CN118206858B - High-toughness bio-based PLA degradable composite material and preparation method thereof - Google Patents
High-toughness bio-based PLA degradable composite material and preparation method thereof Download PDFInfo
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- CN118206858B CN118206858B CN202410249262.5A CN202410249262A CN118206858B CN 118206858 B CN118206858 B CN 118206858B CN 202410249262 A CN202410249262 A CN 202410249262A CN 118206858 B CN118206858 B CN 118206858B
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- 239000002131 composite material Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 43
- 238000006243 chemical reaction Methods 0.000 claims abstract description 249
- 239000004626 polylactic acid Substances 0.000 claims abstract description 112
- 229920000747 poly(lactic acid) Polymers 0.000 claims abstract description 111
- 238000002156 mixing Methods 0.000 claims abstract description 96
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims abstract description 90
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims abstract description 77
- 239000003063 flame retardant Substances 0.000 claims abstract description 77
- 229920006149 polyester-amide block copolymer Polymers 0.000 claims abstract description 73
- 229920001971 elastomer Polymers 0.000 claims abstract description 71
- 239000000806 elastomer Substances 0.000 claims abstract description 71
- 239000000654 additive Substances 0.000 claims abstract description 64
- 230000000996 additive effect Effects 0.000 claims abstract description 64
- 229910052901 montmorillonite Inorganic materials 0.000 claims abstract description 62
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 61
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims abstract description 41
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims abstract description 41
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims abstract description 41
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims abstract description 41
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims abstract description 41
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229920000728 polyester Polymers 0.000 claims abstract description 29
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 claims abstract description 26
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims abstract description 24
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims abstract description 22
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 claims abstract description 22
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000001361 adipic acid Substances 0.000 claims abstract description 20
- 235000011037 adipic acid Nutrition 0.000 claims abstract description 20
- 239000001384 succinic acid Substances 0.000 claims abstract description 17
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000001125 extrusion Methods 0.000 claims abstract description 15
- 238000001816 cooling Methods 0.000 claims abstract description 11
- DWSWCPPGLRSPIT-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinin-6-ium 6-oxide Chemical compound C1=CC=C2[P+](=O)OC3=CC=CC=C3C2=C1 DWSWCPPGLRSPIT-UHFFFAOYSA-N 0.000 claims abstract description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 105
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 58
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 52
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 29
- 238000010438 heat treatment Methods 0.000 claims description 27
- 238000002390 rotary evaporation Methods 0.000 claims description 26
- 239000002904 solvent Substances 0.000 claims description 26
- 238000001035 drying Methods 0.000 claims description 25
- 238000005406 washing Methods 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- 230000008018 melting Effects 0.000 claims description 14
- 238000002844 melting Methods 0.000 claims description 14
- 239000002244 precipitate Substances 0.000 claims description 14
- 238000010992 reflux Methods 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- 238000002604 ultrasonography Methods 0.000 claims description 4
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 3
- 238000010534 nucleophilic substitution reaction Methods 0.000 abstract description 4
- 239000002861 polymer material Substances 0.000 abstract description 2
- BSYJHYLAMMJNRC-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-ol Chemical compound CC(C)(C)CC(C)(C)O BSYJHYLAMMJNRC-UHFFFAOYSA-N 0.000 description 64
- 239000012043 crude product Substances 0.000 description 26
- 239000000463 material Substances 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 19
- 230000000694 effects Effects 0.000 description 13
- 238000009210 therapy by ultrasound Methods 0.000 description 13
- 229920003023 plastic Polymers 0.000 description 6
- 239000004033 plastic Substances 0.000 description 6
- 238000011056 performance test Methods 0.000 description 5
- 239000004014 plasticizer Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 239000012796 inorganic flame retardant Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 3
- 230000005496 eutectics Effects 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000012745 toughening agent Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000007112 amidation reaction Methods 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000010976 amide bond formation reaction Methods 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000005501 phase interface Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000010517 secondary reaction Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229920006346 thermoplastic polyester elastomer Polymers 0.000 description 1
- 230000009466 transformation Effects 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
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/44—Polyester-amides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- 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
- C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
-
- 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
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention relates to the technical field of high polymer materials, and discloses a high-toughness bio-based PLA degradable composite material and a preparation method thereof. The preparation method comprises the following steps: mixing montmorillonite with dicyandiamide, mixing the obtained aminated montmorillonite with cyanuric chloride to perform nucleophilic substitution reaction, and performing nucleophilic substitution reaction with ethylenediamine again after the reaction to obtain functional montmorillonite; the flame retardant additive is obtained through the mixed reaction of the functionalized montmorillonite and methyl acrylate; mixing DOPO and itaconic acid for reaction, mixing the obtained modified DOPO with 1, 4-butanediol, ethylene glycol, adipic acid, succinic acid and p-toluenesulfonic acid for reaction to obtain a polyester prepolymer, and mixing the polyester prepolymer with 1, 6-hexamethylenediamine for reaction to obtain a polyesteramide elastomer; mixing polylactic acid, a flame retardant additive, tert-butyl peroxybenzoate and a polyesteramide elastomer, carrying out melt extrusion, cooling and granulating to obtain the high-toughness bio-based PLA degradable composite material.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a high-toughness bio-based PLA degradable composite material and a preparation method thereof.
Background
Polylactic acid (PLA) is a novel biodegradable material, and is prepared by using starch extracted from renewable plant resources as a raw material through transformation and biological fermentation. Polylactic acid is used as a biological base material, has good biodegradability, can be completely degraded by microorganisms in the nature, finally generates carbon dioxide and water, is a recognized environment-friendly material, has great potential for replacing the traditional petroleum-based plastic, and is widely applied to various fields.
However, although polylactic acid has various excellent properties, the polylactic acid has strong brittleness, poor impact resistance and low elongation at break, which severely restricts the application of the polylactic acid in general plastics. Polylactic acid is used as a bio-based plastic, the Limiting Oxygen Index (LOI) of the polylactic acid is only 21%, the polylactic acid is extremely easy to burn, only a just visible carbonized layer is formed during combustion, and the polylactic acid has a dripping phenomenon, so that the application of the polylactic acid in multiple fields is limited. Therefore, how to enhance the flame retardancy of polylactic acid while toughening the polylactic acid is very important and necessary in the current research.
At present, a method for enhancing the toughness and the flame retardance of the polylactic acid is generally adopted, and a plasticizer and a flame retardant are added to the polylactic acid, so that the toughness and the flame retardance of the polylactic acid are improved, but the plasticizer and the flame retardant gradually migrate to the surface of the material in the use process to lose effect, and the long-term stability of the obtained polylactic acid material is reduced.
The prior art, such as Chinese patent application CN101724236A, discloses a polylactic acid flame retardant material composition, a polylactic acid flame retardant material and a preparation method thereof, and the prepared polylactic acid flame retardant material has excellent flame retardant property by adding an inorganic flame retardant with the melting point of 400-600 ℃ into polylactic acid, such as glass powder, carbon fiber and the like. However, the inorganic flame retardant is only used for being combined with the polylactic acid through melt blending, the inorganic flame retardant has low dispersibility and is easy to agglomerate, and the prepared polylactic acid material still has the defect of insufficient toughness due to limited compatibilization effect of the inorganic flame retardant on the polylactic acid.
