JPH0618884B2 - Polysiloxane compound having bifunctional phenyl group - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel polysiloxane compound having a bifunctional phenyl group at one end and a repeating unit consisting of an organosiloxane. The compounds of the present invention are
By utilizing the reactivity of the bifunctional phenyl group at one end, for example, a graft copolymer in which the main chain is composed of a condensation polymer such as polyamide, polyamic acid or polyimide, and the side chain is composed of polyorganosiloxane. It is particularly useful as a raw material macromonomer or a precursor thereof when synthesizing.

BACKGROUND OF THE INVENTION AND PRIOR ART In recent years, synthesis of graft copolymers using macromonomers has been actively carried out. Macromonomer means an oligomer or polymer having a polymerizable functional group,
By using this, the number and length of branches of the graft copolymer can be easily controlled, and various combinations of trunks and branches can be selected (for review, Yuya Yamashita, Kobunshi, Vol. 31, 988 pages, Ryuzo Asami, Polymer processing, 3
Volume 4, Page 439, Koichi Ito, Polymer Processing, Volume 35,
262, etc.).

Monomers used in the synthesis of macromonomers known so far include, for example, styrene, isoprene,
Various types of macromonomers are known over a wide variety such as vinyl pyridine, vinyl chloride, vinyl acetate, isobutylene, methyl methacrylate, ethylene oxide, tetrahydrofuran, oxazoline, and hexamethylcyclotrisiloxane. In addition, as a terminal polymerizing group of these macromonomers, a styryl group, an acryloyl group, a methacryloyl group or the like is mainly used because of its ease of introduction. However, in this case, the macromonomer is mainly used for radical polymerization, and the comonomer used when synthesizing the graft copolymer is limited to vinyl monomers such as styrene, acrylic acid ester, and methacrylic acid ester. The main chain polymer of the obtained graft copolymer is a so-called radical polymer. On the other hand, as macromonomers for polycondensation and polyaddition, macromonomers having a dicarboxylic acid or a diol at the terminal have been reported, and grafts using these macromonomers as main chain polymers such as polyurethane and polyamide. Copolymers have been synthesized (for example, Yamashita et al., Poly
m. Bull., Volume 5, 361, (1981), Yamashita et al., Polym. Bull., Volume 8, 239, (1982).
), Tezuka et al., Polymer Preprints, Japan, 36, 3
61, (1987) etc.).

[Problems to be solved by the invention]

However, no macromonomer having a diaminophenyl group at one end as a terminal polymerization group is known at all,
If such a macromonomer for polycondensation is obtained, it is expected that a new graft copolymer having a main chain of aromatic polyamide, polyamic acid, polyimide or the like can be synthesized using the macromonomer.

The present invention expands the range of applications of the above-mentioned conventional macromonomers, and is particularly useful as macromonomers and their precursors for synthesizing aromatic polyamide and polyimide-based graft copolymers. The purpose of the present invention is to provide a novel polysiloxane compound having a phenyl group.

[Means for solving problems]

The present inventors diligently studied to obtain a novel macromonomer having a diaminophenyl group at one end and which can be used as a macromonomer for polycondensation. as a result,
A new polysiloxane macromonomer having a diaminophenyl group at one end and a repeating unit consisting of an organosiloxane can be synthesized from a precursor having a dinitrophenyl group at one end, and polycondensation reaction using the macromonomer. The inventors have reached the present invention by finding out what can be done.

That is, the present invention has the general formula (In the formula, A is a divalent organic group, Y is a nitro group or an amino group, R ^{1 to} R ⁵ are the same or different alkyl groups, substituted alkyl groups, phenyl groups or substituted phenyl groups, m
Is an integer of 1 or more. However, R ¹ and R ² may be different for each repeating unit. And a polysiloxane compound having a bifunctional phenyl group at one end.

The divalent organic group represented by A in the general formula (I) is a substituted or unsubstituted methylene group, a polymethylene group having 2 or more carbon atoms, a silylene polymethylene group, a phenylene polymethylene group, an oxypolymethylene group. , A phenyleneoxypolymethylene group, and the like.

The compound of the present invention can be synthesized, for example, by the production method described below.

That is, the general formula (In the formula, m and R ^{1 to} R ⁵ are the same as those in the above general formula (I)), and one-end hydropolyorganosiloxane represented by the general formula (In the formula, Y is the same as above, and B is a group having a carbon-carbon double bond.) A hydrosilylation reaction with a compound represented by The polysiloxane compound represented by the general formula (I) can be synthesized.

