JPS61118411A - Silylarylacetylene polymer and its production - Google Patents

Abstract

PURPOSE:The polymerization of a specific silylarylacetylene is conducted in the presence of a catalyst of a carbene of a metal such as Mo to give a specific linear polymer which is suitable for use as a material for separation of a gas mixture, because the polymer has excellent gas separation and permeation properties. CONSTITUTION:Preferably in an inert atmosphere such as nitrogen, the polymerization of a silylarylacetylene of formula I (R1, R2, R3 are 1-10C alkyl; 6-20C aryl, 7-20C arylalkyl, 4-20C cycloalkyl; A is 6-20C aryl) such as trimethylsylylphenylacetylene is effected to give a linear polymer with recurring units of formula II and 1,000-5,000,000mol.wt.

Description

Detailed Description of the Invention [Industrial Application] The present invention has good separation properties and permeability, especially excellent separation properties and permeability for gases, and is suitable for separating substance mixtures, especially gas mixtures. The present invention relates to a polymer of lylaryl acetylene compounds useful as membrane materials and a method for producing the same.

[Conventional technology]

As materials for mixed gas separation membranes, polydimethylsiloxane, polydimethylsiloxane-polycarbonate block copolymers (U.S. Pat. No. 10.μ56, No. j, I
7), polydimethylsiloxane copolymer (JP-A No. 4-21204c), poly(Hiroshi-methylpentene-/) (JP-A No. 7-Hiroshi 203), alkyl group or phenyl Polyalkynes with groups as substituents (
JP-A No. 7-/90607, JP-A It-/1!3-01, Il! I Kaisho! polyalkynes with silyl groups as substituents (J, Amay, C
Hew, sow,,! +F! 74C7J (/913>
) etc. are known.

[Problem that the invention seeks to solve]

Conventional materials for separation membranes do not simultaneously satisfy the two required characteristics of high gas permeability and performance stability that allows for long-term use.

[Means for solving problems]

As a result of intensive study of the above problems, the present inventors came up with the invention of an acetylene polymer substituted with a silyl group and an aryl group.

That is, the silylaryl acetate/silicone polymer in the present invention is a polymer having a weight average molecular weight of 1,000 or less, consisting of repeating units having a structure represented by the following structural formula (!).
It is a linear polymer of aooo.

Table 2 (Rs% R1, R in the structural formula is an alkyl group having 1 to 10 carbon atoms, an aryl group having 2 to 20 carbon atoms, an arylalkyl group having 7 to 0 carbon atoms, and a carbon alkyl group having 1 to 10 carbon atoms.
It is a group selected from 7-chloroalkyl groups with a prime number μ to coO. AFi is an aryl group having 6 to 0 carbon atoms. ) R1, Rs, and R1 in the structural formula (!) K are as follows:
For example, an alkyl group such as a methyl group, an ethyl group, an n-propyl group, a l-propyl group, a butyl group, a 7-chloroalkyl group or a cyclohexyl group, and an aryl group such as a phenyl group, a tolyl group, a 67-tyl group, or an arylalkyl group. Examples include benzyl group.

Examples of structural formulas include phenyl, naratyl, tolyl, and anthryl groups.

Various methods can be used to produce the silylaryl acetylene polymer of the present invention. A method of polymerization using a carbene compound as a catalyst is preferred because of the simplicity of the process.

The compound represented by structural formula (1) is hereinafter referred to as a monomer.

R, -Sl -C5C-A value) S (R1 and Rs in the structural formula are an alkyl group having 1 to 1 carbon atoms and 10 to 10 carbon atoms, an aryl group having 6 to 1 carbon atoms, and an aryl group having 7 to 0 carbon atoms, respectively. (A is a group selected from arylalkyl groups and cycloalkyl groups having from 1 to 10 carbon atoms. A is an aryl group having from 6 to 0 carbon atoms.) Specific examples of the above monomers include trimethylsilylphenylacetylene. , triethylsilylphenylacetylene 1
, triphenylsilylphenylacetylene, trimethylsilyltolylacetylene, trimethylsilyl-1-naphthylacetylene, trimethylsilyl-teranthryl acetylene 7, and the like.

