CN106146832A - Process for the manufacture of aliphatic urethane dicarbamates, aliphatic urethane polycarbamates and polyureas using diaryl carbonates - Google Patents

Abstract

The present invention relates to a method for preparing aliphatic amino dicarboxylic acid ester, aliphatic amino polycarboxylic acid ester and polyurea by using diaryl carbonate. In a solvent or in the absence of a solvent, aliphatic diamine compounds, aliphatic polyamine compounds or mixtures thereof are subjected to carbonylation reaction by using diaryl carbonate to prepare aliphatic amino dicarboxylic acid ester, aliphatic amino polycarboxylic acid ester, polyurea and waterborne polyurea. With diaryl carbonate as the main raw material, aliphatic amino di/polycarboxylic acid ester intermediates, aliphatic amino di/polycarboxylic acid ester prepolymers, urea elastomers, urea plastics and waterborne polyurea can be prepared in a milder and safer environment; in this novel transureation polymerization reaction, volatile organic solvents, highly toxic phosgene or diisocyanates can be eliminated, and excellent yields can be achieved, which meets the purpose of green chemistry/processing.

Description

Manufacture of aliphatic urethane dicarboxylates, aliphatic urethane polycarbamates and diaryl carbonates Polyurea method

technical field

The present invention relates to the production of fatty acids from aliphatic diamine compounds, aliphatic polyamine compounds, especially aliphatic triamine compounds and aliphatic tetramine compounds, or mixtures thereof and diaryl carbonates without the presence of any catalyst. It is a green synthetic method for the preparation of polyurea through the production of aliphatic urethane dicarboxylates or aliphatic urethane polycarbamates. Further studies have found that high-performance polymer polyurea (urea) elastomers or cross-linked polyurea thermosetting polyurea products can be prepared by a one-pot three-step method, and the method can be used in solvent-free or aqueous solution Completing the preparation of polyurea is more in line with the purpose of green chemistry.

Background technique

Polyurea (Polyurea) and polyurethane (Polyurethane; PU) are both copolymers synthesized by step-growth polymerization using isocyanate as raw material [1]. They have excellent mechanical properties at room temperature [2]. It is widely used in life and is an indispensable substance in modern society [3]. According to the current PU production method, isocyanate (such as MDI or HDI) is the necessary polymerization initiator [4]. However, isocyanate is highly toxic and harmful to human health. The Bhopal incident has made isocyanate notorious and discolored; moreover, in the process of mass production of isocyanate [5], highly toxic light is also used Hydrogen chloride gas is the main reagent, and a large amount of corrosive hydrogen chloride gas by-products are produced, causing doubts in environmental safety and environmental protection. Therefore, in the past forty years, many studies have been devoted to the new non-phosgene/non-isohydrogenate (NPR/NIR) polyurethane-polyurea elastomer (Polyurethane-Polyurea Elastomer; PUaE) process, if this green chemical goal can Successful realization has more positive implications for the sustainable development of PUaE.

In the research on the synthesis of PU by the non-isocyanate method (NIR), the research of Mejere[6] et al. in 2005 and 2006 was the most prominent, which used di-tert-butyl tricarbonate (Di-tert-butyl tricarbonate; DTBTC) to replace iso Cyanate as a starting material, and then react with long-chain poly(tetrahydrofuran)-diamine (Poly(tertahydrofuran)-diamine) and short-chain diamine compounds, such as 1,2-ethylenediamine (1,2-ethylenediamine) Synthesis of polyurea can be carried out in chloroform solution at a reaction temperature of 20°C, and the reaction equation is shown in Figure 1. In this study, Mejere gave an example that the different elastomeric properties of PUaE products in thermal analysis and mechanical property analysis [7] can be adjusted by DTBTC and long-chain and short-chain diamine compounds at different molar ratios. This paper is in line with the ideal way of synthesis by NIR method, but DTBTC is expensive, not a cheap industrial raw material or reagent, and cannot be widely used in industrial mass production; and the molecular weight of the polymer synthesized by NIR method is not high (about 68,000g/mol) , so the selection of green polymer raw materials and polymer synthesis methods have room for improvement and in-depth research.

In 2011, C.E.Koning[8] and others used natural raw materials (such as 1,4-butanediamine (1,4-butanediamine, BDA)) and catalysts to synthesize intermediate diformic acid esters first, and then carry out polymerization reactions To synthesize polyurea, as shown in Figure 2, synthesize diformic acid esters with different chain segment lengths, and then continue to use dicarboxylic acid esters with different chain segment lengths as raw materials, dimethylacetamide (DMAc) or N-formaldehyde Base-pyrrolidone (NMP) as solvent, PPGda-400 with a molecular weight of 400 or PPGda-2000 with a molecular weight of 2000 It is a soft segment, reacting at 130°C for 4 to 24 hours to synthesize polyurea. However, the polymerization steps are cumbersome and the temperature is too high. Then the synthesized diurethane (Biscarbamate) and PPGda- Take the polyurea synthesized in 2000 as an example, the molecular weight is only 35,700g/mol, the elongation is about 42.4%, the tensile strength is 5.12MPa, and the physical properties are relatively poor. However, this document uses organic matter as a catalyst to replace the previous technology. Metal catalysts, and the use of C4 natural biomass materials as raw materials, also partly in line with the principles of green chemistry. Carry out transesterification during polymerization, and adjust the length of the hard chain segment, determine the properties of PU according to the length of the hard refining segment, It has contributed to the advancement of NIR methods, but the yield of PUaE obtained by the preparation method is generally low.

In the application of more practical carbonyl-containing raw materials, in 1979, Yamazaki [9] tried to use diphenyl carbonate (Diphenyl Carbonate; DPC) as the starting material and aromatic methylenedianiline (Methylenedianiline; MDA) Reactive polymerization into polyurea, as shown in Figure 3, shows that DPC has its advantages and possibilities in replacing phosgene, but the synthesis yield (80%) and viscosity of polyurea are all low (ηinh=0.23), so that The poor performance of polyurea and the lack of market competitiveness show that the activity and synthesis conditions of this transesterification are insufficient, and innovation and improvement of more optimal conditions are needed. The improvement of the synthesis route of diphenyl carbonate is the main axis of this research .

The applicant has devoted himself to the research of the non-phosgene method for many years, and has developed a strategy and chemical procedure for the preparation of isocyanate and polyurea by the non-phosgene/non-isocyanate method, as shown in FIG. 4 .

The applicant has pointed out in the literature published in 2012 [10] that diphenyl carbonate (DPC) is used as a starting material to react with aromatic diamine compounds, such as methylenedianiline (MDA) to synthesize the main The intermediate diphenyl aromatic diisocyanate is used to synthesize high-purity isocyanate and high-molecular-weight polyurea through thermal cracking or transesterification polymerization. In the study of polyurea synthesis, it was known that B. Thavonekham [11] in 1997 showed that dimethyl sulfoxide (DMSO) and sulfolane (TMS) were solvents with higher efficiency for transesterification reactions, but the DMSO and by-product phenols The boiling point (180°C) is close, and it is not easy to separate from the by-products after solvent recovery. Therefore, the applicant selects TMS (289°C) with a high boiling point as the solvent for transesterification polymerization [10]. , 7x10-3mmHg) is easily separated from phenol, so as to achieve the goal of green chemistry that the solvent and by-products can be separated, recovered and reused.

The present invention breaks through the previous research pattern, directly replaces the functional group of phosgene with diaryl carbonate, especially improves Yamazaki to directly carry out transesterification polymerization reaction with diaryl carbonate and diamine compound, successfully through solvent The improvement of the method and the assistance of vacuum distillation lead to the formation of PUaE with high molecular weight. The present invention also fully studies the effect of different aliphatic diamine, triamine or tetramine compounds and their feeding sequence on the structure and properties of the polymer, and unexpectedly finds that the polymer has excellent synthetic properties and a significant separation of soft and hard blocks. The key to the synthetic procedure of urea.

Contents of the invention

The invention provides a method for the continuous feeding of a one-pot method to synthesize high-molecular-weight polyurea products. The method directly utilizes diaryl carbonate and one or more aliphatic diamines and triamines in the presence of a suitable solvent. , Tetraamine compounds or mixtures thereof.

In order to be more in line with the goal of green chemistry, the present invention also provides a melt polymerization method, which produces polyurea without the presence of any organic solvent. The amine compound, the aliphatic triamine compound, the aliphatic tetramine compound or a mixture thereof undergoes a transurea reaction.

