CN115725058A - Preparation method of degradable recyclable copolyester and application of degradable recyclable copolyester in aspect of pressure-sensitive adhesive - Google Patents
Preparation method of degradable recyclable copolyester and application of degradable recyclable copolyester in aspect of pressure-sensitive adhesive Download PDFInfo
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- CN115725058A CN115725058A CN202211673470.5A CN202211673470A CN115725058A CN 115725058 A CN115725058 A CN 115725058A CN 202211673470 A CN202211673470 A CN 202211673470A CN 115725058 A CN115725058 A CN 115725058A
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- sensitive adhesive
- caprolactone
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- 239000004820 Pressure-sensitive adhesive Substances 0.000 title claims abstract description 26
- 229920001634 Copolyester Polymers 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims description 9
- RZTOWFMDBDPERY-UHFFFAOYSA-N Delta-Hexanolactone Chemical compound CC1CCCC(=O)O1 RZTOWFMDBDPERY-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 42
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 33
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 239000003054 catalyst Substances 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 13
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical compound CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 claims description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- 239000011541 reaction mixture Substances 0.000 claims description 11
- 239000003446 ligand Substances 0.000 claims description 10
- 229920006378 biaxially oriented polypropylene Polymers 0.000 claims description 9
- 239000011127 biaxially oriented polypropylene Substances 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 9
- 239000003999 initiator Substances 0.000 claims description 8
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 claims description 8
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 6
- -1 2-diphenylethanol Chemical compound 0.000 claims description 4
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 4
- 229920001721 polyimide Polymers 0.000 claims description 4
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 3
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 3
- 239000004800 polyvinyl chloride Substances 0.000 claims description 3
- 229910000105 potassium hydride Inorganic materials 0.000 claims description 3
- NTTOTNSKUYCDAV-UHFFFAOYSA-N potassium hydride Chemical group [KH] NTTOTNSKUYCDAV-UHFFFAOYSA-N 0.000 claims description 3
- 229920005604 random copolymer Polymers 0.000 claims description 3
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 3
- 239000012312 sodium hydride Substances 0.000 claims description 3
- VAJVDSVGBWFCLW-UHFFFAOYSA-N 3-Phenyl-1-propanol Chemical compound OCCCC1=CC=CC=C1 VAJVDSVGBWFCLW-UHFFFAOYSA-N 0.000 claims description 2
- 239000005711 Benzoic acid Substances 0.000 claims description 2
- DYUQAZSOFZSPHD-UHFFFAOYSA-N Phenylpropyl alcohol Natural products CCC(O)C1=CC=CC=C1 DYUQAZSOFZSPHD-UHFFFAOYSA-N 0.000 claims description 2
- 239000007983 Tris buffer Substances 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 235000010233 benzoic acid Nutrition 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- QILSFLSDHQAZET-UHFFFAOYSA-N diphenylmethanol Chemical compound C=1C=CC=CC=1C(O)C1=CC=CC=C1 QILSFLSDHQAZET-UHFFFAOYSA-N 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- 229920002627 poly(phosphazenes) Polymers 0.000 claims description 2
- 229920001225 polyester resin Polymers 0.000 claims description 2
- 239000004645 polyester resin Substances 0.000 claims description 2
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 239000004014 plasticizer Substances 0.000 abstract description 4
- 239000002028 Biomass Substances 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000007151 ring opening polymerisation reaction Methods 0.000 abstract description 3
- 239000000654 additive Substances 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 14
- 229920000642 polymer Polymers 0.000 description 13
- 229910052757 nitrogen Inorganic materials 0.000 description 9
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- 239000011347 resin Substances 0.000 description 7
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 6
- CGCOVQSKNBEYNN-UHFFFAOYSA-N [4-(trifluoromethyl)phenyl]urea Chemical compound NC(=O)NC1=CC=C(C(F)(F)F)C=C1 CGCOVQSKNBEYNN-UHFFFAOYSA-N 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 4
- 230000005311 nuclear magnetism Effects 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
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- 238000001291 vacuum drying Methods 0.000 description 2
- SOTSKDZKNSOBBM-UHFFFAOYSA-N 1-cyclohexyl-3-[4-(trifluoromethyl)phenyl]urea Chemical compound C1=CC(C(F)(F)F)=CC=C1NC(=O)NC1CCCCC1 SOTSKDZKNSOBBM-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- NVVHWGDHBXRSPL-UHFFFAOYSA-N [3,5-bis(trifluoromethyl)phenyl]urea Chemical compound NC(=O)NC1=CC(C(F)(F)F)=CC(C(F)(F)F)=C1 NVVHWGDHBXRSPL-UHFFFAOYSA-N 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
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- 235000013373 food additive Nutrition 0.000 description 1
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- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 description 1
- 150000002596 lactones Chemical group 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
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- LOZAIRWAADCOHQ-UHFFFAOYSA-N triphosphazene Chemical compound PNP=NP LOZAIRWAADCOHQ-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention provides a method for preparing a bio-based degradable copolyester by utilizing ring-opening copolymerization of delta-caprolactone and trans-hexahydro- (4, 5) -benzofuranone, and application of the copolyester in the aspect of pressure-sensitive adhesive. Compared with the method provided by the prior art, the method has the following advantages: 1) The copolyester can be directly used as a pressure-sensitive adhesive, can be completely degraded under natural conditions, and does not need to be additionally added with other additives such as a tackifier, a plasticizer and the like; 2) The raw material of the copolyester is derived from renewable biomass; 3) The prepared pressure-sensitive adhesive has the peel strength similar to or even higher than that of the commercialized pressure-sensitive adhesive.
Description
Technical Field
The invention relates to the fields of high polymer materials and chemical engineering, in particular to a preparation method of degradable recyclable bio-based copolyester and application of the degradable recyclable bio-based copolyester in the aspect of pressure-sensitive adhesive.
Background
Pressure-sensitive adhesives are important polymeric materials that can be used to bond surfaces of adherends under relatively low pressures. Pressure sensitive adhesives are typically composed of a resin matrix, tackifiers, plasticizers, and other adjuvants. At present, most of commercial pressure-sensitive adhesives have non-degradable acrylate polymers or styrene block copolymers as resin matrixes, and are difficult to degrade under natural conditions after being discarded, so that environmental pollution is caused. And the raw materials of the resin matrix are derived from non-renewable petroleum resources, so that the development of a novel bio-based degradable polymer for the resin matrix of the pressure-sensitive adhesive is necessary.
Aliphatic polyesters are polymers having good biodegradability and are widely used in the fields of food packaging, clothing, biomedicine and the like. The viscoelastic property of the copolyester can be regulated and controlled by utilizing two or more than two cyclic lactone monomers for copolymerization, so that a resin matrix suitable for being used as a pressure-sensitive adhesive is obtained. Delta-caprolactone (delta CL), a six-membered ring lactone substituted with a methyl group at the delta position, naturally occurs in fruits and hot milk, can be produced from 5-hydroxymethylfurfural of biomass origin, is currently commercially available and is commonly used as a food additive. Poly (delta-caprolactone) (P delta CL), obtained by ring-opening polymerization of delta-caprolactone, is an amorphous polyester with a low glass transition temperature. Trans-hexahydro- (4, 5) -benzofuranone (4, 5-T6 GBL) has a trans-hexatomic ring and gamma-butyrolactone structure, and a homopolymer thereof has a high glass transition temperature. The random copolymerization of delta CL and 4,5-T6GBL is realized by selecting a proper catalytic system, and the copolyester with different glass transition temperatures and viscoelastic properties can be obtained by regulating the proportion of the delta CL and the 4,5-T6GBL, and can be used as a resin matrix of a pressure-sensitive adhesive.
The invention provides a method for preparing a bio-based degradable copolyester by utilizing delta-caprolactone and trans-hexahydro- (4, 5) -benzofuranone ring-opening copolymerization, and the copolyester can be directly used as a pressure-sensitive adhesive without adding other auxiliary agents such as a tackifier, a plasticizer and the like. Compared with the method provided in the prior art, the method has the following advantages: 1) The resin matrix is aliphatic copolyester which can be completely degraded under natural conditions, and the copolyester can be directly used as a pressure-sensitive adhesive without adding other auxiliary agents such as a tackifier, a plasticizer and the like; 2) The raw material of the copolyester is derived from renewable biomass; 3) The prepared pressure-sensitive adhesive has the peel strength similar to or even higher than that of the commercialized pressure-sensitive adhesive.
Disclosure of Invention
The invention aims to provide a preparation method of bio-based degradable copolyester applied to a pressure-sensitive adhesive, so as to solve the problem that the pressure-sensitive adhesive is not degradable in the prior art.
The biodegradable copolyester is a random copolymer of delta-caprolactone and trans-hexahydro- (4, 5) -benzofuranone, and has a structure shown in a formula (I):
wherein n is a natural number of 50 to 300 and m is a natural number of 100 to 600.
The invention also provides a preparation method of the delta-caprolactone and trans-hexahydro- (4, 5) -benzofuranone random copolymer (P delta CL-co-P (4, 5-T6 GBL)), which comprises the following steps:
(1) Mixing and stirring the initiator, the catalyst and the cocatalyst for 5-10 min at room temperature;
(2) Adding delta-caprolactone and trans-hexahydro- (4, 5) -benzofuranone into the mixed solution, reacting at room temperature for 10-120 min, adding an acidic substance to terminate the reaction, and adding the reaction mixture into methanol to precipitate to obtain the copolyester.
In the preparation method, the initiator is one of methanol, ethanol, isopropanol, tert-butanol, benzyl alcohol, phenethyl alcohol, phenylpropyl alcohol, diphenylmethanol, 2-diphenylethanol, ethylene glycol, 1, 4-phenyl dimethanol, glycerol and pentaerythritol;
the catalyst is potassium hydride, sodium hydride, potassium methoxide, sodium methoxide, hexa [ tri (dimethylamine) phosphazene]Polyphosphazene ({ [ (NMe) s) 2 ) 3 P＝N] 2 P＝N} 3 ) Phosphazene ligand P4-tert-butyl ([ (NMe) 2 ) 3 P＝N] 3 P＝NtBu，tert-Bu-P 4 ) Phosphazene ligand P2-tert-butyl ([ (NMe) 2 ) 3 P＝N](NMe 2 ) 2 P＝NtBu，tert-Bu-P 2 ) At least one of (a) and (b); the cocatalyst has one of the structures shown in formula (II);
the acidic substance is at least one of acetic acid, benzoic acid, hydrochloric acid, sulfuric acid or phosphoric acid;
the molar ratio of the catalyst to the initiator is 1/3-10/1; the molar ratio of the catalyst to the cocatalyst is 1/1-1/10; the molar ratio of the delta-caprolactone to the trans-hexahydro- (4, 5) -benzofuranone is 1/20-50/1; the molar ratio of the total molar weight of the delta-caprolactone and the trans-hexahydro- (4, 5) -benzofuranone to the molar weight of the initiator is 50/1-1000/1; the molar ratio of the acidic substance to the catalyst is 1/1-10/1.
Another object of the present invention is to provide a method for preparing degradable pressure sensitive adhesive tape based on P delta CL-co-P (4, 5-T6 GBL), comprising the following steps:
uniformly coating the P delta CL-co-P (4, 5-T6 GBL) on a base material, and adjusting for 6-24 h in a constant temperature and humidity box with the temperature of 20-40 ℃ and the humidity of 40-60%. The base material is any one of a polyester resin film (PET), a polyimide film (PI), a polyvinyl chloride film (PVC) and a biaxially oriented polypropylene film (BOPP).
Drawings
FIG. 1 shows the preparation of P.delta.CL-co-P (4, 5-T6 GBL) from example 1 1 H NMR spectrum.
FIG. 2 is a GPC chart of P.delta.CL-co-P (4, 5-T6 GBL) obtained in examples 1 to 7.
Detailed Description
The following embodiments specifically describe the present invention, but the present invention is not limited to these embodiments.
The materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
Comparative example 1:
the resulting mixture was washed with (0.04mmol, 4.32mg) benzyl alcohol, (0.04mmol, 14.7mg) phosphazene ligand P2-t-butyl catalyst, (0.08mmol, 38.7mg) 1,3- (3, 5-bistrifluoromethylphenyl) urea
Mixing at room temperature, mixing(8mmol, 0.904mL) delta-caprolactone and (12mmol, 1.541mL) trans-hexahydro- (4, 5) -benzofuranone were added to the reaction tube. The reaction was carried out for 120 minutes under nitrogen and stopped by adding 10 drops of acetic acid. The reaction mixture was poured into 40mL of methanol, no polymer precipitate was obtained, and the nuclear magnetic hydrogen spectrum showed that the conversion of both delta-caprolactone and trans-hexahydro- (4, 5) -benzofuranone was less than 2%.
Comparative example 2:
the resulting mixture was washed with (0.04mmol, 4.32mg) benzyl alcohol, (0.04mmol, 14.7mg) phosphazene ligand P2-tert-butyl catalyst, (0.08mmol, 22.9mg) 1-cyclohexyl-3- (4-trifluoromethylphenyl) urea
After mixing at room temperature, (8 mmol, 0.904mL) delta-caprolactone and (12mmol, 1.541mL) trans-hexahydro- (4, 5) -benzofuranone were added to the reaction tube by syringe. The reaction was carried out for 120 minutes under nitrogen and stopped by adding 10 drops of acetic acid. The reaction mixture was poured into 40mL of methanol and precipitated by centrifugation to give a polymer, which showed a delta-caprolactone and trans-hexahydro- (4, 5) -benzofuranone conversion of less than 15% by nuclear magnetic hydrogen spectroscopy, a number average molecular weight of 4.3kg/mol by CPC and a molecular weight distribution of 1.22. The product was vacuum dried and coated on BOPP using a coater and conditioned for 12 hours at 20 ℃ in a constant temperature and humidity cabinet with 50% humidity, and the peel strengths are shown in table 1.
Example 1:
the resulting mixture was washed with (0.04mmol, 4.32mg) benzyl alcohol, (0.04mmol, 14.7mg) phosphazene ligand P2-t-butyl catalyst, (0.04mmol, 25.9mg) 1,1' - (oxybis (ethylene)) bis (3- (3, 5-bis (trifluoromethyl) phenyl) urea
After mixing at room temperature, a mixed solution of (4 mmol, 0.452mL) delta-caprolactone and (4 mmol, 0.514mL) trans-hexahydro- (4, 5) -benzofuranone was added to the reaction tube by syringe. The reaction was carried out for 30 minutes under nitrogen and stopped by adding 10 drops of acetic acid. Pouring the reaction mixture into 40mL of methanol, centrifuging and precipitating to obtain a polymer, and characterizing the polymer as a ring-opening copolymer by nuclear magnetism, namely P delta CL-co-P(4, 5-T6 GBL). CPC gave a number average molecular weight of 12.6kg/mol and a molecular weight distribution of 1.08. The product was vacuum dried and coated on BOPP using a coater and conditioned for 12 hours in a constant temperature and humidity cabinet at 20 ℃ and 50% humidity, with peel strengths as shown in table 1.
Example 2:
methanol (0.04mmol, 1.28mg), potassium hydride (0.04mmol, 1.6mg), 1' - (oxybis (ethylene)) bis (3- (4- (trifluoromethyl) phenyl) urea (0.04mmol, 19.14mg)
After mixing at room temperature, a mixed solution of (8 mmol, 0.90mL) delta-caprolactone and (8 mmol, 1.03mL) trans-hexahydro- (4, 5) -benzofuranone was added to the reaction tube by syringe. The reaction was carried out for 30 minutes under nitrogen protection and stopped by adding 10 drops of acetic acid. The reaction mixture was poured into 40mL of methanol and the precipitate was centrifuged to give a polymer characterized by NMR as a ring-opened copolymer, i.e., P.delta.CL-co-P (4, 5-T6 GBL). The number-average molecular weight of CPC was 13.5kg/mol, and the molecular weight distribution was 1.11. The product was dried under vacuum, coated on PET using a coater, and conditioned for 24 hours in a constant temperature and humidity cabinet at 20 ℃ and 50% humidity, and the peel strength was shown in table 1.
Example 3:
a mixture of (0.04mmol, 4.33mg) benzyl alcohol, (0.04mmol, 0.94mg) sodium hydride, (0.04mmol, 19.14mg) 1,1' - (oxybis (ethylene)) bis (3- (4- (trifluoromethyl) phenyl) urea
After mixing at room temperature, a mixed solution of (8 mmol, 0.90mL) delta-caprolactone and (8 mmol, 1.03mL) trans-hexahydro- (4, 5) -benzofuranone was added to the reaction tube by syringe. The reaction was carried out for 30 minutes under nitrogen and stopped by adding 10 drops of acetic acid. The reaction mixture was poured into 40mL of methanol and the precipitate was centrifuged to give a polymer characterized by nuclear magnetism as a ring-opened copolymer, i.e., P.delta.CL-co-P (4, 5-T6 GBL). The number-average molecular weight of CPC was found to be 16.7kg/mol, and the molecular weight distribution was 1.13. The product is dried in vacuum, then the pressure-sensitive adhesive is coated on the BOPP by a coater and is placed at 20 ℃ and 50 percentThe humidity was adjusted in a constant temperature and humidity chamber for 24 hours, and the peel strength was shown in Table 1.
Example 4:
the resulting mixture was washed with (0.04mmol, 4.32mg) benzyl alcohol, (0.04mmol, 14.7mg) phosphazene ligand P2-t-butyl catalyst, (0.04mmol, 19.14mg) 1,1' - (oxybis (ethylene)) bis (3- (4- (trifluoromethyl) phenyl) urea
After mixing at room temperature, a mixed solution of (8mmol, 0.904mL) delta-caprolactone and (12mmol, 1.54mL) trans-hexahydro- (4, 5) -benzofuranone was added to the reaction tube by syringe. The reaction was carried out for 120 minutes under nitrogen and stopped by adding 10 drops of acetic acid. The reaction mixture was poured into 40mL of methanol and the precipitate was centrifuged to give a polymer characterized by nuclear magnetism as a ring-opened copolymer, i.e., P.delta.CL-co-P (4, 5-T6 GBL). The number-average molecular weight of CPC was 20.7kg/mol, and the molecular weight distribution was 1.07. The product was dried under vacuum and coated on BOPP using a coater, and conditioned for 12 hours in a constant temperature and humidity cabinet at 20 ℃ and 50% humidity, with peel strengths as shown in table 1.
Example 5:
the resulting mixture was washed with (0.08mmol, 8.64mg) benzyl alcohol, (0.08mmol, 29.4 mg) phosphazene ligand P2-t-butyl catalyst, (0.08mmol, 38.3 mg) 1,1' - (oxybis (ethylene)) bis (3- (4- (trifluoromethyl) phenyl) urea
After mixing at room temperature, a mixed solution of (116mmol, 1.81mL) delta-caprolactone and (32mmol, 4.11mL) trans-hexahydro- (4, 5) -benzofuranone was added to the reaction tube by syringe. The reaction was carried out for 30 minutes under nitrogen protection and stopped by adding 10 drops of acetic acid. The reaction mixture was poured into 40mL of methanol and the precipitate was centrifuged to give a polymer characterized by NMR as a ring-opened copolymer, i.e., P.delta.CL-co-P (4, 5-T6 GBL). The number-average molecular weight of CPC was 29.6kg/mol, and the molecular weight distribution was 1.07. After vacuum drying, the product was coated with pressure sensitive adhesive on PI using a coater, and conditioned for 24 hours in a constant temperature and humidity cabinet at 20 ℃ and 50% humidity, and the peel strength was shown in table 1.
Example 6:
ethylene glycol (0.2mmol, 12.4 mg), (0.2mmol, 73.5mg) phosphazene ligand P2-tert-butyl catalyst, (0.2mmol, 95.68mg) 1,1' - (oxybis (ethylene)) bis (3- (4- (trifluoromethyl) phenyl) urea
After mixing at room temperature, a mixed solution of (20mmol, 2.26mL) delta-caprolactone and (60mmol, 7.7mL) trans-hexahydro- (4, 5) -benzofuranone was added to the reaction tube by a syringe. The reaction was carried out for 30 minutes under nitrogen protection and stopped by adding 10 drops of acetic acid. The reaction mixture was poured into 40mL of methanol and the precipitate was centrifuged to give a polymer characterized by nuclear magnetism as a ring-opened copolymer, i.e., P.delta.CL-co-P (4, 5-T6 GBL). CPC gave a number average molecular weight of 30.2kg/mol and a molecular weight distribution of 1.08. After vacuum drying, the product was coated with a pressure sensitive adhesive on BOPP using a coater, and conditioned for 24 hours in a constant temperature and humidity cabinet at 20 ℃ and 50% humidity, and the peel strength was shown in table 1.
Example 7:
the mixture was prepared by mixing (0.2mmol, 12.4mg) ethylene glycol, (0.2mmol, 239.6mg) hexa [ tris (dimethylamine) phosphazene]Triphosphazene, (0.2mmol, 95.68mg) 1,1' - (oxybis (ethylene)) bis (3- (4- (trifluoromethyl) phenyl) urea
After mixing at room temperature, a mixed solution of (20mmol, 2.26mL) delta-caprolactone and (60mmol, 7.7mL) trans-hexahydro- (4, 5) -benzofuranone was added to the reaction tube using a syringe. The reaction was carried out for 30 minutes under nitrogen protection and stopped by adding 10 drops of acetic acid. The reaction mixture was poured into 40mL of methanol and the precipitate was centrifuged to give a polymer characterized by NMR as a ring-opened copolymer, i.e., P.delta.CL-co-P (4, 5-T6 GBL). The number-average molecular weight of CPC was 31.3kg/mol, and the molecular weight distribution was 1.16. The product was vacuum dried and coated on BOPP using a coater and conditioned for 24 hours at 20 ℃ in a constant temperature and humidity chamber with 50% humidity, and the peel strengths are shown in table 1.
The above examples tested the 180 ° peel strength of the tape according to GB/T2792, with the test results shown in table 1:
TABLE 1 Peel Strength for the examples
It can be seen from comparative example 1, comparative example 2 and example 4 that the choice of cocatalyst is crucial for the random copolymerization of delta-caprolactone and trans-hexahydro- (4, 5) -benzofuranone. When monourea is selected as a co-catalyst, the conversion of delta-caprolactone and trans-hexahydro- (4, 5) -benzofuranone is low, no polymer is obtained or the molecular weight of the obtained polymer is low, and the peel strength is low when the pressure-sensitive adhesive is used.
Although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications may be made to the embodiments described in the foregoing embodiments, or equivalents may be substituted for elements thereof. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. The biodegradable copolyester is a random copolymer of delta-caprolactone and trans-hexahydro- (4, 5) -benzofuranone, and has a structure shown in a formula (I):
n is a natural number of 50 to 300, and m is a natural number of 100 to 600.
2. The method for preparing the biodegradable copolyester according to claim 1, comprising the steps of:
(1) Mixing and stirring the initiator, the catalyst and the cocatalyst for 5-10 min at room temperature;
(2) Adding delta-caprolactone and trans-hexahydro- (4, 5) -benzofuranone into the mixed solution, reacting at room temperature for 10-120 min, adding an acidic substance to terminate the reaction, and adding the reaction mixture into methanol to precipitate to obtain copolyester;
characterized in that the cocatalyst has one of the structures shown in formula (II).
3. The method of claim 2, wherein the initiator is one of methanol, ethanol, isopropanol, tert-butanol, benzyl alcohol, phenethyl alcohol, phenylpropyl alcohol, diphenylmethanol, 2-diphenylethanol, ethylene glycol, 1, 4-phenyl dimethanol, glycerol, and pentaerythritol.
4. The method according to claim 2, wherein the catalyst is potassium hydride, sodium hydride, potassium methoxide, sodium methoxide, hexa [ tris (dimethylamine) phosphazene]Polyphosphazene ({ [ (NMe) s) 2 ) 3 P＝N] 2 P＝N} 3 ) Phosphazene ligand P4-tert-butyl ([ (NMe) 2 ) 3 P＝N] 3 P＝NtBu，tert-Bu-P 4 ) Phosphazene ligand P2-tert-butyl ([ (NMe) 2 ) 3 P＝N](NMe 2 ) 2 P＝NtBu，tert-Bu-P 2 ) At least one of them.
5. The method according to claim 2, wherein the acidic substance is at least one of acetic acid, benzoic acid, hydrochloric acid, sulfuric acid, or phosphoric acid.
6. The preparation method according to claim 2, wherein the molar ratio of the catalyst to the initiator is 1/3 to 10/1; the molar ratio of the catalyst to the cocatalyst is 1/1-1/10; the molar ratio of the delta-caprolactone to the trans-hexahydro- (4, 5) -benzofuranone is 1/20-50/1; the molar ratio of the total molar weight of the delta-caprolactone and the trans-hexahydro- (4, 5) -benzofuranone to the molar weight of the initiator is 50/1-1000/1; the molar ratio of the acidic substance to the catalyst is 1/1-10/1.
7. Use of the bio-based degradable copolyester according to claim 1 in pressure-sensitive adhesive tape, wherein the preparation of the pressure-sensitive adhesive tape comprises the following steps:
uniformly coating P delta CL-co-P (4, 5-T6 GBL) on a base material, and adjusting for 6-24 h in a constant temperature and humidity box with the temperature of 20-40 ℃ and the humidity of 40-60%; the base material is any one of a polyester resin film, a polyimide film, a polyvinyl chloride film and a biaxially oriented polypropylene film.
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| CN111253556A (en) * | 2020-03-20 | 2020-06-09 | 南京工业大学 | Functionalized recyclable high-molecular homopolymer and preparation method and application thereof |
| CN111320747A (en) * | 2020-03-20 | 2020-06-23 | 南京工业大学 | Functionalized high-molecular polymer and preparation method thereof |
| CN114409880A (en) * | 2021-12-27 | 2022-04-29 | 青岛科技大学 | Preparation method of recyclable bio-based polyester |
| CN114479023A (en) * | 2022-01-26 | 2022-05-13 | 青岛科技大学 | Novel bio-based degradable thermoplastic elastomer and preparation method thereof |
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| CN111253556A (en) * | 2020-03-20 | 2020-06-09 | 南京工业大学 | Functionalized recyclable high-molecular homopolymer and preparation method and application thereof |
| CN111320747A (en) * | 2020-03-20 | 2020-06-23 | 南京工业大学 | Functionalized high-molecular polymer and preparation method thereof |
| CN114409880A (en) * | 2021-12-27 | 2022-04-29 | 青岛科技大学 | Preparation method of recyclable bio-based polyester |
| CN114479023A (en) * | 2022-01-26 | 2022-05-13 | 青岛科技大学 | Novel bio-based degradable thermoplastic elastomer and preparation method thereof |
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