JPS60163923A - Novel polymer and its production - Google Patents

Abstract

PURPOSE:To produce a polymer excellent in heat resistance, flame retardancy and moldability, by reacting a reaction product between a dihalogenobenzonitrile and an alkali metal salt of a dephenol with a methylene halide. CONSTITUTION:A reaction product obtained by reacting a dihalogenobenzonitrile of formula I (wherein X is a halogen) with an alkali metal salt of a diphenol of formula II [wherein Ar is a group of formula III, IV, or the like (where R is a 1-10C aliphatic hydrocarbon group), and M is an alkali metal] in a solvent is reacted with a methylene halide of formula V (wherein X' is Cl and/or Br) and treating the reaction product with water or alcohol to obtain a polymer having K repeating units of formula VI and l repeating units of formula VII(wherein K and l are integers which can satisfy the relationship: 0.5<=k/(k+l)<= 0.98), terminated with -H, -OH, a group of formula VIII or IX (wherein R' is H, a 1-8C alkyl group or the like) and having a reduced viscosity, as measured in N-methylpyrrolidone in a concentration of 0.2g/dl at 30 deg.C, >=0.2dl/g.

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. The present invention relates to a cyanaryloxy polymer having a novel structure whose heat resistance can be easily controlled by the following methods, and a method for producing the same.

[Technical background of the invention and its problems 3 Various cyanaryloxy polymers have been disclosed in Japanese Patent Application Laid-Open No. 47-14
Publication No. 270 has been published. Although these polymers have heat resistance, their glass transition temperature (Tg)
is 136 to 178°C, thermal decomposition onset temperature (Td) is 400
℃, and it is difficult to say that the heat resistance of British soil is necessarily the same as that of light.

Furthermore, as disclosed in the above publication, a polymer produced using bisphenol A as a dihydric phenol is
Its Tg is constant at 173°C and cannot be changed. That is, the heat resistance of the cyanaryloxy polymer cannot be adjusted by the method described in the above publication. Therefore, the obtained polymer cannot be flexibly applied to various fields of application requiring heat resistance.

Furthermore, the conventional cyanarylic-egg polymer has problems in terms of practicality due to its poor moldability.

[Purpose of the invention]

The present invention uses the above-mentioned polymers which also have excellent heat resistance and flame retardancy, and furthermore, by changing the copolymer composition, the heat resistance can be changed as appropriate, and furthermore, it has good moldability. The purpose of this invention is to provide a novel cyanaryloxy polymer and a method for producing the same.

[Summary of the invention]

The novel polymer of the present invention is CN (wherein R is an aliphatic hydrocarbon having 1 to 10 carbon atoms, and n
represents an integer from 1 to 6)), the following formula: 0-CH,! -0-Ar
---(II) (In the formula, Ar has the same meaning as above) (where k and t each represent an integer that satisfies the relationship of 5≦+A≦98 ) and an alkyl group whose end group is a prime number of 1 to 10, 'T
(representing either a aryl group or an aralkyl group) or having a aryl group, and using N-methylpyrrolidone as a solvent at a concentration of 0.2 f/dL at 30°C.
The reduced viscosity (η8P/C) at is 0.2 dt/f/
The production method is characterized by the following formula: MO-Ar-OM --(IV) (wherein, Ar
has the same meaning as above; M represents an alkali metal) in the presence of a solvent, and the resulting reaction product has the following formula: CH
2X, '...(■) (wherein, X' represents either one or both of chlorine and bromine) is reacted with the methylene halide, and then the resulting reaction product is mixed with water. Or, it is characterized by treatment with alcohol.

In the polymer of the present invention, repeating unit 1 of formula (1)
or a plurality of repeating units of formula (n) connected in an appropriate linear chain; and a connection unit consisting of one repeating unit of formula (n) or a plurality of repeating units appropriately connected in a linear chain. are connected to each other in a disordered or ordered linear chain, and the terminals of the whole are -H and -OH.

It represents any one of an alkyl group, an aryl group, and an aralkyl group having 1 to 10 carbon atoms. Among these, R' and CH.

is preferable.

In this polymer, the total number of each repeating unit k.

t is an integer that satisfies the relationship 5≦”L≦0.98 +/
It is necessary that = . −When the knee is less than 0.5+
4, the molecular weight of the obtained polymer tends to decrease, leading to a decrease in heat resistance. Also, -”-1 becomes 0.98 +/
II.

If it exceeds, fluidity during molding will decrease. Preferably 0.
7≦kit≦0.95.

The polymer of the present invention has a reduced viscosity (ηSP/C) of the resin solution at 30°C of 0.2 when the polymer is dissolved in N-methylpyrrolidone to a concentration of 0.2 f/dt. It is a polymer having a molecular weight of dL/ or more. Is this ηS P/C 0.2dt/? If the degree of polymerization is less than the above, the polymer has a low molecular weight and therefore has low heat resistance.

