JPH0292931A - Wholly aromatic copolyimide ester and production thereof - Google Patents

Abstract

PURPOSE:To obtain the subject compound, having specific structural units and capable of providing electrical and electronic parts excellent in MD and TD dimensional stability with a high accuracy. CONSTITUTION:A thermoplastic wholly aromatic copolyimide ester having structural units expressed by formulas I, II, III and IV (X is O or CO; group X in units expressed by formula II and imide groups and two carbonyl groups in units expressed by formula IV each are mutually present at the p- or the m-positions; both terminals of the units expressed by formulas I, II, III and IV are linked through ester bonds; n is 0 or 1) at (20:80)-(90:10) molar ratio of the units expressed by formula I:total units expressed by formulas II, III and IV and (0.1:99.9)-(99.9:0.1) molar ratio of the units expressed by formulas II:III in substantially equimolar amounts of the total units expressed by formulas II and III with the units expressed by formula IV when X is O and at (2:80)-(90:10) molar ratio of the total units expressed by formulas l and II to the total units expressed by formulas III and IV and (0.1:99.9)-(99.9:0.1) molar ratio of the units expressed by formulas I:II in substantially equimolar amounts of the units expressed by formulas III with IV when X is CO with 1.0 to 1.0X10<5>Pa.S melt viscosity at 300-400 deg.C under 0.025MPa shearing stress.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a thermoplastic wholly aromatic copolyimide ester with excellent dimensional stability and a method for producing the same. More specifically, the present invention relates to a novel polyimide ester suitable for use in electrical and electronic parts that require excellent dimensional stability and dimensional accuracy both in the flow direction (MD) and in the transverse direction (TD).

[Conventional technology]

In recent years, thermoplastic resins that have an extremely small coefficient of linear expansion in MD have become known. These are a group of resins called thermotropic liquid crystal polymers.
Examples include wholly aromatic copolyesters described in Japanese Patent No. 77691 and the like.

These polyesters have a small linear expansion coefficient in the MD, but in the TD, the linear expansion coefficient is comparable to that of ordinary thermoplastic resins, and it cannot be said that the dimensional stability is sufficient.

In addition, polyimide esters containing imide bonds and ester bonds in the polymer molecule are well known. For example, a polyimide ester with high heat resistance is disclosed in U.S. Pat. The one with improved heat resistance, mechanical properties, and processability is disclosed in JP-A-55-84.
No. 326 has a high modulus of elasticity, published in Japanese Patent Application Laid-open No. 58-11.
No. 3222 has a tough version published in Japanese Unexamined Patent Publication No. 60-45
Although high rigidity polyimide esters are described in Publication No. 31, these polyimide esters could not be said to have sufficient dimensional stability.

[Problem that the invention seeks to solve]

The object of the present invention is to provide a novel thermoplastic wholly aromatic copolymerized polyimide ester having excellent dimensional stability and dimensional accuracy in both MD and TD, and a suitable method for producing the same.

[Means for solving problems]

The present inventors conducted extensive research to solve the above problems, and found that the above object could be achieved by a polyimide ester obtained by introducing a specific imide group into an aromatic polyester, thereby completing the present invention. reached.

That is, the present invention provides structural units -0-σ represented by the following formulas ■, ■, ■, and ■.
co- (I) -0-■ki0→-w-o-(m) (in the formula, n is O or 1) (here, X is 0 or CO, and the X group and imide group of the unit The two carbonyl groups of unit I,
Both ends of , and ■ are connected by an ester bond. ), shear stress 0.025 MPa (megapascal),
Melt viscosity at 300-400°C is 1.0-1. OX
A thermoplastic wholly aromatic copolymerized polyimide ester having an excellent dimensional stability of I O' Pa-5 (Pascal seconds) is prepared.

The polyimide ester of the present invention is thermoplastic and MD
, TD both have excellent dimensional stability and dimensional accuracy.

The polyimide ester of the present invention essentially comprises the above (1),
The ratio of each structural unit consisting of (It), (III) and (IV) is as follows: When X is 0, the molar ratio of I:I+I+IV is 20:
80-90:10, molar ratio of ■:■ 0.1:99
°9~99.9:0.1. II+III and ■ are substantially equimolar, and when X is CO, I + I[: lI+IV (7) -1
The molar ratio of 20:80 to 90:10, the molar ratio of 2:2 to 0.1:999 to 99.9:0.1, and 2 and 2 are substantially equimolar.

If the molar ratio of the structural units is outside this range, the desired dimensional stability and dimensional accuracy cannot be fully satisfied. In addition, the molar ratio of the imide-containing component (1) to the other component I
99.5-20: 80. In this case, if the molar ratio (2) is less than 0.1, there will be no effect of improving directionality such as coefficient of linear expansion and shrinkage, and if it exceeds 30 mol%, problems such as a decrease in strength will occur.

Moreover, the polyimide ester of the present invention has a shear stress of 0.02
5MPa, melt viscosity at 300-400'C is 1
．． 0-1. It has OX 10' Pa-5, is thermoplastic, and can be easily molded by injection molding or the like.

The polyimide ester of the present invention is, for example, the following ■'V, ■'
The compound represented by and ■′ is y+o-ecooz+
(1') Yak-@÷@→rO-Ys (I
II') (in the formula, n is O or 1) hydrogen or R, C01R*C01R3CO1R4CO or R8C0, R1, Rg, R1, R4 and R3
each represents a hydrocarbon group having 1 to 18 carbon atoms, 20,
z2 and 2° each represent hydrogen or a hydrocarbon group having 1 to 18 carbon atoms, and the yto group and imide group of compound V,
The two carbonyl groups of compound (1) and (2) are located at para or meta positions with respect to each other. )1' :V+II
The molar ratio of I' + IV' is 20:80 to 90:10
, the molar ratio of v:m' is 0.1:99.9 to 99.9:0
．． 1SV+IN' and ■' are reacted in substantially equimolar amounts to give the general formula y, oz.

(p is a code of 1 to 5, and q is a code of 1 to 3).

In addition, compounds represented by 1', V', III' and ■' below, (wherein, Vls Yt, Yl, Y4 and Y, respectively, are OQ OYs (III') (in the formula, n is O or l) ~99.9: 0.1, reacted so that v' + m' and ■' are substantially equimolar, and the imide ring of compound V' It can also be produced by removing a compound represented by the general formula y, oz, (p is a code of 1 to 5, q is a code of 1 to 3).Furthermore, the following I, VI, Ill
' and ■', (wherein, Ylx Yz
, Y3, Y4 and Y are each hydrogen or RICO
, RzCOlR, C01R4CO or R, CO, R,, R1, R3, R4 and R3 each represent a hydrocarbon group having 1 to 18 carbon atoms, and zl, z! and 2. each represents hydrogen or a hydrocarbon group having 1 to 18 carbon atoms.

In addition, the Y2O group and amide group of compound V′, and the compound
The two carbonyl groups ' are located at para or meta positions with respect to each other. ) I' : V' + II ['-MV' molar ratio is 20
: 80~so:to%v':m' molar ratio is 0.11
9.9y, o-0cooz, (bi) Y, o-@←@→tsuOYs (m') (in the formula, n is 0 or 1) (in the formula, Yl, Y4, Y, and Y are each , hydrogen or R, CO1R, CO1RsCO or R, CO, and R1, Ra, R3 and R1 each have 1 to 1 carbon atoms.
18 hydrocarbon groups, Z,, zx, 2. and z4
each represents hydrogen or a hydrocarbon group having 1 to 18 carbon atoms, and the Z400C group and amide group of compound (1) and the two carbonyl groups of compound (2) each exist in the para or meta position with respect to each other. ) I' VI: m' + IV' molar ratio is 20:
80-9o:io, I':VI molar ratio is 0.1=
99.9 to 99, 9: 0.1, reacted so that ■' and ■' were substantially equimolar, and the general formula YpOZq
(P is 1.4.5, q is a code of 1 to 4) can be produced by eliminating the compound.

Furthermore, the compounds represented by 1', Vl', III' and
ToC → "DYs [■'] (In the formula, n is 0 or 1) (In the formula, Yls '1m, Y, and Y6 are respectively,
Hydrogen or RICO, R4GO1RsCO or R,C
O, and R6,1, ns and R& each have 1 carbon number
~18 hydrocarbon groups, 28.2! , z3 and z4
each represents hydrogen or a hydrocarbon group having 1 to 18 carbon atoms, and the z, ooc group and amide group of compound (1), and the two carbonyl groups of compound (2) each exist in the para or meta position with respect to each other. . ) 1' + VI' : m' + ■' molar ratio is 20:8
0-90:10. The molar ratio of I':VI' is 0.1:
99.9 to 99.9: 0.1, react so that ■' and ■' are substantially equimolar, imide cyclization of compound ■' and general 2 Y, OZ, (p is 1.4 .5, q is 1 to 4
It can also be produced by eliminating a compound represented by the symbol ).

As raw material 1', parahydroxybenzoic acid or a compound obtained by acylating it with R, a COOH derivative (R3 has the same meaning as above), or parahydroxybenzoic acid with ZIOH (Z+ has the same meaning as above). has the same meaning as ). Among these, parahydroxybenzoic acid and paraacetoxybenzoic acid are preferably used.

As the raw material (V), the above-mentioned imide compounds obtained by various production methods are used. As a manufacturing method, for example, the general formula [wherein Y and Y have the same meanings as above] is used.

] is produced, which is then dehydrated,
By cyclization, an imide compound of formula V is obtained.

As the raw material [VI), the above-mentioned imide compounds obtained by various production methods are used. As a manufacturing method, for example, it is represented by the general formula [wherein Y has the same meaning as above],
A hydroxyphthalic anhydride derivative and a -111u formula [wherein yg has the same meaning as above. ) by the reaction with an aromatic amino compound derivative represented by the general formula [wherein Y has the same meaning as above],
A hydroxyphthalic anhydride derivative and the general formula [wherein, z
2 has the same meaning as above. ) by reaction with an aromatic amino compound derivative represented by the general formula [wherein, Y has the same meaning as above]. The imide compound of the formula (1) can be obtained by producing an amic acid represented by the following formula, followed by dehydration and cyclization.

The reaction between the above-mentioned hydroxyphthalic anhydride derivative (A) and aromatic amino compound derivatives (B) and [C] proceeds easily by simply bringing both components into contact, preferably in the form of a solution. The 0 reaction that produces (V) and (VI) and usually precipitates proceeds satisfactorily at room temperature, but the preferred reaction temperature conditions are in the range of -50°C to 100°C, and in many cases 0 to 80°C. 0 reactions carried out in the °C range proceed in a short time and usually do not require the presence of special catalysts.

Various methods are used for the cyclodehydration of the amic acid shown above. Specific examples include (1) a method of cyclodehydration in the coexistence of a carboxylic acid anhydride, (2) a method of cyclodehydration with an inorganic acid having a dehydrating effect and a condensate thereof, and (3) a method of cyclodehydration in the presence of an acid catalyst. The azeotropic dehydration cyclization method below,
(4) A cyclization method using a special dehydrating agent, (5) A cyclization method using heating, and the like.

Imide compounds of formula (V) [VI) in which yz, Y, and Z4 are groups other than hydrogen can be reacted using starting materials of formula (A) and formula CB) having corresponding substituents. It can also be obtained by the formula [V) (V
l) (7)Y! , Y3 and z4 are hydrogen.

As the raw material [■]', hydroquinone, 4,4-dihydroxybiphenyl, or a compound acylated using R, C00COR4 or RaC00CORs is used. Preferably hydroquinone, 4.
4'-dihydroxybiphenyl, 1°4-diacetoxybenzene, 4,4'-diacetoxybiphenyl, etc. are used.

Raw materials ■' include terephthalic acid derivatives, isophthalic acid derivatives, or each of them (z20), ZsOH (Zz, Z
, has the same meaning as above. ) is used. Preferably, terephthalic acid, isophthalic acid, dimethyl terephthalate, dimethyl isophthalate, etc. are used.

In compounds I', III', IV', Yl, Y
, , Y, and ZI% Z! , and compounds in which Zs is a group other than hydrogen may be synthesized individually or simultaneously.

Compound 1', V or VI (V' or Vl'), III
The reactions of ' and
The reaction time at Torr is usually several minutes to several tens of hours depending on the melt viscosity of the target polymer.
Several minutes to avoid polymer degradation at reaction temperature
Preferably, the duration is several hours.

Although a catalyst is not particularly required for the above reaction, a suitable polycondensation catalyst such as antimony oxide, germanium oxide, etc. can be used.

