Embodiment
According to a first aspect of the invention; The invention provides a kind of preparation method of lignin modification thing; This method comprises: under 100-135 ℃, straw lignin material, polyvalent alcohol and an acidic catalyst were carried out the first contact reacts 1-4 hour, add starch then and carry out second contact reacts.
According to said method provided by the invention, said first contact reacts is for said straw lignin is carried out modification, to improve its reactive behavior.The said first catalytic reaction conditions preferably includes: temperature of reaction is 120-135 ℃, and the reaction times is 1-2 hour.
According to said method provided by the invention, said second contact reacts is in order to control the condensation side reaction of straw lignin, to make the final lignin modification thing that obtains have high reaction activity and high.The said 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 first contact reacts; Then 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 the lignin modification thing.
According to said method provided by the invention, with respect to the straw lignin material of 100 weight parts, the add-on of said polyvalent alcohol can be the 90-200 weight part, is preferably the 120-160 weight part; The add-on of said 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, said straw lignin material can be the stalk of various conventional plants, for example can be the stalk of grass, is preferably wheat stalk and/or corn straw.The particle size of said straw lignin material does not have special qualification, and under the preferable case, the particle size of said straw lignin material is the 10-200 order.
In the present invention, said polyvalent alcohol can be the polyvalent alcohol of various routines, can be macromolecular polyol, also can be the small molecules polyvalent alcohol, as long as contain at least 2 hydroxyls simultaneously in a molecule.Under the preferable case, said polyvalent alcohol is one or more in terepthaloyl moietie, polyoxyethylene glycol and the glycerine, and the weight-average molecular weight of said polyoxyethylene glycol can be 200-5000, is preferably 400-1000; Under the preferred situation; Said polyvalent alcohol is the mixture of 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 lignin modification thing of final acquisition.
According to said method provided by the invention, when said polyvalent alcohol was the mixture of polyoxyethylene glycol and glycerine, the mixed weight ratio of polyoxyethylene glycol and glycerine was preferably 1-15: 1, and 1.5-10 more preferably: 1.Further under the preferable case, with respect to the straw lignin material of 100 weight parts, the add-on of said polyoxyethylene glycol is preferably the 80-150 weight part, and the add-on of said glycerine is preferably the 10-50 weight part.
In the present invention, said an acidic catalyst can be in phosphoric acid, hydrochloric acid, sulfuric acid, formic acid, acetate, oxalic acid, propanedioic acid, Succinic Acid, Phenylsulfonic acid and the phenylformic acid one or more, most preferably is sulfuric acid.
In the present invention, said starch can be in yam starch, W-Gum, tapioca(flour) and the sweet potato starch one or more.The particle size of said starch is preferably the 10-200 order.
According to a second aspect of the invention, the present invention also provides the lignin modification thing by method for preparing.
According to a third aspect of the present invention, the present invention also provides the application of said lignin modification thing in the preparation of biomass-based polyurethane foam.
In the present invention; The method that the lignin modification thing that adopts said method provided by the invention to prepare prepares biomass-based polyurethane foam can comprise: with said lignin modification thing, polyether glycol, amines catalyst and whipping agent uniform mixing; Be that 1-1.4 adding isocyanic ester carries out contact reacts by isocyanate index then, and the product that this contact reacts is obtained is cured.
In the method, said 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.Said solidified condition can comprise: the solidified temperature is 60-120 ℃, is preferably 60-80 ℃; The solidified time is 2-24 hour, is preferably 2-10 hour.Said curing can adopt conventional curing to implement, for example baking oven for drying solidification.
The add-on of said lignin modification thing, polyether glycol, amines catalyst and whipping agent can change separately in the larger context.Under the preferable case, with respect to the said lignin modification thing of 100 weight parts, the add-on of said polyether glycol is the 50-300 weight part, and the add-on of said amines catalyst is the 1-10 weight part, and the add-on of said whipping agent is the 10-100 weight part.When said 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 the preferable case, with respect to the said lignin modification thing of 100 weight parts, the add-on of said polyether glycol is the 100-200 weight part, and the add-on of said amines catalyst is the 1.5-8 weight part, and the add-on of said whipping agent is the 20-50 weight part.Said 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, for example can be polyether glycol 4110 or polyether glycol 403.
Said amines catalyst can be in triethylene diamine, triethylamine, trolamine and the dimethylcyclohexylamine one or more, most preferably is triethylene diamine.
