CN114957940A - Preparation method and application of polylactic acid melt-blown material - Google Patents
Preparation method and application of polylactic acid melt-blown material Download PDFInfo
- Publication number
- CN114957940A CN114957940A CN202210426301.5A CN202210426301A CN114957940A CN 114957940 A CN114957940 A CN 114957940A CN 202210426301 A CN202210426301 A CN 202210426301A CN 114957940 A CN114957940 A CN 114957940A
- Authority
- CN
- China
- Prior art keywords
- polylactic acid
- melt
- blown material
- blown
- cellulose nanocrystals
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000004626 polylactic acid Substances 0.000 title claims abstract description 113
- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 111
- 239000000463 material Substances 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 6
- 239000001913 cellulose Substances 0.000 claims abstract description 89
- 229920002678 cellulose Polymers 0.000 claims abstract description 89
- 239000002159 nanocrystal Substances 0.000 claims abstract description 73
- 238000002156 mixing Methods 0.000 claims abstract description 41
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 32
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 27
- 238000004260 weight control Methods 0.000 claims abstract description 27
- 239000004970 Chain extender Substances 0.000 claims abstract description 25
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 24
- 239000000314 lubricant Substances 0.000 claims abstract description 24
- 239000002667 nucleating agent Substances 0.000 claims abstract description 24
- 239000004744 fabric Substances 0.000 claims abstract description 22
- 239000012745 toughening agent Substances 0.000 claims abstract description 22
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 48
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 24
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 24
- 229910052786 argon Inorganic materials 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 24
- 238000005406 washing Methods 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 23
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- 239000007864 aqueous solution Substances 0.000 claims description 11
- -1 polybutylene adipate-terephthalate Polymers 0.000 claims description 10
- 238000005303 weighing Methods 0.000 claims description 10
- 238000002844 melting Methods 0.000 claims description 9
- 230000008018 melting Effects 0.000 claims description 9
- MYMSJFSOOQERIO-UHFFFAOYSA-N 1-bromodecane Chemical compound CCCCCCCCCCBr MYMSJFSOOQERIO-UHFFFAOYSA-N 0.000 claims description 8
- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 claims description 8
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 5
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 4
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 4
- 239000000194 fatty acid Substances 0.000 claims description 4
- 229930195729 fatty acid Natural products 0.000 claims description 4
- 150000004665 fatty acids Chemical class 0.000 claims description 4
- 229920001610 polycaprolactone Polymers 0.000 claims description 4
- 239000004632 polycaprolactone Substances 0.000 claims description 4
- 239000004593 Epoxy Chemical class 0.000 claims description 3
- 239000000155 melt Substances 0.000 claims description 3
- 239000004629 polybutylene adipate terephthalate Substances 0.000 claims description 3
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- QLZHNIAADXEJJP-UHFFFAOYSA-N Phenylphosphonic acid Chemical compound OP(O)(=O)C1=CC=CC=C1 QLZHNIAADXEJJP-UHFFFAOYSA-N 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 150000003961 organosilicon compounds Chemical class 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 2
- 239000000344 soap Substances 0.000 claims description 2
- 239000000600 sorbitol Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 150000007970 thio esters Chemical class 0.000 claims description 2
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 9
- 230000015556 catabolic process Effects 0.000 abstract description 3
- 238000006731 degradation reaction Methods 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000006065 biodegradation reaction Methods 0.000 abstract 1
- 238000001914 filtration Methods 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- YOCIJWAHRAJQFT-UHFFFAOYSA-N 2-bromo-2-methylpropanoyl bromide Chemical compound CC(C)(Br)C(Br)=O YOCIJWAHRAJQFT-UHFFFAOYSA-N 0.000 description 6
- UZBRNILSUGWULW-UHFFFAOYSA-N 3,8-dioxabicyclo[8.2.2]tetradeca-1(12),10,13-triene-2,9-dione;hexanedioic acid Chemical compound OC(=O)CCCCC(O)=O.O=C1OCCCCOC(=O)C2=CC=C1C=C2 UZBRNILSUGWULW-UHFFFAOYSA-N 0.000 description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 241000894006 Bacteria Species 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 230000001580 bacterial effect Effects 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 210000000170 cell membrane Anatomy 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000001963 growth medium Substances 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 206010016322 Feeling abnormal Diseases 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 235000003434 Sesamum indicum Nutrition 0.000 description 1
- 244000000231 Sesamum indicum Species 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001347 alkyl bromides Chemical class 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920002988 biodegradable polymer Polymers 0.000 description 1
- 239000004621 biodegradable polymer Substances 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 238000012668 chain scission Methods 0.000 description 1
- 238000012258 culturing Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/44—Preparation of metal salts or ammonium salts
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Biological Depolymerization Polymers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a preparation method and application of a polylactic acid melt-blown material. The polylactic acid melt-blown material comprises the following components in percentage by weight: 80-90% of modified polylactic acid, 5-20% of toughening agent, 0.5-5% of molecular weight control agent, 0.1-5% of chain extender, 0.1-1% of antioxidant, 0.5-1% of lubricant and 0.1-2% of nucleating agent. The melt-blown fabric is prepared by using the melt-blown material provided by the invention, wherein the modified polylactic acid is prepared by blending polylactic acid and quaternized cellulose nanocrystals, the cellulose nanocrystals are degradable and recyclable green materials and have excellent mechanical properties, and the polylactic acid and the quaternized cellulose nanocrystals are blended, so that the mechanical properties and antibacterial property of the melt-blown fabric can be improved while the degradation property of the melt-blown fabric is ensured, and the melt-blown fabric meets the requirements of industrial production. The polylactic acid melt-blown material prepared by the invention has the advantages of high fluidity, high toughness and the like, can be used for preparing melt-blown cloth with soft texture and high filtering efficiency, and the used main raw materials all meet the biodegradation requirement.
