CN102965070B - The preparation method of conjugated protein sizing agent - Google Patents
The preparation method of conjugated protein sizing agent Download PDFInfo
- Publication number
- CN102965070B CN102965070B CN201110262489.6A CN201110262489A CN102965070B CN 102965070 B CN102965070 B CN 102965070B CN 201110262489 A CN201110262489 A CN 201110262489A CN 102965070 B CN102965070 B CN 102965070B
- Authority
- CN
- China
- Prior art keywords
- protein
- mussel
- preparation
- urea
- soybean
- 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.)
- Expired - Fee Related
Links
Landscapes
- Adhesives Or Adhesive Processes (AREA)
- Meat, Egg Or Seafood Products (AREA)
Abstract
The present invention relates to a kind of preparation method of conjugated protein sizing agent, step is: first prepare mussel protein powder, take water as solvent, add alkali, urea successively, make pH value be 9-10.5, the concentration of urea is 2-3.5mol/L, then adds BIT, the concentration of BIT is made to be 0.1%, after again mussel protein powder and soybean protein being mixed according to the mass ratio that mussel protein powder accounts for 20 ~ 80%, be added to the water, make liquid-solid ratio be 10-15mL/g, in stirred at ambient temperature 2-4 hour, obtain conjugated protein tackiness agent.The structure of mussel protein matter in the basic conditions, with the sex change of urea inducing soybean protein molecular, is introduced in soybean protein, is overcome soybean protein poor water resistance, poor mechanical property by the present invention, and mussel byssus protein poorly water-soluble and be difficult to the shortcoming of crystallization.This preparation method have simple to operate, raw material is easy to get, cost is lower, the simple feature of equipment requirements, it is high that obtained mussel protein/soybean protein composite adhesive has adhesive strength, and high tenacity, strong water-repellancy feature, be applicable to industrial production.
Description
Technical field
That the present invention relates to is a kind of preparation method of conjugated protein sizing agent, specifically a kind of preparation method of mussel protein/Hybrid Adhesive Based on Soy Protein.
Background technology
Protein adhesive is a kind of tackiness agent using protein as main raw material.Different by the source of protein raw material, animal protein tackiness agent (as blood glue, casein adhesive, osteoderm glue etc.) and vegetable protein tackiness agent (as bean powder glue, soybean glue etc.) two classes can be divided into
[4].Protein uses long-standing as tackiness agent.Just bring into use egg, gelatin etc. to make tackiness agent as far back as B.C. 3000 ~ 4000 years ancient Egyptians, be widely used in building field.The raw material of protein sizing agent is all renewable resources, does not pollute environment, and impregnation equipment is simple, modulation and easy to use, and dry shape glue glued adhesion intensity better, can meet the bonding requirement of the wood-based plate of general indoor use.
Soybean protein is the principal by product of large processing of farm products, and have aboundresources, best in quality, cheap, reproducible advantage, but its bonding strength, water tolerance, thermotolerance etc. are all not high, time limit of service is shorter.But soybean protein belongs to globular protein, its water tolerance and thermotolerance are all undesirable.What the Mussels biology lived in the ocean of the length and breadth of land can be secreted by its foot makes its applied solid alow, seashore reef, and other marine organisms surface.Research shows this adhesive capacity mainly because mussel contains 6 kinds of different albumen with Adhering capacity, containing 3,4-a large amount of dihydroxy phenolic group L-Ala in mussel body, is the major cause producing adhesive power.For the applied research of mussel protein, generally directly from mussel pedal gland, extract natural attachment proteins composition, such as, BioPolymers company starts directly to extract from mussel pedal gland from the eighties in 20th century and is developed into the adhesive product of tissue culture, can be used for the adhesion of non-adherent cell and culture dish in cell cultivation process.But because the secretory volume of mussel byssus protein is very low, cause the adhesive product of this extracting directly expensive.Although carried out large quantifier elimination for mussel byssus protein at present, still have many unsolved difficult problems, such as, mussel byssus protein molecular weight is comparatively large, poorly water-soluble and be difficult to crystallization.
