TWI297003B - Synthesis of amides, amide-imides and their polymers from aryl n-acylurea for use as intermediate in sequential self-repetitive reaction (ssrr) - Google Patents

Description

1297003 IX. Description of the Invention: [Technical Field] The present invention relates to a method for synthesizing a high selectivity and high yield of aromatic N-mercaptourea under mild conditions, and the obtained Ni Sulfhydryl urea as an intermediate and via a sequential self-repetitive reaction (expressed as "SSRR") to form indoleamine, guanamine-imine and its polymers (eg polyamine, polyfluorene) Use of amine-imine and polyamidamine-imine elastomers. • [Prior Art] carbodiimide (CDI), especially made from isocyanate (see Monagle, JJ; Campbell, TW; Mcshane, HFJ Am. Chem. Soc., 1962, <54, 4288), known to react with carboxylic acids to form anhydrides (anhydrides), N, Nf-substituted ureas (ureas) and N-mercapto- Mixture of N,N' disubstituted urea (N-mercaptourea). Khorana (see Khorana, H. G. Chem. Rev., 1953, 53, 145 and Smith, Μ·; Moffatt, J. G.; Khorana, HG J· Am· Chem. Soc·, 1958, 50, 62 04) and Silver stein (see Detar • DF; Silverstein, R. J. Am. Chem. Soc., 1966, 55, 1013 and Detar, DF; Silverstein, RJ Am. Chem. Soc〇5 1966, 88, 1020) Early mechanism studies showing carboxylic acid The reaction with carbodiimide has two parallel reaction paths and explains the diversity of the observed products. The initially formed 0-mercapto-isourea intermediate can be reorganized by rearrangement reaction. It is N-mercapto urea, or undergoes further substitution reaction with additional carboxylic acid molecules to produce urea and anhydride as final products. Earlier articles pointed out that aromatic CDI tends to form N-107400 when treated with carboxylic acid. Sulfhydryl urea, on the other hand, aliphatic CDI usually leads to the formation of a mixture of anhydrides and N, N, disubstituted urea (see Mikolajczyk, Μ·; Kielbasinski, P. Tetrahedron, 1980, 37, 233 and Volonterio, Α· Arellano, C. R.; Zanda, J. Org Chem, 2005, 70, 2161). Recent evidence suggests that ferrocenecarboxylic acid can be selectively added to aromatic CDI to produce N-mercaptourea as the main product (see Schetter, B.; Speiser, B. J. Organomet Chem., 2004). , 6 (59, 1472). Another study by Lau shows (see Rave, J.; Ankersen, Μ. ; Begtrup, Μ. ; Lau, JF Tetrahedron Lett, 2003, 44, 6931), in solid The synthesis of di- and tri-substituted N-mercapto ureas on the support can also achieve excellent yields. Although the thermal conversion reaction for the thermal conversion of N-mercaptourea to isocyanates and guanamines has been widely accepted in the literature. Research (see Schotman, Α·Η·M·Reel. Trav. Chim. Pays-Bas, 1991, 110, 319, Schotman, AHM; Mijs, WJ Reel. Trav. Chim. Pays-Bas, 1992, 111, 88 and Schotman, A. Η. M· ; Weber, TMJ ; Mijs, WJ Macromol· Chem. Phys·, 1999, 635), but using N-mercapto urea as a synthetic intermediate or as a source of potential isocyanate Decomposition reaction, and conversion of the resulting isocyanate to CDI and subsequent conversion from CDI to guanamine The comprehensive conversion reaction has not 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, N-mercapto urea has not been developed as isocyanic acid. a precursor of a salt or a synthetic method as a separable intermediate for the synthesis of polyamine. Therefore, the present invention provides a high selectivity and high yield of aromatic N-mercaptourea 10740.doc 1297003 preparation , the subsequent thermal reaction, and the use of a stepwise and one-step synthesis of aromatic amine, guanamine-imine and polyamidamine, polyamine-imine. [Invention] The purpose of the present invention is to provide A method for synthesizing high selectivity and high yield of an aromatic ruler-mercapto urea, comprising reacting a carbodiimide (CDI) with a carboxylic acid at a temperature lower than about 120 C to obtain the aromatic fluorenyl group Urea. Another object of the present invention is to provide a method for synthesizing high selectivity and two yields of aromatic poly(sulfonium) urea, which comprises agglomerating aromatics with a carboxylic acid, a decanoic acid, a polyphenolic acid or The mixture is below about 120 The reaction temperature, to obtain the aromatic polyimide N- acyl urea. Still further object of the present invention is to provide a self about 12〇. A method of synthesizing a guanamine or a guanamine-imine by a continuous self-reaction (SSRR) at a temperature of about 28 〇C and in the presence of a CDI catalyst and a carboxylic acid, which comprises: a) Group N-mercapto urea is thermally decomposed into an aromatic isocyanate and a guanamine or guanamine imine as a product; b) the aromatic isocyanate is subjected to a catalyst in the presence of the CDI catalyst Conversion to aromatic CDI; and c) reacting the aromatic CDI with the carboxylic acid to form the separable aromatic N-mercapto urea as a reaction intermediate; wherein steps a), b) and c) are self-repetitive The tarenic acid equivalent used in step c) is sufficient to substantially consume all of the aromatic isotonic acid salt, the aromatic CDI and the aromatic N-mercapto urea. The object of the present invention is also to provide a method for synthesizing guanamine or guanamine by a reaction of from 12 〇t to about 28 (rc temperature of 107400 Zheng 1297003 degrees and in the presence of CDI catalyst by repeated vapors). - an imine method comprising: a) reacting an aromatic CDI with a carboxylic acid to form an X separable aromatic N-mercapto urea as a reaction intermediate; b) heating the aromatic N-mercapto urea Decomposed into an aromatic iso(tetra) salt and a guanamine or guanamine-imine as a product; and c) in the presence of the CDI catalyst, the Guanhe^4 fragrant isocyanate is converted into a catalyst by Aromatic CDI; wherein steps a), b) and c) are carried out by themselves, and the carboxylic acid equivalent used in the step is sufficient to substantially consume all of the aromatic isocyanate, the aromatic CDI and the aromatic N-mercapto urea. It is also an object of the present invention to provide a method of synthesizing an indoleamine of the formula:

