CN102585248B - Modified lignin, and preparation method and application thereof - Google Patents
Modified lignin, and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses modified lignin and a preparation method thereof. The method comprises the following steps of: performing first contact reaction on a straw lignin material, polyol and an acid catalyst for 1 to 4 hours at 100 to 135 DEG C, and adding starch for second contact reaction. The invention also discloses the application of the modified lignin to the preparation of biomass-based flame retardant polyurethane foams. The biomass-based flame retardant polyurethane foams prepared from the modified lignin prepared by the method have high mechanical properties.
Description
Technical field
The present invention relates to a kind of preparation method of modified lignin, the modified lignin prepared by the method, and the application of this modified lignin in the preparation of biomass-based polyurethane foam.
Background technology
Along with people are constantly deep to the understanding of ecocrisis and crisis of resource, the exploitation of the natural polymer novel materials such as xylogen, starch comes into one's own day by day.Xylogen and starch belong to natural high moleculer eompound, are the huge and reproducible organic resources of reserves, extensively are present in plant materials.Urethane, because it is cheap, superior performance, has become one of modern Polymeric Industry kind with fastest developing speed.Because xylogen, starch have the multiple functional groups such as hydroxyl, can petroleum replacing base chemical (as the petroleum base polyvalent alcohol) after exploitation, become the important sources of organic compound, for the synthesis of macromolecular materials such as urethane.
For xylogen being applied in the preparation process of the macromolecular materials such as urethane, those skilled in the art once attempted straw lignin is extracted and modification.For example, disclose in CN 101280049A and take straw and prepare the method for polyurethane foamed material as raw material, the method relates to the extraction of straw lignin and modification, concrete process comprises: (1) straw becomes 45-100 purpose fiber through crushing and screening, is dried to constant weight and obtains fiber A under 105 ℃; (2) process fiber A by microwave-Ethanol Method, using the aqueous ethanolic solution of 40-60% (volume ratio of ethanol and water) as extraction agent, the liquid-solid ratio of aqueous ethanolic solution and fiber A is 10: 1 (mass ratio), laser heating backflow 10-30 minute in microwave oven, filtration, drying obtain fiber B; (3) ethylene glycol of the polyoxyethylene glycol of 60-90% and 10-40% is mixed and is made into liquefied reagent; (4) fiber B, described liquefied reagent and sulfuric acid catalyst are mixed, and 150-180 ℃ of lower continuously stirring heating 1 hour.Yet, carry out according to the method for this patent application the xylogen that extraction and modification obtain and there is lower reactive behavior, therefore, in preparing the process of urethane, sufficient polyreaction can not occur with isocyanic ester in the hydroxyl of the xylogen so obtained, and most xylogen composition can only be present in the urethane of final preparation with the form of filler.Therefore, can't realize that on the one hand the xylogen composition can not play the effect of the crosslinked core of macromole polyfunctionality in urethane on the other hand, causes the bonding properties of xylogen composition and urethane poor by the purpose of xylogen composition petroleum replacing polylol.
Summary of the invention
First purpose of the present invention is extraction in order to overcome existing straw lignin and the above-mentioned defect of method of modifying, and a kind of preparation method of new biomass modified thing is provided.
Second purpose of the present invention is to provide the modified lignin prepared by described method.
The 3rd purpose of the present invention is to provide the application of described modified lignin in the preparation of biomass-based polyurethane foam.
The invention provides a kind of preparation method of modified lignin, wherein, the method comprises: under 100-135 ℃, make straw lignin material, polyvalent alcohol and an acidic catalyst carry out the first contact reacts 1-4 hour, then add starch to carry out the second contact reacts.
The present invention also provides the modified lignin prepared by aforesaid method.
The present invention also provides the application of described modified lignin in the preparation of biomass-based polyurethane foam.
The modified lignin prepared according to described method provided by the invention has higher reactive behavior, makes this modified lignin can replace the petroleum base polyvalent alcohol to participate in the polyreaction of urethane, realizes components of biomass substituting the petroleum base reactant.And the modified lignin prepared by described method is suitable for preparing biomass-based polyurethane foam.
Embodiment
According to a first aspect of the invention, the invention provides a kind of preparation method of modified lignin, the method comprises: under 100-135 ℃, make straw lignin material, polyvalent alcohol and an acidic catalyst carry out the first contact reacts 1-4 hour, then add starch to carry out the second contact reacts.
According to described method provided by the invention, described the first contact reacts is for described straw lignin is carried out to modification, to improve its reactive behavior.The described first catalytic reaction conditions preferably includes: temperature of reaction is 120-135 ℃, and the reaction times is 1-2 hour.
According to described method provided by the invention, described the second contact reacts is in order to control the condensation side reaction of straw lignin, makes the modified lignin of final acquisition have higher reactive behavior.The described second catalytic condition can comprise: temperature of reaction is 60-100 ℃, is preferably 80-90 ℃; Reaction times is 0.5-1 hour, is preferably 0.5-0.8 hour.
In the present invention, if straw lignin material, polyvalent alcohol, an acidic catalyst and starch are directly mixed and carry out the first contact reacts, starch can consume properties-correcting agent and catalyzer, thereby greatly reduce the modified effect of xylogen, thereby be difficult to reach the purpose of the reactive behavior that improves modified lignin.
According to described method provided by the invention, with respect to the straw lignin material of 100 weight parts, the add-on of described polyvalent alcohol can be the 90-200 weight part, is preferably the 120-160 weight part; The add-on of described an acidic catalyst can be the 0.1-3 weight part, is preferably the 0.5-2 weight part; The add-on of starch can be the 60-200 weight part, is preferably the 100-150 weight part.
In the present invention, described straw lignin material can be the stalk of various conventional plants, can be for example the stalk of grass, is preferably wheat stalk and/or maize straw.There is no particular limitation for the particle size of described straw lignin material, and under preferable case, the particle size of described straw lignin material is the 10-200 order.
In the present invention, described polyvalent alcohol can be the polyvalent alcohol of various routines, can be macromolecular polyol, can be also the small molecules polyvalent alcohol, as long as contain at least 2 hydroxyls in a molecule simultaneously.Under preferable case, described polyvalent alcohol is one or more in ethylene glycol, polyoxyethylene glycol and glycerine, and the weight-average molecular weight of described polyoxyethylene glycol can be 200-5000, is preferably 400-1000; In preferred situation, the mixture that described polyvalent alcohol is polyoxyethylene glycol and glycerine, under this preferable case, glycerine and polyoxyethylene glycol acting in conjunction can suppress the condensation reaction of xylogen, thereby can further improve the reactive behavior of the modified lignin of final acquisition.
According to described method provided by the invention, when mixture that described polyvalent alcohol is polyoxyethylene glycol and glycerine, the mixed weight ratio of polyoxyethylene glycol and glycerine is preferably 1-15: 1, and 1.5-10 more preferably: 1.Further, under preferable case, with respect to the straw lignin material of 100 weight parts, the add-on of described polyoxyethylene glycol is preferably the 80-150 weight part, and the add-on of described glycerine is preferably the 10-50 weight part.
In the present invention, described an acidic catalyst can be one or more in phosphoric acid, hydrochloric acid, sulfuric acid, formic acid, acetic acid, oxalic acid, propanedioic acid, succinic acid, Phenylsulfonic acid and phenylformic acid, most preferably is sulfuric acid.
In the present invention, described starch can be one or more in yam starch, W-Gum, tapioca (flour) and sweet potato starch.The particle size of described starch is preferably the 10-200 order.
According to a second aspect of the invention, the present invention also provides the modified lignin prepared by aforesaid method.
According to a third aspect of the present invention, the present invention also provides the application of described modified lignin in the preparation of biomass-based polyurethane foam.
In the present invention, the method that the modified lignin that adopts described method provided by the invention to prepare prepares biomass-based polyurethane foam can comprise: described modified lignin, polyether glycol, amines catalyst and whipping agent are evenly mixed, then by isocyanate index, be that 1-1.4 adds isocyanic ester to carry out contact reacts, and the product that this contact reacts is obtained is cured.
