CN104119491A - Soybean protein modified polyurethane, and preparation method and application thereof - Google Patents
Soybean protein modified polyurethane, and preparation method and application thereof Download PDFInfo
- Publication number
- CN104119491A CN104119491A CN201310143667.2A CN201310143667A CN104119491A CN 104119491 A CN104119491 A CN 104119491A CN 201310143667 A CN201310143667 A CN 201310143667A CN 104119491 A CN104119491 A CN 104119491A
- Authority
- CN
- China
- Prior art keywords
- soy
- soybean protein
- protein
- polyurethane
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/36—Hydroxylated esters of higher fatty acids
-
- 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
- C08G18/6415—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63 having nitrogen
- C08G18/6446—Proteins and derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention provides a soybean protein modified polyurethane, and a preparation method and an application thereof. The preparation method comprises the following steps: adding sulfoxide and diamine to a soybean protein solution with the pH value of 8-13, reacting, and separating products to obtain a soybean protein modified derivative PDSP; and carrying out dissolving and mixing on a polyurethane prepolymer and the PDSP, adding a chain extender, and reacting to obtain the soybean protein modified polyurethane. The above product obtained by using a natural polymer material is biodegradable and environmentally-friendly; the modification of a soybean protein membrane material improves the mechanical properties and the water resistance, and realizes good tensile strength and elongation at break; and materials with various mechanical properties from plastics to elastomers can be obtained through toughening soybean protein plastics by polyurethane and reinforcing polyurethane by rigid PDSP. The soybean protein modified polyurethane has the advantages of simple synthetic process, low cost, and suitableness for application and popularization.
Description
Technical field
The present invention relates to a kind of polymer materials and method of modifying thereof, relate in particular to a kind of soy-protein modified polyurethane and method of modifying thereof.
Background technology
For the Sustainable development of human society, the research of the biodegradable polymer based on renewable resources is day by day noticeable.USDOE plan will account for 10% to the year two thousand twenty from the basic chemical structure material of animal and plant renewable resources, and will reach 20% to the year two thousand fifty.In natural reproducible resource, the application of the materials such as protein, starch, xylogen has caused investigator's broad interest, as the disclosed whey-protein based aqueous macromolecule of people sizing agent (J.Appl.Polym.Sci. such as Zhenhua Gao, 2011,120: 220-225), the disclosed tackiness agent of patent WO2007/120653A, comprises starch and protein, and does not contain artificial-synthetic copolymer.
Soybean protein has the characteristics such as abundant, renewable and fully biodegradable of originating, therefore be a kind of raw material that has very much application prospect, as methods such as hot-forming, extrusion moulding or injection moldings, can prepare plastic of soybean protein by traditional plastic shaping method.But there is water sensitivity (poor water resistance), fragility and be difficult for the shortcomings such as processing in plastic of soybean protein, greatly limits its development and utilization.In order to overcome these problems, improve its performance through methods such as conventional blend, derivatize and graft copolymerizations.
Patent CN100494299C discloses the natural polymers such as soybean protein and polyurethane comixing tackiness agent, patent JP2010-65214A and discloses a kind of natural protein (as soybean protein) Yu the mixture of oxazoline polymkeric substance, but between soybean protein and general synthetic polymer because polarity differs greatly, cause consistency very poor, to such an extent as to adopt the method for physical blending to be difficult to obtain desirable matrix material.Other the conventional method of modifying that is used for preparing plastic of soybean protein comprise plasticization and modification, cross-linking modified, increase the methods such as soybean protein molecular weight.Wherein the conventional softening agent of plasticization and modification method is glycerine or other polyalcohols, and mostly be single softening agent modification mode, plasticizing soy protein film as disclosed in patent CN102453328A, CN102002243A or plastics, can not improve snappiness and the processing characteristics of plastics fully; Cross-linked modification method utilizes maleic anhydride and polymine (PEI) linking agent (the International Journal of Adhesion & Adhensive as soybean protein base adhesive as: people such as Liu, 2007,27: 487), the people such as Li utilizes the reaction product of polymeric amide polyamine and epoxy chloropropane, with soybean protein effect, form cross-linked network structure, to improve water tolerance (J.Am.Oil.Chem.Soc., 2004,8: 487), but cross-linked modification method can make the processing characteristics of plastics decline.
Soybean protein has been applied to the fields such as plastics, tackiness agent, coating at present, and wherein, soybean protein base adhesive is widely used in wood industry, as the disclosed urea-modified soybean protein of people (J.Am.Oil.Chem.Soc., 1999,76: 977) such as Sun S.X..Along with the restriction of the increase of market to tackiness agent consumption demand, petroleum chemicals resource and to environmental problem growing interest, environmentally friendly tackiness agent renewable, with low cost is more and more subject to people's attention, the adhesive strength and the water resistance that focus on how improving tackiness agent of research work now.
Summary of the invention
For the problem such as current soybean protein sill poor water resistance, gluing intensity be low, the invention provides a kind of soy-protein modified castor oil based polyurethanes, method of modifying and application thereof.
First aspect of the present invention is to provide a kind of preparation method of soy-protein modified polyurethane, and the step of described method comprises:
Step 1, provides the soybean protein soln that pH value is 8-13, adds the hydrochlorate of sulfoxide and diamines to react, and separated product obtains soy-protein modification derivant;
Step 2, polyurethane prepolymer dissolves and mixes with gained soy-protein modification derivant in step 1, adds chainextender reaction, obtains Soybean Protein Modification urethane.
Wherein, described soybean protein can be soybean protein isolate and/or soybean protein concentrate.
Wherein, described sulfoxide is preferably dialkyl sulfoxide, and described alkyl is preferably C
1-6alkyl, C
6-12aromatic base or C
6-12arylalkyl or alkylaryl (total carbon number of arylalkyl or alkylaryl be 6-12), described aryl most preferably is phenyl.
Described alkyl for example as any one or two kinds in methyl, ethyl, phenyl, benzyl, aminomethyl phenyl, and most preferably be methyl (being that sulfoxide most preferably is dimethyl sulfoxide (DMSO)).
Wherein, the hydrochlorate of described diamines can be inorganic acid salt and/or the organic acid salt of diamines.
Described inorganic acid salt is preferably and is selected from: hydrochloride, bromate, iodate, vitriol, sulphite, nitrate, carbonate, phosphoric acid salt, hydrosulfate, hydrosulphite, supercarbonate, hydrophosphate etc.
Described organic salt is preferably and is selected from: acetate, formate, propionic salt, butyrates, lactic acid salt, Citrate trianion, sulfonate etc.
The hydrochlorate of described diamines is preferably inorganic salt, and hydrochloride more preferably.
Wherein, described diamines is preferably and is selected from H
2n-R-NH
2, wherein, R is C
1-10(more preferably C
4-10, as C
5, C
6, C
8) saturated hydrocarbyl, or C
6-12arylene, or C
6-12saturated hydrocarbyl aromatic base or aromatic base saturated hydrocarbyl.
Described aromatic base most preferably is phenyl.When in the situation that R is phenyl, amino can be that ortho position replaces, a position replaces or para-orientation, and most preferably is para-orientation (being that diamines most preferably is Ursol D).
Wherein, in described diamines, two amino all can salify, or only has an amino salify, and is preferably two equal salifies of amino.
The hydrochlorate of described diamines most preferably is para-phenylene diamine dihydrochloride.
Wherein, in step 1, every 0.01-.0.5g soybean protein is preferably the hydrochlorate 1-20mmol with diamines; Or in gained soy-protein modification derivant, the shared weight ratio of diamines is preferably 1-8wt%.
Wherein, the pH value of soybean protein soln is preferably and uses the alkali lye of 0.001-2.0M concentration to regulate, and described salt is preferably metal hydroxides or ammoniacal liquor, and is preferably metal hydroxides, is preferably and is selected from: NaOH, KOH, LiOH, Zn (OH)
2, Mg (OH)
2, Ca (OH)
2in at least one or any several mixture.
The most preferred working method of step 1 is: the soy bean proteinous soln of 1-50% mass concentration,, be uniformly mixed after 0.5-4 hour, after filtration under 30-90 ° of C to 8-13 by 0.01-2.0M alkaline solution adjusting pH value, the soybean protein aqueous solution is cooled to room temperature, obtains alkaline soy bean proteinous soln; The methyl-sulphoxide of 100-400ml is joined in the alkaline soy bean proteinous soln of 1.0g, stir, the acid salt solution of the diamines of 1-20mmol slowly drops in mixing solutions and reacts; Reaction finishes rear separated product.
Wherein, the time of described reaction is preferably 12-48h.
Wherein, described separated product is preferably: in reaction system, add ketone or alcohol to precipitate, isolate and precipitate the derivative that obtains soy-protein modification.Described separation can be implemented by filtration, filtration under diminished pressure or centrifugation.
Those skilled in the art can understand, and at after separating, can also comprise the step of washing, and described washing can be to wash with ketone or alcohol.The product pH value being preferably after washing is controlled within the scope of 6-8.
In foregoing, described ketone is preferably and is selected from: acetone, butanone, pentanone, most preferably be acetone.
In foregoing, described alcohol is preferably and is selected from: methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, most preferably be methyl alcohol and/or ethanol.
Those skilled in the art can understand, and after described separation and/or washing, can also comprise drying step.
Described being dried can be oven dry, air-dry, vacuum-drying, and the present invention is preferably spraying and is dried and/or lyophilize.
In step 2, described polyurethane prepolymer can be commercially produced product, and the present invention is preferably by the carboxylic acid of isocyanic ester and hydroxyl and prepares.
In described polyurethane prepolymer, [NCO]/[OH] is preferably 1/ (2-3).
Wherein, described isocyanic ester can be vulcabond and/or polyisocyanates, and is preferably vulcabond.Described vulcabond is preferably and is selected from: tolylene diisocyanate, diphenylmethanediisocyanate, hexamethylene diisocyanate etc., most preferably be diphenylmethanediisocyanate.
The carboxylic acid of described hydroxyl can be hydroxyl carboxylic acid cpd, dihydroxy carboxylic acid, trihydroxy-carboxylic acid cpd or multi-hydroxy carboxylic acid cpd more, and be preferably monohydroxy carboxylic acid cpd, most preferably be vegetables oil, be preferably and be selected from: soybean oil, Viscotrol C, Oleum Gossypii semen, peanut oil, rapeseed oil, Semen Maydis oil, plam oil, oleum lini, Rice pollard oil, Oleum Cocois, most preferably be Viscotrol C in the present invention.
In most preferred embodiment of the present invention, polyurethane prepolymer preparation method is: isocyanic ester reacts under anhydrous and oxygen-free condition with Viscotrol C.Wherein, temperature of reaction is preferably 30-70 ° of C, reaction times and is preferably 1-8 hour.
Wherein, most preferred isocyanic ester is diphenylmethanediisocyanate, is preferably (10-70): (20-90) with the part by weight of Viscotrol C.Or in gained polyurethane prepolymer, [NCO]/[OH] is preferably 1/ (2-3).
In step 2, the part by weight of polyurethane prepolymer and soy-protein modification derivant is preferably: polyurethane prepolymer accounts for the 5-80wt% of soy-protein modification derivant weight.
In step 2, the solvent that polyurethane prepolymer reacts with soy-protein modification derivant is preferably at least one in N-Methyl pyrrolidone, DMF, N,N-dimethylacetamide, dimethyl sulfoxide (DMSO), diphenyl sulfoxide.
Described chainextender is preferably binary or polyvalent alcohol, containing any one or a few the mixture in amino or imino-compound, ethers alcohol, be preferably and be selected from: 1,4-butyleneglycol, 1,6-hexylene glycol, TriMethylolPropane(TMP), glycol ether, triglycol, neopentyl glycol, sorbyl alcohol, diethylaminoethanol, quinhydrones-bis-(β mono-hydroxyethyl) ether, quadrol, N, at least one in N-dihydroxyl (di-isopropyl) aniline, 2-imidazolidone.
In the molar weight and reaction system of described chainextender-NCO group molar weight ratio is preferably 1: (0.5-2), more preferably 1: (0.5-1.5), most preferably be 1: 1.
In most preferred embodiment of the present invention, in polyurethane prepolymer and soy-protein modification derivant reaction process: reaction system solid content is preferably 5-30wt%, add after chainextender reaction 0.5-4 hour.
Second aspect of the present invention is to provide the soy-protein modified polyurethane that above-mentioned any means obtains.
Third aspect of the present invention is to provide the application of above-mentioned soy-protein modified polyurethane, and wherein, described soy-protein modified polyurethane is for the preparation of coating, tackiness agent, film, duroplasts, elastomerics etc.
In first preferred embodiment of third aspect of the present invention, described soy-protein modified polyurethane is heated to flow casting molding under 30-90 ° of C condition and obtain mould material.
In second preferred embodiment of third aspect of the present invention, the solution of described soy-protein modified polyurethane is coated on to wanted bonding body surface, then heat pressure adhesive, cooling.
Wherein, in second preferred embodiment of third aspect of the present invention, hot pressing temperature is preferably 80-200 ° of C, and hot pressing time is preferably 0-30min, and hot pressing pressure is preferably 0-40MPa.
Advantage of the present invention comprises:
1) the Soybean Protein Modification polyurethane material that the present invention obtains, with low cost, synthesis technique is simple, is applicable to actual application and popularization.
2) present method is utilized the natural macromolecular material of renewable resources, and the product obtaining is Biodegradable material, environmentally friendly, building-up process green non-pollution, and the tackiness agent environmental protection of gained, can be applicable to the fields such as plank is gluing, shaving board, fiberboard.
3) modified soy protein mould material provided by the invention has improved mechanical property and water resistance by selecting suitable cross-linking agent to carry out modification to soybean protein mould material, and is easy to processing, has good tensile strength and elongation at break.
4) and, by regulating soy proteinaceous content, can obtain the product from hard plastic to elastomeric different mechanics and mechanical property.
Embodiment
Below in conjunction with concrete embodiment, the present invention is further illustrated.
Embodiment 1
The preparation of soy-protein modification derivant:
Configuration quality concentration is 20% soy bean proteinous soln, and then regulating the pH value of soybean solution with the alkaline solution of 0.5M is 8.Under 30 ° of C, be uniformly mixed after 1h hour, after filtration, the soybean protein aqueous solution be cooled to room temperature, obtain alkaline soy bean proteinous soln.The methyl-sulphoxide of 200ml is joined in the alkaline soy bean proteinous soln of 1.0g, gained solution stirring 20min, the speed of stirring is 200r/min, then slowly drops in mixing solutions with the para-phenylene diamine dihydrochloride solution of 5mmol.After reaction 12h, with acetone precipitation, then centrifugal, the speed of centrifugation is 1000rpm, and each 8 minutes, repetitive scrubbing was precipitated to the pH value to 6 of system, and lyophilize obtains pure products soy-protein p-phenylene diamine derivative, is labeled as PDSP.
Embodiment 2
The preparation of soy-protein modification derivant:
Configuration quality concentration is 30% soy bean proteinous soln, and then regulating the pH value of soybean solution with the alkaline solution of 1.0M is 9.Under 50 ° of C, be uniformly mixed after 2h hour, after filtration, the soybean protein aqueous solution be cooled to room temperature, obtain alkaline soy bean proteinous soln.The methyl-sulphoxide of 250ml is joined in the alkaline soy bean proteinous soln of 1.0g, gained solution stirring 40min, the speed of stirring is 300r/min, then slowly drops in mixing solutions with the para-phenylene diamine dihydrochloride solution of 10mmol.After reaction 24h, with acetone precipitation, then centrifugal, the speed of centrifugation is 1500rpm, and each 8 minutes, repetitive scrubbing was precipitated to the pH value to 7 of system, and lyophilize obtains pure products soy-protein p-phenylene diamine derivative, is labeled as PDSP.
Embodiment 3
The preparation of soy-protein modification derivant:
Configuration quality concentration is 40% soy bean proteinous soln, and then regulating the pH value of soybean solution with the alkaline solution of 1.5M is 10.Under 60 ° of C, be uniformly mixed after 3h hour, after filtration, the soybean protein aqueous solution be cooled to room temperature, obtain alkaline soy bean proteinous soln.The methyl-sulphoxide of 300ml is joined in the alkaline soy bean proteinous soln of 1.0g, gained solution stirring 60min, the speed of stirring is 300r/min, then slowly drops in mixing solutions with the para-phenylene diamine dihydrochloride solution of 15mmol.After reaction 48h, with acetone precipitation, then centrifugal, the speed of centrifugation is 3000rpm, and each 8 minutes, repetitive scrubbing was precipitated to the pH value to 7 of system, and lyophilize obtains pure products soy-protein p-phenylene diamine derivative, is labeled as PDSP.
Embodiment 4
The preparation of mould material:
30g diphenylmethanediisocyanate (MDI) is heated under 30 ° of C and is stirred, after MDI melting, dropwise add 50g Viscotrol C, under nitrogen protection, react 1h and obtain urethane (PU) prepolymer.The PDSP of the embodiment of PU prepolymer and calculated amount 1 is dissolved in respectively in N-Methyl pyrrolidone (NMP), wherein the content of PU prepolymer accounts for the 20wt% of PDSP quality, after mixing, add N, it is 5wt% that dinethylformamide (DMF) regulates the solid content of this solution, after fully stirring, adds BDO, after mixing, obtain soy-protein modified castor oil based polyurethanes, solution casting is molded over to 30 ° of C heating 12h of baking oven and obtains transparent film material, thickness is about 100 ± 20 μ m;
Embodiment 5
The preparation of mould material:
40g diphenylmethanediisocyanate (MDI) is heated under 50 ° of C and is stirred, after MDI melting, dropwise add 60g Viscotrol C, under nitrogen protection, react 2h and obtain urethane (PU) prepolymer.The PDSP of PU prepolymer and calculated amount is dissolved in respectively in dimethyl sulfoxide (DMSO) (DMSO), wherein the content of PU prepolymer accounts for the 40wt% of PDSP quality, after mixing, adding dimethyl formamide (DMF) to regulate the solid content of this solution is 10wt%, after fully stirring, add quinhydrones one or two (β mono-hydroxyethyl) ether (HQEE), after mixing, obtain soy-protein modified castor oil based polyurethanes, solution casting is molded over to 50 ° of C heating 24h of baking oven and obtains transparent mould material, thickness is about 100 ± 20 μ m;
Embodiment 6
The preparation of mould material:
50g diphenylmethanediisocyanate (MDI) is heated under 60 ° of C and is stirred, after MDI melting, dropwise add 70g Viscotrol C, under nitrogen protection, react 4h and obtain urethane (PU) prepolymer.The PDSP of PU prepolymer and calculated amount is dissolved in respectively in dimethyl formamide (DMF), wherein the content of PU prepolymer accounts for the 60wt% of PDSP quality, after mixing, adding dimethyl sulfoxide (DMSO) (DMSO) to regulate the solid content of this solution is 15wt%, after fully stirring, add diethylaminoethanol (DEAE), after mixing, obtain soy-protein modified castor oil based polyurethanes, solution casting is molded over to 60 ° of C heating 48h of baking oven and obtains transparent mould material, thickness is about 100 ± 20 μ m;
Embodiment 7
The preparation of glued board:
The soy-protein modified castor oil based polyurethanes solution that embodiment 4 is prepared, be coated on two veneer surfaces with laboratory spreadometer, the thickness of plank is 6mm, bonding area is on the test panel of 12mm × 25mm, under thermocompressor, the time of hot pressing is 10min, the temperature of hot pressing is 120 ° of C, and the pressure of hot pressing is 20MPa, and cooling rear taking-up obtains glued board.
Embodiment 8
The preparation of glued board:
The soy-protein modified castor oil based polyurethanes solution that embodiment 5 is prepared, be coated on two veneer surfaces with laboratory spreadometer, the thickness of plank is 6mm, bonding area is on the test panel of 12mm × 25mm, under thermocompressor, the time of hot pressing is 15min, the temperature of hot pressing is 90 ° of C, and the pressure of hot pressing is 25MPa, and cooling rear taking-up obtains glued board.
Embodiment 9
The preparation of glued board:
The soy-protein modified castor oil based polyurethanes solution that embodiment 6 is prepared, be coated on two veneer surfaces with laboratory spreadometer, the thickness of plank is 6mm, bonding area is on the test panel of 12mm × 25mm, under thermocompressor, the time of hot pressing is 8min, the temperature of hot pressing is 120 ° of C, and the pressure of hot pressing is 30MPa, and cooling rear taking-up obtains glued board.
Performance test
Mechanical property adopts CMT-6503 type universal electrical tension testing machine (material-testing machine company is newly thought carefully in Shenzhen, domestic) according to international standard ISO527-3-1995(E) test.Rate of extension is 5mm/min, and each test piece is surveyed 5 times and averaged.
Table 1, the mechanical property of embodiment 4-9 sample
| Embodiment | Tensile strength | Elongation at break | Young's modulus | Bonding strength |
| Embodiment 4 | 27MPa | 30% | 870MPa | - |
| Embodiment 5 | 26MPa | 120% | 260MPa | - |
| Embodiment 6 | 25MPa | 170% | 70MPa | - |
| Embodiment 7 | - | - | - | 2.3MPa |
| Embodiment 8 | - | - | - | 3.1MPa |
| Embodiment 9 | - | - | - | 3.7MPa |
The soy-protein modified castor oil based polyurethanes Mechanical Properties of Materials that table 1 obtains for embodiment 4-9, wherein:
Tensile strength reduces with the increase of polyurethane component content; Elongation at break increases with the increase of PU component concentration; Young's modulus reduces with the increase of polyurethane component content.Strengthen urethane by polyurethane toughened soy protein plastic and rigidity PDSP plastics, can obtain the material from plastics to elastomeric various mechanical properties.
Meanwhile, its bonding strength of the cementing agent making is all greater than 2MPa, can be used as the based Wood Adhesives of excellent performance.
Above specific embodiments of the invention be have been described in detail, but it is just as example, the present invention is not restricted to specific embodiment described above.To those skilled in the art, any equivalent modifications that the present invention is carried out and alternative also all among category of the present invention.Therefore, equalization conversion and the amendment done without departing from the spirit and scope of the invention, all should contain within the scope of the invention.
Claims (10)
1. the preparation method of a soy-protein modified polyurethane, it is characterized in that, the step of described method comprises: step 1, provides the soybean protein soln that pH value is 8-13, add the hydrochlorate of sulfoxide and diamines to react, separated product obtains soy-protein modification derivant;
Step 2, polyurethane prepolymer dissolves and mixes with gained soy-protein modification derivant in step 1, adds chainextender reaction, obtains Soybean Protein Modification urethane.
2. the preparation method of soy-protein modified polyurethane according to claim 1, is characterized in that, described diamines is H
2n-R-NH
2, wherein, R is C
1-10saturated hydrocarbyl, or C
6-12arylene, or C
6-12saturated hydrocarbyl aromatic base or aromatic base saturated hydrocarbyl.
3. method according to claim 1, is characterized in that, the hydrochlorate of described diamines is para-phenylene diamine dihydrochloride.
4. according to the method described in any one in claim 1-3, it is characterized in that, in step 1, the hydrochlorate 1-20mmol of diamines for every 0.01-.0.5g soybean protein; Or in gained soy-protein modification derivant, the shared weight ratio of diamines is 1-8wt%.
5. method according to claim 1, is characterized in that, described polyurethane prepolymer is isocyanic ester and the preparation of hydroxyl carboxylic acid.
6. method according to claim 5, is characterized in that, in described polyurethane prepolymer, [NCO]/[OH] is 1/ (2-3).
7. method according to claim 5, is characterized in that, is vegetables oil described in described hydroxyl.
8. according to the method described in any one in claim 5-7, it is characterized in that, in step 2, polyurethane prepolymer accounts for the 5-80wt% of soy-protein modification derivant weight.
9. the soy-protein modified polyurethane described in an above-mentioned any one claim.
10. an application for the soy-protein modified polyurethane as described in above-mentioned any one claim, is characterized in that, described soy-protein modified polyurethane is for the preparation of any one or a few in coating, tackiness agent, film, duroplasts, elastomerics.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310143667.2A CN104119491A (en) | 2013-04-24 | 2013-04-24 | Soybean protein modified polyurethane, and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310143667.2A CN104119491A (en) | 2013-04-24 | 2013-04-24 | Soybean protein modified polyurethane, and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104119491A true CN104119491A (en) | 2014-10-29 |
Family
ID=51765146
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310143667.2A Pending CN104119491A (en) | 2013-04-24 | 2013-04-24 | Soybean protein modified polyurethane, and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104119491A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108424632A (en) * | 2018-04-19 | 2018-08-21 | 钱兴 | A kind of waterproof tensile stretches the preparation method of strap |
| CN108676481A (en) * | 2018-05-23 | 2018-10-19 | 沈阳师范大学 | A kind of preparation method of soya-bean milk modified polyurethane paint |
| CN109627409A (en) * | 2018-12-20 | 2019-04-16 | 浙江诚迅新材料有限公司 | A kind of aqueous polyurethane, dumb light aqueous polyurethane and preparation method |
| CN111218119A (en) * | 2020-04-09 | 2020-06-02 | 北京林业大学 | Self-repairing, high-strength and antibacterial soybean protein film and preparation method thereof |
| CN111334181A (en) * | 2020-03-20 | 2020-06-26 | 东莞市东彩印刷包装有限公司 | Degradable environmental protection wood grain lacquer eye shadow box |
| CN115516024A (en) * | 2020-05-01 | 2022-12-23 | 现代牧场股份有限公司 | Protein polyurethane alloy and layered material comprising same |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101130678A (en) * | 2006-08-22 | 2008-02-27 | 贺宏彬 | Aquosity polymer isocyanic ester adhesion agent of soy protein, preparing method and application of the same |
| CN102439056A (en) * | 2009-03-06 | 2012-05-02 | 生物高聚物技术有限公司 | Protein-containing emulsions and adhesives, and manufacture and use thereof |
-
2013
- 2013-04-24 CN CN201310143667.2A patent/CN104119491A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101130678A (en) * | 2006-08-22 | 2008-02-27 | 贺宏彬 | Aquosity polymer isocyanic ester adhesion agent of soy protein, preparing method and application of the same |
| CN102439056A (en) * | 2009-03-06 | 2012-05-02 | 生物高聚物技术有限公司 | Protein-containing emulsions and adhesives, and manufacture and use thereof |
Non-Patent Citations (3)
| Title |
|---|
| DAGANG LIU等: "Structure and Properties of Blend Films Prepared from Castor Oil-Based", 《INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH》 * |
| WEINING HUANG等: "Adhesive Properties of Soy Proteins Modified", 《JOURNAL OF THE AMERICAN OIL CHEMISTS SOCIETY》 * |
| 周晓燕 等: "《胶合板制造学》", 31 December 2012, 中国林业出版社 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108424632A (en) * | 2018-04-19 | 2018-08-21 | 钱兴 | A kind of waterproof tensile stretches the preparation method of strap |
| CN108676481A (en) * | 2018-05-23 | 2018-10-19 | 沈阳师范大学 | A kind of preparation method of soya-bean milk modified polyurethane paint |
| CN108676481B (en) * | 2018-05-23 | 2020-10-30 | 沈阳师范大学 | Preparation method of soybean milk modified polyurethane coating |
| CN109627409A (en) * | 2018-12-20 | 2019-04-16 | 浙江诚迅新材料有限公司 | A kind of aqueous polyurethane, dumb light aqueous polyurethane and preparation method |
| CN111334181A (en) * | 2020-03-20 | 2020-06-26 | 东莞市东彩印刷包装有限公司 | Degradable environmental protection wood grain lacquer eye shadow box |
| CN111218119A (en) * | 2020-04-09 | 2020-06-02 | 北京林业大学 | Self-repairing, high-strength and antibacterial soybean protein film and preparation method thereof |
| CN115516024A (en) * | 2020-05-01 | 2022-12-23 | 现代牧场股份有限公司 | Protein polyurethane alloy and layered material comprising same |
| EP4143258A4 (en) * | 2020-05-01 | 2024-05-22 | Modern Meadow, Inc. | Protein polyurethane alloys and layered materials including the same |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104119491A (en) | Soybean protein modified polyurethane, and preparation method and application thereof | |
| CN101358114B (en) | Adhisive for polaroid, polaroid and manufacure method thereof | |
| CN108570305B (en) | Soybean-based protein adhesive and preparation method thereof | |
| CN101240101B (en) | Method for preparing ketohydrazine cross-linked acrylic ester-polyurethane composite weaving emulsion and use thereof | |
| CN103865477B (en) | A kind of cross-linking modified soybean albumen adhesive | |
| US8937025B2 (en) | Formaldehyde-free protein-containing binders for spunbond products | |
| CN105111399B (en) | A kind of water pressure resistance waterborne polyurethane resin | |
| CN110205090B (en) | Preparation method of bio-based soybean protein adhesive based on ultrahigh pressure modification | |
| CN107033833A (en) | A kind of polyaminoacid composition and its preparation method and application | |
| CN105153660A (en) | Full-biodegradation bacterial cellulose/polylactic acid composite material and preparing method thereof | |
| CN109554160B (en) | Aldehyde-free soybean meal protein adhesive and preparation method thereof | |
| CN105153679A (en) | TPU (thermoplastic polyurethane) composite membrane used for fan blades and preparation method for TPU composite membrane | |
| CN106398565A (en) | Novel PVC composite veneer and preparation method thereof | |
| CN105713409A (en) | Full-degradable cellulose foam material and preparation method thereof | |
| CN111139030B (en) | Enzyme modified biomacromolecule wood adhesive and preparation method thereof | |
| CN105949807B (en) | Polyvinyl alcohol-based wood-plastic composite material and melting processing method thereof | |
| CN103952118B (en) | A kind of modified soy protein adhesive and preparation method thereof | |
| CN103554415B (en) | The preparation method of waterborne polyurethane hot melt adhesive | |
| CN104910425A (en) | Preparation method of completely biodegradable thermoplastic starch composite material | |
| CN106827161A (en) | A kind of preparation method without aldehyde bamboo shaving plate | |
| CN114571550B (en) | Digital veneer spraying process with veneer opening effect | |
| CN103709350B (en) | Melamine-urea-formaldehyde resin for laminated wood and preparation process and use method thereof | |
| CN109810527A (en) | A kind of preparation method of stalk padded coaming | |
| CN115124944A (en) | Heat-resistant high-fluidity thermoplastic polyurethane hot melt adhesive film and preparation method thereof | |
| CN109825248B (en) | Modified soybean protein adhesive and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20141029 |