JPS60161428A - Novel polymer and its preparation - Google Patents

Abstract

PURPOSE:A cyanoaryloxy polymer having improved heat resistance, flame retardance, and solvent resistance, varying Tg and Td and showing various heat resistance by changing its composition, obtained by reacting a dihalogenobenzonitrile with a bihydric phenol metal salt, and a sulfone compound. CONSTITUTION:A polymer having k repeating units shown by the formula I [Ar is group shown by the formula II, formula III, formula IV, formula V (R is 1- 10C bifunctional aliphatic hydrocarbon group), or group shown by the formula IV(n is 1-6), etc.], and l repeating units shown by the formula VII (Ar is as shown in the formula I ) in such a way that relationship 0.1<=k/(k+l)<=0.99 is satisfied, having a terminal group of any of -H, -OH, group shown by the formula VIII or IX(R' is H, 1-10C alkyl, etc.), and a reduced viscosity in a solution of 0.2g/ dl in N-methylpyrrolidone as a solvent at 30 deg.C of 0.3dl/g. This polymer is obtained by reacting a dihalogenoenzonitrile with a bihydric phenol alkali metal salt, and a 4,4'-dihalogenophenylsulfone in the presence of a solvent, treating the reaction product with water or an alcohol.

Description

[Detailed Description of the Invention] [Technical Field of the Invention] The present invention relates to a novel polymer and a method for producing the same.
Excellent heat resistance, S-furnace resistance, and solvent resistance.

The present invention relates to an arylox heppolymer with a new composition whose heat resistance can be easily adjusted by changing the copolymerization composition, and a method for producing the same.

(Technical background of the invention and its problems) Various cyanogens - Luoki heptapolymer was disclosed in Japanese Patent Application Laid-Open No. 47-14
It is disclosed in Japanese Patent No. 270. Although these polymers have heat resistance, their glass transition temperature (TF) is 1
To 36: 178℃, thermal decomposition start temperature (Td) is 400℃
Front and rear, not necessarily practical.

It is difficult to say that its heat resistance is sufficient.

Furthermore, as disclosed in the above publication, a polymer produced using bisphenol A as a dihydric phenol is
The TP is constant at 173°C and cannot be changed. That is, the heat resistance of the aryloxy polymer cannot be adjusted by the method described in the above-mentioned publication. therefore.

The obtained polymer also cannot be flexibly applied to various fields of application requiring heat resistance.

[Purpose of the invention]

The present invention is a novel polymer that has better heat resistance than the above-mentioned polymers, as well as excellent flame retardancy and solvent resistance, and furthermore, its heat resistance can be changed as appropriate by changing the copolymer composition. The purpose is to provide the □ manufacturing method.

[Summary of the invention]

The novel polymer of the present invention is:

(KaStsu-,-@-0-@-,(gicO(sawa.

+R-◇X (wherein R represents an aliphatic hydrocarbon divalent group having 1 to 10 carbon atoms), or (wherein n is 1 to 6
(represents one of the integers of)) The following formula: -0 go5O40-Ar-・・・・・・・・・ω
) (in the formula, Ar has the same meaning as above) j repeating units k (however, k and l each represent an integer satisfying the relationship 0.1≦−7≦0.99) atoms ;representing or having an alkyl group, aryl group, or aralkyl group having 1 to 10 carbon atoms, and using N-methylpyrrolidone as a solvent.
The reduced viscosity at 30°C of a solution having a concentration of with nitrile.

An alkali metal salt of a dihydric phenol represented by the following formula: MO-Ar-OM...0 (in the formula, Ar has the same meaning as above; M represents an alkali metal) .

The following formula; ) te sign 4, 4
'-Dihalogenophenyl sulfone is reacted in the presence of a solvent, and the resulting reaction product is then treated with water or alcohol.

In the polymer of the present invention, repeating unit 1 of formula (I)
or a plurality of repeating units of formula (Il) connected in an appropriate linear chain; , R' is water □
Elementary atom; represents any one of an alkyl group, an aryl group, and an aralkyl group having 1 to 10 carbon atoms. Among these, R'
as (CH3) 3 C + the total number of each repeating unit k in this polymer.

