JPS63275632A - Novel curable wholly aromatic polyamide - Google Patents

Abstract

PURPOSE:To obtain the title polyamide excellent in thermoformability, heat resistance and chemical resistance, by introducing a sodium atom into a wholly aromatic polyamide and subjecting the product to an N-substitution reaction. CONSTITUTION:A sodium atom is introduced into a wholly aromatic polyamide obtained by reacting a diamine with a dicarboxylic acid chloride in the presence of ammonia and sodium, and the product is subjected to an N-substitution reaction with a propargyl halide, an alkyl halide or an aralkyl halide to obtain a curable wholly aromatic polyamide consisting of repeating units of formulas II and/or II (wherein X, Y and Z are composed of 0-95mol.% H, 3-90mol.% propargyl groups and 2-97mol.% groups of formulas III and/or IV (wherein Ar1-3 are each a bivalent aromatic group, 1<=n<=30, 1<=m<=6, and Ar4 is an aromatic group of any one of formulas V-VII, etc.).

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a curable wholly aromatic polyamide, and more specifically, the present invention relates to a curable wholly aromatic polyamide. The present invention relates to a curable wholly aromatic polyamide that is at least partially N-substituted and has excellent solubility and thermoformability.

[Conventional technology]

As a heat-resistant polymer, molded products such as fibers and films made of so-called fully aromatic polyamides, in which all of the divalent hydrocarbon groups bonded through amide bonds are aromatic groups, have high strength and high modulus. It is known that it gives the properties of However, since wholly aromatic polyamides have no or extremely high melting points, they cannot usually be melt-molded, and are made into fibers or films using a solvent. Moreover, these solvents are strong inorganic acids such as concentrated sulfuric acid or highly polar solvents such as hexamethylphosphoramide, and the types of solvents are limited. In order to improve this drawback, N-substituted derivatives were proposed (JP-A-55-116727, JP-A-57-427).
No. 29). All of these are extremely effective as means for improving solubility and thermoplasticization, but as products such as fibers, films, and molded products, they lack chemical resistance.

USF No. 4,395,540 and U8P4 are methods that combine the contradictory functions of improving the solubility of wholly aromatic polyamides and imparting chemical resistance, heat resistance, etc. to the obtained product.
, 431,792. That is, U8P
No. 4, 395, 540 discloses a wholly aromatic polyamide represented by the general formula (R is 1 to 100 mol % of propargyl groups and 0 to 99 mol % of methyl groups).

USI'4,431,792 discloses a wholly aromatic polyamide represented by the general formula (X is 10-, -CO-, R is a pro/J?rugyl group and a methyl group) has been done. These two 08Ps do not disclose anything other than the above polyamide.

This USP fully aromatic polyamide has a diamine component -〇-
, -CO-), diol diphosphoric acid as a group that binds the enylene group, flexible -0)12 +-O-, -
Because it contains CO-, the entire polymer chain is flexible,
The mechanical properties of molded products such as fibers and films made of the wholly aromatic polyamide are inferior to molded products made of the wholly aromatic polyamide, which is composed entirely of rigid and rigid components. Since N,N'-propargyl and methyl group-substituted diamines, which have a flexible structure, and heptatalyl chloride or dicardin acid chloride, which has a flexible structure, are used, solution polymerization can be performed at low temperatures and high molecular weight. easily obtained. However, the polymerization of rigid N,N'-pronoglucyl group-substituted diamines and rigid dicarzenic acids must be carried out at high temperatures, which may not only cause coloring problems but also lead to the formation of high molecular weight substances. It has disadvantages that are difficult to obtain. Furthermore, this N, N'
-The synthesis of pro-gurgyl group-substituted diamines required a large number of steps, which was a significant industrial disadvantage.

Thermid MO-600 (manufactured by National Starch & Chemical Company), which is an aromatic polyimide having acetylene groups at both ends, is well known as an acetylene-containing oligoimide. This aromatic polyimide has a melting point of 19Q to 210'C and a thermosetting start temperature of about 22
Since the temperature is 0°C, the temperature range in which it can be melt-processed is about 10°C, which is a very narrow disadvantage.

