JPH02277813A - Polyether copolymer fiber and production thereof - Google Patents

Abstract

PURPOSE:To easily obtain the subject fiber having excellent heat-resistance and mechanical strength and useful as a raw material for composite material, a material for woven or knit fabric, etc., by spinning a specific polyether copolymer and drawing the spun fiber under a specific condition. CONSTITUTION:The objective fiber is produced by spinning a polyether copolymer containing the recurring units of formula I and formula II at a molar ratio of the unit I of 0.15-0.35 and having a melt viscosity (zero-shear viscosity) of 8,000-50,000 poise at 400 deg.C and drawing the obtained undrawn fiber at a temperature higher than the glass transition temperature of said polyether copolymer by 10-30% at a draw ratio of >=1.5. The above copolymer can be produced e.g. by reacting a dihalogeno-benzonitrile with an alkali metal compound of 4,4'-biphenol in the presence of a neutral polar solvent and copolymerizing the reaction product with a 4,4'-dihalogenobenzophenone.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a polyether copolymer fiber and a method for producing the same. More specifically, the present invention relates to a polyether copolymer fiber and a method for producing the same. For example, polyether copolymer fibers useful as materials for composite materials, woven and knitted materials, filters, canvas fabrics, belts, brushes, sewing threads, etc.
The present invention relates to a manufacturing method that can efficiently obtain fibers.

[Prior art and problems to be solved by the invention] In recent years,
Various engineering resins with excellent heat resistance, mechanical strength, etc. have been developed, and MA fibers made of these resins have come to be used in a wide range of fields2, but their performance is fully satisfactory in all aspects. This has not yet been achieved, and furthermore,
As performance requirements become more stringent, the development of new materials is desired.

On the other hand, a polyether ketone copolymer is known as one of these engineering resins, and a polyether copolymer aa made of this polyether ketone copolymer is
Several proposals have been made regarding aa.

For example, in JP-A-59-191322, a polymer obtained by melt-spinning a polymer having an intrinsic viscosity of 0.1 dl/g or more and consisting of 80 mol% or more of repeating constitutional units or units represented by the following formula: Aromatic polyetherketone LA fibers having a tensile strength of 4.0 g/d or more have been proposed.

However, aromatic polyetherketones have the disadvantage that their glass transition temperature is not sufficiently high and it is difficult to apply them to applications that require high heat resistance.
The above-mentioned aromatic polyetherketone fiber also has a problem in that its heat resistance is still insufficient.

In addition, because aromatic polyetherketone is manufactured under relatively harsh conditions, it is easy to contain gel in the pentapolymer and M4
There is also the problem that it can cause problems when being processed into males.

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

The object of the present invention is to create a polyether copolymer that exhibits sufficient heat resistance, has excellent mechanical strength, is easy to produce, and can be suitably used in fields of application that require high heat resistance. With fiber.

The object of the present invention is to provide a manufacturing method that can efficiently obtain this polyether copolymer fiber.

[Means for Solving the Problems] In order to solve the above-mentioned problems, the present inventor has made extensive studies and has developed a polyether copolymer that is composed of specific repeating units and has a specific composition ratio. The present invention was achieved by discovering that fibers drawn at the same ratio have excellent heat resistance and mechanical strength and are easy to manufacture, and that j5 and this fiber can be efficiently obtained by a specific method.

The structure of the invention of claim 1 is as follows.

It has a repeating unit represented by the following formula (I): N and a repeating unit represented by the following formula (■): DI), and the composition ratio or molar ratio of the repeating unit represented by the formula (I) is 0, 15-0
．． 35, the melt viscosity (zero shear viscosity) at a temperature of 400°C is 3,000 to 50,00 (1 poise), and the stretching ratio is 1.
It is a polyether-based copolymer fiber characterized by being drawn to a length of 5 or more. and the repeating unit represented by the formula (I) has a composition ratio of 0.15 to 0.15 in molar ratio.
After spinning a polyether copolymer having a temperature of 0°35 and a melt viscosity (zero shear viscosity) of 3,000 to so, ooo poise at a temperature of 400°C, a glass of the polyether copolymer is spun. 10-3 above the transition temperature
2. The method for producing a polyether copolymer fiber according to claim 1, wherein the stretching is carried out at a temperature 0° C. higher and at a stretching ratio of $1.5 or more.

- The polyether copolymer fiber according to claim 1 - The polyether copolymer fiber according to claim 1 has a reverse unit represented by the formula (I) and the formula (II>). It consists of a repeating unit represented by the formula (
The composition ratio of the repeating unit represented by I) is 0.0 in terms of molar ratio.
A polyetherketone copolymer having a molecular weight of 15 to 0.35 is used.

If the composition ratio or molar ratio of the repeating units represented by formula (I) is less than 0.15, the glass transition temperature of the copolymer may become low, resulting in a decrease in heat resistance, or the melting point may become high, resulting in poor spinnability. It may cause deterioration.

On the other hand, if it exceeds 0.35, the copolymer will lose its crystallinity and its heat resistance and solvent resistance will decrease.

Further, the polyether copolymer has a melt viscosity (zero shear viscosity) at a temperature of 400°C: l, 000 to 50
．． It is necessary to be within the range of 000 poise. A low molecular weight copolymer having a melt viscosity of less than 0,000 poise may not be able to achieve sufficient heat resistance and mechanical strength.

On the other hand, if it exceeds 50,000 poise, spinnability may deteriorate.

The polyether copolymer m! according to claim 1! 1 is obtained by stretching the polyether copolymer at a stretching ratio of 1.5 or more. If the stretching ratio is less than 1.5, the improvement in tensile strength etc. may not be sufficient and the effect of stretching may not be sufficiently exhibited.

The polyether copolymer mra according to claim 1 exhibits sufficient heat resistance, has excellent mechanical strength, is easy to produce, and is suitably used in application fields that require high heat resistance. Something comes up.

The polyether copolymer miscellaneous according to claim 1 having such excellent features can be efficiently obtained by suitably adopting the manufacturing method according to claim 2, which will be detailed in the first section. can.

N m - Production method according to claim 2 - Production of mono-polyether copolymer - In the production method according to claim 2, the repeating unit represented by the formula (I) and the formula (■) and a repeating unit represented by formula (I), the composition ratio of the scraping unit represented by formula (I) is 0.15 to 0.35 in molar ratio, and the melt viscosity at a temperature of 400'C (zero A polyether copolymer having a shear viscosity of 1,000 to 0,000 poise is used as a raw material.

The polyether copolymer can be prepared, for example, by reacting dihalogenobenzonitrile with an alkali metal compound of 4,4'-biphenol in the presence of a neutral polar solvent, and then reacting the reaction product with 4,4'-biphenol. It can be obtained by carrying out a copolymerization reaction with dihalogenobenzophenone.

Examples of the dihalogenobenzonitrile include 2,4-dihalogenobenzonitrile represented by the following formula; X has the same meaning as above.) 2,6-dihalogenobenzonitrile and the like can be mentioned.

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

For example, to obtain the polyether copolymer by the method described above, the dihalogenobenzonitrile and 4,4'-biphenol represented by the following formula are reacted in the presence of an alkali metal compound and a neutral polar solvent. let

The alkali metal compound is not particularly limited as long as it can convert the 4,4'biphenol into an alkali metal salt, but alkali metal carbonates and 2-alkali metal bicarbonates 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 rubidium hydrogen carbonate and cesium hydrogen carbonate.

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

In the above method, among the various alkali metal compounds, sodium carbonate and potassium carbonate can be particularly preferably used.

Examples of the neutral polar solvent include N,N-dimethylformamide, N,N-diethylformamide, N,N
-dimethylacetamide, N,N-diethylacetamide, N,N-dipropylacetamide, N,N-dimethylbenzoic acid amide, N-methyl-2-pyrrolidone, N-
Ethyl-2-pyrrolidone, N-isopropyl-2-pyrrolidone, N-isobutyl-2-pyrrolidone, N-n-propyl-2-pyrrolidone, N-n-butyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone , N-methyl-3-methyl-2-pyrrolidone, N-ethyl-3-methyl-2-pyrrolidone, N-methyl:l, 4.5-)
2-methyl-2-pyrrolidone, N-methyl-2-piperidone, N-ethyl-2- and beryton, N-isopropyl-
2-piperidone, N-methyl-6-methyl-2-piperidone, N-methyl-3-ethyl bibesotone, dimethyl sulfoxide, diethyl sulfoxide, 1-methyl-1-
Examples include oxosulfolane, 1-ethyl-1-oxosulfolane, l-phenyl-1-oxosulfolane, dimethylimidazolidinone, and diphenylsulfone.

The usage ratio of the dihalogenobenzonitrile, the 4°4'-biphenol, and the alkali metal compound is a molar ratio of the dihalogenobenzonitrile to the 4.4'-biphenol, usually 0°15 to 0. .35, preferably 0.20 to 0.30, and when the alkali metal compound uses the alkali metal carbonate, the ratio is usually 1.03 to 2.50, preferably 1.05.
~1.25, and when the alkali metal hydrogen carbonate is used, the ratio is usually twice that of the alkali metal carbonate.

There is no particular restriction on the amount of the neutral polar solvent used, but usually, the amount of the dihalogenobenzonitrile and the 4.
The total amount of 4'-biphenol and the alkali metal compound is 100 parts by weight, and the amount is selected in the range of 200 to 2,000 parts by weight.

In the above method, a reaction product obtained by reacting the dino-10genobenzonitrile with the 4,4'-biphenol in the presence of the alkali metal compound and the neutral polar solvent, and 4. 4”-dihalogenobenzophenone.

In obtaining the polyether copolymer, the 4,4'-dihalogenobenzophenone used is a compound represented by the following linear formula: (wherein, X has the same meaning as above). , more specifically, 4,4'-dichlorobenzophenone, 4,4' difluorobenzophenone,
Examples include 4-chloro-4'fluorobenzophenone.

In the above method, the 4;4'-dihalogenobenzophenone has a total molar ratio of the dihalogenobenzonitrile to the 4,4'-biphenol, or usually,
0.98-1.02. Preferably 1.00 to 1.01
Use at a ratio of .

In order to obtain the polyether copolymer by the method described above, for example, the dihalogenobenzonitrile and the 4,4'-biphenol are added to the neutral polar solvent;
The alkali metal compound is added at the same time to cause the dihalogenobenzonitrile to react with the 4,4'-biphenol, and then the 4,4'-dihalogenobenzophenone is further added, and usually halogenobenzonitrile is reacted with the 4,4'-biphenol. ~380℃,
A series of reactions is preferably carried out at a temperature in the range of 180 to 330°C. If the reaction temperature is less than 150°C, the reaction rate is too slow 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 1 to 0.1 to I
O hours, preferably 1 hour to 5 hours.

For example, the polyether copolymer obtained in this manner consists of a repeating unit represented by the formula (I) and a repeating unit represented by the formula (■), Unit composition ratio is 0.15
~0.35, and the melt viscosity at two temperatures of 400''C is in the range of 3.000~so, ooo poise.

In the manufacturing method according to claim 2, this polyether copolymer is then spun.

-Spinning- For spinning the polyether copolymer, a conventionally known melt spinning method can be suitably employed.

The spinning temperature is usually 10 to 70°C higher than the melting point of the polyether copolymer, preferably 20 to 50°C higher than the melting point of the polyether copolymer. If the spinning temperature is less than 10° C. higher than the melting point of the polyether copolymer, the amount discharged from the spinneret may decrease, making it difficult to adjust the yarn diameter. On the other hand, the melting point of the polyether copolymer is 7
If the temperature exceeds 0° C., the quality of the spun yarn may deteriorate.

In the manufacturing method according to claim 2, the spun yarn is 1.00
In the case of thick denier yarn of 0 denier or more, a cooling liquid bath is provided directly below the spinneret, and after cooling and solidifying the spun yarn in this cooling liquid bath, the spun yarn is processed using a Dork winder or the like. When a cooling liquid bath is provided, the temperature in the cooling liquid bath is usually 100 to 200°C lower than the spinning temperature.
On the other hand, if the spun yarn is a fine denier yarn of less than 1.000 denier, it is not necessarily necessary to provide the cooling liquid bath, and it is preferable to set the temperature at a temperature lower than 0.00°C. It can be solidified by cooling.

Note that there is no particular restriction on the spinning device 5, winding device, etc. that can be used in the manufacturing method according to claim 2, and any of those used in conventional methods can be suitably used.

In the manufacturing method according to the second aspect of the present invention, the polyether copolymer is spun in one or more ways, and then stretched as described in detail below.

-Stretching- Any conventionally used stretching device can be suitably used for stretching the undrawn yarn obtained as described above. Specifically, for example, a non-contact stretching device using heated steam, a heating medium electric heater, etc., a heating multi-stage stretching device equipped with one or more stages of contact heaters, etc. can be suitably used.

In any case, in the manufacturing method according to claim 2,
It is necessary that the stretching temperature is 10 to 30° C. higher than the glass transition temperature of the polyether copolymer. If the stretching temperature is less than 1[1''C higher than the glass transition temperature of the polyether copolymer, the stretching properties may be lowered and a sufficient stretching effect may not be obtained.

On the other hand, if the stretching temperature exceeds a temperature 30"C higher than the glass transition temperature of the polyether copolymer, fuzz or lapping may occur during stretching, making stable stretching impossible.

In the manufacturing method according to claim 2, the stretching ratio is 1.
It needs to be 5 or more, preferably 2 to 10.

If this stretching ratio is less than 1.5, fibers having a predetermined strength may not be obtained.

In the production method according to claim 2, after the polyether copolymer is spun and stretched in one or more steps, it may be subjected to heat treatment as described in detail below, if desired.

Heat Treatment - The heat treatment, which can be carried out as desired, can be suitably carried out at a temperature range higher than the crystallization temperature and lower than the melting point of the polyether copolymer. By performing this heat treatment, the strength of the obtained polyether copolymer fiber can be further improved.

Note that this heat treatment may be performed under tension of the drawn yarn obtained by performing the above-mentioned drawing, or may be performed under no tension.

According to the production method according to claim 2, a polyether copolymer which has excellent heat resistance and mechanical strength as described above and can be suitably used in fields of application requiring particularly high heat resistance. Fibers can be obtained easily and efficiently.

[Example] Next, an example of the present invention and a comparative example will be shown to further specifically explain the present invention.

(Example 1) ■ 32.34 ml of 2,6-cyclobenzonitrile was added to a reactor with a content of 5M, which was equipped with a Dean Starck Traub, a stirrer, and an argon gas blowing tube filled with Bomaer toluene.
g (0,188 mol), 4,4'-biphenol 1:1
9.66 g (0.75 mol), potassium carbonate 124,
:19 g (0.9 mol) and 1.5 Jl of N-methylpyrrolidone were added, while blowing argon gas.

The temperature was raised from room temperature to 195°C over 1 hour.

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

Next, after carrying out a reaction at a temperature of 195°C for 30 minutes,
4.4'-difluorobenzophenone 122.85g
(0,563 mol) to N-methylpyrrolidone 1.51
A solution dissolved in was added and the reaction was further carried out for 1 hour.

After the reaction, the product was pulverized with a blender (manufactured by Warning), washed with acetone, methanol, water, and acetone in that order, and dried to obtain 259.36 g of a white powdery copolymer. 98%). In this copolymer, the molar ratio of the repeating unit represented by the formula (I) was 0.25.

In addition, when the properties of this copolymer were measured, the melt viscosity (zero shear viscosity) at a temperature of 400°C13,
000 poise, glass transition temperature 182℃, crystal melting point 37
9℃, thermal decomposition start temperature 562℃ (in air).

5% weight loss).

■IJ and the polyether copolymer obtained in the above (■) were heated to 400°C.
After heating and melting, the inner diameter is 1. (law, length 1.
Spinning was performed using a 0 am nozzle at a nozzle temperature of 390°C.

Immediately thereafter, the spun yarn was passed through a heating tube with a length of 30 cm maintained at a temperature of 300°C, and then air-cooled at a speed of 120°C.
The yarn was wound at a speed of m/min to obtain an undrawn yarn of 35 denier.

Next, this undrawn yarn was stretched twice by a stretching roller at a temperature of 200°C, and further heat-treated at a temperature of 240°C using a hot plate heater to obtain a polyether copolymer fiber.

The tensile strength, elongation, knot strength 3, and Young's modulus of the obtained polyether copolymer fiber were measured.

The results are shown in Table 1.

In addition, each item is measured according to JIS-L-1013.
-8I.

(Example 2) The same procedure as in Example 1 was carried out except that the stretching ratio was changed from 2 times to 3 times in step (2) of Example 1 above.

The results are shown in Table 1.

(Example 3) The same procedure as in Example 1 was carried out except that the stretching ratio was changed from 2 times to 4 times in step (2) of Example 1.

The results are shown in Table 1.

(Example 4) The polyether copolymer obtained in Example 1 (1) was melted at a temperature of 400°C, and the inner diameter was 0.45cm1. Length 1.
:15m5. Spinning was performed using a spinneret with 60 holes.

The temperature of the spinneret was set at 390°C, and a length of 300 am was maintained at 300°C at the outlet of the spinneret.
A heating cylinder was installed.

The spun yarn passed through this heating cylinder was air-cooled, then oiled and wound at a speed of ISh/min to 800 denier/60
An undrawn filament yarn was obtained.

Next, this undrawn yarn was drawn twice in the same manner as in Example 1 (2) and heat treated to obtain a polyether copolymer fiber.

The physical properties of this drawn yarn are shown in Table 1.

(Example 5) The same procedure as in Example 4 was carried out except that the stretching ratio was changed from 2 times to 3 times.

The results are shown in Table 1.

(Example 6) The same procedure as in Example 4 was carried out except that the stretching ratio was changed from 2 times to 4 times.

The results are shown in Table 1.

(Example 7) (1) In (1) of Example 1 for Bo1 ether, the molar ratio of 2,6-cyclobenzonitrile and 4,4'-difluorobenzophenone was 2.5, 5 to 3. A polyether copolymer was produced in the same manner as in Example 1 (2) above, except that the value was changed to 7.

In the obtained copolymer, the content ratio of the repeating unit represented by the above formula (I) was 0.30 in terms of molar ratio.

In addition, when the properties of this copolymer were measured, the melt viscosity at a temperature of 400°C (zero shear viscosity) 16,
000 voice, glass transition temperature 185℃, crystal melting point 34
8℃, thermal decomposition start temperature 560℃ (in air).

5% weight loss).

■Kamegengo 1] Using the copolymer obtained in the above (■),
A drawn yarn with a draw ratio of 2 times was obtained in the same manner as above.

The physical properties of this drawn yarn are shown in Table 1.

(Example 8) The same procedure as in Example 7 was carried out except that the stretching ratio was changed from 2 times to 3 times.

The results are shown in Table 1.

(Example 9) The same procedure as in Example 7 was carried out except that the stretching ratio was changed from 2 times to 4 times.

The results are shown in Table 1.

(Examples 1O to 12) Using the copolymer obtained in Example 7 (2), experiments were carried out in the same manner as in Examples 4 to 6, respectively.

The results are shown in Table 1.

(Comparative Examples 1 to 3) Polyetheretherketone [manufactured by IC1;
Drawn yarns were obtained in the same manner as in Examples 1 to 3, except that rVictrex PEE (450 GJ) was used and the conditions shown in Table 1 were adopted.

Table 1 shows the physical properties of the obtained drawn yarn.

(Comparative Examples 4 to 6) Polyetheretherketone [I (manufactured by I Company);
Stretched yarns were obtained in the same manner as in Examples 4 to 6, except that the conditions shown in Table 1 were used and the conditions shown in Table 1 were used.

Table 1 shows the physical properties of the obtained drawn yarn.

(Raiko, hereafter blank) (Evaluation) As is clear from Table 1, the polyether copolymer fiber according to claim 1 obtained by the manufacturing method according to claim 2 is different from the fiber of comparative example. It was confirmed that the mechanical strength is superior to that of

A method for producing the ether copolymer mis can be provided.

[Effects of the Invention] (1) According to the invention of claim 1, a specific polyether copolymer is composed of specific repeating units having a composition ratio within a specific range and exhibits a specific melt viscosity.
Since the copolymer has been stretched more than twice as long, it has excellent heat resistance and mechanical strength, and there is no gel formation in the copolymer, making it easy to manufacture, making it suitable for applications that require particularly high heat resistance. It is possible to provide an industrially useful polyether copolymer fiber that can

Claims (2)

[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): ▲There are mathematical formulas, chemical formulas, tables, etc.▼Represented by (II) The composition ratio of the repeating units represented by the formula (I) is from 0.15 to 0.15 in molar ratio.
0.35, and has a melt viscosity (zero shear viscosity) of 3,000 to 50,000 poise at a temperature of 400°C, and a stretching ratio of 1.
A polyether copolymer fiber characterized by being stretched to a length of 5 or more. (2) It has a repeating unit represented by the above formula (I) and a repeating unit represented by the above formula (II), and the composition ratio of the repeating unit represented by the above formula (I) is 0.15 in molar ratio. ~0.35, and the melt viscosity (zero shear viscosity) at a temperature of 400°C is 3,000 to 50,
000 poise is spun and then stretched at a stretching ratio of 1.5 or more at a temperature 10 to 30°C higher than the glass transition temperature of the polyether copolymer. The method for producing a polyether copolymer fiber according to claim 1.