CN103788327A - Method for preparing rigid polyurethane foam by using bamboo processing residue microwave liquidation product - Google Patents
Method for preparing rigid polyurethane foam by using bamboo processing residue microwave liquidation product Download PDFInfo
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- CN103788327A CN103788327A CN201410043459.XA CN201410043459A CN103788327A CN 103788327 A CN103788327 A CN 103788327A CN 201410043459 A CN201410043459 A CN 201410043459A CN 103788327 A CN103788327 A CN 103788327A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6685—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
- C08G18/6492—Lignin containing materials; Wood resins; Wood tars; Derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0025—Foam properties rigid
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The invention relates to a method for preparing rigid polyurethane foam by using a bamboo processing residue microwave liquidation product. The method is characterized by comprising the following steps: adding a mixed liquefying agent of polyethylene glycol 400, glycerol and ethylene carbonate, 98 percent sulfuric acid and dried and smashed bamboo processing residues into a three-necked bottle, placing into a microwave liquidation reaction kettle having condensing, stirring and infrared temperature measuring functions for performing microwave heating, reacting, adding a neutralizing reagent, and neutralizing a liquidation product till the pH is 7-8 to obtain plant polyhydric alcohol; uniformly mixing and stirring the prepared plant polyhydric alcohol with polyether polyol, a catalyst, a curing agent, water, silicone oil and a foaming agent, adding MDI (Diphenylmethane Diisocyanate) and nano-active carbon or titanium dioxide, mixing and stirring for 10-15 seconds, feeding into a die, standing and foaming at the room temperature, curing and demolding to obtain rigid polyurethane foam. By using the method, the bamboo resources are fully utilized, the liquidation cost is reduced, all components of a liquidation product can be utilized, and the aim of converting all components of bamboo processing residues into a synthetic polyurethane raw material is fulfilled. The product has the characteristic of capability of absorbing PM2.5, and is an environment-friendly bio-based rigid polyurethane foam product.
Description
Technical field
The present invention relates to a kind of Bamboo leftover microwave liquefied product and prepare the method for hard polyurethane foam.
Background technology
Hard polyurethane foam, as a kind of synthesized polymer material of excellent performance, has been widely used in the fields such as building, electrical equipment, packing, transportation and medical science, has obtained in recent years development rapidly.Hard polyurethane foam is to react through addition polycondensation a kind of polymkeric substance with carbamate segment repeated structural unit made from polyethers or polyester polyol by isocyanic ester.The raw material of producing at present polyethers, polyester polyol all derives from petrochemicals, a large amount of uses of these petrochemical industry resources, cause day by day serious environmental problem, as caused global air temperature warming, infringement ozonosphere, destroy ecosphere carbon balance, discharge objectionable impurities, cause the natural disasteies such as acid rain etc.
Because petroleum resources are day by day exhausted, the rise of oil price and the unreliability of supply have seriously limited the development of polyurethane industrial.Develop and find new alternate resources, the chemical in development renewable biomass source has become the key subjects that human society must be solved in the new millennium.Bamboo leftover cheap and easy to get is the natural polymer that is rich in hydroxyl, these polymkeric substance can substitute polyethers or polyester polyol and isocyanic ester generation nucleophilic addition and prepare polyurethane material in theory, so not only can improve the utilization ratio of bamboo resource, reduce polyurethane material production cost, reduce the dependence of polyurethane industrial to petroleum products, and the polyurethane products of producing have biodegradability and environment amenable feature.
Bamboo leftover is the natural macromolecular material of indissoluble, infusibility, easy machine-shaping unlike plastics.Bamboo liquefied, as a kind of new processing technology, is under some organic solvent or catalyst action, and making Mierocrystalline cellulose, hemicellulose and lignin conversion in bamboo wood is the fluent meterial with certain reactive behavior, i.e. plant polyatomic alcohol.Contrast previous literature and patent, lignocellulose raw material was prepared polyurethane material as timber, stalk, bamboo wood, sugarcane etc. are all once used to liquefaction, and its liquefaction temperature is 170 ℃ of left and right, and liquefying time is at 90-180min.Patent CN101362818A is with raw glycerine/polyoxyethylene glycol under sulfuric acid catalysis, and at 120-180 ℃ of liquefaction bamboo waste 90-180min, liquefied product is for the preparation of hard polyurethane foam.Patent CN102304213A reacts 45-90min liquefied straw residues with polyvalent alcohol and an acidic catalyst at 120-160 ℃, and the liquefied product obtaining is for the preparation of urethane.Aforesaid method liquefying time is long, easily causes liquefied product condensation to form new residue, affects the application of liquefied product.
