CN113174042A - Preparation method and product of self-repairable self-flame-retardant polyamide material based on disulfide bonds - Google Patents
Preparation method and product of self-repairable self-flame-retardant polyamide material based on disulfide bonds Download PDFInfo
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Abstract
The invention discloses a preparation method of a self-repairable self-flame-retardant polyamide material based on disulfide bonds, which comprises the following steps: 1) mixing diamine, dibasic acid, diamino silicon ether and diamino disulfide monomers; 2) keeping the system at the temperature of 190-280 ℃ and the pressure of 1.0-2.0MPa for 0.5-3h under the inert gas atmosphere, then reducing the system pressure to the normal pressure within 0.5-3h, then vacuumizing for 0.5-5h, and discharging to obtain the catalyst. Compared with the prior art, no by-product is generated in the reaction process, the reaction time is greatly shortened, and the reaction efficiency is improved. The test result shows that the self-repairable self-flame-retardant polyamide material prepared by the invention has excellent mechanical properties, the self-repairing efficiency (120 ℃) can reach 98%, the self-flame-retardant grade can reach V-0 grade, and the crack problem and the polyamide flammability problem in the use process can be well solved.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a preparation method and a product of a self-repairable self-flame-retardant polyamide material based on disulfide bonds.
Background
Polyamides refer to a class of polymers that contain amide groups in the main chain. The intermolecular hydrogen bonding has excellent properties such as high strength, high toughness, high impact strength, excellent wear resistance, excellent alkali resistance and the like. Polyamide is one of five engineering plastics, and the application field of the polyamide is very wide. However, the occurrence of microcracks during use has a great limit to the service life and mechanical strength of the material. The artificial self-repairing polyamide (SHPA) can recover mechanical properties and original functions when being injured, and has important significance for prolonging service life, improving durability, reducing maintenance cost and the like. With the development of bionics and material science, various well-designed SHPAs have emerged over the past decades. Due to its wide range of potential applications, it has attracted the attention of various subject researchers, from traditional protective products to the latest fashion consumer electronics.
Patent CN 111732727A discloses a preparation method of a self-repairable polyamide material based on Diels-Alder. The method is a three-step method. Firstly, obtaining furan methylamine diester through acrylic ester and furan methylamine, and then carrying out polycondensation with polyether diamine to obtain a prepolymer. Piperazine reacts with butenedioic acid diester and then reacts with furan methylamine to generate star-shaped tetra-amide. The self-repairing polyamide material obtained by the method has high mechanical strength and certain self-repairing efficiency. However, the reaction steps are complicated and require a long time period.
Patent CN 111690132 a discloses a preparation method of a self-repairable polyamide material based on disulfide bonds. Because the diamine with disulfide has lower reactivity, the method prepares the diamine with disulfide into acyl chloride in the presence of cosolvent, and then carries out interfacial polymerization on the prepared diacyl chloride and the diamine, thereby obtaining the polyamide material based on disulfide bond and capable of self-repairing. The polyamide film material capable of self-repairing prepared by the method has excellent mechanical properties, and has certain room temperature self-repairing performance on microcracks in the using process. However, the method is a two-step operation, the reaction period is long, the yield is not high, the solvent used in the reaction process has certain toxicity, the operation requirement is high, and the method is not beneficial to mass production.
Patent CN 110317740a discloses a method for preparing self-repairable conductive polyamide by using two-dimensional materials such as carbon nanotubes. The polyamide matrix in the method is prepared from dimer fatty acid and diethylenetriamine. However, the reflux time is 30 hours, and the cost is high.
In addition, fire safety is an important property of the material in use. The polyamide material, in particular the aliphatic polyamide material belongs to the combustible material, and harmful gas escapes during combustion. The fire-proof and flame-retardant property has very important significance for polyamide materials. Therefore, the polyamide material which is fast and efficient, can self-repair and is self-flame retardant and the preparation method thereof are developed, and the polyamide material has very high application value.
Disclosure of Invention
The invention aims to provide a preparation method of a novel self-repairing self-flame-retardant polyamide material based on disulfide bonds, and the invention also aims to provide a product prepared by the method. By introducing dynamic disulfide bonds in the polymerization process, the self-healing self-flame-retardant polyamide material with a homogeneous system is synthesized by a random copolymerization method. The method greatly shortens the reaction time, improves the reaction efficiency, and can quickly and efficiently obtain the polyamide material with higher molecular weight.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a disulfide bond-based self-repairing self-flame-retardant polyamide material comprises the following steps:
1) mixing diamine, diacid, disulfide and silicon ether;
2) keeping the system at the temperature of 190-280 ℃ and the pressure of 1.0-2.0MPa for 0.5-3h under the inert gas atmosphere, then reducing the system pressure to the normal pressure within 0.5-3h, vacuumizing to the negative pressure, keeping the pressure for 0.5-5h, and discharging to obtain the catalyst.
Preferably, in the step 1), the molar ratio of the diamine, the dibasic acid, the silicon ether and the disulfide is (0.75-1.5): (4.55-4.95): (3.25-3.5): (0.25-1.0).
Preferably, in the step 1), the diamine is one or more of pentamethylene diamine, hexamethylene diamine, decamethylene diamine, undecamethylene diamine, dodecamethylene diamine, tridecylene diamine, tetradecylene diamine and cyclohexane diamine.
Further preferably, the dibasic acid is one or more of adipic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, cyclohexanedicarboxylic acid and terephthalic acid.
Further preferably, the disulfide is one or more of 4,4 '-diaminodiphenyl disulfide, 3' -diaminodiphenyl disulfide, dithiodiethylamine, 3 '-dithiodipropylamine, 3' -dihydroxydiphenyl disulfide, 4 '-dicarboxydiphenyl disulfide and 4,4' -dithiodibutanoic acid.
More preferably, the silicon ether is one or more of bisaminopropyltetramethylsiloxane, 1, 3-bis (4-hydroxybutyl) tetramethyldisiloxane and dipentapropyltetramethylsiloxane.
Preferably, in step 1), the inert gas is one or two of nitrogen, argon and carbon dioxide.
Preferably, in the step 2), vacuumizing is performed again until the negative pressure is maintained for 0.5-5 h.
Meanwhile, the invention also provides the self-repairing self-flame-retardant polyamide material based on the disulfide bond prepared by the method.
Compared with the prior art, the melt polymerization method adopted by the invention has the advantages that only water is generated in the reaction process, the side reaction is less, no solvent is needed, the reaction time is greatly shortened, the reaction efficiency is improved, the self-repairing self-flame-retardant elastomer material with stable quality can be quickly and efficiently obtained, and the melt polymerization method has the following remarkable advantages:
(1) the polymerization is carried out through amidation reaction among monomers, so that the yield is high, the operation is simple, a catalyst is not needed, the reaction time is short, the efficiency is high, the cost is low, and the batch production is facilitated;
(2) the self-repairing self-flame-retardant polyamide is prepared by melt polymerization, and the molecular weight of the product can be controlled by controlling the reaction time, the vacuumizing time and the acid-amine charge ratio. The method can rapidly prepare products with higher molecular weight and large melt viscosity;
(3) the reaction of the invention does not need organic solvent and does not discharge micromolecular organic matters, thus being green and environment-friendly.
Drawings
FIG. 1 is an infrared characteristic spectrum of a self-repairable self-flame-retardant polysilicamide material obtained in example 1 of the invention;
FIG. 2 shows the self-repairable self-flame-retardant polysilicamide material obtained in example 1 of the invention1H nuclear magnetic characteristic spectrum.
Detailed Description
The present invention will be further described with reference to the following examples, but the present invention is not limited thereto.
Example 1:
the self-repairable self-flame-retardant polyamide material based on the disulfide bond and the preparation method thereof comprise the following steps:
1) 1093g (4.75mol) of dodecanedioic acid, 264g (1.5mol) of decamethylenediamine, 900g (3.5mol) of bisaminopropyltetramethylsiloxane, 62g (0.25mol) of 4,4' -diaminodiphenyl disulfide were charged in a 5L autoclave;
2) replacing the gas with inert gas nitrogen for 5 times, then pressurizing to 0.3MPa, starting heating and stirring to 190 ℃, wherein the pressure is 1.7MPa, maintaining the pressure for 3 hours, then deflating, deflating for 3 hours, vacuumizing for 5 hours, then inflating to normal pressure, and then discharging.
Example 2:
the procedure of example 2 was as in example 1 except that the polymerization temperature, the degassing time and the evacuation time were varied, wherein the polymerization temperature was 280 ℃, the degassing time was 0.5h and the evacuation time was 0.5h, and the specific ratios are shown in Table 1.
Example 3:
the procedure of example 3 was as in example 1 except that the polymerization temperature, the degassing time and the evacuation time were varied, wherein the polymerization temperature was 240 ℃, the degassing time was 1.5h and the evacuation time was 2.5h, and the specific ratios are shown in Table 1.
Example 4:
the procedure of example 4 was as in example 3, except that the kind of diamine and disulfide was changed, wherein the diamine was hexamethylenediamine and the disulfide was 3, 3' -diaminodiphenyldisulfide. The specific ratio is shown in table 1.
Example 5:
the procedure of example 5 was as in example 3, except that the kind of diamine and disulfide was changed, wherein the diamine was 1, 4 cyclohexanediamine and the disulfide was dithiodiethylamine. The specific ratio is shown in table 1.
Example 6:
the procedure of example 6 was as in example 3 except that the type of diacid and disulfide was varied, wherein the diacid was terephthalic acid and the disulfide was dithiodiethylamine. The specific ratio is shown in table 1.
Example 7:
the procedure of example 7 is as in example 3, except that the type of diacid and disulfide is varied, wherein the diacid is 1, 4 cyclohexanedicarboxylic acid and the disulfide is 3, 3' -diaminodiphenyl disulfide. The specific ratio is shown in table 1.
Example 8:
the procedure of example 8 is as in example 3, except that the type of diacid and disulfide is varied, the diacid being adipic acid and the disulfide being 4,4' -dicarboxydiphenyl disulfide. The specific ratio is shown in table 1.
Comparative example 1
The synthesis of this comparative example differs from that of example 1 only in that the monomers synthesized are diamines, diacids and diaminosiloxanes without disulfides.
Comparative example 2
The synthesis of the polyamide of this comparative example differs from that of example 1 only in that the monomers synthesized are diamines, diacids and no silicon and disulfide.
The specific components and proportions of the examples and comparative examples are shown in Table 1
TABLE 1 Components and proportions of examples 1-8 and comparative examples 1-2
In other embodiments, the dibasic acid may also be selected from one of sebacic acid, undecanedioic acid, tridecanedioic acid, tetradecanedioic acid. The disulfide may be selected from one of 3, 3 '-dithiodipropylamine and 4,4' -dithiodibutanoic acid. The silicon ether can be selected from one of 1, 3-bis (4-hydroxybutyl) tetramethyldisiloxane and dipentylpretaethyltetramethylsiloxane, and details in the examples are not repeated.
Testing of the product Structure of the invention
The product prepared by the method is subjected to structure determination by adopting infrared spectroscopy (FT-IR) and nuclear magnetic resonance hydrogen spectrum (F)1H-NMR) test results confirmed that the product obtained in the present invention is a polysilicamide. The following description will be made by taking example 1 as an example. FIG. 1 and FIG. 2 show the IR (FT-IR) and NMR spectra of the polysilicamide obtained in example 11H-NMR) test results.
In the IR spectrum of FIG. 1, Si-CH is simultaneously present3The stretching vibration absorption peak of the middle C-H bond (795cm-1) Stretching vibration absorption peak of Si-O-Si bond (1041cm-1)，Si-CH3Middle C-H bending deformation absorption peak (1252cm-1) Absorption peaks of C-N stretching vibration and C ═ O in-plane bending vibration in amide bond (1537cm-1) C ═ O bond stretching vibration absorption peak (1637cm-1) The stretching vibration absorption peak of C-H bond in methylene (2928cm-1) Expansion and contraction vibration absorption peak of N-H bond (3305cm-1) Thus, the successful synthesis of PA1212/Si12 series copolymer was confirmed.
FIG. 2 is a schematic diagram of the utilization of1H-NMR measured chemical shifts of hydrogen atoms in the product of example 1 and calibrated.
From the results of fig. 1 and 2, the product obtained in example 1 was polysilamide.
Testing of the physical Properties of the products of the invention
In the examples of the present invention, the physical properties of the obtained polysilicamide were characterized, and the measurement instruments and the measurement standards used for the characterization are shown below.
TABLE 2 test items, instruments and standards
Examples 1-8 reflect the results of testing a variety of samples of polysilicamide prepared by the melt polymerization process, as shown in table 3.
TABLE 3 Properties of Polysilamides obtained in examples 1 to 8 and comparative examples 1 to 2
Mechanical properties were characterized and the material and repair effects were calculated by tensile testing for examples 1-8 and comparative examples 1-2.
As can be seen from Table 3, in examples 1 to 8, the self-repairable self-flame-retardant polyamide material obtained by using different monomers and ratios has excellent mechanical properties, self-repair efficiency and self-flame-retardant performance.
In comparative example 1, since no disulfide bond-carrying monomer was introduced, no self-repairing effect was obtained. And the introduction of disulfide is equivalent to or more excellent in mechanical strength and self-flame retardant effect.
In comparative example 2, since no silyl ether and no disulfide bond were introduced, the self-repairing and self-flame-retardant properties were not exhibited.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (9)
1. A preparation method of a disulfide bond-based self-repairing self-flame-retardant polyamide material is characterized by comprising the following steps:
1) mixing diamine, diacid, silicon ether and disulfide monomers;
2) keeping the system at the temperature of 190-280 ℃ and the pressure of 1.0-2.0MPa for 0.5-3h under the inert gas atmosphere; then, the gas is discharged to the normal pressure within 0.5 to 3 hours; vacuumizing to negative pressure, maintaining for 0.5-5 hr, and discharging.
2. The method for preparing the self-repairable self-flame-retardant polyamide material based on disulfide bonds as claimed in claim 1, wherein in the step 1), the molar ratio of the diamine, the diacid, the silicon ether and the disulfide is (0.75-1.5): (4.55-4.95): (3.25-3.5): (0.25-1.0).
3. The method for preparing the disulfide bond-based self-healing and self-flame-retardant polyamide material as claimed in claim 1, wherein in step 1), the diamine is one or more of pentamethylenediamine, hexamethylenediamine, decamethylenediamine, undecamethylenediamine, dodecamethylenediamine, tridecylenediamine, tetradecylenediamine, and cyclohexanediamine.
4. The method for preparing the disulfide bond-based self-healing self-flame-retardant polyamide material as claimed in claim 1, wherein in step 1), the dibasic acid is one or more of adipic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, cyclohexanedicarboxylic acid and terephthalic acid.
5. The method for preparing the self-healing self-flame-retardant polyamide material based on disulfide bonds according to claim 1, wherein in step 1), the disulfide is one or more of 4,4 '-diaminodiphenyl disulfide, 3' -diaminodiphenyl disulfide, dithiodiethylamine, 3 '-dithiodipropylamine, 3' -dihydroxydiphenyl disulfide, 4 '-dicarboxydiphenyl disulfide and 4,4' -dithiodibutanoic acid.
6. The preparation method of the self-healing self-flame-retardant polyamide material based on disulfide bonds according to claim 1, characterized in that the silyl ether is one or more of bisaminopropyltetramethylsiloxane, 1, 3-bis (4-hydroxybutyl) tetramethyldisiloxane and bispentapropyltetramethylsiloxane.
7. The preparation method of the self-healing self-flame-retardant polyamide material based on disulfide bonds according to claim 1, characterized in that in step 2), the inert gas is one or more of nitrogen, argon or carbon dioxide.
8. The preparation method of the self-healing self-flame-retardant polyamide material based on the disulfide bonds as claimed in claim 1, wherein in the step 2), the vacuum is further pumped to the negative pressure for 0.5-5 h.
9. The product obtained by the preparation method of the self-healing self-flame-retardant polyamide material based on disulfide bonds as claimed in any one of claims 1 to 8.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014029966A1 (en) * | 2012-08-24 | 2014-02-27 | Croda International Plc | Polyimide composition |
| CN109293916A (en) * | 2018-09-30 | 2019-02-01 | 郑州大学 | Polyamide/silicone copolymers and preparation method thereof |
| CN111690132A (en) * | 2020-06-01 | 2020-09-22 | 电子科技大学 | Preparation method of self-repairing polyamide packaging material for lithium battery soft package |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014029966A1 (en) * | 2012-08-24 | 2014-02-27 | Croda International Plc | Polyimide composition |
| CN109293916A (en) * | 2018-09-30 | 2019-02-01 | 郑州大学 | Polyamide/silicone copolymers and preparation method thereof |
| CN111690132A (en) * | 2020-06-01 | 2020-09-22 | 电子科技大学 | Preparation method of self-repairing polyamide packaging material for lithium battery soft package |
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