CN102093698A - Polyurethane foam plastic composition, polyurethane foam and reutilization method of lignin-containing material - Google Patents
Polyurethane foam plastic composition, polyurethane foam and reutilization method of lignin-containing material Download PDFInfo
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Abstract
The invention provides a polyurethane foam plastic composition which is characterized by containing modified biomass liquefied heavy oil, isocyanate, foaming agent and catalyst, wherein the isocyanate is present as an independent component relative to the modified biomass liquefied heavy oil and the foaming agent; and the hydroxyl value of the modified biomass liquefied heavy oil is 350-580mg KOH/g. The invention also provides a polyurethane foam prepared from the polyurethane foam plastic composition and a reutilization method of a lignin-containing material. The invention not only lowers the production cost of the polyurethane foam, but also improves the compression strength, thermal decomposition temperature and biodegradability of the polyurethane foam, thereby developing a new method for preparing the polyurethane foam, widening the range of raw material sources of the polyurethane, effectively utilizing the lignin-containing material taken as waste, and implementing the high-efficiency full utilization of the biomass materials.
Description
Technical field
What the present invention related to polyurethane foam compositions and polyurethane foam and contained lignin material utilizes method again.
Background technology
In energy dilemma and environmental pollution serious day by day today, develop reproducible biomass resource and be subjected to showing great attention to of researcher and national governments.The thermochemistry catalytic liquefaction is a kind of method of Wood Adhesives from Biomass efficiently, can change solid into liquid starting material.Contain lignin material and be meant the various natural materialss that contain xylogen, comprise that green plants passes through photosynthesis synthetic organism, be generally solid-stately, principal mode has forest such as branch, agricultural stalk such as wheat straw, rice straw, cornstalk, and careless class such as Chinese silvergrass.Contain lignin material and change sun power into chemical energy, the carbon with in the renewable form storage biosphere is the important step of carbon cycle on the earth.China contains the lignin material aboundresources, and theoretical annual production is about 5,000,000,000 tons, and high-valued product are produced in lignin material liquefaction and liquid fuel has huge resources advantage to contain.
Contain lignin material liquefaction at present and mainly contain two kinds of technologies: a kind of is biochemical process, mainly be to be converted into ethanol with the carbohydrate superpolymer such as Mierocrystalline cellulose/hemicellulose that biochemical methods such as hydrolysis, fermentation will contain in the lignin material, xylogen is as the residue abandoned; Another kind is a thermochemical method, comprises the liquefaction of fast pyrogenation and solvent.Compare with fast pyrogenation, therefore the solvent liquefaction process reaction conditions gentleness under the acid catalysis has very big potentiality to be exploited.But adopt solvent liquefaction to have two problems: the one, biomass liquefying mink cell focus and residue rate height generally can be up to the 40-70% of biomass material quality.In addition, biomass liquefying solvent commonly used as phenol, polyvalent alcohol and carbonic ether, combines with the biomass macromole in liquefaction process, therefore contains both to be not easy solvent recuperation after lignin material liquefies, and also is not easy various liquefied product are effectively separated.Thereby whole liquefied product can only be used to prepare inferior macromolecular material at present.
CN101255112A disclose a kind of by with cellulose-containing material and acidifying Fatty Alcohol(C12-C14 and C12-C18) after contacting 30-90 minute under 120-140 ℃, and acetic ester can be separated by simple distillation, in addition, also can in still-process, reclaim excess fats alcohol, the liquid ingredient viscosity of isolating behind acetic ester and the Fatty Alcohol(C12-C14 and C12-C18) is low, be the sorrel transparence, have combustibility, can be used as organic-fuel.This method is produced high-valued product and liquid fuel with cellulose-containing material liquefaction, and this has huge resources advantage undoubtedly.But this method is only mentioned and isolate acetic ester and Fatty Alcohol(C12-C14 and C12-C18) from liquefied product, and the liquid of isolating behind acetic ester and the Fatty Alcohol(C12-C14 and C12-C18) is used for organic-fuel, to the effective utilization that contains lignin material, and realize that the efficient complete utilization of biological material is also insufficient as waste.
Polyurethane material is one of kind with fastest developing speed in the modern plastics industry.Generally, urethane is to be reacted in the presence of catalyzer and whipping agent by binary or polynary organic isocyanate and binary or polyol compound (polyether glycol or polyester polyol) to make.Usually, polyurethane material can be used as plastics, rubber, fiber, tamanori, synthetic leather, water-proof material and laying material etc.The polyvalent alcohol raw material that is used to prepare urethane foam mainly contains two kinds: polyether glycol and polyester polyol.By polyester polyol is that the urethane foam of feedstock production has favorable mechanical mechanical property and oil resistance usually, but owing to mostly be waxy solid under the polyester polyol room temperature, viscosity behind the heating and melting is bigger, make that raw material mixes difficulty in the synthesis of polyurethane process, and the polyester polyol cost of material also is higher than polyether glycol.Polyether glycol is because its intramolecularly cumulative is lower, and ehter bond is easy to rotation, so polyurethane foam feel prepared therefrom is more soft, and anti-hydrolytic performance is good, because the raw material viscosity is low, be easy to mix with raw materials such as isocyanic ester, auxiliary agents simultaneously, processing characteristics is good.Because urethane is difficult to degraded and recycles difficulty at occurring in nature, so flourish its waste pollution problem of environment of also having brought of urethane, exploitation biodegradable polyurethane material is considered to one of desirable approach that solves this difficult problem.
Summary of the invention
The purpose of this invention is to provide a kind of polyurethane foam compositions and a kind of polyurethane foam, also provide a kind of contain lignin material utilize method again.