Microwave, as a kind of novel energy-conserving, cheap and environment amenable heating technique, has been successfully applied to chemical field.The present invention utilizes Bamboo leftover for raw material, makes plant polyatomic alcohol by the liquefaction of polyvalent alcohol microwave, and petroleum replacing based polyether polyol reacts low, the eco-friendly polyurethane material of preparation cost with thick MDI.The present invention has not only realized the target that the alternative petrochemical industry polyether glycol of Bamboo leftover is produced urethane, for polyurethane industrial raw material sources provide a new way, simultaneously also for the higher value application of Bamboo leftover provides a kind of new method.
Summary of the invention
The object of the present invention is to provide a kind of Bamboo leftover polyvalent alcohol microwave liquefaction to prepare the method for hard polyurethane foam, take Bamboo leftover as raw material, the liquefaction take polyvalent alcohol as liquefying agent microwave, the liquefied product obtaining is that the alternative polyether glycol of plant polyatomic alcohol reacts and prepares hard polyurethane foam with thick MDI, in foamed material, add the material that can adsorb PM2.5, give the function that hard polyurethane foam purifies air simultaneously.
For achieving the above object, the present invention by the following technical solutions:
(1) a kind of method of utilizing Bamboo leftover microwave liquefied product to prepare hard polyurethane foam, it is characterized in that: by poly(oxyethylene glycol) 400, glycerol and NSC 11801 mixed solution agent, Bamboo leftover after 98% sulfuric acid and drying and crushing adds in three-necked bottle, be placed in condensation, stir, in the microwave liquefaction reaction still of infrared temperature measuring function, carry out microwave heating, after reaction finishes, add neutralization reagent, liquefied product is neutralized to pH7-8, make plant polyatomic alcohol, then by the above-mentioned plant polyatomic alcohol making and polyether glycol, catalyzer, solidifying agent, water, silicone oil, after whipping agent mixing and stirring, add MDI, nano active charcoal or titanium dioxide, mix and blend 10s-15s, enter mould, under room temperature, leave standstill foaming, slaking, the demoulding obtains hard polyurethane foam.
(2) method according to (1), wherein, the Bamboo leftover after drying and crushing be produce, bamboo wood drying and crushing discarded in life is to 40-100 object powder.
(3) according to the method (1) described, wherein, the mass ratio of poly(oxyethylene glycol) 400 and glycerol is 70:30-80:20, and the add-on of NSC 11801 is the 3%-6% of poly(oxyethylene glycol) 400 and glycerol total mass.
(4) according to the method (1) described, wherein, microwave heating time is 5min-30min.
(5) according to the method (1) described, wherein, the curing time is 24h-72h.
(6) according to the method (1) described, wherein, microwave power is 100W-800W.
(7), according to the method (1) described, wherein, neutralization is highly basic, weak base, basic oxide with reagent.
(8) method according to (1) or (7), wherein, neutralization is to be selected from any one of calcium oxide, magnesium oxide, sodium hydroxide with reagent.
(9) method according to (1), wherein, described polyether glycol is to be selected from one or both in model 4110,635,4501L, 400,403.
(10) method according to (1), wherein, described catalyzer is for being selected from triethylene diamine, N, one or both in N ‵-dimethylethanolamine, trolamine, dilaurate ester dibutyl tin, stannous octoate; Described solidifying agent is 2,4,6-tri-(dimethylaminomethyl) phenol (DMP-30); Described silicone oil is to be selected from one or both in model AK8810,8850,8867; Described whipping agent is the one being selected from Skellysolve A, iso-pentane, pentamethylene.
Method of the present invention has the following advantages:
1. compared with conventional heating means, liquefying time has been shortened in microwave liquefaction greatly, has reduced liquefaction cost, has reduced liquefied residue rate, and liquefied product is component utilization entirely.