The present invention is directed to the bottleneck of current soybean albumen adhesive exploitation and the present Research of sea-mussel mucin, the structure of shellfish protein is introduced in soybean protein, to strengthen adhesive effect and the water resistance of soybean albumen adhesive, overcome the shortcoming of soybean protein poor water resistance, poor mechanical property.In the basic conditions, with the sex change of urea inducing soybean protein molecular, launch soy-protein molecular structure, then mussel protein is introduced, by forming firm combination between the DOPA structure of mussel protein and soy-protein molecule, obtain a kind of mussel protein/soybean protein composite adhesive with high strength, high tenacity, strong water-repellancy and strong Adhering capacity.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of preparation method of conjugated protein sizing agent, the structure of mussel protein matter is introduced in soybean protein, obtain a kind ofly having that adhesive strength is high, the mussel protein/Hybrid Adhesive Based on Soy Protein of water-tolerant, preparation technology is simple simultaneously, cost is lower.
The present invention solves the problems of the technologies described above adopted technical scheme: a kind of preparation method of conjugated protein sizing agent, is characterized in that comprising the following steps:
1) preparation of mussel protein powder: take clean mussel meat, adds a small amount of 0.015 ~ 0.025molL
-1pBS buffered soln, smashs to pieces with tissue mashing machine; The PBS buffered soln adding 1.5 ~ 2.5 times of liquid-solid ratioes (v/w) slowly stirs 20 ~ 40min, extracts 20 ~ 28h, then centrifugal treating, get supernatant liquor at 3 ~ 5 DEG C; By the mussel crude extract extracted, under condition of ice bath, slowly add excessive (NH
4)
2sO
4fine particle, limit edged stirs, and treats (NH
4)
2sO
4fine particle dissolves completely, and after leaving standstill 20 ~ 28h, low-temperature and high-speed is centrifugal, obtains mussel (NH
4)
2sO
4protein precipitation, dissolves the PBS buffered soln of protein precipitation with 1.5 ~ 2.5 times of liquid-solid ratioes (v/w), at 3 ~ 5 DEG C, and PBS buffered soln dialysed overnight, lyophilize becomes powder, for subsequent use;
2) agent of alkalinuria complex denaturation is prepared: get a certain amount of water, add a certain amount of alkali, make the pH value of the aqueous solution be 9-10.5, then add a certain amount of urea, make the concentration of urea be that 2 ~ 3.5mol/L obtains the agent of alkalinuria complex denaturation;
3) in the agent of above-mentioned alkalinuria complex denaturation, add BIT, make the mass concentration of BIT be 0.09 ~ 0.11%;
4) by step 1) obtained mussel protein powder and soybean protein according to mussel protein powder account for 20 ~ 80% mass ratio (preferably 40 ~ 80%) mix after, join step 3) in the solution prepared, liquid-solid ratio is made to be 10 ~ 15mL/g, in stirred at ambient temperature 2 ~ 4 hours, make the full and uniform mixing of each component, reaction, obtained conjugated protein tackiness agent.
As improvement, described step 1) in centrifugal treating be secondary centrifuging, rotating speed is respectively 4000 ~ 6000rmin
-1, 13000 ~ 15000rmin
-1, the time is respectively 10 ~ 20min, 15 ~ 25min.
As preferably, described step 1) in low-temperature and high-speed centrifugal be 13000 ~ 15000rmin at 3 ~ 5 DEG C of rotating speeds
-1.
As preferably, described step 1) in mussel meat tissue mashing machine smash to pieces after add the PBS buffered soln of 2 times of liquid-solid ratioes (v/w), slowly stir 30min, extract 24h at 4 DEG C.
Preferred again, described step 1) middle mussel (NH
4)
2sO
4the protein precipitation PBS buffered soln of 2 times of liquid-solid ratioes (v/w) dissolves, at 4 DEG C, and PBS buffered soln dialysed overnight.
Preferred again, described step 2) in alkali be sodium hydroxide.
Finally, described step 3) in the mass concentration of BIT be 0.1%..Described step 4) in mussel protein powder and the soybean protein mass ratio that accounts for 60% according to mussel protein powder mix.
Described PBS buffered soln preferably selects 0.015 ~ 0.025molL
-1.
Compared with prior art, the invention has the advantages that: in the basic conditions, with the sex change of urea inducing soybean protein molecular, the structure of mussel protein matter is introduced in soybean protein, overcome soybean protein poor water resistance, poor mechanical property, and mussel byssus protein poorly water-soluble and be difficult to the shortcoming of crystallization.The present invention have simple to operate, raw material is easy to get, cost is lower, the simple feature of equipment requirements, it is high that obtained mussel protein/soybean protein composite adhesive has adhesive strength, and high tenacity, strong water-repellancy feature, be applicable to industrial production.