I aryl-NH-C-|| JN~aryl It comprises: a) reacting aromatic CDI with trimeilitic anhydride to form an anhydride functional N-mercapto urea ary b- C —NH—aryl 〇4 0

b) treating the anhydride functional N-mercapto urea with water or R-oxime (wherein R is a c1-8 alkyl group) to form an acid-functionalized ester-mercapto urea having the formula: 107400.doc 1297003 - Aryl aryl-N-C-N ·

I

0=C

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 Acid-deamine derivatives:

At the same time, a continuous self-repetitive reaction is carried out to form the guanamine-imine, wherein the continuous self-reacting reaction involves repeating the following three consecutive steps: i) the aromatic isocyanate is present in the presence of the CDI catalyst. The catalyst is converted to aromatic CDI; H) the aromatic CDI is reacted with the acid-nitramine derivative to form a mercapto urea having the formula:

(1)) The mercapto urea obtained in the step ii) is thermally decomposed into the aromatic isocyanate and the indoleamine-imine as a product. The ultimate goal of this month is to provide a method for synthesizing poly(an amine-imine) having the following structural formula:

107400.doc 1297003 wherein η is an integer from 1 to 24, the method comprising:

a) make a poly CDI with the following formula

Reacting with trimellitic anhydride to form a corresponding poly-N-branched urea having the following formula

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

c) heating the reaction mixture to a temperature of from about 120 ° C to about 280 ° C to effect a continuous self-repetition reaction as defined above to form the poly(guanamine-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 the surface selectivity and high yield of aromatic N-branched urea under mild conditions. 107400.doc -11 - !297〇〇3 Scheme 1 describes the synthesis of N-mercaptourea 5 from CDI 1 and tannic acid 2, and possibly by-products, in which two parallel reaction paths occur. The initially formed hydrazine-hydrazine-based urea intermediate can be recombined into N-mercaptourea 5, or undergoes further substitution reactions with additional acid molecules to produce the corresponding urea 4 and anhydride 3 as the final product. Process 1

RiNH-CrrNRi

R1N=C=NR1 + R2c〇〇H R2 0-Aryl iso-urea R2-C-〇-C-R2 + R^NH-C-NH-Ri Jyf 3 4

Ri-NC-NH-R! Ri-NH.}&gt;«R2 + R^NCO C=0 I r2 N-醮棊 urea 5 guanamine isononate based on the selectivity of CDI reaction, carboxylic acid can be separated Reacts with two CDI type compounds, one of which is aliphatic CDI with dicyclohexylcarbodiimide (DCC) as an example, and the other is aromatic CDI with diphenylcarbodiimide (DPcdI) as an example. It is prepared by phenyl isocyanate and a cdi catalyst such as i,3-dimethyl-3-cyclophosphonium oxide (DMPO)i.

