MULTIFUNCTIONAL SYNERGISTIC MACROMOLECULAR ANTI-OXIDATION STABILIZER AND PREPARATION METHOD AND USE THEREOF

Abstract

Disclosed is an anti-oxidation stabilizer, which has the following structure (A), wherein R1 is a connection chain, and the connection chain is a fatty chain, an aromatic structural chain or a fatty and aromatic structurally combined chain; R2 is (B), and X is O, S, N or NH or —CONR—, Z is O, S, N or NH, and X is different from Z; R is a fatty chain, an aromatic group, a sterically hindered amine or sterically hindered phenol, R3 is a fatty chain, an aromatic group, a sterically hindered amine or sterically hindered phenol, and R is identical to R3, or R is different from R3; n is a positive integer including 1, n1 is a positive integer including 1, and n is identical to n1, or n is different from n1.

Claims

1. A multifunctional synergistic macromolecular anti-oxidation stabilizer, which is characterized by the following formula: ##STR00019## wherein R1 is a connection chain which is a fatty chain, an aromatic structural chain or a fatty and aromatic structurally combined chain; R2 is ##STR00020## X is O, S, N or NH, or —CONR—, Z is O, S, N or NH, and X is different from Z; R is a fatty chain, an aromatic group, a sterically hindered amine or a sterically hindered phenol, R3 is a fatty chain, an aromatic group, a sterically hindered amine or a sterically hindered phenol, R is identical to R3, or R is different from R3; n is a positive integer including 1, n1 is a positive integer including 1, n is identical to n1, or n is different from n1.

2. The multifunctional synergistic macromolecular anti-oxidation stabilizer as claimed in claim 1, wherein the multifunctional synergistic macromolecular anti-oxidation stabilizer is: ##STR00021## the R3 is H, an aliphatic side chain, an aromatic side chain, a mixed aromatic/aliphatic side chain, or a side chain having heteroatoms; n is a positive integer.

3. The multifunctional synergistic macromolecular anti-oxidation stabilizer as claimed in claim 2, wherein the multifunctional synergistic macromolecular anti-oxidation stabilizer is: ##STR00022## ##STR00023##

