CN110156952A - One kind can the polyurethane toughened resin of dual cure and the preparation method and application thereof - Google Patents
One kind can the polyurethane toughened resin of dual cure and the preparation method and application thereof Download PDFInfo
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- CN110156952A CN110156952A CN201910378444.1A CN201910378444A CN110156952A CN 110156952 A CN110156952 A CN 110156952A CN 201910378444 A CN201910378444 A CN 201910378444A CN 110156952 A CN110156952 A CN 110156952A
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- Prior art keywords
- diisocyanate
- preparation
- oxetanes
- resin
- toughened resin
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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
-
- 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
-
- 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
It is a kind of can the polyurethane toughened resin of dual cure preparation method, include the following steps: S1, take the oxetanes containing hydroxyl, crylic acid hydroxy ester, diisocyanate, polymerization inhibitor, catalyst hybrid reaction, it is spare to obtain the semiclosed composition C of isocyanates；S2, addition macromolecular polyol keep 60-90 DEG C of reaction 2-8h into composition C, and i.e. acquisition can the polyurethane toughened resin of dual cure.Advantage is: polyurethane toughened resin of the invention can carry out the dual photocuring of free radical-cation or radical UV curing-cation heat cure dual cure；Curing rate can be promoted, volume contraction is small when solidification, promotes system to the adhesive force of substrate；The polyurethane toughened resin of the present invention is added to cycloaliphatic epoxy resin system by a certain percentage can effectively promote the elasticity, extensibility, toughness of system, and oxa- Ding Huanwei four-membered ring, and volume contraction is small when solidification, can promote system to the adhesive force of substrate.
Description
Technical field
The present invention relates to ultraviolet light solidification and cationic curing fields, and specifically one kind can dual cure polyurethane
Tough resin and the preparation method and application thereof.
Background technique
Cycloaliphatic epoxy resin is a kind of very widely used epoxy resin, has that of light color, viscosity is small, solidifies volume
Shrink small, the advantages that adhesive force is good, and high temperature resistance is preferable.It is small but there is also elongations, the problems such as stress is big, easy sagging,
Limit its use under the environment that high/low temperature changes greatly.
Therefore, how to carry out toughening to cycloaliphatic epoxy resin is always research hotspot, and traditional toughening includes that addition is received
Rice corpuscles, introduces not curable resin component at core shell rubbers, is modified to epoxy resin itself, but these methods are all
There is certain limitation.For example the introducing of nanoparticle and core shell rubbers will affect transparency and be easy to appear poor dispersion
Problem, storage stability be not good enough；Curing rate can be reduced by introducing not curable resin component, influence tolerance of the product to solvent
Property, also it is easy to happen migration；Epoxy resin itself is modified and technics comparing is cumbersome, higher cost, and modified epoxy
Some superperformances of resin itself may change, such as Tg is reduced, adhesive force decline.
Summary of the invention
Present invention aim to address above-mentioned technological deficiencies, and providing one kind can the polyurethane toughened resin of dual cure and its system
Preparation Method and application, principle is: introducing miscellaneous fourth ring by modified mode and participates in cationic curing, introduces acrylic acid ester bond ginseng
With radical UV curing, therefore, resin of the invention can carry out the dual photocuring of free radical-cation or free radical light is solid
Change-cation heat cure dual cure.So that the polyurethane toughened resin of preparation is added to cycloaliphatic epoxy resin system, have
The characteristics of effectively promoting elasticity, the extensibility, toughness of system, and oxa- Ding Huanwei four-membered ring, volume contraction is small when solidification, can
To promote system to the adhesive force of substrate；Meanwhile it can solve that photocuring deep cure under certain applications is impermeable, and heat cure can flow again
The technological deficiency of extension.
First aspect present invention protect it is a kind of can the polyurethane toughened resin of dual cure preparation method, including walk as follows
It is rapid:
S1, take the oxetanes containing hydroxyl, crylic acid hydroxy ester, diisocyanate, polymerization inhibitor, catalyst mixing anti-
It answers, it is spare to obtain the semiclosed composition C of isocyanates；
S2, addition macromolecular polyol keep 60-90 DEG C of reaction 2-8h into composition C, and i.e. acquisition can the poly- ammonia of dual cure
Ester toughened resin.
