CN114957665A - Polyamide based on mercapto-Michael addition click reaction and synthetic method thereof - Google Patents

Polyamide based on mercapto-Michael addition click reaction and synthetic method thereof Download PDF

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CN114957665A
CN114957665A CN202210784624.1A CN202210784624A CN114957665A CN 114957665 A CN114957665 A CN 114957665A CN 202210784624 A CN202210784624 A CN 202210784624A CN 114957665 A CN114957665 A CN 114957665A
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michael addition
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CN114957665B (en
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李禹函
魏柳荷
吴凯
朱军
朱士虎
刘兴江
孙爱灵
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Zhengzhou University
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Abstract

The invention discloses polyamide based on sulfydryl-Michael addition click reaction and a synthesis method thereof, wherein a dimercapto compound and an amide compound containing an electroabsorption conjugated double bond are subjected to sulfydryl-Michael addition click reaction under the action of a tertiary amine or an organic phosphine catalyst to realize the head-tail coupling of two molecules, so as to obtain an amide bond-rich polymer. The synthesis method comprises the following steps: dissolving 1.0 equivalent part of amide compound containing the electro-absorption conjugated double bond and 1.0 equivalent part of dimercapto compound in a redistilled polar solvent, adding 0.002-0.020 equivalent part of catalyst, heating to 40-60 ℃, stirring for at least 6 hours, cooling to room temperature when an infrared characteristic peak of the mercapto group disappears, removing the solvent, and drying to obtain the polyamide. The polymerization route of the invention does not need high temperature and high vacuum, has mild process conditions, low energy consumption, high polymerization degree, multiple synthetic monomers and flexible molecular designability, and can be used for synthesizing conventional nylon engineering plastics, high-temperature nylon engineering plastics, nylon elastomers, polyamide hot melt adhesives and the like with excellent performance.

Description

Polyamide based on mercapto-Michael addition click reaction and synthetic method thereof
Technical Field
The invention relates to the technical field of polyamide synthesis, in particular to a method for synthesizing polyamide based on sulfydryl-Michael addition click reaction.
Background
The synthesis principle of most commercial polyamides is the polymerization by means of the dehydrocondensation of dicarboxylic acids and diamines to form amide bonds. According to the difference of synthesis process, there are three main synthesis methods: melting method, solid phase method, solution method. The dehydration condensation of carboxylic acid group and amino group is a dynamic reversible process, and in order to obtain high molecular weight polymer, the technological conditions need to be controlled to make the chemical equilibrium move towards the polymerization direction, so that the above-mentioned method needs high temperature, high vacuum degree and other conditions, and its production energy consumption is huge. The polyester polycondensation method is a synthesis method for carrying out ester-amine exchange reaction by utilizing macromolecular polyester and diamine, the synthesis route can reach reaction balance only at high temperature, and the relative molecular weight of a target polymer is not easy to control, the molecular weight of the polymer at the later stage of the reaction is difficult to increase, the molecular weight distribution is wider, the molecular chain segments are randomly distributed, and the development variety is single, so the industrial popularization and application of the ester-amine exchange method are limited to a certain extent.
In order to overcome the problem of huge production energy consumption, DuPont invented a low-temperature interfacial polymerization method, and applied the method in the synthesis of semi-aromatic polyamide, the synthesis process is to dissolve or disperse aromatic ring-containing acyl chloride compound in an organic solvent phase immiscible with water, dissolve or disperse diamine in an aqueous phase dissolved with an acid-binding agent, and react at the interface of the organic phase and the aqueous phase to obtain high molecular weight polyamide. The main advantages of the interfacial polymerization method are that the reaction conditions are mild, it can be carried out at room temperature or several tens of degrees, the reaction is irreversible, and even if one raw material is in excess, a high molecular weight polymer can be produced. However, the number of the diacid chloride compounds used in the interfacial polymerization method is rare, and the number of the polyamide varieties is small.
The direct synthesis of polyamides via compounds containing amide linkages is not limited by the dynamic equilibrium of the amidation reaction. Polyamides (commonly known as PA6) are obtained industrially by ring-opening polymerization of caprolactam, pure caprolactam cannot be polymerized, and small amounts of water, acid, ammonia or 6-aminocaproic acid as an initiator must be added to polymerize. However, the ring-opening polymerization of caprolactam needs to be carried out at high temperature and high pressure, and the production energy consumption is still large. Tube and bin et al (j.am. chem. soc.2011,133,1159) use a Milstein catalyst (CAS number 863971-63-5) to catalyze the dehydrogenation reaction of diamine and diol to obtain high molecular weight polyamide. Researches show that high conversion rate can be obtained only by dissolving monomers in anisole, and hydrogen is generated in the reaction process, so that the method has certain danger. Stefan filling et al (Macromolecules 2015,48,1463) use (ADMET) acyclic diene metathesis reaction to select amide bond and aliphatic long-chain double-terminal alkenyl monomer for copolymerization to synthesize long-carbon-chain polyamide, the synthesis process of the monomer in the synthesis route is tedious and low in yield, the first step of copolymerization reaction needs high vacuum and expensive ruthenium catalyst, and the second step of hydrogenation reaction needs high pressure and expensive rhodium catalyst. Tang soldier et al (nat. Commun.2019,10,1315) also studied the synthesis of long carbon chain polyamide from amide bond-containing compounds, and the principle of the synthesis was that the polymerization was carried out by thiol-ene click reaction of a dimercapto compound and a double-terminal alkenyl amide monomer, although the click reaction conditions were mild and the molecular weight of the polymerization product was high, the amide monomer was prepared by ester-amine exchange reaction, and the monomer species were few, the conversion rate was not high, and the large-scale production was difficult.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a polyamide based on a mercapto-Michael addition click reaction and a synthesis method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
a polyamide based on sulfydryl-Michael addition click reaction is a polymer rich in amido bonds, which is prepared by carrying out sulfydryl-Michael addition click reaction on a dimercapto compound and an amide compound containing an electroabsorption conjugated double bond under the action of a catalyst to realize the head-tail coupling of two molecules.
The dimercapto compound is 3-6-dioxa-1-8-octane dithiol (CAS number 14970-87-7), tetraethylene glycol di (ethylene glycol) (CAS number 89141-22-0), 3, 7-dithia-1, 9-nonanedithiol (CAS number 25676-62-4), 1-propanedithiol (CAS number 88497-17-0), 1, 2-ethanedithiol (CAS number 540-63-6), 1, 6-hexanedithiol (CAS number 1191-43-1), 2, 7-naphthyl dithiol (CAS number 71977-56-5), 1, 11-undecanedithiol (CAS number 63476-06-2), 1, 16-hexadecanedithiol (CAS number 79028-45-8), 2, 6-Naphthalenedithiol (CAS No. 96892-95-4), 1, 9-nonanedithiol (CAS No. 3489-28-9), 1, 5-glutarethiol (CAS No. 928-98-3), 1, 3-propanedithiol (CAS No. 109-80-8), 1, 4-phenyldithiol (CAS No. 624-39-5), 1, 10-decanedithiol (CAS No. 1191-67-9), 1, 2-propanedithiol (CAS No. 814-67-5), p-terphenyl-4, 4' -dithiol (CAS No. 174706-21-9), 1, 5-dimercaptonaphthalene (CAS No. 5325-88-2), 1, 2-benzenedithiol (CAS No. 17534-15-5), Lubutanedithiol (CAS No. 10230-61-2), 4-chloro-1, 3-benzenedithiol (CAS No. 58593-78-5), 1, 3-butanedithiol (CAS No. 24330-52-7), biphenyl-4, 4 '-dithiol (CAS No. 6954-27-4), 1, 8-octanedithiol (CAS No. 1191-62-4), 1, 2-butanedithiol (CAS No. 16128-68-0), benzenethiol (CAS No. 626-04-0), 4' -dimercaptostilbene (CAS No. 614756-39-7), 4 '-dimercaptodiphenyl ether (CAS No. 17527-79-6), 1, 4-dithioerythritol (CAS No. 92-68-8), 4' -dimercaptodiphenyl sulfide (CAS No. 62-77-7), 193193193193, Dithiothreitol (CAS number 3483-12-3), dithiothreitol (CAS number 27565-41-9), L-1, 4-dithiothreitol (CAS number 16096-97-2), ethyleneglycol dimercaptoacetate (CAS number 123-81-9), di (mercaptoacetic acid) -1, 4-butanediyl ester (CAS number 10193-95-0), toluene-3, 4-dithiol (CAS number 496-74-2), 2, 3-butanedithiol (CAS number 4532-64-3), 1, 4-butanedithiol (CAS number 1191-08-8), dimercaprol (CAS number 59-52-9), dimercaptomethane (CAS number 6725-64-0), polyethylene glycol dithiol, and difunctional polysulfide rubber.
