TWI364432B - Synthesis of polyimides (pi) from poly-carbodiimides and dianhydrides by sequential self-repetitive reaction (ssrr) - Google Patents

Description

1364432 IX. Description of the Invention: [Technical Field] The present invention relates to a sequential self-repetitive reaction (ie, by a polycarbodiimide or a diisocyanate and a dianhydride) "SSRR")) A method for synthesizing polyimine (PI). [Prior Art] Polyimine (PI) is one of the high-temperature polymer materials widely used at present. Polyimine has excellent performance. Its thermal properties, mechanical properties, flame retardancy and chemical resistance are widely used in the aerospace, automotive, aerospace, and electronics industries (see Maier, G., Prog. Polym. Sci. 2001, 26, 3). Since polyimine was commercialized and developed in the early 1960s, many different properties of polyimine have been developed to suit various industrial and consumer industries (see Kharitonov, AP; Taege, R.; Ferrier, G.; Teplyakov, VV; Syrtsova, DA; Koops, G.-H., J. Fluorine Chem. 2005, 126, 251, and

Ameduri, B.; Boutevin, B., J. Fluorine Chem. 2005, 126, 221, and Rusanov, AL; Komarova, LG; Likhatchev, DY; Shevelev, SA; Tartakovsky, VA, Russ. Chem. Rev. 72, 899) ° The method for synthesizing polyimine has been developed quite well, and its synthesis is mainly obtained by dehydration condensation reaction between diamine and dianhydride. However, the process of preparing polyimine is often due to the disadvantage that polyimine itself is not easily dissolved in organic solvents (especially polyimine which is structurally completely aromatic), and polyimine is added. Difficulties in application. Therefore, poly 110995.doc 1364432

The brewing imine usually first produces a solvent-soluble poly-imine (amic acid) intermediate by diamine and a diacid needle at a low temperature, and then coats the polyphosphite. The film is formed, and then in the final step, the high temperature closed-loop amidine amination reaction (> 300 ° C) is used to dehydrate and remove the solvent to form the product polyimine. In order to improve the solubility and processing properties of polyimine, there are many studies dedicated to introducing large groups or elastomers that can help the solubility of polyimine in the main chain or side chain of polyimine. Segments such as -Ο-, S02-, -00, -CF3, and -CH3, etc. (see Eastm〇nd, G C.; Paprotny J., React. Funct. Polym. 1996, 30, 27). The present invention utilizes a novel continuous self-reacting reaction (SSRR), particularly in a one-pot operation, by bringing a poly(arylcarbodiimide) derived from an aryl diisocyanate (p) -CDI)i is derived from the oxime-ester acid reaction of the dianhydride to synthesize the polyimine. Alternatively, the phthalic acid can be synthesized via a polycondensation reaction using a dianhydride and a common diisocyanate plus a carbodiimide catalyst (CDI catalyst). SUMMARY OF THE INVENTION It is therefore an object of the present invention to provide a method of synthesizing a polyimine having the following structural formula:

Wherein η is an integer selected from the range of 1 to 1 Å, and the quaternary series comprises optionally substituted tetravalent aromatic organic groups of at least one benzene ring or optionally substituted four containing at least two carbon atoms Valency aliphatic organic group, 110995.doc The method comprises the following steps: a) a dianhydride having the formula

0 〇Η II 〇 ( \r/C, 0 乂I· 〇〇 and l-OH (wherein R 2 is Cl_8 alkyl) reacts in a molar ratio of about 1:1 to form an acid-ester function having the formula Acid anhydride:

0 0 II μ

0= \R/C, 〇H η Ο ο ; b) reacting the acid-g functionalized acid needle with poly(arylcarbodiimide) (p_cm) to form a polyp group having the following formula - Sulfhydryl urea-functionalized vinegar _ δλ. Sf (p〇ly-acylurea-functionalized ester-anhydride (p-AEA)): 〇

〇-faryl-N-C-NH+ O R U v〇R2

0 O

p-AEA C) reacts the p-AEA with RyOH (wherein the R2 series cN8 alkyl group) at a molar ratio of about 1:1 to form a poly-hydrazino urea having the formula: Poly-acylurea-functionalized ester-acid-ester (p-AEAE): 110995.doc 1364432

-^aryl-N-C-NH Yang Ren R Ren 〇 HOr y0R2 0 o

p-AEAE d) heating the p-AEAE to a temperature of from about 120 ° C to about 280 ° C in the presence of a CDI catalyst to form an aryl isocyanate having the formula and a poly(acid-ester-oxime) amine):

ywwaryl—NCO

NH-aryl OR〇 simultaneously undergoes a continuous self-repetitive reaction to form the polyimine, wherein the continuous self-repetitive reaction involves repeated three consecutive steps: 1) in the presence of the CDI catalyst, the aryl group Converting an isocyanate catalyst to the p-CDI;

