CN109206589A - Crack the preparation method of lignin and lignin-base hard polyurethane foam - Google Patents
Crack the preparation method of lignin and lignin-base hard polyurethane foam Download PDFInfo
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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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
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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
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4081—Mixtures of compounds of group C08G18/64 with other macromolecular compounds
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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
- C08G18/48—Polyethers
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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
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two 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
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
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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
- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
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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
- C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0025—Foam properties rigid
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0083—Foam properties prepared using water as the sole blowing agent
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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
- C08G2230/00—Compositions for preparing biodegradable polymers
Abstract
The present invention provides a kind of cracking lignin, are obtained by cracking wood fibre hydrogenation catalyst.The present invention also provides the preparation method of lignin-base hard polyurethane foam, cracking lignin provided by the invention substitutes part petroleum-based polyols.The lignin-base hard polyurethane foam that preparation method through the invention obtains not only is had excellent performance, but also has degradable, reproducible environmental-protecting performance, great prospects for commercial application.
Description
Technical field
The invention belongs to the field of polymers, and in particular to a kind of cracking lignin and lignin-base hard polyurethane foam
Preparation method.
Background technique
Due to hard polyurethane foam have excellent heat-proof quality, so generally be widely used in buildings in general every
Hot material etc..In general, hard polyurethane foam is prepared using the following method: first preparing polyisocyanate component liquid and mixing
Liquid, the mixed liquor contain polyether polyol and/or polyester polyol, foaming agent, be also mixed with as needed catalyst and
Then surfactant etc. mixes polyisocyanate component liquid and mixed liquor, makes its solidification after foaming in the short time.
As petroleum, coal etc. is not with regard to the reduction increasingly of volume regenerated resources total amount, shape is converted by plant and microbial resources
Just becoming a kind of development trend at new material, the high heating value energy and chemical industry new raw material.Lignin as a kind of molecular structure very
Many and diverse phenol polymer, is widely present in plant cell tissue, is the fibre-forming polymer abundant of content second on the earth.
CN 102206320B discloses a kind of preparation method done as straw base biomass polyurethane foamed material.It should
Method has the drawback that: biomass castoff selects corn stover, rice straw, cotton stalk etc. to mix, complicated component, no
Conducive to processing, additional amount is few, influences on the performance of polyurethane foam very big；Biological material liquefied reagent is concentrated hydrochloric acid or dense
Sulfuric acid, temperature reach 200 DEG C, and energy consumption is larger, are unfavorable for industrializing；It not only joined biomass castoff in polyurethane, industry
Rugose wood element is also added into lignosulfonates, and component partial size, molecular weight, hydroxyl value differ greatly, and can be total to polyurethane component
It mixes foaming and causes complicated influence, easily cause properties of product unstable.
Summary of the invention
The first aspect of the invention provides a kind of cracking lignin, by the way that wood fibre is carried out hydrogenation catalyst
Cracking obtains.Cracking lignin provided by the invention is liquid condition at room temperature (usually 15-40 DEG C), can be directly used for giving birth to
The synthesis of material.
According to the present invention, the wood fibre can be wood fibre commonly used in the art, preferable particle size 40-100
Mesh.
Some preferred embodiments according to the present invention, the catalytic pyrolysis is existing for the supported ruthenium metallic catalyst
Under the conditions of carry out.
Some preferred embodiments according to the present invention, the first pressing that the catalytic pyrolysis uses is 1MPa-3MPa, preferably
For 1MPa-2MPa.
Some preferred embodiments according to the present invention, the temperature that the catalytic pyrolysis uses are excellent for 230 DEG C -250 DEG C
It is selected as 240 DEG C -250 DEG C.In one embodiment, the temperature is 250 DEG C.
Some preferred embodiments according to the present invention, the time that the catalytic pyrolysis carries out are 1-6 hours, preferably 3-6
Hour, it is 3-4 hours more preferable.
Some preferred embodiments according to the present invention, the catalytic pyrolysis carry out in the presence of a solvent.It is described
Solvent is preferably selected from one of methanol, ethyl alcohol, tetrahydrofuran and dioxane or a variety of.
