CN1180017C - Flame retardant thermoplastic engineering plastic without halogen - Google Patents
Flame retardant thermoplastic engineering plastic without halogen Download PDFInfo
- Publication number
- CN1180017C CN1180017C CNB011269014A CN01126901A CN1180017C CN 1180017 C CN1180017 C CN 1180017C CN B011269014 A CNB011269014 A CN B011269014A CN 01126901 A CN01126901 A CN 01126901A CN 1180017 C CN1180017 C CN 1180017C
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- CN
- China
- Prior art keywords
- flame retardant
- engineering plastic
- thermoplastic engineering
- weight part
- retardant thermoplastic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000003063 flame retardant Substances 0.000 title claims abstract description 33
- 229910052736 halogen Inorganic materials 0.000 title claims abstract description 14
- 150000002367 halogens Chemical class 0.000 title claims abstract description 14
- 229920001169 thermoplastic Polymers 0.000 title claims abstract description 13
- 239000004416 thermosoftening plastic Substances 0.000 title claims abstract description 13
- 229920006351 engineering plastic Polymers 0.000 title claims abstract description 12
- 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 description 23
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229920005989 resin Polymers 0.000 claims abstract description 13
- 239000011347 resin Substances 0.000 claims abstract description 13
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 12
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 12
- 238000002485 combustion reaction Methods 0.000 claims abstract description 6
- 229910000000 metal hydroxide Inorganic materials 0.000 claims abstract description 6
- 150000004692 metal hydroxides Chemical class 0.000 claims abstract description 6
- 150000003440 styrenes Chemical class 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 235000006708 antioxidants Nutrition 0.000 claims description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000003112 inhibitor Substances 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 239000010703 silicon Substances 0.000 claims description 7
- 239000000835 fiber Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 229920001296 polysiloxane Polymers 0.000 claims description 6
- 230000036571 hydration Effects 0.000 claims description 4
- 238000006703 hydration reaction Methods 0.000 claims description 4
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 4
- 239000000347 magnesium hydroxide Substances 0.000 claims description 4
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 4
- 229920002554 vinyl polymer Polymers 0.000 claims description 4
- 229920000877 Melamine resin Polymers 0.000 claims description 3
- 229920003244 diene elastomer Polymers 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
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000000945 filler Substances 0.000 claims description 2
- 229920001519 homopolymer Polymers 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 239000000314 lubricant Substances 0.000 claims description 2
- 150000007974 melamines Chemical class 0.000 claims description 2
- 239000000178 monomer Substances 0.000 claims description 2
- 150000002989 phenols Chemical class 0.000 claims description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical class OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 2
- 239000000049 pigment Substances 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 230000003068 static effect Effects 0.000 claims description 2
- 239000000779 smoke Substances 0.000 abstract description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract 1
- 230000002349 favourable effect Effects 0.000 abstract 1
- 150000008301 phosphite esters Chemical class 0.000 abstract 1
- 239000003053 toxin Substances 0.000 abstract 1
- 231100000765 toxin Toxicity 0.000 abstract 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 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 5
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229920002545 silicone oil Polymers 0.000 description 4
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 3
- -1 bromos dibenzodioxin alkane Chemical class 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 3
- 230000001988 toxicity Effects 0.000 description 3
- 231100000419 toxicity Toxicity 0.000 description 3
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 229920005669 high impact polystyrene Polymers 0.000 description 2
- 239000004797 high-impact polystyrene Substances 0.000 description 2
- 229910000039 hydrogen halide Inorganic materials 0.000 description 2