In order to expand the applicability of the product, the present invention further provides a method for manufacturing water-based polyurea, the method comprising obtaining the polyurea prepolymer by the above method, and then adding a compound selected from sodium sulfonic acid, 3-aminopropyl Triethoxysilane, or other amine-containing hydrophilic dispersants, such as dimethylolpropionic acid (DMPA)/triethylamine (TEA) ionic groups), to provide As a water-dispersible functional group, it can be combined with methyl ethylketone (MEK) or acetone (Acetone) to reduce the viscosity of the product solution, and successfully make the polyurea product water-based.

Every aspect and every embodiment of the invention disclosed herein is intended to be combined individually and in all possible aspects thereof with all other disclosed aspects and embodiments of the invention.

Description of drawings

Figure 1 shows the reaction formula of DTBTC reacting with diamine to form polyurea.

Figure 2 is the synthesis reaction formula of Biscarbamate with different chain lengths.

Figure 3 is the reaction formula of direct synthesis of polyurea by Yamazaki with DPC and MDA.

Fig. 4 is the manufacturing method of the non-phosgene polyurea of the present invention.

Figure 5 is a three-stage synthesis method for synthesizing polyurea elastomers using TMS as a solvent.

Figure 6 is a flow chart of water-based polyurea elastomer.

Fig. 7 is a graph showing the FT-IR transmittance-wave number variation of the synthetic polyurea elastomer.

detailed description

In this specification and claims, unless the context clearly dictates otherwise, the singular forms "a" and "the" include plural. The use of any and all examples, or exemplary language (eg, "such as") provided herein, is intended merely to better illuminate the invention and does not pose a limitation on the scope of the invention unless otherwise claimed. No language in the specification should be construed as indicating any non-claimed element as essential to the practice of the invention.

<Diaryl carbonate>

The diaryl carbonate used in the method of the present invention is a compound represented by the following formula (1):

Wherein R ¹ and R ² are each independently a C ₆ -C ₂₀ aryl group, and preferably a C ₆ -C ₁₂ aryl group. R1 and ^R2 can be unsubstituted or substituted with ^one or more aliphatic or aromatic substituents. In the case where the aryl group has two or more substituents, these substituents may be the same as or different from each other.

^The substituents of R and R are selected from C ¹ -C ₈ alkyl groups, such as methyl, ethyl, propyl and butyl; C ₃ -C ₁₂ cycloalkyl groups; C ₇ -C _{15 aralkyl} groups, such as Benzyl and phenethyl; C ₆ -C ₁₄ aryl, such as phenyl and tolyl; C ₁ -C ₁₂ alkoxy (ether), such as methoxy, ethoxy, propoxy, butyl Oxygen and trifluoromethoxy; C ₁ -C ₁₂ thioalkoxy, such as thiomethoxy and thioethoxy; C ₆ -C ₁₄ aryloxy, such as phenoxy; Halogen, such as fluorine, chlorine and bromine; nitro; hydroxyl; cyano; and dialkylamines such as dimethylamine.

^R and ^R can be, for example, phenyl, naphthyl, anthracenyl, tolyl, xylyl, ethylphenyl, propylphenyl, octylphenyl, nonylphenyl, dodecylphenyl , biphenyl, methoxyphenyl, chlorophenyl, dichlorophenyl, trichlorophenyl, pentachlorophenyl, bromophenyl, dibromophenyl, tribromophenyl, pentabromophenyl, nitro Phenyl, dinitrophenyl, hydroxyphenyl, cyanophenyl and dimethylaminophenyl, the above groups may be unsubstituted or substituted.

In addition, the above-mentioned aryl group includes its ortho, meta and para isomers, and the substituent attached to the aryl group includes normal, iso, second and third isomers.

Specifically, diaryl carbonates having unsubstituted aryl groups identical to each other may be selected from, but not limited to, diphenyl carbonate, di-1-naphthyl carbonate, di-2-naphthyl carbonate and bis-9-anthracenyl carbonate.

Diaryl carbonates having aryl groups identical to each other and each substituted with at least one alkyl group may be selected from, but not limited to, bis(2-tolyl)carbonate and bis[4-{tert-butyl}phenyl] Carbonate.

The diaryl carbonates having aryl groups identical to each other and each substituted with at least one aryl group may be, but not limited to, bis(4-biphenylphenyl)carbonate.

Diaryl carbonates having aryl groups identical to each other and each substituted with at least one alkoxy group may be selected from, but not limited to, bis(2-methoxyphenyl)carbonate and bis(3-butoxyphenyl) )Carbonate.

Diaryl carbonates having aryl groups identical to each other and each substituted by at least one halogen atom may be selected from, but not limited to, bis(2-chlorophenyl)carbonate, bis(2,4-dichlorophenyl)carbonate esters and bis(2,4,6-trichlorophenyl)carbonate.

Diaryl carbonates having aryl groups identical to each other and each substituted with at least one nitro group may be selected from, but not limited to, bis(2-nitrophenyl)carbonate and bis(2,4-dinitrophenyl) )Carbonate.

Diaryl carbonates having an unsubstituted aryl group and an aryl group substituted with at least one alkyl group may be selected from, but not limited to, 3-tolylphenyl carbonate and 4-tolylphenyl carbonate.

Diaryl carbonates having an unsubstituted aryl group and an aryl group substituted with at least one aralkyl group can be, but are not limited to, 4-benzylphenyl (phenyl) carbonate.

Diaryl carbonates having an unsubstituted aryl group and an aryl group substituted with at least one alkoxy group may be selected from, but not limited to, 4-methoxyphenylphenyl carbonate and 4-ethoxy-1 - Naphthylphenyl carbonate.

Diaryl carbonates having an unsubstituted aryl group and an aryl group substituted with at least one thioalkoxy group may be selected from, but are not limited to, 4-methylthiophenylphenyl carbonate.

Diaryl carbonates having an unsubstituted aryl group and an aryl group substituted with at least one aryloxy group can be, but are not limited to, 4-phenoxyphenylphenyl carbonate.

Diaryl carbonates having an unsubstituted aryl group and an aryl group substituted with at least one halogen atom may be selected from, but not limited to, 2-chlorophenylphenyl carbonate and 4-chlorophenylphenyl carbonate.

Diaryl carbonates having an unsubstituted aryl group and an aryl group substituted with at least one hydroxy group may be selected from, but not limited to, 3-hydroxyphenylphenyl carbonate and 4-hydroxyphenylphenyl carbonate.

Other diaryl carbonates suitable for use in the process of the invention include, for example, 4-methoxyphenyl-4'-nitrophenyl carbonate, 4-cyanophenyl-4'-nitrophenyl carbonate, 4 -thiomethoxyphenyl-4'-nitrophenyl carbonate, 2-chlorophenyl-4'-nitrophenyl carbonate, 2-dimethylaminophenylphenyl carbonate, 2- Bromo-4-cyano-6-nitrophenyl phenyl carbonate, and pentabromophenyl-2',4',6'-tribromophenyl carbonate.

Among the above-mentioned diaryl carbonates, diphenyl carbonate, bis(2-tolyl)carbonate, bis(4-chlorophenyl)carbonate, bis(4-nitrophenyl)carbonate and Bis(3,5-dimethoxyphenyl)carbonate, and diphenylcarbonate is more preferably used.

The aliphatic diamine compound suitable for preparing the aliphatic urethane dicarboxylate and polyurea of the present invention is selected from the group consisting of aliphatic C ₁ -C ₆ alkyl diamine, aromatic C ₁ -C ₆ alkyl diamine, The group consisting of aliphatic polyetherdiamines having a molecular weight of 400 to 3000, aromatic polyetherdiamines having a molecular weight of 400 to 3000, xylenediamines and combinations thereof, which include etherdiamines such as 1,8- Diamino-3,6-dioxaoctane; long-chain polyether diamines, such as polyethoxylated or polypropoxylated diamines (D-2000); aliphatic diamines, such as 1,6- Hexamethylenediamine (1,6-HDA); cyclic aliphatic diamines such as isophoronediamine (IPDA) or hydrogenated MDA (H ₁₂ MDA).

The aliphatic triamine compound suitable for preparing the aliphatic urethane trimcarboxylate and polyurea of the present invention is selected from the group consisting of aliphatic C ₁ -C ₆ alkyl triamines, aromatic C ₁ -C ₆ alkyl triamines, molecular weight A group consisting of aliphatic polyether triamines with a molecular weight of 400 to 3000, aromatic polyether triamines with a molecular weight of 400 to 3000, and combinations thereof.

The aliphatic tetramine compound suitable for preparing the aliphatic aminotetracarboxylates and polyureas of the present invention is selected from the group consisting of aliphatic C ₁ -C ₆ alkyl tetramines, aromatic C ₁ -C ₆ alkyl tetramines, A group consisting of aliphatic polyether tetramines with a molecular weight of 400 to 3000, aromatic polyether tetramines with a molecular weight of 400 to 3000, and combinations thereof.

<Manufacturing polyurea>

According to the present invention, polyurea can be directly prepared by a one-pot method from diaryl carbonate and aliphatic diamine compound, aliphatic triamine compound or aliphatic tetramine compound or a mixture thereof. In the presence of a polar solvent, or in the state of molten diaryl carbonate, the reaction intermediate aliphatic amino dicarboxylate, aliphatic amino polycarboxylate and aliphatic amine obtained by the above method The reaction of aliphatic amino polycarboxylates such as aliphatic tetracarboxylates with aliphatic diamine compounds, aliphatic triamine compounds or aliphatic tetramine compounds or mixtures thereof to produce the final product polyurea.

When diaryl carbonate is reacted with aliphatic diamine compound, the resulting polyurea is a thermoplastic polymer; when diaryl carbonate is reacted with aliphatic triamine compound or aliphatic tetraamine compound When the amine compounds are reacted, the resulting end product is a thermoset polymer. Of course, react with the mixture of diaryl carbonate and aliphatic diamine compound and aliphatic triamine compound and/or aliphatic tetramine compound, and wherein aliphatic triamine compound and/or aliphatic tetramine compound account for When the proportion is about 2 to 5% by weight of the total aliphatic di/polyamine compound, the crosslinking situation is not obvious, and only changes the physical properties of the final product, but does not change its substantially thermoplastic polymer properties; and when the aliphatic When the proportion of the triamine compound and/or the aliphatic tetraamine compound exceeds 10%-50% by weight of the total aliphatic di/polyamine compound, the crosslinking becomes obvious, and the final product is a thermosetting polymer.

Preferred polar solvents suitable for use in the transureaization process for making polyureas according to the present invention include dimethylacetamide (DMAc), N-methyl-pyrrolidone (NMP), dimethylsulfoxide (DMSO) or sulfolane ( TMS; boiling point = 289° C.); preferably DMSO or TMS is used; more preferably TMS.

TMS (boiling point = 289°C) has the best utility in this process because the transureidation polymerization reaction can be performed at higher temperature (140°C) while applying reduced pressure to the reaction mixture. Furthermore, it was found that the removal of phenol from the mixture was extremely beneficial in accelerating the rate of polymerization, resulting in the formation of high molecular weight polymers in a short period of time. For example, aromatic diamines (such as MDA) and cyclic diamines (such as H ₁₂ MDA) that cannot produce polyurea elastomeric films in DMSO due to insufficient macromolecular polymerization at 80° C., by the method of the present invention using TMS as solvent, It can improve the polyurea membrane to be synthesized.

The reaction temperature is generally in the range of about 20°C to about 200°C, preferably in the range of about 20°C to about 160°C, and more preferably in the range of about 20°C to about 100°C. The reaction pressure may be reduced pressure, normal pressure or high pressure, wherein normal pressure is preferred.

There is no particular limitation on the reaction time. The reaction time is generally 0.001 hour to 100 hours, preferably 0.005 hour to 50 hours, and more preferably 0.1 hour to 10 hours.

Having generally described this invention, a further understanding can be obtained by reference to certain specific examples which are provided herein for purposes of illustration only and are not intended to be limiting unless otherwise specified.

