JPH0340066B2 - - 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. The properties of the polymer molded product as a polymer chain assembly depend on the symmetry, electron density, three-dimensional structure, molecular weight, molecular weight distribution, etc. of the molecule, and secondarily, the molding method. 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.
Polymer blends, in which two or more appropriate polymeric substances are mixed together to impart certain properties or to obtain intermediate properties, are also often carried out. For example, impact-resistant polystyrene made by blending a rubber component with polystyrene, polystyrene and polyphenylene oxide, polyvinylidene fluoride and polymethyl methacrylate, polyvinyl chloride and acrylonitrile.
Many homopolymers, such as butadiene copolymer rubber,
Along with copolymers, 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 wholly aromatic polyamide were modified with various substituents to N-
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 Application Laid-Open No. 49-116322, Japanese Patent Publication No. 51-1593, etc.)
is proposed. However, these methods sacrifice the high strength, high elastic modulus, and excellent heat resistance that are characteristics of para-oriented wholly aromatic polyamides. 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 conducted extensive research and found that the above-mentioned problems could be solved by blending a novel N-substituted wholly aromatic polyamide. That is, N- with different substituents
The inventors have discovered that a composition with excellent properties can be obtained by blending substituents, and have arrived at the present invention. That is, the present invention has the following general formula:

[Formula] and and/or

[formula], where X, Y, and 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 Group represented by Ar ₄ , or (3) -H and/or general formula

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

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【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} , _{-C3H7 ,}

【formula】

[Formula] -CH ₂ -O-CH ₂ -CH=CH ₂ , M is -
Represents H or an alkali metal selected from Li, Na, K, Rb, and Cs. ) A polymer composition consisting of two or more selected from (1) to (4). The present invention will be explained in more detail below. In the present invention, the general formula

[expression] and/or teeth

[formula], where X, Y, and 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 A group represented by Ar ₄ ,
or (3)-H and/or general formula

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

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【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} , _{-C3H7 ,}

【formula】

[Formula] -CH ₂ -O-CH ₂ -CH=CH ₂ , M is -
Represents H or an alkali metal selected from Li, Na, K, Rb, and Cs. ) is used. Ar ₁ , Ar ₂ , and Ar ₃ represent divalent para-oriented aromatic groups, and the divalent bonding groups are 1,4-phenylene (paraphenylene), 4,4'-biphenylene, 1,4- The aromatic rings are arranged coaxially in the opposite direction from the aromatic ring, such as naphthylene, or in the opposite direction parallel to the aromatic ring, such as 1,5-naphthylene and 2,6-naphthylene. The ring may be substituted with one or more alkyl groups such as methyl and ethyl, alkoxy groups such as methoxy and ethoxy, and halogen groups such as chlorine and bromine. In addition to the above-mentioned carbocyclic groups, the para-oriented aromatic group also includes heterocyclic aromatic groups such as 2,5-pyridylene. Here, (1) X, Y, and Z are -H and/or the general formula -
In the case of the group represented by CkH _2k+1 , k is preferably from 7 to 25, particularly preferably from 10 to 20. 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) X, Y, and Z are -H and/or the general formula (-
CH ₂ −) _l In the case of a group represented by Ar ₄ , l is 1 to 6
It is preferable that If l is 7 or more,
This 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. Also
Examples of Ar ₄ include a phenyl group, a naphthyl group, an anthryl group, and a phenanthryl group. (3) X, Y, Z are -H and/or general formula

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

[Table] (4) X, Y, Z are -H and/or general formula (-
CH ₂ −) _o When indicated by COOM, n is 1 to 10
It is preferable that Particularly preferred is a range of 1 to 6 for n. Also, as M, H,
Examples include Li, Na, K, etc. What is the substitution rate of N-substituent of N-substituted polyamide?
When the substituent is (1), (2), or (4), X in the polymer,
This is the proportion of Y and Z that is not -H (N-substitution rate). When the substituent is (3), it is expressed as the proportion of graft reaction in the polymer (grafting ratio),
The grafting rate is defined as 100 mol% when one molecule is added per amide unit. When the substitution rate of the N-substituent of the polymer is low,
Since there are many unsubstituted amide groups, 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, even a substitution ratio of about 2 mol % may exhibit an effect. Therefore, the substitution rate of the N-substituent (N-substitution rate or grafting rate) is preferably 2 mol% or more, generally 10 mol% or more, and more preferably 30 mol% or more. be. Further, in the case of the present invention, the upper limit of the substitution rate of the N-substituent is 100 mol% in N-substitution rate and 1000 mol% in grafting rate. 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. at a concentration of 0.5 g/100 ml is 0.1 or more. To produce N-substituted wholly aromatic polyamide,
The para-oriented wholly aromatic polyamide described above was treated with dimethyl sulfoxide (hereinafter abbreviated as DMSO) and/or hexamethylphosphoramide (hereinafter abbreviated as DMSO).
(abbreviated as HMPA), sodium or sodium hydride, or
In the presence of reactants with DMSO and/or HMPA, the general formula X-CkH _2k+1 , or X(-CH ₂ -) _l Ar ₄ , or Alternatively, it may be reacted with a compound represented by X( _-CH2- ) _oCOOM (in the general formula, X represents a halogen group selected from chlorine, bromine, or iodine). In carrying out this reaction, the
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. The amount of sodium or sodium hydride or the reactant thereof with DMSO and/or HMPA may be arbitrarily set based on the amount of wholly aromatic polyamide introduced into the reaction system and the amount of substituents to be introduced. The temperature and time of the reaction are not particularly limited, and should be adjusted appropriately depending on the polymer concentration and substitution rate of the reaction system, but generally the reaction temperature is between 0°C and the boiling point of the system, especially between 10°C and the boiling point of the system. A temperature between 50°C is preferably used, and a suitable time is about 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-CkH _2k+1 , X(-CH ₂ -) _l Ar ₄ ,

[Formula] X(-CH ₂ -) _o COOM reacts with para-oriented wholly aromatic polyamide to form
(3) and (4) are given. The polyamide (1) is soluble in phenol, tetrahydrofuran, benzene, bromoform, etc., and has a softening temperature of 100-350°C and a thermal decomposition temperature of 200-400°C. The polyamide (2) is dissolved in DMSO, phenol, tetrahydrofuran, bromoform, etc., and has a softening temperature of 200-450°C and a thermal decomposition temperature of 400-500°C. The polyamide (3) is soluble in organic solvents such as DMSO, phenol, and bromoform, or in water when R ₁ to _{R 4} are H or lower alkyl groups, such as N-hydroxypropyl substituted products, and the thermal decomposition temperature
The temperature is 250-400℃. The polyamide (4) is dissolved in an organic solvent such as phenol or bromoform, or in water or an aqueous alkali solution, and has a thermal decomposition temperature of 150 to 400°C. All (1) to (4) are dissolved in concentrated sulfuric acid. For mixing methods (1) to (4), a solution method using a co-solvent, a melting method, or a method of dry blending and then melting these methods is used, and molded products such as fibers and films are made from these methods. Obtainable. Since the composition ratio of the polymer composition of the present invention exhibits its respective properties depending on the mixing ratio, it can be mixed in accordance with the desired properties. The polymer composition obtained by the present invention is a composition with excellent heat resistance, breaking strength, bending strength, etc. The composition may also contain other reinforcing materials such as glass fibers, carbon fibers, whiskers, glass beads, asbestos, and the like. 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-lauryl-polyparaphenylene terephthalamide (hereinafter, polyparaphenylene terephthalamide is abbreviated as PPTA) (N-substitution rate 65 mol%,
ηinh=1.9) 2g and N-9-anthrylmethyl
Dissolve 2 g of PPTA (N-substitution rate 55 mol%, ηinh = 1.3) in 15 ml of 99.4% sulfuric acid at 40°C, pour this stock solution onto a glass plate, and solidify in water to completely remove the sulfuric acid. By washing with water and drying until
A film with a thickness of 45 μm was obtained. Tensile breaking strength is
It was 13Kg/ ^mm2 . Example 2 In the same manner as in Example 1, N-stearyl PPTA
(N-substitution rate 45 mol%, ηinh=3.3)/N-carboxymethyl PPTA (N-substitution rate 33 mol%, ηinh=
1.2) = 1/1 (weight ratio) mixing ratio, thickness 35μ
A film of m was obtained. Tensile breaking strength is 18Kg/mm ²
It was hot. Example 3 In the same manner as in Example 1, N-decylpolyparabenzamide (N-substitution rate 95 mol%, ηinh=
A film having a thickness of 60 μm was obtained with a mixing ratio of 0.80)/N-hydroxypropyl PPTA (grafting rate: 320 mol%, ηinh=0.3)=3/1 (weight ratio). The tensile strength at break was 6 Kg/mm ² . Example 4 In the same manner as in Example 1, N-hydroxypropyl PPTA (grafting rate 20 mol%, ηinh = 3.5)/N
-Carboxymethyl PPTA (N-substitution rate 15 mol%,
The mixing ratio is ηinh=3.9)=40/60 (weight ratio),
A film with a thickness of 35 μm was produced. The film was transparent and flexible, and had a tensile strength at break of 11 Kg/mm ² . Example 5 N-benzyl PPTA (N-substitution rate 82 mol%,
ηinh=0.22) 20g and N-hydroxyethyl PPTA
(grafting ratio 150 mol%, ηinh=3.7) and 20 g were mixed in a small melt kneader, and a sheet sample with a thickness of 3 mm was produced using a compression molding machine. The tensile strength at break of this composition was 7.1 Kg/mm ² . Example 6 In the same manner as in Example 5, N-(1-naphthyl)
Methyl PPTA (N-substitution rate 85 mol%, ηinh=
A sheet with a thickness of 0.5 mm was produced at a mixing ratio of 0.31)/N-carboxyethyl PPTA (N-substitution rate 75 mol%, ηinh=2.9) = 30/70 (weight ratio). The tensile strength at break was 8.2 Kg/mm ² .

Claims (1)

[Claims] 1 Consists of a repeating unit of the general formula [Formula] and/or [Formula], where X, Y, and Z are represented by (1) -H and/or 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 - ₎ - Substituted wholly aromatic polyamide (in the above formula, Ar ₁ , Ar ₂ , Ar ₃ each independently represent a divalent para-oriented aromatic group, k, l, n are 7≦k≦25, 1 An integer in the range of ≦l≦6, 1≦n≦10, m is any integer, and Ar ₄ is [formula] [formula] [formula] [formula] [formula] [formula] [formula] [formula] [Formula] [Formula] [Formula] [Formula] The aromatic group selected from [Formula], R ₁ , R ₂ , R ₃ , and R ₄ are the same or different -
H, _-CH3 , -CH= _{CH2 , -C2H5} , _{-C3H7 ,}
[Formula] [Formula] -CH ₂ -O-CH ₂ -CH=CH ₂ , M is -
Represents H or an alkali metal selected from Li, Na, K, Rb, and Cs. ) A polymer composition consisting of two or more selected from (1) to (4). 2. The polymer composition according to claim 1, wherein in the general formula, Ar ₁ , Ar ₂ , and Ar ₃ are each paraphenylene groups.