CN113980360B - Bio-based flame retardant applied to polylactic acid film, and manufacturing method and application thereof - Google Patents
Bio-based flame retardant applied to polylactic acid film, and manufacturing method and application thereof Download PDFInfo
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- CN113980360B CN113980360B CN202111127345.XA CN202111127345A CN113980360B CN 113980360 B CN113980360 B CN 113980360B CN 202111127345 A CN202111127345 A CN 202111127345A CN 113980360 B CN113980360 B CN 113980360B
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 71
- 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 64
- 229920006381 polylactic acid film Polymers 0.000 title claims abstract description 32
- 238000004519 manufacturing process Methods 0.000 title description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 63
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 claims abstract description 31
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 31
- 235000002949 phytic acid Nutrition 0.000 claims abstract description 31
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims abstract description 30
- 229940068041 phytic acid Drugs 0.000 claims abstract description 30
- 239000000467 phytic acid Substances 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- WYFZFRKSMYOAOW-UHFFFAOYSA-N 2-(triazinan-1-yl)ethanol Chemical compound OCCN1CCCNN1 WYFZFRKSMYOAOW-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- 229910001629 magnesium chloride Inorganic materials 0.000 claims abstract description 15
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 11
- 239000010439 graphite Substances 0.000 claims abstract description 11
- 238000002360 preparation method Methods 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims description 42
- 238000003756 stirring Methods 0.000 claims description 30
- 239000011550 stock solution Substances 0.000 claims description 19
- 239000006185 dispersion Substances 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 8
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 239000011787 zinc oxide Substances 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 229920000877 Melamine resin Polymers 0.000 abstract description 4
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 abstract description 4
- 238000003763 carbonization Methods 0.000 abstract description 3
- 229920006238 degradable plastic Polymers 0.000 abstract description 3
- 230000018044 dehydration Effects 0.000 abstract description 3
- 238000006297 dehydration reaction Methods 0.000 abstract description 3
- 235000013305 food Nutrition 0.000 abstract description 3
- 238000005979 thermal decomposition reaction Methods 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract 1
- 239000008367 deionised water Substances 0.000 description 16
- 229910021641 deionized water Inorganic materials 0.000 description 16
- 229920000747 poly(lactic acid) Polymers 0.000 description 9
- 239000004626 polylactic acid Substances 0.000 description 9
- 238000001816 cooling Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000009264 composting Methods 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000009775 high-speed stirring Methods 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229920003232 aliphatic polyester Polymers 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000008408 compound extracted from plant Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- -1 phytic acid modified graphene Chemical class 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- 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
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- 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
- C08K3/16—Halogen-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
-
- 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
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/16—Halogen-containing compounds
- C08K2003/166—Magnesium halide, e.g. magnesium chloride
-
- 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
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
Abstract
The invention provides a bio-based flame retardant applied to a polylactic acid film, which comprises the following raw materials in parts by weight: 50-70 parts of phytic acid; 60-70 parts of hydroxyethyl hexahydrotriazine; 20-40 parts of a carbon source; 2-5 parts of a synergist; 10-15 parts of a catalyst; 5-10 parts of magnesium chloride; 100-400 parts of water; the carbon source is graphene oxide and/or graphite oxide. According to the invention, graphene oxide and graphite oxide are used as carbon sources, the carbon residue rate of dehydration, thermal decomposition and carbonization is high in the temperature rise process, the thickness and the heat resistance of a carbon layer can be effectively increased by adding the synergist, and the flame retardant property of the whole system is further improved. The phytic acid can enable the flame retardant disclosed by the invention to be more favorably used in degradable plastics. And the bio-based flame retardant does not contain melamine, and is more beneficial to the field of food. The invention also provides a preparation method and application of the bio-based flame retardant applied to the polylactic acid film.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a bio-based flame retardant applied to a polylactic acid film, a preparation method and application thereof.