When Y is an amino group, a polysiloxane compound having a dinitrophenyl group at one end, in which Y is a nitro group in the general formula (I), is reduced by an ordinary method to convert the dinitro group into a diamino group. By doing
It can also be synthesized. This production method is more preferable in view of the stability of the diaminophenyl group and the reaction efficiency in the hydrosilylation reaction.

The one-terminal hydropolyorganosiloxane represented by the general formula (II) has a polymerization degree m of 1, and a part thereof is commercially available (for example, pentamethyldisiloxane manufactured by Shin-Etsu Chemical Co., Ltd.). When m is 2 or more, for example, as shown in the following reaction formula, a cyclosiloxane compound is obtained by using a silanolate anion obtained by adding an equimolar amount of an alkyllithium compound (RLi) to trisubstituted silanol as an initiator. After the living ring-opening polymerization, the reaction can be stopped by using a diorganohalogenosilane compound having one Si—H bond to synthesize the compound.

(In the formula, R ^{1 to} R ⁵ , R ¹ ′ and R ² ′ are the same or different and are an alkyl group, a substituted alkyl group, a phenyl group or a substituted phenyl group, R is an alkyl group and X is a halogen atom. However, R ¹ and R ² may be different for each repeating unit, q is an integer of 3 to 6, and p is 1
Is an integer above, and qp + 1 is equal to m in the general formulas (I) and (II)).

Further, in the above reaction, it is possible to synthesize the polyorganosiloxane represented by the general formula (II) by using an alkyllithium compound instead of the silanolate anion as the initiator, in which case one end is The alkyl group R of the used alkyllithium compound is introduced into [R ⁴ in the above general formula (II)].

(In the formula, R ¹ , R ² , R ¹ ′, R ² ′ and q and p are the same as above, and R is an alkyl group, provided that qp is the above general formula (I) and (II)). In the formula (II), R ³ and R ^{4 in the} general formula (II).
Are the same as R ¹ and R ² , respectively.

Alkyl lithium compound used here (RL in the above formula
As i), methyllithium, ethyllithium, n-
Butyl lithium, sec-butyl lithium, t-butyl lithium, n-hexyl lithium, etc. can be illustrated.

The following general formula IV used in synthesizing the above-mentioned one-end hydropolyorganosiloxane: (In the formula, R ^{3 to} R ⁵ are the same as above), and examples of the trisubstituted silanol include trimethylsilanol, triethylsilanol, dimethyloctylsilanol, dimethyloctadecylsilanol, 3-chloropropylmethylsilanol, 3,3. , 3-trifluoropropyldimethylsilanol, tridecafluoro-1,1,2,2-tetrahydrooctyldimethylsilanol, diphenylmethylsilanol, triphenylsilanol, pentafluorophenyldimethylsilanol and the like can be exemplified. Some of these silanol compounds are commercially available and can also be easily synthesized from the corresponding chlorosilane compounds. In addition, the following general formula V: (Wherein R ¹ , R ² and q are the same as above), the cyclosiloxane compound represented by Etc. can be illustrated. Moreover, you may use the mixture of 2 or more types of these cyclosiloxane compounds. The following general formula VI used as a terminating agent: (Wherein R ¹ ′, R ² ′ and X are the same as above), the diorganohalogenosilane compound is
Examples thereof include dimethylchlorosilane, diethylchlorosilane, methyloctylchlorosilane, 3,3,3-trifluoropropylmethylchlorosilane, phenylmethylchlorosilane, diphenylchlorosilane, and pentafluorophenylmethylchlorosilane.

When the one-end hydropolyorganosiloxane represented by the general formula (II) is synthesized by the above-mentioned method, it is preferably carried out in a solvent, and examples of the solvent used include tetrahydrofuran, diethyl ether, n-hexane,
Organic solvents such as cyclohexane and benzene may be mentioned.
In addition, it is desirable to carry out this reaction in an inert atmosphere such as argon or nitrogen.

The reaction is usually carried out at room temperature, and the reaction time is different in each reaction step, but the reaction between the trisubstituted silanol represented by the general formula (IV) and the alkyllithium compound is 15 minutes or more, and The living ring-opening polymerization reaction of the cyclosiloxane compound represented is 2 hours or more, more preferably 10
The reaction proceeds suitably by carrying out the termination reaction of adding the diorganohalogenosilane compound represented by the general formula (VI) for at least 30 minutes, respectively.

As described above, the one-terminal hydropolyorganosiloxane represented by the general formula (II) can be easily synthesized by continuously adding the respective reaction reagents in the same container. Further, the degree of polymerization m of the one-end hydropolyorganosiloxane represented by the general formula (II) is controlled by adjusting the amount of the cyclosiloxane compound represented by the general formula (V) used in the above reaction. be able to.