The structural formula of the amide compound containing the electro-absorption conjugated double bond is shown as
Figure BDA0003720215330000031
Wherein R is 1 Is H or CH 3 Can be selected from commercial compounds such as N, N '-methylenebisacrylamide (CAS number 110-26-9), N' -vinylbisacrylamide(CAS No. 2956-58-3), N' -methylenebisallylamine (CAS No. 2359-15-1), or by reacting a primary diamine with acryloyl chloride.
The primary diamines are 1, 2-propane diamine (CAS number 78-90-0), 1, 3-propane diamine (CAS number 109-76-2), 1, 4-butane diamine (CAS number 110-60-1), 2-methyl-1, 2-butane diamine (CAS number 44513-48-6), 2, 3-dimethyl-1, 4-butane diamine (CAS number 127292-54-0), 2, 3-dimethyl-2, 3-butane diamine (CAS number 20485-44-3), 1-pyridine-4-yl-1, 4-butane diamine (CAS number 374064-03-6), (R) -2-methyl butane-1, 4-diamine (CAS number 15657-58-6), 1, 5-diaminopentane (CAS number 462-94-2), 2, 4-pentanediamine-2, 4-dimethyl (CAS number 908298-06-6), 1, 2-cyclopentediamine (CAS number 41330-23-8), 1, 4-pentanediamine (CAS number 591-77-5), cis-1, 3-cyclopentediamine (CAS number 63486-45-3), trans-1, 3-cyclopentediamine (CAS number 573704-66-2), 1, 3-diaminopentane (CAS number 589-37-7), 2' -oxybis (ethylamine) (CAS number 2752-17-2), dimethylpropanediamine (CAS number 7328-91-8), 1, 5-diamino-2-methylpentane (CAS number 15520-10-2), 1, 6-hexanediamine (CAS No. 124-09-4), 1, 2-cyclohexanediamine (CAS No. 694-83-7), 1, 3-cyclohexanediamine (CAS No. 3385-21-5), 1, 4-cyclohexanediamine (CAS No. 3114-70-3), 2-methyl-1, 3-cyclohexanediamine (CAS No. 13897-56-8), methylcyclohexanediamine (CAS No. 13897-55-7), 1, 7-diaminoheptane (CAS No. 646-19-5), 1, 8-octanediamine (CAS No. 373-44-4), 1, 9-nonanediamine (CAS No. 646-24-2), 1, 10-diaminodecane (CAS No. 646-25-3), 1, 12-diaminododecane (CAS No. 2783-17-7), 4, 9-dioxa-1, 12-dodecanediamine (CAS No. 7300-34-7), 4' -diaminodiphenyl sulfone (CAS No. 80-08-0), p-phenylenediamine (CAS No. 106-50-3), o-phenylenediamine (CAS No. 95-54-5), m-phenylenediamine (CAS No. 108-45-2), benzidine (CAS No. 92-87-5), 1, 7-naphthalenediamine (CAS No. 2243-64-3), (6-amino-2-naphthyl) amine (CAS No. 2243-67-6), 2, 3-diaminonaphthalene (CAS No. 771-97-1), 1, 5-naphthalenediamine (CAS No. 2243-62-1), 1, 4-diaminonaphthalene (CAS No. 2243-61-0), 1, 8-diaminonaphthalene (CAS No. 479-27-6), isophoronediamine (CAS No. 2855-13-2), bicyclo [2.2.1] heptanedimethylamine (CAS No. 56602-77-8), 4' -diaminodicyclohexylmethane (CAS No. 1761-71-3), greater than Croda dimer diamine Priamine1075, amino-terminated polyoxypropylene ether, amino-terminated polytetramethylene ether, poly-1, 4-butanediol bis (4-aminobenzoate), amino-terminated polybutadiene, amino-terminated poly (butadiene-acrylonitrile), amino-terminated polyisoprene, amino-terminated polyisobutylene, amino-terminated polyoxyethylene ether.
The catalyst is a tertiary amine compound or an organic phosphine compound, preferably one or a mixture of more of o-hydroxybenzyl dimethylamine DMP-10, 2,4, 6-tris (dimethylaminomethyl) phenol DMP-30, bis (dimethylaminoethyl) ether BDMAEE, N-methylmorpholine NEM, benzyl dimethylamine BDMA, triethylamine TEA, N-dimethylaniline DMA, N-diethylaniline DEA, 1,5, 7-triazabicyclo (4.4.0) dec-5-ene TBD, diazabicyclo DBU, diazabicyclo DBN, triphenylphosphine, tri-N-butyl phosphine, triisopropyl phosphine, tribenzyl phosphine, tricyclopentyl phosphine, tri (dimethylamino) phosphine, tripyrrolidine phosphine and tri-N-octyl phosphine.
The synthesis method of the amide compound containing the electro-absorption conjugated double bond comprises the following steps:
(1) dissolving 1.0 equivalent part of primary diamine in a redistilled polar solvent; wherein the polar solvent is one or a mixture of N, N-dimethylformamide DMF, N-dimethylacetamide DMAc, N-methylpyrrolidone NMP, dimethyl sulfoxide DMSO and acetonitrile;
(2) adding 2.0-2.5 equivalent parts of an acid-binding agent and uniformly stirring; wherein the acid-binding agent is one or a mixture of triethylamine, N-diisopropylethylamine, sodium hydroxide, sodium acetate and potassium carbonate;
(3) and (2) dropwise adding 2.0 equivalent parts of acryloyl chloride into the mixed system at room temperature, stirring while dropwise adding, reacting for 2-4 hours, adding deionized water to dissolve a by-product and precipitate a target product, and repeatedly filtering, washing, distilling and purifying to obtain the purified amide compound containing the electro-absorption conjugated double bond.
The invention also provides a synthesis method of the thiol-Michael addition click reaction-based polyamide, which comprises the following steps:
(1) dissolving 1.0 equivalent part of amide compound containing the electroabsorption conjugated double bond and 1.0 equivalent part of dimercapto compound in a heavy steaming polar solvent; wherein the polar solvent is one or a mixture of N, N-dimethylformamide DMF, N-dimethylacetamide DMAc, N-methylpyrrolidone NMP, dimethyl sulfoxide DMSO and acetonitrile;
(2) adding 0.002-0.020 equivalent part of catalyst, heating to 40-60 ℃, stirring for at least 6 hours, and monitoring a mercapto characteristic peak (2550-2590 cm) by Fourier transform infrared FTIR -1 ) And (4) changing, when the characteristic peak of the sulfydryl disappears, reducing to room temperature, removing the solvent through a solvent recovery device, and drying to obtain the polyamide.
