CN116534880A - Preparation of graphene oxide siloxane hydrophobically modified nano Mg (OH) 2 and flame-retardant antibacterial polylactic acid material thereof - Google Patents
Preparation of graphene oxide siloxane hydrophobically modified nano Mg (OH) 2 and flame-retardant antibacterial polylactic acid material thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 66
- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 59
- 239000004626 polylactic acid Substances 0.000 title claims abstract description 59
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 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 title claims abstract description 37
- 239000000463 material Substances 0.000 title claims abstract description 37
- 239000003063 flame retardant Substances 0.000 title claims abstract description 34
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000011777 magnesium Substances 0.000 claims abstract description 111
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 7
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 41
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 40
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 39
- 239000006185 dispersion Substances 0.000 claims description 32
- 238000003756 stirring Methods 0.000 claims description 23
- 239000007788 liquid Substances 0.000 claims description 22
- 238000002156 mixing Methods 0.000 claims description 16
- 239000000758 substrate Substances 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 12
- 239000011347 resin Substances 0.000 claims description 12
- 229920005989 resin Polymers 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 238000002844 melting Methods 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 5
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 4
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 159000000003 magnesium salts Chemical class 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 4
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 claims description 4
- 239000003242 anti bacterial agent Substances 0.000 claims description 3
- 239000012757 flame retardant agent Substances 0.000 claims description 3
- 239000004094 surface-active agent Substances 0.000 claims description 3
- 238000001125 extrusion Methods 0.000 claims description 2
- 238000005469 granulation Methods 0.000 claims description 2
- 230000003179 granulation Effects 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 230000004048 modification Effects 0.000 abstract description 12
- 238000012986 modification Methods 0.000 abstract description 12
- 239000011159 matrix material Substances 0.000 abstract description 4
- 230000002708 enhancing effect Effects 0.000 abstract description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 abstract 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 abstract 1
- 239000000347 magnesium hydroxide Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 10
- -1 aminosiloxane Chemical class 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 239000002135 nanosheet Substances 0.000 description 8
- 239000002356 single layer Substances 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 238000004321 preservation Methods 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- 238000009210 therapy by ultrasound Methods 0.000 description 4
- 241000894006 Bacteria Species 0.000 description 3
- 229920013822 aminosilicone Polymers 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000007731 hot pressing Methods 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 230000000845 anti-microbial effect Effects 0.000 description 2
- 230000001580 bacterial effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 241000588724 Escherichia coli Species 0.000 description 1
- 101000915639 Homo sapiens Zinc finger protein 470 Proteins 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- 102100029038 Zinc finger protein 470 Human genes 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229920003232 aliphatic polyester Polymers 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 230000036512 infertility Effects 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 230000002040 relaxant effect Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F5/00—Compounds of magnesium
- C01F5/14—Magnesium hydroxide
- C01F5/22—Magnesium hydroxide from magnesium compounds with alkali hydroxides or alkaline- earth oxides or hydroxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/2224—Magnesium hydroxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- 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
-
- 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)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a preparation method of hydrophobically modified nano magnesium hydroxide and a flame-retardant antibacterial polylactic acid material, and relates to the technical field of polylactic acid functional modification, and the invention adopts amino-containing silane coupling agent to prepare nano Mg (OH) 2 Modified to improve nano Mg (OH) 2 Interfacial bonding force and compatibility with polylactic acid, and siloxane can also cooperate with nano Mg (OH) 2 Plays a role of enhancing flame retardance; and the amphipathy of the graphene oxide is utilized to effectively improve the modified nano Mg (OH) 2 Compatibility with polylactic acid matrix and graphene oxide surfaceCOOH and amino modified nano Mg (OH) 2 surface-NH 2 The reaction is carried out to form a covalent bond, so that the modification fastness is improved; graphene oxide/siloxane modified nano Mg (OH) prepared by adopting the method 2 The flame-retardant antibacterial polylactic acid material can be obtained by performing functional modification on polylactic acid.
Description
Technical field:
the invention relates to the technical field of polylactic acid functional modification, in particular to preparation of graphene oxide siloxane hydrophobically modified nano Mg (OH) 2 and a flame-retardant antibacterial polylactic acid material thereof.
The background technology is as follows:
polylactic acid (PLA) is an environment-friendly high polymer material with good biocompatibility and degradability, and is considered as a green bio-based material with wide development prospect for replacing petroleum-based polyester. However, the elemental composition (carbon, hydrogen, oxygen) and molecular chain structure (ester bonds are easily broken at high temperatures to produce volatile combustibles) of PLA determine that it has the same disadvantages of being flammable as general polymers. The flammability of polylactic acid limits its use in certain special applications. In addition, PLA itself does not have antibacterial properties, and when used in food packaging films, biomedical materials or textile fiber materials, uncontrolled bacteria on PLA can seriously cause adverse effects such as diseases, discoloration and malodor. The high flammability and sterility of PLA limits its range of applications, particularly those requiring flame retardant and antimicrobial properties, and thus flame retardant and antimicrobial functional modification of PLA is necessary.
Nanometer Mg (OH) 2 Is an inorganic material with nanometer size, has the advantages of good chemical stability and thermal stability, and is an ideal flame-retardant material of high polymer materials. In addition, nano Mg (OH) 2 The antibacterial material also has broad-spectrum antibacterial performance, is representative of inorganic antibacterial materials, and has good stability and durable antibacterial property. Thus, nano Mg (OH) 2 The flame retardant and antibacterial agent can be used for flame retardant and antibacterial function modification of PLA materials.
But nanometer Mg (OH) 2 The following problems also exist in the use process as a flame retardant: mg (OH) 2 The flame retardance is mostly generated by a physical mode, the flame retardance efficiency is low, a large addition amount is needed to achieve a required flame retardance effect, and although the flame retardance efficiency can be improved to a certain extent by preparing nano particles, the flame retardance requirement of low addition amount can not be met; nanometer Mg (OH) 2 Agglomeration is easy to occur among particles, and the dispersibility of the particles in PLA is affected; due to nano Mg (OH) 2 Is a hydrophilic inorganic material, and polylactic acid is hydrophobic aliphatic polyester, so that nano Mg (OH) 2 Poor compatibility with PLA materials and weak interface bonding.
The invention comprises the following steps:
the invention aims to provide graphene oxide/siloxane modified nano Mg (OH) 2 The preparation method and the application thereof in the preparation of flame-retardant antibacterial polylactic acid material, and aims to improve nano Mg (OH) 2 Flame retardant and antibacterial properties of (a).
The technical problems to be solved by the invention are realized by adopting the following technical scheme:
a first object of the present invention is to provide a nano Mg (OH) 2 The preparation method of (2), the method comprises: slowly dripping the magnesium salt solution and the NaOH solution containing the surfactant into the substrate solution in a double dripping mode, stirring for reaction, filtering after the reaction is finished, washing with water, and drying to obtain nano Mg (OH) 2 。
Preferably, the substrate solution is prepared by adding deionized water into ammonia water or NaOH, and the concentration is 0-1.0 mol/L.
Preferably, the surfactant is polyethylene glycol or sodium stearate, and the dosage is 1-3% of the mass of NaOH.
Preferably, the concentration of the NaOH solution is 1.5-3.0 mol/L.
Preferably, the magnesium salt solution consists of MgCl 2 ·6H 2 O or MgSO 4 ·7H 2 O is added with deionized water to prepare the water with the concentration of 1-2 mol/L.
Preferably, the temperature of the stirring reaction is 40-60 ℃.
A second object of the present invention is to provide nano Mg (OH) obtained according to the aforementioned preparation method 2 。
A third object of the present invention is to provide graphene oxide/siloxane modified nano Mg (OH) 2 The preparation method of (2) comprises the following steps:
(1) Dissolving a silane coupling agent in a solvent, and adding the nano Mg (OH) 2 Stirring for reaction to obtain siloxane modified nano Mg (OH) 2 A dispersion;
(2) Ultrasonic stripping of graphene oxide in a solvent, and then adding siloxane modified nano Mg (OH) prepared in the step (1) 2 Stirring the dispersion liquid for reactionCentrifugal separation, water washing and drying are carried out after the reaction is finished, and graphene oxide/siloxane modified nano Mg (OH) is obtained 2 。
Preferably, the silane coupling agent is an amino-containing silane coupling agent, preferably gamma-aminopropyl triethoxysilane or gamma-aminopropyl trimethoxysilane.
Preferably, the nano Mg (OH) 2 The mass ratio of the silane coupling agent to the silane coupling agent is 1 (3-5).
Preferably, the graphene oxide is used in an amount of silane coupling agent and nano Mg (OH) 2 10 to 20 percent of the total mass.
Preferably, in the step (1) and the step (2), the temperature of the stirring reaction is 60-80 ℃.
Preferably, in the step (1) and the step (2), the solvent is an ethanol/water mixed solvent, and the volume fraction of the ethanol is 10-30%.
A fourth object of the present invention is to provide graphene oxide/siloxane modified nano Mg (OH) obtained according to the aforementioned preparation method 2 。
A fifth object of the present invention is to provide the graphene oxide/siloxane modified nano Mg (OH) 2 As flame retardant and antibacterial agents.
A sixth object of the present invention is to provide the graphene oxide/siloxane modified nano Mg (OH) 2 The application in the preparation of flame-retardant antibacterial polylactic acid material.
The seventh object of the invention is to provide a flame-retardant antibacterial polylactic acid material, which comprises polylactic acid resin and the graphene oxide/siloxane modified nano Mg (OH) 2 。
The graphene oxide/siloxane modified nano Mg (OH) 2 The mass ratio of the flame-retardant antibacterial polylactic acid material is 8-15%.
The eighth object of the present invention is to provide a method for preparing a flame retardant and antibacterial polylactic acid material, which comprises the steps of: modifying nano Mg (OH) with the dried polylactic acid resin and the graphene oxide/siloxane 2 And (3) adding the mixture into a double-screw extruder for extrusion granulation after uniformly mixing to obtain the flame-retardant antibacterial polylactic acid material.
Preferably, the melting temperature of the twin-screw extruder is 180-200 ℃ and the rotating speed is 200-250 rpm.
The flame-retardant antibacterial polylactic acid material can also comprise functional auxiliary agents commonly used in the field, such as reinforcing agents, antioxidants, antistatic agents, ultraviolet screening agents and the like.
The beneficial effects of the invention are as follows:
1) The invention adopts a double-drop reverse precipitation method to prepare nano Mg (OH) 2 The pH value of the reaction system can be ensured to be always higher than the isoelectric point, and the coagulation phenomenon in the reaction process can be effectively avoided; the double-dripping mode is also beneficial to reducing the supersaturation degree of the reaction system and improving the dispersibility of the product.
2) The invention adopts silane coupling agent containing amino to prepare nano Mg (OH) 2 On the one hand, the silane coupling agent is modified in nano Mg (OH) 2 A flexible deformation layer can be formed on the interface between the polylactic acid polymer matrix, and the deformation layer can play a role of relaxing interface stress and improve nano Mg (OH) 2 Interfacial bonding force with polylactic acid; on the other hand, siloxane is used as hydrophobic group to endow nano Mg (OH) 2 Certain hydrophobicity, improving nano Mg (OH) 2 Compatibility with polylactic acid; furthermore, the siloxane has high thermal stability and can cooperate with nano Mg (OH) 2 Plays a role of enhancing flame retardance.
3) The invention utilizes the amphipathy of the graphene oxide to effectively improve the modified nano Mg (OH) 2 Compatibility with polylactic acid matrix, and-COOH and amino modified nano Mg (OH) on graphene oxide surface 2 surface-NH 2 And the reaction is carried out to form a covalent bond, so that the modification fastness is improved.
4) Graphene oxide, siloxane, nano Mg (OH) 2 The graphene oxide/siloxane modified nano Mg (OH) prepared by the invention has certain flame retardant effect, and the three substances are organically combined and then flame-retardant modified on PLA, compared with the method of independently adding the three substances 2 Excellent compatibility and synergistic effect with polylactic acid matrix.
The specific embodiment is as follows:
the invention is further described in connection with the following embodiments in order to make the technical means, the creation features, the achievement of the purpose and the effect of the invention easy to understand.
The limiting oxygen index of the material was measured according to standard GB/T5454-1997 using an FAA type oxygen index meter.
The vertical burn performance of the materials was tested according to standard ASTM D3801-2010 using a vertical burn tester model CZF-1.
The antibacterial performance of the material is tested according to the standard GB/T20944-2008, and the antibacterial rate of the material on escherichia coli and staphylococcus aureus is improved.
Example 1
Into the four-necked flask, 20mL of an aqueous NaOH solution (referred to as a substrate solution) having a concentration of 0.5mol/L was charged. Another 250mL aqueous NaOH solution with concentration of 2mol/L is prepared, and then 0.2g polyethylene glycol is added, and the mixture is mixed and stirred uniformly (called solution 1). Another 250mL of MgCl with the concentration of 1mol/L is prepared 2 An aqueous solution (referred to as solution 2). The temperature of the substrate solution is raised to 40 ℃, the solution 1 and the solution 2 are slowly added into the substrate solution in a dropwise manner, and the reaction is carried out for 60min under the condition of heat preservation and stirring. Centrifuging and filtering the obtained suspension, washing with deionized water for 2 times, and drying in an oven at 80 ℃ for 2 hours to obtain nano Mg (OH) 2 。
60g of gamma-aminopropyl triethoxysilane is added into 300mL of ethanol/water mixed solution (30 mL of ethanol+270 mL of water), and 12g of nano Mg (OH) is added after being uniformly mixed and stirred 2 Continuously stirring uniformly, heating to 60 ℃ and reacting for 60min to obtain aminosiloxane modified nano Mg (OH) 2 And (3) a dispersion.
7.5g of graphene oxide is added into 150mL of ethanol/water mixed solution (15 mL of ethanol+135 mL of water), ultrasonic treatment is carried out for 60min, and the graphene oxide monolayer nano-sheet dispersion liquid is obtained after stripping. Adding graphene oxide monolayer nano-sheet dispersion liquid into aminosiloxane modified nano Mg (OH) 2 In the dispersion liquid, keeping the temperature of the reaction system at 60 ℃, stirring and reacting for 4 hours to obtain graphene oxide/siloxane hydrophobically modified nano Mg (OH) 2 And (3) a dispersion. Centrifuging the dispersion liquid, washing 3 times with clear water, and placing the dispersion liquid in an oven to be dried for 6 hours at 60 ℃ to obtain graphene oxide/siloxane hydrophobically modified nano Mg (OH) 2 。
Hydrophobically modified graphene oxide/siloxane nano Mg (OH) 2 And drying the polylactic acid resin in a vacuum oven at 60 ℃ for 12 hours, and removing water. Drying 20g graphene oxide/siloxane hydrophobically modified nano Mg (OH) 2 After being evenly mixed with 180g of polylactic resin, the mixture is added into a double-screw extruder to be melt blended at 170 ℃ and a rotating speed of 200rpm, extruded and granulated, and then hot-pressed at 170 ℃ to form a strip-shaped material with the thickness of 2 mm.
Example 2
Into the four-necked flask, 50mL of an aqueous ammonia solution (referred to as a substrate solution) having a concentration of 1mol/L was charged. Another 250mL aqueous NaOH solution with a concentration of 3mol/L was prepared, and then 0.5g sodium stearate was added thereto, and the mixture was stirred well (referred to as solution 1). Another 250mL of MgCl with the concentration of 2mol/L is prepared 2 An aqueous solution (referred to as solution 2). The temperature of the substrate solution is raised to 40 ℃, the solution 1 and the solution 2 are slowly added into the substrate solution in a dropwise manner, and the reaction is carried out for 60min under the condition of heat preservation and stirring. Centrifuging and filtering the obtained suspension, washing with deionized water for 2 times, and drying in an oven at 80 ℃ for 2 hours to obtain nano Mg (OH) 2 。
80g of gamma-aminopropyl trimethoxysilane was added to 270mL of ethanol/water mixture (67.5 mL of ethanol+202.5 mL of water), and 20g of nano Mg (OH) was added after mixing and stirring well 2 Continuously stirring uniformly, heating to 60 ℃ and reacting for 60min to obtain aminosiloxane modified nano Mg (OH) 2 And (3) a dispersion.
15g of graphene oxide is added into 200mL of ethanol/water mixed solution (50 mL of ethanol+150 mL of water), ultrasonic treatment is carried out for 60min, and the graphene oxide monolayer nano-sheet dispersion liquid is obtained after stripping. Adding graphene oxide monolayer nano-sheet dispersion liquid into aminosiloxane modified nano Mg (OH) 2 In the dispersion liquid, keeping the temperature of the reaction system at 80 ℃, stirring and reacting for 4 hours to obtain graphene oxide/siloxane hydrophobically modified nano Mg (OH) 2 And (3) a dispersion. Centrifuging the dispersion liquid, washing 3 times with clear water, and placing the dispersion liquid in an oven to be dried for 4 hours at 80 ℃ to obtain graphene oxide/siloxane hydrophobically modified nano Mg (OH) 2 。
Hydrophobically modified graphene oxide/siloxane nano Mg (OH) 2 Vacuum mixing with polylactic acid resinDrying in an oven at 60 ℃ for 12 hours, and removing water. The dried 24g graphene oxide/siloxane hydrophobically modified nano Mg (OH) 2 Mixing with 176g polylactic resin, adding into a double screw extruder, melting and blending at 180 ℃ and 220rpm, extruding and granulating, and hot-pressing at 180 ℃ to obtain strip material with the thickness of 2 mm.
Example 3
Into a four-necked flask was added 20mL of deionized water (referred to as a substrate solution). Another 250mL aqueous NaOH solution with a concentration of 1.5mol/L was prepared, and then 0.45g of polyethylene glycol was added thereto, and the mixture was stirred well (referred to as solution 1). 250mL of MgSO with a concentration of 1mol/L was prepared 4 An aqueous solution (referred to as solution 2). The temperature of the substrate solution is increased to 60 ℃, the solution 1 and the solution 2 are slowly added into the substrate solution in a dropwise manner, and the reaction is carried out for 30min under the condition of heat preservation and stirring. Centrifuging and filtering the obtained suspension, washing with deionized water for 2 times, and drying in an oven at 60 ℃ for 4 hours to obtain nano Mg (OH) 2 。
50g of gamma-aminopropyl trimethoxysilane is added into 250mL of ethanol/water mixed solution (50 m ethanol+200 mL water), and 10g of nano Mg (OH) is added after being uniformly mixed and stirred 2 Continuously stirring uniformly, heating to 60 ℃ and reacting for 60min to obtain aminosiloxane modified nano Mg (OH) 2 And (3) a dispersion.
12g of graphene oxide is added into 240mL of ethanol/water mixed solution (48 mL of ethanol+192 mL of water), ultrasonic treatment is carried out for 60min, and the graphene oxide monolayer nano-sheet dispersion liquid is obtained after stripping. Adding graphene oxide monolayer nano-sheet dispersion liquid into aminosiloxane modified nano Mg (OH) 2 In the dispersion liquid, keeping the temperature of the reaction system at 60 ℃, stirring and reacting for 6 hours to obtain graphene oxide/siloxane hydrophobically modified nano Mg (OH) 2 And (3) a dispersion. Centrifuging the dispersion liquid, washing 3 times with clear water, and placing the dispersion liquid in an oven to be dried for 4 hours at 80 ℃ to obtain graphene oxide/siloxane hydrophobically modified nano Mg (OH) 2 。
Hydrophobically modified graphene oxide/siloxane nano Mg (OH) 2 And drying the polylactic acid resin in a vacuum oven at 60 ℃ for 12 hours, and removing water. The dried 24g graphene oxide/siloxane hydrophobically modified nano Mg (OH) 2 Mixing with 176g polylactic acid resinThen, the mixture is added into a double-screw extruder to be melt blended at 180 ℃ and 220rpm, extruded and granulated, and then hot-pressed at 180 ℃ to obtain a strip-shaped material with the thickness of 2 mm.
Example 4
Into the four-necked flask, 50mL of an aqueous ammonia solution (referred to as a substrate solution) having a concentration of 0.5mol/L was charged. Another 250mL aqueous NaOH solution with a concentration of 2mol/L was prepared, and then 0.5g sodium stearate was added thereto, and the mixture was stirred well (referred to as solution 1). 250mL of MgSO with a concentration of 1mol/L was prepared 4 An aqueous solution (referred to as solution 2). The temperature of the substrate solution is raised to 40 ℃, the solution 1 and the solution 2 are slowly added into the substrate solution in a dropwise manner, and the reaction is carried out for 60min under the condition of heat preservation and stirring. Centrifuging and filtering the obtained suspension, washing with deionized water for 2 times, and drying in an oven at 80 ℃ for 2 hours to obtain nano Mg (OH) 2 。
60g of gamma-aminopropyl triethoxysilane is added into 240mL of ethanol/water mixed solution (48 mL of ethanol+196 mL of water), and 15g of nano Mg (OH) is added after being uniformly mixed and stirred 2 Continuously stirring uniformly, heating to 60 ℃ and reacting for 60min to obtain aminosiloxane modified nano Mg (OH) 2 And (3) a dispersion.
12g of graphene oxide is added into 200mL of ethanol/water mixed solution (40 mL of ethanol+160 mL of water), ultrasonic treatment is carried out for 60min, and the graphene oxide monolayer nano-sheet dispersion liquid is obtained after stripping. Adding graphene oxide monolayer nano-sheet dispersion liquid into aminosiloxane modified nano Mg (OH) 2 In the dispersion liquid, keeping the temperature of the reaction system at 80 ℃, stirring and reacting for 4 hours to obtain graphene oxide/siloxane hydrophobically modified nano Mg (OH) 2 And (3) a dispersion. Centrifuging the dispersion liquid, washing 3 times with clear water, and placing the dispersion liquid in an oven to be dried for 4 hours at 80 ℃ to obtain graphene oxide/siloxane hydrophobically modified nano Mg (OH) 2 。
Hydrophobically modified graphene oxide/siloxane nano Mg (OH) 2 And drying the polylactic acid resin in a vacuum oven at 60 ℃ for 12 hours, and removing water. The dried 24g graphene oxide/siloxane hydrophobically modified nano Mg (OH) 2 Mixing with 176g polylactic resin, adding into double screw extruder, melting at 180deg.C and 220rpm, extruding, granulating, and hot-pressing at 180deg.C to obtain 2 mm thick stripAnd (5) material.
Examples 5 to 7
In examples 5-7, graphene oxide/siloxane hydrophobically modified nano Mg (OH) 2 The preparation method of (2) is the same as in example 4, and graphene oxide/siloxane hydrophobic modified nano Mg (OH) is changed 2 Blending ratio with polylactic acid resin to prepare different graphene oxide/siloxane hydrophobically modified nano Mg (OH) 2 Flame-retardant antibacterial polylactic acid material with content. In examples 5-7, graphene oxide/siloxane hydrophobically modified nano Mg (OH) in the final bar material produced 2 The mass ratio of (2) is 8%,10% and 15%, respectively.
Comparative example 1
In comparative example 1, nano Mg (OH) 2 The preparation method of (2) is the same as in example 4, nano Mg (OH) 2 Melt blending with polylactic acid, the melt blending ratio and conditions were the same as in example 4.
Comparative example 2
In comparative example 2, aminosilicone modified nano Mg (OH) 2 The preparation method of (2) is the same as in example 4, and aminosilicone modified nano Mg (OH) is obtained 2 Melt blending with polylactic acid, the melt blending ratio and conditions were the same as in example 4.
Comparative example 3
In comparative example 3, nano Mg (OH) 2 The preparation method is the same as in example 4, and the preparation method is directly modified by graphene oxide without aminosilicone modification, and the graphene oxide modification conditions are the same as in example 4. The obtained graphene oxide modified nano Mg (OH) 2 Melt blending with polylactic acid, the melt blending ratio and conditions were the same as in example 4.
Comparative example 4
Directly adding polylactic acid resin into a double-screw extruder, melting and blending at 180 ℃ and 220rpm, extruding and granulating, and performing hot pressing treatment at 180 ℃ to obtain a strip-shaped material with the thickness of 2 mm.
TABLE 1 flame retardant antibacterial Properties of polylactic acid materials obtained in examples 1 to 7 and comparative examples 1 to 4
As can be seen from Table 1, nano Mg (OH) 2 Has excellent antibacterial property, which benefits from nano Mg (OH) on one hand 2 May be able to penetrate directly the cell wall of the bacteria, disrupting the protein structure, leading to bacterial death; on the other hand, when nano Mg (OH) 2 When contacting bacteria, the nano particles can destroy bacterial cell membranes to destroy cells, thereby playing a role in bacteriostasis. As can be seen by comparing the comparative example with the example, nano Mg (OH) was obtained by using graphene oxide and siloxane 2 Modified to improve nano Mg (OH) 2 The compatibility with PLA further improves the antibacterial property of the functional modified PLA. Nanometer Mg (OH) 2 When used as flame retardant, generally higher addition levels (30-50% or even higher) are required to impart the desired flame retardant effect to the material, as is evident from comparative example 3, using nano Mg (OH) directly 2 When the flame retardant is melt-blended with PLA, the flame retardant performance of PLA is limited to be improved under the addition amount (12%), the oxygen index is slightly improved, and the flame retardant is free from grade of vertical combustion. When graphene oxide and siloxane are used for nano Mg (OH) 2 After modification, the graphene oxide/siloxane hydrophobically modified nano Mg (OH) is obtained 2 The improvement effect on the flame retardant property of PLA is obvious, and as can be seen from examples 1-4, the improvement effect is positively related to the modification degree. When graphene oxide/siloxane hydrophobically modified nano Mg (OH) 2 When the addition amount was 15% (example 7), the flame retardant effect was excellent.
The foregoing has shown and described the basic principles and main features of the present invention and the advantages of the present invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that the above embodiments and descriptions are merely illustrative of the principles of the present invention, and various changes and modifications may be made without departing from the spirit and scope of the invention, which is defined in the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (10)
1. Nanometer Mg (OH) 2 The preparation method of (2) is characterized in that: mixing magnesium salt solution with NaOH containing surfactantSlowly dripping the solution into the substrate solution in a double dripping mode, stirring for reaction, filtering after the reaction is finished, washing with water, and drying to obtain nano Mg (OH) 2 。
2. The method of manufacturing according to claim 1, wherein: the substrate solution is prepared by ammonia water or NaOH and deionized water, and the concentration is 0-1.0 mol/L;
preferably, the surfactant is polyethylene glycol or sodium stearate, and the dosage is 1-3% of the mass of NaOH;
preferably, the concentration of the NaOH solution is 1.5-3.0 mol/L;
preferably, the magnesium salt solution consists of MgCl 2 ·6H 2 O or MgSO 4 ·7H 2 O is added with deionized water to prepare the mixture, and the concentration is 1-2 mol/L;
preferably, the temperature of the stirring reaction is 40-60 ℃.
3. Nano Mg (OH) obtained by the preparation method according to claim 1 or 2 2 。
4. Graphene oxide/siloxane modified nano Mg (OH) 2 The preparation method of (2) is characterized by comprising the following steps:
(1) Dissolving a silane coupling agent in a solvent, and adding the nano Mg (OH) as claimed in claim 3 2 Stirring for reaction to obtain siloxane modified nano Mg (OH) 2 A dispersion;
(2) Ultrasonic stripping of graphene oxide in a solvent, and then adding siloxane modified nano Mg (OH) prepared in the step (1) 2 Stirring the dispersion liquid for reaction, centrifuging after the reaction is finished, washing with water, and drying to obtain graphene oxide/siloxane modified nano Mg (OH) 2 。
5. The method of manufacturing according to claim 4, wherein: the silane coupling agent is an amino-containing silane coupling agent, preferably gamma-aminopropyl triethoxysilane or gamma-aminopropyl trimethoxysilane;
preferably, the nano Mg (OH) 2 The mass ratio of the silane coupling agent to the silane coupling agent is 1 (3-5);
preferably, the graphene oxide is used in an amount of silane coupling agent and nano Mg (OH) 2 10-20% of the total mass;
in the step (1) and the step (2), the temperature of the stirring reaction is 60-80 ℃; the solvent is ethanol/water mixed solvent, and the volume fraction of the ethanol is 10-30%.
6. Graphene oxide/siloxane modified nano-Mg (OH) obtained by the preparation method according to claim 4 or 5 2 。
7. The graphene oxide/siloxane modified nano-Mg (OH) of claim 6 2 As flame retardant and antibacterial agents.
8. The graphene oxide/siloxane modified nano-Mg (OH) of claim 6 2 The application in the preparation of flame-retardant antibacterial polylactic acid material.
9. A flame-retardant antibacterial polylactic acid material, which comprises polylactic acid resin and graphene oxide/siloxane modified nano Mg (OH) as claimed in claim 6 2 ；
Preferably, the graphene oxide/siloxane modified nano-Mg (OH) 2 The mass ratio of the flame-retardant antibacterial polylactic acid material is 8-15%.
10. The method for preparing the flame-retardant and antibacterial polylactic acid material according to claim 9, which is characterized in that: modifying nano Mg (OH) with the dried polylactic acid resin and the graphene oxide/siloxane 2 After being uniformly mixed, the mixture is added into a double-screw extruder for extrusion granulation, and the flame-retardant antibacterial polylactic acid material is obtained;
preferably, the melting temperature of the twin-screw extruder is 180-200 ℃ and the rotating speed is 200-250 rpm.
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