CN109554153A - A kind of preparation method and application of collagen base adhesive - Google Patents
A kind of preparation method and application of collagen base adhesive Download PDFInfo
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- CN109554153A CN109554153A CN201811474222.1A CN201811474222A CN109554153A CN 109554153 A CN109554153 A CN 109554153A CN 201811474222 A CN201811474222 A CN 201811474222A CN 109554153 A CN109554153 A CN 109554153A
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- 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
-
- 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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
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- 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
- C08G18/4825—Polyethers containing two hydroxy groups
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- 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
- C08G18/58—Epoxy resins
-
- 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
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- 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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6625—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/34
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- 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
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- Chemical Kinetics & Catalysis (AREA)
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- Adhesives Or Adhesive Processes (AREA)
Abstract
The present invention is a kind of production method using polyurethane, epoxy resin modification collagen synthesis Aqueous Adhesives, the collagen hydrolysate liquor for extracting number-average molecular weight 10000-30000 from the raw materials containing collagen such as leather producing corner material, bone first, then in 50-80oThe isocyano base polyurethane prepolymer for use as of end containing hydrophilic radical is synthesized under C and is mixed with a certain amount of epoxy resin, salt forming agent and carboxyl is added into salt, it is eventually adding deionized water collagen hydrolysate liquor and polyurethane, epoxy resin in dispersion, emulsion process and graft reaction occurs, synthesis of polyurethane, epoxy resin modification collagen-base aqueous adhesive are not added or are added a certain amount of curing agent, filler in application and bond for glued board.For the adhesive using tanning waste as main production raw material, raw material is renewable, product without formaldehyde, there is good water resistance and adhesive strength, lower production cost, can reach the requirement of II class glued board, it is simple production process, easily-controllable.
Description
Technical field
The present invention relates to technical field of fine, and in particular to a kind of preparation method of collagen class adhesive with answer
With.
Background technique
Adhesive has very important status in timber industry.The biological materials such as protein, starch, lignin are very early
Just it is applied to wood bonding.Early in the 1920s, soybean protein is just applied to the bonding of glued board, core-board, and
It is widely used in next 40 years.But it is especially water-fast since its working life is short, solid content is low, resistance to bioerodible is poor
The disadvantages of property is poor and can be only applied to interior.Since the sixties in last century, soy protein binders are gradually artificial synthesized
Adhesive is replaced.It counts according to " 2011 China's timber market trend observational study prediction address ", is calculated according to contents on dry basis,
China's timber industry glue in 2009 is up to 535.68 ten thousand tons, and wherein 504.49 ten thousand tons of Lauxite, account for the 94.18% of total amount；Phenol
25.67 ten thousand tons of urea formaldehyde, account for 4.79%；5.52 ten thousand tons of melamine resin, account for 1.03%.
Traditional " three-aldehyde glue " production and using when can release the toxic small molecule of the volatility such as formaldehyde, application by
Biggish limitation.The characteristics of adhesives such as polyurethane, epoxy resin are because of excellent glue performance and less pollution, becomes close
The emerging glue kind in wood-based plate field over year, but since the higher occupation rate of market of price is smaller.In this context, it is based on albumen
" green " adhesive of the natural biomass matrix such as matter, starch, lignin has become a hot topic of research again.