2) reacting the p-CDI with the poly(acid-ester-decalamine) to form a poly- acylurea-functionalized amide-ester having the following formula (p- AAE))

V 〇 aryl—N—C—N—aryl'^ 〇 0^^ R ^^NH—aryl^ R20^/ \^0R2 o o

p-AAE and 3) thermally decomposing the p-AAE obtained in the step 2) into the aryl isocyanate 110995.doc 1364432 salt and the poly-bis(ester-nonylamine) having the formula: 'heart and R The progress of human 屮ΝΗγ 0 使 causes the poly-di (vinegar-bristamine) to undergo a ring closure reaction to liberate RsOHs and form a polyimine as a product. Another object of the present invention is to provide a method for the formation of a polyfluorene imine having the following structural formula: 0 0 ary} 〇〇n wherein η is an integer selected from the range of 1 to 100, and the ruler is a tetravalent aromatic organic group optionally substituted with at least one benzene ring or an optionally substituted tetravalent aliphatic organic group containing at least two carbon atoms, the method comprising the steps of: a) The second anhydride anhydride ί? i? <x> and R2-OH (wherein R_2 is a ci.8 alkyl group) are inversely reacted at a molar ratio of about 1:2 to form a second formula (ester-acid): 0 0 R2 〇人R °vv - ο 0 ;

OH.OR, b) The bis(ester-acid) and poly(arylcarbodiimide) are heated to about 12 Torr. 110至110995.doc •10-1364432 A temperature of about 280 ° C to effect a continuous self-repetitive reaction as defined above to form the polyimine. The various advantages and objects of the present invention are readily apparent to those skilled in the art in light of the teachings disclosed herein. First, the present invention provides a method for synthesizing polyimine by using the SSRR anti-corridor.

The method of the present invention begins with the quaternary saccharide having the formula: wherein (10) contains at least one benzene ring, optionally substituted tetravalent aromatic organic group or optionally substituted tetravalent, containing at least two carbon atoms Aliphatic organic group) i? i? 〇\C/R, C>

II II Ο 反应 reacts with R2-ΟΗ (wherein I is a c丨-s alkyl group) (preferably in a molar ratio of about 1:1) to form an acid-ester functional anhydride having the formula:

i? i?

Suitable aromatic dianhydrides include, but are not limited to, 3,3',4,4,-dibenzophenone tetracarboxylic dianhydride (BTDA), both Pyromellitic dianhydride (PMDA), 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,6-tetradecanoic dianhydride, 3,3,,4,4,- Diphenyltetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,2',3,3,-diphenyltetradecanoic acid dianhydride, 2,2-bis (3,4 ,-Dicarboxyphenyl)propane dianhydride, 3,4 91 〇-mercaptotetracarboxylic dianhydride, bis(3,4-dicarboxybenzene 110995.doc 1364432) ether dianhydride, naphthalene·U2,4,5 _tetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride, decahydronaphthalene-ι, 4,5,8-tetracarboxylic dianhydride, 4,8-dimethyl{mu hexahydronaphthalene-1,2,5,6- Tetracarboxylic acid dianhydride, 2,6-dichloronaphthalene_M,5,8-rocarboxylic dianhydride, 2,7·dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,3,6,7 - tetrachloronaphthalene-1,4,5,8 tetracarboxylic acid monoanhydride, phenanthrene tetraruthenate dianhydride, bis(3,4-dicarboxyphenyl) dianhydride, (3i, 4i-dicarboxyphenyl) 2_Dicarboxy 5,6 benzimidazole monohydride, (3',4'-didecylphenyl) 2-dicarboxy 5,6-benzoxazole Needle (3 '4 - a rebel base) 2-di-lower 5,6-benzopyrene dianhydride, bis (3'4 fluorenyl-based quinone) 2,5-° dioxin. Take 1,3,4 dianhydride or 3,3',4,4,-oxydiphthalic dianhydride (3,3,4,4,_〇xydiphthalic dianhydride; ODPA). Suitable aliphatic dianhydrides include, but are not limited to, tetrahydrofuran tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, bicyclo-[2,2,2]-octene _(7)_2,3,5,6_four甲西文 - 2,3,5,6 - a traitor, 1,2,3,4-ί singer burning tetracarboxylic acid dixanthine and 丨24 5 cyclobutane tetracarboxylic dianhydride. As is well known to those of ordinary skill in the art, the acid/RrOH reaction can be carried out in the presence of a catalyst such as triethylamine (TEA). Next, the obtained acid-ester functional anhydride is reacted with poly(arleny carbon-imine) (P-CDI) to form a poly-hydrazino urea having the following formula, - acid needle (p-AEA): r 〇-aryl - C - νη