Description
Technical Field
The invention relates to the technical field of biodegradable high polymer materials, in particular to a preparation method and application of a polylactic acid melt-blown material.
Background
Polylactic acid (PLA) is used as a biodegradable polymer, is derived from renewable plant resources existing in a large amount in the nature, can be completely degraded by microorganisms in soil, is an ideal environment-friendly material, has the great advantages of being renewable, biodegradable, low-carbon-emission and low-energy-consumption, and becomes a hotspot of application research. The biodegradable melt-blown material has less reports, and the invention patent with the publication number of CN113684557A (application number of CN202110990267.X) adopts peroxide used by polypropylene melt-blown material as a molecular weight control agent, and the chain breaking effect of the peroxide on polylactic acid cannot be realized. And the non-woven fabric material prepared from the polylactic acid melt-blown material has poor mechanical property and antibacterial property.
Therefore, how to solve the problems is important to invent a degradable polylactic acid melt-blown material with antibacterial property.
Disclosure of Invention
The invention aims to provide a preparation method and application of a polylactic acid melt-blown material, so as to solve the problems in the background technology.
In order to solve the technical problems, the invention provides the following technical scheme:
a method for preparing polylactic acid melt-blown material is characterized in that: the method comprises the following steps:
the method comprises the following steps: taking 4-dimethylaminopyridine, triethylamine, N-methylpyrrolidone and cellulose nanocrystal, uniformly stirring, introducing argon, dropwise adding at-2-0 ℃, reacting for 22-26 h, washing and drying to obtain brominated cellulose nanocrystal;
step two: taking N, N-dimethylformamide, methacrylic dimethylamino ethyl ester, cuprous bromide, pentamethyl diethylenetriamine and brominated cellulose nanocrystals, uniformly stirring, reacting at-2-0 ℃ for 1-2 h, introducing argon, reacting at 58-62 ℃ for 22-26 h, washing and drying to obtain the cellulose nanocrystals grafted and polymerized with the methacrylic dimethylamino ethyl ester;
step three: taking the cellulose nanocrystal of grafted polymerized methacrylic dimethylamino ethyl methacrylate, 1-bromodecane and ethanol, introducing argon, washing and drying after the reaction is finished to obtain the quaternized cellulose nanocrystal; adding polylactic acid into the quaternized cellulose nanocrystals, mechanically blending for 5-10 min, melting, blending, extruding, and granulating to obtain modified polylactic acid; the addition amount of the quaternized cellulose nanocrystals is 1.8-2.6 wt% of the polylactic acid;
step four: weighing modified polylactic acid, a toughening agent, a molecular weight control agent, a chain extender, an antioxidant, a lubricant and a nucleating agent, and uniformly mixing by using a high-speed mixer at the mixing speed of 300-1000 rpm for 3-20 min; and then adding the mixture into a double-screw extruder for plasticizing, dispersing, extruding and granulating to obtain the polylactic acid melt-blown material.
Preferably, the formula of the polylactic acid melt-blown material comprises the following components in parts by weight:
80-90 parts of modified polylactic acid, 5-20 parts of toughening agent, 0.5-5 parts of molecular weight control agent, 0.1-5 parts of chain extender, 0.1-1 part of antioxidant, 0.5-1 part of lubricant and 0.1-2 parts of nucleating agent.
Preferably, in the third step, the melt index of the polylactic acid is 5-25 g/10 min.
Preferably, the toughening agent is any one or a mixture of polycaprolactone, polybutylene adipate-terephthalate and polymethyl ethylene carbonate.
Preferably, the molecular weight control agent is an aqueous solution of an alkaline substance, and the pH value is 7-9.
Preferably, the chain extender is any one or a mixture of more of alcohol compounds, amine compounds and epoxy compounds.
Preferably, the antioxidant is any one or a mixture of more of hindered phenol antioxidants, hindered amine antioxidants, phosphite antioxidants and thioester antioxidants.
Preferably, the lubricant is a mixture of any one or more of fatty acid and ester thereof, fatty acid amide and organosilicon compound.
Preferably, the nucleating agent is any one or a mixture of more of phenyl phosphonic acid soap mixture, hydrazide compound, metal organic phosphate compound and sorbitol compound.
Preferably, the polylactic acid melt-blown material can be used for melt-blown cloth.
Compared with the prior art, the invention has the following beneficial effects:
(1) the polylactic acid can be subjected to chain scission by means of hydrolysis, and the effect is better particularly under the condition of weak acid or weak base. The invention comprehensively considers that the physique of a human body is alkalescence, selects weak base solution as a molecular weight control agent, controls the molecular weight of polylactic acid, and has little influence of residues on the human body. In addition, a part of toughening materials are added, the main reason is that polylactic acid molecular chains are rigid chain segments, the toughening materials can improve the soft feeling of the prepared melt-blown fabric, and then an epoxy multifunctional group chain extender is preferably selected to enable the PLA chain segments to form a net-shaped entanglement structure, so that the comprehensive performance is improved. The molecular weight control agent is an aqueous solution of sodium hydroxide, potassium hydroxide and sodium bicarbonate, the pH value is controlled to be 7-9, sanitation and safety are guaranteed, and a dilute solution of the molecular weight control agent can be contacted with a human body.
(2) The cellulose nanocrystal is a degradable and recyclable green material, has good heat resistance and excellent mechanical property, and can be blended with the quaternized cellulose nanocrystal to ensure the degradation property of the melt-blown fabric and increase the mechanical property of the melt-blown fabric.
The quaternized cellulose nanocrystals have antibacterial property, bacterial cell plasma membranes and the quaternized cellulose nanocrystals are mutually adsorbed due to electrostatic interaction, and long alkyl chains grafted on the surfaces penetrate through the bacterial cell membranes through diffusion to damage cell structures, so that cell contents are lost, and finally bacteria are killed. Therefore, the polylactic acid and the quaternized cellulose nanocrystalline are blended, and the antibacterial performance of the melt-blown material is also improved.
(3) After the cellulose nanocrystalline of the grafted polymerized methacrylic dimethylamino ethyl ester is quaternized by long-chain alkyl bromide, a large number of long alkyl chains are grafted on the surface of the cellulose nanocrystalline, so that the surface hydrophobicity of the quaternized cellulose nanocrystalline is increased, the surface hydrophobicity of the quaternized cellulose nanocrystalline is increased due to modification, and the polylactic acid also has hydrophobicity, and the cellulose nanocrystalline and the polylactic acid are blended, so that the compatibility is better, the agglomeration is not easy, the product is more uniform to mix, and the mechanical property and the antibacterial property of the melt-blown fabric are improved.
Controlling the addition amount of the quaternized cellulose nanocrystals to be 1.8-2.6 wt% of the polylactic acid; (ii) a The addition amount of the quaternized cellulose nanocrystals is less than 1.8 wt%, the mechanical properties of the material are poor, the addition amount of the quaternized cellulose nanocrystals is more than 2.6 wt%, the agglomeration phenomenon of the mixture is serious, the compatibility of the material is poor, and the mechanical properties are poor.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The raw materials used in each example were as follows:
polylactic acid (PLA): the designation LX175, the supplier is: dadalke benne.
Polybutylene adipate-terephthalate: brand No. THJS-6802, supplier: blue mountain tun river.
Polymethyl ethylene carbonate: under the designation T9, the supplier is Jiangsu Zhongke Jinlong.
Polycaprolactone: under the designation 6800, from suwei, usa.
Chain extender: the trade mark is: SG-20, supplier: the daily rise.
Antioxidant: the trade name is: antioxidant-1010, supplier: BASF corporation, Germany.
Lubricants, trade names: calcium stearate, supplier: the King of Japan flowers.
Nucleating agent: hydrazide compounds, designation TMC-300, were supplied by: shanxi institute of chemical engineering.
Example 1
The method comprises the following steps: taking 4-dimethylaminopyridine, 15g triethylamine, 200ml N-methylpyrrolidone and 7.5g cellulose nanocrystals, stirring uniformly, introducing argon, dropwise adding 10g 2-bromoisobutyryl bromide at-1 ℃, reacting for 24h, washing and drying to obtain brominated cellulose nanocrystals;
step two: taking 30ml of N, N-dimethylformamide, 4.7g of methacrylic dimethylamino ethyl ester, 2.1g of cuprous bromide, 2.3g of pentamethyldiethylenetriamine and 5g of brominated cellulose nanocrystals, uniformly stirring, reacting at-1 ℃ for 1.5h, introducing argon, reacting at 60 ℃ for 24h, washing, and drying to obtain the cellulose nanocrystals of the grafted and polymerized methacrylic dimethylamino ethyl ester;
step three: taking 3g of cellulose nanocrystalline of grafted polymerized methacrylic dimethylamino ethyl ester, 20g of 1-bromodecane and 200ml of ethanol, introducing argon, washing and drying after the reaction is finished to obtain the quaternized cellulose nanocrystalline; adding polylactic acid into the quaternized cellulose nanocrystals, mechanically blending for 7min, melting, blending, extruding and granulating to obtain modified polylactic acid; the addition amount of the quaternized cellulose nanocrystals was 2 wt% of the polylactic acid.
Step four: weighing modified polylactic acid, a toughening agent, a molecular weight control agent, a chain extender, an antioxidant, a lubricant and a nucleating agent, uniformly mixing by using a high-speed mixer, wherein the mixing speed is 700rpm, and the mixing time is 12 min; and then adding the mixture into a double-screw extruder for plasticizing, dispersing, extruding and granulating to obtain the polylactic acid melt-blown material.
The formula of the polylactic acid melt-blown material comprises the following components in parts by weight:
85 parts of modified polylactic acid, 12 parts of toughening agent poly adipic acid-butylene terephthalate, 3 parts of molecular weight control agent sodium hydroxide aqueous solution, 3 parts of chain extender, 0.7 part of antioxidant, 0.7 part of lubricant and 1 part of nucleating agent.
Example 2
The method comprises the following steps: taking 4-dimethylaminopyridine, 15g triethylamine, 200ml N-methylpyrrolidone and 7.5g cellulose nanocrystals, stirring uniformly, introducing argon, dropwise adding 10g 2-bromoisobutyryl bromide at-2 ℃, reacting for 22h, washing and drying to obtain brominated cellulose nanocrystals;
step two: taking 30ml of N, N-dimethylformamide, 4.7g of methacrylic dimethylamino ethyl ester, 2.1g of cuprous bromide, 2.3g of pentamethyldiethylenetriamine and 5g of brominated cellulose nanocrystals, uniformly stirring, reacting at-2 ℃ for 1h, introducing argon, reacting at 58 ℃ for 22h, washing, and drying to obtain the cellulose nanocrystals of the grafted polymerized methacrylic dimethylamino ethyl ester;
step three: taking 3g of cellulose nanocrystal of grafted polymerized methacrylic dimethylamino ethyl ester, 20g of 1-bromodecane and 200ml of ethanol, introducing argon, washing and drying after the reaction is finished to obtain quaternized cellulose nanocrystal; adding polylactic acid into the quaternized cellulose nanocrystals, mechanically blending for 5min, melting, blending, extruding and granulating to obtain modified polylactic acid; the addition amount of the quaternized cellulose nanocrystals was 1.8 wt% of the polylactic acid.
Step four: weighing modified polylactic acid, a toughening agent, a molecular weight control agent, a chain extender, an antioxidant, a lubricant and a nucleating agent, and uniformly mixing by using a high-speed mixer at the mixing speed of 300rpm for 3 min; and then adding the mixture into a double-screw extruder for plasticizing, dispersing, extruding and granulating to obtain the polylactic acid melt-blown material.
The formula of the polylactic acid melt-blown material comprises the following components in parts by weight:
80 parts of modified polylactic acid, 10 parts of toughening agent polymethyl ethylene carbonate, 1 part of molecular weight control agent potassium hydroxide aqueous solution, 1 part of chain extender, 0.5 part of antioxidant, 0.5 part of lubricant and 0.5 part of nucleating agent.
Example 3
The method comprises the following steps: taking 4-dimethylaminopyridine, 15g triethylamine, 200ml N-methylpyrrolidone and 7.5g cellulose nanocrystals, stirring uniformly, introducing argon, dropwise adding 10g 2-bromoisobutyryl bromide at 0 ℃, reacting for 26h, washing and drying to obtain brominated cellulose nanocrystals;
step two: taking 30ml of N, N-dimethylformamide, 4.7g of methacrylic dimethylamino ethyl ester, 2.1g of cuprous bromide, 2.3g of pentamethyldiethylenetriamine and 5g of brominated cellulose nanocrystal, uniformly stirring, reacting at 0 ℃ for 2 hours, introducing argon, reacting at 62 ℃ for 26 hours, washing, and drying to obtain the cellulose nanocrystal of the grafted and polymerized methacrylic dimethylamino ethyl ester;
step three: taking 3g of cellulose nanocrystalline of grafted polymerized methacrylic dimethylamino ethyl ester, 20g of 1-bromodecane and 200ml of ethanol, introducing argon, washing and drying after the reaction is finished to obtain the quaternized cellulose nanocrystalline; taking quaternary ammonium cellulose nanocrystals, adding polylactic acid, mechanically blending for 10min, melting, blending, extruding and granulating to obtain modified polylactic acid; the addition amount of the quaternized cellulose nanocrystals was 2.6 wt% of the polylactic acid.
Step four: weighing modified polylactic acid, a toughening agent, a molecular weight control agent, a chain extender, an antioxidant, a lubricant and a nucleating agent, and uniformly mixing by using a high-speed mixer at the mixing speed of 1000rpm for 20 min; and then adding the mixture into a double-screw extruder for plasticizing, dispersing, extruding and granulating to obtain the polylactic acid melt-blown material.