4. A method for preparing the multifunctional synergistic macromolecular anti-oxidation stabilizer as claimed in claim 2, which is characterized by comprising steps of: n is an integer which is ≧1 adding 1 equivalent of alcoholic raw material to a solvent which is anhydrous THF, DMF, acetone, ethyl acetate, toluene, MTBE, DME or acetonitrile that contains 1.5-3 equivalents of NaH or t-BuONa or t-BuOK under nitrogen protection, stirring for 10-30 minutes to 1 hour at room temperature, adding dropwise 1.0 to 2.5 equivalents of iodides, bromides or chlorides with 10% NaI or KI, or activated alcohols, stirring the mixtures at room temperature for 30 minutes to 1 hour, monitoring the reaction by TLC, heating to 40-90° C., until the reaction is complete; quenching saturated NH.sub.4Cl aqueous solution, adding ethyl acetate or dichloromethane or petroleum ether or toluene or MTBE or DME and fully mixing, separating organic phases, extracting aqueous phase three times, drying the combined organic phase with Na.sub.2OS.sub.4, filtering, removing the organic solvent in vacuum; obtaining solid product by recrystallization and oil or liquid product by purification through extraction or silica gel column chromatography; or adding 1 equivalent of alcoholic raw material to a solvent which is THF, acetone, ethyl acetate or acetonitrile, dichloromethane, chloroform, toluene, DME, MTBE, chlorobebzene or DMF that contains 1-3 equivalents of NaOH or KOH or Bu4OH and 10-20% tetrabutylammonium bromide under nitrogen protection, stirring for 5-30 minutes at room temperature, adding dropwise 1.0-3.0 equivalents of iodides, bromides or chlorides with 5-30% NaI or KI, or activated alcohols, stirring the mixtures at room temperature for 1-3 hours, heating to 40-100° C. and reacting for 1-25 hours , monitoring the reaction by TLC until the reaction is complete, obtaining solid product by recrystallization, and oil or liquid product by purification through extraction; or adding dropwise 1 equivalent of thiol to a solution which is dried THF, to DCM, acetone, THF, DME, acetonitrile or ethyl alcohol, methyl alcohol, chloroform, toluene or DMF that contains 1.0-3.5 equivalents of iodides, bromides or chlorides with 5-30% NaI or KI, or activated alcohols, then adding Na.sub.2CO.sub.3 or K.sub.2CO.sub.3, NaOH, KOH, Bu4OH or NEt3 or DMAP or DBU or DIPEA or pyridine, stirring the mixtures at room temperature for 30 minutes, and then heating to 40-90° C. and stirring for 5-12 hours, monitoring the reaction by TLC until the reaction is complete; adding NaCl saturated aqueous solution and an equal amount of ethyl acetate or dichloromethane to the reaction system, fully mixing, separating organic phases, washing aqueous phase three times with the same organic solvent, drying the combined organic phases with Na2OS4, filtering, removing the organic solvent in vacuum; obtaining solid product by recrystallization, and obtaining liquid or oil product by extraction or silica gel column chromatography; or dissolving 1 equivalent of amine in a solvent which is dichloromethane, ethyl acetate, acetone, acetonitrile, THF, ethanol, methanol, chloroform, MTBE, DME, toluene or DMF, stirring under nitrogen and adding dropwise 1-3 equivalents of organic iodides, organic bromides or organic chlorides, or activated alcohol compounds to the same organic solvent containing1-3 equivalents of NaOH or KOH or Bu.sub.4OH or K.sub.2CO.sub.3 or Na.sub.2CO.sub.3 or DIPEA or NEt.sub.3 or pyridine, adding 5-30% butyltin bromide at the time of the addition of the inorganic base, reacting for 1-3 hours at room temperature, heating to 40 to 90° C. and stirring for additional 1-25 hours; cooling, washing alkaline and water-soluble impurities with the aqueous solution of NH.sub.4Cl, obtaining solid product in organic phases by recrystallization, and oil or liquid product by purification through extraction or silica gel column chromatography; or dissolving or suspending 1 equivalent of amine and 1 equivalent of base in a solvent which is anhydrous dichloromethane, THF, MTBE, DME, acetone, cyano cyanide, chloroform, toluene or DMF, adding dropwise a solution of 1-2 equivalents of carboxyl chloride in the same dry solvent at 0-10° C. under nitrogen protection. stirring the mixture at 0-10° C. for 30 minutes to 2 hours at room temperature, monitoring the reaction by TLC until the reaction is complete; adding dichloromethane, ethyl acetate, toluene, DME or MTBE and 0.1N iced hydrochloric acid solution, mixing and then isolating organic phases, washing aqueous phase with the same organic solvent twice, drying the combined organic phases with anhydrous Na.sub.2SO.sub.4, filtering, concentrating; obtaining solid product in organic phase by recrystallization, and obtaining oil or liquid product by silica gel column chromatography or extraction; or controlling the average molecular weight of the macromolecular products ranging from 1000 to 5000 daltons by adjusting the number of n dissolving 1 equivalent of diamine, polyamine in dry dichloromethane, ethyl acetate, THF, acetone, acetonitrile, ethanol, methanol, chloroform, toluene or DMF (1:5-15, w/v), and then stirring and adding dropwise polyiodinated, polybrominated or polychlorinated organic raw materials under nitrogen protection, stirring for 30 minutes at room temperature, and then heating to 40-100° C. and reacting for 6-72 hours, controlling the average molecular weight of the macromolecular product with reaction temperature and time, filtering to produce solid powder product, obtaining solid product by washing 3 times with dichloromethane to, or obtaining oil product sticky oil product by extraction.

5. The method for preparing multifunctional synergistic macromolecular anti-oxidation stabilizer as claimed in claim 4, comprising reaction scheme as following: ##STR00024##

6. A use of the multifunctional synergistic macromolecular anti-oxidation stabilizer as claimed in any claim of claim 1-3 as an antioxidant.

7. The use of the multifunctional synergistic macromolecular anti-oxidation stabilizers as claimed in claim 6 in plastics, rubbers, petroleum, coatings, fiber products or paintings.

Description

DETAILED DESCRIPTION OF EMBODIMENTS

[0036] The present invention will now be described in further detail with reference to specific embodiments, but the scope of the present invention is not limited thereto.

Example 1

1. Formula

[0037] ##STR00007##

2. Synthetic Routes:

[0038] ##STR00008##

3. Step 1 of the synthesis of 4-bromomethyl-2,6-di-tert-butyl phenol (Intermediate 1):
5 g of 2,6-di-tert-butyl-p-cresol (22.69 mmol) was dissolved in a solvent such as CC14 or CHC1.sub.3 or dichloromethane or THF or toluene or DMF (20-50 ml). A solution of liquid bromine (1.2-1.5 mmol) was added dropwise to the solvent above (15-50 ml) under nitrogen protection and UV lamp (350 watts of mercury lamp) irradiation. The rate of dropwise adding varied depending on the reaction rate. The reaction was monitored by TLC. Oily product was obtained by stirring for 5-20 minutes after the end of the titration and removing the organic solvent in vacuum, which was used directly in the next step.
4. Step 2 of the synthesis of of 4-bromomethyl-2,6-di-tert-butyl phenol (Intermediate 1):

[0039] 5.0 g of 2,6-di-tert-butyl-p-cresol (22.69 mmol) was dissolved in a solvent such as CCl.sub.4 or CHCl.sub.3 or THF or chlorobenzene (25-50 ml), and added dropwise to a solution of 4.1 g of NBS (22.90 mmol) containing 3-10% benzoyl peroxide of the same solvent (20-60 ml). The mixture was refluxed for 2-5 hours and cooled to room temperature. The solid suspension was filtered off. Light brown liquid is obtained by removing the organic solvent in vacuum, which was used directly in the next step.

5. Preparation of Target Product 1:

[0040] 2 g of pentaerythritol (1.98 mmol), potassium hydroxide or sodium hydroxide (11.89 mmol) and tetrabutylammonium bromide (0.5 mmol) were dissolved in 20 ml of THF or acetonitrile or acetone or DMF. The mixture was stirred at room temperature for 1 hour and heated to 50-70° C. for 30 minutes to 2 hours, and cooled to room temperature. 3.49 g of 2,6-di-tert-butyl-4-bromomethylbenzene (15.45 mmol) under nitrogen. The mixture was refluxed for 18 hours and the reaction was monitored by TLC until the starting material of pentaerythritol disappeared and had a major product point formed. 0.1N iced hydrochloric acid solution and the same volume of dichloromethane or ethyl acetate was added. Organic phase was separated after fully mixing. Aqueous phase was washed with the same solvent. The organic phase was dried with anhydrous Na.sub.2SO.sub.4. Target Product 1 was obtained by filtering, removing organic solvent in vacuum and purification through silica gel column chromatography, 83.7% yield.

.sup.1H NMR (400 MHz, CHCl.sub.3), δ(ppm): 7.26 (s, CHCl.sub.3 in CDCl.sub.3), 7.15 (s, 2H, 2CH), 7.00 (s, 2H, 2CH), 6.92(s, 2H, 2CH), 6.87 (s, 2H, 2CH), 6.66 (s, 4H, 2CH.sub.2), 5.62 (s, 4H), 3.17 (s, 4H, 2CH.sub.2), 2.29 (s, 4H, 2CH.sub.2), 2.26 (s, 4H, 2CH.sub.2), 1.22-1.43(m, 72H, 24CH.sub.3).

Example 2

1. Formula:

[0041] ##STR00009##

2. Synthetic Routes:

[0042] ##STR00010##

3. Predation of Intermediate 1

[0043] 6.1 g of thiol (42.30 mmol) was added dropwise in a solution such as THF or acetone or acetonitrile or dichloromethane or ethanol containing 2,2-dichloroethylamine (21.12 mmol) and 10-50% KI (1:5-20, w/v). The mixture was heated to 40-90° C. , reacted for 3-9 hours. The reaction was monitored by TLC until the reaction was completed. The organic solvent was removed in vacuum.

[0044] NaCl aqueous solution and dichloromethane or ethyl acetate were added, to fully mixed, the organic phases were separated the same volume of dichloromethane or ethyl acetate was added and fully mixed. The organic phase was separated, and the aqueous phase was extracted twice. The organic phase was dried with Na.sub.2SO.sub.4. Intermediate 1 was obtained by filtering and concentrating, which was used directly in the next step

4. Preparation of Intermediate 2

[0045] 5.93 g of 3-(3,5-di-tert-butyl-4-hydroxybenzene) propionic acid (21.30 mmol) was dissolved in dry THF or dichloromethane or ethyl acetate or MTBE or acetone (1:5-20, w/v). After cooling to 0-10° C., 1.82 ml of oxalyl chloride (21.50 mmol) and 0.5 ml of dropping DMF were added dropwise under nitrogen, and the mixture was stirred for 30 minutes. The temperature was raised to room temperature and the mixture was stirred for 2-7 hours. The reaction was monitored by TLC until the reaction was complete. The organic solvent and excess oxalyl chloride were removed in vacuum and the remaining Intermediate 2 was used directly in the next step.

