CN103833949B - A kind of preparation method of polyurethane foam - Google Patents
A kind of preparation method of polyurethane foam Download PDFInfo
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- CN103833949B CN103833949B CN201210488345.7A CN201210488345A CN103833949B CN 103833949 B CN103833949 B CN 103833949B CN 201210488345 A CN201210488345 A CN 201210488345A CN 103833949 B CN103833949 B CN 103833949B
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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
- C08G18/6505—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6511—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38 compounds of group C08G18/3203
- C08G18/6517—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38 compounds of group C08G18/3203 having at least three hydroxy groups
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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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3218—Polyhydroxy compounds containing cyclic groups having at least one oxygen atom in the ring
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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
- C08G18/40—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
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H8/00—Macromolecular compounds derived from lignocellulosic materials
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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
- C08G2101/00—Manufacture of cellular products
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Abstract
The invention discloses a kind of preparation method of polyurethane foam.Comprise the steps: that (1) corn cob meal is hydrolyzed reaction under the effect of dilute sulphuric acid; In citrate buffer solution, the filter residue after described hydrolysis reaction carries out enzyme digestion reaction under the effect of cellulase, and suction filtration must through the corn cob residue of enzymolysis; (2) describedly under the effect at liquefying agent and the vitriol oil of the corn cob residue of enzymolysis and the mixture of corn cob meal, liquefied product is obtained through liquefaction processing; (3) black material is obtained after described liquefied product and stablizer and catalyst mix; (4) ethylene glycol and dextrose anhydrous carry out being obtained by reacting thick glycol polyglucoside under the katalysis of phosphoric acid; (5) isocyanic ester obtains white material after mixing with described thick glycol polyglucoside; (6) described white material and described black material are under agitation mixed to get mixture, this mixture is through foaming and get final product.The thinking that present method provides is emphasized that combination technology is ripe and has also been applied to industrial agricultural waste material Application way (i.e. manufacture ethanol and crystalline xylose), has more practical significance and feasibility.
Description
Technical field
The present invention relates to a kind of preparation method of polyurethane foam, being specifically related to a kind of take corn cob as the method that polyurethane foam prepared by raw material.
Background technology
Polyurethane material is one of kind with fastest developing speed in modern plastics industry, by binary or polynary organic isocyanate and binary or polyol compound, namely polyether glycol or polyester polyol reaction obtained.Raw material sources due to polyol compound are oil, therefore polyurethane industrial has very strong dependency for oil.Oil have impact on the development of polyurethane industrial because of the fluctuation of price and the wretched insufficiency of supply in recent years.Corn cob is the natural compounds being rich in hydroxyl, and research proves, these compounds can replace polyethers or polyester polyol and isocyanic ester generation nucleophilic addition to prepare polyurethane material.Select corn cob not only can improve the utilization ratio of resource as the raw material of polyol compound aborning, and make polyurethane industrial decrease dependence to oil, raw materials cost reduces.
Utilize corn cob enzymatic hydrolysis and fermentation to produce in the process of alcohol fuel and can produce a large amount of corn cob residue after enzymolysis, if using these residues as production starting material, use in the preparation of polyurethane foam, further will improve the utilization ratio of resource, reduce production cost, save energy.
The agricultural and sideline waste corn cob being rich in hemicellulose, by dilute acid hydrolysis, can obtain based on wood sugar and hydrolyzed solution containing the assorted sugar such as a small amount of glucose, seminose and pectinose.This hydrolyzed solution, through scavenging process such as ion-exchange, vacuum concentration, crystallizations, can obtain crystalline xylose.Isolate in the mother liquor after crystal wood sugar and contain a large amount of glucose, glycosyl shift reaction can be carried out with alcohols and prepare thick glycol polyglucoside.Experiment proves to add the adjustable speed of response of glycol polyglucoside in synthesis of polyurethane foam materials process, and make material have the abundant time to mix, speed of response is even, and foam stabilization, compact structure, not easily produces space.Test proof, rough glycol polyglucoside is owing to being liquid state, use more more convenient than solid-state pure glycol polyglucoside simultaneously.If utilize the discarded assorted sugared hydrolyzed solution produced in xylose production process to prepare thick glycol polyglucoside, add to plant polyatomic alcohol as auxiliary agent and be in the polyurethane foam prepared of raw material, urethane performance will be improved when cost increase is very little.
