JPH04110322A - Preparation of molten liquid crystalline polyester - Google Patents

Abstract

PURPOSE:To improve the balance between mechanical properties and heat resistance, weld strength esp., and mechanical anisotropy of a molded article by reacting five specific materials and acetic anhydride and polymerizing the reaction product under a reduced pressure. CONSTITUTION:An arom. hydroxycarboxylic acid of formula I, 2'-hydroxyethyl 4-(2-hydroxyethoxy)benzoate of formula II, an arom. dihydroxy compd. of formula III (wherein R1 is a group of formula IV, V, or VI), an arom. dicarboxylic acid of formula VII (wherein R2 is a group of formula IV, V, or VIII), a compd. selected from the group consisting of a polyester or oligomer comprising an arom dicarboxylic acid of formula VII with ethylene glycol or with the compd. of formula II and a bis(beta-hydroxyethyl) ester of arom. dicarboxylic acid, and acetic anhydride are reacted, and the reaction product is polymerized under a reduced pressure to give the title polyester having a logarithmic viscosity of 0.5-5.0dl/g and contg. structural units of formulas IX-XIII in such molar ratios that the ratio of X/(IX+X+XI+XII) is 0.1-10mol% and that of IX/(IX+X +XI+XII) is 5-40mol%.

Description

[Detailed Description of the Invention] <Industrial Application Field> The present invention provides a polymer with a high degree of polymerization obtained only by melt polymerization, can be molded with a normal injection molding machine, has excellent fluidity,
The present invention relates to a method for producing a molten liquid crystalline polyester that can provide a molded article with improved mechanical properties, particularly the strength and mechanical anisotropy of the weld area.

<Conventional technology> In recent years, the demand for higher performance plastics has been increasing, and many polymers with various new performances have been developed.Among them, optically anisotropic liquid crystal polymers have excellent mechanical properties. (Japanese Unexamined Patent Publication No. 51-83)
No. 95, JP-A-49-72393).

As the above-mentioned liquid crystal polymer, for example, a liquid crystal polymer obtained by copolymerizing polyethylene terephthalate with p-hydroxybenzoic acid is known (Japanese Patent Application Laid-Open No. 72393/1983). However, injection molded products made of this polymer have drawbacks such as insufficient heat resistance and poor mechanical properties, and it has been found that injection molded products satisfying both properties cannot be obtained from this polymer. Moreover, in order to improve heat resistance, the amount of p-hydroxybenzoic acid must be 80 mol % or more, but it was also found that assimilation occurs during polymerization and solid phase polymerization is necessary.

On the other hand, as a means to improve the fluidity of such polymers, improve melt moldability, and further improve mechanical properties, for example, as described in Japanese Patent Application Laid-Open No. 51-8395, polyethylene A method has been proposed in which terephthalate is copolymerized with p-acyloxybenzoic acid, dicarboxylic acid, and aromatic diol, but although this method also improves the mechanical properties of the injection molded product obtained, the heat resistance is insufficient. I understand. On the other hand, the special public official
As described in Japanese Patent Application No. 7870, injection molded products made of completely aromatic polyester made by copolymerizing p-hydroxybenzoic acid with 4,4-dihydroxybiphenyl and terephthalic acid have good heat resistance, but have a low softening temperature. It was found that melt polymerization was difficult because the temperature was 400°C or higher, and its mechanical properties were not fully satisfactory.

Furthermore, as a method to solve these problems,
Although the polymer described in Publication No. 3-30523, which is made by copolymerizing polyethylene terephthalate with p-hydroxybenzoic acid, a specific aromatic dihydroxy compound, and aromatic dicarboxylic acid, has a satisfactory balance of mechanical properties and heat resistance, it is difficult to form. Regarding the mechanical properties of the product, there remains the problem that the strength of the weld part is not sufficient, and the strength and elastic modulus in the direction perpendicular to the flow direction are slightly low, resulting in slightly large mechanical anisotropy. I understand.

<Problems to be Solved by the Invention> The present invention solves the above-mentioned problems and provides a molded product that has an excellent balance between mechanical properties and heat resistance, and in particular has improved strength and mechanical anisotropy in the weld part. The object of the present invention is to obtain a molten liquid crystalline polyester that can give the following properties.

