CN112321821B - Recyclable polyester polyamide and preparation method thereof - Google Patents
Recyclable polyester polyamide and preparation method thereof Download PDFInfo
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- CN112321821B CN112321821B CN202011178593.2A CN202011178593A CN112321821B CN 112321821 B CN112321821 B CN 112321821B CN 202011178593 A CN202011178593 A CN 202011178593A CN 112321821 B CN112321821 B CN 112321821B
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- 239000004952 Polyamide Substances 0.000 title claims abstract description 39
- 229920002647 polyamide Polymers 0.000 title claims abstract description 39
- 229920000728 polyester Polymers 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000000178 monomer Substances 0.000 claims abstract description 21
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 229920000642 polymer Polymers 0.000 claims description 87
- 238000006243 chemical reaction Methods 0.000 claims description 85
- 230000015556 catabolic process Effects 0.000 claims description 25
- 238000006731 degradation reaction Methods 0.000 claims description 25
- 230000009477 glass transition Effects 0.000 claims description 19
- 238000002844 melting Methods 0.000 claims description 19
- 230000008018 melting Effects 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 7
- HBANVIFSNSRJNS-UHFFFAOYSA-N C(C1=CC=CC=C1)(=O)N1C(C(CCCC1)OCC1=CC=CC=C1)=O Chemical group C(C1=CC=CC=C1)(=O)N1C(C(CCCC1)OCC1=CC=CC=C1)=O HBANVIFSNSRJNS-UHFFFAOYSA-N 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 3
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 claims description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 2
- 239000003341 Bronsted base Substances 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 79
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 51
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 51
- 238000005160 1H NMR spectroscopy Methods 0.000 description 38
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 34
- 239000006185 dispersion Substances 0.000 description 34
- 239000007787 solid Substances 0.000 description 33
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N Caprolactam Natural products O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 24
- 239000003708 ampul Substances 0.000 description 22
- 239000005711 Benzoic acid Substances 0.000 description 17
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 17
- 235000010233 benzoic acid Nutrition 0.000 description 17
- 238000001035 drying Methods 0.000 description 17
- 238000001914 filtration Methods 0.000 description 17
- 238000001291 vacuum drying Methods 0.000 description 17
- 238000003756 stirring Methods 0.000 description 15
- BOWUOGIPSRVRSJ-UHFFFAOYSA-N 2-aminohexano-6-lactam Chemical compound NC1CCCCNC1=O BOWUOGIPSRVRSJ-UHFFFAOYSA-N 0.000 description 10
- GSLDEZOOOSBFGP-UHFFFAOYSA-N alpha-methylene gamma-butyrolactone Chemical compound C=C1CCOC1=O GSLDEZOOOSBFGP-UHFFFAOYSA-N 0.000 description 8
- -1 amino- Chemical class 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000004033 plastic Substances 0.000 description 6
- 229920003023 plastic Polymers 0.000 description 6
- 238000011084 recovery Methods 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- 238000007334 copolymerization reaction Methods 0.000 description 5
- QGLBZNZGBLRJGS-UHFFFAOYSA-N Dihydro-3-methyl-2(3H)-furanone Chemical compound CC1CCOC1=O QGLBZNZGBLRJGS-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000004305 biphenyl Substances 0.000 description 3
- 239000011592 zinc chloride Substances 0.000 description 3
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical group [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 3
- VSCBATMPTLKTOV-UHFFFAOYSA-N 2-tert-butylimino-n,n-diethyl-1,3-dimethyl-1,3,2$l^{5}-diazaphosphinan-2-amine Chemical compound CCN(CC)P1(=NC(C)(C)C)N(C)CCCN1C VSCBATMPTLKTOV-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Substances OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- JCYWCSGERIELPG-UHFFFAOYSA-N imes Chemical compound CC1=CC(C)=CC(C)=C1N1C=CN(C=2C(=CC(C)=CC=2C)C)[C]1 JCYWCSGERIELPG-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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
- C08G69/44—Polyester-amides
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyamides (AREA)
Abstract
The invention discloses a polyester polyamide. The invention also provides a preparation method of the polyester polyamide, which comprises the step of mixing and reacting the monomer M1, the monomer M2, the coinitiator and the catalyst. The polyester polyamide provided by the invention has the advantage of recyclingAnd has excellent thermal and mechanical properties. The preparation method of the polyester polyamide is simple to operate, the catalyst is a commercialized compound, the source is wide, the cost is low, the catalytic activity is high, the controllability is strong, and the product yield is high.
