CN115873252B - Urethane-based elastomer and preparation method thereof - Google Patents
Urethane-based elastomer and preparation method thereof Download PDFInfo
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- CN115873252B CN115873252B CN202211409354.2A CN202211409354A CN115873252B CN 115873252 B CN115873252 B CN 115873252B CN 202211409354 A CN202211409354 A CN 202211409354A CN 115873252 B CN115873252 B CN 115873252B
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- based elastomer
- elastomer
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- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 229920001971 elastomer Polymers 0.000 title claims abstract description 40
- 239000000806 elastomer Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 27
- RRAFCDWBNXTKKO-UHFFFAOYSA-N eugenol Chemical compound COC1=CC(CC=C)=CC=C1O RRAFCDWBNXTKKO-UHFFFAOYSA-N 0.000 claims abstract description 26
- -1 urethane group compound Chemical class 0.000 claims abstract description 22
- 238000007259 addition reaction Methods 0.000 claims abstract description 17
- 150000001875 compounds Chemical class 0.000 claims abstract description 17
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims abstract description 15
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims abstract description 15
- NPBVQXIMTZKSBA-UHFFFAOYSA-N Chavibetol Natural products COC1=CC=C(CC=C)C=C1O NPBVQXIMTZKSBA-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000005770 Eugenol Substances 0.000 claims abstract description 13
- UVMRYBDEERADNV-UHFFFAOYSA-N Pseudoeugenol Natural products COC1=CC(C(C)=C)=CC=C1O UVMRYBDEERADNV-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229960002217 eugenol Drugs 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 125000003396 thiol group Chemical group [H]S* 0.000 claims abstract description 9
- 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 claims abstract description 7
- JOBBTVPTPXRUBP-UHFFFAOYSA-N [3-(3-sulfanylpropanoyloxy)-2,2-bis(3-sulfanylpropanoyloxymethyl)propyl] 3-sulfanylpropanoate Chemical compound SCCC(=O)OCC(COC(=O)CCS)(COC(=O)CCS)COC(=O)CCS JOBBTVPTPXRUBP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 230000001681 protective effect Effects 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 6
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 238000011534 incubation Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 7
- 150000002148 esters Chemical class 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 238000010586 diagram Methods 0.000 description 9
- 230000008439 repair process Effects 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 229920006311 Urethane elastomer Polymers 0.000 description 8
- 230000002441 reversible effect Effects 0.000 description 8
- 239000000047 product Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000005698 Diels-Alder reaction Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004936 stimulating effect Effects 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Abstract
The invention belongs to the technical field of elastomer materials, and particularly relates to a urethane-based elastomer and a preparation method thereof. The preparation method of the invention comprises the following steps: mixing hexamethylene diisocyanate, eugenol and benzene solvent, and carrying out addition reaction under the conditions of protective atmosphere and catalyst to obtain a urethane group compound; mixing the urethane-based compound and a sulfhydryl compound, and performing sulfhydryl clicking reaction under ultraviolet irradiation condition to obtain a urethane-based elastomer; the mercapto compound includes trimethylolpropane tris (3-mercaptopropionate) or pentaerythritol tetrakis (3-mercaptopropionate). The self-healing efficiency of the ester-based elastomer prepared by the preparation method provided by the invention is higher.
Description
Technical Field
The invention belongs to the technical field of elastomer materials, and particularly relates to a urethane-based elastomer and a preparation method thereof.
Background
The elastomer is a very important polymer material, and has wide application prospect in the fields of adhesives, coatings, electronic and electric appliances, aerospace, tires, clothing, soft robots and the like due to high mechanical toughness and elasticity. Moreover, with the development of soft robot intelligent materials, elastomers with high mechanical toughness and elasticity are also increasingly used in the field of electronic skin. However, when the elastomer bears stronger physical and mechanical actions in the service process, the internal structure of the elastomer is easy to generate fatigue and microcrack, so that the material function is invalid, the service life of the elastomer is shortened, the self-healing performance of the elastomer cannot be fully exerted, and the global resource is wasted, so that the elastomer with the self-healing performance is urgently needed currently, and is a hot spot for research of contemporary students.
At present, the preparation method reported in the literature can only prepare the self-healing elastomer with single reversible bond (such as D-A (Diels-Alder) bond, disulfide bond, ester bond, hydrogen bond and other single reversible bond), realize countercurrent flow of molecular structure under the condition of external stimulus (light, heat and the like), so that the molecular chain structure of the damaged part of the material, which is broken at the microcosmic part, can be crosslinked again, and the macroscopic crack plane is refilled, thereby realizing the self-healing function of the elastomer material. However, the self-healing is realized by stimulating the material through a single reversible chemical bond, so that the self-healing efficiency is low, for example, the self-healing time is more than 1h when the temperature of a single D-A bond is more than 120 ℃, and the self-healing degree can reach 90% at most; the single disulfide bond can realize self-healing within 30min at 50-60 ℃, and the self-healing degree is generally 80-90%.
Disclosure of Invention
Therefore, the invention aims to provide the urethane elastomer and the preparation method thereof, and the self-healing efficiency of the urethane elastomer prepared by the preparation method is higher.
In order to solve the problems, the invention provides a preparation method of a urethane elastomer, which comprises the steps of mixing hexamethylene diisocyanate, eugenol and benzene solvent, and carrying out addition reaction under the conditions of protective atmosphere and an organotin catalyst to obtain a urethane compound; mixing the urethane-based compound and a sulfhydryl compound, and performing sulfhydryl clicking reaction under ultraviolet irradiation condition to obtain a urethane-based elastomer;
the mercapto compound includes trimethylolpropane tris (3-mercaptopropionate) or pentaerythritol tetrakis (3-mercaptopropionate).
Preferably, the organotin catalyst comprises dibutyltin dilaurate.
Preferably, the molar ratio of the hexamethylene diisocyanate to the eugenol is 1:1.5-2.5.
Preferably, the temperature of the addition reaction is 75-85 ℃, and the heat preservation time is 1.5-2.5 h.
Preferably, the molar ratio of urethane groups in the urethane-based compound to mercapto groups in the mercapto compound is 1:0.95 to 1.05.
Preferably, the power of the ultraviolet irradiation is 95-110W, and the time is 5-15 min.
Preferably, after the addition reaction, the method further comprises the steps of sequentially cooling, solid-liquid separation, washing and drying the system obtained by the addition reaction.
Preferably, the temperature of the cooling is-5-0 ℃; the drying temperature is 75-85 ℃ and the drying time is 4-5 h.
The invention also provides the urethane-based elastomer prepared by the preparation method, which is characterized in that chemical bonds in the urethane-based elastomer comprise urethane bonds and hydrogen bonds.
Preferably, the molar ratio of urethane bond to hydrogen bond is 1:0.5.
the invention provides a preparation method of a urethane elastomer, which comprises the following steps: mixing hexamethylene diisocyanate, eugenol and benzene solvent, and carrying out addition reaction under the conditions of protective atmosphere and an organotin catalyst to obtain a urethane compound; mixing the urethane-based compound and a sulfhydryl compound, and performing sulfhydryl clicking reaction under ultraviolet irradiation condition to obtain a urethane-based elastomer; the mercapto compound includes trimethylolpropane tris (3-mercaptopropionate) or pentaerythritol tetrakis (3-mercaptopropionate). The invention adopts hexamethylene diisocyanate with high reactivity as a reaction site, uses eugenol to end-cap the hexamethylene diisocyanate under the catalysis of dibutyl tin dilaurate to generate a urethane group compound, thereby introducing a characteristic group urethane group, and then preparing the urethane group elastomer through a mercapto-clicking reaction. The invention utilizes the thermal reversible characteristics that the urethane groups can be unsealed and re-sealed at low temperature under the high temperature condition, and a large number of hydrogen bonds can be formed between urethane bond molecular chains in the elastomer network due to the action of the urethane bonds, the hydrogen bonds are also dynamically converted along with the change of temperature, and the self-healing efficiency of the obtained urethane elastomer is improved through the construction of two reversible chemical bonds (hydrogen bonds and urethane bonds).
Drawings
FIG. 1 is a schematic diagram of the products EUHDI/3SH and EUHDI/4SH prepared in example 1 and example 2;
FIG. 2 is a graph showing scratch repair tests performed on the products EUHDI/3SH and EUHDI/4SH prepared in example 1 and example 2;
FIG. 3 is a drawing showing tensile strength test conducted on the products EUHDI/3SH and EUHDI/4SH prepared in examples 1 and 2.