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 such as 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-branched urea 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 - 1297003 is mainly N-mercapto urea. For example, a relatively high yield of hail-based urea 5' can be obtained by reacting a carboxylic acid (e.g., benzoic acid and acetic acid with DPCDI at room temperature) to form only small amounts of by-products, i.e., anhydrides and diphenylurea. Furthermore, the reaction between DPCDI and an aromatic carboxylic acid having a pull-electron or electron-donating substituent can also produce a sulfhydryl urea at a very high selectivity. N-mercaptourea is less than about 12 〇〇. It is still stable at c degrees, but it is also known to decompose into isocyanates and guanamine at higher temperatures. According to the present invention, the high selectivity of a kind of Fangxiang N-mercapto urea and A high yield synthesis process comprising reacting aromatic CDI with a carboxylic acid at a temperature below about 120 ° C to obtain the aromatic mercapto urea. The process of the invention preferably exceeds 75%, more preferably exceeds 85. The selectivity of %, and preferably more than 70%, more preferably more than 80%, the synthesis of aromatic hail-based urea. In the case of the reaction of benzoic acid with DPCDZ, the yield of synthetic sulfhydryl urea has been found and The selection rates were 80% and 93%, respectively. These results show that the method of the invention can be used in mild conditions. In the case of aromatic isocyanates as starting materials, aromatic mercapto ureas are produced in high yield and high selectivity. Broadly speaking, any aromatic CDI can be used in the practice of the present invention. Aromatic CDI includes, but is not limited to, diphenyl CDI wherein one or both of the phenyl groups are optionally substituted by (^-8 alkyl, Cm alkoxy, nitro or dentate. Aromatic CDI Examples include o-toluene isocyanate, p-toluene isocyanate, o-nitroisocyanate, p-aeroisocyanate, p-methoxyisocyanate, p-phenylene Isocyanate and decahydrochalcyl isocyanate. In addition to the amino-acid or hydroxy-acid, other functionalized acids do not require complex 107400.doc -13 · 1297003 operation, can be used in the present invention as a preparation The type of the carboxylic acid to be used is not particularly limited, and an aliphatic carboxylic acid or an aromatic carboxylic acid having an electron-withdrawing or electron-donating substituent may be used in the practice of the present invention. Acids include, but are not limited to, monocarboxylic acids (eg, acetic acid and benzoic acid), dicarboxylic acids (eg, adipic acid) Azelaic acid), other long-chain aliphatic diacids, aromatic diacids (such as terephthalic acid and isophthalic acid), diacids or anhydrides (such as phthalic anhydride, polyacids derived from anhydrides, anhydrides) And polyanhydride) and mixtures thereof. In the consistent embodiment of the present invention, only the acid functional side of the phthalic acid (or trimellitic anhydride) having an acid and an acid Sf s month b group in the molecular structure is combined with CDI. The reaction retains its anhydride functional group immobility. As will be described later, this allows for further manipulation of the anhydride functional moiety of the resulting adduct. In this manner, the present invention provides for the acquisition of a polymer having a precise structural sequence. The stepwise polymerization method of the material, the obtained polymer has higher thermal stability and better properties. As is well known in the art, the aromatic CDI used in the present invention can be firstly present in the presence of a CDI catalyst. It is formed by converting an aromatic isocyanate by a catalyst. This reaction is preferably carried out in anhydrous tetramethylethylene sulfone (TMS). However, other suitable solvents can also be used. Suitable solvents include hydrazine, hydrazine-dimethylacetamide, N-methylpyrrolidone (NMP), N,N-dimethylformamide (DMF), and dimethyl sulfoxide (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- 1297003 Cyanates include, but are not limited to, aromatic mono-isocyanates, aromatic di-isocyanates, 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 CDI catalysts include, but are not limited to, various organic derivatives of 'scale compounds and cyclic phosphorus compounds, such as 3-methyl-3-cyclophosphene oxide (MPO), 1,3-dimethyl-3- Cyclophosphene oxide (DMPO) '1,3-1,3-mercapto-l,3,2-diazaphophorolidine, triphenylarsenic oxide, and these are described in Tetrahedr〇n

Report R101 in Tetrahedron (Vol. 37, pages 233~284, 1981) page 235 and CDI catalyst 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 ditoponic acid, a polycarboxylic acid or a mixture thereof at less than about 120 The reaction was carried out at a temperature of ° C to obtain the 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 stated previously, aromatic N-mercaptourea is known to be up to about 12 Torr. The temperature at 〇 is thermally stable and, at higher temperatures, is rapidly converted to isocyanates and guanamines. Accordingly, the present invention further provides a novel and effective method for synthesizing a stimulating amine or a guanamine-imine 10740.doc -15- 1297003 by a continuous self-repetitive reaction (SSRR), which is based on CDI catalysts and rebellion. In the presence of acid, and at about 1 20 from. (: to about 28 ° C, preferably from about 120 ° C to about 270 ° C, more preferably from about 140 ° C to about 250 ° C, at a temperature, the method comprises: a) N-mercapto urea is thermally decomposed into an aromatic isocyanate and a guanamine or guanamine-imine as a product; b) in the presence of the CDI catalyst, the aromatic isocyanate catalyst is converted into Aromatic CDI; and c) reacting a far aromatic CDI with the carboxylic acid to form a separable aromatic sulfhydryl urea as a reaction intermediate; wherein steps a), b) and c) are self-repeating, 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. As shown in Flow 2, the SSRR method consists of three self-repetitive steps. The first step is the thermal decomposition of 1.0 mole of aromatic N_mercaptourea to form the product as a product of hydrazine or guanamine-imine and simultaneously produce the aromaticity of i. Cyanate. The second step is the conversion of 10 moles of aromatic isocyanate to a 0.5 molar aromatic CDI2 catalyst. Finally, the first step is the reaction of 0.5 mole of aromatic CDI with a slow acid to form an additional 〇·5 mole of aromatic amido urea as a separable intermediate. Therefore, in summary, 5% of the aromatic isocyanate will be consumed in this continuous self-repetitive reaction (SSRR) in a single complete cycle, forming a guanamine or guanamine-imine. . When a sufficient amount of acid is provided, repeating the above-mentioned continuous reaction will eventually liberate all aromatic N-mercaptouridine, aromatic isocyanate and aromatic CDI. The inventors of the present invention have demonstrated high 107400.doc 1297003 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 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. Scheme 2 aryl-NH-C-R: decylamine (final product)

