CN103012744B - A kind of method of spirane structure base polyurethane prepolymer for use as modified epoxy - Google Patents
A kind of method of spirane structure base polyurethane prepolymer for use as modified epoxy Download PDFInfo
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- CN103012744B CN103012744B CN201210555290.7A CN201210555290A CN103012744B CN 103012744 B CN103012744 B CN 103012744B CN 201210555290 A CN201210555290 A CN 201210555290A CN 103012744 B CN103012744 B CN 103012744B
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Abstract
A kind of method of spirane structure base polyurethane prepolymer for use as modified epoxy, relate to a kind of method of modified epoxy, the sub-methoxyl group-3 of the poly-3-methylene radical-9-of synthesis, 9--dihydroxymethyl-1,5,7,11-tetra-oxaspiro [5.5] undecane spirocyclic compound: add dipentaerythritol and di-nbutyltin oxide in there-necked flask, add the mixed solvent of toluene and pyrrolidone, stir, heating; Solution is added ethyl acetate mix, then add sherwood oil, add DMSO heating and make it to dissolve, drip distilled water after cooling until separate out precipitation, after suction filtration, drying, obtain white powdery solids be purer spirocyclic compound; The ratio that performed polymer and epoxy resin account for 20% of total mass in performed polymer quality is placed in small beaker, the boron trifluoride ethylamine solidifying agent adding hybrid resin weight 3% stirs evenly, modified epoxy adhesive shear strength increases, and shock strength and flexural strength all have significant improvement.
Description
Technical field
The present invention relates to a kind of method of modified epoxy, particularly relate to a kind of method of spirane structure base polyurethane prepolymer for use as modified epoxy.
Background technology
Thermosetting resin, particularly epoxy resin, be widely used as sqtructural adhesive to the non-metallic material such as the metallic substance such as steel, aluminium and timber, glass, pottery, rubber, fiber, plastics that bond.In the composite, what embed in resin matrix is glass fibre or carbon fiber etc., and the thermal expansivity of resin and metal, fiber and other material is different, a thermal expansivity generally order of magnitude larger than metal of such as polymkeric substance.After at high temperature completing curing process, be cooled in the process of room temperature, due to the difference of the thermal expansivity between bi-material, cause the unrelieved stress between interface.
When thermosetting resin is shaping as structured material, always have a process from curing reaction to curing and demolding, resin is just equivalent to the process of a quenching once the demoulding, and this also can produce unrelieved stress.
Materials specialist have adopted multiple method to compensate and have offset this three kinds of unrelieved stresss.The third unrelieved stress causes in moulding process, if slowly lower the temperature the demoulding, can eliminate.The second unrelieved stress is the difference due to material, the interface internal stress caused when solidifying different with use temperature, the means control bi-materials such as the solidification value can passing through the resilient tackiness agent of selection close with use temperature be solidified, filled have close thermal expansivity and carry out basically eliminate.The first unrelieved stress is the synthesized polymer material problem that will solve inherently.
Summary of the invention
The object of the present invention is to provide a kind of method of spirane structure base polyurethane prepolymer for use as modified epoxy, the method selects dipentaerythritol and di-nbutyltin oxide Reactive Synthesis New-type spiro compound to gather the sub-methoxyl group-3 of 3-methylene radical-9-, 9--dihydroxymethyl-1,5,7,11-tetra-oxaspiro [5.5] undecane, and by the modified epoxy of itself and the excellent benefit of TDI Reactive Synthesis physical index.
The object of the invention is to be achieved through the following technical solutions:
A kind of method of spirane structure base polyurethane prepolymer for use as modified epoxy, described method comprises following process: the sub-methoxyl group-3 of poly-3-methylene radical-9-, 9--dihydroxymethyl-1, the synthesis of 5,7,11-tetra-oxaspiro [5.5] undecane spirocyclic compound: add dipentaerythritol and di-nbutyltin oxide in there-necked flask, add the mixed solvent of toluene and pyrrolidone composition, install water trap, reflux condensing tube, induction stirring, heating; Remove water trap after falling oily territory temperature, load onto constant pressure funnel and reflux condensate device, and on reflux condensing tube, Cacl is installed
2drying tube, adds CS in funnel
2slowly add in reaction flask, after dropwising, remove constant pressure funnel, slowly heated, reflux in oily territory; Remove reaction unit, reaction solution is moved in round-bottomed flask, Rotary Evaporators connects oil pump vacuum extractor, be warming up to solution azeotropy temperature under pressure, underpressure distillation goes out toluene and low-boiling-point substance, solution is added ethyl acetate and mixes, then add sherwood oil, collect lower floor's yellow viscous liquid, with normal hexane ultrasonic vibration washing removing n-Bu
2snO, inclines and washing lotion, and underpressure distillation removing residual solvent, obtains yellow viscous liquid, adds DMSO heating and makes it to dissolve, drip distilled water until separate out precipitation, obtain white powdery solids and be purer spirocyclic compound after suction filtration, drying after cooling; Modified epoxy: the ratio that performed polymer and epoxy resin account for 20% of total mass in performed polymer quality is placed in small beaker, oily territory pot induction stirring beaker being placed in 60 DEG C is even, the boron trifluoride ethylamine solidifying agent adding hybrid resin weight 3% stirs evenly, and the mixture after stirring evenly is put into vacuum drying oven and vacuumizes the bubble removing and be mixed into.
