JPH01500358A - Method for producing spiro(bis)indane copolyamide - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Spiro(bis)indane copolyamides and their production method The present invention relates to spirobiin Dan copolymers, especially spirobiindane copolyamides and methods for producing them It is something.

Polyamides are used in a variety of applications, including the production of fibers, molding and the production of blends with other polymers. are a valuable group of resinous materials useful in the field of Particularly useful for polyamides Characteristic properties are high tensile strength and solvent resistance. In most cases, polyamide is by reaction of amines with dicarboxylic acids or their derivatives or by ring opening of lactams Manufactured by polymerization.

A recent innovation in the production of certain linear polymers is the use of cyclic oligomers as intermediates. It consists in using the composition. For example, US Pat. No. 4,644,053 The cyclic polycarbonate oligomer mixture disclosed in It can be easily converted into linear polycarbonate of extremely high molecular weight. Book The invention relates to a family of novel copolyamides and methods for producing them from cyclic polyamides. A similar method is provided.

In one form, the present invention provides spiro(bis)indanamide structural units and formulas %formula% (wherein R1 is an unsubstituted or substituted alkylene group containing a chain of about 2-20 carbon atoms) It includes a linear spirobiindane copolyamide consisting of the structural unit of

The R1 group is preferably a straight alkylene chain containing about 4-12 carbon atoms.

These are CH2(CH2)2, (CH2)4, (CH2)s and (CH2)n vivalolactam, δ-valerolactam, ε-caprolactam and laurolactam. ε-ka Prolactam is particularly preferred.

The spirobiindanamide structural unit has the formula %formula% (In the formula, each R2 is C1-4 primary or secondary alkyl or halo, respectively. and n is 0-3). Such A group is clearly a 6,6'-bifunctional 3,3,3' which can be substituted or unsubstituted.

3'-tetramethylspiro(bis)indane (hereinafter simply referred to as "spiro" in some cases) The R2 group is derived from methyl, ethyl, Alkyl groups such as propyl or 2-propyl or halo such as chloro or bromo It can be a gen atom. Among the compounds containing the protective R2 group, methyl and chloro are preferred. however, the most preferred compound is an unsubstituted 6.6' compound in which n is 0. - is a difunctional 3,3.3',3'-tetramethylspiro(bis)indane .

The A group and the amide part of the spirobiindane structural unit are bonded by any type of bond. It is possible. Examples of bonds are single bonds, imide bonds (e.g. present in cyclic polyamide-imide). ), ether bonds, unsubstituted or substituted alkylene and arylene bonds and combinations thereof.

Often preferred spirobiindane structural units are of the formula %formula% (wherein A is as defined above, and each of R3 and R4 is independently unsubstituted or is a substituted alkylene or an arylene group other than 0-arylene; Y is; C-O and Z is NH or Y is NH and Z is ;C-O; and m is 0 or 1).

The R3 group can be alkylene or arylene and is most often non- Substituted m- or p-phenylene. The value of m can be 0 or 1; i.e. -〇-R3 moiety may or may not be present.

The R4 group may also be alkylene or arylene. The alkylene group is generally about 2 - Contains 8 carbon atoms, about 2-4 of which are usually linear. these Examples of radicals are ethylene, trimethylene and tetramethylene and their branched forms. It is an isomer. Arylene groups are often preferred and generally about 6-25 carbon atoms, examples of which are m-phenylene, p-phenylene, and the corresponding Tolylene group, 4,4'-biphenylene, 1,4-naphthylene, 1,8-naphthylene keys and formulas (wherein R2 and n are as defined above) derived from phenyl indanol It is the basis. Most preferred are arylene hydrocarbon groups, especially m-phenylene.

Any substituent that does not interfere with the reaction according to the invention is present on the R3 and/or R4 groups. It is possible. Examples of such substituents are halo, nitro and alkoxy.