Description
Technical Field
The invention belongs to the field of polymer synthesis, and particularly relates to recyclable polyester polyamide and a preparation method thereof.
Background
With the increase in global plastic production, the production can reach millions of tons per year. However, the waste plastics are mainly incinerated and buried, which causes a lot of environmental pollution, and development of environment-friendly materials is urgently needed. The poly (gamma-butyrolactone) has the characteristic of complete recyclability, can be completely degraded to a monomer, can realize closed-loop circulation, solves the problem of final treatment of plastics, and can provide a raw material capable of being used continuously. However, poly (gamma-butyrolactone) has insufficient thermal and mechanical properties to meet the daily requirements.
The copolymerization method is an important synthetic method for material modification. The polyamide has excellent thermal property and mechanical property, and is a good copolymerization material. However, gamma-butyrolactone and caprolactam monomers have great thermodynamic differences and different polymerizable properties, copolymerization of gamma-butyrolactone and caprolactam presents a serious challenge, and copolymerization of gamma-butyrolactone and caprolactam has not been reported in the literature. Therefore, the copolymerization of the gamma-butyrolactone and the caprolactam has important research value.
Disclosure of Invention
The invention aims to: the invention aims to solve the technical problem of providing a recyclable polyester polyamide high polymer material aiming at the defects of the prior art.
The technical scheme is as follows: in order to solve the technical problems, the invention discloses a polyester polyamide, which has the following structural formula:
wherein n and m are respectively and independently selected from any integer of 10-100;
wherein R is1、R2Each independently selected from ethyl, propyl, butyl, hexyl, benzyl, allyl or diethylene glycol monomethyl ether; r3Selected from hydrogen, methyl or methylene.
Preferably, the polyester polyamide has the following structural formula:
more preferably, the polyester polyamide has the following structural formula:
Such as:
preferably, the polyester polyamide has a number average molecular weight of 1000 to 50000g mol-1Preferably, the number average molecular weight is 5610 to 26860g mol-1。
Preferably, the polyester polyamide has a melting point of 40-200 ℃, preferably 69-182 ℃; the initial degradation temperature is 150-400 ℃, preferably 236-338 ℃; the glass transition temperature is-60 to 140 ℃, preferably-15 to 110 ℃.
Preferably, the polyester polyamide is capable of rapidly degrading under certain conditions to obtain the starting monomer.
Wherein the degradation conditions are as follows: the catalyst is ZnCl2(1-2 mol% of homopolymer), the reaction temperature is 30-200 ℃, the solvent is toluene (the concentration of the polymer is 0.5g/mL), the reaction time is 2-24 h, and the recovery rate is 20-70%.
Preferably, the polyester polyamide is polymerized from a monomer M1 and a monomer M2; wherein, the monomer M1 is any one of the structural formulas shown in the formula I; the monomer M2 is any one of the structural formulas shown in the formula II;
the invention also provides a preparation method of the polyester polyamide, which comprises the step of mixing and reacting the monomer M1, the monomer M2, the coinitiator and the catalyst.
Preferably, the molar ratio of the monomer M1 to the monomer M2 to the co-initiator to the catalyst is 10-100: 10-100: 1: 0.1 to 10.
Preferably, the reaction temperature is-60 to 100 ℃, and the reaction time is 5 to 1440 min.
Preferably, the co-initiator is N-benzoyl- α -benzyloxy-e-caprolactam which is any one of the formulas described in formula iii:
preferably, the catalyst is a bronsted base which is any one of the structural formulas described by formula iv:
the invention also provides the application of the polyester-polyamide in the preparation of chemically recyclable materials; the material capable of being recycled chemically is a plastic product, and the material capable of being recycled chemically is various plastic products such as packaging bags and plastic bottles.
Has the beneficial effects that: the polyester polyamide provided by the invention has recyclability and excellent thermal and mechanical properties. The preparation method of the polyester polyamide is simple to operate, the catalyst is a commercialized compound, the source is wide, the cost is low, the catalytic activity is high, the controllability is strong, and the product yield is high.
Detailed Description
The invention will be better understood from the following examples. However, those skilled in the art will readily appreciate that the description of the embodiments is only for illustrating the present invention and should not be taken as limiting the invention as detailed in the claims.
