CN117362764A - Bio-based flame retardant, preparation method thereof and bio-based flame retardant TPU material - Google Patents
Bio-based flame retardant, preparation method thereof and bio-based flame retardant TPU material Download PDFInfo
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 102
- 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 101
- 239000000463 material Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 229920001661 Chitosan Polymers 0.000 claims abstract description 116
- 239000004114 Ammonium polyphosphate Substances 0.000 claims abstract description 64
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims abstract description 64
- 229920001276 ammonium polyphosphate Polymers 0.000 claims abstract description 64
- 239000004005 microsphere Substances 0.000 claims abstract description 48
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 27
- 239000003963 antioxidant agent Substances 0.000 claims description 21
- 230000003078 antioxidant effect Effects 0.000 claims description 21
- 238000005406 washing Methods 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- 239000007822 coupling agent Substances 0.000 claims description 13
- 239000000314 lubricant Substances 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 239000003365 glass fiber Substances 0.000 claims description 10
- 238000000576 coating method Methods 0.000 claims description 7
- 238000004108 freeze drying Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 6
- 239000002736 nonionic surfactant Substances 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 2
- 230000006196 deacetylation Effects 0.000 claims description 2
- 238000003381 deacetylation reaction Methods 0.000 claims description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims 1
- 235000011130 ammonium sulphate Nutrition 0.000 claims 1
- 230000009881 electrostatic interaction Effects 0.000 abstract description 4
- 239000002861 polymer material Substances 0.000 abstract description 2
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 57
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 57
- 230000000052 comparative effect Effects 0.000 description 11
- 238000002791 soaking Methods 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 8
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 8
- 238000002485 combustion reaction Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 7
- 235000021355 Stearic acid Nutrition 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 description 7
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 7
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 7
- 229910052938 sodium sulfate Inorganic materials 0.000 description 7
- 235000011152 sodium sulphate Nutrition 0.000 description 7
- 239000008117 stearic acid Substances 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 230000001105 regulatory effect Effects 0.000 description 6
- 239000000779 smoke Substances 0.000 description 6
- 229920001971 elastomer Polymers 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000009210 therapy by ultrasound Methods 0.000 description 5
- 239000000806 elastomer Substances 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 4
- 229920000053 polysorbate 80 Polymers 0.000 description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- -1 aliphatic phenols Chemical class 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- VONWDASPFIQPDY-UHFFFAOYSA-N dimethyl methylphosphonate Chemical compound COP(C)(=O)OC VONWDASPFIQPDY-UHFFFAOYSA-N 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000000707 layer-by-layer assembly Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000009972 noncorrosive effect Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 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
- C08L5/00—Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
- C08L5/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
-
- 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
- C08K3/32—Phosphorus-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
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
-
- 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
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/322—Ammonium phosphate
- C08K2003/323—Ammonium polyphosphate
-
- 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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/18—Spheres
Abstract
The invention belongs to the technical field of high polymer materials, and particularly relates to a bio-based flame retardant, a preparation method thereof and a bio-based flame retardant TPU material. The bio-based flame retardant comprises a multi-layer self-assembled structure flame retardant with chitosan microspheres as cores and ammonium polyphosphate layers and chitosan layers coated layer by layer, wherein the chitosan microspheres are used as cores, the multi-layer self-assembled structure flame retardant with the chitosan microspheres as cores and the ammonium polyphosphate layers/the chitosan layers coated layer by layer is formed through the mutual electrostatic interaction between the chitosan microspheres and the ammonium polyphosphate layers, and is added into a TPU material, so that the compatibility with the TPU material is good, and the obtained bio-based flame retardant TPU material has good mechanical property and flame retardant property.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a bio-based flame retardant, a preparation method thereof and a bio-based flame retardant TPU material.
Background
Thermoplastic polyurethane elastomers (TPU) have both high strength of plastics and high elasticity of rubber, and are widely used in many fields such as automobile parts, electric wires and cables, sports soles, hoses, films and sheets, fabrics, adhesives, and the like. But TPU has a high risk of fire, is extremely easy to ignite, and has a high flame propagation speed. As the polymer burns, the material is continuously heated and decomposed to generate combustible gas, the polymer burns in a gas phase, a bombing phenomenon is easy to form, heat release is severe, and a large amount of toxic gas is generated. In a fire, the melted TPU can drip, so that the fire spreads, the capability of the rescue workers to control the fire scene is seriously affected, and the life of the escape workers is greatly endangered. Therefore, for public safety, the TPU needs to be flame retardant before use.
Chinese patent CN109385071A discloses a TPU material with flame retardant property reaching V0 grade of vertical combustion, which is obtained by mixing 100 parts of thermoplastic polyurethane, 35-65 parts of phosphorus single-group combustion system, 2-10 parts of char forming agent and 3-15 parts of flame retardant auxiliary agent, and the TPU material with excellent flame retardant property and V0 grade of vertical combustion is obtained by applying the phosphorus-nitrogen flame retardant system to the thermoplastic polyurethane and changing the proportioning relation among the components, but the phosphorus-nitrogen flame retardant can not reduce the release of toxic smoke.
Chinese patent CN103665829B discloses a method for preparing a high flame retardant environment friendly thermoplastic polyurethane elastomer, which comprises preparing thermoplastic polyurethane elastomer particles, preparing a high flame retardant environment friendly thermoplastic polyurethane elastomer, using dimethyl methylphosphonate or triphenyl phosphate and other phosphorus-containing products as flame retardant, wherein the halogen-free flame retardant thermoplastic polyurethane material has excellent flame retardant property, but the mechanical property is greatly weakened, while the smoke is suppressed, a small amount of black smoke is still generated.
Disclosure of Invention
The invention aims at solving the technical problems and provides a bio-based flame retardant which can inhibit the heat transfer process and the generation of combustible gas and smoke and has good flame retardant effect.
The bio-based flame retardant in the technical scheme of the invention comprises a multi-layer self-assembled structure flame retardant with chitosan microspheres as cores and an ammonium polyphosphate layer and a chitosan layer which are coated layer by layer.
The chitosan is a natural and easily available polysaccharide polymer with low cost, and has biological degradabilityThe molecular skeleton is rich in carbon, contains a certain amount of side chain groups of hydroxyl and amino, can be carbonized in the polymer to block the combustion in the thermal decomposition process, and can release CO 2 、NH 3 And N 2 Non-toxic and non-corrosive non-combustible gas, and has flame retardant effect. In addition, the amino and hydroxyl groups on the chitosan molecules enable the chitosan molecules to have good reactivity, various flame retardant elements can be introduced, the physicochemical properties of the chitosan molecules are changed, the flame retardant efficiency is improved, and the applicability of the chitosan molecules is expanded.
According to the flame retardant disclosed by the invention, chitosan is used as a carbon source, ammonium polyphosphate is used as an air source and an acid source, the flame retardant is heated and combusted in the combustion process to form an expansion layer, the expansion carbon layer can inhibit heat transfer, smoke generation and severe dripping of TPU in the combustion process, and simultaneously polyurethane materials generated in the TPU pyrolysis process react with amino groups in a chitosan microsphere chain segment, so that the flame retardant can inhibit the generation of combustible gas, and has a good flame retardant effect. The bio-based flame retardant takes chitosan microspheres as cores, and forms an assembly layer structure with chitosan microspheres as cores and layer by layer coated with ammonium polyphosphate/chitosan through the mutual electrostatic interaction between the chitosan microspheres and ammonium polyphosphate, and is similar to a sandwich structure, so that the carbon forming process of the flame retardant can be ensured to be uniform and stable, and a three-dimensional blocking structure is formed, so that the intumescent bio-based flame retardant is obtained.
Further, the total number of layers of the multi-layer self-assembled flame retardant is 7-15.
Further, the degree of polymerization of the ammonium polyphosphate is greater than 1000.
Further, the diameter of the chitosan microsphere is 2.0-5.0 mu m, and the deacetylation degree is more than 95%.
Further, the preparation method of the chitosan microsphere comprises the steps of adding a nonionic surfactant into a chitosan solution, stirring, dripping a sodium sulfate solution until the sodium sulfate solution is completely precipitated, and freeze-drying after ultrasonic treatment and washing.
The chitosan microsphere is prepared by a precipitation method, so that amino and hydroxyl in chitosan are reserved, and the chitosan and ammonium polyphosphate react to form an assembly layer.
Further, the mass concentration of the chitosan solution is 1.5-2.5%.
Further, the addition amount of the nonionic surfactant is 1-5% of the mass of the chitosan.
Further, the concentration of the sodium sulfate solution is 0.5-2.0 mol/L.
Further, the freeze drying temperature is-45 to-35 ℃ and the time is 20 to 30 hours.
Further, the preparation method of the bio-based flame retardant comprises the steps of soaking the chitosan microsphere in an ammonium polyphosphate solution to coat the ammonium polyphosphate layer, washing and drying the chitosan microsphere coated with the ammonium polyphosphate layer, soaking the chitosan layer in the chitosan solution, washing and drying the chitosan microsphere, and then repeatedly coating the ammonium polyphosphate layer and the chitosan layer in sequence.
The ammonium polyphosphate is adsorbed on the surface of the chitosan microsphere through electrostatic interaction to form an ammonium polyphosphate layer, and the chitosan layer is formed on the surface of the ammonium polyphosphate layer through an electrostatic self-assembly mode, so that the bio-based flame retardant is obtained in a circulating way.
Further, the chitosan solution is obtained by dissolving chitosan in acetic acid, and the mass concentration is 1-3%.
Further, the concentration of the ammonium polyphosphate solution is 1 to 3%.
Further, the pH of the chitosan solution is adjusted to 4.5-5.0 by using a hydrochloric acid solution with a mass concentration of 1.0-3.0%, and/or the pH of the ammonium polyphosphate solution is adjusted to 9.5-10.0 by using a sodium hydroxide solution with a mass concentration of 1.0-3.0%.
Further, the time for soaking the chitosan microsphere in the chitosan solution and the ammonium polyphosphate solution is 15-30 min.
The invention also provides a bio-based flame retardant TPU material, which comprises the following components in parts by weight: 60-80 parts of TPU, 10-20 parts of the bio-based flame retardant, 5-10 parts of ammonium polyphosphate, 10-30 parts of glass fiber, 0.1-0.5 part of lubricant, 0.3-0.6 part of antioxidant and 0.1-0.5 part of coupling agent.
The bio-based flame retardant is added into the TPU material, has good compatibility with the TPU material, and can improve the mechanical property of the TPU material.
Further, the hardness of the TPU is 70 to 95A, preferably 80 to 95A.
Further, the antioxidant is one or more of antioxidant 1010, antioxidant 168, antioxidant 126, antioxidant 225 and antioxidant 215.
Further, the lubricant is one or more of saturated hydrocarbons, metal soaps, aliphatic phenols, fatty acids, fatty alcohols and silicone powder.
Further, the coupling agent is one or more of silane coupling agent, titanate coupling agent and aluminate coupling agent.
The preparation method of the bio-based flame retardant TPU material comprises the steps of mixing TPU, bio-based flame retardant, glass fiber, antioxidant, lubricant and coupling agent, extruding and granulating.
Further, the screw speed of the twin-screw extruder is 150-300 rpm and the temperature is 185-205 ℃ during extrusion granulation.
