CN103923243A - Rotatory polyacetylene infrared low-transmission material and preparation method thereof - Google Patents
Rotatory polyacetylene infrared low-transmission material and preparation method thereof Download PDFInfo
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Abstract
The invention aims to provide a rotatory polyacetylene infrared low-transmission material and a preparation method thereof. The material is prepared by polymerizing L or D-tyrosine alcohol ester and alkynyl-containing carboxylic acid monomer in the action of a rhodium catalyst. The structural general formula of the material is as shown in the specification, the polymerization degree n is an integer of 1-1000, wherein R1 is one component as shown in the specification, m and p are 0, 1, 2, 3 and 4; R2 is one component as shown in the specification, k is 0, 1, 2, 3 and 4. The material has an excellent thermal stability, relatively high optical activity and stable conformation, the glass transition temperature is more than 200 DEG C, the thermal decomposition temperature is 300-400 DEG C, the absolute value of specific rotation is 50-200 degrees, and the infrared transmission rate in the wave band of 8-4mu m at 25 DEG C is 0.35-0.65.
Description
Technical field
The present invention relates to a kind of optically-active polyacetylene infrared low-emissivity material and preparation method thereof, belong to the category of preparing of organic functions polymer materials, can be used for infrared stealth material.
Background technology
Infrared stealth material is at human-body safety protection, hertzian wave abatement apparatus, electromagnetic interference, electromagnetic compatibility, heat preservation energy-saving and stealthy and counterreconnaissance technology etc. are civilian, military domain is all widely used basis.Modern war frequently relies on infrared thermal imagery reconnaissance location technology, for ensureing the disguise of military target, uses the material with infrared stealth, can to a certain degree accomplish camouflage and " stealthy ", strengthens existence and the attack ability of military target.At present, a large amount of military vehicles has used infrared stealth material, but in use has some problems.Such as, the most of tinting pigments in infrared stealth material are generally difficult to turn down the emittance of coating, once add these tinting pigments in some stealth material, its emittance can sharply raise etc.Therefore,, for addressing these problems, research new infrared stealth material and the lower material of exploration infrared emittance are directions of infrared stealth Materials.Organic polymer has the advantage that structure is adjustable, diversified, physical and chemical performance is unique and is studied widely and apply, and wherein optically active polymer is the novel high polymer material that developed recently gets up.From structure, the specificity on the configuration that the inducing action of the dissymmetrical field that optically active polymer produces by chiral radicals forms forms metastable one-way spiral structure.This structural performance makes such material have good optically-active, point light action and easily makes to see through ripple generation red shift.As the dielectric material in infrared wave communication process, its absorbing property and frequency shift property can be obtained good effect on reduction material infrared emissivity.At present, patent CN1865300A discloses alkynes the third ureas monomer and opticity spiropolymer and preparation method thereof, mainly obtains by catalytic ligand polyreactions such as transition metal rhodium, tungsten, molybdenums the replaced acetylene base polymer that has stable helical conformation, optical activity is stronger.Patent CN101696260A openly reports a kind of polarimetric polyurethane-urea infrared low emissivity material, and dinaphthalene group is introduced in polymer chain, carrys out the infrared emittance of regulation and control polymer chain structure and polymkeric substance by adjusting polymer architecture.The invention provides a kind of optically-active polyacetylene infrared low-emissivity material, this material is by L or D-Tyrosine alcohol ester and contain alkynyl carboxylic acid monomer, and polymerization obtains under rhodium catalyst, this material is a kind of rising infrared stealth material, its research and application have potential economic benefit and social benefit, to military and civilianly all have broad application prospects.
Summary of the invention
Technical problem: the object of this invention is to provide a kind of optically-active polyacetylene infrared low-emissivity material and preparation method thereof.This material has good thermostability, higher optical activity and stable conformation, can be used as infrared low-emissivity material and uses.
