CN115677969A - UV (ultraviolet) curing self-repairing self-adhesive polyurethane resin and preparation method and application thereof - Google Patents
UV (ultraviolet) curing self-repairing self-adhesive polyurethane resin and preparation method and application thereof Download PDFInfo
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- CN115677969A CN115677969A CN202211403633.8A CN202211403633A CN115677969A CN 115677969 A CN115677969 A CN 115677969A CN 202211403633 A CN202211403633 A CN 202211403633A CN 115677969 A CN115677969 A CN 115677969A
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- 229920005749 polyurethane resin Polymers 0.000 title claims abstract description 42
- 239000000853 adhesive Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 229920005989 resin Polymers 0.000 claims abstract description 30
- 239000011347 resin Substances 0.000 claims abstract description 30
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 23
- 229920000570 polyether Polymers 0.000 claims abstract description 23
- 229920002635 polyurethane Polymers 0.000 claims abstract description 23
- 239000004814 polyurethane Substances 0.000 claims abstract description 23
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims abstract description 19
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims abstract description 18
- 150000001412 amines Chemical class 0.000 claims abstract description 17
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims abstract description 14
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims abstract description 11
- 238000000016 photochemical curing Methods 0.000 claims abstract description 11
- 229920005862 polyol Polymers 0.000 claims abstract description 6
- 150000003077 polyols Chemical class 0.000 claims abstract description 6
- 230000001070 adhesive effect Effects 0.000 claims description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 7
- 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
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 6
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 6
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical group CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 5
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 claims description 4
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 4
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 claims description 4
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 150000005846 sugar alcohols Polymers 0.000 claims description 4
- MUTNCGKQJGXKEM-UHFFFAOYSA-N tamibarotene Chemical compound C=1C=C2C(C)(C)CCC(C)(C)C2=CC=1NC(=O)C1=CC=C(C(O)=O)C=C1 MUTNCGKQJGXKEM-UHFFFAOYSA-N 0.000 claims description 4
- 229910052797 bismuth Inorganic materials 0.000 claims description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 3
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000001723 curing Methods 0.000 abstract description 6
- 239000000758 substrate Substances 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 4
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- BJZYYSAMLOBSDY-QMMMGPOBSA-N (2s)-2-butoxybutan-1-ol Chemical compound CCCCO[C@@H](CC)CO BJZYYSAMLOBSDY-QMMMGPOBSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
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- 230000001588 bifunctional effect Effects 0.000 description 2
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- 229910052739 hydrogen Inorganic materials 0.000 description 2
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- 238000011056 performance test Methods 0.000 description 2
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- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
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- 238000010008 shearing Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
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- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a preparation method and application of UV (ultraviolet) curing self-repairing self-adhesive polyurethane resin, belonging to the technical field of functional polyurethane materials. The preparation method of the polyurethane resin comprises the following steps: (1) Adding diisocyanate and polyol into a reaction container, dropwise adding a catalyst, heating to react until NCO reaches a theory, adding 1, 4-butanediol, and heating to react to obtain a polyurethane prepolymer; (2) Adding polyether amine into the polyurethane prepolymer prepared in the step (1) to react to obtain polyurethane with partial polyether end capping; (3) And (3) adding hydroxyethyl acrylate into the polyurethane prepared in the step (2) for end-capping treatment to obtain the photo-curing polyurethane elastic resin. Compared with the traditional end-capped resin, the UV-cured polyurethane resin prepared by the invention has greatly improved mechanical properties, and has good self-repairing performance and certain bonding performance to different substrates.
Description
Technical Field
The invention relates to the technical field of functional polyurethane materials, in particular to UV (ultraviolet) curing self-repairing self-adhesive polyurethane resin and a preparation method and application thereof.
Background
With the rapid development of socioeconomic of China, the demand for resources is increasing day by day, thus bringing about huge environmental pressure. Compared with the traditional solvent type resin, the ultraviolet curing resin has the advantages of high curing speed, low VOC (volatile organic compound) emission, good energy-saving and environment-friendly effects and the like, can be widely paid attention to once being put out, and has wide application prospect.
