TW200827327A - Marcrocyclic carbodiimide (MC-CDI) and their derivatives, syntheses and applications of the same - Google Patents

Abstract

Disclosed are a macrocyclic carbodiimide (MC-CDI) and a process for synthesizing the same through condensation of a molecule including multiple-isocyanate functional groups under high dilution in the presence of a phospholene catalyst. Also disclosed are macrocyclic carbodiimide (MC-CDI) derivatives, such as MC-urea, MC-acylurea, acid functionalized MC-acylurea, and anhydride functionalized MC-acylurea, processes for synthesizing the same as well as the applications of such derivatives in organic polymer materials, such as polyurethane (PU) and polyesters.

Description

200827327 IX. Description of the invention: [Technical field to which the invention pertains] The present invention relates to a macrocyclic carbodiimide (MC-CDI) and a synthetic method thereof, and the macrocyclic carbodiimide can be converted by further reaction. It is a giant ring-based urea (MC acylurea) and giant ring urea (MC-urea). MC-CDI can be used as an additive in organic high molecular materials as a hydrolysis stabilizer. The MC acylurea functionalized by acid or anhydride can be used as an intermediate in the synthesis of modified PU by the thermal decomposition characteristics of thiourea. [Prior Art] According to the definition of IUPAC, the macrocyclic molecule (macr〇CyCle, jyjc) is a cyclic polymer, usually composed of more than 15 atoms (see IUPAC Compendium of Chemical Terminology 2nd).

Edition (1997)). Ring polymers or giant ring molecules have many interesting and different physical properties from general linear molecules and linear polymers (see J. Roovers, ρ·M· Toporowski, Macromolecules 1983; 16, 843; JA Semiyen , Cyclic polymers, 2nd ed.

Dordrecht: Kiuwer Publishers; 2000; and C. W. Bielawski, D. Benitez, R. H. Grubbs, Science 2002, 297, 2041), such as low viscosity (viscosity), high solubility (s〇iubility), lower Hydrodynamic volume, etc. In recent years, it has attracted great research interest in the basic science of polymers and the development of applications. For example, it has good compatibility with solvents in solution, resulting in lower viscosity and higher solubility. These phenomena mainly come from the fact that the structure of the ring-shaped polymer itself is relatively less than the fimctionality of terminal end groups, which leads to special properties different from linear molecules and polymers. The characteristics of the current ring-shaped high-molecular structure are mainly determined by the low-hydraulic volume of the ring-shaped polymer.

In the 1980s, many studies were conducted on the synthesis of cyclic oligomers (Cyclic Oligomers) and used in Ring-Opening Polymerization, in which the US GE company in the ring carbonate oligomer (Oligomeric Cyclic) The most representative and commercial potential of Carbonates) (see J. C. Camahan, US Patent, patent no 4, 273, 717 (1981); DJ Brunelle, TL Evens, et. al, Polymer Preprints 1989, 30, 569; EP Boden, D. J. Brunelle, et. al, Polymer Preprints 1989, 30, 571; TL Evens, CB Berman, et. al, Polymer Preprints 1989, 30, 573; K. R. Stewart, Polymer Preprints 1989, 30, 575). This technology uses Bisphenol A to prepare a precursor, Bisphenol A bischloroformate, and then synthesizes a ring in a pseudo-high dilution solution. Carbonic acid oligomer. The cyclic carbonate condensate can be subjected to ring opening polymerization (11 § - Opening Polymerization, ROP) at 250 under the action of an anionic catalyst. It can be converted into high molecular weight polycarbonate (Polycarbonate, PC) in about 2-5 minutes. In addition, the low viscosity of the cyclic carbonate oligomer not only improves the productivity, but also solves the problem that large objects are not easily formed by injection. Such a processing method using a giant ring molecule as a reaction injection molding (RIM) raw material will be an important technology in the polymer industry 110507.doc 200827327. However, the ring-opening polymerization of the cyclic carbonate oligomer requires a high Tg, high molecular weight product at a high temperature of 250 ° C or higher. Such high energy consumption: The production method is obviously a giant ring molecule. The shortcomings of ring-opening polymerization to prepare polymer materials. The synthesis of cyclic carbodiimide (cyclic CDI) is mainly divided into two parts, aliphatic and aromatic cyclic carbodiimides. R. Richter et al. (Ref. R. Richter, Β·Tuker, Η· Ulrich, J. Org. Chem. • 1981, 46, 5226; R. Richter, B. Tuker, H. Ulrich, J. Org. Chem. 1983, 48, 1894; and R. Richter, EA Barsa, J_ Org. Chern. 1986, 5 1, 41 7) Teaching the synthesis of a tricyclic aliphatic ring-shaped carbon dioxide by using 2-Azacyclododecanone as a starting agent Amine (Cycloaliphatic CDI), which is an aliphatic small ring cyclic carbodiimide. In addition, the aromatic cyclocarbene CDI: was not successfully synthesized by P. Molina et al. in 1994 (see P. Molina, M. Majarin, and P. Stinchez-Andrada, J. Org Chem. 1994, 59, 7306; P. Molina, M. Majarin, and P. Stinchez-Andrada, J. Org. Chem. 1996, 61, 4289; and P. Molina, M. Majarin, and P. Stinchez - Andrada, et.al, J. Org. Chem. '1998 63, 2922), but Molina's method requires the preparation of an expensive azophosphoraneCN^P) intermediate followed by tBac20/4-(didecylamino). The aza-Wittig reaction is carried out by a [4-(dimethylamino)pyridine (DMAP)] reagent, and a cyclization reaction is carried out under high dilution to obtain an aromatic small ring cyclic carbodiimide. I10507.doc 200827327 Secondly, in 1991, Japan Νίρρ〇η Coatings Company used N_mercapto_N,w· disubstituted urea to have the thermal cracking characteristics of recessive isocyanate, with hexagonal propylene urea (Propylene Urea) Direct reaction with chloro-f-ester (Chl〇r〇f〇rma^) to prepare Propylene Acylurea, and further to open the six-ring Propyls by pyrolysis (Pyr〇lySiS) The ring produces a linear diisocyanate. Although the cyclic sulfhydryl urea has been successfully produced, but the starting material Pr〇pyiene Urea is relatively expensive, only a small ring (ie, six rings) of cyclic sulfhydryl urea is synthesized, and due to its physical properties and structural limitations. The inability to effectively enhance the mechanical properties of the polymer itself limits the application of this intermediate. Up to now, no effective intermediates have been developed to synthesize cyclic macromolecules or macrocyclic open interstitials, or even effective cyclic intermediates to synthesize cyclic south molecules. Thus, the present invention provides macrocyclic carbodiimides. Synthetic method ^Extra large % A; anti-imine reacts with organic acid to form macrocyclic acid-based urea with high selectivity, which can be used in the field of new molecular intermediates, which can be used for The synthesis of an organic polymer material modified with a polyurethane (ρυ). Further, 'the carbodiimide functional group in the macrocyclic molecule can react with tickic acid and water', thus the giant ring provided by the present invention The carbodiimide may also be added to the polymer material as a dehydrating agent and an acid scavenger, thereby improving the durability of the polymer material. [Invention] Therefore, the object of the present invention is to provide a macrocyclic carbodiimide. And its combination: the straw is highly diluted with a plurality of isocyanate ends s, the base / knife 'and the condensation of the isocyanate in the presence of a ring-like rare catalyst U0507.doc 200827327 functional group Carbon dioxide A macrocyclic molecule of a functional group. Another object of the present invention is to provide a macrocyclic sulfhydryl urea and a synthetic method thereof, which comprises highly diluting a molecule having a plurality of isocyanate terminal functional groups, and The condensation of the isocyanate functional group - α in the presence of a cyclophosphene-based catalyst to produce a macrocyclic carbon carbodiene 35, and a macrocyclic carbodiimide and a monocarboxylic acid, a monocarboxylic acid, a polycarboxylic acid or The mixture is reacted at a temperature lower than about 8 〇1 to obtain the giant annular sulfhydryl urea. The second object of the present invention is to provide a giant annular thiourea urea and a method for synthesizing the same. The method comprises dilute dilution with a plurality a molecule of an aromatic isocyanate terminal functional group, and condensing an isocyanate functional group in the presence of a cyclophosphene-based catalyst to produce an aromatic macrocyclic carbodiimide, and the aromatic giant ring The carbodiimide and the monocarboxylic acid, the dicarboxylic acid, the polycarboxylic acid or a mixture thereof are reacted at a temperature lower than about 80 C to obtain the giant cyclic mercapto urea. A further object of the present invention is to provide a giant urea. And its synthesis method, the method comprises a high degree of dilution a sub-gt; with a plurality of isocyanate end functional groups, and an isocyanate functional group condensed in the presence of a cyclophosphene catalyst to produce a macrocyclic carbodiimide, and the giant ring The carbodiimide and water are reacted in a temperature range of 10 ° C to obtain the giant ring urea. Another object of the present invention is to provide a carboxylic acid functionalized/anhydride functionalized giant bad form sulfhydryl urea and its synthesis a method comprising: highly diluting a molecule having a plurality of isocyanate terminal functional groups, and condensing an isocyanate functional group in the presence of a cyclophosphene-based catalyst to produce a macrocyclic carbodiimide, and The macrocyclic carbodiimide and the dicarboxylic acid/trimellitic anhydride are reacted at a temperature below about 8 Torr to obtain the carboxylic acid functionalized/anhydride functionalized macrocyclic enthalpy 110507.doc -10- 200827327 urea . ί: The purpose of this 5% is to provide a purified macrocyclic carbodiimide. · "Liquid column chromatography (LC) ~ ' and maintain the macrocyclic carbodiimide The activity and the integrity of the structure are separated into high-tonar sonar γ η, ,, %% of the ring-shaped carbodiimide. The purpose of n' advancement is to provide a method for utilizing a cyclic polymer intermediate = °, a linear organic polymer comprising aromatic anhydride, • 彳# & ortho binary m acid, aromatic ortho Μ单_, aliphatic Wei-based, or aliphatic trans-functionalized macrocyclic sulfhydryl urea is dissolved in an inert organic solvent and added to the temperature of · 、 、 、 〇 温度 加 温度 t t t t ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) The functionalized macrocyclic basal urea is further polymerized into a linear modified urethane (pu) polymer material. ..., the purpose of the further step of the invention is to provide an organic polymer material that can effectively remove the acid and moisture in the polymer material to prevent hydrolysis degradation of the polymer material, and includes The macrocyclic carbodiimide obtained by the invention method. & Month's progress is to provide a method for preventing the prevention of organic polymer materials...# hydrolysis, which includes the addition of a ring-shaped carbodiimide to an organic polymer material, so that the carbodiimide functional group can be organically high. The reaction of several acid functional groups in the molecular material to form an N-mercapto urea functional group and a urea functional group can reduce the carboxylic acid functional group content and water content of the organic high molecular material. The various advantages and objects of the present invention will be readily apparent to those skilled in the art. Definition II0507.doc 200827327 Carbodiimide (CDI) is a molecule with a carbodiimide functional group. , macrocyclic carbodiimide (MC-CDI) is a macrocyclic molecular structure with a carbodiimide functional group; cyclic carbodiimide is a ring with a carbodiimide functional group. Molecules, generally known examples of the literature are ring molecules of lower molecular weight. However, in the present invention, the macrocyclic carbodiimide and the cyclic carbodiimide refer to the same ones, and the molecular weight thereof is at least more than 400. MacroCyelic acylurea (MC-acylurea, MC-ACU) is a giant ring molecule with N-mercapto urea functional group; cyclic acylurea is a N• sulfhydryl urea functional group The ring molecule is generally a smaller ring molecule. However, in the present invention, the macrocyclic sulfhydryl urea and the cyclic sulfhydryl urea refer to the same. Macrocyclic urea (MC-urea5 MC-U) is a macrocyclic molecule with a urea functional group; eyclic urea is a cyclic molecule with a urinary functional group, generally a small circular molecule. However, in the present invention, macrocyclic urea and cyclic urea refer to the same. Acid functi〇naHzed acylurea is a giant cyclic sulfhydryl urea with a carboxylic acid functional group at the end; carboxylic acid s 匕 匕 环形 环形 酿 酿 ae ae ae ae ae ae ae ae ae ae ae ae ae ae ae ae ae ae ae ae ae ae ae ae ae ae ae ae ae ae ae ae ae ae ae ae ae ae ae aCyiurea) is a cyclic sulfhydryl urea having a carboxylic acid functional group, generally a smaller circular knives. However, in the present invention, a carboxylic acid functionalized macrocyclic sulfhydryl urea and a carboxylic acid functionalized cyclic guanyl urea system Refers to the same. 酉文肝 s fbized giant sulfhydryl urea (anhydride functi〇nalized 110507.doc -12- 200827327 MC-acylurea) is a giant ring-based urea with an anhydride functional group at the end; anhydride functionalized ring 醯Anhydride functicmalized cyeHe • acylurea is a cyclic sulfhydryl urea with an anhydride functional group at the end, generally a * smaller circular molecule. However, in the present invention, an anhydride functionalized macrocyclic sulfhydryl-urea and anhydride functionalized The cyclic thiourea urea refers to the same. Carbonodiimide (CDI) carbodiimide (CDI) compounds have a wide range of uses, such as dehydrating agents in organic synthesis φ, hardeners in aqueous resins. And liquefaction modifiers for 4,4,-MDI in the PU industry. As far as is known, CDI can react with carboxylic acids to form anhydrides and N,N,-disubstituted ureas (urea), or form κ The reaction of thiol N,N-disubstituted urea (N-branched urea, ν·Acylurea) adducts depends on the type of aromatic CDI or aliphatic cm. The aromatic CDI and carboxylic acid are high. Selectively generate N-mercapto urea, and the reaction of aliphatic CDI with organic acid results in the formation of a mixture of anhydride and urea. 0 φ Process 1 describes the synthesis of N-mercaptourea E from aromatic CDI A and carboxylic acid B, and possibly a by-product in which two parallel reaction paths occur. The initially formed thiol isocyanate intermediate can be recombined into N-mercaptourea E, or undergoes further substitution reactions with additional acid molecules to produce the final product. The corresponding anhydride C and urea D. N-mercaptourea E has stability at less than about 80 ° C. However, it is known to decompose to isocyanate and guanamine at higher temperatures. I10507.doc 0200827327 Scheme 1 + R2COOH A b R^H-CriNRr C=0 \ r2 O-isoacylurea