The method of described a kind of spirane structure base polyurethane prepolymer for use as modified epoxy, the optimum reaction condition material ratio 1:2.1 of described spirocyclic compound synthesis; Temperature of reaction 135 DEG C; Reaction times 11h; Curing carbon amounts 8ml; Reflux temperature 100 DEG C; Return time 12h.
The method of described a kind of spirane structure base polyurethane prepolymer for use as modified epoxy, described modified epoxy solidification value is 190 DEG C of solidifications 4 hours.
Advantage of the present invention and effect are:
The present invention's dipentaerythritol and di-nbutyltin oxide Reactive Synthesis go out the sub-methoxyl group-3 of polymer poly 3-methylene radical-9-containing spirane structure, 9--dihydroxymethyl-1,5,7,11-tetra-oxaspiro [5.5] undecane, and by itself and TDI Reactive Synthesis base polyurethane prepolymer for use as modified epoxy.Solve the problem of spirocyclic compound and epoxy resin compatibility difference, with spirocyclic compound and TDI(Toluene-2,4-diisocyanate, 4-vulcabond) the obtained base polyurethane prepolymer for use as of reaction, the adhesive shear strength of the epoxy resin of performed polymer modification increases, when performed polymer content is 20%, it is 16.6MPa that adhesive shear strength reaches maximum value.Shock strength and the flexural strength of the epoxy resin of performed polymer modification all have significant improvement, and shock strength is by 6.8KJ/m
2bring up to 14.4KJ/m
2, improve 112%; Flexural strength brings up to 132.3Mpa by 102Mpa, improves 29.7%.The epoxy resin of performed polymer modification has more excellent performance.Test shows that the thermal characteristics of modified epoxy decreases, and adhesive shear strength increases, and shock strength and flexural strength all have significant improvement.
Accompanying drawing explanation
Fig. 1 is the synthetic route chart of spirocyclic compound (poly-3-methylene radical-9-sub-methoxyl group-3,9--dihydroxymethyl-1,5,7,11-tetra-oxaspiro [5.5] undecane);
Fig. 2 is the infrared spectrogram of spirocyclic compound;
Fig. 3 is the shock strength changing trend diagram of modified epoxy;
Fig. 4 is the flexural strength changing trend diagram of modified epoxy.
Embodiment
Below in conjunction with embodiment, the present invention is described in detail.
Embodiment:
The synthesis of poly-3-methylene radical-9-sub-methoxyl group-3,9--dihydroxymethyl-1,5,7,11-tetra-oxaspiro [5.5] undecane spirocyclic compound:
1. in clean, dry there-necked flask, add 0.05mol (12.714g) dipentaerythritol and 0.10mol(24.894g) di-nbutyltin oxide, add the mixed solvent of 110ml toluene and 60ml pyrrolidone composition, install water trap, reflux condensing tube, interpolation thermometer.Induction stirring, temperature rises to 135 DEG C, reacts and stops heating to the generative theory water yield (about 11 hours).
2. oily territory temperature is down to less than 80 DEG C, removes water trap, load onto constant pressure funnel and reflux condensate device, and on reflux condensing tube, Cacl is installed
2drying tube.8mlCS is added in funnel
2slowly add in reaction flask, after dropwising, remove constant pressure funnel, oily territory is slowly heated to 100 DEG C, reflux 12 hours.
3. remove reaction unit, moved into by reaction solution in round-bottomed flask, Rotary Evaporators connects oil pump vacuum extractor, is warming up to solution azeotropy temperature under pressure, and underpressure distillation goes out toluene and low-boiling-point substance.Solution is poured in pyriform funnel, add 50ml ethyl acetate and mix, then add 100ml sherwood oil, after vibration, leave standstill half an hour, collect lower floor's yellow viscous liquid.Divide 5 ultrasonic vibration washings to remove n-Bu with 100ml normal hexane
2snO, inclines and washing lotion, and underpressure distillation removing residual solvent, obtains yellow viscous liquid.Add DMSO heating to make it to dissolve, drip distilled water after cooling until separate out precipitation.After suction filtration, drying, obtain white powdery solids be purer spirocyclic compound.