R human n 〇OR, r γ ο 〇ρ-ΑΕΑ 110995.doc -12 - 1364432 As is well known to those of ordinary skill in the art, the p-CDI used in the present invention may first exist in the presence of a CDI catalyst. It is formed by converting a aryl diisocyanate by a catalyst. This reaction is preferably carried out in anhydrous methylpyrrolidone (NMP). However, other suitable solvents may also be used. Suitable solvents include N,N-dimethylacetamide (DMAC), cyclobutane (TMS), N,N-methylformamidine (DMF) and monomethyl hydride (DMSO). Those of ordinary skill in the art can readily determine the type of solvent that is suitable for carrying out the reaction. The types of CDI catalysts have also been extensively documented in the literature, and are suitable for those skilled in the art. Suitable (:1) 1 catalysts include, but are not limited to, various organic derivatives of 'filled compounds and cyclic phosphorus compounds. For example, 3_mercapto-3-cyclophosphene oxide (MPO), 1,3-dimethyl-3·cyclophosphene oxide (DMPO), 1,3-dimethyl-i, 3, 2 -diazaphophorolidine, triphenylene oxide (triPhenylarsenic oxide), and these are described in Tetrahedr〇n Report Rl〇l in Tetrahedron (V〇l. 37, pages 233-284, 1981) page 235 and Angew.Chem. internt. Edit. Vol. 1,621 (1962) CDI catalyst. The contents of these documents are incorporated herein by reference. The type of the aryl diisodecanoate is not particularly limited. In general, any bis-isoisocyanate can be used in the practice of the process of the invention. According to the present invention, the term "square" means a monovalent monocyclic or bicyclic aromatic hydrocarbon molecular group which may be substituted by one or more (preferably one, two or three) substituents as needed. The substituents present are preferably independently selected from the group consisting of 〇1-8 alkyl, Ci 8 alkoxy, nitro, dentate and aryl Cw alkyl. More preferred aryl substituents are methyl, methoxy, schiffyl, guanyl, chloro, molybdenum, oxy, thio, zephyr or benzyl. More specifically, the "aryl" group of the formula H0995.doc -13 - 1364432 contains, but is not limited to, a phenyl group, a tolyl group or a phenylmethylene group. Suitable aryl diisocyanates according to the invention include, but are not limited to, 4,4^ diphenylmethane diisocyanate (MDI), 4,4·-diphenyl diisocyanate, 4,4'-diisocyanatodiphenyl sulfide, 4,4'-diisocyanato diphenyl sulfone, 4,4 '-Diisocyanate diphenyl ether, m-naphthalene diisocyanate (MNDI), p-naphthalene diisocyanate (pndI), m-phenylene diisocyanate (MPDI), p-phenylene Isocyanate (PPDI), terpene diisocyanate (TDI), 4,4'-diisocyanate-3,3,-dimethyldiphenyl decane, 4,4,_Methylene Bis(1-diisocyanate-2-methoxybenzene), m-diphenylene diisocyanate, p-xylene diisocyanate or a mixture thereof. According to one embodiment of the invention, the reaction of the acid-ester functional anhydride with p_CDI comprises mixing the acid-ester functional anhydride with an aryl diisocyanate, followed by the aryl group in the presence of a CDI catalyst. The isocyanate catalyst is converted to p_CDI and finally p_CDI is reacted with the acid-ester functional anhydride to form the aforementioned poly-mercapto urea-functionalized ester-anhydride (P_AEA). It is known in the art that aryl N-mercaptourea is thermally stable at temperatures up to about 120 〇c, and at higher temperatures, it is rapidly converted to isocyanates and guanamines. It is also known that isocyanate can be converted into carbodiimide (CDI) in the presence of CDI catalyst. According to this, the p-AEA and R2-〇H obtained firstly (where the ruler 2 system (^.8) The alkyl group is again reacted in a molar ratio of about 1:1 to form a poly-hydrazino urea-functionalized ester-acid-ester having the formula (p〇ly_acylurea_functionalized ester-acid-ester (p-AEAE) ): 110995.doc -14- 1364432 Ο

p-AEAE

The obtained p-AEAE is then further heated to a temperature of from about 12 ° C to about 280 in the presence of a CDI catalyst. 〇 (preferably from about 120 ° C to about 27 (TC, better about I40t)

To about 250. . The temperature 'to thereby form an aryl isocyanate having the formula: and a poly(acid-ester-decylamine): 0 j

Wide aryl-NCO R2CT H〇r · ' V〇R2 ο ο person ^ NH-aryl·^ and simultaneously carry out a continuous self-reaction to form a polyimine of the formula:

