CN115109315B - Jet type core-shell structure flame retardant, and preparation method and application thereof - Google Patents
Jet type core-shell structure flame retardant, and preparation method and application thereof Download PDFInfo
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- CN115109315B CN115109315B CN202210716148.XA CN202210716148A CN115109315B CN 115109315 B CN115109315 B CN 115109315B CN 202210716148 A CN202210716148 A CN 202210716148A CN 115109315 B CN115109315 B CN 115109315B
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- flame retardant
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 185
- 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 175
- 239000011258 core-shell material Substances 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims abstract description 17
- 239000010410 layer Substances 0.000 claims abstract description 13
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- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 15
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- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 12
- 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 claims description 12
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 10
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- 239000003999 initiator Substances 0.000 claims description 8
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- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 claims description 7
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- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 5
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- 230000008018 melting Effects 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- BZQKBFHEWDPQHD-UHFFFAOYSA-N 1,2,3,4,5-pentabromo-6-[2-(2,3,4,5,6-pentabromophenyl)ethyl]benzene Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1CCC1=C(Br)C(Br)=C(Br)C(Br)=C1Br BZQKBFHEWDPQHD-UHFFFAOYSA-N 0.000 claims description 2
- DEIGXXQKDWULML-UHFFFAOYSA-N 1,2,5,6,9,10-hexabromocyclododecane Chemical compound BrC1CCC(Br)C(Br)CCC(Br)C(Br)CCC1Br DEIGXXQKDWULML-UHFFFAOYSA-N 0.000 claims description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 2
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 claims description 2
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 claims description 2
- 125000004573 morpholin-4-yl group Chemical group N1(CCOCC1)* 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
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- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 11
- 238000005516 engineering process Methods 0.000 description 11
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
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- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical group CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 description 6
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
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- 238000002485 combustion reaction Methods 0.000 description 4
- 229910021389 graphene Inorganic materials 0.000 description 4
- 230000002209 hydrophobic effect Effects 0.000 description 4
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 3
- 230000001934 delay Effects 0.000 description 3
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- 239000012796 inorganic flame retardant Substances 0.000 description 3
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- 239000004114 Ammonium polyphosphate Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000004964 aerogel Substances 0.000 description 2
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 2
- 229920001276 ammonium polyphosphate Polymers 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
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- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical group [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 2
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- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 1
- 229920001817 Agar Polymers 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
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- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 239000000728 ammonium alginate Substances 0.000 description 1
- 235000010407 ammonium alginate Nutrition 0.000 description 1
- KPGABFJTMYCRHJ-YZOKENDUSA-N ammonium alginate Chemical compound [NH4+].[NH4+].O1[C@@H](C([O-])=O)[C@@H](OC)[C@H](O)[C@H](O)[C@@H]1O[C@@H]1[C@@H](C([O-])=O)O[C@@H](O)[C@@H](O)[C@H]1O KPGABFJTMYCRHJ-YZOKENDUSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- YYRMJZQKEFZXMX-UHFFFAOYSA-N calcium;phosphoric acid Chemical compound [Ca+2].OP(O)(O)=O.OP(O)(O)=O YYRMJZQKEFZXMX-UHFFFAOYSA-N 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
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- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 235000019359 magnesium stearate Nutrition 0.000 description 1
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- ZQMHJBXHRFJKOT-UHFFFAOYSA-N methyl 2-[(1-methoxy-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanoate Chemical compound COC(=O)C(C)(C)N=NC(C)(C)C(=O)OC ZQMHJBXHRFJKOT-UHFFFAOYSA-N 0.000 description 1
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- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 239000010455 vermiculite Substances 0.000 description 1
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- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
- B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
- C08F283/008—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00 on to unsaturated polymers
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- 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
- C08K5/34922—Melamine; Derivatives thereof
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- 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
- C08K5/523—Esters of phosphoric acids, e.g. of H3PO4 with hydroxyaryl compounds
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- 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
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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The invention discloses a flame retardant with a jet type core-shell structure, a preparation method and application thereof, wherein a shell layer of the flame retardant comprises polyolefin; the core layer of the flame retardant at least comprises a heat-fusible flame retardant and an infusible flame retardant. The flame retardant with the jet type core-shell structure is thermally excited by the heated meltable flame retardant and the non-meltable flame retardant, one part of the flame retardant is melted into liquid (namely the heated meltable flame retardant) to be wrapped with solid flame retardant components (namely the non-meltable flame retardant), and the flame retardant is jetted by heating at first to aim at a firing point or a higher temperature point for directional fire extinguishment.
Description
Technical Field
The invention belongs to the field of new materials, relates to a flame retardant with a jet type core-shell structure, a preparation method and application thereof, and in particular relates to a flame retardant with a jet type core-shell structure, a preparation method thereof and application thereof in the field of photo-curing 3D printing.
