TW200800867A - Synthesis of amides, amide-imides and their polymers from aryl n-acylurea for use as intermediate in sequential self-repetitive reaction (ssrr) - Google Patents

Abstract

Disclosed is a process for synthesizing an aryl N-acylurea in both high selectivity and high yield, comprising reacting an aryl carbodiimide with a carboxylic acid under mild conditions. Thermolysis of N-acylureas at above about 120 DEG C gives amides and isocyanates, and the latter will undergo the repetitive reaction sequences in the presence of a carbodiimide catalyst. Based on this unique model, a sequential self-repetitive reaction (SSRR) is also developed in a versatile manner for converting aryl carbodiimides into amides, polyamides, polyamide-imides and polyamide-imide elastomers.

Description

200800867 IX. Description of the invention: [Technical field to which the invention pertains] The present invention relates to a method for synthesizing a high selectivity and high yield of aromatic N-mercaptourea under mild conditions, to obtain the obtained N - mercapto urea as an intermediate and via a sequential self-repetitive reaction (indicated by nSSRR" abbreviations) to form indoleamine, > indoleamine-imine and its polymers (eg polyamine, Use of polyamine-imine and polyamine-imine elastomers. φ [Prior Art] carbodiimide (CDI), especially made from isocyanate (see Monagle, J. JL; Campbell, TW; Mcshane, HFJ Am. Chem. Soc., 1962, 54, 428 8) It is known that it can react with a carboxylic acid to form an acid anhydride (anhydride), N, Nf-substituted urea (urea) and N-mercapto-N, Nf-disubstituted urea (N-mercapto urea). mixture. Khorana (see Khorana, H. G. Chem. Rev., 1953, 53, 145 and Smith, Μ· ; Moffatt, JL G· ; Khorana, Η·G·J· Am·Chem·Soc·, 1958, S0, 6204) and Silverstein (see Detar, ^ DF; Silverstein, RJ Am. Chem. Soc., 1966, (§5, 1013 and

Early studies of Detar, DF; Silverstein, RJ Am. Chem. Soc.? 1966, 88, 1020) showed that the reaction between carboxylic acid and carbodiimide has two parallel reaction pathways and is interpreted accordingly. The variety of products to be " sex. The initially formed 0-mercapto-isourea intermediate can be recombined into N-mercapto urea by a rearrangement reaction, or subjected to further substitution reactions with additional carboxylic acid molecules to produce urea and anhydride as final products. Early papers pointed out that aromatic CDI tends to form N-107400.doc 200800867 mercapto urea when treated with carboxylic acid. On the other hand, aliphatic CDI usually leads to the formation of a mixture of anhydride and N, N, disubstituted urea (see Mikolajczyk, Μ.; Kielbasinski, R Tetrahedron, 1980, 37, 233 and Volonterio, A··, Arellano, CR » Zanda, M. J. Org. Chem., 2005, 70, 2161). Recent evidence indicates that ferrocenecarboxylic acid can be selectively added to aromatic 〇1 to produce ^-mercapto urea as the main product (see Schetter, Β· ; Speiser, B. J. Organomet. Chem ·, 2004, Yang 9,1472). Another study by Lau shows (see Rave, J. Ankersen, Μ. ; Begtrup, Μ. ; Lau, JF Tetrahedron Lett, 2003, 44, 6931), synthesizing di- and tri- on solid supports Excellent yields can also be achieved by substituting N-mercaptourea. Although thermal conversion reactions for the thermal conversion of N-mercaptourea to isocyanates and guanamines have been extensively studied in the literature (see Schotman, A. Η. M. Reel. Trav. Chim. Pays-Bas, 1991). , 110, 319, Schotman, A, HM ; Mijs, WJ Reel. Trav, Chim. Pays-Bas, 1992, 111, 88 and Schotman, A. Η· M. ; Weber, TM Jf. ; Mijs, WJ Macromol· Chem. Phys., 1999, 20 (9, 635), but using N-Si urea as a synthesis intermediate or as a thermal decomposition reaction of a potential isocyanate source, and converting the resulting isocyanate to CDI and The comprehensive conversion reaction from CDI to decylamine has not yet been fully utilized. In addition, the pollution caused by by-products such as urea and acid anhydride may hinder the clean separation of N-mercapto urea. Until now, no N has been developed. - Acid-based urea as a precursor of isocyanate or as a synthetic method for the separable intermediate for the synthesis of polyamide. Therefore, the present invention provides high selectivity and high yield of aromatic hydrazine-mercapto urea The combination of 107400.doc 200800867 into the preparation of its subsequent thermal reaction, and for The invention relates to the application of aromatic amine, amide-imine and polyamine and polyamine-imine in one step. SUMMARY OF THE INVENTION Therefore, the object of the present invention is to provide a high selectivity of aromatic N-mercapto urea and A synthesis method for yield comprising reacting a carbodiimide (CDI) with a carboxylic acid at a temperature of less than about 120 ° C to obtain the aromatic N-mercapto urea. Another object of the present invention is to provide A method for synthesizing high selectivity and high yield of aromatic polyfluorenyl urea, which comprises reacting an aromatic polymer with a carboxylic acid, a bis-acid, a polycarboxylic acid or a mixture thereof at less than about 1 2 (^c) Reacting at a temperature to obtain the aromatic poly N-mercapto urea. A still further object of the present invention is to provide a temperature of from about 12 〇〇c to about 28 ° C, and in a CDI catalyst and a carboxylic acid. The method of synthesizing decylamine or guanamine-imine by continuous self-reaction (S SRR) in the presence of: a) thermal decomposition of aromatic < 1-mercapto urea into aromatic isocyanate And as a product of amidoxime or guanamine-imine; b) in the presence of the CDI catalyst, the aromatic isocyanate Converting the catalyst to aromatic CDI; and c) reacting the aromatic CDI with the carboxylic acid to form the separable aromatic N-demethyl urea as a reaction intermediate; wherein steps a), b) and c) The self-repetition proceeds and the carboxylic acid equivalent used in step c) is sufficient to substantially consume all of the aromatic isocyanate, the aromatic CDI and the aromatic N-mercapto urea. The object of the present invention is also to provide a temperature of 107400.doc 200800867 degrees from about 120 ° C to about 280 ° C, and in the presence of CDI catalyst, by continuous self-reaction to synthesize guanamine or guanamine - The imine method comprises the following steps: a) reacting C. sinensis CDI with a slow acid to form a separable aromatic basal urea as a reaction intermediate; & b) thermally decomposing the aromatic N-mercapto urea Is an aromatic isocyanate and a guanamine or guanamine-imine as a product; and c) converting the aromatic isocyanate into a aromatic CDI by a catalyst in the presence of the CDI catalyst; Wherein steps b, b) and c) are carried out on their own, and the tickic acid equivalent used in step a) is sufficient to substantially consume all of the aromatic isocyanate, the aromatic CDI and the aromatic N- Sulfhydryl urea. It is also an object of the present invention to provide a method of synthesizing an indoleamine of the formula:

It comprises: a) reacting aromatic CDI with trimellitic anhydride to form an anhydride functional hailyl urea having the formula:

b) treating the anhydride functional N-mercapto urea with water or R-OH (including a Han-type Cu alkyl group) to form an acid-functionalized ester having the formula: 400-based urine 107400.doc 200800867

c) The acid-functionalized ester-mercapto urea is heated to about 120 in the presence of a CD1 catalyst. 〇 to about 280. (: the temperature to form an aromatic isocyanate and an acid-decanamine derivative having the formula:

And continuously performing a self-repetitive reaction to form the guanamine-imine, wherein the continuous self-reacting reaction involves repeatedly performing the following three consecutive steps: 1) making the aromatic isocyanate in the presence of the CDI catalyst The catalyst is converted to aromatic CDI; H) the aromatic CDI is reacted with the acid-decalamine derivative to form a mercapto urea having the formula:

Iii) thermally decomposing the mercapto urea obtained in step ii) into the aromatic isocyanate and the guanamine-imine as a product. •, the type of poly

The ultimate object of the present invention is to provide a method for synthesizing the following dip-amine (imine-imine): 107400.doc •10- 200800867

Wherein η is an integer from 1 to 24, the method comprising: a) bringing a poly CDI having the formula

Reacting with trimellitic anhydride to form a corresponding polyurea urea having the formula

b) treating the poly N-mercapto urea with water or R-OH (wherein R is a Cw alkyl group) to form a poly N-mercapto urea having an open anhydride functional group:

c) heating the reaction mixture to a temperature of from about 120 ° C to about 280 ° C for the continuous self-reaction as defined previously to form the poly(acid amine-imine). The various advantages and objects of the present invention will be readily apparent to those skilled in the art in light of the <RTIgt; First, the present invention provides a method for synthesizing an aromatic 1-mercapto urea under mild conditions and a high yield. 107400.doc -11· 200800867 Scheme 1 describes the synthesis of N-mercaptourea 5 from CDI 1 and carboxylic acid 2, and possibly by-products, in which two parallel reaction paths occur. The initially formed sulphur-based urea intermediate can be recombined into hydrazine-mercapto urea 5, or undergoes further substitution reactions with additional acid molecules to produce the corresponding urea 4 and anhydride 3 as final products. Process 1

Η Π II R2—C~〇~C—R2 + Rt-NH-C-NH-Ri rRtNH-CrrMR n 3 4

RiN^C-NR, + r2co〇h 7 ’

C=〇, O 0

1 2 t J M U MU D 140 °c I I

R2, Rrfjl-C-NH-R, —- R MH-C-R2 + RrNCO 〇-mercapto-iso-urea^=0 r2 Oleamine isotonic acid Ν·醯蓦 urea 5 Based on selectivity of CDI reaction The carboxylic acid can be reacted with two kinds of cD][type compounds, one of which is aliphatic CDI with dicyclohexylcarbodiimide (DCC) as an example, and the other is diphenylcarbodiimide (DpcDi). As an example, aromatic CDI is prepared by phenyl isocyanate and a CDI catalyst such as 1,3-dimethyl-3-cyclophosphene oxide (dmpo). Thus, the inventors of the present invention have found two distinct product types which indicate that there are two different reaction paths in the reaction of CDI. When dcc is used as a starting material for the reaction with a carboxylic acid (e.g., benzoic acid and acetic acid), the main products obtained by the reaction are anhydride 3 and urea 4, and only a low yield of N_mercaptourea 5 is observed in the product mixture. When other carboxylic acids were used to react with DCC, only low yields of N-mercaptourea 5 were observed. However, when DPCDI is used instead of DCC, the selectivity for N-mercaptourea 5 can be highly improved. The rearrangement reaction of the sulfhydryl group of the reaction intermediate 〇-mercaptoisourea from the oxygen atom to the nitrogen atom seems to be dominant, so the product 107400.doc •12- 200800867 is mainly N-mercaptourea. For example, a carboxylic acid (for example, benzoic acid and acetic acid) can be reacted with DPCDI at room temperature to obtain a relatively high yield of hydrazine urea 5 ' at this time only a small amount of by-products, ie, an acid anhydride and a diphenyl group, are formed. Urea. Furthermore, the reaction between DPCDI and an aromatic acid having a pull-electron or electron-donating substituent can also produce N-mercaptourea at a very high selectivity. N-mercaptourea is still stable at less than about 12 (r degree, but it is also known to decompose into isocyanates and guanamine at relatively low temperatures. According to this, the present invention provides an aromatic A method for synthesizing high selectivity and hydrazine yield of N-mercaptourea comprising reacting an aromatic compound with a carboxylic acid at a temperature of less than about 12 ° C to obtain the aromatic N-fluorenyl group Urea. The process of the invention preferably has a selectivity of more than 75%, more preferably more than 85%, and preferably more than 70%, more preferably more than 8%, of synthetic aromatic n-mercapto urea. In the case of DPCDm, the yield and selectivity of synthetic urea have been found to be 8〇% and 93%, respectively. These results show that the method of the present invention can be used under mild conditions, using aromatic isocyanates. As a starting material, aromatic mercapto urea is produced in the same yield and high selectivity. Broadly speaking, any aromatic CDI can be used in the practice of the invention. Suitable aromatic CDI includes, but is not limited to, a two-part base in which one or both of the phenyl groups are optionally subjected to Ci.8 alkyl, Cis alkoxy, nitro or halogen Substituted. Examples of aromatic CDI-free include o-toluene isocyanate, p-toluene isocyanate, o-β-nitroisocyanate, p-gas isocyanate, p-methoxyisocyanate. Acidate, p-monophenyl isocyanate and decahydrofurfuryl isocyanate. In addition to amino-acid or succinic acid, other functionalized acids do not need to be complex 107400.doc -13- 200800867 It can be used in the present invention as a carboxylic acid for preparing mercapto urea. The type of carboxylic acid which can be used is not particularly limited, and an aliphatic carboxylic acid and an aromatic carboxylic acid having an electron-withdrawing or electron-donating substituent are optionally required. Acids can be used in the practice of the invention. Suitable carboxylic acids include, but are not limited to, monocarboxylic acids (such as acetic acid and benzoic acid), dicarboxylic acids (such as adipic acid and sebacic acid), other long chain aliphatic dimers. Acids, aromatic diacids (such as terephthalic acid and isophthalic acid), diacids or anhydrides (such as trimellitic anhydride, polyacids derived from anhydrides, anhydrides and polyanhydrides) and mixtures thereof. In the consistent manner, only the benzenetricarboxylic acid having acid and anhydride functional groups in the molecular structure is obtained ( The acid functional side of trimellitic anhydride reacts with CDI while retaining its anhydride functional group immobility. As will be described later, this allows for further intimidation of the anhydride functional moiety of the resulting adduct. The present invention provides a stepwise polymerization process for obtaining a polymer having a precise structural sequence, the resulting polymer having higher thermal stability and better properties. As is well known to those skilled in the art, it is used in the present invention. The aromatic CDI can be formed by converting an aromatic isocyanate by a catalyst in the presence of a CDI catalyst. The reaction is preferably carried out in tetramethylethylene sulfone (TMS). You can also use pots of suitable solvents. Suitable solvents include N,N-dimethylacetamide, N-methylpyrrolidone (NMP), N,N-dimethyldecylamine (DMF) and dimercapto-hard (DMSO). Those skilled in the art can readily determine the type of solvent that is suitable for carrying out the reaction. The type of the aromatic isocyanate is not particularly limited. Suitable aromatics 107400.doc -14- 200800867 Cyanates include, but are not limited to, aromatic mono-isocyanates, aromatic diisocyanates, aromatic polyisocyanates or mixtures thereof. Preferred aromatic isocyanates include phenyl isocyanate, toluene diisocyanate (TDI), methylene diphenylene diisocyanate (MDI), p-phenylene diisocyanate An acid salt (PPDI), an MDI polymer, and an isocyanate prepolymer prepared from one or more of the foregoing. The types of CDI catalysts have also been extensively documented in the literature and are well known to those skilled in the art. Suitable cm catalysts include, but are not limited to, various organic derivatives of phosphorus compounds and cyclic phosphorus compounds, such as methyl-3-cyclophosphene oxide (MP0), 1&gt; 3-dimethylcyclopentene oxidation. (DMPO) 1,3-indolyl], 3,2-diazapli〇phorolidine, arsenic oxide (tdphenylarsenic oxide), and these are described in