- 239000012433 hydrogen halide Substances 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 229920001897 terpolymer Polymers 0.000 description 2
- WMEZQSMQWRQKOE-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol phosphoric acid 1,3,5-triazine-2,4,6-triamine Chemical compound OCC(CO)(CO)CO.P(=O)(O)(O)O.N1=C(N)N=C(N)N=C1N WMEZQSMQWRQKOE-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 208000005623 Carcinogenesis Diseases 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229920009204 Methacrylate-butadiene-styrene Polymers 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- LEHOTFFKMJEONL-UHFFFAOYSA-N Uric Acid Chemical compound N1C(=O)NC(=O)C2=C1NC(=O)N2 LEHOTFFKMJEONL-UHFFFAOYSA-N 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- WWNGFHNQODFIEX-UHFFFAOYSA-N buta-1,3-diene;methyl 2-methylprop-2-enoate;styrene Chemical compound C=CC=C.COC(=O)C(C)=C.C=CC1=CC=CC=C1 WWNGFHNQODFIEX-UHFFFAOYSA-N 0.000 description 1
- 230000036952 cancer formation Effects 0.000 description 1
- 231100000504 carcinogenesis Toxicity 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000006353 environmental stress Effects 0.000 description 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N ethyl acetate Substances CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 150000002193 fatty amides Chemical class 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- XFZRQAZGUOTJCS-UHFFFAOYSA-N phosphoric acid;1,3,5-triazine-2,4,6-triamine Chemical compound OP(O)(O)=O.NC1=NC(N)=NC(N)=N1 XFZRQAZGUOTJCS-UHFFFAOYSA-N 0.000 description 1
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- QMRNDFMLWNAFQR-UHFFFAOYSA-N prop-2-enenitrile;prop-2-enoic acid;styrene Chemical compound C=CC#N.OC(=O)C=C.C=CC1=CC=CC=C1 QMRNDFMLWNAFQR-UHFFFAOYSA-N 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 239000012815 thermoplastic material Substances 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention relates to fire-retardant thermoplastic engineering plastics without halogen, which comprise styrene resin, a fire retardant system and an antioxidant, wherein the styrene resin accounts for 200 to 600 weight portions; the fire retardant system comprises 200 to 600 weight portions of a hydrated metal hydroxide, 100 to 500 weight portions of a nitrogen-contained fire retardant and 1 to 10 weight portions of an organosilicon fire retardant; the antioxidant comprises 1 to 10 weight portions of a primary antioxidant of hindered phenol and 1 to 10 weight portions of a secondary antioxidant of phosphite ester. Compared with the prior art, the present invention has the advantages of less smoke of combustion, less toxin, etc., so that the present invention is favorable for environment protection.
Description
Technical field
The present invention relates to a kind of flame-retardant thermoplastic compositions, relate in particular to a kind of flame retardant thermoplastic engineering plastic without halogen.
Background technology
The thermoplastic material that is used for materials such as household electrical appliance and computer housing has certain requirement to heat resistant fire-proof.And styrene resin can discharge a large amount of smog and obnoxious flavour, so that cause " secondary disaster " in combustion processes originally as a kind of inflammable macromolecular material during burning.For example: the oxygen index of ABS material is about 18, and the amount of being fuming is illustrated in about 720 with maximum smoke density (Dm).Make the application of ABS be subjected to certain limitation like this.
At present, improving the most frequently used method of styrenic flame retardant properties is to add halogen containing flame-retardant.The cost effectiveness balance of halogenated flame retardant is good, adapt to wide, but because the amount of being fuming is big, the gas that discharges has highly corrosive, and bromide fire retardant decomposites many bromos dibenzodioxin alkane (PBDD) and PBDF (PBDF) material under given conditions, and they have stronger carcinogenesis.For this reason, traditional halogen containing flame-retardant is faced with huge environmental stress, the non-halogenated main trend that has become fire-retardant Application and Development.
Summary of the invention
Purpose of the present invention is exactly that the amount of being fuming is low when providing a kind of burning for the defective that overcomes above-mentioned prior art existence, toxicity is little, environmentally friendly flame retardant thermoplastic engineering plastic without halogen.