Example

Example 1

Using TMS as solvent to synthesize polyurea elastomer, the proportion of hard segment is 30%

Add diphenyl carbonate (17.14g, 0.08mole) and about half equivalent of HDA (4.65g, 0.04mole) into a three-neck reaction flask first, use TMS (186g, solid content 20%) as solvent, and use mechanical stirring Make it mix evenly, react at room temperature for 1 hour, first form a compound similar to diphenyl isocyanate, and then add polypropylene glycol bis (2-aminopropyl ether) Long-chain polyetherdiamine (26g, 0.013mole), heat up to 90°C for 1 hour, and finally add IPDA (4.6g, 0.027mole), let it react at the same temperature for 1 to 2 hours, and it can be tested in FT-IR Observing that the characteristic peak 1781cm ^-1 disappears completely and then generates the characteristic peak at 1640cm ^-1 (as shown in Figure 7), and then the reaction temperature is slowly raised to 140°C under reduced pressure distillation for about 1 to 2 hours while distilling out the transesterification Generated phenol until there is no distillate (the mixture of phenol and TMS), to promote the completion of transesterification. After the distillation reaction step finishes, the product is poured into ultrapure water to precipitate, after suction filtration, the filtrate is reduced Concentrate under pressure, recover the solvent TMS, and dry the solid product (SPUaE) in a vacuum oven at 120°C for 6 to 12 hours to remove the solvent, as shown in Figure 5, then dissolve the product (SPUaE) in NMP, and then Pour it into a Teflon dish, and circulate the oven at 60°C for 2 to 3 days to form a film, and perform TGA, DSC, GPC, intrinsic viscosity and mechanical properties tests, as shown in Table 1.

Table 1 - Comparison of properties of polyurea polymers synthesized by non-isocyanate three-step method

Example 2

Synthesis of Polyurea Elastomer by Melt Method

The same procedure, reagent amounts, and analysis as in Example 1 were performed, except that no solvent (TMS) was added and the starting diphenyl carbonate was a molten fluid at about 90°C. The properties of the products obtained are compared as shown in Table 2. It can be seen from the data in Table 2 that the product obtained in the solvent-free state has excellent thermal stability and mechanical properties.

Table 2 - Comparison of properties of polyurea polymers synthesized by non-isocyanate three-step method in a solvent-free environment

Example 3

Synthesis of Waterborne Polyurea Using Sodium Sulfonate (ESA) as Surfactant

Carry out the same program and analysis as in Example 1, except that the prepolymer is synthesized by melt method and uses sulfonic acid sodium salt to replace part of the chain extender. Polyurea turned water-based. It can be seen from Table 3 that when the sulfur content of the sodium sulfonate salt accounts for 0.6% by weight of the total product, the water-based polyurea product has better mechanical and thermal properties, as shown in Table 3.

Table 3 - Comparison of various properties of water-based polyurea elastomers using sodium sulfonate (ESA) as a surfactant

Example 4

Synthesis of Waterborne Polyurea Using 3-Aminopropyltriethoxysilane (APTES) as Surfactant

The same procedure and analysis as in Example 1 were carried out, except that the prepolymer was synthesized by the melt method and 3-aminopropyltriethoxysilane was used to replace part of the chain extender. It can be found from Table 4 that the particle size of the product can be successfully reduced by using the sol-gel method. Among them, the solution-gel method can make the silane group at the end of the polyurea enter into the water, first undergo a hydrolysis reaction to form a silanol group, and then condense to form a siloxane after removing the water.

Table 4 - Comparison of properties of water-based polyurea elastomers with APTES as surfactant

According to the present invention, a novel simplified polyurea synthesis method by completely omitting the step of producing isocyanate from diurethane is a feasible economical and efficient green chemical synthesis method, which does not use toxic isocyanate and metal catalysts, and Can be widely used.

Those skilled in the art of the present invention should understand that the concepts and specific embodiments disclosed above can be easily used to modify or design other structures or processes to achieve the same purpose as the present invention. Those with ordinary knowledge in the technical field of the present invention should also understand that such equivalent constructions cannot depart from the spirit and scope of the present invention defined by the appended claims.

references:

[1] Xu Wujun, Introduction to Polymer Materials, Wunan Book Publishing Co., Ltd. (2004).

[2] Huang W.B., Xiang, J.Y., Lv P.and Li X.M., "Study on Mechanical Properties Aging of Spray Pure Polyurea for Hydraulic Concrete Protection", Advanced Materials Research, 374-377, pp.1325-1329(2011).

[3] Microwave Huang, Spray Polyurea Elastomer Technology, Chemical Industry Press (2005).

[4] Randall, D. and Lee, S., The Polyurethanes Book, John Wiley: New York (2000)

[5] Zhang Fengzhi, Handbook of Applied Polymers, Wunan Books (2003)

[6] Versteegen, Ron M., Sijbesma, Rint P., Meijer, E.W., Macromolecules, 38(8), pp.3176-3184(2005).