In order to polymerize these monomers, a catalyst that generally polymerizes acetylene compounds may be used, but the K that can be used to obtain the linear polymer of the present invention with good yield is 1, 2, 1, 1, 2, Preferably, ethyl metal carbene compounds are used.

Examples of metal carbene compounds with strong catalytic action include compounds having the following structure.

Preferred specific examples of compounds represented by structural formula (11) Toshiteha, methoxyphenylcarbenepentacarbonyltungsten, cyphenylcarbene/tacarbonyltungsten, methoxymethylcarbenepentacarbonyltungsten, methoxyphenylcarbenepentacarbonylmolybten, cyphenylcarbene/penotacarbonyl Examples include morphene.

Another example of a metal carbene compound catalyst with strong catalytic action is a catalyst obtained by reacting molybdenum pentachloride or large tungsten chloride with a monosubstituted ethylamine compound having a structure represented by the following structural formula (T). It will be done.

R, -CmiC-H(t) (in the formula, - is an alkyl group having io or less carbon atoms, an aryl group or arylalkyl group having 20 or less carbon atoms, io carbon atoms
It is a group selected from the following 7-chloroalkyl groups, alkyl groups having 10 or less carbon atoms, aryl groups, or silyl groups having an arylalkyl group as a substituent. ) As a compound represented by the structural formula (g), for example, phenyl-7-thire 1,! - or λ-naphthylacetylene,
/-7'tene, 1-pebutene, 1-hexyne, trimethylcryla heptaprene, etc. are preferred.

In order to cause the compound represented by the structural formula (T) to act on molybdenum pentachloride or macrotungsten chloride, mol equivalents of these metal cyclides (l)/N10, preferably 2 to 1 molar equivalent, are added. Monosubstituted acetylene (structural formula (5)
) in the polymerization solvent described below at 0 to ioo°C, preferably 20 to tO°C. The subsequent polymerization reaction is carried out by directly adding this catalyst solution to the upper Zummer solution.

To obtain a metal carbene compound catalyst, a method in which niobium pentachloride, niobium pentabromide, tantalum pentachloride, or tantalum pentabromide is reacted with a disubstituted acetylene having a structure represented by the following structural formula M is also suitable.

R? CE5C1 entrance lock (RT, R during ceremony)
a is an alkyl group having 10 or less carbon atoms, and 20 carbon atoms, respectively;
The following aryl group or arylalkyl group, carbon number 2
The substituent group is a 7-chloroalkyl group having 0 or less carbon atoms, an alkyl group having 10 or less carbon atoms, an aryl group having io or less carbon atoms, or an arylalkyl group as a substituent.

However, compounds in which Ry and RJ are both silyl groups are excluded. ) Examples of the compound represented by the structural formula (7) include cohexin, cooctin, copsin, /-7xdis,
-t-7' Robin, l-phenyl-7-hexyne,
/-t-+) methylsilyl-/-globin, etc., are mixed with niobium pentachloride, niobium pentabromide, tantalum pentachloride, or tantalum pentabromide in a polymerization solvent, and heated at 0 to 100°C. , preferably #iSO~10
The catalyst solution was prepared by reacting at ℃ for 0,/hr to λ hours. For every 7 molar equivalents of niobium pentachloride, niobium pentabromide, tantalum pentachloride, or tantalum pentabromide, the disubstituted acetylene compound (structural formula CV1) is used in an amount of /N10 mol equivalents, preferably 2 to j mol equivalents. The monomer has the structural formula■
), a simple method can be used to automatically generate metal carbene compounds by adding niobium pentachloride, niobium pentabromide, tantalum pentachloride, or tantalum pentabromide to the monomer solution. - Molybdenum pentachloride or tungsten hexachloride is reacted with the same molar equivalent of tetra-7enyltin, and when added to the monomer solution, the mixture changes from black or bluish black to a deep brown solution, forming a metal carbene compound. is generated within the system and polymerization progresses. In this case, molybdenum pentachloride or large tungsten chloride and an equimolar equivalent of tetraphenyltin are mixed in a polymerization solvent at a temperature of 0 to 100°C, preferably Fi20 to rO°C of 0. /hour to 2 hours and then added to the monomer solution.

