CN109135663A - Chitosan oligosaccharide is aoxidized for the purposes of modified polyurethane, aqueous polyurethane, adhesive and the preparation method of its preparation - Google Patents
Chitosan oligosaccharide is aoxidized for the purposes of modified polyurethane, aqueous polyurethane, adhesive and the preparation method of its preparation Download PDFInfo
- Publication number
- CN109135663A CN109135663A CN201810600192.8A CN201810600192A CN109135663A CN 109135663 A CN109135663 A CN 109135663A CN 201810600192 A CN201810600192 A CN 201810600192A CN 109135663 A CN109135663 A CN 109135663A
- Authority
- CN
- China
- Prior art keywords
- chitosan oligosaccharide
- aqueous polyurethane
- oxidation
- oxidation chitosan
- modified
- 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.)
- Granted
Links
Classifications
-
- 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
- C09J189/00—Adhesives based on proteins; Adhesives based on derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
- C08B37/0027—2-Acetamido-2-deoxy-beta-glucans; Derivatives thereof
- C08B37/003—Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof
-
- 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
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
-
- 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
- C08G18/6484—Polysaccharides and derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Engineering & Computer Science (AREA)
- Biochemistry (AREA)
- Materials Engineering (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The present invention relates to the preparation methods of industrial gelatine (INGE) crosslinking functionalization water soluble polyurethane wood adhesive.It is swollen being dissolved in deionized water from the industrial gelatine of solid leather wastes, is heated to being completely dissolved, obtain certain density aqueous gelatin solution.With the oxidation chitosan oligosaccharide (COS) of sodium metaperiodate selectivity, modified aqueous polyurethane (OCOS-WPU) lotion of a certain amount of oxidation chitosan oligosaccharide is added in the oxidation chitosan oligosaccharide (OCOS) for obtaining certain aldehyde group content in the above solution, stirring at normal temperature reacts certain time, can be prepared by INGE/OCOS-WPU based Wood Adhesives.Using OCOS-WPU crosslinking industrial gelatine as based Wood Adhesives, its water resistance and adhesive strength can be improved.
Description
Technical field
The present invention relates to polyurethanes technology fields, and in particular to purposes, its system of oxidation chitosan oligosaccharide for modified polyurethane
Standby aqueous polyurethane, adhesive and preparation method.
Background technique
China possesses rawhide resource abundant, is one of process hides big country in the world.Leather industry is thrown with the height of raw material
Enter the traditional industry being characterized with the low output of product.According to incompletely statistics, China will generate 1,400,000 tons of leather corner every year
Waste, these solid waste be largely the tannings such as leftover pieces under former skin is repaired, grey skin bit before not chromium-containing collagen, with
And the chromium-containing collagen waste of the generations such as blue skin shaving, deburring, production gelatin, feed etc. can be used directly to.
Gelatin is as a kind of natural biomass macromolecule from a wealth of sources, cheap, compatibility and degradability are excellent
Material, the functional groups such as amino rich in, hydroxyl, carboxyl on strand, and itself has certain viscosity, is preparing gluing
There is certain advantage in terms of agent.But gelatin it is heat-resisting, water resistance and mechanical property are poor the defects of limit its extensive use.
So must be modified to gelatin, to meet the needs of human society production and living.
A kind of mode that polymer is also modification is added in substance to being modified.Polyurethane has certain flexibility, adopts
Gelatin is modified with polyurethane or base polyurethane prepolymer for use as, the hard crisp disadvantage of gelatin film forming can be improved.Polyurethane itself
With certain viscosity, there is certain advantage in terms of modified gelatin prepares adhesive.Aqueous polyurethane is dispersion with water
Agent reduces pollution of the solvent to environment to a certain extent.This just needs a kind of crosslinking agent of multifunctionality, can be used as " point
Sub- bridge ", by polyurethane in conjunction with gelatin.Chitosan oligosaccharide is the catabolite of chitosan oligosaccharide, and is uniquely largely existed in natural carbohydrate
Basic amine group oligosaccharides, good water solubility is safe and non-toxic.Ke Gua Tang is aoxidized with sodium metaperiodate, on chitosan oligosaccharide 2,3
Carbon is partly or entirely oxidized to aldehyde radical, therefore may be used as crosslinking agent, and bridging aqueous polyurethane and industrial gelatine prepare gluing
Agent, adhesive itself and its cementitious article will not release free formaldehyde in use, safe and non-toxic.
Based on this, new product is synthesized using the industrial gelatine extracted in discarded leather bits, with the widow of shell existing for nature
Sugar is cooked molecular bridge, is not only realized waste resource recycling, is turned waste into wealth；And avoid to a certain extent " toxic capsule " and
The generation of " leather milk " event, has both economic benefit and environmental benefit, meets the requirement of clean manufacturing and sustainable development, to system
The sustainable development of leather industry is of great significance.
Summary of the invention
It is an object of the invention to realize the resource utilization of Leather Solid Waste, its high level conversion is realized, and utilize
The oxidation chitosan oligosaccharide of biomass does molecular bridge, bridging gelatin and aqueous polyurethane, prepares a kind of biomass-based, environmentally friendly
Adhesive, and it is applied to wood bonding.
The technical scheme adopted by the invention is as follows:
It is swollen, is heated to completely molten by being dissolved in deionized water from the industrial gelatine of solid leather wastes (INGE)
Solution, obtains certain density aqueous gelatin solution.With the oxidation chitosan oligosaccharide (COS) of sodium metaperiodate selectivity, obtains certain aldehyde radical and contain
Modified aqueous polyurethane (the OCOS- of a certain amount of oxidation chitosan oligosaccharide is added in the oxidation chitosan oligosaccharide (OCOS) of amount in the above solution
WPU) lotion, stirring at normal temperature react certain time, can be prepared by INGE/OCOS-WPU based Wood Adhesives.
Specifically, industrial gelatine-oxidation chitosan oligosaccharide type Aqueous Polyurethane Adhesives preparation method, comprising the following steps:
Step 1: the preparation of industrial gelatine aqueous solution:
10 ~ 20g of industrial gelatine is added in 80 ~ 90g deionized water, is swollen 30min at normal temperature, heating is until complete at 40 DEG C
Fully dissolved obtains aqueous gelatin solution.
Step 2: the preparation of chitosan oligosaccharide is aoxidized:
(1) sodium metaperiodate of 2.12 ~ 25g is placed in light resistant container, a certain amount of deionized water is added, be stirred well to molten
Solution；
(2) chitosan oligosaccharide of 2 ~ 10g is weighed in above-mentioned solution, is protected from light normal-temperature reaction 2d；
(3) obtained product is dialysed 1d in the bag filter of 500 interceptions, and is lyophilized in freeze drier, after grinding
To white solid.
Step 3: the preparation of oxidation chitosan oligosaccharide type aqueous polyurethane:
(1) 5 ~ 20g of diisocyanate cpd, polyether polyol 8 ~ 20g and 2 ~ 3d dibutyl tin dilaurate are added to dress
In the three-necked flask for having thermometer, blender, glass bottle stopper, it is uniformly mixed, 50 DEG C of reaction 20min are warming up to 60 ~ 70 DEG C, instead
1 ~ 2h is answered, base polyurethane prepolymer for use as is made；
(2) oligomer 0.7 ~ 1.2g of glycol chain extender containing hydrophilic radical, heat up 70 ~ 90 DEG C, react 2 ~ 3h after be added 0.2 ~
The oxidation chitosan oligosaccharide of 0.6g, the reaction was continued 1h；
(3) above-mentioned gained system is cooled to 40 DEG C, three second with the oligomer dihydric alcohol equimolar amounts containing hydrophilic radical is added
In amine and 20 ~ 60min；
(4) deionized water for being then added 2 ~ 6 times stirs 30 ~ 60min under high speed shear active force, can obtain after reaction
The aqueous polyurethane emulsion modified to oxidation chitosan oligosaccharide.
Step 4: the preparation of industrial gelatine-oxidation chitosan oligosaccharide type Aqueous Polyurethane Adhesives:
10% ~ 50% aqueous poly- ammonia of oxidation chitosan oligosaccharide type on the basis of aqueous gelatin solution quality is added into aqueous gelatin solution
Ester is stirred to react under room temperature, and industrial gelatine-oxidation chitosan oligosaccharide type Aqueous Polyurethane Adhesives are made.
Industrial gelatine molecular weight described in step 1 is 15000~250000Da.
The chitosan oligosaccharide degree of polymerization is 2 ~ 10 described in step 2.
Diisocyanate cpd described in step 3 is isophorone diisocyanate, diphenylmethane diisocyanate
Ester, toluene di-isocyanate(TDI).
Polyether polyol described in step 3 is polytetrahydrofuran (Mn=1000), polyethylene glycol (Mn=1000), gathers
Propylene glycol (Mn=1000).
The oligomer glycol chain extender in step 3 is dihydromethyl propionic acid or dimethylolpropionic acid.
The aldehyde group content of chitosan oligosaccharide is aoxidized described in step 3 20 ~ 80%.
The dosage of chitosan oligosaccharide is aoxidized in step 3 on the basis of 1% ~ 6%(is by the sum of diisocyanate and polyol quality).
By the adhesive uniform gluing of synthesis in board using poplar board two sides, two-sided resin added is 300g/m2, organize Bear-grudge after in 120
DEG C, hot pressing 6min under conditions of 1.0MPa.
Industrial gelatine-oxidation chitosan oligosaccharide type Aqueous Polyurethane Adhesives that preparation method as mentioned obtains.
The preparation method of industrial gelatine-Waterborne Blocked Polyurethane adhesive as mentioned, it is characterised in that:
Such adhesive is used for the bonding of timber.
By the adhesive uniform gluing of synthesis in board using poplar board, two-sided resin added is 300g/m2, organize Bear-grudge after in 120 DEG C,
Hot pressing 6min under conditions of 1.0MPa.
The invention has the following advantages that
1, the present invention is that crosslinking agent prepares aqueous polyurethane, then bridging gelatin using the chitosan oligosaccharide of sodium periodate oxidation biomass,
It is reacted at normal temperature using the aldehyde radical on oxidation chitosan oligosaccharide with the amino of gelatin, further increases the extent of reaction, formed more
Intensive cross-linked network structure improves the cohesive force of adhesive, increases gluing intensity.
2, the present invention is few using the industrial gelatine extracted in discarded leather and natural biological mass shell on raw material
Sugar realizes the resource utilization of biomass, turns waste into wealth.
3, the adhesive synthesized can be applied to wood industry, such as: the bonding of glued board, particieboard.
Detailed description of the invention
Fig. 1 is COS oxidation process schematic diagram；
Fig. 2 is the infrared spectrum of COS oxidation front and back；
Fig. 3 is the infrared spectrum of the modified WPU of OCOS；
Fig. 4 is that INGE/OCOS-WPU synthesizes infrared spectrum；
Fig. 5 is shearing force testing method schematic diagram.
Specific embodiment
Case study on implementation one:
Step 1: the preparation of industrial gelatine aqueous solution:
Industrial gelatine 10g is added in 90g deionized water, is swollen 30min at normal temperature, the heating at 40 DEG C is until completely molten
Solution, obtains aqueous gelatin solution.
Step 2: the preparation of chitosan oligosaccharide is aoxidized:
(1) sodium metaperiodate of 17g is placed in light resistant container, a certain amount of deionized water is added, be stirred well to dissolution；
(2) chitosan oligosaccharide of 8g is weighed in above-mentioned solution, is protected from light normal-temperature reaction 2d；
(3) obtained product is dialysed 1d in the bag filter of 500 interceptions, and is lyophilized in freeze drier, after grinding
To white solid.
Step 3: the preparation of oxidation chitosan oligosaccharide type aqueous polyurethane:
(1) isophorone diisocyanate 7.78g, polytetrahydrofuran (Mn=1000) 10g and 3d dibutyl tin dilaurate are added
Entering to being equipped in the three-necked flask of thermometer, blender, glass bottle stopper, is uniformly mixed, 50 DEG C of reaction 20min are warming up to 70 DEG C,
1h is reacted, base polyurethane prepolymer for use as is made；
(2) dihydromethyl propionic acid 1.06g is added into above-mentioned system, heats up 80 DEG C, reacts the oxidation shell of addition 0.36g after 2.5h
Oligosaccharides, the reaction was continued 1h；
(3) above-mentioned gained system is cooled to 40 DEG C, three second with the oligomer dihydric alcohol equimolar amounts containing hydrophilic radical is added
In amine and 30min；
(4) deionized water for being then added 3 times stirs 30min under high speed shear active force, and oxygen can be obtained after reaction
Change the modified aqueous polyurethane emulsion of chitosan oligosaccharide.