[7] Versteegen, Ron M.; Sijbesma, Rint P.; Meijer, E.W., Macromolecules, 39(2), pp.772-783(2006).

[8] Tang, D., Mulder, D.J., Noordover, B.A.J., Koning, C.E., "Well-defined Biobased Segmented Polyureas Synthesis via a TBD-catalyzed Isocyanate-free Route", Macromol. Rapid Commun., 32, pp.1379- 1385(2011).

[9]Yamazaki, N. and Iguchi, T., "The reaction of diphenyl carbonate withamines and its application to polymer synthesis", Polymer Science: Polymer Chemistry Edition., 17, pp.835-841(1979).

[10] Chen, H.Y., Pan, W.C., Lin, C.H., Huang, C.Y. and Dai, S.A., Journal of Polymer Research, 19(2), pp.9754-9765(2012).

[11] Thavonekham, B., "A Practical Synthesis of Ureas from PhenylCarbamates", Synthesis, pp.1189-1194(1997).

Claims (19)

1. A method of making polyurea comprising: Diaryl carbonates are provided having the formula; Wherein R ¹ and R ² are each independently C ₆ -C ₂₀ aryl; R ¹ and R ² can be unsubstituted or substituted by one or more of the same or different following substituents: C ₁ -C ₈ alkyl , C ₃ -C ₁₂ cycloalkyl, C ₇ -C ₁₅ aralkyl, C ₆ -C ₁₄ aryl, C ₁ -C ₁₂ alkoxy, C ₁ -C ₁₂ sulfur alkoxy, C ₆ -C ₁₄ aryloxy, halogen, nitro, hydroxyl, cyano and dialkylamino; providing an amine compound selected from the group consisting of aliphatic diamine compounds, aliphatic triamine compounds, aliphatic tetramine compounds, and mixtures thereof; making the diaryl carbonate and the amine compound exist in a solvent under the reaction; Polyurea is obtained by transurea reaction. 2. The method of claim 1, wherein said diaryl carbonate is selected from the group consisting of diphenyl carbonate, bis(2-tolyl)carbonate, bis(4-chlorophenyl) Carbonates and bis(3,5-dimethoxyphenyl)carbonate and mixtures thereof. 3. The method of claim 2, wherein the diaryl carbonate is diphenyl carbonate. 4. The method according to any one of claims 1 to 3, wherein the aliphatic diamine compound is selected from the group consisting of ether diamines, long chain polyether diamines, aliphatic diamines, cyclic aliphatic diamines, xylylenediamine, and combinations thereof. 5. The method according to any one of claims 1 to 3, wherein the aliphatic triamine compound is selected from the group consisting of: aliphatic C ₁ -C ₆ alkyl triamines, aromatic C ₁ - C ₆ alkyl triamines, aliphatic polyether triamines with a molecular weight of 400 to 3000, aromatic polyether triamines with a molecular weight of 400 to 3000, and combinations thereof. 6. The method according to any one of claims 1 to 3, wherein the aliphatic tetramine compound is selected from the group consisting of: aliphatic C ₁ -C ₆ alkyltetramines, aromatic C ₁ - C ₆ alkyl tetramines, aliphatic polyether tetramines with a molecular weight of 400 to 3000, aromatic polyether tetramines with a molecular weight of 400 to 3000, and combinations thereof. 7. The method according to any one of claims 1 to 3, wherein the reaction is carried out at a temperature of 20°C to 200°C. 8. The method of claim 7, wherein the reaction is carried out at a temperature of 20°C to 160°C. 9. The method of claim 7, wherein the reaction is carried out at a temperature of 20°C to 100°C. 10. The method according to any one of claims 1 to 3, wherein the solvent is selected from the group consisting of dimethylacetamide (DMAc), N-methyl-pyrrolidone (NMP), dimethylsulfoxide (DMSO) and The group consisting of sulfolane (TMS). 