The prior art, such as chinese patent application CN101955639a, discloses a polylactic acid modified material, a preparation method and use thereof, wherein the flexibility of the polylactic acid material is improved through synergistic effect by adding thermoplastic polyester elastomer and plasticizer into the polylactic acid material. However, the plasticizer used is a small molecular plasticizer, and gradually migrates to the surface of the material in the use process of polylactic acid, so that the toughening effect of the material is reduced, and meanwhile, although the inorganic filler provides a certain flame retardant effect, the flame retardance of the material still needs to be improved.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a high-toughness bio-based PLA degradable composite material and a preparation method thereof.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a preparation method of a high-toughness bio-based PLA degradable composite material comprises the following steps:
Step (1), preparation of flame retardant additive and polyester amide elastomer
Wherein, the preparation of the flame retardant additive comprises the following steps:
mixing montmorillonite, dicyandiamide and water, carrying out a first reaction, centrifuging after the reaction is finished, taking a centrifugal precipitate, washing, and drying to obtain aminated montmorillonite;
mixing the aminated montmorillonite, cyanuric chloride and dioxane with ultrasound, uniformly mixing, carrying out a second reaction, adding ethylenediamine and triethylamine after the reaction is finished, carrying out a third reaction, removing solvent dioxane by rotary evaporation after the reaction is finished, washing, and drying to obtain the functionalized montmorillonite;
Mixing functionalized montmorillonite, methyl acrylate and acetone with ultrasound, adding potassium hydroxide after uniform mixing, reacting for the fourth time, removing solvent acetone by rotary evaporation after the reaction is finished, washing, and drying to obtain a flame retardant additive;
wherein the preparation of the polyesteramide elastomer comprises the following steps:
Mixing pretreated DOPO (9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) with itaconic acid, stirring for reaction, adding acetone after the reaction is finished, carrying out reflux reaction, and removing solvent acetone by rotary evaporation after the reaction is finished to obtain modified DOPO; mixing 1, 4-butanediol, ethylene glycol, modified DOPO and adipic acid, adding p-toluenesulfonic acid after the first reaction, carrying out the second reaction, adding succinic acid after the reaction, and carrying out the third reaction to obtain a polyester prepolymer; mixing the polyester prepolymer with 1, 6-hexamethylenediamine, carrying out a fourth reaction, and carrying out a fifth reaction after the reaction is finished to obtain a polyester amide elastomer;
and (2) mixing polylactic acid, a flame retardant additive and tert-butyl peroxybenzoate, carrying out a melting reaction, adding a polyester amide elastomer after the reaction is finished, carrying out melting extrusion, cooling and granulating to obtain the high-toughness bio-based PLA degradable composite material.
Preferably, in the step (1), when preparing the flame retardant additive: the mass ratio of montmorillonite, dicyandiamide and water is 100 (1-3) (300-500); the first reaction conditions are as follows: the first reaction is carried out for 4 to 5 hours at the rotating speed of 150 to 300r/min and the temperature of 90 to 100 ℃.
Preferably, in the step (1), when preparing the flame retardant additive: the mass ratio of the aminated montmorillonite to the cyanuric chloride to the dioxane to the ethylenediamine to the triethylamine is (3000-3200), 20-60, 3600-4000, 60-180 and 100-300; the second reaction conditions are as follows: reacting for 2-3h at 80-90 ℃; the third reaction conditions are as follows: and reacting for 6-7h at 50-55 ℃.
Preferably, in the step (1), when preparing the flame retardant additive: the mass ratio of the functionalized montmorillonite to the methyl acrylate to the acetone to the potassium hydroxide is (30-50)/(10-15)/(250-300)/(0.01-0.03); the fourth reaction conditions are as follows: and reacting for 6-8h at 90-95 ℃ in nitrogen atmosphere.
Preferably, in the step (1), when preparing the polyesteramide elastomer: the mass ratio of DOPO, itaconic acid and acetone is (20-22): 10-15): 80-100; the stirring reaction conditions are as follows: stirring and reacting for 4-5h at 155-165 ℃ in nitrogen atmosphere; the reflux reaction conditions are as follows: reflux reaction is carried out for 2-3h at 50-60 ℃.
Further, the pretreatment operation of DOPO is as follows: DOPO was melted at 120℃under vacuum of 0.04MPa for 2h.
Preferably, in the step (1), when preparing the polyesteramide elastomer: the mass ratio of the 1, 4-butanediol, the ethylene glycol, the modified DOPO, the adipic acid, the succinic acid, the p-toluenesulfonic acid and the 1, 6-hexamethylenediamine is (90-150), (60-100), (120-200), (220-380), (110-180), (10-20) and (60-100).
Preferably, in the step (1), when preparing the polyesteramide elastomer: the first reaction conditions are as follows: heating from 120 ℃ to 170-180 ℃ at a speed of 1-2 ℃/min in a nitrogen atmosphere for a first reaction for 2-3h; the second reaction conditions are as follows: heating to 210-225 ℃ at a speed of 1-2 ℃/min under the condition of nitrogen atmosphere and vacuum degree of 0.001Mpa for a second reaction for 1-3h; the third reaction conditions are as follows: reacting for 2-3h in a nitrogen atmosphere at 225 ℃; the fourth reaction conditions are as follows: heating from 150 ℃ to 170-180 ℃ at a speed of 1-2 ℃/min in a nitrogen atmosphere for a fourth reaction for 4h; the fifth reaction conditions are as follows: and carrying out fifth reaction for 2h in a nitrogen atmosphere at the temperature of 180 ℃ and the vacuum degree of 300-500 pa.
Preferably, in the step (2): the mass ratio of polylactic acid to flame retardant additive to polyester amide elastomer to tert-butyl peroxybenzoate is (85-92), 3-5, 5-10 and 2-3; the conditions of the melting reaction are as follows: carrying out melt reaction for 8-10min at 180-185 ℃; the conditions of melt extrusion were: melt extrusion was performed by a twin screw extruder at a temperature of 185 ℃.
Preferably, the high-toughness bio-based PLA degradable composite material is prepared by adopting the preparation method of the high-toughness bio-based PLA degradable composite material.
Compared with the prior art, the invention has the beneficial effects that:
Montmorillonite is a nano-scale mineral with a layered structure, and is an excellent char forming agent, so that the montmorillonite can be used as a filler to be compounded with a high polymer, and the heat-resistant and flame-retardant effects of the material are improved. The dicyandiamide is used for intercalation of montmorillonite, so that the distance between montmorillonite sheets is increased, the obtained aminated montmorillonite and cyanuric chloride are mixed to generate nucleophilic substitution reaction, cyanuric chloride is grafted on the aminated montmorillonite, after the reaction, the residual chlorine on cyanuric chloride and ethylenediamine are subjected to nucleophilic substitution reaction again, the dispersibility of montmorillonite in a matrix and the stability of cyanuric chloride are improved, cyanuric chloride is not easy to migrate, and the obtained functionalized montmorillonite has amino groups and better flame-retardant effect. Mixing amino groups of ethylenediamine grafted on the functional montmorillonite with ester groups of methyl acrylate to perform amidation reaction to obtain a flame retardant additive with double bonds and amide groups; the double bond on the flame retardant additive can be grafted in the molecular main chain of the polylactic acid under the condition of an initiator, and the amide bond can form eutectic with the amide bond in the polyester amide during melt blending, so that the compatibility of the flame retardant additive with the polylactic acid and the polyester amide elastomer is improved.