Purpose of the present invention can be achieved through the following technical solutions: a kind of flame retardant thermoplastic engineering plastic without halogen, comprise styrene resin, fire retardant systems, antioxidant, described styrene resin is the 200-600 weight part, described fire retardant systems comprise weight part be the hydration metal hydroxides of 200-600 and weight part be 100-500 contain nitrogen combustion inhibitor and weight part is the organic silicon fibre retardant of 1-10, described antioxidant comprises that weight part is the Hinered phenols primary antioxidant of 1-10 and the phosphorous acid esters auxiliary anti-oxidant that weight part is 1-10.
Described styrene resin is the homopolymer of vinylbenzene or styrene derivatives, as alpha-methyl styrene, Vinyl toluene; And the multipolymer of vinylbenzene or styrene derivatives and vinyl monomer such as vinyl cyanide or methyl methacrylate, maleic anhydride, vinyl-acetic ester; Vinylbenzene or styrene derivatives, or vinylbenzene or styrene derivatives and other vinyl monomer-grafted go up in the resin that generates one or more to diene rubber (as polyhutadiene, ethylene/propylene thiazolinyl rubber, acrylic rubber).This resin can be polystyrene (PS), high-impact polystyrene (HIPS), styrene-acrylonitrile copolymer (AS), methyl methacrylate-acrylate-styrene copolymer (MAS), acrylonitrile-butadiene-styrene terpolymer (ABS), acrylonitrile-acrylate-styrene terpolymer (ASA), acrylonitrile-styrene-ethylene-propylene diene copolymer graft copolymer (AES), methyl methacrylate-butadiene-styrene terpolymer (MBS), maleic anhydride graft acrylonitrile-butadiene-styrene terpolymer (ABS-g-MAH) or the like.
Described hydration metal hydroxides is magnesium hydroxide or aluminium hydroxide.
The described nitrogen combustion inhibitor that contains is selected from Dyhard RU 100, melamine, the melamine salt one or more.As melamine phosphate, bis phosphoric acid tetramethylolmethane melamine salt (MPP), melamine urate etc.
Described organic silicon fibre retardant is selected from a kind of in the organopolysiloxane of liquid or solid and the acrylate-silicone composite material.
Contain in the described organic silicon fibre retardant-the Si-O-key or-the Si-C-key.This organic silicon fibre retardant be contain-the Si-O-key or-a kind of silicon polymer of Si-C-key, it can be silicone oil, polysiloxane and acrylate-silicone composite material, polysiloxane wherein contains alkyl groups such as methyl, ethyl, as: the linear polydimethylsiloxane-of dimethyl silicone oil, ultra-high molecular weight etc.
Also comprise in stablizer, lubricant, releasing agent, nucleator, static inhibitor, filler, strongthener and the pigment one or more.
The present invention adopts the halogen-free flame-retardant system based on the hydrated inorganic metal hydroxides to carry out flame-retardant modified to the styrene analog thermoplastic resin; the material that uses prescription blend of the present invention to form not only has excellent flame-retardant; and burning the time has advantages such as the amount of being fuming is low, toxicity is little, helps environment protection.
Embodiment
Below be the embodiment that does according to the prescription that technical solution of the present invention provides, in order to further explanation the present invention.
Embodiment 1
| Parts by weight | |
| ABS | 295 |
| ABS-g-MAH | 100 |
| Magnesium hydroxide | 200 |
| Trimeric cyanamide | 400 |
| Silicone oil | 5 |
| Irganox 1076 | 2 |
| Irgafos 168 | 2 |
| The two fatty amides of N, N '-ethylene | 2 |
Annotate: Irganox 1076, Irgafos 168 are Switzerland Ciba-Geigy company oxidation inhibitor.
The following GB of the test result of gained blend material (GB):
| Flexural strength (MPa) | 62 |
| Modulus in flexure (MPa) | 3100 |
| charPY notched Izod impact strength (KJ/m 2) | 27 |
| Smoke density (Dm) | 160 |
| Flame retardant resistance UL94 (1.6mm) | V0 |
| Burning back hydrogen halide (mg/g) | 0 |
As can be seen, the material that flame-retardant system of the present invention and ABS resin blend obtain, flame retardant resistance improves to some extent, and smoke density and toxicity after the burning have all obtained good inhibition.