Preferably, in step S1, include the following steps:
S11, first the ratio of the oxetanes containing hydroxyl and crylic acid hydroxy ester 1:0.2~1:2 in molar ratio mixed
It closes uniformly, obtains substance A；
S12, diisocyanate is added into substance A according still further to molar ratio-NCO:-OH=1:0.95~1:1.05 to obtain
Substance B；
It is uniformly mixed, and maintains after in S13, the substance B that addition polymerization inhibitor, catalyst are obtained with step S12 into substance B
40-60 DEG C of 1~4h of reaction, to obtain the semiclosed composition C of isocyanates；
In step S1, the oxetanes containing hydroxyl includes but is not limited to 3- oxetanes propyl alcohol, 3- oxa-
Cyclobutane butanol, 3- oxetane methanol, 3- phenyl -3- hydroxyl -1- oxa- ring, 3- ethyl -3- oxa- fourth ring methanol, 3- first
One of base -3- hydroxymethyl-oxetane or a variety of mixtures in any proportion；
In step S1, the crylic acid hydroxy ester is hydroxy-ethyl acrylate, hydroxypropyl acrylate, hy-droxybutyl, third
The mixture of one of olefin(e) acid caprolactone or a variety of arbitrary proportions.
In step S1, the diisocyanate is hexamethylene diisocyanate (HDI), isophorone diisocyanate
(IPDI), benzene dimethylene diisocyanate (XDI), toluene di-isocyanate(TDI) (TDI), trimethyl di-isocyanate
(TMDI), one of dicyclohexyl methyl hydride diisocyanate (HMDI) or a variety of mixtures, preferably IPDI, have compared with
Highly selective and non yellowing.
In step S1, the catalyst is dibutyl tin dilaurate or organo-bismuth class catalyst, preferably environmentally friendly
Organo-bismuth class catalyst.
In step S1, the polymerization inhibitor is p-hydroxyanisole.
Preferably, in step S2, according to the molar ratio-NCO:-OH of the reactive group in composition C and macromolecular polyol
Macromolecular polyol is added in=1:0.95~1:1.05.
In step S2, the macromolecular polyol is by ethylene oxide, propylene oxide, epoxy butane, tetrahydrofuran, methyl
One of tetrahydrofuran or the polyether polyol of arbitrary proportion synthesis, polycaprolactone polyol, with above-mentioned polyether polyol work
For initiator synthesis polycaprolactone polyol, end hydroxy butadiene, the hydroxy-end capped dimethyl silicone polymer of alkane, new penta 2
Alcohol and one of tetrahydrofuran copolymer glycols, polytrimethylene ether glycol, UNIPOL-B series liquid polyesters polyalcohol or more
The mixture of kind arbitrary proportion.Number-average molecular weight is between 400 to 6000, between preferably 600 to 2000.
Preferably, in step S1, quality used in polymerization inhibitor is the oxetanes containing hydroxyl, crylic acid hydroxy ester, two
The 0.01~0.5% of isocyanates, macromolecular polyol gross mass；Quality used in catalyst is the oxa- ring fourth containing hydroxyl
Alkane, crylic acid hydroxy ester, diisocyanate, macromolecular polyol gross mass 0.01~0.2%.
The present invention second facilitates the polyurethane toughened resin of protection first aspect the method preparation.
Third of the present invention conveniently includes polyurethane toughened resin described in first aspect in cycloaliphatic epoxy resin system
Using.
One kind of the present invention can the polyurethane toughened resin of dual cure and the preparation method and application thereof, its advantage is that:
First, polyurethane toughened resin of the invention can carry out the dual photocuring of free radical-cation or free radical light
Solidification-cation heat cure dual cure；
Second, polyurethane toughened resin cationic curing group of the invention is oxetanes, oxa- Ding Huanwei quaternary
Ring, the three-membered ring than epoxy are easier to open loop, can promote curing rate, and volume contraction is small when solidification, can promote system to base
The adhesive force of material；
Third, polyurethane toughened resin of the invention can be used as main body, can also be used as the addition of Formula type resin
Into in epoxy resin, dual cure is realized, that is, the polyurethane toughened resin of the present invention is added to alicyclic epoxy by a certain percentage
Resin system can effectively promote the elasticity, extensibility, toughness of system, and oxa- Ding Huanwei four-membered ring, and volume is received when solidification
It reduces, system can be promoted to the adhesive force of substrate；
4th, being added to polyurethane toughened resin of the invention may be implemented radical UV curing sizing at room temperature, high temperature
The molding construction technology of lower cation heat cure, impermeable to solve photocuring deep cure under certain applications, heat cure can flow again
The problem of extension.
Specific embodiment
Following embodiment is provided as a specific embodiment of the invention, and for illustrating the embodiment and advantages of the present invention.
It should be understood that these embodiments are merely illustrative, and have no intention any mode and this specification or appended claims are limited
System.
Embodiment one
The preparation of PPG1000-PU
It is S1, first that 26.78g 3- oxetane methanol and the ratio of 34.09 hydroxy-ethyl acrylates (molar ratio 1:1) is mixed
It closes uniformly, obtains substance A；
135.12g isophorone diisocyanate (IPDI) is added to obtain substance B；
The catalyst dibutyltin dilaurylate of polymerization inhibitor p-hydroxyanisole, 0.5g that 0.5g is added into substance B is mixed
60 DEG C are maintained to react 2 hours after closing uniformly, to obtain the semiclosed composition C of isocyanates；
S2,304.01g is added by the molar ratio-NCO:-OH=1:1 of the reactive group in composition and macromolecular polyol
Macromolecular polyol polypropylene glycol 2000 (PPG2000,2 functions) keeps 70 DEG C of reactions finished product PPG1000- to can be obtained in 6 hours
PU。
Embodiment two
The preparation of PPG600-PU
S1, first by 58.75g 3- methyl -3- hydroxymethyl-oxetane and 37.43g hydroxypropyl acrylate (molar ratio 1:
0.5) ratio is uniformly mixed, and obtains substance A；
144.96g hexamethylene diisocyanate (IPDI) is added to obtain substance B；
The catalyst dibutyltin dilaurylate of polymerization inhibitor p-hydroxyanisole, 0.4g that 0.4g is added into substance B is mixed
50 DEG C are maintained to react 3 hours after closing uniformly, to obtain the semiclosed composition C of isocyanates；
S2,258.86g is added by the molar ratio-NCO:-OH=1:1 of the reactive group in composition and macromolecular polyol
Macromolecular polyol Macrogol 600 (PEG600,2 functions) keeps 80 DEG C of reactions finished product PPG600-PU to can be obtained in 4 hours.
Embodiment three
The preparation of PTMG1400-PU
S1, first by the ratio of 21.21g 3- oxetanes propyl alcohol and 39.49g hy-droxybutyl (molar ratio 1:1.5)
It is uniformly mixed, obtains substance A；
119.76g dicyclohexyl methyl hydride diisocyanate (HMDI) is added to obtain substance B；
The polymerization inhibitor p-hydroxyanisole of 0.45g, the new certain herbaceous plants with big flowers of catalyst organic bismuth catalyst of 0.45g are added into substance B
Sour bismuth maintains 40 DEG C to react 4 hours after mixing, to obtain the semiclosed composition C of isocyanates；
S2,319.54g is added by the molar ratio-NCO:-OH=1:1 of the reactive group in composition and macromolecular polyol
Macromolecular polyol polytetrahydrofuran ether 1400 (PTMG1400,2 functions) keeps 88 DEG C of reactions finished product to can be obtained in 3 hours
PTMG1400-PU。
The application effect of the various embodiments described above of the present invention is as follows:
It is as follows to design four groups of comparative examples, wherein reagent is mass percent meter in each group comparative example, to obtain after mixing
Corresponding product, and measure its elongation (as shown in table 1 below).
Comparative example 1:97%2021P epoxy resin, 3% cation light initiator Easepi 6976；
Comparative example 2:56%2021P epoxy resin, 30%PPG1000-PU, 1% photoinitiator 184,3% cationic photopolymerization draw
Send out agent Easepi 6976；
Comparative example 3:56%2021P epoxy resin, 30%PEG600-PU, 1% photoinitiator 184,3% cationic photopolymerization draw
Send out agent Easepi 6976；
Comparative example 4:56%2021P epoxy resin, 30%PTMG1400-PU, 1% photoinitiator 184,3% cationic photopolymerization
Initiator Easepi 6976；
Table 1
According to upper table 1 it is found that the elongation for being added to the corresponding product of toughened resin of the present invention is obviously improved, explanation
Toughened resin effect of the present invention is obvious.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all in spirit of the invention and
Within principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (10)
1. one kind can the polyurethane toughened resin of dual cure preparation method, it is characterised in that: include the following steps
S1, the oxetanes containing hydroxyl, crylic acid hydroxy ester, diisocyanate, polymerization inhibitor, catalyst hybrid reaction are taken,
It is spare to obtain the semiclosed composition C of isocyanates；
S2, addition macromolecular polyol keep 60-90 DEG C of reaction 2-8h into composition C, and i.e. acquisition can dual cure polyurethane
Tough resin.
2. preparation method according to claim 1, it is characterised in that: in step S1, include the following steps:
S11, first the ratio of the oxetanes containing hydroxyl and crylic acid hydroxy ester 1:0.2~1:2 in molar ratio mixed it is equal
It is even, obtain substance A；
S12, diisocyanate is added into substance A according still further to molar ratio-NCO:-OH=1:0.95~1:1.05 to obtain substance
B；
It is uniformly mixed after in S13, the substance B that addition polymerization inhibitor, catalyst are obtained with step S12 into substance B, and maintains 40-
60 DEG C of 1~4h of reaction, to obtain the semiclosed composition C of isocyanates.
3. preparation method according to claim 1, it is characterised in that: in step S1, the oxetanes containing hydroxyl
Including but not limited to 3- oxetanes propyl alcohol, 3- oxetanes butanol, 3- oxetane methanol, 3- phenyl -3- hydroxyl -
One of 1- oxa- ring, 3- ethyl -3- oxa- fourth ring methanol, 3- methyl -3- hydroxymethyl-oxetane are a variety of by any
The mixture of ratio.
4. preparation method according to claim 1, it is characterised in that: in step S1, the crylic acid hydroxy ester is acrylic acid
The mixture of one of hydroxyl ethyl ester, hydroxypropyl acrylate, hy-droxybutyl, caprolactone or a variety of arbitrary proportions.
5. preparation method according to claim 1, it is characterised in that: in step S1, the diisocyanate is hexa-methylene
Diisocyanate (HDI), isophorone diisocyanate (IPDI), benzene dimethylene diisocyanate (XDI), toluene diisocyanate
Acid esters (TDI), trimethyl di-isocyanate (TMDI), one of dicyclohexyl methyl hydride diisocyanate (HMDI) or a variety of
Mixture, preferably IPDI have more highly selective and non yellowing.
6. preparation method according to claim 1, it is characterised in that: in step S1, the catalyst is two fourth of tin dilaurate
Base tin or organo-bismuth class catalyst；The polymerization inhibitor is p-hydroxyanisole.
7. preparation method according to claim 1, it is characterised in that: in step S2, according to composition C and macromolecular polyol
In reactive group molar ratio-NCO:-OH=1:0.95~1:1.05 be added macromolecular polyol.
8. preparation method according to claim 1, it is characterised in that: in step S1, quality used in polymerization inhibitor is containing hydroxyl
Oxetanes, crylic acid hydroxy ester, diisocyanate, macromolecular polyol gross mass 0.01~0.5%；Catalyst institute
With quality be the oxetanes containing hydroxyl, crylic acid hydroxy ester, diisocyanate, macromolecular polyol gross mass 0.01
~0.2%.
9. according to claim 1 to the polyurethane toughened resin of 8 any the method preparations.
10. application of the polyurethane toughened resin in cycloaliphatic epoxy resin system according to claim 9.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN113372868A (en) * | 2021-05-20 | 2021-09-10 | 武汉长盈鑫科技有限公司 | Ultraviolet activated double-component super-hydrophobic polyurethane ring winding adhesive |
| 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 |
| CN114213626A (en) * | 2021-12-09 | 2022-03-22 | 江苏三木化工股份有限公司 | Preparation method of vegetable oil-based photocuring urethane acrylate |
| 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 |
| CN115368529A (en) * | 2021-05-17 | 2022-11-22 | 常州强力先端电子材料有限公司 | Epoxy-modified polyurethane resin, preparation method thereof, photocuring composition containing epoxy-modified polyurethane resin and application of photocuring composition |
| CN116323204A (en) * | 2020-10-07 | 2023-06-23 | 株式会社大赛璐 | Curable composition and cured product thereof |
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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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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
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| CN115368529A (en) * | 2021-05-17 | 2022-11-22 | 常州强力先端电子材料有限公司 | Epoxy-modified polyurethane resin, preparation method thereof, photocuring composition containing epoxy-modified polyurethane resin and application of photocuring composition |
| 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 |
| CN113372868A (en) * | 2021-05-20 | 2021-09-10 | 武汉长盈鑫科技有限公司 | Ultraviolet activated double-component super-hydrophobic polyurethane ring winding adhesive |
| CN114213626A (en) * | 2021-12-09 | 2022-03-22 | 江苏三木化工股份有限公司 | Preparation method of vegetable oil-based photocuring urethane 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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