O O It ft R2 一一一 O—C—R2 C

RtNH-C-NH-R! D

o o o C-NH-Rt 152^9 R^NH-C-R2 + Ri~NCO c=o I amide isocyanate R2 N-acyturea E Macrocyclic carbodiimide (MC-CDI)

First, the present invention provides a macrocyclic carbodiimide, particularly a macrocyclic carbodiimide (MC-CDI) of the formula 1.

R X \ N=C=N〆

X

R.

Wherein R is an aromatic group or an aliphatic group; X is an amine ester (NHCOO) or urea (NHCONH); Y is a polyether, polyester or poly having a molecular weight of from 100 to 7000. ), polycarbonate, poly(carbonate), polyolefin, or poly(10) hydrocarbon-ether); η is an integer from 0 to 10. The invention also provides a giant cyclic carbodiimide (MC-CDI) of the formula 3, 110507.doc • 14- 200827327

Wherein R, X, Υ, η are as defined in the macrocyclic ring-like rai 匕 long carbodiimide (MC-CI) I) of the formula 1; rn is an integer from 1 to 5. The present invention also provides a H e... mountain of the formula 5, < mega-shaped carbodiimide (MC-CDI), R,

N II C II N Υ1·χ-R 〜1 R-

-X

N R-Χ-χ g \ N where R1 and X are as defined in the macrocyclic carbodiimide (mc_cdi) of formula 1; Y1 is any of the species having a molecular weight of _ to 〇 (4), poly s, Or poly(ester-ether). This month also provides a giant ring carbodiimide of the formula 7 (Magic, 110507.doc -15 - 200827327

Wherein R: x is as defined in the macrocyclic carbodiimide (mc_cdi) of the formula 1; Y is a polyether having a molecular weight of from 1 Å to 7 Å, and any of the hydrazines, poly (S, ). κ Ώ曰, or the macrocyclic carbodiimide of the above formula 1, formula 3, formula 5, var. 7 and formula 7 of the present invention, R is preferably 2

Process for the preparation of macrocyclic carbodiimide (MC-CDI) The present invention provides a method for synthesizing macrocyclic carbodiimide by dilutely diluting a molecule having a plurality of isocyanate terminal functional groups, preferably It is prepared at a concentration of 0·02 Μ or less, more preferably at a concentration of 〇·015 μ or less, and condensing an isocyanate functional group in the presence of a cyclodecene-based catalyst. According to the present invention, a molecule having a plurality of guanidinium isocyanate terminal functional groups is a polyether, a polyester, a poly(__ether), a polycarbonate, a poly(carbonate) having a plurality of terminal hydroxyl groups or amine groups. An isocyanate prepolymer consisting of an ether, a polyolefin, or a poly(olefin-ether) and a polyvalent H0507.doc -16-200827327 isocyanate. The molecules of the polyisocyanate are basically classified into an aromatic isocyanate and an aliphatic isocyanate. The type of the aromatic isocyanate is not particularly limited. Suitable aromatic isocyanates include, but are not limited to, aromatic diisocyanates, aromatic polyisocyanates or mixtures thereof. Preferred aromatic isocyanates include Toluene diisocyanate (TDI), Diphenylmethane diisocyanate (MDI), p-phenylene diisocyanate Para-phenylene diisocyanate (PPDI), meta-phenylene diisocyanate (m-PDI), naphthalene diisocyanate (NDI), and plural species A mixture of diisocyanates; more preferably 2,4-toluene diisocyanate (2,4-TDI). The type of aliphatic isocyanate is not particularly limited. Suitable aliphatic isocyanates include isophorone diisocyanate (IPDI), Dicyclohexylmethane diisocyanate (H12MDI), xylene diiso isocyanate Xylylene diisocyanate (XDI), hexane diisocyanate (HDI); more preferably isophorone diisocyanate (IPDI) 〇 isocyanate prepolymer is polyamine A key intermediate in the urethane (PU) synthesis industry, typically used in the manufacture of plastics, elastomers, coatings, adhesives, and foams. Most of the prepolymers are obtained by reacting diisocyanate with a polyol at a functional group ratio of more than 2. Since the reactivity of the isocyanate is affected by chemical structures such as steric hindrance and electron-pushing effect of the substituent, the diisocyanate from which the prepolymer is produced can be classified into a symmetric type and an asymmetric type.