The formula of the polylactic acid melt-blown material comprises the following components in parts by weight:
90 parts of modified polylactic acid, 20 parts of flexibilizer polycaprolactone, 5 parts of molecular weight control agent sodium bicarbonate aqueous solution, 5 parts of chain extender, 1 part of antioxidant, 1 part of lubricant and 2 parts of nucleating agent.
Example 4:
the method comprises the following steps: taking 4-dimethylaminopyridine, 15g triethylamine, 200ml N-methylpyrrolidone and 7.5g cellulose nanocrystals, stirring uniformly, introducing argon, dropwise adding 10g 2-bromoisobutyryl bromide at-1 ℃, reacting for 24h, washing and drying to obtain brominated cellulose nanocrystals;
step two: taking 30ml of N, N-dimethylformamide, 4.7g of methacrylic dimethylamino ethyl ester, 2.1g of cuprous bromide, 2.3g of pentamethyldiethylenetriamine and 5g of brominated cellulose nanocrystals, uniformly stirring, reacting at-1 ℃ for 1.5h, introducing argon, reacting at 60 ℃ for 24h, washing, and drying to obtain the cellulose nanocrystals of the grafted and polymerized methacrylic dimethylamino ethyl ester;
step three: taking 3g of cellulose nanocrystalline of grafted polymerized methacrylic dimethylamino ethyl ester, 20g of 1-bromodecane and 200ml of ethanol, introducing argon, washing and drying after the reaction is finished to obtain the quaternized cellulose nanocrystalline; adding polylactic acid into the quaternized cellulose nanocrystals, mechanically blending for 7min, melting, blending, extruding and granulating to obtain modified polylactic acid; the addition amount of the quaternized cellulose nanocrystals was 2 wt% of the polylactic acid.
Step four: weighing modified polylactic acid, a toughening agent, a molecular weight control agent, a chain extender, an antioxidant, a lubricant and a nucleating agent, and uniformly mixing by using a high-speed mixer at the mixing speed of 700rpm for 12 min; and then adding the mixture into a double-screw extruder for plasticizing, dispersing, extruding and granulating to obtain the polylactic acid melt-blown material.
The formula of the polylactic acid melt-blown material comprises the following components in parts by weight:
90 parts of modified polylactic acid, 15 parts of toughening agent poly adipic acid-butylene terephthalate, 4 parts of molecular weight control agent sodium bicarbonate aqueous solution, 4 parts of chain extender, 0.6 part of antioxidant, 0.6 part of lubricant and 1.5 parts of nucleating agent.
Example 5:
the method comprises the following steps: taking 4-dimethylaminopyridine, 15g triethylamine, 200ml N-methylpyrrolidone and 7.5g cellulose nanocrystals, stirring uniformly, introducing argon, dropwise adding 10g 2-bromoisobutyryl bromide at-1 ℃, reacting for 24h, washing and drying to obtain brominated cellulose nanocrystals;
step two: taking 30ml of N, N-dimethylformamide, 4.7g of methacrylic dimethylamino ethyl ester, 2.1g of cuprous bromide, 2.3g of pentamethyldiethylenetriamine and 5g of brominated cellulose nanocrystals, uniformly stirring, reacting at-1 ℃ for 1.5h, introducing argon, reacting at 60 ℃ for 24h, washing, and drying to obtain the cellulose nanocrystals of the grafted and polymerized methacrylic dimethylamino ethyl ester;
step three: taking 3g of cellulose nanocrystalline of grafted polymerized methacrylic dimethylamino ethyl ester, 20g of 1-bromodecane and 200ml of ethanol, introducing argon, washing and drying after the reaction is finished to obtain the quaternized cellulose nanocrystalline; adding polylactic acid into the quaternized cellulose nanocrystals, mechanically blending for 7min, melting, blending, extruding and granulating to obtain modified polylactic acid; the addition amount of the quaternized cellulose nanocrystals was 2 wt% of the polylactic acid.
Step four: weighing modified polylactic acid, a toughening agent, a molecular weight control agent, a chain extender, an antioxidant, a lubricant and a nucleating agent, and uniformly mixing by using a high-speed mixer at the mixing speed of 800rpm for 13 min; and then adding the mixture into a double-screw extruder for plasticizing, dispersing, extruding and granulating to obtain the polylactic acid melt-blown material.
The formula of the polylactic acid melt-blown material comprises the following components in parts by weight:
90 parts of modified polylactic acid, 15 parts of toughening agent poly adipic acid-butylene terephthalate, 2 parts of molecular weight control agent potassium hydroxide aqueous solution, 3 parts of chain extender, 1 part of antioxidant, 0.7 part of lubricant and 1.4 parts of nucleating agent.
Example 6: the cellulose nanocrystals were not modified, and the rest was the same as in example 1.
The method comprises the following steps: taking cellulose nanocrystals, adding polylactic acid, mechanically blending for 7min, melting, blending, extruding and granulating to obtain modified polylactic acid; the addition amount of the cellulose nanocrystal is 2 wt% of the polylactic acid.
Step two: weighing modified polylactic acid, a toughening agent, a molecular weight control agent, a chain extender, an antioxidant, a lubricant and a nucleating agent, and uniformly mixing by using a high-speed mixer at the mixing speed of 700rpm for 12 min; and then adding the mixture into a double-screw extruder for plasticizing, dispersing, extruding and granulating to obtain the polylactic acid melt-blown material.
The formula of the polylactic acid melt-blown material comprises the following components in parts by weight:
85 parts of modified polylactic acid, 12 parts of toughening agent poly adipic acid-butylene terephthalate, 3 parts of molecular weight control agent sodium hydroxide aqueous solution, 3 parts of chain extender, 0.7 part of antioxidant, 0.7 part of lubricant and 1 part of nucleating agent.
Example 7: the procedure of example 1 was repeated except that polylactic acid was not modified.
The method comprises the following steps: weighing modified polylactic acid, a toughening agent, a molecular weight control agent, a chain extender, an antioxidant, a lubricant and a nucleating agent, and uniformly mixing by using a high-speed mixer at the mixing speed of 700rpm for 12 min; and then adding the mixture into a double-screw extruder for plasticizing, dispersing, extruding and granulating to obtain the polylactic acid melt-blown material.
The formula of the polylactic acid melt-blown material comprises the following components in parts by weight:
85 parts of modified polylactic acid, 12 parts of toughening agent poly adipic acid-butylene terephthalate, 3 parts of molecular weight control agent sodium hydroxide aqueous solution, 3 parts of chain extender, 0.7 part of antioxidant, 0.7 part of lubricant and 1 part of nucleating agent.
Example 8: the amount of the quaternary ammonium cellulose nanocrystals added was 2.8 wt% of the polylactic acid, and the rest was the same as in example 1.
The method comprises the following steps: taking 4-dimethylaminopyridine, 15g triethylamine, 200ml N-methylpyrrolidone and 7.5g cellulose nanocrystals, stirring uniformly, introducing argon, dropwise adding 10g 2-bromoisobutyryl bromide at-1 ℃, reacting for 24h, washing and drying to obtain brominated cellulose nanocrystals;
step two: taking 30ml of N, N-dimethylformamide, 4.7g of methacrylic dimethylamino ethyl ester, 2.1g of cuprous bromide, 2.3g of pentamethyldiethylenetriamine and 5g of brominated cellulose nanocrystals, uniformly stirring, reacting at-1 ℃ for 1.5h, introducing argon, reacting at 60 ℃ for 24h, washing, and drying to obtain the cellulose nanocrystals of the grafted and polymerized methacrylic dimethylamino ethyl ester;
step three: taking 3g of cellulose nanocrystalline of grafted polymerized methacrylic dimethylamino ethyl ester, 20g of 1-bromodecane and 200ml of ethanol, introducing argon, washing and drying after the reaction is finished to obtain the quaternized cellulose nanocrystalline; adding polylactic acid into the quaternized cellulose nanocrystals, mechanically blending for 7min, melting, blending, extruding and granulating to obtain modified polylactic acid; the addition amount of the quaternized cellulose nanocrystals was 2.8 wt% of the polylactic acid.
Step four: weighing modified polylactic acid, a toughening agent, a molecular weight control agent, a chain extender, an antioxidant, a lubricant and a nucleating agent, and uniformly mixing by using a high-speed mixer at the mixing speed of 700rpm for 12 min; and then adding the mixture into a double-screw extruder for plasticizing, dispersing, extruding and granulating to obtain the polylactic acid melt-blown material.
The formula of the polylactic acid melt-blown material comprises the following components in parts by weight:
85 parts of modified polylactic acid, 12 parts of toughening agent poly adipic acid-butylene terephthalate, 3 parts of molecular weight control agent sodium hydroxide aqueous solution, 3 parts of chain extender, 0.7 part of antioxidant, 0.7 part of lubricant and 1 part of nucleating agent.
Experiment:
the polylactic acid meltblown prepared in examples 1 to 8 was subjected to melt extrusion, spun-drawn into a web, and hot-rolled to obtain a meltblown fabric. And (3) carrying out performance test on the prepared melt-blown fabric, and testing the mechanical property of the melt-blown fabric by using a tensile testing machine, wherein the tensile speed is 50 mm/min. Cutting the melt-blown fabric into a square shape of 4cm multiplied by 4cm, placing the cut melt-blown fabric into a culture medium, adding an equal amount of bacteria into the culture medium, culturing for 24 hours at 36 ℃, calculating the antibacterial rate, and obtaining the data shown in the following table:
and (4) conclusion: as can be seen from the comparison of the data, the cellulose nanocrystals are not modified in the example 6, and the melt-blown material is seriously agglomerated, so that the tensile strength is greatly reduced, and the antibacterial performance is poor. Example 7 the melt blown fabric made without modification of the polylactic acid was poor in antimicrobial properties. Example 8 the amount of the quaternized cellulose nanocrystals added was 2.8 wt% of the polylactic acid, the mixture agglomerated seriously, the compatibility of the material worsened, and the mechanical properties worsened. The meltblown fabric prepared by the embodiments 1-5 provided by the invention uses the blending of the quaternized cellulose nanocrystals and polylactic acid as the modified polylactic acid to prepare the meltblown fabric, the cellulose nanocrystals are degradable and recyclable green materials and have excellent mechanical properties, and the polylactic acid and the quaternized cellulose nanocrystals are blended, so that the mechanical properties and antibacterial properties of the meltblown fabric can be improved while the degradation properties of the meltblown fabric are ensured, and the meltblown fabric meets the requirements of industrial production.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of polylactic acid melt-blown material is characterized by comprising the following steps: the method comprises the following steps:
the method comprises the following steps: taking 4-dimethylaminopyridine, triethylamine, N-methylpyrrolidone and cellulose nanocrystals, uniformly stirring, introducing argon, dropwise adding at-2-0 ℃, reacting for 22-26 h, washing and drying to obtain brominated cellulose nanocrystals;
step two: taking N, N-dimethylformamide, methacrylic dimethylamino ethyl ester, cuprous bromide, pentamethyl diethylenetriamine and brominated cellulose nanocrystals, uniformly stirring, reacting at-2-0 ℃ for 1-2 h, introducing argon, reacting at 58-62 ℃ for 22-26 h, washing and drying to obtain the cellulose nanocrystals grafted and polymerized with methacrylic dimethylamino ethyl ester;
step three: taking the cellulose nanocrystal grafted with the methacrylic dimethylamino ethyl ester, 1-bromodecane and ethanol, introducing argon, washing and drying after the reaction is finished to obtain the quaternized cellulose nanocrystal; adding polylactic acid into the quaternized cellulose nanocrystals, mechanically blending for 5-10 min, melting, blending, extruding, and granulating to obtain modified polylactic acid; the addition amount of the quaternized cellulose nanocrystals is 1.8-2.6 wt% of the polylactic acid;
step four: weighing modified polylactic acid, a toughening agent, a molecular weight control agent, a chain extender, an antioxidant, a lubricant and a nucleating agent, and uniformly mixing by using a high-speed mixer at the mixing speed of 300-1000 rpm for 3-20 min; and then adding the mixture into a double-screw extruder for plasticizing, dispersing, extruding and granulating to obtain the polylactic acid melt-blown material.
2. The method for preparing polylactic acid melt-blown material according to claim 1, wherein: the formula of the polylactic acid melt-blown material comprises the following components in parts by weight:
80-90 parts of modified polylactic acid, 5-20 parts of toughening agent, 0.5-5 parts of molecular weight control agent, 0.1-5 parts of chain extender, 0.1-1 part of antioxidant, 0.5-1 part of lubricant and 0.1-2 parts of nucleating agent.
3. The method for preparing polylactic acid melt-blown material according to claim 1, wherein: in the third step, the melt index of the polylactic acid is 5-25 g/10 min.
4. The method for preparing polylactic acid melt-blown material according to claim 1, wherein: the toughening agent is any one or a mixture of a plurality of polycaprolactone, polybutylene adipate-terephthalate and polymethyl ethylene carbonate.
5. The method for preparing polylactic acid melt-blown material according to claim 1, wherein: the molecular weight control agent is an aqueous solution of an alkaline substance, and the pH value is 7-9.
6. The method for preparing polylactic acid melt-blown material according to claim 1, wherein: the chain extender is any one or a mixture of more of alcohol compounds, amine compounds and epoxy compounds.
7. The method for preparing polylactic acid melt-blown material according to claim 1, wherein: the antioxidant is any one or a mixture of more of hindered phenol antioxidants, hindered amine antioxidants, phosphite antioxidants and thioester antioxidants.
8. The method for preparing polylactic acid melt-blown material according to claim 1, wherein: the lubricant is a mixture of any one or more of fatty acid and esters thereof, fatty acid amide and organosilicon compounds.
9. The method for preparing polylactic acid melt-blown material according to claim 1, wherein: the nucleating agent is any one or a mixture of more of phenyl phosphonic acid soap mixture, hydrazide compound, metal organic phosphate compound and sorbitol compound.
10. Use of a meltblown material prepared by the process according to any of claims 1 to 9, characterized in that: the polylactic acid melt-blown material can be used for melt-blown cloth.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210426301.5A CN114957940B (en) | 2022-04-22 | 2022-04-22 | Preparation method and application of polylactic acid melt-blown material |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210426301.5A CN114957940B (en) | 2022-04-22 | 2022-04-22 | Preparation method and application of polylactic acid melt-blown material |
Publications (2)
Publication Number | Publication Date |
---|---|
CN114957940A true CN114957940A (en) | 2022-08-30 |
CN114957940B CN114957940B (en) | 2024-02-02 |
Family
ID=82979950
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202210426301.5A Active CN114957940B (en) | 2022-04-22 | 2022-04-22 | Preparation method and application of polylactic acid melt-blown material |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN114957940B (en) |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105175637A (en) * | 2015-09-02 | 2015-12-23 | 江南大学 | Modified cellulose nanometer crystal and preparation method thereof |
CN107312137A (en) * | 2017-06-28 | 2017-11-03 | 安庆师范大学 | A kind of nano-cellulose base dendritic macromole temperature sensing material and preparation method thereof |
CN109306544A (en) * | 2018-09-29 | 2019-02-05 | 杨成云 | A kind of modified pla tow and preparation method thereof |
CN113736069A (en) * | 2020-05-28 | 2021-12-03 | Skc株式会社 | Biodegradable polyester resin composition, nonwoven fabric, film and process for producing the same |
CN113845652A (en) * | 2021-12-01 | 2021-12-28 | 北京石墨烯技术研究院有限公司 | Modified polylactic acid material, polylactic acid composite material and preparation method thereof |
-
2022
- 2022-04-22 CN CN202210426301.5A patent/CN114957940B/en active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105175637A (en) * | 2015-09-02 | 2015-12-23 | 江南大学 | Modified cellulose nanometer crystal and preparation method thereof |
CN107312137A (en) * | 2017-06-28 | 2017-11-03 | 安庆师范大学 | A kind of nano-cellulose base dendritic macromole temperature sensing material and preparation method thereof |
CN109306544A (en) * | 2018-09-29 | 2019-02-05 | 杨成云 | A kind of modified pla tow and preparation method thereof |
CN113736069A (en) * | 2020-05-28 | 2021-12-03 | Skc株式会社 | Biodegradable polyester resin composition, nonwoven fabric, film and process for producing the same |
CN113845652A (en) * | 2021-12-01 | 2021-12-28 | 北京石墨烯技术研究院有限公司 | Modified polylactic acid material, polylactic acid composite material and preparation method thereof |
Non-Patent Citations (3)
Title |
---|
咸玉龙(浙江理工大学): "聚乳酸/纤维素纳米晶复合材料的制备及其熔喷材料性能的研究", 《工程科技Ⅰ辑》, pages 1 - 62 * |
王毅豪: "聚乳酸与常用纳米材料复合工艺的研究进展", 《工程塑料应用》, vol. 45, no. 6, pages 141 - 144 * |
谭磊(东北林业大学): "纤维素/聚乳酸复合材料的制备与性能研究", 《工程科技Ⅰ辑》, pages 1 - 53 * |
Also Published As
Publication number | Publication date |
---|---|
CN114957940B (en) | 2024-02-02 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN101735636B (en) | Biodegradation time controlled plastic film and preparation method thereof | |
CN1320063C (en) | Anti-bacterial composite particles and anti-bacterial resin composition | |
CN103059391B (en) | A kind of toughness reinforcing foaming master batch and its production and use | |
CN102408587B (en) | Environmentally-friendly controllable degradation agricultural film and preparation method thereof | |
CN101942146B (en) | Controllable rheological high-gloss polypropylene resin and preparation method thereof | |
KR101965990B1 (en) | Composite polyester material, composite polyester fiber, processes for preparing the same and uses thereof | |
CN103589125B (en) | A kind of Polylactic acid/polypropylene blend and preparation method thereof | |
CN102040814A (en) | Special black master batch for polylactic acid based degradable plastics and preparation method thereof | |
CN103849032A (en) | Antibacterial antistatic slippery polyethylene masterbatch and preparation method thereof | |
CN106432971A (en) | Preparation and application of novel environment-friendly foaming PVC specific uracil zinc composite stabilizer | |
CN108676246A (en) | A kind of antibacterial nonwoven cloth and preparation method thereof | |
CN105348635A (en) | Nano cooperative intumescent flame retardant and toughening polypropylene blend composite material and preparation method thereof | |
CN110229372A (en) | Low molding energy consumption polypropylene foamed particles of one kind and preparation method thereof | |
CN114957940A (en) | Preparation method and application of polylactic acid melt-blown material | |
JP3739003B2 (en) | Biodegradable resin composition | |
CN102702655B (en) | Polyvinyl alcohol/high amylose biodegradable material and melting preparation method thereof | |
CN102127256A (en) | Pearl wool material | |
CN110358189A (en) | A kind of non-woven fabrics softness master batch and preparation method thereof | |
CN112662063A (en) | PP melt-blown material and preparation method thereof | |
CN112175369A (en) | High-fluidity medical antibacterial degradable composite material and preparation method thereof | |
CN110964298A (en) | Biodegradable modified material and preparation method thereof | |
CN111205583B (en) | Easily degradable environment-friendly plastic and preparation method thereof | |
JP6480345B2 (en) | Aliphatic polyester resin composition and aliphatic polyester resin molding | |
CN111074373A (en) | Flame-retardant antibacterial PTT fiber material and preparation method therefor | |
CN112552586B (en) | Glass fiber reinforced polypropylene composition and preparation method thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |