CN116144191B - Degradable plastic prepared from plant wood fibers and preparation method thereof - Google Patents
Degradable plastic prepared from plant wood fibers and preparation method thereof Download PDFInfo
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- 229920002522 Wood fibre Polymers 0.000 title claims abstract description 101
- 239000002025 wood fiber Substances 0.000 title claims abstract description 101
- 229920006238 degradable plastic Polymers 0.000 title claims abstract description 93
- 238000002360 preparation method Methods 0.000 title claims abstract description 41
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 38
- 229920002873 Polyethylenimine Polymers 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000007787 solid Substances 0.000 claims abstract description 19
- 239000000243 solution Substances 0.000 claims description 58
- 238000003756 stirring Methods 0.000 claims description 54
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 45
- 239000002202 Polyethylene glycol Substances 0.000 claims description 35
- 238000010438 heat treatment Methods 0.000 claims description 21
- 239000000843 powder Substances 0.000 claims description 18
- 239000011550 stock solution Substances 0.000 claims description 18
- JAJRRCSBKZOLPA-UHFFFAOYSA-M triethyl(methyl)azanium;hydroxide Chemical compound [OH-].CC[N+](C)(CC)CC JAJRRCSBKZOLPA-UHFFFAOYSA-M 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 11
- 235000015110 jellies Nutrition 0.000 claims description 10
- 239000008274 jelly Substances 0.000 claims description 10
- 238000010992 reflux Methods 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 2
- 239000008187 granular material Substances 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- 229920003023 plastic Polymers 0.000 abstract description 17
- 239000004033 plastic Substances 0.000 abstract description 17
- 230000015556 catabolic process Effects 0.000 abstract description 9
- 238000006731 degradation reaction Methods 0.000 abstract description 9
- 238000010521 absorption reaction Methods 0.000 abstract description 7
- 229920005610 lignin Polymers 0.000 abstract description 6
- 229920002678 cellulose Polymers 0.000 abstract description 4
- 239000001913 cellulose Substances 0.000 abstract description 4
- 239000002245 particle Substances 0.000 abstract description 4
- 239000004705 High-molecular-weight polyethylene Substances 0.000 abstract description 3
- 239000002689 soil Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 26
- 238000005303 weighing Methods 0.000 description 14
- 238000000034 method Methods 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 5
- 239000002028 Biomass Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 229920000704 biodegradable plastic Polymers 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 229920002488 Hemicellulose Polymers 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 230000009878 intermolecular interaction Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
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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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/02—Polyalkylene oxides
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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
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/02—Polyamines
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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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
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- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
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Abstract
本发明公开了一种利用植物木质纤维制备的可降解塑料及其制备方法，属于可降解塑料制备领域，包括植物木质纤维制备的可降解塑料以及植物木质纤维制备可降解塑料的制备方法。将植物木质纤维、高分子量聚乙二醇和聚乙烯亚胺用植物木质纤维溶液溶解后，加水析出大量的稳定的含有纤维素木质素高韧性的固体塑料颗粒。再生出来的固体塑料颗粒可用于制备可降解塑料，制得的可降解塑料土埋后180天可降解74.40％，降解能力强；拉伸强度可达59.31Mpa，断裂伸长率可达251.31％具有良好的拉伸强度和断裂伸长率，湿度为80％的条件下吸水率仅为0.29％，耐水性能良好。The invention discloses a degradable plastic prepared by using plant wood fiber and a preparation method thereof, belonging to the field of preparation of degradable plastics, including a degradable plastic prepared by using plant wood fiber and a preparation method of the degradable plastic prepared by using plant wood fiber. After the plant wood fiber, high molecular weight polyethylene glycol and polyethyleneimine are dissolved in a plant wood fiber solution, water is added to precipitate a large amount of stable solid plastic particles containing cellulose lignin with high toughness. The regenerated solid plastic particles can be used to prepare degradable plastics. The prepared degradable plastics can be degraded by 74.40% after being buried in the soil for 180 days, and have strong degradation ability; the tensile strength can reach 59.31Mpa, and the elongation at break can reach 251.31%, with good tensile strength and elongation at break, and the water absorption rate is only 0.29% under the condition of 80% humidity, and the water resistance is good.