Il0507.doc 17 200827327 In the method of the present invention, 斛-&gt; is used for the % monoisocyanate molecule and the asymmetric monoisocyanate molecule, in the giant % carbon In the synthesis of an amine and its related macromolecules, an asymmetric diisocyanate molecule is preferred. The reason is that in the symmetric diisocyanate molecule, the nc〇 functional group has similar reactivity, and the same diisocyanate molecule has the opportunity to interact with two more than one in the synthesis of the prepolymer. The scholars combine the same knives and knives to form a high molecular weight formation/minus of the product: while increasing the free diisocyanate in the product, and the asymmetric diisocyanate The acid salt molecule has two NCO functional groups with large difference in activity. When the higher activity is combined with the polyol, the other NCO has lower activity and is less prone to chain elongation. When using this difference in activity In addition to the moderate blending on chemistry 1, the isocyanate prepolymer can have narrow molecular weight distribution, low viscosity, and low free monomer properties. The most typical example of asymmetric diisocyanate is Toluylene diisocyanate (Tm), especially 2,4·τ〇ι, and isophorone diisocyanate (IPDI). According to the invention, 'isocyanate prepolymerization Preferably, the asymmetric is a diisocyanate with a plurality of secondary The hydroxyl terminated polyether polyol is obtained by reacting an aromatic 2,4-TDI with a polyhydric diol having a terminal alcohol (in the molecule, 192 to 2000, p〇iy (pr〇pyiene giyC〇i), For example, ppg, that is, TPG, PPG400, PPG700 and PPG2000), the prepolymers of different molecular weights are used as important precursors for the cyclization reaction, and the reaction is shown in Scheme 2: 110507.doc - 18- 200827327 CH,

NCO NCO 2,4’-TDI Process 2

+ HO—CH ^CH2&gt;

H3C CH2 〆〇, CH I . CH3 _ PPG n = 1, 4, 10 and 32

Ch3 CH CH; 〇H overall response

H3c OCN

Ϊ O ch3 i l\ I Bu c—〇—hc-h2c 一o

—2C-C丨H 一吒M

Ch3 NCO

Narrow MW dispersed prepolymer In the present invention, it is preferred to obtain a narrow molecular weight distribution of a prepolymer to facilitate subsequent cyclization, and to obtain a more selective cyclic product, wherein the cyclization reaction is carried out at a temperature ranging from normal temperature to It is preferably carried out at °5 ,, and it is preferably from 50 ° C to 120 for aromatic 杈. (: proceeding downward, preferably for an aliphatic group of from k12 〇cc to 150 C. In fact, because the active isocyanate functional group at the end of the prepolymer is difficult to store, the condensation is directly carried out after completion of the reaction. According to the present invention, the prepared narrow molecular weight distribution prepolymer is diluted in an organic solvent, and then subjected to intramolecular condensation reaction in the presence of a cyclophosphene catalyst to obtain a macrocyclic carbodiimide. The yield is 2% 8% 8%, preferably about 5%, more preferably about 70%, and the intramolecular cyclization reaction is shown in Scheme 3. M0507.doc 19 200827327 Process 3

MC-Acylurea In the present invention, a suitable solvent is an inert organic solvent which does not react with an isocyanate functional group and a CDI functional group in a cyclization reaction, and the organic solvent may be, but not limited to, petroleum ether, cyclohexyl Alkyl, terpene, diphenyl, or mixtures thereof; preferably toluene or xylene, depending on the desired cyclization temperature. The class of cyclophosphene catalysts has also been extensively documented in the literature and is well known to those skilled in the art. Suitable cyclophosphene catalysts include, but are not limited to, various organic derivatives of cyclic phosphorus compounds, such as 3-mercapto-3-cyclophosphene oxide (MPO), 1,3-dimethyl_3_ Cyclophosphene oxide (DMPO), 3-methyl-1-phenyl-3-cyclophosphene oxide (MPPO), 1,3-dimercapto-1,3,2-diazaphosphorolidine, triphenyl oxide Triphenylarsenic oxide, and these are described in Tetrahedron Report R101 in Tetrahedron (VoL 3 7,0 〇8〇5 233~284,1981) on page 235 and VIII11§6¥/.(31^111.111^〇11 :, cyclophosphene catalyst in Edit. Vol. 1,621 (1962). These documents are incorporated herein by reference. The implementation of the method for the production of macrocyclic carbodiimide (MC-CDI) In the present invention, the first embodiment provides a method for producing a macrocyclic carbodiimide (MC-CDI) of the formula 1, I10507.doc -20-200827327 n=c=n.

K R

X

X

Y

X

R'N=C=N/R includes the following steps: (1) Highly diluting 2 molecules with an inert organic solvent; OCN-RXYXR-NCO 2 (2) Catalytic condensation of isocyanide in the presence of a cyclophosphene catalyst Acid salt functional group: wherein R is an aromatic group or an aliphatic group; X is an amine ester (NHCOO) or urea (NHCONH); Y is a polyether or polyester having a molecular weight of 100 to 7000. Poly(vinegar-3⁄4), polycarbonate, poly(carbonate-scale), polyolefin, or poly(lean hydrocarbon-ether); η is an integer from 0 to 10; thereby, a macrocyclic carbodiimide is produced. In the present invention, the second embodiment provides a method for producing an elongated carbodiimide (MC-CDI) of the formula 3, U0507.doc -21 -

X 200827327

The method comprises the following steps: (1) highly diluting 4 molecules with an inert organic solvent; OCM-R-X+YXR~x^_丫-X-R-NC〇4 (2) in the presence of cyclophosphene catalyst Catalytically condensing an isocyanate functional group; wherein R, X, Υ, η are as defined in the first embodiment; m is an integer from 1 to 5; thereby producing a macrocyclic carbodiimide. In the above-described first and second embodiments of the present invention, the macrocyclic carbodiimide obtained is a macrocyclic carbodiimide having one to eleven carbodiimide functional groups or a mixture thereof 1 and In the method of the first aspect of the present invention, the molecule of the formula 4 (formula 2) may be added to the step (1) and highly diluted, or before being highly diluted with an inert organic solvent, the molecule 2 and the molecule are That is, in the presence of a mixture and in an inert organic solvent, a mixture of a knife and a mixture of 4 molecules, followed by catalytic condensation of the isocyanate in the presence of a cyclophosphorus-catalyst 110507.doc -22-200827327, A macrocyclic carbodiimide is produced. A mixture of a molecule of the formula 2 and a molecule of the formula 4 is a representative of one of a plurality of molecules of an isocyanate terminal functional group. In the present invention, the third embodiment provides a method for producing a macrocyclic carbodiimide (MC-CDI) of the formula [

The following steps are included: (1) Highly diluted 6 molecules with an inert organic solvent; ocn, r 'X,

;Υ1-X - R-NCO /

OCN 6 (2) Catalytic condensation of isocyanate bureaucrane in the presence of a cyclophosphene catalyst; wherein R and X are as defined in the first embodiment; Y is in the molecule at 1〇〇 Any of the 7 〇〇〇 poly, shouting, poly (ester-ether); good, to produce a giant ring carbodiimide. In the present invention, the fourth embodiment provides a method for producing, for example, a package of %110150.doc •23·200827327 diimide (MC-CDI).

The following steps are included: (1) Highly diluted 8 molecules with an inert organic solvent;

- NCO OCN&gt; X χ〆 &gt;&lt; , Χ χ

OCN

Rv

NCO (2) catalyzes the condensation of isocyanate functional groups in the presence of a cyclophosphene catalyst; wherein R, X are as defined in the first embodiment; Y is a molecular weight of from 1 to 7 Any of poly-, polyester, or poly(ester-scale) of hydrazine; thereby, a macrocyclic carbodiimide is produced. In the above first to fourth embodiments of the present invention, R is preferably obtained from the macrocyclic carbodiimide of the formula Ϊ, Formula 3, Formula 5, and Formula 7.

, -,

ΆΛΛ / 110507.doc -24 - 200827327

Use of macrocyclic carbodiimide (Mc-cm) carbodiimide hydrolysis stabilizer

The ester group or acid group in the organic polymer material is often the main factor for the use of the material. The sufficiency of the acidity of the acid group and the alcohol group in the presence of moisture and the acidity of the acid group will further accelerate the water of the ester group.

solution. Therefore, the durability of the organic polymer material can be increased by inhibiting the hydrolysis reaction, that is, removing the acid group and the water gas. In order to overcome this problem, a hydrolysis stabilizer with a carbodiimide is currently used on the market. Such additives are mainly classified into two types: mono-carbodiimide and polycarbodiimide (p〇ly_carbodiimide). Unit carbodiimide, such as bis(2,6-diisopropylphenyl)carbodiimide (di(2,6,diiS0pr0pylphenyl)carbicarbodiimide) and dicyclohexylcarbodiimide (DCC) ), etc., low melting point, easy to mix with organic polymer materials, but the small molecular weight characteristics of such additives lead to incompatibility with organic polymer materials, easy to attack turtles / IL loss under high temperature processing, in addition, small molecule additives High reactivity, easy to react with water vapor to form small molecule urea, these shortcomings not only reduce the efficiency of hydrolysis resistance, but also affect the quality of use of materials. a carbodiimide, such as the sterically hindered aromatic polycarbodiimide disclosed in US Pat. No. 5, 094, 096, US Pat. Synthesized from diisocyanate, the molecular chain is rigid, carbon II 110507.doc -25- 200827327 The amine functional group is densely packed on the same-molecular chain and lacks the mobility, although the molecular weight is large, it can be combined with the organic polymer material. The capacity, but the relative viscosity of the melt is relatively south, which causes the diimine functional group to be difficult to self-disperse in the organic polymer material and cannot effectively remove acid and remove water. Macrocyclic carbodiimide (MC-CDI) as a hydrolysis stabilizer. Accordingly, the present invention provides a macrocyclic carbodiimide which is obtained by the method of the first to fourth embodiments. It can be used as a hydrolysis stabilizer for organic polymer materials. Different from the polycarbodiimide synthesized by diisocyanate, the macrocyclic carbodiimide molecule has more polyether, polyester, poly(ester-ether), polycarbonate, poly(carbonate-ether), Soft segments such as polyolefins or poly(olefins) can increase the separation distance of carbodiimide functional groups, improve the excessive concentration of carbodiimide functional groups on hard segments and lack mobility. By adjusting the type and length of the soft segment and the structure of the hard chain break, the macrocyclic carbodiimide molecules of the present invention can be tailor-made for specific organic polymer materials to improve compatibility with organic polymer materials. . For example, t, the anti-sub-15 functional group in the macroquinone carbodiimide molecule can react with the decanoic acid functional group in the polymer material to form a fluorene-hydrazine urea functional group, so that the macrocyclic carbodiimide additive can be Covalently bonded to the organic polymer material; the carbodiimide functional group can react with the carboxylic acid functional group in the polymer material to form a urea functional group; or the carbodiimide functional group can be combined with the polymer material The moisture reaction forms a urea functional group, thereby reducing the content of the carboxylic acid functional group and the water content of the organic polymer material, and preventing deterioration of the organic polymer material due to acidic catalytic hydrolysis. In addition, the low melting viscosity of the giant ring/molecule is more conducive to the stable dispersion of the carbodiimide functional group in the organic polymer material. These characteristics make it possible to reduce the acid group content of the organic high molecular material with a small addition of the macrocyclic carbodiimide molecule of the present invention. The organic polymer material is selected from the group consisting of polyester, polyamine, polyurethane, polyurea, poly(amine-urea), carboxylic acid-based acrylic resin, carboxylic acid or carboxylate. An aqueous resin, a group comprising at least one of the above polymers, a mixture thereof, and a covalent bond thereof. The present invention also provides a method for preventing hydrolysis of an organic polymer material, which comprises adding a macrocyclic carbodiimide obtained by the method of any one of the first to fourth embodiments to an organic polymer material, such that The carbodiimide functional group can react with a carboxylic acid functional group in the organic polymer material to form a sulfhydryl urea functional group and a urea functional group, which can reduce the carboxylic acid functional group content and water content of the organic high molecular material, and can prevent Degradation of organic polymer materials due to acid catalyzed hydrolysis. The organic polymer material is as described above. Macrocyclic carbodiimide (MC-CDI) as a chain extender The macrocyclic ring-shaped carbodiimide provided by the present invention can be added to the recycled waste of thermoplastic organic polymer materials as a chain extender. The carbodiimide functional group can react with the terminal carboxylic acid functional group of the thermoplastic organic polymer material to form an N-mercapto urea functional group, so that the macrocyclic carbodiimide additive can be covalently bonded to the organic polymer material. And under high temperature processing, the N-mercapto urea functional group thermally decomposes by itself, so that the thermoplastic organic polymer material has an isocyanate functional group at the end of the molecular chain, and further reacts with the isocyanate reactive hydrogen functional group. The reaction; thereby, increasing the molecular weight of the recovered waste of the thermoplastic organic polymer material. The thermoplastic organic polymer material is polyester, polyamine, polyurethane, poly 110507.doc -27-200827327 urea, poly(amine-urea), a polymer containing at least one of the above, a mixture thereof, and a covalent amount thereof A group of bond combinations. Purification of macrocyclic carbodiimide j The macrocyclic carbodiimide prepared in the present invention has high activity and purification: it will be limited. The present inventors have unexpectedly discovered that macrocyclic carbodiimides can be stably present in different organic solvents and are subjected to thin layer chromatography (Thin).

Layer Chromatography (TLC) was analyzed. It was found in tlc that the CDI of the ring structure has a better water volume and better phase with the solvent, so it can effectively distinguish between ring and linear CDI on KTLC. . Also by the discovery of TLC, the present invention provides a method for purifying macrocyclic carbodiimide which is purified by liquid column chromatography (LC) and maintained in a giant annular carbon dioxide. The high-purity monocyclic macrocyclic carbodiimide is isolated under the constant structure and activity of the amine. Giant annular sulfhydryl urea, functionalized macrocyclic guanyl urea, in addition to providing a giant annular guanyl urea (]^1(:4(^1111^^, MC-ACU), and providing a functionalization in accordance with the present invention Functionalized MC-acylurea, such as carboxylic acid functionalized macrocyclic sulfhydryl urea, and anhydride functionalized macrocyclic sulfhydryl urea, [including, for example, aromatic anhydrides, An aromatic ortho dicarboxylic acid, an aromatic aryl ortho monocarboxylic acid monoester, an aliphatic carboxy group, or an aliphatic hydroxy functionalized macrocyclic fluorenyl urea. The present invention provides a giant circular fluorenyl group of the formula 9. Urea (Mc%acyiurea), U0507.doc -28- 200827327

HN R 〇6 R2—Ri^Niv X- -Y,

HN h° X, N 丫 Ri - R2 〇 where R3 is an aromatic group;

X, Y

And η is defined in the macrocyclic carbodiimide (MC_CDI) of Formula 1;

Ri is a hydrocarbon radical having 2 to 20 carbon atoms; R2 is a thiol or aliphatic radical. The invention also provides a giant ring-based urea (MC_ acylurea) of the formula U,

Wherein R3 is an aromatic group; x, Y, and η are as in the formula! The macrocyclic carbodiimide (MC-CDI) is defined. The invention also provides a giant ring-based urea (MC-acylurea) of the formula 12, !!0507.doc -29- 200827327

In the middle

R3 is an aromatic group; X, Y, m, n are as defined in the macrocyclic carbodiimide (Mc_cm) of Formula 3; K is a hydrocarbon radical having 2 to 20 carbon atoms; R2 is Carboxyl or aliphatic. This month also provides a giant ring-shaped urea (MC-acylurea) of the type 13

Wherein R3 is an aromatic group; X, Y, η are as defined in the macrocyclic carbodiimide of formula 1 (MC-CDI); H0507.doc -30- 200827327 m is an integer from 1 to 5 . In the macrocyclic carbon sulfhydryl urea of the above formula 9, formula 式, formula 12, and formula 13 of the present invention, R3 is preferably

I

Method for preparing giant annular sulfhydryl urea and functionalized giant cyclic sulfhydryl urea

In the present invention, the fifth embodiment provides a method for producing a macrocyclic guanyl urea (MC-acylurea) of the formula 9,

The method comprises the following steps: (1) dissolving a macrocyclic carbodiimide of the formula prepared according to the first embodiment described above in an inert organic solvent to form a solution; (2) adding a solution of the formula 1 molecule to the solution of the step (1); R2 - RrCOOH 10 wherein H0507.doc -31 - 200827327 R3 is an aromatic group; X, γ, η are as defined in the first embodiment above; R1 is a carbon having 2 to 20 carbon atoms Hydrogen radical; R2 is a carboxyl group or an aliphatic hydroxyl group; whereby a carboxyl group is added to a carbodiimide functional group to form a giant cyclic mercapto urea. In the present invention, the sixth embodiment provides a formula u. E. Method of making MC-acylurea, 乂

The method comprises the following steps: (1) dissolving the macrocyclic carbodiimide of the formula prepared according to the first embodiment described above in an inert organic solvent to form a solution; (2) adding the trimellitic anhydride to the solution of the step (1); R3 is a scented group; X, Y, η are as defined in the first embodiment above; thereby forming a macrocyclic guanyl urea having an anhydride functional group. In the present invention, the seventh embodiment provides a method for producing a macrocyclic guanyl urea (MC-acylurea) of the formula 12, H0507.doc-32-200827327

ΝΗ

Rs ΗΝ

R2~R Ν h° corpse RfR2 3 〇

, X x- 12 includes the following steps··

(1) dissolving the macro-form carbodiimide of the formula 3 prepared as in the second embodiment described above in an inert organic solvent to form a solution; (2) adding a solution of the formula 10 to the solution of the step (1);

R2—RfC00H wherein R3 is an aromatic group; and X, Y, m, and n are as defined in the second embodiment above;

Ri is a hydrocarbon radical having 2 to 20 carbon atoms. R2 is a slow or aliphatic radical; whereby a carboxyl group is added to a carbodiimide functional group, and the soil forms a giant quinone-based uridine. In the present invention, the eighth embodiment is a method for providing a silk-like ring-like urea-based urea (MC-acylurea) of the formula 13, 110507.doc -33· 200827327

Includes the following steps:

(1) dissolving the macrocyclic carbodiimide of the formula 3 prepared as in the second embodiment described above in an inert organic solvent to form a solution; (2) adding a solution of the trimellitic anhydride in the step (1); Is an aromatic group; X, Υ, η are as defined in the first embodiment above; m is an integer from 1 to 5; thereby forming a giant cyclic mercapto urea having an anhydride functional group. In the above-described or fifth to eighth embodiments of the present invention, the obtained macrocyclic carbon-based urea of the formula 9, the formula 11, the formula 12, and the formula 13 is preferably &amp;

Il0507.doc • 34- 200827327 In the above-mentioned sixth and eighth embodiments of the present invention, the following steps may be further included: (3) dissolving the macrocyclic sulfhydryl urea of the formula 11 in an inert organic solvent to form a solution; (4) adding water or a first-grade fatty alcohol of C1 to C6 to the solution of the step (3); thereby, forming a macrocyclic fluorenyl group having an ortho-dicarboxylic acid functionalization or an ortho-monocarboxylic acid monoester functionalization Urea. Process for the preparation of a carboxylic acid functionalized macrocyclic sulfhydryl urea/anhydride functionalized giant fluorenyl urea. According to the present invention, the macrocyclic carbodiimide and the dicarboxylic acid are reacted at a temperature of less than about 80 C to obtain Carboxylic acid functionalized giant cyclic mercapto urea. The macrocyclic carbodiimide and trimellitic anhydride are reacted at a temperature of less than about 8 〇 to obtain an anhydride functionalized macrocyclic guanyl urea. Furthermore, 'the anhydride functionalized macrocyclic sulfhydryl urea and excess low boiling anhydrous alcohol' such as decyl alcohol, ethanol, etc. are subjected to a hydrolysis reaction, and after completion of the reaction, the low boiling anhydrous monohydric alcohol is removed and Drying, the macrocyclic sulfhydryl urea product, ie, the acid ester g, having an ester functional group at the end can be obtained to convert the giant cyclic sulfhydryl urea with a yield of about 1 〇〇〇/0. The ring-shaped polymer intermediate is subjected to ring-opening polymerization to form a linear organic polymer material. According to the present invention, the isocyanate-reactive group-functionalized macro-type fluorenyl urea can be regarded as a cyclic polymer intermediate. According to the principle that the sulfhydryl urea functional group thermally decomposes the "cyanate salt" and is applied to synthesize a linear 5L organic south molecular material. According to the present invention, the present invention also provides a method for synthesizing a linear organic polymer material: The following steps are included: I10507.doc -35· 200827327 (1) Dissolving aromatic anhydride, aromatic ortho-dicarboxylic acid, aromatic ortho-monocarboxylic acid monoester, aliphatic carboxyl group, or fat in an inert organic solvent a hydroxy-functionalized macrocyclic sulfhydryl urea to form a solution;