Technical scheme: a kind of optically-active polyacetylene infrared low-emissivity material of the present invention is to be obtained under rhodium catalyst with containing alkynyl carboxylic acid synthon by L or D type tyrosine derivative, and its general structure is:
polymerization degree n is 1～1000 integer;
Wherein R
1for:
in one, m, p are 0,1,2,3,4;
R2 is:
in one, k is 0,1,2,3,4.
The preparation method of this optically-active polyacetylene infrared low-emissivity material is:
Step a) at room temperature, the tetrahydrofuran solution of the L that is 1～2mol/L by concentration or D type tyrosine alcohol ester adds in reactor, adding with L or D type tyrosine alcohol ester mol ratio is 1:1～1.5:1 containing alkynyl carboxylic acid again, stirring at room temperature 0.5～1h, the N-Dimethylamino pyridine that to add with L or D-Tyrosine alcohol ester mol ratio be 0.1:1～0.2:1 again and the N of 1:1～1.3:1, N '-dicyclohexylcarbodiimide, reaction 10～12h, reactant is poured in the deionized water of tetrahydrofuran solution volume of 1～5 times of L or D-Tyrosine alcohol ester, with the ethyl acetate extraction of 1～5 times of L or D-Tyrosine alcohol ester tetrahydrofuran solution volume, and use successively the saturated NaHCO of the tetrahydrofuran solution volume of 1～5 times of L or D-Tyrosine ester
3the aqueous solution, the HCl aqueous solution, the saturated NaCl aqueous solution and deionized water wash this acetic acid ethyl acetate extract, and HCl concentration of aqueous solution is 1～2mol/L.The anhydrous MgSO of acetic acid ethyl acetate extract after washing
4dry, after filtering, steam and obtain L or D-chirality containing alkynyl monomer except ethyl acetate solvent.
Step b) N
2under atmosphere, by preparation process, a) L or D-chirality add in reaction flask containing alkynyl monomer, adding tetrahydrofuran (THF) configuration concentration is the tetrahydrofuran solution of 0.5～2mol/L, the ratio that is 1:50 containing alkynyl monomer mole ratio in rhodium catalyst and L or D-chirality adds the tetrahydrofuran solution of the rhodium catalyst of 0.1～0.5mol/L, be heated to 30～50 DEG C, reaction 20～24h.Be cooled to room temperature, pour in 20～50 times of L or the D-chirality normal hexane containing the tetrahydrofuran solution volume of alkynyl monomer, separate out precipitation, filter, 30～50 DEG C of vacuum-drying 10～20h, obtain optically-active polyacetylene infrared low-emissivity material.
In above-mentioned preparation method, L or the D-Tyrosine alcohol ester of preparation process described in a) is L or D-Tyrosine C
1～C
5one in straight chain saturated fatty alcohol ester, L or D-Tyrosine phenol ester, L or D-Tyrosine phenylcarbinol ester, L or D-Tyrosine phenylglycollic ester, L or D-Tyrosine phenylpropyl alcohol alcohol ester, L or D-Tyrosine benzene butyl alcohol ester, L or D-Tyrosine Suidisin ester.Be propynoic acid, butynoic acid, pentynoic acid, hexynoic acid, heptynoic acid or to the one in acetylenylbenzene formic acid containing alkynyl carboxylic acid.Rhodium catalyst in step b) is chlorination norbornadiene rhodium dimer or chlorination cyclooctadiene rhodium dimer.
Beneficial effect: the invention provides a kind of optically-active polyacetylene infrared low-emissivity material and preparation method thereof, this material has good thermostability, higher optical activity and stable conformation, can be used as infrared low-emissivity material and uses.
Feature of the present invention is:
(1) ethynyl is introduced in main polymer chain, chiral amino acid is as side chain, thereby in polymer molecule, form spirane structure, obtain the higher polyacetylene material of specific rotation, this material has good thermostability and higher optical activity, can be used for the infrared low-emissivity material higher for stability requirement.
(2) change the amino acid alcohol ester of different molecular structures by adjustment, the side chain steric hindrance size of adjustable polymkeric substance, and then reach the object that regulates its optically active and infrared emittance.
It is 300～400 DEG C that the second-order transition temperature of the above-mentioned optically-active polyacetylene infrared low-emissivity material preparing is greater than 200 DEG C, heat decomposition temperature, specific rotatory power absolute value is about 50 °～200 °, and at 25 DEG C, the infrared emittance of 8～14 mu m wavebands is 0.35～0.65.
Embodiment
Embodiment 1
At room temperature, 0.98g TYR methyl esters is dissolved in to 5mL tetrahydrofuran (THF), add again 0.44g butynoic acid, stirring at room temperature 0.5h, then add the N-Dimethylamino pyridine of 60mg and the N of 1.24g, N '-dicyclohexylcarbodiimide, under room temperature, react 12h, reactant is poured in the deionized water of 15mL, with the extraction of 20mL ethyl acetate, and used successively the saturated NaHCO of 20mL
3the saturated NaCl aqueous solution of the HCl aqueous solution, 20mL and 20mL deionized water that the aqueous solution, 20mL concentration are 1mol/L wash this acetic acid ethyl acetate extract, and use anhydrous MgSO
4dry, after filtering, steaming removes ethyl acetate solvent and obtains N-butine acyl group-L-butyric acid methyl esters 0.88g.
At N
2under protection, 0.55g N-butine acyl group-L-butyric acid methyl esters is dissolved in to 1mL tetrahydrofuran (THF), gets 10mg chlorination norbornadiene rhodium dimer and be dissolved in 1mL tetrahydrofuran (THF), be heated to 40 DEG C, reaction 20h.Be cooled to room temperature, pour in 100mL normal hexane, separate out precipitation, filter, 50 DEG C of vacuum-drying 10h, obtain L-type optically-active polyacetylene infrared low-emissivity material 0.41g.The specific rotatory power of this material is+69.7 °, and heat decomposition temperature is 313 DEG C, and (8～14 μ are m) 0.574 to infrared emittance under room temperature.
Embodiment 2
At room temperature, 1.05g D-Tyrosine ethyl ester is dissolved in to 5mL tetrahydrofuran (THF), add again 0.51g pentynoic acid, stirring at room temperature 0.5h, then add the N-Dimethylamino pyridine of 60mg and the N of 1.24g, N '-dicyclohexylcarbodiimide, under room temperature, react 12h, reactant is poured in the deionized water of 15mL, with the extraction of 20mL ethyl acetate, and used successively the saturated NaHCO of 20mL
3the saturated NaCl aqueous solution of the HCl aqueous solution, 20mL and 20mL deionized water that the aqueous solution, 20mL concentration are 1mol/L wash this acetic acid ethyl acetate extract, and use anhydrous MgSO
4dry, after filtering, steaming removes ethyl acetate solvent and obtains N-pentyne acyl group-D-butyric acid ethyl ester 0.97g.
At N
2under protection, 0.56g N-pentyne acyl group-D-butyric acid ethyl ester is dissolved in to 1mL tetrahydrofuran (THF), gets 10mg chlorination norbornadiene rhodium dimer and be dissolved in 1mL tetrahydrofuran (THF), be heated to 50 DEG C, reaction 24h.Be cooled to room temperature, pour in 100mL normal hexane, separate out precipitation, filter, 50 DEG C of vacuum-drying 10h, obtain D type optically-active polyacetylene infrared low-emissivity material 0.48g.The specific rotatory power of this material is-72.6 °, and heat decomposition temperature is 331 DEG C, and (8～14 μ are m) 0.401 to infrared emittance under room temperature.
Embodiment 3
At room temperature, 1.29g TYR phenol ester is dissolved in to 5mL tetrahydrofuran (THF), add again 0.44g butynoic acid, stirring at room temperature 0.5h, then add the N-Dimethylamino pyridine of 60mg and the N of 1.24g, N '-dicyclohexylcarbodiimide, under room temperature, react 12h, reactant is poured in the deionized water of 15mL, with the extraction of 20mL ethyl acetate, and used successively the saturated NaHCO of 20mL
3the saturated NaCl aqueous solution of the HCl aqueous solution, 20mL and 20mL deionized water that the aqueous solution, 20mL concentration are 1mol/L wash this acetic acid ethyl acetate extract, and use anhydrous MgSO
4dry, after filtering, steaming removes ethyl acetate solvent and obtains N-butine acyl group-L-butyric acid phenol ester 1.15g.
