JPH11228687A - Polyether derivative and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polyether derivative capable of exhibiting excellent variety of use, affinity for resins and function maintenance of agent used together with the derivative, useful as an antistatic agent, etc., by including a specific nonionic hydrophilic group and an aromatic ring-containing hydrophobic group in the molecule. SOLUTION: This compound is shown by the formula [R<1> is a 6-26C dihydric phenol residue; A is a 2-4C alkylene; Y is an (aromatic ring-containing) 1-15C dihalide residue; Z is an aromatic ring-containing 6-15C monohalide residue or a 1-15C monohalide residue containing no aromatic ring; 1<=n<=100; 0<m<=20] and is obtained, for example, by subjecting an alkylene oxide addition polymerization to a dihydric phenol to give a polyether diol and reacting the diol with a monohalide.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a novel polyether derivative. More specifically, the present invention relates to a polyether derivative having excellent heat resistance and having no reactive group in the molecule.

[0002]

2. Description of the Related Art Polyether derivatives are synthesized by subjecting compounds having active hydrogen to addition polymerization of alkylene oxides such as ethylene oxide and propylene oxide, and adding various modifications as necessary. Those having various properties such as low viscosity to high viscosity, oil solubility to water solubility, and low melting point to high melting point can be obtained. Since derivatives having a wide range of properties can be obtained, the uses are widely used in the fields of medicine, cosmetics, fermentation industry, lubricating oils, resins, and silicone resins. The study of metamorphic technology is also active, and attempts are being made to expand applications.

For example, among polyether derivatives, oligomers having a relatively large molecular weight include antistatic agents for resins and fibers,
It has been put to practical use in a variety of applications such as surface hydrophilizing agents, water-absorbing agents, plasticizers, solid polymer electrolytes, surfactants and lubricating oils. It is possible to respond to new market needs by developing a metamorphic method.

First, the antistatic agent includes a surfactant type low molecular weight compound and a polymer type permanent antistatic agent. Representative polymer antistatic agents that are currently in practical use include polyethylene glycol methacrylate, as described in Kiyoshi Akamatsu, “Latest Technologies and Applications of Antistatic Materials,” CMC, p99 (1996). There are copolymers, polyetheresteramides, polyetheramideimides, polyethylene oxide-epichlorohydrin copolymers and the like, but they have problems in heat resistance, discoloration resistance, falling off during processing, and the like. In addition, when the thermoplastic resin is melt-kneaded, for example, with a polyester resin, if the compound has a functional group that causes a transesterification reaction, the resin is reduced in the degree of polymerization and the physical properties are reduced. Further, in the case of polycarbonate resin, for example, as disclosed in Japanese Patent Application Laid-Open No. 9-25335, an antistatic agent which does not impair the transparency of the inherent resin has been studied. Improvement is required due to low cost. As described above, not only the antistatic property but also various functions are required, and there is a demand for fine material handling and technical innovation according to the application.

On the other hand, in various fields such as ink, toner, paint, resin, rubber, fiber, paper, photograph, film, etc., strength, rigidity, adhesiveness, heat resistance, weather resistance, color tone, deep color, matte and Silica, carbonic acid, etc. for the purpose of improving various properties such as whitening (hiding properties), tactile properties, slipperiness, abrasion resistance, viscosity, adding cost as an extender, and adding new functions such as conductivity Calcium, titanium dioxide, talc,
Inorganic fine particles such as ferrite, metal powder, metal fiber, and glass fiber, and organic pigments are used. However, the surface of the inorganic fine particles is generally poor in lipophilicity because it is covered with a polar group such as a hydroxyl group or adsorbed water, and as it is, it is difficult to uniformly disperse it in an organic medium such as a resin or rubber.
Even pigments do not fulfill their purpose, such as agglomeration in non-aqueous vehicles and loss of color unevenness and gloss.

In order to improve the dispersibility by changing the surface properties of the inorganic fine particles and the pigment, a method of treating with various coupling agents or coating with various surfactants or resins has been used. For example, Japanese Patent Publication No. 7-98657 discloses a special silylating agent, and Japanese Patent Publication No.
Surface modifiers consisting of long-chain amides are each described. These conventional surface modifiers and dispersants have problems in dispersibility, heat resistance, economy, compatibility with matrix resin, etc., especially non-reactivity with matrix resin,
Few satisfy the requirements such as not hindering the performance of other additives and modifiers, and preventing fine particles from adsorbing and deactivating other additives and modifiers.

