JPS646232B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to novel polymeric compositions. In general, the properties of polymeric substances are basically the properties of the polymeric chains that make up the polymeric substance, such as the bonding energy between atoms that constitute the main chain, the degree of thermal restraint of free rotation of those bonds, and the degree of dipole polarization. , depends on molecular symmetry, electron density, three-dimensional structure, molecular weight, molecular weight distribution, etc., and secondarily, on the molding method.
The properties of the polymer molded product as a polymer chain aggregate are expressed. Therefore, polymeric substances composed of various monomers have been synthesized, and random, block, and graft copolymers have also been synthesized and put into practical use to satisfy individual required properties. However, manufacturing polymers according to individual required properties poses economic problems such as cost.
Many polymer blends are also carried out in which two or more appropriate polymeric substances are mixed to impart certain properties or to obtain intermediate properties. For example, there are many homopolymers and copolymers, such as impact-resistant polystyrene made by blending a rubber component with polystyrene, polystyrene and polyphenylene oxide, polyvinylidene fluoride and polymethyl methacrylate, polyvinyl chloride and acrylonitrile-butadiene copolymer rubber, etc. It has been put into practical use to meet diversifying market demands. As heat-resistant polymers, so-called fully aromatic polyamides, in which all of the divalent hydrocarbon groups bonded through amide bonds are aromatic cyclic groups, are being used practically as fibers, films, etc., and are attracting attention. This is known. Among them, according to Japanese Patent Publication No. 47-2489 and others, molded products such as fibers and films made of para-oriented wholly aromatic polyamides whose aromatic cyclic groups are represented by paraphenylene groups have high strength, high elastic modulus, and excellent properties. Due to its heat resistance, it is useful in a variety of applications. However, since these polymers have rigid molecular chains with poor flexibility, they do not exhibit a melting or softening temperature and begin to decompose at temperatures above 500°C.
Normal thermoforming processing was difficult. Therefore,
Although these polymers are only soluble in very special solvents such as sulfuric acid, hydrofluoric acid, and tetramethylurea, they are dissolved in the above-mentioned solvents and formed into fibers, films, and other forms. This method uses highly corrosive solvents such as sulfuric acid, so
It is disadvantageous to implement it industrially. In order to solve this problem, the amide bonds of para-oriented fully aromatic polyamides were modified by various substituents to
Substitution method (Japanese Patent Publication No. 46-3996, Japanese Patent Publication No. 49-1989)
2917, Japanese Patent Publication No. 53-31915, etc.), or a method of copolymerization using a flexible group instead of a para-aromatic group (Japanese Patent Laid-Open No. 49-116322, Japanese Patent Publication No. 51-1593, etc.). Proposed. However, these methods have not been able to overcome the high strength and
This was at the expense of high elastic modulus and excellent heat resistance. On the other hand, the present inventors have proposed a polymer composite as a use of para-oriented wholly aromatic polyamide (Japanese Patent Laid-Open No. 65747/1983). This uses para-oriented wholly aromatic polyamide, which has poor flexibility and is rigid.
By dispersing it in extremely small units in a general flexible polymer matrix, a structure with improved mechanical properties can be obtained. However, as a result of intensive research to obtain even higher effects, the present inventors found that para-oriented wholly aromatic polyamide has a high affinity between self-molecules and creates a stable finely dispersed system in the matrix. It has become clear that the compatibility with matrix molecules must be improved. In view of these current circumstances, the present inventors have conducted extensive research and found that the above-mentioned problems can be solved by blending a novel N-substituted wholly aromatic polyamide. That is, we discovered a new phenomenon in which when a novel N-substituted wholly aromatic polyamide is blended with a para-oriented wholly aromatic polyamide, it becomes thermoplastic at high temperatures. Furthermore, the inventors have discovered that this N-substituted product is soluble in a solvent, and as a result, a composition with excellent properties can be obtained, leading to the present invention. That is, the present invention provides polymeric substances of the following groups and groups: Group General Formula

[Formula] O and/or

[Formula] repeating unit Para-oriented wholly aromatic polyamide consisting of group general formula