Background
The polylactic acid film is a thermoplastic aliphatic polyester film which can be completely biodegraded, has the characteristics of no toxicity, no stimulation, good biocompatibility and absorbability and high mechanical strength. The polylactic acid is prepared from renewable plant resources through biological fermentation to obtain lactic acid and chemical synthesis. Therefore, the polylactic acid film has the advantages of both environment and resources, and has the characteristics of both functional and structural materials. Since the end of the last century, polylactic acid films as biodegradable high molecular materials for disposable consumer products have developed very rapidly, but have lacked competitiveness in terms of cost performance compared with general-purpose plastics. From the viewpoint of long-term use, the application of polylactic acid films is being attempted to be expanded to wider fields, such as electronic and electric products, automobile fields, and the like. However, polylactic acid films have poor flame retardant properties, have a Limiting Oxygen Index (LOI) of about 20, and liquefy quickly after burning, drip and burn. Therefore, in order to realize the application of the polylactic acid film in the fields of electronic appliances, automobiles and the like, the flame retardance of the polylactic acid film needs to be improved, so that the LOI of the polylactic acid film is more than 28, and the combustion grade of the polylactic acid film reaches UL94 VTM-0 grade.
The invention CN 111393814A of China provides a polylactic acid film material which is polymerized by taking phytic acid modified graphene, melamine and chitosan as flame retardants and lactide. All raw materials are grafted on a molecular chain of polylactic acid through polymerization reaction, no matter the macromolecular chain for modification is copolymerized on a main chain or a branched chain of a polylactic acid molecule, the flexibility of the polylactic acid chain is poor, the film hardness is high, the breaking performance of the film is poor, and the polymerization reaction is excessive in the preparation process, so that the production process is long.
Disclosure of Invention
The invention aims to provide a bio-based flame retardant applied to a polylactic acid film, a manufacturing method and application.
The invention provides a bio-based flame retardant applied to a polylactic acid film, which comprises the following raw materials in parts by weight:
50-70 parts of phytic acid; 60-70 parts of hydroxyethyl hexahydrotriazine; 20-40 parts of a carbon source; 2-5 parts of a synergist; 10-15 parts of a catalyst; 5-10 parts of magnesium chloride; 100-400 parts of water;
the carbon source is graphene oxide and/or graphite oxide.
Preferably, the synergist is one or more of silicon dioxide, zinc oxide and calcium carbonate.
Preferably, the catalyst is concentrated sulfuric acid or concentrated nitric acid.
The invention provides a preparation method of the bio-based flame retardant applied to the polylactic acid film, which comprises the following steps:
A) mixing hydroxyethyl hexahydrotriazine with an aqueous solution of phytic acid to obtain a mixed solution;
B) heating the mixed solution to 80-90 ℃, adding a catalyst under the stirring condition, and reacting to obtain a reaction solution;
C) mixing the reaction solution with a dispersion liquid of a carbon source, and reacting at 60-70 ℃ to obtain a flame retardant stock solution;
D) and adding a synergist and magnesium chloride into the flame retardant stock solution, filtering and drying to obtain the bio-based flame retardant.
Preferably, the temperature of the mixing process of the step A) is kept between 40 and 60 ℃.
Preferably, the catalyst is dripped in the step B), and the dripping time is 1-3 hours.
Preferably, the stirring speed in the step B) is 40-60 rpm.
Preferably, the carbon source is added into water, and the mixture is stirred at a high speed of 10000-20000 rpm and uniformly dispersed to obtain a carbon source dispersion liquid.
Preferably, the reaction time in the step C) is 1-3 hours.
The invention provides application of the bio-based flame retardant applied to the polylactic acid film in preparation of the polylactic acid film.
The invention provides a bio-based flame retardant applied to a polylactic acid film, which comprises the following raw materials in parts by weight: 50-70 parts of phytic acid; 60-70 parts of hydroxyethyl hexahydrotriazine; 20-40 parts of a carbon source; 2-5 parts of a synergist; 10-15 parts of a catalyst; 5-10 parts of magnesium chloride; 100-400 parts of water; the carbon source is graphene oxide and/or graphite oxide. According to the invention, graphene oxide and graphite oxide are used as carbon sources, the carbon residue rate of dehydration, thermal decomposition and carbonization is high in the temperature rise process, the thickness and the heat resistance of a carbon layer can be effectively increased by adding the synergist, and the flame retardant property of the whole system is further improved. Compared with petrochemical flame retardant, the phytic acid as a natural plant acid has the advantages of degradability and reproducibility, so that the flame retardant disclosed by the invention can be more favorably used in degradable plastics. The bio-based flame retardant does not contain melamine, and is more favorable for adding the polylactic acid film to be used in the field of food.