ο Ο

Wherein the continuous self-repetitive reaction involves repeating the following three consecutive steps: 1) converting the aryl isocyanate catalyst to the p-CDI in the presence of the CDI catalyst; 2) rendering the p-CDI Reacting with the poly(acid-ester-decalamine) to form a poly-acylurea-functionalized amide-ester (p-AAE) having the following formula. 110995.doc -15- 1364432 Ο Η

III, aryl-Ν-C-Ν-aryl ' Ο R R20 ΝΗ-aryl·OR2 r γ ο ο ρ-ααε ; and 3) thermally decomposing the ρ-ΑΑΕ obtained in the step 2) into the aryl isocyanate Salt and poly-bis(ester-decylamine) having the formula:

The poly-bis(ester-decylamine) is further subjected to a ring closure reaction to liberate R 2 〇Hs and form a polyimine as a product. As shown in Flow 1, the SSRR method consists of three self-repetitive steps. The first step is a catalyst conversion reaction of 1.0 mole of aryl isocyanate to 05 moles of aryl P-CDI. The second step is 〇5莫耳的基基卜

The reaction of CDI with 0.5 mole of poly(acid-ester decylamine) to form 莫. 5 moles of p _ AAE. Finally, the third step is thermal decomposition of 0.5 mole of p_AAE to produce 0.5 mole of aryl isocyanate and simultaneously produce 〇·5 moles of poly-bis(ester-decylamine), wherein poly-di (Ester-decalamine) is further subjected to a ring closure reaction to form a polyimine as a product. Therefore, in summary, 50% of the aryl isocyanate and the poly(acid-esteramine) will be consumed in this continuous self-repetitive reaction (SSRR) in a single complete cycle. Formed 5 % by weight of the polyimine. Repeating the above two consecutive reactions will eventually consume all of the aryl isocyanate and the poly(acid-ester-guanamine). 110995.doc -16- 1364432 Process 1

R2〇 HO

Ο O^aryl——N—C—N—aryl*^ 人丄 r v0R2 O 〇

p-AEAE

O o

R2o aryl-NH person r NH- OR2

-2R2OH

O O poly-bis(6I-® amine)

Polyimine (final product) In one embodiment of the present invention, the above method for synthesizing polyimine by SSRR can be started directly from the ring opening reaction of dianhydride, and is one-pot. operating. As described above, the aryl diisocyanate and the CDI catalyst may be used in place of ρ-CDI to react with the product obtained by ring-opening reaction of the dianhydride. Accordingly, the above method for synthesizing polyimine by SSRR can be operated in a single pot manner, starting directly from the ring opening reaction of dianhydride, followed by mixing of aryl diisocyanate and CDI catalyst. 110995.doc -17- 1364432 Preferably all starting materials are dissolved in a suitable solvent, such as anhydrous tetrahydrofuran (THF), N-decylpyrrolidone (NMP), cyclobutyl (tms), hydrazine, π dimethyl Indoleamine (DMAC), hydrazine, hydrazine-dimethylformamide (DMF) and dimercaptopurine (DMSO) are used to carry out the SSRR* method to produce the desired polyimine. Those of ordinary skill in the art can readily determine the type of solvent that is suitable for carrying out the reaction.

In a particular embodiment of the invention, the p-AAE is thermally decomposed into poly-bis(ester-decylamine) and aryl isocyanide at a temperature from about 丨2 (TC to about 18 ° C). The acid salt is then raised to a temperature of about 18 (rc to about 28 Torr (> c for a sufficient period of time, for example from about 15 minutes to about 12 minutes, to effect a ring closure reaction to form the desired poly. In one embodiment of the present invention, the ring-opening reaction of the aryl dianhydride can be completed at the outset to obtain an aryl-bis(ester-acid). The aryl group-II obtained will be obtained. The (ester-acid) is reacted with p-CDI or mixed with an aryl diisocyanate and a ruthenium catalyst to carry out the aforementioned "ruthenium method" to synthesize polyimine.

Accordingly, the present invention further provides a method of synthesizing a polyimine having the following structural formula:

Wherein η is an integer selected from the range of 1 to 100, and R is an optionally substituted tetravalent aromatic organic group containing at least one benzene ring or an optionally substituted tetravalent fat containing at least two carbon atoms a group organic group, the method comprising the steps of: a) having a diacid of the formula: 110995.doc -18- 1364432 S i? <〇X> ϋ n and R2-0H (wherein R 2 is a Cu alkyl group) Reacts in a molar ratio of about 1:2 to form a second (ester-acid) of the formula:

R2o OH 0 Ο

Ο Ο and

b) heating the bis(ester-acid) and p_CDI to a temperature of from about 120 ° C to about 28 〇t (preferably from about 120 ° C to about 270 〇; more preferably about 140. (: to about 250 ° 〇 temperature) The continuous self-reacting reaction as defined above is carried out to form the polyimine. According to an embodiment of the invention, the reaction of the bis(ester-acid) with p_CDI comprises first combining the bis (vinegar-acid) with The aryl diisocyanate is mixed, and then the aryl diisocyanate catalyst is converted into p_CDI in the presence of a CDI catalyst, and finally the ρ-CDI and the di(ester-acid) are further heated to carry out the aforementioned continuous self-repetition reaction.