Description
Technical Field
The invention relates to the field of degradable plastic preparation, in particular to degradable plastic prepared from plant wood fibers and a preparation method thereof.
Background
Today, around 14000 ten thousand tons of different kinds of synthetic plastics are produced annually around the world, mostly in the form of industrial waste into the ecological environment. Although some of these materials, such as polyesters, are biodegradable, most of the plastics articles in use are either not degradable or take decades to degrade, and their accumulation can present a significant environmental hazard. Therefore, research and development and utilization of degradable plastics have received unprecedented attention and importance.
The degradation plastics can be classified into photodegradable, biodegradable and photo-biodegradable plastics according to different degradation mechanisms. Over the course of decades, biodegradable plastics among degradable plastics have become the dominant form of degradable plastics. Lignin is a renewable plant resource, and forms plant wood fiber together with cellulose and hemicellulose, and is abundant in source and low in cost, and widely exists in plant tissues, but because the plant wood fiber is poor in processing performance and poor in mechanical performance, the plant wood fiber is rarely manufactured into structural components for use independently.
Lignin in plant wood fibers has highly cross-linked supramolecular structures and intermolecular interactions such as hydrogen bonding, dipole-dipole interactions and van der waals interactions, and can be blended with different macromolecules (synthetic or natural macromolecules). After being blended with the polymer, the polymer can eliminate the weakness of the plant wood fiber performance and obtain the degradable plastic with good processing performance. However, in order to improve the tensile strength and the elongation at break of the plant wood fiber, the proportion of the polymer to be added is often high during blending, the prepared plastic can be degraded after a long time, and meanwhile, the prepared degradable plastic has poor waterproof and heat-resistant effects. Therefore, a new method is needed to find a degradable plastic which enables the interaction of the high polymer and the plant wood fiber to play the advantages of the respective components, and the plastic prepared by the method has good natural degradation, deformation resistance and waterproof effects and simultaneously has high tensile strength and elongation at break.
Disclosure of Invention
In view of the above, the present invention aims to provide a degradable plastic prepared from plant wood fiber and a preparation method thereof, so as to solve the problems of poor waterproof effect and long natural degradation time of the degradable plastic prepared by blending the plant wood fiber with polymer, wherein the tensile strength and the elongation at break of the degradable plastic are low.
The invention solves the technical problems by the following technical means:
A degradable plastic prepared from plant wood fiber comprises plant wood fiber solution, polyethylene glycol of 4000-6000Da and polyethylenimine of 30000-50000 Da.
Further, the degradable plastic has the raw material proportion of (1-2) g (1-3) g (0.8-1.2) L (volume mass ratio of plant wood fiber solution, 4000-6000Da polyethylene glycol and 30000-50000Da polyethylene imine.
Further, the plant wood fiber solution comprises plant wood fiber powder, methyl triethyl ammonium hydroxide, polyethylene glycol of 500-1500Da and sodium hydroxide solution of 1 mol/L.
Still further, the plant wood fiber solution has the raw materials of methyl triethyl ammonium hydroxide, polyethylene glycol of 500-1500Da and sodium hydroxide solution of 1mol/L in the mass volume ratio of (3-5) to (1-2) to (0.05-0.15).
The invention also provides a preparation method of the degradable plastic, which comprises the following specific steps:
S1, preparing a degradable plastic stock solution, namely adding 4000-6000Da polyethylene glycol and 30000-50000Da polyethylene imine into a plant wood fiber solution, heating while stirring, and stirring at constant temperature to obtain the degradable plastic stock solution;
S2, preparing the degradable plastic, namely cooling the raw material of the degradable plastic to room temperature, adding water to precipitate jelly, filtering and separating to obtain solid after the jelly is not precipitated any more, drying the solid at 50-60 ℃, and sending the solid into a double-screw extruder to be melted, blended, extruded and granulated at the temperature of 180-220 ℃ and the screw rotating speed of 40-60r/min to obtain the degradable plastic.
In the step S1, the constant temperature stirring temperature is 60-80 ℃ and the constant temperature stirring time is 1-2h.
Further, the preparation method of the plant wood fiber solution comprises the following steps:
A. The preparation method of the plant wood fiber dissolvent comprises mixing 500-1500Da polyethylene glycol and methyl triethyl ammonium hydroxide, stirring, adding 1mol/L sodium hydroxide solution, stirring for 5-15min, stirring at constant temperature of 40-50deg.C for 20-30min, pouring into a reactor, and heating, refluxing and stirring to obtain plant wood fiber dissolvent;
B. The plant wood fiber solution is prepared by adding plant wood fiber powder into plant wood fiber dissolvent, heating to 50-60deg.C under stirring, stirring for 20-30min, and vacuum filtering.
Still further, the heating reflux stirring time in the step A is 1-2h, and the temperature is 85-95 ℃.
Still further, the mass to volume ratio of the plant wood fiber powder to the plant wood fiber dissolving agent in the step B is (1-2) kg (3-5) L.
The plant wood fiber can be made into lignocellulose biomass plastic, but has the defects of low tensile strength, low elongation at break and poor heat resistance and water resistance. In order to improve the tensile strength, elongation at break and waterproof performance of the lignocellulose biomass plastic, the plant lignocellulose fiber can be blended with polyethylene glycol and polyethyleneimine to prepare the modified lignocellulose biomass plastic. However, polyethylene glycol and polyethyleneimine with high molecular weight are difficult to dissolve at normal temperature, cannot be well blended with lignocellulose, are easily unevenly distributed after being melted at high temperature, and thus the tensile strength, elongation at break and waterproofness of the formed lignocellulose biomass plastic cannot be well improved.
The invention takes plant wood fiber, polyethylene glycol with 4000-6000Da and polyethyleneimine with 30000-50000Da as raw materials, and the plant wood fiber solution is prepared by dissolving plant wood fiber powder after mixing methyl triethyl ammonium hydroxide, polyethylene glycol with 500-1500Da and sodium hydroxide solution with 1 mol/L. And then adding 4000-6000Da polyethylene glycol and 30000-50000Da polyethyleneimine, after dissolving, adding water to quickly regenerate lignin from the plant lignocellulose solution, and intertwining and crosslinking the regenerated lignin with 4000-6000Da polyethylene glycol and 30000-50000Da polyethyleneimine, and filling the cellulose nano-network structure to obtain a large number of stable solid plastic particles containing cellulose lignin with high toughness. The degradable plastic prepared by the regenerated solid plastic particles after extrusion granulation has good tensile strength, elongation at break and waterproof capability, and meanwhile, the degradable plastic is naturally degradable for a short time, and can be used for preparing disposable plastic bags, packaging boxes and the like.
The beneficial effects are that:
1. The invention successfully separates out the biodegradable material with good tensile strength, elongation at break and waterproof performance after adding water after the plant wood fiber solution, the polyethylene glycol with 4000-6000Da and the polyethyleneimine with 30000-50000Da are co-dissolved.
2. The plant wood fiber solution is prepared from plant wood fiber powder, methyl triethylammonium hydroxide, polyethylene glycol with the molecular weight of 500-1500Da and sodium hydroxide solution with the molecular weight of 1mol/L, and can dissolve plant wood fiber, high-molecular-weight polyethylene glycol and polyethyleneimine simultaneously to fully mix the plant wood fiber powder, the high-molecular-weight polyethylene glycol and polyethyleneimine, so that the prepared degradable plastic structure has compact tensile strength, elongation at break and waterproof performance which are effectively improved.
3. The prepared plant wood fiber solution is degradable by a green solvent, and can be added with plant wood fiber powder again for recycling, so that the whole synthesis process is mild in condition and environment-friendly.
Detailed Description
The present invention will be described in detail with reference to examples below:
example 1 preparation of degradable plastics A
Before the degradable plastic is prepared, a plant wood fiber solution is prepared, and the specific method is as follows:
A. The preparation of the plant wood fiber dissolvent comprises the steps of respectively weighing 1.5L of polyethylene glycol with the molecular weight of 1000Da and 4L of methyl triethyl ammonium hydroxide, uniformly mixing and stirring, adding 0.1L of 1mol/L sodium hydroxide solution, continuously stirring for 10min, stirring at a constant temperature of 45 ℃ for 25min, then pouring into a reactor, heating, stirring and refluxing for 1.5h at 90 ℃ to obtain the plant wood fiber dissolvent;
B. The preparation of the plant wood fiber solution comprises the steps of weighing 1.5kg of plant wood fiber powder, adding the plant wood fiber powder into 1L of plant wood fiber dissolvent, stirring and heating to 55 ℃, continuing stirring for 25min, and carrying out suction filtration and separation to obtain the plant wood fiber solution.
Preparation of degradable plastics:
s1, preparing a degradable plastic stock solution, namely weighing 1L of a plant wood fiber solution, adding 1.5g of polyethylene glycol with the molecular weight of 5000Da and 2g of polyethyleneimine with the molecular weight of 40000Da, heating to 70 ℃ while stirring, and stirring at constant temperature for 1.5h to obtain the degradable plastic stock solution;
s2, preparing the degradable plastic, namely cooling the raw material of the degradable plastic to room temperature, adding water to precipitate jelly, filtering and separating to obtain solid after the jelly is not precipitated any more, drying the solid at 55 ℃, and sending the solid into a double-screw extruder to be melted, blended, extruded and granulated at the temperature of 200 ℃ and the screw rotating speed of 50r/min to obtain the degradable plastic.
EXAMPLE 2 preparation of degradable Plastic
Before the degradable plastic is prepared, a plant wood fiber solution is prepared, and the specific method is as follows:
A. The preparation of the plant lignocellulose dissolvent comprises the steps of respectively weighing and uniformly mixing 1L of polyethylene glycol with molecular weight of 500Da and 3L of methyltriethylammonium hydroxide, adding 0.05L of 1mol/L sodium hydroxide solution, continuously stirring for 5min, stirring at constant temperature for 30min at 40 ℃, then pouring into a reactor, heating, stirring and refluxing for 2h at 85 ℃ to obtain the plant lignocellulose dissolvent;
B. The preparation of the plant wood fiber solution comprises the steps of weighing 1kg of plant wood fiber powder, adding the plant wood fiber powder into 0.5L of plant wood fiber dissolvent, heating to 50 ℃ while stirring, continuously stirring for 30min, and carrying out suction filtration and separation to obtain the plant wood fiber solution.
Preparation of degradable plastics:
s1, preparing a degradable plastic stock solution, namely weighing 0.8L of a plant wood fiber solution, adding 1g of polyethylene glycol with the molecular weight of 6000Da and 1g of polyethyleneimine with the molecular weight of 50000Da, heating to 60 ℃ while stirring, and stirring at constant temperature for 2 hours to obtain the degradable plastic stock solution;
S2, preparing the degradable plastic, namely cooling the raw material of the degradable plastic to room temperature, adding water to precipitate jelly, filtering and separating to obtain solid after the jelly is not precipitated any more, drying the solid at 50 ℃, and sending the solid into a double-screw extruder to be melted, blended, extruded and granulated at the temperature of 220 ℃ and the screw rotating speed of 40r/min to obtain the degradable plastic.
EXAMPLE 3 preparation of degradable plastics
Before the degradable plastic is prepared, a plant wood fiber solution is prepared, and the specific method is as follows:
A. The preparation of the plant lignocellulose dissolvent comprises the steps of respectively weighing and uniformly mixing polyethylene glycol 2L with molecular weight of 1500Da and methyl triethyl ammonium hydroxide 5L, adding sodium hydroxide solution 0.15L with 1mol/L, continuously stirring for 15min, stirring at constant temperature for 20min at 50 ℃, then pouring into a reactor, heating, stirring and refluxing for 1h at 95 ℃ to obtain the plant lignocellulose dissolvent;
B. the preparation of the plant wood fiber solution comprises weighing 2kg of plant wood fiber powder, adding into 1.5L of plant wood fiber dissolvent, heating to 50deg.C under stirring, stirring for 30min, and suction filtering to obtain plant wood fiber solution.
Preparation of degradable plastics:
s1, preparing a degradable plastic stock solution, namely weighing 0.8L of a plant wood fiber solution, adding 2g of polyethylene glycol with the molecular weight of 4000Da and 3g of polyethyleneimine with the molecular weight of 30000Da, heating to 60 ℃ while stirring, and stirring at constant temperature for 2 hours to obtain the degradable plastic stock solution;
S2, preparing the degradable plastic, namely cooling the raw material of the degradable plastic to room temperature, adding water to precipitate jelly, filtering and separating to obtain solid after the jelly is not precipitated any more, drying the solid at 50 ℃, and sending the solid into a double-screw extruder to be melted, blended, extruded and granulated at the temperature of 220 ℃ and the screw rotating speed of 40r/min to obtain the degradable plastic.
Comparative example 1:
This comparative example is in contrast to example 1, which differs in that 1mol/L sodium hydroxide solution is not added in step A for preparing the plant wood fiber solution during the preparation of the degradable plastic, and the rest steps are the same, and the preparation of the plant wood fiber solution is specifically as follows:
A. The preparation of the plant wood fiber dissolvent comprises the steps of respectively weighing and uniformly mixing polyethylene glycol 2L with molecular weight of 1500Da and methyl triethyl ammonium hydroxide 5L, and stirring at constant temperature for 20min at 50 ℃ to obtain the plant wood fiber dissolvent.
Comparative example 2:
this comparative example is in contrast to example 1, which differs in that 1000Da polyethylene glycol is not added in step A of preparing the plant wood fiber solution during the preparation of the degradable plastic, and the rest steps are the same, and the preparation of the plant wood fiber solution is specifically as follows:
A. The preparation of the plant wood fiber dissolvent comprises the steps of weighing and uniformly stirring 5.5L of methyltriethylammonium hydroxide, adding 0.1L of 1mol/L sodium hydroxide solution, continuously stirring for 10min, stirring at a constant temperature of 45 ℃ for 25min, then pouring into a reactor, heating, stirring and refluxing for 1.5h at 90 ℃ to obtain the dissolvent.
The prepared dissolving agent can not dissolve plant wood fibers, so that the subsequent steps can not be performed, and the degradable plastic can not be prepared.
Comparative example 3:
This comparative example is in contrast to example 1, which differs in that in the preparation of the degradable plastic, no methyltriethylammonium hydroxide is added in the preparation step A of the plant lignocellulosic solution, and the other steps are the same, and the preparation of the plant lignocellulosic solution is specifically as follows:
A. The preparation of the plant wood fiber dissolvent comprises weighing 5.5L of polyethylene glycol with molecular weight of 1000Da, adding 0.1L of 1mol/L sodium hydroxide solution, stirring for 10min, stirring at constant temperature for 25min at 45 ℃, pouring into a reactor, heating, stirring and refluxing for 1.5h at 90 ℃ to obtain the plant wood fiber dissolvent;
The prepared dissolving agent can not dissolve plant wood fibers, so that the subsequent steps can not be performed, and the degradable plastic can not be prepared.
Comparative example 4:
this comparative example is in contrast to example 1, which differs in that step S2 is a degradable plastic stock solution prepared without addition of polyethyleneimine, and in that the remaining steps are the same, and step S2 is a degradable plastic stock solution prepared specifically as follows:
s1, preparing a degradable plastic stock solution, namely weighing 1L of a plant wood fiber solution, adding 3.5g of polyethylene glycol with the molecular weight of 5000Da, heating to 70 ℃ while stirring, and stirring at constant temperature for 1.5h to obtain the degradable plastic stock solution;
comparative example 5:
The comparison example is compared with the example 1, and the difference is that polyethylene glycol is not added in the preparation of the step S2 degradable plastic stock solution, and the rest steps are the same, and the preparation of the step S2 degradable plastic stock solution is specifically as follows:
S2, preparing a degradable plastic stock solution, namely weighing 1L of plant wood fiber solution, adding 3.5g of 40000Da polyethyleneimine, heating to 70 ℃ while stirring, and stirring at constant temperature for 1.5h to obtain the degradable plastic stock solution;
comparative example 6:
this comparative example is in contrast to example 1, which differs in that the degradable plastic is directly melt drawn after mixing with plant lignocellulosic powder, polyethylene glycol of 5000Da and polyethylenimine of 40000Da, the degradable plastic being prepared in particular as follows:
1.5kg of plant wood fiber powder, 1.5g of polyethylene glycol with the weight of 5000Da and 2g of polyethyleneimine with the weight of 40000Da are respectively weighed, and are evenly mixed, and then are sent into a double-screw extruder to be melted, blended, extruded and granulated at the temperature of 200 ℃ and the screw rotating speed of 50r/min, so as to obtain the degradable plastic.
1. Degradable plastic mechanical property test
The degradable plastics prepared in example 1, comparative example 1 and comparative examples 4 to 6 were injection molded according to a standard type I sample mold, five groups of each sample were tested, tensile strength, flexural strength and elongation at break were recorded, and then the average value was calculated, with the results shown in table 1, referring to GB/T1040.1-2018, determination of tensile properties of plastics;
TABLE 1
| Tensile strength/(Mpa) | Elongation at break% | |
| Example 1 | 59.31 | 251.31 |
| Comparative example 1 | 41.52 | 177.45 |
| Comparative example 4 | 32.16 | 112.34 |
| Comparative example 5 | 33.61 | 124.59 |
| Comparative example 6 | 50.23 | 204.67 |
2. Degradable plastic waterproof ability test
The degradable plastics prepared in example 1, comparative example 1 and comparative examples 4-6 were injection molded according to a standard type I sample mold to obtain samples, the water resistance was reacted by the water absorption of the plastics, the lower the water absorption was, the better the water resistance was, the water absorption was measured by drying the samples in a 50 ℃ oven for 24 hours, the recording mass was m 1, then placing the samples at 25 ℃ and humidity of 50%,65% and 80% for 24 hours, respectively, the recording mass was m 2, the water absorption of the samples was calculated according to the following formula, and the measurement results are shown in table 2 below:
water absorption= ((m 2-m1)/m1) ×100%
TABLE 2
3. Degradable plastic degradation capability test
The degradable plastics prepared in example 1, comparative example 1 and comparative examples 4-6 were injection molded according to a standard type I specimen mold to obtain samples, and degradation performance tests were performed according to GB/T20197-2006, the results of which are shown in Table 3.
TABLE 3 Table 3
Data analysis:
As can be seen from the data in tables 1 to 3, the degradable plastic prepared from the plant wood fiber in the protection scope of the invention has good tensile strength and elongation at break, the tensile strength obtained by testing can reach 59.31Mpa, the elongation at break can reach 251.31%, the water resistance is good, the water absorption rates under the conditions of 50%, 65% and 80% are respectively 0.14%, 0.21% and 0.29%, the degradation capability is strong, and the weight loss rates under the conditions of 30 days, 90 days and 180 days of soil burying are respectively 20.00%, 45.90% and 74.40%.
As can be seen from the data of examples 1, comparative examples 1 and comparative examples 4 to 5 in comparative tables 1 to 3, the plant wood fiber solution prepared without adding 1mol/L sodium hydroxide solution in the preparation of the plant wood fiber solution is used for the preparation of the degradable plastics, and the polyethylene imine of 30000-50000Da and polyethylene glycol of 4000-6000Da are not added in the preparation process of the degradable plastics in comparative examples 4 to 5, so that the tensile strength, elongation at break and water resistance are reduced, and the application range of the degradable plastics is narrowed. As can be seen from the data of examples 1 and 6 in tables 1 to 3, the tensile strength, elongation at break and water resistance of the plastics obtained by melt drawing after mixing plant wood fiber powder, polyethylene glycol of 5000Da and polyethyleneimine of 40000Da in comparative example 6 are improved to some extent, but the degradation performance is extremely poor and is not a degradable plastic.
The above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications and equivalents may be made thereto without departing from the spirit and scope of the technical solution of the present invention, which is intended to be covered by the scope of the claims of the present invention. The technology, shape, and construction parts of the present invention, which are not described in detail, are known in the art.
Claims (4)
1. The degradable plastic prepared from plant wood fiber is characterized in that the raw materials of the degradable plastic comprise plant wood fiber solution, 4000-6000 Da polyethylene glycol and 30000-50000 Da polyethyleneimine;
The degradable plastic comprises raw materials of plant wood fiber solution, 4000-6000 Da polyethylene glycol and 30000-50000 Da polyethylene imine in a volume-mass ratio of (0.8-1.2) L (1-2) g (1-3) g;
The preparation method of the degradable plastic comprises the following steps:
S1, preparing a degradable plastic stock solution, namely adding 4000-6000 Da of polyethylene glycol and 30000-50000 Da of polyethyleneimine into a plant wood fiber solution, heating while stirring, and stirring at constant temperature to obtain the degradable plastic stock solution;
S2, preparing the degradable plastic, namely cooling the original liquid of the degradable plastic to room temperature, adding water to precipitate jelly, filtering and separating to obtain solid after the jelly is not precipitated any more, drying the solid, and sending the solid into a double-screw extruder to melt, blend, extrude and granulate to obtain the degradable plastic;
The plant wood fiber solution comprises the following raw materials of plant wood fiber powder, methyl triethyl ammonium hydroxide, 500-1500Da polyethylene glycol and 1mol/L sodium hydroxide solution, wherein the raw materials of the plant wood fiber solution comprise the methyl triethyl ammonium hydroxide, 500-1500Da polyethylene glycol and 1mol/L sodium hydroxide solution in a volume ratio of (3-5): 1-2): 0.05-0.15;
the preparation method of the plant wood fiber solution comprises the following steps:
A. The preparation method of plant wood fiber dissolvent comprises mixing polyethylene glycol 500-1500 Da and methyl triethyl ammonium hydroxide, stirring, adding 1mol/L sodium hydroxide solution, stirring for 5-15min, stirring at constant temperature of 40-50deg.C for 20-30min, pouring into a reactor, and heating under reflux to obtain plant wood fiber dissolvent;
B. The plant wood fiber solution is prepared by adding plant wood fiber powder into plant wood fiber dissolvent, heating to 50-60deg.C under stirring, stirring for 20-30min, and vacuum filtering.
2. The degradable plastic made from plant wood fiber according to claim 1, wherein in the step S1, the constant temperature stirring is performed at 60-80 ℃ for 1-2 hours.
3. The degradable plastic made from plant wood fiber according to claim 2, wherein the heating reflux stirring time in the step a is 1-2h, and the temperature is 85-95 ℃.
4. A degradable plastic made from plant wood fiber according to claim 3, wherein the mass to volume ratio of plant wood fiber powder and plant wood fiber dissolving agent in step B is (1-2) kg (3-5) L.
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| CN102076784A (en) * | 2008-05-08 | 2011-05-25 | 3M创新有限公司 | Surface-modified nanoparticles |
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| WO2004099288A1 (en) * | 2003-05-09 | 2004-11-18 | Carlsberg A/S | Polyethyleneimine polymers |
| EP2564931B1 (en) * | 2005-03-24 | 2014-08-06 | Xyleco, Inc. | Methods of making fibrous materials |
| WO2008117593A1 (en) * | 2007-03-26 | 2008-10-02 | Jsr Corporation | Aqueous dispersion for chemical mechanical polishing and chemical mechanical polishing method for semiconductor device |
| US8212087B2 (en) * | 2008-04-30 | 2012-07-03 | Xyleco, Inc. | Processing biomass |
| KR102571874B1 (en) * | 2015-09-29 | 2023-08-28 | 미쯔비시 케미컬 주식회사 | Polycarbonate resin composition, and molded product thereof |
| CN105219004B (en) * | 2015-11-05 | 2017-12-29 | 广州景盛纸制品有限公司 | A kind of degradable plant fibre paper and preparation method thereof |
| CN111171329A (en) * | 2020-01-21 | 2020-05-19 | 翁秋梅 | Plastic dilatancy polymer and method for realizing dilatancy thereof |
| CN113605094B (en) * | 2021-08-28 | 2023-04-28 | 苏州鱼得水电气科技有限公司 | Antibacterial degradable composite fiber and preparation method thereof |
| CN114316542B (en) * | 2021-12-28 | 2022-07-19 | 青岛中宝塑业有限公司 | High-strength biodegradable plastic and preparation method thereof |
| CN114479090B (en) * | 2022-02-16 | 2023-04-14 | 东南大学 | A kind of fluorinated polyethylene glycol-polyethyleneimine and its preparation method and application |
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| CN101203315A (en) * | 2005-03-24 | 2008-06-18 | 希乐克公司 | Fibrous Materials and Composites |
| CN102076784A (en) * | 2008-05-08 | 2011-05-25 | 3M创新有限公司 | Surface-modified nanoparticles |
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