(2) heating the solution of the step (1) at a temperature of 9 〇 2 〇 (Γ (:, preferably 120 to 170 ° C, reacting between;; thereby, thermally decomposing the small annular sulfhydryl urea) a thiol urea functional group that converts a macrocyclic sulfhydryl urea into a linear molecular chain having an isocyanate functional group at one end and an anhydride functional group or a carboxyl group or a hydroxyl group having an active hydrogen at the other end, via a linear molecular chain The terminal isocyanate functional group reacts with the target anhydride of the other linear knife chain or the reactive group or the reactive group to form a linear organic polymer material, especially with quinone imine and hydrazine. A linear organic polymer material with an amine or an amine ester chain. In the above method, when the other end of the linear molecular chain is a carboxyl group, a cyclophosphene catalyst may be added as needed to increase the reaction rate. The present invention is a synthetic linear organic polymer material obtained by using the above-mentioned fifth to eighth embodiments, and the method comprises the following steps: (1) dissolving the above-mentioned giant annular sulfhydryl group in an inert organic solvent. Urea or fifth to eighth The macrocyclic sulfhydryl urea prepared by the state forms a solution; (2) heating the solution of the step (1) at a temperature of 9 〇 2 〇〇 t, preferably 120 〜 170 ° C, for the reaction; Thus, the thermal decomposition of the macrocyclic ring-based urea, the hydrazine-based urea functional group, the giant cyclic sulfhydryl urea, is converted into a continuous-hearted wenma green stalk knife chain, one end of which is an isocyanate. An anhydride functional group or a slow or trans-group having an active hydrogen, a terminal isotonic acid ester functional group via a -linear molecular bond and an anhydride functional group of another molecular type 110507.doc -36-200827327 molecular chain or a carboxyl group having an active hydrogen Or a hydroxyl group reacts to form a linear organic polymer material. Giant Ring Urea Further, the present invention provides a giant annular urea, in particular to provide a giant urea (MC-urea, MC-U) of the formula 14, R〆

R

X

X

Y

Y

X

X R Ο D〆 N-C - Ν Η Η 14 wherein R, χ, Υ, η are as defined in the macrocyclic carbodiimide (MC-CDI) of Formula 1. The invention also provides a giant annular urea (MC-U) according to formula 15,

Il0507.doc -37- 200827327 R, X, γ, n, defined. The present invention also provides a macrocyclic urea (MC-U) in the macrocyclic carbodiimide (MC-CDI) of the formula 3 as in Formula 16 > 丫1χ-&gt;/

HN NH I C=0 I m X, 16

Wherein R X and Y are as defined in the macrocyclic carbodiimide (MC-CDI) of the formula 5. The invention also provides a giant annular urea (MC-U) of the formula 17,

HN I o=c I HN

R\ NH I c=o I /NH R

R

Wherein R, X and Y2 are as defined in the macrocyclic carbodiimide (MC-CDI) of the formula 7. In the macrocyclic urea of the above formula 14, formula 15, formula 16, and formula 17 of the present invention, R is preferably

iI0507.doc • 38 - 200827327

Or 0 macrocyclic urea process. In another aspect, the present invention provides a method for synthesizing macrocyclic urea comprising highly diluting a molecule having a plurality of isocyanate terminal functional groups, and in the presence of a cyclophosphene catalyst The isocyanate functional group is reduced to produce a macrocyclic carbodiimide, and the macrocyclic carbodiimide and water are reacted in a temperature range of 〇 ° Cl 〇 5QC to obtain the macrocyclic urea. 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 patents of the present application but do not limit the remaining disclosure in any way. [Embodiment] In the following examples, the identification and physical property test of the obtained product were carried out in the following manner: - Nuclear magnetic resonance spectrometer OH-NMR) Identification: The ring-shaped polymer was dissolved in d-Acetone at 200 MHz Varian Unity Inova FT- Analysis by NMR spectrometer identified the molecular structure of the circular polymer. • Fourier infrared spectrometer (FTIR) identification: using a Fourier transform infrared spectrometer (Perkin Elmer Spectrum One FTIR Spectrometer), the coating film is dried on a salt sheet (KBr) and analyzed, and under the resolution of t OcnT1, the ring-shaped oligo is detected. The absorption spectrum of the polymer and the ring-opening polymer on IR. - Refining point meter · The apparatus for melting point measurement (Fargo Melting Point Apparatus U0507.doc -39- 200827327 MP-2D) was used to measure the melting point of the ring-shaped oligomer at a heating rate of 3 °C /min. - Differential Scanning Analyzer (DSC): Measured on a SeikoSIImodelSSC/5200 instrument at a temperature of -85 ° C to 210 ° C (open loop polymer measured to 250 ° C), ramp rate l 〇 ° C / Min, the glass transition temperature (Tg) of the ring-shaped oligomer and the ring-opening polymer on the soft and hard segments was measured under a nitrogen atmosphere. - Gel Permeation Chromatography (GPC)... (DMF system). The molecular weight and molecular weight distribution (PDI) of the ring-opening polymerization product were measured by a Hitachi Apparatus (including L-2130 Pump, L-2400 UV Detector). At 60 ° C, DMF solvent flow rate of 1 · 〇 ml / min, first use the PS standard known molecular weight to make the calibration curve, and then take each sample 〇. 〇〇 2g dissolved in 4.0g LC grade DMF (Concentration is 0. 05%). After the detection wavelength is set at 284 nm or 308 nm, it is injected into the instrument for analysis. - Mass Spectroscope · The molecular weight of MC-CDI was measured by a Fast Atom Bombardment (FAB) using a Finnigan/Thermo Quest MAT 95XL mass spectrometer. Elemental Analysis: The weight percentage of carbon, hydrogen, and nitrogen on the MC-CDI structure was determined using Elementar vario EL III. Example 1: Synthesis of a prepolymer having a narrow molecular weight distribution and containing a terminal isocyanate functional group 0.02 mol of PPG of different molecular weight and 0.042 mol of 2,4-TDI were placed in a 250 ml three-necked flask under a nitrogen system. The reaction was carried out under the reaction control conditions of Table 1. When finished, the products were all transparent and colorless liquid. (See 110507.doc -40- 200827327, Process 4). Table 1: Optimal reaction control conditions for the synthesis of 2,4-TDI and PPG prepolymers Sample number Polyisopropyl diol (PPG) used Reaction control conditions Temperature (.C) Reaction time (min) T2P192 TPG 45 50 T2P400 400 50 40 T2P700 700 50 50 T2P2000 2000 — a 65, 70 30 (65〇C), 15 (70〇C) An example of an isocyanate prepolymer prepared from PPG700 and 2,4-TDI, i The NMR chart is shown in Figure 1. Example 2: Preparation of macrocyclic carbodiimide (MC-CDI) was directly poured into a reactor with a large amount of solvent (1500 ml of toluene (conc. = 〇.〇13 mol/L)) to dilute the different molecular weights after completion of the reaction of Example 1. The prepolymer (T2Pm) was heated to 90 ° C for cyclization after the addition of DMPO. The cyclization reaction was monitored by FTIR. When the characteristic peak of NCO (IR= 2269 cm·1) on FTIR was completely converted to CDI (IR= 2134 cnT1), the reaction was completed and the concentration reaction solution was completed at 4 ° °. C to 5 (dry under reduced pressure at TC to obtain MC-CDI-T2Pm crude product (see Scheme 4). MC-CDI-T2Pm crude product with silica gel (60-230 micron) and ethyl acetate (EAc) or acetic acid Ethyl ester (EAc) / n-hexane volume ratio 9:1 is purified by liquid column chromatography to obtain the EAc solution of the target product MC-CDI. Concentrated with 40. (: to 50 ° C under reduced pressure, can be Purified MC-CDI-T2Pm was obtained. The yields of mc-CDI of different molecular weights are shown in Table 2. Table 2: Results of purification of MC-CDI with different molecular weights by liquid chromatography column chromatography H0507.doc -41 - 200827327 Sample number Cyclization reaction time (hr) Yield (%) State melting point 聚醚 Polyether segment Tg (°C) MC-CDI-T2P192 21 60 Yellowish powder crystal 80.5-85.23 18.0 MC-CDI-T2P400 18 67 Slightly yellow colloids 16 and 22b 6.7 MC-CDI-T2P700 20 40 yellowish colloid - 3.8 MC-CDI-T2P2000 27 18 yellowish colloid -49.0 a: measured by melting point a Pparatus(3〇C/niin) b: measured by DSC(10°C/min) 1H-NMR chart of MC-CDI-T2P700 prepared by taking T2P700 as an example

as shown in picture 2. In order to avoid the complex structure and molecular weight unequal distribution of high molecular weight PPG segments, it is not possible to accurately confirm that the MC-CDI compound prepared according to the present invention has a ring structure, and the MC synthesized by TPG with precise polyether segment length is synthesized. -CDI-T2P192 to illustrate, its elemental analysis and mass spectrum are shown in Table 3 and Figure 3, respectively. From the results of Table 3, the experimental values of each element are almost the same as the theoretical values, and the errors are all within 0.2%. Figure 3 shows that the absolute molecular weight (496.3) of MC-CDI-T2P192 is consistent with the theoretical value (496.23218). It is believed that the MC-CDI compound prepared by the present invention has a ring structure. Table 3 · Results of MC-CDI-T2P192 elemental analysis MC-CDI results N% C% H% 0%a - Experimental value 11.30 63.04 6.34 19.32 ~ 11.18 63.03 6.48 19.31 Theoretical value 11.28 62.89 6.50 19.33 ~ a. 0% =100%-N%-G%-H% 110507.doc -42- 200827327 Process 4

OCN NCO + HO-

-OH

40-60 ° C OCN- o o

2,4-TDI PPG diol

HOAc RT T2Pm (exact prepolymer)

MC-ACU-T2Pm-AcA

EtOH O h3c-c-nh m = 192, 400, 700, 2000

7 ΚΙ—C—O ^A/WWUW 〇 —C N \\ //- \=/ Η H O NH-C-OEt

Linear amide-urethane product (ί-Αυ-ΤΣΡΐϊΐ) Example 3: Synthesis of MC-acylurea (MC-ACU) in a 100 ml three-necked flask. The MC of different PPG chain lengths obtained by the example 2 was purified. -CDI-T2Pm (9_3xl0·4 mol), and an excess of acetic acid (AcA) (9.3xlO'3 mol, 0.56g), and finally 20 ml of toluene, reacted at room temperature -43-110507.doc 200827327, During the reaction, the FTIR and TLC were monitored. When the CDI characteristic peak (IR= 2134 cnT1) on the FTIR completely disappeared, the reaction was completed (8 hours) and the anhydrous MgS04 was added to remove water. After filtration, the solvent was removed. The product was obtained in a yield of over 98%. (See Flow 4). Example 4: Ring-opening reaction of giant annular sulfhydryl urea. 2 g of macrocyclic sulfhydryl urea 700 (MC-ACU-T2P700-AcA) synthesized in acetic acid was dissolved in 30 ml of xylene and placed in a 100 ml three-necked flask. Under the nitrogen system, the temperature was slowly increased in the oil bath mode, and the FTIR was monitored during the ring-opening reaction, and the temperature and rate of the NCO characteristic peak (111=2270 (:111-1)) were observed, as shown in Fig. 4. After the completion of the monitoring at 140 ° C, the heat source was removed and the excess absolute ethanol was slowly added and stirred for 30 minutes. After the reaction was completed, the solvent was removed and dried to obtain the indoleamine-urethane (Amide- Urethane) linear product (L-AU-T2P700). The ring opening reaction formula is shown in Scheme 4. Taking MC-ACU-T2P700-AcA as an example, the 1H-NMR chart of the obtained Amicfe-Urethane linear product is shown in Fig. 5. The indicated 0 is an example of a PPG 700 chain length isocyanate prepolymer (T2P700), MC-CDI-T2P700, MC-ACU-T2P700-AcA, and its ring-opening product L-AU-T2P700. GPC analysis is as follows. As shown in Figure 5, the giant circular molecule has a lower hydraulic volume relative to the linear molecule, that is, it exhibits a longer lag in gel permeation chromatography. It can be seen from Fig. 6 that the macrocyclic molecules have a longer residence time than their corresponding linear molecules, thereby demonstrating that the molecules of the present invention have a ring structure. Example 5: Carboxy-functionalized giant cyclic guanyl urea ( Synthesis of Acid Functionalized M0507.doc -44- 200827327 MOacylurea) and its ring-opening polymerization in a 100ml three-necked flask. The purified MC-CDI-T2P700 (9·3χ l (T4mol), and excess adipic acid (adipic) Acid, AdA) (9.3xl〇-3mol, 1.3 6g), finally added 15 ml of anhydrous THF and 10 ml of hydrazine, reacted at room temperature, monitored by FTIR and TLC during the reaction, when CDI characteristic peak on FTIR (IR = 2134 cnT1) When the disappearance is complete, the reaction is completed (about 20 to 22 hours). After removing the solvent at normal temperature, 20 ml of toluene is added, at which time a large amount of unreacted adipic acid white powder precipitate is produced and filtered. The solvent in the filtrate is removed and the above purification step is repeated several times. Finally, anhydrous MgS04 is added to remove water, and after filtration, it is dried in a vacuum oven at 30 ° C for 5 hours to obtain a giant terminal having a carboxylic acid functional group. Cyclic sulfhydryl urea product (MC-ACU-T2P700-AdA), the yield is more than 98%. The reaction formula is shown in Scheme 5. The 1H- of the ferulic acid functionalized giant cyclic acid urea (MC-ACU-T2P700-AdA) was prepared. The NMR chart is shown in Figure 7. The carboxylic acid-functionalized macrocyclic sulfhydryl urea can be obtained by ring-opening polymerization in the SSRR mode to prepare a linear poly(amide-urethane) (PAU) polymer. The reaction formula is as shown in Scheme 5. The SSRR mode is a sequential self-repetitive reaction consisting of three self-repetitive steps. The first step is thermal decomposition of 1.0 mole of aromatic N-mercapto urea to form 1.0 mole of decylamine or guanamine-imine as product and simultaneously produce 1 · 〇 molar aromatic isocyanate . The second step is a catalyst conversion reaction of 1.0 mole of aromatic isocyanate to 0.5 mole of aromatic CDI. Finally, the third step is the reaction of 0.5 mole of aromatic CDI with a carboxylic acid to form an additional 0.5 mole of aromatic N-mercaptourea which is separable from the intermediate of ii0507.doc -45.200827327. Therefore, in summary, 50% of the aromatic isocyanate is consumed in this continuous self-reaction (SSRR) in a single complete cycle to form 50% of the guanamine or guanamine-imine. . When a sufficient amount of carboxylic acid is provided, the above three consecutive reactions are repeated, eventually consuming all of the aromatic N-mercapto urea, aromatic isocyanate, and aromatic CDI.

0.5 g of MC-ACU-T2P700-AdA was dissolved in 10 ml of anhydrous toluene, placed in a 100 ml three-necked flask, and refluxed with an oil bath under an atmosphere of nitrogen to 110 ° C. In order to complete the monomer reaction, it was traced by TLC until the monomer in the solution completely disappeared. After the reaction is completed, the solid solution is filtered and dissolved in a small amount of DMF, and then added to a large amount of toluene and filtered. The above purification steps are repeated several times, and finally placed in a vacuum oven at 80 ° C for 4 hours to obtain a PAU line type. The copolymer had a yield of 86%, a number average molecular weight (??) of about 50,000, a PDI of 1.894, a soft segment of Tg - 43 ° C, and a hard segment of Tg of 147 °C. Process 5

HOOC-(CH2)4-COOH adipic acid MC-CDI-T2P700 -

DMPO, Δ -^ SSRR

MC-ACU-T2P700-AdA

Poly(amide-urethane), PAU 110507.doc -46- 200827327 Example 6: Anhydride Functionalized MC-acylurea and Acid-Ester Functionalized MC-Acid-Ester Functionalized MC- Synthesis of acylurea) and its ring-opening polymerization in a 100 ml three-necked flask, the purified MC-CDI-T2P700 (9·3χ 10·4 mol), and an excess of benzene trimellitic anhydride (ΤΜΑ) (9·3χ10·3) Mol, 1.79 g), finally added 15 ml of anhydrous THF and 10 ml of toluene, and reacted at room temperature. The reaction was monitored by FTIR and TLC. When the CDI characteristic peak (IR = 2134 cm·1) on the FTIR completely disappeared, the reaction was completed (about 12 to 15 hours). After the solvent was removed, 20 ml of toluene was further added, after which a large amount of unreacted TMA white powder precipitate was produced and filtered, the solvent in the filtrate was removed and the above purification steps were repeated several times, and finally anhydrous MgS〇4 was added. After removing water, filtering and drying, a giant cyclic mercapto urea product (MC-ACU-T2P700-TMA) with an anhydride functional group at the end can be obtained, and the yield is over 98%. The reaction formula is as shown in Scheme 6. The 1H-NMR chart of the anhydride-functionalized giant fluorenyl urea (MC_ACU-T2P700-TMA) prepared is shown in Figure 8. The 0 anhydride-functionalized macrocyclic sulfhydryl urea can be further converted into an ester functionalized macrocyclic fluorenyl group. Urea. MC-ACU-T2P700-TMA (9.3xl (T4mol) and 50ml excess absolute ethanol were placed in a 100 ml three-necked flask and allowed to react at room temperature for three hours under nitrogen flow. Finally, the anhydrous ethanol was removed. After drying, a giant cyclic mercapto urea product (MC-ACU-T2P700-TAE) with an ester functional group at the end can be obtained with a yield of about 100%. The reaction formula is shown in Scheme 6. The polycyclic sulfhydryl urea can be prepared by the ring-opening polymerization of 110507.doc •47- 200827327 by the SSRR mode to prepare a poly(amide-imide-urethane) (poly(amide-imide-urethane)). PAIU) Polymer. The reaction formula is shown in Scheme 6. 0.5 g of MC-ACU-T2P700-TAE was dissolved in 10 ml of anhydrous benzoquinone (anisole) and placed in a 100 ml three-necked flask under gas flow. The temperature was controlled to 130 °C in an oil bath. In order to complete the monomer reaction, the TLC was traced until the monomer in the solution disappeared completely. After the reaction was completed, the solvent was removed by a rotary evaporator, and the concentrate was placed in a vacuum oven at 120°. Drying for 5 hours under C. The purpose of this high vacuum heating and drying is to completely remove the ester from the ester and convert it to im. Ide functional group. Finally, the gelatinous solid is dissolved in a small amount of DMF, and then added to a large amount of cyclohexane and filtered. The above purification step is repeated several times and dried to obtain a PAIU linear copolymer. 88 %. The molecular weight of the product is double-distributed, one is 760η about 760,000, the PDI is 1.620, the integral area is about 60%, the other is Μη about 44,000, the PDI is 1.233, the integral area is about 40%, and the soft and hard segments are mixed with Tg- 6.6 ° C, hard segment Tg 213 〇 C.