Similarly, the aforementioned synthesis method can be started directly from the ring opening reaction of dianhydride, and is carried out in a single (four) manner. Furthermore, the synthesis is preferably carried out in a suitable solvent such as anhydrous tetrahydrofuran (THF), N-methylpyrrolidone (NMP), cyclobutyrene (TMS), N-dimethyl ethanoamine (dmac), n, n_-methylformamide (DMF) and dimethylmethylene (DMS®) to produce the desired product. Those of ordinary skill in the art can easily decide; t is suitable for carrying out this counter-solution. Further, as described above, the acid 2-〇H reaction can be carried out in the presence of a catalyst such as triethylamine. In the absence of further elaboration, the skilled person can use the above disclosure and the following examples of 110995.doc -19- 1364432 to make the present invention profitable. The following examples are merely illustrative of how the skilled artisan can operate the present patent but do not limit the remaining disclosure in any way. [Examples] Examples Measurement procedure: 咕 NMR spectroscopy was recorded on a Varian In〇va 2〇〇 MHz or 600 MHz instrument. The chemical shift is represented by s, and the coupling constant is expressed in Hz. The spectrum is recorded in a solvent (e.g., acetone _d6 or DMs 〇d6) at room temperature and the chemical shift is relative to the solvent signal. Example 1 50 ml of sterol was placed in a 1 liter, three-necked round bottom flask and equipped with a thermometer, a nitrogen inlet, a reflux condenser, an oil bath, and a magnetic stirrer. 2 g of millimolar pyromellitic dianhydride (pyrme) was added to dianhydride; PMDA, and the mixture was heated to 5 〇〇c and allowed to continue to react for one hour. After the end of the reaction, the remaining solvent was removed by distillation under reduced pressure, and a 93% yield of a white powder of m-dimethyl pyromellitate (PMDE) was obtained. Example 2 100 ml of methanol A 250 ml, three-necked round bottom bottle was placed in a flask equipped with a thermometer, a nitrogen inlet tube, a reflux condenser, an oil bath, and a magnetic stirrer. Adding 9_95 g (30.1 mmol) of 3,3|,4,4,benzophenonene tetracarboxylic dianhydride (BTDA) to methanol The mixture was heated to 6 ° C and allowed to continue to react for two hours. After the end of the reaction, the remaining solvent was removed by distillation under reduced pressure to I10995.doc -20 - 1364432, and a yield of 89% of a yellow powder of phthalic acid _4,4, yl-2,2·- Methyl ester (1,2,-benzenedicarboxylic acid-4, 4'-carbonyl bis-2, 2', -dimethyl ester; BTDE). Example 3 50 ml of sterol was placed in a 100 ml, three-necked round bottom flask equipped with a thermometer, a nitrogen inlet tube, a reflux condenser, an oil bath, and a magnetic stirrer. Add 5 g (16. U mmol) of 3,3',4,4'-oxydiphthalic dianhydride (ODPA)) In methanol, the mixture was heated to 60 ° C and allowed to continue to react for two hours. After the end of the reaction, the remaining solvent was removed by distillation under reduced pressure, and a yield of 92% of phthalic acid-4,4.-oxy-2,2'-dimethyl(n benzenedicarboxylic acid-4,4) was obtained. '-oxy bis-2,2',-dimethyl ester; ODPE). Example 4 20 ml of NMP was placed in a 100 ml, three-necked round bottom bottle and equipped with a thermometer, a nitrogen inlet tube, a reflux condenser, an oil bath and a magnetic stirrer. Will be 20 mg DMPO and 1 g (3.55 mmol) example! The obtained PMDE was added to the mixture and heated to 18 ° C while stirring for 1 Torr. 〇.887g (3.55 house mole)]\1〇1 was added to the mixture, followed by heating to 2 Torr. 0 and stirring for 5 hours. The product polyimine (Helan 1_phenyl-polyimine) was precipitated from NMP. The precipitate was collected by filtration, and a product of 96% yield was obtained. The detailed reaction process is as follows: 110995.doc -21· 1364432 Process 2

PMDA PMDE

-C〇2, -RaOH PMDE + OCN— Ar—NCO -»

SSRR

Example 5

30 ml of NMP was placed in a 100 ml, three-necked round bottom bottle and equipped with a thermometer, nitrogen inlet tube, reflux condenser, oil bath and magnetic stirrer. 20 mg of DMPO and 1.542 g (3.99 mmol) were added to the mixture and heated to 180 ° C while stirring for 10 minutes. 1 g (3.99 mmol) of MDI was added, and the mixture was then warmed to 200 ° C. Stirring was continued for 5 hours. The product MDI-keto-polyimine (MDI-ketone-PI) was precipitated from NMP and collected by filtration (yield 99%). The detailed reaction scheme is shown in Scheme 3. Example 6 30 ml of NMP was placed in a 100 ml, three-necked round bottom flask equipped with a thermometer, nitrogen inlet tube, reflux condenser, oil bath and magnetic stirrer. Add 20 mg 〇]\00 and 1.108 3 grams of gram (2.87 mmol), and the mixture was heated to 180 ° C while stirring for 10 minutes. 0.5 g (2.87 mmol) of TDI was added to the mixture, followed by heating to 200 ° C and stirring for 5 Small 110995.doc -22- 1364432. The obtained solution was poured into 500 ml of water. The obtained product was filtered and dried to obtain 1.16 g of the product TDI-ketone-polyimine (TDI-ketone-PI). 99%), its 1H NMR spectral structure analysis is shown in Figure 1. The detailed reaction scheme is shown in Scheme 3. Example 7 20 ml of hydrazine was placed in a 100 ml, three-necked round bottom flask equipped with a thermometer, a nitrogen inlet tube, a reflux condenser, an oil bath and a magnetic stirrer. 20 mg of DMPO and 1.00 g were added ( 2.67 mmol of ODPE, and the mixture was warmed to 180 ° C while stirring for 10 minutes. 0.67 g (2.67 mmol) of MDI was added, followed by warming to 200 ° C and stirring for 5 hours. Into 500 ml of water, the obtained product was filtered and dried to obtain 1.153 g of the product MDI-ether-polyimine (MDI-ether-PI) (yield 91%), and its 1H NMR spectral structure analysis is shown in FIG. The detailed reaction procedure is shown in Scheme 3. Example 8 20 ml of hydrazine was placed in a 100 ml, three-neck round bottom bottle equipped with a thermometer, nitrogen inlet tube, reflux condenser, oil bath and magnetic scrambler. In a flask, 20 mg of DMPO and 1.0 g (2.67 mmol) of ODPE were added, and the mixture was heated to 180 ° C while stirring for 10 minutes. 0.465 g (2.67 mmol) of TDI was added, and then the mixture was warmed to Stir at 200 ° C for 5 hours. Pour the solution In 500 ml of water, the obtained product was filtered and dried to obtain 1.06 g of the product TDI-ether-polyimine (TDI-ether-PI) (yield 99.9%), and its 1H NMR spectral structure analysis is shown in FIG. The detailed reaction process is shown in Flow 3. 110995.doc -23- (1)1364432 Process 3 ο ο

ο χ= —c— BTDA Ο ο

(2)

Or —Ο — ODPA

-C〇2, -R2OH diester acid + OCN- Ar-NCO -1 SSRR

MDI

Or ODPE

It should be readily understood that various modifications of the present invention are possible and are familiar with this technique.

It is easy to associate with and anticipate. BRIEF DESCRIPTION OF THE DRAWINGS Figures 1 to 3 show the 1H NMR spectrum of the polyimine obtained according to the method of the present invention. 110995.doc 24-

Claims (1)

^04432 Patent Application No. 097108232 X. Shen Tie Patent Fan Chinese Patent Application Range Replacement (February 1st, 2011) L-Synthesis of a method of polyimine having the following structural formula, Where π is selected from! An integer in the range of ι〇〇, and the ruthenium contains at least one tetravalent aromatic organic group to be substituted, or an optionally substituted tetravalent aliphatic organic group containing at least two carbon atoms. The method comprises the steps of: a) reacting a dianhydride having the formula: VRV° II II Ο 0 and R 2 — 0H (wherein R 2 is a C 丨-8 alkyl group) at a molar ratio of about 1:1 Thereby forming an acid ester functionalized anhydride having the formula: 〇 OH 0R2 b) reacting the acid-ester functional anhydride with poly(arylcarbodiimide) (p_cdi) to form a poly-mercapto urea-functionalized ester of the formula _ acid lf (poly-acylurea) -functionalized ester-anhydride (p- AEA)): 110995-1010217.doc O^aryl-NC-VRrR: 〇C-NH p-AEA 1364432 c) reacting the p-AEA with R2-OH (wherein R2 is C, -8 alkyl) at a molar ratio of about 1:1 to form a poly-mercapto urea of the formula: Poly-acylurea-functionalized ester-acid-ester (p-AEAE): ο -f aryl-NC-NH^V HO R or2 p-AEAE d) in carbodiimide The p-AEAE is heated to a temperature of from about 120 ° C to about 280 ° C in the presence of a catalyst (CDI catalyst) to form an aryl isocyanate and a poly(acid-ester-decylamine) having the formula : R2〇HO NH-aryl·OR? ΛΛΛ/*\Λ aryl-NCO Ο 〇人Λ R and simultaneously perform a self-repetitive reaction to form the polyimine, wherein the continuous self-repetition reaction involves repeating the following three Continuous steps: 1) converting the aryl isocyanate catalyst to the P-CDI in the presence of the CDI catalyst, 2) reacting the p-CDI with the poly(acid-ester-decylamine) To form a P〇ly-acylurea-functionalized amide-ester (p-AAE) having the following formula: 110995-1010217.doc 1364432 ««•aryl-N_C~ -N-aryl' 0 NH-aryl, 〇R2 p-AAE Π lio o , and 3) thermally decomposing the p-AAE obtained in the step 2) into the aryl isocyanate and the poly-bis(ester-decylamine) having the formula : The poly-bis(ester decylamine) is further subjected to a ring closure reaction to liberate R 2 〇Hs and form a polyimine as a product. 2. The method according to claim 1 wherein the aromatic diacid liver is selected from the group consisting of 3, 3, 4, 4 benzophenone tetracarboxylic acid (3, 3, 4) , 4-benzophenone tetracarboxylic dianhydride; BTDA), pyromellitic dianhydride (pyr〇memtic xiancaxin; PMDA), 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3,,4, 4,_diphenyltetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,2,3,3,-diphenyltetracarboxylic dianhydride, 2,2-bis (3 , 4,-dicarboxyphenyl)propane dianhydride '3,4,9,1〇•mercaptotetracarboxylic acid monoanhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, naphthalene-tetracarboxylic acid two needle Naphthalene-1,4,5,8-tetracarboxylic dianhydride, decalin _M,5,8-tetracarboxylic acid two-needle, 4,8-dimethyl-l,2,3,5,6,7 - hexahydronaphthalene 4,2,5,6-tetracarboxylic dianhydride, 2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,7-dichloronaphthalene _ 1,4, 5,8-tetracarboxylic acid di-hepatic, 2,3,6,7-tetra-naphthalene 4,4,5,8-tetracarboxylic dianhydride, phenanthrene-1,8,9,10-tetracarboxylic dianhydride, double ( 3,4_dicarboxyphenyl) nucleus 110995-1010217.doc 1364432 needle (3,4- cytosylphenyl) 2-diradyl 5,6·benzimidic dianhydride, (3,4_ Carboxyphenyl) 5,6-benzo-2-yl slow. Sitting on dianhydride, (3',4·-dimercaptophenyl) 2-dicarboxy 5,6-benzopyrazole dianhydride, bis(3,4,-di-di-diphenyl ether) 2, 5-oxadiazole 1,3,4 dianhydride and 3,3,,4,4,-oxybisphthalic dianhydride (3,3',4,4,-oxydiphthalic dianhydride; ODPA) 〇3 The method according to claim 1, wherein the aliphatic dianhydride is selected from the group consisting of tetrahydrofuran tetracarboxylic dianhydride, cyclopentane tetradecanoic acid di-needle, bicyclo-[2,2,2]-octane Alkene-(7)·2,3,5,6-tetracarboxylic acid-2,3,5,6-dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride and i,2,4, 5-cyclobutane tetraphthalic acid dianhydride. 4. The method of claim 1, wherein the step (b) comprises mixing the acid-ester functional anhydride with an aryl diisocyanate and the aryl diisocyanate in the presence of a CDI catalyst. The catalyst is converted to the p-CDI. 5. The method of claim 4, wherein the aryl diisocyanate is selected from the group consisting of 4,4,-diphenylnonane diisocyanate (MDI), 4, 4 ,-Diphenyl diisocyanate, 4,4'-diisocyanatodiphenyl sulfide, 4,4'-diisocyanate diphenyl (tV- Diisocyanato diphenyl sulfone), 4,4'-diisocyanate diphenyl ether, m-naphthalene diisocyanate (MNDI), p-naphthalene diisocyanate (PNDI), m-phenylisocyanate (MPdi), p-stactyl diisocyanate (PPDI), toluene diisocyanate (TDI), 4,4,-diisocyanate-3,3,-dimercaptodiphenylmethane, 4,4'-methylenebis(1-diisocyanate-2-methoxybenzene), m-xylene diisocyanate 'p-diphenylene diisocyanate and its 110995-1010217 .doc 1364432 Mixture. According to request item 1 to about 270 °g. The method wherein the temperature of the step (d) is from about i2 (TC, wherein the temperature of the step (d) is from about 140 °C according to the method of claim 6 to about 25 〇t. a method, which is a single pot (one_p0t) operation 9. According to the method of claim 4, it is a single pot operation. 10. - a method for synthesizing a polyimine having the following structural formula, N-aryl Wherein n is an integer selected from the range of 1 to 100, and R is an optionally substituted tetravalent aromatic organic group containing at least one benzene ring or an optionally substituted tetravalent fat containing at least two carbon atoms. Group organic group, the method comprises the following steps: a) bismuth anhydride having the formula <c> II Ο is reacted with R2-OH (wherein R_2 is C!·8 alkyl) at a molar ratio of about 1:2 to form a bis(ester-acid) having the formula: Ο Ο r2o OH ο ο and b) heating the bis(ester-acid) and ρ-CDI to a temperature of from about 120 ° C to about 280 ° C, 110995-1010217.doc 11 degrees for continuous self-repetition as defined in claim 1 The reaction thus forms the polyimine. The method according to claim 1G, wherein the aromatic dianhydride is selected from the group consisting of: 3, 3, 4, 4, _ dibenzoic acid, tetrazoic acid dianhydride, and pyromellitic acid Anhydride, 2,3,1,2·naphthalenetetracarboxylic dianhydride, 1,4,5,6-tetracarboxylic dianhydride, 3,3′,4,4··diphenyltetradecanoic acid dianhydride, 1, 2,5,6-naphthalenetetracarboxylic acid, 2,2',3,3'-diphenyltetracarboxylic dianhydride, 2,2-bis(3,4,-dicarboxybenzophenone)-propanone 3,4,9,1〇_Stationic tetracarboxylic acid two-needle, bis(3 4-di-reylphenyl) bond dihepatic, naphthalene·u, 4,5_tetracarboxylic acid di wild, tea ^', to - Tetramethacrylate, decalin, 1,4,3,4-tetracarboxylic dianhydride, 4,8-dimercapto·1'2,3,5'6,7-hexahydronaphthalene tetracarboxylic dianhydride , 2,6·dichloronaphthalene_ 1,4,5,8-tetracarboxylic dianhydride, 2,7-dichloronaphthalene_M,5,8-tetradecanoic acid dianhydride, 2,3,1,7_ Tetraxane-anthracene tetracarboxylic dianhydride, phenanthrene-1,8,9,1〇tetradecanoic acid anhydride, bis(3,4-dicarboxyphenyl)ruthenium anhydride, (3,4,-di Carboxyphenyl) 2_ monocarboxy 5,6-benzimidazole dianhydride, (3,4,_dicarboxyphenyldicarboxy-6 - 1 oxadicarboxylic anhydride, bis(3',4·-dicarboxydiphenyl) Ether 2,5-oxadiazole^4 dianhydride 2 and 3,3',4,4'-oxybis-o-p-dicarboxylic acid dianhydride. 3,1·benzoxazole dianhydride, (3,,4,- Dicarboxyphenyl) 2-dicarboxy 5,6-benzopyrimidine 4 12. The method according to claim 1 , wherein the aliphatic dianhydride is selected from the group consisting of lower 〇44J2 and aryl diisocyanate, And converting the aryl diisocyanate catalyst to the P-CDI in the presence of a CDI catalyst, followed by heating the bis (ester acid) and ρ-CDI. 14. The following composition according to the method of claim 13 Group of: wherein the aryl diisocyanate is selected from the group consisting of 4,4'-diphenylmethane diisocyanate, 4,4 ι-diphenyl diisocyanate, Μ'·diisocyanate Diphenyl thioate, 4,4,-diisocyanato-phenyl sulfone, 4,4,-diisocyanate, di-naphthalene diisocyanate, p-naphthalene diisocyanate , m-benzene diisocyanate, p-benzene diisocyanide SIL salt toluene monoisocyanate, 4,4,-diisocyanatodimethyl diphenyl methane, 4'4 methylene Bis(diisocyanato-2-methoxybenzene), m-dimethylisocyanate, p-xylene diisocyanate and mixtures thereof. According to the method of claim 10 °C to about 270 ° C. wherein the temperature of the step (b) is from about 120 16 · according to the scope of claim 15 _ 10,000 to the temperature of the step is about 140 ° C to about 250 ° C. According to the method of claim 10, it is operated in a single pot. According to the method of claim 13, the system is operated by a single steel. 110995-1010217.doc