The polymer of the present invention is produced as follows.

In the first step, horn-lognopenzonitrile represented by the formula (III) and an alkali metal salt of a dihydric phenol represented by the formula (IV) are dissolved in the below-mentioned solvent and reacted.

In the compound of formula (Ill), halo r7X is F, C
L is preferred. Further, in the compound of formula (■), M may be any alkali metal, but especially K, Na
is preferable. In the compound of formula (1), Ar may be any of the compounds listed above.

has the same meaning as above) and an alkali metal salt such as potassium carbonate or potassium hydroxide.

In addition, in proceeding with the reaction of this step, for example, without using the compound of formula (IV) from the beginning of the reaction,
The above-mentioned dihydric phenol and the above-mentioned alkali metal salt may be added together to the reaction system. In this case, as the reaction progresses, the reaction system of this step has the formula (E
The compound V) will be produced.

The usage lid for each compound is the unit (
It is determined from the relationship between the total number of units (I) and the total number t of units (II). That is, if the number of moles used of the compounds of formula (■) and formula (IV) is m and 11, respectively, then m=k,
m and n may be set so that n=+t.

However, there is no problem even if this relationship breaks down.

In this process, it is preferable to add monovalent phenol as a molecular ft regulator.

It can be opened. Further, the lid to be used is determined based on the relationship with the 1° molecule of the target polymer.

The reaction is carried out in a solvent. Various organic solvents can be used, such as N-methylpyrrolidone, dimethylacetamide, and diphenylsulfone.

Sophenyl sulfoxide and sulfolane can be mentioned, and their use may be as long as they are capable of dissolving the compounds of formulas (lil) and (IV).

The reaction temperature is usually 100-300°C, preferably 150-300°C.
The temperature is 250°C. The reaction time is 0.5 to 3 hours, preferably 1 to 2 hours. Moreover, even if the reaction is carried out under normal pressure,
It may be carried out under slight pressure.

In this way, low molecular weight oligomers are produced.

Next, in the second step, a third step is added to the reaction system of the first step described above.
This is a step of supplying a predetermined amount of methylene halide of formula (V), which is a raw material, to finally produce the polymer of the present invention.

As the methylene halide to be used, in formula (V), X' is C
Preference is given to L , Br , ie methylene chloride or methylene bromide. The reaction proceeds in the presence of a solvent. The solvent is the same as in the first step.

In reality, since the reaction products, that is, the generated oligomers and solvent, are present in the reaction system of the first step, it is sufficient to simply supply methylene halide to this system1. The amount of methylene halide supplied is in units of ( II) may be selected in relation to the total number t, specifically, at least L=n-
It is mmol. Although methylene halide may be used in either a gaseous or liquid state, a method in which gaseous methylene halide is blown into the reaction system in the first step is preferred. At the time of this blowing, the blowing l'' per time υ is appropriately adjusted so that the total amount of blowing at the end of the reaction is the amount necessary for the reaction.

The reaction temperature is 100 to 250°C, preferably 150 to 20°C.
0°C, reaction time is 1-3 hours, preferably 5-1.
It is 5 hours. Further, the reaction may be carried out under normal pressure or under slightly increased pressure.

The final step is a step in which the product produced in the second step is treated with water or alcohol to remove the alkali metal at the end of the reaction product and block it with -H and -OH.

In this step, after cooling the entire reaction system after completing the second step, the reaction product is diluted with a solvent such as methylene chloride or N-methylpyrrolidone, and by-products such as sodium chloride are removed. Pour the solution into water or methanol and reprecipitate. This treatment may be performed at room temperature or under slight heating.

By heating and drying the obtained precipitate, the polymer of the present invention can be obtained6. In addition, in the present invention, the process has been divided into three and explained, but this is divided depending on the difference in the type of reaction. It goes without saying that the actual operations may be performed continuously.

[Embodiments of the invention]

Example 1 2.2-bis(4.0
-hydroxyphenyl) f-ropane 11.415t (0
,05 mol), potassium carbonate 8.98 r (0,06
5 mol), 2,6-cyclobenzonitrile 7.741
? (0-045 mol), N-methylpyrrolidone 100
- and toluene 40- were charged and held at 140 to 160°C for 3 hours, and the produced water was distilled off together with toluene. Next, the temperature of the whole was raised to 90'C to distill off the remaining toluene, and then the reaction was carried out at 190 tll for 3 hours. Next, add methylene chloride to 0 at 150℃.
．． The blowing reaction was carried out for 3 hours at a feed rate of 46 t/min. After the reaction was completed, the product was diluted with 500% of N-methylpyrrolidone, the salt was removed in a furnace, and the product was poured into methanol to precipitate and recover the polymer1. It was vacuum dried at 130°C for 10 hours.

The yield of polymer was 15.9 tons (yield: 100 tons).

This polymer was analyzed by infrared absorption spectroscopy (IR analysis) at 3030 cm-'! : 830o
Absorption due to the C-H bond of the benzene ring at the n-' (r) position, absorption due to the C-C bond of the benzene ring at the 159° crn-' position, absorption due to aromatic ether at the 1240 cm-' position, 2230 Absorption due to nitrile groups was observed at the cm-' position. When subjected to nuclear magnetic resonance analysis (NMR analysis), it was found that δ5.6 pp
A peak due to the methylene proton of 10-CH, -0- was observed at m. k+e=0.9.

ηSP/CO, 83dt/f, Tg of this polymer
The temperature was 168'C, Td 480°C.

In addition, when this polymer was press-molded into a film and a lighter's flame was applied to it for 10 seconds, the flame was moved away and the flame retardance was examined, the fire was immediately extinguished and no melting and dripping of the film was observed. .

Example 2 Biphenol 9.39 (0,
A polymer was obtained in the same manner as in Example 1 except that 05 mol) was used. The results of IR analysis and flame retardancy test are shown in Example 1.
It was the same. The yield was 13.8r (yield 10096). i=0.9゜lP/C
2,20dt/f, Tg 205°C, Td 52
9°c.

Example 3 4,4′-thiophenol 10 was substituted for 2,2-bis(4-hydroxyphenyl) f-lonon 9 in Example 1.
．． Using 914 f (0.05 mol),
The amount of cyclobenzonitrile used was 8.171 r(0
. The results of IR analysis and flame retardancy test were the same as in Example 1. Yield ii 15.6 r (100%)
. −1− +t=0.95, η8P/C=1.17dt/
l, Tg 149°C, Td 496°C.

Example 4 Vinenol 9.3r (0,0
A polymer was obtained in the same manner as in Example 1. . The results of the IR analysis and flame retardancy test were the same as in Example 1.

Yield [12,4F (yield 99%).

fi = 0.6, 17 SP/C4, 66dL/?
, Tg 182°C.

Td　530℃.

Example 5 In the same separable flask as mflJ1, 9.3 t (0.05 mol) of biphenol and 8.9 t of potassium carbonate were added.
8r (0,065 mol), 2.6-v chlorobenzonitrile 8.17 ? (0,0475%), N-methylpyrrolidone 100-, toluene 40- and p-cumylphenol 0.212- as molecular weight regulator. (0
,001 mol) and the subsequent operations were carried out in the same manner as in Example 1 to obtain a polymer. The results of IR analysis and flame retardancy test were similar to Example 1. In addition, as a result of NMR analysis, a peak due to the methylene proton of the 10-CH2-0- bond was observed at δ5.6 ppm, and a peak at δ1.5 ppm was observed.
A peak due to the methyl proton of cumylphenol was observed at 8 ppm. Yield 14.2 f (100% yield). 7 = 0.95, ISP/C2
, 09dt/r, Tg 207°C, Td 536°C.

[Effects of the Invention] As is clear from the above description, the polymer of the present invention has superior heat resistance and flame retardancy compared to conventional cyanaryloxy polymers. In addition, the polymer of the present invention can change both Tg and Td by changing its co-polymerization composition, and can meet various side heat property requirements.3 The polymer of the present invention has excellent heat resistance, Mt1 flammability, etc. It is useful as a material for mechanical parts of various electrical and electronic devices.

Claims (1)

[Scope of Claims] and R is aliphatic reverted hydrogen having 1 to 10 carbon atoms (however, n
represents an integer from 1 to 6)), the following formula: OCHt OAr --
(II) (in the formula, Ar has the same meaning as above) (where k and t are each 0.5≦-, -1c 4-
hydrogen atom (representing an integer satisfying the relationship t≦0.98);
0, 22/dt concentration using N-methylpyrrolidone as a solvent; The viscosity (ηSr/C) of the solution at 30°C is 0.
2 dt/? A novel polymer characterized by the above. (wherein, X represents /.rodane atom) and the following formula: MO-Ar-OM
-... (IV), R represents any aliphatic hydrocarbon having 1 to 10 carbon atoms (where n represents an integer of 1 to 6; M represents an alkali metal) is reacted with an alkali metal salt of a dihydric phenol in the presence of a solvent, and the resulting reaction product has the following formula: CH2X2' (V) (where X' is 2GIT (representing either one or both of chlorine and bromine) is reacted, and the resulting reaction product is then treated with water or alcohol. (Ar has the same meaning as above), represented by the following formula: -0-CH2-0-Ar --- (II) (wherein Ar has the same meaning as above) has a repeating unit (k and t each represent an integer satisfying the relationship of 0.5≦function≦0.98), and is a hydrogen atom; an alkyl group having 1 to 10 carbon atoms. Reduced viscosity at 30°C of a solution with a concentration of 0.2 f/dt and using N-methylpyrrolidone as a solvent. (77sP7'c
) is 0.2 dt/f or more. 3. A method for producing a novel polymer according to claim 2, using 3-valent phenol as a molecular 31M moderating agent.