[Problem that the invention seeks to solve]

In view of the above circumstances, the present invention provides a curable wholly aromatic polyamide with improved solubility and a large temperature difference between the melting temperature and the curing start temperature, that is, excellent thermoformability. The present invention aims to provide a curable wholly aromatic polyamide that is heat resistant and chemical resistant after molding.

[Means for solving problems]

In order to solve this problem, the present inventors conducted research on Eido and came to invent a polymeric material with a novel structure that meets the purpose of the present invention.

That is, the present invention is substantially composed of repeating units of the general formula % -N Ar3- oo-, where X, Y, and Z are -H(1) 0 to 95 mol%,
Pro JR Lugyl group (II) 3-90 mol% Oyohi, (a
) General formula Q□=-CnH2n+1 and/or (b)
A group consisting of the general formula (h= + OH element r4 (IID2
A curable wholly aromatic polyamide characterized by t-97 mol %.

(In the above formula, Arl+ Ar2. Ar3 each independently represents a divalent aromatic group, and n and m each represent 1≦
It is an integer in the range of n≦30.1≦m≦6, and Art may be substantially composed of entirely aromatic polyamide in the present invention. That is, in the fully aromatic polyamide of the present invention, at least 85 mol% or more of the amide bonds are aromatic diamines,
Any substance that can be obtained from the aromatic dicarzene acid component may be used. Examples of A r 1 include lyamide.

Specific polyamides include, for example, poly-zorapenzamide, poly(nozo-rough ethylene terephthalamide),
poly(metaphenylene terephthalamide), poly(orthophenylene terephthalamide), poly()zo rough phenylene isophthalamide), poly(metaphenylene isophthalamide), poly(orthophenylene isophthalamide), poly()zo rough enylene phthalamide), poly(
Meta-phenylene phthalamide), Bori (ortho-phenylene phthalamide), Poly()gu-diphenylene-2,6-
Naphthalituku amide), Hori()zo diphenylene-1,
5-naphthalicamide), poly(metaphenylene-2)
, 6-natalic amide), poly(metaphenylene-
Poly(1,5-naphthalene terephthalamide), Poly(2,6-naphthalene terephthalamide), Bori(2,6-naphthalene isophthalamide), Poly(1°5-naphthalene terephthalamide), Poly(1,5-naphthalene 6) inphthalamide), and compounds in which a portion of the benzene nucleus of these aromatic diamines is substituted with norogen;
Examples include aromatic polyamides containing alicyclic amines, typified by compounds substituted with 5-dimethylpiperazine, 2.5-dimethylpiperazine, and 2.5-diethylpiperazine.

The wholly aromatic polyamide of the present invention may contain less than 15 mole % of aliphatic diamine, aliphatic dicarzene acid component. Specific examples include diamines such as tetramethylene diamine and hexamethylene diamine, and dicardic acids such as adipic acid, heptanothenic acid, and dodecanedicarzenic acid.

Further, the wholly aromatic polyamide of the present invention may be a random or block copolymer of the general formula Mido and the polyamide constituted by the general formula -N Ars 00-. The composition ratio of this copolymer is not particularly limited.

The method for producing these wholly aromatic polyamides is not limited in carrying out the present invention, and for example, from the corresponding diamine and cyclocarpic acid chloride,
It can be easily produced by the solution polymerization method known from Publication No. 5-14399 and the like.

The molecular weight of the wholly aromatic theramide used in the present invention is not particularly limited, and ranges from oligomers to high molecular weight ones can be used.

N-propargyl group, alkyl group, which is a feature of the present invention,
To produce an aralkyl group-substituted fully aromatic polyamide,
Method for washing and sodiumizing the above-mentioned wholly aromatic polyamide in the presence of ammonia and sodium (Journal of Polymer Science, Polymer Chemistry Edition, 16
Vol., p. 533 (1978)) or in dimethyl sulfoxide (DMSO) and hexamethylphosphoramide (HMPA).
Sodiumization may be carried out in the presence of sodium or sodium hydride, or a reaction product of these with DMSO and/or HMPA, and then N-substitution reaction may be carried out with propargyl halide, alkyl halide, or aralkyl halide.