Further, it is generally said that polyether derivatives are susceptible to deterioration due to heat and oxidation, and although they exhibit excellent performance as resins and lubricating oil raw materials, they suffer from problems of thermal decomposition and thermal deterioration, and are therefore improved. Has been studied a lot. By introducing an aromatic ring into the molecule or by using a stabilizer such as an antioxidant in combination, heat resistance can be improved, and as a method of introducing an aromatic ring, an aromatic ring such as a polyhydric phenol or an aromatic amine is used. Produced by adding an alkylene oxide to an active hydrogen compound having the same (JP-A-57-151613)
), And those prepared by adding an aromatic ring-containing alkylene oxide such as styrene oxide to an active hydrogen-containing compound (L. Shechter et al., Ind. Eng. Chem., 48, 1107 (195
7) etc.), but these heat-resistant polyether derivatives are limited in the content of aromatic ring that can be introduced, the structure in which the aromatic ring is not in the main chain, and the effect of improving heat resistance is small,
In addition, there is a problem that the resin has a reactive group in the molecule, which causes a decrease in physical properties of the resin and a hindrance to the performance of other additives.

[0008] The molecular structure of the polyether derivative which is desirable for the above-mentioned uses and problems consists of a hydrophilic group and a hydrophobic group, the amount of which can be controlled by the use and necessary functions. From the viewpoint of applicability, a nonionic polyalkylene oxide chain is appropriate, and it is necessary that the molecular weight can be controlled between several hundreds and several tens of thousands in accordance with compatibility with the resin and required functions. The hydrophobic group preferably has an aromatic ring in consideration of heat resistance and affinity with an aromatic resin which is a matrix resin assumed for use as a resin modifier. Furthermore, it is also important not to have a reactive group because it does not lower the resin properties by melt-kneading with a polyester resin or the like and does not inhibit the functions of various concomitant drugs. Polyether derivatives satisfying these items are not known.

[0009]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide both a hydrophilic group comprising a nonionic polyalkylene oxide and a hydrophobic group having an aromatic ring, and to have a reactive group in the molecule. Another object of the present invention is to provide a polyether derivative without controlling the amount and molecular weight of a hydrophilic group and a hydrophobic group.

[0010]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that polyether derivatives having a structure represented by the following general formula (1) have various functions. To complete the present invention.

[0011]

Embedded image Z - [(OA) n- OR 1 O- (AO) n -Y] m- (OA) n-OR 1 O- (AO) n-Z (1)

(Wherein, R ¹ represents a residue of a dihydric phenol having 6 to 26 carbon atoms, A represents an alkylene group having 2 to 4 carbon atoms, and Y represents a carbon atom having or not having an aromatic ring. Number 1
Represents a residue of a dihalide of 15; Z represents a residue of a monohalide having 6 to 15 carbon atoms having an aromatic ring or a residue of a monohalide having 1 to 15 carbon atoms having no aromatic ring; 1 ≦ n ≦ 100, 0 <m ≦ 20)

Further, the present invention is characterized in that a polyether diol obtained by addition polymerization of a dihydric phenol with an alkylene oxide is reacted with a dihalide and then a monohalide is further reacted. Equation (1)
A process for producing a polyether derivative of

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The polyether derivative of the present invention comprises
After cross-linking by reacting a dihalide having or not having an aromatic ring with a polyether diol obtained by addition-polymerizing an alkylene oxide to a dihydric phenol, the above general compound obtained by reacting a monohalide having or not having an aromatic ring is reacted. A polyether oligomer represented by the formula (1), which has both a hydrophilic group composed of a nonionic polyalkylene oxide and a hydrophobic group having an aromatic ring, and has a controlled amount and molecular weight. It is characterized by becoming.

Further, the present invention provides a polyether derivative which is synthesized by reacting a dihalide with a polyether diol obtained by addition-polymerizing an alkylene oxide to a dihydric phenol and then reacting with a monohalide. Which is the most preferable example of the compound of the formula (1).

As the residue R ¹ of the dihydric phenol, monocyclic phenols such as hydroquinone, catechol, resorcin, orcin, urushiol, bisphenol A, bisphenol F, bisphenol S, 4,4′-dihydroxydiphenyl-2, 2'-butane, 4,4'-
[1,3-phenylenebis (1-methylethylidene)]
Bisphenols such as bisphenol (trade name: BisP-M, manufactured by Mitsui Petrochemical Industries), 4,4'-dihydroxybiphenyl, 4,4'-bis (hydroxybenzyl)
Dihydroxybiphenyls such as biphenyl, dihydroxynaphthalenes such as 1,4-dihydroxynaphthalene,
And residues of binaphthols such as 4,4′-bi-1-naphthol. Of these, bisphenol A, bisphenol F, and bisphenol S are particularly preferred.
And other residues of bisphenols.

The alkylene group A is an alkylene group having 2 to 4 carbon atoms, and preferably contains an ethylene group in order to impart hydrophilicity. Propylene groups and butylene groups can also be appropriately incorporated for the purpose of imparting hydrophobicity, changing fluidity or crystallinity, but need not necessarily be included. The residue Y of the dihalide is not particularly limited,
Residues of methylene dihalide such as methylene chloride (methylene group), residues of ethylene dihalide (ethylene group), residues of propylene dihalide (propylene group), and residues of bis (halomethyl) benzene (xylylene group) There can be. The residue Z of the monohalide is not particularly limited, and examples thereof include a residue of benzyl halide such as benzyl chloride. In the polyether derivative of the present invention, the type and content of the aromatic ring in the compound can be controlled by appropriately selecting the types of the above-mentioned dihalides and monohalides.

Here, the average value n of the number of moles of the alkylene oxide added in the general formula (1) is 1 ≦ n ≦ 100, but the optimum value varies depending on the application. The average value m of the degree of cross-linking in the general formula (1) is 0 <m ≦ 20 in consideration of various uses of the present compound. If there is no cross-linking (m = 0), desired physical properties cannot be obtained. On the other hand, when m is larger than 20, the performance as an additive or a modifier cannot be obtained, and the viscosity becomes high, so that the synthesis becomes difficult. As for the type of alkylene oxide, it is particularly preferable that ethylene oxide is contained as a hydrophilic group. Propylene oxide, butylene oxide and the like can be appropriately incorporated for the purpose of imparting hydrophobicity, changing fluidity or crystallinity, but need not necessarily be included. A in the general formula (1) is determined according to the type of the alkylene oxide used here. N can be controlled by the amount of alkylene oxide charged to phenols, etc.

When the alkylene oxide is added, the reaction is carried out in the presence of a catalyst such as an acid catalyst or an alkali catalyst, preferably under pressure, at a high temperature (for example, 80 to 200 ° C., preferably 1 to 200 ° C.).
(00-180 ° C.) by known methods. The catalyst can be an acid catalyst, for example a Lewis acid such as boron trifluoride or aluminum chloride, but more preferably an alkali catalyst, for example an alkali metal or alkaline earth metal alcoholate, hydroxide, oxide. , Carbonates, hydrides or amides. Particularly preferred catalysts are sodium or potassium alcoholates (eg methylates or ethylates) and hydroxides. The catalyst is usually used in an amount of from 0.05 to
It is used in an amount of 3% by weight, preferably 0.1-1% by weight. After completion of the reaction, the catalyst is removed by neutralization, filtration, treatment with an adsorbent or the like as necessary.

The polyether derivative of the present invention basically does not have a highly reactive functional group such as a hydroxyl group, an amino group, an ester bond or a urethane bond. Therefore, there is no decrease in the physical properties of the resin, no inhibition of the function of the concomitant drug, and no coloring. Also, heat resistance is good as a polyether derivative.

As a method for producing the polyether derivative of the present invention from the obtained polyether diol, the polyether diol is reacted with a dihalide to crosslink the polyether diol, and then the remaining polyether diol is further reacted. A method of etherifying a derived hydroxyl group with a monohalide can be preferably used. According to this method, a polyether derivative having an arbitrary amount of an aromatic ring introduced therein can be synthesized. That is, the degree of crosslinking m of the polyether diol can be controlled by changing the charge ratio of the dihalide to the polyether diol. Further, the amount of the aromatic ring can be controlled by using a dihalide containing or not containing an aromatic ring.