Example 1
N-benzoyl-. alpha. -benzyloxy-. epsilon. -caprolactam (0.0323g, 0.10 mmol) and gamma-butyrolactone (0.4305g, 5 mmol), alpha- (. alpha. -N-diethyl) amino-. epsilon. -caprolactam (0.9212g, 5 mmol) were added to a water-free and oxygen-free ampoule, and after stirring at 200rpm for 10 minutes, BEMP (0.1 ml, 0.1 mmol) was added and allowed to react at-50 ℃ for 14 hours. After the reaction was completed, a benzoic acid/methylene chloride solution (5 mg/ml) was added thereto and dissolved, and then the solution was taken out and added to a cold methanol solution, whereby a polymer precipitated. And filtering and separating to obtain a white solid, and transferring the white solid to a vacuum drying oven for drying to obtain the polymer. Conversion by the reaction solution1H NMR calculated to obtain a polymer structure1H NMR identifies the molecular weight and the degree of dispersion of the polymer by GPC. The conversion of gamma-butyrolactone was 76%, the conversion of alpha- (N-diethyl) amino-epsilon-caprolactam was 71%, and the number average molecular weight of the polymer was 10250 g/molThe dispersion coefficient was 1.21. The initial degradation temperature is 236 ℃, the melting point is 121 ℃ and the glass transition temperature is 60 ℃.
Example 2
N-benzoyl-. alpha. -benzyloxy-. epsilon. -caprolactam (0.0323g, 0.10 mmol) and gamma-butyrolactone (0.4305g, 5 mmol), epsilon-caprolactam (0.5654g, 5 mmol) were added to an anhydrous oxygen-free treated ampoule, stirred at 200rpm for 10 minutes, and then added tBu-P2(0.1 ml, 0.1 mmol), left to react at room temperature for 14 hours. After the reaction was completed, a benzoic acid/methylene chloride solution (5 mg/ml) was added thereto and dissolved, and then the solution was taken out and added to a cold methanol solution, whereby a polymer precipitated. And filtering and separating to obtain a white solid, and transferring the white solid to a vacuum drying oven for drying to obtain the polymer. Conversion by the reaction solution1H NMR calculation gave the polymer structure1H NMR identifies the molecular weight and the degree of dispersion of the polymer by GPC. The conversion of gamma-butyrolactone was 32%, the conversion of epsilon-caprolactam was 82%, the number average molecular weight of the polymer was 5610 g/mol, and the dispersion coefficient was 1.17. The initial degradation temperature is 290 ℃, the melting point is 168 ℃, and the glass transition temperature is 102 ℃.
Example 3
N-benzoyl-alpha-benzyloxy-epsilon-caprolactam (0.0323g, 0.10 mmol) and alpha-methyl-gamma-butyrolactone (0.5005g, 5 mmol), alpha- (N-butylphenyl) amino-epsilon-caprolactam (3.0819g, 10 mmol) were added to an anhydrous, oxygen-free treated ampoule, and after stirring at 200rpm for 10 minutes, the mixture was addedtBu-P4(0.3 ml, 0.3 mmol) and left to react at 40 ℃ for 24 hours. After the reaction was completed, a benzoic acid/methylene chloride solution (5 mg/ml) was added thereto and dissolved, and then the solution was taken out and added to a cold methanol solution, whereby a polymer was precipitated. Filtering and separating to obtain a white solid, and transferring the white solid to a vacuum drying oven for drying to obtain the polymer. Conversion rate is also determined by the reaction solution 1H NMR calculated to obtain a polymer structure1H NMR confirmed, and the molecular weight and the degree of dispersion of the polymer were determined by GPC. The conversion rate of the alpha-methyl-gamma-butyrolactone is 60 percent, the conversion rate of the alpha- (N-butyl phenyl) amino-epsilon-caprolactam is 80 percent,the polymer had a number average molecular weight of 15210 g/mole and a dispersion coefficient of 1.33. The initial degradation temperature is 296 ℃, the melting point is 162 ℃ and the glass transition temperature is 99 ℃.
Example 4
N-benzoyl- α -benzyloxy- ε -caprolactam (0.0323g, 0.10 mmol) and α -methylene- γ -butyrolactone (0.4955g, 5 mmol), α - (N-butylphenyl) amino- ε -caprolactam (1.3720g, 5 mmol) were added to an anhydrous, oxygen-free treated ampoule, and after stirring at 200rpm for 10 minutes, IMes (0.0152g, 0.05 mmol) was added and allowed to react at 60 ℃ for 24 hours. After the reaction was completed, a benzoic acid/methylene chloride solution (5 mg/ml) was added thereto and dissolved, and then the solution was taken out and added to a cold methanol solution, whereby a polymer was precipitated. Filtering and separating to obtain a white solid, and transferring the white solid to a vacuum drying oven for drying to obtain the polymer. Conversion rate is also determined by the reaction solution1H NMR calculation gave the polymer structure1H NMR identifies the molecular weight and the degree of dispersion of the polymer by GPC. The conversion of α -methylene- γ -butyrolactone was 42%, the conversion of α - (N-butylphenyl) amino-e-caprolactam was 74%, the number average molecular weight of the polymer was 26860 g/mol, and the dispersion coefficient was 1.37. The initial degradation temperature is 338 ℃, the melting point is 182 ℃ and the glass transition temperature is 110 ℃.