110507.doc 48- 200827327 Process 6 ΐνΐΟ-ΟΟΙ-Τ2Ρ700 〇

ο

MC-ACU-T2P700-TMA

WIC-ACU-T2P700-TAE

C ο. , Hu

Po!y(amide-imide-urethane), PAIU

dmpo.A

-C〇2, - EtOH SSRR Example 7: Synthesis of macrocyclic urea (MC-urea, MC-U) The purified MC-CDI-T2Pm (9.3xlO·4mol) was placed in a 100ml three-necked flask and dissolved. After 20 ml of acetone/water mixed solvent, the concentrated hydrochloric acid (cone. HC1 37%) was added to the catalyst, and the reaction was monitored by FTIR. When the CDI characteristic peak (IR = 2134 cnT1) completely disappeared, the reaction was completed. After the reaction is completed, the solvent is removed at a normal temperature by a high vacuum rotary evaporator, and then placed in a vacuum oven at 110507.doc -49-200827327, and dried at 50 ° C for 3 hours to obtain a giant annular urea product (MC). -U-T2Pm), the yield is over 99%. The reaction formula is shown in Scheme 7 (reaction formula and structure of MC-Urea). Taking MC-CDI-T2P700 as an example, the 1 H-NMR chart of the giant ring-shaped urea MC-U-T2P700 V prepared is shown in Fig. 9. Process 7

MC-CDI-T2Pm

Example 8: Macrocyclic carbodiimide (MC-CDI) hydrolysis stabilizer The synthesized unbrominated macrocyclic carbodiimide molecule was added to a polyester polyol and stirred at 120 ° C for 6 times a day. Hours, a total of 8 days of treatment, and finally titrated to measure the acid value of the polyester polyol. It can be seen from Table 4 that the addition of 0.5 wt% of the macrocyclic carbodiimide molecule can greatly reduce the acid value of the polyester polyol to 0.1, even the MC-CDI-T2P2000 with the lowest carbodiimide functional group. Table 4: Acid value change after addition of macrocyclic carbodiimide molecules to polyester polyols Sample number Giant ring carbodiimide Molecular addition amount (wt%) Acid value (mgKOH/g) 0 No ___ 0 1.2 400-1 MC- CDI-T2P400 0.5 0.1 110507.doc -50· 200827327 400-2 ΜΟ-ΟΟΙ-Τ2Ρ400 1.0 0.1 700-1 MC-CDI_T2P700 0.5 0.1 700-2 MC-CDI-T2P700 1.0 0.1 700-3 MC-CDI-T2P700 2.0 0.1 2000-1 MC-CDI-T2P2 (10) 0 0.5 0.1 2000-2 MC-CDI-T2P2000 1.0 0.1 2000-3 MC-CDI-T2P2000 2.0 0.1 It should be easy to understand that various improvements of the present invention are feasible and easy for those skilled in the art. Associated and expected. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a 1H-NMR chart showing the isocyanate prepolymer (T2P700) prepared in Example 1 of the present invention as a d-acteone solvent; Fig. 2 shows the preparation of the example 2 of the present invention. 1H-NMR chart of MC-CDI-T2P700 tested by d-acteone solvent; Fig. 3 shows the mass spectrum of MC-CDI-T2P192 obtained in Example 2 of the present case; Fig. 4 shows MC-ACU_T2P700-AcA of Example 4 of the present case IR monitoring of the ring opening reaction: (a) original MC-ACU-T2P700-AcA; (b) MC-ACU-T2P700-AcA opened at 130 ° C; Figure 5 shows the open loop of Example 4 of the present case The reaction product L-AU-T2P700 was subjected to the 1H-NMR chart of the d-acteone solvent test; Fig. 6 is a GPC chart showing the linear type molecules and macrocyclic molecules mainly composed of PPG 700 in Examples 1-4 of the present invention: (a) Cyanate prepolymer (T2P700); (b) MC-CDI-T2P700; (c) MC-ACU-T2P700-AcA; (d) L-AU-T2P700; Figure 7 shows the preparation of Example 5 of the present case The carboxylic acid functionalized macrocyclic guanyl urea (MC-ACU-T2P700_AdA) was tested by d-acteone solvent - 110507.doc -51 - 200827327 NMR chart, Fig. 8 shows the anhydride functionalized giant obtained in Example 6 of the present case Cyclic sulfhydryl urea (MC- ACU-T2P700-TMA) 1H-·: NMR chart for d-acteone solvent test; V Figure 9 shows d-acteone solvent test for giant ring urea (MC-U-T2P700) prepared in Example 7 of this case 1 Η-NMR chart.

110507.doc -52-

Claims (1)