Background
The fire-retardant science and technology is a science developed for adapting to social safety production and living needs, preventing fire occurrence and protecting life and property safety of people. With the progress of modern science, the human production and living data are greatly enriched. In particular, polymer materials have been widely used since the last century, and the application fields relate to aspects of production and living, and highly concentrated production and living data have higher requirements for preventing fire. For this, there are many colleges and universities at home and abroadThe research institutes are involved in the development of flame retardant science and technology, and many high efficiency flame retardants have been developed for application in the fire fighting field. Laura Geoffreoy et al, K 2 CO 3 The fire-retardant hydrogel is prepared by agar, ammonium alginate or polyvinyl alcohol, vermiculite and the like, and 3D printed grid units are filled, so that a composite material with fast flame extinction, low heat release rate peak value (pHRR) and small Total Heat Release (THR) is obtained, and the design of the sandwich fire-retardant structure provides a new thought and method for preparing the fire-retardant composite material (DOI: 10.1016/j. Polymdegradstar.2020.109269). Lei Wang et al also adopts a structural design method to carry out flame retardant modification on organic glass (PMMA), prepares the ammonium polyphosphate (APP) and the Graphene Oxide (GO) into composite graphene oxide aerogel together through covalent bonding, and finally fills the composite graphene oxide aerogel with Methyl Methacrylate (MMA). The composite material has excellent fire safety performance while ensuring excellent mechanical performance, and opens up a new path (DOI: 10.1039/c8ta00736 e) for preparing the graphene-based flame-retardant composite material. Over the years, researchers have been dedicated to the development of a wide variety of flame retardants for use in various fields. However, for some emerging fields, such as the field of 3D printing, in particular the field of photo-curing 3D printing, there is a lack of development of flame retardant science and technology.
Photo-curing 3D printing and fused deposition type 3D printing (FDM), metal 3D printing and other 3D printing technologies belong to additive manufacturing, and are one of earliest additive manufacturing methods. Unlike other 3D printing modes, photo-curing 3D printing is to initiate polymerization reaction in resin or monomer solution by ultraviolet light (or electron beam) to make the resin solution crosslinked and cured into solid in a layered manner. Specifically, the digital program controls the laser path to be injected into the resin tank, and one surface sweep is completed in the resin tank, so that the resin is initiated to be solidified to form a specific solid section. And then the platform is sunk, the solidification of the next layer is continuously finished, and the photocuring 3D printing process is finished by the layer by layer printing mode.
The flame retardant is a functional auxiliary agent, and after the flame retardant is added into a flammable or inflammable matrix according to a certain content, the matrix can be endowed with certain flame retardance, and combustion is slowed down, stopped and prevented, and is usually added in the material processing process. Analysis in terms of flame retarding mechanism is achieved by:
1. the flame retardant prevents or delays thermal decomposition of the matrix material in the solid phase matrix;
2. the addition of a large amount of flame retardants increases the hot melting and heat conductivity coefficients of the composite material, achieves the purposes of heat storage and material temperature rise limitation, and delays the thermal decomposition of the composite material;
3. after the flame retardant is added, the flame retardant can be decomposed earlier than the matrix material after being heated, absorbs surrounding heat, delays the time of forming combustion conditions, and achieves the aim of flame retardance;
4. a heat-resistant and nonflammable protective layer is formed on the surface of the matrix material, so that the combustible gas decomposed by the matrix material is prevented from entering a combustion gas phase, and the combustion condition is destroyed to realize flame retardance.
The core-shell structure may also be referred to as a capsule structure, which is considered as fine particles of 1-1000 μm for the flame retardant of the core-shell structure. The technology is firstly applied to carbonless copy paper by Americans in the 50 th century of 20 th, is widely applied to the fields of medicines, pesticides, essence, foods, cosmetics and the like, and the application field of the technology is continuously expanded. For core-shell structured core materials, solid, liquid, or even gaseous materials, typically functional materials, are possible. The shell material is mostly a transition material, has similar physical and chemical properties to the matrix material, and mainly prevents the core material from influencing the performance of the collective material due to large physical and chemical property differences between the core material and the matrix material.
Disclosure of Invention
In order to further improve the flame retardant efficiency of the flame retardant and expand the application field of the flame retardant, the invention provides a flame retardant with a jet type core-shell structure, and a preparation method and application thereof. The flame retardant with the jet type core-shell structure is characterized in that after the flame retardant reaches a certain temperature under external conditions, the flame retardant which can be melted by internal heating and the flame retardant which cannot be melted can be heated and expanded, and the flame retardant is jetted from the shell structure. The heated meltable flame retardant can be melted into liquid after the external condition is raised to a certain temperature, so that the liquid can be promoted to be sprayed to a fire source (or called a base material) together with other non-meltable flame retardants, and the flame retardant purpose is achieved. And after the shell structure is adopted to coat the heated meltable flame retardant and the infusible flame retardant, the invention avoids the direct contact between the heated meltable flame retardant and the infusible flame retardant and the matrix material, reduces the influence of the flame retardant on the matrix material, and is beneficial to the maintenance of the mechanical strength of the matrix material.
In order to achieve the above experimental purposes, the technical scheme of the invention is as follows:
a flame retardant of a jet core-shell structure, the shell layer of the flame retardant comprising a polyolefin; the core layer of the flame retardant at least comprises a heat-fusible flame retardant and an infusible flame retardant.
According to the invention, the heat-fusible flame retardant and the non-fusible flame retardant are both hydrophobic flame retardants.
According to the invention, the heat-fusible flame retardant is solid at normal temperature.
According to the invention, the heat-fusible flame retardant is changed from a solid state to a liquid state at 60-400 ℃.
According to the invention, the low-melting-point flame retardant is one, two or more selected from triphenyl phosphate, hexabromocyclododecane, decabromodiphenylethane and the like.
According to the invention, the non-fusible flame retardant is at least one selected from a high molecular flame retardant, an inorganic flame retardant, a high molecular flame retardant modified by a silane coupling agent and an inorganic flame retardant modified by a silane coupling agent;
the polymeric flame retardant is selected, for example, from melamine;
the inorganic flame retardant is at least one selected from ammonium superphosphate, antimonous oxide, magnesium hydroxide and aluminum hydroxide;
the silane coupling agent is at least one selected from KH550, KH560, KH579, KH791, A151, A171, etc.
In the invention, the hydrophobic flame retardant means that the adopted flame retardant has hydrophobicity or the flame retardant has hydrophobicity after modification treatment. The invention adopts the hydrophobic flame retardant, and the flame retardant which can be melted by heating and the flame retardant which can not be melted are quickly stirred, dispersed and mixed together in water at a proper temperature (for example, 35-250 ℃) to form emulsion, and after the temperature is reduced, the flame retardant mixture particles are formed.
According to the invention, the polyolefin is obtained by polymerization of at least one olefin monomer: methyl Methacrylate (MMA), styrene (St), glycidyl Methacrylate (GMA), 2-hydroxyethyl acrylate (HEA), isoboronate acrylate (IBOA).
According to the invention, the mass ratio of the heat-fusible flame retardant to the non-fusible flame retardant is 1-20:1, preferably 1-10:1.
According to the invention, the mass ratio of the heat-fusible flame retardant to the olefin monomer is 1:0.1-8, preferably 1:0.3-5.
According to the invention, the flame retardant with the jet type core-shell structure is converted into liquid at the temperature of 40-260 ℃ and is jetted from the shell layer.
The invention also provides a preparation method of the flame retardant with the jet type core-shell structure, which comprises the following steps:
(1) Mixing the heated meltable flame retardant and the non-meltable flame retardant with water, and heating to at least dissolve the heated meltable flame retardant;
(2) Adding an auxiliary agent into the step (1) for mixing, and reducing the temperature to solidify the heated meltable flame retardant to form a mixture;
(3) And mixing the mixture with an initiator and an olefin monomer, and reacting under ultraviolet irradiation to prepare the jet type core-shell structure flame retardant.
According to the invention, in step (1), the heating temperature is higher than the melting point of the heat-fusible flame retardant; for example, the heating temperature is 40 to 400℃and preferably 40 to 100 ℃.
According to the invention, in step (1), the mass to volume ratio of the heat-fusible flame retardant to water is 1g (20-200) mL, preferably 1g (50-100) mL.
According to the invention, in step (2), the temperature is reduced to 5-35 ℃, for example room temperature.
According to the invention, in step (2), the mass ratio of the auxiliary agent to the heat-fusible flame retardant is 0.01-0.2:1, preferably 0.02-0.1:1.
According to the invention, the auxiliary agent is a stable suspension system formed by the heat-fusible flame retardant, the non-fusible flame retardant and water in the temperature reduction process. For example, the auxiliary agent is one, two or more selected from hydrophilic surfactant, emulsifier, stabilizer and the like.
Preferably, the hydrophilic surfactant is span 80;
the emulsifier is OP-10;
the stabilizer is magnesium stearate.
According to the invention, the particle size of the core is 50 nm-50 microns.
According to the invention, the olefin monomers are one, two or three of Methyl Methacrylate (MMA), styrene (St), glycidyl Methacrylate (GMA), 2-hydroxyethyl acrylate (HEA) and isoboronate acrylate (IBOA).
According to the invention, in the step (3), the initiator is at least one of a photoinitiator and a thermal initiator.
Wherein the photoinitiator is at least one of (2, 4, 6-trimethylbenzoyl) diphenyl phosphine oxide (TPO), 1173 (2-hydroxy-2-methyl-1-phenylpropionyl), 184 (1-hydroxycyclohexyl phenyl ketone), 907 (2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-acetone) and the like.
The thermal initiator can decompose free radicals at about 65 ℃ and can initiate polymerization of olefin monomers, for example, at least one selected from azodiisobutyronitrile, azodiisoheptanenitrile, dimethyl azodiisobutyrate and the like.
According to the invention, in step (3), the mass ratio of the initiator to the olefin-based monomer is from 0.01 to 0.1:1, preferably from 0.01 to 0.05:1.
According to the invention, the ultraviolet light has a wavelength of 190-430 nanometers.
According to the invention, in step (3), the illumination time is 0.1-2h, for example 0.5h.
As a preferred embodiment of the invention, the preparation method of the flame retardant with the jet type core-shell structure specifically comprises the following steps:
1) Adding the heated meltable flame retardant and the non-meltable flame retardant into water, and heating at least to dissolve the heated meltable flame retardant into liquid;
2) Adding an auxiliary agent into the step 1), rapidly stirring and dispersing to form uniform and stable emulsion, slowly reducing the system temperature, solidifying the heated meltable flame retardant, and dispersing the heated meltable flame retardant and the infusible flame retardant together to form tiny particles in water;
3) Slowly dropwise adding an olefin monomer in the step 2), and adding a photoinitiator after the olefin monomer is dropwise added;
4) And (3) irradiating the reaction system by ultraviolet light to solidify the olefin monomer to form a shell layer, filtering, and then washing and drying by using an ethanol aqueous solution to obtain the flame retardant with the jet type core-shell structure.
The invention also provides application of the flame retardant with the jet type core-shell structure in the field of photo-curing 3D printing.
The invention has the beneficial effects that:
1) The flame retardant with the jet type core-shell structure is thermally excited by the heated meltable flame retardant and the non-meltable flame retardant, one part of the flame retardant is melted into liquid (namely the heated meltable flame retardant) to be wrapped with solid flame retardant components (namely the non-meltable flame retardant), and the flame retardant is jetted by heating at first to aim at a firing point or a higher temperature point for directional fire extinguishment;
2) Because the shell structure is the same as or similar to the structure of the matrix material, the core-shell structure injection type flame retardant can reduce the influence of the flame retardant on the matrix material, and maintain or improve the mechanical property of the matrix material;
3) The invention has wide application field and can be mixed with other polymer flame-retardant materials for use;
4) The invention firstly provides a shell structure of the core-shell structure injection type flame retardant prepared by adopting an ultraviolet light curing means, the reaction is carried out at a lower temperature (room temperature) to polymerize, the flame retardant which can be melted by heating and the non-meltable flame retardant in the core structure are ensured to be in a solid state, and the influence of the core structure on a system is reduced;
5) The invention can be applied to the field of photo-curing 3D printing.
Drawings
FIG. 1 is a schematic diagram of the spray type core-shell flame retardant of the present invention after being heated;
FIG. 2 is a micrograph of a flame retardant of a jet core-shell structure prepared in example 1.
Detailed Description
The technical scheme of the invention will be further described in detail below with reference to specific embodiments. It is to be understood that the following examples are illustrative only and are not to be construed as limiting the scope of the invention. All techniques implemented based on the above description of the invention are intended to be included within the scope of the invention.
Unless otherwise indicated, the starting materials and reagents used in the following examples were either commercially available or may be prepared by known methods.
The flame retardant composites prepared in examples 1-5 were subjected to Limiting Oxygen Index (LOI), vertical burn (UL-94) and tensile properties tests, as follows:
limiting Oxygen Index (LOI) test: the sample size of the flame retardant composite material was set to 130mm x 6mm x 3mm according to standard GB/T2406-2009, and the sample was tested with a limiting oxygen index instrument (Nanjing Jiang Ning analytical instrument, JF-3).
Vertical burn (UL-94) test: the sample size of the flame retardant composite material was set to 127mm x 12.7mm x 3mm according to standard GB/T2408-2008, and the sample was tested with a horizontal vertical Combustion tester (analytical instrumentation Co., jiang Ning in Nanj, CZF-5).
Tensile property test: the tensile properties of the flame retardant composite samples were tested according to the ISO 527 standard using a universal tester (AGX-100 plus, shimadzu), under the following conditions: 25+ -2deg.C, humidity: 50+/-5% of stretching speed: 2mm/min.
Example 1
Firstly, 3g of melamine (Zhengzhou Zhuochuang chemical product Co., ltd. With purity more than or equal to 99.95%) is added into 45g of absolute ethyl alcohol (national medicine Shanghai test, analytical purity), the stirring speed is set to be 100r/min, the temperature is set to be 80 ℃, then 0.05g of 3- (2, 3-epoxypropoxy) propyl trimethoxy silane (Allatin, KH560, molecular weight 236.33800) is added, stirring is continued for 5 hours, and the hydrophobic modified melamine powder is obtained after filtering, washing and drying.
In the second step, the hydrophobically modified melamine obtained in the first step was added to a 250ml three-necked flask. 3g of triphenyl phosphate (Allatin, 98%) and 75ml of deionized water are added, the system is heated to 75 ℃, 0.05g of span 80 (Allatin, pharmaceutical grade) and 0.03g of OP-10 (Allatin, AR) are added dropwise, the mixture is stirred at a high speed until the emulsion state, the stirring speed is kept at 400r/min, the heating is turned off, and the temperature is slowly reduced to 25 ℃ at room temperature. Obtaining solid modified melamine/triphenyl phosphate mixed particles.
Thirdly, 0.05g TPO is added into a three-neck flask to keep the rotating speed at 400r/min, and the mixing ratio of slow dripping is 1:1 (HEA, shadoma Guangzhou chemical Co., ltd.) together with 3g of isoboronate acrylate (IBOA, shadoma Guangzhou chemical Co., ltd.). Stirring was continued until the TPO was completely dissolved.
Fourth, illuminate the three-necked flask with a low power portable LED-UV lamp (Ji Weiyi, WFH-204B hand-held UV analyzer, ultraviolet wavelength 365 nm) to induce a mixing ratio of 1:1 with isoborone acrylate (IBOA). Continuously irradiating for 0.5 hour, filtering, washing and drying to obtain the jet type core-shell structure flame retardant with the shell thickness of 50-800 nanometers, wherein the particle size of the flame retardant is 500 nanometers-80 micrometers.
And fifthly, preparing the flame-retardant composite material by using a photocuring 3D printing technology. A certain amount of polyethylene glycol diacrylate-200 (SR 259, sartomer, chemical company limited) was added to the flame retardant of the jet type core-shell structure, and the mixture was stirred and dispersed for 1 hour. Pentaerythritol triacrylate (SR 444, shadoma Guangzhou chemical Co., ltd.) was then added, polyurethane acrylate oligomer (CN 991, shadoma Guangzhou chemical Co., ltd.) and photoinitiator (2, 4, 6-trimethylbenzoyl) diphenylphosphine oxide (TPO) were stirred for 1.5 hours in the absence of light. The flame retardant with the jet type core-shell structure accounts for 10% of the total mass of the photo-curing resin (the total mass of the photo-curing resin refers to the total mass after polymerization of polyethylene glycol diacrylate-200, polyurethane acrylate oligomer and pentaerythritol triacrylate), and then the sample preparation is carried out on a desktop-level SLA3D printer (stream 3D-C200, guolizhongke) with a wavelength of 405 nanometers. The thickness of the printed layer was set to 0.1 mm, and after printing was completed, the sample was transferred to a multifunctional UV curing machine (intell-ray 400) and cured for 20 minutes to obtain a flame retardant composite material.
FIG. 2 is a micrograph of a flame retardant of a jet core-shell structure prepared in example 1.
The limiting oxygen index of the sample was measured to be 27 when the flame retardant of the jet type core-shell structure accounted for 10% of the total mass of the photocurable resin.
The UL-94 rating of the sample was measured to be V2 when the flame retardant of the jet type core-shell structure accounted for 10% of the total mass of the photocurable resin.
When the flame retardant with the jet type core-shell structure accounts for 10% of the total mass of the photo-curing resin, the tensile strength of the sample is 35.3+/-0.5 Mpa, and the elongation at break is 3.5+/-0.3%.
Example two
In the first step, a hydrophobically modified melamine powder was prepared by the same method as in example one.
In the second step, the hydrophobically modified melamine obtained in the first step was added to a 250ml three-necked flask. 3g of triphenyl phosphate (Allatin, 98%) and 75ml of deionized water are added, the system is heated to 75 ℃, 0.05g of span 80 (Allatin, pharmaceutical grade) and 0.03g of OP-10 (Allatin, AR) are added dropwise, the mixture is stirred at a high speed until the emulsion state, the stirring speed is kept at 400r/min, the heating is turned off, and the temperature is slowly reduced to 25 ℃ at room temperature. Obtaining solid modified melamine/triphenyl phosphate mixed particles.
Third, 0.04g of TPO and 0.01g of azobisisobutyronitrile (Alatine, 98%) were charged into a three-necked flask at a rotation speed of 400r/min with a slow dropwise mixing ratio of 5:5:1:1 (HEA, shadoma Guangzhou chemical Co., ltd.) together with 3g of isobornyl acrylate (IBOA, shadoma Guangzhou chemical Co., ltd.), styrene (St, aladine, purity > 99.5%), glycidyl methacrylate (GMA, aladine, purity 97%). Stirring was continued until the TPO was completely dissolved.
Fourth, illuminate the three-necked flask with a low power portable LED-UV lamp (Ji Weiyi, WFH-204B hand-held UV analyzer, ultraviolet wavelength 365 nm) to induce a mixing ratio of 1:1 with isoborone acrylate (IBOA). Continuously irradiating for 0.5 hour, filtering, washing and drying to obtain the jet type core-shell structure flame retardant with the shell thickness of 50 nanometers-10 micrometers, wherein the particle size of the flame retardant is 400 nanometers-80 micrometers.