3. Preparation of Target Product 1:

[0046] Intermediate 1 (21.12 mmol) and Intermediate 2 (21.30 mmol) were dissolved in dry organic solvents such as acetone or THF or ethyl acetate or ethyl cyanide or toluene or methylene chloride, cooled to 0-10° C. Ethylamine (21.30 mmol) was added dropwise and the mixture was stirred at 0-10° C. for 1 hour and then at room temperature for 3-7 hours. The reaction was monitored by TLC until the reaction was complete. 0.1N of iced hydrochloric acid aqueous solution and the same volume of dichloromethane or ethyl acetate were added to the reaction system. The organic phase was separated and the organic phase was washed twice with 0.1N iced hydrochloric acid aqueous solution and twice with saturated NaCl solution, and dried with anhydrous Na.sub.2SO.sub.4. 9.87 g of Target Product 1 was obtained by filtering, removing organic solvent in vacuum, and purification through silica gel column chromatography, 75.1% yield.

.sup.1H NMR (400 MHz, CDCl.sub.3), δ(ppm): 7.25 (s, CHCl.sub.3, from CDCl.sub.3), 6.97 (s, 2H, 2CH), 2.76-2.99 (m, 8H, 4CH.sub.2), 1.52-1.59 (m, 4H, 2CH.sub.2), 1.43 (s, 18H, 2Bu.sup.t), 1.26-1.43 (m, 24H, 12CH.sub.2), 0.88 (t,6H,.sup.3J.sub.HH=7.20, 2CH.sub.3).

Example 3

1. Formula

[0047] ##STR00011##

2. Synthetic Route:

[0048] ##STR00012##

3. Step 1 of the synthesis of 2,2,6,6-di-tert-butyl-4-bromomethylphenol (Intermediate 1):

[0049] 5 g of 2,2,6,6-di-tert-butyl-p-cresol (27.11 mmol) was dissolved in a solvent such as CCl.sub.4 or CHCl.sub.3 or CH.sub.2Cl.sub.2 or THF or chlorobenzene or toluene or dibromoethane (1:5-20, w/v). A solution of bromine (28.01-37.57 mmol) in the same volume of solvent was added dropwise with 350 watts of mercury lamp under nitrogen protection. The reaction was monitored by TLC. After completion of the dropwise addition, the mixture was stirred for 5 to 40 minutes and the organic solvent was removed in vacuum to give a pale reddish brown oil which was used directly in the next reaction, 95-100% yield.

4. Step 2 of the synthesis of 2,2,6,6-di-tert-butyl-4-bromomethyl phenol (Intermediate 1):

[0050] 5 g of 2,2,6,6-di-tert-butyl-p-cresol (27.11 mmol) was dissolved in CCl.sub.4 or CHCl.sub.3 or CH.sub.2Cl.sub.2 or THF or chlorobenzene or toluene or dibromoethane solvent (1:5-20, w/v), 3-10% benzoyl peroxide was added, heated to reflux, and 6.3 g of NBS (35.25 mmol) was added dropwise into the solution with the same volume and the same solvent, and refluxed for 2-5 hours after dropwise addition. The mixture was cooled to room temperature, filtered to a suspended solid, and the filtrate was concentrated in vacuum to give a pale red oil which was used directly in the next step, 90-95% yield.

5. Step of the synthesis of 2,2,6,6-di-tert-butyl-4-aminomethylphenol (Intermediate 2)

[0051] 3 grams of 2,2,6,6-di-tert-butyl-4-bromomethylphenol was dissolved in THF or acetone or ethanol or methanol and other solvents, ammonia or ammonia air was added and reacted for 2-6 hours at room temperature. The reaction was monitored by TLC until benzyl bromide disappeared.

[0052] Dichloromethane or petroleum ether or ethyl acetate or toluene or MTBE was added to extract the benzylamine product into the organic phase (10 ml×3). The combined organic phases were dried with anhydrous Na.sub.2SO.sub.4 and filtered. The filtrate was removed in vacuum to remove the organic solvent. A pale yellow waxy solid was obtained which was used directly in the next step, 81-93% yield.