Further, the twin screw extruder has two vacuum ports at the beginning of the melt section and at the metering section, respectively.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
(1) The bio-based flame retardant takes the chitosan microsphere as a core, and forms a multi-layer self-assembled structure flame retardant with the chitosan microsphere as a core and the ammonium polyphosphate layer coated layer by layer through the mutual electrostatic interaction between the chitosan microsphere and the ammonium polyphosphate, so that the bio-based flame retardant has a good flame retardant effect;
(2) The bio-based flame retardant chitosan is used as a carbon source, ammonium polyphosphate is used as an air source and an acid source, and the flame retardant is heated and combusted in the combustion process to form an expansion layer, and the expansion carbon layer can inhibit heat transfer, the generation of combustible gas and smoke and serious dripping of TPU in the combustion process;
(3) Polyurethane materials generated in the TPU pyrolysis process react with amino groups in the chitosan microsphere chain segments, so that the generation of combustible gas can be inhibited, and a good flame-retardant effect is achieved;
(4) The chitosan microsphere is prepared by a precipitation method, so that amino and hydroxyl in chitosan are reserved, and the chitosan and ammonium polyphosphate are facilitated to react to form an assembly layer;
(5) The bio-based flame retardant is added into the TPU material, has good compatibility with the TPU material, and has good mechanical property and flame retardant property.
Detailed Description
The technical scheme of the present invention will be further described by the following specific examples, and it should be understood that the specific examples described herein are only for aiding in understanding the present invention, and are not intended to be limiting. The raw materials used in the examples of the present invention are all common raw materials in the art, and the methods used in the examples are all conventional methods in the art, unless otherwise specified.
Example 1
The preparation method of the bio-based flame retardant comprises the following steps:
(1) Dissolving chitosan in acetic acid to obtain a chitosan solution with the mass concentration of 2%, adding tween 80 into the chitosan solution, uniformly stirring, dripping sodium sulfate solution, performing ultrasonic treatment to obtain a chitosan microsphere solution, fully washing with water and ethanol, and performing freeze drying to obtain chitosan microspheres with the particle size of 2.0-5.0 mu m;
(2) Dissolving chitosan in acetic acid to obtain a chitosan solution with the mass concentration of 1%, regulating the pH value to 5.0 by using a hydrochloric acid solution with the mass concentration of 1%, obtaining an ammonium polyphosphate solution with the mass concentration of 1%, and regulating the pH value to 10.0 by using a sodium hydroxide solution with the mass concentration of 1%;
(3) Soaking 10 parts of chitosan microspheres in 500 parts of ammonium polyphosphate solution for 20min to coat an ammonium polyphosphate layer, washing and drying, soaking the chitosan microspheres coated with the ammonium polyphosphate layer in 500 parts of chitosan solution for 20min to coat a chitosan layer, wherein the ammonium polyphosphate layer and the chitosan layer are one layer of an assembly layer, washing and drying, and repeating the coating process to ensure that the number of layers of the assembly layer reaches 7, thereby obtaining the bio-based flame retardant;
the bio-based flame retardant TPU material is prepared by mixing 70 parts of TPU, 10 parts of bio-based flame retardant, 5 parts of ammonium polyphosphate, 20 parts of glass fiber, 0.5 part of antioxidant (Irganox 1010 and antioxidant Irgafos168 are mixed in a mass ratio of 1:1), 0.5 part of lubricant (ethylene bis-stearamide and stearic acid are mixed in a mass ratio of 1:1) and 0.5 part of coupling agent KH550, extruding and granulating by a double-screw extruder, wherein the temperature is controlled at 185-205 ℃, the screw speed is 200rpm, and the double-screw extruder is provided with two vacuumizing ports, wherein the first part is at the beginning of a melting section, and the second part is at a metering section.