Summary of the invention
The object of this invention is to provide a kind of preparation method of polyurethane foam, being specially a kind of utilization through the corncob powder that cellulase degradation is crossed is raw material, add the method that rough glycol polyglucoside prepares polyurethane foam, simultaneously for a kind of providing a kind ofly utilizes two kinds of industrial produced wastes to prepare the technical scheme of polyurethane foamed material.
The preparation method of a kind of polyurethane foam provided by the present invention, comprises the steps:
(1) corn cob meal is hydrolyzed reaction under the effect of dilute sulphuric acid; In citrate buffer solution, the filter residue after described hydrolysis reaction carries out enzyme digestion reaction under the effect of cellulase, and suction filtration must through the corn cob residue of enzymolysis;
(2) describedly under the effect at liquefying agent and the vitriol oil of the corn cob residue of enzymolysis and the mixture of corn cob meal, liquefied product is obtained through liquefaction processing; Described liquefying agent is the mixture of poly(oxyethylene glycol) 400 and glycerol;
(3) black material is obtained after described liquefied product and stablizer and catalyst mix; Described stablizer is silicone oil or polydimethylsiloxane, and described catalyzer is the mixture of dibutyl tin laurate and triethylamine;
(4) ethylene glycol and dextrose anhydrous carry out being obtained by reacting thick glycol polyglucoside under the katalysis of phosphoric acid;
(5) isocyanic ester obtains white material after mixing with described thick glycol polyglucoside;
(6) described white material and described black material are under agitation mixed to get mixture, namely this mixture obtains described polyurethane foam through foaming.
In above-mentioned preparation method, in step (1), the particle diameter of described corn cob meal can be 20 order ~ 80 orders, specifically can be 20 order ~ 50 orders, 20 orders, 50 orders or 80 orders; The mass percentage of described dilute sulphuric acid can be 1.2 ~ 1.5%, specifically can be 1.2% ~ 1.4%, 1.25% ~ 1.4%, 1.2%, 1.25%, 1.4% or 1.5%;
In described hydrolysis reaction, the ratio of quality and the number of copies of described corn cob meal and dilute sulphuric acid can be 1:(8 ~ 12), specifically can be 1:(8 ~ 11), 1:(9 ~ 10), 1:(11 ~ 12), 1:8,1:9,1:10,1:11 or 1:12, the temperature of described hydrolysis reaction can be 110 ~ 130 DEG C, specifically can be 110 ~ 121 DEG C, 110 DEG C, 121 DEG C or 130 DEG C, time can be 1.5 ~ 2 hours, specifically can be 1.5 ~ 1.8 hours, 1.5 hours, 1.8 hours or 2 hours;
In described enzyme digestion reaction, the pH value of described citrate buffer solution can be 4.5 ~ 5.5, as 5.0, the temperature of described enzyme digestion reaction can be 48 ~ 52 DEG C, as 48 ~ 51 DEG C, 49 ~ 52 DEG C, 48 DEG C, 49 DEG C, 51 DEG C or 52 DEG C, the time can be 22 ~ 24 hours, specifically can be 22 hours, 23 hours or 24 hours;
The consumption of described cellulase can be corn cob meal described in 750 ~ 850U/g, as 750 ~ 800U/g, 750U/g, 800U/g or 850U/g.
In above-mentioned preparation method, in step (2), in described liquefying agent, the ratio of quality and the number of copies of described poly(oxyethylene glycol) 400 and glycerol can be (3.5 ~ 4.6): 1, specifically can be (3.5 ~ 4.3): 1, (3.8 ~ 4.0): 1,3.5:1,3.8:1,4.0:1,4.3:1 or 4.6:1; The temperature of described liquefaction processing can be 130 ~ 160 DEG C, specifically can be 130 ~ 150 DEG C, 145 ~ 160 DEG C, 130 DEG C, 145 DEG C, 150 DEG C or 160 DEG C, time can be 120 ~ 150min, specifically can be 120 ~ 140min, 135 ~ 150min, 120min, 135min, 140min or 150min.