Some preferred embodiments according to the present invention, the partial size of the wood fibre are 40 mesh or less.
Second invention of the invention provides a kind of preparation method of lignin-base hard polyurethane foam.The system
Preparation Method will crack lignin as polyol component and substitute petroleum-based polyols synthesising biological matter polyurethane foam, synthesis side
Method is simple, convenient for operation, has reference significance to further developmental research biological material.
The preparation method of lignin-base hard polyurethane foam provided by the invention includes:
Step 1): cracking lignin, petroleum-based polyols, catalyst and foaming agent are mixed, to obtain premixing components；
Step 2): isocyanates being added into premixing components, foams.
Some preferred embodiments according to the present invention, it is more that the petroleum-based polyols are selected from the pure and mild polyester of polyether polyols
First alcohol.Preferably, the polyether polyol is selected from EP3600, PTMG-1000 (polytetrahydrofuran ether glycol), PPG-1000 (gathers
Propylene glycol) and one of PEG (polyethylene glycol) or a variety of.Preferably, the polyester polyol is selected from PBT (poly- terephthalic acids
Fourth diester), PBA (butyl polyacrylate), one of PEA (polyacrylate) and PCL (polycaprolactone polyol) or more
Kind.
Some preferred embodiments according to the present invention, the isocyanates be selected from polymethylene multi-phenenyl isocyanate,
One of toluene di-isocyanate(TDI) and methyl diphenylene diisocyanate are a variety of.
Some preferred embodiments according to the present invention, the cracking lignin and the mass ratioes of petroleum-based polyols are
1:9-7:3, preferably 1:9,1:1,3:7 etc..Cracking lignin of the invention can substitute 10 weight %-70 weight % (such as 10
Weight %, 20 weight %, 30 weight %, 50 weight %, 60 weight %, 70 weight %) petroleum-based polyols.
Some preferred embodiments according to the present invention, the foaming agent are selected from water, Foam agent ADC (two formyl of azo
Amine) and one of sodium bicarbonate and ammonium carbonate or a variety of.
Some preferred embodiments according to the present invention, the catalyst are selected from stannous octoate, potassium acetate, dibutyl tin
Dilaurate, N, N- Dimethylcyclohexyl, triethanolamine, triethylamine and N, one of N- dimethylethanolamine or a variety of.
The invention has the advantages that.
(1) by the way that wood fibre catalytic degradation to be obtained to the cracking lignin of liquid, it can be directly used for biological material
Synthesis.
(2) will cracking lignin as polyol component substitution part petroleum-based polyols, (such as substitution 10-70% is heavy
The petroleum-based polyols of amount) synthesising biological matter polyurethane foam, synthetic method is simple, convenient for operation, to further developmental research
Biological material has reference significance.
(3) the lignin-base hard polyurethane foam process costs of preparation method synthesis through the invention are lower, performance
Stablize, the purer polyurethane foam of performance is (i.e. not using cracking lignin, but using petroleum-based polyols as polyol component
The polyurethane foam of preparation) there is certain promotion, and also product has degradable, reproducible environmental-protecting performance, great industrial application
Prospect.
Detailed description of the invention
Fig. 1 is the infrared spectroscopy of the hard polyurethane foam of embodiment 1-3 and the preparation of comparative example 1.
Fig. 2 is the electromicroscopic photograph of hard polyurethane foam prepared by comparative example 1.
Fig. 3 is the electromicroscopic photograph of hard polyurethane foam prepared by embodiment 1.
Fig. 4 is the electromicroscopic photograph of hard polyurethane foam prepared by embodiment 2.
Fig. 5 is the electromicroscopic photograph of hard polyurethane foam prepared by embodiment 3.
Fig. 6 is the DTG figure of the hard polyurethane foam of embodiment 1-3 and the preparation of comparative example 1.
Specific embodiment
Below in conjunction with drawings and examples, the present invention is described in detail, but the present invention is not limited by following embodiments
It is fixed.