It is essential that the compound represented by the general formula (III) used in the method for producing the polysiloxane compound of the present invention has a carbon-carbon double bond. An example is a compound represented by the following formula. However, in the formula, Y represents the same meaning as described above, and Y is assumed to be bonded to any two carbons of the carbons at the 2 to 6-positions of the bonded benzene ring.

These compounds are not generally commercially available, but can be relatively easily synthesized by, for example, the method shown as a reference example later.

In the method for producing the compound of the present invention, the hydrosilylation reaction of the one-end hydropolyorganosiloxane represented by the general formula (II) and the compound represented by the general formula (III) in the presence of a catalyst is carried out. Chloroplatinic acid (H ₂ PtCl ₆ .6H ₂ O) is most commonly used as the catalyst used in the process, but other metal complexes containing palladium or rhodium can also be used. For example, (Ph ₃ P) ₄ P
d, (Ph ₃ P) ₂ PdCl ₂ , and (PhCN) ₂ PdC
l ₂ , (Ph ₃ P) ₃ RhCl, (Ph ₂ PH) ₂ RhC
1, (Ph ₃ P) ₂ (CO) RhCl, [(C ₂ H ₅ ).
₃ P] ₂ (CO) RhCl can be used as a catalyst. The amount of the catalyst used is usually about 1/100 to 1/1000 equivalent with respect to the group having a carbon-carbon double bond. This reaction is preferably carried out in a solvent, and as the solvent, hexane, benzene, toluene, acetone, trichloroethylene, carbon tetrachloride, tetrahydrofuran (THF) or the like can be used. The reaction temperature is 40 ° C. to 100 ° C., and it is preferable to carry out the reaction in an atmosphere of an inert gas such as argon or nitrogen.

The compound of the present invention represented by the above general formula (I) obtained by the above-described production method is optionally subjected to a reduction step, for example, in the form of a compound having a diaminophenyl group, such as an aromatic dicarboxylic acid or an aromatic compound. By carrying out a polycondensation reaction with a difunctional compound having reactivity with a diaminophenyl group such as an aromatic dicarboxylic acid dichloride or an aromatic tetracarboxylic dianhydride, the main chain is composed of an aromatic polyamide, a polyamic acid or a polyimide. It can be used for synthesizing a novel graft copolymer having a side chain of polyorganosiloxane (see the usage example). In this polycondensation reaction, a graft copolymer having two or more diamine components can also be obtained by reacting in the presence of another diamine compound as the third component.

Such a graft copolymer is composed of a polymer having both a main chain and a side chain having heat resistance, and also has flexibility which is a characteristic of polyorganosiloxane. Could be. In particular, a graft copolymer having a main chain of polyimide and a side chain of polyorganosiloxane has a high heat resistance by taking advantage of heat resistance and chemical resistance of polyimide, flexibility of polyorganosiloxane, and high substance permeability. It can be expected as a new type of gas separation membrane and liquid separation membrane material having properties. It is also possible to improve the drawbacks of conventional polyimides such as rigidity, hygroscopicity, poor moldability, etc. by introducing polyorganosiloxane chains.

The degree of polymerization m of the polysiloxane compound of the present invention is basically 1 or more. However, when used in the polycondensation reaction as described above, considering the reactivity of the terminal bifunctional phenyl group, m is preferably in the range of 1-100.

〔The invention's effect〕

Since the polysiloxane compound of the present invention has a diaminophenyl group having condensation reactivity or a dinitrophenyl group which is a precursor thereof at one end, it is polycondensed with other condensation monomers by utilizing its reactivity. By carrying out the reaction, it is possible to easily achieve the synthesis of a novel graft copolymer having a main chain of aromatic polyamide, polyamic acid or polyimide and a side chain of polyorganosiloxane.

[Reference Examples, Examples and Usage Examples]

Hereinafter, the present invention will be described in more detail with reference to Examples, Examples and Usage Examples. However, it goes without saying that the present invention is not limited to these.

Reference Example 1 Synthesis of 3,5-dinitrostyrene 64 g of diethyl malonate 30 dry tetrahydrofuran
It was dissolved in 0 ml, and a solution of methylmagnesium iodide in diethyl ether (methyl iodide 5
6.8 g, 10.8 g of magnesium and 60 ml of dry diethyl ether were synthesized by a usual method) from a dropping funnel and stirred for 30 minutes. Next, 46 g of 3,5-dinitrobenzoyl chloride and 200 m of purified chloroform
1 solution was added from a dropping funnel and the mixture was stirred for 13 hours, then the reaction solution was concentrated under reduced pressure, 500 ml of diethyl ether and 200 ml of 2N sulfuric acid were added to the residue, and the organic layer was separated. The aqueous layer was extracted with 100 ml of diethyl ether, combined with the above organic layer, washed with 200 ml of water and 100 ml of saturated saline, dried over sodium sulfate, and the solvent was distilled off under reduced pressure to obtain a C-acyl derivative.