Example 2
The preparation method of the bio-based flame retardant comprises the following steps:
(1) Dissolving chitosan in acetic acid to obtain a chitosan solution with the mass concentration of 2%, adding tween 80 into the chitosan solution, uniformly stirring, dripping sodium sulfate solution, performing ultrasonic treatment to obtain a chitosan microsphere solution, fully washing with water and ethanol, and performing freeze drying to obtain chitosan microspheres with the particle size of 2.0-5.0 mu m;
(2) Dissolving chitosan in acetic acid to obtain a chitosan solution with the mass concentration of 1.5%, regulating the pH value to 5.0 by using a hydrochloric acid solution with the mass concentration of 1%, obtaining an ammonium polyphosphate solution with the mass concentration of 1.5%, and regulating the pH value to 10.0 by using a sodium hydroxide solution with the mass concentration of 1%;
(3) Soaking 15 parts of chitosan microspheres in 800 parts of ammonium polyphosphate solution for 20min to coat an ammonium polyphosphate layer, washing and drying, soaking the chitosan microspheres coated with the ammonium polyphosphate layer in 800 parts of chitosan solution for 20min to coat a chitosan layer, wherein the ammonium polyphosphate layer and the chitosan layer are one layer of an assembly layer, washing and drying, and repeating the coating process to ensure that the number of layers of the assembly layer reaches 10, thereby obtaining the bio-based flame retardant;
the bio-based flame retardant TPU material is prepared by mixing 70 parts of TPU, 15 parts of bio-based flame retardant, 5 parts of ammonium polyphosphate, 20 parts of glass fiber, 0.5 part of antioxidant (Irganox 1010 and antioxidant Irgafos168 are mixed in a mass ratio of 1:1), 0.3 part of lubricant (ethylene bis-stearamide and stearic acid are mixed in a mass ratio of 1:1) and 0.5 part of coupling agent KH550, extruding and granulating by a double-screw extruder, wherein the temperature is controlled at 185-205 ℃, the screw speed is 200rpm, and the double-screw extruder is provided with two vacuumizing ports, wherein the first part is at the beginning of a melting section, and the second part is at a metering section.
Example 3
The preparation method of the bio-based flame retardant comprises the following steps:
(1) Dissolving chitosan in acetic acid to obtain a chitosan solution with the mass concentration of 2%, adding tween 80 into the chitosan solution, uniformly stirring, dripping sodium sulfate solution, performing ultrasonic treatment to obtain a chitosan microsphere solution, fully washing with water and ethanol, and performing freeze drying to obtain chitosan microspheres with the particle size of 2.0-5.0 mu m;
(2) Dissolving chitosan in acetic acid to obtain a chitosan solution with the mass concentration of 1.8%, regulating the pH value to 5.0 by using a hydrochloric acid solution with the mass concentration of 1%, obtaining an ammonium polyphosphate solution with the mass concentration of 2.0%, and regulating the pH value to 10.0 by using a sodium hydroxide solution with the mass concentration of 1%;
(3) Soaking 10 parts of chitosan microspheres in 500 parts of ammonium polyphosphate solution for 20min to coat an ammonium polyphosphate layer, washing and drying, soaking the chitosan microspheres coated with the ammonium polyphosphate layer in 500 parts of chitosan solution for 20min to coat a chitosan layer, wherein the ammonium polyphosphate layer and the chitosan layer are one layer of an assembly layer, washing and drying, and repeating the coating process to ensure that the number of layers of the assembly layer reaches 12, thereby obtaining the bio-based flame retardant;
the bio-based flame retardant TPU material is prepared by mixing 80 parts of TPU, 10 parts of bio-based flame retardant, 8 parts of ammonium polyphosphate, 10 parts of glass fiber, 0.3 part of antioxidant (Irganox 1010 and antioxidant Irgafos168 are mixed in a mass ratio of 1:1), 0.5 part of lubricant (ethylene bis-stearamide and stearic acid are mixed in a mass ratio of 1:1) and 0.3 part of coupling agent KH550, extruding and granulating by a double-screw extruder, wherein the temperature is controlled at 185-205 ℃, the screw speed is 200rpm, and the double-screw extruder is provided with two vacuumizing ports, wherein the first part is at the beginning of a melting section, and the second part is at a metering section.
Example 4
The difference between the embodiment and the embodiment 1 is that the chitosan microsphere is soaked in the ammonium polyphosphate solution for 20min to coat the ammonium polyphosphate layer in the step (2), the chitosan microsphere coated with the ammonium polyphosphate layer is soaked in the chitosan solution for 20min to coat the chitosan layer after washing and drying, the ammonium polyphosphate layer and the chitosan layer are one layer of assembled layer, and the coating process is repeated after washing and drying, so that the number of layers of the assembled layer reaches 3, and the bio-based flame retardant is obtained.
Example 5
The difference between the embodiment and the embodiment 1 is that the chitosan microsphere is soaked in the ammonium polyphosphate solution for 20min to coat the ammonium polyphosphate layer in the step (2), the chitosan microsphere coated with the ammonium polyphosphate layer is soaked in the chitosan solution for 20min to coat the chitosan layer after washing and drying, the ammonium polyphosphate layer and the chitosan layer are one layer of assembled layer, and the coating process is repeated after washing and drying, so that the number of layers of the assembled layer reaches 15, and the bio-based flame retardant is obtained.
Comparative example 1
The preparation method of the bio-based flame retardant TPU material of the comparative example comprises the following steps:
(1) Dissolving chitosan in acetic acid to obtain a chitosan solution with the mass concentration of 2%, adding tween 80 into the chitosan solution, uniformly stirring, dripping sodium sulfate solution, performing ultrasonic treatment to obtain a chitosan microsphere solution, fully washing with water and ethanol, and performing freeze drying to obtain chitosan microspheres with the particle size of 2.0-5.0 mu m;
(2) 70 parts of TPU, 10 parts of chitosan microspheres, 5 parts of ammonium polyphosphate, 20 parts of glass fibers, 0.5 part of antioxidant (Irganox 1010 and antioxidant Irgafos168 are mixed according to the mass ratio of 1:1), 0.5 part of lubricant (ethylene bisstearamide and stearic acid are mixed according to the mass ratio of 1:1) and 0.5 part of coupling agent KH550 are mixed, and then extruded and granulated through a double screw extruder, wherein the temperature is controlled at 185-205 ℃, the screw rotating speed is 200rpm, and the double screw extruder is provided with two vacuumizing ports, the first part is at the beginning of a melting section, and the second part is at a metering section.
Comparative example 2
The preparation method of the biological-based flame-retardant TPU material of the comparative example comprises the steps of mixing 70 parts of TPU, 10 parts of isopropylated triphenyl phosphate environment-friendly flame retardant, 5 parts of ammonium polyphosphate, 20 parts of glass fiber, 0.5 part of antioxidant (Irganox 1010 and antioxidant Irgafos168 are mixed according to the mass ratio of 1:1), 0.5 part of lubricant (ethylene bis-stearamide and stearic acid are mixed according to the mass ratio of 1:1) and 0.5 part of coupling agent KH550, extruding and granulating by a double-screw extruder, wherein the temperature is controlled to 185-205 ℃, the screw rotating speed is 200rpm, and the double-screw extruder is provided with two vacuumizing ports, wherein the first part is at the beginning of a melting section and the second part is at a metering section.
Comparative example 3
This comparative example differs from example 1 only in that the bio-based flame retardant TPU material was pelletized by extrusion through a twin screw extruder with a temperature of 185 to 205 c and a screw speed of 200rpm, the twin screw extruder having two vacuum ports, the first at the beginning of the melt section and the second at the metering section, after mixing 70 parts TPU, 5 parts bio-based flame retardant, 5 parts ammonium polyphosphate, 20 parts glass fiber, 0.5 part antioxidant (Irganox 1010 and antioxidant Irgafos168 mixed in a mass ratio of 1:1), 0.3 part lubricant (ethylene bis-stearamide and stearic acid mixed in a mass ratio of 1:1) and 0.5 part coupling agent KH 550.
Comparative example 4
This comparative example differs from example 1 only in that the bio-based flame retardant TPU material was pelletized by extrusion through a twin screw extruder with a temperature of 185 to 205 c and a screw speed of 200rpm, the twin screw extruder having two vacuum ports, the first at the beginning of the melt section and the second at the metering section, after mixing 70 parts TPU, 25 parts bio-based flame retardant, 5 parts ammonium polyphosphate, 20 parts glass fiber, 0.5 part antioxidant (Irganox 1010 and antioxidant Irgafos168 mixed in a mass ratio of 1:1), 0.3 part lubricant (ethylene bis-stearamide and stearic acid mixed in a mass ratio of 1:1) and 0.5 part coupling agent KH 550.
The bio-based flame retardant TPU materials obtained in the above examples and comparative examples were subjected to performance tests, and the test results are shown in table 1.
Table 1 table of performance data for biobased flame retardant TPU materials
The bio-based flame retardant TPU material obtained in the examples 1-3 has good mechanical properties and flame retardant properties, the bio-based flame retardant obtained in the example 4 has too few layers and poor flame retardant effect, the obtained TPU material has reduced flame retardant properties, the bio-based flame retardant obtained in the example 5 has too many layers and too large granularity, the compatibility with the TPU material is poor, the mechanical properties of the obtained TPU material are reduced, the bio-based flame retardant is not used in the preparation of the bio-based flame retardant TPU material in the comparative example 1, chitosan microspheres and ammonium polyphosphate are directly added, the flame retardant effect is poor, the compatibility with the TPU material is poor, the obtained TPU material has reduced flame retardant properties and mechanical properties, the compatibility with components in the TPU material is general, the flame retardant effect is poor, the obtained TPU material has reduced flame retardant properties and mechanical properties, the TPU material has reduced flame retardant properties due to the fact that a small amount of the bio-based flame retardant is used in the preparation of the bio-based flame retardant TPU material in the comparative example 4, and the TPU material has poor compatibility with the mechanical properties.
Finally, it should be noted that the specific embodiments described herein are merely illustrative of the spirit of the invention and are not limiting of the invention's embodiments. Those skilled in the art to which the invention pertains may make various modifications or additions to the described embodiments or may be substituted in a similar manner, without and without all of the embodiments herein being fully understood. While these obvious variations and modifications, which come within the spirit of the invention, are within the scope of the invention, they are to be construed as being without departing from the spirit of the invention.
Claims (10)
1. A bio-based flame retardant is characterized by comprising a multi-layer self-assembled structure flame retardant which takes chitosan microspheres as cores and is coated with an ammonium polyphosphate layer and a chitosan layer by layer.
2. The bio-based flame retardant according to claim 1, wherein the total number of layers of the multi-layer self-assembled structured flame retardant is 7 to 15.
3. The bio-based flame retardant according to claim 1, wherein the chitosan microsphere has a diameter of 2.0 to 5.0 μm and a degree of deacetylation of more than 95%.
4. The bio-based flame retardant according to claim 1, wherein the chitosan microsphere is prepared by adding a nonionic surfactant into a chitosan solution, stirring, dripping an ammonium sulfate solution until precipitation is complete, and freeze-drying after ultrasonic and washing.
5. The method for preparing the bio-based flame retardant according to claim 1, wherein the method comprises the steps of immersing the chitosan microspheres in an ammonium polyphosphate solution to coat the ammonium polyphosphate layer, immersing the chitosan microspheres coated with the ammonium polyphosphate layer in the chitosan solution to coat the chitosan layer after washing and drying, and repeating the coating of the ammonium polyphosphate layer and the chitosan layer after washing and drying.
6. The method according to claim 5, wherein the chitosan solution is obtained by dissolving chitosan in acetic acid, and the mass concentration is 1 to 3%.
7. The method according to claim 5, wherein the concentration of the ammonium polyphosphate solution is 1 to 3%.
8. The preparation method according to claim 5, wherein the chitosan solution is adjusted to pH 4.5 to 5.0 with a hydrochloric acid solution having a mass concentration of 1.0 to 3.0%, and/or the ammonium polyphosphate solution is adjusted to pH 9.5 to 10.0 with a sodium hydroxide solution having a mass concentration of 1.0 to 3.0%.
9. The method according to claim 5, wherein the chitosan microspheres are immersed in the chitosan solution and the ammonium polyphosphate solution for 15 to 30 minutes.
10. The bio-based flame retardant TPU material is characterized by comprising the following components in parts by weight: 60-80 parts of TPU, 10-20 parts of the bio-based flame retardant according to claim 1, 5-10 parts of ammonium polyphosphate, 10-30 parts of glass fiber, 0.1-0.5 part of lubricant, 0.3-0.6 part of antioxidant and 0.1-0.5 part of coupling agent.
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