CN111320836A - Halogen-free flame-retardant ABS composite material and preparation method thereof - Google Patents
Halogen-free flame-retardant ABS composite material and preparation method thereof Download PDFInfo
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- CN111320836A CN111320836A CN202010219961.7A CN202010219961A CN111320836A CN 111320836 A CN111320836 A CN 111320836A CN 202010219961 A CN202010219961 A CN 202010219961A CN 111320836 A CN111320836 A CN 111320836A
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 64
- 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 61
- 239000002131 composite material Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000000463 material Substances 0.000 claims abstract description 8
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims description 33
- 239000000314 lubricant Substances 0.000 claims description 13
- 239000003999 initiator Substances 0.000 claims description 11
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 11
- 229910019142 PO4 Inorganic materials 0.000 claims description 9
- 239000003963 antioxidant agent Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- -1 nitrogen-containing free radical Chemical class 0.000 claims description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 9
- 239000010452 phosphate Substances 0.000 claims description 9
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 8
- 230000003078 antioxidant effect Effects 0.000 claims description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- 150000001336 alkenes Chemical group 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000003086 colorant Substances 0.000 claims description 6
- 125000001424 substituent group Chemical group 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 230000000694 effects Effects 0.000 claims description 5
- 239000002250 absorbent Substances 0.000 claims description 4
- 230000002745 absorbent Effects 0.000 claims description 4
- 150000001335 aliphatic alkanes Chemical group 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 229920006395 saturated elastomer Polymers 0.000 claims description 4
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 3
- 239000012752 auxiliary agent Substances 0.000 claims description 3
- 229920002379 silicone rubber Polymers 0.000 claims description 3
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 claims description 3
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- 150000001408 amides Chemical class 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 2
- 239000012965 benzophenone Substances 0.000 claims description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 2
- 239000012964 benzotriazole Substances 0.000 claims description 2
- 239000004611 light stabiliser Substances 0.000 claims description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 2
- 229920001296 polysiloxane Polymers 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- 239000012745 toughening agent Substances 0.000 claims description 2
- 150000002831 nitrogen free-radicals Chemical class 0.000 claims 1
- 229910052787 antimony Inorganic materials 0.000 abstract description 7
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 abstract description 7
- 238000000034 method Methods 0.000 abstract description 7
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 abstract description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052794 bromium Inorganic materials 0.000 abstract description 6
- 238000012545 processing Methods 0.000 abstract description 3
- 230000005684 electric field Effects 0.000 abstract description 2
- 238000002844 melting Methods 0.000 abstract description 2
- 230000008018 melting Effects 0.000 abstract description 2
- 230000000704 physical effect Effects 0.000 abstract description 2
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 19
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 19
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 7
- 150000003254 radicals Chemical class 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 239000005457 ice water Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 230000002195 synergetic effect Effects 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000000843 powder Substances 0.000 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 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910003849 O-Si Inorganic materials 0.000 description 2
- 229910003872 O—Si Inorganic materials 0.000 description 2
- LXWPJAGZRHTAOO-UHFFFAOYSA-N [Sb].[Br] Chemical compound [Sb].[Br] LXWPJAGZRHTAOO-UHFFFAOYSA-N 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000010559 graft polymerization reaction Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- CFMZSMGAMPBRBE-UHFFFAOYSA-N 2-hydroxyisoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(O)C(=O)C2=C1 CFMZSMGAMPBRBE-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 1
- CTMFECUQKLSOGJ-UHFFFAOYSA-N 4-bromotriazine Chemical compound BrC1=CC=NN=N1 CTMFECUQKLSOGJ-UHFFFAOYSA-N 0.000 description 1
- XVMSFILGAMDHEY-UHFFFAOYSA-N 6-(4-aminophenyl)sulfonylpyridin-3-amine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=N1 XVMSFILGAMDHEY-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000004114 Ammonium polyphosphate Substances 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229920001893 acrylonitrile styrene Polymers 0.000 description 1
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 1
- 229920001276 ammonium polyphosphate Polymers 0.000 description 1
- 150000001463 antimony compounds Chemical class 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- OJZNZOXALZKPEA-UHFFFAOYSA-N chloro-methyl-diphenylsilane Chemical compound C=1C=CC=CC=1[Si](Cl)(C)C1=CC=CC=C1 OJZNZOXALZKPEA-UHFFFAOYSA-N 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- IBDMRHDXAQZJAP-UHFFFAOYSA-N dichlorophosphorylbenzene Chemical compound ClP(Cl)(=O)C1=CC=CC=C1 IBDMRHDXAQZJAP-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
- C08L25/12—Copolymers of styrene with unsaturated nitriles
-
- 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
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Fireproofing Substances (AREA)
Abstract
The invention relates to a halogen-free flame-retardant ABS composite material and a preparation method thereof. The flame retardant adopted by the invention has proper melting temperature, can be melted in the processing process, and has little harm to the physical properties of the material; the whole addition amount is low, and the adjustable range of the performance is large; the flame-retardant ABS composite material can be used in the electronic and electrical fields with flame-retardant requirements, the application field of replacing the original bromine and antimony flame-retardant ABS composite material, and other fields needing flame-retardant ABS.