Collagen is the albumen in the skin for being widely present in animal, bone, cartilage, ligament, tendon and other connective tissues
Matter macromolecular.It will be enriched in the high-molecular polypeptide high polymer gelatin pair that the purified and appropriate hydrolysis of raw material of collagen obtains
Glass, paper, fabric, metal, leather, timber etc. have very strong bonding force, and because have to drop under field conditions (factors)
The advantages that solution and the fields such as casting, bonding wood materials widely apply.But such gelatin there is also the easy gelations of room temperature (must be 60 DEG C
The above hot water dissolving and quickly use), poor water resistance, intolerant to microorganism, film forming it is more crisp the disadvantages of.Wang Hongru etc. (Wang Hongru,
Luo Qiong, Zhang Xiaobo wait research [J] the Shaanxi Tech Univ journal of the polyurethane-modified gelatin of epoxy radicals end-blocking, and 2013,31
(06): 77-81. ring) is introduced in polyurethane molecular chain using the base polyurethane prepolymer for use as sealing end of glycidol opposite end isocyano
Oxygen groups react progress graft modification with gelatin solution after being dispersed into polyaminoester emulsion, improve the filming performance of gelatin, use
In leather finish, but the synthon glycidol price that the method uses is more expensive, and synthesis process, which is easy to react with carboxyl, to be caused to coagulate
Glue, reaction process are not easy to control.Jin Yuanmin discloses end isocyano base polyurethane prepolymer for use as in its research paper, and pre-
Aggressiveness end introduces salicylide, and polyurethane/gelatin copolymerization is then prepared using the reaction of amino on aldehyde radical and gelatin segment
Object has obtained a series of polyurethane/gelatin copolymer, has improved the performance of gelatin.Since the aldehyde radical of salicylide can be with polyurethane
Amide groups react, synthesis process is equally not easy to control.Chinese patent CN 106753225 discloses " collagen class
Sealer sodium hydrogensulfite or sulfurous is added in adhesive and the preparation method and application thereof " in polyisocyanates based compound
Potassium hydrogen phthalate is stirred at room temperature to obtain blocked polyisocyanate based compound；Enclosed type polyisocyanic acid is added into aqueous gelatin solution
Ester group compound, stirring at normal temperature obtain collagen class adhesive, are used for bonding wood.Inorganic salts sealer sulfurous acid used
Hydrogen sodium or potassium bisulfite and organic multiple isocyanate reaction process are not easy to control.105199662 A of Chinese patent CN is disclosed
" a kind of using Hydrolyzed Collagen as the preparation method of the based Wood Adhesives of raw material ", is added 1.5 in Hydrolyzed Collagen liquid
~3 parts of silane coupling agents are reacted with 0~2 part of difunctional aldehyde, continue to be stirred to react 8~12h, can be obtained hydrolysis glue
Former albumen base adhesive effectively improves the water resistance and intensity of collagen adhesive for bonding wood materials, but adhesive synthesizes
Raw material contains aldehyde material, unfavorable to production environment and consumer.
Summary of the invention
Technical problem to be solved by the invention is to provide a kind of preparation methods of collagen base adhesive, and providing should
The application method of adhesive produces Formaldehyde-free adhesive with renewable, environmentally friendly collagen, while to improve natural collagen
Easy gelation, poor water resistance, glue-line are crisp, combine polyurethane, epoxy resin from molecular level, synthesis technology is simple, easily
Control, the bonding of adhesive application timber obtain higher adhesive strength.
Technical scheme is as follows:
A kind of preparation method of collagen base adhesive, it is characterised in that the following steps are included:
Polyalcohol, polyisocyanates and proper catalyst are mixed, react 30-60min at 40-70 DEG C；It then will be warm
Degree rises to 75-85 DEG C, then reacts 60-90min；Then 60-75 DEG C is cooled to, hydrophilic chain extender and small molecule chain extender is added,
After reacting 30-40min, be warming up to 78-85 DEG C, the reaction was continued 2~3h is cooled to 30-40 DEG C, be added organic solvent reduce it is viscous
Degree obtains end isocyano base polyurethane prepolymer for use as to 100-3000mPas；At room temperature, it holds in isocyano base polyurethane prepolymer for use as
Epoxy resin and amine salt forming agent is added, stirs into salt, obtains component A；
Collagen hydrolysate liquor is added in component A, stirs lower reaction 50-90min, solvent is removed in vacuum, obtains collagen egg
White base adhesive；
Wherein, polyalcohol is that the polyester polyol that molecular weight is 400-4000 or the polyethers that molecular weight is 400-4000 are more
First alcohol；
Wherein, polyisocyanates is toluene di-isocyanate(TDI) (TDI), isophorone diisocyanate (IPDI), diphenyl
Methane diisocyanate (MDI), dicyclohexyl methyl hydride diisocyanate (HMDI) or hexamethylene diisocyanate (HDI)；
Wherein, catalyst is the metal-based catalysts including organotin, organo-bismuth, Organic leadP and organic zinc；
Wherein, amine salt forming agent is triethylamine, N-methyl diethanol amine or N, N- dimethylethanolamine；
Wherein, the collagen hydrolysate liquor molecular weight 10000-30000；
Wherein, the mass ratio between polyalcohol, polyisocyanates, hydrophilic chain extender and small molecule chain extender is: (45-
60): (15-30): (3-12): (0-3)；Polyalcohol, polyisocyanates, hydrophilic chain extender and small molecule chain extender quality sum
It is calculated as monomer gross mass；Mass ratio between monomer gross mass, epoxy resin and amine salt forming agent is: 100:(30-100):
(2.3-6)；Mass ratio between component A and collagen hydrolysate liquor is 100:100-300, and collagen hydrolysate liquor is with solid
Object weight calculation.
