JPH03227456A - Method for treating aromatic polyamide fiber - Google Patents

Abstract

PURPOSE:To improve heat-resistant adhesion of aromatic polyamide fiber to rubber by subjecting the aforementioned aromatic polyamide fiber to plasma treatment, then treating the resultant fiber with a treating liquid containing a polyepoxide compound and specific two components and then with a liquid containing specific two components blended with RFL at a specified weight ratio. CONSTITUTION:Aromatic polyamide fiber is subjected to plasma treatment and then treated with the first treating liquid containing (A) a polyepoxide compound, (B) a blocked polyisocyanate and (C) a rubber latex (preferred example; a vinylpyridine.styrene.butadiene.terpolymer latex) and further with the second treating liquid prepared by adding (D) an ethyleneurea compound expressed by formula I (R is aromatic or aliphatic hydrocarbon; n is 0, 1 or 2; the terminal group is hydrogen when n is 0) and (E) an epoxy-modified phenol formalin condensate expressed by formula II [R' is O-(CH2)k-Cl, O-(CH2)l-OH, etc.; R'' is H, CH3, etc.; k and l are 1-4; a+b is 1-5; a+b<=6] to RFL at (50/50)-(80/20) weight ratio of the components (D/E) to afford the objective fiber, excellent in durable peel strength and useful for reinforcing rubber.

Description

[Detailed Description of the Invention] Industrial Application Fields The present invention relates to a method for treating aromatic polyamide fibers, and its purpose is to produce an aromatic material that dramatically improves the heat-resistant adhesion between the fibers and rubber. An object of the present invention is to provide a method for treating group polyamide fibers.

In particular, the present invention improves the rate of rubber adhesion to aromatic polyamide III (Rubber coverage) when peeling aromatic polyamide fibers from rubber composite molded products, and also improves aromatic polyamide fibers that are flexible and have excellent fatigue resistance. The present invention relates to a processing method for processing the same.

<Prior art> Aromatic polyamide fibers generally have high tensile strength and elastic modulus, as well as excellent dimensional stability and heat resistance, so they are used in tires, conduction belts, belts, hoses, etc. that are used under harsh conditions. Suitable as a reinforcement material for rubber products. However, because aromatic polyamide fibers are inert and crystalline due to their molecular structure, they have poor adhesion to rubber, and are usually used as an adhesive between aliphatic polyamide fibers and rubber. If resorcinol-formalin-rubber latex (RFL) is used as it is, it has the disadvantage that it cannot form strong adhesion to rubber. Therefore, many proposals have been made in an attempt to improve the adhesiveness between aromatic polyamide fibers and rubber. For example, a method of bonding the fibers to rubber by subjecting aromatic polyamide I to epoxy treatment, heat treatment, RFL treatment, and heat treatment (Japanese Patent Publication No. 10514/1983)
, a method in which aromatic polyamide fibers are treated with a treatment liquid containing an epoxy compound, a condensate of phenols and aldehydes, and a tertiary amine, and heat treated, and then subjected to RFL treatment and heat treatment to adhere to rubber (Japanese Patent Publication No. 52 -436
No. 73), RFL after treating aromatic polyamide fiber with a treatment liquid consisting of an epoxy compound and rubber latex.
A method of performing treatment and heat treatment (Japanese Patent Publication No. 53-37467), a method of making isocyanate and its derivatives exist at the interface between an aromatic polyamide fiber and a thermosetting resin (Japanese Patent Publication No. 53-37468), aromatic polyamide A method of treating fibers with a treatment solution containing a blocked polyisocyanate compound, a polyethyleneimine compound, and a methylolmelamine compound alone or in combination (Japanese Patent Publication No. 53-314
73 Publication) etc. have been proposed.

In addition, the surface of the aromatic polyamide fiber is activated by low-temperature plasma treatment under reduced pressure, and then treated with a mixture of resorcinol/formalin initial condensate and rubber latex to improve its adhesion to rubber. Attempts are being made to improve it.

This method includes, for example, [Processing of aromatic polyamide fibers for rubber reinforcement characterized by subjecting the aromatic polyamide fibers to low-temperature plasma treatment and then treating them with a mixed solution of a resorcinol/formaldehyde initial condensate and rubber latex. ``Method'' (Japanese Unexamined Patent Publication No. 19881/1988), ``The surface of aromatic polyamide 1IIIi is treated in a low-temperature plasma gas atmosphere under reduced pressure, and then this treatment 1III11 is combined with a high molecular weight resorcinol/formaldehyde initial condensate and rubber latex. A method for adhering aromatic polyamide fibers and rubber, characterized by adhesion treatment with an adhesive composition consisting of
(Japanese Unexamined Patent Publication No. 60-250036).

However, aromatic polyamide fibers treated by these conventional methods have a low rate of rubber adhesion to the 8M material when the miscellaneous materials are peeled off from the rubber composite molded product, and the adhesion between the aromatic polyamide fiber material and rubber is low. This is a major obstacle to the use of aromatic polyamide fibers for rubber reinforcement because of the problem of insufficient adhesion and insufficient adhesion.

<Object of the invention> The present invention was made against the background of the above circumstances,
An object of the present invention is to provide excellent adhesive performance between aromatic polyamide fibers and rubbers.

<Structure of the Invention> That is, the present invention provides the following steps: (1) After treating the aromatic polyamide meg in an atmosphere of an ionized active gas (plasma treatment), the polyepoxide compound (A), the blocked polyisocyanate compound (B) and The first containing rubber latex (C)
After treatment with a processing agent, an ethylene urea compound represented by the following general formula (D) and an epoxy-modified phenol-formalin condensate represented by the following general formula (E) are added to resorcinol-formalin-rubber latex (RFL). D/E = 5
This is a method for treating aromatic polyamide I miscellaneous materials, which is characterized by treating with a second treating agent having a ratio of 0150 to 80/20.

OHHO The aromatic polyamide fiber in the present invention means a fiber made of a polymer in which repeating units having an aromatic ring account for at least 80% or more of the total fiber.

For example, I consisting of a polymer or copolymer consisting of one or more types of repeating units represented by the following general formula
I can list miscellaneous things.

Here, R+ and R2 may be the same or different and are selected from hydrogen atoms and alkyl groups having 5 or less carbon atoms. Examples of the alkyl group having 5 or less carbon atoms include a methyl group, ethyl group, propyl group, butyl group, and pentyl group, but preferably a hydrogen atom. Also, for Ar, KFY÷.

can be exemplified. In addition, -x- is -〇--8-
, -N-, preferably -0-N-, more preferably 10-.

-Y- is 10- S- 5Ot- Hs- R3 represents an alkyl group having 5 or less carbon atoms) -0--S-, -
C- is preferred, and -0- is more preferred. A r
+ indicates an aromatic ring. Examples of aromatic rings include 1.
4-phenylene group, 1.3-phenylene group, 4.4'-
Examples include biphenylene group, 1.5-naphthylene group, 2,6-naphthylene group, 2.5-pyridylene group, and preferably 1.4-phenylene group.

Aromatic rings include, for example, halogen groups (e.g. chlorine, bromine, fluorine), lower alkyl groups (methyl, ethyl, isopropyl, n-propyl), lower alkoxy groups (methoxy, ethoxy), cyano, acetyl. group, nido O group, etc. may be included as a substituent.

Typical examples of fibers made of these polymers or copolymers include polypara-aminobenzamide, polyparaphenylene terephthalamide, polyvaraminobenzhydrazide terephthalamide, polyterephthalic acid hydrazide, polymetaphenylene isophthalamide, etc. Fibers made of copolymers can be mentioned.

The plasma treatment in the present invention includes oxygen, ammonia, -
The aromatic polyamide fiber is treated in an ionized atmosphere of carbon oxide, -nitrogen oxide, tetrafluoromethane, air, etc., or a mixture of these with an inert gas such as nitrogen, argon, helium, etc. to reduce the reactivity of the Ii1 surface. It is something that enhances.

The reason for the improvement in heat-resistant adhesion and fatigue resistance is not clear, but plasma treatment of aromatic polyamide cords results in the generation of functional groups on the fiber surface or the formation of unevenness on the fiber surface, which increases the resistance to treatment agents. This is thought to be because it improves publicity. This is thought to be due to the fact that the treatment agent can be applied uniformly to the surface of the cord, making it possible to uniformly disperse external stress at the time of adhesive failure or fatigue failure, making it difficult for stress concentration to occur. In order to form an ionized state of active gas, a so-called plasma processing device is used.

There are various types of plasma processing apparatuses, such as external polarity, internal polarity, collapsible coupling type, and inductive coupling type, and any of these types may be used.

The operation processing conditions vary depending on the time, but for example, 1
A high frequency glow discharge of O-3 Torr to 10 Torr is suitable. If the gas pressure in the treatment tank exceeds 10 T orr, it is not preferable because the temperature rise during glow discharge may significantly alter the surface of the aromatic polyamide fiber. On the other hand, at a vacuum level of 10-5 Torr with no vortex, the glow discharge is not stable and it is difficult to perform normal processing. Thus, by plasma treatment, the surface of the aromatic polyamide fiber can be treated at low temperature and in a short time without impairing the mechanical properties of the aromatic polyamide fiber.

The polyepoxide compound used in the first treatment agent of the present invention is a compound containing at least two or more epoxy groups in the molecule in an amount of 0.2 g equivalent or more per 100 g of the compound, and includes ethylene glycol, glycerol, sorbitol, pentaerythritol, polyethylene Reaction products of polyhydric alcohols such as glycols and halogen-containing epoxides such as epichlorohydrin,
4-Hydroxyphenyl)dimethylmethane, phenol-formaldehyde resin, resorcinol-formaldehyde resin and other polyhydric phenols and the above-mentioned halogen-containing epoxides, and by oxidizing unsaturated compounds with peracetic acid or hydrogen peroxide, etc. The resulting polyepoxide compound, namely 3.4-epoxycyclohexene epoxide, 3.4
-Eboxycyclohexylmethyl-3,4-■boxycyclohexenecarboxylate, bis(3,4-epoxy-6-methyl-cyclohexylmethyl)adipate, and the like. Among these, reaction products of polyalcohols and epichlorohydrin, ie, polyglycidyl ether compounds of polyhydric alcohols, are particularly preferred because they exhibit excellent performance. Such polyepoxide compounds are usually used as emulsions. To make an emulsion, for example, such a polyepoxide compound as it is or dissolved in a small amount of solvent as necessary is mixed with a known emulsifier such as sodium alkylbenzene sulfonate, dioctyl sulfosuccinate sodium salt, nonylphenol ethylene oxide adduct. Emulsify using etc.

Next, the blocked polyisocyanate compound used in the first treatment agent of the present invention is an addition compound of a polyisocyanate compound and a blocking agent, and the blocking component is liberated by heating to produce an active polyisocyanate compound. be. Examples of polyisocyanate compounds include polyisocyanates such as tolylene diisocyanate, metaphenylene diisocyanate, metaphenylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, polymethylene polyphenylisocyanate, triphenylmethane triisocyanate, and triphenylmethane triisocyanate. Polyisocyanates, or these polyisocyanates and compounds having two or more active hydrogen atoms, such as trimethylolpropane, pentaerythritol, etc., are combined in a molar ratio of incyanate groups (-NCO) to hydroxyl groups (-OH) exceeding 1. Examples include polyalkylene glycol adduct polyisocyanates containing terminal isocyanate groups, which are obtained by reacting at a specific temperature.

In particular, aromatic polyincyanates such as tolylene diincyanate, diphenylmethane diincyanate, and polymethylene polyphenylisocyanate are preferred because they exhibit excellent performance.

Examples of blocking agents include phenols such as phenol, thiophenol, cresol, and resorcinol;
Examples include aromatic secondary amines such as diphenylamine and xylidine, lactams such as phthalic acid imides, caprolactam and barolactam, oximes such as acetoxime, methyl ethyl ketone oxime, and cyclohexane oxime, and acidic sodium sulfite.

Examples of the rubber latex used in the first treatment agent of the present invention include natural rubber latex, styrene butadiene,
There are copolymer latex, vinylpyridine-styrene-butadiene, terpolymer latex, nitrile rubber latex, chloroprene rubber latex, etc., and these can be used alone or in combination. Among these, vinylpyridine-styrene-butadiene terpolymer latex shows excellent performance when used alone or when used in an amount of 1/2 or more.

As the first treatment agent, the above polyepoxide compound (A)
, a blocked polyisocyanate compound (B), and a rubber latex (C) (A).

(B), (C) The blending ratio of each component is (A)/[(A)
X (B,)] is 0.05 to 0.9, (C)/[(
A)+(B)] is preferably in the range of 1 to 10. Here (A>/ [(A)+(B)]
If it is out of the above range, the rate of rubber adhesion to aromatic polyamide II tends to deteriorate and the adhesiveness tends to decrease, and if (C)/[(A)+(B)] is smaller than the above range. The treated aromatic polyamide fiber becomes hard, which may lead to a decrease in fatigue resistance, and on the other hand, if it exceeds the above range, adhesiveness will decrease.

The total solid content concentration including the polyepoxide compound (A), blocked polyisocyanate compound (B) and rubber latex (C) is adjusted to be 1 to 30% by weight, preferably 3 to 20% by weight based on the weight of the fiber. use. If the concentration is too low, the adhesion will decrease, and if the concentration is too high, it will become hard and the fatigue resistance will decrease.

A dispersant when using the first treatment composition as an aqueous dispersion,
That is, an appropriate amount of the surfactant is 0 to 15% by weight, preferably 10% by weight or less, based on the total solid content of the first treatment agent, and if the above range is exceeded, the adhesiveness tends to decrease slightly. .

The second treatment agent of the present invention is a composition containing resorcinol/formalin/rubber latex, and the resorcinol/formalin/rubber latex used here is usually called RFL, which is a combination of resorcinol and formaldehyde. The molar ratio is 1:0.1 to 1:8, preferably 1:0.
It is used in a range of 5 to 1:5, more preferably 1:1 to 1:4.

Examples of rubber latex include natural rubber latex,
There are styrene/butadiene medium copolymer latex, vinylpyridine/styrene/butadiene terpolymer latex, nitrile rubber latex, chloroprene rubber latex, etc., and these may be used alone or in combination.

Among these, vinylpyridine-styrene-butadiene terpolymer latex shows excellent performance when used alone or when used in an amount of 1/2 or more.

The blending ratio of rubber latex to resorcinol/formalin depends on the addition ratio of the ethylene urea compound (D) and the epoxy-modified phenol/formalin resin condensate (E) described below, but the solid content weight ratio is 1:1 to 1. :15,
Preferably, the ratio is 1:3 to 1:12. If the proportion of rubber latex is too small, the treated aromatic polyamide fiber material will become hard, resulting in poor fatigue resistance. On the other hand, if the amount is too large, satisfactory adhesive strength and rubber adhesion rate cannot be obtained.

Ethylene urea compound (D) and epoxy modified phenol
The mixing ratio with formalin condensate (E) is 50/50~
80/20 (weight ratio) is preferred, and the mixture has the above RF
0.5 to 30% by weight, preferably 1.0 to 2% by weight based on L
0I amount% is added. If the amount of the mixture added is too small, good adhesion and rubber adhesion cannot be obtained. On the other hand, examples of ethylene urea compounds include reaction products of aromatic or aliphatic isocyanates such as triphenylmethane triisocyanate and hexamethylene cysocyanate with ethyleneimine, and aromatic ethylene urea compounds such as diphenylmethane diethylene urea are particularly good. Give results.

Epoxy-modified phenol, which is also added to the second treatment agent.
The formalin condensate is represented by the following general formula (E).

Various compounds can be considered that satisfy the above (E), but those with a molecular weight of 1200 to 1300 and an epoxy value of 4.0 to 4.5 eq
/Kg gives good results.

In the present invention, the ethylene urea compound (D) and the epoxy-modified phenol/formalin condensate (E) have a catalytic effect on each other, and the ethylene urea compound has an ethylene imine ring opened and an epoxy-modified phenol/formalin condensate. In this product, the epoxy ring opens and reacts, increasing adhesive properties and at the same time increasing the cohesive force of the adhesive itself.As a result, it creates a strong chemical bond with the amines generated in the rubber, preventing adhesive deterioration. It is something to do.

The above-mentioned second processing agent is usually adjusted to contain 10 to 25% by weight as a solid content.

In order to attach the first treatment agent and the second treatment agent to the aromatic polyamide miscellaneous material, any method such as contact with a roller, application by spraying from a nozzle, or immersion in a bath liquid can be adopted. .

The amount of solid content deposited on the aromatic polyamide fiber is 0.1 to 10% by weight, preferably 0.5 to 5% by weight as the first treatment agent.
% by weight, 0.5-10% heavy haze as the second treatment agent composition
, preferably 1 to 5 weight. In order to control the amount of solid matter adhering to the lIN, means such as squeezing with a pressure roller, scraping off with a souffle bar, blowing off with air, suction, and beating with a beater may be used.

In the present invention, after the aromatic polyamide fiber is treated with the first treatment agent, the temperature is 50°C or higher, preferably 220 to 250°C.
It is then dried and heat treated at a temperature of 120°C or higher, preferably 180 to 250°C. If the drying/heat treatment temperature is too low, adhesion with rubber will be insufficient, while if the temperature is too high, the treatment agent will deteriorate and the adhesive performance will decrease.

By plasma-treating the aromatic polyamide fibers in this manner and then treating them with the treatment agent of the present invention, it became possible to improve the adhesive strength between the aromatic polyamide fibers and rubbers. By plasma-treating the aromatic polyamide fibers, it is possible to improve the wettability of the aromatic polyamide fibers to the treatment agent, making it possible to uniformly apply the treatment agent to the surface of the aromatic polyamide fibers, eliminating uneven adhesion. It is also believed that the plasma treatment improved the adhesion between the aromatic polyamide fiber and the treatment agent. It is thought that the synergistic effect of this plasma treatment effect and the treatment agent effect described above dramatically improved the adhesion performance between fibers and rubber.

<Effects of the Invention> Compared to the conventional method, mu treated by the method of the present invention has
Heat-resistant adhesion and peel strength are improved without impairing moldability with rubber.

<Example> Hereinafter, the present invention will be specifically explained with reference to Examples.

In addition, in the examples, cord peeling adhesive strength, T adhesive strength,
The inter-braid peeling force is a value determined as follows.

・Cord peeling adhesive strength This shows the adhesive strength between the treated cord and rubber.

Five cords were buried near the surface layer of the rubber sheet, and 15 cords were buried under pressure.
The force required to peel 5 cords from the rubber sheet at a speed of 200 aa+/m+ after vulcanization at 0° C. for 30 minutes is expressed in 15 kg.

・■Adhesive strength Treatment] - indicates the adhesive strength between the rubber and the rubber.

The cord was embedded in a rubber block and vulcanized at 150°C for 30 minutes under pressure, then the cord was removed from the rubber block for 20 minutes.
It was handled at a speed of 0.05m+/sin, and the force required for handling was expressed in Kl/cm.

- Indicates the adhesive strength with the inter-ply peel force treated cord. Embedded 2-bly treated cords in the rubber as cross-plies (cord density 27 cords/inch) at a 90 degree angle.15
After vulcanization at 0°C for 30 minutes, both plies were vulcanized at 2QQam/W.
The force required to peel off at a tensile speed of in is Ng/1n.
It is displayed in ch.

・Rubber adhesion rate This is a measure of the adhesion of rubber to fibers.

The cord peeled off from the rubber during the inter-ply peel force measurement described above was observed with the naked eye, and the portion of the cord surface to which the rubber was attached is expressed as a percentage.

Examples 1 to 3, Comparative Examples 1 to 7 6 g of Bunacol EX-611 (manufactured by Nagase Sangyo ■, sorbitol polyglycidyl ether) as a surfactant,
Neocol ■5W-30 (manufactured by Daiichi Kogyo Seiyaku, 30% aqueous solution of dioctyl sulfosuccinate sodium salt) 4
Add g and dissolve uniformly. This was added to 805 g of water with stirring to uniformly dissolve Bunacol EX-611 in the water. Next, Hiren ■MP (manufactured by DuPont ■, 4,4
- A dispersion obtained by mixing 14 g of phenol block of diphenylmethane diisocyanate, 4 g of Neocol SW-30 and 42 g of water in a ball mill for 24 hours, and Nilaball 2518GL (manufactured by Nippon Zeon),
Add 1259 (40% by weight water emulsion of vinylpyridine-styrene-butadiene terpolymer) and mix uniformly. The obtained liquid mixture is used as a first treatment agent.

In addition, 30 g of 10% caustic soda aqueous solution and 109.28% ammonia aqueous solution was added to 260 g of water and stirred well.
Add 60 g of formalin initial condensate (40% acetone solution) and stir thoroughly to disperse.