Antinia, D used in carrying out this reaction;
It is preferable to use MSO and HMPA after pretreatment such as purification and dehydration.
, it is also possible for a second solvent to be present.

There are no particular limitations on the temperature and time of the sodium conversion reaction and the N-substitution reaction. In the case of sodium conversion, the reaction temperature is between 0°C and the boiling point of the system, particularly preferably 0°C.
It is carried out at a temperature of ~80°C for a time of about 1 second to about 50 hours, more preferably about 1 minute to about 10 hours. When the N-substitution reaction is carried out with a zolonozolgyl group, an alkyl group, or an aralkyl group, the reaction temperature is between 0°C and the boiling point of the system, particularly preferably between 10°C and 100°C, and the reaction time is between 1 second and 50°C. A suitable time is about 1 minute to 10 hours, more preferably about 1 minute to 10 hours.

The substitution ratio of prono-lugyl groups in the present invention is defined as the ratio of N-propargyl groups to all amide groups constituting the polymer, and at 3 to 90 mol%, the polymer becomes insoluble in heating solvents and at the same time has heat resistance. It becomes a curable wholly aromatic diaryamide with excellent physical properties. Therefore, the substitution rate should be 3 mol% or more, particularly preferably 5 mol% or more. If the substitution rate is less than 3 mol %, it will not become insoluble in the solvent, which is not preferable.

If the substitution rate exceeds 90 mol%, the wholly aromatic polyamide after curing becomes extremely brittle, which is not preferable.

The substitution rate of alkyl groups and/or aralkyl groups is 2 to
The content is in the range of 97 mol%, particularly preferably 10 mol% or more. When two types of substituents, an alkyl group and an aralkyl group, coexist, the mixing ratio of each substituent is not particularly limited. If the substitution rate is less than 2 mol %, no improvement in solubility will be observed, which is not preferable. Otherwise, it is not preferable because it does not melt and plasticize, or the melt layering temperature is extremely high and the difference from the curing start temperature is small, making thermoforming difficult. If the substitution rate exceeds 97 mol %, the degree of substitution of the propargyl group, which is a crosslinking group, will be low, resulting in poor solvent resistance, which is not preferred.

The sum of the substitution rate of the pro-zorugyl group and the substitution rate of the alkyl group and/or aralkyl group is 5 to 100 mol %, that is, the number of hydrogen atoms -H is θ to 95 moles. When the hydrogen atoms exceed 95 mol2, not only solubility and thermoformability but also
It is not preferred because the solvent resistance after curing is also poor.

The propargyl group, alkyl group, and aralkyl group introduced into the ON-propargyl group, alkyl group, and aralkyl group-substituted fully aromatic polyamide of the present invention can be detected by methods such as infrared absorption spectroscopy and nuclear magnetic resonance (hereinafter abbreviated as NMR) spectroscopy. Can be detected. Further, the degree of curing reaction of the wholly aromatic polyamide of the present invention can be detected by infrared absorption spectroscopy, NMR spectroscopy, and the decrease in the number of substituted pro-zorugyl groups.

Furthermore, the curing reaction of the pro-gurgyl group can also be detected by differential scanning calorimetry (hereinafter abbreviated as DSO). The curing reaction of the pronoglucyl group is an exothermic reaction in the range of about 2000 to 350°C, and the peak temperature at which the exotherm is maximum is about 280 to 320°C.

[Action of the invention]

The propargyl group contained in the curable wholly aromatic polyamide of the present invention is crosslinked by heat, light, etc. to improve the heat resistance and chemical resistance of the polytemide. Furthermore, since the pro-gurgyl group is substituted at the N-position of the amide group, it reduces the cohesive force between polymer chains and improves solubility in various solvents.

Since the alkyl group and/or aralkyl group contained in the polyamide of the present invention is substituted at the N-position of the amide group, solubility in various solvents, particularly low boiling point solvents, is improved. Since these groups are nonpolar, they are effective in reducing cohesion between polymer chains. This effect becomes greater as the alkyl chain length becomes longer and as the aralkyl group becomes more ruky. Furthermore, as the substitution rate increases, solubility also decreases. These alkyl groups and aralkyl groups lower the melting temperature of the wholly aromatic polyamide. That is, similar to solubility, the degree of decrease in the meltability temperature increases as the alkyl chain length increases and the aralkyl group becomes more nordic. Set.

The polyamide of the present invention has a lugyl group and an alkyl group and/or an aralkyl group simultaneously in the polymer chain, so that the solubility and melt plasticization temperature are lower than that of the polyamide containing an alkyl group and/or an aralkyl group. is equivalent to Furthermore, the fully aromatic polyamide after curing exhibits chemical resistance to solvents and at the same time provides excellent heat resistance2. In particular, heat resistance is affected by alkyl groups that reduce heat resistance.
Despite containing aralkyl groups, the heat resistance of the alkyl and/or aralkyl group-substituted wholly aromatic polyamides was also high and comparable to that of propylgyl group-containing wholly aromatic tetraamides.

That is, the wholly aromatic polyamide of the present invention can lower the solubility and melt plasticization temperature without impairing the heat resistance of the wholly aromatic polyamide containing propalyl groups. Although the curing reaction process is not clear, it is assumed that the triple bond in the pro-nilugyl group polymerizes or that the three triple bonds form a cyclization reaction to form a nyoshibenzene ring to give a cured product of fully aromatic polyamide. be done.

〔Example〕

EXAMPLES Hereinafter, in order to further clarify the present invention, the present invention will be explained using Examples, but the scope of the present invention is not limited to these Examples.

Examples 1 to 6 and Comparative Examples 1 to 3 Dimethyl sulfoxide (hereinafter abbreviated as DMSO) 15
Sodium hydride (approx. 60% purity) 1.
214 was added and heated at 70°C for 40 minutes in a nitrogen stream to completely dissolve, and then cooled to 30'C.

The intrinsic viscosity Q Inh defined by the following formula is 3.75.

(Value measured in 97% sulfuric acid at a concentration of 0.5 t/rift at 30°C) Poly(・9 rough ethylene terephthalamide)
(hereinafter abbreviated as PPTA) powder was added to the above reaction system, and a sodium conversion reaction was carried out at 30° C. for 4 hours. Then, 2.5Of methyl iodide was added and the mixture was heated at 30°C for 1
After the reaction for an additional 0.95 hours, propargyl bromide
After adding F and reacting at 30° C. for 2 hours, the reaction was stopped with dilute hydrochloric acid and poured into a large amount of methanol to precipitate a polymer. The precipitated polymer was dried to obtain a powdered product. The propargyl group substitution rate determined by IH-NMR spectrum was 19 mol2, and the methyl group substitution rate was 80 mol%. This is referred to as Example 1.

Similarly, P having an intrinsic viscosity of 3.75 was used in Example 1.
Using PTA, in place of methyl iodide, ethyl bromide 1.92P, propyl bromide 2.17SF, methyl bromide 2.42F, octyl bromide 3.40
Examples 2 to 6 were obtained by repeating the same experiment as in Example 1, except that 5.87 t of octadecyl bromide was used. Table 1 shows the pro-zorugyl group substitution rate and each moderate alkyl group substitution rate. Figure 1 shows the N-pronozorugyl-N'-ethyl PPT obtained in Example 2.
The 0DO43 solution'N-NMR spectrum of A is shown.

Furthermore, for comparison, using PPTA with an intrinsic viscosity of 3.75, N-propargyl PPTA (/1' lonozorugyl group substitution rate 42 mol%; Comparative Example 1), N-propargyl PPTA
(Propyl group substitution rate 97 mol%: Comparative Example 2), and N
-Propargyl-N'-octyl PPTA (Pronorgyl group substitution rate 2 mol%, octyl group substitution rate 88 mol%:
Comparative Example 3) was prepared. Comparative Example 4 uses PPTA as a raw material.

Table 1 shows the solubility of the polymers obtained in Examples 1 to 6 and Comparative Examples 1 to 4 in various solvents, the temperature at which the curing reaction starts and the temperature at which the heat generation of the curing reaction is maximum, as measured by DSC. It showed softening temperature and heat resistance.

The polymers of Examples 1 to 6 were well dissolved in low boiling point solvents. The curing initiation reaction was in the range of 204-230°C, especially for the polymer of Example 4, it was the lowest at 204°C, '& fc
The Tmax was 266°C and the temperature was low, so it was cured at a very low temperature.

Further, a sample in which the above polymer was heated to 320° C. in DSC and immediately cooled was insoluble in all the solvents used in Table 1. The difference between hardening start temperature and softening temperature is approximately 0
It could be easily molded at temperatures ranging from 160°C to about 160°C. Furthermore, the heat resistance was all good at 410°C or higher.

The polymer of Comparative Example 1 is not suitable for thermoforming because it is insoluble in solvents other than DM80 and is also infusible. Heat resistance was 43C1.

The polymer of Comparative Example 2 was soluble in various solvents and softened, so it could be thermoformed. However, 320℃
It does not become insoluble in solvents even after heat treatment. Moreover, the heat resistance was 370°C.

Although the polymer of Comparative Example 3 contained a small amount of propargyl groups, it did not become solvent insoluble even after heat treatment at 320°C, and its heat resistance was as low as 360°C.

Since the PPTA of Comparative Example 4 is insoluble and infusible, wet processing and thermoforming using ordinary solvents are impossible.

Example 7 N-propargyl-N'-butyl PPrA was prepared in the same manner as in Example 1 using PPTA with an intrinsic viscosity of 0.66.
was prepared. Its characteristics are shown in Table 1. Samples heated to 320°C were insoluble in solvent.

Comparative Example 5 Table 1 shows the characteristics of PPTA having an intrinsic viscosity of 0.66.

Examples 8 to 12 Using PPTA with an intrinsic viscosity of 3.75, various N
-7'Lonozorugil-N/-Ethyl PPTA All Examples 1 Prepared in a similar manner. The properties of these polymers are shown in Table 2. It has been shown that the polymer has excellent solubility, has a wide thermoformable temperature range, has good thermoformability, is insoluble in solvents after curing, and has excellent heat resistance.

Comparative Example 6 N-Prozorugil P prepared in the same manner as Example 1
The properties of PTA are shown in Table 2. Thermoforming was not possible since this polymer did not melt and soften.

Example 13 The experiment of Example 1 was repeated using benzyl chloride in place of methyl iodide. The substitution rate and properties are shown in Table 2.

The polymer heated to 320°C was insoluble in the solvent.

Example 14 The experiment of Example 1 was repeated using 1-naphthylmethyl bromide in place of methyl iodide.

The substitution rate and properties are shown in Table 2. The polymer heated to 320°C was insoluble in the solvent.

Example 15 The experiment of Example 1 was repeated using 9-anthrylmethyl bromide in place of methyl iodide, and the properties of the resulting polymer are shown in Table 2. The polymer heated to 320°C was insoluble in the solvent.

Example 16 Propargyl bromide and 9-anthrylmethyl bromide were reacted in the same manner as in Experiment 1 using PPTA having an intrinsic viscosity of 0.40. Table 2 shows the properties of the obtained polymer. When this polymer was heated to 320°C, it was insoluble in the solvent.

Example 17 Poly(metaphenylene isophthalamide) 3? was sodified at 5°C in a reaction system consisting of liquid ammonia and metallic sodium, and then converted into butyl bromide 2.
After adding 429 and reacting at 5°C for 2 hours, 0.95 rf of propargyl bromide was further added and after reacting at 5°C for 2 hours, the reaction was stopped with dilute hydrochloric acid and poured into a large amount of methanol to precipitate a polymer. The resulting polymer had a propargyl group substitution rate of 27 mol% and a butyl group substitution rate of 58 mol%.
It was soluble in acacia, DMSO, DMF, NMP, chloroform, and acetone, but was insoluble in the above solvents after heating to 320°C. The softening temperature is about 100°C, and thermoforming is easy.

Example 18 Poly(barabenzamide) 3? Using the same method as in Example 1, 0.41' of pronozolgyl bromide and 2.42 f of butyl bromide were reacted. The prozorgyl group substitution rate of the product was 8 mol%, and the butyl group substitution rate was 63 mol%.DMSO, DMF, NMP.

Although it was dissolved in chloroform and acetone, it became insoluble in the above solvents after heating to 320°C. The softening temperature was 110°C, and thermoforming was easy.

Example 19 Example 1 using PPTA 3 F with an intrinsic viscosity of 3.75
Propargyl bromide 0.952 to 5 in the same manner as
- phenylpentyl chloride 3.239. The propargyl group substitution rate of the product is 20 mol%, 5
- The conversion rate of phenylpentyl group is sz mol%te,
9 It was soluble in DMSO, THF, chloroform, and toluene, but was insoluble in the above solvents after heating to 320°C. The softening temperature is about 90°C, and thermoforming is easy.

〔Effect of the invention〕

According to the present invention, the solubility of wholly aromatic polyamides, which have poor solubility in organic solvents, can be greatly improved. That is, it becomes soluble not only in high boiling point polar solvents such as DM80 but also in low boiling point solvents such as chloroform and acetone. Further, since it is plasticized at a relatively low temperature, it is easy to perform thermoforming processing in which the difference between the hardening start temperature and the melting softening temperature is large. In addition, after being formed into a film, molded product, etc., it becomes a curable 4-reamer in a short time when exposed to heat, light, etc., and therefore chemical resistance and heat resistance are imparted to the curable wholly aromatic polyamide.

The fully aromatic polyamide of the present invention is a professional, ? Since it contains a Lugyl group, it can be used not only as a thermosetting heat-resistant resin, but also as a photosensitive resin and an electron beam resist. Also,
Since no by-products such as gas or water are produced during curing of the propargyl group, there are also advantages such as the ability to produce molded products with uniform pores and no voids.

[Brief explanation of the drawing]

Figure 1 shows N-propargyl-N'-ethyl P of Example 2.
This is an IHNMR spectrum of PTA. Patent applicant Asahi Kasei Kogyo Co., Ltd. Procedural amendment (spontaneous) June 1986 Commissioner of the Patent Office Kuro 1) Akio Yu 1, Indication of the case 1989 Patent Application No. 109893 2, New title of the invention Curable wholly aromatic polyamide 3, Relationship with the case of the person making the amendment: Patent applicant 1-2-6-4 Dojimahama, Kita-ku, Osaka-shi, Osaka Prefecture, ``Detailed Description of the Invention'' of the specification to be amended. Column 5, Contents of Amendment (1), Specification, page 12, line 1, "antinia" is corrected to "ammonia". (2), page 16, line 9, "propylgyl" is corrected to "propargyl". that's all

Claims (1)

[Claims] 1) Substantially composed of repeating units of the general formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼ and/or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, where X, Y, Z -H(I)0~9
5 mol%, propargyl group (II) 3-90 mol% and (a) general formula Q_1=-C_nH_2_n_+_1 and/or (b) general formula Q_2=-(CH_2)-_m
A curable wholly aromatic daughter polyamide characterized by having 2 to 97 mol% of the group (III) consisting of Ar_4 (in the above formula, Ar_1, Ar_2, and Ar_3 each independently represent a divalent aromatic group). , n, and m are integers in the range of 1≦n≦30 and 1≦m≦6, respectively, and A
r_4 has ▲mathematical formulas, chemical formulas, tables, etc.▼, ▲mathematical formulas,
There are chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼,▲Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ Represents an aromatic group selected from. ) 2) The curable wholly aromatic polyamide according to claim 1, in which Ar_1 and Ar_2 are each paraphenylene groups; 3) The curable wholly aromatic polyamide according to claim 1, in which Ar_1 and Ar_2 are each metaphenylene groups. Fully aromatic polyamide