The polyalcohol is that polyalcohol is polyethylene glycol adipate glycol, adipic acid hexylene glycol esterdiol, adipic acid
Butyl glycol ester diol or polypropylene glycol.
The organic solvent is in acetone, butanone or ethyl acetate.
The collagen hydrolysate liquor is extracted from leather producing corner material, and the degree of hydrolysis of collagen is 6-10%.
The hydrophilic chain extender is dihydromethyl propionic acid (DMPA) or dimethylolpropionic acid (DMBA).
The epoxy resin is bisphenol A-type ethylene oxidic ester.
The small molecule chain extender is 1,4-butanediol or diethylene glycol.
The catalyst amount is the 0.05%-0.3% of polyester polyol and polyisocyanates quality sum.
The collagen base adhesive is applied to bonding wood.
The collagen base adhesive is applied to the method for bonding wood, it is characterised in that: by collagen base rubber
Glutinous agent is uniformly coated to the two sides of wood single-plate, glue-spread 80-120g/m2(by solid quality in terms of), after dry,
In 120-150 DEG C, hot pressing, glued board is produced.
The invention has the characteristics that:
The present invention combines the Hydrolyzed Collagen that specified molecular weight is extracted from leather producing corner material using lime with enzyme process,
Aqueous polyurethane package epoxy resin to synthesize forms active emulsion particle and reacts shape with the collagen cross-linking in water phase
At New Emulsion system, the disadvantages of overcoming the easy gelation of collagen solution, poor water resistance, brittleness big, intolerant to microorganism, and will
It applies the bonding of timber, obtains the requirement that higher adhesive strength reaches II class glued board (GB/T 9846-2015).
Present invention employs reproducible leather producing corner material, and green, environmentally friendly Aqueous Adhesives are produced as raw material, no
Generate formaldehyde；Polyurethane, epoxy resin disadvantage at high cost are overcome, while having adhesive strength high, water-tolerant excellent
Point.
Using enzyme process or lime+Enzymatic Extraction Hydrolyzed Collagen, hardly saliferous, molecular weight distribution is concentrated, favorably
In the stabilization of synthesis water-based latex and the raising of bond properties.
The present invention overcomes traditional gelatin adhesive poor water resistance, easy gelation and toughness are insufficient the disadvantages of.
The present invention combines polyurethane, epoxy resin from molecular level, and synthesis technology is simple, easily-controllable.
The present invention has a good application prospect, and can be applied to the fields such as glued board, particieboard, core-board.
Detailed description of the invention
Fig. 1 is collagen base adhesive synthetic route schematic diagram.
Fig. 2 is the infrared spectrum of acetone extract adhesive glue film remaining solid.
Fig. 3 is collagen grafting rate histogram in different synthetic adhesive samples.
Fig. 4 be synthetic adhesive at glue film differential scanning calorimeter curve graph.
Fig. 5 is the tensile property line chart of synthetic adhesive glue film.
Fig. 6 a is the bonding effect figure (dry state adhesive strength) that adhesive is applied to bonding wood materials.
Fig. 6 b is the bonding effect figure (peel strength after water retting) that adhesive is applied to bonding wood materials.
Fig. 7 is the collagen hydrolysate liquor graph of molecular weight distribution that collagen hydrolysate liquor preparation example two of the present invention is extracted.
Specific embodiment
The present invention will be described in detail With reference to embodiment.
Collagen hydrolysate liquor preparation example one: collagen hydrolysate liquor is extracted from chromium-free leather producing corner material.