〇 Step 1

Aryl-N-S-NH-aryl 14〇 0C I ----^ 〇=c r2 arylsulfonyl urea Iaryl-NC〇j 5 isocyanate R2C〇0H,140. Eight steps 3 Steps ^ DMP0 ^ -C02 Aryl-N^C^N-aryl is preferred, aromatic N-mercapto urea, CDI catalyst and carboxylic acid are dissolved in anhydrous tetrahydrofuran (THF) The SSRR method is performed. However, other solvents such as N,N-dimethylacetamide, N-methylpyrrolidone (NMP), N,N-dimethylformamide (DMF) and dimethyl sulfoxide (DMS0) may also be used. ). 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 method from about 120 ° C to about 280 ° C, preferably from about 120 ° C to about 107400.doc -17 1297003 270 ° C, more preferably from about t to about 250 t, a method of synthesizing a guanamine or a guanamine-imine by a SSRR reaction at a temperature and in the presence of a catalyst, which comprises: / 〃 a) reacting aromatic CDI with a carboxylic acid to form a separable aromatic 1 Sulfhydryl urea as a reaction intermediate; b) thermal decomposition of the aromatic N-mercapto urea into an aromatic isocyanate and a guanamine or guanamine-imine as a product; and C) in the CDI catalyst In the presence of the aromatic isocyanate catalyst, it is converted to aromatic CDI; "Steps a), b) and c) are carried out by themselves, and the carboxylic acid equivalent used in step a) Sufficiently consuming all of the aromatic isocyanate, the aromatic CDI and the aromatic N-mercapto urea. Similarly, the aromatic CDI can be converted into an aromatic difference by a catalyst in the presence of a CDI catalyst. Formed by cyanate. Alternatively, the aforementioned continuous self-repetitive reaction (SSRR) may even start directly from the aromatic isocyanate. No matter which In this case, it is preferred that all starting materials are dissolved in a suitable solvent, such as no THF, THF, NMP, TMS, N,N-didecyl hydrazine. Amine, N,N-dimethylformamide (DMF) and dimercaptosulfoxide (DMSO) to carry out the SS.RR process to produce the desired guanamine or guanamine-imine. A person 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 ruthenium carboxylic acid carries an imine group at the R2 position and the resulting product is a guanamine-sub- An amine. For example, when 5-isoindolinecai: boxylic acid is used as the carboxylic acid and the aromatic CDI is diphenyl CDI, the resulting product has the indoleamine-imine of the formula: 107400.doc -18- 1297003

According to another embodiment of the invention, the indoleamine-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, it is used in the SSRR method to consume all the aromas ^

The carboxylic acid of isocyanate, aromatic CDI and aromatic N-mercapto urea is trimellitic anhydride. Accordingly, the present invention further provides a method of synthesizing a guanamine-imine having the formula: aryl-NH-^^yvi-aryl Ο which comprises: a) an aromatic CDI and a trimellitic anhydride functional N- Sulfhydryl urea: an anhydride reacts to form the following formula

b) treating the anhydride functional N-mercapto urea with water or R-ΟΗ (wherein the Cl_s alkyl group) to form an acid-functionalized ester of the formula: sulfhydryl urea: aryl-N-C-N —aryl

π I ο=ς

• COOH • COOR 107400.doc -19· 1297003 c) heating the acid-functionalized ester-branched urea in the presence of a CDI catalyst to from about 120 ° C to about 280 ° C, preferably from about From 120 ° C to about 270 C 'more preferably from about i4 ° ° C to about 250 ° C, to form aromatic known isocyanates and acid derivatives of the formula:

COOH • COOR and simultaneous SSRR process to form the guanamine-imine, wherein the continuous self-repetitive reaction (SSRR) involves repeating the following three consecutive steps: 1) in the presence of the CDI catalyst, the aromatic The isocyanate catalyst is converted to aromatic CDI; u) 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 helmet water tetrahydrofuran (THF), N-mercapto, pirone (NMp) 'cyclobutite wind (10)... N , N-dimethylacetamide, N,N-dimethyl decylamine (1)^^) and Dimethoate 107400.doc -20- 1297003 sulfone (DMSO) to carry out the SSRR method to produce desired The amine, 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 acid field / R-OH reaction can be carried out in the presence of a catalyst such as triethylamine (TEA). In a particular embodiment of the invention, it is first at about 12 Torr. The N-mercapto urea is decomposed into guanamine and isocyanate at a temperature of about 18 〇C. Then, raise the reaction temperature to about 180 ° C to about 28 (a range of TC is sufficient)

The time, for example, from about 15 minutes to about 12 minutes, is effected by 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 reacting aromatic poly CDI with a slow acid, a bis-acid, a polycarboxylate, or a mixture thereof at a temperature below about 120 ° C to obtain a fragrance. Gathering _n_ stimulating urea, and this will be. The scented poly-sulphur-based urea is heated to a temperature greater than about 12 passages, preferably greater than about 14 Torr C to form polyamine and isocyanate. Accordingly, the present invention further provides a method for synthesizing a poly(nitramine-imine) having the following structural formula:

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

•n=c=n

Or CH2H^

Rc^〇 / partial methic anhydride reacts to form a corresponding poly group with a lower gas 107_.doc -21 - 1297003 N-mercapto urea: ο

-S-NH

b) treating the poly&gt;- mercapto urea with water or R-OH (wherein R is a Cl-8 alkyl group) to form a poly N-mercapto urea having an open anhydride functional group.

c) The reaction mixture is heated to about 12 Torr. (: to about 280 ° C, preferably from about 120 ° C to about 270 ° C, more preferably from about i 4 ° ° C to about 250 ° C, the temperature to carry out the aforementioned SSRR method to form the poly(amine - Imine). Preferably, the integer of η series 1 to 24 is shown in the above poly(amine-imine) structural formula. When η is more than 24, the obtained poly(pentaamine) is soluble in some solvents. For example, monomethylmethionamine (DMF) or hydrazine-methyl valproate _ (ΝΜΡ). The SSRR method according to the present invention can also be used for synthesizing polyamine-imine elastomers by means of a long bond soft segment (for example, a molecular group) in at least one diacid component of one or more acid components. . In this case, all the acid forming knives and the isocyanate components can be reacted together in a single pot (;ne_P〇t); alternatively, the isocyanate component and an acid can be reacted first, followed by other species. acid. For example, a polyamine-imine-ether elastomer can be prepared in a single pot by using a diisocyanate (such as MDi), a polyether diacid, and azelaic acid (107400.doc -22- 1297003). One-pot 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 such as DMP0 and sebacic acid. It is also known to those of ordinary skill in the art that the SSRR process of the present invention can also be used to synthesize polyurethane elastomers if the long chain soft segments are included in the isocyanate component. As described in numerous documents in this technical field, methylene diphenyl phenyl diisocyanate (MDI) and mono-functional stupid isocyanate can be used in the presence of (: 〇1 catalyst) The poly-CDI is prepared by a molar ratio of 16:1. For example, Albenno, L.M., and Farrissey, W.J., U.S. Patent No. 3,929,733 (1975), the entire contents of which is 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-methylacetamide, N, N-dimethylformamide (DMF) and dimethyl nitrous oxide (DMSO) are used to produce the desired product. It is generally known in the art that the type of solvent suitable for carrying out the reaction can be easily determined. As is known in the art, the anhydride/R-OH reaction can be carried out in the presence of a catalyst such as triethylamine (TEA). According to the present invention, the aromatic N-mercapto urea is high. Synthesis method for selectivity and high yield' and by using aromatic N-based urea as the intermediate in the SSRR method The method of synthesizing guanamine H imine or its polymer (9) such as 醯月*, polyamidimide and polyamidamine-imine elastomer can be carried out in a single pot (in the process). The use of the method of the invention is convenient and 107400.doc • 23 - 1297003 is advantageous. Without further elaboration, the skilled artisan can utilize the invention to its fullest extent in light of the above disclosure and the following examples. The following is a description of how the skilled artisan can operate the patents of the present application without limiting the remaining disclosure in any way. [Examples] Example Measurement Procedures · iHNMR and 13C NMR spectra were recorded on a Varinalnova 200 MHz or 600 MHz instrument. The chemical shift is represented by δ, the coupling constant J is expressed in Hz. The spectrum is recorded in a solvent (eg acetone-d6 or DMSO-d6) at room temperature, and the chemical shift is relative to the solvent signal. Perkin Elmer is used. Spectrum one FT-IR spectrometer for FT-IR 〇 using 5 μιη shell particle/lOOA column (Hypersil-100 C18) and UV detection at 254 nm with MeCN/H20=50/50 as eluent (in 0.5 ml / min flow rate HPLC was performed. Thermal differential scanning analysis (DSC) was performed on a Perkin Elmer Pyris 6 instrument at a heating and cooling rate of 1 〇 ° C / min. Heating at 10 ° C / min with a Perkin Elmer Pyris 1 instrument. Thermogravimetric analysis (TGA) was performed at a rate of up to 850 ° C and in nitrogen. The number average molecular weight (??) was 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- l297〇03 Example 1: Preparation of aromatic N-mercapto urea with the following formula

Stupid isocyanate (5 g; 42 mmol) and 1,3-dimethyl-3-cyclophosphonate (DMPO; 0.15 g) were dissolved in 50 ml of anhydrous THF, and Heat to 60 ° C for 3 hours under nitrogen. Next, 5-iso(penta)porphyrincarboxylic acid 2f (5.19 g; 21 mmol) synthesized from trimellitic anhydride and butylamine was added to the reaction mixture and stirred at 25 ° C for 3 hours. The title product (88%) was precipitated from 1 liter of hexane and the selectivity was over 99% (as shown in Table 1). iH-NMR (600 MHz, acetate) δ (ppm): 0.90 (t, "/ = 7.2 Hz, 3H), 1.29 (sxt, J = 7.2 Hz, 2H), 1.58-1.63 (m, 2H), 3.59 ( t, J = 7.2 Hz, 2H), 7.12 (dt, J = 7.2, Hz, 1H), 7.25-7.37 (m, 5H), 7.45 (dd, 8.4, 0.6 Hz, 2H), 7.60 (d, J = 8.4 Hz, 2H), 7.75 (d, 7.8 Hz, 1H), 7.91 (dd, 6.6, 1.8 Hz, 2H), 10.80 (bs, 1H), C-NMR (150 MHz, acetate) 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 C26H23N3O4 · N, 9.52%, C, 70.73 % ; H, 5.25 %. Found ^ N, 9.76 %, C, 71.59 %, H, 5·65 % · mp 105.1-105.8〇C 0 Example 2 Repeat the procedure as described in Example 1, using phenyl isocyanate and 107400.doc • 25-1297003 DMPO to react with various carboxylic acids as shown in Table 1 to form the corresponding aromatic N-fluorenyl group. Urea. 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. Process 1 0 0 ο • RiNH-〒=NfV 0 1 c=o L I J r2 0-decylisourea r1n=c=nr1 + r2cooh 1 2

R2-C-O-C-R2 + Ri1NH-C-ΝΗ-R-j ^ 3 4

O O

V. ii 140 0C II

RrfJl-C-NH-R! -► RfNH-C-R2 + R1—NCO ?=decylamine iso-IL acid salt R2 N-mercapto urea Table 1: Aromatic CDI and carboxylic acid (R2COOH) reaction examples aromatic Group CDI carboxylic acid (r2) N-mercapto urea selectivity (mol%) &quot; Yield (% Γ 1 DPCDI 〇 (2f) &gt; 99 88 (5h) 2 DPCDI ^ (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-Ph (2c) 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- 1 * 2 Separation by precipitation or recrystallization 2 Calculated by 1H NMR integration 1297003 Example 9: Preparation of indoleamine-imine from anhydride-functional N-mercapto urea via SSRR method