Report R101 in Tetrahedron (Vol. 37, pages 233^284, 1981) page 235 and CDI catalysts in Angew. Chem. internt·Edit·Vol· 1,621 (1962). The contents of these documents are incorporated herein by reference. The present invention also provides a method for synthesizing a high selectivity and high yield of aromatic poly N-mercapto urea, comprising comprising an aromatic poly CDI with a carboxylic acid, a diacid, a polyhical acid or a mixture thereof at less than about 12 The reaction is carried out at a temperature of 0 ° C to obtain an aromatic poly N-mercapto urea. Similarly to the above aromatic CDI, the aromatic poly CDI can be obtained by a known mixture of an aromatic diisocyanate, an aromatic polyisocyanate or a mixture obtained by mixing the above isocyanate. As previously mentioned, it is known that the scent of N-branched urea is thermally stable at temperatures up to about 12 Torr and is rapidly converted to isocyanates and guanamines at temperatures of more than 13 Å. Accordingly, the present invention further provides a novel and effective method for synthesizing guanamine or guanamine-imine 10740.doc -15 - 200800867 by continuous self-reaction (SSRR), which is based on CDI catalyst and ruthenium. In the presence of an acid, and from about i2 ° C to about 280 ° C, preferably from about 120. (: to about 27 (TC, more preferably from about 丨 buckle it to about 250 ° C, at a temperature of, the method comprises: a) thermal decomposition of aromatic N· mercapto urea into aromatic isocyanate and a product of a guanamine or a guanamine-imine; b) converting the sulphate salt catalyst to an aromatic CDI in the presence of the (10) catalyst; and c) reacting the aromatic CDI with the carboxylic acid Reacting to form the separable aromatic N-mercapto urea as a reaction intermediate; wherein steps a), b) and c) are carried out by themselves, and the carboxylic acid equivalent used in step c) is sufficiently consumed All of the aromatic isocyanate, the aromatic CDI and the aromatic N-mercapto urea. As shown in Flow 2, the SSRR method consists of three self-repetitive steps. The first step is the thermal decomposition of L0 Moer's aryl (IV) N, based urea to form 1 〇 耳 醯 醯 amine or guanamine-imine as a product and simultaneously produce i. 〇 之 aromatic isocyanate . The second step is a catalyst conversion reaction of an aromatic isocyanide &amp; L salt of 丨. 〇mol into 0.5 mole of aromatic CDI. Finally, the third step is 0. 5 moles of aromatic C D ] [reaction with carboxylic acid to form an additional 〇·5 mole of aromatic N• thiourea as a separable intermediate. Therefore, in summary, in a single complete cycle, 5% of the aromatic isocyanate is consumed in this continuous self-reaction (SSRR) to form 50% of the guanamine or guanamine-Asia. amine. When a sufficient amount of carboxylic acid is provided, repeating the above three consecutive reactions will eventually consume all of the aromatic N-mercaptouridine, aromatic isocyanate, and aromatic CDI. The inventors of this case have demonstrated high 107400.doc •16-200800867 Reactive aromatic isocyanates or aromatic CDI compounds can be transiently converted to soluble aromatic N-mercapto urea intermediates. The aromatic N-mercapto urea can be further separated and directly converted into a high melting point decylamine or a guanamine-imine. The self-continuous reaction of the present invention provides low temperature reaction conditions and the advantages of synthesizing guanamine or guanamine-imine at a high selectivity compared to conventional methods for directly reacting aromatic isocyanates and carboxylic acids. Process 2 Ο

aryl-NH-C-R2 decylamine (final product) Ο aryl-N-C-NH-aryl 〇:C] R2 aryl sulfhydryl urea 5