Then the water repeated washing 2 of tare weight 300% is added in the drain after common process deliming of liming ox-hide leftover pieces
It is secondary, to remove remaining dirt and surfactant in ox-hide rawhide and make rawhide pH value close to neutrality；Then by ox-hide corner
Material is cut into 10 mm × 10mm fritter, weighs, and the neutral proteinase of tare weight 0.5% and the Papain of tare weight 0.5% is added
Enzyme, 4 times of tare weight of water hydrolyze 3-5h；Then it filters hydrolyzate and hydrolyzate is brought rapidly up to 90 DEG C, keep 10min to water
It solves enzyme and carries out inactivation treatment；It will be refrigerated after hydrolyzate filtering after inactivation using Rotary Evaporators concentrated by rotary evaporation to 30%, for glue
Glutinous agent preparation example one, two uses stand-by.
Collagen hydrolysate liquor preparation example two: collagen hydrolysate liquor is extracted from process hides indigo plant hide offal.
Shavings is cleaned with clear water, adds the calcium hydroxide of shavings quality 10%, hydrolyzes 4-5h at 95 DEG C, be cooled to 60 DEG C
Afterwards, it filters, dilute sulfuric acid is added and is adjusted to neutrality, the neutral proteinase and shavings quality of shavings quality 0.025-0.125% is added
The papain of 0.025-0.125%% hydrolyzes 2-3h at 60 DEG C, is brought rapidly up to 90 DEG C, keep 10min to hydrolase into
Row inactivation treatment；It, using Rotary Evaporators concentrated by rotary evaporation to 30%, will be prepared for real adhesive after hydrolyzate filtering after inactivation
Example three uses.The collagen hydrolysate liquor molecular weight distribution of preparation is as shown in Figure 7, it can be seen that extracted collagen number
Average molecular weight is 13900, and molecular weight is 4900 or more, and (small-molecular-weight ingredient is unfavorable for adhesive to no relatively small molecular weight ingredient
Adhesive strength).
Adhesive preparation example one
Step 1: synthesizing the PU performed polymer containing hydrophilic radical, end isocyano.It is specific as follows:
By the 56g polyethylene glycol adipate glycol (PEA) of molecular weight 2000,19.23g isophorone diisocyanate
(IPDI) it is added in three-necked flask, 0.16g organotin catalysts, is warming up to 80 DEG C after reacting 30min at 50 DEG C and keeps the temperature 1h；
Then 70 DEG C are cooled to, 4.34g dihydromethyl propionic acid (DMPA), 11.9g butanone (MEK) is added, after reacting 30min, heating
To 80 DEG C, the reaction was continued 2~3h is cooled to 35 DEG C, is added until-NCO content is close to theoretical value (detection of di-n-butylamine method)
The acetone (ACE) of 20 mass parts obtains PU performed polymer after reducing viscosity to 1000mPas, be added in PU performed polymer epoxy 828,
Carboxyl is at salt in 2.37g triethylamine (TEA) and PU performed polymer.
Step 2: polyurethane, epoxy resin graft collagen hydrolysate liquor.It is specific as follows:
In the base polyurethane prepolymer for use as of above-mentioned synthesis, deionized water is added, with the speed stirring 5min emulsification of 2000r/min
Mixing speed is reduced after uniformly to 500r/min, collagen hydrolysate liquor is added the reaction was continued 1h, then in 60 DEG C, 0.09MPa
Solvent synthesis solid content about 30%, viscosity at ambient temperature 90mPas, the gluing with good fluidity is removed in vacuum in 0.5h under negative pressure
Agent emulsion, polyurethane or epoxy resin are successfully grafted on collagen molecules.Its specific raw material dosage proportion is as shown in table 1.
The basic recipe and lotion basic performance of 1 Aqueous Adhesives of table synthesis
Note: PU performed polymer and Hydrolyzed Collagen quality are in terms of solid content.PU performed polymer is finger tip isocyano
Base polyurethane prepolymer for use as.
The poplar wood particle (moisture content 5~8%, size 40mm × 30mm × 8mm) that two pieces are cut out is carried out with sand paper
Then surface polishing uses line grain stick spreader by synthetic latex in its surface even spread, glue-spread 100g/m2(with resin
Subject to quality), after being put into 60 DEG C of baking ovens dry 5min, the hot pressing 10min on 150 DEG C of vulcanizing presses, pressure 1MPa,
It takes out and (impregnates for 24 hours) bond strength test in 20 ± 3 DEG C of water after carrying out dry state and water retting respectively after placing 48.Dry state is viscous
It closes intensity and reaches 3.0~3.5MPa, water retting adhesive strength reaches 1.7~2.0MPa, can reach Group III glued board (GB/T
Requirement (dry state >=0.7MPa impregnates rear >=0.7MPa for 24 hours in 20 DEG C of water) 9846-2015), concrete outcome such as Fig. 6
Shown in (Fig. 6 a and Fig. 6 b)；The aziridines curing agent of 0.5-1% is added, test bonding afterwards is impregnated for 24 hours at 63 DEG C ± 3 DEG C
Intensity reaches 1.4~2.0MPa, meets the requirement of II class glued board (GB/T 9846-2015).
Adhesive preparation example two
Step 1: synthesizing the PU performed polymer containing hydrophilic radical, end isocyano.It is specific as follows:
Take adipic acid hexylene glycol esterdiol (PHA) 40.00g of molecular weight 2000 in three-neck flask, the oil bath at 50 DEG C
10.44gTDI, 0.16g organic bismuth catalyst are successively added into flask and reacts 30min for heating；65 DEG C are warming up to, reaction
Then temperature is risen to 80 DEG C, then reacts 60min by 20min；Cool the temperature to 70 DEG C, into flask be added 2.657g DMPA,
2.6705g butanone reacts 30min, is warming up to 80 DEG C, reacts 2h, the PU performed polymer of synthesis-NCO sealing end.Flask is down to room
10.7g acetone reduction viscosity is added to 1200mPas in temperature, and addition 19.767g epoxy 828,2.002gTEA stir 1min, at
Salt.
0.0534gH can also be added in this step3PO4, it is added together with catalyst.
Step 2:PU, epoxy resin graft collagen hydrolysate liquor.It is specific as follows:
Add 58g deionized water, high-speed stirred 5min, collagen hydrolysate liquor 177g is added, and (collagen content is
30%), continue stirring, react 60min at room temperature, solvent synthetic adhesive lotion is removed in vacuum.
The water dispersible aziridine hardener of adhesive quality 0.5-1%, glue-spread 100g/m is added2(with adhesive
Subject to contained resin quality), after being put into 60 DEG C of baking ovens dry 5min, the hot pressing 10min pressure on 150 DEG C of vulcanizing presses
For 1MPa, takes out and (impregnate for 24 hours) adhesive strength survey after carrying out dry state and Hot water immersion after placing 48 respectively in 63 ± 3 DEG C of water
Examination, dry state adhesive strength are all larger than 3MPa, and adhesive strength is all larger than 2MPa after hot-water soak, reaches II class glued board (GB/T
Requirement 9846-2015).
Adhesive preparation example three
Step 1: synthesizing the PU performed polymer containing hydrophilic radical, end isocyano.It is specific as follows:
Take tetramethylene adipate glycol (PBA) 40.00g of molecular weight 2000 in three-neck flask, the oil bath at 50 DEG C
10.44gTDI, 0.1g organic bismuth catalyst are successively added into flask and reacts 30min for heating；65 DEG C are warming up to, reaction
Then temperature is risen to 80 DEG C, then reacts 60min by 20min；Cool the temperature to 70 DEG C, into flask be added 2.657g DMPA,
2.6705g butanone reacts 30min, is warming up to 80 DEG C, reacts 2h, the PU performed polymer of synthesis-NCO sealing end.Acetone, which is added, to be reduced
Viscosity is added 19.767g epoxy 828,2.002gTEA, 1min is stirred, at salt to 1200mPas.
0.05gH can also be added in this step3PO4, it is added together with catalyst.
Step 2:PU, epoxy resin graft collagen hydrolysate liquor.It is specific as follows:
Flask is down to room temperature, 10.682g acetone, adds 58g deionized water, collagen water is added in high-speed stirred 5min
It solves liquid 177g (collagen content 30%), continues stirring, reacts 60min at room temperature, solvent synthetic adhesive is removed in vacuum
Lotion.
The water dispersible aziridine hardener of adhesive quality 0.5-1%, glue-spread 100g/m is added2(with adhesive
Subject to contained resin quality), after being put into 60 DEG C of baking ovens dry 5min, the hot pressing 10min pressure on 150 DEG C of vulcanizing presses
For 1MPa, takes out and (impregnates for 24 hours) bond strength test in 63 DEG C of water after carrying out dry state and Hot water immersion respectively after placing 48,
Dry state adhesive strength is all larger than 2.5MPa, and adhesive strength is all larger than 1.8MPa after hot-water soak, reaches II class glued board (GB/T
Requirement 9846-2015).
Adhesive preparation example four
Step 1: synthesizing the PU performed polymer containing hydrophilic radical, end isocyano.It is specific as follows:
Take tetramethylene adipate glycol (PBA) 30.00g of molecular weight 2000, the polypropylene glycol (PPG) of molecular weight 2000
10g is in three-neck flask, the oil bath heating at 50 DEG C, and 10.44gTDI, 0.16g organic bismuth catalyst are successively added into flask
React 30min；65 DEG C are warming up to, 20min is reacted, temperature is then risen to 80 DEG C, then react 60min；Cool the temperature to 60
DEG C, 2.5g DMPA, 2.6705g butanone, 0.4g 1,4-butanediol are added into flask and reacts 30min, is warming up to 80 DEG C, instead
3h is answered, acetone, which is added, reduces the PU performed polymer that viscosity is blocked to 900mPas synthesis-NCO.Addition 14.2g epoxy 828,
1.9gTEA stirs 1min, at salt.
0.05gH can also be added in this step3PO4, it is added together with catalyst.
Step 2:PU, epoxy resin graft collagen hydrolysate liquor.It is specific as follows:
Flask is down to room temperature, 10.7g acetone, adds 58g deionized water, collagen hydrolysate is added in high-speed stirred 5min
Liquid 106g (collagen content 30%) continues stirring, reacts 60min at room temperature, and solvent synthetic adhesive cream is removed in vacuum
Liquid.
The water dispersible aziridine hardener of adhesive quality 0.5-1%, glue-spread 100g/m is added2(with adhesive
Subject to contained resin quality), after being put into 60 DEG C of baking ovens dry 5min, the hot pressing 10min pressure on 150 DEG C of vulcanizing presses
For 1MPa, takes out and (impregnates for 24 hours) bond strength test in 63 DEG C of water after carrying out dry state and Hot water immersion respectively after placing 48,
Dry state adhesive strength is all larger than 2.4MPa, and adhesive strength is all larger than 1.9MPa after hot-water soak, reaches II class glued board (GB/T
Requirement 9846-2015).
Entire synthesis process schematic diagram is as shown in Figure 1.Fig. 2, Fig. 3 show: polyurethane, epoxy resin and collagen occur
Graft reaction is successfully connected on collagen molecules chain, and epoxy resin is added and improves grafting rate, collagen and polyurethane
Ratio increase grafting rate and increase, as polyurethane and collagen hydrolysate liquor 1:1 in synthesis material and when epoxy 828 is added
Grafting rate highest, up to 85%.Fig. 4 be synthetic latex film forming DSC curve, wherein the glass transition temperature of resin be -12 DEG C with
Under, there is good resistance to low temperature；Fig. 5 is the tensile property curve of synthetic latex film forming, and it is good to illustrate that synthetic latex has
Tensile property, the disadvantage that elongation is low, brittleness is big that overcomes collagen itself.
Claims (10)
1. a kind of preparation method of collagen base adhesive, it is characterised in that the following steps are included:
Polyalcohol, polyisocyanates and proper catalyst are mixed, react 30-60min at 40-70 DEG C；Then by temperature liter
To 75-85 DEG C, then react 60-90min；Then 60-75 DEG C is cooled to, hydrophilic chain extender and small molecule chain extender, reaction is added
After 30-40min, it is warming up to 78-85 DEG C, the reaction was continued 2 ~ 3h is cooled to 30-40 DEG C, and organic solvent, which is added, reduces viscosity extremely
100-3000mPas obtains end isocyano base polyurethane prepolymer for use as；At room temperature, it holds in isocyano base polyurethane prepolymer for use as and ring is added
Oxygen resin and amine salt forming agent, stir into salt, obtain component A；
Collagen hydrolysate liquor is added in component A, stirs lower reaction 50-90min, solvent is removed in vacuum, obtains collagen-base
Adhesive；
Wherein, polyalcohol is the polyester polyol that molecular weight is 400-4000 or the polyether polyols that molecular weight is 400-4000
Alcohol；
Wherein, polyisocyanates is toluene di-isocyanate(TDI) (TDI), isophorone diisocyanate (IPDI), diphenyl methane
Diisocyanate (MDI), dicyclohexyl methyl hydride diisocyanate (HMDI) or hexamethylene diisocyanate (HDI)；
Wherein, catalyst is the metal-based catalysts including organotin, organo-bismuth, Organic leadP and organic zinc；
Wherein, amine salt forming agent is triethylamine, N-methyl diethanol amine or N, N- dimethylethanolamine；
Wherein, the collagen hydrolysate liquor molecular weight 10000-30000；
Wherein, the mass ratio between polyalcohol, polyisocyanates, hydrophilic chain extender and small molecule chain extender is: (45-60):
(15-30): (3-12): (0-3)；Polyalcohol, polyisocyanates, hydrophilic chain extender and small molecule chain extender quality sum are calculated as list
Body gross mass；Mass ratio between monomer gross mass, epoxy resin and amine salt forming agent is: 100:(30-100): (2.3-6)；
Mass ratio between component A and collagen hydrolysate liquor is 100:100-300, and collagen hydrolysate liquor is counted weight with solid content.
2. the preparation method of collagen base adhesive as described in claim 1, it is characterised in that the polyalcohol is more
First alcohol is polyethylene glycol adipate glycol, adipic acid hexylene glycol esterdiol, tetramethylene adipate glycol or polypropylene glycol.
3. the preparation method of collagen base adhesive as described in claim 1, it is characterised in that the organic solvent is
In acetone, butanone or ethyl acetate.
4. the preparation method of collagen base adhesive as described in claim 1, it is characterised in that the collagen water
Solution liquid is extracted from leather producing corner material, and the degree of hydrolysis of collagen is 6-10%.
5. the preparation method of collagen base adhesive as described in claim 1, it is characterised in that the hydrophilic chain extender
It is dihydromethyl propionic acid (DMPA) or dimethylolpropionic acid (DMBA).
6. the preparation method of collagen base adhesive as described in claim 1, it is characterised in that the epoxy resin is
Bisphenol A-type ethylene oxidic ester.
7. the preparation method of collagen base adhesive as described in claim 1, it is characterised in that the small molecule chain extension
Agent is 1,4-butanediol or diethylene glycol.
8. the preparation method of collagen base adhesive as described in claim 1, it is characterised in that the catalyst amount
For the 0.05%-0.3% of polyester polyol and polyisocyanates quality sum.
9. the collagen base adhesive of claim 1-8 any one preparation is applied to bonding wood.