In the method, described catalytic reaction conditions can comprise: temperature of reaction is 15-30 ℃, is preferably 15-20 ℃; Reaction times is 0.5-5min, is preferably 1-2min.Described curing condition can comprise: curing temperature is 60-120 ℃, is preferably 60-80 ℃; The curing time is 2-24 hour, is preferably 2-10 hour.Described solidifying can adopt conventional curing to implement, for example baking oven for drying solidification.
The add-on of described modified lignin, polyether glycol, amines catalyst and whipping agent can change separately in the larger context.Under preferable case, with respect to the described modified lignin of 100 weight parts, the add-on of described polyether glycol is the 50-300 weight part, and the add-on of described amines catalyst is the 1-10 weight part, and the add-on of described whipping agent is the 10-100 weight part.When described xylogen, polyether glycol, amines catalyst and whipping agent all add fashionablely in above-mentioned numerical range, the biomass-based polyurethane foam of final preparation has mechanical property preferably.Further, under preferable case, with respect to the described modified lignin of 100 weight parts, the add-on of described polyether glycol is the 100-200 weight part, and the add-on of described amines catalyst is the 1.5-8 weight part, and the add-on of described whipping agent is the 20-50 weight part.Described polyether glycol can be the polyether glycol of commercially available various routines, and its weight-average molecular weight can be 200-5000, is preferably 400-1000, can be for example polyether glycol 4110 or polyether glycol 403.
Described amines catalyst can be one or more in triethylene diamine, triethylamine, trolamine and dimethylcyclohexylamine, most preferably is triethylene diamine.
Described whipping agent can be the whipping agent of various routines, it can be for example a fluorine ethylene dichloride, 1, 1, 1, 3, the 3-pentafluoropropane, 1, 1, 1, 3, the 3-3-pentafluorobutane, N, the N-dinitrosopentamethlyene tetramine, Cellmic C 121, Diisopropyl azodicarboxylate, diisopropyl azodiformate, diethyl azodiformate, Barium azodicarboxylate, 4, the 4-disulfonyl hydrazide diphenyl ether, p-toluene sulfonyl hydrazide, 1, the 3-benzene disulfohydrazide, 1, the 4-benzene disulfohydrazide, normal butane, Skellysolve A, normal hexane, normal heptane, sherwood oil, trichlorofluoromethane, dichlorofluoromethane, one or more in Refrigerant 12 and dichloro tetrafluoro ethane.Under preferable case, described whipping agent is the unreactive hydrocarbons compounds that boiling point is lower, and as a fluorine ethylene dichloride, 1,1,1,3, one or more in 3-pentafluoropropane and 1,1,1,3,3-3-pentafluorobutane, most preferably be a fluorine ethylene dichloride.
Described isocyanic ester is preferably the isocyanic ester (being also vulcabond or polyisocyanates) with two above isocyanos, and the described isocyanic ester with two above isocyanos can be for example one or more in tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, poly methylene poly phenyl poly isocyanate and diphenylmethanediisocyanate.
For the mechanical property of the biomass-based polyurethane foam that improves final preparation, the preparation method of described biomass-based polyurethane foam can also comprise and adds suds-stabilizing agent to mix with described modified lignin, polyether glycol, amines catalyst and whipping agent.With respect to the described modified lignin of 100 weight parts, the add-on of described suds-stabilizing agent can be the 1-10 weight part, is preferably the 1.5-8 weight part.In the present invention, described suds-stabilizing agent is preferably dimethyl siloxane and/or silicone oil.
