CN103833949A - Preparation method of polyurethane foam - Google Patents
Preparation method of polyurethane foam Download PDFInfo
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- CN103833949A CN103833949A CN201210488345.7A CN201210488345A CN103833949A CN 103833949 A CN103833949 A CN 103833949A CN 201210488345 A CN201210488345 A CN 201210488345A CN 103833949 A CN103833949 A CN 103833949A
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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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- 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 preparation method of polyurethane foam. The preparation method comprises the following steps: (1) carrying out hydrolysis reaction on corncob powder under the action of dilute sulphuric acid, carrying out enzymatic hydrolysis on hydrolyzed filter residue in a citric acid buffer liquid under the action of cellulose, and carrying out suction filtration to obtain corncob residues after being subjected to enzymatic hydrolysis; (2) carrying out liquidation on the mixture of the corncob residues and the corncob powder under the action of a liquefier and concentrated sulfuric acid so as to obtain a liquidated product; (3) mixing the liquidated product with a stabilizer and a catalyst to obtain a black material; (4) reacting glycol with anhydrous dextrose under a catalytic action of phosphoric acid to obtain rough glycol glucoside; (5) mixing isocyanate with the rough glycol glucoside to obtain a white material; (6) mixing the white material with the black material while stirring to obtain the mixture, and carrying out foaming forming on the mixture to obtain polyurethane foam. According to a concept provided by the method, a crop waste utilization method which is mature in technique and is applied to the industrial production (namely the production of industrial alcohol and crystallized xylose) is emphasized to be combined, and the method has practical significance and feasibility.
Description
Technical field
The present invention relates to a kind of preparation method of polyurethane foam, be specifically related to a kind of method of preparing polyurethane foam take corn cob as raw material.
Background technology
Polyurethane material is one of kind with fastest developing speed in modern plastics industry, and by binary or polynary organic isocyanate and binary or polyol compound, i.e. polyether glycol or polyester polyol reaction makes.Because the raw material sources of polyol compound are oil, therefore polyurethane industrial has very strong dependency for oil.Oil has affected 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 that is rich in hydroxyl, studies have shown that, these compounds can replace polyethers or polyester polyol and isocyanic ester generation nucleophilic addition to prepare polyurethane material.Select aborning corn cob not only can improve the utilization ratio of resource as the raw material of polyol compound, and make polyurethane industrial reduce the 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 residues after enzymolysis, if using these residues as producing starting material, use in the preparation of polyurethane foam, will further improve the utilization ratio of resource, reduce production costs, save energy.
Be rich in the agricultural and sideline waste corn cob of hemicellulose by dilute acid hydrolysis, can obtain the hydrolyzed solution take wood sugar as leading and 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 make crystalline xylose.Isolate in the mother liquor after crystal wood sugar and contain a large amount of glucose, can carry out glycosyl shift reaction with alcohols and prepare thick ethylene glycol glucoside.Experimental results show that in synthesis of polyurethane foam materials process and add the adjustable speed of response of ethylene glycol glucoside, make material have the abundant time to mix, speed of response is even, foam stabilization, and compact structure, is difficult for producing space.Experiment showed, that rough ethylene glycol glucoside is owing to being liquid, than the solid-state more convenient use of pure ethylene glycol glucoside simultaneously.If utilize the discarded assorted sugared hydrolyzed solution producing in xylose production process to prepare thick ethylene glycol glucoside, as auxiliary agent add to plant polyatomic alcohol be in the polyurethane foam prepared of raw material, will in the situation that cost increase is very little, improve urethane performance.
Summary of the invention
The object of this invention is to provide a kind of preparation method of polyurethane foam, being specially the corn cob powder that a kind of utilization crosses through cellulase degradation is raw material, add rough ethylene glycol glucoside and prepare the method for polyurethane foam, provide a kind of and utilize two kinds of industrial produced wastes to prepare the technical scheme of polyurethane foamed material for a kind of simultaneously.