Examples of solvents that can be used when polymerizing 7lyaryla-7thyl of the present invention using the catalyst and 7mer described above include aromatic hydrocarbons such as benzene and toluene; Typical examples include halogenated hydrocarbons such as carbon tetrachloride and chloroform, and ethers such as diethyl ether and dioxane.The reaction temperature is generally 0 to 720°C.
C., preferably 20 to t0.degree. C. All six reactions are preferably carried out in an inert atmosphere such as nitrogen or argon.

In the present invention, the concentration of carbon dioxide is generally K O,/rnol
/ノ~zOrrtrl/l is selected. Preferably/
moVl'' / OrmVl, the amount of catalyst is preferably such that the ratio of molybdenum, tungsten, niobium or tantalum metal carbene compound/monomer is less than //J0, especially / / / 0-/ / / 00
0 is preferable.The amount of catalyst used can be larger or smaller, but if a large amount is used, the molecular weight of the polymer tends to decrease, and 8t) If a small amount of K is used, the polymerization progresses extremely slowly. Become.

The polymerization reaction is stopped using a lower alcohol such as methanol, a lower ketone such as acetone, water, or the like.

The obtained polymer is generally an orange powder and is generally soluble in halogenated hydrocarbons, aromatic hydrocarbons, alicyclic hydrocarbons, ketone hydrocarbons, ester hydrocarbons, etc.
Insoluble in lower alcohols and aliphatic hydrocarbons.

[For production]

The polymer obtained in this manner has inherently high gas permeability because it has a bulky cryl group as a substituent.
Furthermore, since one of the substituents is an aryl group, the main chain resists deterioration reactions such as oxidation and decomposition, and is highly durable.

〔Example〕

Next, the present invention will be explained in detail with reference to Examples, but the present invention is not limited thereto.

Example 1 0.0% of tungsten hexachloride in a dry nitrogen atmosphere. Hiro I! I
(2) Weigh 1 and dissolve it in 10-liter of toluray. This solution was stirred at room temperature for 30 minutes, after which 1/mmol of phenylacetylene was added and stirred again for 1 hour to obtain a catalyst solution. 20 m of trimethylsilylzenyla
The above acWI solution was added to a 7-mer solution dissolved in toluene IO-, and the solution was added to the acWI solution in a dry nitrogen atmosphere.
The reaction was carried out at ℃. The amount of monomer consumed was measured by gas chromatography using 1-methylnaphthalene as an internal standard, and it was found that the monomer of FCIFJ/r- was consumed after j hours. After the reaction was stopped by adding acetonate, the reaction solution was poured into 100% methanol to precipitate a polymer, filtered and dried under vacuum at room temperature. The polymer yield was about 7. The weight-average molecular weight of the polymer obtained in this way was about 0.05 mm by gel permeation chromatography (hereinafter abbreviated as GPC).

Met.

The obtained polymer was an orange powder, and the polymer was an orange powder. Soluble in halogenated hydrocarbons such as roform, aromatic hydrocarbons such as benzene and toluene, ketone hydrocarbons such as acetono, alicyclic hydrocarbons such as 7-chlorohexane and medelshik-a-hequina 7, and lower-grade hydrocarbons such as methanol. It was insoluble in chain hydrocarbons such as alcohol and hexane.

Figure 1 shows the grot/'! of this polymer. l! c Magnetic resonance spectrum ('I (abbreviated as NMR) is shown. M!~lP
K aromatic proton signal, -o, r~1,j
A signal of a methyl group proton attached to silicon was observed on P.

Figure 2 shows the results of measuring the weight loss on heating of this polymer while heating it up to 00°C at a rate of 10°C/min in nitrogen and air. 3ts
Met.

Example λ 0.00% of tungsten hexachloride/in a dry nitrogen atmosphere. μmmo
l and tetraphenyltin0. ura mel and toluene were added, and the mixture was stirred at room temperature for 30 minutes. This catalyst mixture was added to a monomer solution in which trimethylsilylphelacetylene (OmlT101) was dissolved in toluene ion and reacted at t0° C. under a dry nitrogen atmosphere. 5
After an hour, the consumption of % of the polymer was about 60%. After the reaction was stopped by adding acetone, the reaction solution was poured into methanol and the polymer was recovered. After drying, the yield of the polymer was determined by weighing and found to be approximately 20%. Polymer 1! The weight average molecular weight was determined from GPC to be approximately /l, 0θ0.

The solubility and 'HNMR of the obtained polymer were the same as in Example 1.

Example J Trimethylsilylphenylacetylenol
Toluene/JOwtK dissolved monomer solution 1 under dry nitrogen atmosphere, tantalum pentachloride 0Jrnrrvol t
Add ffs. When reacted at 10℃ for a short time,
After terminating the reaction with about 4 c0 of monomer consumed with methanol, the reaction solution was diluted with chloroform, solids such as catalyst residue were removed, and the weight average molecular weight was determined using GPCK. It was about □00.

Example 0.4 nmole of cyphenylcarbenbentacaryltungsten in methane was added to a seven-mer solution prepared by dissolving 2□mole of trimethylsilylphenylacetylene in toluene and OgItK under a dry nitrogen atmosphere.

When the reaction was carried out at to℃ for ≠ hours, approximately /
J Chi's seven tsumas had been consumed. The reaction was stopped with 2-acetone, and the reaction solution was poured into methanol to recover the polymer. The yield of polymer was approximately tS. The weight average molecular weight of the polymer was calculated from GPCK to be approximately 9.

The solubility and 'HNMR of the obtained polymer were the same as in Example 1.

Example! ~10 Polymerization was carried out in the same manner as in the method described in Example 1~D, except that the monomers and catalysts were changed. A catalyst of the type of Example I, the results of which are shown in Table 1, including Example 1-μ, was used, for example, in wet,
/ (-substituted acetylene compound) etc. A catalyst of the type of Example 2 can be used, for example w(5/5n(C@Its)
It is abbreviated as n etc. When using the method of Example J, the catalyst is expressed as, for example, 1 g of TaC, which represents the case where a metal carbene compound catalyst is prepared from niobium pentachloride, niobium pentabromide, tantalum pentachloride, or tantalum pentabromide and disubstituted acetylene. is generally written as MZs / (disubstituted acetylene compound) (where M is Nb or Ta%2
is CI or Br).

(Leaving space below) Application example/Example/Measurement of gas separation by casting a solution of 1 polymer part of the polymer obtained in Example/ in 3 parts by weight of toluene onto a membrane/filter TM-λP manufactured by Toyo Roshi Co., Ltd. A sample was prepared. The hydrogen and nitrogen permeability of this sample was measured, the permeability of the cellulose filter membrane carrier was corrected, and the hydrogen permeability coefficient was heat-treated at 70°C for 3 hours. The value of permeability coefficient did not change from before heating.

〔Effect of the invention〕

The polymer of the present invention had excellent gas permeability and gas separation properties because it had a bulky silyl group. Additionally, the substitution with aryl groups resulted in durability.

[Brief explanation of the drawing]

FIG. 1 is a proton nuclear magnetic resonance spectrum of a deuterated chloroform solution of the polymer of Example 1. FIG. 2 is a heating loss curve of one combination of Example 1.

Claims (2)

[Claims] (1), a weight average molecular weight of 1,000 to 5,00 consisting of a repeating unit of the structure represented by the following structural formula (I)
0,000 linear polymer. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (1) (R_1, R_2, and R_3 in the structural formula are an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aryl group having 7 to 20 carbon atoms, respectively. (A is a group selected from alkyl groups and cycloalkyl groups having 4 to 20 carbon atoms. A is an aryl group having 6 to 20 carbon atoms.) (2), a weight average molecular weight of 1,000 to 5,000, consisting of repeating units having a structure represented by structural formula (I);
000 linear polymer, the compound represented by the following structural formula (II) is polymerized using at least one metal carbene compound selected from molybdenum, tungsten, niobium, and tantalum as a catalyst. A method for producing a polymer. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (III) (R_1, R_2, and R_3 in the structural formula are an alkyl group having 1 to 10 carbon atoms, an aryl group having 7 to 20 carbon atoms, and an arylalkyl group having 7 to 20 carbon atoms, respectively. A is a group selected from cycloalkyl groups having 4 to 20 carbon atoms. A is an aryl group having 6 to 20 carbon atoms.)