CN117757417A - Lactose-based hyperbranched boiling-resistant water-type adhesive and preparation method thereof - Google Patents
Lactose-based hyperbranched boiling-resistant water-type adhesive and preparation method thereof Download PDFInfo
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- CN117757417A CN117757417A CN202310622553.XA CN202310622553A CN117757417A CN 117757417 A CN117757417 A CN 117757417A CN 202310622553 A CN202310622553 A CN 202310622553A CN 117757417 A CN117757417 A CN 117757417A
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- 239000000853 adhesive Substances 0.000 title claims abstract description 93
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 93
- GUBGYTABKSRVRQ-QKKXKWKRSA-N Lactose Natural products OC[C@H]1O[C@@H](O[C@H]2[C@H](O)[C@@H](O)C(O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@H]1O GUBGYTABKSRVRQ-QKKXKWKRSA-N 0.000 title claims abstract description 85
- 239000008101 lactose Substances 0.000 title claims abstract description 85
- 238000009835 boiling Methods 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 48
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 239000008367 deionised water Substances 0.000 claims abstract description 24
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 24
- 229920000768 polyamine Polymers 0.000 claims abstract description 23
- 239000007787 solid Substances 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 5
- 229920002873 Polyethylenimine Polymers 0.000 claims description 27
- 238000007731 hot pressing Methods 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 9
- MBYLVOKEDDQJDY-UHFFFAOYSA-N tris(2-aminoethyl)amine Chemical compound NCCN(CCN)CCN MBYLVOKEDDQJDY-UHFFFAOYSA-N 0.000 claims description 9
- 239000011120 plywood Substances 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 238000003825 pressing Methods 0.000 claims description 2
- 239000002028 Biomass Substances 0.000 abstract description 9
- 239000007810 chemical reaction solvent Substances 0.000 abstract description 4
- 239000003960 organic solvent Substances 0.000 abstract description 4
- 238000006482 condensation reaction Methods 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 abstract 1
- 238000005303 weighing Methods 0.000 abstract 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 33
- 239000000376 reactant Substances 0.000 description 8
- 238000011161 development Methods 0.000 description 6
- 235000013336 milk Nutrition 0.000 description 6
- 210000004080 milk Anatomy 0.000 description 6
- 239000008267 milk Substances 0.000 description 6
- 239000002023 wood Substances 0.000 description 6
- 230000007613 environmental effect Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 4
- 241000124008 Mammalia Species 0.000 description 3
- 238000004026 adhesive bonding Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- WQZGKKKJIJFFOK-SVZMEOIVSA-N (+)-Galactose Chemical compound OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@H]1O WQZGKKKJIJFFOK-SVZMEOIVSA-N 0.000 description 2
- 241000219000 Populus Species 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- 241000283690 Bos taurus Species 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 206010019233 Headaches Diseases 0.000 description 1
- 206010020751 Hypersensitivity Diseases 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 208000003251 Pruritus Diseases 0.000 description 1
- 238000007718 adhesive strength test Methods 0.000 description 1
- 230000007815 allergy Effects 0.000 description 1
- -1 amine compound Chemical class 0.000 description 1
- 208000006673 asthma Diseases 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
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- 238000000605 extraction Methods 0.000 description 1
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- 235000020256 human milk Nutrition 0.000 description 1
- 230000007803 itching Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
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- 229920001542 oligosaccharide Polymers 0.000 description 1
- 150000002482 oligosaccharides Chemical class 0.000 description 1
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- 239000002356 single layer Substances 0.000 description 1
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- 208000024891 symptom Diseases 0.000 description 1
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Landscapes
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention relates to the technical field of adhesives, in particular to a lactose-based hyperbranched boiling-resistant water-type adhesive and a preparation method thereof, wherein the adhesive is prepared from lactose and hyperbranched polyamine as raw materials, and the molar ratio of lactose to hyperbranched polyamine is 100: (6-35), the preparation method of the invention is as follows: weighing lactose and hyperbranched polyamine, adding into a reaction bottle, adding deionized water, controlling the solid content of the adhesive to be 40% -60%, heating at 70-90 ℃ for reaction for 1-3 hours, and performing condensation reaction to obtain the lactose-based hyperbranched boiling-resistant water-type adhesive. The lactose-based hyperbranched boiling water-type adhesive prepared by the invention takes water as a reaction solvent, does not contain any organic solvent such as formaldehyde, is environment-friendly, and has no harm to human bodies; lactose is used as biomass source, so that the method is low in cost, and raw materials are simple and easy to obtain and wide in source.
Description
Technical Field
The invention relates to the technical field of adhesives, in particular to a lactose-based hyperbranched boiling-resistant water-type adhesive and a preparation method thereof.
Background
The adhesive "trialdehyde glue" widely used in wood processing and products thereof at present is an adhesive containing formaldehyde. Formaldehyde is a deleterious substance and prolonged exposure to formaldehyde can lead to symptoms such as asthma, allergies, skin itching, headache, etc., and severe cases can lead to cancer. Thus, the use of adhesives containing formaldehyde presents health and environmental risks.
In solving the detrimental problem of "trialdehyde glue", lactose has been proposed as a raw material for biomass adhesives. Lactose is a compound of one molecule of D-glucose and one molecule of D-galactose which are connected by beta-1, 4-glycosidic bond. Lactose is present in mammalian milk, human milk contains about 7% lactose and bovine milk contains about 4% lactose, the most important carbohydrate in the milk family. The lactose with higher purity can be obtained through separation and extraction. The lactose has wide sources, is cheap and easy to obtain, provides raw materials for the environment-friendly biomass adhesive, and has wide application prospect in the production of the environment-friendly biomass adhesive.
However, there are still some problems with using lactose as a biomass adhesive. Firstly, lactose has low viscosity and needs to be modified to obtain lactose suitable for the adhesive. Secondly, when lactose is used for gluing, a proper catalyst is needed to react lactose with other components, which also increases the difficulty of producing the gluing agent. Therefore, in future research and development, there is a need to find more efficient and sustainable lactose modification methods and to develop more efficient and environmentally friendly catalysts to increase the application level of lactose as a biomass adhesive.
Disclosure of Invention
The invention aims to provide a lactose-based hyperbranched boiling-resistant water-type adhesive and a preparation method thereof, wherein the lactose-based hyperbranched boiling-resistant water-type adhesive is extracted from milk of mammals, has wide sources and low cost, and belongs to renewable biomass materials; the reaction takes water as a reaction solvent, does not contain any organic solvent, is environment-friendly, and does not use formaldehyde in the reaction, so that the adhesive has no formaldehyde release, and accords with the concept of green development.
In order to achieve the technical purpose and the technical effect, the invention is realized by the following technical scheme:
a lactose-based hyperbranched boiling-resistant water-type adhesive is prepared from lactose and hyperbranched polyamine as raw materials, deionized water and binary copolycondensation.
Preferably, the molar ratio of lactose to hyperbranched polyamine is 100: (6-35); the reaction temperature of the adhesive is 70-90 ℃.
Preferably, the reaction time of the adhesive is 1-3 hours; the theoretical solid content of the adhesive is maintained at 40% -60% after deionized water is added.
On the other hand, the invention provides a preparation method of the adhesive, which comprises the following steps of;
s1: lactose and hyperbranched polyamine were added to the reactor in a molar ratio of lactose to hyperbranched polyamine of 100: (6-35);
s2: deionized water is added according to the solid content of 40-60 percent, so that the deionized water is uniformly mixed;
s3: placing the reactor in a stirrer at 70-90 ℃ for reaction for 1-3h, and cooling to room temperature to obtain the prepared lactose-based hyperbranched boiling-resistant water-based adhesive.
Preferably, the hyperbranched polyamine is any one of tris (2-aminoethyl) amine or polyethyleneimine.
Preferably, the molecular weight of the polyethyleneimine is 300, 600 or 1200.
Preferably, the hyperbranched polyamine is a tris (2-aminoethyl) amine or polyethyleneimine having the formula:
on the other hand, the invention provides a preparation method of the adhesive for preparing the plywood, the adhesive is pressed, the hot pressing pressure is 1.0MPa, the hot pressing time is 6 minutes, and the hot pressing temperature is 180-220 ℃.
The invention has the beneficial effects that:
the lactose-based hyperbranched boiling-resistant water-type adhesive and the preparation method thereof provided by the invention are extracted from milk of mammals, have wide sources and low cost, and belong to renewable biomass materials; the reaction takes water as a reaction solvent, does not contain any organic solvent, is environment-friendly, and does not use formaldehyde in the reaction, so that the adhesive has no formaldehyde release, and accords with the concept of green development. Meanwhile, the adhesive provided by the invention has high bonding strength, excellent water resistance and stable color. The reaction is completed in one step, the operation is simple, and the reaction product can be directly used as a wood adhesive. Harmful substances such as formaldehyde are not used in the reaction process, so that the adhesive is an environment-friendly adhesive.
The adhesive provided by the invention has the following beneficial effects:
1. wide sources and low cost: the raw material lactose of the adhesive is an oligosaccharide naturally existing in the milk of mammals and can be fully recycled from the processing of dairy products, so that the raw material lactose of the adhesive has the advantages of low cost and wide sources. Meanwhile, lactose is also a renewable biomass material, and accords with the development direction of sustainable development.
2. Green and environment-friendly: the lactose-based hyperbranched boiling-resistant water-type adhesive takes water as a reaction solvent in the reaction, does not contain any organic solvent, does not contain harmful substances such as formaldehyde and the like, and accords with the concept of green environmental protection. In addition, the hyperbranched polyamine used in the invention is a polymer compound with a molecular structure more branched and complicated than that of a common amine compound, so that the hyperbranched polyamine has better environmental protection performance.
3. Excellent water resistance: the hyperbranched polyamine has a high three-dimensional network structure and strong crosslinking capacity, and can effectively increase the crosslinking density of the adhesive, thereby improving the water resistance of the adhesive. In addition, the molecular structure formed after the reaction of the lactose-based hyperbranched boiling-resistant water-based adhesive also has higher stability, so that the color of the adhesive is stable, and the adhesive can be suitable for various requirements.
4. The operation is simple: the lactose-based hyperbranched boiling-resistant water-type adhesive adopts binary copolycondensation reaction, the reaction is completed in one step, the operation is simple, and the reaction product can be directly used for wood adhesives.
5. Green environmental protection type: as the lactose-based hyperbranched boiling-resistant water-based adhesive does not contain formaldehyde and other harmful substances, the emission of VOC can be effectively reduced, and the development direction of the modern environment-friendly adhesive is met.
Meanwhile, the preparation method provided by the invention mainly comprises the following advantages:
1. the reaction temperature and the reaction time of the adhesive are adjustable: the hyperbranched polyamines used in the present invention are typically tris (2-aminoethyl) amine or polyethyleneimine in a molar ratio of 100: (6-35), in the preparation process of the adhesive, the reaction temperature and the reaction time can be adjusted according to the requirement.
2. The theoretical solid content is controllable: the theoretical solid content of the lactose-based hyperbranched boiling water-resistant adhesive prepared by the invention is maintained between 40% and 60% after deionized water is added, and the theoretical solid content of the adhesive can be controlled by adjusting the dosage of the deionized water.
3. The application range is wide: the preparation method provided by the invention can be suitable for various types and structures of hyperbranched polyamines, such as tri (2-amino ethyl) amine or polyethyleneimine, and the like, so that the preparation method has better applicability.
In conclusion, the lactose-based hyperbranched boiling-resistant water-type adhesive and the preparation method thereof provided by the invention have wide application prospect and market potential, have wide application prospect in the fields of wood processing, furniture manufacturing, building materials and the like, and simultaneously accord with the development direction of modern environmental protection technology.
Of course, it is not necessary for any one product to practice the invention to achieve all of the advantages set forth above at the same time.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed for the description of the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic illustration of a sample adhesive according to various embodiments of the present invention;
fig. 2 is a graph of wood failure for various examples of adhesives of the invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
A lactose-based hyperbranched boiling-resistant water-type adhesive is prepared from lactose and hyperbranched polyamine as raw materials, deionized water and binary copolycondensation.
In a further preferred embodiment of the invention, the lactose and hyperbranched polyamine are present in an optimum molar ratio of 100:10.
in a further preferred embodiment of the invention, the adhesive has an optimal reaction temperature of 80 ℃.
In a further preferred embodiment of the invention, the optimal reaction time is 3 hours.
In a further preferred embodiment of the invention, the optimal solids content is 50%.
In a further preferred embodiment of the present invention, the hyperbranched polyamine is a tris (2-aminoethyl) amine or polyethyleneimine having the formula:
a preparation method of a plywood prepared from a lactose-based hyperbranched boiling-resistant water-type adhesive comprises the steps of pressing the plywood by the lactose-based hyperbranched boiling-resistant water-type adhesive, wherein the hot pressing pressure is 1.0MPa, the hot pressing time is 6 minutes, the hot pressing temperature is 180-220 ℃, and the plywood is poplar plywood.
Example 1
The invention relates to a lactose-based hyperbranched boiling-resistant water-type adhesive and a preparation method thereof, comprising the following steps:
(1) 10.3g of lactose as a reactant and 6.0g of polyethyleneimine are added into the reactor; the molar ratio is lactose: the polyethyleneimine is 100:33.3;
(2) Deionized water is added according to the solid content of 50 percent, so that the deionized water is uniformly mixed;
(3) And (3) placing the reactor in a stirrer at 80 ℃ for reaction for 2 hours, and cooling to room temperature to obtain the prepared lactose-based hyperbranched boiling-resistant water-based adhesive.
The molecular weight of the polyethyleneimine in the above examples was 600.
Example 2
The invention relates to a lactose-based hyperbranched boiling-resistant water-type adhesive and a preparation method thereof, comprising the following steps:
to the reactor was added 8.6g of reactant lactose and 3.0g of polyethyleneimine; the molar ratio of lactose polyethylene imine is 100:20, a step of;
(2) Adding deionized water according to the solid content of 40%, and uniformly mixing;
(3) And (3) placing the reactor in a stirrer at 70 ℃ for reaction for 3 hours, and cooling to room temperature to obtain the prepared lactose-based hyperbranched boiling-resistant water-based adhesive.
The molecular weight of the polyethyleneimine in the above examples was 600.
Example 3
The invention relates to a lactose-based hyperbranched boiling-resistant water-type adhesive and a preparation method thereof, comprising the following steps:
(1) 10.3g of lactose as a reactant and 3.0g of polyethyleneimine are added into the reactor; the molar ratio is lactose: the polyethyleneimine is 100:16.6;
(2) Deionized water is added according to the solid content of 60 percent, so that the deionized water is uniformly mixed;
(3) And (3) placing the reactor in a stirrer at 90 ℃ for reaction for 2 hours, and cooling to room temperature to obtain the prepared lactose-based hyperbranched boiling-resistant water-based adhesive. The molecular weight of the polyethyleneimine in the above examples was 300.
Example 4
The invention relates to a lactose-based hyperbranched boiling-resistant water-type adhesive and a preparation method thereof, comprising the following steps:
(1) 13.7g of lactose as a reactant and 3.0g of polyethyleneimine are added into the reactor; the molar ratio is lactose: the polyethyleneimine is 100:12.5;
(2) Deionized water is added according to the solid content of 50 percent, so that the deionized water is uniformly mixed;
(3) And (3) placing the reactor in a stirrer at 90 ℃ for reaction for 2 hours, and cooling to room temperature to obtain the prepared lactose-based hyperbranched boiling-resistant water-based adhesive. The molecular weight of the polyethyleneimine in the above examples was 1200.
And then the prepared lactose-based hyperbranched boiling-resistant water-based adhesive is obtained.
Example 5
The invention relates to a lactose-based hyperbranched boiling-resistant water-type adhesive and a preparation method thereof, comprising the following steps:
(1) 10.3g of lactose as a reactant and 1.8g of polyethyleneimine are added into the reactor; the molar ratio is lactose: the polyethyleneimine is 100:10;
(2) Deionized water is added according to the solid content of 55 percent, so that the deionized water is uniformly mixed;
(3) And (3) placing the reactor in a stirrer at 85 ℃ for reaction for 2 hours, and cooling to room temperature to obtain the prepared lactose-based hyperbranched boiling-resistant water-based adhesive.
The molecular weight of the polyethyleneimine in the above examples was 600.
Example 6
The invention relates to a lactose-based hyperbranched boiling-resistant water-type adhesive and a preparation method thereof, comprising the following steps:
(1) 12.3g of lactose as a reactant and 1.8g of polyethyleneimine are added into the reactor; the molar ratio is lactose: the polyethyleneimine is 100:8.3;
(2) Adding deionized water according to the solid content of 45%, and uniformly mixing;
(3) And (3) placing the reactor in a stirrer at 90 ℃ for reaction for 2 hours, and cooling to room temperature to obtain the prepared lactose-based hyperbranched boiling-resistant water-based adhesive.
The molecular weight of the polyethyleneimine in the above examples was 300.
Example 7
The invention relates to a lactose-based hyperbranched boiling-resistant water-type adhesive and a preparation method thereof, comprising the following steps:
(1) 15.4g of lactose as a reactant and 1.8g of tri (2-aminoethyl) amine as a reactant are added into the reactor; the molar ratio is lactose: tris (2-aminoethyl) amine was 100:6.6;
(2) Deionized water is added according to the solid content of 50 percent, so that the deionized water is uniformly mixed;
(3) And (3) placing the reactor in a stirrer at 80 ℃ for reaction for 1h, and cooling to room temperature to obtain the prepared lactose-based hyperbranched boiling-resistant water-based adhesive.
As shown in fig. 1, a picture of a different example sample adhesive.
The bonding strength test of the adhesive is carried out according to the requirements of national standard GB/T17657-2013 on the physicochemical property test method of artificial boards and veneered artificial boards, and the physical and mechanical properties of the boards are tested. The method comprises the following specific steps: the synthesized lactose-based hyperbranched boiling-resistant water-type adhesive is prepared according to the sizing amount of 320g/m 2 Double-sided sizing is carried out on a single-layer poplar board, the hot pressing temperature is 200 ℃, the hot pressing is carried out for 6 minutes, then the board is cut into 36 test pieces, the dry strength and the wet strength of the board are respectively tested in 3 parts (the test pieces are soaked in water at 63 ℃ for 3 hours) and the boiling water resistance of the board are respectively tested, the board is taken out and placed for ten minutes at normal temperature, and then the board is respectively subjected to gluing strength test by using an electronic universal mechanical tester, wherein the test results are shown in the following table:
table 1 properties of plywood made with different adhesives
As shown in fig. 2, wood breakage diagrams (dry strength) of the adhesives of different examples after the respective adhesive strength tests were performed using an electronic universal mechanical tester; the adhesive provided by the invention has the beneficial effect of high adhesive strength.
The preferred embodiments of the invention disclosed above are intended only to assist in the explanation of the invention. The preferred embodiments are not exhaustive or to limit the invention to the precise form disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best understand and utilize the invention. The invention is limited only by the claims and the full scope and equivalents thereof.
Claims (8)
1. A lactose-based hyperbranched boiling-resistant water-type adhesive is characterized in that the adhesive is prepared by taking lactose and hyperbranched polyamine as raw materials, adding deionized water, and performing binary copolycondensation.
2. The lactose-based hyperbranched boiling-resistant water-based adhesive as claimed in claim 1, wherein: the molar ratio of lactose to hyperbranched polyamine is 100: (6-35); the reaction temperature of the adhesive is 70-90 ℃.
3. The lactose-based hyperbranched boiling-resistant water-based adhesive as claimed in claim 1, wherein: the reaction time of the adhesive is 1-3 hours; the theoretical solid content of the adhesive is maintained at 40% -60% after deionized water is added.
4. A method of preparing an adhesive according to any one of claims 1 to 3, wherein: the method comprises the following steps:
s1: lactose and hyperbranched polyamine were added to the reactor in a molar ratio of lactose to hyperbranched polyamine of 100: (6-35);
s2: deionized water is added according to the solid content of 40-60 percent, so that the deionized water is uniformly mixed;
s3: placing the reactor in a stirrer at 70-90 ℃ for reaction for 1-3h, and cooling to room temperature to obtain the prepared lactose-based hyperbranched boiling-resistant water-based adhesive.
5. The method of manufacturing according to claim 4, wherein: the hyperbranched polyamine is any one of tri (2-aminoethyl) amine or polyethyleneimine.
6. The method of manufacturing according to claim 4, wherein: the molecular weight of the polyethyleneimine is 300, 600 or 1200.
7. The method of manufacturing according to claim 4, wherein: the structural formula of the hyperbranched polyamine is tri (2-aminoethyl) amine or polyethyleneimine as follows:
8. a method for preparing plywood by using the adhesive according to any one of claims 1 to 3, which is characterized in that: and pressing the adhesive into the plywood, wherein the hot pressing pressure is 1.0MPa, the hot pressing time is 6 minutes, and the hot pressing temperature is 180-220 ℃.
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| CN202310622553.XA CN117757417A (en) | 2023-05-30 | 2023-05-30 | Lactose-based hyperbranched boiling-resistant water-type adhesive and preparation method thereof |
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