Description
Technical Field
The invention belongs to the field of flame-retardant plastic materials, and particularly relates to a halogen-free flame-retardant ABS composite material and a preparation method thereof.
Background
The acrylonitrile-butadiene-styrene copolymer resin, namely ABS resin, has the performance between that of engineering plastics and general plastics, has excellent comprehensive mechanical properties and processing and forming properties, and is widely applied to the fields of electronics, electrics, machinery, buildings and the like. However, the ABS resin has many defects and shortcomings due to the limitation of the polymer structure and composition, such as poor wear resistance, low heat resistance, poor weather resistance, and only HB-level flame retardance.
The flame retardant system used by the flame retardant ABS on the market at present mainly takes bromine and antimony as a synergistic system. Bromine of the bromine-antimony synergistic system is mainly from common bromine flame retardants in the market, such as tetrabromobisphenol A, bromotriazine, decabromodiphenylethane, brominated polystyrene and the like; the antimony is mainly from flame retardant synergist of antimony-containing compound, such as antimony oxide, antimonate, etc. Among the antimony-containing flame retardant synergists, antimony trioxide is most commonly used. For example, in Chinese patent CN102391608, 10-25% of brominated flame retardant (decabromodiphenylethane and brominated epoxy, used alone or in combination according to a certain proportion) is used, and 2-8% of flame retardant synergist (compound flame retardant synergist containing antimony compound) is compounded to prepare flame retardant ABS with vertical burning grade reaching 1.6-3.0mm UL 94V-0 grade; in the Chinese patent CN103289293, the flame-retardant ABS material with the vertical combustion level of more than 1.5-3.0mm V-2 level, even 1.5-3.0mm V-0 level can be prepared by using 10-25% of bromine flame retardant tri (tri-bromophenyl) cyanurate, compounding 0-1% of antimony flame-retardant synergist and 1-5% of phosphorus flame-retardant synergist.
In order to meet the requirement of non-halogenation of the flame-retardant ABS, phosphorus and nitrogen or a compound system thereof needs to be selected. The most commonly used phosphorus-containing flame retardants and compositions thereof at present mainly comprise microencapsulated red phosphorus, phosphate esters, an intumescent flame retardant system mainly comprising ammonium polyphosphate, and the like. These flame retardant systems all achieve flame retardancy via a solid phase mechanism. Compared with the traditional bromine-antimony compound flame retardant system, the phosphorus-containing flame retardant and the compound flame retardant system thereof with a solid-phase flame retardant mechanism have the defect of low flame retardant efficiency. The spirocyclic phosphate is a phosphorus-containing flame retardant which can act on gas phase, can be used for halogen-free flame retardance of an ABS system and a PP system, and can achieve UL 94V-0 level flame retardance only by a large addition amount when the flame retardant is used alone.
Disclosure of Invention
The invention aims to solve the technical problem of providing a halogen-free flame-retardant ABS composite material and a preparation method thereof, and the composite material overcomes the defects of large addition amount of a flame retardant and large influence on the overall physical and chemical properties of the material in the conventional flame-retardant ABS.
The invention provides a halogen-free flame-retardant ABS composite material, which comprises the following components in percentage by weight:
ester flame retardant and nitrogen-containing free radical initiator; the nitrogen-containing free radical initiator is SONGFLAME 203 or SONGFLAME
The ABS resin comprises 12-35 wt% of acrylonitrile, 8-35 wt% of butadiene and 30-80 wt% of styrene.
The ABS resin can be prepared by a one-step polymerization process with a core-shell structure, or by a two-step process of blending butadiene-grafted SAN copolymer subjected to emulsion graft polymerization with acrylonitrile-styrene copolymer (AS resin, SAN); commercially available ABS resin may be used as the matrix resin, or a blend of butadiene-grafted SAN copolymer and SAN may be used as the matrix resin.
The structural formula of the spirocyclic phosphate flame retardant is shown as follows:
Preferably, the saturated alkane substituent group is a C1-C10 alkyl substituent group; the unsaturated olefin is C2-C15 olefin; the aromatic substituent group containing a benzene ring structure is phenyl, tolyl or polyalkyl substituted phenyl. More preferably, R, R' are each independently H, methyl, ethyl, phenyl or allyl. Most preferably, R, R' is both methyl or phenyl.
Further, the mass ratio of the spirocyclic phosphate flame retardant to the nitrogen-containing radical initiator is 2:1-50:1, preferably 5:1-30:1, and more preferably 5:1-20: 1.
Further, the butadiene-grafted SAN copolymer is subjected to graft polymerization by an emulsion process, wherein the acrylonitrile accounts for 2-20 wt%, the butadiene accounts for 50-80 wt%, and the styrene accounts for 18-30 wt%; the weight average molecular weight distribution range of the silicon rubber is 5-100 ten thousand, and the silicon content range is 10-40 wt%.
The other auxiliary agents comprise one or more of an antioxidant, a lubricant, a weather-resistant agent and a colorant.
The antioxidant comprises hindered phenol antioxidant and phosphite antioxidant.
The lubricant comprises an amide lubricant, a stearate lubricant, an ester lubricant or a silicone lubricant.
The weather-resistant agent comprises a benzophenone ultraviolet absorbent, a benzotriazole ultraviolet absorbent or a hindered amine light stabilizer.
The colorants include pigment-type, dye-type, or other colorants having special aesthetic effects.
The invention also provides a preparation method of the halogen-free flame-retardant ABS composite material, which comprises the following steps:
proportionally adding the raw materials into a mixer for mixing, adding the mixed materials into a feed hopper of a double-screw extruder, carrying out melt blending through a co-rotating double-screw extruder, and carrying out water-cooling bracing and granulating to obtain the high-strength high-toughness high-strength high.
The parameters of the co-rotating twin-screw extruder are as follows: the temperature of each section of the extruder is set within the range of 180-240 ℃, and the screw rotating speed is set within the range of 200-800 rpm.
Advantageous effects
(1) The nitrogen-containing free radical initiator is prepared by linking a free radical initiating structure (N-O-R, N-N, N-S, N-O-Si and the like) to a group capable of improving thermal stability through structure screening. The free radical initiator can stably exist in the melt blending modification process of the ABS resin (under the conditions of 200 ℃ and 280 ℃), can be rapidly decomposed when combustion occurs (under the conditions of 350 ℃ and 600 ℃) to generate free radicals, and the spiro-ring phosphate flame retardant with the synergistic gas phase effect quenches the free radicals together to realize the flame retardance of the ABS resin together;
(2) the flame retardant adopted by the invention has proper melting temperature, can be melted in the processing process, and has little harm to the physical properties of the material; the whole addition amount is low, and the adjustable range of the performance is large; the flame-retardant ABS composite material can be used in the electronic and electrical fields with flame-retardant requirements, the application field of replacing the original bromine and antimony flame-retardant ABS composite material, and other fields needing flame-retardant ABS.
Drawings
FIG. 1 is an FTIR spectrum of B-12 in example.
FIG. 2 is an FTIR spectrum of B-23 in example.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
The raw materials of the components used are as follows:
ABS resin:
① blending ABS resin by two-step method, i.e. emulsion ABS resin, LGHI-121H, marked as A-11;
② ABS of one-step method, i.e. bulk ABS, DOW, marked as A-12;
③ SAN resin, 310TR, Korea brocade lake, ABS graft rubber powder, MAG 50, benzene collar, wherein the two are mixed according to the mass ratio of 7:3 and marked as A-21, and the two are mixed according to the mass ratio of 3:7 and marked as A-22.
Flame retardant composition:
① the structural formula of the spirocyclic phosphate ester flame retardant is shown as follows:
b-11: r, R' are both methyl; PCO 900, toler chemistry;
b-12: r, R' are both phenyl groups.
FTIR spectrum of B-12 is shown in FIG. 1, KBr pellet;
the synthesis method comprises the following steps: dissolving 31.6 grams (0.1mol) of pentaerythritol and 31.6 grams (0.4mol) of pyridine in 300ml of dichloromethane (solution 1), placing solution 1 in a 500ml round bottom flask equipped with a condenser, mechanical stirrer and dropping funnel, placing the flask containing the solution in a bath of ice and water and cooling to 0 ℃ with stirring; dissolving 39 g (0.2mol) of phenylphosphonic dichloride in 50ml of dichloromethane (solution 2), placing the solution 2 in a dropping funnel, and slowly dropwise adding the solution 1 cooled to 0 ℃ while keeping an ice-water mixed bath and stirring; after the dropwise addition, stirring was continued for 15min in an ice-water mixed bath, and then the temperature was slowly raised to 50 ℃ and the reaction was refluxed for 6 hours at that temperature. After the reaction is finished, the solvent is distilled and recovered, the reaction product is washed and filtered for three times, and is dried for 72 hours at 70 ℃ in vacuum, 28.5 g of white powder which is the flame retardant B-12 is obtained, and the yield is 75%.
② nitrogenous radical initiator:
b-21: NOR 116, basf;
b-22: SONGFLAME 203, international pine source;
b-23 is a free radical initiator with an N-O-Si structure,
the FTIR spectrum of B-23 is shown in FIG. 2, KBr pellet;
the synthesis method comprises the following steps: adding 300ml of dried dichloromethane, 16.4 g (0.1mol) of N-hydroxyphthalimide, 2 g of triethylamine and 20 g of potassium carbonate into a 500ml round-bottom flask equipped with a condenser, a mechanical stirrer and a dropping funnel, placing the flask in an ice-water mixed bath and cooling to 0 ℃ by stirring; 24 g (0.1mol) of diphenylmethylchlorosilane is put into a dropping funnel and slowly dropped into the flask solution under the condition of keeping the ice-water mixed bath and stirring; after the dropwise addition, stirring was continued for 15min in an ice-water mixed bath, and then the temperature was slowly raised to 30 ℃ and reacted at that temperature for 12 hours. After the reaction is finished, the solvent is distilled and recovered, the reaction product is washed and filtered for three times, and is dried for 72 hours at 70 ℃ in vacuum, 28.5 g of white powder which is the flame retardant B-23 is obtained, and the yield is 80%.
③ other halogen-free flame retardants
B-31: OP 1230, clariant;
b-32: PX-220, Zhejiang prosperity;
a toughening agent: butadiene-grafted SAN copolymer, MBS, acrylate rubber, silicone rubber and the like;
other auxiliary agents: common processing aids such as antioxidants, lubricants and the like, functional aids such as anti-dripping agents, weather-resistant agents and the like, and fillers, pigments, dyes and the like.
The performance test method comprises the following steps:
and (3) testing the flame retardant grade: vertical burning, test standard UL94, bars of 125mm 13mm 1.5 mm;
notched impact strength test: and (3) injection molding to obtain a bar-shaped sample strip meeting the requirements of ISO 180 cantilever beam notch impact strength test, testing the notch impact strength at 25 ℃, and recording the strength data of the sample strip when the sample strip is broken.