At this time, since the reaction rate varies depending on the type of dihalide, the terminal group of the crosslinked product and the desired degree of crosslinking m
The charging ratio for obtaining is different. In the following reaction formula,

[0023]

Embedded image

[In the above reaction formula, HO-Q-OH represents a polyether diol and XPX represents a dihalide.] The reaction rate is, for example, when methylene dihalide is used as the dihalide, the reaction (1) Reaction (2) is faster than bis (halomethyl) benzene.
The rates of (1) and reaction (2) are close, and as a result, the product has a higher proportion of (c) when methylene dihalide is used than when bis (halomethyl) benzene is used It is possible. In the present invention, it is not preferable that a large amount of hydroxyl groups is present, and etherification is performed using a monohalide. The halogen of (b) is removed by treating with sodium methylate or the like depending on the use of the product and required physical properties. The degree of crosslinking m can be controlled by changing the charge ratio of the dihalide to the polyether diol,
The relationship between the ratio and the degree of crosslinking varies depending on the type of dihalide. For example, in the case of using methylene dihalide, the degree of crosslinking m
However, when bis (halomethyl) benzene is used, the degree of crosslinking m shows a maximum at a certain ratio.

The reaction for forming an ether bond by reacting a dihalide or a monohalide with a polyether diol is performed by treating a terminal hydroxyl group of a polyether with an alkali metal compound and then reacting with a dihalide or a monohalide. Do. In addition, it can also synthesize | combine using a quaternary ammonium salt, such as a tetrabutylammonium halide, instead of an alkali metal, or using it together with an alkali metal. By-produced salt and the like are dissolved or dispersed by adding water, and separated from the polyalkylene oxide derivative by two layers. A small amount of residual salt or the like is filtered by filtration or treatment with an adsorbent. A method of diluting the product with a solvent such as toluene and filtering off salt and the like is also possible.

Examples of the alkali metal compound include caustic alkalis such as sodium hydroxide and potassium hydroxide, metal alcoholates of lower alcohols such as sodium methylate, sodium ethylate and potassium t-butoxide, and alkali metal such as metal sodium and metal potassium. Etc. are raised,
Usually, some or all of the hydroxyl groups of the polyether are converted to alcoholates and subjected to a reaction with a halide. Among these, preferred are metal alcoholates and caustic alkalis, and more preferred are sodium methylate, sodium hydroxide and potassium hydroxide. In addition,
When a metal alcoholate (such as sodium methylate) is used as the alkali metal, a product having an alkoxy group (such as a methoxy group) may be contained in the product, but this does not hinder the operation. This corresponds to HO-Q-0-P in the above reaction formula.
-X is HO-Q-OP-0C by a metal alcoholate
It would be due to a change in H _3.

The compound represented by the general formula (1) of the present invention is obtained by reacting a polyetherdiol obtained by addition-polymerizing a divalent phenol with an alkylene oxide with a dihalide, and further reacting with a monohalide. Can be reacted to be synthesized. Examples of the dihydric phenol include monocyclic phenols such as hydroquinone, catechol, resorcin, orcin, urushiol, bisphenol A, bisphenol F, bisphenol S, 4,4′-dihydroxydiphenyl-2,2′-butane, 4,4 '-[1,3-phenylenebis (1-methylethylidene)] bispheno-
Bisphenols such as 1,4-dihydroxybiphenyl, dihydroxybiphenyls such as 4,4'-bis (hydroxybenzyl) biphenyl, dihydroxynaphthalenes such as 1,4-dihydroxynaphthalene,
Binaphthols such as 4'-bi-1-naphthol; and the like. Of these, particularly preferred are bisphenols such as bisphenol A, bisphenol F and bisphenol S.

As the dihalide, methylene chloride,
Alkylene dihalides such as methylene dihalide and ethylene dihalide such as methylene bromide, halogenated aromatic ring-containing hydrocarbons such as benzal chloride and bis (chloromethyl) benzene, and halogenated ethers such as bis (chloromethyl) ether And halogenated ketones such as bis (chloromethyl) ketone. Of these, methylene chloride and bis (chloromethyl) benzene are particularly preferred. Monohalides include alkyl chlorides such as methyl chloride, methyl bromide, ethyl chloride, propyl chloride, butyl chloride, lauryl chloride, cyclohexyl chloride, alkenyl halides such as allyl chloride, benzyl chloride,
And aromatic ring-containing monohalides such as phenyl-1-chloropropane. Particularly preferred among these is benzyl chloride.

In the present invention, a solvent can be used if necessary. As the solvent, those which do not have active hydrogen such as ethers, aliphatic hydrocarbons, aromatic hydrocarbons and ketones are suitable. For example, when a polyether is converted to an alcoholate and then reacted with a halide. Can also use tertiary alcohols such as t-butanol. In general, the polyether derivatives are heated under alkaline conditions and, in particular, become colored when in contact with air. This is thought to be due to the presence of oxidation products such as aldehydes in the polyether derivative, which can be improved by performing a reduction treatment in advance by sodium borohydride treatment or the like and avoiding contact with air during the reaction. Incidentally, the balance between the hydrophobic group and the hydrophilic group and the magnitude of the surface energy are determined by R in the general formula (1).
The number of ¹ aromatic ring, the kind of Y and Z, it is possible to control the alkylene oxide type and addition molar number n, the degree of crosslinking m.

The polyether derivative of the present invention can be designed in a wide range of structures, and thus has a wide variety of uses. The optimum structure depends on the application. Applications of the polyether derivative of the present invention include microphase-separated structures, amphipathic properties, and fields requiring complex physical properties and functions such as surface activity. Plasticizers, melt viscosity lowering agents, compatibilizers, adhesives, inorganic fine particle dispersants, surface treatment agents, polymer solid electrolytes, etc. Further, a lubricating base oil having excellent heat resistance and oxidative stability can be used.

[0031]

EXAMPLES Hereinafter, the present invention will be further described with reference to Examples, but it should be understood that the present invention is not limited to the following Examples unless it exceeds the gist thereof. The “parts” in the examples are by weight. In the examples, the number of moles of the alkylene oxide added to the phenol was determined from the hydroxyl value. The average degree of crosslinking m of the polyether diol due to the reaction between the polyether diol and the dihalide was determined by GPC (Tosoh HPLC-802 type GPC apparatus). The ¹ H-NMR measurement was performed by JEOL JNM-
The measurement was performed using an LA400 type FT-NMR apparatus.

Example 1 A polyether diol prepared by adding an average of 17 moles of ethylene oxide to bisphenol A (hereinafter referred to as bisphenol A)
* 17EO adduct) (hydroxyl value 120mgKOH)
/ G) 0.4 part of SWS (Nomura office, 12% sodium borohydride aqueous alkali solution) was charged into 100 parts and stirred at 80 ° C. for 1 hour. Then, 45 parts of 28% sodium methylate was charged, and 85 to 120 under reduced pressure. The methanol was removed at ° C. After returning to atmospheric pressure with nitrogen and cooling to 40 ° C., t
After adding 20 parts of butanol, 12 parts of methylene chloride were gradually added dropwise. Thereafter, the temperature was raised and the reaction was carried out at 70 to 90 ° C. for 3 hours. Next, water was added, neutralized to pH 6 with phosphoric acid, and allowed to stand to remove the lower aqueous layer and salt. Volatiles were removed under reduced pressure to obtain an intermediate product (abbreviated as BPA / 17EO / DCM). 100 parts of this intermediate product was charged with 10 parts of 28% sodium methylate, and methanol was removed under reduced pressure at 85 to 120 ° C. Return to atmospheric pressure with nitrogen and 40 ℃
And 20 parts of t-butanol was added, and 6.6 parts of benzyl chloride were added dropwise. Thereafter, the temperature is raised to 70 to 90 ° C.
For 2 hours. Next, water was added and neutralized to pH 6 with phosphoric acid, and the mixture was allowed to stand, and the lower aqueous layer and salt were removed.

After removing volatile components under reduced pressure, 10 parts of Kyoward 600S (manufactured by Kyowa Chemical Industry Co., Ltd.)
After treatment at 0 ° C., the adsorbent was removed by filtration to obtain a polyether derivative (abbreviated as BPA / 17EO / DCM / BC). About the obtained polyether derivative, the average degree of crosslinking of the bisphenol A / 17EO adduct (general formula (1)
M) was 1.8. The structure of the obtained polyether derivative and the assignment (δ value) of ¹ H-NMR signal are shown below.

[0034]

Embedded image

Example 2 A polyether derivative (BPA / 17EO / DCM) was synthesized in the same manner as in Example 1 except that 17 parts of methylene chloride was used for 100 parts of polyether diol obtained by adding 17 mol of ethylene oxide to bisphenol A. / BC). About the obtained polyether derivative, the average degree of crosslinking (m) of the adduct of bisphenol A / 17EO was 3.1. The structure of the obtained polyether derivative and
The assignment (δ value) of the ¹ H-NMR signal is shown below.

[0036]

Embedded image

Example 3 A polyether diol obtained by adding 10 mol of ethylene oxide to bisphenol A (hereinafter referred to as bisphenol A · 10
EO adduct) (hydroxyl value 170 mgKOH / g)
100 parts of 0.4 parts of SWS (Nomura office, 12% sodium borohydride aqueous alkaline solution) 80
After stirring at 1 ° C. for 1 hour, 64 parts of 28% sodium methylate was charged, and methanol was removed at 85 to 120 ° C. under reduced pressure. After returning to atmospheric pressure with nitrogen and cooling to 40 ° C., 20 parts of t-butanol was added, and 18 parts of methylene chloride was gradually added dropwise. Thereafter, the temperature was raised and the reaction was carried out at 70 to 90 ° C. for 3 hours. Next, salt was removed in the same manner as in Example 1 to obtain an intermediate product (abbreviated as BPA / 10EO / DCM). 100 parts of this intermediate product was charged with 15 parts of 28% sodium methylate, and methanol was removed at 85 to 120 ° C. under reduced pressure. After returning to atmospheric pressure with nitrogen and cooling to 40 ° C., 20 parts of t-butanol was added, and 9.6 parts of benzyl chloride were added dropwise. Thereafter, the temperature was raised and the reaction was carried out at 70 to 90 ° C. for 3 hours.
Next, salt removal and adsorbent treatment were performed in the same manner as in Example 1, and the polyether derivative (BPA / 10EO / DCM /
BC). About the obtained polyether derivative, the average degree of crosslinking (m) of the bisphenol A / 10 EO adduct was 1.7. The structure of the obtained polyether derivative and the assignment (δ value) of ¹ H-NMR signal are shown below.

[0038]

Embedded image

Example 4 α, α'-dichloroxylene 2 instead of methylene chloride
The polyether derivative (abbreviated as BPA / 17EO / DCX / BC) was obtained using 2 parts according to Example 1. About the obtained polyether derivative, the average degree of crosslinking (m) of the bisphenol A / 17EO adduct was 3.2. Structure and ¹ H-N of the obtained polyether derivative
The assignment (δ value) of the MR signal is shown below.

[0040]

Embedded image

Example 5 A polyether derivative (B) was synthesized in the same manner as in Example 1 except that 2.7 parts of methyl chloride was used instead of benzyl chloride.
PA / 17EO / DCM / Me). About the obtained polyether oligomer, bisphenol A
-The average degree of crosslinking (m) of the 17EO adduct was 1.8. Structure and ¹ H-NMR of the obtained polyether derivative
The assignment (δ value) of the signal is shown below.

[0042]

Embedded image

Comparative Example 1 Bisphenol A / 17EO adduct synthesized in Example 1 (abbreviated as BPA / 17EO). Comparative Example 2 0.4 parts of SWS (Nomura Office, 12% aqueous sodium borohydride solution) was added to 100 parts of the bisphenol A / 17EO adduct (hydroxyl value 120 mgKOH / g) of Comparative Example 1 and stirred at 80 ° C. for 1 hour. Thereafter, 45 parts of 28% sodium methylate was charged, and 85 to 12
At 0 ° C., the methanol was removed. After returning to atmospheric pressure with nitrogen and cooling to 40 ° C., 6.8 parts of methyl chloride were gradually injected. Thereafter, the temperature was raised and the reaction was carried out at 70 to 90 ° C. for 3 hours.
Next, the salt was removed in the same manner as in Example 1, the adsorbent treatment was performed in the same manner as in Example 1, and the polyether derivative (B
PA / 17EO / Me).

Comparative Example 3 The intermediate product of Example 1 (abbreviated as BPA / 17EO / DCM). Comparative Example 4 A polyether derivative (BP) was synthesized according to Comparative Example 2 except that 16 parts of benzyl chloride was used instead of methyl chloride.
A / 17EO / BC).

REFERENCE EXAMPLE Regarding the polyether derivative of the present invention in each of the above examples and the polyether derivative of each comparative example, the temperature at which thermal decomposition starts, and the specific properties of the polyester resin after melt-kneading each polyether derivative into the polyester resin. The viscosity was measured.
The measurement results are shown in Table 1 below. In addition, the measuring method and conditions are as follows. [Measurement of Thermal Decomposition Temperature] Using a thermogravimetric analysis (TGA) measuring device, the temperature was raised from room temperature to 600 ° C. at a rate of 10 ° C./min in a stream of nitrogen or air, and the inflection point temperature at which weight loss started was determined. I asked.

[Production of Polyester Resin Containing Polyether Derivative] Five parts of each of the polyether derivatives of Examples and Comparative Examples were mixed and mixed with 100 parts of a polyester resin dried at 150 ° C. for 15 hours. The obtained mixture was used as a Toyo Seiki Seisakusho Labo Plastomill (setting conditions were:
Test rotation speed: 15 rpm, test temperature T1: 250 ° C., T
2: 260 ° C, T3: 270 ° C, T4: 280 ° C) to obtain pellets. [Intrinsic Viscosity] The intrinsic viscosity of the polyester resin containing each polyether derivative was measured at 30 ° C. with phenol / ethane tetrachloride (weight ratio 1: 1) using a viscosity tube. The intrinsic viscosity of the polyester resin not containing the polyether derivative was 0.62 cm ³ / g, which was measured in the same manner.

[0047]

[Table 1]

As described above, the polyether derivative of the present invention has excellent thermal stability and does not lower the intrinsic viscosity of the resin when blended with the resin.

[0049]

According to the present invention, a novel polyether derivative comprising an aromatic ring and a polyalkylene oxide chain is provided. The polyether derivative of the present invention has a high degree of freedom in molecular design, and can control the balance of hydrophobic groups and hydrophilic groups and the molecular weight arbitrarily, so that a polyether derivative having an arbitrary structure suitable for use and required physical properties can be obtained. Becomes possible. Furthermore, since it has good heat resistance and no reactive groups, it does not degrade the performance of the resin when added to the matrix resin, nor does it hinder the performance of other additives or modifiers. is there.

Claims (5)

[Claims] 1. A polyether derivative represented by the following general formula (1). Embedded image Z-[(OA) n -OR ¹ O- (AO) n -Y] m- (OA) n -OR ¹ O- (AO) n -Z (1) (wherein R ¹ is Y represents a residue of a dihydric phenol having 6 to 26 carbon atoms; A represents an alkylene group having 2 to 4 carbon atoms;
Represents a residue of a dihalide having 1 to 15 carbon atoms having or not having an aromatic ring, and Z represents 6 to 6 carbon atoms having an aromatic ring.
Represents a residue of a monohalide having 15 or a residue of a monohalide having 1 to 15 carbon atoms having no aromatic ring, and 1 ≦ n
≦ 100, 0 <m ≦ 20) 2. The polyether derivative according to claim 1, wherein R ¹ is selected from the group consisting of residues of bisphenol A, bisphenol F and bisphenol S. 3. The polyether derivative according to claim 1, wherein Z is selected from the group consisting of benzyl halide and methyl halide residues. 4. The method according to claim 1, wherein Y is selected from the group consisting of a methylene group, an ethylene group, a propylene group, and a xylylene group.
4. The polyether derivative according to any one of 3. 5. A method for producing a polyether derivative represented by the general formula (1), wherein a polyether diol obtained by addition-polymerizing an alkylene oxide to a dihydric phenol is reacted with a dihalide, and further reacted with a monohalide. Method.