At N
2under protection, 0.64g N-butine acyl group-L-butyric acid phenol ester is dissolved in to 1mL tetrahydrofuran (THF), gets 10mg chlorination norbornadiene rhodium dimer and be dissolved in 1mL tetrahydrofuran (THF), be heated to 30 DEG C, reaction 24h.Be cooled to room temperature, pour in 100mL normal hexane, separate out precipitation, filter, 50 DEG C of vacuum-drying 10h, obtain L-type optically-active polyacetylene infrared low-emissivity material 0.56g.The specific rotatory power of this material is+89.2 °, and heat decomposition temperature is 342 DEG C, and (8～14 μ are m) 0.428 to infrared emittance under room temperature.
Embodiment 4
At room temperature, 1.36g D-Tyrosine phenylcarbinol ester is dissolved in to 5mL tetrahydrofuran (THF), add again 0.51g pentynoic acid, stirring at room temperature 0.5h, then add the N-Dimethylamino pyridine of 60mg and the N of 1.2g, N '-dicyclohexylcarbodiimide, under room temperature, react 12h, reactant is poured in the deionized water of 15mL, with the extraction of 20mL ethyl acetate, and used successively the saturated NaHCO of 20mL
3the saturated NaCl aqueous solution of the HCl aqueous solution, 20mL and 20mL deionized water that the aqueous solution, 20mL concentration are 1mol/L wash this acetic acid ethyl acetate extract, and use anhydrous MgSO
4dry, after filtering, steaming removes ethyl acetate solvent and obtains N-pentyne acyl group-D-butyric acid phenylcarbinol ester 1.64g.
At N
2under protection, 0.67g N-pentyne acyl group-D-butyric acid phenylcarbinol ester is dissolved in to 1mL tetrahydrofuran (THF), gets 10mg chlorination norbornadiene rhodium dimer and be dissolved in 1mL tetrahydrofuran (THF), be heated to 50 DEG C, reaction 24h.Be cooled to room temperature, pour in 100mL normal hexane, separate out precipitation, filter, 50 DEG C of vacuum-drying 10h, obtain D type optically-active polyacetylene infrared low-emissivity material 0.54g.The specific rotatory power of this material is-79.4 °, and heat decomposition temperature is 328 DEG C, and (8～14 μ are m) 0.526 to infrared emittance under room temperature.
Embodiment 5
At room temperature, 0.98g TYR methyl esters is dissolved in to 5mL tetrahydrofuran (THF), add again 0.44g butynoic acid, stirring at room temperature 0.5h, then add the N-Dimethylamino pyridine of 60mg and the N of 1.24g, N '-dicyclohexylcarbodiimide, under room temperature, react 12h, reactant is poured in the deionized water of 15mL, with the extraction of 20mL ethyl acetate, and used successively the saturated NaHCO of 20mL
3the saturated NaCl aqueous solution of the HCl aqueous solution, 20mL and 20mL deionized water that the aqueous solution, 20mL concentration are 1mol/L wash this acetic acid ethyl acetate extract, and use anhydrous MgSO
4dry, after filtering, steaming removes ethyl acetate solvent and obtains N-butine acyl group-L-butyric acid methyl esters 0.88g.
At N
2under protection, 0.55g N-butine acyl group-L-butyric acid methyl esters is dissolved in to 1mL tetrahydrofuran (THF), gets 8mg chlorination cyclooctadiene rhodium dimer and be dissolved in 1mL tetrahydrofuran (THF), be heated to 40 DEG C, reaction 24h.Be cooled to room temperature, pour in 100mL normal hexane, separate out precipitation, filter, 50 DEG C of vacuum-drying 10h, obtain L-type optically-active polyacetylene infrared low-emissivity material 0.32g.The specific rotatory power of this material is+59.4 °, and heat decomposition temperature is 313 DEG C, and (8～14 μ are m) 0.605 to infrared emittance under room temperature
Embodiment 6
At room temperature, 1.05g D-Tyrosine ethyl ester is dissolved in to 5mL tetrahydrofuran (THF), add again 0.51g pentynoic acid, stirring at room temperature 0.5h, then add the N-Dimethylamino pyridine of 60mg and the N of 1.24g, N '-dicyclohexylcarbodiimide, under room temperature, react 12h, reactant is poured in the deionized water of 15mL, with the extraction of 20mL ethyl acetate, and used successively the saturated NaHCO of 20mL
3the saturated NaCl aqueous solution of the HCl aqueous solution, 20mL and 20mL deionized water that the aqueous solution, 20mL concentration are 1mol/L wash this acetic acid ethyl acetate extract, and use anhydrous MgSO
4dry, after filtering, steaming removes ethyl acetate solvent and obtains N-pentyne acyl group-D-butyric acid ethyl ester 0.97g.
At N
2under protection, 0.56g N-pentyne acyl group-D-butyric acid ethyl ester is dissolved in to 1mL tetrahydrofuran (THF), gets 8mg chlorination cyclooctadiene rhodium dimer and be dissolved in 1mL tetrahydrofuran (THF), be heated to 50 DEG C, reaction 24h.Be cooled to room temperature, pour in 100mL normal hexane, separate out precipitation, filter, 50 DEG C of vacuum-drying 10h, obtain D type optically-active polyacetylene infrared low-emissivity material 0.35g.The specific rotatory power of this material is-64.3 °, and heat decomposition temperature is 331 DEG C, and (8～14 μ are m) 0.352 to infrared emittance under room temperature.
Claims (5)
1. an optically-active polyacetylene infrared low-emissivity material, is characterized in that this material is obtained with containing alkynyl carboxylic acid monomer polymerization under rhodium catalyst by L or D-Tyrosine alcohol ester, and its general structure is:
Polymerization degree n is 1～1000 integer,
Wherein R1 is:
in one, m, p are 0,1,2,3,4;
R
2for:
in one, k is 0,1,2,3,4.
2. a preparation method for a kind of optically-active polyacetylene infrared low-emissivity material as claimed in claim 1, is characterized in that this preparation method is:
Step a) at room temperature, the tetrahydrofuran solution of the L that is 1～2mol/L by concentration or D type tyrosine alcohol ester adds in reactor, adding with L or D type tyrosine alcohol ester mol ratio is 1:1～1.5:1 containing alkynyl carboxylic acid monomer again, stir 0.5～1h, add again with L or D-Tyrosine alcohol ester mol ratio the N-Dimethylamino pyridine that is 0.1:1～0.2:1, the N that mol ratio is 1:1～1.3:1, N '-dicyclohexylcarbodiimide, room temperature reaction 10～12h; To add the tetrahydrofuran (THF) in reactor, reactant is poured in the deionized water of 1～5 times of tetrahydrofuran (THF) volume, with the ethyl acetate extraction of 1～5 times of tetrahydrofuran (THF) volume, obtain acetic acid ethyl acetate extract, and use successively the saturated NaHCO of 1～5 times of tetrahydrofuran (THF) volume
3the aqueous solution, the HCl aqueous solution, the saturated NaCl aqueous solution and deionized water wash this extraction liquid, and the concentration of the HCl aqueous solution is 1～2mol/L, the anhydrous MgSO of the extraction liquid after washing
4dry, filter, steam except ethyl acetate solvent, must contain alkynyl carboxylic acid monomer;
Step b) N
2under atmosphere, what step a) was made adds in reactor containing alkynyl carboxylic acid monomer, add tetrahydrofuran (THF), concentration is 0.5～2mol/L containing alkynyl carboxylic acid monomer tetrahydrofuran solution, add the tetrahydrofuran solution of the rhodium catalyst of 0.1～0.5mol/L in rhodium catalyst and the ratio that is 1:20 containing alkynyl carboxylic acid monomer mol ratio, at 30～50 DEG C, react 20～24h, be chilled to room temperature, pour reactant into 20～50 times containing in the normal hexane of alkynyl carboxylic acid monomer tetrahydrofuran solution volume, separate out precipitation, filter, 30～50 DEG C of vacuum-drying 10～20h, obtain optically-active polyacetylene infrared low-emissivity material.
3. the preparation method of optically-active polyacetylene infrared low-emissivity material according to claim 2, is characterized in that the L described in this preparation method's step a) or D-Tyrosine alcohol ester are L or D-Tyrosine C
1～C
5one in straight chain saturated fatty alcohol ester, L or D-Tyrosine phenol ester, L or D-Tyrosine phenylcarbinol ester, L or D-Tyrosine phenylglycollic ester, L or D-Tyrosine phenylpropyl alcohol alcohol ester, L or D-Tyrosine benzene butyl alcohol ester, L or D-Tyrosine Suidisin ester.
4. the preparation method of optically-active polyacetylene infrared low-emissivity material according to claim 2, is characterized in that described in this preparation method's step a) being propynoic acid, butynoic acid, pentynoic acid, hexynoic acid, heptynoic acid or to the one in acetylenylbenzene formic acid containing alkynyl carboxylic acid.
5. the preparation method of optically-active polyacetylene infrared low-emissivity material according to claim 2, is characterized in that the rhodium catalyst described in this preparation method's step b) is chlorination norbornadiene rhodium dimer or chlorination cyclooctadiene rhodium dimer.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106987024A (en) * | 2017-04-13 | 2017-07-28 | 东南大学 | A kind of nano combined absorbing material of infrared compatible with microwave and preparation method thereof |
| CN110396156A (en) * | 2019-07-08 | 2019-11-01 | 东南大学 | A kind of stimuli responsive type spiral carbene infrared radiant material and preparation method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002072020A2 (en) * | 2001-03-12 | 2002-09-19 | Cerno Biosciences, Llc. | Novel anti-adhesive compounds and uses thereof |
| CN101696260A (en) * | 2009-10-12 | 2010-04-21 | 东南大学 | Polarimetric polyurethane-urea infrared low emissivity material and preparation method thereof |
| CN101864055A (en) * | 2010-06-13 | 2010-10-20 | 东南大学 | Optically active helical polyurethane material and preparation method thereof |
-
2014
- 2014-04-11 CN CN201410145234.5A patent/CN103923243B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002072020A2 (en) * | 2001-03-12 | 2002-09-19 | Cerno Biosciences, Llc. | Novel anti-adhesive compounds and uses thereof |
| CN101696260A (en) * | 2009-10-12 | 2010-04-21 | 东南大学 | Polarimetric polyurethane-urea infrared low emissivity material and preparation method thereof |
| CN101864055A (en) * | 2010-06-13 | 2010-10-20 | 东南大学 | Optically active helical polyurethane material and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106987024A (en) * | 2017-04-13 | 2017-07-28 | 东南大学 | A kind of nano combined absorbing material of infrared compatible with microwave and preparation method thereof |
| CN110396156A (en) * | 2019-07-08 | 2019-11-01 | 东南大学 | A kind of stimuli responsive type spiral carbene infrared radiant material and preparation method |
| CN110396156B (en) * | 2019-07-08 | 2021-09-28 | 东南大学 | Stimulus-response type spiral polyacetylene infrared radiation material and preparation method thereof |
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Address after: 210093 Nanjing University Science Park, 22 Hankou Road, Gulou District, Nanjing City, Jiangsu Province Patentee after: Southeast University Address before: 210033 Xigang office, Qixia District, Nanjing, Jiangsu, No. 8, Qi Min Dong Road, Xingshan City, Patentee before: Southeast University |
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