CN114957773A - Preparation method of light high-strength polylactic acid biomass foamed particles - Google Patents
Preparation method of light high-strength polylactic acid biomass foamed particles Download PDFInfo
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- CN114957773A CN114957773A CN202210666548.4A CN202210666548A CN114957773A CN 114957773 A CN114957773 A CN 114957773A CN 202210666548 A CN202210666548 A CN 202210666548A CN 114957773 A CN114957773 A CN 114957773A
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- polylactic acid
- biomass
- particles
- preparation
- foaming agent
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- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 133
- 239000004626 polylactic acid Substances 0.000 title claims abstract description 133
- 239000002028 Biomass Substances 0.000 title claims abstract description 90
- 239000002245 particle Substances 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000004088 foaming agent Substances 0.000 claims abstract description 32
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 14
- 238000005191 phase separation Methods 0.000 claims abstract description 13
- 239000011148 porous material Substances 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 238000013329 compounding Methods 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 239000010902 straw Substances 0.000 claims description 18
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 9
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 230000032683 aging Effects 0.000 claims description 8
- JVTAAEKCZFNVCJ-UWTATZPHSA-N D-lactic acid Chemical compound C[C@@H](O)C(O)=O JVTAAEKCZFNVCJ-UWTATZPHSA-N 0.000 claims description 6
- 239000001569 carbon dioxide Substances 0.000 claims description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 6
- 229940022769 d- lactic acid Drugs 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 239000004604 Blowing Agent Substances 0.000 claims description 5
- 229960000448 lactic acid Drugs 0.000 claims description 4
- 238000003801 milling Methods 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000007790 solid phase Substances 0.000 claims description 4
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims description 3
- 235000017491 Bambusa tulda Nutrition 0.000 claims description 3
- 241001330002 Bambuseae Species 0.000 claims description 3
- 229930182843 D-Lactic acid Natural products 0.000 claims description 3
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims description 3
- 229920002472 Starch Polymers 0.000 claims description 3
- 239000011425 bamboo Substances 0.000 claims description 3
- 239000001273 butane Substances 0.000 claims description 3
- 239000001913 cellulose Substances 0.000 claims description 3
- 229920002678 cellulose Polymers 0.000 claims description 3
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 3
- 229920005610 lignin Polymers 0.000 claims description 3
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 3
- 229920001432 poly(L-lactide) Polymers 0.000 claims description 3
- 239000008107 starch Substances 0.000 claims description 3
- 235000019698 starch Nutrition 0.000 claims description 3
- 239000002023 wood Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 235000013312 flour Nutrition 0.000 claims 3
- KYKAJFCTULSVSH-UHFFFAOYSA-N chloro(fluoro)methane Chemical compound F[C]Cl KYKAJFCTULSVSH-UHFFFAOYSA-N 0.000 claims 1
- 238000005187 foaming Methods 0.000 abstract description 24
- 239000000463 material Substances 0.000 abstract description 13
- 241001391944 Commicarpus scandens Species 0.000 abstract description 4
- 238000002425 crystallisation Methods 0.000 abstract description 4
- 230000008025 crystallization Effects 0.000 abstract description 4
- 239000000843 powder Substances 0.000 description 21
- 239000005022 packaging material Substances 0.000 description 6
- 239000003963 antioxidant agent Substances 0.000 description 4
- 239000000314 lubricant Substances 0.000 description 4
- 230000003078 antioxidant effect Effects 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 239000006260 foam Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 239000012744 reinforcing agent Substances 0.000 description 3
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- LMYMBVLOZKGWBR-UHFFFAOYSA-N [C].[F].[Cl] Chemical class [C].[F].[Cl] LMYMBVLOZKGWBR-UHFFFAOYSA-N 0.000 description 2
- 229940088990 ammonium stearate Drugs 0.000 description 2
- JPNZKPRONVOMLL-UHFFFAOYSA-N azane;octadecanoic acid Chemical compound [NH4+].CCCCCCCCCCCCCCCCCC([O-])=O JPNZKPRONVOMLL-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920000609 methyl cellulose Polymers 0.000 description 2
- 239000001923 methylcellulose Substances 0.000 description 2
- 235000010981 methylcellulose Nutrition 0.000 description 2
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000010944 ethyl methyl cellulose Nutrition 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000006261 foam material Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 229920003087 methylethyl cellulose Polymers 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 description 1
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229940037312 stearamide Drugs 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/16—Making expandable particles
- C08J9/18—Making expandable particles by impregnating polymer particles with the blowing agent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/122—Hydrogen, oxygen, CO2, nitrogen or noble gases
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/22—After-treatment of expandable particles; Forming foamed products
- C08J9/228—Forming foamed products
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/06—CO2, N2 or noble gases
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2497/00—Characterised by the use of lignin-containing materials
- C08J2497/02—Lignocellulosic material, e.g. wood, straw or bagasse
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
The invention relates to the technical field of polylactic acid materials, in particular to a preparation method of light high-strength polylactic acid biomass foaming particles, which comprises the following steps: (1) blending and compounding polylactic acid and biomass; (2) slowly diffusing and dissolving a foaming agent into the polylactic acid/biomass master batch to obtain expandable polylactic acid/biomass particles; (3) quickly releasing the pressure to normal pressure or quickly raising the temperature to enable the polylactic acid/biomass/foaming agent to be subjected to quick phase separation, and forming air holes in the polylactic acid/biomass particles; (4) curing the foamed polylactic acid/biomass particles to further grow and stabilize the formed pores to obtain the foamed polylactic acid/biomass particles; the invention overcomes the problem that the cells are easy to break due to low melt strength and slow crystallization rate of polylactic acid in the traditional foaming means, and forms a polylactic acid biomass foaming particle product with uniform cells and easily adjustable cell size and foaming ratio.
Description
Technical Field
The invention relates to the technical field of polylactic acid materials, and particularly relates to a preparation method of light high-strength polylactic acid biomass foaming particles.
Background
At present, most plastic packaging materials, such as plastic bags or lunch boxes, are continuously produced and become wastes after being used, the wastes are extremely difficult to decompose under natural conditions, and if a landfill or incineration mode is adopted, the land or air is extremely easy to be polluted, and the living environment of human beings is seriously harmed.
In recent years, in order to fundamentally solve the problem of harmless treatment of plastic packaging materials, researchers have continuously proposed a series of degradable composite materials, wherein the most important is polylactic acid composite material. Polylactic acid is a novel biodegradable material, can be completely degraded by microorganisms in the nature after being used, finally generates carbon dioxide and water, does not pollute the environment, is very beneficial to environmental protection, and is a well-known environment-friendly material. However, in the prior art, the cost of the synthetic polylactic acid is high, the yield is low, and the market demand is difficult to meet, so that a new substance is needed to be found to completely or partially replace the polylactic acid, so as to reduce the production cost.
In addition, in some special scenes, the packaging material made of the polylactic acid is required to have better heat insulation property and impact resistance, and at the moment, the packaging material made of the polylactic acid is usually subjected to foaming treatment, so that the foamed polylactic acid material not only meets the use requirements of the special scenes, but also reduces the use amount of the polylactic acid, and is favorable for reducing the cost; however, the low melt strength of polylactic acid is disadvantageous to the process (such as foaming treatment) involving melt elongation/stretching, and the molecular chain of polylactic acid is semi-rigid, the number of branches is small, the molecular weight distribution is wide, and the melt strength is low and the crystallization rate is slow, so that the cells are easy to break after being prepared into a foam material, and the mechanical properties are poor.
Disclosure of Invention
The invention aims to overcome the defects in the prior art, and provides a preparation method of light high-strength polylactic acid biomass foamed particles, which can reduce the preparation cost of polylactic acid packaging materials and improve the strength of the packaging materials based on polylactic acid foaming so as to meet the use requirements.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of light high-strength polylactic acid biomass foaming particles comprises the following steps:
(1) blending and compounding: blending and compounding polylactic acid/biomass by utilizing solid-phase mechanochemical milling to improve the compatibility of the polylactic acid/biomass and extruding and granulating to prepare polylactic acid/biomass master batches;
(2) dissolving a foaming agent: introducing a foaming agent into the reaction kettle filled with the polylactic acid/biomass master batch, adjusting to a certain temperature and pressure, and slowly diffusing and dissolving the foaming agent into the polylactic acid/biomass master batch to obtain expandable polylactic acid/biomass particles;
(3) phase separation: quickly releasing the pressure to normal pressure or quickly raising the temperature to enable the polylactic acid/biomass/foaming agent to be subjected to quick phase separation, and forming air holes in the polylactic acid/biomass particles;
(4) curing: and (3) carrying out aging treatment on the foamed polylactic acid/biomass particles to further grow and stabilize the formed pores, thereby obtaining the polylactic acid/biomass foamed particles with different pore sizes.
In a further technical scheme, the polylactic acid is selected from one or the combination of poly-L-lactic acid, poly-D-lactic acid and poly-DL-lactic acid;
preferably, the weight average molecular weight of the polylactic acid is 10-30 ten thousand;
preferably, the polylactic acid has a content of D-lactic acid of 1.2-1.6%.
In a further technical scheme, the biomass is selected from at least one of starch, cellulose, lignin, wood powder, bamboo powder and straw powder.
In a further technical scheme, the polylactic acid/biomass master batch is prepared from the following raw materials in parts by mass: 60-90 parts of polylactic acid and 10-40 parts of biomass.
In a further aspect, the blowing agent is a physical blowing agent.
In a further technical scheme, the physical foaming agent is selected from any one of carbon dioxide, nitrogen, butane, pentane, hexane or fluorine chlorine carbon compounds.
In a further technical scheme, in the step (2), after the foaming agent is introduced into the reaction kettle, the temperature of the reaction kettle is adjusted to 80-120 ℃, and the pressure is adjusted to 6-20 MPa.
In a further technical scheme, in the step (3), the temperature is rapidly increased to 100-160 ℃, and the polylactic acid/biomass/foaming agent is subjected to phase separation.
In a further technical scheme, the curing treatment conditions at least comprise that the curing temperature is 60-100 ℃, and the curing time is 1-5 h.
The invention also provides polylactic acid biomass foamed particles prepared based on the method, and the size of the foam holes of the polylactic acid biomass foamed particles is 10-500 mu m.
Compared with the prior art, the invention has the following technical effects:
the preparation method of the polylactic acid biomass foamed particles provided by the invention overcomes the problem that the cells are easy to break due to low melt strength and slow crystallization rate of polylactic acid in the traditional foaming means, and finally forms a polylactic acid biomass foamed particle product with uniform cells and easily adjustable cell size and foaming ratio.
Detailed Description
In order to make the technical means, the creation features, the achievement purposes and the effects of the invention easy to understand, the invention is further clarified with the specific embodiments.
As mentioned above, the invention provides a preparation method of light high-strength polylactic acid biomass foamed particles, which comprises the following steps:
(1) blending and compounding: blending and compounding polylactic acid/biomass by utilizing solid-phase mechanochemical milling to improve the compatibility of the polylactic acid/biomass and extruding and granulating to prepare polylactic acid/biomass master batches;
(2) dissolving a foaming agent: introducing a foaming agent into the reaction kettle filled with the polylactic acid/biomass master batch, adjusting to a certain temperature and pressure, and slowly diffusing and dissolving the foaming agent into the polylactic acid/biomass master batch to obtain expandable polylactic acid/biomass particles;
(3) phase separation: quickly releasing the pressure to normal pressure or quickly raising the temperature to enable the polylactic acid/biomass/foaming agent to be subjected to quick phase separation, and forming air holes in the polylactic acid/biomass particles;
(4) curing: and (3) carrying out aging treatment on the foamed polylactic acid/biomass particles to further grow and stabilize the formed pores, thereby obtaining the polylactic acid/biomass foamed particles with different pore sizes.
Based on the preparation method provided by the invention, the biomass and the polylactic acid are blended and compounded to be uniformly dispersed in the polylactic acid particles, so that the mechanical property, the heat resistance and the degradation property of the foamed polylactic acid particles are effectively improved; further, a foaming agent is introduced into a reaction kettle containing polylactic acid/biomass master batches, the foaming agent is diffused and dissolved into the polylactic acid/biomass master batches under certain temperature and pressure conditions to obtain expandable polylactic acid/biomass particles, then the polylactic acid/biomass/foaming agent is subjected to phase separation by quickly releasing pressure or raising the system temperature to form a pore structure inside the polylactic acid/biomass particles, and finally the cell structure and the foaming rate of the polylactic acid biomass foamed particles are regulated and controlled in a curing stage to obtain a finished polylactic acid biomass foamed particle product.
The preparation method of the polylactic acid biomass foamed particles provided by the invention overcomes the problem that the cells are easy to break due to low melt strength and slow crystallization rate of polylactic acid in the traditional foaming means, and finally forms a polylactic acid biomass foamed particle product with uniform cells and easily adjustable cell size and foaming ratio.
According to the preparation method provided by the invention, the polylactic acid can be selected from one or the combination of poly-L-lactic acid, poly-D-lactic acid and poly-DL-lactic acid; further, in the invention, the weight average molecular weight of the polylactic acid is 10-30 ten thousand; further, the content of the D-lactic acid in the polylactic acid is 1.2-1.6%.
In the invention, the biomass is selected from at least one of starch, cellulose, lignin, wood powder, bamboo powder and straw powder.
According to the preparation method provided by the invention, the polylactic acid/biomass master batch is prepared from the following raw materials in parts by mass: 60-90 parts of polylactic acid and 10-40 parts of biomass.
According to the method provided by the invention, the foaming agent is a physical foaming agent, and further, the physical foaming agent is any one selected from carbon dioxide, nitrogen, butane, pentane, hexane or a fluorine-chlorine-carbon compound.
In the invention, after a foaming agent is introduced into a reaction kettle, the temperature of the reaction kettle is adjusted to 80-120 ℃, and the pressure is adjusted to 6-20 MPa. Under the conditions of temperature and pressure, the foaming agent is ensured to be stably diffused and dissolved into the polylactic acid/biomass master batch, and the expandable polylactic acid/biomass particles are obtained.
According to the preparation method provided by the invention, the phase separation of the polylactic acid/biomass and the foaming agent is realized by quickly releasing the pressure of the reaction kettle or quickly raising the temperature of the reaction kettle, so that an air hole structure is formed inside the polylactic acid/biomass particles. Specifically, when the means of quickly raising the temperature of the reaction kettle is adopted, the temperature of the reaction kettle is quickly raised to 100-160 ℃, and in the temperature range, polylactic acid particles are softened, so that the polylactic acid/biomass/foaming agent are separated.
In the invention, the purpose of the aging treatment is to regulate and stabilize the pore structure formed in the phase separation stage, the conditions of the aging treatment can be selected according to the specific required cell size and expansion ratio of polylactic acid/biomass particles, and specifically, the conditions of the aging treatment at least comprise that the aging temperature is 60-100 ℃ and the aging time is 1-5 h.
The invention also provides the light high-strength polylactic acid biomass foamed particles prepared based on the preparation method, and the size of the foam pores of the polylactic acid biomass foamed particles is 10-500 mu m.
The invention also provides application of the light high-strength polylactic acid biomass foaming particles, and specifically comprises the steps of uniformly mixing the polylactic acid biomass foaming particles and an auxiliary agent, carrying out compression molding under the conditions of temperature of 170-185 ℃ and pressure of 10-15MPa for 5-10min, then carrying out rapid pressure relief, naturally cooling to room temperature, and then carrying out demolding to obtain the polylactic acid biomass foaming material.
In the invention, the performance of the polylactic acid biomass foaming material is improved or enhanced by adding auxiliary agents, wherein the auxiliary agents include but are not limited to lubricants, antioxidants and reinforcing agents; more specifically, the lubricant comprises one of, but is not limited to, oleic acid amide, ammonium stearate, ethylene bis stearamide, and alkylene bis stearamide; the antioxidant includes but is not limited to one of pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxy) propionate ], o-diphenol or hydroquinone; the reinforcing agent includes, but is not limited to, one of methyl cellulose or ethyl cellulose.
In a specific embodiment of the invention, the polylactic acid biomass foaming material is prepared from the following raw materials in parts by weight: 80-95 parts of polylactic acid biomass foaming particles, 0.2-1.0 part of lubricant, 0.3-1.0 part of antioxidant and 0.5-1.5 parts of reinforcing agent.
The following provides a further description of the preparation method of the light-weight high-strength polylactic acid biomass foamed particles provided by the invention through specific examples.
Example 1
The embodiment provides a preparation method of polylactic acid biomass foamed particles, which comprises the following steps:
(1) blending and compounding: blending and compounding the polylactic acid/straw powder by utilizing solid-phase force chemical milling to improve the compatibility of the polylactic acid/straw powder and the straw powder, and extruding and granulating to prepare polylactic acid/straw powder master batches;
the poly (A-CO-Lactic acid available under the tradename 4032D from NatureWorks, USA, and has a weight average molecular weight of 2.1 × 10 5 g/mol, density 1.25g/cm 3 ；
The polylactic acid/straw powder master batch is prepared from the following raw materials in parts by weight: 85 parts of polylactic acid and 15 parts of straw powder;
(2) dissolving a foaming agent: introducing foaming agent carbon dioxide into the reaction kettle filled with the polylactic acid/straw powder master batch, adjusting the temperature of the reaction kettle to 90 ℃, keeping the pressure at 15MPa for 2 hours, and slowly diffusing and dissolving the carbon dioxide into the polylactic acid/straw powder master batch to obtain expandable polylactic acid/straw powder particles;
(3) phase separation: rapidly releasing the pressure of the reaction kettle to normal pressure (rapidly reducing the pressure in the reaction kettle to half of the pressure in the reaction kettle within 0.1 s), rapidly separating the polylactic acid/straw powder/foaming agent, and forming air holes in the polylactic acid/straw powder particles;
(4) curing: and (3) carrying out curing treatment on the foamed polylactic acid/straw powder particles, specifically curing treatment at the temperature of 80 ℃ for 3h to further grow and stabilize the formed pores, thereby obtaining the foamed polylactic acid/straw powder particles.
Performing brittle fracture on a sample by using liquid nitrogen to prepare a sample wafer, spraying gold on the fracture surface, observing the fracture morphology by using an SEM (scanning electron microscope), and processing an electron microscope scanning picture by using a graphic analysis software Image-pro, wherein the counted number of the pores is more than 100. Cell size is the average diameter of the cells of the foamed sample and is calculated directly by the software.
The polylactic acid foamed particles prepared in example 1 were sampled and tested to have an average cell size of 158.6. mu.m and a density of 0.35g/cm 3 。
Preparation example 1
The polylactic acid straw powder foamed particles prepared in example 1 were used as test materials.
Samples were taken at the following formula: 88 parts of polylactic acid straw powder foaming particles, 0.5 part of lubricant (ammonium stearate), 10100.7 parts of antioxidant and 1.2 parts of methyl cellulose;
the raw material components are uniformly mixed, put into a mould, molded under the conditions of 178 ℃ and 15MPa, and subjected to pressure maintaining for 10min, then quickly decompressed, naturally cooled to room temperature, and demoulded to obtain the polylactic acid foaming material.
The polylactic acid foamed material obtained in preparation example 1 was tested according to GB/T9641-1988 (rigid foam tensile Property test method) using a standard sample having a length of 150mm and a width of 25mm at a tensile speed of 5mm/min, and subjected to a tensile test using an Instron's 3400 series Universal Material test System.
The polylactic acid biomass foaming material prepared based on the preparation example 1 is tested to have the tensile strength of 25.8 MPa.
The foregoing shows and describes the general principles, principal features, and aspects of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (10)
1. The preparation method of the light high-strength polylactic acid biomass foamed particles is characterized by comprising the following steps:
(1) blending and compounding: blending and compounding polylactic acid/biomass by utilizing solid-phase mechanochemical milling to improve the compatibility of the polylactic acid/biomass and extruding and granulating to prepare polylactic acid/biomass master batches;
(2) dissolving a foaming agent: introducing a foaming agent into the reaction kettle filled with the polylactic acid/biomass master batch, adjusting to a certain temperature and pressure, and slowly diffusing and dissolving the foaming agent into the polylactic acid/biomass master batch to obtain expandable polylactic acid/biomass particles;
(3) phase separation: quickly releasing the pressure to normal pressure or quickly raising the temperature to enable the polylactic acid/biomass/foaming agent to be subjected to quick phase separation, and forming air holes in the polylactic acid/biomass particles;
(4) curing: and (3) carrying out aging treatment on the foamed polylactic acid/biomass particles to further grow and stabilize the formed pores, thereby obtaining the polylactic acid/biomass foamed particles with different pore sizes.
2. The method according to claim 1, wherein the polylactic acid is selected from poly-L-lactic acid, poly-D-lactic acid, poly-DL-lactic acid, or a combination thereof;
preferably, the weight average molecular weight of the polylactic acid is 10-30 ten thousand;
preferably, the polylactic acid has a content of D-lactic acid of 1.2-1.6%.
3. The method according to claim 1, wherein the biomass is at least one selected from the group consisting of starch, cellulose, lignin, wood flour, bamboo flour, and straw flour.
4. The preparation method of claim 1, wherein the polylactic acid/biomass master batch is prepared from the following raw materials in parts by mass: 60-90 parts of polylactic acid and 10-40 parts of biomass.
5. The production method according to claim 1, wherein the blowing agent is a physical blowing agent.
6. The method of claim 5, wherein the physical blowing agent is selected from any one of carbon dioxide, nitrogen, butane, pentane, hexane, and chlorofluorocarbon.
7. The preparation method according to claim 1, wherein in the step (2), after the foaming agent is introduced into the reaction kettle, the temperature of the reaction kettle is adjusted to 80-120 ℃ and the pressure is adjusted to 6-20 MPa.
8. The preparation method according to claim 1, wherein in the step (3), the temperature is rapidly raised to 100-160 ℃, and the polylactic acid/biomass/foaming agent is subjected to phase separation.
9. The preparation method according to claim 1, wherein the curing treatment is carried out under conditions at least including a curing temperature of 60-100 ℃ and a curing time of 1-5 hours.
10. The polylactic acid biomass foamed particles prepared by the preparation method according to any one of claims 1 to 9, wherein the cell size of the polylactic acid biomass foamed particles is 10-500 μm.
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