2. the liquefied product of Bamboo leftover is without filtering or centrifugal, and the tiny residue of its liquefied product and minute quantity all can be used as the raw material that synthesis of polyurethane hard bubbles, and has realized Bamboo leftover full component and be converted into the target of synthesis of polyurethane raw material.
3. in foaming raw material, added a small amount of nano active carbon that can adsorb PM2.5 or titanium dioxide, given hard polyurethane foam product and there is the function that can purify air.
embodiment
One, hard polyurethane foam compressive strength performance test
The compressive strength performance test of the environmentally friendly hard polyurethane foam of above-mentioned bio-based is with reference to GB/T8813-1988 " rigid foam compression testing method ", polyurethane foamed material is processed into the square sample that the length of side is 50 ± 1mm, be placed in the central authorities of digital display universal testing machine two flat boards, with constant speed (about 5mm/min) compression sample, reach 10% with relative deformation, stress when 5mm represents ultimate compression strength.Calculation formula is as follows:
σ
m=
In formula: σ
mfor compressive strength, unit is kPa; Fm is the force of compression of relative deformation while reaching 10%, and unit is N; S
0for sample cross initial area, unit is mm
2.
Two, hard polyurethane foam absorption PM2.5 index test
Be 1m by total surface area
2hard polyurethane foam in air, place after 6 hours, adopt hinaway CW-HAT200 hand-held PM2.5 specialty air purification efficiency tester, survey PM2.5 index apart from 0.5 meter of hard polyurethane foam, 5 meters of.
Embodiment
Below by embodiment, the present invention will be further described, but protection scope of the present invention is not limited to following examples.
embodiment 1
By 80g poly(oxyethylene glycol) 400,20g glycerol, 3g NSC 11801,2g 98% sulfuric acid and 25g bamboo powder add in three-necked bottle, are placed in microwave oven, open condensation reflux unit, start agitator, microwave power 800W, heating 5min, reaction finish rear with calcium oxide neutralization to pH7-8.Get 50g plant polyatomic alcohol, 25g polyether glycol 4110,25g polyether glycol 635,3g triethylene diamine, 1g DMP-30,1g water, 2g silicone oil AK8810,2g silicone oil 8850,8g Skellysolve A, after high-speed stirring is even, add the thick MDI of 100g, 2g nano active carbon, after high-speed stirring 10s, pour rapidly mold cured, sizing into.After placing 24h under normal temperature, pour out mould, obtain hard polyurethane foams, the compressive strength that records hard polyurethane foam is 158.24KPa.Apart from 88,5 meters of PM2.5 indexes 100 of 0.5 meter of PM2.5 index of hard polyurethane foam.
embodiment 2
By 75g poly(oxyethylene glycol) 400,25g glycerol, 4g NSC 11801,3g 98% sulfuric acid and 34g bamboo powder add in three-necked bottle, are placed in microwave oven, open condensation reflux unit, start agitator, microwave power 700W, heating 10min, reaction finishes to neutralize with magnesium oxide afterwards.Get 60g plant polyatomic alcohol, 20g polyether glycol 4501L, 20g polyether glycol 635,2g dilaurate ester dibutyl tin, 1.5g DMP-30,1.5g water, 1.5g silicone oil AK8810,2g silicone oil 8867,12g pentamethylene, after high-speed stirring is even, add 100g polymeric MDI, 2g nano active carbon, after high-speed stirring 11s, pour rapidly mold cured, sizing into.After placing 24h under normal temperature, pour out mould, obtain hard polyurethane foams, the compressive strength that records hard polyurethane foam is 182.01KPa.Apart from 76,5 meters of PM2.5 indexes 100 of 0.5 meter of PM2.5 index of hard polyurethane foam.
embodiment 3
By 72g poly(oxyethylene glycol) 400,28g glycerol, 5g NSC 11801,4g 98% sulfuric acid and 28g bamboo powder add in three-necked bottle, are placed in microwave oven, open condensation reflux unit, start agitator, microwave power 600W, heating 15min, uses calcium oxide neutralization after reaction finishes.Get 70g plant polyatomic alcohol, 20g polyether glycol 400,10g polyether glycol 635,1g N, N ‵-dimethylethanolamine, 2g DMP-30,2g water, 3g silicone oil AK8810,10g iso-pentane, after high-speed stirring is even, add 100g polymeric MDI, 2g nano active carbon, after high-speed stirring 12s, pour rapidly mold cured, sizing into.After placing 24h under normal temperature, pour out mould, obtain hard polyurethane foams, the compressive strength that records the hard polyurethane foam making is 177.23KPa.Apart from 88,5 meters of PM2.5 indexes 130 of 0.5 meter of PM2.5 index of hard polyurethane foam.
embodiment 4
By 76g poly(oxyethylene glycol) 400,24g glycerol, 6g NSC 11801,2.5g 98% sulfuric acid and 25g bamboo powder add in three-necked bottle, are placed in microwave oven, open condensation reflux unit, start agitator, microwave power 500W, heating 20min, reaction finishes to neutralize with sodium hydroxide afterwards.Get 80g plant polyatomic alcohol, 20g polyether glycol 403,1.5g stannous octoate, 2.5g DMP-30,3g water, 2.5g silicone oil AK8810,11g Skellysolve A, after high-speed stirring is even, adds 100g polymeric MDI, 2g nano active carbon, after high-speed stirring 13s, pours rapidly mold cured, sizing into.After placing 24h under normal temperature, pour out mould, obtain hard polyurethane foams, the compressive strength that records the hard polyurethane foam making is 167.23KPa.Apart from 65,5 meters of PM2.5 indexes 120 of 0.5 meter of PM2.5 index of hard polyurethane foam.
embodiment 5
By 70g poly(oxyethylene glycol) 400,30g glycerol, 4g NSC 11801,4g 98% sulfuric acid and 22g bamboo powder add in three-necked bottle, are placed in microwave oven, open condensation reflux unit, start agitator, microwave power 400W, heating 25min, reaction finishes to neutralize with magnesium oxide afterwards.Get 90g plant polyatomic alcohol, 10g polyether glycol 4110,2.5g stannous octoate, 3g DMP-30,4g water, 2g silicone oil AK8867,9g pentamethylene, after high-speed stirring is even, adds 100g polymeric MDI, 2g nano active carbon, after high-speed stirring 14s, pours rapidly mold cured, sizing into.After placing 24h under normal temperature, pour out mould, obtain hard polyurethane foams, the compressive strength that records the hard polyurethane foam making is 200.10KPa.Apart from 58,5 meters of PM2.5 indexes 110 of 0.5 meter of PM2.5 index of hard polyurethane foam.
embodiment 6
By 77g poly(oxyethylene glycol) 400,23g glycerol, 4.5g NSC 11801,4.5g 98% sulfuric acid and 20g bamboo powder add in three-necked bottle, are placed in microwave oven, open condensation reflux unit, start agitator, microwave power 300W, heating 30min, uses calcium oxide neutralization after reaction finishes.Get 100g plant polyatomic alcohol, 2g trolamine, 1g dilaurate ester dibutyl tin, 1g DMP-30,5g water, 1g silicone oil AK8850,6g iso-pentane, after high-speed stirring is even, adds 100g polymeric MDI, 2g nano active carbon, after high-speed stirring 15s, pours rapidly mold cured, sizing into.After placing 24h under normal temperature, pour out mould, obtain hard polyurethane foams, the compressive strength that records the hard polyurethane foam making is 155.21KPa.Apart from 56,5 meters of PM2.5 indexes 123 of 0.5 meter of PM2.5 index of hard polyurethane foam.
embodiment 7
By 70g poly(oxyethylene glycol) 400,30g glycerol, 5g NSC 11801,5g 98% sulfuric acid and 16g bamboo powder add in three-necked bottle, are placed in microwave oven, open condensation reflux unit, start agitator, microwave power 200W, heating 25min, reaction finishes to neutralize with magnesium oxide afterwards.Get 55g plant polyatomic alcohol, 20g polyether glycol 400,25g polyether glycol 635,2g triethylene diamine, 0.5g stannous octoate, 1.5g DMP-30,2.5g water, 1.5g silicone oil AK8810,4g Skellysolve A, after high-speed stirring is even, add 100g polymeric MDI, 2g nano active carbon, after high-speed stirring 15s, pour rapidly mold cured, sizing into.After placing 24h under normal temperature, pour out mould, obtain hard polyurethane foams, the compressive strength that records the hard polyurethane foam making is 150.02KPa.Apart from 89,5 meters of PM2.5 indexes 115 of 0.5 meter of PM2.5 index of hard polyurethane foam.
Claims (10)
1. a method of utilizing Bamboo leftover microwave liquefied product to prepare hard polyurethane foam, it is characterized in that: by poly(oxyethylene glycol) 400, glycerol and NSC 11801 mixed solution agent, Bamboo leftover after 98% sulfuric acid and drying and crushing adds in three-necked bottle, be placed in condensation, stir, in the microwave liquefaction reaction still of infrared temperature measuring function, carry out microwave heating, after reaction finishes, add neutralization reagent, liquefied product is neutralized to pH7-8, make plant polyatomic alcohol, then by the above-mentioned plant polyatomic alcohol making and polyether glycol, catalyzer, solidifying agent, water, silicone oil, after whipping agent mixing and stirring, add MDI, nano active charcoal or titanium dioxide, mix and blend 10s-15s, enter mould, under room temperature, leave standstill foaming, slaking, the demoulding obtains hard polyurethane foam.
2. method according to claim 1, wherein, the Bamboo leftover after drying and crushing be produce, in life discarded bamboo wood drying and crushing to 40-100 object powder.
3. method according to claim 1, wherein, the mass ratio of poly(oxyethylene glycol) 400 and glycerol is 70:30-80:20, the add-on of NSC 11801 is the 3%-6% of poly(oxyethylene glycol) 400 and glycerol total mass.
4. method according to claim 1, wherein, microwave heating time is 5min-30min.
5. method according to claim 1, wherein, the curing time is 24-72h.
6. method according to claim 1, wherein, microwave power is 100W-800W.
7. method according to claim 1, wherein, neutralization is highly basic, weak base, basic oxide with reagent.
8. according to the method described in claim 1 or 7, wherein, neutralization is to be selected from any one of calcium oxide, magnesium oxide, sodium hydroxide with reagent.
9. method according to claim 1, described polyether glycol is to be selected from one or both in model 4110,635,4501L, 400,403.
10. method according to claim 1, described catalyzer is for being selected from triethylene diamine, N, one or both in N ‵-dimethylethanolamine, trolamine, dilaurate ester dibutyl tin, stannous octoate; Described solidifying agent is 2,4,6-tri-(dimethylaminomethyl) phenol (DMP-30); Described silicone oil is to be selected from one or both in model AK8810,8850,8867; Described whipping agent is the one being selected from Skellysolve A, iso-pentane, pentamethylene.
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| CN111285992A (en) * | 2020-03-17 | 2020-06-16 | 浙江工业大学 | Method for preparing foamed cultivation substrate material by adopting bamboo liquefied resin |
| CN112430303A (en) * | 2020-11-20 | 2021-03-02 | 中国林业科学研究院林产化学工业研究所 | Method for preparing degradable seedling raising pot by using bamboo as raw material |
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| CN103964970A (en) * | 2014-05-28 | 2014-08-06 | 山东农业大学 | Waste paper modified coated control release fertilizer and preparation method thereof |
| CN103964970B (en) * | 2014-05-28 | 2015-07-08 | 山东农业大学 | Waste paper modified coated control release fertilizer and preparation method thereof |
| CN104941331A (en) * | 2015-06-02 | 2015-09-30 | 江苏华强新能源科技有限公司 | High efficiency air filter element for gas turbine and production process thereof |
| CN104941331B (en) * | 2015-06-02 | 2017-01-11 | 江苏华强新能源科技有限公司 | High efficiency air filter element for gas turbine and production process thereof |
| KR102245442B1 (en) * | 2019-11-01 | 2021-04-28 | 경희대학교 산학협력단 | Method for producing biopolyol from lignocellulosic biomass and method for producing biopolyurethane using thereof |
| CN111285992A (en) * | 2020-03-17 | 2020-06-16 | 浙江工业大学 | Method for preparing foamed cultivation substrate material by adopting bamboo liquefied resin |
| CN112430303A (en) * | 2020-11-20 | 2021-03-02 | 中国林业科学研究院林产化学工业研究所 | Method for preparing degradable seedling raising pot by using bamboo as raw material |
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