Method of producing polymers with conjugated double bonds

专利摘要:

公开号:SU1655302A3
申请号:SU864027650
申请日:1986-06-17
公开日:1991-06-07
发明作者:Бройнлинг Херманн；Йира Райнхард
申请人:Вакер-Хеми (Фирма)；
IPC主号:

专利说明:

The invention relates to polymer chemistry, in particular to a method for producing polymers with conjugated double bonds, which can be used as electrically conducting or semiconductor materials in the electronic and electrical industries.
FIG. 1 and 2 are diagrams explaining the proposed method.
Example 1. Condensation of pyrrole with 5-chloromethylfurfural.
At room temperature, 2.32 g (34.6 mmol) of pyrrole is dissolved in 50 ml of chloroform and 5 g (34.6 mmol) of 5-chloromethylfurfurol is also dissolved in 50 ml of chloroform. Cooked
the solutions are combined. After a short period of time, the resulting solution turns green, then it turns brown, and finally, when the mixture is significantly heated, a black precipitate is formed. The reaction mixture is incubated overnight at room temperature. Directly thereafter, filtration is performed, the powdery black substance is washed with chloroform and dried at room temperature and a pressure of 1.3 Pa. Yield 7.35 g.
Found,%: C 58.5; H 4.33; N 7.93; C1 17.3.
Immediately after this, the product is heated for 4 hours at 50 ° C and a pressure of 1.3 Pa.
Found,%: C 74.0; H 4.4; 5 9.4; C1 2.5
(C, 0H7NOV
Calculated,%: C 76.4; H 4.5; 8.9.
The polymer has a structure
-f-sn-oh, which is confirmed by the IR spectrum of the sample pressed from KBG (Fig. 1). Weak bands between 2900 and 3000 (CHXl-groups) and weak carbonyl bands in the region of 1700-1750 cm (/.
Example 2. Condensation of N-me-JQ tilpyrrole with 5-chloromethyl furfural.
Example 1 is repeated with the change that instead of pyrrole, 1.683 g (20.7 mmol) of N-methylpyrrole are used, and instead of 5 g, 3 g (20.7 mmol) of 25 5-chloromethylfurfurol are taken, each indicated The case is dissolved in 25 ml of chloroform.
Yield 4.14 g of a black powder., "
Found (before heating),%: C 58.9; , 11 5.12; N 8.06; C1 10.7.
Found (after heating),%: C 77.6; H N 9.30; C1 0.5.
(CUH, NO).
35
Calculated,%: C 77.2; H 5.30; N 5.2.
Example 3. Condensation of 2-methylpyrrole with 5-chloromethyl furfural. ,
Example 1 is repeated with the change that 1.633 g (20.7 mmol) of 2-methylpyrrole is used instead of pyrrole, and 3 g (20.7 mmol) of 5-chloromethylfurfurol are taken instead of 5 g.
Yield 4.9 g of a black powdered substance.
Found (before heating),%: C 57.4; H 5.5; N 6.3; C1 12.2.
Found (after heating),%: C 68.3; H 5.1; N 7.7; C1 0.5.
(S “, N9NO) Y.
Calculated,%: C 77.2; H 5.3; N 8.2.
PRI me R 4. Condensation of N-butyl-pyrrole with 5-chloromethylfurfural.
A solution of 2.556 g (20.7 mmol) of 1-n-butylpyrrole and 3 g (20.7 mmol) of 5-chloromethyl furfural in 100 ml of chloroform is mixed with 2-3 bubbles of gas 50
"
five
"
five
0
shaped hydrogen chloride. The mixture was incubated for 13 hours at room temperature and then for 4 hours at 50 ° C. The reaction mixture was worked up as in example 1.
Yield 4.92 g of a friable, black solid.
Found (before heating),%: C 61.7; H 7.1; N 6.1; C1 13.0.
Found (after heating),%: C 78.3; H 7.7; N 8.2; C1 1.8.
(C,) irr
Calculated,%: C 78.8; H 7.1; N 6,6.
Example 5. Furan condensation with 5-chloromethylfurfural.
A solution of 3.35 g (34.6 mmol) of furan and 5 g (34.6 mmol) of 5-chloromethylfurfurol in 50 ml of chloroform is mixed with 0.1 ml of boron trifluoride diethyl ether. The mixture is kept for
