CN110156952B - Dual-curable polyurethane toughened resin and preparation method and application thereof - Google Patents
Dual-curable polyurethane toughened resin and preparation method and application thereof Download PDFInfo
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- CN110156952B CN110156952B CN201910378444.1A CN201910378444A CN110156952B CN 110156952 B CN110156952 B CN 110156952B CN 201910378444 A CN201910378444 A CN 201910378444A CN 110156952 B CN110156952 B CN 110156952B
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- 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
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
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- 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
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
Abstract
A preparation method of dual-curable polyurethane toughening resin comprises the following steps: s1, mixing hydroxyl-containing oxetane, hydroxyl acrylate, diisocyanate, a polymerization inhibitor and a catalyst for reaction to obtain an isocyanate semi-closed composition C for later use; s2, adding macromolecular polyol into the composition C, keeping the temperature of 60-90 ℃ and reacting for 2-8h to obtain the dual-curable polyurethane toughening resin. The advantages are that: the polyurethane toughening resin can be subjected to free radical-cation dual light curing or free radical light curing-cation heat curing dual curing; the curing speed can be improved, the volume shrinkage is reduced during curing, and the adhesive force of the system to the base material is improved; the polyurethane toughening resin is added into an alicyclic epoxy resin system according to a certain proportion, so that the elasticity, extensibility and toughness of the system can be effectively improved, and the oxetane ring is a four-membered ring, so that the volume shrinkage is reduced during curing, and the adhesive force of the system to a base material can be improved.
Description
Technical Field
The invention relates to the field of ultraviolet curing and cationic curing, in particular to dual-curable polyurethane toughened resin and a preparation method and application thereof.
Background
The alicyclic epoxy resin is a kind of epoxy resin with wide application, and has the advantages of light color, small viscosity, small shrinkage of curing volume, good adhesive force, good high temperature resistance, etc. However, the method also has the problems of small elongation, large stress, easy sagging and the like, and limits the use of the method in the environment with large high and low temperature changes.
Therefore, it is a research focus to toughen cycloaliphatic epoxy resin, and the traditional toughening includes adding nanoparticles, core-shell rubber, introducing a non-curable resin component, modifying the epoxy resin, and the like, but the methods have certain limitations. For example, the introduction of the nanoparticles and the core-shell rubber affects the transparency and is easy to cause the problem of poor dispersibility, and the storage stability is poor; the introduction of the non-curable resin component can reduce the curing speed, influence the tolerance of the product to a solvent and easily cause migration; the epoxy resin is modified by a complex process, the cost is high, and some good performances of the modified epoxy resin may be changed, such as Tg reduction, adhesion reduction and the like.
Disclosure of Invention
The invention aims to solve the technical defects and provides a dual-curable polyurethane toughened resin as well as a preparation method and application thereof, and the principle is as follows: the hetercyclobutane is introduced to participate in cationic curing in a modification mode, and the acrylate bond is introduced to participate in free radical photocuring, so that the resin disclosed by the invention can be subjected to free radical-cationic dual photocuring or free radical photocuring-cationic thermosetting dual curing. The prepared polyurethane toughening resin is added into an alicyclic epoxy resin system, so that the elasticity, extensibility and toughness of the system are effectively improved, and the oxetane ring is a four-membered ring, so that the volume shrinkage is reduced during curing, and the adhesive force of the system to a base material can be improved; meanwhile, the technical defects that the light curing deep layer is not cured completely and the heat curing is sagging under certain application can be overcome.
The first aspect of the invention provides a preparation method of dual-curable polyurethane toughened resin, which comprises the following steps:
s1, mixing hydroxyl-containing oxetane, hydroxyl acrylate, diisocyanate, a polymerization inhibitor and a catalyst for reaction to obtain an isocyanate semi-closed composition C for later use;
s2, adding macromolecular polyol into the composition C, keeping the temperature of 60-90 ℃ and reacting for 2-8h to obtain the dual-curable polyurethane toughening resin.
Preferably, step S1 includes the following steps:
s11, uniformly mixing the hydroxyl-containing oxetane and the hydroxyl acrylate according to the molar ratio of 1: 0.2-1: 2 to obtain a substance A;
s12, and adding diisocyanate to the substance A according to a molar ratio of-NCO: -OH ═ 1: 0.95-1: 1.05 to obtain a substance B;
s13, adding a polymerization inhibitor and a catalyst into the substance B, uniformly mixing the substance B with the polymerization inhibitor and the catalyst obtained in the step S12, and reacting for 1-4 hours at 40-60 ℃ to obtain an isocyanate semi-closed composition C;
in step S1, the oxetane containing hydroxyl includes, but is not limited to, one or more of 3-oxetanylpropanol, 3-oxetanylbutanol, 3-oxetanemethanol, 3-phenyl-3-hydroxy-1-oxoheterocycle, 3-ethyl-3-oxooxetanemethanol, and 3-methyl-3-hydroxymethyloxetane;
in step S1, the hydroxy acrylate is one or more of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, and caprolactone acrylate.
In step S1, the diisocyanate is one or more selected from Hexamethylene Diisocyanate (HDI), isophorone diisocyanate (IPDI), Xylylene Diisocyanate (XDI), Toluene Diisocyanate (TDI), trimethyl hexamethylene diisocyanate (TMDI), dicyclohexylmethane diisocyanate (HMDI), preferably IPDI, which has high selectivity and is not yellowing.
In step S1, the catalyst is dibutyltin dilaurate or an organic bismuth-based catalyst, preferably an environmentally friendly organic bismuth-based catalyst.
In step S1, the polymerization inhibitor is p-hydroxyanisole.
Preferably, in step S2, the macropolyol is added in a molar ratio of composition C to the reactive groups in the macropolyol-NCO: -OH ═ 1:0.95 to 1: 1.05.
In step S2, the macromolecular polyol is one or a mixture of polyether polyol synthesized by any proportion of ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran and methyltetrahydrofuran, polycaprolactone polyol synthesized by taking the polyether polyol as an initiator, hydroxyl-terminated polybutadiene, alkylhydroxyl-terminated polydimethylsiloxane, one or a mixture of any proportion of liquid polyester polyol of neopentyl glycol and tetrahydrofuran copolymer glycol, polytrimethylene ether glycol and UNIPOL-B series. The number average molecular weight is between 400 and 6000, preferably between 600 and 2000.
Preferably, in step S1, the mass of the polymerization inhibitor is 0.01-0.5% of the total mass of the hydroxyl-containing oxetane, the hydroxyl acrylate, the diisocyanate and the macromolecular polyol; the mass of the catalyst is 0.01-0.2% of the total mass of the hydroxyl-containing oxetane, the hydroxyl acrylate, the diisocyanate and the macromolecular polyol.
The second aspect of the invention is to protect the polyurethane toughened resin prepared by the method of the first aspect.
A third aspect of the invention comprises the use of the polyurethane toughened resin of the first aspect in a cycloaliphatic epoxy resin system.
The invention relates to a dual-curable polyurethane toughened resin and a preparation method and application thereof, and has the advantages that:
firstly, the polyurethane toughening resin can be subjected to free radical-cation dual light curing or free radical light curing-cation heat curing dual curing;
secondly, the cationic curing group of the polyurethane toughening resin is oxetane, and the oxetane ring is a four-membered ring, so that the epoxy resin is easier to open than an epoxy three-membered ring, the curing speed can be improved, the volume shrinkage is small during curing, and the adhesive force of the system to a base material can be improved;
thirdly, the polyurethane toughening resin can be used as a main body and can also be added into epoxy resin as formula resin to realize dual curing, namely, the polyurethane toughening resin can be added into an alicyclic epoxy resin system according to a certain proportion to effectively improve the elasticity, extensibility and toughness of the system, and the oxetane ring is a four-membered ring, so that the volume shrinkage is reduced during curing, and the adhesive force of the system to a base material can be improved;
fourthly, the polyurethane toughening resin can realize the construction process of free radical photocuring setting at room temperature and cationic thermocuring forming at high temperature by adding the polyurethane toughening resin, so as to solve the problems that the photocuring deep layer is not cured thoroughly and the thermocuring can be sagging under certain applications.
Detailed Description
The following examples are given as particular embodiments of the present invention and to illustrate the practice and advantages thereof. It should be understood that these examples are illustrative only and are not intended to limit this specification or the appended claims in any way.
Example one
Preparation of PPG1000-PU
S1, uniformly mixing 26.78g of 3-oxetanemethanol and 34.09 hydroxyethyl acrylate (the molar ratio is 1:1) to obtain a substance A;
135.12g of isophorone diisocyanate (IPDI) were added again to obtain substance B;
adding 0.5g of polymerization inhibitor p-hydroxyanisole and 0.5g of catalyst dibutyltin dilaurate into the substance B, uniformly mixing, and maintaining the temperature at 60 ℃ for reaction for 2 hours to obtain an isocyanate semi-closed composition C;
s2, adding 304.01g of macromolecular polyol polypropylene glycol 2000(PPG2000, 2 functional) according to the molar ratio of the composition to the reactive groups in the macromolecular polyol-NCO: -OH ═ 1:1, and keeping the mixture at 70 ℃ for reacting for 6 hours to obtain the finished product PPG 1000-PU.
Example two
Preparation of PPG600-PU
S1, uniformly mixing 58.75g of 3-methyl-3-hydroxymethyl oxetane and 37.43g of hydroxypropyl acrylate (the molar ratio is 1:0.5) to obtain a substance A;
144.96g of hexamethylene diisocyanate (IPDI) were additionally added to obtain substance B;
adding 0.4g of polymerization inhibitor p-hydroxyanisole and 0.4g of catalyst dibutyltin dilaurate into the substance B, uniformly mixing, and maintaining the temperature at 50 ℃ for reaction for 3 hours to obtain an isocyanate semi-closed composition C;
s2, adding 258.86g of macromolecular polyol polyethylene glycol 600(PEG600, 2 functional) according to the molar ratio of the composition to the reactive groups in the macromolecular polyol-NCO: -OH ═ 1:1, and reacting at 80 ℃ for 4 hours to obtain the finished PPG 600-PU.
EXAMPLE III
Preparation of PTMG1400-PU
S1, uniformly mixing 21.21g of 3-oxetane propanol and 39.49g of hydroxybutyl acrylate (the molar ratio is 1:1.5) to obtain a substance A;
119.76g of dicyclohexylmethane diisocyanate (HMDI) were additionally added to obtain substance B;
adding 0.45g of polymerization inhibitor p-hydroxyanisole and 0.45g of catalyst organic bismuth catalyst bismuth neodecanoate into the substance B, uniformly mixing, and maintaining the temperature at 40 ℃ for reaction for 4 hours to obtain an isocyanate semi-closed composition C;
s2, adding 319.54g of macromolecular polyol polytetrahydrofuran ether 1400(PTMG1400, 2 functional group) according to the molar ratio of the composition to the reactive groups in the macromolecular polyol-NCO: -OH 1:1, and reacting for 3 hours at 88 ℃ to obtain the finished product PTMG 1400-PU.
The application effects of the above embodiments of the present invention are as follows:
four sets of comparative examples, in which the reagents were measured in mass percent for each set of comparative examples, were designed as follows to obtain corresponding products after mixing, and the elongation thereof was measured (as shown in table 1 below).
Comparative example 1: 97% 2021P epoxy resin, 3% cationic photoinitiator easipi 6976;
comparative example 2: 56 percent of 2021P epoxy resin, 30 percent of PPG1000-PU, 1 percent of photoinitiator 184 and 3 percent of cationic photoinitiator Easepi 6976;
comparative example 3: 56% of 2021P epoxy resin, 30% of PEG600-PU, 1% of photoinitiator 184 and 3% of cationic photoinitiator Easepi 6976;
comparative example 4: 56 percent of 2021P epoxy resin, 30 percent of PTMG1400-PU, 1 percent of photoinitiator 184 and 3 percent of cationic photoinitiator Easepi 6976;
TABLE 1
As can be seen from the above Table 1, the elongation of the corresponding product added with the toughened resin of the present invention is significantly improved, which indicates that the toughened resin of the present invention has a significant effect.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A preparation method of dual-curable polyurethane toughened resin is characterized by comprising the following steps: comprises the following steps
S1, mixing hydroxyl-containing oxetane, hydroxyl acrylate, diisocyanate, a polymerization inhibitor and a catalyst for reaction to obtain an isocyanate semi-closed composition C for later use;
s2, adding macromolecular polyol into the composition C, keeping the temperature of 60-90 ℃ and reacting for 2-8h to obtain the dual-curable polyurethane toughening resin;
in step S2, the macromolecular polyol is one or a mixture of polyether polyol synthesized by any proportion of ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran and methyltetrahydrofuran, polycaprolactone polyol, hydroxyl-terminated polybutadiene, alkylhydroxyl-terminated polydimethylsiloxane, neopentyl glycol and tetrahydrofuran copolymerized glycol, polytrimethylene ether glycol and UNIPOL-B series liquid polyester polyol.
2. The method of claim 1, wherein: in step S1, the method includes the steps of:
s11, uniformly mixing the hydroxyl-containing oxetane and the hydroxyl acrylate according to the molar ratio of 1: 0.2-1: 2 to obtain a substance A;
s12, and adding diisocyanate to the substance A according to a molar ratio of-NCO: -OH ═ 1: 0.95-1: 1.05 to obtain a substance B;
s13, adding a polymerization inhibitor and a catalyst into the substance B, uniformly mixing with the substance B obtained in the step S12, and reacting for 1-4 hours at 40-60 ℃ to obtain the isocyanate semi-closed composition C.
3. The method of claim 1, wherein: in step S1, the oxetane containing hydroxyl includes, but is not limited to, one or more of 3-oxetanylpropanol, 3-oxetanylbutanol, 3-oxetanemethanol, 3-phenyl-3-hydroxy-1-oxetane, 3-ethyl-3-oxetanemethanol, and 3-methyl-3-hydroxymethyloxetane in any proportion.
4. The method of claim 1, wherein: in step S1, the hydroxy acrylate is one or more of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, and caprolactone acrylate.
5. The method of claim 1, wherein: in step S1, the diisocyanate is one or more of Hexamethylene Diisocyanate (HDI), isophorone diisocyanate (IPDI), Xylylene Diisocyanate (XDI), Toluene Diisocyanate (TDI), trimethyl hexamethylene diisocyanate (TMDI), dicyclohexylmethane diisocyanate (HMDI).
6. The method of claim 1, wherein: in step S1, the catalyst is dibutyltin dilaurate or an organic bismuth-based catalyst; the polymerization inhibitor is p-hydroxyanisole.
7. The method of claim 1, wherein: in step S2, the macropolyol is added in a molar ratio of composition C to the reactive groups in the macropolyol-NCO ═ OH ═ 1:0.95 to 1: 1.05.
8. The method of claim 1, wherein: in the step S1, the mass of the polymerization inhibitor is 0.01-0.5% of the total mass of hydroxyl-containing oxetane, hydroxyl acrylate, diisocyanate and macromolecular polyol; the mass of the catalyst is 0.01-0.2% of the total mass of the hydroxyl-containing oxetane, the hydroxyl acrylate, the diisocyanate and the macromolecular polyol.
9. A polyurethane toughened resin prepared according to any one of claims 1 to 8.
10. Use of the polyurethane toughening resin of claim 9 in a cycloaliphatic epoxy resin system.
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| CN109734860A (en) * | 2019-01-10 | 2019-05-10 | 四川东树新材料有限公司 | A kind of urethane composition for vacuum introducing technology |
| CN116323204A (en) * | 2020-10-07 | 2023-06-23 | 株式会社大赛璐 | Curable composition and cured product thereof |
| CN115368529B (en) * | 2021-05-17 | 2024-02-13 | 常州强力先端电子材料有限公司 | Epoxy modified polyurethane resin, preparation method thereof, photo-curing composition containing epoxy modified polyurethane resin and application of photo-curing composition |
| CN113372868B (en) * | 2021-05-20 | 2022-06-24 | 武汉长盈鑫科技有限公司 | Ultraviolet activated double-component super-hydrophobic polyurethane ring winding adhesive |
| CN114213626B (en) * | 2021-12-09 | 2023-04-28 | 江苏三木化工股份有限公司 | Preparation method of vegetable oil-based photo-curing polyurethane acrylate |
| CN114106291A (en) * | 2021-12-28 | 2022-03-01 | 巩义市泛锐熠辉复合材料有限公司 | Toughening auxiliary agent, preparation method and application thereof in unsaturated resin |
| CN114276518A (en) * | 2021-12-28 | 2022-04-05 | 巩义市泛锐熠辉复合材料有限公司 | Toughening agent, preparation method and application thereof in unsaturated resin |
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| CN108456290A (en) * | 2017-12-28 | 2018-08-28 | 滁州金桥德克新材料有限公司 | A kind of dual cure polyurethane acrylate resin and preparation method thereof |
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| US6838515B2 (en) * | 2001-01-11 | 2005-01-04 | Dsm Ip Assets B.V. | Process for the preparation of esters of (meth)acrylic acid |
| US11299430B2 (en) * | 2016-11-30 | 2022-04-12 | Hrl Laboratories, Llc | Formulations with active functional additives for 3D printing of preceramic polymers, and methods of 3D-printing the formulations |
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| CN104774312A (en) * | 2015-04-28 | 2015-07-15 | 烟台德邦科技有限公司 | Resin with mixing and solidification functions and synthetic method thereof |
| CN108456290A (en) * | 2017-12-28 | 2018-08-28 | 滁州金桥德克新材料有限公司 | A kind of dual cure polyurethane acrylate resin and preparation method thereof |
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