Embodiment 1
Wood fibre is crushed, 80 mesh standard sieves is crossed, obtains the wood fibre of uniform particle diameter, smashed wood fibre
3h is dried under the conditions of 60 DEG C through vacuum constant temperature drying box.It takes quantitative wood fibre to be put into autoclave, checks high pressure before reacting
The airtightness of kettle, is then sealed, and then uses 1MPa H2Pressurization, makes whole system air pressure reach 2MPa, is slowly heated to
250℃.Reaction uses supported ruthenium metallic catalyst, reacts 4h, and methanol carries out catalytic cracking reaction as solvent.Take product
The liquid lignin and methanol on upper layer, the rotary evaporation under 40 DEG C of decompressions, after methanol removal, the cracking for obtaining liquid is wooden
Element.
Cracking the lignin 2g, in mass ratio 1:9 prepared is added in beaker, corresponding polyether polyol is added
5110, and 0.5g catalyst A33,0.5g stannous octoate T9,0.8g foam stabiliser, 0.6g crosslinking agent L580 and 1g hair is added
Infusion water waits until in beaker, is uniformly mixed at room temperature with electric blender, revolving speed is set as 600r/min.It is added mostly sub-
The more phenyl isocyanate PMDI of methyl, stirring are allowed to uniformly mixed, and revolving speed is set as 600r/min.Have when observing in mixture
Bubble issues, foam is when whitening, and injects from molding jig free foaming immediately, swollen determines molding.At room temperature by foam obtained
Progress post curing processing in 12 hours is placed, so that wherein unfinished reaction continues, obtains lignin-base rigid poly urethanes
Foam L10PU.
Embodiment 2
Wood fibre is crushed, 100 mesh standard sieves is crossed, obtains the wood fibre of uniform particle diameter, smashed wood fibre
2h is dried under the conditions of 100 DEG C through vacuum constant temperature drying box.It takes quantitative wood fibre to be put into autoclave, is checked before reacting high
The airtightness for pressing kettle, is then sealed, and is then pressurizeed with 1MPa H2, whole system air pressure is made to reach 3MPa, is slowly heated
To 240 DEG C.Reaction uses supported ruthenium metallic catalyst, reacts 5h, and methanol is used to carry out catalytic cracking reaction as solvent.
The liquid lignin and methanol for taking product upper layer, the rotary evaporation under 40 DEG C of decompressions after methanol removal, obtain splitting for liquid
Solve lignin.
The cracking lignin 6g, in mass ratio 3:7 prepared is added in beaker, corresponding PEG (polyethylene glycol) is added,
And 0.5g catalyst A33,0.5g stannous octoate T9,0.8g foam stabiliser, 0.6g crosslinking agent L580 and 1g foaming agent water is added
Into beaker, it is uniformly mixed at room temperature with electric blender, revolving speed is set as 700r/min.Toluene diisocynate is added
Ester, stirring are allowed to uniformly mixed, and revolving speed is set as 700r/min.When observing in mixture has bubble sending, foam to whiten,
Free foaming is injected from molding jig immediately, swollen determines molding.Foam obtained is placed into progress post curing in 24 hours at room temperature
Processing obtains lignin-base hard polyurethane foam L30PU so that wherein unfinished reaction continues.
Embodiment 3
Wood fibre is crushed, 40 mesh standard sieves is crossed, obtains the wood fibre of uniform particle diameter, smashed wood fibre
3h is dried under the conditions of 80 DEG C through vacuum constant temperature drying box.It takes quantitative wood fibre to be put into autoclave, checks high pressure before reacting
The airtightness of kettle, is then sealed, and is then pressurizeed with 1MPa H2, so that whole system air pressure is reached 1MPa, be slowly heated to
230℃.Reaction uses supported ruthenium metallic catalyst, reacts 3h, and methanol is used to carry out catalytic cracking reaction as solvent.It takes
The liquid lignin and methanol on product upper layer, the rotary evaporation under 40 DEG C of decompressions after methanol removal, obtain the cracking of liquid
Lignin.