Example 5
N-benzoyl-. alpha. -benzyloxy-. epsilon. -caprolactam (0.0323g, 0.10 mmol) and γ -butyrolactone (0.44305g, 5 mmol), a- (. alpha. - (N-diphenyl) amino-. epsilon. -caprolactam (1.5422g, 5 mmol) were added to a water-free and oxygen-free treated ampoule, and after stirring at 200rpm for 10 minutes, the mixture was addedtBu-P4(0.05 ml, 0.05 mmol) and left to react at 80 ℃ for 12 hours. After the reaction was completed, a benzoic acid/methylene chloride solution (5 mg/ml) was added thereto and dissolved, and then the solution was taken out and added to a cold methanol solution, whereby a polymer precipitated. And filtering and separating to obtain a white solid, and transferring the white solid to a vacuum drying oven for drying to obtain the polymer. Conversion by the reaction solution1H NMR calculation gave the polymer structure1H NMR identifies the molecular weight and the degree of dispersion of the polymer by GPC. Gamma-butyrolactone conversion of30%, the conversion of alpha- (N-butylphenyl) amino-epsilon-caprolactam was 46%, the number-average molecular weight of the polymer was 9350 g/mol, and the dispersion factor was 128. The initial degradation temperature was 298 ℃, the melting point was 166 ℃ and the glass transition temperature was 90 ℃.
Example 6
N-benzoyl-. alpha. -benzyloxy-. epsilon. -caprolactam (0.0323g, 0.10 mmol) and gamma-butyrolactone (0.44305g, 5 mmol), alpha- (. alpha. -diphenyl) amino-. epsilon. -caprolactam (1.5422g, 5 mmol) were added to a dry, oxygen-free treated ampoule, and after stirring at 200rpm for 10 minutes, the mixture was added tBu-P2(0.10 ml, 0.10 mmol) and left to react at 80 ℃ for 12 hours. After the reaction was completed, a benzoic acid/methylene chloride solution (5 mg/ml) was added thereto and dissolved, and then the solution was taken out and added to a cold methanol solution, whereby a polymer precipitated. And filtering and separating to obtain a white solid, and transferring the white solid to a vacuum drying oven for drying to obtain the polymer. Conversion by the reaction solution1H NMR calculated to obtain a polymer structure1H NMR confirmed, and the molecular weight and the degree of dispersion of the polymer were determined by GPC. The conversion of gamma-butyrolactone was 30%, the conversion of alpha- (N-diphenyl) amino-epsilon-caprolactam was 46%, the number average molecular weight of the polymer was 9350 g/mol, and the dispersion coefficient was 1.28. The initial degradation temperature was 298 ℃, the melting point was 166 ℃ and the glass transition temperature was 90 ℃.
Example 7
N-benzoyl- α -benzyloxy- ε -caprolactam (0.0323g, 0.10 mmol) and α -methyl- γ -butyrolactone (0.5005g, 5 mmol), α - (N-dihexyl) amino- ε -caprolactam (1.4825g, 5 mmol) were added to an anhydrous, oxygen-free treated ampoule and after stirring at 200rpm for 10 minutes, BEMP (0.05 ml, 0.05 mmol) was added and allowed to react at 60 ℃ for 12 hours. After the reaction was completed, a benzoic acid/methylene chloride solution (5 mg/ml) was added thereto and dissolved, and then the solution was taken out and added to a cold methanol solution, whereby a polymer was precipitated. Filtering and separating to obtain a white solid, and transferring the white solid to a vacuum drying oven for drying to obtain the polymer. Conversion rate is also determined by the reaction solution 1H NMR calculation gave the polymer structure1H NMR determination, molecular weight of the polymer andthe degree of dispersion is determined by GPC. The conversion of α -methyl- γ -butyrolactone was 50%, the conversion of α - (N-dihexyl) amino-e-caprolactam was 69%, the number average molecular weight of the polymer was 13790 g/mol, and the dispersion coefficient was 1.42. The initial degradation temperature is 302 ℃, the melting point is 170 ℃, and the glass transition temperature is 97 ℃.
Example 8
N-benzoyl-alpha-benzyloxy-epsilon-caprolactam (0.0323g, 0.10 mmol) and alpha-methylene-gamma-butyrolactone (0.4955g, 5 mmol), alpha- (N-diethyl) amino-epsilon-caprolactam (0.9208g, 5 mmol) were added to a dry, oxygen-free treated ampoule and after stirring at 200rpm for 10 minutes, addedtBu-P4(0.08 ml, 0.08 mmol) and left to react at 60 ℃ for 12 hours. After the reaction was completed, a benzoic acid/methylene chloride solution (5 mg/ml) was added thereto and dissolved, and then the solution was taken out and added to a cold methanol solution, whereby a polymer was precipitated. Filtering and separating to obtain a white solid, and transferring the white solid to a vacuum drying oven for drying to obtain the polymer. Conversion rate is also determined by the reaction solution1H NMR calculation gave the polymer structure1H NMR identifies the molecular weight and the degree of dispersion of the polymer by GPC. The conversion of α -methylene- γ -butyrolactone was 36%, α - (N-diethyl) amino-e-caprolactam was 62%, the number average molecular weight of the polymer was 8800 g/mol, and the dispersion coefficient was 1.29. The initial degradation temperature was 270 ℃, the melting point was 120 ℃ and the glass transition temperature was 66 ℃.
Example 9
N-benzoyl-. alpha. -benzyloxy-. epsilon. -caprolactam (0.0323g, 0.10 mmol) and γ -butyrolactone (0.4305g, 5 mmol), a- (. alpha. - (N-diallyl) amino-. epsilon. -caprolactam (0.9208g, 5 mmol) were added to a water-free and oxygen-free treated ampoule, and after stirring at 200rpm for 10 minutes, the mixture was addedtBu-P4(0.10 ml, 0.10 mmol) and left to react at 30 ℃ for 24 hours. After the reaction was completed, a benzoic acid/methylene chloride solution (5 mg/ml) was added thereto and dissolved, and then the solution was taken out and added to a cold methanol solution, whereby a polymer precipitated. And filtering and separating to obtain a white solid, and transferring the white solid to a vacuum drying oven for drying to obtain the polymer. Conversion by the reaction solution1H NMR meterCalculated, the polymer structure is obtained by1H NMR identifies the molecular weight and the degree of dispersion of the polymer by GPC. The gamma-butyrolactone conversion was 56%, the alpha- (N-diallyl) amino-epsilon-caprolactam was 72%, the number average molecular weight of the polymer was 10300 g/mol, and the dispersion coefficient was 1.24. The initial degradation temperature was 283 ℃, the melting point was 112 ℃ and the glass transition temperature was 54 ℃.
Example 10
N-benzoyl-. alpha. -benzyloxy-. epsilon. -caprolactam (0.0323g, 0.10 mmol) and gamma-butyrolactone (0.6887g, 8 mmol), epsilon-caprolactam (0.2261g, 2 mmol) were added to an anhydrous oxygen-free treated ampoule, stirred at 200rpm for 10 minutes, and then added tBu-P4(0.10 ml, 0.10 mmol) and left to react at 30 ℃ for 24 hours. After the reaction was completed, a benzoic acid/methylene chloride solution (5 mg/ml) was added thereto and dissolved, and then the solution was taken out and added to a cold methanol solution, whereby a polymer precipitated. And filtering and separating to obtain a white solid, and transferring the white solid to a vacuum drying oven for drying to obtain the polymer. Conversion by the reaction solution1H NMR calculated to obtain a polymer structure1H NMR confirmed, and the molecular weight and the degree of dispersion of the polymer were determined by GPC. The conversion of gamma-butyrolactone was 66%, the epsilon-caprolactam was 87%, the number average molecular weight of the polymer was 7600 g/mol, and the dispersion coefficient was 1.21. The initial degradation temperature is 263 ℃, the melting point is 69 ℃, and the glass transition temperature is-15 ℃.
Example 11
N-benzoyl-. alpha. -benzyloxy-. epsilon. -caprolactam (0.0323g, 0.10 mmol) and γ -butyrolactone (0.8606g, 10 mmol), a- (. alpha. - (N-diallyl) amino-. epsilon. -caprolactam (3.0843g, 10 mmol) were added to a water-free and oxygen-free treated ampoule, and after stirring at 200rpm for 10 minutes, the mixture was addedtBu-P4(1 ml, 1 mmol) and left to react at 100 ℃ for 24 hours. After the reaction was completed, a benzoic acid/methylene chloride solution (5 mg/ml) was added thereto and dissolved, and then the solution was taken out and added to a cold methanol solution, whereby a polymer was precipitated. Filtering and separating to obtain a white solid, and transferring the white solid to a vacuum drying oven for drying to obtain the polymer. Conversion rate is also determined by the reaction solution 1H NMRCalculated by the polymer structure1H NMR confirmed, and the molecular weight and the degree of dispersion of the polymer were determined by GPC. The conversion of gamma-butyrolactone was 32%, alpha- (N-diallyl) amino-epsilon-caprolactam was 90%, the number average molecular weight of the polymer was 49920 g/mol, and the dispersion coefficient was 1.76. The initial degradation temperature is 400 ℃, the melting point is 200 ℃, and the glass transition temperature is 140 ℃.
Example 12
N-benzoyl-. alpha. -benzyloxy-. epsilon. -caprolactam (0.0323g, 0.10 mmol) and gamma-butyrolactone (0.0860g, 1 mmol), epsilon-caprolactam (0.3084g, 1 mmol) were added to a dry, oxygen-free treated ampoule and after stirring at 200rpm for 10 minutes, addedtBu-P4(0.1 ml, 0.1 mmol) and left to react at-60 ℃ for 5 minutes. After the reaction was completed, a benzoic acid/methylene chloride solution (5 mg/ml) was added thereto and dissolved, and then the solution was taken out and added to a cold methanol solution, whereby a polymer was precipitated. And filtering and separating to obtain a white solid, and transferring the white solid to a vacuum drying oven for drying to obtain the polymer. Conversion rate is also determined by the reaction solution1H NMR calculation gave the polymer structure1H NMR identifies the molecular weight and the degree of dispersion of the polymer by GPC. The gamma-butyrolactone conversion was 87%, the epsilon-caprolactam was 21%, the number average molecular weight of the polymer was 1210 g/mol, and the dispersion coefficient was 1.11. The initial degradation temperature is 150 ℃, the melting point is 44 ℃, and the glass transition temperature is-46 ℃.
Example 13
N-benzoyl-. alpha. -benzyloxy-. epsilon. -caprolactam (0.0323g, 0.10 mmol) and gamma-butyrolactone (0.8602g, 10 mmol), epsilon-caprolactam (0.3084g, 1 mmol) were added to a dry, oxygen-free treated ampoule and after stirring at 200rpm for 10 minutes, addedtBu-P4(0.1 ml, 0.1 mmol) and left to react at-60 ℃ for 60 minutes. After the reaction was completed, a benzoic acid/methylene chloride solution (5 mg/ml) was added thereto and dissolved, and then the solution was taken out and added to a cold methanol solution, whereby a polymer precipitated. And filtering and separating to obtain a white solid, and transferring the white solid to a vacuum drying oven for drying to obtain the polymer. Conversion rate is also determined by the reaction solution1H NMR calculation gave, polymerizedThrough the structure of an object1H NMR identifies the molecular weight and the degree of dispersion of the polymer by GPC. The gamma-butyrolactone conversion was 86%, the epsilon-caprolactam was 11%, the number average molecular weight of the polymer was 13540 g/mol, and the dispersion coefficient was 1.34. The initial degradation temperature is 236 ℃, the melting point is 40 ℃ and the glass transition temperature is-60 ℃.
Example 14
N-benzoyl-. alpha. -benzyloxy-. epsilon. -caprolactam (0.0323g, 0.10 mmol) and gamma-butyrolactone (0.4305g, 5 mmol), alpha- (. alpha. - (N-dipropyl) amino-. epsilon. -caprolactam (1.0612g, 5 mmol) were added to a water-free and oxygen-free treated ampoule, and after stirring at 200rpm for 10 minutes, the mixture was added tBu-P4(0.1 ml, 0.1 mmol) and left to react at 100 ℃ for 240 minutes. After the reaction was completed, a benzoic acid/methylene chloride solution (5 mg/ml) was added thereto and dissolved, and then the solution was taken out and added to a cold methanol solution, whereby a polymer was precipitated. Filtering and separating to obtain a white solid, and transferring the white solid to a vacuum drying oven for drying to obtain the polymer. Conversion rate is also determined by the reaction solution1H NMR calculation gave the polymer structure1H NMR identifies the molecular weight and the degree of dispersion of the polymer by GPC. The conversion of gamma-butyrolactone was 32%, alpha- (N-dipropyl) amino-epsilon-caprolactam was 78%, the number average molecular weight of the polymer was 12780 g/mol, and the dispersion coefficient was 1.38. The initial degradation temperature was 340 ℃, the melting point was 118 ℃ and the glass transition temperature was 83 ℃.
Example 15
N-benzoyl-. alpha. -benzyloxy-. epsilon. -caprolactam (0.0323g, 0.10 mmol) and γ -butyrolactone (0.4305g, 5 mmol), a- (N-dibutyl) amino-. epsilon. -caprolactam (1.2011g, 5 mmol) were added to a water-free and oxygen-free treated ampoule, and after stirring at 200rpm for 10 minutes, the mixture was addedtBu-P4(0.1 ml, 0.1 mmol) and left to react at 30 ℃ for 240 minutes. After the reaction was completed, a benzoic acid/methylene chloride solution (5 mg/ml) was added thereto and dissolved, and then the solution was taken out and added to a cold methanol solution, whereby a polymer was precipitated. Filtering and separating to obtain a white solid, and transferring the white solid to a vacuum drying oven for drying to obtain the polymer. Conversion rate is also determined by the reaction solution 1H NMR calculation of the polymer structure1H NMR identifies the molecular weight and the degree of dispersion of the polymer by GPC. The conversion of gamma-butyrolactone was 47%, alpha- (N-dibutyl) amino-epsilon-caprolactam was 81%, the number average molecular weight of the polymer was 17820 g/mol, and the dispersion coefficient was 1.42. Its initial degradation temperature was 361 ℃, melting point was 125 ℃ and glass transition temperature was 89 ℃.
Example 16
N-benzoyl-. alpha. -benzyloxy-. epsilon. -caprolactam (0.0323g, 0.10 mmol) and gamma-butyrolactone (0.4305g, 5 mmol), alpha- (. alpha. - (N-ethylbenzyl) amino-. epsilon. -caprolactam (1.2318g, 5 mmol) were added to a water-free and oxygen-free treated ampoule, and after stirring at 200rpm for 10 minutes, the mixture was addedtBu-P4(0.5 ml, 0.5 mmol) and left to react at 30 ℃ for 360 minutes. After the reaction was completed, a benzoic acid/methylene chloride solution (5 mg/ml) was added thereto and dissolved, and then the solution was taken out and added to a cold methanol solution, whereby a polymer was precipitated. Filtering and separating to obtain a white solid, and transferring the white solid to a vacuum drying oven for drying to obtain the polymer. Conversion rate is also determined by the reaction solution1H NMR calculation gave the polymer structure1H NMR identifies the molecular weight and the degree of dispersion of the polymer by GPC. The gamma-butyrolactone conversion was 39%, the alpha- (N-ethylbenzyl) amino-epsilon-caprolactam was 47%, the number average molecular weight of the polymer was 11250 g/mol, and the dispersion coefficient was 1.29. The initial degradation temperature is 289 ℃, the melting point is 92 ℃, and the glass transition temperature is 23 ℃.
Example 17
N-benzoyl-alpha-benzyloxy-epsilon-caprolactam (0.0323g, 0.10 mmol) and gamma-butyrolactone (0.4305g, 5 mmol), alpha- (N-ethanediol-based) amino-epsilon-caprolactam (1.2318g, 5 mmol) were added to a dry, oxygen-free treated ampoule and after stirring at 200rpm for 10 minutes, addedtBu-P4(0.8 ml, 0.8 mmol) and left to react at-40 ℃ for 1440 minutes. After the reaction was completed, a benzoic acid/methylene chloride solution (5 mg/ml) was added thereto and dissolved, and then the solution was taken out and added to a cold methanol solution, whereby a polymer was precipitated. Filtering to obtain white solid, transferring into vacuum drying oven, and drying to obtainTo a polymer. Conversion rate is also determined by the reaction solution1H NMR calculation gave the polymer structure1H NMR identifies the molecular weight and the degree of dispersion of the polymer by GPC. The conversion of gamma-butyrolactone was 81%, the conversion of alpha- (N-diethylene glycol) amino-epsilon-caprolactam was 36%, the number average molecular weight of the polymer was 15890 g/mol, and the dispersion coefficient was 1.43. Its initial degradation temperature is 259 deg.C, melting point is 46 deg.C, and glass transition temperature is-37 deg.C.
Experimental example 1
Degradation of polyester polyamide: the polyester polyamide (poly (. gamma. -butyrolactone) -r-poly (. epsilon. -caprolactam)) (0.5000 g, 0.1300 mmol) prepared in example 10 was mixed with ZnCl 2(2 mol%), toluene (1 ml) were transferred to a closed ampoule and after heating at 120 ℃ for 12 hours, the yield was determined by reaction1H NMR calculated, structure by1And H NMR identification. Gamma-butyrolactone was obtained with a recovery of 52%.
Experimental example 2
Degradation of polyester polyamide: the polyester polyamide (poly (. gamma. -butyrolactone) -r-poly (. epsilon. -caprolactam)) (0.5000 g, 0.1300 mmol) prepared in example 10 was mixed with ZnCl2(1.5 mol%), toluene (1 ml) was transferred to a closed ampoule and after 24 hours of reaction at 30 ℃ the yield was passed through the reaction1H NMR calculated, structure by1And H NMR identification. Gamma-butyrolactone was obtained with a recovery of 51%.
Experimental example 3
Degradation of polyester polyamide: the polyester polyamide (poly (. gamma. -butyrolactone) -r-poly (. epsilon. -caprolactam)) (0.5000 g, 0.1300 mmol) prepared in example 10 was mixed with ZnCl2(1 mol%), toluene (1 ml) was transferred to a closed ampoule and after heating at 200 ℃ for 2 hours, the yield passed through the reaction1H NMR calculated, structure by1And H NMR identification. Gamma-butyrolactone was obtained with a recovery of 55%.
Experimental example 4
Degradation of polyester polyamide: the polyesterpolyamide prepared in example 1 (poly (. gamma. -butyrolactone) -r-poly (. alpha. - (N-diethyl) amino-. epsilon. -caprolactam)) (0.5000 g, 0.1300 mmol), ZnCl 2(1 mol%) and toluene (1 ml) were transferred to a closed ampoule and after heating at 30 ℃ for 2 hours, the yield was determined by reaction1H NMR calculated, structure by1And H NMR identification. The gamma-butyrolactone was obtained with a recovery of 20%.
Experimental example 5
Degradation of polyester polyamide: the polyester polyamide (poly (. gamma. -butyrolactone) -r-poly (. epsilon. -caprolactam)) (0.5000 g, 0.1300 mmol) prepared in example 1, ZnCl was used2(2 mol%), toluene (1 ml) was transferred to a closed ampoule and after heating at 180 ℃ for 24 hours, the yield passed through the reaction1H NMR calculated, structure by1And H NMR identification. Gamma-butyrolactone was obtained with a recovery of 70%.
Claims (9)
1. A polyester polyamide having the formula:
wherein n and m are respectively and independently selected from any integer of 10-100;
wherein R is1、R2Each independently selected from ethyl, propyl, butyl, hexyl, benzyl, allyl or diethylene glycol monomethyl ether; r is3Selected from hydrogen, methyl or methylene.
2. A polyester polyamide according to claim 1, characterized in that: the number average molecular weight of the polymer is 1000 to 50000g mol-1(ii) a The melting point is 40-200 ℃; the initial degradation temperature is 150-400 ℃; the glass transition temperature is-60 to 140 ℃.
3. A polyester polyamide according to claim 1, characterized in that: the polyester polyamide is polymerized by a monomer M1 and a monomer M2; wherein, the monomer M1 is any one of the structural formulas shown in the formula I; the monomer M2 is any one of the structural formulas shown in the formula II;
4. the method for preparing polyester-polyamide according to any one of claims 1 to 3, wherein the polyester-polyamide is obtained by mixing and reacting a monomer M1, a monomer M2, a co-initiator and a catalyst.
5. The preparation method of the polyester-polyamide according to claim 4, wherein the molar ratio of the monomer M1 to the monomer M2 to the co-initiator to the catalyst is 10-100: 10-100: 1: 0.1 to 10.
6. The method for preparing polyester-polyamide according to claim 4, wherein the reaction temperature is-60 to 100 ℃ and the reaction time is 5 to 1440 min.
7. The process for the preparation of polyesterpolyamide according to claim 4, wherein said co-initiator is N-benzoyl- α -benzyloxy- ε -caprolactam having the formula shown in formula III:
8. the process for the preparation of the polyester polyamide according to claim 4, characterized in that the catalyst is a Bronsted base of formula IV:
9. Use of the polyester-polyamide according to any of claims 1 to 3 for the preparation of a chemical cycle material.
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