Regarding the addition timing of the reaction raw materials, the reaction may be carried out by mixing all the reaction raw materials in the first stage, or the reaction may be carried out by changing the addition timing.As a result, the composition distribution of the polyimide ester can be controlled. It is possible to arbitrarily control from random copolyester to block copolyester.

The reaction was carried out as described above, and the formula vpoz, (p, q are 1
The reaction is completed by eliminating the compound represented by 5). Y, middle R, and 2. Specific examples include methyl, ethyl, n-butyl, t-butyl, n-amyl, neo-pentyl, n-hexyl, 1so-octyl, nonyl, decyl, phenyl, tolyl, naphthyl, allyl, cyclopentyl, Mention may be made of groups such as cyclohexyl.

The polyimide ester obtained by the present invention can be injection molded at normal molding temperatures (below 400°C), and can be molded using any molding method commonly used for thermoplastic resins, such as extrusion molding, compression molding, and spinning. is also possible. moreover,
The molded article can also be heat treated at a suitable temperature and time.

Therefore, the polyimide ester of the present invention is useful as a material for precision injection molded parts, filaments, films, sheets, etc., which require dimensional accuracy and dimensional stability.

29.54 g (0.18 mol) of hydroxyphthalic anhydride
and p-aminophenol 19.64 g (0.18 mol)
Dissolve in 200ad of DMF. Immediately after the start of DMF reflux, yellow powder crystals were precipitated. After refluxing for 2 hours, it was cooled. After filtering and washing with DMF, washing with acetone and drying, the zero elemental analysis values were as follows. Theoretical value (actual value) C: 65.9 (65,8), H: 3.
6 (3,6), N: 5.5 (5,5) [Example] The present invention will be explained in detail based on Examples below.
The present invention is not limited to this.

Examination Example 1 Hydroxyphthalic anhydride 4.10 g (0,025 mol) p-aminophenol 2. ．． 73g (0,025mol) methyl ethyl ketone 100jd with double helical wings 1, 44! The compound V' (Y!
, Y2:H) was formed.

Next, p-hydroxybenzoic acid 207.18 g (1.5 mol) dihydroxybiphenyl 79.14 g (0.475 mol) terephthalic acid 62.30 g (0.375 mol) isophthalic acid 20.77 g (0.125 mol) acetic anhydride. 2
55.23 g (15 mol) was added, and the temperature was raised to 150° C. with stirring under a nitrogen stream to distill out methyl ethyl ketone. After refluxing acetic anhydride for 1 hour, the temperature was raised to 350° C. for 90 minutes, water and acetic acid were distilled off, and cyclodehydration and polymerization of amic acid proceeded. After that, the system is 1
Reduce the pressure to 00 Torr for 30 minutes, then reduce the pressure to 2 Torr.
The pressure was reduced to , and polymerization was allowed to proceed for 20 minutes. The obtained polymer was taken out in a molten state.

The results of elemental analysis of the obtained polymer were as follows.

Calculated value (%) Actual value (%) 7'2. ．． 6 72.5 3.5 3.2 0.1 0.1 These results show that a polyimide ester having the structural unit and composition represented by the following formula was obtained.

-G-0-@C0-)--・ Koka type flow tester (Shimadzu flow tester CFT-5
The melt viscosity at 370°C was measured using a die with a diameter of 1.0 mm and an L/D -10 at an extrusion pressure of 10 kgf/cd and found to be 54 Pa-s.

When this polymer was observed using a Nikon polarizing microscope equipped with a Linkam hot stage, optical anisotropy was observed in the molten state.

Example 2 12.31 g (0,075 mol) of hydroxyphthalic anhydride, 8.18 g (0,075 mol) of p-aminophenol, and 100 m of methyl ethyl ketone were charged into a No. 1, 41 autoclave equipped with double helical blades, and the mixture was heated at room temperature. Stir for an hour and add compound V' (Yz, Y
A precipitate of s:H) was formed.

Next, P-hydroxybenzoic acid 207.18 g (1.5 mol) dihydroxybiphenyl 79.14 g (0.475 mol) terephthalic acid 62.30 g (0.375 mol) isophthalic acid 20.77 g (0.125 mol) acetic anhydride. 2
55.23g (2.5 mol) was added, and under a nitrogen stream,
The temperature was raised to 150°C without stirring, and methyl ethyl ketone was distilled out. After refluxing acetic anhydride for 1 hour, 90
The temperature was raised to 350°C for 1 minute, water and acetic acid were distilled off, and cyclodehydration and polymerization of amic acid proceeded. After that, the pressure inside the system was reduced to 100 Torr for 30 minutes, and then 2 T.
The pressure was reduced to orr, and polymerization was allowed to proceed for 13 minutes. The obtained polymer was taken out in a molten state.

The results of elemental analysis of the obtained polymer were as follows.

CHN Calculated value (%)? 2.2 3.5 0.3 Actual value (%
) 72.0 3.4 0.3 These results show that a polyimide ester having the structural unit and composition represented by the following formula was obtained.

-4-0-@C0-)-a.

-G-COGGO-+-rs The melt viscosity of this polymer was measured using the same test method as in Example 1, and was 191 Pa-s, indicating optical anisotropy in the molten state.

The IR spectrum of the obtained polymer is shown in FIG.

Example 3 20.52 g (0.125 mol) of hydroxyphthalic anhydride, 13.64 g (0.125 mol) of m-aminophenol, and 100 yd of methyl ethyl ketone were charged into a No. 1,41 autoclave equipped with double helical blades, and the mixture was heated at room temperature. Stir for an hour and add compound V'(yz, Y
A precipitate of s:H) was formed.

Next, p-hydroxybenzoic acid 207.18 g (1.5 mol) dihydroxybiphenyl 46.55 g (0.25 mol)
mol) Hydroquinone 13.76 g (0; 125 mol) Terephthalic acid 41.53 g (0.25 mol) Isophthalic acid 41.53 g (0.25 mol) Acetic anhydride 2
55.23g (2.5 mol) was added, and under a nitrogen stream,
The temperature was raised to 150°C while stirring, and methyl ethyl ketone was distilled out. After refluxing acetic anhydride for 1 hour, 90
The temperature was raised to 350°C for minutes, and water and acetic acid were distilled off.
Cyclodehydration and polymerization of amic acid proceeded. After that, the pressure inside the system was reduced to 100 Torr for 30 minutes, and then to 2 Torr.
The pressure was reduced to r, and polymerization was allowed to proceed for 5 minutes. The obtained polymer was taken out in a molten state.

The results of elemental analysis of the obtained polymer were as follows.

CHN -4-0-@CO+6° -G-CO-@C0-)-+.

Calculated value (%) 71.2 3.4 0.5 Actual value (%
)? 1.2 3.3 0.5 These results show that a polyimide ester having the structural unit and composition represented by the following formula was obtained.

The melt viscosity of this polymer was measured using the same test method as in Example 1, and was 310 Pa-s, indicating optical anisotropy in the molten state.

Example 4 Hydroxyphthalic anhydride 41.03 g (0,25
mol) 27.28 g (0.25 mol) of p-aminophenol and 100 d of methyl ethyl ketone were charged into a No. 1, 42 autoclave equipped with double helical blades, stirred at room temperature for 1 hour, and the compound V' (yz, Y
, : A precipitate of H) was formed.

Then p-hydroxybenzoic acid 207.18 g (1.5 mol) dihydroxybiphenyl 46.55 g (0.25 mol) terephthalic acid 41.53 g (0.25 mol) isophthalic acid 41.53 g (0.25 mol) 255.23 g (2.5 mol) of acetic anhydride was added, and the temperature was raised to 150°C under a nitrogen stream without stirring to distill out methyl ethyl ketone. After refluxing acetic anhydride for 1 hour,
The temperature was raised to 350°C for 90 minutes, water and acetic acid were distilled off, and dehydration cyclization and polymerization of amic acid proceeded. After that, the pressure inside the system was reduced to 100 Torr for 30 minutes, and then
The pressure was reduced to Torr, and polymerization was allowed to proceed for 2 minutes. The obtained polymer was taken out in a molten state.

The results of elemental analysis of the obtained polymer were as follows.

CHN Calculated value (%)? 0.9 3.3 1.0 Actual value (%
) 70.7 3.1 0.9 These results show that a polyimide ester having the structural unit and composition represented by the following formula was obtained.

-4-0-@CO+411 4-CO-eCO 呵.

The melt viscosity of this polymer was measured using the same test method as in Example 1, and was 462 Pa·3, indicating optical anisotropy in the molten state.

Example 5 12.31 g (0,075 mol) of hydroxyphthalic anhydride, 8.18 g (0,075 mol) of p-aminophenol, and 100 d of methyl ethyl ketone were charged into a No. 1,41 autoclave equipped with double helical blades, and the mixture was heated at room temperature. Stir for an hour, compound V′Crt,
A precipitate of Ys:■) was produced.

Next, p-hydroxybenzoic acid 172.65 g (1.25 mol) dihydroxybiphenyl 102.42 g (0.55 mol) terephthalic acid 74.76 g (0.45 mol) isophthalic acid 29.07 g (0.175 mol) acetic anhydride. 25
5.23 g (2.5 mol) was added, and the temperature was raised to 150° C. with stirring under a nitrogen stream to distill out methyl ethyl ketone. After refluxing acetic anhydride for 1 hour, the temperature was raised to 350°C for 90 minutes, water and acetic acid were distilled off, and cyclodehydration and polymerization of amic acid proceeded. Thereafter, the pressure inside the system was reduced to 100 Torr for 30 minutes, and the pressure was further reduced to 2 Torr, and polymerization was allowed to proceed for 11 minutes. The obtained polymer was taken out in a molten state.

The results of elemental analysis of the obtained polymer were as follows.

CHN Calculated value (%) 72.8 3.5 0.3 Actual value (%
) 72.8 3.4 0.3 These results show that a polyimide ester having the structural unit and composition represented by the following formula was obtained.

-G-o-@co+,.

The melt viscosity of the second polymer was measured using the same test method as in Example 1, and was 381 Pa-s, indicating optical anisotropy in the molten state.

Example 6 Hydroxyphthalic anhydride 12.31 g (0,075 mol) p-aminophenol &18 g (0,075 mol) Methyl ethyl ketone 1001d! was put into a No. 1, 41 autoclave equipped with double helical blades, stirred at room temperature for 1 hour, and the compound V' (yz, Y
, : H) precipitate was formed.

Next, P-hydroxybenzoic acid 241.71 g (1.75 mol) dihydroxybiphenyl 55.86 g (0.3 mol) terephthalic acid 33.23 g (0.2 mol) isophthalic acid 29.07 g (0.175 mol) acetic anhydride. 255
．． 23 g (2.5 mol) was added, and the temperature was raised to 150°C with stirring under a nitrogen stream to distill out methyl ethyl ketone. After refluxing acetic anhydride for 1 hour, the temperature was raised to 350°C for 90 minutes, water and acetic acid were distilled off, and dehydration cyclization and polymerization of amic acid proceeded. After that, the pressure inside the system was reduced to 100 Torr for 30 minutes, and then to 2 Torr.
The pressure was reduced to 1, and polymerization was allowed to proceed for 7 minutes. The obtained polymer was taken out in a molten state.

The results of elemental analysis of the obtained polymer were as follows.

CHN Calculated value (%) 71.6 3.4 0.3 Actual value (%
) 71.6 3.3 0.3 These results show that a polyimide ester having the structural unit and composition represented by the following formula was obtained.

The melt viscosity of this polymer was measured using the same test method as in Example 1, and was 115 Pa-s, indicating optical anisotropy in the molten state.

Example 7 p-Hydroxybenzoic acid 207.18 g (1.5 mol) Dihydroxybiphenyl 79.14 g (0.425 mol) Terephthalic acid 62.30 g (0.375 mol) Isophthalic acid 20.77 g (0.125 mol) Compound [V:
119.14 g (0,075 mol) of 4-hydroxy-N-(p-hydroxyphenyl)phthalimide and 255.23 g (2.5 mol) of acetic anhydride were added to the double helical winged 1, 41! The mixture was placed in an autoclave, and the temperature was raised to 150°C with stirring under a nitrogen stream, and acetic anhydride was refluxed for 1 hour.

Subsequently, the temperature was raised to 350°C for 90 minutes, acetic acid was distilled off, and polymerization was allowed to proceed. Thereafter, the pressure inside the system was reduced to 100 Torr for 30 minutes, and the pressure was further reduced to 2 Torr to allow polymerization to proceed for 5 minutes. The obtained polymer was taken out in a molten state.

The results of elemental analysis of the obtained polymer were as follows.

CHN +0-@CO+,.

-c-CO@CO-+-0 Calculated value (%) 72.2 3.5 0.3 Actual value (%
) 72.0 3.2 0.3 These results show that a polyimide ester having the structural unit and composition represented by the following formula was obtained.

The melt viscosity of this polymer was measured using the same test method as in Example 1, and was 196 Pa-s, indicating optical anisotropy in the molten state.

Example 8 p-acetoxybenzoic acid 270.24 g (1.5 mol) 4.4'-diacetoxybiphenyl 114.87 g (
0,425 mol) Terephthalic acid 62.30 g (0,315 mol) Isophthalic acid 20.77 g (0,125 mol) Compound (■:
25.45 g (0,075 mol) of 4-acetoxy N-(p-acetoxyphenyl)phthalimide) was placed in a No. 1, 42 autoclave equipped with double helical blades, and the mixture was stirred for 90 minutes under a nitrogen stream. 35
The temperature was raised to 0°C, acetic acid was distilled off, and polymerization was allowed to proceed.

Thereafter, the pressure inside the system was reduced to 100 Torr for 30 minutes, and the pressure was further reduced to 2 Torr to allow polymerization to proceed for 9 minutes. The obtained polymer was taken out in a molten state.

The results of elemental analysis of the obtained polymer were as follows.

CHN I understand that.

The melt viscosity of this polymer was measured using the same test method as in Example 1, and was 221 Pa-s, indicating optical anisotropy in the molten state.

Calculated value (%) 72.2 3.5 0.3 Actual value (%
)? 2.1 3.5 0.3 Synthesis Example 2 From these results, a polyimide ester having the structural unit and composition shown by the following formula was obtained. 29.54 g (0.18 mol) of hydroxyphthalic anhydride and p- 24.69g (0.18 mol) of aminobenzoic acid 20011! i
! Dissolve in DMF. Immediately after the start of DMF reflux, yellow powder crystals were precipitated. After refluxing for 2 hours, it was cooled. After filtering and washing with DMF, washing with acetone and drying, the zero elemental analysis values were as follows. Theoretical value (actual value) C: 63.6 (63,6), H: 3.2 (
3,2), N: 4.9 (4,8) Example 9 Hydroxyphthalic anhydride 4.10 g (0,025 mol) p-aminobenzoic acid 3.43 g (0,025 mol) Methyl ethyl ketone 100 d was mixed into a double helical The mixture was poured into a 1, 4 A autoclave equipped with wings, stirred at room temperature for 1 hour, and the compound ■'(Y&
, Z4: A precipitate of H) was formed.

Then p-hydroxybenzoic acid 203.73 g (1,4
75 mol) Dihydroxybiphenyl 93.11 g (0.5 mol) Terephthalic acid 62.30 g (0.375 mol) Isophthalic acid 20.77 g (0.125 mol) Acetic anhydride 2
55.23g (2.5 mol) was added, and under a nitrogen stream,
The temperature was raised to 150°C without stirring, and methyl ethyl ketone was distilled out. After refluxing acetic anhydride for 1 hour, 90
The temperature was raised to 350°C for 1 minute, water and acetic acid were distilled off, and cyclodehydration and polymerization of amic acid proceeded. After that, the pressure inside the system was reduced to 100 Torr for 30 minutes, and then 2 Torr.
The pressure was reduced to rr, and polymerization was allowed to proceed for 18 minutes. The obtained polymer was taken out in a molten state.

The results of elemental analysis of the obtained polymer were as follows.

It exhibited optical anisotropy in the molten state.

Calculated value (%) Actual value (%) 72.7 7λ5 3.6 3.5 0, 1 0.1 From these results, it was found that a polyimide ester having the structural unit and composition shown by the following formula was obtained. Recognize.

-G-COGCO-)-+s The melt viscosity of the second polymer was measured using the same test method as in Example 1, and was 381 Pa-s. mole) p-aminobenzoic acid 10.29g (0,075 mole)
100 m of methyl ethyl ketone was put into a No. 1, 42 autoclave equipped with double helical blades, stirred at room temperature for 1 hour, and the compound ■'(Y&, Z
4: A precipitate of H) was formed.

Next, p-hydroxybenzoic acid 196.82g (1,425
mol) Dihydroxybiphenyl 93.11 g (0.5 mol) Terephthalic acid 62.30 g (0.375 mol) Isophthalic acid 20.77 g ((1125 mol) Acetic anhydride 2
55.23g (2.5 mol) was added, and under a nitrogen stream,
The temperature was raised to 150° C. while stirring, and methyl ethyl ketone was distilled out. After refluxing acetic anhydride for 1 hour, 9.0
The temperature was raised to 350°C for 1 minute, water and acetic acid were distilled off, and cyclodehydration and polymerization of amic acid proceeded. After that, the pressure inside the system was reduced to 100 Torr for 30 minutes, and then 2 Torr.
The pressure was reduced to rr, and polymerization was allowed to proceed for 14 minutes. The obtained polymer was taken out in a molten state.

The elemental analysis results of the obtained polymer were as follows: CHN Calculated value (%) 72.6 3.5 0.3 Actual value (%)
) 72.4 3.5 0.3 These results show that a polyimide ester having the structural unit and composition represented by the following formula was obtained.

-G-0-Gco hand T -4-CO-@-CO-+-+s The melt viscosity of this polymer was measured using the same test method as in Example 1, and was 201 Pa-s, in the molten state. It showed optical anisotropy.

/4q5Unξwide°I/To's ッヱshaekum Ibf Science z/
F/=show @Example 11 Hydroxyphthalic anhydride 20.52g (0,125 mol) m-aminobenzoic acid 17.14g (0,125 mol) Methyl ethyl ketone 100d was added to 1,4j with double helical wings! The mixture was poured into an autoclave and stirred at room temperature for 1 hour.
Z4: A precipitate of u) was formed.

Next, p-hydroxybenzoic acid 189.92g (1,375
mol) Dihydroxybiphenyl 69.83 g (0.375 mol) Hydroquinone 13.76 g (0.125 mol) Terephthalic acid 41.55 g (0.25 mol) Isophthalic acid 41.55 g (0.25 mol) Acetic anhydride 2
55.23g (2.5 mol) was added, and under a nitrogen stream,
The temperature was raised to 150'C without stirring, and methyl ethyl ketone was distilled out. After refluxing acetic anhydride for 1 hour, 9
The temperature was raised to 350°C for 0 minutes, water and acetic acid were distilled off, and cyclodehydration and polymerization of amic acid proceeded. After that, the pressure inside the system was reduced to 100 Torr for 30 minutes, and then 2 T
The pressure was reduced to orr, and polymerization was allowed to proceed for 6 minutes. The obtained polymer was taken out in a molten state.

The elemental analysis results of the obtained polymer were as follows: CHN Calculated value (%) Actual value (%) 71.8 71.4 3.5 0.5 3.40.4 From these results, the following formula It can be seen that a polyimide ester having the structural unit and composition shown by is obtained.

The melt viscosity of this polymer was measured using the same test method as in Example 1, and was 360 Pa-s, indicating optical anisotropy in the molten state.

Example 12 Hydroxyphthalic anhydride 41.03 g (0,25
mole) P-aminobenzoic acid 34.29 g (0.25 mole) methyl ethyl ketone 1 pOd into a double helical winged 1,44! The mixture was poured into an autoclave and stirred at room temperature for 1 hour.
A precipitate of Z, :H) was formed.

Next, p-hydroxybenzoic acid 1'72.65 g (1,25
mol) Dihydroxybiphenyl 93.11 g (0.5 mol) Terephthalic acid 41.53 g (0.25 mol) Isophthalic acid 41.53 g (0.25 mol) Acetic anhydride 255.23 g (2.5 mol) were added. Then, under a nitrogen stream, the temperature was raised to 150°C without stirring, and methyl ethyl ketone was distilled out. After refluxing acetic anhydride for 1 hour,
The temperature was raised to 350°C for 90 minutes, water and acetic acid were distilled off, and dehydration cyclization and polymerization of amic acid proceeded. After that, the pressure inside the system was reduced to 100 Torr for 30 minutes, and then 2T
The pressure was reduced to orr, and polymerization was allowed to proceed for 3 minutes. The obtained polymer was taken out in a molten state.

The results of elemental analysis of the obtained polymer were as follows.

CHN Calculated value (%) 72.1 3.4 0.9 Actual value (%
) 72.2 3.4 0.9 These results show that a polyimide ester having the structural unit and composition represented by the following formula was obtained.

-G-0-@CO+s.

-G-CO@-CO-)-+.

The melt viscosity of this polymer was measured using the same test method as in Example 1, and was 415 Pa-s, indicating optical anisotropy in the molten state.

Example 13 12.31 g (0,075 mol) of hydroxyphthalic anhydride, 10.29 g (0,075 mol) of p-aminobenzoic acid, and 100 d of methyl ethyl ketone were charged into an autoclave No. 1 and 41 equipped with double helical blades and heated at room temperature. After stirring for 1 hour, compound ■' (Y!, Z
a: A precipitate of H) was formed.

Next, 162.29 g (1,175 g) of p-hydroxybenzoic acid
mole) dihydroxybiphenyl 116.38g (0,62
5 mol) Terephthalic acid 74.76 g (0.45 mol) Isophthalic acid 29.07 g (0.175 mol) Acetic anhydride 25
5.23 g (2.5 mol) was added, and the temperature was raised to 150° C. with stirring under a nitrogen stream to distill out methyl ethyl ketone. After refluxing acetic anhydride for 1 hour, the temperature was raised to 350° C. for 90 minutes, water and acetic acid were distilled off, and cyclodehydration and polymerization of amic acid proceeded. After that, the system is 1
The pressure was reduced to 00 Torr for 30 minutes, and the pressure was further reduced to 2 Torr to allow polymerization to proceed for 13 minutes. The obtained polymer was taken out in a molten state.

The results of elemental analysis of the obtained polymer were as follows.

C -4-0-@CO-+-4? Calculated value (%) Actual value (%) 73.2 73.0 3.6 3.7 0.3 0.3 From these results, a polyimide ester having the structural unit and composition shown by the following formula was obtained. I understand that.

The melt viscosity of this polymer was measured using the same test method as in Example 1, and was 416 Pa-s, indicating optical anisotropy in the molten state.

Example 14 12.31 g (0,075 mol) of hydroxyphthalic anhydride, 10.29 g (0,075 mol) of p-aminobenzoic acid, and 100 m of methyl ethyl ketone were charged into an autoclave No. 1 and 41 equipped with double helical blades, and the mixture was heated at room temperature. After stirring for 1 hour, compound ■' (Y &, Z
a: A precipitate of H) was formed.

Next, 231.35 g (1,675 g) of p-hydroxybenzoic acid
mol) Dihydroxybiphenyl 69.83 g (0.375 mol) Terephthalic acid 33.23 g (0.2 mol) Isophthalic acid 29.07 g (0.175 mol) Acetic anhydride 255
．． 23 g (2.5 mol) was added, and the temperature was raised to 150°C under a nitrogen stream without stirring to distill out methyl ethyl ketone. After refluxing acetic anhydride for 1 hour, the temperature was raised to 350°C for 90 minutes, water and acetic acid were distilled off, and dehydration cyclization and polymerization of amic acid proceeded. After that, the pressure inside the system was reduced to 100 Torr for 30 minutes, and then the pressure was increased to 100 Torr.
The pressure was reduced to r, and polymerization was allowed to proceed for 10 minutes. The obtained polymer was taken out in a molten state.

The results of elemental analysis of the obtained polymer were as follows.

Calculated value (%) Actual value (%) 72.0 71.9 3.50.3 3.5 0.3 From these results, a polyimide ester having the structural unit and composition shown by the following formula was obtained. I understand.

+0−@CO+b? -4-CO@-CO+s The melt viscosity of this polymer was measured using the same test method as in Example 1, and was 195 Pa-5, indicating optical anisotropy in the molten state.

Example 15 p-hydroxybenzoic acid 196.82g (1,425
mol) Dihydroxybiphenyl 93.11 g (0.5 mol) Terephthalic acid 62.30 g (0.375 mol) Isophthalic acid 20.77 g (0.125 mol) 4-Hydroxy-N-(p-carboxyphenyl)phthalimide
21.24g (0,075g) Acetic anhydride 255.2
3g (2.5 mol) in a double helical winged 1,4
The mixture was placed in the autoclave No. 1, and the temperature was raised to 150°C under a nitrogen stream without stirring, and acetic anhydride was refluxed for 1 hour.

Subsequently, the temperature was raised to 350°C for 90 minutes, acetic acid was distilled off, and polymerization was allowed to proceed. Thereafter, the pressure inside the system was reduced to 100 Torr for 30 minutes, and the pressure was further reduced to 2 Torr to allow polymerization to proceed for 8 minutes. The obtained polymer was taken out in a molten state.

The results of elemental analysis of the obtained polymer were as follows.

CHN Calculated value (%) Actual value (%) 72.6 3.5 0.3 72.3 3.4 0.3 From these results, a polyimide ester having the structural unit and composition shown by the following formula was obtained. I know that there is.

-4-0-@CO+s t -G-CO-0CO-+-Is The melt viscosity of this polymer was measured using the same test method as in Example 1, and was 182 Pa-s, with optical anisotropy in the molten state. showed his sexuality.

Example 16 p-acetoxybenzoic acid 256.73g (1,425
mole) 4.4'-diacetoxybiphenyl 135.14g
(0,5 mol) Terephthalic acid 62.30 g (0,375 mol) Isophthalic acid 20.77 g (0,125 mol) 4-acetoxy-N-(p-carboxyphenyl)phthalimide 2
4.40 g (0,075 g) was put into an autoclave No. 1 and 41 equipped with double helical blades, and the temperature was raised to 350 ° C for 90 minutes with stirring under a nitrogen stream to distill off acetic acid. Polymerization was allowed to proceed. After that, the system is 100
The pressure was reduced to Torr for 30 minutes, and the pressure was further reduced to 2 Torr to allow polymerization to proceed for 12 minutes. The obtained polymer was taken out in a molten state.

The results of elemental analysis of the obtained polymer were as follows.

CHN Calculated value (%) Actual value (%) 72.6 3.5 0.3 72.6 3.4 0.3 From these results, a polyimide ester having the structural unit and composition shown by the following formula was obtained. I know that there is.

-G-0-@C0-)-s q The melt viscosity of this polymer was measured using the same test method as in Example 1, and was 241 Pa-s, indicating optical anisotropy in the molten state.

Comparative Example 1 Commercially available polybutylene terephthalate (DURANEX 2000, manufactured by Celanese) was used.

Comparative Example 2 Commercially available polycarbonate (A2200 manufactured by Idemitsu Petrochemical Co., Ltd.)
) was used.

Comparative Example 3 Commercially available polyetherimide (Ultem 1000, manufactured by General Electric Company) was used.

Comparative Example 4 A commercially available thermotropic liquid crystal copolymer polyester (Econol E6000 manufactured by Sumitomo Chemical Co., Ltd.) was used.

Comparative Example 5 A commercially available thermotropic liquid crystalline copolyester (Vectra A950, manufactured by Celanese) was used.

The linear expansion coefficients, molding shrinkage rates, bending properties, and heat distortion temperatures of the polymers of Examples 1 to 16 and Comparative Examples 1 to 5 are shown in the table.

Note that these characteristics were measured as follows.

Using a test piece injection molding machine (Toshiba 1545P), the molding temperature was 25
Molding was carried out at a temperature of 0 to 350'C and a mold temperature of 120C.

Vol.] C1 1, linear expansion coefficient Seiko thermal analyzer 5SC-300 and TMA-10
A test piece cut out from the center of a 63.5 x 63.5 x 1.6 square plate to a size of approximately 10 (measurement direction) /sin.

2. Molding shrinkage rate The MD and TD of the above flat plate were calculated using the following formula.

Using a test piece with a molding shrinkage rate of 7 x 3.2 mm, a load of 18.6
Measured in kg/cd.

Other test conditions were in accordance with ASTM D648.

Mold cavity inner dimension
．． Measurements were taken at 23°C on a 7x3.2m test piece.

Other test conditions were in accordance with ASTM D790.

4. Heat deformation temperature: 127 x 12° using a device manufactured by Toyo Seiki Co., Ltd. It can be seen that the polyimide ester of the present invention has a small coefficient of linear expansion and a small molding shrinkage rate, and is excellent in dimensional stability and dimensional accuracy. Furthermore, compared to the conventional liquid crystalline polymer (Comparative Example 4), the anisotropy in MD and TD is small, and furthermore, it has excellent dimensional stability and dimensional accuracy. Moreover, it is clear that it is greatly superior in terms of strength and elastic modulus. This means that
In particular, when used in conjunction with inorganic materials such as metal materials, glass, and ceramics, or when used in injection molding insert molding, dimensional changes due to temperature changes may cause peeling, bending, twisting, increased internal distortion, or Problems that could not be solved with conventional liquid crystal polymers, such as increased stress, can be avoided. In addition, even when the polymer is used alone, both the MD and TDO linear expansion coefficients are close to O, and the anisotropy is small, so the anisotropy of dimensional changes due to temperature changes is small, and problems such as warping and deformation are less likely to occur. It has extremely excellent characteristics. Also,
The polyimide ester of the present invention is also excellent in strength and heat resistance.

〔Effect of the invention〕

The thermoplastic wholly aromatic polyimide ester obtained by the present invention can be injection molded, has excellent dimensional stability and dimensional accuracy both in the direction of flow and in the direction perpendicular thereto, and has high strength and modulus of elasticity (rigidity). ), it also has excellent heat resistance, and its industrial value as a material for electrical and electronic parts is extremely large.

[Brief explanation of drawings]

Figures 1 and 2 show the IR spectra of the polymers obtained in Example 2 and Example 10, respectively.

Claims (1)

[Claims] 1. Structural units represented by the following formulas I, II, III, and IV ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [I] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼[III] (In the formula, n is 0 or 1) ▲There are mathematical formulas, chemical formulas, tables, etc.▼[IV] (Here, X is O or CO, and the unit II The X group, the imide group, and the two carbonyl groups of unit IV are respectively present in para or meta positions with respect to each other, and in units I, II,
Both ends of III and IV are connected by an ester bond. )
When X is O, the molar ratio of I:II+III+IV is 20:80~
90:10, and the molar ratio of II:III is 0.1:99.
9 to 99.9:0.1, II+III and IV are substantially equimolar, and when X is CO, the molar ratio of I+II:III+IV is 20:80
~90:10, and the molar ratio of I:II is 0.1:99
．． 9 to 99.9:0.1, III and IV are substantially equimolar, and the shear stress is 0.025 MPa and the melt viscosity at 300 to 400°C is 1.0 to 1.0 x 10^5 Pa. A thermoplastic wholly aromatic copolymerized polyimide ester which is s. 2. For the compounds represented by I ′, V, III′, and IV′ below, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [ I ′] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [V] ▲ Mathematical formulas, There are chemical formulas, tables, etc. ▼ [III'] (n in the formula is 0 or 1) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [VI'] (In the formula, Y_1, Y_2, Y_3, Y_4 and Y_5 are respectively , hydrogen or R_1CO, R_2CO, R_3
CO, R_4CO or R_5CO, R_1,
R_2, R_3, R_4 and R_5 each have 1 carbon number
~18 hydrocarbon groups, Z_1, Z_2 and Z_3
each represents hydrogen or a hydrocarbon group having 1 to 18 carbon atoms. In addition, the Y_2O group and imide group of compound V, and the compound
The two carbonyl groups of IV' are located in para or meta positions with respect to each other. ) The molar ratio of I′:V+III′+IV′ is 20:80-90:
10. The molar ratio of V:III' is 0.1:99.9 to 99.
9:0.1, reacted so that V+III' and IV' became substantially equimolar, and the general formula Y_pOZ_q (p is 1 to 5,
q is a sign from 1 to 3) ▲There are mathematical formulas, chemical formulas, tables, etc.▼[I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼[II'] ▲There are mathematical formulas, chemical formulas, tables, etc.▼[III] (n in the formula is 0 or 1) ▲There are mathematical formulas, chemical formulas, tables, etc.▼[IV] Substantially consists of the structural unit represented by .0
The melt viscosity at 25 MPa and 300 to 400°C is 1.
A method for producing a thermoplastic wholly aromatic copolymerized polyimide ester having a pressure of 0 to 1.0×10^5 Pa·s. 3.For the compounds represented by I ′, V′, III′, and IV′ below, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [ I ′] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [V′] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [III'] (n in the formula is 0 or 1) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [IV'] (In the formula, Y_1, Y_2, Y_3, Y_4 and Y_5 are , respectively, hydrogen or R_1CO, R_2CON, R_
3CO, R_4CO or R_5CO, and R_1
, R_2, R_3, R_4 and R_5 each represent a hydrocarbon group having 1 to 18 carbon atoms, and Z_1, Z_2 and Z_
3 each represents hydrogen or a hydrocarbon group having 1 to 18 carbon atoms. Further, the Y_2O group and the amide group of the compound V' and the two carbonyl groups of the compound IV' are present at the para or meta positions, respectively. ) The molar ratio of I′:V′+III′+IV′ is 20:80-90
:10, molar ratio of V':III' is 0.1:99.9-9
9.9:0.1, reacted so that V'+III' and IV' were substantially equimolar, imide cyclization of compound V' and general formula Y_pOZ_q (p is 1 to 5, q is 1 to There are formulas, ▲mathematical formulas, chemical formulas, tables, etc. that are characterized by the elimination of the compound shown by the symbol 3)▼[I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼[II′] ▲mathematical formulas, There are chemical formulas, tables, etc. ▼ [III] (n in the formula is 0 or 1) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [IV] Substantially consists of the structural unit represented by, shear stress 0.0
The melt viscosity at 25 MPa and 300 to 400°C is 1.
A method for producing a thermoplastic wholly aromatic copolymerized polyimide ester having a pressure of 0 to 1.0×10^5 Pa·s. 4. For the compounds represented by I ′, VI, III′, and IV′ below, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [ I ′] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [VI] ▲ Mathematical formulas, There are chemical formulas, tables, etc. ▼ [III'] (n in the formula is 0 or 1) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [IV'] (In the formula, Y_1, Y_4, Y_5 and Y_6 are each hydrogen or R_1CO, R_4CO, R_5CO or R_6CO, and R_1, R_4, R_5 and R
_6 each represents a hydrocarbon group having 1 to 18 carbon atoms, and Z
_1, Z_2, Z_3 and Z_4 each represent hydrogen or a hydrocarbon group having 1 to 18 carbon atoms. Also, Z of compound VI
The _4OOC group, the imide group, and the two carbonyl groups of compound IV' are located at para or meta positions with respect to each other. The molar ratio of I′+VI:III′+IV′ is 20:80 to 90:
10. The molar ratio of I′:VI is 0.1:99.9 to 99.
9:0.1, reacted so that III' and IV' were substantially equimolar, and the general formula Y_pOZ_q (p is 1, 4, 5,
q is a code from 1 to 4) ▲There are mathematical formulas, chemical formulas, tables, etc.▼[I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼[II'] ▲There are mathematical formulas, chemical formulas, tables, etc.▼[III] (n in the formula is 0 or 1) ▲There are mathematical formulas, chemical formulas, tables, etc.▼[IV] Substantially consists of the structural unit represented by .0
The melt viscosity at 25 MPa and 300 to 400°C is 1.
A method for producing a thermoplastic wholly aromatic copolymerized polyimide ester having a pressure of 0 to 1.0×10^5 Pa·s. 6. For the compounds represented by I ′, VI′, III′, and IV′ below, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼〔 I ′〕 ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [VI′] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [III'] (n in the formula is 0 or 1) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [IV'] (In the formula, Y_1, Y_4, Y_5 and Y_6 are respectively , hydrogen or R_1CO, R_4CO, R_5CO or R_6CO, R_1, R_4, R_5 and R
_6 each represents a hydrocarbon group having 1 to 18 carbon atoms, and Z
_1, Z_2, Z_3 and Z_4 each represent hydrogen or a hydrocarbon group having 1 to 18 carbon atoms. Also, Z of compound VI
The _4OOC group, the amide group, and the two carbonyl groups of compound IV' are located at para or meta positions with respect to each other. ) The molar ratio of I′+VI′:III′+IV′ is 20:80-90
:10, the molar ratio of I':VI' is 0.1:99.9-9
9.9:0.1, reacted so that III' and IV' were substantially equimolar, imide cyclization of compound VI' and general formula Y_
There are formulas, ▲mathematical formulas, chemical formulas, tables, etc. that are characterized by the elimination of the compound represented by pOZ_q (p is 1, 4, 5, q is the sign of 1 to 4)▼[I] ▲Mathematical formulas, There are chemical formulas, tables, etc. ▼ [II″] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [III] (n in the formula is 0 or 1) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [IV] Represented by consists essentially of structural units and has a shear stress of 0.0
The melt viscosity at 25 MPa and 300 to 400°C is 1.
A method for producing a thermoplastic wholly aromatic copolymerized polyimide ester having a pressure of 0 to 1.0×10^5 Pa·s.