10. collagen base adhesive as claimed in claim 9 is applied to the method for bonding wood, it is characterised in that: by glue
Former albumen base adhesive is uniformly coated to the two sides of wood single-plate, glue-spread 80-120g/m2(it is with solid quality
Meter), after dry, in 120-150 DEG C, hot pressing, produce glued board.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110256651A (en) * | 2019-05-20 | 2019-09-20 | 齐鲁工业大学 | A kind of preparation method of collagen-base papermaking function sizing agent |
| CN110368516A (en) * | 2019-07-06 | 2019-10-25 | 袁斯曼 | A kind of preparation method of high bonding degradable adhesive fibrin |
| CN111171277A (en) * | 2020-01-20 | 2020-05-19 | 北京林业大学 | Polyurethane elastic cross-linking agent and high-strength vegetable protein adhesive and its application |
| CN111704879A (en) * | 2020-07-22 | 2020-09-25 | 徐州鸿丰高分子材料有限公司 | Air-permeable leather adhesive and preparation method thereof |
| CN112277392A (en) * | 2020-10-26 | 2021-01-29 | 无锡市辰华包装有限公司 | Preparation method of antibacterial anti-static corrugated board |
| CN114605962A (en) * | 2022-04-18 | 2022-06-10 | 北京京都大成新材料科技有限公司 | A water-resistant flexible packaging adhesive based on hydrolyzed collagen and oxidized starch, preparation method and application thereof |
| CN114672281A (en) * | 2022-04-18 | 2022-06-28 | 北京京都大成新材料科技有限公司 | Bio-based adhesive for laminating kraft paper to metal plate and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030212235A1 (en) * | 2001-07-09 | 2003-11-13 | Nowicki James W. | Reactive hot melt adhesive |
| CN106753159A (en) * | 2016-11-16 | 2017-05-31 | 四川大学 | One kind degraded polyurethane aqueous wood adhesive of collagen and preparation method thereof |
| CN106800907A (en) * | 2016-12-27 | 2017-06-06 | 东莞市联洲知识产权运营管理有限公司 | A kind of environment-friendly water-based wood adhesive based on degraded collagen solution and preparation method thereof |
| CN106867441A (en) * | 2016-12-30 | 2017-06-20 | 东莞市佳乾新材料科技有限公司 | A kind of preparation method of inexpensive water-fast formaldehyde-free plywood |
-
2018
- 2018-12-04 CN CN201811474222.1A patent/CN109554153A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030212235A1 (en) * | 2001-07-09 | 2003-11-13 | Nowicki James W. | Reactive hot melt adhesive |
| CN106753159A (en) * | 2016-11-16 | 2017-05-31 | 四川大学 | One kind degraded polyurethane aqueous wood adhesive of collagen and preparation method thereof |
| CN106800907A (en) * | 2016-12-27 | 2017-06-06 | 东莞市联洲知识产权运营管理有限公司 | A kind of environment-friendly water-based wood adhesive based on degraded collagen solution and preparation method thereof |
| CN106867441A (en) * | 2016-12-30 | 2017-06-20 | 东莞市佳乾新材料科技有限公司 | A kind of preparation method of inexpensive water-fast formaldehyde-free plywood |
Non-Patent Citations (2)
| Title |
|---|
| 李子东: "《现代胶粘技术手册》", 31 January 2002, 新时代出版社 * |
| 薛新顺等: ""胶原的化学交联改性技术研究进展"", 《皮革科学与工程》 * |
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| CN110256651A (en) * | 2019-05-20 | 2019-09-20 | 齐鲁工业大学 | A kind of preparation method of collagen-base papermaking function sizing agent |
| CN110256651B (en) * | 2019-05-20 | 2021-08-31 | 齐鲁工业大学 | Preparation method of collagen-based papermaking functional sizing agent |
| CN110368516A (en) * | 2019-07-06 | 2019-10-25 | 袁斯曼 | A kind of preparation method of high bonding degradable adhesive fibrin |
| CN111171277A (en) * | 2020-01-20 | 2020-05-19 | 北京林业大学 | Polyurethane elastic cross-linking agent and high-strength vegetable protein adhesive and its application |
| CN111171277B (en) * | 2020-01-20 | 2024-04-19 | 北京林业大学 | Polyurethane elastic crosslinking agent, high-strength and high-toughness vegetable protein adhesive and application |
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| CN112277392A (en) * | 2020-10-26 | 2021-01-29 | 无锡市辰华包装有限公司 | Preparation method of antibacterial anti-static corrugated board |
| CN112277392B (en) * | 2020-10-26 | 2022-05-10 | 无锡市辰华包装有限公司 | Preparation method of antibacterial anti-static corrugated board |
| CN114605962A (en) * | 2022-04-18 | 2022-06-10 | 北京京都大成新材料科技有限公司 | A water-resistant flexible packaging adhesive based on hydrolyzed collagen and oxidized starch, preparation method and application thereof |
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| CN114672281B (en) * | 2022-04-18 | 2024-03-08 | 北京京都大成新材料科技有限公司 | Bio-based adhesive for laminating kraft paper to metal plate, and preparation method and application thereof |
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