Through mixing DOPO and itaconic acid to react, the modified DOPO with double carboxyl groups is obtained, and the double carboxyl groups can react with hydroxyl groups, so that the modified DOPO is polymerized on a polyester main chain in the polymerization reaction of polyester, the dispersibility of the modified DOPO in a polyester prepolymer is improved, agglomeration is not easy, and the flame retardance of the polyester prepolymer is improved. Copolymerizing carboxylic acid, alcohol and modified DOPO with dicarboxyl to obtain a polyester prepolymer terminated by carboxyl, wherein the modified DOPO is taken as a reaction monomer to participate in the polymerization reaction of the polyester prepolymer, and the obtained polyester prepolymer has flame retardance; the polyester amide elastomer is obtained through amidation reaction of carboxyl end groups of the polyester prepolymer and amino groups of ethylenediamine, and the polyester is used as a degradable material to endow the polyester amide elastomer with degradability, and meanwhile, the existence of an amide bond enables the elastomer to have better mechanical properties, so that the prepared polyester amide elastomer has degradability and better mechanical properties. In addition, the polyester amide elastomer is rich in ester bonds, has certain compatibility with polylactic acid, and has toughening effect on the polylactic acid when being used as an organic toughening material to be mixed with the polylactic acid.
Melt blending reaction is carried out on the flame retardant additive and the bio-based polylactic acid under the condition of an initiator, so that double bonds on the flame retardant additive can be grafted in a molecular main chain of the polylactic acid, and the dispersibility of montmorillonite is further improved; the polyester amide elastomer is added into a blending system of the flame retardant additive and the polylactic acid, and the obtained high-toughness bio-based PLA degradable composite material has high toughness and flame retardance and is degradable.
In addition, the flame retardant additive with montmorillonite is used as an inorganic filler to be filled into a blend system of polylactic acid and polyester amide elastomer, so that the flame retardant additive can be used as a nucleating agent and an inorganic toughening agent to promote polymer nucleation and toughen the polylactic acid, and the strength and heat resistance of the composite material are improved; on the other hand, the montmorillonite can be used as a compatibilizer of a polylactic acid and polyester amide elastomer blending system, and the interfacial surface energy of the system is reduced, the size of the dispersed phase is thinned, and the two-phase compatibility of the polylactic acid and polyester amide elastomer blending system is improved by utilizing the effect that montmorillonite sheets can be orderly and selectively distributed at the interface of the dispersed phase, so that the toughness of the material is further improved to a certain extent.
Drawings
FIG. 1 is a process flow diagram of preparing a high toughness bio-based PLA degradable composite material in accordance with the invention;
FIG. 2 is a bar graph of elongation at break in the synthetic performance test of the high toughness bio-based PLA degradable composites prepared in examples 1-5 and comparative examples 1-3 of this invention;
FIG. 3 is a bar graph of notched impact strength in the performance test of the high toughness bio-based PLA degradable composites prepared in examples 1-5 and comparative examples 1-3 of this invention;
FIG. 4 is a bar graph of limiting oxygen index in the synthetic performance test of the high toughness bio-based PLA degradable composites prepared in examples 1-5 and comparative examples 1-3 of this invention.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments, and all other embodiments obtained by those skilled in the art without making any inventive effort based on the embodiments of the present invention are within the scope of protection of the present invention.
Example 1
The embodiment discloses a preparation method of a high-toughness bio-based PLA degradable composite material, which comprises the following steps:
Step (1), preparation of flame retardant additive and polyester amide elastomer
Wherein, the preparation of the flame retardant additive comprises the following steps:
Mixing montmorillonite, dicyandiamide and water in a mass ratio of 100:3:500, reacting for 5 hours at the temperature of 90 ℃ at the rotating speed of 300r/min for the first time, centrifuging after the reaction is finished, taking a centrifugal precipitate, adding water with the mass 5 times of that of the centrifugal precipitate for washing, and drying for 8 hours at the temperature of 110 ℃ to obtain aminated montmorillonite;
mixing the aminated montmorillonite, cyanuric chloride and dioxane, performing ultrasonic treatment, uniformly mixing, performing a second reaction at 90 ℃ for 2 hours, adding ethylenediamine and triethylamine after the reaction is finished, performing a third reaction at 55 ℃ for 6 hours, performing rotary evaporation at 90 ℃ after the reaction is finished to remove the solvent dioxane to obtain a reaction crude product, adding water with the mass 5 times of that of the reaction crude product, and performing drying at 60 ℃ for 12 hours to obtain the functionalized montmorillonite;
wherein the mass ratio of the aminated montmorillonite to the cyanuric chloride to the dioxane to the ethylenediamine to the triethylamine is 3200:60:4000:180:300;
Mixing functionalized montmorillonite, methyl acrylate and acetone by ultrasonic treatment, adding potassium hydroxide after uniform mixing, reacting for 6 hours at 95 ℃ in nitrogen atmosphere, removing solvent acetone by rotary evaporation at 50 ℃ after the reaction is finished, obtaining a reaction crude product, adding water with the mass 8 times of that of the reaction crude product, washing, and drying for 20 hours at 55 ℃ to obtain a flame retardant additive;
wherein the mass ratio of the functionalized montmorillonite to the methyl acrylate to the acetone to the potassium hydroxide is 50:15:300:0.03;
wherein the preparation of the polyesteramide elastomer comprises the following steps:
mixing the pretreated DOPO with itaconic acid, stirring in a nitrogen atmosphere at 165 ℃ for reaction for 4 hours, adding acetone after the reaction is finished, carrying out reflux reaction at 60 ℃ for 2 hours, and removing solvent acetone by rotary evaporation at 50 ℃ after the reaction is finished to obtain modified DOPO;
Wherein, the mass ratio of DOPO, itaconic acid and acetone is 20:10:80, and the pretreatment operation of DOPO is as follows: melting DOPO for 2h at the temperature of 120 ℃ and the vacuum degree of 0.04 Mpa;
Mixing 1, 4-butanediol, ethylene glycol, modified DOPO and adipic acid in a nitrogen atmosphere at 120 ℃, heating to 180 ℃ at a rate of 2 ℃/min for a first reaction for 2 hours, adding p-toluenesulfonic acid after the reaction is finished, heating to 210 ℃ at a rate of 1 ℃/min for a second reaction for 3 hours under the condition of 0.001Mpa of vacuum degree, adding succinic acid after the reaction is finished, and reacting for a third reaction for 3 hours at a temperature of 225 ℃ to obtain a polyester prepolymer; mixing the polyester prepolymer with 1, 6-hexamethylenediamine in a nitrogen atmosphere at the temperature of 150 ℃, heating to 180 ℃ at the speed of 2 ℃/min for a fourth reaction for 4 hours, and reacting for 2 hours at the temperature of 180 ℃ at the vacuum degree of 500pa after the reaction is finished to obtain a polyester amide elastomer;
wherein the mass ratio of the 1, 4-butanediol to the ethylene glycol to the modified DOPO to the adipic acid to the succinic acid to the p-toluenesulfonic acid to the 1, 6-hexamethylenediamine is 90:60:200:220:110:10:60;
Step (2), mixing polylactic acid, a flame retardant additive and tert-butyl peroxybenzoate, carrying out melt reaction for 8min at 185 ℃, adding a polyesteramide elastomer after the reaction is finished, carrying out melt extrusion at 185 ℃ by a double-screw extruder, cooling and granulating to obtain the high-toughness bio-based PLA degradable composite material;
wherein the mass ratio of the polylactic acid to the flame retardant additive to the polyester amide elastomer to the tert-butyl peroxybenzoate is 85:5:10:3.
Example 2
The embodiment discloses a preparation method of a high-toughness bio-based PLA degradable composite material, which comprises the following steps:
Step (1), preparation of flame retardant additive and polyester amide elastomer
Wherein, the preparation of the flame retardant additive comprises the following steps:
Mixing montmorillonite, dicyandiamide and water in a mass ratio of 100:1:300, reacting for 4 hours at a rotating speed of 150r/min and a temperature of 100 ℃, centrifuging after the reaction is finished, taking a centrifugal precipitate, adding water with the mass 8 times of that of the centrifugal precipitate for washing, and drying for 12 hours at the temperature of 100 ℃ to obtain aminated montmorillonite;
Mixing the aminated montmorillonite, cyanuric chloride and dioxane, performing ultrasonic treatment, uniformly mixing, performing a second reaction at 80 ℃ for 3 hours, adding ethylenediamine and triethylamine after the reaction is finished, performing a third reaction at 50 ℃ for 7 hours, performing rotary evaporation at 80 ℃ after the reaction is finished to remove the solvent dioxane to obtain a reaction crude product, adding water with the mass 8 times of that of the reaction crude product, and performing drying at 55 ℃ for 20 hours to obtain the functionalized montmorillonite;
wherein the mass ratio of the aminated montmorillonite to the cyanuric chloride to the dioxane to the ethylenediamine to the triethylamine is 3000:20:3600:60:100;
Mixing functionalized montmorillonite, methyl acrylate and acetone by ultrasonic treatment, adding potassium hydroxide after uniform mixing, reacting for 8 hours at 90 ℃ in nitrogen atmosphere, removing solvent acetone by rotary evaporation at 40 ℃ after the reaction is finished, obtaining a reaction crude product, adding water with the mass 5 times of that of the reaction crude product, washing, and drying at 60 ℃ for 12 hours to obtain a flame retardant additive;
wherein the mass ratio of the functionalized montmorillonite to the methyl acrylate to the acetone to the potassium hydroxide is 30:10:250:0.01;
wherein the preparation of the polyesteramide elastomer comprises the following steps:
Mixing the pretreated DOPO with itaconic acid, stirring in a nitrogen atmosphere at 155 ℃ for reaction for 5 hours, adding acetone after the reaction is finished, carrying out reflux reaction at 50 ℃ for 3 hours, and removing solvent acetone by rotary evaporation at 40 ℃ after the reaction is finished to obtain modified DOPO;
Wherein, the mass ratio of DOPO, itaconic acid and acetone is 22:15:100, and the pretreatment operation of DOPO is as follows: melting DOPO for 2h at the temperature of 120 ℃ and the vacuum degree of 0.04 Mpa;
Mixing 1, 4-butanediol, ethylene glycol, modified DOPO and adipic acid in a nitrogen atmosphere at 120 ℃, heating to 170 ℃ at a speed of 1 ℃/min for a first reaction for 3 hours, adding p-toluenesulfonic acid after the reaction is finished, heating to 225 ℃ at a speed of 2 ℃/min for a second reaction for 1 hour under a condition of 0.001Mpa of vacuum degree, adding succinic acid after the reaction is finished, and reacting for a third reaction for 2 hours at 225 ℃ to obtain a polyester prepolymer; mixing the polyester prepolymer with 1, 6-hexamethylenediamine in a nitrogen atmosphere at 150 ℃, heating to 170 ℃ at a speed of 1 ℃/min for a fourth reaction for 4 hours, and reacting for 2 hours at a temperature of 180 ℃ under 300pa of vacuum degree after the reaction is finished to obtain a polyester amide elastomer;
Wherein the mass ratio of the 1, 4-butanediol to the ethylene glycol to the modified DOPO to the adipic acid to the succinic acid to the p-toluenesulfonic acid to the 1, 6-hexamethylenediamine is 100:70:180:260:130:12:70;
Step (2), mixing polylactic acid, a flame retardant additive and tert-butyl peroxybenzoate, carrying out melt reaction for 10min at the temperature of 180 ℃, adding a polyesteramide elastomer after the reaction is finished, carrying out melt extrusion at the temperature of 185 ℃ by a double-screw extruder, cooling and granulating to obtain the high-toughness bio-based PLA degradable composite material;
Wherein the mass ratio of the polylactic acid to the flame retardant additive to the polyester amide elastomer to the tert-butyl peroxybenzoate is 87.5:4.5:8:3.
Example 3
The embodiment discloses a preparation method of a high-toughness bio-based PLA degradable composite material, which comprises the following steps:
Step (1), preparation of flame retardant additive and polyester amide elastomer
Wherein, the preparation of the flame retardant additive comprises the following steps:
Mixing montmorillonite, dicyandiamide and water in a mass ratio of 100:2:400, reacting for 4.5 hours at a rotating speed of 200r/min and a temperature of 95 ℃, centrifuging after the reaction is finished, taking a centrifugal precipitate, adding water with the mass 6 times of that of the centrifugal precipitate for washing, and drying for 10 hours at a temperature of 105 ℃ to obtain aminated montmorillonite;
Mixing the aminated montmorillonite, cyanuric chloride and dioxane, carrying out ultrasonic treatment, uniformly mixing, carrying out a second reaction at 85 ℃ for 2.5 hours, adding ethylenediamine and triethylamine after the reaction is finished, carrying out a third reaction at 55 ℃ for 6 hours, carrying out rotary evaporation at 85 ℃ after the reaction is finished to remove the solvent dioxane to obtain a reaction crude product, adding water with the mass 6 times of the reaction crude product, and carrying out drying at 55 ℃ for 18 hours to obtain the functionalized montmorillonite;
wherein the mass ratio of the aminated montmorillonite to the cyanuric chloride to the dioxane to the ethylenediamine to the triethylamine is 3100:40:3800:120:200;
Mixing functionalized montmorillonite, methyl acrylate and acetone by ultrasonic treatment, adding potassium hydroxide after uniform mixing, reacting for 8 hours at 90 ℃ in nitrogen atmosphere, removing solvent acetone by rotary evaporation at 50 ℃ after the reaction is finished, obtaining a reaction crude product, adding water with the mass 6 times of that of the reaction crude product, washing, and drying for 15 hours at 60 ℃ to obtain a flame retardant additive;
wherein the mass ratio of the functionalized montmorillonite to the methyl acrylate to the acetone to the potassium hydroxide is 40:12:270:0.02;
wherein the preparation of the polyesteramide elastomer comprises the following steps:
Mixing the pretreated DOPO with itaconic acid, stirring in a nitrogen atmosphere at 160 ℃ for reaction for 4.5 hours, adding acetone after the reaction is finished, carrying out reflux reaction at 55 ℃ for 2.5 hours, and removing solvent acetone by rotary evaporation at 50 ℃ after the reaction is finished to obtain modified DOPO;
Wherein, the mass ratio of DOPO, itaconic acid and acetone is 21:12:90, and the pretreatment operation of DOPO is as follows: melting DOPO for 2h at the temperature of 120 ℃ and the vacuum degree of 0.04 Mpa;
Mixing 1, 4-butanediol, ethylene glycol, modified DOPO and adipic acid in a nitrogen atmosphere at 120 ℃, heating to 175 ℃ at a speed of 2 ℃/min for a first reaction for 2.5 hours, adding p-toluenesulfonic acid after the reaction is finished, heating to 220 ℃ at a speed of 1 ℃/min for a second reaction for 2 hours under a condition of 0.001Mpa, adding succinic acid after the reaction is finished, and reacting for a third reaction for 2.5 hours at a temperature of 225 ℃ to obtain a polyester prepolymer; mixing the polyester prepolymer with 1, 6-hexamethylenediamine in a nitrogen atmosphere at 150 ℃, heating to 175 ℃ at a speed of 2 ℃/min for a fourth reaction for 4 hours, and reacting for a fifth reaction for 2 hours at a temperature of 180 ℃ and a vacuum degree of 400pa after the reaction is finished to obtain a polyesteramide elastomer;
Wherein the mass ratio of 1, 4-butanediol, ethylene glycol, modified DOPO, adipic acid, succinic acid, p-toluenesulfonic acid and 1, 6-hexamethylenediamine is 110:80:160:300:150:15:80;
Step (2), mixing polylactic acid, a flame retardant additive and tert-butyl peroxybenzoate, carrying out melt reaction for 9min at the temperature of 183 ℃, adding a polyesteramide elastomer after the reaction is finished, carrying out melt extrusion at the temperature of 185 ℃ by a double-screw extruder, cooling and granulating to obtain the high-toughness bio-based PLA degradable composite material;
Wherein the mass ratio of the polylactic acid to the flame retardant additive to the polyester amide elastomer to the tert-butyl peroxybenzoate is 89:4:7:2.
Example 4
The embodiment discloses a preparation method of a high-toughness bio-based PLA degradable composite material, which comprises the following steps:
Step (1), preparation of flame retardant additive and polyester amide elastomer
Wherein, the preparation of the flame retardant additive comprises the following steps:
Mixing montmorillonite, dicyandiamide and water in a mass ratio of 100:1:350, reacting for 4.5 hours at the temperature of 95 ℃ at the rotating speed of 250r/min for the first time, centrifuging after the reaction is finished, taking a centrifugal precipitate, adding water with the mass 8 times of that of the centrifugal precipitate for washing, and drying for 10 hours at the temperature of 100 ℃ to obtain aminated montmorillonite;
Mixing the aminated montmorillonite, cyanuric chloride and dioxane, performing ultrasonic treatment, uniformly mixing, performing a second reaction at 90 ℃ for 2 hours, adding ethylenediamine and triethylamine after the reaction is finished, performing a third reaction at 50 ℃ for 7 hours, performing rotary evaporation at 85 ℃ after the reaction is finished to remove the solvent dioxane to obtain a reaction crude product, adding water with the mass 8 times of that of the reaction crude product, and performing drying at 55 ℃ for 18 hours to obtain the functionalized montmorillonite;
wherein the mass ratio of the aminated montmorillonite to the cyanuric chloride to the dioxane to the ethylenediamine to the triethylamine is 3050:30:3700:100:180;
Mixing functionalized montmorillonite, methyl acrylate and acetone by ultrasonic treatment, adding potassium hydroxide after uniform mixing, reacting for 8 hours at 90 ℃ in nitrogen atmosphere, removing solvent acetone by rotary evaporation at 40 ℃ after the reaction is finished, obtaining a reaction crude product, adding water with the mass 8 times of that of the reaction crude product, washing, and drying for 18 hours at 55 ℃ to obtain a flame retardant additive;
Wherein the mass ratio of the functionalized montmorillonite to the methyl acrylate to the acetone to the potassium hydroxide is 35:12:280:0.01;
wherein the preparation of the polyesteramide elastomer comprises the following steps:
Mixing the pretreated DOPO with itaconic acid, stirring in a nitrogen atmosphere at 155 ℃ for reaction for 5 hours, adding acetone after the reaction is finished, carrying out reflux reaction at 60 ℃ for 2 hours, and removing solvent acetone by rotary evaporation at 50 ℃ after the reaction is finished to obtain modified DOPO;
Wherein, the mass ratio of DOPO, itaconic acid and acetone is 21:15:90, and the pretreatment operation of DOPO is as follows: melting DOPO for 2h at the temperature of 120 ℃ and the vacuum degree of 0.04 Mpa;
Mixing 1, 4-butanediol, ethylene glycol, modified DOPO and adipic acid in a nitrogen atmosphere at 120 ℃, heating to 170 ℃ at a speed of 1.5 ℃/min for a first reaction for 3 hours, adding p-toluenesulfonic acid after the reaction, heating to 225 ℃ at a speed of 2 ℃/min for a second reaction for 1 hour under a condition of a vacuum degree of 0.001Mpa, adding succinic acid after the reaction, and reacting for a third reaction for 2 hours at a temperature of 225 ℃ to obtain a polyester prepolymer; mixing the polyester prepolymer with 1, 6-hexamethylenediamine in a nitrogen atmosphere at 150 ℃, heating to 175 ℃ at a speed of 2 ℃/min for a fourth reaction for 4 hours, and reacting for a fifth reaction for 2 hours at a temperature of 180 ℃ and a vacuum degree of 350pa after the reaction is finished to obtain a polyesteramide elastomer;
Wherein the mass ratio of the 1, 4-butanediol to the ethylene glycol to the modified DOPO to the adipic acid to the succinic acid to the p-toluenesulfonic acid to the 1, 6-hexamethylenediamine is 130:90:140:340:170:18:90;
Step (2), mixing polylactic acid, a flame retardant additive and tert-butyl peroxybenzoate, carrying out melt reaction for 8min at 185 ℃, adding a polyesteramide elastomer after the reaction is finished, carrying out melt extrusion at 185 ℃ by a double-screw extruder, cooling and granulating to obtain the high-toughness bio-based PLA degradable composite material;
wherein the mass ratio of the polylactic acid to the flame retardant additive to the polyester amide elastomer to the tert-butyl peroxybenzoate is 90.5:3.5:6:2.
Example 5
The embodiment discloses a preparation method of a high-toughness bio-based PLA degradable composite material, which comprises the following steps:
Step (1), preparation of flame retardant additive and polyester amide elastomer
Wherein, the preparation of the flame retardant additive comprises the following steps:
Mixing montmorillonite, dicyandiamide and water in a mass ratio of 100:3:450, reacting for 4 hours at a rotating speed of 300r/min and a temperature of 100 ℃, centrifuging after the reaction is finished, taking a centrifugal precipitate, adding water with the mass 6 times of that of the centrifugal precipitate for washing, and drying for 8 hours at a temperature of 110 ℃ to obtain aminated montmorillonite;
Mixing the aminated montmorillonite, cyanuric chloride and dioxane, performing ultrasonic treatment, uniformly mixing, performing a second reaction at 80 ℃ for 3 hours, adding ethylenediamine and triethylamine after the reaction is finished, performing a third reaction at 50 ℃ for 7 hours, performing rotary evaporation at 85 ℃ after the reaction is finished to remove the solvent dioxane to obtain a reaction crude product, adding water with the mass 8 times of that of the reaction crude product, and performing drying at 60 ℃ for 12 hours to obtain the functionalized montmorillonite;
Wherein the mass ratio of the aminated montmorillonite to the cyanuric chloride to the dioxane to the ethylenediamine to the triethylamine is 3150:40:3900:150:250;
Mixing functionalized montmorillonite, methyl acrylate and acetone by ultrasonic treatment, adding potassium hydroxide after uniform mixing, reacting for 6 hours at 95 ℃ in nitrogen atmosphere, removing solvent acetone by rotary evaporation at 50 ℃ after the reaction is finished, obtaining a reaction crude product, adding water with the mass 5 times of that of the reaction crude product, washing, and drying for 18 hours at 55 ℃ to obtain a flame retardant additive;
Wherein the mass ratio of the functionalized montmorillonite to the methyl acrylate to the acetone to the potassium hydroxide is 45:14:300:0.02;
wherein the preparation of the polyesteramide elastomer comprises the following steps:
mixing the pretreated DOPO with itaconic acid, stirring in a nitrogen atmosphere at 165 ℃ for reaction for 4 hours, adding acetone after the reaction is finished, carrying out reflux reaction at 50 ℃ for 3 hours, and removing solvent acetone by rotary evaporation at 50 ℃ after the reaction is finished to obtain modified DOPO;
wherein, the mass ratio of DOPO, itaconic acid and acetone is 20:10:100, and the pretreatment operation of DOPO is as follows: melting DOPO for 2h at the temperature of 120 ℃ and the vacuum degree of 0.04 Mpa;
Mixing 1, 4-butanediol, ethylene glycol, modified DOPO and adipic acid in a nitrogen atmosphere at 120 ℃, heating to 170 ℃ at a speed of 1 ℃/min for a first reaction for 3 hours, adding p-toluenesulfonic acid after the reaction is finished, heating to 215 ℃ at a speed of 2 ℃/min for a second reaction for 1 hour under a condition of 0.001Mpa of vacuum degree, adding succinic acid after the reaction is finished, and reacting for a third reaction for 2 hours at a temperature of 225 ℃ to obtain a polyester prepolymer; mixing the polyester prepolymer with 1, 6-hexamethylenediamine in a nitrogen atmosphere at 150 ℃, heating to 180 ℃ at a speed of 2 ℃/min for a fourth reaction for 4 hours, and reacting for a fifth reaction for 2 hours at a temperature of 180 ℃ and a vacuum degree of 450pa after the reaction is finished to obtain a polyesteramide elastomer;
Wherein the mass ratio of the 1, 4-butanediol to the ethylene glycol to the modified DOPO to the adipic acid to the succinic acid to the p-toluenesulfonic acid to the 1, 6-hexamethylenediamine is 150:100:120:380:180:20:100;
Step (2), mixing polylactic acid, a flame retardant additive and tert-butyl peroxybenzoate, carrying out melt reaction for 10min at the temperature of 180 ℃, adding a polyesteramide elastomer after the reaction is finished, carrying out melt extrusion at the temperature of 185 ℃ by a double-screw extruder, cooling and granulating to obtain the high-toughness bio-based PLA degradable composite material;
wherein the mass ratio of the polylactic acid to the flame retardant additive to the polyester amide elastomer to the tert-butyl peroxybenzoate is 92:3:5:2.
Comparative example 1
The comparative example discloses a preparation method of a high-toughness bio-based PLA degradable composite material, which comprises the following steps:
Step (1), preparing a polyesteramide elastomer;
The method comprises the following steps: mixing the pretreated DOPO with itaconic acid, stirring in a nitrogen atmosphere at 165 ℃ for reaction for 4 hours, adding acetone after the reaction is finished, carrying out reflux reaction at 60 ℃ for 2 hours, and removing solvent acetone by rotary evaporation at 50 ℃ after the reaction is finished to obtain modified DOPO;
Wherein, the mass ratio of DOPO, itaconic acid and acetone is 20:10:80, and the pretreatment operation of DOPO is as follows: melting DOPO for 2h at the temperature of 120 ℃ and the vacuum degree of 0.04 Mpa;
Mixing 1, 4-butanediol, ethylene glycol, modified DOPO and adipic acid in a nitrogen atmosphere at 120 ℃, heating to 180 ℃ at a rate of 2 ℃/min for a first reaction for 2 hours, adding p-toluenesulfonic acid after the reaction is finished, heating to 210 ℃ at a rate of 1 ℃/min for a second reaction for 3 hours under the condition of 0.001Mpa of vacuum degree, adding succinic acid after the reaction is finished, and reacting for a third reaction for 3 hours at a temperature of 225 ℃ to obtain a polyester prepolymer; mixing the polyester prepolymer with 1, 6-hexamethylenediamine in a nitrogen atmosphere at the temperature of 150 ℃, heating to 180 ℃ at the speed of 2 ℃/min for a fourth reaction for 4 hours, and reacting for 2 hours at the temperature of 180 ℃ at the vacuum degree of 500pa after the reaction is finished to obtain a polyester amide elastomer;
wherein the mass ratio of the 1, 4-butanediol to the ethylene glycol to the modified DOPO to the adipic acid to the succinic acid to the p-toluenesulfonic acid to the 1, 6-hexamethylenediamine is 90:60:200:220:110:10:60;
Step (2), mixing polylactic acid, montmorillonite and tert-butyl peroxybenzoate, carrying out melt reaction for 8min at 185 ℃, adding a polyester amide elastomer after the reaction is finished, carrying out melt extrusion at 185 ℃ through a double-screw extruder, cooling and granulating to obtain a high-toughness bio-based PLA degradable composite material;
wherein the mass ratio of polylactic acid to montmorillonite to polyester amide elastomer to tert-butyl peroxybenzoate is 85:5:10:3.
Comparative example 2
The comparative example discloses a preparation method of a high-toughness bio-based PLA degradable composite material, which comprises the following steps:
Step (1), preparation of flame retardant additive and polyester amide elastomer
Wherein, the preparation of the flame retardant additive comprises the following steps:
Mixing dicyandiamide, cyanuric chloride and dioxane, carrying out ultrasonic treatment, carrying out secondary reaction for 2 hours at the temperature of 90 ℃ after uniform mixing, adding ethylenediamine and triethylamine after the reaction is finished, carrying out tertiary reaction for 6 hours at the temperature of 55 ℃, carrying out rotary evaporation at the temperature of 90 ℃ after the reaction is finished to remove the solvent dioxane to obtain a reaction crude product, adding water with the mass 5 times of that of the reaction crude product, and drying for 12 hours at the temperature of 60 ℃ to obtain a flame retardant additive;
Wherein the mass ratio of dicyandiamide to cyanuric chloride to dioxane to ethylenediamine to triethylamine is 30:60:4000:180:300;
wherein the preparation of the polyesteramide elastomer comprises the following steps:
mixing the pretreated DOPO with itaconic acid, stirring in a nitrogen atmosphere at 165 ℃ for reaction for 4 hours, adding acetone after the reaction is finished, carrying out reflux reaction at 60 ℃ for 2 hours, and removing solvent acetone by rotary evaporation at 50 ℃ after the reaction is finished to obtain modified DOPO;
Wherein, the mass ratio of DOPO, itaconic acid and acetone is 20:10:80, and the pretreatment operation of DOPO is as follows: melting DOPO for 2h at the temperature of 120 ℃ and the vacuum degree of 0.04 Mpa;
Mixing 1, 4-butanediol, ethylene glycol, modified DOPO and adipic acid in a nitrogen atmosphere at 120 ℃, heating to 180 ℃ at a rate of 2 ℃/min for a first reaction for 2 hours, adding p-toluenesulfonic acid after the reaction is finished, heating to 210 ℃ at a rate of 1 ℃/min for a second reaction for 3 hours under the condition of 0.001Mpa of vacuum degree, adding succinic acid after the reaction is finished, and reacting for a third reaction for 3 hours at a temperature of 225 ℃ to obtain a polyester prepolymer; mixing the polyester prepolymer with 1, 6-hexamethylenediamine in a nitrogen atmosphere at the temperature of 150 ℃, heating to 180 ℃ at the speed of 2 ℃/min for a fourth reaction for 4 hours, and reacting for 2 hours at the temperature of 180 ℃ at the vacuum degree of 500pa after the reaction is finished to obtain a polyester amide elastomer;
wherein the mass ratio of the 1, 4-butanediol to the ethylene glycol to the modified DOPO to the adipic acid to the succinic acid to the p-toluenesulfonic acid to the 1, 6-hexamethylenediamine is 90:60:200:220:110:10:60;
Step (2), mixing polylactic acid, a flame retardant additive and tert-butyl peroxybenzoate, carrying out melt reaction for 8min at 185 ℃, adding a polyesteramide elastomer after the reaction is finished, carrying out melt extrusion at 185 ℃ by a double-screw extruder, cooling and granulating to obtain the high-toughness bio-based PLA degradable composite material;
wherein the mass ratio of the polylactic acid to the flame retardant additive to the polyester amide elastomer to the tert-butyl peroxybenzoate is 85:5:10:3.
Comparative example 3
The comparative example discloses a preparation method of a high-toughness bio-based PLA degradable composite material, which comprises the following steps:
Step (1), preparing a flame retardant additive;
the method comprises the following steps: mixing montmorillonite, dicyandiamide and water in a mass ratio of 100:3:500, reacting for 5 hours at the temperature of 90 ℃ at the rotating speed of 300r/min for the first time, centrifuging after the reaction is finished, taking a centrifugal precipitate, adding water with the mass 5 times of that of the centrifugal precipitate for washing, and drying for 8 hours at the temperature of 110 ℃ to obtain aminated montmorillonite;
mixing the aminated montmorillonite, cyanuric chloride and dioxane, performing ultrasonic treatment, uniformly mixing, performing a second reaction at 90 ℃ for 2 hours, adding ethylenediamine and triethylamine after the reaction is finished, performing a third reaction at 55 ℃ for 6 hours, performing rotary evaporation at 90 ℃ after the reaction is finished to remove the solvent dioxane to obtain a reaction crude product, adding water with the mass 5 times of that of the reaction crude product, and performing drying at 60 ℃ for 12 hours to obtain the functionalized montmorillonite;
wherein the mass ratio of the aminated montmorillonite to the cyanuric chloride to the dioxane to the ethylenediamine to the triethylamine is 3200:60:4000:180:300;
Mixing functionalized montmorillonite, methyl acrylate and acetone by ultrasonic treatment, adding potassium hydroxide after uniform mixing, reacting for 6 hours at 95 ℃ in nitrogen atmosphere, removing solvent acetone by rotary evaporation at 50 ℃ after the reaction is finished, obtaining a reaction crude product, adding water with the mass 8 times of that of the reaction crude product, washing, and drying for 20 hours at 55 ℃ to obtain a flame retardant additive;
wherein the mass ratio of the functionalized montmorillonite to the methyl acrylate to the acetone to the potassium hydroxide is 50:15:300:0.03;
Step (2), mixing polylactic acid, a flame retardant additive and tert-butyl peroxybenzoate, carrying out melt reaction for 8min at 185 ℃, carrying out melt extrusion at 185 ℃ through a double-screw extruder after the reaction is finished, cooling and granulating to obtain the high-toughness bio-based PLA degradable composite material;
Wherein the mass ratio of the polylactic acid to the flame retardant additive to the tert-butyl peroxybenzoate is 95:5:10:3.
In the above examples and comparative examples: montmorillonite was obtained from Shanghai Ala Biochemical technology Co., ltd., model K-10, cat# M109698, CAS number: 1318-93-0; dicyandiamide from atanan mountain sea chemical engineering limited, CAS no: 461-58-5; cyanuric chloride from Shandong Polymer chemistry Co., ltd., CAS number: 108-77-0; dioxane was from the name of Mao Ming, male Mao chemical Co., ltd., CAS number: 123-91-1; ethylenediamine is from mountain east sea boarding new materials limited, CAS no: 107-15-3; triethylamine from Shanghai Ala Biochemical technologies Co., ltd., CAS number: 121-44-8; methyl acrylate comes from Mao Ming, male Max chemical Co., ltd., CAS number: 96-33-3; acetone was obtained from Shandong Wensao chemical Co., ltd., CAS number: 67-64-1; potassium hydroxide was from the tin-free City, chemie Co., ltd., CAS number: 1310-58-3; DOPO from shanghai eukarst, inc., CAS number: 35948-25-5; itaconic acid is available from Guangdong Weng Jiang chemical Co., ltd., CAS number: 97-65-4;1, 4-butanediol was from the Kyoto Biotechnology Co., ltd., CAS number: 110-63-4; ethylene glycol was obtained from the company Wuhan Hua Xiangke, jie Biotechnology, inc., CAS number: 107-21-1; adipic acid was obtained from medal chemical company, model analytically pure, CAS number: 124-04-9; p-toluenesulfonic acid was from europaea biotechnology limited, CAS number: 104-15-4; succinic acid was from the company of the sciences, the company of the ridge, CAS number: 110-15-6;1, 6-hexamethylenediamine from Mao Ming, male chemical Co., ltd., CAS number: 124-09-4; polylactic acid is from Xiang Yi New Material Co., dongguan, hei Zheng, manufacturer, marine organism, cat# REVODE, CAS#: 26100-51-6; t-butyl peroxybenzoate is available from the company, lvshenfeida chemical Co., ltd., st., CAS number: 614-45-9.
Test examples
(1) Comprehensive performance test
Comprehensive performance tests were performed on the high-toughness bio-based PLA-degradable composites prepared in examples 1 to 5 and comparative examples 1 to 3. The specific test results are shown in Table 1:
TABLE 1
The detection of each index in table 1 is based on the following criteria: elongation at break is determined by GB/T1040-1992 method for testing tensile Properties of plastics; the notch impact strength is measured by GB/T1843-2008 "determination of Plastic cantilever impact Strength"; limiting oxygen index is determined by ISO4589-1981 "Plastic oxygen index method for determination of flammability"; the combustion rating is determined by ANSI/UL-94-1985.
From the test results of table 1, it can be seen that the high-toughness bio-based PLA degradable composite material prepared by the present invention has excellent flame retardancy and toughness.
The montmorillonite in comparative example 1 is not subjected to surface modification, so that the dispersibility of the montmorillonite in a blending system of polylactic acid and polyester amide elastomer is reduced, aggregation is easy, meanwhile, the montmorillonite is not provided with double bonds and amide bonds on the surface, cannot be grafted in a molecular main chain of the polylactic acid, cannot form eutectic with the amide bonds in the polyester amide during melt blending, so that the compatibility of the montmorillonite with the polylactic acid and the polyester amide elastomer is reduced, and the sheets of the montmorillonite are not easy to disperse at a disperse phase interface, so that the compatibilization and toughening effects on the polylactic acid cannot be achieved, and the breaking elongation and the notch impact strength of comparative example 1 are lower than those of examples. Meanwhile, since montmorillonite is not grafted with flame retardant components, the flame retardance of the obtained comparative example 1 is lower than that of the example, although montmorillonite per se and the polyester amide elastomer have a certain flame retardant effect.
The flame retardant additive of comparative example 2 was free of montmorillonite grafting and amide bond formation by reaction with methyl acrylate, and the flame retardant additive obtained was free of montmorillonite component, double bond and amide bond, and could not form eutectic with the molecular main chain of polylactic acid grafting and amide bond in polyester amide during melt blending, so that the flame retardant additive was reduced in flame retardancy and easily migrated in the material, and the flame retardancy of comparative example 2 was lower than that of example. Meanwhile, because montmorillonite is lack as an inorganic toughening agent and the compatibilizing effect of the montmorillonite on the polylactic acid and the polyester amide elastomer is reduced, the compatibility of the polylactic acid and the polyester amide elastomer is reduced, so that the elongation at break and the notch impact strength of comparative example 2 are lower than those of examples.
In comparative example 3, the polyester amide elastomer is not added, the toughening effect of the polyester amide elastomer on the polylactic acid as an organic toughening agent is absent, and the flame retardant capability of the polyester amide elastomer is absent, so that the prepared comparative example 3 has lower elongation at break, notch impact strength and flame retardance than those of the examples even if the flame retardant additive has toughening and flame retardant effects on the polylactic acid.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. The preparation method of the high-toughness bio-based PLA degradable composite material is characterized by comprising the following steps:
Step (1), preparation of flame retardant additive and polyester amide elastomer
Wherein, the preparation of the flame retardant additive comprises the following steps:
mixing montmorillonite, dicyandiamide and water, carrying out a first reaction, centrifuging after the reaction is finished, taking a centrifugal precipitate, washing, and drying to obtain aminated montmorillonite;
mixing the aminated montmorillonite, cyanuric chloride and dioxane with ultrasound, uniformly mixing, carrying out a second reaction, adding ethylenediamine and triethylamine after the reaction is finished, carrying out a third reaction, removing solvent dioxane by rotary evaporation after the reaction is finished, washing, and drying to obtain the functionalized montmorillonite;
Mixing functionalized montmorillonite, methyl acrylate and acetone with ultrasound, adding potassium hydroxide after uniform mixing, reacting for the fourth time, removing solvent acetone by rotary evaporation after the reaction is finished, washing, and drying to obtain a flame retardant additive;
wherein the preparation of the polyesteramide elastomer comprises the following steps:
Mixing the pretreated DOPO with itaconic acid, stirring for reaction, adding acetone after the reaction is finished, carrying out reflux reaction, and removing the solvent acetone by rotary evaporation after the reaction is finished to obtain modified DOPO; mixing 1, 4-butanediol, ethylene glycol, modified DOPO and adipic acid, adding p-toluenesulfonic acid after the first reaction, carrying out the second reaction, adding succinic acid after the reaction, and carrying out the third reaction to obtain a polyester prepolymer; mixing the polyester prepolymer with 1, 6-hexamethylenediamine, carrying out a fourth reaction, and carrying out a fifth reaction after the reaction is finished to obtain a polyester amide elastomer;
and (2) mixing polylactic acid, a flame retardant additive and tert-butyl peroxybenzoate, carrying out a melting reaction, adding a polyester amide elastomer after the reaction is finished, carrying out melting extrusion, cooling and granulating to obtain the high-toughness bio-based PLA degradable composite material.
2. The method for preparing the high-toughness bio-based PLA degradable composite material according to claim 1, wherein in the step (1), when preparing the flame retardant additive: the mass ratio of montmorillonite, dicyandiamide and water is 100 (1-3) (300-500); the first reaction conditions are as follows: the first reaction is carried out for 4 to 5 hours at the rotating speed of 150 to 300r/min and the temperature of 90 to 100 ℃.
3. The method for preparing the high-toughness bio-based PLA degradable composite material according to claim 1, wherein in the step (1), when preparing the flame retardant additive: the mass ratio of the aminated montmorillonite to the cyanuric chloride to the dioxane to the ethylenediamine to the triethylamine is (3000-3200), 20-60, 3600-4000, 60-180 and 100-300; the second reaction conditions are as follows: reacting for 2-3h at 80-90 ℃; the third reaction conditions are as follows: and reacting for 6-7h at 50-55 ℃.
4. The method for preparing the high-toughness bio-based PLA degradable composite material according to claim 1, wherein in the step (1), when preparing the flame retardant additive: the mass ratio of the functionalized montmorillonite to the methyl acrylate to the acetone to the potassium hydroxide is (30-50)/(10-15)/(250-300)/(0.01-0.03); the fourth reaction conditions are as follows: and reacting for 6-8h at 90-95 ℃ in nitrogen atmosphere.
5. The method for preparing the high-toughness bio-based PLA degradable composite material according to claim 1, wherein in the step (1), when preparing the polyesteramide elastomer: the mass ratio of DOPO, itaconic acid and acetone is (20-22): 10-15): 80-100; the stirring reaction conditions are as follows: stirring and reacting for 4-5h at 155-165 ℃ in nitrogen atmosphere; the reflux reaction conditions are as follows: reflux reaction is carried out for 2-3h at 50-60 ℃.
6. The method for preparing the high-toughness bio-based PLA degradable composite material according to claim 1, wherein in the step (1), when preparing the polyesteramide elastomer: the mass ratio of the 1, 4-butanediol, the ethylene glycol, the modified DOPO, the adipic acid, the succinic acid, the p-toluenesulfonic acid and the 1, 6-hexamethylenediamine is (90-150), (60-100), (120-200), (220-380), (110-180), (10-20) and (60-100).
7. The method for preparing the high-toughness bio-based PLA degradable composite material according to claim 1, wherein in the step (1), when preparing the polyesteramide elastomer: the first reaction conditions are as follows: heating from 120 ℃ to 170-180 ℃ at a speed of 1-2 ℃/min in a nitrogen atmosphere for a first reaction for 2-3h; the second reaction conditions are as follows: heating to 210-225 ℃ at a speed of 1-2 ℃/min under the condition of nitrogen atmosphere and vacuum degree of 0.001Mpa for a second reaction for 1-3h; the third reaction conditions are as follows: and carrying out a third reaction for 2-3h at 225 ℃ in a nitrogen atmosphere.
8. The method for preparing the high-toughness bio-based PLA degradable composite material according to claim 1, wherein in the step (1), when preparing the polyesteramide elastomer: the fourth reaction conditions are as follows: heating from 150 ℃ to 170-180 ℃ at a speed of 1-2 ℃/min in a nitrogen atmosphere for a fourth reaction for 4h; the fifth reaction conditions are as follows: and carrying out fifth reaction for 2h in a nitrogen atmosphere at the temperature of 180 ℃ and the vacuum degree of 300-500 pa.
9. The method for preparing the high-toughness bio-based PLA-degradable composite material according to claim 1, wherein in the step (2): the mass ratio of polylactic acid to flame retardant additive to polyester amide elastomer to tert-butyl peroxybenzoate is (85-92), 3-5, 5-10 and 2-3; the conditions of the melting reaction are as follows: carrying out melt reaction for 8-10min at 180-185 ℃; the conditions of melt extrusion were: melt extrusion was performed by a twin screw extruder at a temperature of 185 ℃.
10. A high-toughness bio-based PLA degradable composite material prepared by the method of preparing a high-toughness bio-based PLA degradable composite material according to any one of claims 1-9.
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