Detailed Description
The invention provides a preparation method of a urethane elastomer, which comprises the following steps:
mixing hexamethylene diisocyanate, eugenol and benzene solvent, and carrying out addition reaction under the conditions of protective atmosphere and an organotin catalyst to obtain a urethane compound;
mixing the urethane-based compound and a sulfhydryl compound, and performing sulfhydryl clicking reaction in ultraviolet to obtain a urethane-based elastomer;
the mercapto compound includes trimethylolpropane tris (3-mercaptopropionate) or pentaerythritol tetrakis (3-mercaptopropionate).
According to the invention, hexamethylene diisocyanate, eugenol and benzene solvents are mixed, and an addition reaction is carried out under the conditions of protective atmosphere and an organotin catalyst to obtain a urethane compound.
In the present invention, the benzene-based solvent preferably includes toluene. In the present invention, the organotin catalyst preferably comprises dibutyltin dilaurate. In the present invention, the molar ratio of hexamethylene diisocyanate to eugenol is preferably 1:1.5 to 2.5, more preferably 1:2. In the present invention, the ratio of the hexamethylene diisocyanate to the benzene solvent is preferably 1g:12.5 to 14mL, more preferably 1g:13mL. In the present invention, the mass of the organotin catalyst is 0.04 to 0.06% of the sum of the mass of hexamethylene diisocyanate and eugenol, and more preferably 0.05%.
In the present invention, the temperature of the addition reaction is preferably 75 to 85 ℃, more preferably 80 ℃, and the time is preferably 1.5 to 2.5 hours, more preferably 2 hours. In the present invention, the addition reaction is preferably carried out under water bath heating. In the present invention, the protective atmosphere for the addition reaction is preferably high purity nitrogen, and the purity of the high purity nitrogen is preferably 99.99%.
In the present invention, the molecular chain structure of the urethane-based compound is highly symmetrical and has a large rigidity. Therefore, the urethane-based compound prepared by the invention has excellent mechanical properties.
In the present invention, it is preferable that the system obtained by the addition reaction is further cooled, solid-liquid separated, washed and dried in this order after the addition reaction.
In the present invention, the temperature of the cooling is preferably-5 to 0 ℃, more preferably 0 ℃. In the present invention, the cooling rate of the cooling is preferably 5 ℃/min. In the invention, white crystals are separated out in the cooling process, namely the crude product of the urethane-based compound. In the present invention, the solid-liquid separation is preferably suction filtration, and the suction filtration is not particularly limited in the present invention, and may be performed by operations well known to those skilled in the art. In the present invention, the washing detergent is preferably absolute ethanol, the number of times of washing is preferably 2 to 3, and in the present invention, the washing is preferably carried out until no benzene solvent is present. In the present invention, the drying temperature is preferably 75 to 85 ℃, more preferably 80 ℃, and the time is preferably 4 to 5 hours, more preferably 4.5 hours.
After the urethane-based compound is obtained, the urethane-based compound and the sulfhydryl compound are mixed, and sulfhydryl clicking reaction is carried out in ultraviolet to obtain the urethane-based elastomer.
In the present invention, the mercapto compound includes trimethylolpropane tris (3-mercaptopropionate) or pentaerythritol tetrakis (3-mercaptopropionate). In the present invention, the molar ratio of the urethane group in the urethane-based compound to the mercapto group in the mercapto compound is preferably 1:0.95 to 1.05, more preferably 1:1.
In the present invention, the power of the ultraviolet irradiation is preferably 95 to 110W, more preferably 100W; the time is preferably 5 to 15 minutes, more preferably 10 minutes.
The invention also provides the urethane-based elastomer prepared by the preparation method, wherein chemical bonds in the urethane-based elastomer comprise urethane bonds and hydrogen bonds.
In the present invention, the molar ratio of urethane bond and hydrogen bond in the urethane-based elastomer is preferably 1:0.5.
The repair method of the urethane elastomer is preferably that the urethane elastomer realizes self-healing under a certain temperature condition. In the present invention, the temperature is preferably 25 to 150 ℃, more preferably 150 ℃.
The technical solutions provided by the present invention are described in detail below in conjunction with examples for further illustrating the present invention, but they should not be construed as limiting the scope of the present invention.
Example 1
118.9mmol of hexamethylene diisocyanate, 237.8mmol of eugenol, 0.5g of dibutyltin dilaurate and 260mL of toluene are added into a three-neck flask in an inert gas (99.99% high-purity nitrogen) atmosphere, the temperature is increased to 80 ℃, the water bath is heated for reaction for 2 hours, the solution becomes milky white, the solution is cooled to 0 ℃, white crystals are separated out, the solution is filtered by suction, the obtained crystals are washed 3 times by absolute ethyl alcohol and then are put into a baking oven at 80 ℃ for drying for 4 hours, and 56.68g of urethane-based compounds are obtained, and the yield is 96%;
the resulting 3g of urethane-based compound and 6.017mmol of trimethylolpropane tris (3-mercaptopropionate) were mixed and irradiated under ultraviolet irradiation at a power of 100W for 10 minutes to carry out a crosslinking reaction, to give a urethane-based elastomer, which was designated EUHDI/3SH.
Example 2
59.45mol of hexamethylene diisocyanate, 118.9mol of eugenol, 0.25g of dibutyltin dilaurate and 130mL of toluene are added into a three-neck flask in an inert gas (99.99% high-purity nitrogen) atmosphere, the temperature is increased to 80 ℃, water bath heating is carried out for 2 hours, the solution turns into milky white, the solution is cooled to 0 ℃, white crystals are separated out, suction filtration is carried out, the obtained crystals are washed for 3 times by absolute ethyl alcohol and then put into an oven at 80 ℃ for drying for 4 hours, 28.34g of urethane-based compound is obtained, and the yield is 96%;
the resulting 3g of urethane-based compound and 9.025mol of pentaerythritol tetrakis (3-mercaptopropionate) were mixed and irradiated for 10 minutes under ultraviolet irradiation at a power of 100W to carry out a crosslinking reaction, to give a urethane-based elastomer, which was designated EUHDI/4SH.
FIG. 1 is a schematic diagram of EUHDI/3SH and EUHDI/4SH of the products prepared in example 1 and example 2, wherein A in FIG. 1 is a schematic diagram of EUHDI/3SH, and B in FIG. 1 is a schematic diagram of EUHDI/4SH, as can be seen from FIG. 1: the crosslink density of the EUHDI/3SH polymer network is higher than that of the EUHDI/4SH polymer.
The scratch repair test is carried out on the products EUHDI/3SH and EUHDI/4SH prepared in the embodiment 1 and the embodiment 2, and the test method is as follows: heating the urethane-based elastomer to 150 ℃ to achieve self-healing, the result is shown in fig. 2, wherein (a) in fig. 2 is a state diagram before EUHDI/3SH repair; in FIG. 2 (A) ， ) The state diagram is the state diagram after EUHDI/3SH repair; FIG. 2 (B) is a state diagram before EUHDI/4SH repair; in FIG. 2 (B) ， ) Is a state diagram of EUHDI/4SH after repair. As can be seen from fig. 2: after the EUHDI/3SH is repaired, the self-healing degree is close to 100%, and after the EUHDI/4SH is repaired, the self-healing degree can reach more than 90%, wherein the repair time of the EUHDI/3SH is 30min, and the repair time of the EUHDI/4SH is 30min.
The tensile strength of the products EUHDI/3SH and EUHDI/4SH prepared in the examples 1 and 2 is tested by a mechanical tensile test, and the test results are shown in figure 3, and can be seen from figure 3: the tensile strength of the EUHDI/3SH original spline is 4.20MPa, the tensile strength of the spline after cutting is 3.8MPa, the mechanical property can be recovered to 90.5% of the original spline, and the self-healing effect is ideal. The tensile strength of the EUHDI/4SH original sample strip is 19.95MPa, the tensile strength of the sample strip after cutting is 15.11MPa, and the mechanical strength can be recovered to 75.7% of the original sample strip, and the EUHDI/4SH elastomer has a higher crosslinking density than the EUHDI/3SH elastomer, so that the reversible collision of dynamic bonds is influenced, and the self-healing efficiency of the EUHDI/4SH elastomer is lower than that of the EUHDI/3SH elastomer. In summary, the cross-linking density of the polymer structure affects the occurrence of reversible bond reversible reaction, and thus affects the self-healing efficiency.
The foregoing is merely illustrative of the preferred embodiments of this invention, and it will be appreciated by those skilled in the art that variations and modifications may be made without departing from the principles of the invention, and such variations and modifications are to be regarded as being within the scope of the invention.
Claims (10)
1. A method for preparing a urethane-based elastomer, comprising the steps of:
mixing hexamethylene diisocyanate, eugenol and benzene solvent, and carrying out addition reaction under the conditions of protective atmosphere and an organotin catalyst to obtain a urethane compound;
mixing the urethane-based compound and a sulfhydryl compound, and performing sulfhydryl clicking reaction under ultraviolet irradiation condition to obtain a urethane-based elastomer;
the mercapto compound includes trimethylolpropane tris (3-mercaptopropionate) or pentaerythritol tetrakis (3-mercaptopropionate).
2. The method of preparation according to claim 1, wherein the organotin catalyst comprises dibutyltin dilaurate.
3. The method according to claim 1, wherein the molar ratio of hexamethylene diisocyanate to eugenol is 1:1.5-2.5.
4. A process according to any one of claims 1 to 3, wherein the temperature of the addition reaction is 75 to 85 ℃ and the incubation time is 1.5 to 2.5 hours.
5. The method according to claim 1, wherein the molar ratio of urethane groups in the urethane-based compound to mercapto groups in the mercapto compound is 1:0.95 to 1.05.
6. The method according to claim 1, wherein the power of the ultraviolet irradiation is 95-110W for 5-15 min.
7. The method according to claim 1, wherein the addition reaction is followed by cooling, solid-liquid separation, washing and drying the system obtained by the addition reaction in this order.
8. The method of claim 7, wherein the cooling temperature is-5 to 0 ℃; the drying temperature is 75-85 ℃ and the drying time is 4-5 h.
9. The urethane-based elastomer produced by the production process according to any one of claims 1 to 8, wherein the chemical bond in the urethane-based elastomer comprises urethane bond and hydrogen bond.
10. The urethane-based elastomer of claim 9, wherein the molar ratio of urethane bonds to hydrogen bonds is 1:0.5.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2163872A5 (en) * | 1971-12-03 | 1973-07-27 | Grace W R Ltd | Polyenes prodn - for reacting with polythiols to yield curable resins |
| US6008296A (en) * | 1995-04-19 | 1999-12-28 | Optima, Inc. | Optical terpolymer of polyisocyanate, polythiol and polyene monomers |
| CN108484912A (en) * | 2018-03-14 | 2018-09-04 | 江西科技师范大学 | A kind of eugenol based high-temp-resistant self-healing polymers and preparation method thereof |
| CN109942773A (en) * | 2019-03-18 | 2019-06-28 | 四川大学 | A kind of selfreparing polyurethane and preparation method thereof of the key of thiourethane containing dynamic |
| CN114163598A (en) * | 2021-12-24 | 2022-03-11 | 中国林业科学研究院林产化学工业研究所 | Self-repairing polyurethane derived from bio-based polyol and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1524289B1 (en) * | 2002-07-08 | 2009-09-16 | Mitsubishi Gas Chemical Company, Inc. | Polymerizable composition, optical material comprising the composition and method for producing the material |
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2022
- 2022-11-11 CN CN202211409354.2A patent/CN115873252B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2163872A5 (en) * | 1971-12-03 | 1973-07-27 | Grace W R Ltd | Polyenes prodn - for reacting with polythiols to yield curable resins |
| US6008296A (en) * | 1995-04-19 | 1999-12-28 | Optima, Inc. | Optical terpolymer of polyisocyanate, polythiol and polyene monomers |
| CN108484912A (en) * | 2018-03-14 | 2018-09-04 | 江西科技师范大学 | A kind of eugenol based high-temp-resistant self-healing polymers and preparation method thereof |
| CN109942773A (en) * | 2019-03-18 | 2019-06-28 | 四川大学 | A kind of selfreparing polyurethane and preparation method thereof of the key of thiourethane containing dynamic |
| CN114163598A (en) * | 2021-12-24 | 2022-03-11 | 中国林业科学研究院林产化学工业研究所 | Self-repairing polyurethane derived from bio-based polyol and preparation method thereof |
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