[Formula] O and/or

It consists of a repeating unit of [formula], where X, Y, Z are (-1)
-H and/or a group represented by the general formula -CkH _2k+1 , or (-2) -H and/or a group represented by the general formula -(CH ₂ -) _l Ar ₄ , or (-
3)-H and/or general formula

A group represented by [Formula], or (- 4)-H and/or general formula -(CH ₂ -) _o
A group represented by COOM, the substitution rate in the polymer is 2 mol% or more, and ηinh is 0.1
The above N-substituted fully aromatic polyamide (In the above formula, Ar ₁ , Ar ₂ , and Ar ₃ each independently represent a divalent para-oriented aromatic group, and k, l, and n each represent 7≦k ≦25, 1≦l≦6, 1≦n≦
An integer in the range of 10, m is any integer, Ar ₄
teeth

【formula】

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Aromatic groups selected from [Formula], R ₁ , R ₂ , R ₃ , R ₄ are the same or different -
H, _-CH3 , -CH= _{CH2 , -C2H5} , _{-C3H7 ,}

【formula】

[Formula] -CH ₂ -O-CH ₂ -CH=CH ₂ , M represents -H or an alkali metal selected from Li, Na, K, Rb and Cs. ) Group and group -1, -2, -3, -4
One or more selected from
It is a polymer composition with a composition ratio of 99% by weight. The present invention will be explained in more detail below. group general formula

[Formula] O and/or

A para-oriented fully aromatic polyamide consisting of repeating units of the formula (however, Ar ₁ , Ar ₂ , and Ar ₃ each independently represent a divalent para-oriented aromatic group): Ar ₁ , Ar ₂ , It is essential that Ar ₃ be substantially para-oriented in order for the wholly aromatic polyamide to maintain rigid properties with poor flexibility. Here, the divalent para-oriented aromatic group means that the divalent bonding groups are 1,4-phenylene (paraphenylene),
Arranged coaxially in the opposite direction from the aromatic ring, such as 4,4'-biphenylene, 1,4-naphthylene, etc., or in a parallel axially opposite direction, such as in 1,5-naphthylene and 2,6-naphthylene. The aromatic ring has one or two alkyl groups such as methyl and ethyl, alkoxy groups such as methoxy and ethoxy, and halogen groups such as chlorine and bromine.
It is also allowed to replace more than one. In addition to the above-mentioned carbocyclic groups, the para-oriented aromatic group also includes heterocyclic aromatic groups such as 2,5-pyridylene. Typical examples of para-oriented wholly aromatic polyamides include polyparabenzamide, polyparaphenylene terephthalamide, poly-4,4'-diaminobenzanilide terephthalamide, poly-N,
N′-p-phenylenebis(p-benzamide)
Terephthalamide, polyparaphenylene-2,6
―Naphthalicamide, copolyparaphenylene/
4,4'-(3,3'-dimethylbiphenylene)-terephthalamide, copolyparaphenylene/2,5
-pyridylene-terephthalamide, copolyparaphenylene-isocincomelonamide/terephthalamide, etc. In the para-oriented wholly aromatic polyamide of the present invention, up to 5 mol% of the aromatic groups constituting the molecule are divalent aromatic groups other than the above-mentioned special aromatic groups, such as metaphenylene groups, 3, 3-biphenylene, etc., divalent aliphatic groups such as ethylene, butylene, etc. may be substituted, and 5 mol% or less of the amide bond may be replaced with a hydrazide bond, ester bond, urea bond, urethane bond, etc. forgiven. The method for producing these para-oriented wholly aromatic polyamides is not particularly limited in carrying out the present invention. It can be easily produced by a low-temperature solution polymerization method. group general formula

[Formula] O and/or

It consists of a repeating unit of [formula], where X, Y, Z are (-1)
-H and/or a group represented by the general formula -CkH _2k+1 , or (-2) -H and/or a group represented by the general formula -(CH-)Ar ₄ , or (-
3)-H and/or general formula

A group represented by [Formula], or (- 4)-H and/or general formula -(CH ₂ -) _o
A group represented by COOM, the substitution rate in the polymer is 2 mol% or more, and ηinh is 0.1
The above N-substituted fully aromatic polyamide (In the above formula, Ar ₁ , Ar ₂ , and Ar ₃ each independently represent a divalent para-oriented aromatic group, and k, l, and n each represent 7≦k ≦25, 1≦l≦6, 1≦n≦
An integer in the range of 10, m is any integer, Ar ₄
teeth

【formula】

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【formula】

【formula】

【formula】

【formula】

Aromatic groups selected from [Formula], R ₁ , R ₂ , R ₃ , R ₄ are the same or different -
H, _-CH3 , -CH= _CH2 , _{-C2H5 ,}

【formula】

[Formula] -CH ₂ -O-CH ₂ - CH=CH ₂ , M is -H or Li,
Represents an alkali metal selected from Na, K, Rb, and Cs. ): Ar ₁ , Ar ₂ , Ar ₃ are the same as described in the group. When (-1) X, Y, and Z are -H and/or a group represented by the general formula -CkH _2k+1 , k is preferably 7 to 25, particularly preferably 10 to 20. be. If k is 6 or less, the solubility in various solvents will be low, and in particular, it will not dissolve at all in aromatic hydrocarbons, which are solvents for polyolefins, which is not preferable. (-2) When X, Y, and Z are -H and/or a group represented by the general formula -(CH ₂ -) _l Ar ₄ , l is 1
It is preferable that it is 6. When l is 7 or more, it is not preferable because the heat resistance, which is a characteristic of this substituent, decreases due to the influence of the length of the hydrocarbon chain, and it is particularly preferable that l is in the range of 1 to 3. Further, as Ar ₄ , phenyl group, naphthyl group, anthryl group,
Examples include phenanthryl group. (-3) X, Y, Z are -H and/or general formula

In the case of the group represented by the formula, since it is a graft form, m is any integer.
Specific examples of combinations of R ₁ , R ₂ , R ₃ , and R ₄ are shown in the table below.

[Table] (-4) When X, Y, and Z are represented by -H and/or the general formula -(CH ₂ -) _o COOM, n is 1
-10 is preferred. Particularly preferred is n
is in the range of 1 to 6. Also, as M, H,
Examples include Li, Na, K, etc. When the substituent is (-1), (-2), or (-4), the substitution rate of the polyamide of the group is the proportion ( N-substitution rate). The substituent is (-3)
In the case of , it is expressed as the proportion of graft reaction in the polymer (grafting rate), and when one molecule is added per amide unit, the grafting rate is defined as 100 mol%. When the substitution rate of the polymers in the group is low, there are many unsubstituted amide groups, and the intermolecular force between the aromatic polyamides becomes strong, which is contrary to the purpose of the present invention. However, due to the bulky effect of the special substituent of the present invention or the effect of long chain and flexible molecules, 2 mol%
Even a moderate substitution rate may be effective. Therefore, the substitution rate (N-substitution rate or grafting rate) is preferably 2 mol% or more, generally 10 mol% or more, and more preferably 30 mol% or more. In addition, in the case of the present invention, the upper limit of the substitution rate is 100 mol% in N-substitution rate,
The grafting rate is 1000 mol%. The molecular weight of the N-substituted wholly aromatic polyamide does not need to be particularly large for the purpose of the present invention, but if it is too low, the desired desired effect cannot be expected, so 100% by weight concentrated sulfuric acid Among them, it is preferable that the logarithmic viscosity number (ηinh) measured at 30° C. and a concentration of 0.5 g/100 ml is 0.1 or more. To produce the N-substituted wholly aromatic polyamides of the group, the para-oriented wholly aromatic polyamides described above are treated with dimethyl sulfoxide (hereinafter abbreviated as DMSO).
and/or sodium or sodium hydride in hexamethylphosphoramide (hereinafter abbreviated as HMPA), or with them.
In the presence of reactants with DMSO and/or HMPA, the general formula X—C _k H _2k+1 , or X—(CH ₂ )—
Ar ₄ , or

It may be reacted with a compound represented by [Formula] or X-(CH ₂ -) _o COOM (in the general formula, X represents a halogen group selected from chlorine, bromine or iodine). used in carrying out this reaction
DMSO and HMPA are preferably used after being subjected to pretreatment such as purification and dehydration if necessary, and it is also possible to include first and second solvents that do not inhibit the reaction. sodium or sodium hydride,
Alternatively, the amount of the reactant with DMSO and/or HMPA may be arbitrarily set based on the amount of the wholly aromatic polyamide introduced into the reaction system and the amount of the substituent to be introduced. The reaction temperature and time are not particularly limited, and should be adjusted appropriately depending on the polymer concentration and substitution rate of the reaction system, but generally between 0°C and the boiling point of the system, especially between 10 and 50°C. It is preferable to use a temperature between 10°C and 10 minutes to 90 hours. During the reaction, the wholly aromatic polyamide is provided in a dissolved or suspended state in the reaction system. General formula for introducing a substituent: X—C _k H _2k+1 ,
X—(CH ₂ —) _l Ar ₄ ,

The compound _represented by [Formula _]
This gives (-2), (-3), and (-4). The composition of the present invention comprises group -1, -
Consisting of one or more types selected from 2, -3, and -4. The compositions of the present invention are made by mixing para-oriented wholly aromatic polyamides with various N-substituted para-oriented wholly aromatic polyamides, particularly preferably by melt mixing with a co-solvent. That is, it is a method in which these two or three or more types of polymers are uniformly dissolved and mixed in a co-solvent such as sulfuric acid or chlorosulfuric acid. From this stock solution, molded products such as fibrous and film-like products can be obtained by wet or dry methods. Other mixing methods include melt processing and molding of a composition obtained by removing the solvent from the above-mentioned stock solution, or methods of dry blending these and then melting and molding them. A preferred group of compositions of the present invention comprises 1 to 99% by weight of para-oriented wholly aromatic polyamide(s) and various N-substituted para-oriented wholly aromatic polyamides (one or two selected from the group). or more) 99-1% by weight
It is a polymer composition consisting of. If the content of the para-oriented wholly aromatic polyamide in the composition is less than 1%, it is not preferred because no substantial effect as a reinforcing material for the N-substituted para-oriented wholly aromatic polyamide is observed. Further, if the content of the para-oriented wholly aromatic polyamide exceeds 99% by weight, it is not preferable because the plasticizing effect of the N-substituted para-oriented wholly aromatic polyamide on the para-oriented wholly aromatic polyamide is not observed. The characteristics of the polymer composition obtained by the present invention are as follows:
It is to show the thermoplasticization phenomenon. That is, para-oriented wholly aromatic polyamide is mixed with 1 to 40% by weight of various N-substituted para-oriented wholly aromatic polyamides, formed into a fiber or film, and then heated to become plastic at a temperature of about 100°C or higher. , and the elongation is at least 40%. Since the elongation of fibers or films obtained from ordinary para-oriented wholly aromatic polyamides is about 3 to 5%, the magnitude of the elongation of the composition can be understood. The plasticization temperature and elongation vary depending on the type of substituent of the N-substituted product and the amount mixed. Molded articles such as hot-stretched fibers or films have excellent mechanical properties such as tensile strength and elastic modulus. Fibers obtained from para-oriented wholly aromatic polyamides exhibit structural defects such as easy fibrillation due to buckling or bending deformation, but the composition can overcome these defects. Further, after film formation, a film made from the composition can be stretched biaxially, and a film with uniform strength in the longitudinal and lateral directions can be obtained. If necessary, N by using a solvent of various N-substituted products.
- It is also possible to selectively remove only the substituted product, and this removal is also possible by heat treatment that takes advantage of the difference in thermal decomposition temperature between the two. Next, in the case of a composition of 40 to 99% by weight of various N-substituted para-oriented wholly aromatic polyamides and 60 to 1% by weight of para-oriented wholly aromatic polyamide, the para-oriented wholly aromatic polyamide is N-substituted. It is dispersed in the substituent and acts as a reinforcing material. In other words, a molded article with better tensile strength, elastic modulus, heat resistance, etc. can be obtained than with a single N-substituted product. Since the para-oriented wholly aromatic polyamide in the composition can be uniformly finely dispersed in the matrix, it is added in small amounts, typically 20% by weight.
The following gives sufficiently favorable results. As described above, the polymer composition of the present invention is a composition with high performance that overcomes the drawbacks of conventional para-oriented wholly aromatic polyamides, and also has high performance N-substituted para-oriented wholly aromatic polyamides. It is also a composition provided. Although the mechanism of the effect of the present invention that occurs when two types of polyamides are mixed is not clear, it is presumed as follows. In other words, when the amount of N-substituted substance added is small, para-oriented wholly aromatic polyamide undergoes phase separation due to strong intermolecular forces to form microfibrils during molding into fibers or films, and heat The N-substituted portion would be plasticized by this. Furthermore, since the N-substituted product acts as an adhesive between microfibrils, it is thought that it prevents fibrillation and is resistant to buckling deformation and bending deformation. On the other hand, if the amount of the N-substituted product added is large, the formation of the above-mentioned microfibrils will be hindered, and the microfibrils will be finely dispersed in the N-substituted product to strengthen the N-substituted product. The polymer composition obtained by the present invention is a composition with excellent heat resistance, breaking strength, elastic modulus, bending strength, etc. The compositions of the invention may also contain reinforcing materials such as glass fibers, carbon fibers, whiskers, glass beads, asbestos and/or other additives for special purposes, such as plasticizers, pigments, flame retardants, stabilizers, etc. It is also possible to contain agents, mold release agents, etc. EXAMPLES Hereinafter, in order to further clarify the present invention, the present invention will be described with reference to Examples, but the scope of the present invention is not limited by the Examples. The various para-oriented wholly aromatic polyamides used in the examples were polymerized by reacting the corresponding diamine and diacid chloride at room temperature in a 1:1 mixture of HMPA and N-methylpyrrolidone. be. In addition, various N-substituted para-oriented wholly aromatic polyamides include para-oriented wholly aromatic polyamides.
The corresponding halogen compound or epoxide compound is reacted in the presence of a reaction product of DMSO and sodium hydride. Example 1 N-stearyl PPTA (N-substitution rate 25 mol%,
0.1 g of ηinh=0.55) and 3 g of PPTA (ηinh=5.2) were dissolved in 9 ml of 99.4% sulfuric acid at 50°C. This stock solution was extruded into the air through a spinneret with a diameter of 0.4 mm kept at 50°C, passed through an air layer at a distance of 1 cm, introduced into water, and wound at a speed of about 20 m/min. The wound fibers were washed with water until the sulfuric acid was completely removed, and then vacuum dried at 100°C for 10 hours.
The diameter of the obtained fibers was 18 μm. The tensile breaking strength of this fiber is 140Kg/mm ² and the initial elastic modulus is 930Kg/
It was warm in ^mm2 . When this fiber is heated to 150℃ and stretched, it shows approximately 60% elongation and the tensile strength at break is
The initial elastic modulus was 210Kg/mm ² and 1850Kg/mm ² . Example 2 N-9-anthrylmethyl PPTA (N-substitution rate 77 mol%, ηinh=
Fibers with a diameter of 15 μm were produced at a mixing ratio of 0.19)/PPTA (ηinh=5.2)=5/95 (weight ratio). This fiber has a tensile strength at break of 120Kg/mm ² and an initial modulus of elasticity of 880.
It was Kg/ ^mm2 . When this fiber is stretched at 180℃,
It shows an elongation of 80% and a tensile strength at break of 200Kg/mm ² .
The initial elastic modulus was 1600Kg/ ^mm2 . Example 3 In the same manner as in Example 1, N-carboxymethyl
PPTA (N-substitution rate 47 mol%, ηinh=0.49)/
Fibers with a diameter of 20 μm were produced with a mixing ratio of PPTA (ηinh=4.8)=10/90 (weight ratio). This fiber had a tensile strength at break of 130 Kg/mm ² and an initial elastic modulus of 910 Kg/mm ² . When this fiber is heated to 180℃ and stretched, approximately
It shows an elongation of 80% and a tensile strength at break of 190Kg/mm ² .
The initial elastic modulus was 1750 Kg/mm ² , and when heated to 250° C., it showed an elongation of about 170%, the tensile strength at break was 230 Kg/mm ² , and the initial elastic modulus was 2050 Kg/mm ² . Example 4 Using the same method as in Example 1, N-hydroxypropyl polyparabenzamide (grafting rate 40 mol%, ηinh = 0.93)/PPTA (ηinh = 5.2) = 20/80
Fibers with a diameter of 14 μm were produced at a mixing ratio of (weight ratio). This fiber had a tensile strength of 105 Kg/mm ² and an initial elastic modulus of 810 Kg/mm ² . When this fiber was heated to 200° C. and drawn, it showed an elongation of about 230%, a tensile strength at break of 185 Kg/mm ² , and an initial elastic modulus of 1450 Kg/mm ² . Comparative Example PPTA fibers with a diameter of 20 μm were produced in the same manner as in Example 1. The tensile breaking strength of this fiber is
The elastic modulus was 120Kg/mm ² and the initial elastic modulus was 950Kg/mm ² . When this fiber was heated to 200° C. and stretched, it broke at about 5%, so it was stretched at about 4% and then subjected to a tensile test. As a result, the tensile strength at break was 125 Kg/mm ² and the initial elastic modulus was 1050 Kg/mm ² . Example 5 N-carboxyethyl PPTA (N-substitution rate 33 mol%, ηinh = 0.82)/PPTA (ηinh = 5.2) = 5/
Dissolved in 99.4% concentrated sulfuric acid at a mixing ratio of 95 (weight ratio),
This stock solution was cast onto a glass plate, coagulated in water, washed with water, and dried to produce a film with a thickness of 40 μm. The tensile strength at break was 16 Kg/mm ² . When this film is heated to 200℃ and biaxially stretched, it shows approximately 60% elongation and the tensile strength at break is
It was 35Kg/ ^mm2 . Example 6 In the same manner as in Example 5, N-stearyl PPTA
(N-substitution rate 45 mol%, ηinh=3.3)/PPTA
(ηinh = 5.2) = 70/30 (weight ratio) mixing ratio,
A film with a thickness of 50 μm was obtained. Tensile breaking strength is
It was 14Kg/ ^mm2 .

Claims (1)

[Scope of Claims] 1 In the following groups or groups of polymeric substances, a group is a para-oriented wholly aromatic polyamide group consisting of repeating units of the general formula [formula] and/or [formula]; a group of general formulas [formula] and/or or [Formula], where X, Y, Z are (--
1) -H and/or a group represented by the general formula -CkH _2k+1 , or (-2) -H and/or a group represented by the general formula -(CH ₂ -) _l Ar ₄ , or (-3) -H and/or a group represented by the general formula [formula], or (- 4) -H and/or the general formula -(CH ₂ -) _o
A group represented by COOM, the substitution rate in the polymer is 2 mol% or more, and ηinh is 0.1
The above N-substituted fully aromatic polyamide (In the above formula, Ar ₁ , Ar ₂ , and Ar ₃ each independently represent a divalent para-oriented aromatic group, and k, l, and n each represent 7≦k ≦25, 1≦l≦6, 1≦n≦
An integer in the range of 10, m is any integer, Ar ₄
is an aromatic group selected from [Formula] [Formula] [Formula] [Formula] [Formula] [Formula] [Formula] [Formula] [Formula] [Formula] [Formula] [Formula] [Formula] [Formula], R ₁ , R ₂ , R ₃ , R ₄ are the same or different.
H, _-CH3 , -CH= _{CH2 , -C2H5} , _{-C3H7 ,}
[Formula] [Formula] -CH ₂ -O-CH ₂ -CH=CH ₂ A group selected from -H or an alkali metal selected from Li, Na, K, Rb, and Cs. ) Group and group -1, -2, -3, -4
One or more selected from
A polymer composition with a composition ratio of 99% by weight. 2. The polymer composition according to claim 1, wherein in the general formula, Ar ₁ , Ar ₂ , and Ar ₃ are each paraphenylene groups.