CN102585142A - Biomass polyurethane foam and method for preparing same - Google Patents
Biomass polyurethane foam and method for preparing same Download PDFInfo
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Abstract
The invention discloses a biomass polyurethane foam and a method for preparing the same, wherein the method comprises the following steps that: (1) under 100-135 DEG C, straw lignin material, polyalcohol and acid catalyst are subjected to first contact reaction for 1-4 hours, then starch is added for carrying out second contact reaction, so modified lignin is obtained; and (2) the modified lignin, polyether polyol, amine catalyst and foaming agent are uniformly mixed, then isocyanate is added for carrying out third contact reaction according to the isocyanate index of 1-1.4, and the product which is obtained from the third contact reaction is solidified. The polyurethane foam which is prepared by the method has excellent mechanical property.
Description
Technical field
The present invention relates to a kind of preparation method of biomass-based polyurethane foam, and by the biomass-based polyurethane foam of this method preparation.
Background technology
Along with people's is constantly deep to the understanding of ecocrisis and crisis of resource, and the exploitation of 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 the plant materials.Urethane is because its cheap, superior performance has become one of the fastest kind of modern polymer industrial development.Because xylogen, starch have multiple functional groups such as hydroxyl, through substituting petroleum base chemical (like the petroleum base polyvalent alcohol) after the exploitation, become the important source of organic cpds, be used for macromolecular materials such as synthesis of polyurethane.
Disclose among the CN1543478A and utilized the xylogen method for producing polyurethanes; This method comprises makes many alcoholic solutions and the POLYMETHYLENE POLYPHENYLISOCYANATE generation polycondensation that contains lignosulfonic acid or its part neutralized salt with dissolved state; Wherein, the amount of this lignosulfonic acid or its part neutralized salt accounts for 1-40% in total urethane.Yet; The reactive behavior of the lignosulfonic acid in this method or its part neutralized salt is lower; Sufficient polyreaction can not take place with POLYMETHYLENE POLYPHENYLISOCYANATE in its hydroxyl; And most xylogen composition can only be present in the form of filler in the urethane of final preparation, therefore, can't realize substituting with the xylogen composition purpose of petroleum base polyvalent alcohol on the one hand; The xylogen composition can not play the effect of the crosslinked nuclear of macromole polyfunctionality in urethane on the other hand, causes the bonding properties of xylogen composition and urethane relatively poor.
Summary of the invention
An object of the present invention is in order to overcome the above-mentioned defective of prior biological matter urethane, a kind of preparation method of biomass-based polyurethane foam newly is provided.
Another object of the present invention provides the biomass-based polyurethane foam by said method preparation.
The invention provides a kind of preparation method of biomass-based polyurethane foam, this method may further comprise the steps:
(1) 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, obtain the lignin modification thing;
(2), be that 1-1.4 adding isocyanic ester carries out the 3rd contact reacts by isocyanate index then, and the product that the 3rd contact reacts is obtained is cured with said lignin modification thing, polyether glycol, amines catalyst and whipping agent uniform mixing.
The present invention also provides a kind of biomass-based polyurethane foam, and this biomass-based polyurethane foam is made by aforesaid method.
In said method provided by the invention; The lignin modification thing of preparation has high reaction activity and high in the step (1); Make xylogen can replace the petroleum base polyvalent alcohol to participate in the polyreaction of urethane, the realization components of biomass substitutes the petroleum base reactant, and modification temperature is lower simultaneously; In addition, according in the process of the biomass-based polyurethane foam of preparation of the present invention not needs use volatile solvent, thereby can not pollute environment.
Embodiment
The preparation method of said biomass-based polyurethane foam provided by the invention may further comprise the steps:
(1) 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, obtain the lignin modification thing;
(2), be that 1-1.4 adding isocyanic ester carries out the 3rd contact reacts by isocyanate index then, and the product that the 3rd contact reacts is obtained is cured with said lignin modification thing, polyether glycol, amines catalyst and whipping agent uniform mixing.
In the present invention; Term " isocyanate index " refers to the ratio of isocyanurate equivalent number and polyvalent alcohol equivalents; The excessive degree of isocyanic ester in the expression polyurethane formulations; Said isocyanurate equivalent number is meant the mole number of the isocyano in the isocyanic ester, and said polyvalent alcohol equivalents is meant the mole number of the alcoholic extract hydroxyl group of polyvalent alcohol.
According to said method provided by the invention, in step (1), 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, in step (1), 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; In step (1); 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 reduces the modified effect of xylogen, thereby is difficult to reach the purpose of the reactive behavior that improves the lignin modification thing.
According to said method provided by the invention, in step (1), 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, in step (1), 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 said method provided by the invention, in step (2), the said the 3rd 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.
According to said method provided by the invention, in step (2), the condition that the product that said the 3rd contact reacts is obtained is cured 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.
According to said method provided by the invention, 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 is preferably 200-5000, and more preferably 400-1000 for example can be polyether glycol 4110 and/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.
According to said method provided by the invention, 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 be included in and add suds-stabilizing agent in the step (2).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.
According to said method provided by the invention, 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 be included in the additive that adds other in the step (2).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 Exolit AP) 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.
The present invention also provides the biomass-based resistance combustion polyurethane foam by method for preparing.
Below through embodiment the present invention is done further detailed explanation.
Embodiment 1
Present embodiment is used to explain said biomass-based polyurethane foam provided by the invention and preparation method thereof.
(1) preparation of lignin modification thing
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.
(2) preparation of biomass-based polyurethane foam
Under agitation; With the triethylene diamine solution of lignin modification thing of preparation in (1) of 100 weight parts, the polyether glycol of 150 weight parts (available from the polyether glycol 4110 of clear month urethane factory of Beijing lark), 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.
Comparative Examples 1
Method according to embodiment 1 prepares biomass-based polyurethane foam; Different is; The lignin modification thing that the following method of weight such as uses to obtain replaces said lignin modification thing of preparation in above-mentioned (1): the corn straw (particle size is the 80-120 order) of 110 weight parts, the polyoxyethylene glycol of 100 weight parts, the glycerine of 30 weight parts and the sulfuric acid (98% the vitriol oil) of 1.5 weight parts mixed, and 120 ℃ of reactions 2.5 hours down.So make biomass-based polyurethane foam D1.
Comparative Examples 2
Method according to embodiment 1 prepares biomass-based polyurethane foam; Different is; In step (1); 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 reacted 3.3 hours down, with preparation lignin modification thing at 120 ℃.Thereby make biomass-based polyurethane foam D2.
Embodiment 2
Present embodiment is used to explain said biomass-based polyurethane foam provided by the invention and preparation method thereof.
Method according to embodiment 1 prepares biomass-based polyurethane foam, and different is that in step (1), the terepthaloyl moietie of weight such as use replaces glycerine, with preparation lignin modification thing.Thereby make biomass-based polyurethane foam A2.
Embodiment 3
Present embodiment is used to explain said biomass-based polyurethane foam provided by the invention and preparation method thereof.
Method according to embodiment 1 prepares biomass-based polyurethane foam, and different is, in step (1), the polyoxyethylene glycol of use and the weight ratio of glycerine are 0.5: 1, and both gross weights are 140 weight parts, with preparation lignin modification thing.Thereby make biomass-based polyurethane foam A3.
Embodiment 4
Present embodiment is used to explain said biomass-based polyurethane foam provided by the invention and preparation method thereof.
Method according to embodiment 1 prepares biomass-based polyurethane foam, and different is, in step (1), the polyoxyethylene glycol of use and the weight ratio of glycerine are 20: 1, and both gross weights are 140 weight parts, with preparation lignin modification thing.Thereby make biomass-based polyurethane foam A4.
Embodiment 5
Present embodiment is used to explain said biomass-based polyurethane foam provided by the invention and preparation method thereof.
(1) preparation of lignin modification thing
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.
(2) preparation of biomass-based polyurethane foam
Under agitation, with 1,1 of the dimethyl siloxane (available from clear month urethane factory of Beijing lark) of the trolamine (available from Beijing China imperial chemical industry ltd) of lignin modification thing of preparation in (1) of 100 weight parts, the polyether glycol of 100 weight parts (available from the polyether glycol 403 of clear month urethane factory of Beijing lark), 1.5 weight parts, 5 weight parts and 40 weight parts; 1,3,3-pentafluoropropane (available from clear month urethane factory of Beijing lark) uniform mixing; Then; To the hexamethylene diisocyanate that wherein adds 302 weight parts (available from Hangzhou Green's chemical industry trade Co., Ltd), so that isocyanate index is adjusted to 1.0, after stirring; Make the mixture that obtains 20 ℃ of following stirring reactions 30 seconds; Then, in 85 ℃ baking oven, solidified 12 hours, obtain biomass-based polyurethane foam A5.
Embodiment 6
Present embodiment is used to explain said biomass-based polyurethane foam provided by the invention and preparation method thereof.
(1) preparation of lignin modification thing
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.
(2) preparation of biomass-based polyurethane foam
Under agitation; With the lignin modification thing of preparation in (1) of 100 weight parts, the polyether glycol of 80 weight parts (available from the polyether glycol 4110 of clear month urethane factory of Beijing lark) and the silicone oil (available from clear month urethane factory of Beijing lark) of the polyether glycol (available from the polyether glycol 403 of clear month urethane factory of Beijing lark) of 120 weight parts, the triethylene diamine solution of 8 weight parts (available from clear month urethane factory of Beijing lark), 1.5 weight parts and a fluorine ethylene dichloride (available from clear month urethane factory of Beijing lark) uniform mixing of 20 weight parts; Then; To the tolylene diisocyanate that wherein adds 597 weight parts (available from Hangzhou Green's chemical industry trade Co., Ltd); So that isocyanate index is adjusted to 1.4; After stirring, make the mixture that obtains 20 ℃ of following stirring reactions 3 minutes, then; In 85 ℃ baking oven, solidified 12 hours, obtain biomass-based polyurethane foam A6.
Test case
(1) detects the density of the biomass-based polyurethane foam D1-D2 for preparing among the biomass-based polyurethane foam A1-A6 for preparing among the embodiment 1-6 and the Comparative Examples 1-2 according to GB/T 6343-1995 " mensuration of porous plastics and rubber apparent (volume) density " method testing method;
(2) detect the compressive strength of the biomass-based polyurethane foam D1-D2 for preparing among the biomass-based polyurethane foam A1-A6 for preparing among the embodiment 1-6 and the Comparative Examples 1-2 according to GB8813-2008 " mensuration of rigid foam compression performance " method;
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 1 | A1 | 0.037 | 0.148 |
| Comparative Examples 1 | D1 | 0.057 | 0.095 |
| Comparative Examples 2 | D2 | 0.051 | 0.109 |
| Embodiment 2 | A2 | 0.041 | 0.127 |
| Embodiment 3 | A3 | 0.038 | 0.133 |
| Embodiment 4 | A4 | 0.039 | 0.131 |
| Embodiment 5 | A5 | 0.038 | 0.125 |
| Embodiment 6 | A6 | 0.034 | 0.278 |
Can find out that from above-mentioned table 1 the prepared according to the methods of the invention polyurethane foam has good mechanical property.And; Through embodiment 1 is compared and can find out with Comparative Examples 1 and 2; In the preparation process of biomass-based polyurethane foam D1 and D2,, thereby cause the compressive strength of the final biomass-based polyurethane foam that obtains lower because xylogen does not adopt method of the present invention to carry out modification.
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.
Claims (11)
1. the preparation method of a biomass-based polyurethane foam, this method may further comprise the steps:
(1) 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, obtain the lignin modification thing;
(2), be that 1-1.4 adding isocyanic ester carries out the 3rd contact reacts by isocyanate index then, and the product that the 3rd contact reacts is obtained is cured with said lignin modification thing, polyether glycol, amines catalyst and whipping agent uniform mixing.
2. method according to claim 1, wherein, the said second catalytic condition comprises: temperature of reaction is 60-100 ℃, the reaction times is 0.5-1 hour.
3. method according to claim 1, wherein, in step (1); Straw lignin material with respect to 100 weight parts; The add-on of said polyvalent alcohol is the 90-200 weight part, and the add-on of said an acidic catalyst is the 0.1-3 weight part, and the add-on of starch is the 60-200 weight part.
4. method according to claim 1, wherein, in step (1); Straw lignin material with respect to 100 weight parts; The add-on of said polyvalent alcohol is the 120-160 weight part, and the add-on of said an acidic catalyst is the 0.5-2 weight part, and the add-on of starch is the 100-150 weight part.
5. according to any described method among the claim 1-4, wherein, said polyvalent alcohol is at least a in terepthaloyl moietie, polyoxyethylene glycol and the glycerine; Said an acidic catalyst is at least a in phosphoric acid, hydrochloric acid, sulfuric acid, formic acid, acetate, oxalic acid, propanedioic acid, Succinic Acid, Phenylsulfonic acid and the phenylformic acid; The particle size of said straw lignin material is the 10-200 order.
6. according to any described method among the claim 1-4, wherein, said polyvalent alcohol is the mixture of polyoxyethylene glycol and glycerine.
7. method according to claim 1; Wherein, In step (2), 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; 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.
8. according to claim 1 or 7 described methods, wherein, said amines catalyst is one or more of triethylene diamine, triethylamine, trolamine and dimethylcyclohexylamine; Said whipping agent is 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; Said isocyanic ester is one or more in tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, polymethylene multi-phenenyl isocyanate and the diphenylmethanediisocyanate.
9. method according to claim 1, wherein, the said the 3rd catalytic reaction conditions comprises: temperature of reaction is 15-30 ℃, the reaction times is 0.5-5 minute.
10. method according to claim 1, wherein, said solidified condition comprises: the solidified temperature is 60-120 ℃, the solidified time is 2-24 hour.
11. a biomass-based polyurethane foam, this biomass-based polyurethane foam is made by any described method among the claim 1-10.
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| CN110467718A (en) * | 2019-07-10 | 2019-11-19 | 厦门大学 | A kind of biomass-based buffering package foamed material and preparation method thereof |
| CN111607062A (en) * | 2020-05-29 | 2020-09-01 | 叶正芬 | Biomass polyurethane foam material and preparation method thereof |
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| CN102977330A (en) * | 2012-11-14 | 2013-03-20 | 华北电力大学 | Preparation method for degradable polyurethane materials |
| CN104530446A (en) * | 2015-01-06 | 2015-04-22 | 青岛科技大学 | Method for preparing polyether polyol by liquifying and modifying peanut shells |
| CN106508898A (en) * | 2015-09-11 | 2017-03-22 | 沈阳化工研究院有限公司 | Biomass-based slow-release pesticide and preparation method thereof |
| 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 |
| CN106832173A (en) * | 2015-12-07 | 2017-06-13 | 财团法人工业技术研究院 | Biological polyol composition and biological polyurethane foam material |
| US10323115B2 (en) | 2015-12-07 | 2019-06-18 | Industrial Technology Research Institute | Bio-polyol composition and bio-polyurethane foam |
| CN106832173B (en) * | 2015-12-07 | 2019-11-05 | 财团法人工业技术研究院 | Biological polyol composition and biological polyurethane foam material |
| CN105694357A (en) * | 2016-01-17 | 2016-06-22 | 浙江省林业科学研究院 | Preparation method of polyether modified biomass resin through normal-temperature fast foaming |
| CN110467718A (en) * | 2019-07-10 | 2019-11-19 | 厦门大学 | A kind of biomass-based buffering package foamed material and preparation method thereof |
| CN111607062A (en) * | 2020-05-29 | 2020-09-01 | 叶正芬 | Biomass polyurethane foam material and preparation method thereof |
| CN112694592A (en) * | 2020-12-29 | 2021-04-23 | 中国林业科学研究院木材工业研究所 | Polyurethane sandwich board and preparation method thereof |
| CN114656671A (en) * | 2022-04-29 | 2022-06-24 | 北华大学 | Preparation method of composite straw-based degradable waste polyurethane foam wall material |
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