JPH0246619B2 - - 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 suitable polymeric substances are mixed 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-butadiene copolymer rubber, and many other homopolymers and copolymers. It has been put into practical use to meet market demands that are diversifying along with the integration, etc. 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, because 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 have conducted extensive research and found that a novel N-substituted wholly aromatic polyamide can be dissolved in a solvent and finely dispersed in general flexible polymers. This has led to the present invention. That is, the present invention has the following general formula:

[expression] 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 _{( -CH2} ) _-lAr4 , 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 in the polymer is 2 mol% or more, and η N-substituted fully aromatic polyamide with inh of 0.1 or more (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 are respectively, An integer in the range of 7≦k≦25, 1≦l≦6, 1≦n≦10, m is any integer, and Ar ₄ is

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[Formula] Aromatic groups selected from R ₁ , R ₂ , R ₃ , and R ₄ are the same or different -H, -CH ₃ , -CH=CH ₂ , -
C ₂ H ₅ , −C ₃ H ₇ ,

【formula】

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

[expression] 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 _{( -CH2} ) _-lAr4 , 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 in the polymer is 2 mol% or more, and η N-substituted fully aromatic polyamide with inh of 0.1 or more (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 are respectively, An integer in the range of 7≦k≦25, 1≦l≦6, 1≦n≦10, m is any integer, and Ar ₄ is

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[Formula] Aromatic groups selected from R ₁ , R ₂ , R ₃ , R ₄ are the same or different -H, -CH ₃ , -CH=CH ₂ , -
C ₂ H ₅ , −C ₃ H ₇ ,

【formula】

[Formula] A group selected from -CH ₂ -O-CH ₂ -CH=CH ₂ ,
M represents -H or an alkali metal selected from Li, Na, K, Rb, and Cs. ) is used. Ar ₁ , Ar ₂ , 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 ring is arranged coaxially in the opposite direction from the aromatic ring, such as naphthylene, or parallel to the reaction direction, 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, 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. In addition, when k is 26 or more, the concentration per unit cross-sectional area of the rigid main chain portion in the wholly aromatic polyamide decreases, so that favorable mechanical properties cannot be imparted even when mixed with a flexible polymer. I don't like it because I can't expect it. (2) X, Y, Z are -H and/or general formula (-
In the case of a group represented by CH ₂ ) _-l Ar ₄ , I 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. _R1 ,
Specific examples of combinations of 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 n is 11 or more,
Even if it is mixed with a flexible polymer, it cannot be expected to impart good mechanical properties, so it is not preferable. Particularly preferred is a range of 1 to 6 for n. Furthermore, examples of M include H, Li, Na, K, and the like. The substitution rate of N-substituted polyamide means that the substituents are (1),
In the cases of (2) and (4), it is the proportion (N-substitution ratio) in which X, Y, and Z in the polymer are not -H. When the substituent is (3), 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 polymer 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, even a substitution ratio of about 2 mol % may exhibit an effect. Therefore, the substitution rate (N-substitution rate or grafting rate) is preferably 2 moles or more, and generally 10
It is preferably mol% or more, more preferably 30 mol% or more. In addition, in the case of the present invention, even if all amide groups are completely substituted, there is often no problem in finely dispersing and modifying other flexible polymers, and the upper limit of the substitution rate is - Substitution rate of 100 mol%
If the grafting ratio exceeds 1000 mol%, good mechanical properties cannot be expected to be imparted even when mixed with a flexible polymer, which is not preferable. 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 (η inh) 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- _CkH2k+1 , or X( _-CH2 ) _-i
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. In 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 ) − _i Ar ₄ ,

_The compound represented by [Formula _]
(4). Flexible polymer: A polymer having a Mark-Houwink index α defined below of 1 or less is a flexible polymer. [η]=KM= Typical examples include polyacrylonitrile and its copolymers and derivatives, nylon 6,
Polyamides such as 6/6, 6/10, 12 and their derivatives, polyethylene terephthalate, polybutylene terephthalate, polyethylene terephthalate-butylene terephthalate block copolymer,
Polyesters and their derivatives such as polyethylene terephthalate-polyethylene glycol block copolymers, polyurethanes, block polyurethanes, polyolefins and their derivatives such as polyethylene, polypropylene, polybutene, ethylene propylene copolymers, polycarbonates, polyacetals, polysulfones, polyesters, etc. Polystyrene such as vinyl chloride and its copolymers, polyvinylidene chloride and its copolymers, polymethyl methacrylates, acrylic acid ester copolymers, polystyrenes, acrylonitrile styrene copolymers, acrylonitrile styrene butadiene copolymers, etc. Copolymers thereof, polyvinyl acetates, polyvinyl formal, acetals, butyrals, ethylene-vinyl acetate copolymers and their hydrolysates, polyvinyl alcohols, styrene-butadiene block copolymers, polybutadiene, polyisoprene, etc. Examples include rubbers, polyvinyl ethers such as polymethoxyethylene and polyethoxyethylene, polyacrylamide, and polyphosphazenes. Composition: The composition of the present invention comprises a flexible polymer and various N-
Made by mixing with substituted para-oriented wholly aromatic polyamides. As the mixing method, a solution method using a co-solvent, a melting method, or a method of dry blending and then melting these methods is used. The composition ratios of the compositions exhibit their respective properties depending on the mixing ratio, so they can be mixed in accordance with the desired properties. When the purpose is to strengthen a flexible polymer, satisfactory results can be obtained even if the proportion of the N-substituted para-oriented wholly aromatic polyamide in the total composition is 30% by weight or less. A preferred group of polymer compositions obtained by the present invention include (2) N-substituted wholly aromatic polyamide and polyolefins such as polyethylene and polypropylene;
A composition comprising one selected from rubbers such as polystyrenes, polyptadiene, and polyisoprene, polyvinylidene chloride and its copolymers, polyester, polycarbonate, and polycarbonate, or the N-substituted wholly aromatic compound of (2) Polyamide and polystyrenes, polystyrene and its copolymers such as acrylonitrile styrene copolymer, acrylonitrile styrene butadiene copolymer, rubbers such as polybutadiene and polyisoprene, polyvinylidene chloride and its copolymers, polyester, polycarbonate , polyurethane, and one selected from polyphosphazenes; A composition comprising one selected from polyester, polyvinyl chloride, polyacetal, polycarbonate, polyvinyl alcohol, polyvinyl formal, acetal, butyrals, polyvinyl ethers, polyacrylamide, or the N-substituted wholly aromatic compound of (4) Group polyamides and polyamides such as nylon 6, 6/6, 6/10, 12, polyester, polyacetal, polycarbonate, polyvinyl alcohol, polyvinyl acetate, polyacrylamide, polymethyl methacrylate, acrylic ester copolymers, This is a composition consisting of one selected from polyacrylic acid and polymethacrylic acid. It is also possible to mix two or more types selected from N-substituted wholly aromatic polyamides with one type selected from flexible polymers. 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 epoxy compound is reacted in the presence of a reaction product of DMSO and sodium hydride. Example 1 9g of low density polyethylene and N-stearyl
PPTA (N-substitution rate 97 mol%, η inh = 0.43) 1 g
were mixed in 150 ml of toluene and heated to 100°C to dissolve, and then this solution was added to n-hexane 2 to precipitate the polymer. Polymer with methanol
After washing twice to remove toluene, in a vacuum dryer,
It was dried at 60°C for 10 hours to obtain a powdery polymer. This powdered polymer was molded using a compression molding machine to produce a sheet sample with a thickness of 1 mm. This composition had a tensile strength at break of 120 Kg/cm ² and an initial elastic modulus of 2500 Kg/cm ² . For comparison, a sheet made of polyethylene alone was manufactured using the same method and a tensile test was conducted, and the breaking strength was 100 Kg/cm ² and the initial elastic modulus was 1300 Kg/cm 2 .
It was warm in ^cm2 . Example 2 9 g of polybutadiene and N-lauryl PPTA (N-
Substitution rate: 93 mol%, η inh = 0.35) 1 g) was dissolved in 150 ml of tetrahydrofuran, and this solution was added to methanol 2 to precipitate the polymer. After washing the polymer five times with methanol, it was dried in a vacuum dryer at room temperature for 20 hours to obtain a polymer composition. This composition was molded using a compression molding machine to produce a sheet sample with a thickness of 5 mm. The tensile strength at break of this composition was 205 Kg/cm ² . The tensile strength at break of polybutadiene obtained by the same method was 90Kg/
It was warm in ^cm2 . Example 3 90 g of polystyrene and 10 g of N-(9-anthryl)methyl PPTA (N-substitution rate 73, η inh = 0.48)
were mixed using 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 590 Kg/cm ² . The tensile breaking strength of polystyrene obtained by a similar method is
It was 430Kg/ ^cm2 . Example 4 In the same manner as in Example 3, ethylene-vinyl acetate copolymer (vinyl acetate content 20% by weight)/N-hydroxyethyl PPTA (grafting rate 25 mol%, η
inh = 0.75) = 93/7 (weight ratio) mixing ratio,
A sheet with a thickness of 0.3 mm was manufactured. The tensile strength at break was 270 Kg/cm ² and the strength of the ethylene-vinyl acetate copolymer was 150 Kg/cm ² . Example 5 In the same manner as in Example 3, ethylene-acrylic acid copolymer (acrylic acid content 7% by weight)/N-carboxymethyl PPTA (N-substitution rate 62 mol%, η
inh = 0.92) = 90/10 (weight ratio) mixing ratio,
A sheet with a thickness of 2 mm was produced. The tensile strength at break of this composition was 210 Kg/cm ² , and the strength of the ethylene-acrylic acid copolymer was 130 Kg/cm ² . Example 6 Polyisoprene/N-
Carboxymethyl PPTA (N-substitution rate 29 mol%,
A sheet with a thickness of 3 mm was produced with a mixing ratio of η inh = 1.15) = 85/15 (weight ratio). The tensile strength at break of this composition was 125 Kg/cm ² and the strength of the polyisoprene was 85 Kg/cm ² .

Claims (1)

[Claims] 1 Consisting of repeating units 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 a group represented by the general formula (-CH ₂ ) _-o COOM, and the substitution rate in the polymer is 2 mol% or more and η inh is 0.1 or more. group 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≦l≦6, respectively) , an integer in the range of 1≦n≦10, m is any integer, and Ar ₄ is [formula] [formula] [formula] [formula] [formula] [formula] [formula] [formula] [formula] [ [Formula] [Formula] [Formula] [Formula] The aromatic groups selected from R ₁ , R ₂ , R ₃ , and R ₄ are the same or different -H, -CH ₃ , -CH=CH ₂ , -
A group selected from C ₂ H ₅ , -C ₃ H ₇ , [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. ) A polymer composition comprising one or more selected from (1) to (4) and one selected from flexible polymers. 2. The polymer composition according to claim 1, wherein in the general formula, Ar ₁ , Ar ₂ , and Ar ₃ are each paraphenylene groups.