CN111647153A - Preparation method of complex color-developing polyamide - Google Patents
Preparation method of complex color-developing polyamide Download PDFInfo
- Publication number
- CN111647153A CN111647153A CN202010576676.0A CN202010576676A CN111647153A CN 111647153 A CN111647153 A CN 111647153A CN 202010576676 A CN202010576676 A CN 202010576676A CN 111647153 A CN111647153 A CN 111647153A
- Authority
- CN
- China
- Prior art keywords
- polyamide
- piperazine
- preparation
- complexing
- cobalt chloride
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/28—Preparatory processes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
- C08J7/14—Chemical modification with acids, their salts or anhydrides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/06—Polyamides derived from polyamines and polycarboxylic acids
Abstract
A preparation method of complex chromogenic polyamide, belonging to the field of polyamide. Firstly, carrying out bulk Michael addition on piperazine and acrylate to synthesize a piperazine diester monomer; the polyamide is subjected to polycondensation with different diamines to obtain linear polyamide with a main chain containing piperazine rings; the cobalt chloride solution is used for complexing modification, so that the glass transition temperature, the mechanical strength and the Young modulus of the cobalt chloride solution are greatly improved; the complexed polyamide has good solvent discoloration performance on water and methanol. The preparation method is simple and convenient to operate, low in production cost and convenient for commercial production, is expected to be applied to the fields of material reinforcement, solvent indicators, anti-counterfeiting materials and the like, and has wide application prospects.
Description
Technical Field
The invention relates to a preparation method of complex color-developing polyamide. In particular to a method for synthesizing piperazine diester monomer by reacting anhydrous piperazine with acrylate, and then carrying out melt polycondensation with diamine to obtain linear polyamide with piperazine ring in the main chain; finally, the cobalt ions are used for carrying out complex modification on the composite material, so that the mechanical property of the material is improved, and the material is endowed with good solvent color-changing capability. Belongs to the technical field of polyamide.
Technical Field
Piperazine is used in small amounts in the biopharmaceutical field as a by-product in the production of ethylenediamine, and is also used in small amounts in the synthesis of polymers. Piperazine has been investigated for the preparation of polyamides. Heinrich et al (WO 2011062850A 2) synthesized a moisture-curing adhesive by direct polycondensation of piperazine with a dibasic acid or the like; nakagawa et al (JP 2010143888A and JP 2010070474A) use a crosslinked polyamide separation membrane containing a piperazine structure to separate and purify bio-based chemical raw materials such as butanol and succinic acid. In the piperazine-based polyamide, an amide bond is formed between a piperazine ring and a diacyl structure, and a nitrogen atom of the amide bond has no complexing ability and cannot be used for complexing color development.
The invention synthesizes piperazine diester through Michael addition reaction of piperazine and acrylic ester, and obtains linear polyamide containing piperazine ring in main chain through polycondensation with diamine. The polyamide has good crystallization performance and complexing ability, the mechanical property of the material is obviously improved after the complexing modification is carried out on the polyamide by cobalt ions, and the polyamide has good solvent discoloration performance. The complex chromogenic polyamide has the advantages of simple synthesis method, mild reaction conditions, high efficiency, low cost and convenient popularization and application.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a method for preparing complex color-developing polyamide with higher crystallinity and good mechanical property by using anhydrous piperazine as a raw material. Through the complexing modification of cobalt ions, the mechanical property of the polyamide can be further improved, and the polyamide has excellent solvent discoloration performance.