Subsequently, 160 ml of acetic acid and concentrated sulfuric acid 2 were added to the C-acyl derivative.
After adding 0 ml and 100 ml of water, heating and refluxing for 3 hours, the mixture was poured into 600 ml of ice water, and the precipitated crystals were collected by filtration.
The obtained crystal was dissolved in chloroform 1 and washed with 400 ml of half-saturated aqueous sodium hydrogen carbonate. The aqueous layer is again chloroform 20
It was extracted with 0 ml, combined with the above organic layer, washed with 100 ml of water and 100 ml of saturated saline, dried over sodium sulfate, and the solvent was distilled off under reduced pressure to give 3,5-dinitroacetophenone 3
6.2 g (yield 86.2%) of pale yellow crystals (melting point: 81
° C).

The results of IR spectrum, ¹ H-NMR spectrum and elemental analysis were as follows.

IR spectrum (cm ^-1 ); 3100 (m) (CH ₃ ),
1698 (s) CO), 1627 (m), 1552
(S) (NO ₂ ), 1350 (s) (NO ₂ ), 12
60 (s), 1145 (m), 1085 (m), 938
(W), 920 (m), 733 (s), ¹ H-NMR spectrum, δ (CDCl ₃ , ppm);
2.8 (s, 3H), 9.2 (d, 2H, J = 2H
z), 9.3 (t, 1H, J = 2 Hz), elemental analysis value (%); C: 45.55, H: 3.14.
N: 13.25 (calculated value; C: 45.72, H: 2.8
8, N: 13.33). The subsequently obtained 3,5-dinitroacetophenone 31.
5 g of ethanol 750 ml and tetrahydrofuran 37
After dissolving in 5 ml and cooling to -10 ° C, 2.84 g of sodium borohydride was added and stirred for 1 hour. Next, 375 ml of cold water was added, the reaction solution was concentrated under reduced pressure, and the residue was extracted 4 times with 200 ml of ethyl acetate. The aqueous layer was salted out, extracted again with 100 ml of ethyl acetate, combined with the above organic layer, dried over sodium sulfate, and the solvent was distilled off under reduced pressure to obtain a crude alcohol. Purified by column chromatography using silica gel (developed with ethyl acetate: hexane = 1: 1), α- (3,5-dinitrophenyl) ethanol 2
0.8 g (yield 65.5%) of yellow-brown solid (melting point: 68
˜69 ° C.).

The results of IR spectrum, ¹ H-NMR spectrum and elemental analysis were as follows.

IR spectrum (cm ^-1 ); 3400 (b) (OH),
3120 (m), 3000 (w), 1545 (s)
(NO ₂ ), 1345 (s) (NO ₂ ), 1120
(M), 1075 (m), 1025, (w), 905
(M), 795 (w), 730 (s), 670 (m). ¹ H-NMR spectrum, δ (CDCl ₃ , ppm ,;
1.63 (d, 3H, J = 6.5 Hz), 2.75 (b
s, 1H), 55.19 (q, 1H, J = 6.5H)
z), 8.60 (d, 2H, J = 2.2 Hz), 8.8
9 (t, 1H, J = 2.2 Hz). Elemental analysis value (%); C: 45.32, H: 3.91
N: 12.98 (calculated value; C: 45.29, H: 3.8
0, N: 13.20). Subsequently, 20.8 g of phosphorus pentoxide was added to 20.8 g of the obtained α- (3,5-dinitrophenyl) ethanol under ice cooling.
Was added, and the mixture was gradually heated to 100 ° C. and stirred at 100 ° C. for 3 hours.

After allowing to cool, about 4 ml of water was added to the reaction mixture, extraction was performed 9 times with 50 ml of diethyl ether, the organic layers were combined, and the solvent was evaporated under reduced pressure to obtain a crude product. Purified by sublimation, 3,5-
11.4 g (yield 59.9%) of dinitrostyrene was obtained as pale yellow crystals (melting point: 86-87 ° C).

The results of IR spectrum, ¹ H-NMR spectrum and elemental analysis were as follows.

IR spectrum (cm ^-1 ); 3100 (m) (C
H ₂ ), 1540 (s) (NO ² ), 1345 (s)
(NO ² ), 1085 (m), 980 (m) (C =
C), 935 (m), 905 (s) (C = C), 80
0 (m), 730 (s), 700 (m). ¹ H-NMR spectrum, δ (CDClR ₃ , ppm);
5.7 (d, 1H, J = 10.8 Hz), 6.1 (d,
1H, J = 17.5 Hz), 6.9 (dd, J = 10.
8 Hz, 17.5 Hz), 8.6 (d, 2H, J = 2.
0 Hz), 8.9 (t, 1H, J = 2.0 Hz). Elemental analysis value (%); C: 49.33, H: 3.35
N: 14.36 (calculated value; C: 49.49, H: 3.1
2, N: 14.43). Example 1 Synthesis of 3,5-dinitrophenethylpolysiloxane 1 3,5-dinitrostyrene 1.00 obtained in Reference Example 1
g and pentamethyldisiloxane (m = 1) 1.68 g were dissolved in toluene 10 ml and heated to 80 ° C. under an argon stream, and then chloroplatinic acid (H ₂ PtCl ₆ · 6H ₂ O) in isopropanol ( 40 μl of 0.1 mol /) was added, and the mixture was stirred for 4 hours and 40 minutes. The solvent was distilled off under reduced pressure to obtain a crude product, which was subjected to column chromatography using silica gel (developed with diethyl ether: hexane = 1: 8).
To give 904 mg (yield 51.3%) of a mixture of α- (3,5-dinitrophenethyl) polysiloxane and β- (3,5-dinitrophenethyl) polysiloxane as a pale yellow oil.

The results of IR spectrum, ¹ H-NMR spectrum and elemental analysis were as follows.

IR spectrum (cm ^-1 ); 3120 (w), 2970
(M) (CH ₃ ), 1545 (s) (NO ₂ ), 13
45 (s) (NO ₂ ), 1255 (s) (Si
C), 1060 (s) (SiOSi), 905
(W), 840 (s), 802 (s), 785 (m),
730 (m). ¹ H-NMR spectrum, δ (CDCl ₃ , ppm); α
Body: 0.01 (s), 0.06 (s) (15 in total)
H), 1.45 (d, 3H, J = 7.4 Hz), 2.4
6 (q, 1H, J = 7.4 Hz), 8.24 (d, 2)
H, J = 2.2 Hz), 8.75 (t, 1H, J = 2.
2 Hz). β-body: 0.08 (s), 0.12 (s) (15 in total)
H), 0.93 (m, 2H) 2.88 (m, 2H),
8.38 (d, 2H, J = 2.1 Hz), 8.82
(T, 1H, J = 2.1 Hz). ^From the integrated value of ¹ H-NMR, the ratio of α to β is about 2: 1.
Met.

Elemental analysis value%; C: 45.63, H: 6.25, N:
8.22 (calculated value; C: 45.59, H: 6.47,
N: 8.18). Example 2 Synthesis 1 of 3,5-diaminophenethyl polysiloxane 1 50 mg of 5% palladium carbon powder (Nippon Engelhardt) was suspended in 2 ml of ethanol, and the catalyst was activated by passing hydrogen for 15 minutes. Then, α, β of 3,5-dinitrophenethylpolysiloxane obtained in Example 1
A solution of 342 mg of the mixture in 1 ml of ethanol was added, and the mixture was reduced by hydrogen for 1 hour and 50 minutes. After the catalyst was filtered off, the solvent was concentrated under reduced pressure and dried under reduced pressure at 60 ° C. to give 266 mg of 3,5-diaminophenethylpolysiloxane (yield 94.1).
%) As a pale brown oil.

The results of IR spectrum, ¹ H-NMR spectrum and elemental analysis were as follows.

IR spectrum (cm ^-1 ); 3450 (w) (NH ₂ ),
3370 (m) (NH ₂ ), 2970 (s) (C
H ₃ ), 1600 (s) (NH ₂ ), 1255 (Si
C), 1060 (SiOSi), 840 (s), 802
(M), 780 (m), 750 (w). ¹ H-NMR spectrum δ (CDCl ₃ , ppm); α
Body: 0.05 (s), 0.09 (s) (15 in total)
H), 1.27 (d, 3H, J = 7.6 Hz), 1.9
6 (q, 1H, J = 7.6 Hz), 3.45 (bs, 4
H), 5.80 (t, 1H, J = 2.1 Hz), 5.8
7 (d, 2H, J = 2.1 Hz). β-body: 0.00 (s), 0.07 (s) (15 in total)
H), 0.83 (m, 2H), 2.45 (m, 2H),
3.45 (bs, 4H), 5.92 (t, 1H, J =
2.0 Hz), 5.99 (d, 2H, J = 2.0H
z). Elemental analysis value (%); C: 55.51, H: 9.32
N: 9.55 (calculated value; C: 55.27, H: 9.2)
8, N: 9.92). Reference Examples 2 to 8 Synthesis of one end reactive polysiloxane 20.3 g of trimethylsilaranol was dissolved in 200 ml of dry tetrahydrofuran, and a hexane solution of n-butyllithium (1.6 mol /) 14 was added under an argon stream.
1 ml was added. After stirring for 10 minutes, a solution of 75.0 g of hexamethylcyclotrisiloxane dissolved in 200 ml of dry tetrahydrofuran was added, and the mixture was allowed to stand at room temperature for 2 minutes.
Stir for 1 hour. 250 ml of dimethylchlorosilane was added to this reaction solution as a terminating agent to terminate the living polymerization reaction. Next, the solvent was distilled off under reduced pressure, and the precipitated salt was filtered off and heated at 120 ° C. for 3 hours under a vacuum of 0.1 mmHg or less to remove unreacted cyclosiloxane and excess terminator. , A hydropolydimethylsiloxane 9 having an average value of the degree of polymerization m (represented below) of 5.5
3.8 g was obtained as a colorless transparent viscous liquid.

Further, by changing the amount of hexamethylcyclotrisiloxane used or the structure of silanol as an initiator, hydropolydimethylsiloxane as shown in Table 1 was obtained in the same manner.

Example 3 Synthesis of 3,5-dinitrophenyl polysiloxane 2 3,5-dinitrostyrene 1.00 obtained in Reference Example 1
g and 2.48 g of the hydropolydimethylsiloxane (= 5.5) obtained in Reference Example 2 were dissolved in 10 ml of toluene and heated to 80 ° C. under an argon stream, and then chloroplatinic acid (H ₂ PtCl ₆ ·. 20 μl of an isopropanol solution (6H ₂ O) (0.1 mol /) was added, and the mixture was stirred for 1 hour and 30 minutes. The solvent was distilled off under reduced pressure to obtain a crude product, which was purified by column chromatography using silica gel (developed with diethyl ether: hexane = 1: 4) to give 3,5-
Dinitrophenethyl polysiloxane (= 5.5) 2.
58 g (74% yield) was obtained as a pale yellow oil.

The results of IR spectrum, ¹ H-NMR spectrum and elemental analysis were as follows.

IR spectrum (cm ^-1 ); 3130 (w), 2980
(S) (CH ₃ ), 1550 (s) (NO ₂ ), 13
50 (s) (NO ₂ ), 1260 (s) (Si
C), 1090 (s) (SiOSi), 1020
(S) (SiOSi), 800 (s), 730
(M), 685 (w). ¹ H-NMR, δ (CDCl ₃ , ppm); α-form: 0.0
7 (m, 42H), 1.51 (d, 2H, J = 7.5H
z), 2.49 (q, 1H, J = 7.5 Hz), 8.2
6 (d, 2H, J = 2.1 Hz), 8.71 (t, 1
H, J = 2.1 Hz). β-body: 0.07 (m, 42H), 0.98 (m, 2)
H), 2.87 (m, 2H), 8.34 (d, 2H, J
= 2 Hz), 8.82 (t, 1H, J = 2 Hz). ^From the integrated value of ¹ H-NMR, the ratio of α to β was about 2: 1.

Elemental analysis value%; C: 36.07, H: 7.67, N: 1.72 Example 4 Synthesis of 3,5-diaminophenethylpolysiloxane 2 100 mg of 5% palladium carbon powder (manufactured by Nippon Engelhardt) was suspended in 4 ml of ethanol, and the catalyst was activated by passing hydrogen for 5 minutes.
A solution of α-β mixture of 5-dinitrophenethylsiloxane in 1.00 g of ethanol in 2 ml was added, and the mixture was stirred for 2 hours 30 minutes.
Reduced through hydrogen splitting. After the catalyst was filtered off, the solvent was concentrated under reduced pressure and dried under reduced pressure at 80 ° C. to obtain 808 mg (yield 87%) of 3,5-diaminophenethylpolysiloxane as a light brown oily substance.

The results of IR spectrum, ¹ H-NMR spectrum and elemental analysis were as follows.

IR spectrum (cm ^-1 ); 3470 (w) (N
_{H 2), 3380 (w)} (NH 2), 2980 (s)
(CH ₃ ), 1600 (m) (NH ₂ ), 1260
(S) (SiC), 1070 (s) (SiOS
i), 1030 (s) (SiOSi), 840
(W), 800 (s), 690 (w). ¹ H-NMR spectrum δ (CDCl ₃ , ppm); α
Body: 0.04 (m, 42H), 1.28 (d, 3H, J
= 7.5 Hz), 1.98 (q, 1H, J = 7.5H)
z), 3.39 (bs, 4H), 5.80 (t, 1H,
J = 2 Hz), 5.88 (d, 2H, J = 2 Hz). β-body: 0.04 (m, 42H), 0.84 (m, 2)
H), 2.46 (m, 2H), 3.39 (bs, 4)
H), 5.92 (t, 1H, J = 2Hz), 5.99
(D, 1H, J = 2 Hz). Elemental analysis value%; C: 37.53, H: 8.84, N: 1.66. Examples 5-10 The same operation as in Example 3 was carried out to synthesize 3,5-dinitrophenethylpolysiloxane using the amounts of the reagents shown in Table 2.