Step 4: the preparation of industrial gelatine-oxidation chitosan oligosaccharide type Aqueous Polyurethane Adhesives:
The 30% oxidation chitosan oligosaccharide type aqueous polyurethane on the basis of aqueous gelatin solution quality is added into aqueous gelatin solution, often
It is stirred to react under temperature, industrial gelatine-oxidation chitosan oligosaccharide type Aqueous Polyurethane Adhesives is made.
Step 5: industrial gelatine-oxidation chitosan oligosaccharide type Aqueous Polyurethane Adhesives application
By the adhesive uniform gluing of synthesis in 120 DEG C after board using poplar board, group embryo, hot pressing 6min under conditions of 1.0MPa is taken
Three groups of samples are averaged.
The adhesive that case study on implementation one synthesizes is best.
The product of each step preparation of the present embodiment is subjected to infrared analysis, obtains Fig. 2 ~ 4 as a result, Fig. 2 is COS oxidation front and back
Infrared spectrum；Fig. 3 is the infrared spectrum of the modified WPU of OCOS；Fig. 4 is that INGE/OCOS-WPU synthesizes infrared spectrum.Fig. 2 shows,
COS is compared, OCOS is in 1722cm-1There is the vibration absorption peak of aldehyde radical in place, it was demonstrated that sodium periodate oxidation chitosan oligosaccharide is in chitosan oligosaccharide knot
Aldehyde radical is introduced in structure.Fig. 3 shows that blank WPU is compared with OCOS-WPU, 1637cm-1There is new absorption peak in place, it may be possible to which shell is few
Amino in sugar is reacted with isocyanates to be formed, it was demonstrated that is successfully prepared the modified aqueous polyurethane emulsion of oxidation chitosan oligosaccharide.
Fig. 4 shows, modified amide Ⅰ and amide II have with place's peak intensity to be remarkably reinforced, and peak position is changed, and is said
Bright-NH2It reacts with aldehyde radical and generates schiff bases, it was demonstrated that oxidation chitosan oligosaccharide type aqueous polyurethane and gelatin are successfully total to
It is poly-, successfully prepare industrial gelatine-oxidation chitosan oligosaccharide type Aqueous Polyurethane Adhesives
Referring to Fig. 5, the adhesive that case study on implementation one is synthesized carries out shearing force testing (timber used according to GBT 17657-1999
For poplar, two-sided resin added is 300g/m2) and calculate its gluing intensity.
Test result is as follows (carrying out parallel test three times):
| Serial number | 1 | 2 | 3 |
| Dry state gluing intensity/MPa | 2.28 | 2.23 | 2.31 |
Shearing test is the results show that industrial gelatine prepared by the present invention-oxidation chitosan oligosaccharide type Aqueous Polyurethane Adhesives can be used for
Bonding wood.
Case study on implementation two:
Step 1: the preparation of industrial gelatine aqueous solution:
Industrial gelatine 10g is added in 90g deionized water, is swollen 30min at normal temperature, the heating at 40 DEG C is until completely molten
Solution, obtains aqueous gelatin solution.
Step 2: the preparation of chitosan oligosaccharide is aoxidized:
(1) sodium metaperiodate of 12.74g is placed in light resistant container, a certain amount of deionized water is added, be stirred well to dissolution；
(2) chitosan oligosaccharide of 8g is weighed in above-mentioned solution, is protected from light normal-temperature reaction 2d；
(3) obtained product is dialysed 1d in the bag filter of 500 interceptions, and is lyophilized in freeze drier, after grinding
To white solid.
Step 3: the preparation of oxidation chitosan oligosaccharide type aqueous polyurethane:
(1) isophorone diisocyanate 8.89g, polytetrahydrofuran (Mn=1000) 10g and 2d dibutyl tin dilaurate are added
Entering to being equipped in the three-necked flask of thermometer, blender, glass bottle stopper, is uniformly mixed, 50 DEG C of reaction 20min are warming up to 70 DEG C,
1h is reacted, base polyurethane prepolymer for use as is made；
(2) dihydromethyl propionic acid 1.13g is added into above-mentioned system, heats up 80 DEG C, reacts the oxygen of addition 0.33mmol after 2.5h
Change chitosan oligosaccharide, the reaction was continued 1h；
(3) above-mentioned gained system is cooled to 40 DEG C, three second with the oligomer dihydric alcohol equimolar amounts containing hydrophilic radical is added
In amine and 30min；
(4) deionized water for being then added 3 times stirs 30min under high speed shear active force, and oxygen can be obtained after reaction
Change the modified aqueous polyurethane emulsion of chitosan oligosaccharide.