Firstly, taking anhydrous piperazine and acrylate as raw materials, and carrying out Michael addition reaction under the conditions of no catalyst and no solvent to synthesize a piperazine diester monomer; then the linear polyamide is polymerized with diamine in a bulk to prepare linear polyamide with a main chain containing piperazine ring; and complexing and modifying the polyamide by using a cobalt chloride solution to obtain the complex color-developing polyamide. The method comprises the following specific steps:
1) preparation of piperazine diester monomer: feeding anhydrous piperazine and acrylate according to a molar ratio of 1 (2-2.5), carrying out Michael addition reaction for 4-5 h at 50-70 ℃, removing excessive acrylate by rotary evaporation, and recrystallizing the obtained solid with petroleum ether to obtain a white piperazine diester crystal;
2) preparation of linear polyamide with main chain containing piperazine ring: feeding piperazine diester prepared in the step 1) and diamine according to a molar ratio of 1 (1-1.05), performing melt polycondensation at 180-210 ℃ under the protection of nitrogen, performing pressure reduction reaction for 0.5-1 h by a water pump, and finally performing pressure reduction reaction for 2-6 h to 1-5 mmHg by an oil pump to obtain linear polyamide with a main chain containing piperazine rings;
3) the preparation method of the complex color-developing polyamide comprises the following steps: hot-pressing the linear polyamide containing piperazine ring prepared in step 2) to form a sample strip, immersing the sample strip into a cobalt chloride solution, and performing sufficient swelling complexation; carefully taking out the sample strip after complexing, washing away the residual cobalt chloride on the surface by deionized water, placing the sample strip on a polytetrafluoroethylene film, drying the sample strip in a 50-60 ℃ oven until the size of the sample strip is basically stable, and heating to 110-130 ℃ for drying for 6h to remove a solvent such as complexing water to obtain cobalt ion complexing linear polyamide; the complex polyamide has good solvent color change response to water and methanol.
Wherein, the structure of the piperazine diester monomer synthesized in the step 1) is shown as the formula (I):
in the above formula R1Is alkyl, preferably methyl, ethyl;
wherein the diamine used in step 2) has a structure represented by the general formula (II):
H2NR2NH2
(II)
in the above formula R2Is- (CH)2)nAn aliphatic chain such as (n-2 to 10) or an aliphatic chain containing an ether bond.
Wherein the cobalt chloride solution used in the step 3) is an aqueous solution or a methanol solution, and the mass concentration is 1-5%.
Wherein, the preparation mechanism of the cobalt ion complex in the step 3) is shown as a formula (III).
The invention has the following effects:
the method comprises the steps of firstly, synthesizing a piperazine diester monomer by using anhydrous piperazine and acrylate as raw materials through Michael addition reaction without adding a solvent or a catalyst; the aromatic polyamide is subjected to melt polycondensation with different diamines to obtain linear polyamide with a main chain containing piperazine rings. The specific structure is shown as a general formula (IV):
wherein R is2Is- (CH)2)n(n is 2 to 10) or an aliphatic chain having an ether bond structure.
The polyamide has excellent mechanical property, and series polymers with tensile strength of 7-31MPa and elongation at break of 58-720 percent can be prepared by using different diamines. The cobalt ions are used for carrying out complexing modification on the material, the glass transition temperature and the mechanical strength of the material are obviously improved, and the material has good solvent color-changing performance. The synthesis and modification method of the polymer is simple and convenient to operate, has low cost, is expected to be applied to the fields of solvent indicators, anti-counterfeiting materials and the like, and has wide application prospects.
Detailed Description
The intrinsic viscosity of the polymer in the present invention was measured by a one-point method using m-cresol as a solvent using an Ubbelohde viscometer. The glass transition temperature of the polymer was measured in accordance with GB/T19466.2-2004, using an apparatus DSC Q20 from TA.
According to the GB/T1040-2006 standard, the product is made into a standard dumbbell type sample, the stretching speed is 5mm/min, and the tensile strength and the elongation at break are measured by an INSTRON-1185 universal tensile machine.
The present invention will be described in detail below with reference to preferred examples according to the above-described embodiments, but the present invention is not limited to the following examples.
Example 1:
1) preparation of piperazine diester monomer: 30.15 parts of anhydrous piperazine and 72.32 parts of methyl acrylate are weighed according to parts by weight, the reaction is stopped after 5 hours of reaction at 55 ℃, excessive methyl acrylate is removed by rotary evaporation, and the obtained solid is recrystallized by petroleum ether to obtain white crystalline solid piperazine diester [ or 1, 4-bis- (methyl propionate) piperazine ], wherein the melting point is 55 ℃ and the yield is 96.7%.
2) Preparation of linear polyamide with main chain containing piperazine ring: weighing 10.33 parts of 1, 4-bis- (methyl propionate) piperazine prepared in the step 1) and 4.88 parts of 1, 6-hexamethylene diamine according to the parts by weight, rapidly heating to 140 ℃ under the protection of nitrogen, gradually increasing the temperature to 180 ℃ at the speed of 10 ℃/30min, preserving the temperature for 2h, rapidly increasing the system temperature to 210 ℃, reducing the pressure to 30mmHg by using a water pump, reacting for 1 hour, and then reducing the pressure by using an oil pump under the pressure of 2-3 mmHg until the system viscosity does not change any more, thus obtaining the yellowish opaque linear polyamide containing piperazine rings, wherein the intrinsic viscosity is 0.37dL/g, the glass transition temperature is 35 ℃, the tensile strength is 31MPa, and the elongation at break is 62%.
3) Preparation of complex color polyamide: carrying out hot press molding on the linear polyamide prepared in the step 2) to obtain a dumbbell-shaped sample strip, and soaking the dumbbell-shaped sample strip into a cobalt chloride aqueous solution with the mass fraction of 5% until the sample strip is fully swelled and complexed. Carefully taking out the complexed sample strips, washing off residual cobalt chloride on the surface by using deionized water, placing the sample strips on a polytetrafluoroethylene film, drying the sample strips in a 60 ℃ oven until the size of the sample strips is basically stable, raising the temperature of the oven to 120 ℃ and continuously drying the sample strips for 6 hours to obtain the cobalt ion complexed linear polyamide. The glass transition temperature is 68 ℃, the tensile strength is 55MPa, and the elongation at break is 15%. After the bamboo shoot is soaked in water or methanol solution, the color is changed from blue-green to pink; the sample is dried to remove water or methanol and the color returns to a blue-green color.
Example 2:
1) weighing 8 parts of 1, 4-bis- (methyl propionate) piperazine and 4.69 parts of 1, 8-octanediamine prepared in the step 1) of the embodiment 1 according to the parts by weight, rapidly heating to 140 ℃ under the protection of nitrogen, gradually heating to 180 ℃ at the speed of 10 ℃/30min, preserving heat for 2 hours, rapidly heating the system temperature to 210 ℃, decompressing to 30mmHg by using a water pump for reaction for 1 hour, and decompressing by using an oil pump under 2-3 mmHg until the viscosity of the system does not change any more, thereby obtaining the yellowish and opaque linear polyamide containing the piperazine ring, wherein the intrinsic viscosity of the linear polyamide is 0.38dL/g, the glass transition temperature of the linear polyamide is 32 ℃, the tensile strength of the linear polyamide is 26MPa, and the elongation at break of the linear polyamide is 58%.
2) The preparation method of the complex color-developing polyamide comprises the following steps: performing hot press molding on the linear polyamide prepared in the step 1) in the example 2 to obtain a dumbbell-shaped sample bar, soaking the dumbbell-shaped sample bar into a cobalt chloride aqueous solution with the mass fraction of 5% until the sample bar is fully swelled and complexed, carefully taking out the complexed sample bar, washing away residual cobalt chloride on the surface by using deionized water, placing the sample bar on a polytetrafluoroethylene film, drying the sample bar in a 60 ℃ drying oven until the size of the sample bar is basically stable, raising the temperature of the drying oven to 120 ℃ and continuously drying for 6 hours to obtain the cobalt ion complexed linear polyamide. The glass transition temperature is 63 ℃, the tensile strength is 48MPa, and the elongation at break is 17%. After the bamboo shoot is soaked in water or methanol solution, the color is changed from blue-green to pink; the sample is dried to remove water or methanol and the color returns to a blue-green color.
Example 3:
1) weighing 8 parts of 1, 4-bis- (methyl propionate) piperazine and 7.16 parts of diethylene glycol bis (3-aminopropyl) ether prepared in the step 1) of the embodiment 1 in parts by weight, rapidly heating to 140 ℃ under the protection of nitrogen and preserving heat for 2 hours, heating to 180 ℃ at the speed of 10 ℃/30min and preserving heat for 2 hours, then reducing the pressure to 30mmHg by using a water pump to react for 1 hour, and then reducing the pressure by using an oil pump under 2-3 mmHg until the viscosity of the system is not changed any more, so that the light yellow semitransparent linear polyamide containing piperazine rings is obtained, wherein the intrinsic viscosity of the light yellow semitransparent linear polyamide containing piperazine rings is 0.39dL/g, the glass transition temperature of the light yellow semitransparent polyamide is-7 ℃, the tensile strength of the light yellow linear polyamide.
2) The preparation method of the complex color-developing polyamide comprises the following steps: performing hot press molding on the linear polyamide prepared in the step 1) in the embodiment 3 to obtain a dumbbell-shaped sample bar, soaking the dumbbell-shaped sample bar into a cobalt chloride aqueous solution with the mass fraction of 5% until the sample bar is fully swelled and complexed, carefully taking out the complexed sample bar, washing away residual cobalt chloride on the surface by using deionized water, placing the sample bar on a polytetrafluoroethylene film, drying the sample bar in a 60 ℃ drying oven until the size of the sample bar is basically stable, raising the temperature of the drying oven to 120 ℃ and continuously drying for 6 hours to obtain the cobalt ion complexed linear polyamide. The glass transition temperature is 37 ℃, the tensile strength is 40MPa, and the breaking elongation is 300%. After the complex polyamide is soaked in water or methanol solution, the color is changed from blue-green to pink; the color turned back to blue-green after the bars were dried to remove water or methanol.
Claims (7)
1. A preparation method of complex color-developing polyamide is characterized in that anhydrous piperazine and acrylate are subjected to Michael addition reaction under the conditions of no catalyst and no solvent to synthesize a piperazine diester monomer; carrying out melt polycondensation on the piperazine derivative and different diamines to prepare linear polyamide with a main chain containing piperazine rings; complexing and modifying the polyamide with cobalt chloride solution to obtain complex color-developing polyamide; the method specifically comprises the following steps:
1) preparation of piperazine diester: feeding anhydrous piperazine and acrylate according to a molar ratio of 1 (2-2.5), carrying out bulk Michael addition reaction for 4-5 h at 50-70 ℃, removing excessive acrylate by rotary evaporation, and recrystallizing solid substances by petroleum ether to obtain white piperazine diester crystals;
2) preparation of linear polyamide with main chain containing piperazine ring: feeding piperazine diester prepared in the step 1) and diamine according to a molar ratio of 1 (1-1.05), performing melt polycondensation at 180-210 ℃ under the protection of nitrogen, performing pressure reduction reaction for 0.5-1 h by a water pump, and finally performing pressure reduction reaction for 2-6 h by an oil pump to 1-5 mmHg to obtain linear polyamide containing piperazine ring in the main chain;
3) preparation of complex color polyamide: hot-pressing the piperazine ring-containing linear polyamide prepared in the step 2) to form a dumbbell-shaped sample strip, and immersing the dumbbell-shaped sample strip into a cobalt chloride solution for sufficient swelling and complexing. Carefully taking out the sample strip after complexing, washing away the residual cobalt chloride on the surface by deionized water, placing the sample strip on a polytetrafluoroethylene film, drying the sample strip in a 50-60 ℃ drying oven until the size of the sample strip is basically stable, and then heating to 110-130 ℃ for drying for 6h to remove complexing water to obtain the cobalt ion complexing linear polyamide.
2. The method according to claim 1, wherein the piperazine diester monomer synthesized in step 1) has the structure shown in (i):
in the above formula R1Is an alkyl group, and is,methyl and ethyl are preferred.
3. The process according to claim 1, wherein the diamine used in step 2) has the structure shown in (II):
H2N-R2-NH2
(II)
in the above formula R2Is- (CH)2)n(n is 2 to 10) or an aliphatic chain having an ether bond structure.
4. The method according to claim 3, wherein the diamine used in step 2) is one or more of 1, 6-hexanediamine, 1, 8-octanediamine and diethylene glycol bis (3-aminopropyl) ether.
5. The method according to claim 1, wherein the cobalt chloride solution used in step 3) is an aqueous solution or a methanol solution, and has a mass concentration of 1% to 5%.
6. A complex-colored polyamide prepared by the process according to any one of claims 1 to 5.
7. Use of a complex chromogenic polyamide prepared according to the process of any one of claims 1 to 5 for a discoloration response to water and methanol solvents.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010576676.0A CN111647153B (en) | 2020-06-22 | 2020-06-22 | Preparation method of complex color-developing polyamide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010576676.0A CN111647153B (en) | 2020-06-22 | 2020-06-22 | Preparation method of complex color-developing polyamide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111647153A true CN111647153A (en) | 2020-09-11 |
| CN111647153B CN111647153B (en) | 2021-12-21 |
Family
ID=72341907
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010576676.0A Active CN111647153B (en) | 2020-06-22 | 2020-06-22 | Preparation method of complex color-developing polyamide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111647153B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4620949A (en) * | 1985-04-05 | 1986-11-04 | Texaco Inc. | Process for amidocarbonylation of cyclic amides |
| CN1608094A (en) * | 2001-12-27 | 2005-04-20 | 赫尔克里士公司 | Methyl acrylate-diamine based polyamide resins and processes for producing the same |
| CN109942824A (en) * | 2019-04-18 | 2019-06-28 | 黑龙江科技大学 | A kind of nitrogenous phosphonate fire retardant and its synthetic method |
-
2020
- 2020-06-22 CN CN202010576676.0A patent/CN111647153B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4620949A (en) * | 1985-04-05 | 1986-11-04 | Texaco Inc. | Process for amidocarbonylation of cyclic amides |
| CN1608094A (en) * | 2001-12-27 | 2005-04-20 | 赫尔克里士公司 | Methyl acrylate-diamine based polyamide resins and processes for producing the same |
| CN109942824A (en) * | 2019-04-18 | 2019-06-28 | 黑龙江科技大学 | A kind of nitrogenous phosphonate fire retardant and its synthetic method |
Non-Patent Citations (2)
| Title |
|---|
| KUAN LIANG ET AL: "Bio-based cross-linked polyitaconamides synthesized through a Michael ene-amine addition and bulk polycondensation", 《JOURNAL OF POLYMER RESEARCH》 * |
| MING-HAO YOU ET AL: "Colorimetric humidity sensors based on electrospun polyamide/CoCl2 nanofibrous membranes", 《NANOSCALE RESEARCH LETTERS》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111647153B (en) | 2021-12-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Ueda et al. | Poly (benzimidazole) synthesis by direct reaction of diacids and diamines | |
| US4937315A (en) | Transparent amorphous polyamide having high Tg from hindered aromatic diamine and branched chain aliphatic diamine | |
| CN105646876B (en) | A kind of method that organic catalysis prepares polyesteramide | |
| JPS63199227A (en) | Production of anhydrous polymer | |
| US4937322A (en) | Crystallized semiaromatic polyamides having high Tg and Tm less than 290 degree C. from hindered aromatic diamine and branched chain aliphatic diamine | |
| US10364251B2 (en) | Polyesters from assymetrical monomers based upon bisanhydrohexitols | |
| US20100152409A1 (en) | Triptycene Derivatives, Method for Synthesizing the Same and Application Thereof | |
| CN111647153B (en) | Preparation method of complex color-developing polyamide | |
| DK150981B (en) | PROCEDURE FOR THE PREPARATION OF DIESTER DIAMIDS | |
| CN114957898B (en) | Reversible stress response material and preparation method and application thereof | |
| CA1049533A (en) | Process for the manufacture of maleimides | |
| CN112795008A (en) | Synthesis process of nylon MXD6 | |
| US4794159A (en) | Heat-resistant polyamide from bis(4-aminophenyl)fluorene | |
| US4195165A (en) | Aliphatic polyamide from disubstituted decane diamine | |
| CA1120190A (en) | Crystalline polyamides | |
| CN114133391A (en) | Mother nucleus substituted naphthalene diimide electrochemical polymerization monomer and preparation method thereof | |
| TWI677514B (en) | Modifying agent, polyamide copolymer and method for preparing polyamide copolymer | |
| US4429109A (en) | Polyamides with high glass transition temperatures prepared from N,N'-terephthaloyldi-beta-alanine and a diamine | |
| US5006636A (en) | Process for the production of SiO2 containing polybenzamides | |
| Saigo et al. | Synthesis and properties of polyamides having anti head-to-head umbelliferone dimer as a component | |
| TWI744125B (en) | Method for manufacturing transparent polyamide copolymer | |
| CN115322173B (en) | Multifunctional hindered amine light stabilizer and preparation method thereof | |
| TWI227251B (en) | Fluoropolyamide and fluoropolyimide and its manufacturing method | |
| CN115449071B (en) | Copolyamide resin containing imide structure and preparation method thereof | |
| US2743248A (en) | Single stage process of polycondensation of alkylene-alkylidene and aralkylidene-bis-halogen substituted-carboxylic acid amides |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |