CN111978917A - Preparation method of rapeseed protein adhesive based on ultrahigh pressure and EGDE composite modification - Google Patents
Preparation method of rapeseed protein adhesive based on ultrahigh pressure and EGDE composite modification Download PDFInfo
- Publication number
- CN111978917A CN111978917A CN202010692114.2A CN202010692114A CN111978917A CN 111978917 A CN111978917 A CN 111978917A CN 202010692114 A CN202010692114 A CN 202010692114A CN 111978917 A CN111978917 A CN 111978917A
- Authority
- CN
- China
- Prior art keywords
- preparation
- egde
- ultrahigh pressure
- rapeseed protein
- rapeseed
- 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
Images
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
- C07—ORGANIC CHEMISTRY
- C07K—PEPTIDES
- C07K1/00—General methods for the preparation of peptides, i.e. processes for the organic chemical preparation of peptides or proteins of any length
- C07K1/14—Extraction; Separation; Purification
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H1/00—Macromolecular products derived from proteins
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Medicinal Chemistry (AREA)
- Biochemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- Biophysics (AREA)
- General Health & Medical Sciences (AREA)
- Genetics & Genomics (AREA)
- Molecular Biology (AREA)
- Proteomics, Peptides & Aminoacids (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses a preparation method of an EGDE composite modified rapeseed protein adhesive based on an ultrahigh pressure technology. Firstly, rapeseed protein is extracted from rape seed meal, then the extracted protein is uniformly dispersed in water, then the dispersed protein solution is subjected to ultrahigh pressure treatment, then EGDE is added into the treated protein solution according to a proportion, and finally NaOH is used for adjusting the pH value, so that the rapeseed protein adhesive with no aldehyde and excellent water resistance is finally prepared. The rapeseed protein adhesive synthesized by ultrahigh pressure and EGDE modification shows excellent adhesive property and water resistance, improves cohesive interaction and forms a compact cross-linked network. The adhesive prepared by the invention has better wettability and lower viscosity, and the dry and wet bonding strength of the adhesive is obviously improved.
Description
Technical Field
The invention discloses a preparation method of a rapeseed protein adhesive with high bonding strength and excellent water resistance based on ultrahigh pressure technology and Ethylene Glycol Diglycidyl Ether (EGDE) composite crosslinking modification, and belongs to the technical field of high polymer materials.
Background
In the area of wood manufacturing, the global wood adhesive market is steadily increasing, and is projected to reach $ 61.8 billion by 2025. Traditional wood adhesives such as Phenol Formaldehyde (PF), Urea Formaldehyde (UF), Melamine Formaldehyde (MF) are mainly derived from non-renewable resources such as petroleum, and harmful substances such as formaldehyde are released during use. Due to the continued consumption of fossil fuels such as petroleum, as well as the potential environmental hazard and health problems of formaldehyde in traditional synthetic binders, renewable feedstocks and green formaldehyde-free bioprotein-based binders are considered as effective substitutes for formaldehyde.
Rapeseed protein has a structure similar to that of other plant proteins, has a spatial structure specific to protein, and is limited by low adhesive strength and poor water resistance. Therefore, a modification treatment of the protein is required. The exposure degree of hydrophobic groups in the protein is increased, and simultaneously, the peptide chain tightly wound by the protein becomes loose, so that more active groups and active sites are exposed and redistributed, and finally, the gluing strength and the water resistance of the adhesive are effectively changed.
The conventional modification method is chemical modification, but the chemical modification mode with a good effect still has a part of formaldehyde-containing modifier, and the problem of formaldehyde slow release in the adhesive bonding process cannot be fundamentally solved. But also still faces the technical problem of poor water resistance.
Disclosure of Invention
The invention overcomes the defects of the prior art, provides a biomass-based formaldehyde-free rapeseed protein adhesive with excellent water resistance by means of composite modification through a physical modification and chemical crosslinking method aiming at the problems of poor water resistance of the adhesive caused by more hydrophilic groups on the surface of rapeseed protein, formaldehyde release in the bonding process of the traditional adhesive and the like, and the bonding strength of the biomass-based formaldehyde-free rapeseed protein adhesive meets the standard of II-type plywood in GB/T9846.3-2004.