Aryl-N-di-C^N-aryl

R2C〇OH, 140°C

Preferably, DMPO-C〇2, aromatic N-S toluene-based urea, CDI catalyst and traconic acid are dissolved in anhydrous tetrahydrofuran (THF) to carry out the 38-foot method. However, other solvents may also be used, such as N,N-dimercaptoacetic acid amine, N-methyl sigma oxime (ΝΜΡ), hydrazine, hydrazine-dimethylformamide (DMF) and dimercapto Sulfone (DMSO). Those of ordinary skill in the art can readily determine the type of solvent that is suitable for carrying out the reaction. In another embodiment of the invention, the aforementioned SSRR process can be initiated directly from the aromatic CDI and operated in a one-pot operation. Accordingly, the present invention further provides a preferred from about 120 ° C to about 280 ° C, preferably from about 120 ° C to about 107400.doc -17 - 200800867 27〇t 'better from about 1401: to about 25 (rc At the temperature and in the presence of a coffee catalyst, by SSRR reaction to synthesize guanamine or guanamine-imine, which comprises: a) reacting aromatic CDI with a carboxylic acid to form a separable aromatic N- Sulfhydryl urea as a reaction intermediate; b) thermal decomposition of the aromatic N-mercapto urea into an aromatic family isocyanate and as a product of amidoxime or guanamine-imine; and c) in the CDI touch In the presence of a medium, the aromatic isocyanate catalyst is converted to aromatic CDI; wherein steps a), b) and c) are carried out by themselves, and the carboxylic acid equivalent system used in the step &amp; It is sufficient to substantially consume all of the aromatic isocyanate, the aromatic CDI and the aromatic N-mercapto urea. Similarly, aromatic CDI can be formed by converting an aromatic isocyanate by a catalyst in the presence of a CDI catalyst. Alternatively, the aforementioned continuous self-repetitive reaction (SSRR) may even begin directly with the aromatic isocyanate. In either case, it is preferred that all starting materials be dissolved in a suitable solvent, such as anhydrous tetrahydrofuran (THF), N-methyl. Bile ketone (NMP), cyclobutane (TMS), N,N-dimercaptoacetamide, N,N-dimethylformate (DMF) and dimercaptosulfoxide (DMSO) for The SSRR process thus produces the desired guanamine or guanamine-imine. Those of ordinary skill in the art can readily determine the type of solvent that is suitable for carrying out the reaction. According to one embodiment of the invention, the buffer acid used carries an imine group at the r2 position and the resulting product is a guanamine-imine. For example, when 5-isoindolinecarboxylic acid is used as the ferulic acid and the aromatic CDI is diphenyl CDI B, the resulting product has the indoleamine-imine of the formula: 107400.doc -18 - 200800867

According to another embodiment of the invention, the guanamine-imine can also be prepared from a specific carboxylic acid having a acid and anhydride functional group in the molecular structure (e.g., trimellitic anhydride). In this case, 'the phthalic acid-based phthalic anhydride used in the SSRR method to consume all aromatic isotonic acid salts, aromatic CDI and aromatic N-mercapto urea. Accordingly, the present invention further provides a method of synthesizing a guanamine-imine of the formula:

It comprises: a) reacting aromatic 0〇1 with _p-trimellitic anhydride to form an anhydride functional N_mercapto urea having the formula: aryl-f

b) treating the anhydride functional N-mercapto urea with water or R-OH (wherein the c..8 alkyl group) to form an acid-functionalized ester-mercapto urea having the formula:

107400.doc • 19· 200800867 c) The acid-functionalized ester-mercapto urea is heated to from about 12 (TC to about 280 ° C, preferably from about 120 ° C in the presence of a C DI catalyst) To a temperature of about 270 C' more preferably from about 14 ° C to about 250 ° 〇, the temperature to form an aromatic isocyanate and an acid derivative having the formula:

η-cooH ^—COOR and simultaneously performing the SSRR method to form the guanamine-imine, wherein the continuous self-repetitive reaction (SSRR) involves repeatedly performing the following three consecutive steps: 0 in the presence of the CDI catalyst, The aromatic isocyanate catalyst is converted to aromatic CDI; Π) the aromatic CDI is reacted with the acid-decalamine derivative to form a mercapto urea having the formula:

Iii) thermally decomposing the mercapto urea obtained in step ii) into the aromatic isocyanate and the guanamine-imine as a product. Similarly, aromatic CDI can be formed by converting an aromatic isocyanate by a catalyst in the presence of a CDI catalyst. Alternatively, the aforementioned continuous self-repetitive reaction (SSRR) may even begin directly with the aromatic isocyanate. In either case, it is preferred that all starting materials are dissolved in a suitable solvent, such as anhydrous tetrahydroanthracene (THF), N-methyl ratio σ ketolone (NMP), cyclobutanthene (TMS). , N,N-dimethylacetamide, N,N-didecylguanamine (DMF) and dimethyl sulfene 107400.doc • 20- 200800867 sulfone (DMSO) to be manufactured by the SSRR method The desired amine and imine. Those of ordinary skill in the art can readily determine the type of solvent that is suitable for use in carrying out the reaction. Further, as is known in the art, the sour/R-OH reaction can be carried out in the presence of a catalyst such as triethylamine (TEA). In a special embodiment of the present invention, the N-mercapto urea is decomposed into a guanamine and an isocyanate at a temperature of from about 12 (rc to about 18 ° C.), and then the reaction temperature is further Raise to a range of about 180 ° C to about 280 ° C for a period of time

The time, for example, from about 15 minutes to about 120 minutes, is carried out to carry out a ring closure reaction to form a guanamine-imine.

The SSRR method according to the present invention has also been successfully applied to the synthesis of polyamine. For example, in the present invention, polyamine can be prepared by subjecting aromatic poly CDI nicotinic acid to a temperature lower than about

04n=c=n-〇-〇h;

• N=c: -ο reacts with trimellitic anhydride to form a corresponding polycondensate of the formula: 107400.doc -21- 200800867 N-mercapto urea:

b) treating the mercapto urea with water or R-OH (wherein the R system is Cl_8 alkyl) to form a polyfluorenyl urea having an open anhydride functional group:

c) heating the reaction mixture to a temperature of from about 12 Torr to about 280, preferably from about 12 (TC to about 270 ° C, more preferably from about i4 ° C to about 250 ° C, to carry out the aforementioned SSRR process thereby The poly(melamine-imine) is formed.