In this case, the molecular weight of the obtained polymer tends to decrease, leading to a decrease in heat resistance. Moreover, when 1;T exceeds 0.99, fluidity during molding decreases.

The polymer of the present invention can be obtained by dissolving this polymer in N-methylpyrrolidone to a concentration of 0.21! /dl,
The reduced viscosity of this resin solution at 30°C (ηsp/a
) is 1), a polymer having a molecular weight of 3dl111 or more. This t18p/e is 0.3d4/
If the degree of polymerization is less than 1, the heat resistance will be low because the monopolymer has a low molecular weight.

The polymer of the present invention is produced as follows.

That is, dihalogenobenzonitrile represented by formula (1), alkali metal salt of dihydric phenol represented by 2〇, and 4,4'-dihalogenophenyl sulfone represented by formula (■) are dissolved in the solvent described below. and react under the conditions described below.

In the compound 2〇), the halogen X is preferably C1, 13r, and the halogen X' in the compound 2M is F, CA! is preferred. In these compounds, X and
may be the same or different. In the compound of formula (■), M may be any alkali metal, but in particular, N! LH is preferred.

Furthermore, Ar may be any of the substances listed above.

Compound No. 2 is easily prepared by the neutralization reaction of a dihydric phenol represented by DoshaArshaOH (Ar has the same meaning as above) and an alkali gold parent salt such as potassium carbonate or potassium hydroxide. be able to.

Note that in order to proceed with the reaction of the present invention, for example, the dihydric phenol described above and the alkali metal salt as described above may be added together to the reaction system without using the compound 20 from the beginning of the reaction. You can leave it there. In this case, as one reaction progresses, 扛弐〇 compounds will be produced in the reaction system.

The amount of each compound to be used is determined in relation to the degree of polymerization of the desired polymer. The number of moles of the compound of formula I used is m02
If the number of moles of the compound of formula 0 used is m2 and the number of moles of the compound of formula M used is m3, it is sufficient that the relationship m2 = m + m3 is satisfied, but there is no problem even if this relationship is broken.

The reaction is carried out in a solvent. Examples of the solvent to be used include various organic solvents such as dimethylsulfoxide, sulfolane, diphenylsulfone, N-methylpyrrolidone, and dimethylacetamide, and the amount used is 201. The amount may be sufficient as long as it dissolves each compound of the formula 201 carbonate.

The reaction temperature is inn~350°C, preferably 150~28
0°C 1 reaction time h o, i ~ 5.0 hours, preferably C
), leave for 5 to 2.0 hours. Further, one reaction may be carried out under normal pressure or under slightly increased pressure.

In this process, it is preferable to add m phenols as molecular weight l1lII agents. Monovalent steel used/k
(!: L Teh, (CHB)sC+OH.

I can give it to you. Moreover, the amount used is determined based on the relationship with the molecular weight of the target polymer.

Next, the reaction product obtained through the above process is mixed with water.

Treatment with alcohol removes the alkali metal present at the end of the reaction product and replaces it with H and OH. As the alcohol, methanol and ethanol are preferred. ′
As a treatment method, it is sufficient to simply put the above reaction product into water or alcohol.

Examples of the Invention Example 1 Biphenol 9.
30 y (0,0 5 mol), 2,6-cyclopenzonitrile 4.30 P C 0,025 mol).

4.4'-Dichlorodiphenylsulfone 7.18 PC
0,025 mol), potassium carbonate 8.98 F (0,0
65 mol), 100 d of N-methylpyrrolidone, and 40 ml of toluene were charged and held at 150°C for 2 hours to distill off the produced water together with the toluene, and the temperature was further raised to 180°C to completely trap and distill off toluene. The polymerization reaction was carried out at 180° C. for 3 hours. After the completion of the reaction, the reaction product was cooled and diluted with 500 g of N-methylpyrrolidone, the salt was removed by F, and the obtained product was poured into methanol. The precipitated polymer was collected and vacuum-dried at 130°C for 10 hours.

Polymerization t'E Yield 11a, 011 (yield 94%).

Next, the obtained polymer was analyzed by infrared absorption spectrum (IR).
When applied with analysis K, 303 Qam-1 and 830 pseudo-1 were absorbed by the C-H bond of the benzene ring, 1590
Absorption by the c-c bond of the benzene ring on "at-", 12
40C11-” absorption by aromatic ether bond, 2
Absorption by nitrile was observed in 220at-''.Also, this polymer was press-molded to form a film, and the nine folded parts of the film were immersed in methanol, acetone, methylene chloride, and chloroform. .

When we conducted a solvent resistance test to check for the occurrence of cracks, we found that no cracks were observed in any of the solvents. When we conducted a flame retardant test by keeping the flame away, the fire was extinguished immediately and no melting or dripping was observed. Furthermore, 0.0% of N-methylpyrrolidone in this polymer was added.
21! Reduced viscosity (η
sp/c) is 1.07 di/f, and the glass transition temperature is 227°C.

The thermal decomposition onset temperature (Td) was 513°C (in air). Further, the value of Ni/ni+J of this polymer was 0.5.

Example 2 The amount of 2.6-dichlorobenzonitrile used was 0.86
F (0,1105 mol), and the amount of 4,4'-dichlorodiphenylsulfone used is 12.92 P(0,
045 mol) was prepared in the same manner as in Example 1 to obtain a polymer. The yield of the polymer was 919.3 (yield 99%). IR
The results of analysis, solvent resistance test, and flame retardancy test were the same as in Example 1. Also, the reduced viscosity ηap/c is 1.34 d
i/f, TF 233℃, Td 511℃,
The value of k/10J was 0.1.

Example 3 The amount of 2.6-dichlorobenzonitrile used was 2.581
! (0,015 mol) and the use of 4,4'-dichlorodiphenylsulfonett'I n, 05 f(
A polymer was obtained in the same manner as in Example 1, except that the amount was changed to 0,035 mol). Polymer yield: 17.81! (Yield 9
7%). The results of the IR analysis, solvent resistance test, and No. 11 flammability test were the same as in Example 1. Also, the reduced viscosity ηsp/e is 1.25 dl/II, the temperature is 230°C, and the Td is 512.
℃, and the value of k/+J was (1,3).

Example 4 The amount of 2.6-dichlorobenzonitrile used was 6.88
F (0,04 mol) and ffl dose of 4,4'-dichlordiphenylsulfone t-2,87F (0,
#1 was obtained in the same manner as in Example 1. Polymer yield, 15.1 PC yield 98%
).

The results of IR analysis, solvent resistance test and 1wA flammability test were the same as in Example 1. In addition, the reduced viscosity ηBP/e is 0.7
9 di71! , TF was 216°C, Td was 516°C, and the value of k/+J was 0.8.

Example 5 p-cumylphenol 0.212F as a molecular lid-binding agent
A polymer was obtained in the same manner as in Example 3 except that (0,01) 1 mol) was added. Yield of polymer: 17.9 F (97% yield). As a result of the IR analysis, in addition to each absorption in Example 1, absorption due to inzolovir group was observed at 2850CII''. The results of the solvent resistance test and flame retardancy test were the same as in Example 1.

ηsp/Q = 0.47 di/l, TF =
216°C, Td = 539°C, +z = 0.3° Example 6 Same as Example 3 except that p-ter7-arybutylphenol o, 151 (0, (101 mol)) was added as a molecular weight regulator. A polymer was obtained in the same manner as above.Polymer yield: 18.4
11 (yield inn%). 1 ton of this polymer
(1,3, ηsp/c = 11.67 dA
! /IP.

'l'p=216°C, 'l'd=551°C.
The results of the IR analysis are the same as those in Example 1.

Absorption due to the methyl group of p-tert-butylphenol was observed at 28501m''. Both solvent resistance and flame retardant test results were the same as in Example 1.

Example 7 A polymer was obtained in the same manner as in Example 1, except that 2,2'-bis(4- and dolo I?7 phenyl)zoloban 11.41P (0.05 mol) was used in place of biphenol. Ta. Polymer yield 19.2 F (yield too).

The results of the IR analysis, solvent resistance test, and flame retardancy test were all the same as in Example 1. ηsp/c =0.43dl
IP, TP = 176°C, Td = 492°C, k/ +/= 0.5° Example 8 Vinenol It, t, 4,4'-thiodiphenol 10.91 F (0.05 mol) Except I used it.

A polymer was obtained in the same manner as in Example 1. Polymer yield17.
6F (yield 94 buns). IR analysis, solvent resistance test, J
I! The results of the flammability test were all the same as in Example 1. ηsp/c = +1.40 dJ/j', T = 157°C.

Td=491℃, +7 to k/? = 0.5゜Example 9 Hydroquinone 5.51jl instead of biphenol
(0,135 mol) was pressed in the same manner as in Example 1 to obtain a polymer. Polymer yield 12.9 F (yield 97
blood). The results of the IR analysis, solvent resistance test, and flammability test were all the same as in Example 1. ηsp/c=0.49
dl force, TP=194°C, 'l'd=503°C.

k7tc+g = 0.5゜Example 1O In the same separable flask as in Example 1, 2,6-cyclopenzonitrile 4.30 F C0,1) 25 mol), 4,4'-difluorodiphenylsulfone 6.3
5611 (0,025 mol), biphenol 9.30
F (0,0s mol), potassium carbonate 7.051 PC
(1.05 mol) and Sulfolane 40d were added, stirred while blowing argon gas, and heated to 230°C for 30°C.
Graining was carried out for 2 hours at 250° C. for 2 hours.

After the polymerization reaction was completed, the product was poured into methanol to precipitate and collect the polymer. The obtained polymer was pulverized using a Waring blender, washed with 11 portions of hot water and then 1 liter of hot methanol, and then dried under reduced pressure at 100° C. for 8 hours.

Polymer yield17. Of (yield 100cm). IR analysis,
The results of the solvent resistance test and flame retardancy test were the same as in Example 1. ηHP/c = 0.79dlIP, TF=
225℃, 'l'd=515℃, k/+l=1
), 5.

[Effects of the Invention] As is clear from the above explanation, the polymer of the present invention not only has superior heat resistance and good flammability compared to conventional cyanarylox heppolymers, but also It also has excellent resistance to air fresheners. Moreover, when the copolymer composition of the polymer of the present invention is changed, both TP and Td can be changed to meet various heat resistance requirements.

The polymer of the present invention is useful as a material for mechanical parts of various electric/electronic devices requiring heat resistance, solvent resistance, flame retardance, etc.

Claims (1)

[Scope of claims] -8O2-@-0-Ar----・-・
...One repeating unit represented by (If) (in the formula, has the same meaning as above in Arts) (where n is an integer that satisfies the relationship of 1≦74≦0.99, respectively) ). The terminal group is -H, -OR, -4' (wherein, R' is a hydrogen atom; an alkyl group having 1 to .lo carbon atoms, an aryl group,
Any of the aralkyl groups has the same meaning as ゎ)
A novel product characterized in that the reduced viscosity at 30°C of a solution using N-methylpyrrolidone as a solvent is 0.3 dl or more (in the formula , X represents a halogen atom). The following formula: MO-Ar-OM ・・・・・・・・・[Stock]
Represents any of the following: S-sha, Kutsuo-ro, lco-sha (■R (represents an integer of N (however, R represents an aliphatic hydrocarbon divalent group having a carbon number of 1 to 1O)), MtlZ alkali metal represents an alkali metal salt of a dihydric phenol represented by the following formula:
) (wherein, X' represents a halogen atom and may be the same as or different from X in the compound of formula (1)) in the presence of a solvent. The reaction product obtained is then treated with water or alcohol (wherein Ar has the same meaning as above). The following formula knee 0@-8O,
・One repeating unit represented by -(11) (in the formula, Ar has the same meaning as above) (where l, , ni, / are o, i≦7 and ≦0.99, respectively)
hydrogen atom; an alkyl group having 1 to 10 carbon atoms, having the same meaning as a), and 0,21/dJ using N-methylpyrrolidone as a solvent. Concentration syneresis 3(1'
A method for producing a novel polymer having a reduced viscosity of (], 3 dl/f or more at c).A method for producing a novel polymer according to claim 2, using trivalent phenol as a molecular weight modifier.