6. Preparation of Target Product 1:

[0053] 1 g of cyanuric chloride (5.42 mmol) was dissolved in anhydrous dichloromethane or THF or MTBE or ethyl acetate or ethanol or a solvent such as acetone or DMF (1: 5-20, w/v). 5.75 g of Na.sub.2CO.sub.3 (5.42 mmol) and the above-prepared crude benzylamine (21.68 mmol) were added under nitrogen protection. The mixture was stirred at room temperature for 1 hour, heated to 40-80° C. for 2-18 hours, and the reaction was monitored by TLC until the reaction was completed. The NaCl aqueous solution was added, the organic phase was extracted with dichloromethane or ethyl acetate (10 ml×3) and dried with anhydrous Na.sub.2SO.sub.3. The organic phase was filtered, concentrated in vacuum. 3.18 g of white solid was obtained by silica gel chromatography, 75.2% yield.

.sup.1H NMR (400 MHz, CDCl.sub.3), δ(ppm): 7.31 (t, 3H, 3CH), 7.30 (s, CHCl.sub.3 from CDCl.sub.3), 7.18 (t, 3H, 3CH), 2.35 (s, 6H, 3CH.sub.2), 1.31 (s, 54H, 18CH.sub.3).

Example 4

1. Formula:

[0054] ##STR00013##

2. Synthetic Route:

[0055] ##STR00014##

3. Preparation of Target Product 2:

[0056] 1 g of 2,2,6,6-di-tert-butyl-4-bromomethylphenol (3.342 mmol) was dissolved in dichloromethane or ethyl acetate or petroleum ether or THF or MTBE or a solvent such as acetone or ethanol (1:5-20, w/v), and then the solution was added dropwise to a solution of N-octadecylamine and K.sub.2CO.sub.3 or Na.sub.2CO.sub.3 or NaOH or triethylamine or DBU or DMAP in the same volume and the same solvent. The mixture was stirred at room temperature for 1-5 hours, the reaction was monitored by TLC until the reaction was complete. NaCl aqueous solution was added. The solvent such as dichloromethane or ethyl acetate or MTBE or petroleum ether was used for extraction (10 ml×3). A yellowish oil was obtained by silica gel chromatography after filtering and removing the organic solvent, 83-92% yield.

.sup.1H MNMR (400 MHz, CDCl.sub.3), δ(ppm): 7.34 (s, CHCl.sub.3 from CDCl.sub.3), 7.15 (s, 2H, 2CH), 3.45 (m, 2H, CH.sub.2N), 2.76 (m, 2H, CH.sub.2N), 1.13-1.49 (m, 52H).

Example 5

1. Formula:

[0057] ##STR00015##

2. Synthetic Route:

[0058] ##STR00016##

3. Synthesis of Intermediate 1:

[0059] 6 g of 1,2-dichloroethoxyethane (32.08 mmol) was dissolved in a solvent which is acetone or ethyl cyanide or toluene or ethanol or MTBE (1:5-20, w/v). 10-20% NaI or KI or 32.08 mmol of organic or inorganic bases such as Na.sub.2CO.sub.3 or K.sub.2CO.sub.3 or NEt.sub.3 or DBU or NaOH and 10.16 g of 4-amino-2,2,6,6-tetramethylpiperidine (65.00 mmol) were added to a solution with the same volume and the same solvent. The mixture was heated to 40-70° C. and stirred for 3-18 hours. The reaction was monitored by TLC, and the mixture was cooled to room temperature. NaCl aqueous solution was added. Dichloromethane or ethyl acetate or MTBE or petroleum ether was used to extract Intermediate 1 three times (20ml×3). The organic phase was dried with Na.sub.2SO.sub.4. Intermediate 1 as light yellow powder was obtained by silica gel chromatography after filtering and concentrating the filtrate, 81-92% yield.

4. Synthesis of Intermediate 2:

[0060] 5.93 g of 3-(3,5-di-tert-butyl-4-hydroxybenzene) propionic acid (21.30 mmol) was dissolved in dry THF or dichloromethane or ethyl acetate or MTBE or acetone (1:5-20, w/v). The mixture was cooled to 0-10° C. 1.82 ml of oxalyl chloride (21.50 mmol) and 0.5 ml of dropping DMF were added dropwise under nitrogen, stirred for 30 minutes, and the mixture was heated to room temperature for 2 to 7 hours. The reaction was monitored by TLC until the reaction was complete. The organic solvent and excess oxalyl chloride were removed in vacuum and the remaining Intermediate 2 was used directly in the next step.

5. Preparation of Target Product 1:

[0061] 3 g of Intermediate 1 (7.06 mmol) and 7.36 mmol of a base such as Na.sub.2CO.sub.3 or K.sub.2CO.sub.3 or NEt.sub.3 or DMAP or DBU were dissolved in a solvent such as anhydrous acetone or THF or dichloromethane or ethyl cyanide or ethyl acetate and cooled to 0-10° C. 14.25 mmol of Intermediate 2 was added dropwise into a solution with the same volume and the same solvent. After completion of the dropwise addition, the mixture was stirred at 0-10° C. for 30 minutes and at room temperature for 1-3 hours, heated to 40-60° C. for an additional 2-5 hours. The insoluble material was filtered and the filtrate was concentrated to remove the general solvent. The same volume of petroleum ether was added and the mixture was cooled to 0° C. with stirring. 4.79 g of the precipitated white solid was collected, 71.7% yield.

1H NMR (400 MHz, DMSO-D6), δ(ppm): 6.92(s, 2H, 2CH), 6.89(s, 2H, 2CH), 6.75(s, CH.sub.2Cl.sub.2, solvent), 4.01 (m, 4H, 2OCH2), 3.58(sb, H.sub.2O), 3.41(m, 4H, 2OCH.sub.2), 2.71(m, 6H,2NCH2, 2NCH), 2.50(m, DMSO from DMSO-do), 2.42 (m, 4H, 2CH.sub.2), 2.26 (m, 4H, 2CH.sub.2), 1.59 (m, 4H), 0.93-1.48(m, 64H).

Example 6

1. Formula:

[0062] ##STR00017##

2. Synthetic Route:

[0063] ##STR00018##

3. Synthesis of Intermediate 3

[0064] 1 g of cyanuric chloride (5.42 mmol) and 5.42 mmol of Na.sub.2CO.sub.3 or K.sub.2CO.sub.3 or NEt3 or DBU or DMAP were dissolved in dry solvent such as acetone or dichloromethane or acetonitrile or THF or toluene. 1.03 g of octanethiol (7.05 mmol) was added under nitrogen protection. The mixture was stirred at room temperature for 1 hour and heated to 35-65° C. for 2-7 hours. The reaction was monitored by TLC until the reaction was complete. This reaction was used directly in the next step.

4. Synthesis of Intermediate 2:

[0065] 3 g of 1,6-dibromohexane (12.30 mmol), 10-30% NaI or KI and 25 mmol of base such as Na.sub.2CO.sub.3 or K.sub.2CO.sub.3 or NEt.sub.3 or DBU or DMAP were dissolved in a solvent such as dichloromethane or acetone or THF or MTBE or acetonitrile or toluene or ethanol (1:7-20, w/v).

[0066] 3.88 g of 4-amino-2,2,6,6-tetramethylpiperidine (24.80 mmol) was added at room temperature. The mixture was stirred at room temperature for 1 hour and heated to 40-70° C. for 3-15 hours. The reaction was monitored by TLC until the reaction was completed. NaCl aqueous solution was added, and dichloromethane or ethyl acetate or MTBE was used for extracting Intermediate 2 (15 ml×3). The combined organic phases are dried with MgSO.sub.4. The crude product Intermediate 2 was obtained by filtering and removing the organic solvent, and used directly in the next step.

5. Preparation of Target Product 1 (Macromolecular Substance)

[0067] The equimolar Intermediate 2 was added to the reaction system of the equimolar Intermediate 1 while equimolar organic or inorganic bases such as Na.sub.2CO.sub.3 or K.sub.2CO.sub.3 or NEt.sub.3 or DBU or DMAP was added. The mixture was reacted and stirred at room temperature for 1 hour, and then heated to 50-90° C. and stirred for 5-18 hours. The high molecular weight of the product could be adjusted with the heating temperature and the reaction time. The mixture was cooled to room temperature and the iced aqueous solution was added thereto to wash water-soluble impurities. An oil which was dissolved in an organic solvent could be obtained, a waxy solid could be obtained, and a white solid product could be obtained as Target Product 1, 73-91% yield.

1H NMR (400 MHz, CDCl.sub.3), δ(ppm): 7.32 (s, CHCl3 from CDCl.sub.3), 4.86 (m, 2H, 2CHN), 3.41 (m, 2H, 2CHN), 3.05 (m, 8H, 4CH.sub.2N), 1.98 (m, 2H, CH.sub.2S), 1.67 (m, 8H), 1.11-1.49 (m, 63H).

[0068] The foregoing examples are merely illustrative of the inventive concept of the invention and are not to be construed as limiting the scope of the invention, and any substantial changes to the invention may be made without departing from the scope of the invention.