Preferably, it is shown as an integer of η series 1 to 24 in the poly(酉|amine_imine) structural formula. When η is greater than 24, the resulting poly(amine amine/imine) is soluble in certain solvents such as monomethylguanamine (DMF) or hydrazine-methyl oxazeone (oxime). The SSRR process according to the present invention can also be used to synthesize polyamine-imine elastomers by inserting long-chain soft segments (e.g., ether molecular groups) into at least one acid component of one or more acid components. . In this case, all of the acid component and the isocyanate component may be reacted together in a single pot (one_p0t); alternatively, the isocyanate component and an acid may be reacted first, followed by other acid species. For example, a polyamine-imine-ether elastomer can be prepared in a single pot by means of an isocyanate (such as MDI), a polyether diacid and azelaic acid (I07400.doc -22-200800867). One't) synthesis; or, diisocyanate can be combined with polyether diacid

The reaction forms a prepolymer of a stable isocyanate terminal, followed by the addition of a CDI catalyst (譬 &amp; DMP0) and sebacic acid. It is also known to those skilled in the art that the SSRR method of the present invention can also be used to synthesize polyurethane elastomers if the long chain soft segment is included in the isocyanate forming process. As described in numerous documents in this technical field, it is possible to 'mute fluorenyl diphenyl phenyl diisocyanate (Mm) with mono-functional phenyl isononate in the presence of a cm catalyst at a ratio of 16:1 The molar ratio is reacted to prepare a polycm. For example, U.S. Patent No. 3,929,733 (1975) to Alb (10) L. M4 Fardssey, w. The entire contents of this patent are incorporated herein by reference. Similarly, the synthesis is preferably carried out in a suitable solvent such as anhydrous tetrahydrofuran (THF), N-methylpyrrolidone (NMP), sulfolane (TMS), N,N-methylethylamine, N,N. • Dimethylformamide (dmf) and dimethyl sulfoxide (DMS0) to produce the desired product. It is well known in the art that it is a good type of solvent that is suitable for carrying out this reaction. Further, as is known in the art, the anhydride/R-〇H reaction can be carried out in the presence of a catalyst such as triethylamine (TEA). According to the present invention, the synthesis method of the high selectivity and high yield of the aromatic N-mercapto urea, and the use of aromatic N-mercapto urea as an intermediate in the SSRR method to synthesize decylamine, guanamine-Asia The method of the amine or its polymer (e.g., polyamine, polyamine-imine, and polyamine-imine elastomer) can be carried out in a one-pot operation. It is convenient to use the method of the invention in the process and 107400.doc • 23- 200800867 is advantageous. Without further elaboration, the skilled artisan can utilize the present invention to its fullest extent in light of the above disclosure and the following examples. The following examples are only illustrative of how the skilled artisan can operate the method of the present patent application without limiting the remaining disclosure in any way. [Embodiment] Example

Measurement procedure: hNMR and nC NMR spectra were recorded on a Variantova 200 sin MHz or 600 MHz instrument. The chemical shift is represented by δ, and the coupling constant J Å | J is expressed in Hz. The spectra are recorded in a solvent (eg, propylene-d6 or DMSO-d6) at room temperature, and the chemical shifts are relative to the solvent signal. FT-IR using a Perkin Elmer spectrum one FT-IR spectrometer using a 5 μπι shell particle/lOOA column (Hypersil-100 C18) and UV detection at 254 nm with MeCN/H20=50/50 as elution The liquid (at a flow rate of 0.5 ml/min) was subjected to HPLC. Thermal differential scanning analysis (DSC) was performed on a Perkin Elmer Pyris 6 instrument at a heating and cooling rate of 10 °C /min. With a Perkin Elmer Pyris 1 instrument, heating at 10 ° C / min

Thermogravimetric analysis (TGA) was performed at rates up to 850 ° C and in nitrogen. The number is average. The average molecular weight (Μη) is estimated by gel permeation chromatography (Jasco GPC, RI detector) and calibrated to polystyrene standards. N,N-* dimethyl decylamine (DMF) after degassing was used as an eluent and was carried out at a flow rate of 1.0 ml/min. 107400.doc -24- 200800867 Example 1: Preparation of aromatic N-mercapto urea having the following formula

Phenyl isocyanate (5 g; 42 mmol) and 1,3-dimethyl-3-cyclophosphene oxide (DMPO; 0.15 g) were dissolved in 5 mL of anhydrous THF and Heating to 6 (TC for 3 hours) under nitrogen. Next, 5-isoporphyrincarboxylic acid 2f (5e19 g; 21 mmol) synthesized from trimellitic anhydride and butylamine was added to the reaction mixture at 25 Stir for 3 hours at a temperature of ° C. The title product (88%) was precipitated from 1 liter of hexane and the selectivity was over 99% (as shown in Table 1). ^-NMR (600 MHz,acetone) δ ( Ppm): 0·90 (t,c/ = 7.2 Hz, 3H)5 1.29 (sxt, J = 7.2 Hz, 2H), 1.58-1.63 (m, 2H), 3.59 (t, 7.2 Hz, 2H), 7.12 (dt, 7.2, Hz, 1H), 7.25-7,37 (m,5H), 7.45 (dd, /= 8.4, 0·6 Hz, 2H), 7·60 (d, 8.4 Hz, 2H)5 7.75 (d, J = 7.8 Hz, 1H), 7.91 (dd, 6.6, 1.8 Hz, 2H), 10.80 (bs? 1H), 13C-NMR (150 MHz, acetone) δ (ppm) · 13.8, 20.6, 31· 1,38·3,120.5,120.6,122.7,123.3,124.9,129.1,129.7,129.8,130.8,132.7,133.8,134.1,138·9, 139.5, 142.9, 152.5, 167·9, 172.4. Anal· Calcd. For C26H23N3〇4 : N, 9.52% ; C, 70.73 % ; H, 5.25 %· Found : N, 9.76 %, C, 71·59 %, H, 5.65 % · mp 105.1-105.8 ° C. Examples 2 to 8 • Repeat the procedure described in Example 1 using phenyl isocyanate and 107400.doc -25 - 200800867 DMPO to react with various carboxylic acids as shown in Table 1 to form the corresponding aromatic N-mercaptourea The yield and selectivity of the obtained aromatic N-mercaptourea are shown in Table 1. Figures 1 to 7 show the 1H NMR spectrum of the obtained aromatic N-mercaptourea.

0 R^NH-C-NH-Rt 4 ___ 〇Ο 1 2 L 2 JSR^NH-C-R2 + Rt-NCO 0-fluorenyl isourea?=C&gt; Indole isocyanate R2 N-醯Base urea r1N=C=NR1 + r2cooh

RtNH-C^iNR! Ο R!—C~〇—C—R2 Table 1: Reaction examples of aromatic €01 and carboxylic acid (112(:0011) aromatic CDI carboxylic acid (R2) N-mercapto urea Selection rate (mol%) &quot; Yield (%Γ 1 DPCDI 〇(2f) 0 &gt;99 88 (5h) 2 DPCDI 〇(2e) &gt;99 88 (5g) 3 DPCDI Ph (2a) 93 80 (5c ) 4 DPCDI p-N02-Ph (2b) 89 85 (5d) 5 DPCDI p-OMe-Phpc) 98 88 (5e) 6 DPCDI o-OMe-Ph (2d) &gt;99 93 (5f) 7 DPCDI CH3 ( 2g) 95 90 (5i) 8 DPCDI CH3(CH2)5(2h) &gt;99 88 (5j)