The present inventor is surprised to find that the liquefaction reaction product drying-free in the presence of acid catalyst with n-Octanol and wood powder directly carries out centrifugation, obtains obvious stratified lightweight oil and biomass liquefying mink cell focus.Use this biomass liquefying mink cell focus can replace polyether glycol and isocyanate reaction through modification, can make all very excellent polyurethane foam of anti-compression properties and thermal decomposition performance, and the biological degradability of this polyurethane foam is good, has solved the problem of prior art urethane in occurring in nature non-degradable and recycling difficulty thus.And, can collect acetic ester and diether compounds with lightweight oil distillation or rectifying.Residuum calorific value height after the distillation, can be directly and diesel oil miscible, part substitutes diesel oil.
The invention provides a kind of polyurethane foam compositions, it is characterized in that, this foam composition contains the biomass liquefying mink cell focus of modification, isocyanic ester, whipping agent and catalyzer, isocyanic ester exists with respect to the biomass liquefying mink cell focus of modification and the whipping agent form with independent component, the hydroxyl value of the biomass liquefying mink cell focus of described modification is 350-580mgKOH/g, the biomass liquefying mink cell focus of this modification is by in the presence of acid, can form pure compound contacts and obtains with biomass liquefying mink cell focus and alkylol cpd and/or in the presence of described acid, described biomass liquefying mink cell focus is served as reasons to contain in the product that the liquefaction of lignin material and Fatty Alcohol(C12-C14 and C12-C18) solvent obtains and is separated the heavy component that obtains, the viscosity＞1000000cp of this heavy component in the time of 20 ℃.
The invention provides a kind of polyurethane foam that makes by above-mentioned polyurethane foam compositions.
The present invention also provide a kind of contain lignin material utilize method again, this method is included in acid catalyst and exists down, to contain lignin material carries out first with the Fatty Alcohol(C12-C14 and C12-C18) solvent and contacts, obtain liquefied product, and from this liquefied product, isolate biomass liquefying mink cell focus and lightweight oil, the viscosity of biomass liquefying mink cell focus in the time of 20 ℃ is＞1000000cp, then in the presence of acid, described biomass liquefying mink cell focus and alkylol cpd and/or the compound that can form alcohol in the presence of described acid are carried out second contact, and the product after contacting second is used to prepare above-mentioned polyurethane foam compositions or prepares polyurethane foam as the biomass liquefying mink cell focus of modification.
In the prior art, when directly adopting the biomass liquefying product to be used for polyurethane foam, because Mierocrystalline cellulose, hemicellulose contained in the biomass discharge micromolecular aldehydes, acid in the liquefaction degradation process, easy and the isocyanate component reaction of these small-molecule substances, when having increased raw material consumption, also improved the VOC value of polyurethane products.
And the present invention can separate with the mink cell focus that is rich in the lignin degradation product at an easy rate by the Fatty Alcohol(C12-C14 and C12-C18) lightweight oil that degraded cellulose, half fiber obtain that liquefies.Like this, enrichment the biomass liquefying mink cell focus of aromatic ring of lignin degradation through the twice-modified content that improves activity hydroxy again, improved reactive behavior with isocyanate component, make it help polyurethane material preparation, and further improved indexs such as the heat decomposition temperature of polyurethane material and incompressible intensity.And use the biomass liquefying mink cell focus after this modification to replace expensive polyether glycol to be used to prepare the cost that polyurethane foam compositions can reduce the preparation polyurethane foam greatly, for a kind of new method has been opened up in the preparation of polyurethane foam, also expanded the source range that comes of urethane raw simultaneously.In addition, with lightweight oil distillation or rectifying, can collect acetic ester and ether compound.Residuum calorific value height after the distillation, can be directly and diesel oil miscible, part substitutes diesel oil and uses, thereby makes the lignin material that contains as waste obtain effective utilization, has realized the efficient complete utilization of biological material.
Embodiment
The invention provides, a kind of polyurethane foam compositions, it is characterized in that, this foam composition contains the biomass liquefying mink cell focus of modification, isocyanic ester, whipping agent and catalyzer, isocyanic ester exists with respect to the biomass liquefying mink cell focus of modification and the whipping agent form with independent component, the hydroxyl value of the biomass liquefying mink cell focus of described modification is 350-580mgKOH/g, the biomass liquefying mink cell focus of this modification is by in the presence of acid, can form pure compound contacts and obtains with biomass liquefying mink cell focus and alkylol cpd and/or in the presence of described acid, described biomass liquefying mink cell focus is served as reasons to contain in the product that the liquefaction of lignin material and Fatty Alcohol(C12-C14 and C12-C18) solvent obtains and is separated the heavy component that obtains, the viscosity＞1000000cp of this heavy component in the time of 20 ℃.
Among the present invention, above-mentioned biomass liquefying mink cell focus is in the presence of acid catalyst, to contain the product that obtains of lignin material and Fatty Alcohol(C12-C14 and C12-C18) solvent liquefaction, and from this product isolated heavy component, the condition of liquefaction reaction can be the whole bag of tricks known in the field.Be preferably with respect to 100 mass parts Fatty Alcohol(C12-C14 and C12-C18), the consumption of acid catalyst is the 1-3 mass parts, and the consumption that contains lignin material is the 33-67 mass parts.The pressure of reaction be the temperature of 0.2-0.42 MPa, reaction be 110-170 ℃ down reaction obtained liquefied product in 30-120 minute, liquefied product separated obtain the biomass liquefying mink cell focus, the viscosity＞1000000cp of this biomass liquefying mink cell focus in the time of 20 ℃.
The above-mentioned lignin material that contains can derive from existing various timber, agricultural waste material stalk etc. and contains lignin material, for example can be in softwood plant such as China fir, tamarack, Japanese red pine, the Pinus massoniana Lamb one or more, can also be in pourous wood plant such as robur, Cortex Fraxini mandshuricae, eucalyptus, birch and the poplar one or more, can also expand in agricultural waste material such as wheat straw, rice straw and the cornstalk one or more.