MeOH TEA o=c aCOOH COOMe

5g 6

COOH COOMe

As shown in Scheme 3, the anhydride-functional N-mercaptourea obtained in Example 2 (〇·5 g; L3 mmol) and DMPO (75 mg; 0.57 mmol) were dissolved at room temperature. 30 ml of anhydrous cyclopentane. Methanol (42 mg; 1.3 mmol) was added to the reaction mixture and triethylamine (0.13 g; 1 eq.) was used as a catalyst to form a new acid-functional ester-mercaptourea. Next, the far acid-functionalized from the thiol urea 6 was heated to 140 ° C for 45 minutes to form the acid-decylamine derivative 7. The acid-nonylamine 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 °c for 30 minutes to carry out a ring closure step to form the guanamine-imine 9. Next, 500 ml of water was added to the final solution to form a brown precipitate of the indoleamine-imine 9. The precipitate was filtered, and the precipitate was recrystallized from 25 ml of hot diphenylbenzene and dried under vacuum at 107400.doc -27 - 1297003. By this 〇ne-pot operation, a high yield of indoleamine-imine 9 (93%) was isolated and confirmed to be the sole product by the following analysis. ^-NMR (600 MHz, DMSO) δ (ppm): 7.14 (t, J =: 7.2 Hz5 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 7.8 Hz, 2H), 8.12 (d, J = 7.8 Hz5 1H), 8.45 (dd, 7.8, 1.8 Hz, 1H), 8.54 (s, 1H), 10.64 (s, 1H) ; 13C-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 C21H14N203 : N, 8.20 % ; C, 73.70 % ; H, 4.10 % · Found : N, 8.21 % ; C, 73.59 % ; H, 4.42 %. Mp 271·4-273·Γ(:.

107400.doc 28- 1297003 Example 10: Preparation of poly(amine-imine) via SSRR self-polymerization of N-mercaptourea Scheme 4

〇[

N=C=N

P-CDI Ο

N=C=N

poly-N-mercapto urea

TEA, MeOH

j^V-COOMe

K^—COOH

aCOOMe COOH

DMPO, 202 °C &quot;co2* -MeOH I SSRR

Poly(decylamine-imine) 4 4-4'-arylene-bis(phenyl isocyanate) (MDI; 15 g; 59.9 mmol) in 250 ml, equipped with a thermometer, nitrogen A three-necked round bottom flask of an input tube, a reflux condenser, an oil bath, and a magnet stirrer was dissolved in &lt;RTI ID=0.0&gt;0&gt; The reaction mixture was heated to 90 C and phenyl isocyanate (〇·89 g; 7.47 mmol 107400.doc -29 to 1297003) 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 XP-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 polydecyl urea as shown in Scheme 4. Next, methanol (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 product obtained was filtered and dried to give 23.3 g (92%) of poly(p-amine-imine) (brown solid) characterized by a relatively high rg at 23 8 ° 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 a polyamidimide-ether elastomer by using a mixture of two acids Φ Scheme 5

Diisocyanate polyether diol

-^Qkch2{)- ch3 ch3 r1 = —chch2 十〇ch2ch·)— r2 =

107400.doc -30- 1297003 See polyether diacids (Wei, KL; Hung, FY·; Lin, J. J. J. Polym. Sci. Part A: Polym Chem, 2006, 44, 646) 4.53 g; 1.87 mmol; and sebacic acid (1·53 g; 8.13 mmol) dissolved in 100 ml of TMS, placed in 250 ml, equipped with a thermometer, nitrogen inlet tube, A three-necked round bottom flask with a reflux condenser, oil bath and a magnetic stirrer. The solution was heated to 180 ° C, followed by the addition of DMPO (〇25 g) and MDI (3.0 g; 12 mmol) and stirred for 30 minutes. The solution was then heated to 2 ° C and stirred for 2 hours. The resulting solution was poured into 1.25 liters of water. After filtration and drying in a vacuum oven to remove moisture, the resulting product is a polyamidamine-Asian: ic-ether elastomer characterized by a relatively high concentration of _33 °c (polyether) And at 378 ° C: Td. Example 12 ·· PAI single steel (〇ne_p〇t) synthesis

OCN NCO

MDI Process 6

+ HOOC~^~^—COOH COOMe 1-mercapto-p-benzoic acid ester

SSRR

-C02&gt; -MeOH ^ΰ ΐ80 °C1h (2) 202 °C 1h Poly(aniline-imine) Shuoguo, and equipped with NMP (15 house liter) into a 250 ml meter, nitrogen inlet tube In the continuous bottle of reflux condenser, oil bath and magnet mixer. The NMP was heated to i80 ° C, followed by the addition of DMp 〇 (4 〇 mg) and 1 methyl phthalate gram; 4.47 mM Mob added MDI (U 2 gram; 4.47 mmol) to the mixture, followed by Heat to 2 〇 (107400.doc • 31 - 1297003 C and disturb 2 xiaoxiao. Pour the resulting solution into 5 liters of water to form a standard PAI precipitate. Filter and dry the precipitate under vacuum. Single pot_training operation 'separated high yield PAI (9〇%), _ shows W's 丨H leg analysis' Figure 12 is % ugly analysis. The resulting PAI is characterized by a relatively high temperature of 289 ° C And at 479. (: Td. Comparative Examples 1 and 2 Under the same operating conditions as exemplified in Example 1, dicyclohexylcarbodiimide (DCC) was used as a starting material to be compared with benzoic acid (Comparative Example) or Acetic acid (Comparative Example 2) reaction. As shown in Table 2, the main products of the above reaction were anhydrides and urea, and only a low selectivity was observed in the product mixture (comparative examples 二 and 2 were 38% and 25%, respectively). - Sulfhydryl urea.

107400.doc -32·

1H NMR spectrum and DSC and TGA analysis of 1297003 amine-imine. Figures 11 to 12 show the 1H NMR and 13C 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)

1297003 X. Patent application scope: 1 · A high selectivity and high yield synthesis method of aromatic N-mercapto urea (N-acy lure a), which comprises aromatic carbodiimide (CDI) and carboxylic acid Reacting at a temperature below about 12 (TC to obtain an aromatic N_mercapto urea. 2. According to the method of claim 1, wherein the aromatic CDI is in the presence of a CDI catalyst] Formed by converting aromatic mono-isocyanate, aromatic di-isocyanate, aromatic polyisocyanate or a mixture thereof. 3. The method according to claim 1, wherein the aromatic CDI is Storage of CDI Catalyst • Conversion of phenyl isocyanate, toluene diisocyanate (TDI), methylene diphenyl phenyl diisocyanate (MDI), p-phenylene by catalyst a diisocyanate (PPDI), an MDI polymer, and an isocyanate prepolymer prepared by one or more of the above, wherein the aromatic cdi is selected from the group consisting of A group consisting of diphenyl CDI in which one or both of the phenyl groups are optionally substituted with a Ci8 alkyl group, a Cw alkoxy group, a nitro group or a halogen. The method of claim 1, wherein the carboxylic acid is selected from the group consisting of monocarboxylic acids, dicarboxylic acid, other long chain aliphatic diacids, aromatic diacids, diacids or anhydrides, and mixtures thereof. 6) The method according to claim 5, wherein the carboxylic acid is selected from the group consisting of acetic acid, benzoic acid, hexanoic acid, sebacic acid, terephthalic acid, isophthalic acid, trimellitic anhydride a group of polyacids, anhydrides, polyanhydrides, and mixtures thereof derived from an anhydride. 7. The method according to claim 1, wherein the selectivity is more than 75%, and the yield is more than 7〇〇/ 107400.doc 1297003 8· 9. According to the request item 7 $, + and the production, method, wherein the selection rate is more than 85%, the rate is more than 8〇〇 / Q., species: aromatic poly-based The synthesis of high selectivity and high yield of urea = 'which comprises reacting the aromatic polyc__, diphet, polylysate or its substance at a temperature lower than about 12 (TC) to obtain the N-mercapto urea. 1 ί according to the method of claim 9, wherein the aromatic poly. is composed of aromatic two _ wind aromatic private An acid salt or a mixture of the above isocyanate to obtain a mixture of #. By a continuous self-reaction reaction at a temperature of 120 C to about 280 C and in the presence of a CDI catalyst and a sulfonium to synthesize a guanamine or A method of amidoxime-imine comprising: a) thermally decomposing a scented sulphonyl urea into a mesogenic isocyanate and a guanamine or guanamine-imine as a product; b) in the CDI catalyst In the presence of the group, the isocyanate catalyst is converted to aromatic CDI; and #c) the aromatic CDI is reacted with the slow acid to form the separable aromatic N-mercapto urea as a reaction intermediate The carboxylic acid equivalents used in the phantom of the step are sufficient to substantially consume all of the aromatic isocyanate, the aromatic CDI, and the aromatics in the steps of 8), b), and c). Group N-mercapto urea. 12. The method according to claim n, wherein the aromatic sinyl urea is obtained by the method according to claim 1. 13. The method according to claim U, wherein the carboxylic acid is selected from the group consisting of monocarboxylic acids, 2,107,400.doc 1297003 acid, other long chain aliphatic diacids, aromatic diacids, diacids or anhydrides, and mixtures thereof Group of. The method according to claim 13, wherein the carboxylic acid is selected from the group consisting of acetic acid, benzoic acid, adipic acid, sebacic acid, terephthalic acid, isophthalic acid, trimellitic anhydride, and polyacid derived from anhydride. a group of anhydrides, polyanhydrides, and mixtures thereof. According to the method of claim u, wherein the temperature is from about i2 (rc to about 27 〇 t. 16. The method of claim 15, wherein the temperature is from about i4 〇 0C to about 25 〇 V. 17. The method of claim u, wherein the carboxylic acid bears an imine group and the product is a guanamine, an imine. The method of claim 7, wherein the oxoline is 5-isoind〇linecarboxylic acid, and the product has the hydrazine-imine of the formula: 19· One at about 12 自. (: to a temperature of about 280 ° C and in the presence of a CDI catalyst by continuous self-reaction to synthesize a guanamine or guanamine-imine, which comprises: a) reacting aromatic CDI with citric acid Forming a separable aromatic N-mercapto urea as a reaction intermediate; 107400.doc 1297003 b) Thermal decomposition of the aromatic N-mercapto urea into an aromatic isocyanate and a guanamine or guanamine as a product - The imine; and C) converting the aromatic isocyanate catalyst into aromatic CDI in the presence of the CDI catalyst; wherein steps a), b) and c) are carried out by themselves, and the The carboxylic acid equivalent in step a) is sufficient to substantially consume all of the aromatic isocyanate, the aromatic CDI and the aromatic N-mercapto urea. I 20. The method according to claim 19, wherein the aromatic cD1 is in the presence of a cm catalyst to convert an aromatic mono-isocyanate, an aromatic diisocyanate, an aromatic poly group by a catalyst. It is formed by isocyanate or a mixture thereof. 21. The method of claim 19, wherein the aromatic CD] [in the presence of a CDI catalyst] converts phenyl isocyanate, toluene diisocyanate (TDI), methylene by a catalyst. Diphenyl diisocyanate (mdi), p-phenylenediphenyl isocyanate (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 group is selected from the group consisting of diphenyl-based CDI, wherein one or both of the phenyl groups are optionally subjected to Ci8 alkyl group, Cw alkoxy group, and nitrate Substituted by halogen or halogen. The method according to claim 19, wherein the carboxylic acid is selected from the group consisting of monocarboxylic acids, dibasic acids, other long-chain aliphatic diacids, aromatic diacids, diacids or oximes, and mixtures thereof. . The method according to claim 23, wherein the carboxylic acid is selected from the group consisting of acetic acid, benzoic acid, arachidonic acid, sebacic acid, terephthalic acid, isophthalic acid, stearic anhydride, and anhydride. A group of polyacids, anhydrides, polyanhydrides, and mixtures thereof, 107400.doc 1297003. 25. The method of claim 19, wherein the temperature is from about 120 ° C to about 270 ° C. 26. The method of claim 25, wherein the temperature is from about 140 °C to about 250 〇c. 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-isoporphyrincarboxylic acid, and the product has the indoleamine-imine of the formula: 29. A method of synthesizing a guanamine-imine having the formula: a) reacting aromatic CDI-free with trimellitic anhydride to form an anhydride functional N-mercapto urea having the formula: b) treating the anhydride functional N-mercapto urea with water or R-〇h (wherein the alkyl group) to form an acid-functionalized ester of the formula: hydrazino-based 10740.doc 1297003 , f ΐ aryl—Ν—C—N—aryl 0=(: j^^COOH—COOR c) The acid-functionalized ester-mercapto urea is heated to about 120° in the presence of a CDI catalyst. C to a temperature of about 280 ° C to form an aromatic isocyanate and an acid-decanamine derivative of the formula aryl-NH-C-, COOH C00R and simultaneously carry out a continuous self-reaction to form the guanamine - an imine, wherein the continuous self-repetitive reaction involves repeating the following three consecutive steps: 1) converting the aromatic isocyanate catalyst to aromatic CDI in the presence of the CDI catalyst; ♦ Fragrant CDI reacts with the acid-decalamine derivative to form a mercapto urea having the formula: 1U) The mercapto urea obtained in the step U) is thermally decomposed into the aromatic isocyanate and the indoleamine-imine as a product. 3. The method according to claim 29, wherein the aromatic (10) is converted into an aromatic mono-isocyanate, an aromatic di-isomeric acid salt, an aromatic by a catalyst under the presence of a catalyst of (10) catalyst. Formed from polyisocyanates or mixtures thereof. L〇74〇〇.d〇c 1297003 3 1. According to the method of claim 30, wherein the aromatic CDI is converted to phenyl isocyanate or toluene by a catalyst in the presence of a CDI catalyst. Cyanate (TDI), methylene diphenylene diisocyanate (mdi), p-phenylene monoisocyanate (PPDI), MDI polymer, and one or more of the above Formed from an isocyanate prepolymer. 32. The method of claim 29, wherein the temperature of step c) is from about 12 Torr. 〇 to about 270 ° C. 33. The method according to claim 32, wherein the temperature of the step c) is from about i4 〇 (3c to about 250 ° C. 34) a method of synthesizing a poly(imamine/imine) having the following structural formula, 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 poly(1) mercapto urea having the following formula 107400.doc 0 .0 0 !297〇〇3 b) treating the poly N-mercapto urea with water or R-OH (wherein R is a Cu alkyl group) to form a poly N-fluorene having an open anhydride functional group Base urea: c) heating the reaction mixture to a temperature of from about 120 ° C to about 28 (TC to carry out a continuous self-repetition reaction as defined in claim 29 to form the poly(amine-imine). 35. According to claim 34 The method, wherein the poly CDI is formed by reacting methylene diphenyl phenyl diisocyanate and phenyl isocyanate in the presence of a CDI catalyst. 36. The method according to claim 34, wherein The temperature of this step c) is from about 12 Torr. 〇 to about 270 ° C. 37. The method of claim 36, wherein the temperature of step c) is from about i4 ° C to about 250 ° C. 38. The method of claim 34, which is a one-pot operation. 39. A method of synthesizing polyamine which comprises heating the aromatic poly N-mercapto urea obtained by the method of claim 9 to a temperature exceeding about 120 ° C to form polyamine and isocyanide Acid salt. 40. The method of claim 39, wherein the temperature is about 14 (TC. 41. A method of synthesizing poly(nidimine), the method comprising: a) reacting poly CDI with an acid anhydride to form a corresponding poly N-mercapto urea; b) treating the poly N-mercaptourea 107400.doc 1297003 with water or R-OH (wherein an alkyl group) to form a poly N-mercapto urea having an open anhydride group;醯amine-imine) c) heating the reaction mixture to a temperature of about 12 (rc to about 28 ° C to enter ~ continuous self-repetition reaction as defined in claim 29 to form the poly 42. According to eye 4 The method of 1, wherein the mixture of acids or anhydrides in step a). A method according to claim 42, wherein the acid in the step a) comprises a long-chain soft segment portion, and the product is a poly(amine-imine) elastomer. 44. The method of claim 43, wherein the acid in step a) comprises one of the ether moieties and the product is a polyamidamine-imine-ether elastomer. 107400.doc