11. A method of making polyurea comprising: A molten diaryl carbonate is provided having the formula; Wherein R ¹ and R ² are C ₆ -C ₂₀ aryl; R ¹ and R ² can be unsubstituted or substituted by one or more of the same or different following substituents: C ₁ -C ₈ alkyl, C ₃ -C ₁₂ cycloalkyl, C ₇ -C ₁₅ aralkyl, C ₆ -C ₁₄ aryl, C ₁ -C ₁₂ alkoxy, C ₁ -C ₁₂ thioalkoxy, C ₆ -C ₁₄ aryloxy group, halogen, nitro, hydroxyl, cyano and dialkylamine; providing an amine compound selected from the group consisting of aliphatic diamines, aliphatic triamine compounds, aliphatic tetramine compounds, and mixtures thereof; The molten diaryl carbonate is subjected to a transurea reaction with the amine compound. 12. A method of manufacturing waterborne polyurea, comprising Adding a surfactant selected from the group consisting of sulfonic acid sodium salt and 3-aminopropyltriethoxysilane into the polyurea obtained in any one of claims 1 to 11; and Addition of ketone completes the reaction. 13. The method of claim 12, wherein the surfactant is sodium sulfonate. 14. The method of claim 13, wherein the sulfur content is 0.2-1.0% by weight based on the weight of the whole product. 15. The method of claim 14, wherein the sulfur content is 0.6% by weight based on the weight of the total product. 16. A method for producing aliphatic urethane dicarboxylates, comprising: Diaryl carbonates are provided having the formula; Wherein R ¹ and R ² are each independently C ₆ -C ₂₀ aryl; R ¹ and R ² can be unsubstituted or substituted by one or more of the same or different following substituents: C ₁ -C ₈ alkyl , C ₃ -C ₁₂ cycloalkyl, C ₇ -C ₁₅ aralkyl, C ₆ -C ₁₄ aryl, C ₁ -C ₁₂ alkoxy, C ₁ -C ₁₂ sulfur alkoxy, C ₆ -C ₁₄ aryloxy, halogen, nitro, hydroxyl, cyano and dialkylamino; An aliphatic diamine compound is provided, wherein the aliphatic diamine compound is selected from the group consisting of ether diamine, long chain polyether diamine, aliphatic diamine, cyclic aliphatic diamine, xylene Diamines, and combinations thereof; where reacting the diaryl carbonate in a molten state with the amine compound to synthesize an aliphatic amino dicarboxylate; or reacting the diaryl carbonate and the amine compound in the presence of a solvent , to synthesize aliphatic urethane dicarboxylates. 17. The method of claim 16, wherein the solvent is selected from the group consisting of dimethylacetamide (DMAc), N-methyl-pyrrolidone (NMP), dimethyl sulfoxide (DMSO) and sulfolane (TMS). composed of groups. 18. A method of making an aliphatic urethane polycarbamate, comprising: Diaryl carbonates are provided having the formula; Wherein R ¹ and R ² are each independently C ₆ -C ₂₀ aryl; R ¹ and R ² can be unsubstituted or substituted by one or more of the same or different following substituents: C ₁ -C ₈ alkyl , C ₃ -C ₁₂ cycloalkyl, C ₇ -C ₁₅ aralkyl, C ₆ -C ₁₄ aryl, C ₁ -C ₁₂ alkoxy, C ₁ -C ₁₂ sulfur alkoxy, C ₆ -C ₁₄ aryloxy, halogen, nitro, hydroxyl, cyano and dialkylamino; Aliphatic triamine compounds and/or tetramine compounds are provided, wherein the compounds are selected from the group consisting of: aliphatic C ₁ -C ₆ alkyl triamines, aromatic C ₁ -C ₆ alkyl triamines , Aliphatic polyether triamines with a molecular weight of 400 to 3000, aromatic polyether triamines with a molecular weight of 400 to 3000, aliphatic C ₁ -C ₆ alkyl tetramines, aromatic C ₁ -C ₆ alkyl tetramines , aliphatic polyether tetramines with a molecular weight of 400 to 3000, aromatic polyether tetramines with a molecular weight of 400 to 3000, and combinations thereof; wherein reacting the diaryl carbonate in a molten state with the amine compound to synthesize an aliphatic amino dicarboxylate; or reacting the diaryl carbonate and the amine compound in the presence of a solvent , to synthesize aliphatic urethane dicarboxylates. 19. The method of claim 18, wherein the solvent is selected from the group consisting of dimethylacetamide (DMAc), N-methyl-pyrrolidone (NMP), dimethyl sulfoxide (DMSO) and sulfolane (TMS). composed of groups.