For other additional properties of the biomass-based polyurethane foam that improves final preparation, the preparation method of described biomass-based polyurethane foam can also comprise that the additive that adds other mixes with described modified lignin, polyether glycol, amines catalyst and whipping agent.For example, for the biomass-based polyurethane foam that makes final preparation has flame retardant properties, can in step (2), add fire retardant.Described fire retardant can be the fire retardant of various routines, for example, halogen-containing fire retardant and phosphorous fire retardant, described halogen-containing fire retardant has pentabromodiphenyl oxide and dibromo phenyl glycidyl ether, and described phosphorous fire retardant mainly contains take the phosphonium flame retardant that ammonium polyphosphate is base (as Exolit RP) etc. as base (as ExolitAP), the organo phosphorous compounds of take as base (as Exolit OP) or the red phosphorus of take.Yet, in order further to improve the flame retardant properties of the biomass-based urethane of final preparation, described fire retardant preferably adopts following methods to prepare: under 100-180 ℃ (preferably 120-160 ℃), make phosphoric acid and tetramethylolmethane carry out contact reacts 0.5-5 hour (preferably 1-2 hour), then add polyether glycol, ammonium polyphosphate and trimeric cyanamide in the product obtained after this contact reacts, and continue contact reacts 0.5-4 hour (preferably 0.5-2 hour) 100-180 ℃ (preferably 120-160 ℃) is lower.In the preparation method of above-mentioned fire retardant, with respect to the tetramethylolmethane of 100 weight parts, the add-on of described phosphoric acid can be the 75-125 weight part, is preferably the 80-110 weight part; The add-on of described polyether glycol can be the 125-225 weight part, is preferably the 150-210 weight part; The add-on of described ammonium polyphosphate can be the 125-200 weight part, is preferably the 140-185 weight part; The add-on of described trimeric cyanamide can be the 100-200 weight part, is preferably the 120-180 weight part.Described polyether glycol can be the polyether glycol of commercially available various routines, and its weight-average molecular weight can be 200-5000, is preferably 400-1000, can be for example polyether glycol 4110 and or polyether glycol 403.The polymerization degree of described ammonium polyphosphate can be 50-2000, is preferably 100-1500.
The present invention is further detailed explanation by the following examples.
Embodiment 1
The present embodiment is for illustrating described modified lignin provided by the invention and preparation method thereof.
The sulfuric acid (98% the vitriol oil) of the glycerine of the polyoxyethylene glycol (PEG400) of the maize straw of 100 weight parts (particle size is the 80-120 order), 110 weight parts, 30 weight parts and 1.5 weight parts is mixed, and react 2 hours under 120 ℃.Then, to the yam starch (particle size is the 80-120 order) that adds 100 weight parts in reaction gained mixture, and, 80 ℃ of lower stirring reactions 0.8 hour, obtain modified lignin.
Comparative Examples 1
The sulfuric acid (98% the vitriol oil) of the glycerine of the polyoxyethylene glycol of the maize straw of 100 weight parts (particle size is the 80-120 order), 110 weight parts, 30 weight parts and 1.5 weight parts is mixed, and react 2.5 hours under 120 ℃, obtain modified lignin.
Comparative Examples 2
The sulfuric acid (98% the vitriol oil) of the glycerine of the polyoxyethylene glycol (PEG400) of the maize straw of 100 weight parts (particle size is the 80-120 order), 110 weight parts, 30 weight parts, 1.5 weight parts and 100 weight part yam starchs (particle size is the 80-120 order) are directly mixed, and react 3.3 hours under 120 ℃, obtain modified lignin.
Embodiment 2
The present embodiment is for illustrating described modified lignin provided by the invention and preparation method thereof.
Prepare modified lignin according to the method for embodiment 1, difference is that the ethylene glycol of the weight such as use replaces glycerine, thereby makes modified lignin.
Embodiment 3
The present embodiment is for illustrating described modified lignin provided by the invention and preparation method thereof.
Prepare modified lignin according to the method for embodiment 1, difference is, the polyoxyethylene glycol of use and the weight ratio of glycerine are 0.5: 1, and both gross weights are 140 weight parts, thereby makes modified lignin.
Embodiment 4
The present embodiment is for illustrating described modified lignin provided by the invention and preparation method thereof.
Prepare modified lignin according to the method for embodiment 1, difference is, the polyoxyethylene glycol of use and the weight ratio of glycerine are 20: 1, and both gross weights are 140 weight parts, thereby makes modified lignin.
Embodiment 5
The present embodiment is for illustrating described modified lignin provided by the invention and preparation method thereof.
The sulfuric acid (98% the vitriol oil) of the glycerine of the polyoxyethylene glycol of the wheat stalk of 100 weight parts (particle size is the 10-50 order), 80 weight parts, 50 weight parts and 0.5 weight part is mixed, and react 1.5 hours under 135 ℃.Then, to the tapioca (flour) (particle size is the 10-50 order) that adds 120 weight parts in reaction gained mixture, and, 90 ℃ of lower stirring reactions 0.5 hour, obtain modified lignin.
Embodiment 6
The present embodiment is for illustrating described modified lignin provided by the invention and preparation method thereof.
The sulfuric acid (98% the vitriol oil) of the glycerine of the polyoxyethylene glycol of the maize straw of 100 weight parts (particle size is the 100-150 order), 145 weight parts, 15 weight parts and 2 weight parts is mixed, and react 1 hour under 130 ℃.Then, to the sweet potato starch (particle size is the 100-150 order) that adds 150 weight parts in reaction gained mixture, and, 85 ℃ of lower stirring reactions 0.5 hour, obtain modified lignin.
Embodiment 7
The present embodiment is for illustrating the application of described modified lignin provided by the invention in the preparation of biomass-based polyurethane foam.
Under agitation, modified lignin by preparation in the embodiment of 100 weight parts 1, the polyether glycol of 150 weight parts (purchased from the polyether glycol 4110 of the clear month urethane factory of Beijing lark), the triethylene diamine solution of 5 weight parts is (purchased from the clear month urethane factory of Beijing lark, the trade mark is A33), 7.5 a fluorine ethylene dichloride (purchased from the clear month urethane factory of Beijing lark) of the dimethyl siloxane of weight part (purchased from the clear month urethane factory of Beijing lark) and 50 weight parts evenly mixes, then, the diphenylmethanediisocyanate (purchased from Hangzhou Green's Chemical trade company limited) that adds wherein 322 weight parts, so that isocyanate index is adjusted to 1.2, after stirring, make the mixture that obtains 20 ℃ of lower stirring reactions 1.5 minutes, then, in the baking oven of 85 ℃, solidify 12 hours, obtain biomass-based polyurethane foam A1.
Embodiment 8-12
The present embodiment is for illustrating the application of described modified lignin provided by the invention in the preparation of biomass-based polyurethane foam.
Prepare biomass-based polyurethane foam according to aforesaid method, difference is to use respectively the modified lignin prepared in embodiment 2-6 to replace the modified lignin of preparation in embodiment 1, thereby make respectively biomass-based polyurethane foam A2-A6.
Comparative Examples 3-4
Prepare biomass-based polyurethane foam according to aforesaid method, difference is to use respectively the modified lignin prepared in Comparative Examples 1-2 to replace the modified lignin of preparation in embodiment 1, thereby make respectively biomass-based polyurethane foam D1-D2.
Test case
(1) according to the density of GB/T 6343-1995 " mensuration of porous plastics and rubber apparent (volume) density " method testing method detection of biological matter base resistance combustion polyurethane foam A1-A6 and D1-D2;
(2) according to the compressive strength of GB8813-2008 " mensuration of rigid foam compression performance " method detection of biological matter base resistance combustion polyurethane foam A1-A6 and biomass-based flame retardant polyurethane foams D1-D2;
Above-mentioned test result is as shown in table 1 below:
Table 1
| Biomass-based polyurethane foam | Density (g/cm 3) | Compressive strength (kPa) | |
| Embodiment 7 | A1 | 0.037 | 0.148 |
| Comparative Examples 3 | D1 | 0.057 | 0.095 |
| Comparative Examples 4 | D2 | 0.051 | 0.109 |
| Embodiment 8 | A2 | 0.047 | 0.117 |
| Embodiment 9 | A3 | 0.040 | 0.123 |
| Embodiment 10 | A4 | 0.043 | 0.121 |
| Embodiment 11 | A5 | 0.038 | 0.125 |
| Embodiment 12 | A6 | 0.034 | 0.278 |
From above-mentioned table 1, can find out, the biomass-based polyurethane foam that adopts the prepared according to the methods of the invention modified lignin to make has good mechanical property.And, by embodiment 7 is compared and can find out with Comparative Examples 3 and 4, the modified lignin used in preparation process due to biomass-based polyurethane foam D1 and D2 does not adopt method of the present invention to carry out modification, thereby causes the compressive strength of the final biomass-based polyurethane foam obtained lower.
