CN105713166A - Hard polyurethane foam containing organic-inorganic hybrid material and preparation method thereof - Google Patents
Hard polyurethane foam containing organic-inorganic hybrid material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a hard polyurethane foam containing an organic-inorganic hybrid material and a preparation method thereof. The preparation method comprises the following steps: (1) mixing natural inorganic layered silicates with a metal nitrate water solution, evenly stirring, adding a sodium hydroxide water solution; filtering the obtained mixture, drying, burning; and finally placing the obtained modified materials in a chemical vapor deposition furnace to produce a carbon nanotube-inorganic layer silicate hybrid material; (2) dehydrating and drying the hybrid material obtained in the step (1), adding hybrid material into B component (isocyanate), and evenly stirring to obtain a B component mixture; (3) cooling the B component mixture to the room temperature, pouring the B component mixture into an A component, pouring the mixture into a foaming mould, and curing to obtain the hard polyurethane foam containing an organic-inorganic hybrid material. The provided method effectively enhance the toughness, foaming stability and thermal stability of hard polyurethane foam, moreover, the synthesis method is simple, and the service life is long, so the popularization and application is easy.
Description
Technical field
The present invention relates to hard polyurethane foams and preparation method thereof, be specifically related to a kind of hard polyurethane foams adding hybrid inorganic-organic materials and preparation method thereof.
Background technology
It is good that rigid polyurethane foam has insulation effect, the excellent feature of electric property, chemical resistance and soundproof effect, is widely used as heat-insulating material and nonadiabatic structural material.According to statistics, since rigid polyurethane foam comes out, consumption grows steadily, and reaches 2,000,000 tons by the end of whole world rigid polyurethane foam annual production in 2002, and China reaches 250,000 tons.2005, China's rigid polyurethane foam yield reached 400,000 tons.Along with people's energy-saving and environmental protection consciousness is deep all the more, rigid polyurethane foam is because its heat conductivity is low, use procedure clean environment firendly, and demand rapid development, for many-sided considerations such as constructions, its performance is proposed increasingly stricter requirement by national governments, to ensure its life-time service.
The main deficiency of rigid polyurethane foam is in that heat stability relatively low (generally < 100 DEG C), fire retardancy are poor, and the mechanical property (such as compressive strength and bending modulus) of material is not high.Organic/inorganic hybridization material is one of excellent material of the high-elastic gonosome of modified poly ester class.Natural inorganic layered silicate material has thermostability and the dimensional stability of excellence, is increasingly used in the study on the modification of the high-elastic gonosome of polyesters；CNT is functionalization and the reinforcing material of the high-elastic gonosome of polyesters, it is possible to significantly improve intensity and the toughness of the high-elastic gonosome of polyesters.
CN103012738A discloses the preparation method that a kind of modified fly ash micro-sphere strengthens rigid polyurethane foam.First with motor stirrer, polyether polyol, foaming agent, foam stabiliser, catalyst and modified fly ash micro-sphere are sufficiently stirred in a reservoir, secondly the isocyanates of certain proportioning is added, quickly stirring, obtain pre-composition, again pre-composition is poured in off-the-shelf grinding tool, foam under room temperature, curing molding, obtain the rigid polyurethane foam that flyash strengthens after the demoulding.The method part improves mechanical property and the heat resistance of rigid polyurethane foam, but fly ash micro-sphere and foam base plate material exist in fusion process and easily come off, generate the deficiency such as crack, foam reduction of pliability.
The preparation method that CN1724577A discloses a kind of expandable graphite filled high dendensity hard polyurethane foamed plastic.The method is by polyether polyol, foaming agent, catalyst and expansible graphite according to a certain ratio, is uniformly mixed with mechanical stirring device, is then sufficiently mixed with a certain amount of isocyanates, is poured in mould, and maturation process obtains product.The oxygen index (OI) of this RPUF can reach about 40, improves its fire resistance to a certain extent, but the mechanical property of product declines to some extent, and expansible graphite easily comes off.