The invention has the beneficial effects that: the traditional synthetic method comprises the steps of salifying diamine and dicarboxylic acid at high temperature, and then generating amido bond in a dehydration condensation mode under high vacuum degree and high temperature, while the synthetic monomer contains amido bond, and can realize polymerization by utilizing sulfydryl-Michael addition click reaction, without high temperature and high vacuum, the equipment requirement is low, the process condition is mild, the energy consumption is low, the polymerization degree is high, the synthetic monomers are various, the molecular designability is flexible, and the synthetic method can be used for synthesizing conventional nylon engineering plastics, high-temperature nylon engineering plastics, nylon elastomers, polyamide hot melt adhesives and the like with excellent performance.
Detailed description of the preferred embodiment
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to specific examples.
The following raw materials are used in the experiments of the examples and comparative examples of the present invention, but the following raw materials are not limited thereto, and the present invention is only to further illustrate the effects of the thiol-Michael addition click reaction-based polyamide of the present invention by using the following raw materials as specific examples:
primary diamine: polyetheramine D400, number average molecular weight 400g/mol, polyetheramine D2000, number average molecular weight 2000g/mol, Attr chemical; poly-1, 4-butanediol bis (4-aminobenzoate), the number average molecular weight is 1200g/mol, and Yarui chemical industry; p-phenylenediamine, xujie chemical; 1, 12-diaminododecane, Kandis chemical.
Bis-mercapto compounds: 3-6-dioxa-1-8-octane dithiol DODT, mclin; 1, 9-nonanedithiol NDT, a neochemical industry.
Acryloyl chloride, wold chemical industry.
Catalyst: 1,5, 7-triazabicyclo (4.4.0) dec-5-ene TBD, Mecline.
Acid binding agent: triethylamine, pioneering chemical industry.
Polar solvent: n, N-dimethylformamide DMF, wet-abundance petrochemical.
The method for synthesizing the amide compound (amide monomer for short) containing the electro-absorption conjugated double bond comprises the following steps:
(1) respectively dissolving 1.0 equivalent part of primary dibasic amine, namely D400, D2000, poly-1, 4-butanediol bis (4-aminobenzoate), 1, 12-diaminododecane and p-phenylenediamine in a redistilled polar solvent DMF;
(2) 2.25 equivalent parts of acid-binding agent triethylamine is added and stirred uniformly;
(3) under the condition of room temperature, 2.0 equivalent parts of acryloyl chloride is dripped into the mixed system, stirring is carried out while dripping, deionized water is added after reaction is carried out for 3 hours to dissolve by-products and precipitate target products, and the purified amide compound containing the electro-absorption conjugated double bond, namely the amide monomer 1-5, is obtained through repeated filtering, washing, distillation and purification procedures.
The invention sets examples 1-4 and comparative examples 1-4, which show that the route can synthesize nylon elastomer, nylon engineering plastic and high temperature resistant engineering plastic, and the charging equivalent parts are shown in table 1.
TABLE 1 equivalent parts of materials charged in examples 1 to 4 and comparative examples 1 to 4
Figure BDA0003720215330000071
The synthesis method of embodiments 1 to 4 includes the steps of:
(1) 1.0 equivalent part of 1-5 monomers and 1.0 equivalent part of 3-6-dioxa-1-8-octane dithiol DODT or 1.0 equivalent part of 1, 9-nonanedithiol NDT are dissolved in redistilled DMF;
(2) adding 0.005 equivalent part of catalyst 1,5, 7-triazabicyclo (4.4.0) dec-5-ene TBD, heating to 60 ℃, stirring for at least 6 hours, monitoring the change of a mercapto characteristic peak by adopting Fourier transform infrared FTIR (infrared Fourier transform infrared) when the mercapto infrared characteristic peak (2550-2590 cm) -1 ) Cooling to room temperature when the solvent disappears, and recovering the solvent by a solvent recovery deviceRemoving the solvent and drying to obtain the polyamide.
The synthesis method of comparative examples 1 to 4 includes the following steps: 1.0 equivalent part of 1-5 monomers and 1.0 equivalent part of 3-6-dioxa-1-8-octane dithiol DODT or 1.0 equivalent part of 1, 9-nonanedithiol NDT are dissolved in redistilled DMF, the temperature is raised to 60 ℃, stirring is carried out for 72 hours, and a characteristic peak of sulfydryl (2550-2590 cm) is monitored by Fourier transform infrared FTIR -1 ) Alternatively, the solvent is removed by a solvent recovery device.
The success or failure of the synthesis of examples 1 to 4 and comparative examples 1 to 4 was evaluated by a molecular weight test; in the embodiment 1-2, a flexible chain monomer is adopted, a target polymerization product is a nylon elastomer, and the mechanical property evaluation is increased; in the embodiment 3, a long carbon chain monomer is adopted, and a target polymerization product (PA1210) is nylon engineering plastic, so that the mechanical property evaluation is increased; example 4 Using aromatic monomers, the target Polymer (PA10T) was a high temperature nylon engineering plastic with increased intrinsic viscosity and glass transition temperature T g And melting temperature T m And (6) testing.
And (3) molecular weight evaluation: the number average molecular weights M of the various products were measured by Gel Permeation Chromatography (GPC) n Weight average molecular weight M w And molecular weight distribution index PDI, DMF as mobile phase, and 80 deg.C as experimental temperature.
And (3) mechanical property evaluation: the tensile strength and the elongation at break of the nylon elastomer are tested by referring to the method specified in GB/T528-2009, and the tensile strength and the elongation at break of the nylon engineering plastic are tested by referring to the methods specified in GB/T1040.1-2018 and GB/T1040.2-2006.
Performance of high temperature nylon: intrinsic viscosity is tested by referring to the method specified in GB/T12006.1-2009, and glass transition temperature T is tested by referring to the method specified in GB/T19466.3-2004 g And melting temperature T m 。
GPC results of the reaction products of examples 1 to 4 and comparative examples 1 to 4 are shown in Table 2:
TABLE 2 GPC results of the reaction products of examples 1 to 4 and comparative examples 1 to 4
Figure BDA0003720215330000081
Figure BDA0003720215330000091
Examples 1-4 are typical high polymers, indicating successful polymerization, the significant peaks in the leaching curves for comparative examples 1 and 2 correspond to monomer 1, monomer 2 and monomer 3, and no significant peaks are observed for comparative examples 3 and 4, thus none of comparative examples 1-4 was successful.
The mechanical property results of the polymerization products of examples 1 to 4 are shown in Table 3:
table 3 mechanical Properties results of the polymerization products of examples 1 to 4
Tensile strength/MPa Elongation at break/%
Example 1 1.84 884
Example 2 24.6 416
Example 3 48.3 215
Example 4 132.8 2.7
From the tensile strength and elongation at break of example 1, the polymer product has typical elastomer characteristics, the mechanical properties of the polymer product of example 2 are comparable to those of the commercial nylon elastomer PEBAX 7033, and the mechanical properties of the polymer product of example 3 are comparable to those of the commercial long carbon chain nylon PA1012 such as
Figure BDA0003720215330000092
PA1012 performance was comparable.
Example 4 the polymer product had an intrinsic viscosity of 98.2mL/g and a glass transition temperature T g At 151.4 ℃ and a melting temperature T m At 313.8 ℃ with commercial PA10T grades such as Grivory HT3 and
Figure BDA0003720215330000093
HT plus is similar.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.

Claims (10)

1. The polyamide based on the mercapto-Michael addition click reaction is characterized in that the polyamide is synthesized by carrying out the mercapto-Michael addition click reaction on a dimercapto compound and an amide compound containing an electroabsorption conjugated double bond under the action of a catalyst, and the equivalent ratio of the dimercapto compound to the amide compound containing the electroabsorption conjugated double bond to the catalyst is 1:1: 0.002-0.020.
2. The thiol-michael addition click reaction-based polyamide according to claim 1, wherein the dimercapto compound is 3-6-dioxa-1-8-octanedithiol, tetraethylene glycol di (ethylene glycol), 3, 7-dithia-1, 9-nonanedithiol, 1-propanedithiol, 1, 2-ethanedithiol, 1, 6-hexanedithiol, 2, 7-naphthalenedithiol, 1, 11-undecanedithiol, 1, 16-hexadecanedithiol, 2, 6-naphthalenedithiol, 1, 9-nonanedithiol, 1, 5-pentanethiol, 1, 3-propanedithiol, 1, 4-phenylenedithiol, 1, 10-decanedithiol, 1, 2-propanedithiol, 1, 4-propanedithiol, 1, 10-decanedithiol, 1, 2-propanedithiol, 1, 6-propanedithiol, 1, 6-propanedithiol, 1,2, 1,2, 1,2, or, P-terphenyl-4, 4' -dithiol, 1, 5-dimercaptonaphthalene, 1, 2-benzenedithiol, lubutanedithiol, 4-chloro-1, 3-benzenedithiol, 1, 3-butanedithiol, biphenyl-4, 4' -dithiol, 1, 8-octanedithiol, 1, 2-butanedithiol, benzenethiol, 4' -dimercaptostilbene, 4' -dimercaptodiphenylether, 1, 4-dithioerythritol, 4' -dimercaptodiphenylsulfide, dithiothreitol, L-1, 4-dithiothreitol, ethylene glycol dimercaptoacetate, di (thioglycolic acid) -1, 4-butanediyl, toluene-3, 4-dithiol, 2, 3-butanedithiol, 1, 2-butanedithiol, 4-dithiol, 4-dimethyldithiol, and the like, 1, 4-butanedithiol, dimercaprol, dimercaptomethane, polyethylene glycol dithiol and/or difunctional polysulfide rubber.
3. The thiol-michael addition click reaction-based polyamide according to claim 1, wherein the amide compound having an electron-withdrawing conjugated double bond has the formula
Figure FDA0003720215320000011
Wherein R is 1 Is H or CH 3 。
4. The thiol-michael addition click reaction-based polyamide according to claim 3, characterized in that the amide compound containing an electron-withdrawing conjugated double bond is selected from the group consisting of the commercial compounds N, N ' -methylenebisacrylamide, N ' -vinylbisacrylamide, or N, N ' -methylenebismethacrylamide.
5. The thiol-michael addition click reaction-based polyamide according to claim 3, wherein the amide compound having an electrophilic conjugated double bond is obtained by reacting a primary diamine with acryloyl chloride.
6. The thiol-Michael addition click reaction-based polyamide according to claim 5, wherein the primary diamine is 1, 2-propanediamine, 1, 3-propanediamine, 1, 4-butanediamine, 2-methyl-1, 2-butanediamine, 2, 3-dimethyl-1, 4-butanediamine, 2, 3-dimethyl-2, 3-butanediamine, 1-pyridin-4-yl-1, 4-butanediamine, (R) -2-methylbutane-1, 4-diamine, 1, 5-diaminopentane, 2, 4-pentanediamine-2, 4-dimethyl, 1, 2-cyclopentediamine, 1, 4-pentanediamine, cis-1, 3-cyclopentediamine, or a mixture thereof, Trans-1, 3-cyclopentediamine, 1, 3-diaminopentane, 2 '-oxybis (ethylamine), dimethylpropanediamine, 1, 5-diamino-2-methylpentane, 1, 6-hexanediamine, 1, 2-cyclohexanediamine, 1, 3-cyclohexanediamine, 1, 4-cyclohexanediamine, 2-methyl-1, 3-cyclohexanediamine, methylcyclohexanediamine, 1, 7-diaminoheptane, 1, 8-octanediamine, 1, 9-nonanediamine, 1, 10-diaminodecane, 1, 12-diaminododecane, 4, 9-dioxa-1, 12-dodecanediamine, 4' -diaminodiphenylsulfone, p-phenylenediamine, o-phenylenediamine, m-phenylenediamine, benzidine, 1, 7-naphthalenediamine, (6-amino-2-naphthyl) amine, 2, 3-diaminonaphthalene, 1, 5-naphthalenediamine, 1, 4-diaminonaphthalene, 1, 8-diaminonaphthalene, isophoronediamine, bicyclo [2.2.1] heptanedimethylamine, 4' -diaminodicyclohexylmethane, procoloa dimer diamine primine 1075, amino terminated polyoxypropylene ether, amino terminated polytetramethylene ether, poly-1, 4-butanediol bis (4-aminobenzoate), amino terminated polybutadiene, amino terminated poly (butadiene-acrylonitrile), amino terminated polyisoprene, amino terminated polyisobutylene, amino terminated polyoxyethylene ether.
7. The thiol-michael addition click reaction based polyamide according to claim 1, characterized in that the catalyst is a tertiary amine compound or an organophosphine compound.
8. The thiol-michael addition click reaction based polyamide according to claim 7, characterized in that the catalyst is one or more mixtures of o-hydroxybenzyldimethylamine DMP-10, 2,4, 6-tris (dimethylaminomethyl) phenol DMP-30, bis (dimethylaminoethyl) ether BDMAEE, N-methylmorpholine NEM, benzyldimethylamine BDMA, triethylamine TEA, N-dimethylaniline DMA, N-diethylaniline DEA, 1,5, 7-triazabicyclo (4.4.0) dec-5-ene TBD, diazabicyclo DBU, diazabicyclo DBN, triphenylphosphine, tri-N-butyl phosphine, triisopropylphosphine, tribenzylphosphine, tricyclopentylphosphine, tris (dimethylamino) phosphine, tripyrrolidinphosphine, tri-N-octylphosphine.
9. The thiol-michael addition click reaction-based polyamide according to claim 5 or 6, wherein the amide compound having an electron-withdrawing conjugated double bond is synthesized by the following method:
(1) dissolving 1.0 equivalent part of primary diamine in a redistilled polar solvent; wherein the polar solvent is one or a mixture of N, N-dimethylformamide DMF, N-dimethylacetamide DMAc, N-methylpyrrolidone NMP, dimethyl sulfoxide DMSO and acetonitrile;
(2) adding 2.0-2.5 equivalent parts of an acid-binding agent and uniformly stirring; wherein the acid-binding agent is one or a mixture of triethylamine, N-diisopropylethylamine, sodium hydroxide, sodium acetate and potassium carbonate;
(3) and (2) dropwise adding 2.0 equivalent of acryloyl chloride into the mixed system at room temperature, stirring while dropwise adding, reacting for 2-4 hours, adding deionized water to dissolve by-products and precipitate a target product, and repeatedly filtering, washing, distilling and purifying to obtain the purified amide compound containing the electro-absorption conjugated double bond.
10. A synthesis method of a thiol-Michael addition click reaction based polyamide according to any one of claims 1 to 8, characterized in that it comprises the following steps:
(1) dissolving 1.0 equivalent part of amide compound containing the electroabsorption conjugated double bond and 1.0 equivalent part of dimercapto compound in a heavy steaming polar solvent; wherein the polar solvent is one or a mixture of N, N-dimethylformamide DMF, N-dimethylacetamide DMAc, N-methylpyrrolidone NMP, dimethyl sulfoxide DMSO and acetonitrile;
(2) adding 0.002-0.020 equivalent part of catalyst, heating to 40-60 ℃, stirring for at least 6 hours, and monitoring a mercapto characteristic peak of 2550-2590 cm by Fourier transform infrared FTIR -1 And (4) changing, when the characteristic peak of the sulfydryl disappears, reducing to room temperature, removing the solvent through a solvent recovery device, and drying to obtain the polyamide.
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