temperature state (molten state). This shows that. Therefore, it is presumed that when the above-mentioned monohydroxy compound [II] is incorporated at the end of a polymer, very strong and highly heat-resistant physical crosslinking is produced, and a thermoplastic elastomer with excellent heat resistance is produced.

In the monohydroxy compound (II), the alkylene group R2 is preferably an ethylene group or a propylene group, and 1 is 0 or 1.
is preferred, and 4-hydroxy-p-quarterphenyl and 4-(2-hydroxyethoxy)-p-quarterphenyl are preferably used. The method for synthesizing 4-hydroxynyl-quaterphenyl and 4-(2-hydroxyethoxy>-p-quaterphenyl is as described above).

The above monohydroxy compounds (II) may be used alone or in combination.

Polyester is a product obtained by polycondensation of equimolar amounts of dicarboxylic acid and diol.2 In the aliphatic polyester of the present invention, in addition to the above-mentioned monohydroxy compound [■] group, the type of compound as a constituent component and the blending ratio of the compound By changing , the properties of the aliphatic polyester and the physical properties of the molded product obtained from the aliphatic polyester can be freely changed.

(The following is a blank space) The aliphatic polyester suitable as a thermoplastic elastomer has the monohydroxy compound (II), the above-mentioned aliphatic dicarboxylic acid (II[), and an aliphatic diol as main components.

The above-mentioned aliphatic dicarboxylic acid is a dicarboxylic acid represented by the general formula (%). If a dicarboxylic acid having more than 10 carbon atoms is used, the physical properties such as rubber elasticity of the molded product obtained from polyester will deteriorate. .

Examples of the dicarboxylic acid include oxalic acid.

Malonic acid, succinic acid, glutaric acid, adipic acid.

Speric acid and sepathic acid are preferably used.

Examples of the aliphatic diol include glycol and/or polyalkylene oxide.

Examples of the above glycols include ethylene glycol, propylene glycol, trimethylene glycol, 1
．． 4-butanediol, 1,3-butanediol, ■,
5-bentanediol, 1,6-hexanediol, 1
．． 7-hebutanediol, 1,8-octanediol,
1.9-nonanediol, 1.10-decanediol, cyclopencune-1,2-diol, cyclohexane-1,2-diol, cyclohexane-1,3-diol, cyclohexane-1,4-diol, cyclohexane-1, Examples include 4-dimetatool, and these may be used alone or in combination of two or more.

Examples of the above-mentioned polyalkylene oxide include 1.

Polyethylene oxide, polypropylene oxide.

Examples include polytetramethylene oxide, polyhexamethylene oxide, etc., and these may be used alone.
Two or more types may be used in combination.

When the number average molecular weight of the polyalkylene oxide becomes small, the ability to impart flexibility to the polyester produced decreases, and when it becomes too large, the physical properties such as thermal stability of the obtained polyester decrease.

100 to 20,000 is preferable, more preferably 50
It is 0-5.000.

The aliphatic polyester of the present invention may further contain a dihydroxy compound whose general formula is represented by the above formula (IV). These two types of rigid monomers (II
) and (IV) introduced into the polymer chain and at the end of the polymer, more physical crosslinks are formed, and the properties as a thermoplastic elastomer having heat resistance are significantly improved.

If you are looking for outstanding effects like those mentioned above.

The number of benzene rings in (TV) must be at least three. Furthermore, as the number of benzene rings increases, the physical crosslinking becomes stronger and the melting point rises significantly. However, considering the ease of handling during bipolymerization and the difficulty of synthesis, the number of benzene rings in [■] is 3 or 3. 4. That is, a paraterphenyl skeleton or a paraquaterphenyl skeleton is used.

The dihydroxy compound represented by the above formula (IV) is a low molecular compound that exhibits liquid crystallinity, and has alkylene groups R'' and R
4 is preferably an ethylene group or a propylene group, and q and r
is preferably 0 or 1 and is expressed by the quadratic formula (A) 4,4''
-dihydroxy-p-terphenyl.

4,4+ + +-dihydroxy-p-quarterphenyl represented by the following formula (B) and 4,4''-di(2-hydroxyethoxy Lp-quaterphenyl) represented by the following formula (C) are preferred. used for.

[C]

In addition, 4.4''-dihydroxyl p-terphenyl (A
) transition temperature from crystalline state to liquid crystalline state is approximately 260°C
That of 14,4111-dihydroxy-p-quaterphenyl [B] is 336°C, and that of 4,4'"-di(2-hydroxyethoxyLp-quaterphenyl [C] is 403"C. Also, the liquid crystal state This refers to a state in which the compound is in a molten state and the molecules maintain an oriented state.

Each of the above dihydroxy compounds (IV) may be used alone or in combination.

4,4''-dihydroxy-p-quarterphenyl (B) is described, for example, in the Journal of Chem
ical 5ociety+1379-85 (194
It can be synthesized by the method described in 0) or by the method of reacting 4-hydroxy-4'-bromobiphenyl with a palladium catalyst under heat and pressure in the presence of an alkali to synthesize a dimer, followed by acid precipitation. . 4,4111-di(
2-hydroxyethoxy)-p-quarterphenyl C
C) can be obtained by adding ethylene oxide to 4.4+++-dihydroxy-p-quarterphenyl [B]. Also, 4゜4゛゛°-dihydroxy-p-
Quarter phenyl [B] and 4.4+++-di(2-
hydroxyethoxy)-p-quarterphenyl (C)
When polycondensed with dicarboxylic acid to form a polyester, it is acetylated to produce 4.4"-diacetoxy p-quarterphenyl and 4.4"-di(2-acetoxyethoxy)-p- May be used as quarter phenyl.

Liquid crystal molecules generally have high crystallinity, and as mentioned above, 4
．． 4''-dihydroxy-p-terphenyl [A].

4, 4111-dihydroxy-p-quarterphenyl [B] and 4.4”°-di(2-hydroxyethoxy)
-p-Quarterphenyl CC) has a high transition point from crystal to liquid crystal state, so when these dihydroxy compounds (IV) are incorporated into the polymer chain, the polymer exhibits unique properties.

That is, dihydroxy compound (IV) exhibits crystallinity,
Moreover, since its transition point is high, dihydroxy compounds (I
Even when the amount of V) is small, strong physical crosslinks with high heat resistance are formed. the result.

It is presumed that a thermoplastic elastomer with high heat resistance can be obtained without impairing the flexibility derived from the soft segment.

In addition, a three-component aliphatic polyester consisting of the monohydroxy compound (II), an aliphatic diol, and an aliphatic dicarboxylic acid CI [ ], a monohydroxy compound (II), a dihydroxy compound (IV), an aliphatic diol, and an aliphatic polyester are also available. A four-component aliphatic polyester consisting of group dicarboxylic acid [11] and other reactive components.

For example, polysilicone with two hydroxyl groups.

It may contain lactone or aromatic hydroxycarboxylic acid as a constituent component.

The above-mentioned polysilicone has two hydroxyl groups, and includes dimethylpolysiloxane and diethylpolysiloxane having two hydroxyl groups at the molecular ends.

Diphenylpolysiloxane and the like are preferred. As the number average molecular weight of polysilicone decreases, its ability to impart flexibility to the resulting polyester decreases, and as it increases,
100 to 20, since it becomes difficult to produce polyester.
000 is preferable, more preferably 500 to 5.000
It is.

The above-mentioned lactones open the ring and react with acids and hydroxyl groups to add aliphatic chains, giving flexibility to the polyester, and those having 4 or more carbon atoms in the ring. Preferably, it is a 5- to 8-membered ring, and examples include ε-caprolactone, δ-valerolactone,
Examples include γ-butyrolactone.

