CN110746530A - Flame-retardant polydicyclopentadiene composite material and preparation method thereof - Google Patents
Flame-retardant polydicyclopentadiene composite material and preparation method thereof Download PDFInfo
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- 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 91
- 239000003063 flame retardant Substances 0.000 title claims abstract description 91
- 229920001153 Polydicyclopentadiene Polymers 0.000 title claims abstract description 39
- 239000002131 composite material Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000000178 monomer Substances 0.000 claims abstract description 34
- 239000007822 coupling agent Substances 0.000 claims abstract description 28
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims abstract description 27
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 22
- 239000000463 material Substances 0.000 claims abstract description 22
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 20
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- -1 alkyl hypophosphite Chemical compound 0.000 claims abstract description 8
- 239000006185 dispersion Substances 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims abstract description 7
- 239000004114 Ammonium polyphosphate Substances 0.000 claims abstract description 6
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims abstract description 6
- 229920001276 ammonium polyphosphate Polymers 0.000 claims abstract description 6
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 39
- 238000003756 stirring Methods 0.000 claims description 21
- 238000005303 weighing Methods 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 229920000388 Polyphosphate Polymers 0.000 claims description 6
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 6
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 6
- 239000001205 polyphosphate Substances 0.000 claims description 6
- 235000011176 polyphosphates Nutrition 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 4
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 claims description 3
- XESZUVZBAMCAEJ-UHFFFAOYSA-N 4-tert-butylcatechol Chemical compound CC(C)(C)C1=CC=C(O)C(O)=C1 XESZUVZBAMCAEJ-UHFFFAOYSA-N 0.000 claims description 3
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 3
- 229920000877 Melamine resin Polymers 0.000 claims description 3
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 3
- 208000026487 Triploidy Diseases 0.000 claims description 3
- 239000007983 Tris buffer Substances 0.000 claims description 3
- PNPBGYBHLCEVMK-UHFFFAOYSA-N benzylidene(dichloro)ruthenium;tricyclohexylphosphanium Chemical compound Cl[Ru](Cl)=CC1=CC=CC=C1.C1CCCCC1[PH+](C1CCCCC1)C1CCCCC1.C1CCCCC1[PH+](C1CCCCC1)C1CCCCC1 PNPBGYBHLCEVMK-UHFFFAOYSA-N 0.000 claims description 3
- 235000010354 butylated hydroxytoluene Nutrition 0.000 claims description 3
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 claims description 3
- 239000011984 grubbs catalyst Substances 0.000 claims description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 3
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 claims description 3
- ISCJHSMPIXGIFN-UHFFFAOYSA-K aluminum 2-methylpropyl(dioxido)phosphanium Chemical compound C(C(C)C)P([O-])=O.[Al+3].C(C(C)C)P([O-])=O.C(C(C)C)P([O-])=O ISCJHSMPIXGIFN-UHFFFAOYSA-K 0.000 claims 1
- XSAOTYCWGCRGCP-UHFFFAOYSA-K aluminum;diethylphosphinate Chemical compound [Al+3].CCP([O-])(=O)CC.CCP([O-])(=O)CC.CCP([O-])(=O)CC XSAOTYCWGCRGCP-UHFFFAOYSA-K 0.000 claims 1
- GSRMMASLHSOXIJ-UHFFFAOYSA-K aluminum;dioctylphosphinate Chemical compound [Al+3].CCCCCCCCP([O-])(=O)CCCCCCCC.CCCCCCCCP([O-])(=O)CCCCCCCC.CCCCCCCCP([O-])(=O)CCCCCCCC GSRMMASLHSOXIJ-UHFFFAOYSA-K 0.000 claims 1
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 7
- 238000013329 compounding Methods 0.000 abstract description 3
- 238000000034 method Methods 0.000 abstract description 3
- 238000000465 moulding Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- HECLRDQVFMWTQS-UHFFFAOYSA-N Dicyclopentadiene Chemical compound C1C2C3CC=CC3C1C=C2 HECLRDQVFMWTQS-UHFFFAOYSA-N 0.000 description 9
- 229910001377 aluminum hypophosphite Inorganic materials 0.000 description 6
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000779 smoke Substances 0.000 description 3
- LQIIEHBULBHJKX-UHFFFAOYSA-N 2-methylpropylalumane Chemical compound CC(C)C[AlH2] LQIIEHBULBHJKX-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- CQYBWJYIKCZXCN-UHFFFAOYSA-N diethylaluminum Chemical compound CC[Al]CC CQYBWJYIKCZXCN-UHFFFAOYSA-N 0.000 description 2
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical compound CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 description 2
- RYFHUGPCQBOJBL-UHFFFAOYSA-N dioctylaluminum Chemical compound CCCCCCCC[Al]CCCCCCCC RYFHUGPCQBOJBL-UHFFFAOYSA-N 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 239000012796 inorganic flame retardant Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
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- 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
- C08F132/00—Homopolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
- C08F132/08—Homopolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having condensed rings
-
- 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
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-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
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
-
- 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
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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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- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
- C08K2003/387—Borates
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polymerisation Methods In General (AREA)
Abstract
A flame-retardant polydicyclopentadiene composite material and a preparation method thereof, comprises a component A and a component B, wherein the component A is formed by synchronously blending and polymerizing a dicyclopentadiene monomer, a main flame retardant, a flame-retardant synergist, a coupling agent and an antioxidant; the component B comprises a ruthenium catalyst and a dispersion liquid. According to the invention, alkyl hypophosphite is used as a main flame retardant, ammonium polyphosphate and the like are used as flame retardant synergists, zinc borate and the like are used as synergists, a coupling agent is added in the compounding process of the flame retardant to enhance the interface performance of each material, the dispersibility of each component is improved, the mixture is added into dicyclopentadiene to be uniformly dispersed and can be stably suspended in a monomer, A, B components are mixed and stirred uniformly by a mixer, vacuum is extracted and injected into a mold, and the mold is heated to 60 ℃ for molding, so that the flame-retardant polydicyclopentadiene material is obtained, and the flame-retardant polydicyclopentadiene material can achieve the flame-retardant and smoke-suppression effects under the conditions of full dispersion and little influence on the mechanical strength.
Description
Technical Field
The invention relates to a polydicyclopentadiene flame-retardant modified composite material, in particular to a flame-retardant polydicyclopentadiene composite material and a preparation method thereof.
Background
Polydicyclopentadiene belongs to hydrocarbon, is easy to ignite, has extremely low Limiting Oxygen Index (LOI) (about 18.5), and is accompanied by a great amount of black smoke when ignited, thereby limiting the application of polydicyclopentadiene in various fields such as electronics, electrical appliances, traffic, decorative materials and the like. At present, in the existing technology for preparing flame-retardant polydicyclopentadiene, additive inorganic flame retardant with high additive amount is often adopted to realize the flame-retardant property of polydicyclopentadiene, but high-content additive flame retardant can only be properly dispersed in dicyclopentadiene, most additive flame retardant is easy to settle, the dispersibility is not good, the mechanical property of the material can be influenced, and the smoke emission is relatively large.
Disclosure of Invention
The invention aims to provide a flame-retardant polydicyclopentadiene composite material and a preparation method thereof, which can be uniformly dispersed in a system and are not easy to settle, and reduce the influence on the mechanical property of the material.
In order to achieve the purpose, the invention provides the following technical scheme: the flame-retardant polydicyclopentadiene composite material comprises a component A and a component B in parts by weight, wherein the component A is prepared by synchronously blending and polymerizing the following monomers: dicyclopentadiene monomer: 60-100 parts of a main flame retardant: 0-30 parts of flame retardant synergist: 0.5-10 parts of a synergist: 0.5-10 parts of coupling agent: 0-3 parts of antioxidant: 0.1-3 parts;
the component B comprises: ruthenium-based Grubbs catalyst: 0.01-0.03 parts of a dispersion liquid, wherein the dispersion liquid comprises toluene or acetone: 0.5-3 parts.
Furthermore, the dicyclopentadiene content in the dicyclopentadiene monomer in the component A is 92 wt%; the cyclopentadiene triploid content was 8% wt.
Further, the main flame retardant in the component A is alkyl hypophosphite, and comprises diethyl aluminum hypophosphite, isobutyl aluminum hypophosphite, diethyl zinc hypophosphite and dioctyl aluminum hypophosphite.
Further, the flame retardant synergist in the component A comprises: ammonium polyphosphate, triazine polyphosphate and melamine polyphosphate.
Further, the synergist in the component A comprises: zinc borate, antimony trioxide, ferrocene, the average particle size: ≦ 25 μm.
Further, the antioxidants in the A component comprise: phenyl tris (2, 4-di-tert-butyl) phosphite, 4' -dihydroxy-3, 3',5,5' -tetra-tert-butyldiphenylmethane, 2, 6-di-tert-butyl-4-methylphenol, 4-tert-butylcatechol.
Further, the coupling agent in the A component comprises: silane coupling agents and titanic acid coupling agents.
The invention also provides a preparation method of the flame-retardant polydicyclopentadiene composite material, which comprises the following steps:
s1: weighing an antioxidant and a coupling agent according to the weight part ratio, dissolving the antioxidant and the coupling agent in a dicyclopentadiene monomer, adding a main flame retardant, a flame-retardant synergist and a synergist into a mixed system, and uniformly stirring to obtain a polymerization A component material;
s2: dissolving a ruthenium catalyst in a toluene solution to obtain a component B;
s3: adding the component B into the component A, quickly stirring in a mixer at high speed and vacuum, pouring into a mold at 60 ℃, and demolding for 6 minutes to obtain the flame-retardant polydicyclopentadiene composite material.
The invention discloses a flame-retardant polydicyclopentadiene composition, wherein alkyl hypophosphite is used as a main flame retardant, ammonium polyphosphate and the like are used as flame-retardant synergists, and zinc borate and the like are used as synergists. In the compounding process of the flame retardant, the coupling agent is added to enhance the interface performance of each material and improve the dispersibility of each component. The mixture is added into dicyclopentadiene to be dispersed evenly, and can be stably suspended in monomers to be used as a polymerization material A. The material B comprises a catalyst (ruthenium system) and a dispersant. And (3) mixing and stirring the A, B material uniformly by a mixer, vacuumizing, injecting into a mold, heating to 60 ℃ for molding, and demolding after 5 minutes to obtain the flame-retardant polydicyclopentadiene material. Therefore, the flame retardant can be uniformly dispersed in a system and is not easy to settle, the influence on the mechanical property of the material is reduced, the flame retardant is an inorganic flame retardant, the particle size is small, the flame retardant can be uniformly dispersed in a dicyclopentadiene monomer after surface modification treatment, and the flame retardant and smoke suppression effects can be achieved by a small amount of the composition.
Detailed Description
The following examples will explain the present invention in detail, but the present invention is not limited thereto. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The embodiment of the invention provides a flame-retardant polydicyclopentadiene composite material which comprises a component A and a component B in parts by weight, wherein the component A is prepared by synchronously blending and polymerizing the following monomers: dicyclopentadiene monomer: 60-100 parts of a main flame retardant: 0-30 parts of flame retardant synergist: 0.5-10 parts of a synergist: 0.5-10 parts of coupling agent: 0-3 parts of antioxidant: 0.1-3 parts; the component B comprises: ruthenium-based Grubbs catalyst: 0.01-0.03 parts of a dispersion liquid, wherein the dispersion liquid comprises toluene or acetone: 0.5-3 parts.
Wherein, the dicyclopentadiene content in the dicyclopentadiene monomer in the component A is 92 wt%; the content of cyclopentadiene triploid is 8 wt%; the main flame retardant is alkyl hypophosphite which comprises diethyl aluminum hypophosphite, isobutyl aluminum hypophosphite, diethyl zinc hypophosphite and dioctyl aluminum hypophosphite; the flame retardant synergist comprises: ammonium polyphosphate, triazine polyphosphate and melamine polyphosphate; the synergist comprises: zinc borate, antimony trioxide, ferrocene, the average particle size: ≦ 25 μm; the antioxidant includes: tris (2, 4-di-tert-butyl) phenyl phosphite, 4' -dihydroxy-3, 3',5,5' -tetra-tert-butyldiphenylmethane, 2, 6-di-tert-butyl-4-methylphenol, 4-tert-butylcatechol; the coupling agent comprises: silane coupling agents and titanic acid coupling agents.
Based on the composition of the composite material, the invention also provides a preparation method of the flame-retardant polydicyclopentadiene composite material, which comprises the following steps:
the first step is as follows: weighing an antioxidant and a coupling agent according to the weight part ratio, dissolving the antioxidant and the coupling agent in a dicyclopentadiene monomer, adding a main flame retardant, a flame-retardant synergist and a synergist into a mixed system, and uniformly stirring to obtain a polymerization A component material;
the second step is that: dissolving a ruthenium catalyst in a toluene solution to obtain a component B;
the third step: adding the component B into the component A, quickly stirring in a mixer at high speed and vacuum, pouring into a mold at 60 ℃, and demolding for 6 minutes to obtain the flame-retardant polydicyclopentadiene composite material.
To further better illustrate the above invention, the invention provides the following specific examples:
example 1:
weighing 2 parts of antioxidant and 2 parts of coupling agent, dissolving in 100 parts of dicyclopentadiene monomer (DCPD monomer), adding 15 parts of main flame retardant, 5 parts of flame-retardant synergist and 5 parts of synergist into a mixed system, stirring uniformly, adding 0.5 part of toluene solution in which 0.01 part of ruthenium catalyst is dissolved, stirring at high speed in vacuum at high speed, pouring into a 60 ℃ mould, and demoulding for 6 minutes to obtain the flame-retardant polydicyclopentadiene product.
Example 2:
weighing 2 parts of antioxidant, 2 parts of coupling agent, dissolving in 100 parts of dicyclopentadiene monomer (DCPD monomer), adding 20 parts of main flame retardant, 5 parts of flame-retardant synergist and 5 parts of synergist into a mixed system, stirring uniformly, adding 1 part of toluene solution in which 0.01 part of ruthenium catalyst is dissolved, stirring at high speed in vacuum, pouring into a 60 ℃ mould, and demoulding for 6 minutes to obtain the flame-retardant polydicyclopentadiene product.
Example 3:
weighing 2 parts of antioxidant, 2 parts of coupling agent, dissolving in 100 parts of dicyclopentadiene monomer (DCPD monomer), adding 25 parts of main flame retardant, 5 parts of flame-retardant synergist and 5 parts of synergist into a mixed system, stirring uniformly, adding 1.5 parts of toluene solution in which 0.02 part of ruthenium catalyst is dissolved, stirring at high speed in vacuum at high speed, pouring into a 60 ℃ mould, and demoulding for 6 minutes to obtain the flame-retardant polydicyclopentadiene product.
Example 4:
weighing 2 parts of antioxidant, 2 parts of coupling agent, dissolving in 100 parts of dicyclopentadiene monomer (DCPD monomer), adding 20 parts of main flame retardant, 3 parts of flame retardant synergist and 5 parts of synergist into a mixed system, stirring uniformly, adding 2 parts of toluene solution in which 0.02 part of ruthenium catalyst is dissolved, stirring at high speed in vacuum, pouring into a 60 ℃ mould, and demoulding for 6 minutes to obtain the flame-retardant polydicyclopentadiene product.
Example 5:
weighing 2 parts of antioxidant, 2 parts of coupling agent, dissolving in 100 parts of dicyclopentadiene monomer (DCPD monomer), adding 20 parts of main flame retardant, 1 part of flame-retardant synergist and 5 parts of synergist into a mixed system, stirring uniformly, adding 2.5 parts of toluene solution in which 0.03 part of ruthenium catalyst is dissolved, stirring at high speed in vacuum at high speed, pouring into a 60 ℃ mould, and demoulding for 6 minutes to obtain the flame-retardant polydicyclopentadiene product.
Example 6:
weighing 2 parts of antioxidant, 2 parts of coupling agent, dissolving in 100 parts of dicyclopentadiene monomer (DCPD monomer), adding 20 parts of main flame retardant, 5 parts of flame-retardant synergist and 3 parts of synergist into a mixed system, stirring uniformly, adding 3 parts of toluene solution in which 0.03 part of ruthenium catalyst is dissolved, stirring at high speed in vacuum, pouring into a 60 ℃ mould, and demoulding for 6 minutes to obtain the flame-retardant polydicyclopentadiene product.
Example 7:
weighing 2 parts of antioxidant and 2 parts of coupling agent, dissolving in 100 parts of dicyclopentadiene monomer (DCPD monomer), adding 20 parts of main flame retardant, 5 parts of flame-retardant synergist and 1 part of synergist into a mixed system, stirring uniformly, adding 3 parts of toluene solution in which 0.03 part of ruthenium catalyst is dissolved, stirring at high speed in vacuum, pouring into a 60 ℃ mould, and demoulding for 6 minutes to obtain the flame-retardant polydicyclopentadiene product.
Comparative example:
weighing 2 parts of antioxidant, and dissolving 2 parts of coupling agent in 100 parts of dicyclopentadiene monomer (DCPD monomer) to obtain the flame retardant.
As shown in the following table:
| examples | DCPD monomer | Antioxidant agent | Coupling agent | Flame retardant | Flame retardant synergist | Synergist |
| Comparative example | 100 | 2 | 2 | 0 | 0 | 0 |
| Example 1 | 100 | 2 | 2 | 15 | 5 | 5 |
| Example 2 | 100 | 2 | 2 | 20 | 5 | 5 |
| Example 3 | 100 | 2 | 2 | 25 | 5 | 5 |
| Example 4 | 100 | 2 | 2 | 20 | 3 | 5 |
| Example 5 | 100 | 2 | 2 | 20 | 1 | 5 |
| Example 6 | 100 | 2 | 2 | 20 | 5 | 3 |
| Example 7 | 100 | 2 | 2 | 20 | 5 | 1 |
And (3) comparing the material properties:
| examples | Tensile Strength (MPa) | Impact Strength (KJ/m) | Oxygen index (%) | hardness/(Shore D) | Horizontal-vertical combustion |
| Comparative example | 45 | 9 | 18.5 | 80 | Without hierarchy |
| Example 1 | 42 | 8 | 23 | 78 | V-2 |
| Example 2 | 41 | 8 | 25 | 77 | V-1 |
| Example 3 | 40 | 8 | 28 | 76 | V-0 |
| Example 4 | 41 | 8 | 24.5 | 78 | V-1 |
| Example 5 | 41 | 8 | 23.8 | 77 | V-1 |
| Example 6 | 40 | 8 | 27.8 | 81 | V-1 |
| Example 7 | 40 | 8 | 26.2 | 83 | V-2 |
From the comparison of the above examples, it can be seen that: the invention provides a flame-retardant polydicyclopentadiene composite material and a preparation method thereof, which adopt alkyl hypophosphite as a main flame retardant, ammonium polyphosphate and the like as flame-retardant synergists and zinc borate and the like as synergists, in the compounding process of the flame retardant, a coupling agent is added to enhance the interface performance of each material and improve the dispersibility of each component, the mixture is added into dicyclopentadiene to be uniformly dispersed and can be stably suspended in a monomer, the dicyclopentadiene is used as a polymerization material A, the material B comprises a catalyst (ruthenium system) and a dispersing agent, A, B materials are mixed and stirred uniformly by a mixer, then the mixture is pumped into a vacuum and injected into a mold, heated to 60 ℃ for molding, and the mold is removed after 5 minutes, so that the flame-retardant polydicyclopentadiene material is obtained, and the flame-retardant and smoke-suppressing effects can be achieved under the condition that the mechanical strength of the flame-retardant polydicyclopentadiene material is fully dispersed.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (8)
1. A flame-retardant polydicyclopentadiene composite material comprises a component A and a component B in parts by weight,
the component A is prepared by synchronously blending and polymerizing the following monomers: dicyclopentadiene monomer: 60-100 parts of a main flame retardant: 0-30 parts of flame retardant synergist: 0.5-10 parts of a synergist: 0.5-10 parts of coupling agent: 0-3 parts of antioxidant: 0.1-3 parts;
the component B comprises: ruthenium-based Grubbs catalyst: 0.01-0.03 parts of a dispersion liquid, wherein the dispersion liquid comprises toluene or acetone: 0.5-3 parts.
2. The flame-retardant polydicyclopentadiene composite material of claim 1, wherein the dicyclopentadiene content of the dicyclopentadiene monomer in component a is 92 wt%; content of cyclopentadiene triploid: 8% wt.
3. The flame retardant polydicyclopentadiene composite material of claim 1 wherein the primary flame retardant in component a is an alkyl phosphinate comprising aluminum diethylphosphinate, aluminum isobutylphosphinate, zinc diethylphosphinate or aluminum dioctylphosphinate.
4. The flame-retardant polydicyclopentadiene composite material of claim 1, wherein the flame retardant synergist in component a comprises: ammonium polyphosphate, triazine polyphosphate or melamine polyphosphate.
5. The flame-retardant polydicyclopentadiene composite material of claim 1, wherein the synergist in component a comprises: zinc borate or antimony trioxide ferrocene, average particle size: ≦ 25 μm.
6. The flame retardant polydicyclopentadiene composite material of claim 1 wherein the antioxidant in component a comprises: tris (2, 4-di-tert-butyl) phenyl phosphite, 4' -dihydroxy-3, 3',5,5' -tetra-tert-butyldiphenylmethane, 2, 6-di-tert-butyl-4-methylphenol or 4-tert-butylcatechol.
7. The flame-retardant polydicyclopentadiene composite material of claim 1, wherein the coupling agent in component a is a silane coupling agent and/or a titanic acid coupling agent.
8. The preparation method of the flame-retardant polydicyclopentadiene composite material according to claim 1, characterized by comprising the steps of:
s1: weighing an antioxidant and a coupling agent according to the weight part ratio, dissolving the antioxidant and the coupling agent in a dicyclopentadiene monomer, adding a main flame retardant, a flame-retardant synergist and a synergist into a mixed system, and uniformly stirring to obtain a polymerization A component material;
s2: dissolving a ruthenium catalyst in a toluene solution to obtain a component B;
s3: adding the component B into the component A, quickly stirring in a mixer at high speed and vacuum, pouring into a mold at 60 ℃, and demolding for 6 minutes to obtain the flame-retardant polydicyclopentadiene composite material.
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| CN102199252A (en) * | 2011-03-30 | 2011-09-28 | 黎明化工研究院 | Flame-retardant polydicyclopentadiene composition, and thermosetting material and preparation method thereof |
| CN102675801A (en) * | 2011-12-19 | 2012-09-19 | 河南科技大学 | Flame-retardant toughened polydicyclopentadiene composite material and preparation method thereof |
| CN103897215A (en) * | 2012-12-26 | 2014-07-02 | 金发科技股份有限公司 | Composite fire retardant and use thereof |
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| CN102199252A (en) * | 2011-03-30 | 2011-09-28 | 黎明化工研究院 | Flame-retardant polydicyclopentadiene composition, and thermosetting material and preparation method thereof |
| CN102675801A (en) * | 2011-12-19 | 2012-09-19 | 河南科技大学 | Flame-retardant toughened polydicyclopentadiene composite material and preparation method thereof |
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