Next, Nirapol 02518G L (manufactured by Nippon Zeon ■,
Vinylpyridine/styrene/butadiene terpolymer latex 40% water emulsion) 2409 and Nilaball ■L Add the above resorcin-formalin initial condensation dispersion to this diluted solution while stirring slowly, and then add 20 g of formalin (37% aqueous solution).
Add and mix evenly. Next, in this mixed solution, diphenylmethane diethylene urea 149, Neocol ■5W-
An aqueous dispersion obtained by stirring and mixing 3059 and water 369 in a ball mill for 24 hours is added and mixed. Then E CN
1299 (manufactured by Ciba-Geigy, epoxy compound of phenol-formalin resin condensate) 7.29 was dissolved in toluene in advance, and Neocol [F]P (manufactured by Daiichi Kogyo Seiyaku, dioctyl sulfosuccinate sodium salt) was added. 0.19 and 0.6 g of methyl cellulose were added to and dissolved in the aqueous solution 289 with stirring, the resulting mixture was added and mixed, and the resulting liquid mixture was used as a second treatment agent.

As the wholly aromatic polyamide fiber, 25 mol% of rose phenylenediamine, 50 mol% of terephthalic acid chloride, 3
．． 1500 denier/1 obtained by wet spinning a polymer consisting of 25 mol% of 4'-diamino-diphenyl ether
41,112 filaments of 000 filament are twisted together, top twist 40T/10α (S), bottom twist 40T/10α (Z
) 3000 denier/2000 filament cord.

The code obtained in this way is 13.56MH of JEOL.
The sample was placed in a plasma irradiation device using a Z transmitter, and treated in an oxygen gas atmosphere at a reduced pressure of 1O-3 Torr for 5 minutes to obtain a surface-activated ]-de.

This cord was immersed in the first treatment agent using a Computer Treater〇 treatment machine (manufactured by CA Ritzler ■, tire cord treatment machine), dried at 150°C for 2 minutes, and then heat-treated at 230°C for 1 minute. do. Next, after being immersed in a second treatment agent, it was dried at 150°C for 2 minutes, and then dried at 230°C for 1 minute.
Heat treat for minutes. The treated aromatic polyamide tire cord had a solid content of 2.2% by weight of the first treatment agent and 2.5% by weight of the solid content of the second treatment agent.

The treated cord thus obtained was embedded in unvulcanized rubber containing a carcass containing natural rubber as the main component, and heated at 150°C for 30 minutes.
Vulcanization was performed for 0 minutes (initial value) and at 170° C. for 90 minutes (heat resistance value).

As shown in Table 1, the above experiment was carried out using ethylene urea compound (D
) and epoxy-modified phenol/formalin condensate (E)
The experiment was repeated by changing the weight ratio of the sample and the sample treated with plasma or without plasma treatment. The experimental results are shown in Table 1.

Table (Note) In the above table, plasma irradiation treatment was not performed for Comparative Examples 4 to 6 (D> (D)/(E) (E): Ethylene urea compound: solid content ratio (weight ratio) : Epoxy-modified phenol/formalin condensate Book 2 Initial value: Value after embedding a treated cord in unvulcanized rubber in a carcass mixture containing natural rubber as the main component and vulcanizing it at 150°C while the valve is open.

*3 Heat resistance value: A treated cord is embedded in an unvulcanized rubber compound with a carcass containing natural rubber as the main component, and the temperature is 150℃.
Value after further heat treatment at 180°C for 1 minute.

As described above, heat-resistant adhesive performance was significantly improved by treating aromatic polyamide fibers subjected to plasma irradiation treatment with an adhesive having a specific composition.

Claims (1)

[Claims] (1) After ionizing the aromatic polyamide fibers and treating them in an active gas atmosphere (plasma treatment), a first treatment containing a polyepoxide compound (A), a blocked polyisocyanate compound (B), and a rubber latex (C) is continued. Then, an ethylene urea compound represented by the following general formula (D) and an epoxy-modified phenol-formalin condensate represented by the following general formula (E) are added to resorcinol-formalin-rubber latex (RFL). /E=50/5
A method for treating aromatic polyamide fibers, comprising treating with a second treating agent added in a weight ratio of 0 to 80/20. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ Here, R is an aromatic or aliphatic hydrocarbon residue n is 0.1
Or 2. When n=0, the terminal group is hydrogen. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ Here, R' is -O-(CH_2)k-Cl, -O-(C
H_2) l-OH or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, R″ is H, CH_
3, C_2H_5, k, l, m are integers of 1 to 4, m' is an integer of 1 to 5, a, b are integers of 1 to 5, and a+b≦6.