The preparation method of a kind of polyurethane foam provided by the present invention, comprises the steps:
(1) the corn cob meal reaction that is hydrolyzed 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 be through the corn cob residue of enzymolysis;
(2) describedly under the effect of liquefying agent and the vitriol oil, obtain liquefied product through liquefaction processing through the corn cob residue of enzymolysis and the mixture of corn cob meal; Described liquefying agent is the mixture of poly(oxyethylene glycol) 400 and glycerol;
(3) after described liquefied product and stablizer and catalyst mix, obtain black material; 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 react and obtain thick ethylene glycol glucoside under the katalysis of phosphoric acid;
(5) isocyanic ester obtains white material after mixing with described thick ethylene glycol glucoside;
(6) described white material and described black material are under agitation mixed to get to mixture, 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 quality percentage composition 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 ℃, specifically can be 110 ~ 121 ℃, 110 ℃, 121 ℃ or 130 ℃, 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 ℃, as 48 ~ 51 ℃, 49 ~ 52 ℃, 48 ℃, 49 ℃, 51 ℃ or 52 ℃, 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 ℃, specifically can be 130～150 ℃, 145～160 ℃, 130 ℃, 145 ℃, 150 ℃ or 160 ℃, 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 quality percentage composition of the described vitriol oil can be 97～98%, the add-on of the described vitriol oil be poly(oxyethylene glycol) 400 and glycerol mixture quality 3 ~ 4%, specifically can be 3% ~ 3.5%, 3%, 3.5% or 4%.
The described corn cob residue through enzymolysis and the ratio of quality and the number of copies of corn cob meal can be 1:(0.3 ~ 1), 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 described dextrose anhydrous quality 1.3 ~ 1.7%, 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 ℃, specifically can be 120 ℃ or 130 ℃, 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; Described isocyanic ester can be (5 ~ 25) with the ratio of quality and the number of copies of thick ethylene glycol glucoside: 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 ethylene glycol glucoside 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.
The corn cob meal that preparation method's utilization provided by the invention is crossed through cellulase degradation is prepared polyurethane foamed material, and adds thick ethylene glycol glucoside.Product prepared by method of the present invention is than directly the product of agricultural crop straw liquefaction preparation being all greatly improved in mechanical property, color and luster and the apparent properties of material in having been reported.Present method also provides a kind of new approaches of rationally utilizing agricultural waste material, utilizes a large amount of enzymolysis residues that produce in industrial production energy ethanol (making take maize straw as dhdps enzyme hydrolysis and fermentation) process to prepare polyurethane foamed material.The rough ethylene glycol glucoside adding in present method also can make by preparing the assorted sugared waste liquid producing in wood sugar (making through ion-exchange post crystallization take agricultural waste material hydrolyzed solution as raw material) process in industry.And have been reported the middle difference that utilizes maize straw to prepare polyurethane material and be, the thinking that present method provides is emphasized combination technology maturation and has applied to industrial agricultural waste material to utilize method (being 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 using in following embodiment if no special instructions, is ordinary method.
Material, reagent etc. used in following embodiment, if no special instructions, all can obtain from commercial channels.
In following each embodiment, the Young's modulus of gained polyurethane foamed material is measured according to GB/T8813-2008/ISO844:2004; Density is measured according to GB/T6343-1995.
Thermal conductivity is measured in accordance with the following steps: prepare the rectangular parallelepiped style that wide about 10mm, high about 10mm and length are greater than 60mm, by KD2 Thermal characteristic analysis instrument mensuration.
Embodiment 1,
The schema that the present invention prepares polyurethane foam as shown in Figure 1.
(1) dilution heat of sulfuric acid that is 1.25% in the ratio of solid-to-liquid ratio (mass parts) 1:10 with quality percentage composition by the corn cob meal (20 order) after pulverizing mixes in triangular flask, is warming up to 121 ℃ in pressure kettle, is hydrolyzed 2 hours.By hot water wash for residue, to neutral, filter residue and drying is in 5.0 citrate buffer solution to adding pH after constant weight, adds cellulase, enzymolysis 24h at 50 ℃ according to 800U/g corn cob meal.Suction filtration must, through the corn cob residue of enzymolysis, be dried to constant weight.
(2) get the poly(oxyethylene glycol) 400 of 160 weight parts and the glycerol of 40 weight parts put into there is stirring, the there-necked flask of condensing reflux and temperature control unit, then there-necked flask is put into the oil bath pan of 160 ℃, adding concentration is 97% the vitriol oil 7 weight parts.When after oil bath pan temperature-stable, add corn cob residue 25 weight parts of the enzymolysis that corn cob meal 25 weight parts after crushed and step (1) obtain, liquefaction 120min obtains liquefied product, uses the cooling termination reaction of flowing cool water.
(3) get liquefied product 20.00 weight parts, silicone oil 1.00 weight parts, dibutyl tin laurate 1.00 weight parts 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 the rear rising temperature to 80 ℃ of reaction raw materials (ethylene glycol that mol ratio is 4:1 and dextrose anhydrous), be stirred to solution and be vitreous state.Controlling temperature of reaction is 130 ℃, and reaction pressure is 5000Pa, adds catalyzer phosphoric acid, and consumption is dextrose anhydrous 1.5%, react 1.25 hours, utilizes the detection of Fehlin reagent, until glucose complete reaction.Wait to cool to 90 ℃, adding saturated aqueous sodium hydroxide solution to be neutralized to pH is 8, obtains transparent amber thick liquid and is thick ethylene glycol glucoside.
(5) get PAPI 24 weight parts and thick ethylene glycol glucoside 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 of controlling thick ethylene glycol glucoside and liquefied product is 0.05:1, and under room temperature condition, under the gland of 474 weight part sheet glass, 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
-1℃
-1.
Embodiment 2,
The schema that the present invention prepares polyurethane foam as shown in Figure 1.
(1) dilution heat of sulfuric acid that is 1.2% in the ratio of solid-to-liquid ratio (mass parts) 1:8 with quality percentage composition by the corn cob meal (80 order) after pulverizing mixes in triangular flask, is warming up to 110 ℃ in pressure kettle, is hydrolyzed 1.5 hours.By hot water wash for residue, to neutral, filter residue and drying is in 5.0 citrate buffer solution to adding pH after constant weight, adds cellulase, enzymolysis 22h at 48 ℃ according to 750U/g corn cob meal.Suction filtration must, through the corn cob residue of enzymolysis, be dried to constant weight.
(2) get the poly(oxyethylene glycol) 400 of 156 weight parts and the glycerol of 44 weight parts put into there is stirring, the there-necked flask of condensing reflux and temperature control unit, then there-necked flask is put into the oil bath pan of 130 ℃, adding concentration is 98% the vitriol oil 6 weight parts.When after oil bath pan temperature-stable, add corn cob residue 37.5 weight parts of the enzymolysis that corn cob meal 12.5 weight parts after crushed and step (1) obtain, liquefaction 150min obtains liquefied product, uses the cooling termination reaction of flowing cool water.
(3) get liquefied product 20 weight parts, 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 the rear rising temperature to 80 ℃ of reaction raw materials (ethylene glycol that mol ratio is 3:1 and dextrose anhydrous), be stirred to solution and be vitreous state.Controlling temperature of reaction is 120 ℃, and reaction pressure is 6000Pa, adds catalyzer phosphoric acid, and consumption is dextrose anhydrous 1.3%, react 1.2 hours, utilizes the detection of Fehlin reagent, until glucose complete reaction.Wait to cool to 90 ℃, adding saturated aqueous sodium hydroxide solution to be neutralized to pH is 8, obtains transparent amber thick liquid and is thick ethylene glycol glucoside.
(5) get PAPI 28 weight parts and thick ethylene glycol glucoside 2 weight parts 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 of controlling thick ethylene glycol glucoside and liquefied product is 0.1:1, and under room temperature condition, under the gland of 474 weight part sheet glass, 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
-1℃
-1.
Embodiment 3,
The schema that the present invention prepares polyurethane foam as shown in Figure 1.
(1) dilution heat of sulfuric acid that is 1.5% in the ratio of solid-to-liquid ratio (mass parts) 1:9 with quality percentage composition by the corn cob meal (80 order) after pulverizing mixes in triangular flask, is warming up to 130 ℃ in pressure kettle, is hydrolyzed 1.8 hours.By hot water wash for residue, to neutral, filter residue and drying is in 5.0 citrate buffer solution to adding pH after constant weight, adds cellulase, enzymolysis 23h at 49 ℃ according to 850U/g corn cob meal.Suction filtration must, through the corn cob residue of enzymolysis, be dried to constant weight.
(2) get the poly(oxyethylene glycol) 400 of 158 weight parts and the glycerol of 42 weight parts put into there is stirring, the there-necked flask of condensing reflux and temperature control unit, then there-necked flask is put into the oil bath pan of 145 ℃, adding concentration is 97% the vitriol oil 8 weight parts.When after oil bath pan temperature-stable, add corn cob residue 33 weight parts of the enzymolysis that corn cob meal 17 weight parts after crushed and step (1) obtain, liquefaction 140min obtains liquefied product, uses the cooling termination reaction of flowing cool water.
(3) get liquefied product 20.00 weight parts, silicone oil 1.00 weight parts, 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 the rear rising temperature to 80 ℃ of reaction raw materials (ethylene glycol that mol ratio is 4:1 and dextrose anhydrous), be stirred to solution and be vitreous state.Controlling temperature of reaction is 120 ℃, and reaction pressure is 6000Pa, adds catalyzer phosphoric acid, and consumption is dextrose anhydrous 1.4%, react 1.5 hours, utilizes the detection of Fehlin reagent, until glucose complete reaction.Wait to cool to 90 ℃, adding saturated aqueous sodium hydroxide solution to be neutralized to pH is 8, obtains transparent amber thick liquid and is thick ethylene glycol glucoside.
(5) get PAPI 24 weight parts and thick ethylene glycol glucoside 2 weight parts 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 of controlling thick ethylene glycol glucoside and liquefied product is 0.1:1, and under room temperature condition, under the gland of 484 weight part sheet glass, 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
-1℃
-1.
Embodiment 4,
The schema that the present invention prepares polyurethane foam as shown in Figure 1.
(1) dilution heat of sulfuric acid that is 1.4% in the ratio of solid-to-liquid ratio (mass parts) 1:11 with quality percentage composition by the corn cob meal (50 order) after pulverizing mixes in triangular flask, is warming up to 110 ℃ in pressure kettle, is hydrolyzed 2 hours.By hot water wash for residue, to neutral, filter residue and drying is in 5.0 citrate buffer solution to adding pH after constant weight, adds cellulase, enzymolysis 22h at 51 ℃ according to 800U/g corn cob meal.Suction filtration must, through the corn cob residue of enzymolysis, be dried to constant weight.
(2) get the poly(oxyethylene glycol) 400 of 162 weight parts and the glycerol of 38 weight parts put into there is stirring, the there-necked flask of condensing reflux and temperature control unit, then there-necked flask is put into the oil bath pan of 150 ℃, adding concentration is 97% the vitriol oil 7 weight parts.When after oil bath pan temperature-stable, add corn cob residue 28 weight parts of the enzymolysis that corn cob meal 22 weight parts after crushed and step (1) obtain, liquefaction 135min obtains liquefied product, uses the cooling termination reaction of flowing cool water.
(3) get liquefied product 20.00 weight parts, silicone oil 1.00 weight parts, dibutyl tin laurate 1.20 weight parts 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 the rear rising temperature to 80 ℃ of reaction raw materials (ethylene glycol that mol ratio is 4:1 and dextrose anhydrous), be stirred to solution and be vitreous state.Controlling temperature of reaction is 120 ℃, and reaction pressure is 6000Pa, adds catalyzer phosphoric acid, and consumption is dextrose anhydrous 1.6%, react 1.3 hours, utilizes the detection of Fehlin reagent, until glucose complete reaction.Wait to cool to 90 ℃, adding saturated aqueous sodium hydroxide solution to be neutralized to pH is 8, obtains transparent amber thick liquid and is thick ethylene glycol glucoside.
(5) get PAPI 24 weight parts and thick ethylene glycol glucoside 4 weight parts 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 of controlling thick ethylene glycol glucoside and liquefied product is 0.2:1, and under room temperature condition, under the gland of 504 weight part sheet glass, 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
-1℃
-1.
Embodiment 5,
The schema that the present invention prepares polyurethane foam as shown in Figure 1.
(1) dilution heat of sulfuric acid that is 1.5% in the ratio of solid-to-liquid ratio (mass parts) 1:12 with quality percentage composition by the corn cob meal (80 order) after pulverizing mixes in triangular flask, is warming up to 130 ℃ in pressure kettle, is hydrolyzed 2 hours.By hot water wash for residue, to neutral, filter residue and drying is in 5.0 citrate buffer solution to adding pH after constant weight, adds cellulase, enzymolysis 24h at 52 ℃ according to 850U/g corn cob meal.Suction filtration must, through the corn cob residue of enzymolysis, be dried to constant weight.
(2) get the poly(oxyethylene glycol) 400 of 164 weight parts and the glycerol of 36 weight parts put into there is stirring, the there-necked flask of condensing reflux and temperature control unit, then there-necked flask is put into the oil bath pan of 160 ℃, adding concentration is 98% the vitriol oil 8 weight parts.When after oil bath pan temperature-stable, add corn cob residue 25 weight parts of the enzymolysis that corn cob meal 25 weight parts after crushed and step (1) obtain, liquefaction 150min obtains liquefied product, uses the cooling termination reaction of flowing cool water.
(3) get liquefied product 20 weight parts, silicone oil 1.2 weight parts, dibutyl tin laurate 1.2 weight parts 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 the rear rising temperature to 80 ℃ of reaction raw materials (ethylene glycol that mol ratio is 5:1 and dextrose anhydrous), be stirred to solution and be vitreous state.Controlling temperature of reaction is 120 ℃, and reaction pressure is 6000Pa, adds catalyzer phosphoric acid, and consumption is dextrose anhydrous 1.7%, react 1.5 hours, utilizes the detection of Fehlin reagent, until glucose complete reaction.Wait to cool to 90 ℃, adding saturated aqueous sodium hydroxide solution to be neutralized to pH is 8, obtains transparent amber thick liquid and is thick ethylene glycol glucoside.
(5) get PAPI 20 weight parts and thick ethylene glycol glucoside 2 weight parts 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 of controlling thick ethylene glycol glucoside and liquefied product is 0.1:1, and under room temperature condition, under the gland of 444 weight part sheet glass, 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
-1℃
-1.
Claims (10)
1. a preparation method for polyurethane foam, comprises the steps:
(1) the corn cob meal reaction that is hydrolyzed 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 be through the corn cob residue of enzymolysis;
(2) describedly under the effect of liquefying agent and the vitriol oil, obtain liquefied product through liquefaction processing through the corn cob residue of enzymolysis and the mixture of corn cob meal; Described liquefying agent is the mixture of poly(oxyethylene glycol) 400 and glycerol;
(3) after described liquefied product and stablizer and catalyst mix, obtain black material; 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 react and obtain thick ethylene glycol glucoside under the katalysis of phosphoric acid;
(5) isocyanic ester obtains white material after mixing with described thick ethylene glycol glucoside;
(6) described white material and described black material are under agitation mixed to get to mixture, this mixture obtains described polyurethane foam through foaming.
2. method according to claim 1, is characterized in that: in step (1), the particle diameter of described corn cob meal is 20 order ~ 80 orders; The quality percentage composition 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 ℃, 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 ℃, and the time is 22 ~ 24 hours;
The consumption of described cellulase is corn cob meal described in 750 ~ 850U/g.
3. method according to claim 1 and 2, is characterized in that: in step (2), in described liquefying agent, 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 ℃, and the time is 120～150min.
4. according to the method described in any one in claim 1-3, it is characterized in that: in step (2), the quality percentage composition of the described vitriol oil is 97～98%, the add-on of the described vitriol oil is 3 ~ 4% of poly(oxyethylene glycol) 400 and glycerol mixture quality;
Described is 1:(0.3 ~ 1 through the corn cob residue of enzymolysis and the ratio of quality and the number of copies of described corn cob meal).
5. according to the method described in any one in claim 1-4, it is characterized in that: in step (3), 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).
6. according to the method described in any one in claim 1-5, it is characterized in that: in step (4), described ethylene glycol is (3 ~ 5) with the molfraction ratio of dextrose anhydrous: 1; The consumption of described phosphoric acid be described dextrose anhydrous quality 1.3 ~ 1.7%.
7. according to the method described in any one in claim 1-6, it is characterized in that: in step (4), the temperature of described reaction is 120～130 ℃, and pressure is 5000～6000Pa, and the time is 1.2 ~ 1.5 hours.
8. according to the method described in any one in claim 1-7, it is characterized in that: in step (5), described isocyanic ester is polyphenyl polymethylene polyisocyanates; Described isocyanic ester is (5 ~ 25) with the ratio of quality and the number of copies of thick ethylene glycol glucoside: 1.
9. according to the method described in any one in claim 1-8, it is characterized in that: in step (6), the ratio of quality and the number of copies of described thick ethylene glycol glucoside and described liquefied product is (0.05 ~ 0.2): 1.
10. according to the method described in any one in claim 1-9, 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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| 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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| 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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