From the above definitions for Y and 2, preferred copolyamides of the invention are spirobi diamine and another dicarboxylic acid or separate from spirobiindane dicarboxylic acid. It will be clear that it can be derived from the diamine of These are at least one of the expressions Seed lactams and formulas (wherein R, A and m are as defined above, and p is 1 to about 15. ) in the presence of a basic reagent with a composition consisting of a macrocyclic polyamide oligomer of It can be produced by reaction.

In many cases, the macrocyclic polyamide oligomer compositions are composed of oligomers with various degrees of polymerization. It is a mixture of oligomers. However, preparative scale high pressure liquid chromatography Individual oligomers, especially cyclic “monomers,” are isolated by conventional means such as It is often possible to In some cases, higher oligomeric species It is identified as "dimer" etc.

The oligomer composition contains a corresponding diamine and a dicarboxylic acid, as described below. It can be produced from lorido.

Diamines in which R3 is m- or p-phenylene and p is 1 and the corresponding diamines Toro compounds are new compounds: they are filed in a US patent application dated February 27, 1987. No. SN, 20°264.

Nitro compounds (hereinafter sometimes referred to as "bisnitrophenoxy ethers") is halonitrobenzene or dinitrobenzene and spirobiindane bisphenol It is produced by reacting a salt with a dipolar aprotic solvent under alkaline conditions. can be built. Moles of nitro compounds vs. spirobiindane bisphenol salts The ratio is generally about 2.0-2.5:1. Corresponding bis-aminophenoxyates The bis-nitrophenoxy ether is prepared by conventional means such as catalytic hydrogenation. It can be produced by reducing tel. Bis(m-nitrophenoxy ) and bis(m-aminophenoxy)ether. Described and claimed in applicant's own U.S. Patent No. 1ik [RD-17497] has been done.

The production of bis-nitrophenoxy and bis-aminophenoxy ether is carried out as follows. This will be explained using an example.

Example 1 5B145.9 in a reactor equipped with a mechanical stirrer, reflux condenser and nitrogen purge means. g (149 mmol), p-chloronitrobenzene 49. 31 g (31 3 mmol), potassium carbonate 61.68r (447 mmol) and dry dimethyl 700 ml of formamide was charged. Purge the mixture with nitrogen and stir The mixture was heated to 150° C. for 14 hours.

It was then poured into ice water 1,51 kg under rapid stirring and the precipitated 6,6'-bi Su(4-nitrophenoxy)-3゜3.3',3'-tetramethyl-1,1' - Spiro(bis)indane was recrystallized from methyl ethyl ketone. crystalline formation The yield was 73.7 g (90% of theory).

m, p, 200.5-201.5°C. Its structure was confirmed by elemental analysis.

Example 2 5.27 sr (9.58 mmol) of the product of Example 1, 100 mg of platinum oxide and A mixture of 100 ml of water and tetrahydrofuran was pressurized to 50 psi with hydrogen and Shake at room temperature for 3 hours.

The mixture was passed through a passing aid and the mass was washed with methylene chloride. − Vacuum strip the liquid you want to combine to obtain 6.6'-(4-aminophenoxylate). c)-3,3゜3',3'-tetramethyl-1,1'-spiro(bis)indan 4.6r (98% of theory) was obtained, which was recrystallized from toluene to give the pure product. The product was obtained as fine crystals. m.

9.214-215°C. Its structure is confirmed by elemental analysis to be the same as the reactor of Example 1. In a similar reactor, 24.51 g (79.6 mmol) of 5BI, m-dinitroben Zen 27°40sr (163.1 mmol), potassium carbonate 43.93r (3 A mixture of 18.4 mmol) and 175 ml of dimethyl sulfoxide was placed in a nitrogen atmosphere. The mixture was heated to 140° C. for 30 hours under air. The mixture was cooled and diluted with 50% methylene chloride. Dilute with 0 ml and 10% aqueous sodium hydroxide solution, water and sodium chloride. Washed with aqueous solution. The organic phase was removed and the mass was washed with methylene chloride. - cord The product 42.5r was obtained as a thick oil by vacuum stripping the lachrymal fluid. Obtained.

A portion of this oil was transferred onto silica gel using medium pressure liquid chromatography in an ethyl acetate-hexane solution. Purified by chromatography. Purified 6,6'-(3-nitrophenol) c)-3,3゜3',3'-tetramethyl-1,1'-spiro(bis)indan was obtained with a yield of 66%. m, p, 174-175°C.

Its structure was confirmed by elemental analysis.

Example 4 2.5 g (4.5 mmol) of the product of Example 3 were oxidized according to the method of Example 2. Hydrogenated over platinum catalyst. Remove solvent and mix toluene-cyclohexane 6.6'-(3-aminophenoxy)-3 of analytical purity when recrystallized from ,3,3',3'-tetramethyl-1,1'-spiro(bis)indan1. 8r (80% of the theoretical value) was obtained. m, p, 190-197℃ (with decomposition) . Its structure was confirmed by elemental analysis.

formula tetracarboxylic acids and their functional derivatives are used in the preparation of the copolyamides of the invention. is a useful intermediate for the preparation of macrocyclic polyamideimides which can also be used.

These are new compounds, and the applicant's own US patent application NCL [RD-175 No. 96]. Bisimides are the corresponding spirobi Produced by the reaction of bisphenol and nitro-N-alkyl phthalimide can be produced and used for the production of the corresponding bisphenol A reaction products. This can be converted to the dianhydride by methods similar to those used. One In the following example, 115.4 g (50 mmol) of 5B was added to dry dimethylform. A solution of 262 g (102 mmol) of sodium hydride in 100 ml of Muamide Added to the rally in small portions. This mixture was heated to 75°C for 1 hour in a nitrogen atmosphere. , followed by 20.6 g (100 mmol) of 4-nitro-N-methylphthalimide. was added. The resulting mixture was heated to 110°C for 1172 hours, cooled and Pour into twice the volume of cold water. The precipitated solid was treated with toluene and 2% hydroxide. suspended in a mixture of aqueous sodium solution and cooled and treated the mixture. The organic phase of the tear fluid was dried and vacuum stripped. - solids combined is the desired 6,6'-bis(3゜4-dicarboxyphenoxy)-3,3,3' , 3'-tetramethylspiro(bis)indambis-N-methylimide (27 , 07g; 86.5% of the theoretical value). After recrystallization from toluene, its melting point is The temperature was 217.5-218°C. Its structure is shown in proton nuclear magnetic resonance spectroscopy and Confirmed by field desorption mass spectrometry.

1 of this bisimide in 16.7 g of 45% aqueous potassium hydroxide solution and 20 ml of water A solution of 4 g (22°36 mmol) was heated under reflux to remove water and remove methyl amide. The water was removed by distillation and water was added. Heat until the distillate becomes neutral with pH paper. It continued for 4 days. This solution was cooled and slowly added to cold concentrated hydrochloric acid and precipitated. The precipitated tetracarboxylic acid was collected by filtration, dried and purified with 25 m of chlorobenzene. ! and 5 ml of acetic anhydride. Heat under reflux for 2112 hours. On cooling, the desired dianhydride (10.3 g, 77% of theory) precipitated, which was It was washed and dried; it melted at 233-234°C. Its structure is bisui Confirmed by spectral analysis for mido.

Macrocyclic polyamide oligomer compositions substantially inactivate dicarboxylic acid chlorides gradual addition to a solution of the diamine in a neutral organic liquid at a temperature effective to achieve the reaction. wherein the acid chloride and diamine are about 0.8-1 ．． A molar ratio in the range of 2571 is used.

Examples of suitable intermediates for polyamide oligomers are 6°6'-diamino- and 6 ．． 6'-dicarboxy-3,3゜3',3'-tetramethyl-bis-1,1'- It is spiroindane. These compounds are known in the art; Curtis et al. 1. ches, SoC, 1962, 418-421. The corresponding 6,6'-dimethyl compound is oxidized to a dicarboxylic acid, and then the dicarboxylic acid is For the production of amines, treatment with sodium azide and sulfuric acid (i.e. simulated It can be produced by a method (cut reaction).

Any organic liquid that is substantially inert to the diamine and acid chloride used. The body can be used in the production of oligomeric compositions. In the case of aromatic diamines Suitable liquids are halogenated alkanes such as methylene chloride and chloroform; such as dimethylformamide, dimethylacetamide and dimethylsulfoxide aprotic polar solvents such as toluene, xylene and chlorobenzene group hydrocarbons and chlorinated aromatic hydrocarbons; and tetrahydrofuran and ethylene Includes ethers such as recall dimethyl ether. is mostly chlorinated Relatively volatile solvents such as methylene, chloroform and tetrahydrofuran , is preferred because its removal by evaporation after the reaction is complete is convenient.

In this manufacturing process, the acid chloride is gradually added to a solution of the diamine in an organic liquid. be done. Acid chlorides are also added in most cases in the form of solutions in the liquid. child These reaction reagents have a ratio of about 0.8-1.25:1, preferably about 0.95-1.05: used in molar ratios ranging from 1 to 1.

In one embodiment of the invention, the diamine is initially present in the reactor. the In this case, the concentration should be up to about 0.03M to maximize the yield of cyclic product. It is. A second embodiment is to introduce both reaction reagents into the organic liquid at the same time. , so the diamine is also usually added as a solution.

In some cases it may be advantageous to use a hydrogen chloride acceptor in this reaction. suitable Hydrogen chloride acceptors include alkali metal carbonates and tertiary amines, preferably sodium carbonate. medium strength bases such as triethylamine, triethylamine, and pyridine. Applicable The receptor is generally present in the reactor from the beginning or simultaneously with the acid chloride. It is introduced into the reactor so that it is present together with the diamine. The ratio is favorable is at least a stoichiometric amount per calculated equivalent of hydrogen chloride evolved, most often about 1-3 equivalents.

Use any reaction temperature effective to accomplish the reaction between the diamine and the dicarboxylic acid chloride. obtain. Elevated temperatures such as in the range of about 35-100°C are usually satisfactory; 0-80°C is preferred.

The above-mentioned macrocyclic polyamide oligomer composition i also includes linear oligomers and polymers. Also contains molecular weight polymers (i.e., linear polyamides with a degree of polymerization greater than about 20) It is possible. Any high molecular weight polymer is typically flash chromatographed on silica gel. It can be removed by conventional means such as graphics. Isof of the present invention When using talloyl dichloride and bis-aminophenoxyether, the cyclic Product yields are typically 90% or greater.

The preparation of macrocyclic polyamide oligomer compositions is illustrated by the following examples. .

Example 6 Under nitrogen atmosphere in a reactor equipped with a septum cap, reflux condenser and nitrogen purging means. 5 ml of refluxed chloroform was charged. in 5 ml of dry tetrahydrofuran. Diamine 505.4 (1,03 mmol) of Example 2 and triethylamine 2 A solution of 13 mg (2.11 mmol) and isophore in 5 ml of dry chloroform. A solution of 209 g (1.03 mmol) of taloyl chloride was added through two syringes. Additions were made simultaneously over a period of 172 hours. Reflux was continued for 5 minutes, then the mixture was chloroformed. Dilute with 50 ml of form, wash with dilute aqueous hydrochloric acid solution and sodium chloride solution, and remove the phase. The desired cyclic polyamide is separated through separation paper and vacuum stripped. Om-p-24 obtained 520 mg of oligomer mixture (theoretical value 8096) 5-285℃. It is possible to obtain a degree of polymerization of up to about 15 by high pressure liquid chromatography. The monomeric to hexameric species have an approximate ratio of 78:28: It was recognized that the ratio was 8:4:2:1. The presence of monomers and zffi isomers Confirmed by field desorption mass spectrometry.

The cyclic monomer species were isolated by preparative scale high pressure liquid chromatography.

The species identification was also confirmed by field desorption spectroscopy.

Example 7 Chloroform was refluxed in a nitrogen atmosphere in a reactor system similar to that of Example 6. 62ml was charged. Diamine of Example 4 in 10 ml of dry tetrahydrofuran ig (2.04 mmol) and triethylamine 4901Ig (4.85 mmol). isophthaloyl chloride 5001 in 10 ml of dry chloroform g (3.46 mmol) of solution were added simultaneously over 40 minutes. Continue reflux for 15 minutes. then dilute the mixture with methylene chloride, wash with dilute aqueous hydrochloric acid and vacuum 1.33 g of the desired macrocyclic polyamide oligomer mixture after tripping I got it. It is possible to outline monomers or heptamers by high-pressure liquid chromatography. Ratio 18°9:5.6:1.11.6:1. 3go, 9:1 shown to contain Ta.

Example 8 Diamine 1+r of Example 2 (2 mmol) in 36 ml of dry tetrahydrofuran A solution of 410 mg (4 mmol) of triethylamine and of 410 mg (2 mmol) of inphthaloyl chloride in 5 ml of chloroform. The solution was added over 172 hours. After treatment as in Example 6, high pressure More than 90% macrocyclic polyamide oligomer by liquid chromatography A product is obtained which is shown to contain -, with the monomeric to octameric species having an approximate ratio of 1B, 4:1.9:4.5:2.9:2.0:1.6; exists at 1°2=1 It was.

Example 9 Isophthaloyl chloride 2 in 5 ml chloroform according to the method of Example 8 A solution of 2 mmol of the diamine of Example 2 and 650 μm of sodium carbonate (6 mmol) and 200 ml of dry chloroform. Finishing treatment contains approximately 90% macrocyclic products, with monomeric to hexameric species having an approximate ratio of 11 ．． Tan solid 1 which is present at 0:3.6:2.3:1.4F1.271 ．． 2 g of isophthaloyl in 5 ml of chloroform was obtained according to the method of Example 8. A solution of 2 mmol of chloride is dissolved in dry chloroform in the absence of a hydrogen chloride acceptor. Added to a solution of 2 mmol of the diamine of Example 2 in 77 ml. 90% macro Contains cyclic products, with monomeric to hexameric species in an approximate ratio of 16.2:3°1:1.7: 1. 900 μl of a yellow solid was obtained, present in a 1:1 ratio of 1:1.

Example 11-12 The method of Example 8 was repeated using 4°4'-biphenyldica in place of isophthaloyl chloride. rubonic acid chloride and 1.1.3-trimethyl-3-phenylindan-4', 6-dicarboxylic acid chloride was used in each case. These products are It was shown that it contains molecular species in an approximate ratio of .

Example 11 - Monomer to decamer 7.4 near, 3:4.4:3.1:2.3:2.1:1. B:1.4:1.2: 1 Example 12-monomer to heptamer 4.4:5.2:11.3:8.3:3.3:1.7:1 Example 13 A reactor containing 12 ml of dry methylene chloride at reflux temperature was charged with 6t 6'-diamino-3,3,3'.

3'-tetramethyl-1,1'-spiroindan 200 μ (0.65 mmol) and a solution of 1321 g (1°3 mmol) of triethylamine and 4 methylene chloride. A solution of 133 ag (0.65 mmol) of inphthaloyl chloride in ml Added over 1/2 hour with stirring under nitrogen. Cool the mixture to room temperature , diluted with 50 ml of methylene chloride, twice with dilute aqueous hydrochloric acid solution and then diluted with aqueous sodium chloride solution. Washed once with solution, dried over magnesium sulfate and vacuum stripped. did. Approximately by high pressure liquid chromatography and field desorption mass spectrometry analysis 50% macrocyclic polyamide oligomer and the remainder linear oligomers and polymers A white solid was obtained which was shown to contain some polymer.

Example 14 The reactor is equipped with a septum cap, a magnetic stirrer, a reflux condenser and nitrogen purging means. Diamine 840 of Example 2 in 20 ml of chloroform refluxed in a nitrogen atmosphere (1,71 mmol) and a solution of pyridine 270sig (3,42 mmol) was loaded. 6.6'-dicarboxy-3,3 in 14 ml of dry chloroform ,3',3'-tetramethyl-1゜1'-spiro(bis)indane diacid A solution of 1 g (1.71 mmol) of loride was added via syringe over a period of 1 hour.

Refluxing was continued for 15 minutes, after which the mixture was diluted with 100 ml of chloroform and diluted with dilute hydrochloric acid. Wash with aqueous solution and sodium chloride solution, dry over magnesium sulfate, and vacuum stripping to obtain the desired macrocyclic polyamide oligomer mixture. 850 mg of the compound was obtained.

Examples 15-17 According to the method of Example 7, various diamines were prepared in equimolar amounts of 6°6'-dicarboxy- 3,3,3',3'-tetramethyl-1,1'-spiro(bis)indan and Made it react. After washing, the organic phase was dried over magnesium sulfate, washed and vacuumed. Stripped. These products can be analyzed by high pressure liquid chromatography and electrophoresis. Macrocyclic amide polymers with a degree of polymerization of 1 to 3 were determined by field desorption mass spectrometry analysis. It was shown that it consists of sesame. The diamine used in Example 15-m- Dilene diamine; Example 16-4-aminophenyl ether; Example 17-2. 3.3 in 280 ml of 2-bis(4-aminophenyl)0-dichlorobenzene 1.03 g (4.54 mmol) of 1-diaminobenzanilide and sodium pyrophosphate Example of a solution of 15-g thorium in 30 ml of warmed 0-dichlorobenzene A solution of 2.72 g (4.54 mmol) of dianhydride No. 5 was stirred under reflux. The addition took 172 hours. Reflux was continued for 2 hours, and the water was removed and the solvent was distilled off. A total of 180 m1 was removed. The solution is cooled and placed under rapid stirring. Injected into 500 ml of ethanol.

The precipitated solids were extracted with acetone in a Soxhlet extractor. The residue from this extraction The residue was linear polyamideimide.

Evaporation of acetone from the extract revealed the main properties by field desorption mass spectrometry analysis. A white powder was obtained which was shown to be composed of macrocyclic polyamideimide polymers. Ta. The yield was about 70% of theory.

Example 19 1 g of trimellidic anhydride chloride (2.04 ml) in 2 ml of 0-dichlorobenzene 1 m of 0-dichlorobenzene to a solution of 15 μm of sodium pyrophosphate A solution of the diamine 430+ag (2.04 mmol) of Example 2 in 100 The mixture was added at a temperature of 0.degree. C. with stirring. This mixture was heated at 180°C for 1 hour. - 5 ml of dichlorobenzene was added.

Water and solvent were removed by distillation to a total of 5 ml, then O-dichloroben The addition of zene and distillation were repeated. Cool this solution and methane under rapid stirring. Injected into 50 ml of nord. The precipitated solid is passed through a high-pressure liquid chromatograph. Mainly macrocyclic polyamide A substance t, zgc (91% of the theoretical value) which was shown to consist of a mid-dimer was obtained.

Basic reagents that can be used in the method of the invention include alkali and alkaline earth metals and Inorganic bases such as hydrides, hydroxides, carbonates and alkoxides, and tetra Alkylammonium hydroxides, guanidines and Grignard reagents and Olga Includes strong organic bases such as organometallic compounds including nolithium reagents.

Alkali metal hydrides are preferred, especially sodium hydride.

The reaction of lactam, basic reagent and macrocyclic polyamide oligomer composition is typical Typically, this is done at elevated temperatures. Generally, a lactam and a basic reagent are reacted. to form an anionic intermediate at a temperature of about 25-200°C, preferably about 90°C. Temperatures in the range of 50°C are suitable, and this intermediate is then heated in the range of about 200-300°C. react with the oligomeric composition at ambient temperatures. Proportion of lactam and oligomer composition is not critical but may vary according to the desired stoichiometry of the product.

The preparation of the linear copolyamides of the present invention is illustrated by the following examples.

Example 20 Macrocyclic polyamide oligomer mixture 7 similar to the oligomer mixture of Example 6 ．． 5g, caprolactam 7.5g and sodium hydride 237■ 15 mol % based on the total weight) in a test tube at 140°C in a nitrogen atmosphere for 1 hour. During heating, melting occurred and hydrogen was evolved. Then raise it to 265℃ Heat for 10 minutes and cool. The solid product is removed by breaking the test tube. A portion of it was dissolved in chloroform and treated with trifluoroacetic anhydride. Upon treatment, the polymer dissolved. Analysis of this solution by gel permeation chromatography is a copolyamide with a number average molecular weight of 22,000 and a weight average molecular weight of 47,000. showed the existence of

Example 21 1 g of the crude macrocyclic polyamideimide oligomer mixture of Example 18, Caprola A mixture of 10 g of lactam and 290 mg of sodium hydride was added in a test tube under nitrogen atmosphere. During heating to 150°C for 1/2 hour, melting occurred and hydrogen was evolved. . It was then heated to 230°C for 12 minutes and cooled. Tetra solid product When extracted with hydrofuran, the insoluble product has a weight average molecular weight of 27.000. A linear copolyamideimide remained.

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Claims (20)

[Claims] 1. Spiro(bis)indanamide structural unit and formula (I) ▲ Numerical formula, chemical formula, table, etc. ▼ (where R1 is an unsubstituted or substituted atom containing a chain of about 2-20 carbon atoms) A linear spirobiindane copolyamide consisting of structural units of (alkylene group). 2. Spiro(bis)indanamide unit has formula (III) ▲ Numerical formula, chemical formula, table, etc. Yes▼(In the formula, A is (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and each R2 is C1-4 is primary or secondary alkyl or halo; each of R3 and R4 is independently unsubstituted or a substituted alkylene or an arylene group other than o-arylene; Y is the formula ▲ , chemical formulas, tables, etc. ▼ and Z is NH or Y is NH and Z is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼; m is 0 or 1; and n is 0- 3). 3. 3. The copolyamide according to claim 2, wherein n is 0. 4. Y is NH; Z is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼; and R4 is A, m- Phenylene, 4,4'-biphenylene or (IV) ▲ There are mathematical formulas, chemical formulas, tables, etc. The copolyamide according to claim 3, which is ▼. 5. A compound according to claim 4, wherein R3 is m- or p-phenylene and m is 1. polyamide. 6. A copolyamide according to claim 5, wherein R4 is m-phenylene. 7. 7. The copolyamide according to claim 6, wherein R1 is (CH2)5. 8. Copolyamide according to claim 7, wherein m is 0 and R4 is m-phenylene. Do. 9. 9. The copolyamide according to claim 8, wherein R1 is (CH2)5. 10. Y is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, Z is NH, R4 is m- or p- 4. A copolyamide according to claim 3, wherein phenylene and m are zero. 11. A copolyamide according to claim 10, wherein R4 is m-phenylene. 12. The copolyamide according to claim 11, wherein R1 is (CH2)5. 13. formula (V) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ At least one type of lactam and macro Reacting with a composition consisting of a cyclic polyamide oligomer in the presence of a basic reagent A method for producing a copolyamide according to claim 1, comprising: 14. Polyamide oligomer formula (VI) ▲Mathematical formulas, chemical formulas, tables, etc.▼(In the formula, p is 1 to about 15. ) The method according to claim 13. 15. 15. The method according to claim 14, wherein the basic reagent is an alkali metal hydride. 16. 16. The method of claim 15, wherein the reaction temperature is in the range of about 90-300<0>C. 17. 16. The method according to claim 15, wherein R1 is (CH2)5. 18. Y is NH, Z is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, R3 is m- or p- 18. The method of claim 17, wherein phenylene, R4 is m-phenylene and m is 1. 19. Y is NH, Z is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, R4 is m-phenylene 18. The method of claim 17, wherein m and m are zero. 20. Y is ▲There are mathematical formulas, chemical formulas, tables, etc.▼, Z is NH, and R4 is m-phenylene. 18. The method of claim 17, wherein m and m are zero.