The technical scheme adopted by the invention for solving the technical problems is as follows: a preparation method of a rapeseed protein adhesive comprises the following steps:
(1) taking 15-25 parts of rape meal powder according to the weight part ratio of 1: adding n-hexane at a ratio of 8-1:10, stirring for 1-1.5h, circulating for 4-5 times, standing for precipitation, and drying in a fume hood overnight;
(2) screening the air-dried rapeseed meal powder by using a 80-100 mesh inspection sieve, weighing the screened rapeseed meal powder according to the weight ratio of 1: 7-1: 10, adding deionized water, uniformly stirring, adjusting the pH value to 11-13 by using NaOH solution, continuously stirring, centrifuging, taking supernatant, adjusting the pH value to 3-5 by using HCl, centrifuging, taking precipitate, freeze-drying, and storing in a refrigerator at the temperature of-20 ℃.
(3) Taking 1.5-3 parts by weight of protein powder, adding 10-20 parts by weight of deionized water, and stirring at normal temperature until the protein powder is uniformly dispersed;
(4) filling the pretreated rapeseed protein mixture into a soft sealing bag, and performing vacuum heat sealing;
(5) processing the rapeseed protein mixture packed in vacuum in an ultrahigh pressure device under the pressure of 200-600MPa by taking liquid as a pressure transmission medium, wherein the processing time is 10-20min, and the processing temperature is 25-30 ℃;
(6) mixing and transferring the rapeseed protein after the ultrahigh pressure treatment to a beaker, weighing 8-15% of Ethylene Glycol Diglycidyl Ether (EGDE) and adding the mixture to the protein solution, and uniformly stirring.
(7) And regulating the pH value to 9-11 by using a NaOH solution, and stirring for 1.5-4h to obtain the rapeseed protein adhesive.
Preferably, the rapeseed meal powder in the step (1) is residue obtained after commercial rape oil extraction.
Preferably, in the step (2), the stirring speed is 500-700 r/min.
Preferably, in the step (2), the rotating speed of the centrifugal machine is 8000-10000r/min, and the centrifugal time is 7-10 min.
Preferably, the concentration of the NaOH solution in the step (2) is 3-5 mol/L.
Preferably, the stirring time of step (3) is 2-4 h.
Preferably, the soft packing material in the step (4) is a No. 6 polyethylene plastic bag; the vacuum heat sealing time is 15-40s, the heat sealing time is 2-4s, and the heat sealing temperature is 70-100 ℃.
Preferably, the liquid in step (5) is water.
Preferably, the stirring time in step (6) is 2-4 h.
Preferably, the concentration of the NaOH solution in the step (7) is 4-6 mol/L.
According to the invention, rapeseed protein which has biological resistance and does not compete for human food use is selected, and ultrahigh pressure modification and crosslinking modification (EGDE) in physical modification are organically combined, so that the modification effect of 1+1 & gt 2 is achieved, and the effect of no aldehyde release in the use process of the adhesive is realized.
The rapeseed protein extracted from rapeseed meal is used as a main raw material, and the protein is subjected to composite modification by an ultrahigh pressure technology and ethylene glycol diglycidyl ether so as to improve the water resistance and the bonding strength of the synthesized adhesive.
Drawings
The invention is further illustrated by the following figures and examples.
FIG. 1 shows the dry bond strength of adhesives processed at different pressure ranges. Wherein the columns are comparative example 1 and examples 1-3, respectively, from left to right.
FIG. 2 is a graph of the wet bond strength of the adhesive under different pressure range treatments. Wherein the columns are comparative example 1 and examples 1-3, respectively, from left to right.
Fig. 3 shows the thermogravimetric changes of the adhesive samples treated at different pressure ranges.
Fig. 4 is a graph of DTG change for adhesive samples treated at different pressure ranges.
Detailed Description
Firstly, rapeseed protein is prepared by the following specific method:
taking 20 parts of rape seed meal powder according to the weight part, and mixing the raw materials in a ratio of 1: adding n-hexane according to the proportion of 9, stirring for 1.5h, circulating for 5 times, standing for precipitation, and then placing in a fume hood for overnight drying;
(2) screening the air-dried rapeseed meal powder through a 100-mesh inspection sieve, weighing the screened rapeseed meal powder according to the weight-volume ratio of 1: adding deionized water according to the proportion of 8, stirring uniformly, adjusting the pH value to 12 by using NaOH solution, continuously stirring, centrifuging, taking supernatant, adjusting the pH value to 4 by using HCl, centrifuging, taking precipitate, freeze-drying, and storing in a refrigerator at the temperature of-20 ℃.
Comparative example 1
Taking 1.5g rapeseed protein, adding 20mL of ultrapure water, stirring at room temperature for about 2h at the speed of 500r/min to fully disperse the protein in the water, then transferring the pretreated rapeseed protein mixture into a 6# polyethylene plastic bag, marking a sample as 1, and carrying out heat sealing on the sample by using a vacuum heat sealing machine, wherein the vacuumizing time is 25s, the heat sealing time is 2s, and the heat sealing temperature is 60 ℃. And (3) processing the processed sample at normal temperature and normal pressure for 15min, transferring the processed sample to a 25mL beaker, attaching a corresponding label, adding 0.1g of Ethylene Glycol Diglycidyl Ether (EGDE) into the protein mixture, stirring for 1.5h, and then adjusting the pH to 9 by using 6mol/L NaOH to obtain the rapeseed protein adhesive.
Comparative example 2
1.5g rapeseed protein is taken, 20mL of ultrapure water is added, the mixture is stirred for about 2 hours at the speed of 500r/min at room temperature to ensure that the protein is fully dispersed in the water, then the pretreated rapeseed protein mixture is transferred into a 6# polyethylene plastic bag, the sample is marked as 2, the sample is subjected to heat sealing by a vacuum heat sealing machine, the vacuumizing time is 25s, the heat sealing time is 2s, and the heat sealing temperature is 60 ℃. And (3) processing the processed sample at 200MPa for 15min, transferring the processed sample to a 25mL beaker, attaching a corresponding label, and then adjusting the pH to 9 by using 6mol/L NaOH, wherein the rapeseed protein has poor gelling effect and serious gelling.
Example 1
1.5g rapeseed protein is taken, 20mL of ultrapure water is added, the mixture is stirred for about 2 hours at the speed of 500r/min at room temperature to ensure that the protein is fully dispersed in the water, then the pretreated rapeseed protein mixture is transferred into a 6# polyethylene plastic bag, the sample is marked as 3, the sample is subjected to heat sealing by a vacuum heat sealing machine, the vacuumizing time is 25s, the heat sealing time is 2s, and the heat sealing temperature is 60 ℃. The treated sample is treated at 200MPa for 15min and then transferred to a 25mL beaker, labeled with the corresponding label, 0.1g Ethylene Glycol Diglycidyl Ether (EGDE) is added to the protein mixture and stirred for 1.5h, and then the pH is adjusted to 9 with 6mol/L NaOH to obtain the rapeseed protein adhesive.
Example 2
1.5g rapeseed protein is taken, 20mL of ultrapure water is added, the mixture is stirred for about 2 hours at the speed of 500r/min at room temperature to ensure that the protein is fully dispersed in the water, then the pretreated rapeseed protein mixture is transferred into a 6# polyethylene plastic bag, the sample is marked as 4, the sample is subjected to heat sealing by a vacuum heat sealing machine, the vacuumizing time is 25s, the heat sealing time is 2s, and the heat sealing temperature is 60 ℃. The treated sample is treated at 400MPa for 15min and then transferred to a 25mL beaker, labeled with the corresponding label, 0.1g Ethylene Glycol Diglycidyl Ether (EGDE) is added to the protein mixture and stirred for 1.5h, and then the pH is adjusted to 9 with 6mol/L NaOH to obtain the rapeseed protein adhesive.
Example 3
1.5g rapeseed protein is taken, 20mL of ultrapure water is added, the mixture is stirred for about 2 hours at the speed of 500r/min at room temperature to ensure that the protein is fully dispersed in the water, then the pretreated rapeseed protein mixture is transferred into a 6# polyethylene plastic bag, the sample is marked as 5, the sample is subjected to heat sealing by a vacuum heat sealing machine, the vacuumizing time is 25s, the heat sealing time is 2s, and the heat sealing temperature is 60 ℃. The treated sample is treated at 600MPa for 15min and then transferred to a 25mL beaker, labeled with the corresponding label, 0.1g Ethylene Glycol Diglycidyl Ether (EGDE) is added to the protein mixture and stirred for 1.5h, and then the pH is adjusted to 9 with 6mol/L NaOH to obtain the rapeseed protein adhesive.
The rapeseed protein adhesives obtained in the comparative example 1 and the examples 1-3 are subjected to tensile strength test, and the specific test method is as follows:
the wood used for the experiment is beech veneer with the dimension specification of 50mm multiplied by 20mm multiplied by 2 mm. Sizing in a sizing mode, wherein the sizing area is as follows: 20mm multiplied by 20mm, single-side gluing amount of 80g/m2, placing the glued wood board for 30min at room temperature of 25 ℃ and humidity of 50 percent after coating, and then hot-pressing the glued wood board, wherein the hot-pressing temperature is 140 ℃, the hot-pressing pressure is 2MPa, and the hot-pressing time is 10 min. And (3) placing the hot-pressed wood boards at room temperature for 24h, dividing the hot-pressed wood boards into two groups, wherein one group is used for testing dry bonding strength, the other group is placed in a water bath condition at 63 ℃ for soaking for 3h, and the wood boards are taken out and then subjected to wet bonding strength testing. Both groups of boards were tested according to the regulations in the national standard GB/T9846.3-2004. Each adhesive coated sample paralleled 8 groups of wood chips.
FIG. 1 shows a comparison of the bonding strength to rapeseed protein adhesives under different pressure ranges. As can be seen from FIG. 1, the dry adhesive strength after the ultra-high pressure treatment is significantly improved, but the strength change is less significant in the high pressure group.
Fig. 2 shows a comparison of wet bond strength with EGDE addition at different pressure ranges. As can be seen from fig. 2, the synthesized adhesive shows the best water resistance performance at about 400MPa compared with the adhesives synthesized under other pressures.
Fig. 3 and 4 show thermogravimetric comparison of the tacky samples at different pressure ranges. From FIG. 3, it can be seen that the thermal degradation temperature starts to shift to the right with the increase of the pressure, and when the pressure reaches 600MPa, the aggregation phenomenon of protein macromolecules occurs due to the excessive pressure, and the stability is reduced.
Claims (10)
1. A preparation method of rapeseed protein adhesive based on ultrahigh pressure and EGDE composite modification comprises the following steps:
(1) taking 15-25 parts of rape meal powder according to the weight part ratio of 1: adding n-hexane at a ratio of 8-1:10, stirring for 1-1.5h, circulating for 4-5 times, standing for precipitation, and drying in a fume hood overnight;
(2) screening the air-dried rapeseed meal powder by using a 80-100 mesh inspection sieve, weighing the screened rapeseed meal powder according to the weight ratio of 1: 7-1: 10, adding deionized water, uniformly stirring, adjusting the pH value to 11-13 by using NaOH solution, continuously stirring, centrifuging, taking supernatant, adjusting the pH value to 3-5 by using HCl, centrifuging, taking precipitate, freeze-drying, and storing in a refrigerator at the temperature of-20 ℃.
(3) Taking 1.5-3 parts by weight of protein powder, adding 10-20 parts by weight of deionized water, and stirring at normal temperature until the protein powder is uniformly dispersed;
(4) filling the pretreated rapeseed protein mixture into a soft sealing bag, and performing vacuum heat sealing;
(5) processing the rapeseed protein mixture packed in vacuum in an ultrahigh pressure device under the pressure of 200-600MPa by taking liquid as a pressure transmission medium, wherein the processing time is 10-20min, and the processing temperature is 25-30 ℃;
(6) mixing and transferring the rapeseed protein after the ultrahigh pressure treatment to a beaker, weighing 8-15% of ethylene glycol diglycidyl ether, adding the mixture to a protein solution, and uniformly stirring;
(7) and regulating the pH value to 9-11 by using a NaOH solution, and stirring for 1.5-4h to obtain the rapeseed protein adhesive.
2. The preparation method of the rapeseed protein adhesive based on ultrahigh pressure and EGDE composite modification of claim 1, wherein the preparation method comprises the following steps: the rapeseed meal powder in the step (1) is residue obtained after oil extraction of commercially available rape.
3. The preparation method of the rapeseed protein adhesive based on ultrahigh pressure and EGDE composite modification of claim 1, wherein the preparation method comprises the following steps: the stirring speed in the step (2) is 500-700 r/min.
4. The preparation method of the rapeseed protein adhesive based on ultrahigh pressure and EGDE composite modification of claim 1, wherein the preparation method comprises the following steps: the rotating speed of the centrifugal machine in the step (2) is 8000-.
5. The preparation method of the rapeseed protein adhesive based on ultrahigh pressure and EGDE composite modification of claim 1, wherein the preparation method comprises the following steps: and (3) the concentration of the NaOH solution in the step (2) is 3-5 mol/L.
6. The preparation method of the rapeseed protein adhesive based on ultrahigh pressure and EGDE composite modification of claim 1, wherein the preparation method comprises the following steps: and (4) stirring for 2-4 h.
7. The preparation method of the rapeseed protein adhesive based on ultrahigh pressure and EGDE composite modification of claim 1, wherein the preparation method comprises the following steps: in the step (4), the soft packing material is a 6# polyethylene plastic bag; the vacuum heat sealing time is 15-40s, the heat sealing time is 2-4s, and the heat sealing temperature is 70-100 ℃.
8. The preparation method of the rapeseed protein adhesive based on ultrahigh pressure and EGDE composite modification of claim 1, wherein the preparation method comprises the following steps: in the step (5), the liquid is water.
9. The preparation method of the rapeseed protein adhesive based on ultrahigh pressure and EGDE composite modification of claim 1, wherein the preparation method comprises the following steps: the stirring time in the step (6) is 2-4 h.
10. The preparation method of the rapeseed protein adhesive based on ultrahigh pressure and EGDE composite modification of claim 1, wherein the preparation method comprises the following steps: and (7) the concentration of the NaOH solution is 4-6 mol/L.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010692114.2A CN111978917B (en) | 2020-07-17 | 2020-07-17 | Preparation method of rapeseed protein adhesive based on ultrahigh pressure and EGDE composite modification |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010692114.2A CN111978917B (en) | 2020-07-17 | 2020-07-17 | Preparation method of rapeseed protein adhesive based on ultrahigh pressure and EGDE composite modification |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111978917A true CN111978917A (en) | 2020-11-24 |
| CN111978917B CN111978917B (en) | 2021-08-24 |
Family
ID=73437897
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010692114.2A Active CN111978917B (en) | 2020-07-17 | 2020-07-17 | Preparation method of rapeseed protein adhesive based on ultrahigh pressure and EGDE composite modification |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111978917B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110205090A (en) * | 2019-06-17 | 2019-09-06 | 厦门大学 | A kind of preparation method of the biology base soy protein adhesives based on modified by ultra high pressure |
| CN110205089A (en) * | 2019-05-05 | 2019-09-06 | 湖南省林业科学院 | A kind of organic inorganic hybridization soybean base adhesive and the preparation method and application thereof |
| KR20190130714A (en) * | 2018-05-15 | 2019-11-25 | 농업회사법인 에스에스바이오팜 주식회사 | Extraction method of silk peptide by enzymatic hydrolysis under ultra high pressure |
| CN110746927A (en) * | 2019-10-28 | 2020-02-04 | 厦门大学 | Preparation method of rapeseed protein adhesive based on ultrahigh-pressure composite modification |
| CN111040728A (en) * | 2019-12-09 | 2020-04-21 | 华南农业大学 | Yeast protein adhesive and preparation method and application thereof |
-
2020
- 2020-07-17 CN CN202010692114.2A patent/CN111978917B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20190130714A (en) * | 2018-05-15 | 2019-11-25 | 농업회사법인 에스에스바이오팜 주식회사 | Extraction method of silk peptide by enzymatic hydrolysis under ultra high pressure |
| CN110205089A (en) * | 2019-05-05 | 2019-09-06 | 湖南省林业科学院 | A kind of organic inorganic hybridization soybean base adhesive and the preparation method and application thereof |
| CN110205090A (en) * | 2019-06-17 | 2019-09-06 | 厦门大学 | A kind of preparation method of the biology base soy protein adhesives based on modified by ultra high pressure |
| CN110746927A (en) * | 2019-10-28 | 2020-02-04 | 厦门大学 | Preparation method of rapeseed protein adhesive based on ultrahigh-pressure composite modification |
| CN111040728A (en) * | 2019-12-09 | 2020-04-21 | 华南农业大学 | Yeast protein adhesive and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111978917B (en) | 2021-08-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112322254B (en) | Biomass aldehyde-free adhesive and preparation and application methods thereof | |
| Ji et al. | Preparation and characterizations of a chitosan-based medium-density fiberboard adhesive with high bonding strength and water resistance | |
| Norström et al. | Green binders for wood adhesives | |
| Gao et al. | Preparation of wood adhesives based on soybean meal modified with PEGDA as a crosslinker and viscosity reducer | |
| CN107502282B (en) | A kind of graft crosslinking type vegetable protein adhesive and preparation method thereof | |
| Gao et al. | Storage stability of polyamidoamine-epichlorohydrin resin and its effect on the properties of defatted soybean flour-based adhesives | |
| Norström et al. | Xylan–A green binder for wood adhesives | |
| CN108727546B (en) | Polymerization reaction type formaldehyde catching agent and preparation method thereof | |
| Luo et al. | Effect of melamine allocation proportion on chemical structures and properties of melamine-urea-formaldehyde resins | |
| CN113563841B (en) | Modified vegetable protein adhesive and preparation method thereof | |
| Hosseinpourpia et al. | Properties of medium-density fibreboards bonded with dextrin-based wood adhesive | |
| Wang et al. | Properties of soy-based wood adhesives enhanced by waterborne polyurethane modification | |
| He et al. | Adhesive strength of pilot-scale-produced water-washed cottonseed meal in comparison with a synthetic glue for non-structural interior application | |
| Xu et al. | Improved water resistance of soybean meal-based adhesive with SDS and PAM | |
| CN111501416B (en) | Formaldehyde-free impregnation adhesive for decorative paper and preparation method thereof | |
| Wang et al. | Water-resistant whey protein based wood adhesive modified by post-treated phenol-formaldehyde oligomers (PFO) | |
| CN111978917B (en) | Preparation method of rapeseed protein adhesive based on ultrahigh pressure and EGDE composite modification | |
| Kreibich et al. | End jointing green lumber with SoyBond | |
| CN109825249B (en) | Water-resistant and corrosion-resistant soybean protein adhesive and preparation method thereof | |
| CN110746927B (en) | Preparation method of rapeseed protein adhesive based on ultrahigh-pressure composite modification | |
| Jimenez et al. | Effect of tobacco stalk additive particle size on the bond strength and formaldehyde emission of urea formaldehyde bonded plywood | |
| CN113861937A (en) | Phenolic epoxy resin soy protein adhesive, and preparation method and application thereof | |
| CN113913152A (en) | Spirulina protein adhesive and preparation method and application thereof | |
| Du et al. | Bonding performance of plywood with pig blood adhesives prepared by a novel method | |
| CN112063364A (en) | Vegetable protein-based formaldehyde-free adhesive |
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 |