Said whipping agent can be the whipping agent of various routines, for example can be a fluorine ethylene dichloride, 1,1; 1,3,3-pentafluoropropane, 1; 1,1,3; 3-3-pentafluorobutane, N, N-dinitroso five methyne tetramines, Cellmic C 121, Diisopropyl azodicarboxylate, diisopropyl azodiformate, diethyl azodiformate, azoformic acid barium, 4,4-disulfonyl hydrazide diphenyl ether, p-toluene sulfonyl hydrazide, 1; 3-benzene disulfohydrazide, 1, one or more in 4-benzene disulfohydrazide, normal butane, Skellysolve A, normal hexane, normal heptane, sherwood oil, trichlorofluoromethane, dichlorofluoromethane, Refrigerant 12 and the dichloro tetrafluoro ethane.Under the preferable case, said whipping agent is the lower unreactive hydrocarbons compounds of boiling point, like a fluorine ethylene dichloride, 1,1,1,3, and 3-pentafluoropropane and 1,1,1,3, one or more in the 3-3-pentafluorobutane most preferably are a fluorine ethylene dichloride.
Said isocyanic ester is preferably the isocyanic ester (also being vulcabond or POLYMETHYLENE POLYPHENYLISOCYANATE) with two above isocyanos, and said isocyanic ester with two above isocyanos for example can be in tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, poly methylene poly phenyl poly isocyanate and the diphenylmethanediisocyanate one or more.
For the mechanical property of the biomass-based polyurethane foam that improves final preparation, the preparation method of said biomass-based polyurethane foam can also comprise that adding suds-stabilizing agent mixes with said lignin modification thing, polyether glycol, amines catalyst and whipping agent.With respect to the said lignin modification thing of 100 weight parts, the add-on of said suds-stabilizing agent can be the 1-10 weight part, is preferably the 1.5-8 weight part.In the present invention, said 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 said biomass-based polyurethane foam can also comprise that the additive that adds other mixes with said lignin modification thing, polyether glycol, amines catalyst and whipping agent.For example, for the biomass-based polyurethane foam that makes final preparation has flame retardant properties, then can in step (2), add fire retardant.Said fire retardant can be the fire retardant of various routines; For example; Halogen-containing fire retardant and phosphorated fire retardant; Said halogen-containing fire retardant has pentabromodiphenyl oxide and dibromo phenyl glycidyl ether, and it is base (like ExolitAP) that said phosphorated fire retardant mainly contains with the ammonium polyphosphate, be base (like Exolit OP) with the organo phosphorous compounds or be the phosphonium flame retardant of base (like Exolit RP) etc. with red phosphorus.Yet; In order further to improve the flame retardant properties of the biomass-based urethane of final preparation; Said fire retardant preferably adopts following method to prepare: under 100-180 ℃ (preferred 120-160 ℃); Make phosphoric acid and tetramethylolmethane carry out contact reacts 0.5-5 hour (preferred 1-2 hour); Add polyether glycol, ammonium polyphosphate and trimeric cyanamide in the product that after this contact reacts, obtains then, and continued contact reacts 0.5-4 hour down (preferred 0.5-2 hour) at 100-180 ℃ (preferred 120-160 ℃).In the preparation method of above-mentioned fire retardant, with respect to the tetramethylolmethane of 100 weight parts, the add-on of said phosphoric acid can be the 75-125 weight part, is preferably the 80-110 weight part; The add-on of said polyether glycol can be the 125-225 weight part, is preferably the 150-210 weight part; The add-on of said ammonium polyphosphate can be the 125-200 weight part, is preferably the 140-185 weight part; The add-on of said trimeric cyanamide can be the 100-200 weight part, is preferably the 120-180 weight part.Said 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, for example can be polyether glycol 4110 and or polyether glycol 403.The polymerization degree of said ammonium polyphosphate can be 50-2000, is preferably 100-1500.
Below through embodiment the present invention is done further detailed explanation.
Embodiment 1
Present embodiment is used to explain said lignin modification thing provided by the invention and preparation method thereof.
The corn straw (particle size is the 80-120 order) of 100 weight parts, the polyoxyethylene glycol (PEG400) of 110 weight parts, the glycerine of 30 weight parts and the sulfuric acid (98% the vitriol oil) of 1.5 weight parts are mixed, and reacted 2 hours down at 120 ℃.Then, in reaction gained mixture, add the yam starch (particle size is the 80-120 order) of 100 weight parts, and, obtain the lignin modification thing 80 ℃ of following stirring reactions 0.8 hour.
Comparative Examples 1
The corn straw (particle size is the 80-120 order) of 100 weight parts, the polyoxyethylene glycol of 110 weight parts, the glycerine of 30 weight parts and the sulfuric acid (98% the vitriol oil) of 1.5 weight parts are mixed, and reacted 2.5 hours down, obtain the lignin modification thing at 120 ℃.
Comparative Examples 2
The corn straw (particle size is the 80-120 order) of 100 weight parts, the polyoxyethylene glycol (PEG400) of 110 weight parts, the glycerine of 30 weight parts, the sulfuric acid (98% the vitriol oil) and the 100 weight part yam starchs (particle size is the 80-120 order) of 1.5 weight parts are directly mixed; And under 120 ℃, reacted 3.3 hours, obtain the lignin modification thing.
Embodiment 2
Present embodiment is used to explain said lignin modification thing provided by the invention and preparation method thereof.
Method according to embodiment 1 prepares the lignin modification thing, and different is that the terepthaloyl moietie of weight such as use replaces glycerine, thereby makes the lignin modification thing.
Embodiment 3
Present embodiment is used to explain said lignin modification thing provided by the invention and preparation method thereof.
Method according to embodiment 1 prepares the lignin modification thing, and different 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 the lignin modification thing.
Embodiment 4
Present embodiment is used to explain said lignin modification thing provided by the invention and preparation method thereof.
Method according to embodiment 1 prepares the lignin modification thing, and different 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 the lignin modification thing.
Embodiment 5
Present embodiment is used to explain said lignin modification thing provided by the invention and preparation method thereof.
The wheat stalk (particle size is the 10-50 order) of 100 weight parts, the polyoxyethylene glycol of 80 weight parts, the glycerine of 50 weight parts and the sulfuric acid (98% the vitriol oil) of 0.5 weight part are mixed, and reacted 1.5 hours down at 135 ℃.Then, in reaction gained mixture, add the tapioca(flour) (particle size is the 10-50 order) of 120 weight parts, and, obtain the lignin modification thing 90 ℃ of following stirring reactions 0.5 hour.
Embodiment 6
Present embodiment is used to explain said lignin modification thing provided by the invention and preparation method thereof.
The corn straw (particle size is the 100-150 order) of 100 weight parts, the polyoxyethylene glycol of 145 weight parts, the glycerine of 15 weight parts and the sulfuric acid (98% the vitriol oil) of 2 weight parts are mixed, and reacted 1 hour down at 130 ℃.Then, in reaction gained mixture, add the sweet potato starch (particle size is the 100-150 order) of 150 weight parts, and, obtain the lignin modification thing 85 ℃ of following stirring reactions 0.5 hour.
Embodiment 7
Present embodiment is used for explaining the application of said lignin modification thing provided by the invention in the preparation of biomass-based polyurethane foam.
Under agitation; With the triethylene diamine solution of the polyether glycol (available from the polyether glycol 4110 of clear month urethane factory of Beijing lark) of lignin modification thing, 150 weight parts of preparation among the embodiment 1 of 100 weight parts, 5 weight parts (available from clear month urethane factory of Beijing lark; The trade mark is A33), a fluorine ethylene dichloride (available from urethane factory of the clear moon of Beijing lark) uniform mixing of the dimethyl siloxane of 7.5 weight parts (available from clear month urethane factory of Beijing lark) and 50 weight parts, then, to the diphenylmethanediisocyanate that wherein adds 322 weight parts (available from Hangzhou Green's chemical industry trade Co., Ltd); So that isocyanate index is adjusted to 1.2; After stirring, make the mixture that obtains 20 ℃ of following stirring reactions 1.5 minutes, then; In 85 ℃ baking oven, solidified 12 hours, obtain biomass-based polyurethane foam A1.
Embodiment 8-12
Present embodiment is used for explaining the application of said lignin modification thing provided by the invention in the preparation of biomass-based polyurethane foam.
According to the biomass-based polyurethane foam of method for preparing, different is to use the lignin modification thing for preparing among the embodiment 2-6 to replace the lignin modification thing of preparation among the embodiment 1 respectively, thereby make biomass-based polyurethane foam A2-A6 respectively.
Comparative Examples 3-4
According to the biomass-based polyurethane foam of method for preparing, different is to use the lignin modification thing for preparing among the Comparative Examples 1-2 to replace the lignin modification thing of preparation among the embodiment 1 respectively, thereby make biomass-based polyurethane foam D1-D2 respectively.
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 resistance combustion polyurethane foam D1-D2;
Above-mentioned test result is as shown in table 1 below:
Table 1
| Biomass-based polyurethane foam | Density (g/cm3) | 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 |
Can find out that from above-mentioned table 1 the biomass-based polyurethane foam that adopts prepared according to the methods of the invention lignin modification thing to make has good mechanical property.And; Through embodiment 7 is compared and can find out with Comparative Examples 3 and 4; Because the lignin modification thing that uses in the preparation process of biomass-based polyurethane foam D1 and D2 does not adopt method of the present invention to carry out modification, thereby cause the compressive strength of the final biomass-based polyurethane foam that obtains lower.
Above embodiment only is used to describe preferred implementation of the present invention; But; The present invention is not limited to the detail in the 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.
Need to prove that in addition each the concrete technical characterictic described in above-mentioned embodiment under reconcilable situation, can make up through any suitable manner.For fear of unnecessary repetition, the present invention is to the explanation no longer separately of various possible array modes.
In addition, also can carry out arbitrary combination between the various embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be regarded as the disclosed content of the present invention equally.