JPH0441557A - Polyether copolymer composition having good flowability - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a polyether copolymer composition with good fluidity, and more specifically, it has high heat resistance, high fluidity, excellent moldability, and can be used in various types. This invention relates to a polyether copolymer composition with good fluidity useful in the field of polymer applications.

[Prior art and invention or problem to be solved] In recent years, various new resins called super engineering plastics with excellent heat resistance have been developed, and among them, polyether copolymers are・It is becoming widely used as parts for electrical and precision machinery, etc.

However, since these aromatic polyether copolymers generally have a high melting point, the molding temperature is high, and furthermore, due to the molecular structure, the melt viscosity often becomes high, which is an important problem when molding.

Therefore, as a method of improving moldability by lowering the molding temperature or melt viscosity, it may be possible to add various plasticizers to the resin.

However, a plasticizer that can withstand the molding temperature of high melting point aromatic polyether copolymers has not yet been found.
If a conventional plasticizer for general-purpose plastics is blended with an aromatic polyether copolymer and then molded, it will decompose and volatilize during molding, resulting in insufficient plasticizing effect. Moreover, when such a plasticizer is used, problems such as deterioration of various physical properties of the aromatic polyether copolymer composition and coloring of molded products occur.

The present invention has been made based on the above circumstances.

In other words, the object of the present invention is to improve fluidity during molding without reducing the various properties inherent in polyether copolymers, such as heat resistance, flame retardance, and chemical resistance. Therefore, it is an object of the present invention to provide a polyether copolymer composition having excellent moldability.

[Means for Solving the Problems] The present invention to achieve the above object consists of a repeating unit represented by the following formula (1): and a repeating unit represented by the following formula (■): (n), Composition ratio [molar ratio] of the repeating unit represented by the formula (I).

(I)/((I)+(II))] or 0.15 to 0.4
Melt viscosity at 490°C, s,
ooo~500.000 poise polyether copolymer 70~99 wtV%, a repeating unit represented by the above formula (I) and a repeating unit represented by the above formula (II), and the above formula ( I) Composition ratio of repeating units expressed as [molar ratio: (I)/((I)+(II))]
0.15 to 0.4 mol and 30 to 1% by weight of a polyether copolymer having a melt viscosity of 500 to 3,000 poise at 400°C. It is a polyether copolymer composition.

The present invention will be explained in detail below.

Good-flowing polyether copolymer composition - The good-flowing polyether copolymer composition of the present invention is, briefly, as follows:
It is characterized by containing a high molecular weight polyether copolymer having a specific molecular weight and a low molecular weight polyether copolymer having a specific molecular weight in a specific ratio.

Although it is not fully understood why the fluidity of a high molecular weight polyether copolymer is inferior to that of a high molecular weight polyether copolymer when a low molecular weight polyether copolymer is contained, as a result, thermal decomposition occurs during molding. It is surprising that high molecular weight polyether copolymers do not exhibit any deterioration in various properties such as heat resistance and mechanical properties.

The Polymer Research Institute Bot ether copolymer described in 1rs has the formula (
It consists of a repeating center represented by I) and a repeating center represented by the formula (■), and the content ratio of the repeating unit represented by the formula (I) [molar ratio, (I)/
((I) + (II))] is in the range of 0.15 to 0.4, and the composition ratio of the repeating unit represented by formula (II) (
molar ratio) is 0.85 to 0.6.

The composition ratio at the repeating medium represented by the above formula (1) is 0.
If it is less than 15, the glass transition temperature of the polyether copolymer will be low, and therefore a good fluidity polyether copolymer that can be obtained even if the low molecular weight polyether copolymer is blended in a specific proportion. The heat resistance of the composition may decrease, or the melting point may become high, leading to deterioration of moldability. On the other hand, 0.4
If it exceeds this amount, the crystallinity of the high molecular weight polyether polymer will be lost, and the heat resistance and solvent resistance of the well-flowing polyether copolymer composition will decrease.

In addition, in the high molecular weight polyether copolymer used in the present invention, melt viscosity (zero shear viscosity) at a temperature of 400°C or s, ooo to soo is used as an index of molecular weight.
, ooo boys, preferably 20,000~zoo,
It is important that they are ooo boys.

This low molecular weight polyether copolymer having a melt viscosity of less than s, ooo voids is a good fluidity polyether copolymer group Ili! 2. This is because it is impossible to achieve sufficient heat resistance and mechanical strength of the product.

Furthermore, if the melt viscosity exceeds 500,000 voids, it becomes difficult to mold the polyether copolymer composition with good flowability.

The high molecular weight polyether copolymer used in the present invention has, for example, a crystal melting point of about 330 to 400°C,
It has high crystallinity and a sufficiently high molecular weight,
It exhibits sufficient heat resistance and is excellent in solvent resistance and mechanical strength, and these characteristics are reflected in the properties of the well-flowing polyether copolymer composition of the present invention.

The low molecular weight polyether copolymer has the formula (I)
The content ratio of the repeating unit represented by the formula (I) [molar ratio, (I)/((
I) + (n))] or in the range of 0.15 to 0.4,
The composition ratio (molar ratio) of the repeating unit represented by formula (II) is 0.85 to 0.6.

The composition ratio of the repeating unit represented by the formula (I) is 0.
If it is less than 15, the melting point will exceed 400 ° C., so the composition of a polyether copolymer with good fluidity that can be obtained even if it is blended in a specific proportion with the high molecular weight polyether copolymer. This will lead to a decrease in the moldability of the product. On the other hand, if it exceeds 0.4, the low molecular weight polyether copolymer becomes inferior, resulting in a decrease in heat resistance and solvent resistance of the polyether copolymer composition.

In addition, in the low molecular weight ψ polyether copolymer used in the present invention, the melt viscosity (zero shear viscosity) at 400 ° C as an index of molecular weight is 500 voids or more and less than 3.000, Preferably 1,000~
It is important that it is 2,500 voices.

This is because a low molecular weight polyether copolymer having a melt viscosity of less than 500 voices cannot achieve sufficient heat resistance and mechanical strength of the polyether copolymer composition.

Furthermore, if the melt viscosity exceeds 3,000 voices, it becomes difficult to mold the polyether copolymer composition.

One of the important things in the well-flowing polyether copolymer composition of the present invention is that the amount of the high molecular weight polyether copolymer blended is 70 to 99% by bisulfur, preferably 85%.
The content of the low molecular weight polyether copolymer is 30 to 1% by weight, preferably 15 to 5% by weight.

When the blending amounts of the high molecular weight polyether copolymer and the low molecular weight polyether copolymer are each within the above ranges, the polyether copolymer composition with good fluidity can be obtained from a polyether copolymer that originally contains the polyether copolymer. The fluidity during molding process is improved without impairing the properties, resulting in excellent molded layer T properties, or the amount of high molecular weight polyether copolymer is less than 70% by weight. If the blending amount of the low molecular weight polyether copolymer exceeds 30% by weight,
The mechanical strength of the well-flowing polyether copolymer composition may be reduced, and if the amount of the high molecular weight polyether copolymer exceeds 99% by weight, or if the amount of the low molecular weight polyether copolymer is If the blending amount is less than 1% by weight, the effect of improving the fluidity of the polyether copolymer composition will be lost.

Both the high molecular weight polyether copolymer and the low molecular weight polyether copolymer can be produced as follows.

N - Method for producing high (low) molecular weight polyether copolymer - The high molecular weight polyether copolymer is prepared by mixing dihalogenobenzonitrile, 4,4'-biphenol, and an alkali metal compound in a neutral polar solvent. After the reaction, the reaction product is copolymerized with 4,4'-dihalogenobenzophenone.

In addition, a low molecular weight polyether copolymer is produced by reacting dihalogenobenzonitrile, 4.4°-biphenol, and an alkali metal compound in a neutral polar solvent in the presence of a molecular weight modifier. It can be produced by carrying out a copolymerization reaction between the compound and 4.4°-dihalogenobenzophenone.

Specific examples of the dihalogenobenzonitrile that can be used include 2,6-dihalogenobenzonitrile represented by the following formula: (wherein, X is a halogen atom); .4-dihalogenobenzonitrile and the like.

Among these, 2,6-dichlorobenzonitrile, 2,6-difluorobenzonitrile, 2,4
2.6-dichlorobenzonitrile is particularly preferred.

The dihalogenobenzonitrile and 4 represented by the following formula;
, 4°-biphenol in the presence of an alkali metal compound and a neutral polar solvent.

The alkali metal compound to be used is as described in 4.4 above.
Any substance capable of converting '-biphenol into an alkali metal salt may be used, and there are no particular limitations, but alkali metal carbonates and alkali metal hydrogen carbonates are preferred.

Examples of the alkali metal carbonates include lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate,
Examples include cesium carbonate.

Among these, preferred are sodium carbonate and potassium carbonate.

Examples of the alkali metal hydrogen carbonate include lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate,
Examples include ludium hydrogen carbonate and cesium hydrogen carbonate.

Among these, preferred are sodium hydrogen carbonate and potassium hydrogen carbonate.

Examples of the neutral polar solvent include N,N-dimethylformamide, N,N-diethylformamide, N,N
-dimethylacetamide, N.

N-diethylacetamide, N,N-sibropylacetamide, N,N-dimethylbenzoic acid amide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-
Isopropyl-2-pyrrolidone, N-inphthyl-2-
Pyrrolidone, Nn-propyl-2-pyrrolidone, Nn
-phthyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N-methyl-3-methyl-2-pyrrolidone,
N-ethyl-3-methyl-2-pyrrolidone, N-methyl-3,4,5-trimethyl-2-pyrrolidone, N-methyl-2-piperitone, N-ethyl-2-piperitone, N-isopropyl-2-piperitone, N -Methyl-6-methyl-
2-dopesotone, N-methyl-3-ethylpiperitone, dimethyl sulfoxide, ethyl sulfoxide, l-
Methyl-1-oxosulfolane, 1-ethyl-1-oxosulfolane, ■-phenyl l-oxosulfolane, N
, N'-dimethylimidazolidinone, diphenylsulfone, and the like.

As molecular weight regulators, phenol, cresol, p-
Mention may be made of phenylphenol, 0-phenylphenol, xylenol, carvacrol, thymol, naphthol and the like.

As an example of the production method, when producing a high molecular weight polyether copolymer, the reaction of the dihalogenobenzonitrile with the 4,4'-biphenol in the presence of the alkali metal compound and the neutral polar solvent may be used. The reaction product obtained by carrying out this reaction is reacted with 4.4'-dihalogenobenzophenone described in tj. When producing a low molecular weight polyether copolymer, the dihalogenobenzonitrile and the 4,4゛biphenol are reacted in the presence of the molecular weight modifier, the alkali metal compound and the neutral polar solvent. The reaction product obtained by the above 4, 4
゛-React with dihalogenobenzophenone.

The 4,4''-dihalogenobenzophenone used has the following formula.

(X has the same meaning as above.) In the present invention, 4.4''-difluorobenzophenone and 4.4''-cyclopenzophenone are particularly preferred. You can use it.

The molar ratio of the total amount of dihalogenobenzonitrile and 4,4'-dihalogenobenzophenone to the amount of 4,4'-biphenol used is usually 0.98 to 1.02.
, preferably 1.00 to 1.01.

The molar ratio of the alkali metal compound to the amount of 4,4'-biphenol used is usually 1.03 to 2.50, preferably 1.05 to 1.25.

The amount of the molecular weight regulator used is 1 or less in molar ratio to the amount of 4,4'-biphenol used. The amount used is appropriately determined depending on the desired molecular weight of the polyether copolymer.

Is there any particular restriction on the amount of the neutral polar solvent used? Usually, the amount of the dihalogenobenzonitrile, the 4゜4゛-biphenol,
The total number of moles with the dihalogenobenzophenone is 0.2
It is determined to be 5 to 5 moles.

In order to obtain a low molecular weight polyether copolymer, for example, the dihalogenobenzonitrile, the 4,4'-biphenol, the molecular weight regulator, and the alkali metal compound are added to the neutral polar solvent. Add at the same time,
After the dihalogenobenzonitrile and the 4,4"-biphenol are reacted, the 4,4"-biphenol is further reacted with the 4,4"-biphenol.
Add dihalogenobenzophenone to 1 usually 150 to 3
The series of reactions is carried out at a temperature in the range of 80°C, preferably 180-330°C.

The high molecular weight polyether copolymer can be obtained by reacting in accordance with the method for obtaining the low molecular weight polyether copolymer described above, except that no molecular weight regulator is used. However, in order to appropriately adjust the molecular weight of the high molecular weight polyether copolymer within the range of the melt viscosity, the molecular weight regulator may be used as appropriate.

If the reaction temperature is less than +50°C, the reaction rate is too high to be practical, and if it exceeds 380°C, side reactions may occur.

In addition, the reaction time of this series of reactions is usually 0.1 to 10
The time is preferably 0.5 to 5 hours.

After the reaction is completed, the polyether copolymer is separated and purified from the neutral polar solvent solution containing the high molecular weight and low molecular weight copolymers according to a known method. You can get it.

Further, the high molecular weight and low molecular weight polyether copolymers used in the present invention can be obtained by simultaneously adding dihalogenobenzonitrile, biphenol, an alkali metal salt, and dihalogenobenzophenone to a neutral polar solvent. I can bring it.

Next, the well-flowing polyether copolymer combination acid of the present invention can be prepared by using the high molecular weight and low molecular weight polyether copolymers as they are, or by using the high molecular weight and low molecular weight polyether copolymers as they are. It can be formed using a polyether copolymer composition formed by mixing a polyether copolymer and an additive.

The polyether copolymer resin composition includes the high molecular weight and low molecular weight polyether copolymers and additives, which are the sum of the high molecular weight polyether copolymer and the low molecular weight polyether copolymer. On the other hand, although it varies depending on the type of additive, for boat fishing, it is possible to manufacture by blending the additive so that the content thereof is 10 to 50% by weight, preferably 15 to 40% by weight.

When the amount of the additive is within the above range, the properties of the highly fluid polyether copolymer composition of the present invention can be further improved depending on the type of additive.

Examples of the additives include inorganic fillers, fibrous reinforcing agents, crystal nucleating agents, antioxidants, ultraviolet absorbers, antistatic agents, colorants, and the like.

Specific examples of the additive include carbonates such as calcium carbonate, magnesium carbonate, and dolomite, sulfates such as calcium sulfate and magnesium sulfate, sulfites such as calcium sulfite, talc, clay, mica, asbestos, and glass fibers. , glass peas, calcium silicate, montmorillonite, silicates such as bentonite, silicon dioxide (fused silica, crystalline silica), metal powders such as iron alumina, lead vine, aluminum, ceramics such as silicon carbide, silicon nitride, etc. These include whiskers, carbon black, graphite, and carbon fibers. Preferred examples of the present invention include calcium carbonate, silicon dioxide, alumina, clay (kaolin, bentonite, clay, etc.), talc, metal oxides (MgO,
ZnO, Tie, ), etc.

Some of these substances are used as inorganic fillers, fibrous reinforcing agents, and crystal nucleating agents in some cases.

Antioxidants include phenolic, amine, sulfur,
Various antioxidants such as phosphorus, hydrazine, and amide antioxidants can be used.

Examples of ultraviolet absorbers include benzophenone, salicylate, benzotriazole, acrylonitrile,
They include metal complex salts, hindered amines, etc.

The coloring agent may be appropriately selected from the above-mentioned inorganic fillers, such as inorganic pigments such as titanium oxide, red iron oxide, and lead, insoluble azo pigments, soluble azo pigments,
Organic pigments such as Σ and phthalocyanine pigments can be used.

The various additives mentioned above may be in the form of particles, plates, or fibers, and in this invention, the particle size is 5 pm or less.
It is sufficient if the size is smaller than that, and preferably a finer one is used.

These additives may be used alone or in combination of two or more.

The polyether copolymer resin composition is prepared by adding 10 to 50 weight of an appropriately selected additive, such as an inorganic filler, to a polyether copolymer powder obtained by the above-mentioned method for producing a polyether copolymer. It can be obtained by mixing at a ratio of 1.5%, friending, kneading in an extruder, and forming pellets.

It is also possible to obtain a polyether copolymer resin composition by employing a method of producing a polyether copolymer in the presence of an additive such as an inorganic filler.

Production of a well-flowing polyether copolymer composition The well-flowing polyether copolymer composition of the present invention further comprises the high molecular weight polyether copolymer and the low molecular weight polyether copolymer as required. It can be formed by blending additives blended according to the above specific blending ratio.

The blending can be carried out by tri-blending using a blender or the like and then kneading using a twin-screw extruder or the like.

Since the polyether copolymer composition of the present invention has excellent fluidity during molding, it can be suitably spun, film-formed, and molded.

By spinning the polyether copolymer composition of the present invention,
It is possible to form fibers and form various woven fabrics, knitted fabrics, and nonwoven fabrics from the fibers.

Further, by forming films from the polyether copolymer composition of the present invention, various membranes including dialysis membranes used in hemodialysis and the like can be obtained.

By molding the polyether copolymer composition of the present invention,
Base film for flexible printed circuit boards, backing materials for flexible printed circuit boards, electrode plates for membranes, backing materials for membranes, base films for transparent electrodes, film cells for liquid crystals, ICe Yaryatabe (base film for TAB), optical carts, for perpendicular magnetization It is possible to obtain a base film, etc.

[Example] Next, an example of the present invention will be shown and the present invention will be explained in more detail.

(Example 1) Production of a high molecular weight polyether copolymer - 2,6-cyclopene was placed in a fi 200 reactor equipped with a Dean-Starck trap filled with toluene, a stirring device and an argon gas blowing tube. 1,548 g of zonitrile (
9 mol), 4.4'-biphenol 5.580 g
(30 mol), 4,561 g (33 mol) of potassium carbonate and 50 kg of N-methyl-2-pyrrolidone,
While blowing argon gas, it took 1 hour to warm up to room temperature.
The temperature was raised to 95°C.

After raising the temperature, a small amount of toluene was added and the produced water was removed by azeotropy.

Next, after performing a reaction at 195°C for 30 minutes, 4.
4°-difluorobenzophenone 4,582 g (2
A solution of 1 mol) dissolved in N-methyl-2-pyrrolidone 701 was added, and the reaction was further carried out for 1 hour.

After the reaction was completed, the product was washed with wood and methanol in that order, and then dried and smoked to obtain a white copolymer (if) kg. Income +
was 98%.

The properties of this polyether copolymer were measured and found to be melt viscosity at 400°C (5% weight loss during zero shear).

Also, when I conducted an IR measurement, I found that it was 2220cw+-'
It was confirmed that absorption was caused by a nitrile group at the position , absorption was caused by a carbonyl group at the 16 SO cm-' position, and absorption was caused by an ether bond at the 1240 cm-' position.

The polyether copolymer obtained from this result and the elemental analysis result was confirmed to consist of repeating units having the following structure.

(II) (1)/((I)+(II)) -Production of 0,3 low molecular weight polyether copolymer 172 g (1 mol) of p-phenylphenol was added as a molecular value regulator when preparing raw materials. A low molecular weight polyether copolymer was produced in the same manner as in the production of the high molecular weight polyether copolymer except for the following steps.

The yield was 96%.

When the properties of this low molecular weight polyether copolymer were measured, the melt viscosity at 400°C in air was 5.
% weight loss).

In addition, when lR11l was determined, 2220cm-
Absorption due to nitrile group at position ', 16sOcs-
Absorption due to carbonyl group at position 1240cm-
It was confirmed that the absorption was caused by an ether bond at the ' position.

The polyether copolymer obtained from this result and the elemental analysis result was confirmed to consist of repeating units having the following structure.

(II) (I)/((I)+(It))=0.3 High molecular weight boether copolymer I obtained as above Dkg
and 1.2 kg of low molecular weight polyether copolymer, V
After tri-blending in a mold blender for 30 minutes, a twin-screw extruder (manufactured by Ikegai Iron Works Co., Ltd., PCM-3) was heated at 380°C.
0) at 390°C.

At the time of pelletizing, the melt viscosity of the polyether copolymer composition at 400°C was 16,000 poise, indicating good fluidity.

This pellet was injection molded to create a test piece, and A S
Tensile modulus and tensile strength were measured according to T M -D 6:18.

These results are shown in Table 2.

(Example 2) In producing the high molecular weight polyether copolymer and the low molecular weight polyether copolymer described in Example 1, the same procedure as in Example 1 was used except that the raw materials were changed as follows. A high molecular weight polyether copolymer and a low molecular weight polyether copolymer were produced in the same manner as described above.

High molecular weight polyether copolymer 2.6-cyclobenzonitrile...1.290 g (7.5 mol) 4.4'-difluorobenzophenone...4,910 g (22.5 mol) ) Potassium carbonate...4,976 g (35 mol) Low fraction 7
- Polyether copolymer 2.6-cyclobenzonitrile...1,290 g (7.5 mol) 4.4'-difluorobenzophenone... 4,910 g (22.5 mol) ) Potassium carbonate: 4,975 g (36 mol) P-phenylphenol: 172 g (1 mol) of the obtained high molecular weight polyether copolymer and low molecular weight polyether copolymer In both cases, the composition ratio of the repeating unit represented by formula (I) [molar ratio: (1)/(
(I)+(II))] or 0.25.

From the high molecular weight polyether copolymer and low molecular weight polyether copolymer obtained as described above, a pellet of a polyether copolymer composition is produced in the same manner as in Example 1, A test piece was prepared using this pellet in the same manner as in Example 1, and its physical properties were measured in the same manner as in Example 1.

The results are shown in Table 2.

(Comparative Example) The high molecular weight boma-ether copolymer produced in Example 1 was pelletized using a Chinese-made twin-screw extruder.

In addition, the temperature of this high molecular weight polyneedle copolymer at 400°C
The melt viscosity was 95,000 voids, indicating sufficient fluidity. Twin screw extrusion had to be performed at temperatures as high as 410°C.

Physical properties were measured using the pellet in the same manner as in Example 1.

The results are shown in Table 2.

[Effect of the invention] According to the invention Heat-resistant Mechanical strength and resistance Without reducing properties such as solvent properties Molding Polyester with extremely good fluidity suitable for Tel system co A polymer composition is provided. : Tokaru (1ζ5

Claims (1)

[Claims] (1) The following formula (I); ▲There are mathematical formulas, chemical formulas, tables, etc.▼The repeating unit represented by (I) and the following formula (II); ▲Mathematical formula,
There are chemical formulas, tables, etc. ▼ (II) It consists of repeating units represented by the formula (I), and the composition ratio of the repeating units represented by the above formula (I) [molar ratio: (I) / {(
I)+(II)}] is 0.15 to 0.4 mol, and the melt viscosity at 400°C is 5,000 to 500.
,000 poise polyether copolymer 70-9
9% by weight, consisting of a repeating unit represented by the formula (I) and a repeating unit represented by the formula (II),
The composition ratio of the repeating unit represented by the formula (I) [molar ratio: (I)/{(I)+(II)}] is 0.15 to 0.
4 mol, and the melt viscosity at 400°C is 5
30 to 1% by weight of a polyether copolymer having a poise of 00 or more and less than 3,000 poise.