Polyamide with main chain containing thioester group and synthesis method thereof

Abstract

The invention discloses polyamide with a main chain containing a thioester group and a synthesis method thereof, the structural general formula of the polyamide with the main chain containing the thioester group is shown in the following formula (I) or (II), in the formula, n is selected from 1-200; according to the polymer product disclosed by the invention, the polyamide of which the main chain contains the thioester group has a definite structure, a main chain repeating unit has thioester and amide structures and also contains different functional groups, and an end group has further reactivity; the polyamide containing the thioester group also has relatively high molecular mass and excellent mechanical properties; # imgabs0 #

Description

Technical Field

[0001] The invention relates to the technical field of polymer materials, and in particular to a polyamide with a main chain containing a thioester group and a synthesis method thereof. Background Art

[0002] Sulfur-containing polymers generally have excellent mechanical properties, thermal stability, optical functions, biocompatibility and strong ion binding ability due to the introduction of sulfur atoms, and are widely used in general, engineering and functional materials. Compared with polyesters, polythioesters often have better crystallinity, excellent optical properties and degradation and recycling. Polyamide materials containing thioester groups contain both thioester bonds and amide bonds. They have the degradability and excellent optical properties of thioester compounds and retain the excellent mechanical properties of amide compounds. They have been widely used in biomaterials, optical materials, degradable materials, etc.

[0003] However, how to controllably introduce thioester and amide bonds in a simple way remains a challenging problem in the field of synthesis, especially the synthesis of polymers containing both thioester and amide groups in the main chain is less studied. The current method for synthesizing polythioesters mainly relies on the polycondensation of dicarboxylic acids and dithiols, which has the problem of unpleasant odor of dithiols, high energy consumption, and release of water byproducts.

[0004] A Chinese patent document with application publication number CN 113943485 A discloses a method for preparing polythioesters, wherein the technical route is to perform ring-opening polymerization of thiolactide monomers under the catalysis of an organic base to obtain polythioester compounds. However, the ring-opening polymerization method is limited by the types of reactive monomers, and the resulting polymer has a single structure, with only thioester groups present, and it is difficult to introduce amide groups.

[0005] The Chinese patent document with application publication number CN 116640308 A discloses a preparation method of polythioesteramide and a depolymerization method thereof, wherein the preparation method comprises: adding a co-catalyst and an initiator comprising thiourea and an organic base to a thiazinedione monomer solution, so as to cause the thiazinedione monomer to undergo a ring-opening polymerization reaction to obtain a polythioesteramide polymer. The technical scheme claims that the thioester exchange side reaction can be avoided by a two-component catalytic system and a depolymerizable polythioesteramide with a narrow molecular weight distribution can be prepared. However, the ring-opening polymerization method is limited by the small number of reactive monomers, and the preparation, storage and transportation of the thiazinedione monomer are relatively difficult, resulting in a relatively simple structure and type of the polythioesteramide obtained, and a low monomer conversion rate of only 73% at most; in addition, the molecular weight distribution of the polythioesteramide polymer prepared by the technical scheme is relatively narrow, not higher than 1.13, but the number average molecular weight range is only 4000 to 8000 g / mol. Summary of the invention

[0006] In view of the problems existing in the prior art, the present invention discloses a polyamide containing a thioester group in the main chain and a synthesis method thereof. The polyamide containing a thioester group in the main chain has a clear structure, the main chain repeating unit has the structure of thioester and amide, and contains different functional groups at the same time, and the end group has further reactivity; the polyamide containing a thioester group also has a high molecular weight, excellent mechanical properties, and has broad application prospects in food packaging, coatings, biology and electronics. At the same time, based on the mechanism of step-by-step polymerization, the method has a high monomer conversion rate, can be basically completely converted in the early stage, and has a high monomer utilization rate. The synthesis process of the present invention only requires one step, the raw materials are cheap and easy to obtain, the time consumption is short, and there is no need for cumbersome post-processing purification steps, which is conducive to the realization of industrial production.

[0007] The specific technical solutions are as follows:

[0008] A polyamide with a main chain containing a thioester group, the general structural formula of which is shown in the following formula (I) or (II):

[0009]

[0010] Wherein, n is selected from 1 to 200;

[0011] R1 is selected from C2~C 22 Alkylene, terephthalylidene, 2,5-furandimethylene, 1,4-cyclohexylene, (CH2CH2O) m CH2CH2, m = 1 to 3;

[0012] R2 is selected from H or methyl;

[0013] R3 is selected from C2~C 12 Alkylene, (CH2)3Si(CH3)2OSi(CH3)2(CH2)3, (CH2)2O(CH2)2O(CH2)2, isophorone, 1,4-phenylene, 1,3-phenylene, 1,2-phenylene, terephthalylidene, o-terephthalylidene, m-terephthalylidene, 1,4-cyclohexyl, 1,2-cyclohexyl, 1,3-cyclohexyl, CH2C(CH3)2CH2;

[0014] R4 is selected from H, methyl, ethyl, n-propyl, isopropyl.

[0015] According to tests, the polyamide containing thioester groups in the main chain prepared by the present invention has a number average molecular weight of 1 to 200 kg / mol; the molecular weight distribution is 1.1 to 2.5, specifically 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5 or any value within the above range.

[0016] The invention discloses a polyamide with a main chain containing a thioester group. The main chain repeating unit has the structure of thioester and amide, has a clear structure, contains different functional groups, and the end group has further reactivity. The polyamide containing the thioester group also has a high molecular weight, a low molecular weight distribution, and excellent mechanical properties, and has broad application prospects in food packaging, coatings, biology and electronics fields.

[0017] The present invention also discloses a method for synthesizing the polyamide containing thioester groups in the main chain, wherein the raw materials include a carbon-carbon double bond monomer with an electron-withdrawing group, a diamino monomer and a cyclic monothioanhydride monomer, and polymerization is performed under autogenous pressure;

[0018] The structural formula of the carbon-carbon double bond monomer with an electron-withdrawing group is shown in the following formula (III):

[0019]

[0020] The structural formula of the diamino monomer is shown in the following formula (IV):

[0021]

[0022] The structural formula of the cyclic monothioanhydride monomer is as shown in the following formulas (V) to (VI):

[0023]

[0024] In the formula, R1 is selected from C2~C 22 Alkylene, terephthalylidene, 2,5-furandimethylene, 1,4-cyclohexylene, (CH2CH2O) m CH2CH2, m = 1 to 3;

[0025] R2 is selected from H or methyl;

[0026] R3 is selected from C2~C 12 Alkylene, (CH2)3Si(CH3)2OSi(CH3)2(CH2)3, (CH2)2O(CH2)2O(CH2)2, isophorone, 1,4-phenylene, 1,3-phenylene, 1,2-phenylene, terephthalylidene, o-terephthalylidene, m-terephthalylidene, 1,4-cyclohexyl, 1,2-cyclohexyl, 1,3-cyclohexyl, CH2C(CH3)2CH2;

[0027] R4 is selected from H, methyl, ethyl, n-propyl, isopropyl.

[0028] Based on a large number of experimental studies, the inventors discovered that thioester anions and double-bond compounds can react rapidly, and thus developed a new one-step polymerization reaction of di-double-bond monomers, diamino monomers and cyclic monothioanhydrides. Due to the strong nucleophilicity of N, it will preferentially react with the cyclic monothioanhydride to form The group generates sulfur anions under the action of other amino groups, and the sulfur anions can react with the double bond groups to generate thioester group compounds. Wherein, the double bond monomer is a carbon-carbon didouble bond compound with an electron-withdrawing group, and the electron-withdrawing group strengthens the electrophilicity of the double bond functional group, thereby being more conducive to the reaction. Therefore, the present invention can synthesize a high molecular weight product under the condition of no catalyst through the mechanism of stepwise polymerization. The inventors formed the present invention through a large number of experimental studies on the basis of the above mechanism discovery.

[0029] The synthesis process of the present invention only requires one step, the raw materials are cheap and easy to obtain, the time consumption is short, and there is no need for cumbersome post-processing and purification steps, which is conducive to industrial production; at the same time, based on the mechanism of step-by-step polymerization, the method has a high monomer conversion rate, and can be basically completely converted in the early stage, and the monomer utilization rate is high.

[0030] The synthesis process of the present invention is selective for cyclic monothioanhydride monomers. It is found through experiments that suitable cyclic monothioanhydride monomers are selected from monothiosuccinic anhydride and / or monothioglutaric anhydride. If the cyclic monothioanhydride monomer is replaced by monothiophthalic anhydride with a similar structure, polymerization cannot be carried out.

[0031] Preferred:

[0032] The carbon-carbon double bond monomer with an electron-withdrawing group is selected from ethylene glycol diacrylate, 1,3-propylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, 1,10-decanediol diacrylate, 1,12-dodecanediol diacrylate, 1,14-tetradecanediol diacrylate, 1,16-hexadecanediol diacrylate, 1,18-octadecanediol diacrylate, 1,20-eicosanediol diacrylate, 1,22-docosahexadecanediol diacrylate, 2,5-dimethylbenzene diacrylate, 2,5-hexanediol ... One or more of furandimethanol diacrylate, 1,4-cyclohexanediol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, ethylene glycol dimethacrylate, 1,3-propylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1,5-pentanediol dimethacrylate, neopentyl glycol dimethacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol dimethacrylate, 1,10-decanediol dimethacrylate, 1,12-dodecanediol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, and tetraethylene glycol dimethacrylate;

[0033] The diamino monomer is selected from C2 to C 12 One or more of alkyl diamine, p-phenylenediamine, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, o-phenylenediamine, m-phenylenediamine, 1,2-diaminocyclohexane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, 1,8-diamino-3,6-dioxaoctane, 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane, dimethylpropylenediamine, isophoronediamine, N,N′-dimethylethylenediamine, N,N′-diisopropylethylenediamine, N,N′-dimethyl-1,3-propylenediamine, N,N′-dimethyl-1,6-hexanediamine, N,N′-dimethyl-1,8-octanediamine, N,N′-diethylethylenediamine, and N,N′-diethyl-1,3-propylenediamine.

[0034] The synthesis method disclosed in the present invention has good universality for monomers and is applicable to diamino monomers with different structures and properties, which makes it possible to prepare polymers with different properties by simply changing the type of diamino monomer.

[0035] For example, when the diamino monomer is selected from alkyl diamine, p-phenylenediamine, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, o-phenylenediamine, and m-phenylenediamine, the prepared polymer has obvious crystallinity and is a crystalline polymer;

[0036] When the diamino monomer is selected from 1,8-diamino-3,6-dioxaoctane, 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane and other long flexible chains and isophorone diamine, secondary amine diamino monomers (N,N′-dimethylethylenediamine, etc.), cyclohexane diamino monomers, etc., the prepared polymer is a thermoplastic elastomer or a thermoplastic plastic.