107400.doc 26- 200800867 Example 9: Preparation of indoleamine-imine from anhydride-functional N-mercaptourea via SSRR process Scheme 3

MeOH TEA O-r o=c aCOOH COOMe

COOH COOMe

The anhydride-functional N-mercapto urea obtained in Example 2 (0.5 g; 1.3 mmol) and DMPO (75 mg; 〇·57 mmol) were dissolved at room temperature as shown in Scheme 3. 30 ml of anhydrous sulfolane. Methanol (42 g; 1.3 mmol) was added to the reaction mixture and triethylamine (013 g; 1 equivalent) was used as a catalyst to form a new acid-functional ester-mercapto urea 6. Next, the acid-functional ester-mercaptourea 6 was heated to 14 Torr for 45 minutes to form the acid amide derivative 7. The acid amine derivative 7 is reacted with DPCDI to form a new mercapto urea 8 as an intermediate. Finally, the reaction temperature was raised to 21 〇. 〇 3 minutes to perform a ring closure step to form a guanamine-imine$. Next, 500 ml of water was added to the final solution to form a brown precipitate of the indoleamine-imine 9. The sediment was filtered and recrystallized from 25 ml of hot xylene. The precipitate was dried under vacuum at 107400.doc •27-200800867. By this one-pot operation, a high yield of the amine-imine 9 (93%) was isolated and confirmed to be the only product by the following analysis. ^-NMR (600 MHz, DMSO) δ (ppm): 7.14 (t, J = 7.2 Hz, 1H), 7.38 (t, / = 7.8 Hz, 2H), 7.46-7.50 (m, 3H), 7.54 (t , J = 7.8 Hz, 2H), 7.82 (d5 J = 7.8 Hz, 2H), 8.12 (d, J = 7.8 Hz, 1H), 8·45 (dd, /= 7.8, 1.8 Hz, 1H), 8.54 ( s, 1H), 10.64 (s, 1H); nC-NMR (150 MHz, DMSO) δ (ppm): 120.6, 122.2, 123.6, 124.2, 127.4, 128.2, 128.7, 128.9, 131.8, 131·9, 133.9, 134.4, 138.7, 140-3, 163.6, 166.5, 166.6. Anal. Calcd. for C21H14N2〇3: N, 8.20 % ; C5 73.70 % ; H, 4.10 %. Found : N,8·21 % ; C,73· 59 % ; H, 4.42 %·. Mp 271.4-273.1 °C.

107400.doc 28- 200800867 Example 10: Preparation of poly(nitrimine) via SSRR self-polymerization of N-mercaptourea Scheme 4

-N=C=N

η 〇 H〇〇C

Ο

P-CDI

Each νηΌ

o:c

o=c

poly-N-mercapto urea

TEA, MeOH 〇 -M-C-ΗΗ-ί ^

Ofr"HO~cH2Ob

O II C

〇:C

aCOOMe COOH |^T-COOMe ^^L-cooh

DM PO, 202 °C

-C〇2, -MeOH SSRR

O-NH-C n (melamine-imine)

O

- 4 4L of mercapto-bis(phenyl isocyanate) (MDI; 15 g; 59.9 mmol) in 250 ml, equipped with a thermometer, nitrogen inlet, reflux condenser, oil bath It was placed in a three-necked round bottom flask with a magnetic stirrer and dissolved in 200 ml of anhydrous N-methyl-2-pyrrolidone (NMP). The reaction mixture was heated to 90 ° C and phenyl isocyanate (0.89 g; 7.47 mmol 107400.doc -29-200800867 ears) was added. The mixture was stirred and maintained at a temperature of 90 ° C for several minutes until the solution became homogeneous, followed by the addition of DMPO (70 mg). Carbon dioxide is almost immediately released. The solution was heated at a temperature of 90 ° C for 3 hours to form a corresponding poly(carbodiimide) (P-CDI). When the mixture was cooled to room temperature, trimellitic anhydride (12.2 g; 63.5 mmol) was added and stirred for 1 hour to form poly-N-mercapto urea as shown in Scheme 4. Next, rumors (2.04 g; 63.7 mmol) and triethylamine (6.4 g; 63.7 mmol) were added to the mixture and stirred for 30 minutes. The reaction mixture was further heated to 202 ° C for 1 hour and poured into 2 liters of water. The resulting product was filtered and dried to give 23.3 g (92%) of poly(decamine-imine) (brown solid) characterized by a relatively high rg at 238 ° C and a Td at 457 ° C. The number average molecular weight (?n) of the obtained poly(amine-imine) was measured by gel permeation chromatography (GPC) to be 20,600 g/mole. Figures 8 to 10 show the 1 NMR spectrum and DSC and TGA analysis of the obtained poly(amine-imine). Example 11: Preparation of Polyamine-Imine-Ether Elastomers by Using a Mixture of Two Acids Scheme 5

Diisocyanate polyether diol

107400.doc -30- 200800867

The polyether diacid is described (Wei, KL.; Hung, FY·; Lin, J. J. J. Polym. Sci. Part A: Polym. Chem., 2006, 44, 646) (4.53 g; 1.87 Millol) and sebacic acid (1·53 g; 8.13 mmol) dissolved in 100 ml of TMS, placed in 250 ml, equipped with thermometer, nitrogen inlet tube, reflux condenser, oil bath and magnet A three-neck round bottom flask with a stirrer. The solution was heated to 180 ° C, then DMP(R) (25 g) and MDI (3.0 g; 12 mmol) were added and stirred for 30 minutes. The solution was then heated to 200 ° C and stirred for 2 hours. The resulting solution was poured into 1.5 liters of water. After filtration and drying in a vacuum oven to remove moisture, the resulting product is a polyamidamine-imine-ether elastomer characterized by a relatively high rg (polyether) at -33 ° C and at 378 Rd of °C. Example 12: One-pot synthesis of PAI Process 6