The aromatic hydroxycarboxylic acids impart rigidity and liquid crystallinity to polyester, and include salicylic acid, metahydroxybenzoic acid, parahydroxybenzoic acid, and 3-chloro-4-hydroxybenzoic acid.

3-bromo-4-hydroxybenzoic acid, 3-methoxy-
4-hydroxybenzoic acid, 3-methyl-4-hydroxybenzoic acid, 3-phenyl-4-hydroxybenzoic acid, 2
-hydroxy-6-naphthoic acid, 4-hydroxy-4'-carboxybiphenyl, etc., and preferably,
These are parahydroxybenzoic acid, 2-hydroxy-6-naphthoic acid, and 4-hydroxy-4°-carboxybiphenyl.

Furthermore, a dihydroxy compound (
Aromatic diols and aromatic dicarboxylic acids other than IV) may be contained as constituent components.

The aromatic diol mentioned above is hydroquinone.

Resorcinol, chlorohydroquinone, bromohydroquinone, methylhydroquinone, phenylhydroquinone, methoxyhydroquinone, phenoxyhydroquinone, 4.4'
-dihydroxybiphenyl, 4,4″-dihydroxydiphenyl ether, 4.4′-dihydroxydiphenyl sulfide, 4.4′-dihydroxydiphenyl sulfone, 4.4′-dihydroxybenzophenone,
4.4”-dihydroxydiphenylmethane, bisphenol A, 1.1-di(4-hydroxyphenyl)cyclohexane, 1,2-bis(4-hydroxyphenoxy)
Examples include ethane, 1,4-dihydroxynaphthalene, and 2,6-dihydroxynaphthalene.

Examples of the aromatic dicarboxylic acids include metal salts of terephthalic acid, isophthalic acid, and 5-sulfoisophthalic acid; 4.4
'-dicarboxybiphenyl, 4,4'-dicarboxydiphenyl ether, 4,4"-dicarboxydiphenyl sulfide, 4.4"-dicarboxydiphenyl sulfone, 3,3"-dicarboxybenzophenone,
4.4'-dicarboxybenzophenone.

1.2-bis(4-carboxyphenoxy)ethane.

Examples include 1,4-dicarboxynaphthalene and 2,6-dicarboxynaphthalene.

The monohydroxy compound (II) used in the present invention is introduced at the end of the polymer, and its content is preferably 0.1 to 20 mol% in the hydroxy component used. The molar ratio of the monohydroxy compound [■] is 0.
If the amount is less than 1 mol%, physical crosslinking by the hard segments will be insufficient.

Sufficient physical properties and heat resistance are no longer limited. On the other hand, it is 2
If it exceeds 0 mol %, the molecular weight will not increase sufficiently and only products with inferior physical properties will be obtained.

In addition, when the monohydroxy compound (n), the aliphatic diol, and the dihydroxy compound (TV) are used as hydroxy components, the monohydroxy compound (II) and the dihydroxy compound (IVI) are the hydroxy components. It is preferable that the molar ratio of the hydroxy compound in total is 0.1 to 30 mol% in the total hydroxy component.When the molar ratio of (n) + (IV) in the hydroxy component is less than 0.1 mol% The physical crosslinking by the hard segment becomes insufficient, making it difficult to develop sufficient physical properties and heat resistance.Also, when the molar ratio of the hydroxy compound (n) + (IV) in the hydroxy component is 30 mol%
If it exceeds , the aliphatic polyester tends to have a high elastic modulus, making it unsuitable as an elastomer. However, it has high heat resistance and can be suitably used as a thermoplastic resin with excellent mechanical properties.

Any method can be used to polymerize the aliphatic polyester of the present invention. First, a dihydroxy compound (I
The case where monohydroxy compound (II) is used alone without using V) will be described.

for example.

■After esterifying the aliphatic dicarboxylic acid (III),
about 2 molar equivalents of aliphatic diol and 100°C to 250°C
C to produce an aliphatic diol adduct of aliphatic dicarboxylic acid by dealcoholization reaction, and firstly, this adduct and the above monohydroxy compound (I[) were heated at 200"C to
A method for producing aliphatic polyesters by defatting diols at 350°C.

(2) A method in which the constituent aliphatic dicarboxylic acid (I[) is esterified, then reacted with a hydroxy component ([■] decaliphatic diol), and polymerized by dealcoholization.

■ A method in which the halogen compound of the aliphatic dicarboxylic acid (1) and the hydroxy component ([■] Totokachi aliphatic diol are reacted together in a suitable solvent such as pyridine).

■Hydroxy component ([■] Obtaining aliphatic polyester by conventional reaction of dicarboxylic acid and alcohol, such as the method of reacting a metal salt of Totokachi aliphatic diol with a halide of aliphatic dicarboxylic acid (III)) I can do it.

Furthermore, it is also possible to control the structure of the aliphatic polyester by changing the order of addition of the monohydroxy compound ([3] during one polymerization. For example.

In methods ① and ②, the reaction occurs only at the terminal, so after the reaction between the aliphatic dicarboxylic acid (I[r) and the aliphatic diol has sufficiently progressed, the monohydroxy compound (II
) is preferably added.

On the other hand, in case (2), since the reaction occurs even in the polymer chain, there is no particular restriction on the timing of adding the monohydroxy compound (II), and a polymer with a high degree of polymerization can be obtained. In addition, a monohydroxy compound [■] or an acetylated product of a monohydroxy compound is kneaded with a pre-synthesized aliphatic polyester under reduced pressure and heat, and the molecular chain is based on the monohydroxy compound [■] through a dealiphatic diol or transesterification reaction. It is also possible to introduce segments.

Next, a case where a monohydroxy compound (IF) and a dihydroxy compound (IVI) are used together will be described.

The polymerization method for aliphatic polyester is 1. For example, ■ monohydroxy compound (1
Same method as ① except that both compounds 1) and dihydroxy compound [IV) were used.

(2) Same method as (2) except that dihydroxy compound (IV) is added to the hydroxyl component ((II) Tokachi aliphatic diol) in method (2) above.

■After reacting the halide of aliphatic dicarboxylic acid (I [[) and the hydroxy component (aliphatic diol + [■]) in a suitable solvent such as pyridine, the aromatic hydroxy compound (II) is finally reacted. How to do it.

■There are conventionally known methods such as reacting the metal alcoholade of the hydroxy component (aliphatic diol + [■]) with the halide of the aliphatic dicarboxylic acid CIII) and then reacting the metal alcoholade of the monohydroxylated product (n). Aliphatic polyesters can be obtained by reacting dicarboxylic acids containing alcohols with alcohols.

Furthermore, the above dihydroxy compound, a monohydroxy compound or a dihydroxy compound, and an acetylated product of the monohydroxy compound are kneaded with the previously synthesized aliphatic polyester under reduced pressure and heating.

It is also possible to introduce segments based on dihydroxy and monohydroxy compounds into the molecular chain by dealiphatic diol or transesterification reactions.

Further, when double condensation is carried out, catalysts that are generally used in producing polyester may be used. Examples of this catalyst are lithium and sodium.

Potassium, cesium, magnesium, calcium.

Barium, strontium, zinc, aluminum.

Titanium, cobalt, germanium, lead, antimony, arsenic, cerium, boron, cadmium.

Metals such as manganese, their organometallic compounds, organic acid salts,
Examples include metal alkoxides and metal oxides.

Particularly preferred catalysts are calcium acetate, diacyl stannous, tetraacyl stannous, dibutyltin oxide, dibutyltin dilaurate, dimethyltin malate, tin dioctanoate tin tetraacetate, triisobutylaluminum, tetrabutyl titanate, germanium dioxide and trioxide. It is antimony. Two or more of these catalysts may be used in combination. In addition, in order to efficiently distill water, alcohol, glycol, etc., which are by-produced during polymerization, and to obtain a high molecular weight polymer, the reaction system must be adjusted to lmmHg in the late stage of polymerization.
It is preferable to reduce the pressure to below. The reaction temperature is generally 15
It is 0-350°C.

The polyester of the present invention is as described above, and inorganic materials such as glass fiber, carbon fiber, boron fiber, silicon carbide fiber, alumina fiber, amorphous fiber, silicon/titanium/carbon fiber, etc. Organic fibers such as fibers and aramid fibers.

Inorganic fillers such as calcium carbonate, titanium oxide, mica, and talc, triphenyl phosphite, trilauryl phosphite, trisnonylphenyl phosphite, 2-
tert-butyl-α-(3-tert-butyl-4-
Heat stabilizers such as hydroxyphenyl)-p-cumenylbis(p-nonylphenyl) phosphite, hexabromocyclododecane, tris-(2,3-dichloropropyl)
Flame retardants such as phosphate pentabromophenyl allyl ether, p-tert-butylphenyl salicylate 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, 2.4.5-1-lyl UV absorbers such as hydroxybutyrophenone, butylated hydroxyanisole, butylated hydroxytoluene.

Distearyl thiodipropionate, dilauryl thiodipropionate, antioxidants such as hindered phenol antioxidants, antistatic agents such as N,N-bis(hydroxyethyl)alkylamines, alkylarylsulfonates, alkylsulfanates, etc. agents, barium sulfate, alumina, inorganic substances such as silicon oxide, sodium stearate,
Higher fatty acid salts such as barium stearate and sodium balmitate; organic compounds such as benzyl alcohol and benzophenone; and crystallization promoters such as highly crystallized polyethylene terephthalate and polytrans-cyclohexane dimetatool terephthalate may be added. The aliphatic polyester of the present invention is.

The thermoplastic resin 2 may be mixed with other thermoplastic resins such as polyolefin, modified polyolefin, polystyrene, polyamide, polycarbonate, polysulfone, polyester, etc., or may be mixed with a rubber component to modify its properties.

The aliphatic polyester of the present invention is press molded.

It is made into a molded body by extrusion molding, injection molding, blow molding, etc. The physical properties of the molded product can be arbitrarily changed depending on its constituent components, their blending ratios, and the like. Molded objects include flexible molded objects such as automobile parts, hoses, belts, and packing,
Suitable for use in paints, adhesives, etc.

(Example) The present invention will be explained below based on examples.

<Synthesis of p-quarterphenyl derivative> (A) 4-methoxy-p-quarterphenyl well-dried 500-
3.6 Magnesium pieces for Grignard in a three-necked flask
Add g (150 mmol).

A solution of 33.6 g (132 mmol) of 4-bromobiphenyl in anhydrous tetrahydrofuran (THF) was added dropwise under a nitrogen atmosphere. 2
After adding 0.02 g of iodine at room temperature to start the reaction, the entire amount of the THF solution was added dropwise over about 1 hour. The reaction proceeded exothermically and the two reaction solutions turned pale brown. Thereafter, nine reactions were completed by stirring at room temperature for 2 hours to prepare a Grignard reagent.

Another 1! In a three-neck flask, 31.5 g (120 mmol) of 4-bromo-4-methoxybiphenyl and NiCl
z (dppp) 108mg (0.2mmol)
(dppp: 1,3-bis(diphenylphosphino)propane) was added thereto, and 500 d of anhydrous THF was added thereto. The solution was kept at 0°C under nitrogen atmosphere.

The previously prepared Grignard reagent was added dropwise to this over about 1 hour. At the same time as the dropwise addition, the orange color of the Ni catalyst disappeared and the solution turned into a brownish color. After the addition was completed, the mixture was stirred and refluxed for 5 hours to complete the reaction. After the reaction was completed, the produced white solid was collected by filtration and washed with a small amount of THF. Sulfolane (
sulforane). 30.6g
(yield 76%) of 4-methoxy-p-quarterphenyl (hereinafter referred to as MQ) was obtained.

The physical properties between the two were as follows.

Liquid crystal transition temperature 328 °C (DTA) Dish H-NMR (DMSO-d 6.270 MHz) Mass spectrum m/z 336 (M”) (B) 4-Hydroxy-p-quarterphenyl ( MQ25.2g (75n
500 d of methylene chloride was added and stirred. The inside of the flask became turbid. 19.0 g of boron tribromide (
A solution of 50-related methylene chloride (75 mmol) was added dropwise over about 30 minutes. Thereafter, the mixture was stirred and refluxed for 10 hours under a nitrogen atmosphere. After the reaction was completed, the flask was cooled, and the precipitated solid was collected by filtration, washed with methylene chloride, and then dried. Recrystallization was performed using dimethyl sulfoxide. 21.6g (yield 89%)
4-hydroxy-p-quarterphenyl (hereinafter referred to as
HQ) was obtained as a white solid. The physical properties of IQ were as follows.

Liquid crystal transition temperature 352℃ (DTA) Mass spectrum m/z 322 (M”) (C) 4
-(2-Hydroxyethoxy)-ρ-quarterphenyl In a three-necked flask containing 12, H synthesized by method (B)
Q19.2 g (60 mmol) and 500
Add sulfolane from d and dissolve HQ. 7.9 for this
2 g (90 mmol) of ethylene carbonate was added and heated under nitrogen atmosphere. At the reflux temperature of sulfolane, 0.1 g of CO was added, and stirring and refluxing was continued for 4 hours.

After the completion of the reaction, the reaction solution was filtered while hot and cooled.

The target product precipitated, which was collected by filtration and dried. 4-(2
-hydroxyethoxy)-p-quarterphenyl (hereinafter referred to as HEQ) 18.38 g (yield 83%
) was obtained as a white solid. The physical properties of HEQ were as follows.

Liquid crystal transition temperature 335°C (DTA) IR (Nujol)! 10N=3400-3500
cm-' (broad) mass spectrum IIIHz
367 (M") (D) 4.4"'-dihydroxy-p-quarterphenyl 4-hydroxy-4'-bromobiphenyl 60.0 g
To.

4.41 + +-Dihydroxy-p-quarter The disodium salt of phenyl was obtained. After adding N,N-dimethylformamide to this solid and separating the catalyst by heating and filtration, the filtrate was precipitated with dilute sulfuric acid and washed with methanol to form a white crystalline powder of 4.4+ +
+ -dihydroxy-p-quarterphenyl (hereinafter,
DHQ) was obtained. The liquid crystal transition temperature of DHQ is 33
It was 6°C.

<Bis(2-hydroxyethyl)adipate (BHEA)
) Synthesis> In a glass flask with an internal volume of 12 equipped with a stirrer, a thermometer, a gas inlet, and a distillation port, dimethyl adipate 8
7.1 g (0.5 mol), 74.4 g (1.2 mol) of ethylene glycol, and small amounts of calcium acetate and antimony trioxide as catalysts were added. After replacing the inside of the flask with nitrogen, raise the temperature inside the flask to 180°C.
The mixture was allowed to react for 2 hours. Along with the reaction, methanol began to distill out from the flask, and bis(2-hydroxyethyl)
Adipate (hereinafter referred to as BHEA) was produced.

Preparation of aliphatic polyester> HQ was added to the above flask at the molar ratio shown in Table 1, the temperature of the flask was raised to 300°C, and the reaction was carried out in this state for about 1 hour. Next, connect the distillation port to a vacuum vessel,
The reaction was carried out for 2 hours while the pressure inside the flask was reduced to 1 mmHg or less. Along with the reaction, ethylene glycol is distilled out,
A very active liquid was formed inside the flask.

The melting point of the aliphatic polyester thus obtained was measured and the results are shown in Table 1.

Bis (2-hydroxyethyl)
Sebacate (hereinafter referred to as BHES) was synthesized. An aliphatic polyester was obtained in the same manner as in Example 1, except that the obtained 88ES was used instead of B) IEA.

