CN111205453B - Polyamide containing 1, 3-dimethyl-1, 3-diphenylurea structure and preparation method thereof - Google Patents
Polyamide containing 1, 3-dimethyl-1, 3-diphenylurea structure and preparation method thereof Download PDFInfo
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- CN111205453B CN111205453B CN202010133887.7A CN202010133887A CN111205453B CN 111205453 B CN111205453 B CN 111205453B CN 202010133887 A CN202010133887 A CN 202010133887A CN 111205453 B CN111205453 B CN 111205453B
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- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/40—Polyamides containing oxygen in the form of ether groups
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- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
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Abstract
The invention discloses polyamide containing a 1, 3-dimethyl-1, 3-diphenylurea structure and a preparation method thereof, belonging to the technical field of polyamide high polymer materials, wherein the 1, 3-dimethyl-1, 3-diphenylurea structure is directly introduced into polyamide molecules as a structural unit, the structural unit mainly exists in cis-cis conformation, and under the action of external force, the cis-cis conformation of a plurality of structural units is converted into trans-trans conformation to bring extra elongation, so that the tensile property of the polyamide material is improved, and the elongation is 24 times at most.
Description
Technical Field
The invention belongs to the technical field of polyamide high-molecular polymer materials, and particularly relates to a material which contains groups capable of undergoing forward and reverse conformational transition and releases length through the conformational transition so as to improve the elongation performance.
Background
The elongation property of the polymer material is an important physical property of the polymer material, but the elongation at break of the polymer material is generally improved by adding a plasticizer and the like into the existing polymer material, but the introduced plasticizer can cause the other properties of the material to be reduced, so that the method is to directly introduce a structure with the tensile property from the aspect of molecular design.
It was found by studies that diphenylureas tend to exist in trans-trans extended conformations in both solid and liquid phases, as shown in the following formula:
dimethyldiphenylurea predominates in the cis-cis folded conformation as shown in the following formula:
and the energy barrier difference between the three conformations of the dimethyldiphenylurea (i.e., the cis-cis conformation, the trans-cis conformation and the trans-trans conformation) is not very large, and several conformations are dynamically coexistent in the solvent. Therefore, the molecule may undergo a conformational transition under the action of an external force, releasing the length.
Disclosure of Invention
The invention aims to provide a high polymer material with special elongation property, which specifically utilizes the length change brought by the external force to the conformation transformation group to improve the elongation property of the material.
The invention provides a polyamide containing a 1, 3-dimethyl-1, 3-diphenyl urea structure, which has the following structural formula:
wherein, the 1, 3-dimethyl-1, 3-diphenyl urea structure mainly exists in cis-cis conformation, and the number average molecular weight is 20-69 kg/mol.
In the polyamide containing the 1, 3-dimethyl-1, 3-diphenylurea structure, 1, 3-dimethyl-1, 3-diphenylurea is a functional structure which can generate conformation transformation and is directly taken as a structural unit to be introduced into a polyamide molecule, and the polyamide molecule can generate the following transformation under the action of external force:
under the action of external force, the cis-cis conformation of a plurality of structural units is converted into trans-trans conformation, so that extra elongation is brought, the tensile property of the polyamide material is improved, the cis-cis conformation occupies most parts, and the effect is better and obvious when the cis-cis conformation is larger than 50%.
Polyetheramines are used as further structural units of the copolymers. This can achieve a reduction in TgThe aim of improving the tensile property of the material is achieved, and the polyether amine has the advantages of low price and easy availability.
The preparation method of the polyamide containing the 1, 3-dimethyl-1, 3-diphenyl urea structure comprises the following steps:
1) 1, 3-dimethyl-1, 3-di (4-carboxyl-phenyl) urea reacts to generate a corresponding diacid chloride product, and the diacid chloride product is dissolved in an organic solvent for standby.
2) Dissolving polyetheramine and sodium carbonate in water for later use; the polyether amine Mn 230～430g/mol；
3) The aqueous polyetheramine solution was mixed with the organic acid chloride solution to produce a white polymer at the interface. The crude product was washed with water and dried under vacuum.
The step 1) comprises the following specific steps: heating 0.3-1.5 g of 1, 3-dimethyl-1, 3-bis (4-carboxyl-phenyl) urea and 6-16 ml of thionyl chloride at 75-90 ℃, reacting for 5-15 hours, stopping heating, cooling to room temperature, and evaporating thionyl chloride to obtain a diacylchloride product.
Step 2) dissolving 0.7-3.9 g of polyetheramine and 0.18-0.96 g of sodium carbonate in 8-45 ml of deionized water;
in the step 1), the organic solvent is carbon tetrachloride, trichloromethane or a mixture of the two solvents.
The synthesis method has the advantages of simple reaction equipment, high reaction speed, high product purity and the like.
The polymer in the invention has good ductility due to containing a structural unit capable of generating molecular conformation transformation, and the maximum elongation is 24 times.
Drawings
FIG. 1 is a drawing of the product of example 1 of the invention1H NMR(DMSO-d6) A spectrogram;
FIG. 2 shows one-dimensional DOSY of the product of example 1 of the present invention1H NMR(DMSO-d6) A spectrogram;
FIG. 3 is a DSC curve of the product of example 1 of the present invention;
FIG. 4 is a stress-strain curve of the product of example 1 of the present invention;
FIG. 5 is a stress-strain cycle curve of the product of example 1 of the present invention;
FIG. 6 shows one-dimensional DOSY of the product of example 2 of the present invention1H NMR(DMSO-d6) A spectrogram;
FIG. 7 is a DSC curve of the product of example 2 of the present invention;
FIG. 8 shows the product of example 3 of the present inventionOne-dimensional DOSY1H NMR(DMSO-d6) A spectrogram;
FIG. 9 is a DSC curve of the product of example 3 of the present invention;
FIG. 10 shows one-dimensional DOSY of the product of example 4 of the present invention1H NMR(DMSO-d6) A spectrogram;
FIG. 11 is a DSC curve of the product of example 4 of the present invention.
Detailed Description
Example 1
1.5g (about 4.6mmol) of 1, 3-dimethyl-1, 3-bis (4-carboxy-phenyl) urea and 16ml of thionyl chloride are heated under reflux at 90 ℃ to react for 5 hours, then the heating is stopped, the reaction mixture is cooled to room temperature, and thionyl chloride is evaporated to obtain a diacylchloride product. The diacid chloride is dissolved in 45ml of carbon tetrachloride and put into a magnetic stirrer for standby. 3.9g of polyetheramine (M)nApproximately equal to 430g/mol) and 0.96g of sodium carbonate in 45ml of deionized water. And slowly pouring the polyether amine aqueous solution into the diacyl chloride organic solution, turning on a magnetic stirring switch after an interface appears to generate a white polymer, and continuously taking out the product until the polymer is not generated any more. Washing the generated polymer with deionized water, and then putting the polymer into an oven for vacuum drying at 50 ℃ until the product is colorless and transparent.
The dried product was characterized in relation to: FIG. 1 nuclear magnetism of polymer1H NMR(DMSO-d6) The spectra, again measured by diffusion sequence spectroscopy (DOSY) since one of the peaks coincides with the water molecule peak position, are shown in FIG. 2. Analysis of the polymer by DSC gives Tg22.4 ℃ (as shown in fig. 3); molecular weight was characterized by GPC (DMF as mobile phase): mn＝69.8kg/mol，Mw＝98.9kg/mol。
And (3) dissolving the polymer in dichloromethane, pouring the solution into a polytetrafluoroethylene mold, and demolding after the solvent naturally volatilizes to obtain a 520-micrometer-thick film. The film was cut into strips 15mm long and 8mm wide. The mechanical property of the sample strip is represented by a tensile test, and the elongation of the sample strip reaches 2490% as shown in figure 4; fig. 5 is a stress-strain curve for 5 cycles of continuous stretching.
Example 2
0.3g (about 0)85mmol)1, 3-dimethyl-1, 3-bis (4-carboxy-phenyl) urea and 10ml thionyl chloride are reacted at 75 ℃ for 15 hours, heating is stopped and the mixture is cooled to room temperature, and thionyl chloride is pumped out by an oil pump to obtain a diacylchloride product. The diacid chloride is dissolved in a mixed solvent of 7ml of carbon tetrachloride and 1.5ml of trichloromethane, and a magnetic stirrer is placed for standby. 0.39g of polyetheramine (M)nApproximately equal to 430g/mol) and 0.18g of sodium carbonate in 8ml of deionized water. And quickly pouring the polyether amine aqueous solution into the diacyl chloride organic solution, turning on a magnetic stirring switch to generate a white polymer, and taking out the product until the polymer is not generated any more. Washing the generated polymer with deionized water, and then putting the polymer into an oven for vacuum drying at 60 ℃ until the product is colorless and transparent.
The dried product was characterized in relation to: FIG. 6 is one-dimensional DOSY of a polymer1H NMR(DMSO-d6) A spectrum; analysis of the polymer by DSC gives Tg9.89 ℃ (as shown in fig. 7); molecular weight was characterized by GPC (DMF as mobile phase): mn＝25.9kg/mol，Mw＝40.0kg/mol。
And (3) dissolving the polymer in tetrahydrofuran, pouring the solution into a polytetrafluoroethylene mold, and demolding after the solvent is naturally volatilized to obtain a film with the thickness of 470 microns. The film was cut into strips 15mm long and 8mm wide. And the mechanical property of the sample strip is represented by a tensile test, and the elongation of the sample strip reaches 1830%.
Example 3
After 0.5g (about 1.5mmol) of 1, 3-dimethyl-1, 3-bis (4-carboxy-phenyl) urea is reacted with 10ml of thionyl chloride at 95 ℃ for 8 hours under heating, the heating is stopped and cooled to room temperature, and thionyl chloride is pumped out by an oil pump to obtain a diacylchloride product. The diacid chloride is dissolved in 18ml of carbon tetrachloride and put into a magnetic stirrer for standby. 0.7g of polyetheramine (M)nApproximately equal to 230g/mol) and 0.3g of sodium carbonate in 15ml of deionized water. And pouring the polyether amine aqueous solution into the diacid chloride organic solution, stirring to generate a white polymer, and continuously taking out the product along with the generation of the product. Washing the generated polymer with deionized water, and then putting the polymer into an oven for vacuum drying at 60 ℃ until the product is colorless and transparent.
Subjecting the dried product to phase separationAnd (3) performing a correlation characterization: FIG. 8 is one-dimensional DOSY of a polymer1H NMR(DMSO-d6) A spectrum; analysis of the polymer by DSC gives Tg54.16 ℃ (as shown in fig. 9); molecular weight was characterized by GPC (DMF as mobile phase): mn＝31.0kg/mol，Mw＝44.3kg/mol。
Example 4
0.5g (about 1.5mmol) of 1, 3-dimethyl-1, 3-bis (4-carboxy-phenyl) urea and 6ml of thionyl chloride are heated under reflux at 90 ℃ to react for 12 hours, then the heating is stopped, the reaction product is cooled to room temperature, and thionyl chloride is evaporated to obtain a diacylchloride product. The diacyl chloride is dissolved in 15ml of carbon tetrachloride and put into a magnetic stirrer for standby. 1g of polyetheramine (M)nAbout equal to 430g/mol and MnApproximately equal to 230g/mol) was dissolved in 15ml of deionized water with 0.35g of sodium carbonate. And slowly pouring the polyether amine aqueous solution into the diacyl chloride organic solution, turning on a magnetic stirring switch after an interface appears to generate a white polymer, and continuously taking out the product until the polymer is not generated any more. The polymer is washed by deionized water and then is put into an oven for vacuum drying at 55 ℃ until the product is colorless and transparent.
The dried product was characterized in relation to: FIG. 10 is one-dimensional DOSY of a polymer1H NMR(DMSO-d6) A spectrum; analysis of the polymer by DSC gives Tg29.36 ℃ (as shown in fig. 11); molecular weight was characterized by GPC (DMF as mobile phase): mn＝34.9kg/mol，Mw＝47.7kg/mol。
Claims (6)
1. A polyamide containing a 1, 3-dimethyl-1, 3-diphenylurea structure, characterized in that it has the following structural formula:
wherein the 1, 3-dimethyl-1, 3-diphenylurea structure exists mainly in cis-cis conformation.
2. Polyamide containing 1, 3-dimethyl-1, 3-diphenylurea structures according to claim 1, characterized in that it has a number-average molecular weight of 20-69 kg/mol.
3. The process for preparing polyamide containing 1, 3-dimethyl-1, 3-diphenylurea structure according to claim 1, comprising the steps of:
1) 1, 3-dimethyl-1, 3-di (4-carboxyl-phenyl) urea reacts to generate a corresponding diacid chloride product, and the diacid chloride product is dissolved in an organic solvent for standby;
2) dissolving polyetheramine and sodium carbonate in water for later use; the polyether amine Mn230 to 430 g/mol;
3) mixing the polyether amine aqueous solution with the diacid chloride organic solution to generate a white polymer at an interface as a crude product; the crude product was washed with water and dried under vacuum.
4. The method for producing a polyamide containing a 1, 3-dimethyl-1, 3-diphenylurea structure according to claim 3,
the step 1) comprises the following specific steps: heating 0.3-1.5 g of 1, 3-dimethyl-1, 3-bis (4-carboxyl-phenyl) urea and 6-16 ml of thionyl chloride at 75-90 ℃, reacting for 5-15 hours, stopping heating, cooling to room temperature, and evaporating thionyl chloride to obtain a diacylchloride product.
5. The method for producing a polyamide containing a 1, 3-dimethyl-1, 3-diphenylurea structure according to claim 3,
and 2) dissolving 0.7-3.9 g of polyetheramine and 0.18-0.96 g of sodium carbonate in 8-45 ml of deionized water.
6. The method for preparing polyamide containing 1, 3-dimethyl-1, 3-diphenylurea structure according to claim 3, wherein the organic solvent is carbon tetrachloride, chloroform or a mixture of two solvents.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS53141241A (en) * | 1977-05-13 | 1978-12-08 | Ube Ind Ltd | N-p-aminobenzyl-n'-p-aminophenylurea and process for its preparation |
| US4473681A (en) * | 1983-03-21 | 1984-09-25 | Celanese Corporation | Polyester urea capable of forming an anisotropic melt phase |
| CN108026325A (en) * | 2015-07-15 | 2018-05-11 | 巴斯夫欧洲公司 | Daiamid composition with improved optical property |
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2020
- 2020-03-02 CN CN202010133887.7A patent/CN111205453B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS53141241A (en) * | 1977-05-13 | 1978-12-08 | Ube Ind Ltd | N-p-aminobenzyl-n'-p-aminophenylurea and process for its preparation |
| US4473681A (en) * | 1983-03-21 | 1984-09-25 | Celanese Corporation | Polyester urea capable of forming an anisotropic melt phase |
| CN108026325A (en) * | 2015-07-15 | 2018-05-11 | 巴斯夫欧洲公司 | Daiamid composition with improved optical property |
Non-Patent Citations (1)
| Title |
|---|
| U-Shaped Aromatic Ureadicarboxylic Acids as Versatile Building Blocks: Construction of Ladder and Zigzag Networks and Channels;Shugo Hisamatsu et al.;《Crystal Growth & Design》;20111024;第5387-5395页 * |
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