OCN ""-CH2"~NCO + HQOC--^ ^-COOH COOMe MDi 1-methyl-trimellitic phthalate

SSRR poly(amide-imine) Ο

Ν-

-C02t -MeOH (1) 180 °C 1h (2) 202 °C 1h Put hydrazine (15 ml) into a 250 ml, three-neck round bottom bottle equipped with a thermometer, nitrogen inlet tube, reflux condenser, oil bath And in the flask of the magnet stirrer. The crucible was heated to 180 ° C, followed by the addition of DMPO (40 mg) and 1-decyltrimellitic acid ester (at 11^11^&amp; fly 6) (1 g; 4.47 mmol). MDI (1.12 g; 4.47 mmol) was added to the mixture, followed by heating to 200. 107400.doc -31 - 200800867. (:, and stirred for 2 hours. Pour the resulting solution into 5 ml of water to form a brown PM precipitate. Filter and dry the precipitate under vacuum. Via this single: (Caf-(10) operation, separate high yield pai (9〇%), _ shows (four) the dirty analysis of the towel, Figure 12 is the analysis of the % job. The resulting pAi is characterized by a relatively high value of 289. (:\ and Td at 479〇c. Comparative Examples 1 and 2 Under the same operating conditions as exemplified by the real m, dicyclohexylcarbodiimide (dcc) was used as a starting material to react with benzoic acid (Comparative Example i) or acetic acid (Comparative Example 2). It is shown that the main products of the above reaction are wild and urea, and only N-mercapto urea having a low selectivity (comparative example (1) 38% and 25%, respectively) is observed in the product mixture. _^2·aliphatic CDI and carboxylic acid Reaction example of dCOOH)

1 2 Aliphatic CDI decanoic acid (R2) Selection of N-mercapto urea One--- 壹 (mole%# yield (%)*4 Ph &quot; ~----

DCC DCC is calculated by 1H NMR integration* *separation by precipitation or recrystallization - it is easy to understand that various improvements of the present invention are possible due to the complexity of the product mixture (which cannot be judged to be (10) + urea + N-branched urea) Η ^ , and this skill is easily associated with and expected. BRIEF DESCRIPTION OF THE DRAWINGS Figs. 1 to 7 show the 1H NMR spectra of the ruthenium-based urea obtained according to the present inventions in Examples 2 to 8. The aggregation (Figs. 8 to 10 shows the 1H NMR spectrum and DSC and TGA analysis of 107400.doc -32 - 200800867 amine-imine obtained in the method of the present invention in Example 1G). Figures 11 to 12 show the 1H NMR and nC NMR spectra of the poly(melamine-imine) obtained in the one-pot synthesis method according to the present invention in Example 12.

107400.doc -33 -

Claims (1)

200800867 X. Patent application scope: 1. A high selectivity and high yield synthesis method of aromatic N-mercaptourea (N-acylurea), which comprises low aromatic carbodiimide (CDI) and carboxylic acid The reaction was carried out at a temperature of about 120 C to obtain the aromatic N-mercapto urea. 2. The method according to claim i, wherein the aromatic (:] 〇 1 is in the presence of a (:1) 1 catalyst to convert aromatic mono-isocyanate, aromatic di- by a catalyst. The isocyanate, the aromatic polyisocyanate or a mixture thereof. The method according to claim 1, wherein the aromatic CDI is converted to a phenyl isocyanate by a catalyst in the presence of a CDI catalyst. Acid salt, toluene diisocyanate (TDI), methylene diphenylene diisocyanate (mdi), p-phenylene diisocyanate (PPDI), MDI polymer, and Formed from one or more isocyanate prepolymers. 4. The method according to the item i, wherein the aromatic is selected from the group consisting of diphenyl CDI, wherein one of the phenyl groups or The two are optionally substituted by a ci8 alkyl C 1 -8 alkoxy group, a schlossyl group or a halogen. 5. The method according to claim 5, wherein the carboxylic acid is selected from the group consisting of a monocarboxylic acid, a dicarboxylic acid, and other long chain fats. a group consisting of a diacid, an aromatic diacid, a diacid or an acid, and a mixture thereof. 6. The method according to claim 5, wherein the carboxylic acid is selected from the group consisting of acetic acid a group consisting of benzoic acid, adipic acid, sebacic acid, terephthalic acid, isophthalic acid, trimellitic anhydride, polyacids derived from anhydrides, acid anhydrides, polyanhydrides, and mixtures thereof 7. The method according to claim 1, wherein the selectivity is more than 75%, and the yield is more than 70%. 107400.doc 200800867 8. The method according to claim 7, wherein the selectivity is more than 85%, The yield is more than 80%. 9 · 7 kinds of Fangxiang group poly-fluorenyl urea high selectivity and high yield of the synthesis side, ', 匕έ 务 无 无 无 聚 聚 聚 聚 无 无 无, polyacrylic acid or its oral substance is reacted at a temperature lower than about 12 (at the temperature to obtain the aromatic poly-N-S blue-based urea. 10. According to the method of the kiss 9, the aromatic The poly CDI is formed by a mixture of an aromatic di-isocyanate, an aromatic polyisocyanate or a mixture of the above isocyanates. 11. The species is from about 12 ° C to about 280 ° C. a method of synthesizing a guanamine or a guanamine-imine by continuous self-reaction in the presence of a CDI catalyst and a carboxylic acid, which comprises a) thermal decomposition of aromatic N-mercapto urea into aromatic isocyanate and its amine or amine-imine as a product; b) the aromatic isocyanate in the presence of a ruthenium CDI catalyst The salt catalyst is converted to aromatic CDI; and c) the aromatic CDI is reacted with the carboxylic acid to form a separable aromatic N-mercapto urea as a reaction intermediate; and the step (b) of the crucible is small (b) And self-repetitively, and used in step c), the towel is sufficient to substantially consume all of the aromatic isocyanate, the side CDI and the aromatic N-mercapto urea. 12. The method according to claim 11, wherein the aromatic monohydrazine urea is obtained by the method according to claim 1. 13. The method according to claim 11, wherein the carboxylic acid is selected from the group consisting of a monocarboxylic acid, a di-I07400.doc 200800867 wei acid, other long-chain aliphatic diacids, an aroma, a leucovorin, a diacid or a group of anhydrides and mixtures thereof. H. The method of claim 13, wherein the slow acid is selected from the group consisting of acetic acid, benzoic acid, adipic acid, sebacic acid, terephthalic acid, isophthalic acid, trimellitic acid, and anhydride. A group of polyacids, anhydrides, polyanhydrides, and mixtures thereof. 15. The method of claim U, wherein the temperature is from about 12 Torr. 〇 to about 27〇 t. The method of claim 15, wherein the temperature is from about 14 (rc to about 250 〇C. 17. The method according to claim 11, wherein the tickacid has an imine group and the product is acid Amine-imine. The method according to claim 17, wherein the carboxylic acid is 5-isoindoline carboxylic acid, and the product has a guanamine-imine of the formula: 19. A method of synthesizing a guanamine or a guanamine-imine by continuous self-reaction in the presence of a CDI catalyst at a temperature from about i20 ° C to about 280 ° C, comprising: a) aroma Group CDI reacts with a carboxylic acid to form a separable aromatic N-mercapto urea as a reaction intermediate; 107400.doc 200800867 b) The aromatic N-mercapto urea is thermally branched, ..., and the solution is square a family of isocyanates and a guanamine or guanamine-imine as a product; and c) in the presence of the CDI catalyst, you convert the scent of 5 haifang fragrant isocyanate into aroma Group CDI; wherein steps a), b) and c) are carried out by themselves, and are used in step: the carboxylic acid equivalent is sufficient to substantially consume all of the aromatic isocyanate, the aromatic CDI and the aromatic N_mercapto urea. 20. The method according to claim 19, wherein the aromatic (10) is converted into an aromatic mono-isocyanate, a salt, an aromatic di-isocyanate, an aromatic polyisocyanate by a catalyst in the presence of a (10) catalyst. An acid salt or a mixture thereof is formed. The method according to claim 19, wherein the aromatic cm is converted into a phenyl isocyanate, a toluene diisocyanate (TDI), a methylene diene by a catalyst in the presence of a cm catalyst. Phenyl diisocyanate (mdi), p-stactyl diisocyanate (PPDI), an MDI polymer, and an isocyanate prepolymer prepared from one or more of the foregoing. The method according to claim 19, wherein the aromatic 〇] 〇 1 is selected from the group consisting of diphenyl CDI, wherein one or both of the phenyl groups are optionally alkylated by Cy alkyl or Cw. Substituted by nitro or halogen. The method according to claim 19, wherein the carboxylic acid is selected from the group consisting of monocarboxylic acid, mono-acidic acid, other long-chain aliphatic diacids, aromatic diacids, diacids or acid acids, and mixtures thereof. group. The method according to claim 23, wherein the carboxylic acid is selected from the group consisting of acetic acid, benzoic acid, adipic acid, sebacic acid, terephthalic acid, isophthalic acid, meta-dicarboxylic anhydride, and anhydride-derived Groups of acids, anhydrides, polyanhydrides, and mixtures thereof, 107400.doc 200800867. The method of claim 19, wherein the temperature is from about i20 ° C to about 270 26. The method of claim 25, wherein the temperature is from about i40 ° C to about 250. Hey. The method according to claim 19, wherein the carboxylic acid bears an imine group, and the product is a guanamine-imine. 28. The method according to claim 27, wherein the carboxylic acid is 5-isoindole carboxylic acid, and the product is a decylamine-imine of the formula: 29. A method for synthesizing a guanamine-imine of the formula It comprises: a) reacting aromatic CDI with stearic trimic anhydride to form an anhydride functional N-mercapto urea having the formula: aryf~N-c-NH-aryl 0=ά 〇 b) treating the acid liver functional thiourea with water or R 〇Η (which #转Ci.8 alkyl) to form an acid-functionalized vinegar acid-based urine having the formula 107400.doc 200800867 COOH • COOR c) heating the acid-functionalized ester-mercapto urea to a temperature of from about 120 ° C to about 280 ° C in the presence of a CDI catalyst to form an aromatic isocyanate and having the formula Acid-decylamine derivative The COOH COOR is simultaneously subjected to a continuous self-reaction to form the decylamine imine, wherein the continuous self-repetitive reaction involves repeating the following three consecutive steps: 1) in the presence of the CDI catalyst, the aromatic The cyanate catalyst is converted to aromatic CDI; ii) the aromatic CDI is reacted with the acid-decalamine derivative to form a mercapto urea having the formula: m) thermally decomposing the mercapto urea obtained in step U) into the aromatic isocyanate and the guanamine-imine as a product. 30. The method according to claim 29, wherein the aryl: exists in the presence of a catalyst to convert an aromatic monoisocyanate, an aromatic flat s &amp;&amp; 々日佚 异 鼠 或 or; Group CDI is formed by a CDI catalyst isocyanate, a scented mono-isocyanate, an aromatic dicyanate or a mixture thereof. 107400.doc 200800867 31. The method of claim 30, wherein the aromatic (:1) 1 is converted to phenyl isocyanate or toluene diisocyanate by a catalyst in the presence of a catalyst in the presence of a catalyst. (TDI), fluorenylene diphenylene diisocyanate (MDI), p-phenylene diisocyanate (PPDI), MDI polymer, and isocyanic acid obtained from one or more of the above Formed from a salt prepolymer. 32. The method of claim 29, wherein the temperature of step e) is from about 270 °C. 33. The method of claim 32, wherein the temperature of step c) is from about to about 250 °C. 34. A method for synthesizing poly(decylamine-imine) having the following structural formula NH-C Wherein η is an integer from 1 to 24, and the method comprises: a) bringing a poly CDI having the formula β reacts with phthalic anhydride to form a corresponding polyfluorene-acid urea having the following formula 107400.doc 200800867 b) The poly N-mercapto excitin is treated with water or R-hydrazine (wherein l^Cl.8 alkyl) to form a poly N-mercapto urea having an open anhydride functional group: 0-C N^~COOH o=c j^pCOOMe l^L-COOH c) The reaction mixture was heated to about 12 Torr. (: to about 280. (: the temperature to carry out a continuous self-repetition reaction as defined in claim 29 to form the poly(amine-imine). 35. The method according to claim 34, wherein the poly CDI is In the presence of a CDI catalyst, it is formed by reacting a fluorenylene diphenyl phenyl diisocyanate and a phenyl isocyanate. 36. The method according to claim 34, wherein the temperature of the step c) is Approximately 12 〇. 〇 to about 27 (TC. 37. The method according to claim 36, wherein the temperature of the step c) is from about i4〇〇c to about 250 ° C. 3 8 · According to the method of claim 34 And a one-p〇t operation. 39. A method for synthesizing polyamine, which comprises heating the aromatic poly N-mercapto urea obtained by the method according to claim 9 To a temperature of about i 2 Torr to form polyamine and isocyanate. 40. The method according to claim 39, wherein the temperature is about i4 ° C. 41. A synthetic poly(amine-imine) a method comprising: a) reacting a poly CDI with an acid anhydride to form a corresponding poly(fluorenyl) urea; b) using water or R_0H (wherein the r is a Gy alkyl group) The poly(N-mercapto urea) 107400.doc 200800867 to form a poly N-mercapto urea having an open anhydride functional group; c) heating the reaction mixture to about i2 (TC to about 28 (TC temperature to proceed as Continuously self-reacting as defined in claim 29 to form the poly(amine-imine). 42. The method of claim 41, wherein the anhydride in step a) is a mixture of one or more acids or anhydrides. 43. The method of claim 42, wherein the acid in step a) comprises (iv) a soft segment. Sickle, and s Hai product poly (bristamine-imine) elastomer. 44. The method according to claim 41, wherein the acid in the step a) comprises one of the hydrazine moieties, and the product is a polyamine amine-imine-severe elastomer. 107400.doc