Above-mentioned acid can be conventional various acid of using such as in phosphoric acid, hydrochloric acid, sulfuric acid, nitric acid, formic acid, acetate, oxalic acid, propanedioic acid, Succinic Acid, Phenylsulfonic acid, phenylformic acid or its solution one or more in the wood powder liquefaction process, preferred described acid catalyst is a sulfuric acid, and more preferably vitriolic content is not less than the vitriol oil of 95 quality %.
Above-mentioned Fatty Alcohol(C12-C14 and C12-C18) can be the various hydroxy-containing compounds that can generate ester with acetic acidreaction, for example can be that carbonatoms is that 1-20, hydroxyl value are the aliphatic monobasic alcohol of 1-3 or in the polyvalent alcohol one or more.Particularly, described Fatty Alcohol(C12-C14 and C12-C18) can be one or more in methyl alcohol, ethanol, propyl alcohol, Virahol, propyl carbinol, the trimethyl carbinol, Pentyl alcohol, primary isoamyl alcohol, neopentyl alcohol, hexanol, enanthol, n-Octanol, ethylene glycol and the glycerine.Preferred described Fatty Alcohol(C12-C14 and C12-C18) is that carbonatoms is aliphatic monobasic alcohol or the polyvalent alcohol of 6-10, for example hexanol, enanthol, octanol, nonyl alcohol and decyl alcohol, most preferably n-Octanol.
Above-mentioned isolating method can be centrifugal and method quiescent settling and since centrifugal have easy and simple to handle, advantage fast, the present invention is preferably centrifugal.When the present invention adopts centrifugation method to come separation of lighter oil and biomass liquefying mink cell focus, centrifugal speed is 2000-3000rpm/min, the centrifugal time is when being 5-30min, can obtain obvious stratified lightweight oil and biomass liquefying mink cell focus, the viscosity of this biomass liquefying mink cell focus in the time of 20 ℃ is＞1000000cp.
Among the present invention, the preparation method of the biomass liquefying mink cell focus of described modification is in the presence of acid, can form pure compound with biomass liquefying mink cell focus and alkylol cpd and/or in the presence of described acid and contact and obtain.The temperature of described contact is 110-180 ℃, and the time of contact is 30-120min; Be preferably temperature 120-170 ℃ of described contact, be 40-90min duration of contact.Described acid can be various acid known in the field, for example: one or more in sulfuric acid, hydrochloric acid and the nitric acid, be preferably sulfuric acid, more preferably vitriolic content is not less than the vitriol oil of 75 quality %.
The consumption of above-mentioned acid can in very large range change.The present invention can for, be benchmark with biomass liquefying mink cell focus and alkylol cpd and/or the total mass of compound that in the presence of described acid, can form alcohol, the consumption of described acid can be 0.5-5 quality %, is preferably 1-3 quality %.
The hydroxyl value of the biomass liquefying mink cell focus of the described modification that obtains after the contact is 350-580mgKOH/g, and the hydroxyl value that is preferably the biomass liquefying mink cell focus of described modification is 450-580mgKOH/g.
Described alkylol cpd can be in an alcohol, the two pure and mild polyvalent alcohols one or more; Be preferably polyvalent alcohol; More preferably polyether glycol and/or glycerine.Described polyether glycol is preferably one or more in polyoxyethylene glycol, polypropylene glycol and the PTMG.The number-average molecular weight of preferred described polyether glycol is 400-1000.Most preferably be polyoxyethylene glycol and glycerine by 2-5: 1 mixed alcohol mixture.Described polyoxyethylene glycol is preferably PEG 400 especially.
In addition, in the present invention, the described compound that can form alcohol in the presence of described acid is meant can decompose under the condition in above-mentioned modification and generates pure compound.One or more in epoxy compounds and the furans derivative compound for example.The present invention is preferably epoxy compounds.Be preferably the epoxy compounds that carbonatoms is 2-3 especially.Described epoxy compounds is preferably one or more in oxyethane, propylene oxide, tetrahydrofuran (THF), the halogen-containing epoxy compounds.The mixture of oxyethane and propylene oxide more preferably.
Above-mentioned biomass liquefying mink cell focus and alkylol cpd and/or the mass ratio that can form pure compound in the presence of described acid can in very large range change.Under the preferable case, above-mentioned biomass liquefying mink cell focus and alkylol cpd and/or the mass ratio that can form pure compound in the presence of described acid are 1: 1-4.More preferably above-mentioned biomass liquefying mink cell focus and alkylol cpd and/or the mass ratio that can form pure compound in the presence of described acid are 1: 1.5-3.
Among the present invention, each component of described composition can be for existing with the form of independent component separately, also can each component phase blended form exist, the biomass liquefying mink cell focus, whipping agent and the catalyzer that are preferably modification exist with mixed form, and isocyanic ester exists with absolute version.
According to the present invention, in the described polyurethane foam compositions, each components contents can in very large range change, under the preferable case, the biomass liquefying mink cell focus of the modification of 100 mass parts is a benchmark, the content 14-25 mass parts of described whipping agent, the content of catalyzer is the 1.5-3.5 mass parts, the consumption of isocyanic ester makes that the mol ratio of the OH in the biomass liquefying mink cell focus of NCO in the isocyanic ester and modification is 1.02-1.08: 1.More preferably, 100 mass parts the biomass liquefying mink cell focus of modification be benchmark, the content of described whipping agent is the 16-20 mass parts, the content of described catalyzer is the 2.5-3 mass parts, and the content of described isocyanic ester makes that the mol ratio of the OH in the biomass liquefying mink cell focus of NCO in the isocyanic ester and modification is 1.03-1.07: 1.
Described isocyanic ester is the various isocyanic ester that routine is used for polyurethane foam, for example can be in tolylene diisocyanate (TDI), diphenylmethanediisocyanate (MDI) and the poly methylene poly phenyl poly isocyanate (PAPI) one or more, the present invention be preferably TDI.