Accompanying drawing explanation
Fig. 1 is process flow sheet of the present invention;
Fig. 2 is that the wooden unit during adhesive strength measures glueds joint schematic diagram (draw direction when arrow represents that adhesive strength measures in figure);
Fig. 3 is that the urea of different concns is on the impact of SPI viscosity;
Fig. 4 is that the urea of different concns is on the impact of SPI adhesive strength;
Fig. 5 is the impact of different pH value on SPI viscosity;
Fig. 6 is the impact of different pH value on SPI adhesive strength;
Fig. 7 is the soybean protein of different ratios mixing and the adhesive strength change of mussel protein powder;
Fig. 8 is the soybean protein of different ratios mixing and the viscosity B coefficent of mussel protein powder;
Fig. 9 is the impact of different churning time on mussel-Hybrid Adhesive Based on Soy Protein viscosity;
Figure 10 is the impact of different churning time on mussel-Hybrid Adhesive Based on Soy Protein adhesive strength.
Embodiment
Below in conjunction with accompanying drawing embodiment, the present invention is described in further detail.
The preparation of mussel protein powder:
The clean scalpel of mussel picks meat, takes 200g, adds a small amount of 0.02molL
-1pBS (pH7.4) buffered soln (hereinafter referred to as PBS) is smashed to pieces with tissue mashing machine, to be applicable to drawing broken being limited; The PBS adding 2 times of liquid-solid ratioes (v/w) slowly stirs 30min, and 4 DEG C are extracted 24h.4 DEG C centrifugal twice, revolution is respectively 5000rmin
-1, 14000rmin
-1, the time is respectively 15min, and 20min gets supernatant liquor, is mussel crude extract, measurement volumes; Get mussel crude extract, under condition of ice bath, slowly add excessive (NH
4)
2sO
4fine particle, limit edged stirs.Treat (NH
4)
2sO
4fine particle dissolves completely, leaves standstill 24h, 14000rmin-1 low-temperature and high-speed centrifugal, obtains mussel (NH
4)
2sO
4protein precipitation.Precipitation is dissolved with the PBS of 2 times of liquid-solid ratioes (v/w), and 4 DEG C, PBS dialysed overnight, lyophilize becomes powder, is put in refrigerator for subsequent use.
Embodiment 1
Get 1000mL water, add a certain amount of sodium hydroxide, the pH value of the aqueous solution is made to be 10.5, add a certain amount of urea again, the concentration of urea is made to be 2mol/L, add 1,2-benzisothiazole-3-ketone (BIT), make the concentration of BIT be 0.1%, then by mussel protein powder and soybean protein according to 20/60 ratio (weight ratio) mix after, be added to the water, liquid-solid ratio is made to be 10mL/g, in stirred at ambient temperature 3 hours, obtain conjugated protein tackiness agent, adopting rotational viscosimeter method to record adhesive strength is 4.52MPa.
Embodiment 2
Get 1000mL water, add a certain amount of sodium hydroxide, make the pH value of the aqueous solution be 10, add a certain amount of urea again, the concentration making urea is 3.5mol/L, adds BIT, makes the concentration of BIT be 0.1%, again by mussel protein powder and soybean protein according to 15/55 ratio (weight ratio) mix after, be added to the water, make liquid-solid ratio be 12mL/g, in stirred at ambient temperature 4 hours, obtain conjugated protein tackiness agent, adopting rotational viscosimeter method to record adhesive strength is 5.31MPa.
Embodiment 3
Get 1000mL water, add a certain amount of sodium hydroxide, make the pH value of the aqueous solution be 9, add a certain amount of urea again, the concentration making urea is 3mol/L, adds BIT, makes the concentration of BIT be 0.1%, again by mussel protein powder and soybean protein according to 18/50 ratio (weight ratio) mix after, be added to the water, make liquid-solid ratio be 13mL/g, in stirred at ambient temperature 3.5 hours, obtain conjugated protein tackiness agent, adopting rotational viscosimeter method to record adhesive strength is 6.14MPa.
Embodiment 4
Get 1000mL water, add a certain amount of sodium hydroxide, make the pH value of the aqueous solution be 9.5, add a certain amount of urea again, the concentration making urea is 2.5mol/L, adds BIT, makes the concentration of BIT be 0.1%, again by mussel protein powder and soybean protein according to 20/55 ratio (weight ratio) mix after, be added to the water, make liquid-solid ratio be 15mL/g, in stirred at ambient temperature 4 hours, obtain conjugated protein tackiness agent, adopting rotational viscosimeter method to record adhesive strength is 3.75MPa.
Embodiment 5
Get 1000mL water, add a certain amount of sodium hydroxide, make the pH value of the aqueous solution be 9.5, add a certain amount of urea again, the concentration making urea is 2.5mol/L, adds BIT, makes the concentration of BIT be 0.1%, again by mussel protein powder and soybean protein according to 75/50 ratio (weight ratio) mix after, be added to the water, make liquid-solid ratio be 15mL/g, in stirred at ambient temperature 4 hours, obtain conjugated protein tackiness agent, adopting rotational viscosimeter method to record adhesive strength is 4.25MPa.
Embodiment 6
Get 1000mL water, add a certain amount of sodium hydroxide, make the pH value of the aqueous solution be 9.5, add a certain amount of urea again, the concentration making urea is 2.5mol/L, adds BIT, makes the concentration of BIT be 0.1%, again by mussel protein powder and soybean protein according to 200/50 ratio (weight ratio) mix after, be added to the water, make liquid-solid ratio be 16mL/g, in stirred at ambient temperature 4 hours, obtain conjugated protein tackiness agent, adopting rotational viscosimeter method to record adhesive strength is 5.15MPa.
Below in conjunction with experiment, the impact of various processing parameter on composite adhesive performance is illustrated:
One, experimentation
1, urea concentration is investigated
At room temperature prepare urea soln (1mol/L, 3mol/L, 5mol/L), the concentration of urea soln selects based on the research of forefathers, 5g soybean protein isolate is dispersed in 50mL urea soln, add sanitas, 0.1%BIT (V/m, m is sizing agent quality) stir 3 hours by constant temperature blender with magnetic force under room temperature, rotating speed is 1400r/min, makes it fully react.Arrange a blank group, be directly dispersed in 50mL water by 5g soybean protein isolate, stir 3 hours by constant temperature blender with magnetic force under adding 0.1%BIT room temperature, rotating speed is 1400r/min, makes it fully react.
2, pH is on the impact of sizing agent adhesive strength
When other conditions are constant, empirically 3.2.1 prepares best urea soln, and with 0.5mol/L sodium hydroxide solution, urea soln pH is adjusted to 8,9,10,11,12 respectively, is mixed with the agent of alkalinuria complex denaturation.In 5g soybean protein isolate, add the alkalinuria complex denaturation agent of 50mL, stir 3 hours by constant temperature blender with magnetic force under 0.1%BIT (V/m) room temperature, rotating speed is 1400r/min, makes it fully react.
3, the investigation of soybean protein and mussel protein powder ratio
Research object is mixed into respectively, with the top condition configuration alkalinuria complex denaturation agent in 1,2,3 tests with the soybean protein of mass ratio 9: 1,8: 2,6: 4,4: 6,2: 8 and mussel protein powder.In the egg mix white powder of the various ratios of 5g, add the alkalinuria complex denaturation agent of 50mL, stir 3 hours by constant temperature blender with magnetic force under 0.1%BIT (V/m) room temperature, rotating speed is 1400r/min, makes it fully react.
4, churning time is investigated
Keep other conditions constant, churning time is respectively 1h, 2h, 3h, 4h, 6h.
Two, test process
1, the preparation of plank sample
The cherry of buying from the market, deposits before using in silica gel drier.Surface-area is 20 × 50mm
2wood surface process with the sand paper of the three kinds of different sizes be connected on skin grinder, the power be added on sand paper is parallel with board surface, guarantees that wood surface different sites is stressed equal, makes same wood surface roughness everywhere homogeneous.Wherein plank roughness value 90,40,20 represents with 180,280 and 320 object sand paper process, reflects the roughness levels on wooden unit surface, and value is larger, and to represent wooden unit surface more coarse.