4 hours at room temperature and immediately afterwards for
12 hours at. The treatment of the reaction mixture is carried out analogously to example 1
Yield 4.06 g of a black powder.
Found (before heating),%: C 65.0; H 3.92; C1 5.4.
Found (after heating),%: C 76.2; H 4.4; C1 0.5.
(Slon6og) p.
Calculated,%: C 75.9; H 3.8.
Example 6 Condensation of thiophene with 5-chloromethylfurfural
Example 5 is repeated with the difference that instead of furan, 3.64 g (34.6 mmol) of thiophene is used, instead of 50 ml, 20 ml of chloroform is taken, and the mixture is heated for 8 hours at reflux temperature.
Yield 3.36 g of a black powder.
Found (after heating),%: C 65.0; H 3.3; S 15.6.
(C, 0H6SO) n.
Calculated,%: C 68.9; E 3,5;
518.4.
Example 7 Casting film. . To a solution of 360 mg (2.5 mmol) of 5-chloromethylfurfural in 5 ml of diethyl ether, 202 mg (2.5 mmol) of N-methylpyrrole are added at 0 ° C. The resulting solution is poured onto a glass
5165
boards with a thickness of 1 mm glass surfaces 7.4 x 10.4 cm in size. A rast-j thief is kept for 0.5 h at room temperature, as a result of which the solvent evaporates completely and a glossy black film remains on the glass surface.
Example 9. The interaction of benzene with 0, oi, fi / -trichloro-p-xylene ohm.
A solution of 30 g (95.5 mmol) tf. , &, & - trichloro-p-xylene and 7.46 g (95.5 mmol) of benzene in 100 ml of anhydrous nitrobenzene are added dropwise with stirring and 100 ° C for 45 minutes to a solution of 1 g anhydrous aluminum chloride in 100 ml of anhydrous nitrobenzene. After heating the mixture for 1.5 hours at 192-202 ° C, the release of hydrogen chloride ceases, and the mixture solidifies to form a gel-like mass. The residue was ground four times in ethyl alcohol in an IPTcha-Ticcha type TP 18/10 device, each time 400 ml of ethyl alcohol was applied, stirred and filtered using vacuum. The resulting black residue is dried for 2 days in air and in a desiccator over potassium hydroxide at 1.3 Pa, each time being dried at room temperature.
Yield 16.4 g of a black powder.
After heating in accordance with Example 1 yield: 14.8 g (87% of the theoretically calculated value) of a powdery black substance.
Found (after heating),%: C 89.4; II 5, 13; N 1.0; C1 1.5.
(C 4HtoV
Calculated,%: C 94.35; H 5.65. .
The polymer has a structure
which is subject to the IR spectrum of the sample pressed from KBG (Fig. 2). Weak bands between 2900 and 3000 cm talk about a small amount of CH- and CH-GROUP 55.
Example 9. The interaction of benzene with U., 0 /, with trichloro-p-xylene.
Example 8 is repeated with the change that instead of heating for
0 5 0
d
five
five
0
five
1.5 h at 192-202 C the mixture is heated for 24 h at 120 ° C.
The yield after heating is 14.3 g (84.2% of the theoretically calculated value) of the powdery black substance.
Found (after heating,%: C 90.10; H 5.80; C1 1.1; N 0.6.
( )P .
Calculated,%: C 94.35; H 5.65.
PRI me R 10.
The interaction of n-xylene with ot, Vit Of - trichloro-p-xylene.
- Example 8 is repeated with the change that instead of benzene, 10.13 g (95.5 mmol) of n-xylene are used. Yield after heating: 19.29 g (98% of theoretically calculated value) of a dark brown powder.
Found (after heating),%: C 78.9; H 5.13; N 0.87; C1 1.0.
(Cl6H, 4) h.
Calculated,%: C 93.2; H 6.8.
Example 11. The interaction of thiophene with oi, trichloro-p-xylene.

Example 8 is repeated with the change that 8.02 g (95.5 mmol) of thiophene is used instead of benzene.
The yield after heating 16.2 g (86% of the theoretically calculated value) of the powdery substance
dark brown color. I
Found (after heating),%: C 76, 1; H 4.04; N 3.04; S 11.3; C1 1.9.
(С, йН88) „.
Calculated,%: C 78.2; H 4.38; S 17.4.
Example 12. The interaction of o-xylene with pd, (X, (Y-trichloro-p-xylene. I
Example 8 is repeated with the change that 10.13 g (95.5 mmol) of o-xylene is used instead of benzene.
The yield after heating is 19.08 g (96.9% of the theoretically calculated value) of a dark brown powdery substance.
Found (after heating),%: C 90.6; H 7.0; N 1.8; C1 0.1.
“Vl, 4) n. i Calculated,%: C 93.2; H 6.8.
Example 13. The interaction of m-xylene with tf, s, (Y-trichloro-p-xylene.
Example 12 is repeated with the change that an equal amount of m-xylene is used instead of o-xylene.
The yield after heating is 4.81 g (97.8% of the theoretically calculated value) of a powdery black substance.
Found (after heating),%: C 88.8; H 6.8; N 1.23; SK 0.1.
Calculated,%: C 93.2; H 6.8.
Example 14. Interaction of n-xylene with bЈ, D (, ot-trichloro-p-xylol.
Example 8 is repeated with a variation that instead of 20 g, an extra 5 g (23.9 mmol) oЈ, fcЈ of N-trichloro-p-xylene is used, instead of benzene, 2.533 g (23.9 mmol) of n-xylene are used, in each case, instead of 100 ml, only 50 ml of nitrobenzene are taken, and instead of anhydrous aluminum chloride, 250 ml of anhydrous ferric chloride are used.
The yield after heating is 4.81 g (97.8% of the theoretically calculated value) of a powdery black substance.
Found (after heating),%: C 88.3; H 6.8; N 1.23; ,one. (C16H14) P.
Calculated,%: C 93.2; H 6.8. Example 15. The interaction of n-xylene with (X, #, Qi-trichloro-p-xylene.
Example 14 is repeated with the change that 250 mg of anhydrous chlorine tin is used instead of anhydrous ferric chloride.
The yield after heating is 4.98 g (101.2% of the theoretically calculated value) of a powdered black substance.
On the ground (after heating),%: C 90.3; N /, 1; N 1, 58; C1 0.2.
(, 4) p.
Calculated,%: C 93.2; H 6.8.
Example 16. Diphenyl interaction with &, &., &Amp; trichloro-p-xylene.
Example 8 is repeated with the change that 14.72 g (95.5 mmol) of diphenyl is used instead of benzene.
The yield after heating is 23.2 g (95.7% of the theoretically calculated value) of a powdered gray-brown color.
Found (after heating),%: C 92.6; H 5.65; N 1.33; C1 0.1.
(,)and.
Calculated,%: C 94.45; H 5.55.
Example 17. The interaction of di-, phenylmethane with tf, rt, tf-trichloro-p-xylome.
Example 8 is repeated with the change that instead of benzene, 16.06 g (95.05 mmol) of diphenylmethane are used.
The yield after heating 22.48 g (87.8% of the theoretically calculated value) of a brown powder,
Found (after heating),%: C 91.5; H 6.2; N 1.0; C1 0.1.
0
five
0
five
five
(C, H, 6
),
0
Calculated,%: C 94.0; H 6.0.
Example 18. Interaction of naphthalene with b (, tf, & trichloro-p-xylene.
Example 8 is repeated with the change that 12.23 g (95.5 mmol) of naphthalene is used instead of benzene.
The yield after heating is 22.05 g (101.2% of the theoretically calculated value) of a powdered gray-brown color.
Found (after heating),%: C 90.97; H 5.80; N 2.33; C1 0.1.
(G1BHfZ-) n
Calculated,%: C 94.7; H 5.30.
Example 19. The interaction of anthracene with (X., (Y, th-trichloro-p-xylenrm.
A solution of 20 g (95.5 mmol) o (,, # - trichloro-p-xylene and 17.01 g (95.5 mmol) anthracene in 100 ml of anhydrous nitrobenzene with stirring and 100 ° C. Is added dropwise during 45 minutes to a solution of 1 g of anhydrous aluminum chloride in 100 ml of anhydrous nitrobenzene. After heating the mixture at 192-202 ° C for 1.5 h, the evolution of hydrogen chloride ceases. The black precipitate is filtered and washed first with nitrobenzene three times, 10 (5 ml. Of the last, and then three times with methyl alcohol, each time using 100 ml of the latter, after which The product is dried at room temperature and 1.3 Pa over potassium hydroxide for 12 hours. Immediately after this, the product is heated for 4 hours at 250 ° C and 1.3 Pa. The yield is 12.86 g (48.4% of theoretically calculated value of the powdery matter of the black and vevet.
Found,%: C 92.3; H 5.3; N 0.9; C1 0.1.
(
i «v) n
Calculated, 7; С С 94.9; H 5.1.