Embodiment 2,3
| Parts by weight | ||
| ABS | 395 | 595 |
| ABS-g-MAH | 100 | 100 |
| Magnesium hydroxide | 200 | 100 |
| Trimeric cyanamide | 300 | 100 |
| Silicone oil | 5 | 5 |
| Irganox 1076 | 2 | 2 |
| Irgafos 168 | 2 | 2 |
The test result of gained blend composition material following (GB):
| Flexural strength (MPa) | 60 | 55 |
| Modulus in flexure (MPa) | 3000 | 2300 |
| charPY notched Izod impact strength (KJ/m 2) | 30 | 56 |
| Smoke density (Dm) | 200 | 420 |
| Flame retardant resistance UL94 (1.6mm) | V1 | HB |
| Burning back hydrogen halide (mg/g) | 0 | 0 |
Claims (6)
1. flame retardant thermoplastic engineering plastic without halogen, it is characterized in that, comprise styrene resin, fire retardant systems, antioxidant, described styrene resin is the 200-600 weight part, described fire retardant systems comprise weight part be the hydration metal hydroxides of 200-600 and weight part be 100-500 contain nitrogen combustion inhibitor and weight part is the organic silicon fibre retardant of 1-10, described antioxidant comprises that weight part is the Hinered phenols primary antioxidant of 1-10 and the phosphorous acid esters auxiliary anti-oxidant that weight part is 1-10.
2. flame retardant thermoplastic engineering plastic without halogen according to claim 1, it is characterized in that multipolymer, vinylbenzene or the styrene derivatives that described styrene resin is selected from homopolymer, vinylbenzene or the styrene derivatives of vinylbenzene or styrene derivatives and vinyl monomer is grafted to one or more in the resin that the resin, vinylbenzene or the styrene derivatives that generate on the diene rubber and other vinyl monomer-grafted generate to the diene rubber.
3. flame retardant thermoplastic engineering plastic without halogen according to claim 1 is characterized in that, described hydration metal hydroxides is magnesium hydroxide or aluminium hydroxide.
4. flame retardant thermoplastic engineering plastic without halogen according to claim 1 is characterized in that, the described nitrogen combustion inhibitor that contains is selected from Dyhard RU 100, melamine, the melamine salt one or more.
5. flame retardant thermoplastic engineering plastic without halogen according to claim 1 is characterized in that described organic silicon fibre retardant is selected from the organopolysiloxane of liquid or solid.
6. flame retardant thermoplastic engineering plastic without halogen according to claim 1 is characterized in that, also comprises in stablizer, lubricant, releasing agent, nucleator, static inhibitor, filler, strongthener and the pigment one or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011269014A CN1180017C (en) | 2001-09-28 | 2001-09-28 | Flame retardant thermoplastic engineering plastic without halogen |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011269014A CN1180017C (en) | 2001-09-28 | 2001-09-28 | Flame retardant thermoplastic engineering plastic without halogen |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1408758A CN1408758A (en) | 2003-04-09 |
| CN1180017C true CN1180017C (en) | 2004-12-15 |
Family
ID=4666904
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB011269014A Expired - Lifetime CN1180017C (en) | 2001-09-28 | 2001-09-28 | Flame retardant thermoplastic engineering plastic without halogen |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1180017C (en) |
-
2001
- 2001-09-28 CN CNB011269014A patent/CN1180017C/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| CN1408758A (en) | 2003-04-09 |
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Denomination of invention: Halogen-free combustion-proof thermoplastic engineering plastics Effective date of registration: 20150205 Granted publication date: 20041215 Pledgee: Hefei Heng Hai investment holding group company Pledgor: Hefei Genius New Materials Co., Ltd. Registration number: 2015340000004 |
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