[0037] Further preferred:

[0038] The carbon-carbon double bond monomer with an electron-withdrawing group is selected from one or more of ethylene glycol diacrylate, 1,3-propylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, 1,10-decanediol diacrylate, 1,12-dodecanediol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, and terephthalate diacrylate. Further preferred carbon-carbon double bond monomers with electron-withdrawing groups are cheap, easy to obtain, and convenient to store and transport. More importantly, they have good reactivity and excellent effect.

[0039] The diamino monomer is selected from C2 to C 12 One or more of alkyl diamine, 1,8-diamino-3,6-dioxaoctane, 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane, isophorone diamine, N,N′-dimethylethylenediamine, N,N′-diisopropylethylenediamine, N,N′-dimethyl-1,3-propylenediamine, N,N′-dimethyl-1,6-hexanediamine, N,N′-dimethyl-1,8-octanediamine, N,N′-diethylethylenediamine, and N,N′-diethyl-1,3-propylenediamine; further preferred diamino monomers have good reaction efficiency.

[0040] Preferred:

[0041] The molar ratio of the carbon-carbon double bond monomer with electron-withdrawing group to the diamino monomer is 1:

[0042] (0.2-5.0); specifically, it can be 1:0.2, 1:0.5, 1:1.0, 1:1.5, 1:2.0, 1:2.5, 1:3.0, 1:3.5, 1:4.0, 1:4.5, 1:5.0 or any ratio within the above range. More preferably, it is 1:(0.5-2.0); more preferably, it is 1:1.

[0043] Preferred:

[0044] The molar ratio of the carbon-carbon double bond monomer with an electron-withdrawing group to the cyclic monothioanhydride is 1:

[0045] (1.5-5.0); specifically, it can be 1:1.5, 1:1.8, 1:2.0, 1:2.5, 1:3.0, 1:3.5, 1:4.0, 1:4.4, 1:5.0 or any ratio within the above range. More preferably, it is 1:(2-5); more preferably, it is 1:(2-4).

[0046] More preferably, the molar ratio of the carbon-carbon double bond monomer with an electron withdrawing group, the diamino monomer and the cyclic monothioanhydride is 1:1:(2.0-4.0); most preferably, the molar ratio is 1:1:2.

[0047] It has been found through experiments that a polymer with a higher molecular weight can be prepared by using the above-mentioned continuously optimized raw material molar ratio.

[0048] The polymerization reaction of the present invention is carried out under autogenous pressure, and the polymerization can be bulk polymerization or solution polymerization. Studies have found that when the reaction is carried out for 55 minutes, the generated thioester groups can reach saturation, which shows that the reaction system of the present invention still has an extremely high monomer conversion rate without adding a catalyst and under relatively mild reaction conditions.

[0049] The polymerization temperature is 25 to 160°C, and specifically can be 25°C, 40°C, 60°C, 80°C, 100°C, 120°C, 140°C, 160°C or any value within the above range. Preferably, the polymerization temperature is 40 to 90°C; more preferably, the polymerization temperature is 60 to 90°C.

[0050] The polymerization time is 0.5 to 120 hours, and specifically can be 0.5 hours, 2 hours, 6 hours, 12 hours, 24 hours, 48 ​​hours, 72 hours, 96 hours, 120 hours or any value within the above range. Preferably, the polymerization time is 55 minutes to 12 hours.

[0051] If solution polymerization is adopted, the solvent used is selected from one or more of N,N-dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, phenol, dichloromethane, chloroform, tetrahydrofuran, toluene, trichlorobenzene, o-dichlorobenzene, m-dichlorobenzene and p-dichlorobenzene.

[0052] Preferably, the solvent is selected from one or more of N,N-dimethylformamide, N-methylpyrrolidone, and dimethyl sulfoxide. It has been found through experiments that, under the same other process conditions, the polymer prepared using the solvent has a higher molecular weight.

[0053] Compared with the prior art, the present invention has the following beneficial effects:

[0054] (1) Based on a large number of experimental studies, the present invention proposes for the first time that a polymer having a main chain with controllable end groups and containing both thioester groups and amide groups is obtained by a one-step reaction of a carbon-carbon double bond compound with an electron-withdrawing group, a diamino monomer and a cyclic monothioanhydride. The raw materials are cheap and readily available, the reaction conditions are simple, and it is a new polymerization reaction with complete atom economy.

[0055] (2) The present invention can achieve rapid reaction without the need for a catalyst. The thioester groups generated can basically reach saturation after 55 minutes of reaction. The monomer conversion rate is high, and a clear structure, no metal residue, and colorless are obtained. The main chain repeating units contain thioester groups and amide groups, and the terminal group structure is clear. There is no need for cumbersome post-processing and purification steps.

[0056] (3) The polymer prepared by the present invention has a high molecular weight and does not contain metal ions. Moreover, the number average molecular weight and main chain repeating units of the prepared polymer product can be regulated over a wide range only by regulating the types and ratios of the raw materials and the process conditions in the synthesis method, thereby achieving the preparation of crystalline polymers, thermoplastic plastics, thermoplastic elastomers and other products with completely different properties by the same method. The products have excellent mechanical properties and have broad application prospects in food packaging, coatings, biology and electronics. BRIEF DESCRIPTION OF THE DRAWINGS

[0057] Figure 1 The copolymerization product prepared in Example 1 1 H NMR spectrum;

[0058] Figure 2 The copolymerization product prepared in Example 1 13 C NMR spectrum;

[0059] Figure 3 The copolymerization product prepared in Example 22 1 H NMR spectrum;

[0060] Figure 4 The copolymerization product prepared in Example 22 13 C NMR spectrum;

[0061] Figure 5 The copolymerization product prepared in Example 26 1 H NMR spectrum;

[0062] Figure 6 The copolymerization product prepared in Example 26 13 C NMR spectrum;

[0063] Figure 7 The copolymerization product prepared in Example 27 1 H NMR spectrum;

[0064] Figure 8 The copolymerization product prepared in Example 27 13 C NMR spectrum;

[0065] Fig. 9 The copolymerization product prepared in Example 28 1 H NMR spectrum;

[0066] Fig.10 The copolymerization product prepared in Example 28 13 C NMR spectrum;

[0067] Fig.11 The copolymerization product prepared in Example 30 1 H NMR spectrum;

[0068] Fig.12 The copolymerization product prepared in Example 30 13 C NMR spectrum;

[0069] Fig.13 The copolymerization product prepared in Comparative Example 1 1 H NMR spectrum. DETAILED DESCRIPTION

[0070] In order to make the purpose, features and advantages of the present invention more obvious, the following further examples are listed to explain the present invention in detail. The following examples are only used to further illustrate the present invention and cannot be understood as limiting the scope of protection of the present invention. Some non-essential improvements and adjustments made by those skilled in the art based on the principles described in the present invention belong to the scope of protection of the present invention.

[0071] The endpoints and any values ​​of the ranges disclosed in the present invention are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, and these numerical ranges should be regarded as specifically disclosed in the present invention.

[0072] The terms used herein are only for describing specific embodiments and are not intended to limit the present disclosure. The terms "comprise", "include", etc. used herein indicate the existence of the features, steps, operations and / or components, but do not exclude the existence or addition of one or more other features, steps, operations or components.

[0073] All terms (including technical and scientific terms) used herein have the meanings commonly understood by those skilled in the art, unless otherwise defined. It should be noted that the terms used herein should be interpreted as having a meaning consistent with the context of this specification, and should not be interpreted in an idealized or overly rigid manner.

[0074] It should be noted that, unless otherwise defined, the technical terms or scientific terms used in the present invention shall have the usual meanings understood by persons with ordinary skills in the field to which the present invention belongs. If the full text involves descriptions such as "first", "second", etc., the descriptions such as "first", "second", etc. are only used to distinguish similar objects, and cannot be understood as indicating or implying their relative importance, order of precedence, or implicitly indicating the number of technical features indicated. It should be understood that the data described by "first", "second", etc. can be interchangeable under appropriate circumstances.

[0075] The monothiosuccinic anhydride, monothioglutaric anhydride, and monothiophthalic anhydride used as raw material monomers in the following examples are prepared in-house. Taking monothiosuccinic anhydride as an example, the preparation steps are as follows:

[0076] 100.07 g of succinic anhydride was dissolved in 400 mL of tetrahydrofuran, and 270 g of a 14.5 wt% sodium sulfide aqueous solution was added, and the mixture was reacted at room temperature for 4 hours. The tetrahydrofuran was removed in vacuo, and the mixture was extracted three times with methyl tert-butyl ether, and the methyl tert-butyl ether was removed in vacuo and sublimed.

[0077] When preparing monothioglutaric anhydride and monothiophthalic anhydride, succinic anhydride is replaced with glutaric anhydride and phthalic anhydride in equal molar amounts, respectively.

[0078] Example 1 1,4-Butanediol diacrylate / 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane / monothiosuccinic anhydride react to form a main chain repeating unit containing a thioester group polyamide

[0079] Before the polymerization reaction, the 15mL pressure tube was first removed from the water at 110°C for 2 hours, and then placed in a glove box to cool to room temperature; 0.3871g of monothiosuccinic anhydride was added to the reactor in turn and dissolved in 1.5mL DMF, 0.3304g of 1,4-butanediol diacrylate and 0.4142g of 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane. The molar ratio of 1,4-butanediol diacrylate, 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane to monothiosuccinic anhydride was 1 / 1 / 2. The reaction was placed at 60°C under autogenous pressure for 2h. After the reaction was completed, the crude product was first dissolved in chloroform, and then the polymer was precipitated in 200mL of methyl tert-butyl ether, washed three times, and vacuum dried to constant weight. The molecular weight and molecular weight distribution of the polymer were determined by gel chromatography, and the test results are shown in Table 1.

[0080] Figure 1 , 2 are respectively the polymers prepared in this example 1 H NMR spectra and 13 C NMR spectrum, the structural formula of the polymer is shown below:

[0081]

[0082] Embodiments 2 to 5

[0083] The preparation process is basically the same as that of Example 1, except that the polymerization reaction temperature is replaced with 25° C., 90° C., 120° C., and 160° C. The molecular weight and molecular weight distribution of the polymers prepared in each example are measured by gel chromatography, and the test results are shown in Table 1.

[0084] Embodiments 6 to 9

[0085] The preparation process is basically the same as that of Example 1, except that the polymerization reaction time is replaced with 6 h, 12 h, 24 h, and 120 h in sequence. The molecular weight and molecular weight distribution of the polymers prepared in each example are measured by gel chromatography, and the test results are shown in Table 1.

[0086] Embodiments 10 to 13

[0087] The preparation process is basically the same as that of Example 1, except that the mass of the added 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane is different, specifically:

[0088] The molar ratios of 1,4-butanediol diacrylate, 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane and monothiosuccinic anhydride were replaced in sequence as 1 / 0.2 / 2, 1 / 0.5 / 2, 1 / 2 / 2 and 1 / 5 / 2.

[0089] The molecular weight and molecular weight distribution of the polymers prepared in each example were measured by gel chromatography. The test results are shown in Table 1.

[0090] Embodiments 14 to 18

[0091] The preparation process is basically the same as that of Example 1, except that the mass of monothiosuccinic anhydride added is different, specifically:

[0092] The molar ratios of 1,4-butanediol diacrylate, 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane and monothiosuccinic anhydride were replaced in sequence as 1 / 1 / 1.5, 1 / 1 / 1.8, 1 / 1 / 4.0, 1 / 1 / 4.4 and 1 / 1 / 5.0.

[0093] The molecular weight and molecular weight distribution of the polymers prepared in each example were measured by gel chromatography. The test results are shown in Table 1.

[0094] Examples 19 to 21

[0095] The preparation process is basically the same as that of Example 1, except that the solvents of the polymerization reaction are replaced with NMP, DMSO, and CHCl3 in sequence. The molecular weight and molecular weight distribution of the polymers prepared in each example are measured by gel chromatography, and the test results are shown in Table 1.

[0096] Example 221,4-Butanediol diacrylate / N,N′-dimethyl-1,6-hexanediamine / monothiosuccinic anhydride react to form a main chain repeating unit containing a thioester group polyamide

[0097] Before the polymerization reaction, the 15mL pressure tube was first removed from the water at 110°C for 2 hours, and then placed in a glove box to cool to room temperature; 0.3871g of monothiosuccinic anhydride was added to the reactor in turn and dissolved in 1.5mL DMF, 0.3304g of 1,4-butanediol diacrylate and 0.2404g of N,N′-dimethyl-1,6-hexanediamine. The molar ratio of 1,4-butanediol diacrylate, N,N′-dimethyl-1,6-hexanediamine and monothiosuccinic anhydride was 1 / 1 / 2. The reaction was placed at 60°C under autogenous pressure for 2h. After the reaction was completed, the crude product was first dissolved in chloroform, and then the polymer was precipitated in 200mL of methyl tert-butyl ether, washed three times, and vacuum dried to constant weight. The molecular weight and molecular weight distribution of the polymer were determined by gel chromatography, and the test results are shown in Table 1.

[0098] Figure 3 , 4 are respectively the polymers prepared in this example 1 H NMR spectra and 13 C NMR spectrum, the structural formula of the polymer is shown below:

[0099]

[0100] Example 231,4-Butanediol diacrylate / 1,6-hexanediamine / monothiosuccinic anhydride react to form a main chain repeating unit containing a thioester group polyamide

[0101] Before the polymerization reaction, the 15mL pressure tube was first removed from the water at 110°C for about 2 hours, and then placed in a glove box to cool to room temperature; 0.3871g of monothiosuccinic anhydride was added to the reactor in turn and dissolved in 1.5mL DMF, 0.3304g of 1,4-butanediol diacrylate and 0.1937g of 1,6-hexanediamine. The molar ratio of 1,4-butanediol diacrylate, 1,6-hexanediamine and monothiosuccinic anhydride was 1 / 1 / 2. It was placed at 90°C and reacted under autogenous pressure for 2h. After the reaction, the crude product was first dissolved in chloroform, and then the polymer was precipitated in 200mL of methyl tert-butyl ether, washed three times, and vacuum dried to constant weight. The molecular weight and molecular weight distribution of the polymer were determined by gel chromatography, and the test results are shown in Table 1.

[0102] The structural formula of the polymer prepared in this embodiment is shown below:

[0103]

[0104] Example 24: Reaction of 1,9-nonanediol diacrylate / 1,8-diamino-3,6-dioxaoctane / monothiosuccinic anhydride to form a polyamide containing a thioester group as a main chain repeating unit

[0105] Before the polymerization reaction, the 15mL pressure tube was first removed from the water at 110°C for 2 hours, and then placed in a glove box to cool to room temperature; 0.3871g of monothiosuccinic anhydride was added to the reactor in turn and dissolved in 1.5mL DMF, 0.4473g of 1,9-nonanediol diacrylate and 0.2470g of 1,8-diamino-3,6-dioxaoctane. The molar ratio of 1,9-nonanediol diacrylate, 1,8-diamino-3,6-dioxaoctane to monothiosuccinic anhydride was 1 / 1 / 2. The reaction was placed at 60°C under autogenous pressure for 2h. After the reaction was completed, the crude product was first dissolved in chloroform, and then the polymer was precipitated in 200mL of methyl tert-butyl ether, washed three times, and vacuum dried to constant weight. The molecular weight and molecular weight distribution of the polymer were determined by gel chromatography, and the test results are shown in Table 1.

[0106] The structural formula of the polymer prepared in this embodiment is shown below:

[0107]

[0108] Example 251,10-decanediol diacrylate / isophorone diamine / monothiosuccinic anhydride reacts to form a main chain repeating unit containing a thioester group polyamide

[0109] Before the polymerization reaction, the 15mL pressure tube was first removed from the water at 110°C for about 2 hours, and then placed in a glove box to cool to room temperature; 0.3871g of monothiosuccinic anhydride was added to the reactor in turn and dissolved in 1.5mL DMF, 0.4706g of 1,10-decanediol diacrylate and 0.2838g of isophorone diamine. The molar ratio of 1,10-decanediol diacrylate, isophorone diamine and monothiosuccinic anhydride was 1 / 1 / 2. The reaction was placed at 60°C under autogenous pressure for 2h. After the reaction was completed, the crude product was first dissolved in chloroform, and then the polymer was precipitated in 200mL of methyl tert-butyl ether, washed three times, and vacuum dried to constant weight. The molecular weight and molecular weight distribution of the polymer were determined by gel chromatography, and the test results are shown in Table 1.

[0110] The structural formula of the polymer prepared in this embodiment is shown below:

[0111]

[0112] Example 26: Reaction of 1,5-pentanediol diacrylate / 1,7-heptanediamine / monothioglutaric anhydride to form a main chain repeating unit containing a thioester group polyamide

[0113] Before the polymerization reaction, remove the moisture from a 15mL pressure tube at 110°C for about 2 hours, place it in a glove box and cool it to room temperature; add 0.4339g of monothioglutaric anhydride to the reactor and dissolve it in 1.5mL DMF, 0.3538g of 1,5-pentanediol diacrylate and 0.2171g of 1,7-heptanediamine. The molar ratio of 1,5-pentanediol diacrylate, 1,7-heptanediamine and monothioglutaric anhydride is 1 / 1 / 2. Place it at 90°C and react under autogenous pressure for 2h. After the reaction is completed, the crude product is first dissolved in chloroform, and then the polymer is precipitated in 200mL of methyl tert-butyl ether, washed three times, and vacuum dried to constant weight. The molecular weight and molecular weight distribution of the polymer are determined by gel chromatography, and the test results are shown in Table 1.

[0114] Figure 5 , 6 are respectively the polymers prepared in this example 1 H NMR spectra and 13 C NMR spectrum, the structural formula of the polymer is shown below:

[0115]

[0116] Example 27: Reaction of diethylene glycol diacrylate / 1,8-diamino-3,6-dioxaoctane / monothioglutaric anhydride to generate polyamide containing thioester groups as main chain repeating units

[0117] Before the polymerization reaction, remove the moisture from a 15mL pressure tube at 110°C for about 2 hours, place it in a glove box and cool it to room temperature; add 0.4339g of monothioglutaric anhydride to the reactor and dissolve it in 1.5mL DMF, 0.3570g of diethylene glycol diacrylate and 0.2470g of 1,8-diamino-3,6-dioxaoctane. The molar ratio of diethylene glycol diacrylate, 1,8-diamino-3,6-dioxaoctane to monothioglutaric anhydride is 1 / 1 / 2. Place it at 60°C and react under autogenous pressure for 2h. After the reaction is completed, the crude product is first dissolved in chloroform, and then the polymer is precipitated in 200mL of methyl tert-butyl ether, washed three times, and vacuum dried to constant weight. The molecular weight and molecular weight distribution of the polymer are determined by gel chromatography, and the test results are shown in Table 1.

[0118] Figure 7 , 8 are respectively the polymers prepared in this example 1 H NMR spectra and 13 C NMR spectrum, the structural formula of the polymer is shown below:

[0119]

[0120] Example 28: Reaction of tetraethylene glycol diacrylate / 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane / monothioglutaric anhydride to generate polyamide containing thioester groups as main chain repeating units

[0121] Before the polymerization reaction, the 15mL pressure tube was first removed from the water at 110°C for about 2 hours, and then placed in a glove box to cool to room temperature; 0.4339g of monothioglutaric anhydride was added to the reactor in turn and dissolved in 1.5mL DMF, 0.5039g of tetraethylene glycol diacrylate and 0.4142g of 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane. The molar ratio of tetraethylene glycol diacrylate, 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane and monothioglutaric anhydride was 1 / 1 / 2. It was placed at 60°C and reacted under autogenous pressure for 2h. After the reaction, the crude product was first dissolved in chloroform, and then the polymer was precipitated in 200mL of methyl tert-butyl ether, washed three times, and vacuum dried to constant weight. The molecular weight and molecular weight distribution of the polymer were determined by gel chromatography, and the test results are shown in Table 1.

[0122] Fig. 9 , 10 are respectively the polymers prepared in this example 1H NMR spectra and 13 C NMR spectrum, the structural formula of the polymer is shown below:

[0123]

[0124] Example 291,6-Hexanediol diacrylate / isophorone diamine / monothioglutaric anhydride reacts to form a main chain repeating unit containing a thioester group polyamide

[0125] Before the polymerization reaction, remove the moisture from a 15mL pressure tube at 110°C for about 2 hours, place it in a glove box and cool it to room temperature; add 0.4339g of monothioglutaric anhydride to the reactor and dissolve it in 1.5mL DMF, 0.3771g of 1,6-hexanediol diacrylate and 0.2838g of isophorone diamine. The molar ratio of 1,6-hexanediol diacrylate, isophorone diamine and monothioglutaric anhydride is 1 / 1 / 2. Place it at 60°C and react under autogenous pressure for 2h. After the reaction is completed, the crude product is first dissolved in chloroform, and then the polymer is precipitated in 200mL of methyl tert-butyl ether, washed three times, and vacuum dried to constant weight. The molecular weight and molecular weight distribution of the polymer are determined by gel chromatography, and the test results are shown in Table 1.

[0126] The structural formula of the polymer prepared in this embodiment is shown below:

[0127]

[0128] Example 301,4-Butanediol diacrylate / 1,4-butanediamine / monothiosuccinic anhydride react to form a main chain repeating unit containing a thioester group polyamide

[0129] Before the polymerization reaction, the 15mL pressure tube was first removed from the water at 110°C for about 2 hours, and then placed in a glove box to cool to room temperature; 0.3871g of monothiosuccinic anhydride was added to the reactor in turn and dissolved in 1.5mL DMF, 0.3304g of 1,4-butanediol diacrylate and 0.1469g of 1,4-butanediamine. The molar ratio of 1,4-butanediol diacrylate, 1,4-butanediamine and monothiosuccinic anhydride was 1 / 1 / 2. It was placed at 60°C and reacted under autogenous pressure for 2h. After the reaction, the crude product was first dissolved in chloroform, and then the polymer was precipitated in 200mL of methyl tert-butyl ether, washed three times, and vacuum dried to constant weight. The molecular weight and molecular weight distribution of the polymer were determined by gel chromatography, and the test results are shown in Table 1.

[0130] Fig.11 , 12 are respectively the polymers prepared in this example 1 H NMR spectra and 13 C NMR spectrum, the structural formula of the polymer is shown below:

[0131]

[0132] Comparative Example 1 1,4-Butanediol diacrylate / 1,4-butanediamine / monothiophthalic anhydride reaction

[0133] The preparation process is basically the same as that of Example 30, except that monothiosuccinic anhydride is replaced by an equimolar amount of monothiophthalic anhydride. The structure of the product was determined by nuclear magnetic resonance, and the test results are shown in Fig.13 It can be seen that the monomer system of this comparative example cannot be polymerized and can only prepare small molecules.

[0134] Table 1

[0135]

[0136]

[0137] Note: 1 Types of di-double bond monomers: BGDA is 1,4-butanediol diacrylate, PGDA is 1,5-pentanediol diacrylate, HGDA is 1,6-hexanediol diacrylate, NGDA is 1,9-nonanediol diacrylate, DGDA is 1,10-decanediol diacrylate, DEGDA is diethylene glycol diacrylate, and TEGDA is tetraethylene glycol diacrylate; 2 Types of diamino monomers: HMDA is 1,6-hexanediamine, DMHDA is N,N′-dimethyl-1,6-hexanediamine, DHA is 1,7-heptanediamine, BMDA is 1,4-butanediamine, DADOO is 1,8-diamino-3,6-dioxaoctane, BAPTMDSi is 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane, and IPDA is isophoronediamine; 3 Types of cyclic monothioanhydride monomers: STA is monothiosuccinic anhydride, GTA is monothioglutaric anhydride; 4 The molar ratio of the di-double bond monomer, the diamino monomer and the cyclic monothioanhydride; 5 Reaction solvent: DMF is N,N-dimethylformamide, NMP is N-methylpyrrolidone, DMSO is dimethyl sulfoxide, CHCl3 is chloroform; 6 M n : number average molecular weight, determined by gel permeation chromatography; 7 PDI: Molecular weight distribution, determined by gel permeation chromatography.

[0138] Examples 1 to 30 are the results of copolymerization of di-double bond monomers, diamino monomers and cyclic monothioanhydride under catalyst-free conditions. It can be seen that such systems have excellent reactivity and universality.

[0139] The above descriptions are only some specific embodiments of the present invention. It should be pointed out that a person skilled in the art can make many modifications and improvements. All modifications and improvements that do not exceed the scope of protection of the present invention should be regarded as within the scope of protection of the present invention.

Claims

1. A polyamide having a main chain containing thioester groups, characterized in that: The general structural formula is shown in the following formula (I) or (II): Wherein, n is selected from 1 to 200; R1 is selected from C2~C 22 Alkylene, terephthalylidene, 2,5-furandimethylene, 1,4-cyclohexylene, (CH2CH2O) m CH2CH2, m = 1 to 3; R2 is selected from H or methyl; R3 is selected from C2~C 12 Alkylene, (CH2)3Si(CH3)2OSi(CH3)2(CH2)3, (CH2)2O(CH2)2O(CH2)2, isophorone, 1,4-phenylene, 1,3-phenylene, 1,2-phenylene, terephthalylidene, o-terephthalylidene, m-terephthalylidene, 1,4-cyclohexyl, 1,2-cyclohexyl, 1,3-cyclohexyl, CH2C(CH3)2CH2; R4 is selected from H, methyl, ethyl, n-propyl, isopropyl.

2. The polyamide having a main chain containing thioester groups according to claim 1, characterized in that: The number average molecular weight is 1 to 200 kg / mol, and the molecular weight distribution is 1.1 to 2.

5.

3. A method for synthesizing a polyamide having a main chain containing thioester groups according to claim 1 or 2, characterized in that: The raw materials include carbon-carbon double bond monomers with electron-withdrawing groups, diamino monomers and cyclic monothioanhydride monomers, which are polymerized under autogenous pressure; The structural formula of the carbon-carbon double bond monomer with an electron-withdrawing group is shown in the following formula (III): The structural formula of the diamino monomer is shown in the following formula (IV): The structural formula of the cyclic monothioanhydride monomer is as shown in the following formulas (V) to (VI): In the formula, R1 is selected from C2~C 22 Alkylene, terephthalylidene, 2,5-furandimethylene, 1,4-cyclohexylene, (CH2CH2O) m CH2CH2, m = 1 to 3; R2 is selected from H or methyl; R3 is selected from C2~C 12 Alkylene, (CH2)3Si(CH3)2OSi(CH3)2(CH2)3, (CH2)2O(CH2)2O(CH2)2, isophorone, 1,4-phenylene, 1,3-phenylene, 1,2-phenylene, terephthalylidene, o-terephthalylidene, m-terephthalylidene, 1,4-cyclohexyl, 1,2-cyclohexyl, 1,3-cyclohexyl, CH2C(CH3)2CH2; R4 is selected from H, methyl, ethyl, n-propyl, isopropyl.

4. The method for synthesizing a polyamide having a main chain containing thioester groups according to claim 3, characterized in that: The carbon-carbon double bond monomer with an electron-withdrawing group is selected from ethylene glycol diacrylate, 1,3-propylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, 1,10-decanediol diacrylate, 1,12-dodecanediol diacrylate, 1,14-tetradecanediol diacrylate, 1,16-hexadecanediol diacrylate, 1,18-octadecanediol diacrylate, 1,20-eicosanediol diacrylate, 1,22-docosahexadecanediol diacrylate, 2,5-dimethylbenzene diacrylate, 2,5-hexanediol ... One or more of furandimethanol diacrylate, 1,4-cyclohexanediol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, ethylene glycol dimethacrylate, 1,3-propylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1,5-pentanediol dimethacrylate, neopentyl glycol dimethacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol dimethacrylate, 1,10-decanediol dimethacrylate, 1,12-dodecanediol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, and tetraethylene glycol dimethacrylate; The diamino monomer is selected from C2 to C 12 One or more of alkyl diamine, p-phenylenediamine, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, o-phenylenediamine, m-phenylenediamine, 1,2-diaminocyclohexane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, 1,8-diamino-3,6-dioxaoctane, 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane, dimethylpropylenediamine, isophoronediamine, N,N′-dimethylethylenediamine, N,N′-diisopropylethylenediamine, N,N′-dimethyl-1,3-propylenediamine, N,N′-dimethyl-1,6-hexanediamine, N,N′-dimethyl-1,8-octanediamine, N,N′-diethylethylenediamine, and N,N′-diethyl-1,3-propylenediamine.

5. The method for synthesizing a polyamide having a main chain containing thioester groups according to claim 3, characterized in that: The molar ratio of the carbon-carbon double bond monomer with electron-withdrawing group to the diamino monomer is 1: (0.2～5.0)； The molar ratio of the carbon-carbon double bond monomer with an electron-withdrawing group to the cyclic monothioanhydride is 1: (1.5～5.0)。 6. The method for synthesizing a polyamide having a main chain containing thioester groups according to claim 3, characterized in that: The polymerization is bulk polymerization or solution polymerization, the polymerization temperature is 25 to 160° C., and the time is 0.5 to 120 hours; The solution polymerization uses a solvent selected from one or more of N,N-dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, phenol, dichloromethane, chloroform, tetrahydrofuran, toluene, trichlorobenzene, o-dichlorobenzene, m-dichlorobenzene and p-dichlorobenzene.

7. The method for synthesizing a polyamide having a main chain containing thioester groups according to claim 6, characterized in that: The solvent is selected from one or more of N,N-dimethylformamide, N-methylpyrrolidone and dimethyl sulfoxide.

8. The method for synthesizing a polyamide having a main chain containing thioester groups according to any one of claims 3 to 7, characterized in that: The carbon-carbon double bond monomer is selected from one or more of ethylene glycol diacrylate, 1,3-propylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, 1,10-decanediol diacrylate, 1,12-dodecanediol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, and terephthalate diacrylate; The diamino monomer is selected from C2 to C 12 One or more of alkyldiamine, 1,8-diamino-3,6-dioxaoctane, 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane, isophoronediamine, N,N′-dimethylethylenediamine, N,N′-diisopropylethylenediamine, N,N′-dimethyl-1,3-propylenediamine, N,N′-dimethyl-1,6-hexanediamine, N,N′-dimethyl-1,8-octanediamine, N,N′-diethylethylenediamine, and N,N′-diethyl-1,3-propylenediamine; The molar ratio of the carbon-carbon double bond monomer with electron-withdrawing group to the diamino monomer is 1: (0.5～2.0)； The molar ratio of the carbon-carbon double bond monomer with an electron-withdrawing group to the cyclic monothioanhydride is 1: (2.0～5.0)。 9. The method for synthesizing a polyamide having a main chain containing thioester groups according to claim 8, characterized in that: The molar ratio of the carbon-carbon double bond monomer with electron-withdrawing groups, the diamino monomer and the cyclic monothioanhydride is 1:1:(2.0-4.0).

10. The method for synthesizing a polyamide having a main chain containing thioester groups according to claim 8, characterized in that: The polymerization temperature is 40-90°C.

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