Described catalyzer can be the various catalyzer that routine is used for polyurethane foam, for example can be tertiary amine catalyst and organic tin complex catalyst system.Particularly, be triethylene diamine, dibutyl tin laurate and stannous octoate, the present invention is preferably the ethylene glycol solution (triethylene diamine concentration 33%) of triethylene diamine.
Described whipping agent can be the various whipping agents that routine is used for polyurethane foam, for example can be chemical foaming agent (as: water) or various pneumatogen, and described pneumatogen can be lower boiling fluorinated hydrocarbon, alkane derivative, liquid carbon dioxide etc.Based on the consideration to environment protection, the preferred described whipping agent of the present invention is 1,1-two chloro-1-fluoroethanes (HCFC-141b).
Under the preferable case, composition of the present invention can also contain suds-stabilizing agent, and described stablizer can be a polyurethane foam stablizer commonly used, for example can be various silicone oil, as silicone oil B8454.Described stablizer is used for the structure of stabilizing polyurethane foams, make the polyurethane foam abscess thin and evenly, performance is better.Biomass liquefying mink cell focus with the modification of 100 mass parts is a benchmark, and the content of suds-stabilizing agent can be the 1-3 mass parts, is preferably 2 mass parts.
Under the further preferred situation, composition of the present invention can also contain one or more of the wood powder particle, fire retardant, antistatic agent and the pigment that have not liquefied.
The preparation method of polyurethane foam of the present invention is simple, only needs above-mentioned each component mixed get final product, mixes afterwards to carry out moldedly in the adding mould, can make polyurethane foam.
In the preparation method of polyurethane foam of the present invention, generally adopting in humidity is to mix under 30-70%, 15-30 ℃, pours into then in the mould, at room temperature solidifies 0.5-1 hour, can obtain polyurethane foam provided by the invention.
The present invention also provide a kind of contain lignin material utilize method again, this method is included in acid catalyst and exists down, to contain lignin material carries out first with the Fatty Alcohol(C12-C14 and C12-C18) solvent and contacts, obtain liquefied product, and from this liquefied product, isolate biomass liquefying mink cell focus and lightweight oil, the viscosity of biomass liquefying mink cell focus in the time of 20 ℃ is＞1000000cp, then in the presence of acid, described biomass liquefying mink cell focus and alkylol cpd and/or the compound that can form alcohol in the presence of described acid are carried out second contact, and the product after contacting second is used to prepare above-mentioned polyurethane foam compositions or prepares polyurethane foam as the biomass liquefying mink cell focus of modification.
According to the present invention, the preparation method of described biomass liquefying mink cell focus and lightweight oil is described above, does not repeat them here.In addition, need to prove that the lightweight oil viscosity that adopts aforesaid method to obtain is 3-5cp in the time of 20 ℃.
Of the present invention contain lignin material utilize method again, this method also comprises isolates acetic ester and ether compound from described lightweight oil.For Fatty Alcohol(C12-C14 and C12-C18) is low carbon number alcohol such as methyl alcohol, ethanol, propyl alcohol, Virahol, propyl carbinol, the trimethyl carbinol, then because too volatile and decompose, causes the yield of acetic ester too low or need react under condition of high voltage; For ethylene glycol, easy polymerization reaction take place generates polyoxyethylene glycol under contact conditions of the present invention, causes reduction of acetic ester productive rate and product not easily separated; In addition, decomposition reaction very easily takes place in glycerine under this contact conditions, and therefore, the preferred described Fatty Alcohol(C12-C14 and C12-C18) of the present invention is that carbonatoms is aliphatic monobasic alcohol or the polyvalent alcohol of 6-10, for example hexanol, enanthol, octanol and decyl alcohol.The present inventor finds that further the effect when Fatty Alcohol(C12-C14 and C12-C18) is octanol is best, not only contain lignin material liquefied fraction height, and the yield of acetic ester is also the highest, and the separation of liquefaction after product is also the easiest.Therefore, the present invention's n-Octanol most preferably.
According to method provided by the invention, when described Fatty Alcohol(C12-C14 and C12-C18) was n-Octanol, the boiling point that described low-boiling products is depressed at 1 standard atmosphere was 110-380 ℃.Described product with liquefaction carries out isolating method and comprises liquefied product is carried out centrifugation, obtain obvious stratified lightweight oil and biomass liquefying mink cell focus, the biomass liquefying mink cell focus is prepared into a kind of composition, said composition is above-mentioned polyurethane foam compositions, the gained lightweight oil distilled obtain acetic ester (for the acetate n-octyl, boiling range is 210-215 ℃), ether compound is (for dioctyl ether, boiling range is 290-293 ℃) and the liquefaction oil product, this liquefaction oil product is the residual oil in distillation back.The purity of the acetic ester that obtains by distillation is about 60-80%, and the purity of ether compound is about 40-60%, and the liquefaction oil product after the distillation can be directly miscible with diesel oil, partly alternative diesel oil.For different acetic ester, the temperature of target product is different, and the distillatory temperature is also different.Usually, when described Fatty Alcohol(C12-C14 and C12-C18) be n-Octanol, when target product is acetate n-octyl and dioctyl ether, the distillatory temperature is no more than 215 ℃, be higher than 215 ℃ of yields that can not increase acetate n-octyl and dioctyl ether, and serious coking phenomenon takes place the residue in the matrass.
The following examples will be further detailed the present invention.
In following examples, the method for the hydroxyl value of the biomass liquefying mink cell focus of mensuration modification is GB12008.3-1989.
Polyoxyethylene glycol (PEG400 in following examples, available from Beijing chemical reagents corporation), glycerine (available from Beijing chemical reagents corporation), polypropylene glycol is (available from Beijing chemical reagents corporation, number-average molecular weight is 400-1000,), PTMG is (available from Jiangsu many Li Jia of Yixing City trade Co., Ltd, number-average molecular weight is 650-3500), triethylene diamine (available from Shenzhen China space chemical industry trade Co., Ltd), tolylene diisocyanate (available from Beijing chemical reagents corporation), diphenylmethanediisocyanate (available from Xinghua worker company limited in the Suzhou City), HCFC-141b (1,1-two chloro-1-fluoroethanes are available from Dongguan mayor pool chemical industry company limited).
Embodiment 1
This embodiment is used to illustrate the preparation that utilizes method and polyurethane foam again that contains lignin material provided by the invention.
1) be that (the Pinus massoniana Lamb collecting location is Yuexi County, Anhui and Pingxiang sun village for the vitriol oil of 95.98 quality % and 50 gram Pinus massoniana Lamb powder with 100 gram n-Octanols, 3 gram concentration, by 0.45 millimeter aperture screen cloth, water content is 4 quality %) join in 2 liters of closed reactors that agitator and temperature controller are housed, sealing back energising heating makes temperature in the reactor remain on 130-140 ℃, pressure and remained under the 0.2-0.42 MPa stirring reaction 60 minutes.The product that obtains is carried out centrifugation 5 minutes under the speed of 3000rpm/min.Obtain obvious stratified lightweight oil and biomass liquefying mink cell focus, the lightweight oil that obtains is numbered Q1, its viscosity is 4cp (20 ℃), and the biomass liquefying mink cell focus that obtains is numbered Z1, and its viscosity is＞1000000cp (20 ℃) that hydroxyl value is 212mgKOH/g.Lightweight oil Q1 residual liquefaction oil product after distillation obtains isolated acetate n-octyl, dioctyl ether and distillation, show by gas chromatography-mass spectrum (GC-MS) coupling analytical results, the purity of gained acetate n-octyl is about 80%, and the purity of dioctyl ether is 40 quality %.Liquefaction oil product after the distillation, can be directly and diesel oil miscible, part replaces diesel oil.
2) the above-mentioned biomass liquefying mink cell focus Z1 of 15 mass parts and the alcohol mixture of 45 mass parts (this alcohol mixture is by the mass ratio configuration according to 3: 1 of polyoxyethylene glycol (PEG400) and glycerine) are mixed the back add account for the sulfuric acid (concentration is 75 quality %) of biomass liquefying mink cell focus and alcohol mixture total mass 1% after, heat temperature raising to 150 ℃, stir 50min, being neutralized to pH with 10%KOH solution again is 7, at 85 ℃ of vacuum hydro-extraction 30min, obtain the biomass liquefying mink cell focus G1 of modification, the hydroxyl value of the biomass liquefying mink cell focus of this modification is 564.5mgKOH/g.
3) with biomass liquefying mink cell focus G1, the HCFC-141b of 16 mass parts, the 2.5 mass parts of catalyst (ethylene glycol solution of triethylene diamine of the above-mentioned modification of 100 mass parts, the triethylene diamine mass concentration is 33%), the mixture of 2 mass parts silicone oil B8454 and tolylene diisocyanate (the TDI index is 1.05, and the TDI consumption calculates according to following formula:
W in the formula
sThe consumption of-TDI; W
pThe consumption of-polyethers, this example are 100 parts; E
sThe equivalent of-TDI is 87; E
pThe equivalent of-polyethers, by formula
Be calculated as
I
2-TDI index is so the TDI consumption that calculates at last is
Be 50% in humidity, mix under 25 ℃ of the room temperatures, pour into then in the mould, at room temperature solidified 300 seconds, obtain polyurethane foam S1 provided by the invention.
Embodiment 2
This embodiment is used to illustrate the preparation that utilizes method and polyurethane foam again that contains lignin material provided by the invention.
1) be that (the Pinus massoniana Lamb collecting location is Yuexi County, Anhui and Pingxiang sun village for the vitriol oil of 95.98 quality % and 67 gram Pinus massoniana Lamb powder with 100 gram n-Octanols, 1 gram concentration, by 0.45 millimeter aperture screen cloth, water content is 4 quality %) join in 2 liters of closed reactors that agitator and temperature controller are housed, the energising heating of sealing back, make temperature in the reactor remain on 130-140 ℃, pressure and remained under the 0.2-0.42 MPa stirring reaction 80 minutes, the product that obtains is carried out centrifugation 10 minutes under the speed of 3000rpm/min.Obtain obvious stratified lightweight oil and biomass liquefying mink cell focus, the lightweight oil that obtains is numbered Q2, its viscosity is 5cp (20 ℃), and the biomass liquefying mink cell focus that obtains is numbered Z2, and its viscosity is＞1000000cp (20 ℃) that hydroxyl value is 202mgKOH/g.Lightweight oil Q2 residual liquefaction oil product after distillation obtains isolated acetate n-octyl, dioctyl ether and distillation, show by gas chromatography-mass spectrum (GC-MS) coupling analytical results, the purity of gained acetate n-octyl is 80 quality %, and the purity of dioctyl ether is 40 quality %.Liquefaction oil product after the distillation, can be directly and diesel oil miscible, part replaces diesel oil.
2) the above-mentioned biomass liquefying mink cell focus Z1 of 15 mass parts and the alcohol mixture of 33 mass parts (this alcohol mixture is by the mass ratio configuration according to 3: 1 of polypropylene glycol and glycerine) are mixed the back add account for the sulfuric acid (concentration is 75 quality %) of biomass liquefying mink cell focus and alcohol mixture total mass 1.5% after, heat temperature raising to 170 ℃, stir 90min, being neutralized to pH with 10%KOH solution again is 7, at 85 ℃ of vacuum hydro-extraction 30min, obtain the biomass liquefying mink cell focus G2 of modification, the hydroxyl value of the biomass liquefying mink cell focus of this modification is 350mgKOH/g.
3) with biomass liquefying mink cell focus G2, the HCFC-141b of 16 mass parts, the 2.5 mass parts of catalyst (ethylene glycol solution of triethylene diamine of the above-mentioned modification of 100 mass parts, the triethylene diamine mass concentration is 33%), the mixture of 1 mass parts silicone oil B8454 and tolylene diisocyanate ((the TDI index is 1.07, and the TDI consumption calculates according to following formula:
W in the formula
sThe consumption of-TDI; W
pThe consumption of-polyethers, this example are 100 parts; E
sThe equivalent of-TDI is 87; E
pThe equivalent of-polyethers, by formula
Be calculated as
I
2-TDI index is so the TDI consumption that calculates at last is
Be 50% in humidity, mix under 25 ℃ of the room temperatures, pour into then in the mould, at room temperature solidified 300 seconds, obtain polyurethane foam S2 provided by the invention.
Embodiment 3
This embodiment is used to illustrate the preparation that utilizes method and polyurethane foam again that contains lignin material provided by the invention.
1) be that (the Pinus massoniana Lamb collecting location is Yuexi County, Anhui and Pingxiang sun village for the vitriol oil of 98 quality % and 33.3 gram Pinus massoniana Lamb powder with 100 gram n-Octanols, 2 gram concentration, by 0.45 millimeter aperture screen cloth, water content is 4 quality %) join in 2 liters of closed reactors that agitator and temperature controller are housed, the energising heating of sealing back, make temperature in the reactor remain on 130-140 ℃, pressure and remained under 0.2 MPa stirring reaction 100 minutes, the product that obtains is carried out centrifugation 30 minutes under the speed of 2000rpm/min.Obtain obvious stratified lightweight oil and biomass liquefying mink cell focus, the lightweight oil that obtains is numbered Q3, its viscosity is 3cp (20 ℃), and the biomass liquefying mink cell focus that obtains is numbered Z3, and its viscosity is＞1000000cp (20 ℃) that hydroxyl value is 230mgKOH/g.Lightweight oil Q3 residual liquefaction oil product after distillation obtains isolated acetate n-octyl, dioctyl ether and distillation, show by gas chromatography-mass spectrum (GC-MS) coupling analytical results, the purity of gained acetate n-octyl is 80 quality %, and the purity of dioctyl ether is 40 quality %.Liquefaction oil product after the distillation, can be directly and diesel oil miscible, part replaces diesel oil.
2) the above-mentioned biomass liquefying mink cell focus Z1 of 15 mass parts and the alcohol mixture of 22.5 mass parts (this alcohol mixture is by the mass ratio configuration according to 3: 1 of PTMG and glycerine) are mixed the back add account for biomass liquefying mink cell focus and alcohol mixture total mass 3% hydrochloric acid (concentration is 75 quality %) after, heat temperature raising to 170 ℃, stir 40min, being neutralized to pH with 10%KOH solution again is 7, at 85 ℃ of vacuum hydro-extraction 30min, obtain the biomass liquefying mink cell focus G3 of modification, the hydroxyl value of the biomass liquefying mink cell focus of this modification is 347mgKOH/g.
3) with biomass liquefying mink cell focus G3, the HCFC-141b of 20 mass parts, the 3 mass parts of catalyst (ethylene glycol solution of triethylene diamine of 100 mass parts modifications, the triethylene diamine mass concentration is 33%), mixture and the tolylene diisocyanate TDI index of 3 mass parts silicone oil B8454 be 1.03, the TDI consumption calculates according to following formula:
W in the formula
sThe consumption of-TDI; W
pThe consumption of-polyethers, this example are 100 parts; E
sThe equivalent of-TDI is 87; E
pThe equivalent of-polyethers, by formula
Be calculated as
I
2-TDI index is so the TDI consumption that calculates at last is
Be 50% in humidity, mix under 25 ℃ of the room temperatures, pour into then in the mould, at room temperature solidified 300 seconds, obtain polyurethane foam S3 provided by the invention.
Embodiment 4
This embodiment is used to illustrate the preparation that utilizes method and polyurethane foam again that contains lignin material provided by the invention.
1) carry out according to the method in embodiment 1 step 1), different is the n-Octanol that substitutes 100g with the nonylcarbinol of 100g.The lightweight oil that obtains is numbered Q4, and its viscosity is 4cp (20 ℃), and the biomass liquefying mink cell focus that obtains is numbered Z4, and its viscosity is＞1000000cp (20 ℃) that hydroxyl value is 194mgKOH/g.Lightweight oil Q4 is residual liquefaction oil product after distillation obtains isolating acetate ester in the positive last of the ten Heavenly stems, didecyl ether and distillation, show by gas chromatography-mass spectrum (GC-MS) coupling analytical results, the purity of gained acetate ester in the positive last of the ten Heavenly stems is 56 quality %, and the purity of didecyl ether is 60 quality %.Liquefaction oil product after the distillation, can be directly and diesel oil miscible, part replaces diesel oil.
2) the above-mentioned biomass liquefying mink cell focus Z1 of 15 mass parts and the alcohol mixture of 45 mass parts (this alcohol mixture is by the mass ratio configuration according to 3: 1 of polyoxyethylene glycol (PEG400) and glycerine) are mixed the back add account for the sulfuric acid (concentration is 75 quality %) of biomass liquefying mink cell focus and alcohol mixture total mass 1% after, heat temperature raising to 150 ℃, stir 50min, being neutralized to pH with 10%KOH solution again is 7, at 85 ℃ of vacuum hydro-extraction 30min, obtain the biomass liquefying mink cell focus G4 of modification, the hydroxyl value of the biomass liquefying mink cell focus of this modification is 520mgKOH/g.
3) with biomass liquefying mink cell focus G4, the HCFC-141b of 16 mass parts, the 2.5 mass parts of catalyst (ethylene glycol solution of triethylene diamine of 100 parts of modifications, the triethylene diamine mass concentration is 33%), the mixture of 2 mass parts silicone oil B8454 and tolylene diisocyanate (the TDI index is 1.05, and the TDI consumption calculates according to following formula:
W in the formula
sThe consumption of-TDI; W
pThe consumption of-polyethers, this example are 100 parts; E
sThe equivalent of-TDI is 87; E
p---the equivalent of polyethers, by formula
Be calculated as
I
2-TDI index is so the TDI consumption that calculates at last is
Be 50% in humidity, mix under 25 ℃ of the room temperatures, pour into then in the mould, at room temperature solidified 300 seconds, obtain polyurethane foam S4 provided by the invention.
Embodiment 5
This embodiment is used to illustrate the preparation that utilizes method and polyurethane foam again that contains lignin material provided by the invention.
1) carry out according to the method for step 1) among the embodiment 1, different is poplar (poplar collecting location be Anhui Yuexi County and Pingxiang sun village, by 0.45 millimeter aperture screen cloth, water content the be 4 quality %s) replacements of 67 gram Pinus massoniana Lamb powder by equal in quality.The lightweight oil that obtains is numbered Q5, and its viscosity is 4cp (20 ℃), and the biomass liquefying mink cell focus that obtains is numbered Z5, and its viscosity is＞1000000cp (20 ℃) that hydroxyl value is 220mgKOH/g.Lightweight oil Q5 residual liquefaction oil product after distillation obtains isolating acetate n-octyl, dioctyl ether and distillation, show by gas chromatography-mass spectrum (GC-MS) coupling analytical results, the purity of gained acid n-octyl is 80 quality %, and the purity of dioctyl ether is 40 quality %.Liquefaction oil product after the distillation, can be directly and diesel oil miscible, part replaces diesel oil.
2) with the above-mentioned biomass liquefying mink cell focus Z1 of 15 mass parts and the alcohol of 45 mass parts (polyoxyethylene glycol: after PEG400) interpolation of mixing back accounts for the sulfuric acid (concentration is 75 quality %) of biomass liquefying mink cell focus and alcohol mixture total mass 1%, heat temperature raising to 150 ℃, stir 50min, being neutralized to pH with 10%KOH solution again is 7, at 85 ℃ of vacuum hydro-extraction 30min, obtain the biomass liquefying mink cell focus G5 of modification, the hydroxyl value of the biomass liquefying mink cell focus of this modification is 570mgKOH/g.
3) with biomass liquefying mink cell focus G5, the HCFC-141b of 16 mass parts, the 2.5 mass parts of catalyst (ethylene glycol solution of triethylene diamine of 100 parts of modifications, the triethylene diamine mass concentration is 33%), the mixture of 2 mass parts silicone oil B8454 and tolylene diisocyanate (the TDI index is 1.05, and the TDI consumption calculates according to following formula:
W in the formula
sThe consumption of-TDI; W
pThe consumption of-polyethers, this example are 100 parts; E
s---the equivalent of TDI is 87; E
pThe equivalent of-polyethers, by formula
Be calculated as
I
2-TDI index is so the TDI consumption that calculates at last is
Be 50% in humidity, mix under 25 ℃ of the room temperatures, pour into then in the mould, at room temperature solidified 300 seconds, obtain polyurethane foam S5 provided by the invention.
Embodiment 6
Carry out according to the method among the embodiment 1, different is in step 2) in the alcohol mixture of 45 mass parts replace with the polyoxyethylene glycol (PEG400) of 45 mass parts and the mixture of propylene oxide, the mass ratio of polyoxyethylene glycol and propylene oxide is 3: 1.Obtain polyurethane foam S6 provided by the invention.
Embodiment 7
Carry out according to the method among the embodiment 1, different is in step 2) in the alcohol mixture of 45 mass parts replace with the oxyethane of 45 mass parts and the mixture of propylene oxide (mass ratio 20: 80).Obtain polyurethane foam S7 provided by the invention.
Embodiment 8
Carry out according to the method among the embodiment 1, the tolylene diisocyanate that different is in step 3) replaces with diphenylmethanediisocyanate.Obtain polyurethane foam S8 provided by the invention.
Comparative Examples 1
According to step 2 among the embodiment 1) method carry out, different is replaces with polyoxyethylene glycol with the biomass liquefying mink cell focus of modification.Obtain polyurethane foam CS1.
Comparative Examples 2
According to step 2 among the embodiment 1) method carry out, different is, the biomass liquefying mink cell focus of modification is replaced with liquefied product without centrifugation.Obtain polyurethane foam CS2.
The performance test of polyurethane foam
Measure incompressible intensity, heat decomposition temperature, frothing percentage and the biological degradability of the polyurethane foam that makes by the foregoing description 1-8 and Comparative Examples 1-2 respectively according to GB 78813-2008 method, DTG method, apparent density inverse method and GB/T19277-2003 (IDT ISO 14855:1999) method.The result is as shown in table 1.
Table 1
From the result of last table 1 as can be known, adopt the polyurethane foam (S1-S8) of the polyurethane foam compositions preparation of the biomass liquefying mink cell focus that contains modification of the present invention on incompressible intensity, heat decomposition temperature and biological degradability, all to be better than the polyurethane foam (CS1) that Comparative Examples 1 adopts the polyoxyethylene glycol preparation.And in Comparative Examples 2, when directly adopting not separated liquefied product to prepare polyurethane foam, owing to the polyurethane foam of arriving that can't foam.
Claims (12)
1. polyurethane foam compositions, it is characterized in that, this foam composition contains the biomass liquefying mink cell focus of modification, isocyanic ester, whipping agent and catalyzer, isocyanic ester exists with respect to the biomass liquefying mink cell focus of modification and the whipping agent form with independent component, the hydroxyl value of the biomass liquefying mink cell focus of described modification is 350-580mgKOH/g, the biomass liquefying mink cell focus of this modification is by in the presence of acid, can form pure compound contacts and obtains with biomass liquefying mink cell focus and alkylol cpd and/or in the presence of described acid, described biomass liquefying mink cell focus is served as reasons to contain in the product that the liquefaction of lignin material and Fatty Alcohol(C12-C14 and C12-C18) solvent obtains and is separated the heavy component that obtains, the viscosity＞1000000cp of this heavy component in the time of 20 ℃.
2. composition according to claim 1, wherein, the temperature of described contact is 110-180 ℃, the time of contact is 30-120min.
3. composition according to claim 2, wherein, described biomass liquefying mink cell focus and alkylol cpd and/or the mass ratio that can form pure compound in the presence of described acid are 1: 1-4.
4. composition according to claim 1 wherein, is a benchmark with biomass liquefying mink cell focus and alkylol cpd and/or the total mass of compound that can form alcohol in the presence of described acid, and the consumption of described acid is 0.5-5 quality %.
5. according to any described composition among the claim 1-4, wherein, described acid is one or more in sulfuric acid, hydrochloric acid and the nitric acid.
6. according to claim 1,3 or 4 described compositions, wherein, described alkylol cpd is one or more in monohydroxy-alcohol, dibasic alcohol and the polyvalent alcohol; The described compound that can form alcohol in the presence of acid is one or more of epoxy compounds and furans derivative compound.
7. composition according to claim 6, wherein, described polyvalent alcohol is a polyether glycol; Described epoxy compounds is one or more in halogen-containing epoxy compounds, oxyethane, propylene oxide and the tetrahydrofuran (THF).
8. composition according to claim 1, wherein, biomass liquefying mink cell focus with respect to the modification of 100 mass parts, the content of whipping agent is the 14-25 mass parts, the content of catalyzer is the 1.5-3.5 mass parts, and the consumption of isocyanic ester makes that the mol ratio of the OH in the biomass liquefying mink cell focus of NCO in the isocyanic ester and modification is 1.02-1.08: 1.
9. according to according to claim 1 or 8 described compositions, wherein, described composition also contains suds-stabilizing agent, and with respect to the biomass liquefying mink cell focus of the modification of 100 mass parts, the content of suds-stabilizing agent is the 1-3 mass parts.
10. composition according to claim 1, wherein, described liquefaction is carried out in the presence of acid catalyst, the condition of described liquefaction comprises the Fatty Alcohol(C12-C14 and C12-C18) with respect to 100 mass parts, the consumption that contains lignin material is the 33-67 mass parts, and the consumption of acid catalyst is the 1-3 mass parts, and the pressure of liquefaction is the 0.2-0.42 MPa, the temperature of liquefaction is 110-170 ℃, and the time of liquefaction is 30-120 minute; Isolating method is a centrifugal separation.
11. one kind by any polyurethane foam that described polyurethane foam compositions makes among the claim 1-10.
12. one kind contain lignin material utilize method again, this method is included in acid catalyst and exists down, to contain lignin material carries out first with the Fatty Alcohol(C12-C14 and C12-C18) solvent and contacts, obtain liquefied product, and from this liquefied product, isolate biomass liquefying mink cell focus and lightweight oil, the viscosity of biomass liquefying mink cell focus in the time of 20 ℃ is＞1000000cp, then in the presence of acid, described biomass liquefying mink cell focus and alkylol cpd and/or the compound that can form alcohol in the presence of described acid are carried out second contact, and the product after contacting second is used for preparing any described composition of claim 1-10 or prepares the described polyurethane foam of claim 11 as the biomass liquefying mink cell focus of modification.
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| CN105131560A (en) * | 2015-07-17 | 2015-12-09 | 济南骄泰信息技术有限公司 | Modified lignin polyurethane and preparation method thereof |
| CN105175682A (en) * | 2015-09-25 | 2015-12-23 | 南京工业大学 | Process for preparing polyurethane foam by using novel lignin liquefaction method |
| CN110812946A (en) * | 2019-10-09 | 2020-02-21 | 安徽伟创聚合材料科技有限公司 | Preparation process of sewage filtering material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| DE19548350A1 (en) * | 1995-12-22 | 1997-06-26 | Basf Ag | Homogeneous stable poly:hydroxyl compound containing lignin with good processing properties |
| CN101255112A (en) * | 2008-04-02 | 2008-09-03 | 中国林业科学研究院木材工业研究所 | Reutilization method of cellulosic material |
| CN101696261A (en) * | 2009-10-29 | 2010-04-21 | 华南理工大学 | Lignin polyurethane and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| DE19548350A1 (en) * | 1995-12-22 | 1997-06-26 | Basf Ag | Homogeneous stable poly:hydroxyl compound containing lignin with good processing properties |
| CN101255112A (en) * | 2008-04-02 | 2008-09-03 | 中国林业科学研究院木材工业研究所 | Reutilization method of cellulosic material |
| CN101696261A (en) * | 2009-10-29 | 2010-04-21 | 华南理工大学 | Lignin polyurethane and preparation method thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105131560A (en) * | 2015-07-17 | 2015-12-09 | 济南骄泰信息技术有限公司 | Modified lignin polyurethane and preparation method thereof |
| CN105175682A (en) * | 2015-09-25 | 2015-12-23 | 南京工业大学 | Process for preparing polyurethane foam by using novel lignin liquefaction method |
| CN105175682B (en) * | 2015-09-25 | 2017-11-14 | 南京工业大学 | Process for preparing polyurethane foam by using novel lignin liquefaction method |
| CN110812946A (en) * | 2019-10-09 | 2020-02-21 | 安徽伟创聚合材料科技有限公司 | Preparation process of sewage filtering material |
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