2, the mensuration of viscosity
Measure the SPI viscosity under the urea soln process of different concns (1,3,5mol/L), the mensuration of viscosity adopts NDJ-79 rotational viscosimeter method: by the soybean protein isolate viscosity after NDJ-79 rotary viscosity design determining soybean protein isolate and chemically modified.First estimate the range of viscosities of sample, select suitable rotor (making reading within the scope of the 20%-80% of scale card).Testing sample is poured into, simultaneously by the sample in container and rotor water bath with thermostatic control constant temperature to 25 DEG C, opens switch, after pointer is stablized, read the reading on scale card.
Final viscosity=dial reading × rotor coefficient.
3, the mensuration of adhesive strength
(1) according to prepare shown in Fig. 2 bonding after wooden unit sample.The size of every block plank is 3 × 20 × 50mm (high, wide and long), and every three pieces of planks glued joint into a wooden unit sample.
Dripped to by the soybean albumen adhesive of preparation on the splicing face of middle wooden unit, being that 20 × 20mm is upper at surface covered respectively with other two pieces of wooden units sprawls soybean albumen adhesive until surface is completely wetted.After the wooden unit being coated with glue is at room temperature placed 10min, to be taken as shown in Figure 2 by the wooden unit being coated with glue with hand and stick together, be placed on hot pressing 10min on 0.5 type vulcanizing press, temperature is 120 DEG C, pressure is 1MPa, is placed on ambient temperatare in polyethylene bags and puts 4d after cooling.
(2) by the adhesive strength of the omnipotent measuring wood sample of WDT-10 type microcomputer controlled electronic, draw speed is 10mm/min.Sample maximum pull used (N) broken in record, and the data of each sample are the average value measured of 6 Duplicate Samples.The following formulae discovery of adhesive strength draws:
Three, experimental result
1, different urea concentration denatured soy sizing agent viscosity performance measures
As seen from Figure 3, soybean protein isolate (SPI) is after different concns urea is modified, and protein water soln viscosity first raises rear decline: when urea concentration is less than 3mol/L, and along with the increase of urea concentration, viscosity is also increasing; When urea concentration is greater than 3mol/L, along with the increase of urea concentration, viscosity is more and more less on the contrary.When urea concentration is 3mol/L, soybean albumen adhesive viscosity is maximum.
Experimental result illustrates, urea adds makes the space structure part of protein molecule change.Because urea can interact with the hydroxyl of soybean protein, destroy the hydrogen bond in protein, thus destroy Secondary structure.Urea is polar molecule, when a small amount of urea adds in protein solution, urea molecule can form intermolecular hydrogen bonding rapidly with water molecules, protein molecule surrounding environment polarity is changed, the hydrophobic group affected between protein molecule interacts, and protein molecule launches, and more non-polar group exposes, show as beta sheet content to reduce, random coil content increases.Namely the interpolation of urea makes soybean protein beta sheet structure division be converted into random coil and β-corner.The exposure of hydrophobic grouping makes and reactive force between substrate strengthens, and more electronegative group is available in alkaline environment simultaneously plays a role.Electrostatic interaction between charged group increases, the Interaction enhanced therefore between protein molecule, and the viscosity showing as SPI soup compound increases.When urea concentration reaches 5mol/L, soltion viscosity is lower than blank sample, and this may be that the space structure of albumen is almost entirely destroyed because the urea of high density causes the excessive sex change of SPI.
As shown in Figure 4, when urea concentration is 1mol/L and 3mol/L denatured soy protein isolate, the bonding strength of soybean protein isolate increases, and urea concentration is maximum in 1mol/L adhesive strength, but when but the bonding strength that urea concentration is greater than 1mol/L soybean protein isolate progressively reduce, when urea concentration is 5mol/L, adhesive strength is even lower than before protein denaturation.The factor affecting protein adhesive strength is a lot, analysis reason is mainly: 1, consider that soybean isolated protein sticks the viscosity influence of agent: when protein sizing agent is coated on wood surface, if when urea concentration is less than 1mol/L, then sizing agent viscosity is too low, sizing agent is easy to penetrate into wood internal, and producing sagging phenomenon, rate of drying is too fast, and plybonding effect is deteriorated; When urea concentration is greater than 3mol/L, sizing agent viscosity is too high, is not easy again to penetrate into wood internal, can only produce adhesive action at wood surface.So just urea concentration is when 1mol/L-3mol/L, denatured soy protein isolate just shows the glueability being better than non-denatured soy protein isolate.So the sizing agent adhesive strength that the urea distortion soy-protein that concentration is 1mol/L obtains is best.
2, urea concentration denatured soybean protein sizing agent performance measurement under different pH
As shown in Figure 5, under alkaline environment, the viscosity of glue mucus is relative to urea-denatured and very large lifting.When pH is at 8-9, viscosity B coefficent is little, and be stabilized in 4000mPa/s, when pH is raised to about 10.5 from 9, glue mucus viscosity sharply increases.When pH continues to increase afterwards, glue mucus viscosity reduces thereupon on the contrary.Under alkaline condition, protein structure becomes loose, and asymmetry strengthens, and the resistance of motion increases, under also having alkaline condition, protein peptide chain is opened, and all kinds of polar group exposes and interacts, protein molecule is cross-linked with each other, so protein adhesive mucus is just single by time urea-denatured, viscosity increase is very large.But when alkalescence is too strong, protein molecule can be made too to be hydrolyzed, and macromole peptide content sharply reduces, and molecular weight reduces, and macro manifestations is the sharply reduction of viscosity.
As seen from Figure 6, as pH < 9.5, the adhesive strength of soybean adhesive, its almost changes along with ph increases.Along with the further increase of pH, adhesive strength obviously increases, and works as pH=11, and adhesive strength reaches maximum value.As pH > 11, adhesive strength reduces fast.Protein molecule polypeptide chain is in the basic conditions opened, the degree of disorder of protein molecule is increased, protein subunit and the inner hydrophobic grouping surrounded thereof are exposed, this makes the contact surface area of protein molecule and timber increase, and macroscopically shows as sizing agent and increases the cementing ability of wood surface.But when solution alkaline strengthens further, protein peptide chain launches further, and the polar group on peptide chain is cross-linked with each other, and whole colloidal dispersion viscosity strengthens, and adhesive strength declines.If alkalescence is too strong, the peptide chain of protein molecule can be made excessively to be hydrolyzed, and adhesive strength sharply declines.
3, different ratios mussel-soybean composite adhesive performance measurement performance measurement
On the whole in the basic conditions, by mussel protein matter and soybean protein compound, the plybonding effect of soybean albumen adhesive all can be strengthened to a great extent.As Fig. 7,8 shows, when mussel accounts for mixed protein ratio lower than 60%, adhesive strength and the viscosity of mixing sizing agent increase to increase along with mussel accounting, reach maximum value when mussel content is 60%.When mussel content is more than 60%, mixing sizing agent adhesive strength and viscosity but decline gradually.Because the bonding of mussel mainly relies on the multiple attachment proteins in body, and in these attachment proteinses, the amino acid of hydroxyl accounts for up to 60% ~ 70%, DOPA (DOPA, L-DOPA) has good water tolerance and bonding force.Alkaline condition can open protein peptide chain, and the polar group of protein molecule is exposed.The urea of lower concentration fast and can bear water molecule and form hydrogen bond, and protein molecule forms competition.And urea molecule, because having Sauerstoffatom and hydrogen atom, with the hydroxyl effect in protein molecule, thus can destroy the hydrogen bond in protein molecule, make its space structure disintegrate, make protein sulfhydryl (SH) expose.Now mussel protein molecule can combine with soy-protein molecule effectively, crosslinked.The combination of the soybean protein that this process is mainly dissociated and DOPA (DOPA, L-DOPA).
But when adding mussel protein and being too much because its attachment proteins content is limited, the effective sizing agent total amount formed is declined, so stickiness declines to some extent.
4, the mussel-soybean composite adhesive performance measurement of different churning time
Can find out from 9 figure, along with the prolongation of churning time, viscosity first increases rear reduction.Be 3 hours upon agitation, reach and be 15.6pa.s to the maximum.During beginning, stir and protein molecule is unfolded, the degree of disorder increases, and molecular motion resistance strengthens, and stirs simultaneously and also increases molecule crosslinked probability, so viscosity increases in time and increases when starting; But cross long mechanical stirring also can destroy protein molecular structure be destroyed, macromole peptide chain has not existed, molecular weight reduce, molecule crosslinked reduction, so show as viscosity degradation.
As shown in Figure 10, the change of adhesive strength is identical with its viscosity B coefficent trend.From 1 ~ 3 hour upon agitation, adhesive strength strengthens thereupon; Churning time > after 3 hours adhesive strength prolongation in time constantly reduce.Possible cause is, the treatment time long viscosity that causes diminishes on the one hand, is easily penetrate into wood internal when sizing agent is coated on wood surface, and wood surface glue-line is too thin, very little, dry too fast, adhesive property is not good; Reaction times is 3 constantly little, and sizing agent mobility is just in time suitable, so show good viscosifying power.For the urea highly volatile of denatured protein, churning time along with prolongation, too much, deformation effect is deteriorated, and sizing agent adhesive strength declines on the contrary in volatilization.
Claims (7)
1. a preparation method for conjugated protein sizing agent, is characterized in that comprising the following steps:
1) preparation of mussel protein powder: take clean mussel meat, adds a small amount of 0.015 ~ 0.025molL
-1pBS buffered soln, smashs to pieces with tissue mashing machine; The PBS buffered soln adding 1.5 ~ 2.5 times of liquid-solid ratioes (v/w) slowly stirs 20 ~ 40min, extracts 20 ~ 28h, then centrifugal treating, get supernatant liquor at 3 ~ 5 DEG C; By the mussel crude extract extracted, under condition of ice bath, slowly add excessive (NH
4)
2sO
4fine particle, limit edged stirs, and treats (NH
4)
2sO
4fine particle dissolves completely, and after leaving standstill 20 ~ 28h, low-temperature and high-speed is centrifugal, obtains mussel (NH
4)
2sO
4protein precipitation, dissolves the PBS buffered soln of protein precipitation with 1.5 ~ 2.5 times of liquid-solid ratioes (v/w), at 3 ~ 5 DEG C, and PBS buffered soln dialysed overnight, lyophilize becomes powder, for subsequent use;
2) agent of alkalinuria complex denaturation is prepared: get a certain amount of water, add a certain amount of alkali, make the pH value of the aqueous solution be 9-10.5, then add a certain amount of urea, make the concentration of urea be that 2 ~ 3.5mol/L obtains the agent of alkalinuria complex denaturation;
3) in the agent of alkalinuria complex denaturation, add BIT, make the mass concentration of BIT be 0.09 ~ 0.11%;
4) by step 1) after obtained mussel protein powder and soybean protein mix according to the mass ratio that mussel protein powder accounts for 60%, join step 3) in the solution prepared, liquid-solid ratio is made to be 10 ~ 15mL/g, in stirred at ambient temperature 2 ~ 4 hours, make the full and uniform mixing of each component, reaction, obtained conjugated protein tackiness agent.
2. preparation method according to claim 1, is characterized in that described step 1) in centrifugal treating be secondary centrifuging, rotating speed is respectively 4000 ~ 6000rmin
-1, 13000 ~ 15000rmin
-1, the time is respectively 10 ~ 20min, 15 ~ 25min.
3. preparation method according to claim 1, is characterized in that described step 1) in low-temperature and high-speed centrifugal be 13000 ~ 15000rmin at 3 ~ 5 DEG C of rotating speeds
-1.
4. preparation method according to claim 1, is characterized in that described step 1) in mussel meat tissue mashing machine smash to pieces after add the PBS buffered soln of 2 times of liquid-solid ratioes (v/w), slowly stir 30min, extract 24h at 4 DEG C.
5. preparation method according to claim 1, is characterized in that described step 1) middle mussel (NH
4)
2sO
4the protein precipitation PBS buffered soln of 2 times of liquid-solid ratioes (v/w) dissolves, at 4 DEG C, and PBS buffered soln dialysed overnight.
6. preparation method according to claim 1, is characterized in that described step 2) in alkali be sodium hydroxide.
7. preparation method according to claim 1, is characterized in that described step 3) in the mass concentration of BIT be 0.1%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110262489.6A CN102965070B (en) | 2011-08-31 | 2011-08-31 | The preparation method of conjugated protein sizing agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110262489.6A CN102965070B (en) | 2011-08-31 | 2011-08-31 | The preparation method of conjugated protein sizing agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102965070A CN102965070A (en) | 2013-03-13 |
| CN102965070B true CN102965070B (en) | 2015-12-02 |
Family
ID=47795507
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110262489.6A Expired - Fee Related CN102965070B (en) | 2011-08-31 | 2011-08-31 | The preparation method of conjugated protein sizing agent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102965070B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103520766A (en) * | 2013-09-25 | 2014-01-22 | 高敏 | Mussel mucoprotein liquid product as well as preparation method and application thereof |
| CN104594120A (en) * | 2014-12-13 | 2015-05-06 | 济南舜景医药科技有限公司 | Book protective agent and preparation method thereof |
| CN105885771A (en) * | 2015-12-16 | 2016-08-24 | 浙江海洋学院 | Preparation method of compound protein adhesive |
| CN105969203A (en) * | 2016-05-26 | 2016-09-28 | 安徽金兑新材料科技有限公司 | Method for preparing skin glue based on animal skin |
| CN106433557A (en) * | 2016-11-02 | 2017-02-22 | 常州市鼎日环保科技有限公司 | Preparation method of composite wood adhesive |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1307872A (en) * | 2000-12-20 | 2001-08-15 | 青岛海洋大学 | Selenium product of natural marine organism and its preparation |
-
2011
- 2011-08-31 CN CN201110262489.6A patent/CN102965070B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1307872A (en) * | 2000-12-20 | 2001-08-15 | 青岛海洋大学 | Selenium product of natural marine organism and its preparation |
Non-Patent Citations (3)
| Title |
|---|
| Chemical modification of soy protein for wood adhesive;Yuan Liu等;《Macromolecular Rapid Communications》;wiley online library;20021004;第23卷(第13期);第740第3-6段、第740页表1 * |
| 大豆蛋白胶粘剂的化学改性研究进展;梁向晖等;《中国胶粘剂》;20070331;第16卷(第3期);第37-40页 * |
| 尿素变性对大豆分离蛋白粘接强度和分子结构的影响;张忠慧等;《中国胶粘剂》;20071231;第16卷(第12期);第14页第3段、第15页第1.2.2节 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102965070A (en) | 2013-03-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102965070B (en) | The preparation method of conjugated protein sizing agent | |
| CN104497965B (en) | The preparation method of waterproof level soy protein adhesives | |
| Zhao et al. | Changes in physico-chemical properties, microstructures, molecular forces and gastric digestive properties of preserved egg white during pickling with the regulation of different metal compounds | |
| CN107312084B (en) | A kind of collagen extraction process based on little yellow croaker fish scale | |
| JP2003514919A (en) | collagen | |
| CN107090271A (en) | A kind of soy protein adhesives and preparation method thereof | |
| CN108029847A (en) | A kind of soybean protein isolate based on salt ion-carragheen mixed gel and preparation method thereof | |
| Bangar et al. | Ultrasound‐assisted modification of gelation properties of proteins: A review | |
| Bi et al. | Effect of low-frequency high-intensity ultrasound (HIU) on the physicochemical properties of chickpea protein | |
| Shaik et al. | Functional properties of sharpnose stingray (Dasyatis zugei) skin collagen by ultrasonication extraction as influenced by organic and inorganic acids | |
| Zhang et al. | Effect of sodium bisulfite on properties of soybean glycinin | |
| CN110272715A (en) | High temperature peanut meal base Formaldehyde-free adhesive and the preparation method and application thereof | |
| CN107641495A (en) | A kind of vegetable protein adhesive and its preparation method and application | |
| CN107903638A (en) | A kind of soybean protein isolate/chitosan quaternary ammonium salt composite membrane and preparation method and application | |
| CN104177493A (en) | Method for rapidly preparing regenerated collagen with dicationic ionic liquid as solvent | |
| CN104073219B (en) | A kind of aldehyde-free cement for wood-based panel and preparation method thereof | |
| Luo et al. | The role of starch granule-associated proteins in enhancing the strength of indica rice starch gels | |
| KR101424209B1 (en) | Natural adhesives comprising lacquer, and isinglass or animal glue and the method thereof | |
| Ding et al. | Super‐absorbent resin preparation utilizing spent mushroom substrates | |
| CN108902438A (en) | Gadus peptide and its enzymatic extraction method | |
| Zhang et al. | Modified soy protein isolate with improved gelling stability by glycosylation under the conditions of ocean shipping | |
| CN109540994A (en) | A kind of high-sensitivity detecting method of ox-hide historical relic | |
| CN105885771A (en) | Preparation method of compound protein adhesive | |
| Chen et al. | Rheological properties of chitosan and its interaction with porcine myofibrillar proteins as influenced by chitosan's degree of deacetylation and concentration | |
| CN108822793A (en) | A kind of preparation method of the soybean protein base without aldehyde adhesive |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20151202 Termination date: 20170831 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |