JP2995670B2 - New polyether polycarbonate - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel polymer compound. For more details, moderate moisture absorption in blending and kneading into fibers, films and other molded products, surface treatment of fibers, films, resin molded products, paper and metal bodies, and chemical modification of high molecular compounds And a method for producing the same.

[0002]

2. Description of the Related Art In recent years, the need for surface modification of fibers, films, resin moldings, rubber, paper, and metal bodies has increased, and further improvements in antistatic properties, antifouling properties, antifogging properties, and fog resistance have been demanded. It was started. Surface modification methods include kneading fibers, films, resin moldings, and rubber, and converting the chemical structure of fibers, films, resin moldings, and rubber itself to modify the internal structure and modify the surface. And a method of modifying the surface of fibers, films, resin moldings, paper and metal by performing surface treatment.

For example, examples of antistatic materials include electric conduction by free electrons of metal, electric conduction by conjugate double bond, electric conduction by imparting hygroscopicity, and the like. The most common.

[0004] Antistatic agents used as kneading blends into fibers, films and resin moldings utilizing hygroscopicity include bleed-out low molecular weight antistatic agents and non-bleed-out permanent antistatic agents. There is. The bleed-out type antistatic agent is a low molecular compound, and therefore, is excellent in heat resistance and antistatic property. However, bleed out to the surface of the antistatic agent causes various surface contaminations. It causes trouble.

[0005] In order to eliminate the drawbacks of these bleed-out type antistatic agents, there is a strong demand for improvements in non-bleed-out type, that is, permanent antistatic agents which impart appropriate hygroscopicity.

Examples of the hydrophilic group of the antistatic agent that provides hygroscopicity include polyquaternary ammonium salts such as polyvinylbenzyltrimethylammonium salt, polyanions such as polycarboxylates and polysulfonates, and polynonions such as polyethylene oxide groups. is there.

[0007] Polyquaternary ammonium salts such as those represented by polyvinylbenzyltrimethylammonium salt have high hygroscopicity and an extremely good antistatic effect.
If the temperature is higher than ° C., coloration or thermal decomposition occurs, and heat resistance is not sufficient.

Polyanions represented by sodium polyacrylate and sodium polystyrene sulfonate have poor heat resistance, antistatic property and mechanical strength due to thermal decomposition of the polymer main chain or insufficient compatibility with the resin. At the same time, it cannot be a satisfactory permanent antistatic agent.

Polynonions such as polyethylene oxide take advantage of good fluidity during molding and good compatibility with the above-mentioned resins, and as a method for imparting permanent antistatic properties, methoxypolyethylene glycol acrylate and N-vinylpyrrolidone are used. For example, a method of producing an antistatic resin by copolymerizing a hydrophilic monomer with a vinyl-based monomer has been proposed (for example, Japanese Patent Application Laid-Open No. 50-78642). There is a problem that the mechanical properties of the resin for molding are lowered, and the cost of the hydrophilic monomer is high, so that the resulting resin is also expensive.

In order to improve this drawback, Japanese Patent Application Laid-Open No.
No. 42242 (Claims "(A) Polyalkylene oxide containing at least one functional group reactive with a carboxyl group in a molecule or derivatives 1 to 6 thereof)
0% by weight and (B) 99 to 40% by weight of a modified vinyl polymer having a carboxyl group, and a resin composition having excellent antistatic properties ") has been proposed. The average molecular weight of the polyethylene oxide used in the present invention is 400,
1000, 2000, and the heat resistance is not sufficient. or,
In order to solve the drawback of low molecular weight of polyethylene oxide, the purpose is to control the bleed out of polyethylene oxide by using the carboxylic acid group of the modified vinyl polymer, but the intended purpose has not been achieved.

In order to control the bleed-out property of the polyethylene oxide and to exert a permanent antistatic effect, it is necessary to increase the molecular weight of the polyethylene oxide to tens of thousands to hundreds of thousands. However, when the molecular weight of polyethylene oxide increases, the chance of thermal decomposition increases in proportion to the degree of polymerization, and the degree of polymerization decreases significantly, and the compatibility with the resin also decreases. In such a case, the mechanical properties of the molded product are significantly reduced.
In the prior art, especially when used as a permanent antistatic agent, the amount added to the high-temperature molding resin is larger than that in the case where it is used as a bleed-out type antistatic agent, which is around 10%, and this tendency is further increased. .

[0012] High molecular weight polyethylene oxide is manufactured by Iron and Steel Chemical Co., Ltd. and sold under the trade name PEO. The company's PEO has an average molecular weight of 3.3 to 3.8 million, but it is 10
When the temperature is raised at a rate of ° C./min, the weight loss rate by a thermobalance at 220 ° C. reaches as much as 20% or more. At the same time, the degree of polymerization decreases due to thermal decomposition of polyethylene oxide at high temperatures, and the mechanical properties of the molded product are significantly reduced.

Many attempts have been made to remedy the above-mentioned drawbacks of high molecular weight polyethylene oxide, but no satisfactory results have yet been established. Polyetheramide (JP-B-63-53226) is obtained by reacting polyethylene glycol with acrylonitrile and further performing a hydrogenation reaction to obtain polyethylene glycol diamine having amino groups at both ends. The reaction was carried out, and further, hexamethylenediammonium adipate or ε-caprolactam was added, and 22
In this method, polymerization is performed at a temperature of 0 to 270 ° C. This polyether amide uses an expensive polyether diamine because of its complicated production process, and requires a large amount of addition to achieve the desired antistatic effect. I can't say.

Polyetheresteramide (JP-A-62
-265340) has a constitutional unit having a number average molecular weight of 2
Polyethylene glycol (diol component) having a carbon number of 00 to 6000, dicarboxylic acid having 4 to 20 carbon atoms (dicarboxylic acid component), aminocarboxylic acid having 6 or more carbon atoms or lactam or diamine having 6 or more carbon atoms and dicarboxylic acid (polyamide component) ), A polyether ester amide in which a polyether segment and a polyamide segment are linked by an ester bond has been proposed as a permanent antistatic agent.

The polyalkylene oxide chain of the present invention has a number average molecular weight of 200 to 6000, and the polyethylene oxide chain has relatively good heat resistance, but for the purpose of improving mechanical properties and exhibiting a permanent antistatic effect. Since the hydrophilic polyethylene oxide chains are linked by hydrophobic polyamide chains in a block manner, the ratio of the polyamide chains becomes large. For example, as described in Examples, A-1 lactam: 50 PEG: 47 Adipic acid: 3.6 A-2 Nylon 66:60 PEG: 33.8 Adipic acid: 8.7 A-3 ω Aminodecanoic acid: 30 PEG: 50.6 Dodecanediic acid: 19.4: polyethylene cholic acid Weight fraction of 30-50
%. Therefore, in order to exert the antistatic effect of the blend, the amount of polyetheresteramide added becomes considerably large, and an addition amount of 15% is required. In addition, when the polyetheresteramide is produced, a dehydration-condensation reaction at a temperature of 260 ° C. is required, and the production cost becomes large. in addition,
Considering the large amount of addition, it is hard to say that it is an economical method of controlling electricity.

US Pat. No. 2,799,666 relates to linear polycarbonate compounds obtained from bis- (hydroxyethoxy) aromatic compounds. The mole number of ethylene oxide added to the aromatic hydroxyl group of the present invention is 1 mole, the addition of hygroscopicity is small, it is only a partial improvement of the aromatic polycarbonate, and the stretch, elastic recovery, stress relaxation, tensile strength, tearing The purpose of the present invention is to improve mechanical properties such as strength and electrical properties, and the purpose and subject are different from those of the compound of the present invention. JP-A-62-187725 discloses that a compound represented by the formula (III) is synthesized by reacting a carbonate compound represented by the formula (I) with a diol to react with a diol represented by the formula (II). (II) A method for producing a carbonate diol, which comprises reacting a compound of the formula: (Where R is a C ₁ -C ₆ alkyl group or a phenyl group,
R 'is a dihydric alcohol residue, and n is an integer of 1 to 100. ) The polymer compound of the invention has a repeating unit, And -R'OH is bonded as both terminal groups. The repeating unit of the present invention is And the dihydric alcohol residue (R ′) of the present invention
Is a homo-form in which only one is selected from aliphatic dihydric alcohols, alicyclic dihydric alcohols, and aromatic dihydric alcohols. The polymer compound of the present invention generally has low hygroscopicity, and does not improve heat resistance because it is a homo-form as described above even when polyethylene glycol which is a hygroscopic compound is used to improve hygroscopicity. . The polymer compound of the invention has a different chemical structural formula from that of the present invention, and cannot achieve the object of the present invention.

[0017]

SUMMARY OF THE INVENTION Hygroscopic polymers containing a polyalkylene oxide chain as an active ingredient are: (1)
Reduction of raw materials and manufacturing costs, (2) improvement of heat resistance,
(3) improvement of compatibility with other resins, (4) control of bleed-out property, (5) improvement of mechanical properties, (6) prevention of coloring,
(7) There are requirements such as an increase in the effect of preventing permanent charging. Conventionally, there are many inconsistencies among these seven items in the known technology, and there is no one that can simultaneously satisfy these requirements. The present invention seeks to resolve these needs simultaneously.

[0018]

As a result of various studies, the present inventors have invented a novel polymer compound which can substantially satisfy the above seven items. The compound of the present invention has the general formula

Wherein X is an alkylene group having 1 to 6 carbon atoms, an alkylidene group and a haloalkylidene group having 1 to 6 carbon atoms,
₁ is at least one group selected from alkylene groups having 2 to 4 carbon atoms, R ₂ and R ₃ are lower alkyl groups or unsubstituted or substituted phenyl groups, m is an integer of 2 to 100, n is an integer of 1 to 100. ).

The polymer compound C of the present invention is generally produced by the following method. The first stage is

Embedded image Polyether by adding alkylene oxide to

A second step of producing (hereinafter referred to as polyether A) a carbonic ester of the polyether

Embedded image The third step of producing (hereinafter referred to as carbonate B) comprises the step of polymerizing the carbonate B produced in the second step to produce a polymer compound C.

In the first step, the polyether (3) is easily produced at a reaction temperature of 50 to 230 ° C. under normal pressure or pressure under a known method of adding an alkylene oxide to the compound of (2) in the presence of a catalyst. be able to.

X in the polyether A of the present invention has 1 to 1 carbon atoms.
The alkylene group having 6 carbon atoms, the alkylidene group having 1 to 6 carbon atoms and the haloalkylidene group, and R ₁ are selected from at least one group selected from alkylene groups having 2 to 4 carbon atoms. Therefore, as a raw material of polyether A, bis (p-hydroxyphenyl) methane 1,1-bis (p-hydroxyphenyl) ethane 1,2-bis (p-hydroxyphenyl) ethane 2,2-bis (p-hydroxyphenyl) ) Propane 1,1-bis (p-hydroxyphenyl) butane 1,1-bis (p-hydroxyphenyl) isobutane 2,2-bis (p-hydroxyphenyl) butane 2,2-bis (p-hydroxyphenyl) pentane 2,2-bis (p-hydroxyphenyl) hexane bis (p-hydroxyphenyl) difluoromethane 2,2-bis (p-hydroxyphenyl) hexafluoropropane and the like are used.

The number m of moles of the alkylene oxide bonded to both ends of the polyether A is an integer of 2 to 100, and preferably 2 to 20. Measurement of the hydroxyl value gives the average value of m. The catalyst used is not particularly limited and can be selected from those conventionally used in epoxy ring-opening reactions. After completion of the reaction, the next-stage reaction can be carried out without removing these catalysts.However, from a practical point of view such as easy coloring, the catalyst can be removed using neutralization filtration or an inorganic adsorbent. preferable. In the second step, carbonate ester B is produced by a known method in which transesterification is carried out using dimethyl carbonate, diethyl carbonate, dipropyl carbonate, di-n-hexyl carbonate, diisopropyl carbonate, ditertiary butyl carbonate, diphenyl carbonate, or the like. I do.

The amount of carbonate added to the polyether A in the second stage reaction is usually 2 to 50 in molar ratio.
Times, preferably 3 to 10 times. In the reaction for obtaining the polymer compound C in the third step, n is 1 to 100.
N can be arbitrarily selected depending on the required physical properties,
Preferably it is 1.5-20.

In the third step, the carbonate B produced in the second step is converted into the polymer C of the present invention. Normally, the produced carbonate ester B is sequentially converted into the third-stage polymer compound C in parallel with the progress of the second-stage carbonate ester B production reaction. There is also a step in which polyether A reacts with carbonate ester B or polymer compound A. By selecting the reaction conditions, the second stage reaction can be mainly produced, and then the third stage polymerization can be carried out. This method may be preferable in terms of shortening the reaction time and improving the performance of the polymer compound C.

In the second and third steps, a catalyst for the transesterification reaction may or may not be used. A transesterification catalyst is usually used as a catalyst.
Such as alkali metal or alkaline earth elemental metals, oxides, hydroxides, amide compound, alcoholate, phenolate or ZnO, PbO, such basic metal oxides Sb ₂ O _3, organotitanium compounds, soluble manganese compounds of , C
a, mixture of acetate, antimony compound of Mg, Zn, Pb, Sn, Mn, Cd and Co, mixture of hydrosulfite and 2,6-ditert-butyl-p-cresol, basic catalyst and diaryl phosphate Or a salt mixture thereof, quaternary ammonium, quaternary phosphonium,
Or, there are generally basic compounds such as quaternary arsonium salts, especially boranates and silane compounds. The amount of the catalyst used varies depending on the nature and activity of the catalyst.

When a catalyst is used, it is usually necessary to remove the catalyst by filtration, adsorption, washing with water or the like after the completion of the reaction. When caustic soda, caustic potash, sodium alcoholate, and potassium alcoholate are used as the catalyst, the reaction rate is high and the catalyst can be easily removed after the reaction is completed.

The reaction temperature in the second and third steps is reduced,
70 ° C to 230 ° C under normal pressure or pressure, preferably 80 ° C
To 200 ° C. The reactions in the second and third steps are transesterification equilibrium reactions, and it is necessary to expel the reaction product out of the system and quickly transfer the reaction to the production system. Therefore, alcohol produced by transesterification,
It is necessary to fractionate phenol, dialkyl carbonate, etc. and take them out of the system. This is carried out using the usual transesterification technique.

The second and third steps may be carried out in the absence of a solvent or in the presence of a solvent, but usually no solvent is used. Further, since it is preferable to carry out the reaction in the absence of oxygen, it is usually carried out using a material from which oxygen has been removed and in an atmosphere of an inert gas such as nitrogen or argon. In order to remove oxygen in the raw material, for example, a method of reducing the pressure and then substituting with nitrogen or purging with nitrogen gas is used.

The polymer compound C of the present invention can be confirmed by, for example, infrared absorption spectrum, NMR spectrum, GPC, quantification of hydroxyl value and carbonate group. The infrared absorption spectrum of the polyether A of the present invention has a characteristic absorption of OH group at 3,500 to 3,300 Kaiser, an aromatic hydrocarbon at 1,610, 1,510 Kaiser, and a characteristic absorption of ether at 1,120 Kaiser. There are 8
40,950 Kaiser has the characteristic absorption of methylene groups linked to ether groups. When the polymer compound C is produced by reacting the polyether A, the characteristic absorption of the OH group disappears, and the absorption of 1,750, 1,280 and Kaiser ester groups newly appears. The substantial disappearance of the OH group can be quantified by measuring the hydroxyl value.
Further, the carbonate group can be quantified by an alkali hydrolysis method, and from the quantified value, the average degree of condensation of the polymer compound C, that is, the average molecular weight can be obtained. Furthermore, the condensation degree n
Can be measured by GPC.
These results indicate that the polymer compound C of the present invention is a polyether polycarbonate compound.

The progress of the reaction of the polyether A, carbonate ester B and polymer compound C of the present invention can be analyzed with good correlation by measuring the hydroxyl value, carbonate ester value and GPC.

Hereinafter, features of the polymer compound C of the present invention will be described. (1) The manufacturing cost is low. That is, (a) raw materials are polyol, alkylene oxide, dialkyl carbonate,
Alternatively, it is inexpensive with diallyl carbonate. (B)
The reaction process is a clean two-stage reaction consisting of addition of alkylene oxide and transesterification of carbonic acid. (C) By-products can be recycled with alcohol. (D) The reaction can be carried out at a low reaction temperature of 200 ° C. or lower. (E)
Production equipment has high productivity and its proportional and fixed costs are small.

(2) High heat resistance. The polyether A of the present invention is a block type copolymer of an aromatic group having a high heat resistance and an aliphatic group. Further, since these segments are connected by a heat-resistant polycarbonate bond, the heat resistance is low. Is big.

(3) Good compatibility with other polymers. Since it contains an aromatic and aliphatic oxide group and a carbonate group, it has very good compatibility with various polymers. For example, polystyrene that requires an antistatic effect, rubber-modified polystyrene, acrylonitrile styrene resin,
Acrylonitrile butadiene-styrene resin, polymethyl methacrylate, polystyrene methacrylate,
Polyolefin, polycarbonate, polyacetal,
The compatibility is good for polyphenylene oxide, polyphenylene sulfide, polyphenylene sulfone, polysulfone, polyethylene terephthalate, polyarylate, polyamide, and polyimide. It is possible to adjust the compatibility by changing the ratio of the aromatic group, the alkyl group, and the carbonate group according to the resin to be compatible.

(4) Bleed-out is small. Since the polymer compound C of the present invention has a large molecular weight and contains a bisetherphenolalkane group which is difficult to bleed out, the bleed-out property is small.

(5) Excellent mechanical properties. A carbonate group links the copolymerized polyether segment of an aromatic group with high rigidity and an alkylene oxide with high flexibility, and the balance between the hard segment and the soft segment is good. The physical properties are extremely good.

(6) The degree of coloring is extremely small. Since the polyether segments containing no nitrogen atom are linked by a carbonate group, the coloring is small and the resulting polymer has extremely excellent whiteness.

(7) It has moderate hygroscopicity. Moderate moisture absorption by coating on the surface of fiber, film, resin molded product, paper, metal body, or by internally kneading blend and chemical modification of polymer compound when manufacturing fiber, film, resin, rubber molded product Properties can be imparted.

In the polymer compound C of the present invention, m is 2
100, preferably 2 to 20. When the number m is increased, the hygroscopicity is increased and the antistatic effect is increased, but the heat resistance tends to decrease. Conversely, when the number m is small, the heat resistance is particularly improved. The number of n is 1 to 100, preferably 1.5 to 20. The number of m and n can be appropriately selected according to the required physical properties.

Polyalkyl which is a functional group imparting hygroscopicity to polymer compound C Group, the size of the atomic group is extremely small, for example, the decrease in hygroscopicity and the inhibition of the antistatic effect are extremely small as compared with the large segment of polyamide of polyetheresteramide. Further, the carbonate group itself has excellent heat resistance and chemical resistance, and can be said to be a linking group suitable for achieving the object of the present invention.

The proportion of the polymer compound C used to effectively exert the above characteristics is not particularly limited. For example, in the case of kneading blends into fibers, films, resins, and rubber moldings, the polymer compound C may be used. The weight ratio of the compound C to the other polymer is preferably from 1:98 to 30:70. The polymer compound C of the present invention can be used as a kneading blend or a surface treatment agent as a single additive, but can also be used in combination with other surfactants and moisture absorbents. Examples of the substance used in combination include alkali metal salts of sulfonic acids such as sodium alkanesulfonic acid and sodium alkylbenzenesulfonic acid, alkali metal salts of alkyl carboxylic acids, and alkali metal salts of alkyl phosphonic acids. The proportion to be used is not particularly limited, but for example, in a kneaded blend, it is preferably 0.1 to 5 parts by weight based on 100 of the total amount of the polymer compound C and other polymers.

[0041]

As described above, the polymer compound C of the present invention can provide a great number of applications because it has such features. The first field of application is a method for improving the antistatic property, antifogging property, and the like by kneading fibers, films, resins, and rubber moldings inside. The polymer into which the polymer compound C is kneaded is a polymer of an aromatic vinyl compound such as polystyrene, rubber-modified polystyrene, carboxylic acid-modified polystyrene, or polyvinyl toluene, or a polymerization of an aliphatic olefin such as polyethylene, polypropylene, or polybutene. Substance, carboxylic acid, carboxylic ester group,
Aliphatic vinyl compound polymer having chlorine, fluorine, nitrile group, etc., acrylonitrile styrene resin, acrylonitrile butadiene-styrene resin, copolymer of aromatic and aliphatic polystyrene methacrylate and polycarbonate, polyacetal, polyphenylene oxide, polysulfide And addition or condensation polymers such as polyphenylene sulfone, sulfone, polyester, polyamide and polyimide.

The second field of application is the surface treatment of fibers, films, resin moldings and metals. It is possible to meet the demand for imparting a suitable hygroscopic property to the surface of these materials and improving the antistatic property, antifogging property and the like. For example, when a solid surface is brought to a relatively low temperature and then exposed to a warmer, more humid atmosphere, the cooled surface of the solid has a strong tendency to become cloudy or frost-covered. Such condensation of water on the surface or accumulation of icy crystals can be undesirable for various reasons.

The surface is a polyvinyl chloride film or polyester film of a greenhouse, a windshield of an automobile, a heat exchanger aflumifin of a cooler, or the like. Further, there are cases in which a polyester film, a polyvinyl chloride film, or the like, which is easily charged, is used.

As a third field of application, the polymer compound C of the present invention can be used as an intermediate for polymer modification. Mid bonds can also be formed. Further, it can be converted into an ester bond, a urethane bond or an amide bond by reacting with a diol to convert the terminal group into a hydroxyl group.

[0045]

Next, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples. The physical properties of the polymer and the composition in the examples were measured and evaluated by the following methods.

(1) Hydroxyl value The hydroxyl value was measured by the method specified in "JIS K-0070 2.5 hydroxyl value".

(2) Quantification of carbonate groups and calculation of average condensation degree n. "JIS K-0070 2.2 Saponification value"
Saponification was carried out according to the method specified in the above. However, in order to eliminate the influence of carbon dioxide in the air, the inside of the system was purged with nitrogen, and the test was performed in a nitrogen sealed state. Subsequently, potentiometric titration with N / 2 hydrochloric acid was performed. Apparatus: manufactured by Kyoto Electronics, AT-118 carbonate group (% by weight) = [60.01 × 0.025]
× f × (ml number of third inflection point−ml number of first inflection point)]
÷ (g of sample) f: Factor of N / 2 hydrochloric acid Average condensation degree n = [6000− (carbonic acid ester group%) × M
dac] ÷ [carbonate group% × (Mpe + 26) -6
00] Mpe: molecular weight calculated from hydroxyl value of polyether used in reaction Mdac: molecular weight of dialkyl or diphenyl carbonate used in reaction

(3) Measurement was performed using GPC THF as a solvent. Apparatus: TOSOH HLC-820

(4) Thermal decomposition temperature The weight loss temperature was determined by using a thermal analyzer at a heating rate of 1 from normal temperature.
The temperature was raised at 0 ° C./min, and the temperature when the weight was reduced by 10% was measured. Equipment: SEIKO I SSC / 5200 TG / DT
A220

(5) Insulation Resistance Test (Surface Resistance) Measured according to the method specified in JIS Z-3197 6.8 Insulation Resistance Test. A 0.05 gr sample is uniformly applied to a type 2 comb-type electrode of a glass cloth-based epoxy resin copper-clad laminate, dried at 100 ° C. for 30 minutes, cooled in a desiccator, and insulated after 1 minute at 100 VDC. The resistance was measured. Apparatus: Hewlett Packard 4329A High
ResistantMeter

(6) Infrared absorption spectrum Measured using a KBr cell. Equipment: Nicolet 50DXC FT-IR

(7) Contact Angle The polymer compound C is heated to 80 ° C. or at room temperature as necessary, and the bar coater No. 1 is placed on a clean aluminum plate. 20
Was applied uniformly. After cooling to 25 ° C. in a desiccator, deionized water 1
One minute after placing the drop, the contact angle was measured. The average value repeated three times was defined as a measured value. Equipment: Goniometer manufactured by Elma Optical Co., Ltd.

[Synthesis Example] Polyether A-1 2,283 g of 2,2-bis (p-hydroxyphenyl) propane and 1.2 g of potassium hydroxide were charged into a stainless steel autoclave, and oxygen was removed by repeating vacuum and nitrogen pressurization. did. Subsequently, 340 gr of ethylene oxide was added from the dropping tank.
Was heated to 130 ° C. over 2 hours while stirring. Next, while cooling appropriately, the ethylene oxide 14
22 g were introduced over 4 hours. After aging until the pressure became constant, the mixture was cooled to 100 ° C., 12 gr of silica-alumina-based adsorbent powder was added, and the mixture was stirred for 1 hour and filtered under heating to obtain 4030 gr of a colorless and transparent viscous liquid. It had a hydroxyl value of 277 mg KOH / gr, a calculated molecular weight of 405, and thus an average of 4 moles of ethylene oxide added (m = 2). Further, potassium ion by atomic absorption analysis was 5 ppm or less.

[Synthesis Example] Polyether A-2 In the same manner as in Synthesis Example A-1, the amount of ethylene oxide added was increased to obtain a colorless transparent viscous liquid having a hydroxyl value of 167 mgKOH / gr (average of 10 mol of ethylene oxide). Addition, m
= 5). Potassium ion was 5 ppm or less.

[Synthesis Example] Polyether A-3 The dropping amount of ethylene oxide was further increased in the same manner as in Synthesis Example A-1 to obtain a colorless and transparent viscous liquid having a hydroxyl value of 101 mgKOH / gr (average of ethylene oxide). 20 mol addition, m = 10). Potassium ion was 5 ppm or less.

[Synthesis Example] Polyether A-4 In the same manner as in Synthesis Example A-1, the amount of ethylene oxide added was further increased to obtain a colorless, transparent, solid product at room temperature with a hydroxyl value of 72 mgKOH / gr (oxidation Ethylene average 30m
ol addition, m = 15). Potassium ion was 5 ppm or less.

[Synthesis Example] Polyether A-4C In the same manner as in Synthesis Example A-4, a product not separately treated with a silica-alumina-based adsorbent was obtained. The content of potassium hydroxide by neutralization titration was 0.03% by weight.

[0058]

【Example】

Example 1 405 gr (1.0 mol) of polyether A-1 was charged into a 1-liter glass flask equipped with a stirrer, a thermometer, a nitrogen inlet tube, and a Widmer fractionating tube, and nitrogen was replaced by bubbling. Heated to 175 ° C under normal pressure, and dimethyl carbonate 3 previously substituted with nitrogen at the same temperature
60 gr (4.0 mol) was added dropwise over 6 hours. The reaction started at the same time as the start of the dropping, during which the fraction from the top of the fractionation tower gradually rose from 65 ° C to 88 ° C. Gas chromatography analysis revealed that a total of 270 gr of distillate containing 24% methanol and 76% dimethyl carbonate was distilled. When a part of the reaction product in the flask was analyzed by GPC, the degree of condensation n = 1, 23, 4, 5, 6 or more was 10.5%, 14.5%, 14.7%, 14.3%, respectively.
5%, 11.6% and 34.2%. In order to further promote the reaction, gradually increase the pressure to 5 mmHg at the same temperature for another 5 hours.
The pressure was reduced to dimethyl carbonate, and 495 gr of a viscous liquid was obtained.

FIG. 1 shows an infrared absorption spectrum of the polyether A-1, FIG. 2 shows an infrared absorption spectrum of the polymer compound obtained, and FIG. 3 shows a GPC of the polyether A-1 shown in FIG. 4 shows GPC of the obtained polymer compound.

Example 2 In the same apparatus as in Example 1, 405 gr (1.0 mol) of polyether A-1 and 360 gr (4.0 mol) of dimethyl carbonate, and 0.15 gr of tetrabutyl titanate tetramer as a catalyst were used. The charged nitrogen was replaced by bubbling. The mixture was heated under normal pressure and reacted from 95 ° C. to 110 ° C. for 20 hours. During this time, the heating was adjusted so that the top temperature of the distillation tube became 65 to 75 ° C,
The produced methanol was distilled together with dimethyl carbonate. Analysis by gas chromatography revealed that a total of 100 gr of distillate containing 62% of methanol and 38% of dimethyl carbonate was distilled. When a part of the reaction product in the flask was taken and analyzed by GPC, the condensation degree n = 1,
2 and 3 were 83.0%, 15.2% and 1.8%, respectively. Under normal pressure to 150 ° C for further reaction 3
Heat over time to distill dimethime carbonate,
At the same temperature, the pressure was gradually reduced to 5 mmHg over 3 hours, and the mixture was distilled off to obtain 510 g of a viscous liquid.

Example 3 In the same manner as in Example 1, 668 gr (1.0 mol) of polyether A-2 was charged and 360 gr of dimethyl carbonate (4.
0 mol) over 7 hours, and methanol and dimethyl carbonate were simultaneously distilled off. Subsequently, the mixture was cooled to 130 ° C., and the pressure was gradually reduced to 5 mmHg at the same temperature over 5 hours to distill dimethyl carbonate.
0 gr was obtained.

Example 4 As in Example 1, at 60 ° C.
555 gr (0.5 mol) of the polyether A-3 dissolved in the above was charged, and 180 gr (2.0 mol) of dimethyl carbonate was added dropwise at 175 ° C. over 8 hours under normal pressure, and methanol and dimethyl carbonate were simultaneously distilled off. Subsequently, the mixture was cooled to 80 ° C., and the pressure was reduced to 5 mmHg over 6 hours to distill dimethyl carbonate.
r was obtained.

Example 5 As in Example 1, 60 ° C.
775 gr (0.5 mol) of the polyether A-4 dissolved in the above was charged and 180 gr (2.0 mol) of dimethyl carbonate was added dropwise at 175 ° C. over 5 hours under normal pressure, and methanol and dimethyl carbonate were simultaneously distilled off. The temperature was further increased to 200 ° C. at the same temperature for 2 hours, followed by 30 minutes while bubbling with nitrogen, and cooled to obtain 825 gr of a product which became a solid at room temperature.

Example 6 The procedure of Example 2 was repeated at 60 ° C.
And 775 g (0.5 mol) of polyether A-4C containing 0.03% of potassium hydroxide and 180 g (2.0 mol) of dimethyl carbonate were charged and replaced by bubbling with nitrogen. The mixture was heated under normal pressure and reacted from 120 ° C. to 160 ° C. for 12 hours. The methanol produced during this time was distilled together with dimethyl carbonate. Further, dimethyl carbonate was distilled off at 180 ° C. for 2 hours and then at the same temperature under reduced pressure of 5 mmHg for 1 hour. 100 ℃
After cooling to 2.5 g of silica-alumina-based adsorbent powder and stirring for 1 hour, 810 g of a solid product was obtained at room temperature.
r was obtained. Tables 1 and 2 show the results of Examples 1 to 6. The results in Table 1 show that the polymer compound of the present invention was obtained. The following is clear from the results in Table 2. The polymer compound of the present invention has much higher heat resistance than conventional polyethylene oxide and polyethylene glycol, and has the same excellent hygroscopicity.

Example 7 The polymer compound of the present invention was blended with a polystyrene resin, and the antistatic performance was evaluated.
100 parts by weight of pellets of high impact polystyrene "Stylon 492" manufactured by Asahi Kasei Kogyo Co., Ltd. The following parts by weight of the compounds of Examples 3 and 5 and PEO as a comparative example or the sodium salt of branched dodecylbenzenesulfonic acid are shown below. The mixture was dissolved in 2.5 parts by volume of dichloroethane. 7 g of this solution was evenly spread on a Petri dish with an inner diameter of 90 mm, and then left at room temperature for 5 hours.
The film was dried in a dryer at 24 ° C. for 24 hours to form a film. 23
After adjusting for 24 hours under the conditions of 50 ° C. and 50% RH, the surface specific resistivity was measured. Subsequently, this film was immersed in running water for 10 minutes to remove the water on the surface, and was heated at 23 ° C. and 50% RH.
After adjusting for 24 hours under the conditions described above, the surface specific resistivity was measured (washing treatment). Equipment: Hewlett-Packard Company: 4329A Hi
Table 3 shows the results of gh Resistant Meter. The following is clear from the results in Table 3. By blending the polymer compound of the present invention with the resin, a resin composition having a low surface resistivity can be obtained, and hardly changes by the surface washing treatment. That is, a resin composition having excellent permanent antistatic properties is obtained.

Example 8 The polymer compound of the present invention was incorporated into a resin emulsion as a surface treating agent and evaluated. Emulsification was performed at 130 to 140 ° C. for 2.5 hours under pressure according to the following formulation. Each particle size was 100 nm or less. Formula 1 Formula 2 Formula 3 Ethylene acrylic acid (80/20) 200 180 160 Copolymer resin Compound of Example 5 0 20 40 25% aqueous ammonia 29 29 29 Deionized water 570 570 570 It was applied at a thickness of 30 μm using a coater and dried at 120 ° C. In addition, the coating was similarly applied to two aluminum plates having a width of 15 mm, and the coated surfaces were overlapped and fixed with a clip, followed by bonding at 120 ° C. for 1 minute. The evaluation results are shown below. Transparency of film Contact angle of water Peeling strength Formulation 1 Good 80 degrees 500 g / 15 mm or more Formulation 2 Good 64 degrees Same as above Formulation 3 Good 54 degrees Same as above From the results, the following is clear. The polymer compound of the present invention exhibits good compatibility with the ethylene acrylic acid copolymer resin, and has a performance of forming a hydrophilic surface and not reducing the adhesive force at all. It was confirmed that the formed film had antifouling property against dirt.

[0067]

[Table 1]

[0068]

[Table 2]

[0069]

[Table 3]

[0070]

[Brief description of the drawings]

FIG. 1 is an infrared absorption spectrum of Synthesis Example 1.

FIG. 2 is an infrared absorption spectrum of Example 1.

FIG. 3 GPC of Synthesis Example 1.

FIG. 4 is a GPC of Example 1.

────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI C09K 3/16 102 C09K 3/16 102E 102H // (C08K 5/00 5:42 5: 098 5:49) (58) Survey Field (Int.Cl. ⁶ , DB name) C08G 64/00-64/42 CA (STN)

Claims (5)

(57) [Claims] 1. A compound of the general formula (Where X is an alkylene group having 1 to 6 carbon atoms, 1 to 6 carbon atoms)
Is an alkylidene group and a haloalkylidene group, and R ₁ is at least one selected from alkylene groups having 2 to 4 carbon atoms.
The species groups, R ₂ and R _3, are lower alkyl groups or unsubstituted or substituted phenyl groups, m is an integer from 2 to 100, and n is an integer from 1 to 100. ). 2. A polymer composition comprising the polymer compound according to claim 1 and a polymer obtained by addition polymerization or condensation polymerization as essential components. 3. A polymer obtained by addition polymerization or condensation polymerization of the polymer compound according to claim 1 and at least one of an organic low molecular weight sulfonate, an organic low molecular weight carboxylate, and an organic low molecular weight phosphorus-containing salt. A polymer composition comprising as an essential component. 4. A polymer antistatic agent comprising the polymer compound according to claim 1 as an essential component. (5) 2. The method for producing a polymer compound according to claim 1, wherein a dialkyl carbonate or di (unsubstituted or substituted phenyl) carbonate is reacted with the compound represented by the formula (1).