CN102504164B - Manufacture method of enhanced corncob base polyurethane foam materials - Google Patents
Manufacture method of enhanced corncob base polyurethane foam materials Download PDFInfo
- Publication number
- CN102504164B CN102504164B CN 201110374353 CN201110374353A CN102504164B CN 102504164 B CN102504164 B CN 102504164B CN 201110374353 CN201110374353 CN 201110374353 CN 201110374353 A CN201110374353 A CN 201110374353A CN 102504164 B CN102504164 B CN 102504164B
- Authority
- CN
- China
- Prior art keywords
- glass fiber
- fiber powder
- enhanced
- polyurethane foam
- parts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Abstract
The invention discloses a manufacture method of enhanced corncob base polyurethane foam materials and belongs to the field of material chemical engineering. A mixed reagent of polyethyleneglycol 400 and glycerol is used for liquefying crushed corncobs under the catalytic effect of concentrated sulfuric acid, then, a proper amount of MgO is added for neutralizing the liquefied products, the processed liquefied products are mixed with catalysts and foam stabilizing agents, then, a certain amount of glass fiber powder is added into the materials to be sufficiently stirred and uniformly mixed, next, polyaryl polymethylene isocyanate (PAPI) is poured into the materials and is fast and uniformly stirred until oyster white appears, then, the combined materials are immediately poured into a mold for natural foaming, and the enhanced corncob base polyurethane foam materials are obtained. The enhanced biomass base foam has the obviously improved mechanical property indexes such as compression intensity and the like on the premise of maintaining the original physical property unchanged.
Description
Technical field
The invention belongs to the chemical engineering of materials field, relate to the liquefaction of corn-cob product and prepare biodegradable enhancement type polyurethane foamed material.
Background technology
Along with the day by day exhaustion of fossil energy, discarded macromolecular material etc. have limited the development of the polyurethane industrial take petroleum chemicals as raw material to the severe contamination that environment causes.Environmental protection, biodegradable new polyurethane foam materials more and more are subject to people's attention and pay close attention to.At present, the method that the world processes the biomass resources such as agricultural wastes in a lot of areas is to burn, and this does not only make rational use of resources, and also environment and soil has been caused pollution.And biomass-base polyurethane foam material had both relaxed energy starved contradiction, and can to environment, can not take full advantage of discarded biomass resource simultaneously.
At present, the Main Mechanicals such as biomass-based polyurethane foam compressive strength are not very desirable, need to improve.Adding by auxiliary material and strengthen corncob base polyurethane foam materials, make its physicals be improved significantly the Biodegradable polyurethane foam materials.The foam materials that obtains not only compressive strength is significantly improved, and manufacturing cost also has relative significantly reduction.
Glass fiber powder is that the continuous glass fibre precursor that will draw specially forms through chopped, grinding screening, is widely used in various thermosetting resins and thermoplastic resin as filling strongthener.Glass fiber powder to improve goods hardness, ultimate compression strength, reduces shrink of product rate, polishing scratch width, abrasion, production cost as packing material.Therefore, it has wide market outlook and important industrial application value.
Summary of the invention
The purpose of this invention is to provide a kind of processing method for preparing the corncob base polyurethane foam materials of enhancement type, and can reduce its production cost.
A kind of manufacture method of enhanced corncob base polyurethane foam materials mainly may further comprise the steps:
1) according to the mass fraction, 200～300 parts of liquefying agents, 6～13 parts of deliquescence accelerants are added reactor, be heated to 140～170 ℃, then add corn cob, the stirring reaction 30～150min of 50～65 parts of pulverizing, after finishing, reaction with the cold water cooling, obtains the liquefaction of corn-cob product;
2) the liquefaction of corn-cob product is neutralized to neutrality with MgO, then at 100～110 ℃ of lower 10～15h that place, to remove moisture;
3) according to the mass fraction, get 45～55 parts through step 2) liquefied product processed, adds catalyzer and 0.45～0.55 part of suds-stabilizing agent of 0.46～0.55 part, mix, then with the glass fiber powder adding wherein, stir; Add again 45～60 parts of poly methylene poly phenyl poly isocyanates (PAPI), stir until occur milky white, pour in the mould, at room temperature leave standstill foaming, treat that foaming finishes to place 50～70 ℃ of lower slaking 6～15h, at room temperature place more than 20 hours, fully slaking makes enhanced corncob base polyurethane foam materials again.
In step 1) also comprise before the pre-treatment corn cob: corn cob meal is broken to 20～80 orders, under 100～110 ℃, is dried to constant weight.
The mixed solvent of the preferred poly(oxyethylene glycol) 400 of the described liquefying agent of step (1) and glycerol, wherein, the weight ratio of poly(oxyethylene glycol) 400 and glycerol is (2～4): 1; Described deliquescence accelerant is concentrated hydrochloric acid or the vitriol oil, and the preferred mass mark is 98% the vitriol oil.
Step 2) mass ratio of liquefaction of corn-cob product and MgO is 300 in: (6～9).
Step 3) in, described catalyzer is preferably the mixing solutions of dibutyltin dilaurate and triethylamine, wherein, according to the mass fraction, contains 0.23～0.28 part of dibutyltin dilaurate and 0.22～0.27 part of triethylamine.
Step 3) in, after glass fiber powder added, the condition of stirring was generally: stir 50～85s under 1000～1100r/min rotating speed; After adding poly methylene poly phenyl poly isocyanate, the condition of stirring is generally: stir 10～45s with 1100～1300r/min rotating speed.
The add-on of described glass fiber powder is generally 5%～15% of liquefied product quality.
Step 3) leaves standstill foamed time under the room temperature in and be generally 10～90s.
Step 3) in, described suds-stabilizing agent is selected from one or more in methyl-silicone oil, tween-80, the Tween-60, preferable methyl silicone oil.
Be 100～200 purpose milled glass fiber powder and in synthesis of polyurethane foam process, do not use any whipping agent, described glass fiber powder.
The present invention compares with existing biomass-based polyurethane foam has following beneficial effect:
1) mechanical property such as compressive strength is significantly improved, and other performances are also very excellent.
2) strongthener-glass fiber powder that adopts among the present invention, cheap and easy to get, can reduce production costs.
Embodiment
Following examples are used for explanation the present invention, but are not used for limiting the scope of the invention.
Example 1
1) according to the mass fraction, be that 98% the vitriol oil joins in the there-necked flask with 200 parts of PEG400,50 parts of glycerol and 12.5 parts of concentration (massfraction), stir, then there-necked flask is placed in the oil bath pan and heats.After the mixing liquid temperature reaches 160 ℃ in the bottle, add the corn cob of 63 parts of pulverizing, stirring reaction 60min takes out there-necked flask, is cooled to rapidly room temperature with cold water, obtains the liquefaction of corn-cob product.The preparation method of the corn cob of described pulverizing is: corn cob meal is broken to the 20-80 order, is dried to constant weight under 105 ℃.
2) according to the mass fraction, get 300 parts of above-mentioned liquefied product, add 8.5 parts of MgO liquefied product is neutralized to neutrality, then liquefied product is removed moisture at 105 ℃ of lower placement 12h.
3) step 2 of learning from else's experience) liquefied product after processing is in dixie cup, again triethylamine, dibutyltin dilaurate and methyl-silicone oil are added wherein, under the 1100r/min rotating speed, stir 75s, then add PAPI, under identical rotating speed, stir, be stirred to 30s and milky white phenomenon occurs, then be poured into rapidly in the mould, at room temperature leave standstill foaming 85s, the demoulding, at 60 ℃ of lower 10h that place, at room temperature placed again fully slaking 24 hours.Wherein, the mass ratio of liquefied product, triethylamine, dibutyltin dilaurate, methyl-silicone oil and PAPI is 45: 0.23: 0.23: 0.46: 45.Described poly methylene poly phenyl poly isocyanate (PAPI) is dark-brown liquid available from the magnificent urethane in Yantai ten thousand company limited, and functionality is 2.6-2.7, and isocyano-content is 30.5%-32.0%, and flash-point is 230 ℃, and burning-point is 245 ℃, trade mark PM-200.
Example 2
Step 1) with step 2) identical with embodiment 1.
3) according to the mass fraction, get 45 parts through step 2) liquefied product after processing in dixie cup, again 0.23 part of triethylamine, 0.24 part of dibutyltin dilaurate and 0.45 part of methyl-silicone oil are added wherein, mix.Toward 5% the glass fiber powder (glass fiber powder that 100～200 orders grind) that wherein adds with respect to the liquefied product quality, under the 1100r/min rotating speed, stir 75s again.Then add 45 parts of PAPI, stir under identical rotating speed, occur milky white phenomenon when being stirred to 30s, then be poured into rapidly in the mould, at room temperature leave standstill foaming 80s, the demoulding at 60 ℃ of lower 10h that place, was at room temperature placed abundant slaking 24 hours again.
Embodiment 3
Step 1) with step 2) identical with embodiment 1.
3) according to the mass fraction, get 45 parts through step 2) liquefied product after processing in dixie cup, again 0.24 part of triethylamine, 0.25 part of dibutyltin dilaurate and 0.46 part of methyl-silicone oil are added wherein, mix.Toward 10% the glass fiber powder (glass fiber powder that 100～200 orders grind) that wherein adds with respect to the liquefied product quality, under the 1100r/min rotating speed, stir 75s again.Then add 45 parts of PAPI, stir under identical rotating speed, occur milky white phenomenon when being stirred to 35s, then be poured into rapidly in the mould, at room temperature leave standstill foaming 40s, the demoulding at 60 ℃ of lower 10h that place, was at room temperature placed abundant slaking 24 hours again.
Embodiment 4
Step 1) with step 2) identical with embodiment 1.
3) according to the mass fraction, get 45 parts through step 2) liquefied product after processing in dixie cup, again 0.23 part of triethylamine, 0.23 part of dibutyltin dilaurate and 0.46 part of methyl-silicone oil are added wherein, mix.Respectively toward 15% the glass fiber powder (glass fiber powder that 100～200 orders grind) that wherein adds with respect to the liquefied product quality, under the 1100r/min rotating speed, stir 75s again.Then add 45 parts of PAPI, milky white phenomenon occurs when stirring 15s under identical rotating speed, then be poured into rapidly in the mould, at room temperature leave standstill foaming 10s, the demoulding at 60 ℃ of lower 10h that place, was at room temperature placed abundant slaking 24 hours again.
Embodiment 5
Be that 98% the vitriol oil joins in the there-necked flask with PEG400, glycerol and concentration (massfraction), stir, then there-necked flask is placed in the oil bath pan and heats.After the mixing liquid temperature reaches 160 ℃ in the bottle, add the corn cob of pulverizing, stirring reaction 130min takes out there-necked flask, is cooled to rapidly room temperature with cold water, obtains the liquefaction of corn-cob product.Wherein, the mass ratio of the corn cob of PEG400, glycerol, the vitriol oil and pulverizing is 140: 70: 6: 50.The preparation method of described ground corn core is: corn cob meal is broken to the 20-80 order, is dried to constant weight under 105 ℃.
2) get above-mentioned liquefied product, add MgO liquefied product is neutralized to neutrality, then liquefied product is removed moisture at 105 ℃ of lower placement 15h, wherein, the mass ratio of liquefied product and MgO is 300: 6.
3) according to the mass fraction, get 55 parts through step 2) liquefied product after processing in dixie cup, again 0.27 part of triethylamine, 0.28 part of dibutyltin dilaurate and 0.52 part of methyl-silicone oil are added wherein, mix.Respectively toward 10% the glass fiber powder (glass fiber powder that 100～200 orders grind) that wherein adds with respect to the liquefied product quality, under the 1100r/min rotating speed, stir 60s again.Then add 55 parts of PAPI, under identical rotating speed, stir, be stirred to 30s and milky white phenomenon occurs, be poured into rapidly in the mould, at room temperature leave standstill foaming 30s, the demoulding, at 60 ℃ of lower 10h that place, at room temperature placed 24 hours, fully slaking makes enhanced corncob base polyurethane foam materials again.
The physicals of embodiment 1～4 gained foam materials is as shown in table 1:
The physicals of table 1 enhanced corncob base polyurethane foam materials
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | |
| Glass fibre powder content (%) | 0 | 5 | 10 | 15 |
| Density (Kg/m 3) | 80.74 | 79.61 | 82.66 | 75.68 |
| Thermal conductivity (W/mk) | 0.0360 | 0.0380 | 0.0384 | 0.0374 |
| Compressive strength (kMPa) | 106.53 | 169.78 | 227.86 | 106.48 |
Conclusion: test result shows that behind the glass fiber powder of interpolation 10%, material has increased significantly in compressive strength, and density and thermal conductivity also increase.But the compressive strength of material, density and thermal conductivity decline to a great extent after glass fiber powder is increased to 15% on the contrary, so the addition of glass fiber powder is advisable with 5%-10%.
Claims (8)
1. the manufacture method of an enhanced corncob base polyurethane foam materials is characterized in that: take corn cob as raw material, may further comprise the steps:
1) according to the mass fraction, 200～300 parts of liquefying agents and 6～13 parts of deliquescence accelerants are added reactor, be heated to 140～170 ℃, then add corn cob, the stirring reaction 30～150min of 50～65 parts of pulverizing, after finishing, reaction with the cold water cooling, obtains the liquefaction of corn-cob product;
2) the liquefaction of corn-cob product is neutralized to neutrality with MgO, then at 100～110 ℃ of lower 10～15h that place;
3) according to the mass fraction, get 45～55 parts through step 2) liquefied product processed, adds catalyzer and 0.45～0.55 part of suds-stabilizing agent of 0.46～0.55 part, mix, then with the glass fiber powder adding wherein, stir; Add again 45～60 parts of poly methylene poly phenyl poly isocyanates, stir until appearance is milky white, pour in the mould, at room temperature leave standstill foaming, then place 50～70 ℃ of lower slaking 6～15h, at room temperature place more than 20 hours again, make enhanced corncob base polyurethane foam materials;
Need the pre-treatment corn cob before the described step 1): corn cob meal is broken to 20～80 orders, under 100～110 ℃, is dried to constant weight;
The add-on of glass fiber powder is 5%～15% of liquefied product quality in the described step 3).
2. method according to claim 1 is characterized in that: in the step 1), described liquefying agent by poly(oxyethylene glycol) 400 and glycerol by weight being (2～4): 1 ratio is formulated.
3. method according to claim 1, it is characterized in that: in the step 1), described deliquescence accelerant is that massfraction is 98% the vitriol oil.
4. method according to claim 1, it is characterized in that: in the step 3), according to the mass fraction, described catalyzer is the mixing solutions of 0.23～0.28 part of dibutyltin dilaurate and 0.22～0.27 part of triethylamine.
5. method according to claim 1, it is characterized in that: in the step 3), described suds-stabilizing agent is methyl-silicone oil.
6. method according to claim 1, it is characterized in that: described glass fiber powder is 100～200 purpose milled glass fiber powder.
7. method according to claim 1 is characterized in that: step 2) in the mass ratio of liquefaction of corn-cob product and MgO be 300:(6～9).
8. method according to claim 1 is characterized in that: in the step 3), after glass fiber powder added, the condition of stirring was: stir 50～85s under 1000～1100r/min rotating speed; After adding poly methylene poly phenyl poly isocyanate, the condition of stirring is: stir 10～45s with 1100～1300r/min rotating speed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110374353 CN102504164B (en) | 2011-11-22 | 2011-11-22 | Manufacture method of enhanced corncob base polyurethane foam materials |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110374353 CN102504164B (en) | 2011-11-22 | 2011-11-22 | Manufacture method of enhanced corncob base polyurethane foam materials |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102504164A CN102504164A (en) | 2012-06-20 |
| CN102504164B true CN102504164B (en) | 2013-10-16 |
Family
ID=46216303
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201110374353 Expired - Fee Related CN102504164B (en) | 2011-11-22 | 2011-11-22 | Manufacture method of enhanced corncob base polyurethane foam materials |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102504164B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103833949B (en) * | 2012-11-26 | 2016-03-02 | 中国农业大学 | A kind of preparation method of polyurethane foam |
| CN104356346A (en) * | 2014-10-22 | 2015-02-18 | 内蒙古农业大学 | Foaming material, preparation method and application |
| CN107628785A (en) * | 2017-08-29 | 2018-01-26 | 北京禾木之家科技发展有限公司 | The preparation method of Light Wall |
| CN108148177A (en) * | 2018-01-23 | 2018-06-12 | 镇江环太硅科技有限公司 | A kind of preparation method of the incisory high-efficient energy-saving environment friendly resin plate of diamond wire |
| CN109880118B (en) * | 2019-03-04 | 2021-02-09 | 西南石油大学 | Lignin type fiber nanofibril material, stable foam system based on same, preparation method and application thereof |
| CN110467718B (en) * | 2019-07-10 | 2021-02-19 | 厦门大学 | Biomass-based buffer packaging foam material and preparation method thereof |
| CN112521572B (en) * | 2019-09-19 | 2022-06-21 | 北京化工大学 | Polyurethane foamable composition, polyurethane foam, and method for producing same |
| CN114890884B (en) * | 2022-06-08 | 2023-08-22 | 郑州大学 | Method for high-value utilization of corncob acid hydrolysis residues |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1834130A (en) * | 2005-03-04 | 2006-09-20 | 气体运输技术公司 | Glassfiber-reinforced polyurethane-polyisocyanurate foam |
| CN101781395A (en) * | 2010-03-30 | 2010-07-21 | 上海交通大学 | Hard polyurethane adiabatic heat-insulation foam material and preparation method thereof |
| CN102181030A (en) * | 2011-04-07 | 2011-09-14 | 中国农业大学 | Method for preparing corncob-base polyurethane rigid foam damping material |
-
2011
- 2011-11-22 CN CN 201110374353 patent/CN102504164B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1834130A (en) * | 2005-03-04 | 2006-09-20 | 气体运输技术公司 | Glassfiber-reinforced polyurethane-polyisocyanurate foam |
| CN101781395A (en) * | 2010-03-30 | 2010-07-21 | 上海交通大学 | Hard polyurethane adiabatic heat-insulation foam material and preparation method thereof |
| CN102181030A (en) * | 2011-04-07 | 2011-09-14 | 中国农业大学 | Method for preparing corncob-base polyurethane rigid foam damping material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102504164A (en) | 2012-06-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102504164B (en) | Manufacture method of enhanced corncob base polyurethane foam materials | |
| CN102206320B (en) | Preparation method of biomass-base polyurethane foam material | |
| CN102079803B (en) | Full-water-type combined polyether and application method thereof, and polyurethane rigid foam composition | |
| CN103275459B (en) | Urea resin foam thermal-insulation composite material and preparation method thereof | |
| CN102181030B (en) | Method for preparing corncob-base polyurethane rigid foam damping material | |
| CN106117483B (en) | Cast polyurethane protecting housing of storage battery and its manufacturing method | |
| CN101845218B (en) | Polyester type polyurethane microporous sole material and preparation method thereof | |
| CN103224628B (en) | Hydroxymethylated lignin and application thereof | |
| CN104530383A (en) | Method for preparing polyurethane foam through rice straw and prepared polyurethane foam | |
| CN113501924B (en) | Polyurethane hard foam heat insulation material | |
| CN108864404A (en) | A kind of coffee grounds composite material and preparation method of isocyanates enhancing | |
| CN103012738A (en) | Modified fly ash reinforced hard polyurethane foam material and preparation method thereof | |
| CN101280049B (en) | Degradable polyurethane foam material made from straw and preparation thereof | |
| CN101205287B (en) | Corn straw polyhydric alcohol compound and preparation thereof | |
| CN102443130A (en) | Biomass-based polyurethane foam containing vegetable oil residue and preparation method of biomass-based polyurethane foam | |
| CN104927301B (en) | Modified melamine formaldehyde (MF) foam of polyisocyanic acid ester oligomer and preparation method thereof | |
| CN102604027B (en) | Polyurethane foam damping material and preparation method for same | |
| CN103788327A (en) | Method for preparing rigid polyurethane foam by using bamboo processing residue microwave liquidation product | |
| CN102040824B (en) | Cast polyurethane elastomer composition for fashion model | |
| CN103450434B (en) | A kind of plant polyatomic alcohol polyurethane rigid foam material and preparation method thereof | |
| CN109320679B (en) | Environment-friendly combined polyether for high-self-adhesion stainless steel freezer cabinet, preparation method and application | |
| CN101948563B (en) | Pentane type composite polyether and composition containing same, rigid polyurethane rigid foam and application thereof | |
| CN103992412A (en) | Modified dioscorea opposita thunb starch prepolymer and degradable polyurethane foam material prepared from prepolymer | |
| CN103740318B (en) | Regenerative sponge glue | |
| CN103641979B (en) | Mine polyurethane is from antiskinning composition and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20131016 Termination date: 20161122 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |