CN116135943A - Preparation method of a degradable plant-based composite polyester hot-melt adhesive - Google Patents
Preparation method of a degradable plant-based composite polyester hot-melt adhesive Download PDFInfo
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- CN116135943A CN116135943A CN202111359404.6A CN202111359404A CN116135943A CN 116135943 A CN116135943 A CN 116135943A CN 202111359404 A CN202111359404 A CN 202111359404A CN 116135943 A CN116135943 A CN 116135943A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
- C09J167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L97/00—Compositions of lignin-containing materials
- C08L97/02—Lignocellulosic material, e.g. wood, straw or bagasse
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
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- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Dry Formation Of Fiberboard And The Like (AREA)
Abstract
本发明涉及天然纤维材料技术领域，且公开了一种具有可降解性的植物基复合聚酯热熔粘结剂的制备方法，包括以下步骤：第一步：取玻璃皿，放入天然纤维素微晶，再依次放入己二酸、己二醇和金属盐催化剂，得到反应混合物。该具有可降解性的植物基复合聚酯热熔粘结剂的制备方法，采用聚酯反应在纤维素微晶表面合成的复合粘合剂，具有较高的热熔粘结性能，对疏水性材料或亲水材料都具有较高的粘结牢度，合成出复合热粘结剂具有粒度大小可控和粘结强度可控的特点，将其用于木屑、秸秆废弃物的热熔粘结粘结，可以获得无甲醛污染，强度高的特性。The invention relates to the technical field of natural fiber materials, and discloses a preparation method of a degradable plant-based composite polyester hot-melt adhesive, comprising the following steps: Step 1: Take a glass dish and put it into natural cellulose microcrystal, and then add adipic acid, hexanediol and metal salt catalyst in sequence to obtain a reaction mixture. The preparation method of the degradable plant-based composite polyester hot-melt adhesive adopts the composite adhesive synthesized on the surface of cellulose microcrystals by polyester reaction, which has high hot-melt bonding performance and is resistant to hydrophobicity. Materials or hydrophilic materials have high bonding fastness, and the compound thermal adhesive synthesized has the characteristics of controllable particle size and bond strength, and it is used for hot-melt bonding of wood chips and straw waste Bonding can obtain the characteristics of no formaldehyde pollution and high strength.
Description
Technical Field
The invention relates to the technical field of natural fiber materials, in particular to a preparation method of a degradable plant-based composite polyester hot-melt adhesive.
Background
The cellulose microcrystal is mainly prepared from cellulose in natural forest biomass resources or agricultural cellulose resources through physical and chemical treatment, has the characteristics of high strength, low density and small particle structure, can improve the bonding effect of the cellulose microcrystal on filling materials through a surface polymer modification method, has biodegradability of macromolecular chains obtained by polymerization of adipic acid and hexanediol, is obtained from renewable plant resources, can be degraded into water and carbon dioxide in natural environment, and cannot cause any pollution.
The composite adhesive obtained by modifying the surface of cellulose microcrystal can be compounded with various natural plant cellulose materials to form a structural material which is nontoxic, harmless, easy to degrade and circulate and has certain strength, is used for household decoration and small household structural articles for indoor decoration and small structural articles (such as clothes hangers, packaging boxes and the like), is beneficial to improving the added value of agricultural and forestry byproduct waste, can reduce the dependence on petroleum-based resources, and obtains win-win benefits of economy and environmental benefits.
Disclosure of Invention
The invention aims to provide a preparation method of a degradable plant-based composite polyester hot-melt adhesive.
The technical scheme for solving the technical problems is as follows: a preparation method of a degradable plant-based composite polyester hot melt adhesive comprises the following steps:
the first step: taking a glass vessel, putting natural cellulose microcrystals into the glass vessel, and then sequentially putting adipic acid, hexanediol and a metal salt catalyst into the glass vessel to obtain a reaction mixture;
and a second step of: adding the mixture reacted in the first step into a hopper of a double-screw extruder, adjusting the heating temperatures of a first heating zone, a second heating zone, a third heating zone, a fourth heating zone, a fifth heating zone and a sixth heating zone of the double-screw extruder to be 180 degrees, 200 degrees, 230 degrees, 220 degrees and 220 degrees, and controlling the time in a reaction area to be 20-30 minutes;
and a third step of: cooling the material extruded by the double-screw extruder, and crushing the granular material into powder material with the particle size of 0.1-1.5mm by adopting a crusher to obtain the cellulose microcrystalline-polyester composite structural adhesive;
fourth step: mixing the obtained cellulose microcrystalline-polyester composite structural adhesive with natural straw powder, wood dust and corn starch, adopting a compression molding technology of a heating and pressurizing thermosetting composite material, and obtaining the composite structural composite material with different sizes and thicknesses under the conditions that the heating temperature is 160-220 ℃ and the pressurizing is 1.0-2.0 tons/m < 2 >.
