CN102181030B - Method for preparing corncob-base polyurethane rigid foam damping material - Google Patents
Method for preparing corncob-base polyurethane rigid foam damping material Download PDFInfo
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- CN102181030B CN102181030B CN201110086889A CN201110086889A CN102181030B CN 102181030 B CN102181030 B CN 102181030B CN 201110086889 A CN201110086889 A CN 201110086889A CN 201110086889 A CN201110086889 A CN 201110086889A CN 102181030 B CN102181030 B CN 102181030B
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Abstract
The invention discloses a method for preparing corncob-base polyurethane rigid foam damping material. The method includes the steps as follows: liquefying ground and screened corncobs by the mixed agent of polyethylene glycol 400 and glycerol to obtain a liquefied product; adding magnesium oxide to neutralize the liquefied product; and then allowing the liquefied product to polymerize with PAPI (polyphenylmethane polyisocyanate), thus forming the polyurethane rigid foam damping material. In the invention, renewable resources are utilized, the liquefying cost is lowered; the density of the synthesized polyurethane rigid foam damping material is adjustable within the range of 50-200kg/m3, the compressive strength achieves 100-2000kPa, the coefficient of heat conductivity is smaller than or equal to 0.050w/(m DEG C), the damping coefficient is greater than or equal to 0.3 and the temperature range is wide. The product has broad application prospect and remarkable environmental and social benefits.
Description
Technical field
The present invention relates to a kind of method for preparing corn cob based polyurethanes rigid foam damping material.
Background technology
Polyurethane foam because of it has excellent specific tenacity, thermal characteristic and good processing properties, has been widely used in every field such as communications and transportation, building, furniture and packing as a family macromolecule material.
At present the preparation polyurethane foamed material mainly is to be reacted with isocyanic ester generation addition polycondensation and got by the polyvalent alcohol that petroleum chemicals obtain.Yet, had a strong impact on the raw material sources of polyurethane industrial, and then influenced the development of polyurethane industrial along with petroleum resources are exhausted day by day.
With this renewable energy source of biomass cheap and easy to get is raw material; After certain technical qualification liquefaction; Obtain containing the fluent meterial of hydroxyl; With polyethers or the polyester polyol that its alternative petroleum chemicals obtain, the polyurethane foamed material that preparation has various performances becomes one of focus of current polyurethane industrial research.Normal pressure liquefaction is wherein a kind of common biomass liquefying method.Having liquefaction pressure is normal pressure, temperature of reaction is lower, speed of response is fast, after simple process, promptly can be used as advantages such as synthesis of polyurethane foam.But the problem that wherein exists be liquifier such as NSC 11801 etc. in liquefaction process owing to resolve into CO
2And reasons such as volatilization cause a large amount of losses, have improved the liquefaction cost; The price of liquifier PEG 400 is higher; Higher etching apparatus of deliquescence accelerant vitriol oil concentration and contaminate environment; Liquefying time is longer; Problems such as the direct synthesis of polyurethane foamy of undressed liquefaction polyvalent alcohol poor performance.Therefore seek the deliquescence accelerant of cheap liquifier, lower concentration, simple processing mode to reduce the liquefaction cost, improving the polyurethane foam performance is the problem that biomass-based polyurethane foam technology presses for solution.
Summary of the invention
The purpose of this invention is to provide a kind of method for preparing hard polyurethane foam.
The method for preparing hard polyurethane foam provided by the present invention comprises the steps:
1) liquefaction solvent, deliquescence accelerant and corn cob are mixed, reacted 30-90 minute down at 130-160 ℃, reaction finishes postcooling, obtains liquefied product; Wherein, said liquefaction solvent is the mixed solvent of USP Kosher and PEG 400;
2) in said liquefied product, add Natural manganese dioxide, then with mixed solution at 105 ℃ of-120 ℃ of held 8-12h, the liquefied product after obtaining handling;
3) liquefied product after the said processing and dibutyl tin laurate, triethylamine and silicone oil are stirred, again to wherein adding PAPI, it is milky white to continue to be stirred to appearance; Pour foaming, slaking in the mould then into, obtain hard polyurethane foam.
Wherein, in the step 1), the mass ratio of USP Kosher and PEG 400 can be 1/4-9/1 in the said liquefaction solvent; It is 35% hydrochloric acid that said deliquescence accelerant specifically can be sulfuric acid that mass concentration is 72%-98% or mass concentration.
The mass ratio of said liquefaction solvent, deliquescence accelerant and corn cob can be (90-150): (4.2-10.0): 30.
In the step 1), said corn cob is the ground corn core, and particle diameter is the 20-80 order.
The concrete addition sequence of said liquefaction solvent, deliquescence accelerant and corn cob is: earlier with liquefaction solvent and deliquescence accelerant mixing, be heated to 130-160 ℃ after, add corn cob again.
Step 2) in, add Natural manganese dioxide with the unnecessary acid catalyst that neutralizes, said liquefied product and magnesian mass ratio can be 100: (1-4).
In the step 3); The mass ratio of liquefied product after the said processing, dibutyl tin laurate, triethylamine, silicone oil and PAPI (polyphenyl polymethylene polyisocyanates, the trade mark are PM-200) is followed successively by (50-60): (0.2-0.3): (0.2-0.3): (0.45-0.55): (50-60).
In the step 3), the temperature of said foaming is a room temperature, and foamed time is 10-360s; The temperature of said slaking is 40-60 ℃, and the curing time is 2-4h.The rotating speed of said stirring can be 1100-1300r/min.
The present invention utilizes renewable resources, has reduced the liquefaction cost, and synthesis of polyurethane hard foam density is at 50-200kg/m
3Adjustable, compressive strength reaches 100-2000kPa, and thermal conductivity is smaller or equal to 0.050w/ (m ℃), and ratio of damping is bigger more than or equal to 0.3 warm territory scope.Product has broad application prospects, and significant environment and social benefit are arranged.
The present invention compares with existing preparation polyurethane foam has following advantage and effect:
1) the inventive method has comparatively significantly cost advantage.Corn cob is cheap and easy to get, and is renewable resources.In addition, this method liquefying time is shorter, and catalyst levels is few during the synthesis of polyurethane foam, and does not use any whipping agent that adds, and therefore, can reduce production costs.
2) liquefied product is neutralized with Natural manganese dioxide, improved liquefied product synthesis of polyurethane foamy performance.With Natural manganese dioxide liquefied product is carried out neutralizing treatment, solved direct with the bubble that collapses of as easy as rolling off a log generation in the liquefied product synthesis of polyurethane foam process, problem such as synthetic polyurethane foam abscess is thick, inhomogeneous.
Description of drawings
Fig. 1 is the damping temperature characteristics figure of the corn cob based polyurethanes rigid foam damping material of embodiment 1 preparation.
Fig. 2 is the damping temperature characteristics figure of the corn cob based polyurethanes rigid foam damping material of embodiment 2 preparations.
Fig. 3 is the damping temperature characteristics figure of the corn cob based polyurethanes rigid foam damping material of embodiment 3 preparations.
Fig. 4 is the damping temperature characteristics figure of the corn cob based polyurethanes rigid foam damping material of embodiment 4 preparations.
Fig. 5 is the damping temperature characteristics figure of the corn cob based polyurethanes rigid foam damping material of embodiment 5 preparations.
Fig. 6 is the damping temperature characteristics figure of the corn cob based polyurethanes rigid foam damping material of embodiment 6 preparations.
Embodiment
Through specific embodiment method of the present invention is described below, but the present invention is not limited thereto.
Experimental technique described in the following embodiment like no specified otherwise, is ordinary method; Said reagent and material like no specified otherwise, all can obtain from commercial sources.
Used PAPI is available from the magnificent urethane in Yantai ten thousand ltd among the embodiment, trade mark PM-200, and dark-brown liquid, functionality is 2.6～2.7, and isocyano-content is 30.5%～32.0%, and flash-point is 230 ℃, and burning-point is 245 ℃.
Silicone oil is purchased in being the Beijing Chemical Plant.
Embodiment 1, preparation corn cob based polyurethanes rigid foam
With 96 weight part PEG 400s, 24 weight part USP Kosher and 8.4 weight part mass concentrations is that 72% sulfuric acid adds in the reaction vessel; Stir; Be warming up to 160 ℃, add 30 parts of corn cobs (particle diameter 20-80 order), stirring reaction 60min through pulverizing; Immediately with the cold water cooling, obtain liquefied product after the taking-up.
Take out the above-mentioned liquefied product of 100 weight parts, add in the 1.5 weight part Natural manganese dioxide and unnecessary acid, then at 105 ℃ of held 10h to remove moisture.Liquefied product after getting 50 weight parts and handling adds 0.26 weight part dibutyl tin laurate, 0.24 weight part triethylamine and 0.51 weight part silicone oil, stirring 60s under the 1300r/min rotating speed simultaneously in dixie cup; The PAPI that adds 50 weight parts again; Pour in the mould natural foaming 6min, the demoulding rapidly into after under identical rotating speed, stirring 30s (occurring milky white); Place 50 ℃ of following slaking 4h, obtain the hard polyurethane foam damping material.
The hard polyurethane foam density that makes is 79.83kg/m
3, compressive strength 493.95kPa, thermal conductivity 0.037W/ (m ℃).The damping characteristic of this material is as shown in Figure 1, and X-coordinate is the probe temperature of material among the figure, and ordinate zou is a damping loss factor, and testing tool is the DMA Q800 dynamic thermomechanical analysis apparatus that U.S. TA company produces.The ratio of damping that can know this material by figure is 74.22 ℃-141.85 ℃ more than or equal to 0.3 warm territory scope, and the peak of ratio of damping is 0.79, has the warm territory of broad.
With 80 weight part PEG 400s, 40 weight part USP Kosher and 4.2 weight part concentration is that 98% sulfuric acid adds in the reaction vessel; Stir; Be warming up to 130 ℃, add 30 parts of corn cobs (particle diameter 20-80 order), stirring reaction 60min through pulverizing; Immediately with the cold water cooling, obtain liquefied product after the taking-up.
Take out the above-mentioned liquefied product of 100 weight parts, add in the 2 weight part Natural manganese dioxide and unnecessary acid, then at 105 ℃ of held 12h to remove moisture.Liquefied product after getting 50 weight parts and handling adds 0.25 weight part dibutyl tin laurate, 0.26 weight part triethylamine and 0.48 weight part silicone oil, stirring 60s under the 1200r/min rotating speed simultaneously in dixie cup; The PAPI that adds 50 weight parts again; Pour in the mould natural foaming 30s, the demoulding rapidly into after under identical rotating speed, stirring 20s (occurring milky white); Place 50 ℃ of following slaking 3h, obtain the hard polyurethane foam damping material.
The hard polyurethane foam density that makes is 123.77kg/m
3, compressive strength 253.97kPa, thermal conductivity 0.039W/ (m ℃), damping characteristic is as shown in Figure 2, and X-coordinate is the probe temperature of material, and ordinate zou is a damping loss factor, and testing tool is the DMA Q800 dynamic thermomechanical analysis apparatus that U.S. TA company produces.The ratio of damping that can know this material by figure is 29.09 ℃-76.01 ℃ more than or equal to 0.3 warm territory scope, and the peak of ratio of damping is 0.36, has the warm territory of broad.
Embodiment 3, preparation corn cob based polyurethanes rigid foam
With 12 weight part PEG 400s, 108 weight part USP Kosher and 4.2 weight part concentration is that 98% sulfuric acid adds in the reaction vessel; Stir; Be warming up to 160 ℃, add 30 parts of corn cobs (particle diameter 20-80 order), stirring reaction 60min through pulverizing; Immediately with the cold water cooling, obtain liquefied product after the taking-up.
Take out the above-mentioned liquefied product of 100 weight parts, add in the 2 weight part Natural manganese dioxide and unnecessary acid, then at 105 ℃ of held 11h to remove moisture.Liquefied product after getting 50 weight parts and handling adds 0.27 weight part dibutyl tin laurate, 0.24 weight part triethylamine and 0.53 weight part silicone oil, stirring 60s under the 1000r/min rotating speed simultaneously in dixie cup; The PAPI that adds 50 weight parts again; Pour in the mould natural foaming 5min, the demoulding rapidly into after under identical rotating speed, stirring 60s (occurring milky white); Place 55 ℃ of following slaking 3h, obtain the hard polyurethane foam damping material.
The hard polyurethane foam density that makes is 145.68kg/m
3, compressive strength 407.328kPa, thermal conductivity 0.042W/ (m ℃), damping characteristic is as shown in Figure 3, and X-coordinate is the probe temperature of material, and ordinate zou is a damping loss factor, and testing tool is the DMA Q800 dynamic thermomechanical analysis apparatus that U.S. TA company produces.The ratio of damping that can know this material by figure is 117.06 ℃-151.69 ℃ more than or equal to 0.3 warm territory scope, and the peak of ratio of damping is 0.43, has the warm territory of broad.
Embodiment 4, preparation corn cob based polyurethanes rigid foam
With 96 weight part PEG 400s, 24 weight part USP Kosher and 4.2 weight part concentration is that 98% sulfuric acid adds in the reaction vessel; Stir; Be warming up to 150 ℃, add 30 parts of corn cobs (particle diameter 20-80 order), stirring reaction 30min through pulverizing; Immediately with the cold water cooling, obtain liquefied product after the taking-up.
Take out the above-mentioned liquefied product of 100 weight parts, add in the 4 weight part Natural manganese dioxide and unnecessary acid, then at 105 ℃ of held 12h to remove moisture.Liquefied product after getting 50 weight parts and handling adds 0.23 weight part dibutyl tin laurate, 0.26 weight part triethylamine and 0.50 weight part silicone oil, stirring 60s under the 900r/min rotating speed simultaneously in dixie cup; The PAPI that adds 50 weight parts again; Pour in the mould natural foaming 30s, the demoulding rapidly into after under identical rotating speed, stirring 70s (occurring milky white); Place 60 ℃ of following slaking 2h, obtain the hard polyurethane foam damping material.
The hard polyurethane foam density that makes is 77.70kg/m
3, compressive strength 258.45kPa, thermal conductivity 0.037W/ (m ℃), damping characteristic is as shown in Figure 4, and X-coordinate is the probe temperature of material, and ordinate zou is a damping loss factor, and testing tool is the DMA Q800 dynamic thermomechanical analysis apparatus that U.S. TA company produces.The ratio of damping that can know this material by figure is 88.51 ℃-132.60 ℃ more than or equal to 0.3 warm territory scope, and the peak of ratio of damping is 0.58, has the warm territory of broad.
Embodiment 5, preparation corn cob based polyurethanes rigid foam
72 weight part PEG 400s, 18 weight part USP Kosher and 5.4 weight part concentrated hydrochloric acids are added in the reaction vessel, stir, be warming up to 160 ℃; Add 30 parts of corn cobs (particle diameter 20-80 order) through pulverizing; Stirring reaction 60min immediately with the cold water cooling, obtains liquefied product after the taking-up.
Take out the above-mentioned liquefied product of 100 weight parts, add in the 3 weight part Natural manganese dioxide and unnecessary acid, then at 110 ℃ of held 12h to remove moisture.Liquefied product after getting 50 weight parts and handling adds 0.2 weight part dibutyl tin laurate, 0.3 weight part triethylamine and 0.45 weight part silicone oil, stirring 60s under the 1100r/min rotating speed simultaneously in dixie cup; The PAPI that adds 60 weight parts again; Pour in the mould natural foaming 10s, the demoulding rapidly into after under identical rotating speed, stirring 17s (occurring milky white); Place 60 ℃ of following slaking 3h, obtain the hard polyurethane foam damping material.
The hard polyurethane foam density that makes is 170.25kg/m
3, compressive strength 1731.32kPa, thermal conductivity 0.047W/ (m ℃), damping characteristic is as shown in Figure 5, and X-coordinate is the probe temperature of material, and ordinate zou is a damping loss factor, and testing tool is the DMA Q800 dynamic thermomechanical analysis apparatus that U.S. TA company produces.The ratio of damping that can know this material by figure is 103.48 ℃-149.07 ℃ more than or equal to 0.3 warm territory scope, and the peak of ratio of damping is 0.46, has the warm territory of broad, and use range is wide.
Embodiment 6, preparation corn cob based polyurethanes rigid foam
With 121.5 weight part PEG 400s, 37.5 weight part USP Kosher and 5.0 weight part concentration is that 85% the vitriol oil adds in the reaction vessel; Stir; Be warming up to 140 ℃, add 30 parts of corn cobs (particle diameter 20-80 order), stirring reaction 90min through pulverizing; Immediately with the cold water cooling, obtain liquefied product after the taking-up.
Take out the above-mentioned liquefied product of 100 weight parts, add in the 3.5 weight part Natural manganese dioxide and unnecessary acid, then at 120 ℃ of held 8h to remove moisture.Liquefied product after getting 60 weight parts and handling adds 0.3 weight part dibutyl tin laurate, 0.2 weight part triethylamine and 0.55 weight part silicone oil, stirring 60s under the 1150r/min rotating speed simultaneously in dixie cup; The PAPI that adds 50 weight parts again; Pour in the mould natural foaming 19s, the demoulding rapidly into after under identical rotating speed, stirring 13s (occurring milky white); Place 60 ℃ of following slaking 3h, obtain the hard polyurethane foam damping material.