And fifthly, preparing the flame-retardant composite material by using a photocuring 3D printing technology. A certain amount of polyethylene glycol diacrylate-200 (SR 259, sartomer, chemical company limited) was added to the flame retardant of the jet type core-shell structure, and the mixture was stirred and dispersed for 1 hour. Pentaerythritol triacrylate (SR 444, shadoma Guangzhou chemical Co., ltd.) was then added, polyurethane acrylate oligomer (CN 991, shadoma Guangzhou chemical Co., ltd.) and photoinitiator (2, 4, 6-trimethylbenzoyl) diphenylphosphine oxide (TPO) were stirred for 1.5 hours in the absence of light. The sprayed core-shell flame retardant was made to account for 10% of the total mass of the photo-cured resin, and then sample preparation was performed on a 405 nm wavelength desktop level SLA3D printer (stream 3D-C200, guolizhongke). The thickness of the printed layer was set to 0.1 mm, and after printing was completed, the sample was transferred to a multifunctional UV curing machine (Intelli-ray 400) and cured for 20 minutes, and an oven at 70 ℃ was used for 2 hours to obtain a flame retardant composite material.
The limiting oxygen index of the sample was measured to be 27 when the flame retardant of the jet type core-shell structure accounted for 10% of the total mass of the photocurable resin.
The UL-94 rating of the sample was measured to be V2 when the flame retardant of the jet type core-shell structure accounted for 10% of the total mass of the photocurable resin.
When the flame retardant with the jet type core-shell structure accounts for 10% of the total mass of the photo-curing resin, the tensile strength of the sample is 37.3+/-0.3 Mpa, and the elongation at break is 2.5+/-0.3%.
Example III
In the first step, a hydrophobically modified melamine powder was prepared by the same method as in example one.
In the second step, the hydrophobically modified melamine obtained in the first step was added to a 250ml three-necked flask. 3g of triphenyl phosphate (Allatin, 98%) and 75ml of deionized water are added, the system is heated to 75 ℃, 0.05g of span 80 (Allatin, pharmaceutical grade) and 0.03g of OP-10 (Allatin, AR) are added dropwise, the mixture is stirred at a high speed until the emulsion state, the stirring speed is kept at 400r/min, the heating is turned off, and the temperature is slowly reduced to 25 ℃ at room temperature. Obtaining solid modified melamine/triphenyl phosphate mixed particles.
Thirdly, 0.02g of TPO is added into a three-neck flask to keep the rotating speed at 400r/min, and the mixing ratio of the slow dropping is 1:1 (HEA, shadoma Guangzhou chemical Co., ltd.) together with isoboronate acrylate (IBOA, shadoma Guangzhou chemical Co., ltd.). Stirring was continued until the TPO was completely dissolved.
Fourth, illuminate the three-necked flask with a low power portable LED-UV lamp (Ji Weiyi, WFH-204B hand-held UV analyzer, ultraviolet wavelength 365 nm) to induce a mixing ratio of 1:1 with isoborone acrylate (IBOA). Continuously irradiating for 0.5 hour, filtering, washing and drying to obtain the jet type core-shell structure flame retardant with the shell thickness of 50-800 nanometers, wherein the particle size of the flame retardant is 500 nanometers-80 micrometers.
And fifthly, preparing the flame-retardant composite material by using a photocuring 3D printing technology. A certain amount of polyethylene glycol diacrylate-200 (SR 259, sartomer, chemical company limited) was added to the flame retardant of the jet type core-shell structure, and the mixture was stirred and dispersed for 1 hour. Pentaerythritol triacrylate (SR 444, shadoma Guangzhou chemical Co., ltd.) was then added, polyurethane acrylate oligomer (CN 991, shadoma Guangzhou chemical Co., ltd.) and photoinitiator (2, 4, 6-trimethylbenzoyl) diphenylphosphine oxide (TPO) were stirred for 1.5 hours in the absence of light. The sprayed core-shell flame retardant was made to account for 10% of the total mass of the photo-cured resin, and then sample preparation was performed on a 405 nm wavelength desktop level SLA3D printer (stream 3D-C200, guolizhongke). The thickness of the printed layer was set to 0.1 mm, and after printing was completed, the sample was transferred to a multifunctional UV curing machine (intell-ray 400) and cured for 20 minutes to obtain a flame retardant composite material.
The limiting oxygen index of the sample was measured to be 28 when the sprayed core-shell flame retardant accounted for 10% of the total mass of the photocurable resin.
The UL-94 rating of the sample was measured to be V2 when the flame retardant of the jet type core-shell structure accounted for 10% of the total mass of the photocurable resin.
When the flame retardant with the jet type core-shell structure accounts for 10% of the total mass of the photo-curing resin, the tensile strength of the sample is 33.6+/-0.7 Mpa, and the elongation at break is 2.7+/-0.3%.
Example IV
In the first step, a hydrophobically modified melamine powder was prepared by the same method as in example one.
In the second step, the hydrophobically modified melamine obtained in the first step was added to a 250ml three-necked flask. 3g of triphenyl phosphate (Allatin, 98%) and 75ml of deionized water are added, the system is heated to 75 ℃, 0.05g of span 80 (Allatin, pharmaceutical grade) and 0.03g of OP-10 (Allatin, AR) are added dropwise, the mixture is stirred at a high speed until the emulsion state, the stirring speed is kept at 400r/min, the heating is turned off, and the temperature is slowly reduced to 25 ℃ at room temperature. Obtaining solid modified melamine/triphenyl phosphate mixed particles.
Thirdly, 0.05g TPO is added into a three-neck flask to keep the rotating speed at 400r/min, and the mixing ratio of slow dripping is 1:1 (HEA, shadoma Guangzhou chemical Co., ltd.) together with 3g of isoboronate acrylate (IBOA, shadoma Guangzhou chemical Co., ltd.). Stirring was continued until the TPO was completely dissolved.
Fourth, illuminate the three-necked flask with a low power portable LED-UV lamp (Ji Weiyi, WFH-204B hand-held UV analyzer, ultraviolet wavelength 365 nm) to induce a mixing ratio of 1:1 with isoborone acrylate (IBOA). Continuously irradiating for 0.5 hour, filtering, washing and drying to obtain the jet type core-shell structure flame retardant with the shell thickness of 50-800 nanometers, wherein the particle size of the flame retardant is 500 nanometers-80 micrometers.
And fifthly, preparing the flame-retardant composite material by using a photocuring 3D printing technology. A certain amount of polyethylene glycol diacrylate-200 (SR 259, sartomer, chemical company limited) was added to the flame retardant of the jet type core-shell structure, and the mixture was stirred and dispersed for 1 hour. Pentaerythritol triacrylate (SR 444, shadoma Guangzhou chemical Co., ltd.) was then added, polyurethane acrylate oligomer (CN 991, shadoma Guangzhou chemical Co., ltd.) and photoinitiator (2, 4, 6-trimethylbenzoyl) diphenylphosphine oxide (TPO) were stirred for 1.5 hours in the absence of light. The sprayed core-shell flame retardant was allowed to account for 15% of the total mass of the photocurable resin, and then sample preparation was performed on a 405 nm wavelength desktop level SLA3D printer (stream 3D-C200, guolizhongke). The thickness of the printed layer was set to 0.1 mm, and after printing was completed, the sample was transferred to a multifunctional UV curing machine (intell-ray 400) and cured for 20 minutes to obtain a flame retardant composite material.
The limiting oxygen index of the sample was determined to be 29 when the sprayed core-shell structured flame retardant accounted for 15% of the total mass of the photocurable resin.
The UL-94 rating of the sample was measured to be V1 when the flame retardant of the jet type core-shell structure accounted for 15% of the total mass of the photocurable resin.
When the flame retardant with the jet type core-shell structure accounts for 15% of the total mass of the photo-curing resin, the tensile strength of the sample is 34.4+/-0.5 Mpa, and the elongation at break is 3.9+/-0.4%.
Example five
In the first step, a hydrophobically modified melamine powder was prepared by the same method as in example one.
In the second step, the hydrophobically modified melamine obtained in the first step was added to a 250ml three-necked flask. 3g of triphenyl phosphate (Allatin, 98%) and 75ml of deionized water are added, the system is heated to 75 ℃, 0.05g of span 80 (Allatin, pharmaceutical grade) and 0.03g of OP-10 (Allatin, AR) are added dropwise, the mixture is stirred at a high speed until the emulsion state, the stirring speed is kept at 400r/min, the heating is turned off, and the temperature is slowly reduced to 25 ℃ at room temperature. Obtaining solid modified melamine/triphenyl phosphate mixed particles.
Thirdly, 0.05g TPO is added into a three-neck flask to keep the rotating speed at 400r/min, and the mixing ratio of slow dripping is 1:1 (HEA, shadoma Guangzhou chemical Co., ltd.) together with 3g of isoboronate acrylate (IBOA, shadoma Guangzhou chemical Co., ltd.). Stirring was continued until the TPO was completely dissolved.
Fourth, illuminate the three-necked flask with a low power portable LED-UV lamp (Ji Weiyi, WFH-204B hand-held UV analyzer, ultraviolet wavelength 365 nm) to induce a mixing ratio of 1:1 with isoborone acrylate (IBOA). Continuously irradiating for 0.5 hour, filtering, washing and drying to obtain the jet type core-shell structure flame retardant with the shell thickness of 50-800 nanometers, wherein the particle size of the flame retardant is 500 nanometers-80 micrometers.
And fifthly, preparing the flame-retardant composite material by using a photocuring 3D printing technology. A certain amount of polyethylene glycol diacrylate-200 (SR 259, sartomer, chemical company limited) was added to the flame retardant of the jet type core-shell structure, and the mixture was stirred and dispersed for 1 hour. Pentaerythritol triacrylate (SR 444, shadoma Guangzhou chemical Co., ltd.) was then added, polyurethane acrylate oligomer (CN 991, shadoma Guangzhou chemical Co., ltd.) and photoinitiator (2, 4, 6-trimethylbenzoyl) diphenylphosphine oxide (TPO) were stirred for 1.5 hours in the absence of light. The sprayed core-shell flame retardant was made to account for 25% of the total mass of the photo-cured resin, and then sample preparation was performed on a 405 nm wavelength desktop level SLA3D printer (stream 3D-C200, guolizhongke). The thickness of the printed layer was set to 0.1 mm, and after printing was completed, the sample was transferred to a multifunctional UV curing machine (intell-ray 400) and cured for 20 minutes to obtain a flame retardant composite material.
The limiting oxygen index of the sample was measured to be 31 when the sprayed core-shell flame retardant accounted for 25% of the total mass of the photocurable resin.
The UL-94 rating of the sample was measured to be V0 when the flame retardant of the jet type core-shell structure accounted for 25% of the total mass of the photocurable resin.
When the flame retardant with the jet type core-shell structure accounts for 25% of the total mass of the photo-curing resin, the tensile strength of the sample is 31.3+/-0.5 Mpa, and the elongation at break is 4.6+/-0.7%.
The embodiments of the present invention have been described above by way of example. However, the scope of the present invention is not limited to the above embodiments. Any modifications, equivalent substitutions, improvements, etc. made by those skilled in the art, which fall within the spirit and principles of the present invention, are intended to be included within the scope of the present invention.
Claims (5)
1. The application of the flame retardant with the jet type core-shell structure in the field of photo-curing 3D printing is characterized in that the shell layer of the flame retardant comprises polyolefin; the core layer of the flame retardant at least comprises a heat-fusible flame retardant and a non-fusible flame retardant;
the preparation method of the flame retardant with the jet type core-shell structure comprises the following steps:
(1) Mixing the heated meltable flame retardant and the non-meltable flame retardant with water, and heating to at least dissolve the heated meltable flame retardant;
(2) Adding an auxiliary agent into the step (1) for mixing, and reducing the temperature to solidify the heated meltable flame retardant to form a mixture;
(3) Mixing the mixture with an initiator and an olefin monomer, and reacting under ultraviolet irradiation to prepare the jet type core-shell structure flame retardant;
the heated meltable flame retardant is one or more than two selected from triphenyl phosphate, hexabromocyclododecane and decabromodiphenylethane;
the non-fusible flame retardant is at least one of high molecular flame retardants and silane coupling agent modified high molecular flame retardants;
the high molecular flame retardant is selected from melamine;
the silane coupling agent is at least one selected from KH550, KH560, KH579, KH791, A151 and A171;
the initiator is a photoinitiator; the photoinitiator is at least one of (2, 4, 6-trimethylbenzoyl) diphenyl phosphine oxide (TPO), 1173 (2-hydroxy-2-methyl-1-phenylpropionyl), 184 (1-hydroxycyclohexyl phenyl ketone) and 907 (2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-acetone);
in the step (2), the temperature is reduced to 5-35 ℃;
the mass ratio of the heated meltable flame retardant to the non-meltable flame retardant is 1-20:1;
and/or the mass ratio of the heated meltable flame retardant to the olefin monomer is 1:0.1-8;
the flame retardant with the jet type core-shell structure is converted into liquid at the temperature of 40-260 ℃ and is jetted from the shell.
2. Use according to claim 1, characterized in that the polyolefin is obtained by polymerization of at least one olefin monomer: methyl methacrylate, styrene, glycidyl methacrylate, 2-hydroxyethyl acrylate, and isoboronyl acrylate.
3. The use according to claim 1, wherein in step (1) the heating is at a temperature above the melting point of the heat-fusible flame retardant; the heating temperature is 40-400 ℃;
and/or in the step (1), the mass volume ratio of the heated meltable flame retardant to the water is 1g (20-200) mL.
4. The use according to claim 1, wherein in step (1), the mass ratio of auxiliary agent to heat-fusible flame retardant in step (2) is 0.01-0.2:1.
5. The use according to claim 1, characterized in that in step (3) the mass ratio of the initiator to the olefinic monomer is 0.01-0.1:1;
and/or the wavelength of the ultraviolet light is 190-430 nanometers.
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| CN101608060A (en) * | 2009-07-09 | 2009-12-23 | 中国科学技术大学 | Core-shell type ammonium polyphosphate synergetic flame-retardant polyurethane elastic composite material and method for making thereof |
| AU2020102176A4 (en) * | 2020-09-08 | 2020-11-12 | Yantai University | The method for preparing a environment-friendly flame retardant water-borne acrylic resin coating with core shell structure |
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| CN101608060A (en) * | 2009-07-09 | 2009-12-23 | 中国科学技术大学 | Core-shell type ammonium polyphosphate synergetic flame-retardant polyurethane elastic composite material and method for making thereof |
| AU2020102176A4 (en) * | 2020-09-08 | 2020-11-12 | Yantai University | The method for preparing a environment-friendly flame retardant water-borne acrylic resin coating with core shell structure |
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