The preparation method that CN101870808A discloses a kind of carbon nano tube polyurethane composite material.By CNT is carried out acidification, modify carboxyl in its surface, then pass through and acrylamide condensation reaction, prepare amidatioon CNT；By situ aggregation method, amidatioon CNT is polymerized with the raw material isofoer diisocyanate preparing polyurethane, improve CNT dispersibility in polyaminoester emulsion and strengthen the interface binding power with polyurethane matrix, preparing high-dispersibility carbon nanotube compound polyurethane material.Polyurethane matrix is served certain modifying function by this composite, adds the toughness of polyurethane foamed material, but there is the phenomenon that CNT impact is foamed, and the compressive strength of polyurethane foamed material has much room for improvement.
Summary of the invention
In view of the deficiencies in the prior art, the invention provides a kind of hard polyurethane foams containing hybrid inorganic-organic materials and preparation method thereof.The effective activeness and quietness hard polyurethane foams of the inventive method, raising foamed stability and heat stability, synthetic method is simple, and life cycle is long, is conducive to promoting the use of.
The present invention, containing the preparation method of hybrid inorganic-organic materials hard polyurethane foams, comprises the steps:
(1) synthesizing organic-inorganic hybrid material: by natural inorganic layered silicate material and metal nitrate aqueous solution, stir；In gained mixture, add certain density sodium hydrate aqueous solution, stir；Then gained mixture is filtered, dries, calcination process；Finally put into chemical vapor deposition stove by material modified for gained, with inert gas purge boiler tube, it is subsequently passed hydrogen, raise temperature to 450 DEG C～550 DEG C, replace hydrogen with the mixing gas of ethylene and hydrogen again, continue to raise temperature to 600 DEG C～1200 DEG C, it is preferred to 700 DEG C～900 DEG C, reach constant temperature 1h～5h after assigned temperature, obtain CNT-inorganic laminated silicate hybrid material；
(2) by the hybrid inorganic-organic materials dehydrate of step (1), being subsequently added in B component isocyanates, stir under uniform temperature prepared B component mixture；
(3) the full water foamed basic recipe of hard polyurethane foams is adopted, pour into after B component mixture is cooled to room temperature in the component A mixture including polyether polyol, deionized water, catalyst and foam stabilizer etc., pour into after quickly stirring in foaming mould and solidify, prepare the hard polyurethane foams containing hybrid inorganic-organic materials.
Natural inorganic layered silicate material described in step (1) is selected from one or more in kieselguhr, Kaolin, montmorillonite and natural mordenite, it is preferable that natural mordenite.Described metal nitrate is selected from one or more in copper nitrate, aluminum nitrate, ferric nitrate and chromic nitrate, it is preferable that ferric nitrate.The mass concentration of metal nitrate saline solution is 0.05%～0.5%.The solid-liquid volume ratio of natural inorganic phyllosilicate and metal nitrate saline solution is 1:(1～10).
In step (1) described sodium hydrate aqueous solution, OH-With the mol ratio of metal nitrate saline solution metal ion in (0.1～20): 1, it is preferred to (1～5): 1.The solid-liquid volume ratio of natural inorganic layered silicate material and sodium hydrate aqueous solution is 1:(0.1～1).
Baking temperature described in step (1) is at 80 DEG C～150 DEG C, and drying time is 12h～24h；Sintering temperature is at 300 DEG C～500 DEG C, and roasting time is 1h～10h.
In step (1), during with inert gas purge boiler tube, purge time is 10min～40min.When passing into hydrogen in boiler tube, hydrogen flow rate is at 15mL/min～45mL/min；Intensification from room temperature, heating rate is 5 DEG C/min～10 DEG C/min.When being warming up to assigned temperature, replacing pure hydrogen with the mixing gas of ethylene and hydrogen, in mixing gas, the volume ratio of ethylene and hydrogen is (0.5～1): 1, continues to improve reaction temperature, and heating rate is 1 DEG C/min～5 DEG C/min.
Hybrid inorganic-organic materials prepared by step (1) uses front dehydrate 10h～30h at 80 DEG C～130 DEG C.In step (2), the addition of described hybrid inorganic-organic materials is component A and the 0.5wt%～10wt% of B component gross mass, it is preferred to 1.0wt%～5.0wt%.After adding hybrid inorganic-organic materials in B component, in temperature 45 C～150 DEG C, it is preferred to stir at 70 DEG C～110 DEG C.
The hydroxyl value of the polyether polyol described in step (3) is 350mgKOH/g～600mgKOH/g, it is preferred to 400mgKOH/g～500mgKOH/g.Catalyst is selected from one or more in dimethylethanolamine, dimethylamino cyclohexylamine, tripropyl amine (TPA), tri-n-butylamine and triethanolamine etc..Foam stabilizer is selected from one or more in dimethicone, ethyl silicon oil, phenyl silicone oil and Methyl Hydrogen Polysiloxane Fluid etc..Isocyanates is selected from one or more in toluene di-isocyanate(TDI) (TDI), methyl diphenylene diisocyanate (MDI), polymethylene multi-phenenyl isocyanate (PAPI) etc., it is preferable that PAPI.
0.3wt%～the 2.0wt% that addition is polyether polyol quality of catalyst in component A described in step (3), foam stabilizer addition is the 1.0wt%～4.0wt% of polyether polyol quality, and deionized water addition is the 2.0wt%～5.0wt% of polyether polyol quality.The mass ratio of polyether polyol and B component is 1:1.2～1:1.8.
The mixed process of the component A mixture described in step (3), speed of agitator is at 2000rpm～5000rpm, time 10～40s；After pouring B component mixture into component A mixture, stir 10～40s at 2000rpm～4000rpm.
Being cured as first at cold curing 1～5h described in step (3), right fed to boiler solidifies 2～10h, furnace temperature 80～130 DEG C.
The hard polyurethane foams containing hybrid inorganic-organic materials of the present invention is prepared by the invention described above method.
Hard polyurethane foams containing hybrid inorganic-organic materials provided by the invention, concrete advantage is as follows:
(1) hybrid inorganic-organic materials improves mechanical property and the heat stability of hard polyurethane foams simultaneously, organic principle therein (CNT) can significantly improve the pliability of foam base plate, and inorganic constituents (natural inorganic phyllosilicate) plays good effect for the improvement of foam base plate compressive strength.Organic principle and inorganic constituents improve the heat stability of foam base plate jointly, and the metal ingredient contained in hybrid material (such as Fe) improves the heat stability of foam base plate further so that it is be suitably applied under more complicated operating mode.
(2) in hybrid inorganic-organic materials, containing a small amount of oh group (-OH) and metal ingredient (such as Fe) in natural inorganic phyllosilicate, condensation reaction is there is in oh group with the isocyano (-NCO) in isocyanates, make the two be closely joined together, effectively prevent organic-inorganic hybrid from coming off from polyurethane foam；The kicker of metal component inherently rigid polyurethane foam, therefore hybrid inorganic-organic materials can as new polyurethane foam, nuclearing centre.Near new foamed core, owing to there is the pilotaxitic texture of CNT and foam base plate, adds somewhat to the viscosity of foam base plate, slow down bubble growth speed and reduce cell size, namely improve foam rate of closed hole, improve its adiabatic heat-insulation ability, play the effect of even foaming.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscopic picture of the embodiment of the present invention 1 products obtained therefrom A；
Fig. 2 is the optical microscope picture of the embodiment of the present invention 1 products obtained therefrom A；
Fig. 3 is the scanning electron microscopic picture of comparative example 1 products obtained therefrom G of the present invention；
Fig. 4 is the optical microscope picture of comparative example 1 products obtained therefrom G of the present invention.
Detailed description of the invention
Below in conjunction with embodiment, the present invention will be further described.In the present invention, wt% is mass fraction.