The hard polyurethane foam density that makes is 88.36kg/m
3, compressive strength 346.85kPa, thermal conductivity 0.037W/ (m ℃), damping characteristic is as shown in Figure 6, and X-coordinate is the probe temperature of material, and ordinate zou is a damping loss factor, and testing tool is the DMA Q800 dynamic thermomechanical analysis apparatus that U.S. TA company produces.The ratio of damping that can know this material by figure is 99.85 ℃-143.05 ℃ more than or equal to 0.3 warm territory scope, and the peak of ratio of damping is 0.59, has the warm territory of broad.
Claims (6)
1. a method for preparing hard polyurethane foam comprises the steps:
1) liquefaction solvent, deliquescence accelerant and corn cob are mixed, reacted 30-60 minute down at 130-160 ℃, reaction finishes postcooling, obtains liquefied product; Wherein, said liquefaction solvent is the mixed solvent of USP Kosher and PEG 400;
The mass ratio of said liquefaction solvent, deliquescence accelerant and corn cob is (90-150): (4.2-10.0): 30;
The mass ratio of USP Kosher and PEG 400 is 1/4-9/1 in the said liquefaction solvent;
Said deliquescence accelerant is that aqueous sulfuric acid or the mass concentration of mass concentration 72%-98% is 35% aqueous hydrochloric acid;
2) in said liquefied product, add Natural manganese dioxide, then with mixed solution at 105 ℃ of-120 ℃ of held 8-12h, the liquefied product after obtaining handling;
Said liquefied product and magnesian mass ratio are 100: (1-4);
3) liquefied product after the said processing and dibutyl tin laurate, triethylamine and silicone oil are stirred, again to wherein adding PAPI, it is milky white to continue to be stirred to appearance; Pour foaming, slaking in the mould then into, obtain hard polyurethane foam;
The mass ratio of liquefied product after the said processing, dibutyl tin laurate, triethylamine, silicone oil and PAPI is followed successively by (50-60): (0.2-0.3): (0.2-0.3): (0.45-0.55): (50-60).
2. method according to claim 1 is characterized in that: in the step 1), said corn cob is the ground corn core, and particle diameter is the 20-80 order.
3. method according to claim 1 and 2 is characterized in that: in the step 1), the addition sequence of said liquefaction solvent, deliquescence accelerant and corn cob is: earlier with liquefaction solvent and deliquescence accelerant mixing, be heated to 130-160 ℃ after, add corn cob again.
4. method according to claim 3 is characterized in that: in the step 3), the temperature of said foaming is a room temperature, and foamed time is 10-360s; The temperature of said slaking is 40-60 ℃, and the curing time is 2-4h.
5. method according to claim 4 is characterized in that: in the step 3), the rotating speed of said stirring is 1100-1300r/min.
6. the hard polyurethane foam that each said method prepares among the claim 1-5.
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| CN102443127B (en) * | 2011-10-17 | 2013-04-10 | 中国农业大学 | Method for preparing biodegradable polyurethane foam from industrial capsicum waste residue |
| CN102443130A (en) * | 2011-10-21 | 2012-05-09 | 中国农业大学 | Biomass-based polyurethane foam containing vegetable oil residue and preparation method of biomass-based polyurethane foam |
| CN102504164B (en) * | 2011-11-22 | 2013-10-16 | 中国农业大学 | Manufacture method of enhanced corncob base polyurethane foam materials |
| CN102532457B (en) * | 2012-02-09 | 2013-10-02 | 中国农业大学 | Method for synthesizing degradable polyurethane by using corncob and industrial capsicum waste residue |
| CN102604027B (en) * | 2012-03-09 | 2013-10-16 | 中国农业大学 | Polyurethane foam damping material and preparation method for same |
| CN103833949B (en) * | 2012-11-26 | 2016-03-02 | 中国农业大学 | A kind of preparation method of polyurethane foam |
| CN103626948B (en) * | 2013-11-26 | 2016-06-08 | 北京联合大学生物化学工程学院 | A kind of polyurethane foamed material utilizing plant polyatomic alcohol to synthesize |
| CN103601866B (en) * | 2013-11-26 | 2015-11-04 | 北京联合大学生物化学工程学院 | A kind of method utilizing plant polyatomic alcohol synthesis of polyurethane foam materials |
| CN104530446A (en) * | 2015-01-06 | 2015-04-22 | 青岛科技大学 | Method for preparing polyether polyol by liquifying and modifying peanut shells |
| CN106008890A (en) * | 2016-06-25 | 2016-10-12 | 仇颖超 | Preparation method of flame-retardant hard polyurethane foam |
| CN110483737A (en) * | 2019-07-30 | 2019-11-22 | 江南大学 | Bionical spectral simulation material and preparation method with three-dimensional porous structure |
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