The filtrate is combined with the liquids used for washing and mixed with 2 liters of methyl alcohol, as a result of which a flocculent substance colored dark brown is precipitated. This substance is filtered off, washed three times with methyl alcohol, each time using 100 ml, the latter, and then dried and heated by analogy with that described.
Yield 11.8 g (44.6% of the theoretically calculated value) of a black powdery substance
-Found,%: C 92.4; H 5.4; N 1.7.
(s2gn44) h.
Calculated,%: C 94.9; H 5, 1.
Example 20 Condensation of imidazole with 5-chloromethylfurfural.
BUT . Preparation of 5- (1-imidazolyl) -methylfurfural.
A solution of 3 g (2P, 8 mmol) of 5-chloromethylfurfural and 1.41 g (20.8 mmol) of imidazole in 25 ml of chloroform is heated for 4 hours at reflux temperature. After cooling, the solution is washed with an aqueous solution of bicarbonate and water, after which the solvent is distilled off at 80 ° C and a pressure of 2.000 Pa.
Yield 3.25 g (89% of theoretically calculated value) in flowing oily substance of formula
NQN-CH2Hf Vc
ABOUT
about
 H
 B. Polycondensation of imidazole with 5-chloromethylfurfural.
The experiment described in stage A is repeated with the change that, before heating the reaction mixture, 0.1 ml of trifluoride boron diethyl etherate is added and the mixture is heated for 8 hours at reflux temperature. After evaporation of the solvent, by analogy with that described in stage A, the viscous residue is heated in an argon atmosphere, the temperature being raised from 100 to 4 for 4 hours, after which the temperature is maintained at 240 ° C for the next two hours.
Yield 4.16 g of a glossy black glassy foamy solid.
Jq
15
0
50
,
0
five
0
five
Immediately after this, the product is finely ground and 3.5 g of the obtained amount of the substance is heated for 4 hours at 250 ° C and a pressure of 1.3 Pa.
Yield 1.98 g (71.6% of theoretically calculated value) of a black powdery substance.
Found,%: C 64.5; H 3.4; N 11.2; C1 2.8.
(C9HfiN O) h.
Calculated 7.1 C 68.3; H 3.8; N 17, /.
Example 21 To a boiling suspension of 1 g of anhydrous aluminum chloride in 100 g (1282 mmol) of benzene, 20 g (95.5 mmol) of Dd, D tf-trichloro-p-xylene are slowly added with stirring. The mixture was heated under reflux for 10 hours, cooled and worked up as in Example 8. Yield after heating: 13.2 g (78% of theory) of black powder.
Example 22. To 25 g (173 mmol) of 5-chloromethylfurfurol is added slowly at 50 with 11.6 g (173 mmol) of pyrrole, the mixture darkens and becomes cloudy, then solidifies into a black mass. The mass is left for another 2 hours at 50 ° C, then ground to a powder and incubated for 4 hours at a pressure of 1.3 Pa at 250 ° C.
Yield 31.2 g of black powder.
Example 23. The introduction of additives in polymers.
The products obtained in the previous examples, together with a measured amount of iodine, are cooled from the outside with liquid nitrogen in the tube and evacuated to a residual pressure of 1.3 Pa, heated to room temperature, and then incubated for 24 hours at 120 ° C.
The table shows the iodine content in the modified polymers in this way in comparison with the corresponding unmodified products and their electrical conductivity.

权利要求:
Claims (2)
[1]
1. A process for the preparation of polymers with conjugated double bonds, consisting in that a first monomer is subjected to copolycondensation, selected from the group consisting of 5-chloromethylfurfural and X, oi, o-trichloro-p-xylol, and second monomer selected from
groups containing pyrrole, furan, organic solvent at 18thiophene and benzene, their C-C-alkylproduct- 240 C.
aqueous, diphenyl, diphenylmethane, naphtha- 2. The method according to claim 1, is different, anthracene and imidazole, and the process is carried out in bulk or medium
u and so that the process is carried out in the presence of a cationic catalyst
[2]
 2. The method according to claim 1, wherein the process is carried out in the presence of a cationic catalyst.
Polymer by example
Iodine content, May. %
3000
2000
1600
Fig1
1000
Editor N. Bobkova
2000 16PO
Fig 2
Compiled by V. Filimonov
Tehred A. Kravchuk Proofreader N. Revsk
Electrical conductivity, cm / cm
1000 w -1
200

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法律状态:

优先权:

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申请号 | 申请日 | 专利标题

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DE19853531600|DE3531600A1|1985-09-04|1985-09-04|POLYMERS WITH CONJUGATED DOUBLE BINDINGS|

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