200827327 X. Patent application scope: 1 · A macrocyclic carbodiimide (MC-CDI) of formula 1, N=C=N, , / R\ . XX . \ / X γ R, N=C=n /R Wherein R is a scented or aliphatic group; X is an amine ester (NHCOO) or urea (NHCONH); Y is a squama of any of the molecules 1 to 1 7000, and is self-assembled. Or, poly(ester--), polycarbonate, poly(carbonate-ether), polyanthracene, or poly(thick hydrocarbon-ether); and η is an integer from 0 to 10. a macrocyclic carbodiimide (MC-CDI) of the formula 3, N=C=N where U0507.doc 3 200827327 R, X, Υ, η are as requested! The one defined in ; and m is an integer from 1 to 5. 3. A macrocyclic carbodiimide (MC-CDI) of the formula 5, -R Υ1·Χ - R-N=〇N-R - X-Y’1 -X R- R- N II C II N R, X are those as defined in the claims; and Y is a polyether, polyester, or poly(S-ether) having any molecular weight of from 100 to 7,000. 4. A giant cyclic carbodiimide (mc_cdI) of the formula 7, Wherein R and X are as defined in claim 1; and Y2 is a polyether, polyester, or poly(SI-ether) having any one of 100 to 7,000 molecules. 5. The macrocyclic carbodiimide of any one of claims 1 to 4 wherein R is 110507.doc 200827327 6. A method for producing a macrocyclic carbodiimide (MC_CDI) comprising the steps of: (1) isotropically diluting a molecule having a plurality of isocyanate terminal functional groups; and (2) in a cyclophosphene catalyst In the presence of a condensed isocyanate functional group; thereby, a macrocyclic carbodiimide having from one to eleven carbodiimide functional groups is produced. 1 · A method of making a giant ring-shaped diimine (MC-CDI) of the formula 1, /N=C:N, /R, \ X \χ χ\ /Χ 1 includes the following steps: () organic The solvent is highly diluted in 2 molecules; OCN-RX, Y-χ-r-NCO 2 () catalyzes the condensation of isocyanate functional groups in the presence of % squalane catalyst; where R, X, γ goes, ^ Υ, η are as defined in claim 1; thereby, 吝tr m produces a mega-shaped carbodiimide. 8. A method for the preparation of a macrocyclic carbodiimide (MC-CDI) of the formula q, I10507.doc 200827327 n=c=n The method comprises the following steps: (1) highly diluting 4 molecules with an inert organic solvent; 〇CN RX^y-x_r_x^_y_x r_nc〇4 (2) catalytically condensing isocyanate functional groups in the presence of J-disc women's catalyst Wherein H, X, γ, n are as defined in the claim 1; m is an integer from 1 to 5; thereby, a macrocyclic carbodiimide is produced. a method for producing a macrocyclic carbodiimide (MC-CDI) of the formula 5, X ^ \ / ^ γΐ-Χ—R—N=C=N——R-X-Y1 \ / \ X X, 5 Includes the following steps: (1) Highly diluted 6 molecules with an inert organic solvent; Il0507.doc 200827327 \ /Y1-XR-NCO / OCN 6 (2) catalytically condensing isocyanate functional groups in the presence of a cyclophosphene catalyst; wherein R, x are as defined in claim 1; Y is A polyether, polyester, or poly(ester-ether) having any molecular weight of from 100 to 7,000; thereby, a macrocyclic carbodiimide is produced. 10. A method for producing a macrocyclic carboguanamine (Mc_cdi) of the formula 7, The following steps are included: (1) Highly diluted 8 molecules with an inert organic solvent; -NCO OCN, RX,, //\ /XX .FT OCN〆NCO (2) Catalyzed in the presence of cyclophosphene catalyst Condensed isocyanate &amp; I10507.doc 200827327; wherein R, X are as defined in claim 1; Y2 is a polyether, polyester, or poly(ester) of any of molecular weights from 100 to 7000 · Turn); thereby, a giant ring carbodiimide is produced. 11. The method of claim 7, further comprising adding a molecule of formula 4 in step (1) and highly diluting, and then catalytically condensing the isocyanate functional group in the presence of a cyclophosphene catalyst to produce a giant ring Carbodiimide. 12. The method of claim 8, wherein the step of adding the molecular subunit of the formula 2 to the step 〇) is highly diluted, and then catalytically condensing the isocyanate functional group in the presence of a cyclophosphene catalyst to produce a giant ring Carbodiimide. The method for preparing the gentry term 11 or 12, wherein in the step (〗), before the dilution with inert organic/dihydrogen, the molecules of the formula 2 and the molecule of the formula 4 are present as a mixture, and the mixture is highly diluted with an inert organic solvent. . I4. The method of any one of the items 7 to 12, wherein the rule is 1 5. As requested in item 6 5 1. The method of any one of rb / ^, the main 12, wherein the cyclophosphene catalyst is I3-methyl-3-cyclophosphene oxide (DMp 〇 broad. ..., I10507.doc 200827327 16. A macrocyclic carbodiimide of the middle-term, which is a hydrolysis stabilizer for an organic polymer material. 17. The macrocyclic carbodiimide of claim 16, wherein the organic polymer material is selected from the group consisting of polyacetic acid and poly Amidoxime, polyamine vinegar, polyurea, poly(amine vinegar-urea), acidified acrylic resin, (d) a hydroxylated acid-based aqueous resin, a polymer containing at least one of the above, a group consisting of a mixture and a covalent bond thereof. - A method for preventing hydrolysis of an organic polymer material, which comprises adding a large amount of bismuth diimide as claimed in the requester Wang 4 to the organic high In the molecular material, the carbodiimide functional group can react with the carboxylic acid functional group in the organic polymer material to form an N-mercapto urea functional group and a urea functional group, which can reduce the carboxylic acid functional group content of the organic polymer material and Water content. ★ » Monthly method 18, in which organic polymer The material is selected from the group consisting of polyfluorene, polyurethane, polyurea, poly(amine-urea), carboxylic acid group = acrylic resin, carboxylic acid or carboxylate-based aqueous resin, containing at least a group of the above-mentioned polymers, a mixture thereof, and a covalent bond thereof. I. The macrocyclic carbodiimide according to any one of claims 1 to 4, which is added to a thermoplastic organic polymer material. In the recycled waste, as a chain extender. (3) The macrocyclic carbodiimide of claim 20, wherein the carbodiimide functional group: the terminal carboxylic acid functional group of the thermoplastic organic polymer material reacts to form an N-2 based urea palace The energy base enables the macrocyclic carbodiimide additive to be covalently bonded to the organic high-sub-material; and under high temperature processing, the sulfhydryl urea &amp; Chain end II0507.doc 200827327 end with a different "salt functional group" and then reacted with an isocyanate-reactive active hydrogen functional group; thereby increasing the molecular weight of the recovered waste material of the thermoplastic organic polymer material. 20 giant ring carbon two An imine, wherein the organic polymer material is selected from the group consisting of polyester, polyamine, polyurethane, polyurea, poly(amine), a polymer containing at least one of the above, a mixture thereof, and a covalent bond thereof The group formed by. 23·—a giant ring-based urea (MC_aeylurea) of the formula 9 Ten X' R3 9 HN Ο gas ^Ri^N )=〇AR1~R2 /R3 where R3 is an aromatic group; X, Y, n are as defined in claim 1; Ri is 2 to 20 carbon atoms Hydrocarbon radical; and I is a slow or aliphatic base. A giant ring-shaped urea (MC-acylurea) of the formula 11, I10507.doc 200827327 Wherein R3 is an aromatic group; X, Y, and η are as defined in the request item. 25. A giant ring-based urea (MC_acylurea) of the formula 12, X ς — r3-x, R3 0=( NH HN ϊ Ο K3 ^==0 , N 丫 R broad R 2 3 0 x, rW 12 where I is an aromatic group; x, Y, n are as defined in the claim i; m is an integer from 1 to 5; Ri is from 2 to 20 Hydrocarbon radicals of one carbon atom; and R2 is a mercapto group or an aliphatic permeate group. 26. The macro-acidic urea (MC-acylurea) of the formula 13 is used, II0507.doc 200827327 In the middle R3 is an aromatic group; X, y, n are as defined in the claim 1; and πι is an integer from 1 to 5. 27. The giant annular thiourea according to any one of claims 23 to 26, the center of which is 28. A method of producing a macrocyclic guanyl urea (Mc_acylurea), comprising the macrocyclic carbodiimide of any one of claims 1 to 4 and a monocarboxylic acid, a dicarboxylic acid, or a polycarboxylic acid compound, or The mixture is reacted at a temperature below about 8 (rc) to obtain the macrocyclic sulfhydryl urea. 29. A method for synthesizing a linear organic polymer material using a cyclic polymer intermediate, comprising the following steps: 1) Solving a solution of an aromatic anhydride, an aromatic ortho-di-70 carboxylic acid, an aromatic ortho-monocarboxylic monoester, an aliphatic carboxy group, or an aliphatic hydroxy-functional macrocyclic sulfhydryl urea in an inert organic solvent to form a solution 110507.doc -10 - 200827327 (2) The solution of the heating step (1) is carried out at a temperature of 9 Torr to 2 Torr: Thereby, thermally decomposing the N•sulfhydryl urea functional group of the giant cyclic mercapto urea, converting the giant cyclic mercapto urea into a linear molecular chain, one end of which is an isocyanate functional group and the other end is an anhydride functional group or a carboxyl group or a hydroxyl group having an active hydrogen; a terminal organic isocyanate functional group is reacted with an acid anhydride functional group of another linear molecular chain or a carboxyl group or a hydroxyl group having an active hydrogen to form a linear organic polymer material. 30. The method of claim 29, wherein when the other end of the linear molecular chain is a carboxyl group, a ring-filled catalyst can be added to increase the reaction rate. The method of claim 29, wherein the reaction is carried out in the step (2) at a temperature of from 12 〇 to i7 〇 ct. 32. The method of claim 29, wherein the linear organic polymer material is provided with a ruthenium imine, a guanamine, or an amine ester linkage. 33·—The method of making a giant ring-based urea (MC_acylurea) of the formula 9, HN1Γ, 0 HN X, -XJ Π, K3 〇 include the following steps: (1) Dissolving the macrocyclic carbodiimide of formula 1 of claim 1 or the formula 1 of the method of claim 7 in an inert organic solvent. Ring carbodiimide, 110507.doc 200827327 Forming a solution; (2) adding a solution of the formula 1 〇 molecule to the step (1); 13⁄4 a R*j - COOH 10 wherein R 3 is an aromatic group; X, Y, n is as defined in claim 1; Ri is a hydrocarbon radical having 2 to 20 carbon atoms; R 2 is a carboxyl group or an aliphatic hydroxyl group; thereby forming a 'slow addition to a carbodiimide functional group Giant ring sulfhydryl urea. 34. A method of making a giant ring-shaped urea (MC-acylurea), such as _ includes the following steps: (1) dissolving a macrocyclic carbodiimide of the formula 1 of claim 1 or a macrocyclic carbodiimide of the formula 1 prepared in the process of claim 7 in an inert organic solvent to form a solution; Adding a solution of the trimellitic anhydride to the step (1); wherein 110507.doc -12 * 200827327 R3 is an aromatic group; xy, n are as defined in claim 1; The base of the giant sulfhydryl urea 35. The method of the method 33 or 34, wherein &amp; 36. The method of claim 34 includes the following steps: (1) = the organic solvent is dissolved in a giant annular sulfhydryl solution; / knife and (7) water, or a C1 to C6 primary fatty alcohol is added to the solution of step (7) The latter formed a macrocyclic (tetra) urea having an ortho-dicarboxylic acid functionalized vinegar functionalized. Early disproportionation 37.: Synthesis of linear organic polymer materials... including the following steps (1) by inert organic consumption such as the macrocyclic acid urea of claim 23 or 24 or the requirements of items 33 to 36 The giant ring-shaped urea is formed into a solution; (2) the solution of the step (1) is heated at a temperature of 9 〇 2 〇〇. (: reacting; thereby, thermally decomposing the N_mercapto urea-energy group of the giant ring-based urea, making the giant ring-based urinary (four) light-weight molecular chain, and its terminal end is an iso-sodium salt functional group' The other end is an acid-pin functional group or a carboxyl group or a trans-group having an active chlorine; the cyanate functional group via the terminal I of the linear molecular chain reacts with the thiol group of another linear molecular chain of II0507.doc 200827327 to form a straight: : energy base or slow-acting base with active chlorine or generated linear organic polymer material 38. As in the case of claim 37, it can be seen that the linear molecular chain of the 1 w Ί linear molecular chain is the other end of the carboxyl group. The olefinic catalyst increases the reaction rate. For example, the method of the method of 37, wherein the reaction in the step (7) is carried out at a temperature of 120 to 70 ° C. 4 0. If the solution is 3 7 square ^ ', the middle straight line Type organic polymer material with 醯 Imine, guanamine, or amine ester chain.辰开&gt; The method of making MC-acylurea, 4 1 · A Formula 1 ς ς ς 132: The following steps are included: (1) Dissolving the macrocyclic carbodiimide of Formula 3 of claim 2 in an inert organic solvent or Formula 3 as prepared in the Process of Claim 8 a macrocyclic carbodiimide forming solution; (2) adding a solution of the formula 10 to the solution of the step (1); R2 - RfCOOH 10 110507.doc -14- 200827327 wherein R3 is an aromatic group; X, Y, η Is as defined in claim 1; m is an integer from 1 to 5; Ri is a hydrocarbon radical having 2 to 20 carbon atoms; R2 is a carboxyl group or an aliphatic hydroxyl group; thereby, the carboxyl group is added to the carbon two An imine functional group that forms a giant cyclic mercapto urea. 42. — A method of making a giant ring-based urea (MC-acylurea) method of the formula 13, One seven Includes the following steps: The amine 'forms a solution; (2) the trimellitic anhydride is added in the step of the solution of the trimic anhydride in the step (1) An aromatic group; Πι is an integer of 〇5 defined by; 110507.doc -15- 200827327 Thereby, a giant annular thiourea urea having an anhydride functional group is formed. 43. The method of claim 41 or 42, wherein R3 is 44. The method of claim 42, further comprising the steps of: (1) dissolving the macrocyclic sulfhydryl urea of formula 13 in an inert organic solvent to form a solution; (2) adding water, or a C1 to C6 primary fatty alcohol to the step of adding (3) A solution; thereby forming a macrocyclic acid-based urea functionalized with an ortho-dicarboxylic acid functionalized or ortho-monocarboxylic acid mono-g. 45. A method for synthesizing a linear organic polymer material, comprising the steps of: (1) dissolving the macrocyclic sulfhydryl urea of claim 25 or 26 or any one of claims 41 to 44 in an inert organic solvent. The giant ring-based urea is obtained to form a solution; (2) The solution of the step (1) is heated at a temperature of 9 〇 2 〇〇. The reaction is carried out during the day; thereby, the N_mercapto urea functional group of the giant cyclic sulfhydryl urea is thermally decomposed, and the macrocyclic sulfhydryl urea is converted into a linear molecular chain, and the terminal is an isotonic acid functional group Is an acid anhydride functional group or a carboxyl group or a hydroxyl group having an active hydrogen, and a straight line is formed via the terminal isocyanate functional group of the linear molecular chain and the acid or the reactive group of the other linear molecular chain or a reactive group having a reactive nitrogen Type organic polymer material. U0507.doc -16- 200827327 46. The method of claim 45, wherein when the other end of the linear molecular chain is rebellious, the cyclophosphene-based catalyst may be added as needed to increase the reaction rate. 47. The method of claim 45, wherein the step (2) is carried out at a temperature between i2〇~i7〇c. 48. The method of claim 45 wherein the linear organic polymeric material carries a quinone imine, a guanamine, or an amine ester linkage. 49. A giant urea (MC-urea) of the formula 14, wh XXYX Ο -1ST Η Η Υ X where R, X, Υ, η are as defined in the claim 50 50. Giant ring urea (Mc_urea II0507.doc • 17- 200827327 where γ, η, m are as defined in claim 2. 51. - A giant ring of urea of the formula 16 (Μ. -, . In the middle R X, Y are as defined in claim 3. 52. A type of giant urea (MC-urea), Where m and γ are as defined in claim 4. 53. - A giant ring-shaped urea (the method of preparing ruthenium, comprising reacting the macrocyclic carbodiimide and water of the request to * in the temperature range of 0eC - 105 〇C to obtain the giant annular urea. I I0507.doc -18-