<Means for Solving the Problems> As a result of intensive studies to achieve the above object, the present inventors found that p-hydroxybenzoic acid, a specific aromatic dihydroxy compound, aromatic dicarboxylic acid, ethylene glycol, and aromatic dicarboxylic acid It has been discovered that the above object can be achieved by further copolymerizing 4-(2-hydroxyethoxy)benzoic acid-2-monohydroxyethyl ester to a polyester obtained by reacting a polyester generated from an acid, and the present invention Reached.

That is, the present invention provides the following structural units (III) to (V)
The structural unit (In> is the structural unit [(I> +
(II) + (1) + (IV) ] (7) 0.1~
occupies 10 mol%, and the structural unit (IV) is the structural unit [(I
>+ (II)+ (I[>+(IV)] of 55
~40 mole, logarithmic viscosity 0.5~5.0697g
When producing a molten liquid crystalline polyester characterized by (-0-R・-〇+...(I[I
)+0CH2CH20+...(1■)
+CO-R2-CO+...(V) Aromatic hydroxycarboxylic acid represented by the following formula (A), formula (
4-(2-hydroxyethoxy)benzoic acid-2-monohydroxyethyl ester represented by B), an aromatic dihydroxy compound represented by formula (C), an aromatic dicarboxylic acid represented by formula (D), and (E) A polyester or oligomer consisting of aromatic dicarboxylic acid represented by formula (D) and ethylene glycol or a compound represented by formula (B) or bis(β-hydroxyethyl) ester of aromatic dicarboxylic acid and acetic anhydride The present invention relates to a method for producing a molten liquid crystalline polyester, which is characterized in that the polymerization is carried out under reduced pressure after reacting the following.

HO-R-OH (,C) HOOC-R2-COOH, (D) represents a group. Here, Y represents a chlorine atom or a hydrogen atom. Furthermore, the structural unit [(I[>+(IV)] and the structural unit (V) are substantially equimolar.) The above structural unit (I
> is a structural unit of polyester produced from (A>p-hydroxybenzoic acid, and the structural unit (II) is, for example, p-hydroxybenzoic acid.
-Hydroxybenzoic acid] - produced by addition reaction of 2 moles of ethylene oxide to 4 moles.
The structural unit (1) is a structural unit generated from -(2-hydroxyethyl-oxy)benzoic acid-2''-hydroxyethyl ester, 4,4-monodihydroxybiphenyl, hydroquinone, 2,6-dihydroxynaphthalene, 4.4-
monodihydroxydiphenyl ether, t-butylhydroquinone, phenylhydroquinone and 3゜3'', 5
．． The structural unit (1v) is a structural unit produced from one or more aromatic dihydroxy compounds selected from 5-tetramethyl-4,4-monodihydroxybiphenyl, and the structural unit (1v) is a structural unit produced from ethylene glycol. unit(
V) is terephthalic acid, isophthalic acid, 4.4"-diphenyldicarboxylic acid, 2,6-naphthalenedicarboxylic acid,
selected from 1,2-pis(phenoxy)ethane-4,4-dicarboxylic acid, 1,2-bis(2-chlorophenoxy)ethane-4,1-dicarboxylic acid, and 4,4-diphenyletherdicarboxylic acid Each structural unit produced from one or more aromatic dicarboxylic acids is shown below.

On the other hand, among the above structural units, structural unit (II) is the structural unit [(I) + (II) + (III) + (I
V) Must be copolymerized in an amount of 0.1 to 10 mol % with respect to 1. The structural unit (n) is the structural unit [
(I> + (II) + (III) - (IV>)
On the other hand, if the amount is less than 0.1 mol %, the effect of the present invention is not significant, and the weld strength and mechanical anisotropy are not sufficiently improved. Moreover, if it is larger than -0 mol %, heat resistance tends to decrease, which is not preferable.

Furthermore, regarding the structural unit (IV>), the structural unit [(I>
+ (III) + (III) + (IV>] It is necessary to be 5 to 40 mol %.

The structural unit <IV) is the structural unit [(III) + (II
) + (III) + (IV)] If the amount is less than 5 mol %, the melt fluidity will decrease and solidification will occur during polymerization, and if it is more than 40 mol %, the heat resistance will be poor, so both are not preferred.

Furthermore, regarding the structural unit (V), the structural unit [(I)+
(IV)].

Furthermore, the molar ratio of structural unit (1)/(In> is 75/2
5 to 9515 is preferable, and 82/18 to 92/8 is more preferable.

The production method of the present invention is characterized in that (B) 4-(2-hydroxyethyl)benzoic acid-2-monohydroxyethyl ester is used to introduce the structural unit (n) into the polymer. But instead of (B), 4-
When (2-hydroxyethyl)benzoic acid is used, the effect of improving the mechanical anisotropy and welt strength of the obtained polymer is not sufficient. It is presumed that the structural unit shown in 1-) acts effectively.

The structural unit of the above (Formula 1) is the structural unit (
II> and (IV) are connected.

The amounts of starting materials (A) to (E> in the present invention are:
The structural formula of the resulting polymer is the structural units (I>, (II
), (III), (IV) and (V), and the amount required to achieve the copolymerization ratio described above. Therefore, it is preferable to adjust the amount of the raw material monomer having high sublimability within the range of 1.0 to 1.1 times the theoretical amount by molar amount.

Structural unit (IV) indicates a structural unit produced from ethylene glycol, but in the production method of the present invention, the above (IV)
An oligomer or polymer obtained by condensation of the aromatic dicarboxylic acid and ethylene glycol shown in D> or a bis(β-hydroxyethyl) ester compound obtained by adding ethylene oxide to the aromatic dicarboxylic acid shown in D> above. When used as a raw material, structural units (IV>) are produced in the polymer.

The amount of acetic anhydride added is preferably 1.0 to 1.5 times the molar amount, particularly preferably 1.05 to 1.2 times the molar amount of the hydroxyl groups in the starting material.

These starting materials are charged into a reaction system and heated from room temperature to 34°C.
After carrying out the acetylation reaction and the initial polymerization reaction under normal pressure at a temperature of preferably 330°C or lower, 250 to 0°C1
The molten liquid crystalline polyester of the present invention can be produced by further carrying out deacetic acid polymerization at 340°C, preferably from 260 to 330°C under reduced pressure. The reaction of Manako under normal pressure is preferably carried out under an atmosphere of an inert gas such as nitrogen in order to suppress oxidative decomposition reactions.

Although these polycondensation reactions proceed without a catalyst, it is sometimes preferable to add metal compounds such as stannous acetate, tetrabutyl titanate, sodium acetate, potassium acetate, zinc acetate, antimony trioxide, or metallic magnesium. .

There are no particular restrictions on the polymerization apparatus used in the method for producing molten liquid crystalline polyester of the present invention, including vertical, horizontal, multi-stage, -
Various devices can be used, such as stepped walls, continuous type, etc.

Further, the melt viscosity of the molten liquid crystalline polyester produced in the present invention is preferably 10 to 15,000 poise, particularly 20 to 15,000 poise.
~5,000 poise is more preferred.

Note that this melt viscosity is a value measured using a Koka type flow tester at a slip rate of 1,000 (1/sec) at (melting point (Tm) + 10°C). Here, the melting point (T
m) is the endothermic peak temperature observed when measured using a differential scanning calorimeter at a heating rate of 20°C/min, and Tm as described below.
2 is shown.

In other words, the endothermic peak temperature (Tm) observed when the polymer after polymerization is measured from room temperature to a temperature above the melting point at a temperature increase of 20°C/min is Tm + 20°C.
The endothermic peak temperature (T m 2
) is shown.

On the other hand, the logarithmic viscosity of the molten liquid crystalline polyester of the present invention is O
, Ig/dfl concentration, the value measured in pentafluorophenol at 60 ° C is 0.5-5, Odu/g,
1.0-3.0617g is preferable. 0.5d, Q/g
If it is less than 5., the mechanical strength is not sufficient. OdF/
If it is larger than g, fluidity becomes poor, which is not preferable.

In addition, when polycondensing the molten liquid crystalline polyester produced in the present invention, in addition to the components constituting the structural units (III) to (V), 3,3--diphenyldicarboxylic acid,
Aromatic dicarboxylic acids such as 2,2-diphenyldicarboxylic acid, aliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, alicyclic dicarboxylic acids such as hexahydroterephthalic acid, chlorohydroquinone, methyl Aromatic dihydroxy compounds such as hydroquinone, aliphatic and alicyclic diols such as 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, 1,4-cyclohexanediol, and 1,4-cyclohexane dimetatool and aromatic hydroxycarboxylic acids such as m-hydroxybenzoic acid and 2,6-hydroxynaphthoic acid; aromatic imidodicarboxylic acids and aromatic imidodihydroxy compounds having an imide bond in the molecule and capable of producing polyester; Aromatic imidohydroxycarboxylic acid or the like may be further copolymerized within a small proportion that does not impair the object of the present invention.

The molten liquid crystalline polyester produced according to the present invention can be obtained by melt polymerization alone, and has excellent mechanical properties and heat resistance with good melt fluidity, weld strength, and improved mechanical anisotropy. It can be subjected to normal melt molding such as extrusion molding, injection molding, compression molding, and blow molding, and can be used to mold fibers, films, three-dimensional molded products, containers,
It can be processed into hoses, etc.

In addition, the molten liquid crystalline polyester produced in the present invention may contain reinforcing agents such as glass fibers, carbon fibers, and asbestos, fillers, lubricants, mold release agents, nucleating agents, plasticizers, and flame retardants (preferably such as brominated polystyrene). Polymeric flame retardants), heat stabilizers, ultraviolet absorbers, pigments, dyes, other thermoplastic resins, etc. can be added as necessary to impart desired properties.

A reinforcing agent is added to the molten liquid crystalline polyester produced in the present invention.
Any means can be used to mix fillers, additives, etc., but for example, a screw extruder can be preferably used.

In addition, the injection molded product obtained in this way can have its strength increased by heat treatment, and may also have its elastic modulus increased.

This heat treatment can be carried out by heat treating the injection molded article in an inert atmosphere (eg nitrogen, argon, helium or water vapor) or in an oxygen-containing atmosphere (eg air) at a temperature below the melting point of the polymer. This heat treatment may or may not be under tension, and can be carried out for a period of several tens of minutes to several days.

<Example> The present invention will be further explained below with reference to Examples.

Example 1 976 g (7,065 mol) of p-hydroxybenzoic acid, 4-(2-hydroxyethoxy)benzoic acid-2-monohydroxyethyl ester (p-hydroxybenzoic acid) were placed in a reaction vessel equipped with a stirrer and a distillation tube. (2 equivalents of ethylene oxide added to) 30.5 g (0,135 mol),
4゜4-dihydroxybiphenyl 10], g (0゜5
4 mol), terephthalic acid 112g (0,675 mol)
, polyethylene terephthalate with an intrinsic viscosity of 0.6) 21
6 g (1,125 mol) and 959 g acetic anhydride (
9.4 mol) was charged, and acetic acid depolymerization was carried out under the following conditions.

First, under a nitrogen gas atmosphere at 100 to 250°C for 5 hours.
After reacting at 250-320'C for 1.5 hours, 320'
The pressure was reduced to 0.5 mmHg for 21 hours at °C, and the pressure was further reduced to 1.0 mmHg.
When the reaction was carried out for a period of time to complete the polycondensation, a nearly theoretical amount of acetic acid was distilled out, and a polymer having the following theoretical structural formula was obtained.

Child○CH2CH2O→-/ k/, fl/m/n10=78.5/1.5/6.0/
14.0/20 Also, place this polyester on the sample stage of a polarizing microscope,
As a result of confirming the optical anisotropy by raising the temperature, the liquid crystal start temperature was 280°C, indicating good optical anisotropy.

Also, a differential scanning calorimeter (DSC-manufactured by PerkinElmer)
The melting point of the polymer was measured at a heating rate of 20°C/min using a 300°C (Model 7) 303°C.

In addition, in order to avoid the influence of the thermal history before the measurement, the temperature was raised to a temperature 20° C. higher than the initially observed melting point, held for 5 minutes, and then cooled to room temperature before measurement.

The logarithmic viscosity (in pentafluorophenol, 60°C) of this polymer was 1.27 dρ/g, and the melt viscosity was 620 voids at a shear rate of 1,000 (1/sec), indicating extremely good fluidity.

The obtained polymer was subjected to a Sumitomo Necool injection molding machine Promat 40/25 (manufactured by Sumitomo Heavy Industries, Ltd.) and molded to 1/8"
1/2" x 5" rod-shaped test piece, 70ml 11T+ x 70
A rectangular plate-shaped test piece of rlTIT+×21Tff11 thickness and ASTM No. 4 dumbbells were molded.

ASTM No. 4 Dumbbells are molded using both a regular mold (dumbbell ■) with a gate at one end of the dumbbell and a weld mold (dumbbell ■) with gates at both ends of the dumbbell.

Load deflection temperature [HDT] (18,6 kgf/ffl>
When measured, it was found to be 225°C, indicating that it had excellent heat resistance.

In addition, the rectangular plate-shaped test piece was cut out to a width of 14 mm in the flow direction of the resin and in the direction perpendicular to the flow, and the obtained strip-shaped test piece was
using a strain rate of 1 mm/min and a span pressure of M 50.
When the bending elastic modulus was measured under the condition of mm, it was found that the flow direction 1
26.000 perpendicular to 10.000kgf/-
kgf/d, and the ratio was 4.2.

Additionally, in accordance with the ASTM D638 standard, ASTM
M No. 4 Measure the breaking strength of dumbbells, dumbbell ■
The ratio of the breaking strength of the dumbbell (■) to that of the weld strength was defined as the weld strength retention rate.

As a result, the strength of dumbbelle (non-weld) is 1170
kg f / Of, strength of dumbbell ■ (weld > 2
05kgf/,,f, weld strength retention rate is 17
．． It was 5%.

Example 2 In a reaction vessel similar to Example 1, p-hydroxybenzoic acid 9 was added.
63g (6,975 mol>), 4.4゛-dihydroxybiphenyl 83.8g (0゜45 mol), terephthalic acid 74.8g (0.45 mol), acetic anhydride 910g
(8.91 mol) and a polyester copolymer consisting of ethylene glycol, 4-(2-hydroxyethoxy)benzoic acid-2″-hydroxyethyl ester, and terephthalic acid with an intrinsic viscosity of 0.6 and represented by the following structural formula ( A
), and acetic acid removal polymerization was carried out under the same conditions as in Example-1.

+0CH2CH20mo/a/b/c=1/6/6 As a result, a polymer having the following structural formula was obtained.

+0CH2CH20→-/k/41/m/n10=77.5/2.515', O
/15/20 Also, place this polyester on the sample stage of a polarizing microscope,
As a result of confirming the optical anisotropy by increasing the temperature, the liquid crystal start temperature was 272°C, indicating good optical anisotropy.

Furthermore, the melting point measured by the method of Example 1 was 297°C1
The logarithmic viscosity was 1.30 dρ/g, the melt viscosity was 580 voids, and the fluidity was good.

This polymer was injection molded in the same manner as in Example 1, and HDT, flexural modulus, and breaking strength were measured. As a result, the HDT was 220°C and the bending elastic modulus in the flow direction was 105. , OOOkgf/=, bending modulus in the right angle direction 2
8. , OOOkgf/cA, and the ratio is 3.8
Met.

In addition, the strength of dumbbelle (non-welded) 1130 k
g f / cxK, dumbbell strength (weld) 2
15kgf/-, weld strength retention rate is 19.0
%Met.

Comparative Example 1 An experiment similar to Example 1 was carried out on a polymer having a composition that does not contain the structural unit (II) of the present invention.

In a reaction vessel similar to that of Example, 994 g (7.2 mol) of p-hydroxybenzoic acid, 126 g (0,675 mol) of 4,4-dihydroxybiphenyl, and 96 g (0,675 mol) of acetic anhydride were added.
0g (9,4 mol), terephthalic acid 112g (0,
675 mol) and 216 g (1,125 mol) of polyethylene terephthalate having an intrinsic viscosity of about 0.6.
Acetic acid removal polymerization was performed under the same conditions as in Example 1 to obtain a polymer having the following theoretical structural formula.

+0CH2CH20→-/k/,Q/m/n=80/7.5/12.5/Also,
This polyester was placed on the sample stage of a polarizing microscope, and the temperature was raised to confirm the optical anisotropy. As a result, the liquid crystal start temperature was 29
It was 4°C.

This polymer was molded in the same manner as in Example 1, and HD
T, flexural modulus and breaking strength were measured. As a result, HDT231℃, bending elastic modulus in flow direction 116.0
00kgf/cffl, bending modulus in the right angle direction 19.0
00 kgf/cITi, and the ratio was 6.1.

In addition, the strength of dumbbell ■ (non-weld) 1200 kg
f/ca, dumbbell strength (weld) 150k
gf/cmt, weld strength retention rate is 12.5%
was found to be lower than that of the example.

Comparative Example 2 This comparative example shows (B) used in the manufacturing method of the present invention.
Instead of using 4-(2-hydroxyethylhexy)benzoic acid-2-hydroxyethyl ester, 4-(2-
This is an example in which a polymer having the same structure as in Example 1 was produced using (hydroxyethoxy)benzoic acid.

In a reaction vessel similar to Example 1, 976 g (7,065 mol) of p-hydroxybenzoic acid, 24.6 g (0,135 mol) of 4-(2-hydroxyethoxy)benzoic acid,
4.4-dihydroxybiphenyl 126g (0,6
75 mol>, terephthalic acid 112 g (0,675 mol), polyethylene terephthalate 2 with an intrinsic viscosity of approximately 0.6
16 g (1,125 mol) and 960 g of acetic anhydride (
9,405 mol) and subjected to acetic acid depolymerization under the same conditions as in Example 1 to obtain a polymer having the following theoretical structural formula.

→○CH2CH2O→-/k/D/m/n10=78.5/1.5/7.5/1
2.5/20 Also, place this polyester on the sample stage of a polarizing microscope,
As a result of confirming the optical anisotropy by increasing the temperature, the liquid crystal initiation temperature was 294°C.

This polymer was molded in the same manner as in Example 1, and HD
T, flexural modulus and breaking strength were measured. As a result, the bending elastic modulus in the flow direction of HDT231°C1 was 113.
000 kg f/cA, perpendicular bending modulus 1
9,500 kgfZ-, and the ratio was 5.8.

Mana, dumbbell strength (non-weld) 1150 kg
f/aTi, strength of dumbbell ■ (weld) 15
0bf/cot, weld strength retention rate is 13.0
%, which is lower than that of the example.

<Effects of the Invention> The molten liquid crystalline polyester obtained by the method of the present invention has an excellent balance of heat resistance and mechanical properties, and has excellent mechanical properties,
In particular, it is possible to obtain molded products with improved anisotropy and strength of the weld portion, so that they can be used in various applications such as plastic substitutes for metals.

Patent application Daitoshi Co., Ltd. −31=

Claims (1)

[Claims] Consisting of the following structural units (I) to (V), the structural unit (II)
) accounts for 0.1 to 10 mol% of the structural unit [(I) + (II) + (III) + (IV)], and the structural unit (IV) accounts for the structural unit [(I) + (II) + ( III) + (IV)] and has a logarithmic viscosity of 0.5 to 5.0 dl/g. ▲Mathematical formula, chemical formula, table etc.▼...(I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(III) ▲Mathematical formulas, chemical formulas, tables, etc. Yes▼...(IV) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(V) Aromatic hydroxycarboxylic acid represented by the following formula (A),
4-(2-hydroxyethoxy)benzoic acid-2-hydroxyethyl ester represented by formula (B), aromatic dihydroxy compound represented by formula (C), aromatic dicarboxylic acid represented by formula (D) acid and (E) aromatic dicarboxylic acid represented by formula (D) and ethylene glycol or formula (B
) A molten liquid crystalline polyester, which is produced by reacting a polyester or oligomer consisting of a compound represented by () or a bis(β-hydroxyethyl) ester of an aromatic dicarboxylic acid with acetic anhydride, and then polymerizing it under reduced pressure. Production method. ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (A) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (B) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (C) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ( D) (However, R_1 has ▲mathematical formulas, chemical formulas, tables, etc.▼, ▲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.▼,▲Mathematical formulas, chemical formulas,
Indicates one or more groups selected from ▼, which includes tables, etc., and ▲, which includes mathematical formulas, chemical formulas, tables, etc. Also, R_2 has ▲mathematical formulas, chemical formulas, tables, etc.▼, ▲mathematical formulas, chemical formulas, tables, etc.▼, ▲mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
Indicates one or more groups selected from , ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ and ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼. Here, Y represents a chlorine atom or a hydrogen atom. Moreover, the structural unit [(III)+(IV)] and the structural unit (V) are substantially equimolar. )