Step 4: the preparation of industrial gelatine-oxidation chitosan oligosaccharide type Aqueous Polyurethane Adhesives:
The 30% oxidation chitosan oligosaccharide type aqueous polyurethane on the basis of aqueous gelatin solution quality is added into aqueous gelatin solution, often
It is stirred to react under temperature, industrial gelatine-oxidation chitosan oligosaccharide type Aqueous Polyurethane Adhesives is made.
Case study on implementation three:
Step 1: the preparation of industrial gelatine aqueous solution:
Industrial gelatine 15g is added in 80g deionized water, is swollen 30min at normal temperature, the heating at 40 DEG C is until completely molten
Solution, obtains aqueous gelatin solution.
Step 2: the preparation of chitosan oligosaccharide is aoxidized:
(1) sodium metaperiodate of 8.5g is placed in light resistant container, a certain amount of deionized water is added, be stirred well to dissolution；
(2) chitosan oligosaccharide of 8g is weighed in above-mentioned solution, is protected from light normal-temperature reaction 2d；
(3) obtained product is dialysed 1d in the bag filter of 500 interceptions, and is lyophilized in freeze drier, after grinding
To white solid.
Step 3: the preparation of oxidation chitosan oligosaccharide type aqueous polyurethane:
(1) isophorone diisocyanate 10g, polytetrahydrofuran (Mn=1000) 10g and 3d dibutyl tin dilaurate are added
To being equipped in the three-necked flask of thermometer, blender, glass bottle stopper, it is uniformly mixed, 50 DEG C of reaction 20min are warming up to 70 DEG C, instead
1h is answered, base polyurethane prepolymer for use as is made；
(2) dihydromethyl propionic acid 0.93g is added into above-mentioned system, heats up 80 DEG C, reacts the oxidation shell of addition 0.31g after 2.5h
Oligosaccharides, the reaction was continued 1h；
(3) above-mentioned gained system is cooled to 40 DEG C, three second with the oligomer dihydric alcohol equimolar amounts containing hydrophilic radical is added
In amine and 30min；
(4) deionized water for being then added 3 times stirs 30min under high speed shear active force, and oxygen can be obtained after reaction
Change the modified aqueous polyurethane emulsion of chitosan oligosaccharide.
Step 4: the preparation of industrial gelatine-oxidation chitosan oligosaccharide type Aqueous Polyurethane Adhesives:
The 30% oxidation chitosan oligosaccharide type aqueous polyurethane on the basis of aqueous gelatin solution quality is added into aqueous gelatin solution, often
It is stirred to react under temperature, industrial gelatine-oxidation chitosan oligosaccharide type Aqueous Polyurethane Adhesives is made.
Claims (10)
1. aoxidizing the purposes that chitosan oligosaccharide is used for modified polyurethane.
2. a kind of oxidation chitosan oligosaccharide modified polyurethane, which is characterized in that few by oxidation shell using oxidation chitosan oligosaccharide as crosslinking agent
Amino or hydroxyl in sugar are reacted with isocyanate group, modified polyurethane.
3. a kind of oxidation chitosan oligosaccharide modified polyurethane according to claim 2, it is characterised in that: oxidation chitosan oligosaccharide refers to shell
2,3 carbon-carbon bonds in oligosaccharide units are partly or entirely oxidized to aldehyde radical and are formed by substance；The oxidation chitosan oligosaccharide passes through
Sodium periodate solution aoxidizes chitosan oligosaccharide under the conditions of being protected from light and obtains.
4. a kind of oxidation chitosan oligosaccharide modified aqueous polyurethane according to claim 2, which is characterized in that by including with the following group
The reaction system divided obtains:
5 ~ 20 mass parts of isocyanates
8 ~ 20 mass parts of polyether polyol
Dibutyltin dilaurate catalyst dosage
0.7 ~ 1.2 mass parts of hydrophilic chain extender
Aoxidize 0.2 ~ 0.6 mass parts of chitosan oligosaccharide.
5. the aqueous polyurethane emulsion of oxidation chitosan oligosaccharide modified aqueous polyurethane preparation described in claim 4, it is characterised in that: by
Oxidation chitosan oligosaccharide modified aqueous polyurethane, which is dispersed in enough water, to be obtained.
6. a kind of oxidation chitosan oligosaccharide modified aqueous polyurethane emulsion according to claim 5, it is characterised in that: described hydrophilic
Property chain extender be carboxylic acid type hydrophilic chain extender；The oxidation chitosan oligosaccharide modified aqueous polyurethane is additionally added when emulsifying is enough to enable oxidation
Chitosan oligosaccharide modified aqueous polyurethane is dispersed into the neutralizer triethylamine of homogeneous latex emulsion.
7. described in claim 5 aoxidize chitosan oligosaccharide modified aqueous polyurethane emulsion preparation method, which is characterized in that including with
Lower step:
It will include the mixture of isocyanates, polyether polyol and dibutyl tin dilaurate in 50 DEG C of reaction 20min, heating
To 60 ~ 70 DEG C of 1 ~ 2h of reaction；Hydrophilic chain extender is added, is warming up to 70 ~ 90 DEG C of 2 ~ 3h of reaction, oxidation chitosan oligosaccharide reaction is added
1h；Reaction system is cooled to 40 DEG C, the neutralizer for being enough the amount for enabling aqueous polyurethane dispersion stable is added, obtains oxidation shell
Oligosaccharides modified aqueous polyurethane；The water of 2 ~ 6 times of quality of oxidation chitosan oligosaccharide modified aqueous polyurethane total amount, high speed dispersion 30 is added
~ 60min obtains oxidation chitosan oligosaccharide modified aqueous polyurethane emulsion.
8. a kind of industrial gelatine-oxidation chitosan oligosaccharide type Aqueous Polyurethane Adhesives, which is characterized in that by including the mixed of following components
Object is closed to obtain:
100 mass parts of aqueous gelatin solution
Aoxidize 10 ~ 50 mass parts of chitosan oligosaccharide modified aqueous polyurethane emulsion；
Institute's gelatin water solution includes the water of 10 ~ 20 mass parts industrial gelatines and 80 ~ 90 mass parts；
The oxidation chitosan oligosaccharide modified aqueous polyurethane emulsion includes oxidation chitosan oligosaccharide modified aqueous polyurethane and oxidation chitosan oligosaccharide
The water of 2 ~ 6 times of quality of modified aqueous polyurethane.
9. industrial gelatine described in claim 8-oxidation chitosan oligosaccharide type Aqueous Polyurethane Adhesives preparation method, feature exist
In, comprising the following steps: a timing will be reacted under the aqueous gelatin solution aqueous polyurethane emulsion room temperature modified with oxidation chitosan oligosaccharide
Between, obtain industrial gelatine-oxidation chitosan oligosaccharide type Aqueous Polyurethane Adhesives.
10. the application that industrial gelatine described in claim 8-oxidation chitosan oligosaccharide type Aqueous Polyurethane Adhesives are used to bind timber.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810600192.8A CN109135663B (en) | 2018-06-12 | 2018-06-12 | Application of chitosan oxide oligosaccharide in modified polyurethane, waterborne polyurethane and adhesive prepared from chitosan oxide oligosaccharide and preparation method of waterborne polyurethane and adhesive |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810600192.8A CN109135663B (en) | 2018-06-12 | 2018-06-12 | Application of chitosan oxide oligosaccharide in modified polyurethane, waterborne polyurethane and adhesive prepared from chitosan oxide oligosaccharide and preparation method of waterborne polyurethane and adhesive |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109135663A true CN109135663A (en) | 2019-01-04 |
| CN109135663B CN109135663B (en) | 2020-10-16 |
Family
ID=64801913
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810600192.8A Active CN109135663B (en) | 2018-06-12 | 2018-06-12 | Application of chitosan oxide oligosaccharide in modified polyurethane, waterborne polyurethane and adhesive prepared from chitosan oxide oligosaccharide and preparation method of waterborne polyurethane and adhesive |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109135663B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0962818A1 (en) * | 1998-06-04 | 1999-12-08 | Eastman Kodak Company | Gelatin-modified polyurethane |
| CN104109256A (en) * | 2014-06-20 | 2014-10-22 | 苏州科技学院 | Preparation method of thiolated chitosan modified polyurethane foam plastic |
| CN105944139A (en) * | 2016-07-05 | 2016-09-21 | 四川大学 | Soybean protein isolate-based biomedical adhesive and preparation method thereof |
| CN106753225A (en) * | 2016-11-25 | 2017-05-31 | 陕西科技大学 | Collagen class adhesive and preparation method and application |
-
2018
- 2018-06-12 CN CN201810600192.8A patent/CN109135663B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0962818A1 (en) * | 1998-06-04 | 1999-12-08 | Eastman Kodak Company | Gelatin-modified polyurethane |
| CN104109256A (en) * | 2014-06-20 | 2014-10-22 | 苏州科技学院 | Preparation method of thiolated chitosan modified polyurethane foam plastic |
| CN105944139A (en) * | 2016-07-05 | 2016-09-21 | 四川大学 | Soybean protein isolate-based biomedical adhesive and preparation method thereof |
| CN106753225A (en) * | 2016-11-25 | 2017-05-31 | 陕西科技大学 | Collagen class adhesive and preparation method and application |
Non-Patent Citations (2)
| Title |
|---|
| 姚文兵主编: "《生物技术制药概论》", 31 August 2015, 中国医药科技出版社 * |
| 董岸杰等: "壳聚糖-两性聚氨酯接枝共聚物的制备", 《应用化学》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109135663B (en) | 2020-10-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Heinrich | Future opportunities for bio-based adhesives–advantages beyond renewability | |
| Islam et al. | An overview of different types and potential of bio-based adhesives used for wood products | |
| EP1268702B2 (en) | Vegetable protein adhesive compositions | |
| Li et al. | Preparation of a high bonding performance soybean protein-based adhesive with low crosslinker addition via microwave chemistry | |
| CN102439056B (en) | Emulsion containing albumen and tackiness agent and their manufacture and purposes | |
| CN105331325B (en) | A kind of lignin/polyurethane/polyethyleneimine based Wood Adhesives and preparation method thereof | |
| CN106753159B (en) | Degradable collagen-polyurethane water-based wood adhesive and preparation method thereof | |
| CN101358122A (en) | One-component polyurethane adhesive from epoxy resin modification and preparation method thereof | |
| CN109554153A (en) | A kind of preparation method and application of collagen base adhesive | |
| CN104861917A (en) | Water-based polyurethane adhesive and preparation method thereof | |
| CN108570305A (en) | A kind of Soy-based Protein adhesive and preparation method thereof | |
| Yue‐Hong et al. | Effects of crosslinking on the mechanical properties and biodegradability of soybean protein‐based composites | |
| CN107384287A (en) | A kind of biological base adhesive and preparation method thereof | |
| CN104479342A (en) | Preparation method of reinforced and toughened thermoplastic polyurethane/regenerated cellulose (TPU/RC) composite film | |
| CN101701142B (en) | Wood single-component moisture curing polyurethane adhesive and preparation method thereof | |
| Hao et al. | A fully bio-based soy protein wood adhesive modified by citric acid with high water tolerance | |
| Ostendorf et al. | Manufacturing medium-density fiberboards and wood fiber insulation boards using a blood albumin adhesive on a pilot scale | |
| CN106753225A (en) | Collagen class adhesive and preparation method and application | |
| CN104130733B (en) | The preparation method of the modified biomass liquefied resin tackiness agent of enhanced water resistance | |
| CN106800907A (en) | A kind of environment-friendly water-based wood adhesive based on degraded collagen solution and preparation method thereof | |
| Yan et al. | Development of soybean meal based adhesives with excellent wet-resistance and prepressing bonding strength via disulfide bond reshuffling strategy | |
| CN107641495A (en) | A kind of vegetable protein adhesive and its preparation method and application | |
| CN107987262B (en) | A kind of liquid polyesters polyalcohol containing lignin and the environment-protecting polyurethane adhesive using its preparation | |
| CN110229342A (en) | A method of the composite liquefied mulch of collagen-base is prepared by tanning waste | |
| CN109135663A (en) | Chitosan oligosaccharide is aoxidized for the purposes of modified polyurethane, aqueous polyurethane, adhesive and the preparation method of its preparation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |