CN114163598B - Bio-based polyol derived self-repairing polyurethane and preparation method thereof - Google Patents
Bio-based polyol derived self-repairing polyurethane and preparation method thereof Download PDFInfo
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- CN114163598B CN114163598B CN202111600039.3A CN202111600039A CN114163598B CN 114163598 B CN114163598 B CN 114163598B CN 202111600039 A CN202111600039 A CN 202111600039A CN 114163598 B CN114163598 B CN 114163598B
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- 229920002635 polyurethane Polymers 0.000 title claims abstract description 32
- 239000004814 polyurethane Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229920005862 polyol Polymers 0.000 title claims abstract description 9
- 150000003077 polyols Chemical class 0.000 title claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 9
- RRAFCDWBNXTKKO-UHFFFAOYSA-N eugenol Chemical compound COC1=CC(CC=C)=CC=C1O RRAFCDWBNXTKKO-UHFFFAOYSA-N 0.000 claims description 34
- NPBVQXIMTZKSBA-UHFFFAOYSA-N Chavibetol Natural products COC1=CC=C(CC=C)C=C1O NPBVQXIMTZKSBA-UHFFFAOYSA-N 0.000 claims description 17
- 239000005770 Eugenol Substances 0.000 claims description 17
- UVMRYBDEERADNV-UHFFFAOYSA-N Pseudoeugenol Natural products COC1=CC(C(C)=C)=CC=C1O UVMRYBDEERADNV-UHFFFAOYSA-N 0.000 claims description 17
- 229960002217 eugenol Drugs 0.000 claims description 17
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 8
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 claims description 7
- 239000012948 isocyanate Substances 0.000 claims description 7
- 150000002513 isocyanates Chemical class 0.000 claims description 7
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 4
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims description 3
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 2
- 230000004936 stimulating effect Effects 0.000 claims 1
- 230000002441 reversible effect Effects 0.000 abstract description 9
- 239000000853 adhesive Substances 0.000 abstract description 2
- 230000001070 adhesive effect Effects 0.000 abstract description 2
- 229920001971 elastomer Polymers 0.000 abstract description 2
- 239000000806 elastomer Substances 0.000 abstract description 2
- 239000006260 foam Substances 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 abstract description 2
- 239000000565 sealant Substances 0.000 abstract description 2
- 239000002131 composite material Substances 0.000 abstract 1
- 239000003973 paint Substances 0.000 abstract 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 5
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- IMQFZQVZKBIPCQ-UHFFFAOYSA-N 2,2-bis(3-sulfanylpropanoyloxymethyl)butyl 3-sulfanylpropanoate Chemical compound SCCC(=O)OCC(CC)(COC(=O)CCS)COC(=O)CCS IMQFZQVZKBIPCQ-UHFFFAOYSA-N 0.000 description 2
- 238000006596 Alder-ene reaction Methods 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 239000010634 clove oil Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 231100000053 low toxicity Toxicity 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000527 sonication Methods 0.000 description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 description 2
- JJSYPAGPNHFLML-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;3-sulfanylpropanoic acid Chemical compound OC(=O)CCS.OC(=O)CCS.OC(=O)CCS.CCC(CO)(CO)CO JJSYPAGPNHFLML-UHFFFAOYSA-N 0.000 description 1
- 238000005698 Diels-Alder reaction Methods 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- 101000795744 Homo sapiens TPA-induced transmembrane protein Proteins 0.000 description 1
- 102100031626 TPA-induced transmembrane protein Human genes 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
- C08G18/3863—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing groups having sulfur atoms between two carbon atoms, the sulfur atoms being directly linked to carbon atoms or other sulfur atoms
- C08G18/3865—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing groups having sulfur atoms between two carbon atoms, the sulfur atoms being directly linked to carbon atoms or other sulfur atoms containing groups having one sulfur atom between two carbon atoms
- C08G18/3868—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing groups having sulfur atoms between two carbon atoms, the sulfur atoms being directly linked to carbon atoms or other sulfur atoms containing groups having one sulfur atom between two carbon atoms the sulfur atom belonging to a sulfide group
Abstract
A bio-based polyol derived self-healing polyurethane and a preparation method thereof, and a method for preparing the self-healing polyurethane PU-2SH and PU-3SH respectively. Polyurethane is an important polymer and is widely used in many fields such as paint, elastomer, adhesive, surface sealant, foam products, etc. due to its excellent mechanical properties. The invention maintains the performance and function of polyurethane and develops polyurethane with self-repairing composite capability. Compared with other self-repairing polyurethane preparation methods, the method does not need the introduction of specific reversible covalent bonds, and has the advantages of simple preparation process and the like.
Description
Technical Field
The invention belongs to the field of materials, and particularly relates to self-repairing polyurethane derived from bio-based polyol and a preparation method thereof.
Background
Polyurethane is an important polymer and is widely used in many fields such as coating, elastomer, adhesive, surface sealant and foam products due to its excellent mechanical properties. In order to meet the demand for sustainable development, polyurethane with self-repairing compounding ability was developed while maintaining the performance and function of polyurethane during use. In order to provide self-repairing capability to polyurethane, the introduction of reversible covalent bonds is an effective approach.
Typical reversible covalent bonds for the preparation of self-healing polyurethanes are acylhydrazone bonds, disulfide bonds, diels-Alder bonds, dynamic transesterification, alkoxyamine bonds and urea bonds. However, some methods for preparing self-repairing polyurethanes generally require the introduction of specific reversible covalent bonds, limiting the diversity of the polyurethanes and complicating the polyurethane preparation process.
Unlike the urethane linkages formed by the reaction of isocyanate and phenolic hydroxyl groups, the urethane linkages of isocyanate and phenolic hydroxyl groups are reversible. Thus, in the polyurethane industry, reversible reactions of isocyanate and phenolic hydroxyl groups have been used to protect isocyanate groups from water. Inspired by the use of urethane linkages, there have been reports of self-healing polyurethanes made from phenolic hydroxyl groups and isocyanates without introducing additional covalent bonds.
Eugenol is favored as a main component of clove oil because of its low toxicity and low production cost. Eugenol has a structure of trisubstituted rigid benzene ring and has methoxy, allyl and hydroxyl substituents. In addition, allyl and phenolic hydroxyl groups of eugenol are readily available for mercapto-ene reactions and reversible urethane reactions.
Disclosure of Invention
The technical problems to be solved are as follows: in order to solve the problem that reversible covalent bonds need to be introduced in the preparation process of self-repairing polyurethane, the invention provides bio-based polyol-derived self-repairing polyurethane and a preparation method thereof by utilizing the characteristic that allyl and phenolic hydroxyl groups of eugenol are easy to be used for mercapto-ene reaction and reversible urethane reaction. The method does not need to introduce certain specific covalent bonds, has simple process and easy operation, and the obtained self-repairing polyurethane has diversity and good self-repairing performance.
The technical scheme is as follows: a preparation method of bio-based polyol-derived self-repairing polyurethane comprises the following steps of firstly, adding one of 3, 6-dioxa-1, 8-octadithiol or trimethylolpropane tri (3-mercaptopropionate), eugenol and 2, 2-dimethoxy-2-phenyl-acetophenone into a reaction vessel, wherein the dosage of the 2, 2-dimethoxy-2-phenyl-acetophenone is 1-3% of the total mass of the rest raw materials, and carrying out stimulation reaction for 2-5 hours at room temperature by using a 175W ultraviolet lamp (lambda=365 nm) to obtain a target product; and secondly, adding the product obtained in the last step, PTHFTDI and tetrahydrofuran according to the mass ratio of 1 (2.28-4.71) to 10 into a reaction container, forming a uniform system by the components after ultrasonic treatment, heating the mixture at 30-70 ℃ under vacuum to remove part of tetrahydrofuran and bubbles, and pouring the obtained solution into a tetrafluoroethylene plate for solidification.
The dosage of the 2, 2-dimethoxy-2-phenyl-acetophenone in the first step is 2 percent of the total mass of the rest raw materials.
The product of the first step was stimulated with a 175W uv lamp at room temperature, λ=365 nm for a reaction time of 3 hours.
The heating temperature in the second step was 50 ℃.
The temperature of the curing in the second step is 80 ℃/2h+120 ℃/14h.
The bio-based polyol derived self-healing polyurethane prepared by the preparation method is prepared.
The beneficial effects are that: 1. the raw material eugenol of the polyurethane prepared by the method is the main component of clove oil, and has low toxicity and low production cost; 2. the polyurethane prepared by the method does not need to introduce a specific covalent bond, so that the preparation process is simplified, the products are diversified, and the application range of the polyurethane is widened; 3. the polyurethane prepared by the invention has good self-repairing performance and stretching resistance.
Drawings
FIG. 1 is a chart of Fourier transform infrared spectroscopy (FTIR) analysis of eugenol, EDT (2 SH), AEE (2 SH), TTMP (3 SH) and ATE (3 SH). In the spectra of eugenol and EDT (2 SH), at 1637cm -1 、2559cm -1 And 1104cm -1 The absorption at this point corresponds to the double bond of eugenol and the sulfhydryl and ether linkages of EDT (2 SH), respectively. Compared with FTIR spectra of eugenol and EDT (2 SH), 1637cm of AEE (2 SH) spectrum can be seen -1 And 2559cm -1 The peak at the point disappeared and 1104cm -1 The eugenol and thiol groups in the successful reaction EDT (2 SH) of AEE (2 SH) were retained, indicating double bonds. Also, in the spectrum of ATE (3 SH), at 1637cm -1 And 2572cm -1 The peak at the location disappeared while 1730cm remained -1 The peak of the ester group indicates successful synthesis of ATE (3 SH).
Detailed Description
Example 1:
in the first step, eugenol (3.28 g,20 mmol), 3, 6-dioxa-1, 8-octadithiol (1.82 g,10 mmol) and 2, 2-dimethoxy-2-phenyl-acetophenone (102 mg, 2% of the total mass of eugenol and 3, 6-dioxa-1, 8-octadithiol) were added to a round bottom flask, and the reaction was stimulated with a 175W ultraviolet lamp (λ=365 nm) at room temperature for 3 hours to obtain the target product AEE (2 SH).
In the second step, hydroxyl groups and isocyanate groups are added in a molar ratio of 1:1. 2g of AEE (2 SH), 4.56g of the polyurethane prepolymer PTHFTDI (obtained by polymerizing polytetrahydrofuran and toluene diisocyanate, having an isocyanate content of 6.2% and a relative molecular mass of 1350) and 20mL of tetrahydrofuran were added to a round-bottomed flask, and the components formed a homogeneous system after sonication. The mixture was then heated under vacuum at 50 ℃ to remove part of the tetrahydrofuran and air bubbles. Thereafter, the resulting solution was poured into four tetrafluoroethylene plates (70 mm. Times.100 mm) and cured at 80℃2h+120℃14h.
Example 2:
in the first step, eugenol (3.28 g,20 mmol), trimethylolpropane tris (3-mercaptopropionate) (2.66 g,6.67 mmol) and 2, 2-dimethoxy-2-phenyl-acetophenone (119 mg, 2% of the total mass of eugenol and trimethylolpropane tris (3-mercaptopropionate) were added to a round bottom flask, and the reaction was stimulated with a 175W ultraviolet lamp (λ=365 nm) at room temperature for 3 hours to give the target product ATE (3 SH).
In the second step, hydroxyl groups and isocyanate groups are added in a molar ratio of 1:1. 2g of AEE (3 SH), 4.56g of the polyurethane prepolymer PTHFTDI (obtained by polymerizing polytetrahydrofuran and toluene diisocyanate, having an isocyanate content of 6.2% and a relative molecular mass of 1350) and 20mL of tetrahydrofuran were added to a round-bottomed flask, and the components formed a homogeneous system after sonication. The mixture was then heated under vacuum at 50 ℃ to remove part of the tetrahydrofuran and air bubbles. Thereafter, the resulting solution was poured into four tetrafluoroethylene plates (70 mm. Times.100 mm) and cured at 80℃2h+120℃14h.
Comparative example:
experiment group 1: the tensile strength and the self-healing capacity of the PU-2SH polyurethane prepared in example 1 were 73.48% and 84.3%, respectively.
Experiment group 2: the tensile strength and the self-healing capacity of the PU-3SH polyurethane prepared in example 2 were 24.09% and 73.11%, respectively. Compared with PU-3SH, PU-2SH shows better self-repairing capability and better mechanical property.
Claims (2)
1. A process for the preparation of bio-based polyol derived self-healing polyurethane, characterized in that it is prepared by the steps of, in a first step, adding 20mmol of eugenol, 10 mmole of 3, 6-dioxa-1, 8-octadithiol and 2, 2-dimethoxy-2-phenyl-acetophenone to a round bottom flask, wherein 2, 2-dimethoxy-2-phenyl-acetophenone is 2% of the total mass of eugenol and 3, 6-dioxa-1, 8-octadithiol and stimulating the reaction with 175W uv lamp, λ=365 nm, at room temperature for 3 hours to obtain the target product AEE; secondly, adding hydroxyl and isocyanate groups according to a molar ratio of 1:1, adding 2g of AEE, 4.56g of polyurethane prepolymer PTHFTDI and 20mL tetrahydrofuran into a round-bottomed flask, and forming a uniform system by the components after ultrasonic treatment; the PTHFTDI is obtained by polymerizing polytetrahydrofuran and toluene diisocyanate, the isocyanate content is 6.2%, and the relative molecular mass is 1350; the mixture was then heated at 50 ℃ under vacuum to remove part of the tetrahydrofuran and air bubbles, after which the resulting solution was poured into four tetrafluoroethylene plates and cured at 80 ℃/2h+120 ℃/14h.
2. The bio-based polyol derived self-healing polyurethane made by the method of claim 1.
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| CN115197394A (en) * | 2022-07-15 | 2022-10-18 | 中南大学 | Bio-based waterborne polyurethane material with self-repairing performance and preparation method thereof |
| CN115873252B (en) * | 2022-11-11 | 2024-04-16 | 河南省科学院化学研究所有限公司 | Urethane-based elastomer and preparation method thereof |
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