4. product utilization infrared, nuclear-magnetism, mass spectrometric measurement means characterize, and determine its molecular structure.
The optimum reaction condition of spirocyclic compound synthesis: material ratio 1:2.1; Temperature of reaction 135 DEG C; Reaction times 11h; Curing carbon amounts 8ml; Reflux temperature 100 DEG C; Return time 12h
The present invention's dipentaerythritol and di-nbutyltin oxide react obtained spiro orthocarbonate and gather 3-methylene radical-9-sub-methoxyl group-3,9--dihydroxymethyl-1,5,7,11-tetra-oxaspiro [5.5] undecane.Product is by infrared spectra, and nucleus magnetic resonance and ultimate analysis characterize its structure, confirms that products obtained therefrom is re-set target product.Explore by experiment subsequently and obtain best synthetic reaction condition and be: dipentaerythritol and di-nbutyltin oxide material ratio are 1:2.1, react after 11 hours, add 8ml dithiocarbonic anhydride at 135 DEG C, backflow 12 hours at 100 DEG C.Product is 285.67 DEG C through thermal performance test fusing point.
There is cationic ring-opening polymerization in spirocyclic compound, the infrared spectrogram in conjunction with open-loop products infers that its positively charged ion causes the polymerization mechanism of ring-opening polymerization under boron trifluoride ethylamine does the effect of catalyzer.Be 3.68% with the cubical expansivity in swelling agent tracking and measuring ring opening polymerisation process.
The preparation of modified epoxy: performed polymer and epoxy resin are accounted for 5% of total mass by performed polymer quality, 10%, 15%, the ratio of 20% is placed in small beaker, oily territory pot induction stirring beaker being placed in 60 DEG C is even, the boron trifluoride ethylamine solidifying agent adding hybrid resin weight 3% stirs evenly, and the mixture after stirring evenly is put into vacuum drying oven and vacuumizes the bubble removing and be mixed into.
Mould is put in advance the baking oven preheating of 60 DEG C, the hybrid resin after de-bubbled is cast in mould.When DSC measures the solidification value of urethane and epoxy-resin systems, peak temperature can change because of the change of temperature rise rate, but in Curing Process of Epoxy, need isothermal curing, for eliminating temperature contrast, the solidification value that extrapotation tries to achieve epoxy resin need be applied, concrete grammar is as follows: mixed with epoxy resin in the ratio accounting for hybrid resin 20% by performed polymer, and add the boron trifluoride ethylamine solidifying agent of hybrid resin weight 3%, at 60 DEG C, induction stirring is even.Put into vacuum drying oven de-bubbled for several times.Claim modified epoxy 6mg as in aluminum cup, crucible is put into sample pool, and respectively with 5 DEG C/min under nitrogen protection, 10 DEG C/min, 15 DEG C/min, the temperature rise rate of 20 DEG C/min is from room temperature to 300 DEG C.In the curing process, hybrid resin just there will be and is charred and small molecules decomposing phenomenon more than 190 DEG C, occurs a large amount of bubble, considers the phenomenon in actual solidification, therefore determines that solidification value is 190 DEG C of solidifications 4 hours.
The shock strength of table 1 modified epoxy and flexural strength
Can see that shock strength and flexural strength obviously strengthen by table 1 and Fig. 3 and Fig. 4: shock strength is by 6.8KJ/m
2bring up to 14.4KJ/m
2, improve 112%; Flexural strength brings up to 132.3Mpa by 102Mpa, improves 29.7%.Shock strength and the flexural strength of the epoxy resin of performed polymer modification increase, adding mainly due to swelling property performed polymer, in solidification process, the expansion of spiro-cyclic groups open loop reduces volumetric shrinkage when system is solidified, and then reduce the residual of the internal stress brought by volumetric shrinkage, thus improve the physical strength of epoxy resin.Secondly, the carbamate groups in performed polymer is polar functional group, and along with the increase of performed polymer content, system viscosity increases, and performed polymer is evenly distributed in the epoxy, increases the crosslinking reaction of volution and epoxide group.By the shock strength of performed polymer modified epoxy resin and significantly improving of flexural strength, illustrate that the toughness of resin material strengthens, have hard brittle material to change toughness material into.