Examples 11 to 16 The same operation as in Example 4 was carried out to synthesize 3,5-diaminophenethylpolysiloxane using the reactants in the amounts shown in Table 3.

Reference Example 9 Synthesis of 3,5-dinitrobenzyl allyl ether 3,5-dinitrobenzyl alcohol 20.0 g (101 mmol),
Allyl bromide 22 ml (254 mmol) and tetrabutylammonium hydrogen sulfate 2.0 g (5.89 mmol) were dissolved in tetrahydrofuran 100 ml, and sodium hydroxide 8.0 g (200 mmo
A solution prepared by dissolving l) in 16 ml of water was added, and the mixture was stirred overnight at room temperature. The reaction solution was extracted with diethyl ether, the organic circle was separated, and dried over anhydrous sodium sulfate. The solvent was removed under reduced pressure to obtain a crude product, which was purified by column chromatography using silica gel (developed with chloroform: hexane = 1: 1). As a result, the structural formula is 3,5-dinitrobenzyl allyl ether represented by 19.1
g (80% yield) was obtained as a yellow oil. The IR spectrum shown below indicates that the product has the above structure,
^It was confirmed by ¹ H-NMR spectrum and elemental analysis.

IR spectrum (cm ^-1 ); 3110 (s), 2880 (s), 1630 (m), 16
00 (m), 1540 (s, characteristic absorption by nitro group), 1470 (m), 1345
(Characteristic absorption by s, nitro group), 1265 (w), 1225 (w), 1120
(s, characteristic absorption by ether bond), 1075 (s), 990 (m), 910
(m), 810 (m), 758 (m), 725 (s). ¹ H-NMR spectrum, δ (CDCl ₃ , ppm); 4.17 (d, 2H, -OCH ₂ CH
= CH ₂ ), 4.71 (s, 2H, PhCH ₂ O-), 5.35 (m, 2H, -OCH ₂ CH = CH ₂ ),
6.00 (m, 1H, -OCH ₂ CH = CH ₂ ), 8.54 (d, 2H, peak of benzene ring), 8.94 (t, 1H, peak of benzene ring), elemental analysis value (%); C: 50.40, H: 4.05, N: 11.47 (calculated value;
C; 50.42, H: 4.24, N: 11.75). Examples 17 to 19 The amounts of trimethylsilanol shown in Table 4 were each dissolved in 200 ml of dry tetrahydrofuran, and an equimolar amount of n-butyllithium hexane was dissolved under an argon stream. A solution was obtained. After stirring for 1.0 minute, a solution of hexamethylcyclotrisiloxane in the amount shown in Table 4 dissolved in 200 ml of dry tetrahydrofuran was added, and the mixture was stirred at room temperature for 21 hours. An excessive amount of dimethylchlorosilane was added to this reaction solution as a terminating agent to terminate the polymerization reaction. Next, the solvent was distilled off under reduced pressure, and the precipitated salt was filtered off and heated at 120 ° C. for 3 hours under a vacuum of 0.1 mmHg or less to remove unreacted cyclosiloxane and excess terminating agent. The teardown ceremony One-terminal hydropolydimethylsiloxane represented by was obtained as a colorless transparent viscous liquid.

The one-terminal hydropolydimethylsiloxane thus obtained and 3,5-dinitrobenzyl allyl ether (about 1.2 times the molar amount) obtained in Reference Example 9 were dissolved in 50 ml of toluene,
After heating to 80 ° C under an argon stream, chloroplatinic acid (H
₂ PtCl ₆ .6H ₂ O) in isopropanol (0.1 m
ol / 1) 100 μl was added and stirred for about 4 hours. The solvent was distilled off under reduced pressure to obtain a crude product, which was subjected to column chromatography using silica gel (diethyl ether: hexane = 1: 1).
8)), the structural formula was Polydimethylsiloxane having a dinitrophenyl group at one end represented by the following formula was obtained as a pale yellow oil.

Next, 5.0 g of 5% palladium carbon powder (Nippon Engelhardt) was suspended in 50 ml of ethanol, and the catalyst was activated by passing hydrogen for 15 minutes. Then, a solution prepared by dissolving hydropolydimethylsiloxane having a dinitrophenyl group at one end obtained in the above reaction in 50 ml of ethanol was added, and a reduction reaction was carried out for about 2 hours while passing hydrogen. After removing the catalyst by filtration, the solvent was concentrated under reduced pressure to obtain a crude product, which was purified by column chromatography using silica gel (developed with ethyl acetate: hexane = 1: 1).
As a result, the structural formula is Hydropolydimethylsiloxane having a diaminophenyl group at one end as shown was obtained as a light brown viscous liquid. The fact that the product had the above structure was confirmed by the IR spectrum, ¹ H-NMR spectrum and elemental analysis shown below. Yield of polysiloxane obtained, and ¹ H
-Average degree of polymerization m determined from peak area ratio of NMR spectrum
The values of are shown in Table 4.

IR spectrum (cm ^-1 ); 3370 (s, characteristic absorption by amino group), 2950 (m), 2860 (m), 1600 (s), 1530 (s), 1470 (m), 1350
(s, characteristic absorption by diaminophenyl group), 1250 (s, Si-C
Characteristic absorption due to bond), 1190 (s), 1000 to 1100 (s, Characteristic absorption due to Si-O-Si bond), 840 (m). ¹ H-NMR spectrum, δ (CDCl ₃ , ppm); 0.10 (s , Si-CH ₃ ), 0.
89 (t, -OCH ₂ CH ₂ CH ₂ Si-), 1.63 (m, -OCH ₂ CH ₂ CH ₂ Si-), 3,43
(t, -OCH ₂ CH ₂ CH ₂ Si-), 3.58 (bs, Ph-NH ₂ ), 4.35 (s, PhCH ₂ O
-), 5.98 (t, peak of benzene ring), 6.13 (d, peak of benzene ring). Use Example 1 Synthesis of Polyimide / Polysiloxane Graft Copolymer 404 mg of 3,5-diaminophenethylpolysiloxane (m = 5.5) obtained in Example 3 and 127 mg of pyromellitic dianhydride were dissolved in 1 ml of dimethylacetamide. Then
Stirred at room temperature for 1 hour. Then dimethylacetamide 1
Add ml and cast the reaction solution onto a glass plate,
After heating and drying at 00 ℃, the structure (In the formula, C ₂ H ₄ is And -CH ₂ CH _2- ).
A polydimethylsiloxane graft copolymer film was obtained.

The IR spectrum of the obtained graft copolymer was as follows.

IR spectrum (cm ^-1 ); 3330 (m) (NH),
2970 (m) (CH ₃ ), 1730 (m) (CO
OH), 1602 (m) (CONH), 1550
(W), 1450 (m), 1260 (s) (Si
C), 1090 (s) (SiOSi), 1020
(S) (SiOSi), 800 (s), 697
(W). Further, it was dried under reduced pressure (1 mmHg or less) at 200 ° C for 1 day, (In the formula, C ₂ H ₄ has the same meaning as described above.) To obtain a polyimide / polydimethylsiloxane graft copolymer film.

The IR spectrum and the elemental analysis results were as follows.

IR spectrum (cm ^-1 ); 2380 (s) (C
_{H 3), 1780 (s)} (CONCO), 1720
(S) (CONCO), 1600 (m) (Aro
m. ), 1460 (s), 1375 (s), 1345
(S), 1260 (s) (SiC), 1100 (s)
(SiOSi) 1010 (s) (SiOSi),
790 (s), 720 (s) (Arom.), 685
(M) (Arom.). Elemental analysis value (%); C: 47.81; H: 5.90, N: 3.52. In addition, as a result of conducting a gas permeation experiment using the copolymer membrane obtained here, the permeation coefficients PO ₂ , PN ₂ and PCO ₂ of oxygen, nitrogen and carbon dioxide at 25 ° C. And showed high gas permeability.

Further, as a result of conducting a permeation experiment of a water-ethanol mixture by the pervaporation method, it was found that at 50 ° C., 5.6
The feed with a w / w% ethanol concentration could be concentrated to 38.0 w / w%. At this time, the water and ethanol permeation rates PH ₂ O and P _EtOH and the separation coefficient α are respectively And showed a selective permeability to ethanol.

Claims (1)

[Claims] 1. A general formula (In the formula, A is an alkyl-substituted or unsubstituted methylene group or a polymethylene group having 2 or more carbon atoms or an oxypolymethylene group, Y is a nitro group or an amino group, R ^{1 to} R ⁵
Are the same or different alkyl groups, substituted alkyl groups, phenyl groups, or substituted phenyl groups, and m is 1-10.
It is an integer of 0. However, R ¹ and R ² may be different for each repeating unit. ) A polysiloxane compound having a bifunctional phenyl group at one end, represented by