Table 1 shows the melting points of the obtained aliphatic polyesters.

Implementation (2) An aliphatic polyester was obtained in the same manner as in Example 1 except that IEG (instead of soil IQ) was used in the same molar ratio.

Table 1 shows the melting points of the obtained aliphatic polyesters.

Urajo 1 149.1 g of BHEA synthesized in Example 1 (0.5 mo
l), DHQ8.5g (0,025mol), IQ
Add 8.1 g (0,025 mol) and raise the flask to 300 ml.
After raising the temperature to °C and reacting in this state for about 1 hour, the distillation port was connected to a vacuum vessel and the inside of the flask was
The reaction was carried out for 2 hours under reduced pressure as follows. As the reaction progressed, ethylene glycol was distilled out, leaving an extremely active liquid in the flask.

The melting point of the aliphatic polyester thus obtained was measured and the results are shown in Table 1.

An aliphatic polyester was obtained in the same manner as in Example 5, except that the molar ratio of the constituent components of the aliphatic polyester was changed as shown in Table 1. Table 1 shows the melting points of the obtained aliphatic polyesters.

An aliphatic polyester was obtained in the same manner as in Example 5, except that the same mole of BHES was used instead of BHEA.

Table 1 shows the melting points of the obtained aliphatic polyesters.

The melting point of the polymer obtained by polymerizing only Bl(EA) was measured, and the results are shown in Table 1.

Comparison…I-Main commercially available Belprene S-9001 manufactured by Toyobo Co., Ltd.
(Comparative Example 2) and Hytrel 72 manufactured by Azuma DuPont
The melting point of No. 47 (Comparative Example 3) was measured, and the results are shown in Table 1.

(Left below) BHES: Bis(2-hydrothoushenal Jf Hage r
From the results in Table 1, the aliphatic polyester containing monohydroxy compound (II) in its molecular chain has a higher melting point and superior heat resistance than polymers containing no monohydroxy compound (II) or commercially available thermoplastic elastomers. I understand. In addition, by including dihydroxy compound (IV) in the molecular chain,
Furthermore, the melting point can be increased.

(Effects of the Invention) The 4-hydroxy-p-quarterphenyl derivative of the present invention can be used as a monomer for organic polymer compounds 1 such as polyester, polyurethane, polyether, polycarbonate, liquid crystal resin, etc., and has high heat resistance. , provides a resin with excellent flame retardancy, solvent resistance, weather resistance, and other chemical and physical properties.

It also exhibits excellent chemical and physical improvement effects when added to other resins.

Further, the aliphatic polyester of the present invention has high crystallinity, being mainly composed of an aliphatic dicarboxylic acid and an aliphatic diol.

Since segments based on dihydroxy and monohydroxy compounds with high melting points are introduced.

It has the performance as a thermoplastic elastomer, and has excellent heat resistance, mechanical properties, moldability, etc.

that's all

Claims (1)

[Claims] 1. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼[I] In the formula, R^1 is an alkyl group, an acyl group (-C-R') (
R' represents an alkyl group) and -(R^n-O)-_nH (R'' represents an alkylene group, n represents an integer of 0 or 1 or more) 2. A monohydroxy compound whose general formula is represented by the following formula [II], and an aliphatic dicarbonate whose general formula is represented by the following formula [III]. Aliphatic polyester whose main constituents are acid and aliphatic diol. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [II] (In the formula, R^2 represents an alkylene group, and l is 0 or 1.
HOOC-(CH_2)_m-COOH [III] (in the formula, m is an integer of 0 to 10) 3. Furthermore, the main constituent component is a dihydroxy compound whose general formula is represented by the following formula [IV] The aliphatic polyester according to claim 2. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [IV] (In the formula, R^3 and R^4 independently represent an alkylene group, p is 3 or 4, and q and r are independently 0 or 1
Indicates an integer greater than or equal to )