The cubical expansivity of performed polymer modified epoxy resin reaches maximum value when performed polymer content is 20% be 1.08%.When performed polymer content is 20%, it is 16.6Mpa that adhesive shear strength reaches maximum value, and shock strength and the flexural strength of the epoxy resin of performed polymer modification all have significant improvement, and shock strength brings up to 14.4KJ/m2 by 6.8KJ/m2, improves 112%; Flexural strength brings up to 132.3Mpa by 102Mpa, improves 29.7%.
Claims (2)
1. a spirocyclic compound, is characterized in that, described spirocyclic compound is: 3-methylene radical-9-sub-methoxyl group-3,9--dihydroxymethyl-1,5,7,11-tetra-oxaspiro [5.5] undecane, and molecular formula is:
。
2. a preparation method for spirocyclic compound, is characterized in that, described method comprises following process:
(1) in clean, dry there-necked flask, 0.05mol, 12.714g dipentaerythritol and 0.10mol, 24.894g di-nbutyltin oxide is added, add the mixed solvent of 110ml toluene and 60ml pyrrolidone composition, install water trap, reflux condensing tube, interpolation thermometer, induction stirring, temperature rises to 135 DEG C, reacts and stops heating to the generative theory water yield;
(2) oily territory temperature is down to less than 80 DEG C, removes water trap, load onto constant pressure funnel and reflux condensate device, and on reflux condensing tube, CaCl is installed
2drying tube, adds 8mlCS in funnel
2slowly add in reaction flask, after dropwising, remove constant pressure funnel, oily territory is slowly heated to 100 DEG C, reflux 12 hours;
(3) reaction unit is removed, reaction solution is moved in round-bottomed flask, Rotary Evaporators connects oil pump vacuum extractor, be warming up to solution azeotropy temperature under pressure, underpressure distillation goes out toluene and low-boiling-point substance, is poured into by solution in pyriform funnel, add 50ml ethyl acetate to mix, add 100ml sherwood oil again, after vibration, leave standstill half an hour, collect lower floor's yellow viscous liquid; Divide 5 ultrasonic vibration washings to remove n-Bu with 100ml normal hexane
2snO, inclines and washing lotion, and underpressure distillation removing residual solvent, obtains yellow viscous liquid; Add DMSO heating to make it to dissolve, drip distilled water after cooling until separate out precipitation, after suction filtration, drying, obtain white powdery solids be purer spirocyclic compound;
The optimum reaction condition material ratio 1:2.1 of described spirocyclic compound synthesis; Temperature of reaction 135 DEG C; Reaction times 11h; Curing carbon amounts 8ml; Reflux temperature 100 DEG C; Return time 12h.
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| CN110172327B (en) * | 2019-05-31 | 2021-09-14 | 山东领科新材料科技有限公司 | Photocuring composite adhesive and production process thereof |
| CN113501936A (en) * | 2021-08-13 | 2021-10-15 | 中国科学院兰州化学物理研究所 | Modified curing agent for epoxy resin and preparation method thereof |
| US11766643B1 (en) | 2023-04-13 | 2023-09-26 | King Faisal University | Hydrophobic novel biofilm membrane modified with a spiropolyurethane |
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| US5808108A (en) * | 1997-01-15 | 1998-09-15 | Chappelow; Cecil C. | Polymeric compositions and composites prepared from spiroorthocarbonates and epoxy monomers |
| CN101654544A (en) * | 2009-09-21 | 2010-02-24 | 哈尔滨化工研究所 | Insulating encapsulating material |
| CN102181041A (en) * | 2011-04-15 | 2011-09-14 | 沈阳化工大学 | Method for preparing performed polymer modified epoxy resin |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO1990005156A1 (en) * | 1988-11-03 | 1990-05-17 | Electric Power Research Institute, Inc. | Expanding resins and applications thereof in electrical systems |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5808108A (en) * | 1997-01-15 | 1998-09-15 | Chappelow; Cecil C. | Polymeric compositions and composites prepared from spiroorthocarbonates and epoxy monomers |
| CN101654544A (en) * | 2009-09-21 | 2010-02-24 | 哈尔滨化工研究所 | Insulating encapsulating material |
| CN102181041A (en) * | 2011-04-15 | 2011-09-14 | 沈阳化工大学 | Method for preparing performed polymer modified epoxy resin |
Non-Patent Citations (2)
| Title |
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| 2,4,8,10,-四氧杂-3,9-二磷杂螺环[5,5]十一烷-3,9-二氧-3,9-二取代苯甲醛腙的合成及其阻燃性能;刘畅，等;《应用化学》;20070731;第24卷(第7期);第818页 * |
| 螺环预聚物的合成及其对环氧树脂B-63的改性;王长松,等;《辽宁工程技术大学学报（自然科学版）》;20081231;第7卷(第6期);第959页 * |
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