In above-mentioned preparation method, in step (2), the mass percentage of the described vitriol oil can be 97 ~ 98%, and the add-on of the described vitriol oil is 3 ~ 4% of the mixture quality of poly(oxyethylene glycol) 400 and glycerol, specifically can be 3% ~ 3.5%, 3%, 3.5% or 4%.
Describedly can be 1:(0.3 ~ 1 through the corn cob residue of enzymolysis and the ratio of quality and the number of copies of corn cob meal), specifically can be 1:(0.3 ~ 0.8), 1:(0.3 ~ 0.5), 1:(0.5 ~ 0.8), 1:0.3,1:0.5,1:0.8 or 1:1.
In above-mentioned preparation method, in step (3), the ratio of quality and the number of copies of described liquefied product, stablizer and catalyzer can be 1:(0.04 ~ 0.06): (0.05 ~ 0.09), specifically can be 1:0.04:0.05,1:0.05:0.07 or 1:0.06:0.09;
In described catalyzer, the ratio of quality and the number of copies of dibutyl tin laurate and triethylamine can be (4 ~ 6): (1 ~ 3), specifically can be 1:0.4,4:1,4:3,6:1 or 2:1.
In above-mentioned preparation method, in step (4), described ethylene glycol can be (3 ~ 5) with the molfraction ratio of dextrose anhydrous: 1, specifically can be 3:1,4:1 or 5:1; The consumption of described phosphoric acid can be 1.3 ~ 1.7% of the quality of described dextrose anhydrous, specifically can be 1.3 ~ 1.6%, 1.3 ~ 1.5%, 1.4 ~ 1.7%, 1.3%, 1.4%, 1.5%, 1.6% or 1.7%.
In above-mentioned preparation method, in step (4), the temperature of described reaction can be 120 ~ 130 DEG C, specifically can be 120 DEG C or 130 DEG C, pressure can be 5000 ~ 6000Pa, specifically can be 5000Pa or 6000Pa, the time can be 1.2 ~ 1.5 hours, specifically can be 1.2 ~ 1.3 hours, 1.25 ~ 1.5 hours, 1.2 hours, 1.25 hours, 1.3 hours or 1.5 hours.
In above-mentioned preparation method, in step (5), described isocyanic ester is polyphenyl polymethylene polyisocyanates; The ratio of quality and the number of copies of described isocyanic ester and thick glycol polyglucoside can be (5 ~ 25): 1, specifically can be (6 ~ 24): 1, (10 ~ 14): 1, (6 ~ 12): 1,6:1,10:1,12:1,14:1 or 24:1.
In above-mentioned preparation method, in step (6), the ratio of quality and the number of copies of described thick glycol polyglucoside and described liquefied product can be (0.05 ~ 0.2): 1, specifically can be (0.05 ~ 0.1): 1,0.05:1,0.1:1 or 0.2:1.
In above-mentioned preparation method, in step (6), described mixture stirs 7 ~ 12 seconds under the rotating speed of 1100 ~ 1300 revs/min.
Preparation method provided by the invention utilizes the corn cob meal crossed through cellulase degradation to prepare polyurethane foamed material, and adds thick glycol polyglucoside.The product of agricultural crop straw liquefaction preparation is directly all greatly improved in the mechanical property of material, color and luster and apparent properties than in having been reported by the product prepared of method of the present invention.Method also provides for a kind of new approaches of Appropriate application agricultural waste material, namely utilize a large amount of enzymolysis residues produced in industrial production energy ethanol (being that dhdps enzyme hydrolysis and fermentation obtains with maize straw) process to prepare polyurethane foamed material.The rough glycol polyglucoside added in present method also can obtain by preparing in industry the assorted sugared waste liquid produced in wood sugar (with agricultural waste material hydrolyzed solution for raw material obtains through ion-exchange post crystallization) process.And have been reported the middle difference utilizing maize straw to prepare polyurethane material and be, the thinking that present method provides is emphasized that combination technology is ripe and has also been applied to industrial agricultural waste material Application way (i.e. manufacture ethanol and crystalline xylose), has more practical significance and feasibility.
Accompanying drawing explanation
Fig. 1 is the schema of preparation polyurethane foam method provided by the invention.
Embodiment
The experimental technique used in following embodiment if no special instructions, is ordinary method.
Material used in following embodiment, reagent etc., if no special instructions, all can obtain from commercial channels.
In following each embodiment, the Young's modulus of gained polyurethane foamed material measures according to GB/T8813-2008/ISO844:2004; Density measures according to GB/T6343-1995.
Thermal conductivity measures in accordance with the following steps: prepare the rectangular parallelepiped style that wide about 10mm, high about 10mm and length are greater than 60mm, measure with KD2 Thermal characteristic analysis instrument.
Embodiment 1,
The present invention prepares the schema of polyurethane foam as shown in Figure 1.
(1) corn cob meal (20 order) after pulverizing is mixed in the dilution heat of sulfuric acid that ratio and the mass percentage of solid-to-liquid ratio (mass parts) 1:10 are 1.25% in triangular flask, in pressure kettle, be warming up to 121 DEG C, be hydrolyzed 2 hours.Residue is extremely neutral by hot water wash, and adding pH after filter residue and drying to constant weight is in the citrate buffer solution of 5.0, adds cellulase, enzymolysis 24h at 50 DEG C according to 800U/g corn cob meal.Suction filtration through the corn cob residue of enzymolysis, must be dried to constant weight.
(2) glycerol of the poly(oxyethylene glycol) 400 and 40 weight parts of getting 160 weight parts puts into the there-necked flask with stirring, condensing reflux and temperature control unit, then there-necked flask is put into the oil bath pan of 160 DEG C, adds the vitriol oil 7 weight part that concentration is 97%.When after oil bath pan temperature-stable, add corn cob residue 25 weight part of the enzymolysis that corn cob meal 25 weight part after crushed and step (1) obtain, liquefaction 120min obtains liquefied product, uses flowing cool water cooling termination reaction.
(3) get liquefied product 20.00 weight part, silicone oil 1.00 weight part, dibutyl tin laurate 1.00 weight part and triethylamine 0.40 weight part and be placed in Disposable paper cup, with 1250 revs/min of high-speed stirring 25s, make black material.
(4) add reaction raw materials (mol ratio is ethylene glycol and the dextrose anhydrous of 4:1) raised temperature to 80 DEG C afterwards, be stirred to the transparent state of solution.Controlling temperature of reaction is 130 DEG C, and reaction pressure is 5000Pa, adds catalyzer phosphoric acid, and consumption is 1.5% of dextrose anhydrous, reacts 1.25 hours, utilizes Fehlin reagent to detect, until glucose complete reaction.Wait to cool to 90 DEG C, adding saturated aqueous sodium hydroxide solution, to be neutralized to pH be 8, obtains transparent amber thick liquid and be thick glycol polyglucoside.
(5) get PAPI24 weight part and thick glycol polyglucoside 1 weight part in Disposable paper cup, with 1150 revs/min of high-speed stirring 7s, make white material.
(6) by black material and expecting with 1200 revs/min of high-speed mixing 10s in vain, wherein, the ratio of quality and the number of copies controlling thick glycol polyglucoside and liquefied product is 0.05:1, and under room temperature condition, under the gland of 474 parts by weight of glass plates, namely foaming obtains polyurethane foamed material.
The performance perameter of the polyurethane foamed material that the present embodiment is made is: Young's modulus is 6552.67Kpa, and density is 233.15Kg/m
3, thermal conductivity is 0.054wm
-1dEG C
-1.
Embodiment 2,
The present invention prepares the schema of polyurethane foam as shown in Figure 1.
(1) corn cob meal (80 order) after pulverizing is mixed in the dilution heat of sulfuric acid that ratio and the mass percentage of solid-to-liquid ratio (mass parts) 1:8 are 1.2% in triangular flask, in pressure kettle, be warming up to 110 DEG C, be hydrolyzed 1.5 hours.Residue is extremely neutral by hot water wash, and adding pH after filter residue and drying to constant weight is in the citrate buffer solution of 5.0, adds cellulase, enzymolysis 22h at 48 DEG C according to 750U/g corn cob meal.Suction filtration through the corn cob residue of enzymolysis, must be dried to constant weight.
(2) glycerol of the poly(oxyethylene glycol) 400 and 44 weight parts of getting 156 weight parts puts into the there-necked flask with stirring, condensing reflux and temperature control unit, then there-necked flask is put into the oil bath pan of 130 DEG C, adds the vitriol oil 6 weight part that concentration is 98%.When after oil bath pan temperature-stable, add corn cob residue 37.5 weight part of the enzymolysis that corn cob meal 12.5 weight part after crushed and step (1) obtain, liquefaction 150min obtains liquefied product, uses flowing cool water cooling termination reaction.
(3) get liquefied product 20 weight part, silicone oil 0.8 weight part, dibutyl tin laurate 0.8 weight part and triethylamine 0.2 weight part and be placed in Disposable paper cup, with 1250 revs/min of high-speed stirring 25s, make black material.
(4) add reaction raw materials (mol ratio is ethylene glycol and the dextrose anhydrous of 3:1) raised temperature to 80 DEG C afterwards, be stirred to the transparent state of solution.Controlling temperature of reaction is 120 DEG C, and reaction pressure is 6000Pa, adds catalyzer phosphoric acid, and consumption is 1.3% of dextrose anhydrous, reacts 1.2 hours, utilizes Fehlin reagent to detect, until glucose complete reaction.Wait to cool to 90 DEG C, adding saturated aqueous sodium hydroxide solution, to be neutralized to pH be 8, obtains transparent amber thick liquid and be thick glycol polyglucoside.
(5) get PAPI28 weight part and thick glycol polyglucoside 2 weight part in Disposable paper cup, with 1300 revs/min of high-speed stirring 5s, make white material.
(6) by black material and expecting with 1300 revs/min of high-speed mixing 7s in vain, wherein, the ratio of quality and the number of copies controlling thick glycol polyglucoside and liquefied product is 0.1:1, and under room temperature condition, under the gland of 474 parts by weight of glass plates, namely foaming obtains polyurethane foamed material.
The performance perameter of the polyurethane foamed material that the present embodiment is made is: Young's modulus is 8414.5Kpa, and density is 214.54Kg/m
3, thermal conductivity is 0.048wm
-1dEG C
-1.
Embodiment 3,
The present invention prepares the schema of polyurethane foam as shown in Figure 1.
(1) corn cob meal (80 order) after pulverizing is mixed in the dilution heat of sulfuric acid that ratio and the mass percentage of solid-to-liquid ratio (mass parts) 1:9 are 1.5% in triangular flask, in pressure kettle, be warming up to 130 DEG C, be hydrolyzed 1.8 hours.Residue is extremely neutral by hot water wash, and adding pH after filter residue and drying to constant weight is in the citrate buffer solution of 5.0, adds cellulase, enzymolysis 23h at 49 DEG C according to 850U/g corn cob meal.Suction filtration through the corn cob residue of enzymolysis, must be dried to constant weight.
(2) glycerol of the poly(oxyethylene glycol) 400 and 42 weight parts of getting 158 weight parts puts into the there-necked flask with stirring, condensing reflux and temperature control unit, then there-necked flask is put into the oil bath pan of 145 DEG C, adds the vitriol oil 8 weight part that concentration is 97%.When after oil bath pan temperature-stable, add corn cob residue 33 weight part of the enzymolysis that corn cob meal 17 weight part after crushed and step (1) obtain, liquefaction 140min obtains liquefied product, uses flowing cool water cooling termination reaction.
(3) get liquefied product 20.00 weight part, silicone oil 1.00 weight part, dibutyl tin laurate 0.80 weight part and triethylamine 0.60 weight part and be placed in Disposable paper cup, with 1150 revs/min of high-speed stirring 40s, make black material.
(4) add reaction raw materials (mol ratio is ethylene glycol and the dextrose anhydrous of 4:1) raised temperature to 80 DEG C afterwards, be stirred to the transparent state of solution.Controlling temperature of reaction is 120 DEG C, and reaction pressure is 6000Pa, adds catalyzer phosphoric acid, and consumption is 1.4% of dextrose anhydrous, reacts 1.5 hours, utilizes Fehlin reagent to detect, until glucose complete reaction.Wait to cool to 90 DEG C, adding saturated aqueous sodium hydroxide solution, to be neutralized to pH be 8, obtains transparent amber thick liquid and be thick glycol polyglucoside.
(5) get PAPI24 weight part and thick glycol polyglucoside 2 weight part in Disposable paper cup, with 1150 revs/min of high-speed stirring 9s, make white material.
(6) by black material and expecting with 1250 revs/min of high-speed mixing 9s in vain, wherein, the ratio of quality and the number of copies controlling thick glycol polyglucoside and liquefied product is 0.1:1, and under room temperature condition, under the gland of 484 parts by weight of glass plates, namely foaming obtains polyurethane foamed material.
The performance perameter of the polyurethane foamed material that the present embodiment is made is: Young's modulus is 9179.63Kpa, and density is 299.81Kg/m
3, thermal conductivity is 0.061wm
-1dEG C
-1.
Embodiment 4,
The present invention prepares the schema of polyurethane foam as shown in Figure 1.
(1) corn cob meal (50 order) after pulverizing is mixed in the dilution heat of sulfuric acid that ratio and the mass percentage of solid-to-liquid ratio (mass parts) 1:11 are 1.4% in triangular flask, in pressure kettle, be warming up to 110 DEG C, be hydrolyzed 2 hours.Residue is extremely neutral by hot water wash, and adding pH after filter residue and drying to constant weight is in the citrate buffer solution of 5.0, adds cellulase, enzymolysis 22h at 51 DEG C according to 800U/g corn cob meal.Suction filtration through the corn cob residue of enzymolysis, must be dried to constant weight.
(2) glycerol of the poly(oxyethylene glycol) 400 and 38 weight parts of getting 162 weight parts puts into the there-necked flask with stirring, condensing reflux and temperature control unit, then there-necked flask is put into the oil bath pan of 150 DEG C, adds the vitriol oil 7 weight part that concentration is 97%.When after oil bath pan temperature-stable, add corn cob residue 28 weight part of the enzymolysis that corn cob meal 22 weight part after crushed and step (1) obtain, liquefaction 135min obtains liquefied product, uses flowing cool water cooling termination reaction.
(3) get liquefied product 20.00 weight part, silicone oil 1.00 weight part, dibutyl tin laurate 1.20 weight part and triethylamine 0.20 weight part and be placed in Disposable paper cup, with 1200 revs/min of high-speed stirring 30s, make black material.
(4) add reaction raw materials (mol ratio is ethylene glycol and the dextrose anhydrous of 4:1) raised temperature to 80 DEG C afterwards, be stirred to the transparent state of solution.Controlling temperature of reaction is 120 DEG C, and reaction pressure is 6000Pa, adds catalyzer phosphoric acid, and consumption is 1.6% of dextrose anhydrous, reacts 1.3 hours, utilizes Fehlin reagent to detect, until glucose complete reaction.Wait to cool to 90 DEG C, adding saturated aqueous sodium hydroxide solution, to be neutralized to pH be 8, obtains transparent amber thick liquid and be thick glycol polyglucoside.
(5) get PAPI24 weight part and thick glycol polyglucoside 4 weight part in Disposable paper cup, with 1200 revs/min of high-speed stirring 10s, make white material.
(6) by black material and expecting with 1300 revs/min of high-speed mixing 8s in vain, wherein, the ratio of quality and the number of copies controlling thick glycol polyglucoside and liquefied product is 0.2:1, and under room temperature condition, under the gland of 504 parts by weight of glass plates, namely foaming obtains polyurethane foamed material.
The performance perameter of the polyurethane foamed material that the present embodiment is made is: Young's modulus is 5525.52Kpa, and density is 300.77Kg/m
3, thermal conductivity is 0.064wm
-1dEG C
-1.
Embodiment 5,
The present invention prepares the schema of polyurethane foam as shown in Figure 1.
(1) corn cob meal (80 order) after pulverizing is mixed in the dilution heat of sulfuric acid that ratio and the mass percentage of solid-to-liquid ratio (mass parts) 1:12 are 1.5% in triangular flask, in pressure kettle, be warming up to 130 DEG C, be hydrolyzed 2 hours.Residue is extremely neutral by hot water wash, and adding pH after filter residue and drying to constant weight is in the citrate buffer solution of 5.0, adds cellulase, enzymolysis 24h at 52 DEG C according to 850U/g corn cob meal.Suction filtration through the corn cob residue of enzymolysis, must be dried to constant weight.
(2) glycerol of the poly(oxyethylene glycol) 400 and 36 weight parts of getting 164 weight parts puts into the there-necked flask with stirring, condensing reflux and temperature control unit, then there-necked flask is put into the oil bath pan of 160 DEG C, adds the vitriol oil 8 weight part that concentration is 98%.When after oil bath pan temperature-stable, add corn cob residue 25 weight part of the enzymolysis that corn cob meal 25 weight part after crushed and step (1) obtain, liquefaction 150min obtains liquefied product, uses flowing cool water cooling termination reaction.
(3) get liquefied product 20 weight part, silicone oil 1.2 weight part, dibutyl tin laurate 1.2 weight part and triethylamine 0.6 weight part and be placed in Disposable paper cup, with 1300 revs/min of high-speed stirring 15s, make black material.
(4) add reaction raw materials (mol ratio is ethylene glycol and the dextrose anhydrous of 5:1) raised temperature to 80 DEG C afterwards, be stirred to the transparent state of solution.Controlling temperature of reaction is 120 DEG C, and reaction pressure is 6000Pa, adds catalyzer phosphoric acid, and consumption is 1.7% of dextrose anhydrous, reacts 1.5 hours, utilizes Fehlin reagent to detect, until glucose complete reaction.Wait to cool to 90 DEG C, adding saturated aqueous sodium hydroxide solution, to be neutralized to pH be 8, obtains transparent amber thick liquid and be thick glycol polyglucoside.
(5) get PAPI20 weight part and thick glycol polyglucoside 2 weight part in Disposable paper cup, with 1100 revs/min of high-speed stirring 15s, make white material.
(6) by black material and expecting with 1100 revs/min of high-speed mixing 12s in vain, wherein, the ratio of quality and the number of copies controlling thick glycol polyglucoside and liquefied product is 0.1:1, and under room temperature condition, under the gland of 444 parts by weight of glass plates, namely foaming obtains polyurethane foamed material.
The performance perameter of the polyurethane foamed material that the present embodiment is made is: Young's modulus is 4448.54Kpa, and density is 282.33Kg/m
3, thermal conductivity is 0.061wm
-1dEG C
-1.
Claims (11)
1. a preparation method for polyurethane foam, comprises the steps:
(1) corn cob meal is hydrolyzed reaction under the effect of dilute sulphuric acid; In citrate buffer solution, the filter residue after described hydrolysis reaction carries out enzyme digestion reaction under the effect of cellulase, and suction filtration must through the corn cob residue of enzymolysis;
(2) describedly under the effect at liquefying agent and the vitriol oil of the corn cob residue of enzymolysis and the mixture of corn cob meal, liquefied product is obtained through liquefaction processing; Described liquefying agent is the mixture of poly(oxyethylene glycol) 400 and glycerol;
(3) black material is obtained after described liquefied product and stablizer and catalyst mix; Described stablizer is silicone oil, and described catalyzer is the mixture of dibutyl tin laurate and triethylamine;
(4) ethylene glycol and dextrose anhydrous carry out being obtained by reacting thick glycol polyglucoside under the katalysis of phosphoric acid;
(5) isocyanic ester obtains white material after mixing with described thick glycol polyglucoside;
(6) described white material and described black material are under agitation mixed to get mixture, namely this mixture obtains described polyurethane foam through foaming.
2. method according to claim 1, is characterized in that: described stablizer is polydimethylsiloxane.
3. method according to claim 1, is characterized in that: in step (1), and the particle diameter of described corn cob meal is 20 order ~ 80 orders; The mass percentage of described dilute sulphuric acid is 1.2 ~ 1.5%;
In described hydrolysis reaction, the ratio of quality and the number of copies of described corn cob meal and dilute sulphuric acid is 1:(8 ~ 12), the temperature of described hydrolysis reaction is 110 ~ 130 DEG C, and the time is 1.5 ~ 2 hours;
In described enzyme digestion reaction, the pH value of described citrate buffer solution is 4.5 ~ 5.5, and the temperature of described enzyme digestion reaction is 48 ~ 52 DEG C, and the time is 22 ~ 24 hours;
The consumption of described cellulase is corn cob meal described in 750 ~ 850U/g.
4. method according to claim 1 and 2, is characterized in that: in step (2), in described liquefying agent, and the ratio of quality and the number of copies of described poly(oxyethylene glycol) 400 and glycerol is (3.5 ~ 4.6): 1; The temperature of described liquefaction processing is 130 ~ 160 DEG C, and the time is 120 ~ 150min.
5. the method according to any one of claim 1-3, it is characterized in that: in step (2), the mass percentage of the described vitriol oil is 97 ~ 98%, and the add-on of the described vitriol oil is 3 ~ 4% of poly(oxyethylene glycol) 400 and glycerol mixture quality;
Described through the corn cob residue of enzymolysis and the ratio of quality and the number of copies of described corn cob meal be 1:(0.3 ~ 1).
6. the method according to any one of claim 1-3, is characterized in that: in step (3), and the ratio of quality and the number of copies of described liquefied product, stablizer and catalyzer is 1:(0.04 ~ 0.06): (0.05 ~ 0.09);
In described catalyzer, the ratio of quality and the number of copies of dibutyl tin laurate and triethylamine is (0.04 ~ 0.06): (0.01 ~ 0.03).
7. the method according to any one of claim 1-3, is characterized in that: in step (4), and described ethylene glycol is (3 ~ 5) with the molfraction ratio of dextrose anhydrous: 1; The consumption of described phosphoric acid is 1.3 ~ 1.7% of the quality of described dextrose anhydrous.
8. the method according to any one of claim 1-3, is characterized in that: in step (4), and the temperature of described reaction is 120 ~ 130 DEG C, and pressure is 5000 ~ 6000Pa, and the time is 1.2 ~ 1.5 hours.
9. the method according to any one of claim 1-3, is characterized in that: in step (5), and described isocyanic ester is polyphenyl polymethylene polyisocyanates; The ratio of quality and the number of copies of described isocyanic ester and thick glycol polyglucoside is (5 ~ 25): 1.
10. the method according to any one of claim 1-3, is characterized in that: in step (6), and the ratio of quality and the number of copies of described thick glycol polyglucoside and described liquefied product is (0.05 ~ 0.2): 1.
11. methods according to any one of claim 1-3, it is characterized in that: in step (6), described mixture stirs 7 ~ 12 seconds under the rotating speed of 1100 ~ 1300 revs/min.
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| CN105238020A (en) * | 2015-09-18 | 2016-01-13 | 滁州市莎朗新材料科技有限公司 | Antibiotic and flame-retardant plant type soft polyurethane foam for seamless wallpaper, and preparation method thereof |
| CN105238018A (en) * | 2015-09-18 | 2016-01-13 | 滁州市莎朗新材料科技有限公司 | Plant type soft polyurethane foam for environmentally-friendly seamless wallpaper, and preparation method thereof |
| CN107602789A (en) * | 2017-09-29 | 2018-01-19 | 鹤山市杰之星五金实业有限公司 | A kind of plant polyatomic alcohol and its soft polyurethane foam containing plant polyatomic alcohol |
| CN109439711A (en) * | 2018-11-13 | 2019-03-08 | 东北林业大学 | A kind of polyurethane foam immobilized cellulase enzymatic geniposide conversion technique |
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| CN101643513A (en) * | 2009-08-28 | 2010-02-10 | 华南理工大学 | Plant-fiber-base polyether ester polylol, and preparation method and applications 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 |
| CN102504164A (en) * | 2011-11-22 | 2012-06-20 | 中国农业大学 | Manufacture method of enhanced corncob base polyurethane foam materials |
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| CN101643513A (en) * | 2009-08-28 | 2010-02-10 | 华南理工大学 | Plant-fiber-base polyether ester polylol, and preparation method and applications 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 |
| CN102504164A (en) * | 2011-11-22 | 2012-06-20 | 中国农业大学 | Manufacture method of enhanced corncob base polyurethane foam materials |
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