Embodiment 1
Synthesizing organic-inorganic hybrid material: weigh 1mL natural mordenite and 5mL mass concentration be 0.1% iron nitrate aqueous solution, stir.Being subsequently added the sodium hydrate aqueous solution 0.5mL that concentration is 2.96wt%, stir, gained mixed liquor carries out 20h dried after filtering, and temperature is 110 DEG C；To dried sample calcination process, 450 DEG C of roasting 4.5h.Material after processing is put into chemical vapor deposition stove, and with inert gas purge boiler tube 20min, with passing into hydrogen in backward boiler tube, hydrogen flow rate, at 25mL/min, is warming up to 500 DEG C from room temperature, and heating rate is 7.5 DEG C/min；Now passing into the ethylene of volume ratio 1:1 and the mixing gas of hydrogen, improve reaction temperature to 750 DEG C, heating rate is 1 DEG C/min, constant temperature 2h after reaching 750 DEG C, obtains CNT-natural mordenite hybrid material.
CNT-natural mordenite hybrid material uses front freeze-day with constant temperature 20h at 110 DEG C, to remove moisture.
Component A mixture: hydroxyl value is the polyether polyol 100 parts of 430mgKOH/g, deionized water 2 parts, triethanolamine 1 part, dimethicone 2 parts, stirs 25s under 3000rpm.
B component mixture: add above-mentioned CNT-natural mordenite hybrid material 12 parts in 150 parts of PAPI, stir at 90 DEG C.
B component mixture is poured into after being cooled to room temperature in component A mixture, quickly stirs 25s under 3000rpm.Pouring in foaming mould, cold curing 1h, demoulding fed to boiler solidifies 2h, furnace temperature 100 DEG C, prepares the hard polyurethane foams A containing CNT-natural mordenite hybrid material.
Embodiment 2
In embodiment 1, the consumption that makes of CNT-natural mordenite hybrid material increases to 25.5 parts, and other operational approach and material composition are constant, prepare the hard polyurethane foams B containing CNT-natural mordenite hybrid material.
Embodiment 3
In embodiment 1, the consumption that makes of CNT-natural mordenite hybrid material reduces to 1.2 parts, and other operational approach and material composition are constant, prepare the hard polyurethane foams C containing CNT-natural mordenite hybrid material.
Embodiment 4
In embodiment 1, replace PAPI, other operational approach and material composition with MDI constant, prepare the rigid polyurethane foam D containing CNT-natural mordenite hybrid material.
Embodiment 5
In embodiment 1, the polyether polyol 100 parts selecting hydroxyl value to be 370mgKOH/g, other operational approach and material composition are constant, prepare the hard polyurethane foams E containing CNT-natural mordenite hybrid material.
Embodiment 6
In embodiment 1, CNT-natural mordenite hybrid (10 parts) is added in B component (150 parts of PAPI), at 50 DEG C, 4000rpm stirs 60min, other operational approach and material composition are constant, prepare the rigid polyurethane foam F containing CNT-natural mordenite hybrid material.
Embodiment 7
In embodiment 1, natural mordenite being replaced to kieselguhr, other operational approach and material composition are constant, prepare the rigid polyurethane foam G containing CNT-kieselguhr hybrid material.
Comparative example 1
In embodiment 1, constant without CNT-natural mordenite hybrid material, other operational approach and material composition, prepare rigid polyurethane foam H.
Comparative example 2
In embodiment 1, directly add conventional use of CNT and each 6 parts of natural mordenite hybrid material, other operational approach and material composition constant, prepare containing CNT and natural mordenite hybrid material rigid polyurethane foam I.
Comparative example 3
In embodiment 1, CNT-natural mordenite hybrid (12 parts) is added stirring, other operational approach and material in component A mixture and forms constant, prepare the rigid polyurethane foam J containing CNT-natural mordenite hybrid.
Comparative example 4
In embodiment 1, by not prior to B component PAPI and CNT-natural mordenite hybrid material mixed processing, joining in the mixture of component A together, other operational approach and material composition are constant, prepare the rigid polyurethane foam K containing CNT-natural mordenite hybrid.
Comparative example 5
According to the CN103012738A method described, use composite coupler that flyash is modified, obtain modified fly ash micro-sphere.Weigh polyether polyol (hydroxyl value 450 ± 10mgKOH/g) 100 parts, together stir with catalyst, foaming agent, modified fly ash micro-sphere (20 parts) and foam stabilizer.After being uniformly dispersed, adding methyl diphenylene diisocyanate (MDI) 100 parts, quickly stir, cold curing, demoulding fed to boiler solidifies, and prepares the rigid polyurethane foam L of fly ash micro-sphere enhancing modified.
Comparative example 5
According to the CN1724577A method described, weigh polyether polyol (hydroxyl value 430mgKOH/g) 100 parts, together stir with catalyst, foaming agent, expansible graphite (20 parts) and foam stabilizer.After being uniformly dispersed, adding methyl diphenylene diisocyanate (MDI) 100 parts, quickly stir, cold curing, demoulding fed to boiler solidifies, and prepares the rigid polyurethane foam M of fly ash micro-sphere enhancing modified.
Comparative example 6
According to the CN101870808A method described, first prepare amidatioon CNT.Weigh 30g PCDL and the CNT through ultrasonic disperse, at 75 DEG C, add 13.5g isoflurane chalcone diisocyanate (IPDI), add catalyst, cross-linking agent and foaming agent, prepare amidatioon carbon nano tube polyurethane composite material N.
Additionally, in order to further illustrate the hard polyurethane foams containing hybrid inorganic-organic materials and the difference of other hard polyurethane foams prepared by the present invention, list table 1 and compare.In table 1, mechanical property (compressive strength and bending strength) performs according to GB/T21558-2008 examination criteria.The heat stability (heat decomposition temperature) of the hard polyurethane foams containing hybrid inorganic-organic materials is measured by TG, and fire retardancy obtains according to limited oxygen index method.Average pore size passes through optical microscope measuring, and heat conductivity is measured by heat conductivity instrument.
The comparison of table 1 different hardness polyurethane foam physicochemical property
As seen from Table 1, hard polyurethane foams prepared by the hard polyurethane foams containing hybrid inorganic-organic materials prepared by the inventive method and other method, in physicochemical property, has obvious difference.Due to the existence of hybrid inorganic-organic materials, the heat decomposition temperature of foamed materials is generally higher than the sample in comparative example, and in embodiment 1, the heat decomposition temperature of foamed materials is more than 300 DEG C, and this is that the utilization under complex working condition of this type of material creates more chance.Further, under the existence of organic-inorganic hybrid, the compressive strength of foamed materials and bending strength obtain improvement simultaneously, and this is not available for other method.The existence being additionally, since in organic-inorganic hybrid metallic so that it becomes new bubble nucleation center, effectively controlling expansion rate so that foam size reduces (lower than 200 μm), rate of closed hole increases, namely foam thermal conductivity is relatively low, and adiabatic heat-insulation ability is better.From Fig. 1 it can also be seen that, according to the present invention prepare containing the hard polyurethane foams of organic-inorganic hybrid, its abscess-size is more uniform, and rate of closed hole is higher, i.e. better heat preservation.
Claims (13)
1. the preparation method containing hybrid inorganic-organic materials hard polyurethane foams, it is characterised in that include following content:
(1) synthesizing organic-inorganic hybrid material: by natural inorganic layered silicate material and metal nitrate aqueous solution, stir；In gained mixture, add certain density sodium hydrate aqueous solution, stir；Then gained mixture is filtered, dries, calcination process；Finally put into chemical vapor deposition stove by material modified for gained, with inert gas purge boiler tube, it is subsequently passed hydrogen, raise temperature to 450 DEG C～550 DEG C, replace hydrogen with the mixing gas of ethylene and hydrogen again, continue to raise temperature to 600 DEG C～1200 DEG C, it is preferred to 700 DEG C～900 DEG C, reach constant temperature 1h～5h after assigned temperature, obtain CNT-inorganic laminated silicate hybrid material；
(2) by the hybrid inorganic-organic materials dehydrate of step (1), being subsequently added in B component isocyanates, stir under uniform temperature prepared B component mixture；
(3) the full water foamed basic recipe of hard polyurethane foams is adopted, pour into after B component mixture is cooled to room temperature in the component A mixture including polyether polyol, deionized water, catalyst and foam stabilizer etc., pour into after quickly stirring in foaming mould and solidify, prepare the hard polyurethane foams containing hybrid inorganic-organic materials.
2. in accordance with the method for claim 1, it is characterised in that: one or more in kieselguhr, Kaolin, montmorillonite and natural mordenite of the natural inorganic layered silicate material described in step (1)；One or more in copper nitrate, aluminum nitrate, ferric nitrate and chromic nitrate of metal nitrate.
3. the method described in claim 1 or 2, it is characterised in that: the mass concentration of the metal nitrate saline solution described in step (1) is 0.05%～0.5%；The solid-liquid volume ratio of natural inorganic phyllosilicate and metal nitrate saline solution is 1:(1～10).
4. the method described in claim 1 or 2, it is characterised in that: OH in step (1) described sodium hydrate aqueous solution-It is (0.1～20) with the mol ratio of metal nitrate saline solution metal ion: 1；The solid-liquid volume ratio of natural inorganic layered silicate material and sodium hydrate aqueous solution is 1:(0.1～1).
5. in accordance with the method for claim 1, it is characterised in that: the baking temperature described in step (1) is at 80 DEG C～150 DEG C, and drying time is 12h～24h；Sintering temperature is at 300 DEG C～500 DEG C, and roasting time is 1h～10h.
6. in accordance with the method for claim 1, it is characterised in that: time in step (1) with inert gas purge boiler tube, purge time is 10min～40min；When passing into hydrogen in boiler tube, hydrogen flow rate is at 15mL/min～45mL/min；Intensification from room temperature, heating rate is 5 DEG C/min～10 DEG C/min；After replacing pure hydrogen with the mixing gas of ethylene and hydrogen, continuing to improve reaction temperature, heating rate is 1 DEG C/min～5 DEG C/min.
7. in accordance with the method for claim 1, it is characterised in that: hybrid inorganic-organic materials prepared by step (1) uses front dehydrate 10h～30h at 80 DEG C～130 DEG C.
8. in accordance with the method for claim 1, it is characterised in that: the addition of the hybrid inorganic-organic materials described in step (2) is component A and the 0.5wt%～10wt% of B component gross mass, it is preferred to 1.0wt%～5.0wt%.
9. the method described in claim 1 or 8, it is characterised in that: step (2) is described after interpolation hybrid inorganic-organic materials, to stir in B component at temperature 45 C～150 DEG C.
10. in accordance with the method for claim 1, it is characterised in that: the hydroxyl value of the polyether polyol described in step (3) is 350mgKOH/g～600mgKOH/g；Catalyst is selected from one or more in dimethylethanolamine, dimethylamino cyclohexylamine, tripropyl amine (TPA), tri-n-butylamine and triethanolamine；Foam stabilizer is selected from one or more in dimethicone, ethyl silicon oil, phenyl silicone oil and Methyl Hydrogen Polysiloxane Fluid；Isocyanates is selected from one or more in toluene di-isocyanate(TDI) (TDI), methyl diphenylene diisocyanate (MDI), polymethylene multi-phenenyl isocyanate (PAPI).
11. the method described in claim 1 or 10, it is characterized in that: the 0.3wt%～2.0wt% that addition is polyether polyol quality of catalyst in the component A described in step (3), foam stabilizer addition is the 1.0wt%～4.0wt% of polyether polyol quality, and deionized water addition is the 2.0wt%～5.0wt% of polyether polyol quality；The mass ratio of polyether polyol and B component is 1:1.2～1:1.8.
12. in accordance with the method for claim 1, it is characterised in that: the mixed process of the component A mixture described in step (3), speed of agitator is at 2000rpm～5000rpm, time 10～40s；After pouring B component mixture into component A mixture, stir 10～40s at 2000rpm～4000rpm；Described is cured as first at cold curing 1～5h, and right fed to boiler solidifies 2～10h, furnace temperature 80～130 DEG C.
13. the hard polyurethane foams containing hybrid inorganic-organic materials, it is characterised in that adopt the arbitrary described method of claim 1～12 to prepare.
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| CN106278127A (en) * | 2016-08-15 | 2017-01-04 | 马常芳 | A kind of energy-saving sound insulation foam cement polyurethane foam composite insulation boards |
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Application publication date: 20160629 |