Above embodiment is only for describing the preferred embodiment of the present invention; but; the present invention is not limited to the detail in above-mentioned embodiment; in technical conceive scope of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition each the concrete technical characterictic described in above-mentioned embodiment, in reconcilable situation, can be combined by any suitable mode.For fear of unnecessary repetition, the present invention is to the explanation no longer separately of various possible array modes.
In addition, between various embodiment of the present invention, also can carry out arbitrary combination, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (9)
1. the preparation method of a modified lignin, it is characterized in that, the method comprises: under 100-135 ℃, make straw lignin material, polyvalent alcohol and an acidic catalyst carry out the first contact reacts 1-4 hour, then adding particle size is that 10-200 purpose starch carries out the second contact reacts, the described second catalytic condition comprises: temperature of reaction is 60-100 ℃, and the reaction times is 0.5-1 hour; With respect to the straw lignin material of 100 weight parts, the add-on of described polyvalent alcohol is the 90-200 weight part, and the add-on of described an acidic catalyst is the 0.1-3 weight part, and the add-on of starch is the 60-200 weight part.
2. method according to claim 1, wherein, the described first catalytic condition comprises: temperature of reaction is 120-135 ℃, the reaction times is 1-2 hour.
3. method according to claim 1, wherein, the described second catalytic condition comprises: temperature of reaction is 80-90 ℃, the reaction times is 0.5-0.8 hour.
4. according to the described method of any one in claim 1-3, wherein, with respect to the straw lignin material of 100 weight parts, the add-on of described polyvalent alcohol is the 120-160 weight part, the add-on of described an acidic catalyst is the 0.5-2 weight part, and the add-on of starch is the 100-150 weight part.
5. method according to claim 1, wherein, described polyvalent alcohol is at least one in ethylene glycol, polyoxyethylene glycol and glycerine.
6. method according to claim 5, wherein, the mixture that described polyvalent alcohol is polyoxyethylene glycol and glycerine, the weight ratio of polyoxyethylene glycol and glycerine is 1-15:1.
7. method according to claim 1, wherein, described an acidic catalyst is at least one in phosphoric acid, hydrochloric acid, sulfuric acid, formic acid, acetic acid, oxalic acid, propanedioic acid, succinic acid, Phenylsulfonic acid and phenylformic acid; The particle size of described straw lignin material is the 10-200 order.
8. a modified lignin, this modified lignin described method of any one in claim 1-7 makes.
9. the application of modified lignin claimed in claim 8 in the preparation of biomass-based polyurethane foam.
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| SI3230463T1 (en) | 2014-12-09 | 2023-01-31 | Sweetwater Energy, Inc. | Rapid pretreatment |
| CN106508898B (en) * | 2015-09-11 | 2020-04-24 | 沈阳化工研究院有限公司 | Biomass-based slow-release pesticide and preparation method thereof |
| CN106832327A (en) * | 2015-12-07 | 2017-06-13 | 中国林业科学研究院木材工业研究所 | A kind of fluorescent base nano lignin and preparation method thereof |
| WO2018053530A1 (en) * | 2016-09-19 | 2018-03-22 | Sweetwater Energy, Inc. | Improved foams and films using specialized lignin |
| CN110402288A (en) | 2017-02-16 | 2019-11-01 | 斯威特沃特能源公司 | It is formed for pretreated higher-pressure region |
| WO2021133733A1 (en) | 2019-12-22 | 2021-07-01 | Sweetwater Energy, Inc. | Methods of making specialized lignin and lignin products from biomass |
| CN111607062B (en) * | 2020-05-29 | 2022-04-08 | 河南恒泰源新材料有限公司 | Biomass polyurethane foam material and preparation method thereof |
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