The beneficial effects of the invention are as follows: the composite adhesive synthesized on the surface of cellulose microcrystal by adopting polyester reaction has higher hot-melt adhesive property and higher adhesive fastness to hydrophobic materials or hydrophilic materials, and the synthesized composite hot adhesive has the characteristics of controllable granularity and controllable adhesive strength, and can be used for hot-melt adhesive bonding of wood dust and straw waste, so that the composite adhesive has the characteristics of no formaldehyde pollution and high strength.
Further: the natural cellulose microcrystal is extracted from bagasse or cotton seed hull fiber in the first step, and has a particle structure of 0.0110mm-1.001000mm
Further: in the first step, the mass percentage of cellulose microcrystals in the reaction mixture is 15-60%, and the molar ratio of adipic acid to hexanediol is 1:1.0-1: 1.05.
Further: in the first step, the metal salt catalyst is one or a plurality of compounds of calcium acetate, magnesium acetate or two salts, and the dosage of the metal salt catalyst is 1/10000-1/100 of the total weight of the reaction mixture.
The beneficial effects of the above-mentioned further scheme are: to promote the esterification reaction of the acid and the hydroxyl in the mixed system.
Further: in the second step, the rotating speed of the screw extruder is controlled to be 1-50 rpm.
The beneficial effects of the above-mentioned further scheme are: the conversion rate of the raw material monomers of the dibasic acid and the dihydric alcohol is more than 98 percent by controlling the reaction temperature and the reaction time.
Detailed Description
The principles and features of the present invention are described below with examples given for the purpose of illustration only and are not intended to limit the scope of the invention.
In a first embodiment, a method for preparing a degradable plant-based composite polyester hot melt adhesive includes the following steps:
the first step: taking a glass vessel, putting natural cellulose microcrystals into the glass vessel, and then sequentially putting adipic acid, hexanediol and a metal salt catalyst into the glass vessel to obtain a reaction mixture;
and a second step of: adding the mixture reacted in the first step into a hopper of a double-screw extruder, adjusting the heating temperatures of a first heating zone, a second heating zone, a third heating zone, a fourth heating zone, a fifth heating zone and a sixth heating zone of the double-screw extruder to be 180 degrees, 200 degrees, 230 degrees, 220 degrees and 220 degrees, and controlling the time in a reaction area to be 20-30 minutes;
and a third step of: cooling the material extruded by the double-screw extruder, and crushing the granular material into powder material with the particle size of 0.1-1.5mm by adopting a crusher to obtain the cellulose microcrystalline-polyester composite structural adhesive;
fourth step: mixing the obtained cellulose microcrystalline-polyester composite structural adhesive with natural straw powder, wood dust and corn starch, adopting a compression molding technology of a heating and pressurizing thermosetting composite material, and obtaining the composite structural composite material with different sizes and thicknesses under the conditions that the heating temperature is 160-220 ℃ and the pressurizing is 1.0-2.0 tons/m < 2 >.
Among them, one preferred: synthesis of cellulose microcrystal-polyester composite hot melt adhesive powder particles:
drying cellulose microcrystalline powder with 800 meshes at 110 ℃ for 6-8 hours in an existing oven, measuring the water content of the cellulose microcrystalline powder to be 0.3%, weighing 100 kg of dried cellulose microcrystalline powder, 92 kg of adipic acid and 75.8 hexanediol into a mixing kettle, adding 0.15 kg of magnesium acetate, mixing to form a reaction mixed system, adding the materials into a sealing hopper of a double-screw extruder after fully mixing, controlling the heating temperature of a first heating area, a second heating area, a third heating area, a fourth heating area, a fifth heating area and a sixth heating area of a screw to be 180 ℃, 200 ℃, 230 ℃, 220 ℃ and 220 ℃, and controlling the rotating speed of the screw to be 30 minutes when the materials stay in the heating areas; the extrudate was air cooled and rotary knife granulated to obtain a pellet product with a diameter of 6mm x 8 mm.
The granular materials are processed into granular powder with the particle size of 0.2-0.8mm by adopting a mechanical crushing method.
In a second embodiment, synthesis of cellulose microcrystal and polyester composite hot melt adhesive powder:
drying cellulose microcrystal powder with the size of 800 meshes at 110 ℃ for 6-8 hours in an existing oven, measuring the water content of the cellulose microcrystal powder to be less than 0.3%, weighing 100 kg of dried cellulose microcrystal, 92 kg of adipic acid and 75.8 hexanediol, putting into a mixing kettle, adding 0.07 kg of magnesium acetate and 0.07 kg of calcium acetate, mixing to form a reaction mixed system, adding the materials into a sealed hopper of a double-screw extruder after fully mixing, controlling the heating temperature of a first heating area, a second heating area, a third heating area, a fourth heating area, a fifth heating area and a sixth heating area of the screw to be 180 ℃, 200 ℃, 230 ℃, 220 ℃ and 220 ℃, and controlling the rotating speed of the screw to be 30 minutes when the materials stay in the heating areas; the extrudate was air cooled and pelletized with a rotary knife to obtain a pellet product having a diameter of 6mm x 8 mm.
The granular material is processed into powder with the size of 0.1-0.4mm by adopting a mechanical crushing method.
Among them, one preferred: the manufacturing process of the composite board comprises the following steps:
mixing the microcrystalline-polyester composite structural adhesive with a certain proportion of natural straw powder, wood dust and corn starch; wherein, the natural straw powder (dried matter, material length 1mm-3 mm) is 45%, the wood dust (dried matter, 10 mesh separation) is 20%, the corn starch (dried matter) is 10%, the microcrystalline-polyester composite structural adhesive is 20%, and the heavy calcium carbonate is 5%; the whole materials are fully mixed in a mixer for 0.5 to 1.0 hour.
The evenly mixed materials are added into a die by adopting a heating and pressurizing die pressing technology, and the heating time is kept for 15 minutes under the pressure condition of 200-220 ℃ and 1.0-2.0 tons/m < 2 >, so that composite boards with different thicknesses can be obtained.
Among them, one preferred: the manufacturing process of the composite board comprises the following steps:
mixing the microcrystalline-polyester composite structural adhesive with a certain proportion of natural straw powder, wood dust and corn starch; wherein, the natural straw powder (dried matter, material length 1mm-3 mm) is 25%, the wood dust (dried matter, 10 mesh separation) is 30%, the corn starch (dried matter) is 15%, the microcrystalline-polyester composite structural adhesive is 25%, and the heavy calcium carbonate is 5%; the whole materials are fully mixed in a mixer for 0.5 to 1.0 hour.
The evenly mixed materials are added into a die by adopting a heating and pressurizing die pressing technology, and the heating time is kept for 10 minutes under the pressure condition of 200-220 ℃ and 1.0-2.0 tons/m < 2 >, so that composite boards with different thicknesses can be obtained.
The composite structural composite material obtained by the process does not contain formaldehyde and other harmful compounds due to the adoption of the cellulose microcrystalline-polyester composite structural adhesive, and meanwhile, the composite fiber board also has the characteristic of swelling and biodegradation of water, so that after the composite structural material is used, the composite structural material can be naturally swelled and disintegrated in water environment and is changed into natural non-toxic and harmless raw materials, the composite structural material can be used as a reusable industrial raw material, even as a feed for artificial breeding industries such as poultry and livestock aquatic products, and the like, can be used as a supplementary feed for poultry, can be used as a structural material for home decoration and small-sized home appliances, and the bending strength of the board can reach 105N/M.
Working principle: the preparation method adopts cellulose microcrystal and adipic acid and hexanediol as raw materials, and under the condition of adopting acetate of calcium, magnesium or antimony as a catalyst, and under the action of certain temperature and time, the synthesis reaction is carried out on the surface of the cellulose microcrystal to realize in-situ growth, so that the cellulose microcrystal-polylactic acid composite structure with the adipic acid hexanediol long-chain structure is synthesized. The composite structure obtained by the synthesis is fully dried and then crushed into irregularly-shaped powder particles with the diameter of between 0.0110 and 1.00000mm by adopting a mechanical crushing method, the micron-sized particles with the cellulose microcrystal-polylactic acid microcomposites are prepared, and are uniformly mixed with natural raw materials containing a large amount of hydroxyl groups such as straw stalk powder, saw dust, corn starch and other macroscopic large particles according to a certain proportion to prepare a mold material, then the mold material is heated and pressed by adopting a high-pressure mold through a compression molding process of a thermosetting composite material, bonding is realized on other materials containing hydroxyl groups by utilizing a polyhexamethylene adipate macromolecular chain on the surface of the cellulose microcrystal-polyester composite structure in the mold material at a certain temperature and pressure, and the natural fiber structure type composite material obtained by the method with high strength, high precision, smooth surface and high temperature resistance is obtained after cooling, solidification and shaping, does not contain formaldehyde, the yield bending rigidity of the material can reach 0.5-1.0105N/M, the use of household indoor decoration and simple structural materials such as clothes hangers and the like can be satisfied, and the composite material does not contain any harmful substances such as formaldehyde.
In the description of the present invention, it should be understood that the terms "center," "longitudinal," "transverse," "length," "width," "thickness," "upper," "lower," "front," "rear," "left," "right," "vertical," "horizontal," "top," "bottom," "inner," "outer," "clockwise," "counterclockwise," "axial," "radial," "circumferential," etc. indicate or refer to the orientation or positional relationship as shown, merely for convenience of description and to simplify the description, and do not indicate or imply that the devices or elements referred to must have a particular orientation, be constructed and operated in a particular orientation, and therefore should not be construed as limiting the invention.
Furthermore, the terms "first," "second," and the like, are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include at least one such feature. In the description of the present invention, the meaning of "plurality" means at least two, for example, two, three, etc., unless specifically defined otherwise.
In the present invention, unless explicitly specified and limited otherwise, the terms "mounted," "connected," "secured," and the like are to be construed broadly, and may be, for example, fixedly connected, detachably connected, or integrally formed; can be mechanically or electrically connected; either directly or indirectly, through intermediaries, or both, may be in communication with each other or in interaction with each other, unless expressly defined otherwise. The specific meaning of the above terms in the present invention can be understood by those of ordinary skill in the art according to the specific circumstances.
In the present invention, unless expressly stated or limited otherwise, a first feature "up" or "down" a second feature may be the first and second features in direct contact, or the first and second features in indirect contact via an intervening medium. Moreover, a first feature being "above," "over" and "on" a second feature may be a first feature being directly above or obliquely above the second feature, or simply indicating that the first feature is level higher than the second feature. The first feature being "under", "below" and "beneath" the second feature may be the first feature being directly under or obliquely below the second feature, or simply indicating that the first feature is less level than the second feature.
In the description of the present specification, a description referring to terms "one embodiment," "some embodiments," "examples," "specific examples," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction.
While embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are illustrative and not to be construed as limiting the invention, and that variations, modifications, alternatives and variations may be made to the above embodiments by one of ordinary skill in the art within the scope of the invention.
Claims (5)
1. A preparation method of a degradable plant-based composite polyester hot melt adhesive is characterized by comprising the following steps: the method comprises the following steps:
the first step: taking a glass vessel, putting natural cellulose microcrystals into the glass vessel, and then sequentially putting adipic acid, hexanediol and a metal salt catalyst into the glass vessel to obtain a reaction mixture;
and a second step of: adding the mixture reacted in the first step into a hopper of a double-screw extruder, adjusting the heating temperatures of a first heating zone, a second heating zone, a third heating zone, a fourth heating zone, a fifth heating zone and a sixth heating zone of the double-screw extruder to be 180 degrees, 200 degrees, 230 degrees, 220 degrees and 220 degrees, and controlling the time in a reaction area to be 20-30 minutes;
and a third step of: cooling the material extruded by the double-screw extruder, and crushing the granular material into powder material with the particle size of 0.1-1.5mm by adopting a crusher to obtain the cellulose microcrystalline-polyester composite structural adhesive;
fourth step: mixing the obtained cellulose microcrystalline-polyester composite structural adhesive with natural straw powder, wood dust and corn starch, adopting a compression molding technology of a heating and pressurizing thermosetting composite material, and obtaining the composite structural composite material with different sizes and thicknesses under the conditions that the heating temperature is 160-220 ℃ and the pressurizing is 1.0-2.0 tons/m < 2 >.
2. The method for preparing the degradable plant-based composite polyester hot melt adhesive according to claim 1, wherein the method comprises the following steps: in the first step, natural cellulose microcrystal is extracted from bagasse or cotton seed hull fiber, and the grain structure of the natural cellulose microcrystal is 0.0110mm-1.001000 mm.
3. The method for preparing the degradable plant-based composite polyester hot melt adhesive according to claim 1, wherein the method comprises the following steps: in the first step, the mass percentage of cellulose microcrystals in the reaction mixture is 15-60%, and the molar ratio of adipic acid to hexanediol is 1:1.0-1: 1.05.
4. The method for preparing the degradable plant-based composite polyester hot melt adhesive according to claim 1, wherein the method comprises the following steps: in the first step, the metal salt catalyst is one or a plurality of compounds of calcium acetate, magnesium acetate or two salts, and the dosage of the metal salt catalyst is 1/10000-1/100 of the total weight of the reaction mixture.
5. The method for preparing the degradable plant-based composite polyester hot melt adhesive according to claim 1, wherein the method comprises the following steps: in the second step, the rotating speed of the screw extruder is controlled to be 1-50 rpm.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1152007A (en) * | 1995-09-26 | 1997-06-18 | 拜尔公司 | Biodegradable plastics filled with reinforcing materials |
| CN100999610A (en) * | 2006-01-12 | 2007-07-18 | 中国林业科学研究院木材工业研究所 | Wood plastic composite material composection and formed board thereof and their preparation process |
| CN104404647A (en) * | 2014-10-15 | 2015-03-11 | 浙江恒逸高新材料有限公司 | Hydrophilic polyester fiber modified by cellulose nanocrystal and preparation method thereof |
| CN106521690A (en) * | 2016-10-27 | 2017-03-22 | 浙江恒逸高新材料有限公司 | Microcrystalline cellulose-modified polyester fiber and preparation method thereof |
| CN106519202A (en) * | 2016-10-27 | 2017-03-22 | 浙江恒逸高新材料有限公司 | Micro-crystalline cellulose modified polyester preparation method |
| CN112063141A (en) * | 2020-08-14 | 2020-12-11 | 安徽丰原生物新材料有限公司 | Cellulose polyester composite material and preparation method thereof |
| CN113272230A (en) * | 2018-12-02 | 2021-08-17 | 塑拉帕克公司 | Compostable wood composites for thin-walled articles |
-
2021
- 2021-11-17 CN CN202111359404.6A patent/CN116135943A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1152007A (en) * | 1995-09-26 | 1997-06-18 | 拜尔公司 | Biodegradable plastics filled with reinforcing materials |
| CN100999610A (en) * | 2006-01-12 | 2007-07-18 | 中国林业科学研究院木材工业研究所 | Wood plastic composite material composection and formed board thereof and their preparation process |
| CN104404647A (en) * | 2014-10-15 | 2015-03-11 | 浙江恒逸高新材料有限公司 | Hydrophilic polyester fiber modified by cellulose nanocrystal and preparation method thereof |
| CN106521690A (en) * | 2016-10-27 | 2017-03-22 | 浙江恒逸高新材料有限公司 | Microcrystalline cellulose-modified polyester fiber and preparation method thereof |
| CN106519202A (en) * | 2016-10-27 | 2017-03-22 | 浙江恒逸高新材料有限公司 | Micro-crystalline cellulose modified polyester preparation method |
| CN113272230A (en) * | 2018-12-02 | 2021-08-17 | 塑拉帕克公司 | Compostable wood composites for thin-walled articles |
| CN112063141A (en) * | 2020-08-14 | 2020-12-11 | 安徽丰原生物新材料有限公司 | Cellulose polyester composite material and preparation method thereof |
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Application publication date: 20230519 |