The cracking lignin 10g, in mass ratio 1:1 prepared is added in beaker, corresponding PPG-1000 (poly- third is added
Glycol), and 0.5g catalyst A33,0.5g stannous octoate T9,0.8g foam stabiliser, 0.6g crosslinking agent L580 and 1g hair is added
Infusion water waits until in beaker, is uniformly mixed at room temperature with electric blender, revolving speed is set as 800r/min.Hexichol is added
Dicyclohexylmethane diisocyanate, stirring are allowed to uniformly mixed, and revolving speed is set as 800r/min.There is bubble hair when observing in mixture
Out, when foam whitens, free foaming is injected from molding jig immediately, swollen determines molding.Foam obtained is placed 8 at room temperature
Hour carries out post curing processing, so that wherein unfinished reaction continues, obtains lignin-base hard polyurethane foam
L50PU。
Comparative example 1
20g polyether polyol 5110,0.5g catalyst A33,0.5g stannous octoate T9,0.8g foam are added in beaker
Stabilizer, 0.6g crosslinking agent L580 and 1g foaming agent water are uniformly mixed with electric blender at room temperature into beaker,
Revolving speed is set as 700r/min.PMDI (poly methylene poly phenyl poly isocyanate) 39.67g is added, it is equal that stirring is allowed to mixing
Even, revolving speed is set as 700r/min.When observing in mixture has bubble sending, foam to whiten, inject immediately from molding jig
Free foaming swollen determines molding.Foam obtained is placed into progress post curing processing in 24 hours at room temperature, so that wherein not complete
At reaction continue, obtain pure hard polyurethane foam L0PU.
Table 1 shows the performance of hard polyurethane foam prepared by embodiment 1-3 and comparative example 1
Table 1
Polyurethane is generated from infrared will be obvious of Fig. 1, and the addition of depolymerization lignin is to polyurethane foam
Chemical structure do not change significantly.
The thermal analysis of hard polyurethane foam L0PUL10PU L30PU L50PU
For the thermal degradation temperature range of all samples about at 200 DEG C~450 DEG C, thermal weight loss is divided into two stages,
200 DEG C~345 DEG C are the first degradation period, and the general temperature defined when sample thermal weight loss is 5wt% is the heat drop of composite material
Solve initial temperature TOD.Compared to sample L30PU, L50PU (225 DEG C), L10PU, L0PU have higher thermal degradation initial temperature
(247 DEG C, 257 DEG C) illustrate that the addition for cracking lignin slightly reduces the initial degradation temperature of polyurethane material.
The thermal weight loss of second stage occurs in 345 DEG C~450 DEG C, the mainly urethane from the cruel rigid foam material of poly- ammonia
The degradation [19] of structure.L10PU, L30PU ratio L0PU have higher second stage thermal degradation rate, although cracking lignin has
Higher hydroxyl value, but still have lower accessibility for isocyanates, cause crosslinking to be not enough, so the urethane bond generated
It is fewer than pure polyurethane foam.It will be apparent that L50PU has very high second stage thermal degradation rate, show that excessive split is added
Solution lignin further hinders the reaction with isocyanate group.In addition, difference quotient thermal mass curve is as shown in fig. 6, four groups of samples
Reach maximum heat degradation rate at 325 DEG C or so；The maximum heat weightlessness rate score about the same (325 of sample L0PU, L30PU
DEG C), and L10PU, L50PU are then promoted to 329 DEG C, since lignin has higher thermal decomposition temperature than polyurethane, so cracking
The addition of lignin improves the thermal stability of polyurethane foam.
The limit oxygen index of hard polyurethane foam L0PUL10PU L30PU L50PU
According to formula, after lignin is added, hard polyurethane foam has become flammable from inflammable.
Although hereinbefore having been made with reference to some embodiments, invention has been described, this hair is not being departed from
In the case where range, various improvement can be carried out to it, and component therein can be replaced with equivalent.Especially, as long as
There is no structural conflict, the various features in presently disclosed each embodiment can be combined with each other by any way
Get up use, in the present specification not to these combination the case where carry out exhaustive description merely for the sake of omit length and
The considerations of economizing on resources.Therefore, the invention is not limited to specific embodiments disclosed herein, but fall into claim
All technical solutions of range.
Claims (10)
1. a kind of cracking lignin is obtained by the way that wood fibre is carried out hydrogenation catalyst cracking.
2. cracking lignin according to claim 1, which is characterized in that the cracking lignin is liquid in room temperature
State.
3. cracking lignin according to claim 1 or 2, which is characterized in that the catalytic pyrolysis is in supported ruthenium metal
It is carried out in the presence of catalyst.
4. cracking lignin according to any one of claim 1-3, which is characterized in that the catalytic pyrolysis uses first
Pressure is 1-3MPa, preferably 1MPa-2MPa；Temperature is 230-250 DEG C, and preferably 250 DEG C, the reaction time is 3-6 hours, preferably
It is 3-4 hours.
5. cracking lignin described in any one of -4 according to claim 1, which is characterized in that the catalytic pyrolysis is deposited in solvent
It carries out under the conditions, the solvent is selected from one of methanol, ethyl alcohol, tetrahydrofuran and dioxane or a variety of.
6. cracking lignin according to any one of claims 1-5, which is characterized in that the partial size of the wood fibre is
Below 40 mesh.
7. a kind of preparation method of lignin-base hard polyurethane foam, comprising:
Step 1): by cracking lignin, petroleum-based polyols, catalyst and foaming agent of any of claims 1-6
Mixing, to obtain premixing components；
Step 2): isocyanates being added into premixing components, foams.
8. the method according to the description of claim 7 is characterized in that the petroleum-based polyols are selected from the pure and mild polyethers of polyester polyols
At least one of polyalcohol, it is preferable that the polyether polyol is selected from EP3600, PTMG-1000 (polytetrahydrofuran ether two
Alcohol), one of PPG-1000 (polypropylene glycol) and PEG (polyethylene glycol) or a variety of；It is (poly- that the polyester polyol is selected from PBT
Terephthalic acids fourth diester), PBA (butyl polyacrylate), one in PEA (polyacrylate) and PCL (polycaprolactone polyol)
Kind is a variety of.
9. method according to claim 7 or 8, which is characterized in that it is different that the isocyanates is selected from polymethylene polyphenyl
One of cyanate, toluene di-isocyanate(TDI) and methyl diphenylene diisocyanate are a variety of；And/or the foaming agent is selected from
Water, Foam agent ADC (azodicarbonamide) and one of sodium bicarbonate and ammonium carbonate or a variety of；The catalyst is selected from octanoic acid
Stannous, potassium acetate, dibutyltin dilaurate, N, N- Dimethylcyclohexyl, triethanolamine, triethylamine and N, N- dimethyl second
One of hydramine is a variety of.
10. the method according to any one of claim 7-9, which is characterized in that the cracking lignin and petroleum base are more
The mass ratio of first alcohol is 1:9-7:3, preferably 1:9,3:7 or 1:1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710532398.7A CN109206589B (en) | 2017-07-03 | 2017-07-03 | Preparation method of pyrolysis lignin and lignin-based polyurethane rigid foam |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710532398.7A CN109206589B (en) | 2017-07-03 | 2017-07-03 | Preparation method of pyrolysis lignin and lignin-based polyurethane rigid foam |
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| Publication Number | Publication Date |
|---|---|
| CN109206589A true CN109206589A (en) | 2019-01-15 |
| CN109206589B CN109206589B (en) | 2021-08-06 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201710532398.7A Active CN109206589B (en) | 2017-07-03 | 2017-07-03 | Preparation method of pyrolysis lignin and lignin-based polyurethane rigid foam |
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| EP3892662A1 (en) | 2020-04-07 | 2021-10-13 | Vito NV | Polyurethanes from depolymerized lignin containing lignin monomers |
| CN113666845A (en) * | 2021-07-21 | 2021-11-19 | 南京工业大学 | Lignin-based diphenylmethane diisocyanate and preparation method and application thereof |
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| CN113666845A (en) * | 2021-07-21 | 2021-11-19 | 南京工业大学 | Lignin-based diphenylmethane diisocyanate and preparation method and application thereof |
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| CN109206589B (en) | 2021-08-06 |
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