Detailed Description
The invention provides a bio-based flame retardant applied to a polylactic acid film, which comprises the following raw materials in parts by weight:
50-70 parts of phytic acid; 60-70 parts of hydroxyethyl hexahydrotriazine; 20-40 parts of a carbon source; 2-5 parts of a synergist; 10-15 parts of a catalyst; 5-10 parts of magnesium chloride; 100-400 parts of water;
the carbon source is graphene oxide and/or graphite oxide.
Phytic Acid (PA), also known as phytic acid or inositol hexaphosphoric acid, is an organic phosphorus compound extracted from plant seeds. The phytic acid (salt) is widely present in crops and agricultural and sideline products, the phytic acid content in many crops and oil crops is up to 1% -3%, and calcium, magnesium, potassium, zinc and other elements exist in the form of phytate. In addition, the phytic acid has the advantages of being non-toxic, renewable, degradable and the like. In the present invention, the phytic acid is used as an acid source and is a dehydrating agent in the flame retardant, and the weight part of the phytic acid is preferably 50 to 70 parts, more preferably 55 to 65 parts, such as 50 parts, 55 parts, 60 parts, 65 parts, and 70 parts, and preferably any of the above values is used as an upper limit or a lower limit.
The hydroxyethyl hexahydrotriazine is used as a gas source, a foaming agent is used in the flame retardant, and the parts by weight of the hydroxyethyl hexahydrotriazine are preferably 60 to 70 parts, such as 60 parts, 61 parts, 62 parts, 63 parts, 64 parts, 65 parts, 66 parts, 67 parts, 68 parts, 69 parts and 70 parts, and preferably any value is used as an upper limit or a lower limit.
The carbon source is preferably graphene oxide and/or graphite oxide, and is a char forming agent in the flame retardant, the weight part of the carbon source is preferably 20-40 parts, more preferably 25-35 parts, such as 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, and preferably any value is a range value with an upper limit or a lower limit.
In the invention, the synergist is preferably one or more of silicon dioxide, zinc oxide and calcium carbonate, and the weight part of the synergist is preferably 2-5 parts, and more preferably 3-4 parts.
The catalyst is preferably concentrated sulfuric acid or concentrated nitric acid, and the parts by weight of the catalyst are preferably 10-15 parts, such as 10 parts, 11 parts, 12 parts, 13 parts, 14 parts and 15 parts, and preferably any value is a range with an upper limit or a lower limit.
The weight portion of the magnesium oxide is preferably 5 to 10 parts, such as 5 parts, 6 parts, 7 parts, 8 parts, 9 parts and 10 parts, and preferably any value is a range with an upper limit or a lower limit.
The water is preferably deionized water, and the weight part of the water is preferably 100 to 400 parts, more preferably 150 to 350 parts, such as 100 parts, 150 parts, 200 parts, 250 parts, 300 parts, 350 parts and 400 parts, and preferably ranges with any of the above values as upper or lower limits.
The invention also provides a preparation method of the bio-based flame retardant applied to the polylactic acid film, which comprises the following steps:
A) mixing hydroxyethyl hexahydrotriazine with an aqueous solution of phytic acid to obtain a mixed solution;
B) heating the mixed solution to 80-90 ℃, adding a catalyst under the stirring condition, and reacting to obtain a reaction solution;
C) mixing the reaction solution with a dispersion liquid of a carbon source, and reacting at 60-70 ℃ to obtain a flame retardant stock solution;
D) and adding a synergist and magnesium chloride into the flame retardant stock solution, filtering and drying to obtain the bio-based flame retardant.
In the present invention, the kinds, amounts and sources of the raw materials used in the preparation process are the same as those of the raw materials described above, and the detailed description of the present invention is omitted.
Firstly, dissolving phytic acid in deionized water, heating to 40-60 ℃, and stirring to quickly dissolve the phytic acid to obtain an aqueous solution of the phytic acid.
In the present invention, the heating temperature is preferably 45 to 55 ℃, such as 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, and is preferably a range value with any of the above values as the upper limit or the lower limit.
Then, the hydroxyethyl hexahydrotriazine and the phytic acid aqueous solution are mixed and stirred to be dissolved, so as to obtain a mixed solution. And in the mixing process, keeping the temperature of the solution at 40-60 ℃.
Then adding the carbon source into deionized water, and stirring at a high speed to disperse uniformly to obtain a dispersion liquid of the carbon source; and then mixing the mixed solution with the dispersion liquid of the carbon source, heating, keeping high-speed stirring, and reacting to obtain the flame retardant stock solution.
In the present invention, the rotation speed of the high speed stirring is preferably 10000 to 20000rpm, more preferably 15000 to 18000rpm, such as 10000rpm, 11000rpm, 12000rpm, 13000rpm, 14000rpm, 15000rpm, 16000rpm, 17000rpm, 18000rpm, 19000rpm, 20000rpm, and preferably ranges in which any of the above values is an upper limit or a lower limit.
The heating temperature, i.e., the reaction temperature, is preferably 60 to 70 ℃, such as 61 ℃, 62 ℃, 63 ℃, 64 ℃, 65 ℃, 66 ℃, 67 ℃, 68 ℃, 69 ℃ and 70 ℃, and is preferably a range value taking any value as an upper limit or a lower limit; the reaction time is preferably 1 to 3 hours, and more preferably 1 to 2 hours.
After the flame retardant stock solution is obtained, the synergist and magnesium chloride are added into the flame retardant stock solution, the mixture is stirred to be uniformly dispersed, the solution is filtered after being cooled, the filtered solid is washed for 3-5 times by using deionized water, and the bio-based flame retardant is obtained after drying.
In the present invention, the rotation speed of the stirring is preferably 200 to 500rpm, and more preferably 300 to 400 rpm. The drying temperature is preferably 150-200 ℃, more preferably 160-190 ℃, and most preferably 170-180 ℃; the drying time is preferably 12 to 24 hours.
The flame retardant is used for the polylactic acid film, namely the invention also provides the application of the flame retardant in the polylactic acid film.
In the present invention, the bio-based flame retardant in the present invention is preferably added in an amount of 1.5 to 4% in the polylactic acid.
The invention provides a bio-based flame retardant applied to a polylactic acid film, which comprises the following raw materials in parts by weight: 50-70 parts of phytic acid; 60-70 parts of hydroxyethyl hexahydrotriazine; 20-40 parts of a carbon source; 2-5 parts of a synergist; 10-15 parts of a catalyst; 5-10 parts of magnesium chloride; 100-400 parts of water; the carbon source is graphene oxide and/or graphite oxide. According to the invention, graphene oxide and graphite oxide are used as carbon sources, the carbon residue rate of dehydration, thermal decomposition and carbonization is high in the temperature rise process, the thickness and the heat resistance of a carbon layer can be effectively increased by adding the synergist, and the flame retardant property of the whole system is further improved. Compared with petrochemical flame retardant, the phytic acid as a natural plant acid has the advantages of degradability and reproducibility, so that the flame retardant disclosed by the invention can be more favorably used in degradable plastics. The bio-based flame retardant does not contain melamine, and is more favorable for adding the polylactic acid film to be used in the field of foods.
In order to further illustrate the present invention, the following examples are provided to describe the bio-based flame retardant, the manufacturing method and the application of the present invention applied to the polylactic acid film in detail, but should not be construed as limiting the scope of the present invention.
Example 1
55 parts of phytic acid is dissolved in 150 parts of deionized water, heated to 50 ℃, and stirred to be rapidly dissolved. Solution A1 was obtained.
60 parts of hydroxyethyl hexahydrotriazine are added to the solution A1, the temperature is kept at 50 ℃, and the solution A2 is obtained after stirring and dissolving.
The solution A2 was heated to 85 ℃ and stirred, 12 parts of concentrated sulfuric acid was added dropwise to the solution over 1.5 hours while maintaining a stirring speed of 40 rpm. After completion of the reaction, a solution a3 was obtained.
Adding 28 parts of graphene oxide into 100 parts of deionized water, stirring at a high speed of 12000rpm for uniform dispersion, then adding the A3 solution into the graphene oxide dispersion liquid, heating to 65 ℃, keeping stirring at the high speed of 12000rpm, and reacting for 2 hours to obtain the flame retardant stock solution.
Adding 2 parts of silicon dioxide and 5 parts of magnesium chloride into the flame retardant stock solution, stirring and dispersing uniformly at 400rpm, cooling the solution, filtering, washing for 3-5 times by using deionized water, and drying in an oven at 150 ℃ to obtain the intumescent flame retardant.
Example 2
60 parts of phytic acid is dissolved in 180 parts of deionized water, heated to 50 ℃, and stirred to be rapidly dissolved. Solution A1 was obtained.
70 parts of hydroxyethyl hexahydrotriazine are added to the solution A1, the temperature is kept at 50 ℃, and the solution A2 is obtained after stirring and dissolving.
The solution A2 was heated to 85 ℃ and stirred, 15 parts of concentrated sulfuric acid was added dropwise to the solution over 1.5 hours while maintaining a stirring speed of 40 rpm. After completion of the reaction, a solution a3 was obtained.
Adding 35 parts of graphene oxide into 110 parts of deionized water, stirring at a high speed of 12000rpm to disperse uniformly, then adding the A3 solution into the dispersion liquid of the graphene oxide, heating to 65 ℃, keeping stirring at the high speed of 12000rpm, and reacting for 2 hours to obtain the flame retardant stock solution.
Adding 5 parts of zinc oxide and 7 parts of magnesium chloride into the fire retardant stock solution, stirring and dispersing uniformly at 400rpm, cooling the solution, filtering, washing for 3-5 times by using deionized water, and drying in an oven at 180 ℃ to obtain the intumescent fire retardant disclosed by the invention.
Example 3
50 parts of phytic acid is dissolved in 150 parts of deionized water, heated to 53 ℃, and stirred to be rapidly dissolved. Solution A1 was obtained.
60 parts of hydroxyethylhexahydrotriazine are added to the solution A1, the temperature is maintained at 53 ℃ and the solution A2 is obtained after dissolution by stirring.
The solution A2 was heated to 85 ℃ and stirred, 12 parts of concentrated nitric acid was added dropwise to the solution over 2.5 hours while maintaining a stirring speed of 60 rpm. After the reaction was completed, a solution a3 was obtained.
Adding 30 parts of graphite oxide into 100 parts of deionized water, stirring at a high speed of 12000rpm to disperse uniformly, then adding the A3 solution into the dispersion liquid of the graphene oxide, heating to 65 ℃, keeping stirring at the high speed of 12000rpm, and reacting for 2 hours to obtain the flame retardant stock solution.
Adding 4 parts of zinc oxide and 8 parts of magnesium chloride into the fire retardant stock solution, stirring and dispersing uniformly at 400rpm, cooling the solution, filtering, washing for 3-5 times by using deionized water, and drying in an oven at 170 ℃ to obtain the intumescent fire retardant disclosed by the invention.
Example 4
55 parts of phytic acid is dissolved in 150 parts of deionized water, heated to 53 ℃, and stirred to be rapidly dissolved. Solution A1 was obtained.
60 parts of hydroxyethylhexahydrotriazine are added to the solution A1, the temperature is maintained at 53 ℃, and the solution A2 is obtained after dissolution by stirring.
The solution A2 was heated to 85 ℃ and stirred, 14 parts of concentrated sulfuric acid was added dropwise to the solution over 2 hours while maintaining a stirring speed of 60 rpm. After completion of the reaction, a solution a3 was obtained.
Adding 28 parts of graphene oxide into 100 parts of deionized water, stirring at a high speed of 12000rpm for uniform dispersion, then adding the A3 solution into the graphene oxide dispersion liquid, heating to 65 ℃, keeping stirring at the high speed of 12000rpm, and reacting for 2 hours to obtain the flame retardant stock solution.
Adding 4 parts of silicon dioxide and 6 parts of magnesium chloride into the flame retardant stock solution, stirring and dispersing uniformly at 500rpm, cooling the solution, filtering, washing for 3-5 times by using deionized water, and drying in an oven at 180 ℃ to obtain the intumescent flame retardant.
TABLE 1 Properties of polylactic acid to which flame retardants in examples 1 to 5 of the present invention were added
| Examples1 | Example 2 | Example 3 | Example 4 | Polylactic acid [ 1 ] | |
| Degradation days [ 2 ] | 263 | 257 | 246 | 279 | 246 |
| Flame retardant rating | V-0 | V-0 | V-0 | V-0 | Non-flame retardant |
| Carbon residue | 8.3％ | 9.2％ | 8.8％ | 8.5％ | 0 |
The test results were obtained by adding the inventive example to a polylactic acid product (added in an amount of 2.5%).
【1】 Polylactic acid is a body without added flame retardant
【2】 The days of degradation were measured under composting conditions (GB/T19277.1-2011 determination of the ultimate aerobic biological decomposition capacity of the material under controlled composting conditions uses part 1 of the method for determining the carbon dioxide released: general method).
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A bio-based flame retardant applied to a polylactic acid film comprises the following raw materials in parts by weight:
50-70 parts of phytic acid; 60-70 parts of hydroxyethyl hexahydrotriazine; 20-40 parts of a carbon source; 2-5 parts of a synergist; 10-15 parts of a catalyst; 5-10 parts of magnesium chloride; 100-400 parts of water;
the carbon source is graphene oxide and/or graphite oxide;
the preparation method of the bio-based flame retardant comprises the following steps:
A) mixing hydroxyethyl hexahydrotriazine with an aqueous solution of phytic acid to obtain a mixed solution;
B) heating the mixed solution to 80-90 ℃, adding a catalyst under the stirring condition, and reacting to obtain a reaction solution;
C) mixing the reaction solution with a dispersion liquid of a carbon source, and reacting at 60-70 ℃ to obtain a flame retardant stock solution;
D) and adding a synergist and magnesium chloride into the flame retardant stock solution, filtering and drying to obtain the bio-based flame retardant.
2. The bio-based flame retardant according to claim 1, wherein the synergist is one or more of silica, zinc oxide and calcium carbonate.
3. The bio-based flame retardant of claim 1, wherein the catalyst is concentrated sulfuric acid or concentrated nitric acid.
4. The method of preparing a bio-based flame retardant according to claim 1, comprising the steps of:
A) mixing hydroxyethyl hexahydrotriazine with an aqueous solution of phytic acid to obtain a mixed solution;
B) heating the mixed solution to 80-90 ℃, adding a catalyst under the stirring condition, and reacting to obtain a reaction solution;
C) mixing the reaction solution with a dispersion liquid of a carbon source, and reacting at 60-70 ℃ to obtain a flame retardant stock solution;
D) and adding a synergist and magnesium chloride into the flame retardant stock solution, filtering and drying to obtain the bio-based flame retardant.
5. The method according to claim 4, wherein the mixing step A) is carried out at a temperature of 40-60 ℃.
6. The preparation method according to claim 4, wherein the catalyst is added dropwise in the step B) for 1 to 3 hours.
7. The method according to claim 4, wherein the stirring speed in step B) is 40 to 60 rpm.
8. The preparation method according to claim 4, wherein the carbon source is added into water, and the mixture is uniformly dispersed by stirring at a high speed of 10000-20000 rpm to obtain a carbon source dispersion liquid.
9. The method according to claim 4, wherein the reaction time in step C) is 1 to 3 hours.
10. The use of the bio-based flame retardant applied to the polylactic acid film according to claim 1 in the preparation of the polylactic acid film.
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| JP2011079950A (en) * | 2009-10-07 | 2011-04-21 | Toyo Ink Mfg Co Ltd | Flame-retardant resin composition |
| CN110054969A (en) * | 2019-06-14 | 2019-07-26 | 江南大学 | A kind of anticorrosive paint and preparation method thereof based on phytic acid modified graphene |
| CN111393814A (en) * | 2020-04-24 | 2020-07-10 | 高慎永 | High-flame-retardancy biomass-based modified polylactic acid film material and preparation method thereof |
| CN111777785A (en) * | 2020-06-29 | 2020-10-16 | 浙江理工大学 | Food-grade oxygen-barrier coating on surface of polylactic acid film and preparation method thereof |
| CN113088054A (en) * | 2021-04-06 | 2021-07-09 | 湖南绿斯达生物科技有限公司 | Polylactic acid material containing continuous conductive structure and preparation method thereof |
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| JP2011079950A (en) * | 2009-10-07 | 2011-04-21 | Toyo Ink Mfg Co Ltd | Flame-retardant resin composition |
| CN110054969A (en) * | 2019-06-14 | 2019-07-26 | 江南大学 | A kind of anticorrosive paint and preparation method thereof based on phytic acid modified graphene |
| CN111393814A (en) * | 2020-04-24 | 2020-07-10 | 高慎永 | High-flame-retardancy biomass-based modified polylactic acid film material and preparation method thereof |
| CN111777785A (en) * | 2020-06-29 | 2020-10-16 | 浙江理工大学 | Food-grade oxygen-barrier coating on surface of polylactic acid film and preparation method thereof |
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