The preparation method comprises the following steps: proportionally, putting the raw materials into a mixer, mixing for 5min at the rotating speed of 1000 rpm, taking out, putting the mixed materials into a feed hopper of a double-screw extruder, carrying out melt blending through a co-rotating double-screw extruder (the temperature setting range of each section of the extruder is 200 ℃, and the screw rotating speed setting range is 600 rpm), and carrying out water-cooling, drawing strips and granulating to obtain the high-strength high-toughness.
As can be seen from the above table, the ABS composite material of the invention has better flame retardant property and notch impact strength. It can be seen from comparative examples 1-2 and examples 1-3 that the nitrogen-containing free radical initiator and the spirocyclic phosphate flame retardant in the invention are used as the synergistic flame retardant composition, the flame retardant performance and the notch impact strength of the composite material can be improved within the addition range of the invention, the flame retardant efficiency of the system is far higher than that of the traditional organic phosphate and organic phosphinate, and the negative effect on the notch impact strength is much smaller. As can be seen from comparative examples 3-6 and examples 1-3, the flame retardant property and notch impact strength of the composite material can be effectively improved by compounding the free radical initiator and the spiro-cyclic phosphate flame retardant in the invention compared with NOR 116.
Claims (9)
1. A halogen-free flame-retardant ABS composite material is characterized in that: comprises the following components in percentage by weight:
a nitrogen free radical initiator; the nitrogen-containing free radical initiator is SONGFLAME 203 or SONGFLAME
2. The composite material of claim 1, wherein: the ABS resin comprises 12-35 wt% of acrylonitrile, 8-35 wt% of butadiene and 30-80 wt% of styrene.
3. The composite material of claim 1, wherein: the structural formula of the spirocyclic phosphate flame retardant is shown as follows:
4. The composite material of claim 3, wherein: the saturated alkane substituent group is a C1-C10 alkyl substituent group; the unsaturated olefin is C2-C15 olefin; the aromatic substituent group containing a benzene ring structure is phenyl, tolyl or polyalkyl substituted phenyl.
5. The composite material of claim 1, wherein: the toughening agent is one or two of butadiene grafted SAN copolymer and silicon rubber.
6. The composite material of claim 1, wherein: the other auxiliary agents comprise one or more of an antioxidant, a lubricant, a weather-resistant agent and a colorant.
7. The composite material of claim 6, wherein: the antioxidant comprises hindered phenol antioxidant and phosphite antioxidant; the lubricant comprises an amide lubricant, a stearate lubricant, an ester lubricant or a silicone lubricant; the weather resisting agent comprises benzophenone ultraviolet absorbent, benzotriazole ultraviolet absorbent or hindered amine light stabilizer; the colorants include pigment-type, dye-type, or other colorants having special aesthetic effects.
8. The preparation method of the halogen-free flame retardant ABS composite material as claimed in claim 1, comprising:
proportionally adding the raw materials into a mixer for mixing, adding the mixed materials into a feed hopper of a double-screw extruder, carrying out melt blending through a co-rotating double-screw extruder, and carrying out water-cooling bracing and granulating to obtain the high-strength high-toughness high-strength high.
9. Use of the halogen-free flame-retardant ABS composite material according to claim 1.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113881153A (en) * | 2021-09-24 | 2022-01-04 | 江苏金发科技新材料有限公司 | Transparent halogen-free flame-retardant master batch and preparation method and application thereof |
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| CN107075202A (en) * | 2014-09-18 | 2017-08-18 | 弗劳恩霍弗应用研究促进协会 | Organic epoxide imide salts are used as the purposes of fire retardant, flame-retardant plastic composition, its preparation method and molded parts, paint or coating |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113881153A (en) * | 2021-09-24 | 2022-01-04 | 江苏金发科技新材料有限公司 | Transparent halogen-free flame-retardant master batch and preparation method and application thereof |
| CN113881153B (en) * | 2021-09-24 | 2024-03-15 | 江苏金发科技新材料有限公司 | Transparent halogen-free flame-retardant master batch and preparation method and application thereof |
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Application publication date: 20200623 |