Pure straight-chain polyurethane resin is cheap and has good performance price, but the existing preparation method is single, and the performance (such as strength, elongation and the like) can not be satisfied in many application aspects. In order to solve the above problems, it is necessary to develop a UV-curable self-healing self-adhesive polyurethane resin.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method and application of a UV-cured self-repairing self-adhesive polyurethane resin. Compared with the traditional double-bond end-capped resin, the photo-cured polyurethane resin prepared by the invention has greatly improved mechanical properties and has good self-repairability and bonding property.
The technical scheme of the invention is as follows:
a preparation method of UV curing self-repairing self-adhesive polyurethane resin comprises the following steps:
(1) Adding diisocyanate and polyalcohol into a reaction container, dropwise adding a catalyst, heating to react until-NCO reaches the theory, adding 1, 4-butanediol, heating to 60-70 ℃, and carrying out chain extension reaction for 2-3 h to obtain a polyurethane prepolymer;
(2) Adding polyether amine into the polyurethane prepolymer prepared in the step (1) to react to obtain polyurethane with partial polyether end capping;
(3) And (3) adding hydroxyethyl acrylate into the polyurethane prepared in the step (2) to carry out end capping treatment, so as to obtain the UV-cured self-repairing self-adhesive polyurethane resin.
Further, in the step (1), the diisocyanate is isophorone diisocyanate or hexamethylene diisocyanate. The polyol is polytetrahydrofuran ether glycol with molecular weight of 2000.
Further, in the step (1), the catalyst is one of dibutyltin dilaurate, an organic bismuth catalyst and dimethylcyclohexylamine.
Further, in the step (1), the molar ratio of the diisocyanate to the polyol is 2:1; the addition amount of the catalyst is 0.09-0.32% of the total mass of the diisocyanate and the polyalcohol.
Further, in the step (1), the temperature rise reaction is carried out for 2-3 h after the temperature rises to 40-50 ℃ at the speed of 2-3 ℃/min.
Further, in the step (1), the molar ratio of the 1, 4-butanediol to the diisocyanate is 0.25:1
Further, in the step (2), the polyether amine is a monofunctional polyether amine with the molecular weight of 1000; the molar ratio of the polyether amine to the diisocyanate is 0.1-0.5: 1; the reaction temperature is 60-70 ℃ and the reaction time is 0.5-1 h.
Further, in the step (3), the molar ratio of the hydroxyethyl acrylate to the diisocyanate is 0.1-0.5: 1; the reaction temperature is 80-90 ℃ and the reaction time is 2-3 h.
The elongation at break of the UV-cured self-repairing self-adhesive polyurethane resin prepared by the preparation method is 400-1300%.
The application of the UV curing self-repairing self-adhesive polyurethane resin is to prepare a polyurethane adhesive.
Further, the polyurethane adhesive comprises the following components in percentage by mass: 70% of the photo-curing polyurethane elastic resin; 10% of isobornyl acrylate and 20% of tetrahydrofurfuryl acrylate.
The UV-cured self-repairing self-adhesive polyurethane resin prepared by the preparation method is greatly improved in mechanical property, and has good self-repairing property and certain bonding property for different substrates. Has wide application prospect in the field of photocuring.
The beneficial technical effects of the invention are as follows:
(1) The invention prepares polyurethane prepolymer by using diisocyanate, polyol and chain extender as raw materials; and then, adding monofunctional polyether amine to perform half-end capping on the prepolymer, so that a long straight chain replacing acrylate is connected to the main chain of the resin, the flexibility of the chain segment is improved, and the extension rate is improved macroscopically. And finally, blocking the residual-NCO in the polyurethane by using hydroxyethyl acrylate, connecting C = C, and providing a site for crosslinking with a photoinitiator, thereby providing a basis for subsequent photocuring.
(2) The UV-cured self-repairing self-adhesive polyurethane resin prepared by the method makes up the defects of the mechanical property of the traditional bifunctional light-cured polyurethane resin, and the polyether amine provides excellent mechanical property support for a system because of having an ether bond (-C-O-C-) with higher flexibility; and the special structure of the mono-NH 2 end capping can also ensure that the main resin has good stability after being connected with PEA end capping. Polyether amine end capping is accessed in a polyurethane system, and a dynamic reversible ureido group is introduced; and the formed cross-linked structure is comb-shaped, and hydrogen bonds and carbamido groups can be enriched on the surface of the resin, so that the resin has certain self-repairing performance and self-adhesive performance, and has good application prospect in the field of photo-curing polyurethane materials.
(3) The photo-curing polyurethane resin prepared by the invention is used for preparing the adhesive, the preparation method is simple, and the prepared adhesive has good adhesive property to a PET film.
Drawings
FIG. 1 shows the mechanical properties of photocurable polyurethane resins prepared in examples 1-4 of the present invention.
FIG. 2 is a graph showing the adhesion test of the photocurable polyurethane resin prepared in example 1 of the present invention to various substrates.
FIG. 3 shows the adhesion mechanical properties of the photocurable polyurethane resin prepared in example 1 of the present invention to different substrates.
Fig. 4 is a self-repairing performance test chart of the photo-curable polyurethane resin prepared in example 1 of the present invention.
FIG. 5 is a graph showing the shear strength of the adhesive prepared in examples 1 to 4 according to the present invention to a PET film.
Detailed Description
The present invention will be described in detail with reference to the accompanying drawings and examples.
Example 1
The preparation method of the UV curing self-repairing self-adhesive polyurethane resin comprises the following steps:
(1) 13.32g (0.06 mol) of isophorone diisocyanate (IPDI) and 60g (0.03 mol) of polytetrahydrofuran ether glycol (PTMG) were charged into a dry three-necked flask equipped with a stirrer, a condenser and a thermometer; adding 0.073g of catalyst dibutyltin dilaurate (DBTDL), heating to 45 ℃ at the speed of 3 ℃/min, and continuing to react for 2h after the temperature is reached; 1.35g (0.015 mol) of 1, 4-Butanediol (BDO) is added, the temperature is raised to 60 ℃, and then the mixture is continuously stirred and reacted for 3 hours to obtain the polyurethane prepolymer.
(2) 15g (0.015 mol) of monofunctional polyether amine is added into the three-neck flask and reacts for 1h at 60 ℃ to obtain the semi-terminated polyurethane resin.
(3) Adding 1.74g (0.015 mol) of hydroxyethyl acrylate (HEA) into the three-neck flask, heating to 80 ℃ and reacting for 3h to obtain the designed polyether and HEA double-end-capped UV curing self-repairing self-adhesive polyurethane resin.
Example 1 the resulting polyetheramine end-capping content of 50 mole percent of the total elastomeric resin end-groups was prepared.
Example 2
The preparation method of the UV curing self-repairing self-adhesive polyurethane resin comprises the following steps:
(1) 6.66g (0.03 mol) of isophorone diisocyanate (IPDI) and 30g (0.015 mol) of polytetrahydrofuran ether glycol (PTMG) were placed in a dry three-necked flask equipped with a stirrer, a condenser and a thermometer; adding 0.072g of catalyst organic bismuth catalyst (DY-20), heating to 45 ℃ at the speed of 2 ℃/min, and continuing to react for 2 hours after the temperature is reached; 0.675g (0.0075 mol) of 1, 4-Butanediol (BDO) was added; heating to 65 ℃, and continuously stirring for reaction for 2h to obtain the polyurethane prepolymer.
(2) 6g (0.006 mol) of monofunctional polyether amine is added into the three-neck flask and reacts for 0.75h at 65 ℃ to obtain the semi-terminated polyurethane resin.
(3) 1.004g (0.009 mol) of hydroxyethyl acrylate (HEA) is added into the three-neck flask, and the temperature is increased to 80 ℃ to react for 3h to obtain the designed polyether and HEA double-end-capped UV curing self-repairing polyurethane resin.
Example 2 the resulting polyetheramine end-capping content of 40 mole percent of the total elastomeric resin end-groups was prepared.
Example 3
The preparation method of the UV curing self-repairing self-adhesive polyurethane resin comprises the following steps:
(1) 20.16g (0.12 mol) of Hexamethylene Diisocyanate (HDI) and 120g (0.06 mol) of polytetrahydrofuran ether glycol (PTMG) were charged into a dry three-necked flask equipped with a stirrer, a condenser and a thermometer; adding 0.438g of catalyst Dimethylcyclohexylamine (DMCHA), heating to 45 ℃ at the speed of 2.5 ℃/min, and continuing to react for 2 hours after the temperature is reached; 2.7g (0.03 mol) of 1, 4-Butanediol (BDO) were added; heating to 65 ℃, and continuously stirring for reaction for 2h to obtain the polyurethane prepolymer.
(2) 18g (0.018 mol) of monofunctional polyether amine is added into the three-neck flask and reacted for 0.75h at 65 ℃ to obtain the semi-terminated polyurethane resin.
(3) 4.872g (0.042 mol) of hydroxyethyl acrylate (HEA) is added into the three-neck flask, and the temperature is raised to 85 ℃ to react for 2.5h to obtain the designed PEA and HEA double-end-capped UV curing self-repairing polyurethane resin.
Example 3 the resulting polyetheramine end-capping content of 30 mole percent of the total elastomeric resin end-groups was prepared.
Example 4
The preparation method of the UV-cured self-repairing self-adhesive polyurethane resin comprises the following steps:
(1) 13.32g (0.06 mol) of isophorone diisocyanate (IPDI) and 60g (0.03 mol) of polytetrahydrofuran ether glycol (PTMG) were charged into a dry three-necked flask equipped with a stirrer, a condenser and a thermometer; adding 0.073g of catalyst dibutyltin dilaurate (DBTDL), heating to 45 ℃ at the speed of 3 ℃/min, and continuing to react for 2h after the temperature is reached; 1.35g (0.015 mol) of 1, 4-Butanediol (BDO) is added, the temperature is raised to 60 ℃, and the mixture is continuously stirred and reacted for 3 hours to obtain the polyurethane prepolymer.
(2) 6g (0.006 mol) of monofunctional polyether amine is added into the three-neck flask to react for 1h at 60 ℃ to obtain the semi-terminated polyurethane resin.
(3) Adding 2.784g (0.024 mol) of hydroxyethyl acrylate (HEA) into the three-neck flask, heating to 80 ℃ and reacting for 3h to obtain the designed polyether and HEA double-end-capped UV-cured self-repairing polyurethane resin.
Example 4 the resulting polyetheramine end-capping content was 20 mole percent of the total elastomeric resin end-groups.
Comparative example 1
The photocuring polyurethane resin has 0% of monofunctional polyetheramine content, 0g of polyetheramine, 3.48g (0.03 mol) of HEA, pure HEA-terminated bifunctional photocuring polyurethane, and other preparation conditions and parameters are the same as those in example 1, so that the photocuring polyurethane resin is prepared.
The tensile elongation at break of the obtained light-cured polyurethane resin is only 142%; and has no adhesive effect on 6 selected base materials (wood, polyethylene terephthalate, polytetrafluoroethylene, tinned plate, glass and plastic).
Application examples 1 to 4
7g of the photocurable resin prepared in examples 1 to 4 was added with 1g of isobornyl acrylate (IBOA) and 2g of tetrahydrofurfuryl acrylate (THFA), and the mixture was stirred uniformly to obtain an adhesive, i.e., the adhesive of application examples 1 to 4. The shear strength of the prepared adhesive to a PET film is tested according to the GB/T7124-2008 standard.
The test results for each example are as follows:
(1) Mechanical property test of light-cured resin
The mechanical properties of the photocurable polyurethane elastic resins prepared in examples 1 to 4 were measured by a universal tester. The results are shown in FIG. 1. As can be seen from FIG. 1, the elongation at break of the resin increases significantly with the amount of PEA used for end-capping, but the tensile strength decreases accordingly. The crosslinking density in the curing system is reduced along with the increase of the PEA content, a loose network structure is formed, the molecular motion is easier, the flexibility is increased, and the elongation is improved; meanwhile, the molecular chain of PEA contains ether bonds with higher flexibility, and the flexibility of the resin is increased along with the continuous increase of the grafting amount of PEA.
The adhesion of the resin prepared in example 1 to different substrates was measured by the single lap tensile shear strength test method in a universal tester. As shown in FIGS. 2 and 3, it can be seen that the obtained resin had a certain viscosity to various substrates. The glass has the highest viscosity of 398Kpa, and the shearing strength of 352Kpa to wood.
(2) Self-repairing performance test of light-cured resin
Polyether amine is connected to polyurethane for end capping, and a dynamic reversible ureido group is introduced; and the formed cross-linking structure is comb-shaped, and hydrogen bonds and carbamido groups can be enriched on the surface of the resin, so that the resin has certain self-repairing performance.
As shown in fig. 4: the photo-curable polyurethane elastic resin sample prepared by the method of example 1 is cut from the middle, put into an oven at 60 ℃ for 2h and then taken out. The sample strips are bonded together again and have certain mechanical properties. The photo-curing polyurethane elastic resin prepared by the invention has excellent self-repairing performance.
(3) Testing the performance of the adhesive:
the shear strength of the adhesive prepared in application examples 1 to 4 to polyethylene terephthalate (PET) was tested by a double lap tensile shear strength test method in a universal testing machine. As shown in FIG. 5, the adhesives prepared from the four resins as the base resin all have excellent adhesion effect on PET, wherein the resin prepared in example 1 has the best effect.
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered in the protection scope of the present invention.
Claims (10)
1. A preparation method of UV-cured self-repairing self-adhesive polyurethane resin is characterized by comprising the following steps:
(1) Adding diisocyanate and polyalcohol into a reaction container, dropwise adding a catalyst, heating to react until-NCO reaches the theory, adding 1, 4-butanediol, heating to 60-70 ℃, and reacting for 2-3 h to obtain a polyurethane prepolymer;
(2) Adding polyether amine into the polyurethane prepolymer prepared in the step (1) to react to obtain polyurethane with partial polyether end capping;
(3) And (3) adding hydroxyethyl acrylate into the polyurethane prepared in the step (2) to carry out end capping treatment, so as to obtain the UV-cured self-repairing self-adhesive polyurethane resin.
2. The production method according to claim 1, wherein in the step (1), the diisocyanate is isophorone diisocyanate or hexamethylene diisocyanate; the polyol is polytetrahydrofuran ether glycol with molecular weight of 2000.
3. The preparation method according to claim 1, wherein in the step (1), the catalyst is one of dibutyltin dilaurate, an organic bismuth catalyst and dimethylcyclohexylamine.
4. The method according to claim 1, wherein in the step (1), the molar ratio of diisocyanate to polyol is 2:1; the addition amount of the catalyst is 0.09-0.32% of the total mass of the diisocyanate and the polyalcohol.
5. The method according to claim 1, wherein in the step (1), the temperature-raising reaction is carried out for 2 to 3 hours after raising the temperature to 40 to 50 ℃ at a rate of 2 to 3 ℃/min.
6. The process according to claim 1, wherein in step (1), the molar ratio of 1, 4-butanediol to diisocyanate is 0.25:1.
7. the method according to claim 1, wherein in the step (2), the polyether amine is a monofunctional polyether amine having a molecular weight of 1000; the molar ratio of the polyether amine to the diisocyanate is 0.1-0.5: 1; the reaction temperature is 60-70 ℃ and the reaction time is 0.5-1 h.
8. The method according to claim 1, wherein in the step (3), the molar ratio of the hydroxyethyl acrylate to the diisocyanate is 0.1 to 0.5:1; the reaction temperature is 80-90 ℃ and the reaction time is 2-3 h.
9. A UV-cured self-repairing self-adhesive polyurethane resin prepared by the preparation method of any one of claims 1 to 8.
10. The use of the UV-curable self-healing self-adhesive polyurethane resin of claim 9, wherein the UV-curable self-healing self-adhesive polyurethane resin is used for preparing a polyurethane adhesive; the polyurethane adhesive comprises the following components in percentage by mass: 70% of the photo-curing polyurethane elastic resin; 10% of isobornyl acrylate and 20% of tetrahydrofurfuryl acrylate.
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| CN117683183A (en) * | 2023-12-18 | 2024-03-12 | 无锡八禾新材料科技有限公司 | Photo-curing flexible conductive polyurethane and preparation method and application thereof |
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| CN112048051A (en) * | 2019-06-05 | 2020-12-08 | 万华化学（北京）有限公司 | Polyurethane acrylate resin and preparation method thereof |
| CN114539481A (en) * | 2022-02-22 | 2022-05-27 | 广东云兔科技有限公司 | Photo-curing polyurethane acrylate prepolymer and application thereof in 3D printing |
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| CN112048051A (en) * | 2019-06-05 | 2020-12-08 | 万华化学（北京）有限公司 | Polyurethane acrylate resin and preparation method thereof |
| CN114539481A (en) * | 2022-02-22 | 2022-05-27 | 广东云兔科技有限公司 | Photo-curing polyurethane acrylate prepolymer and application thereof in 3D printing |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117683183A (en) * | 2023-12-18 | 2024-03-12 | 无锡八禾新材料科技有限公司 | Photo-curing flexible conductive polyurethane and preparation method and application thereof |
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