CN105038258A - Halogen-free flame retardant containing potassium 3-(phenylsulfonyl)benzene sulfonate and application thereof - Google Patents
Halogen-free flame retardant containing potassium 3-(phenylsulfonyl)benzene sulfonate and application thereof Download PDFInfo
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- CN105038258A CN105038258A CN201510519306.2A CN201510519306A CN105038258A CN 105038258 A CN105038258 A CN 105038258A CN 201510519306 A CN201510519306 A CN 201510519306A CN 105038258 A CN105038258 A CN 105038258A
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- halogen
- benzene sulfonate
- free flame
- flame retardants
- potassium phenylsulphonyl
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 84
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 title claims abstract description 34
- HGJYOHAIVZXUML-UHFFFAOYSA-M potassium;3-(benzenesulfonyl)benzenesulfonate Chemical compound [K+].[O-]S(=O)(=O)C1=CC=CC(S(=O)(=O)C=2C=CC=CC=2)=C1 HGJYOHAIVZXUML-UHFFFAOYSA-M 0.000 title abstract 4
- 239000000463 material Substances 0.000 claims abstract description 27
- 229920000098 polyolefin Polymers 0.000 claims abstract description 24
- 239000004114 Ammonium polyphosphate Substances 0.000 claims abstract description 11
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims abstract description 11
- 229920001276 ammonium polyphosphate Polymers 0.000 claims abstract description 11
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910000000 metal hydroxide Inorganic materials 0.000 claims abstract description 7
- 150000004692 metal hydroxides Chemical class 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 7
- MLWPJXZKQOPTKZ-UHFFFAOYSA-N benzenesulfonyl benzenesulfonate Chemical compound C=1C=CC=CC=1S(=O)(=O)OS(=O)(=O)C1=CC=CC=C1 MLWPJXZKQOPTKZ-UHFFFAOYSA-N 0.000 claims description 36
- 239000011591 potassium Substances 0.000 claims description 36
- 229910052700 potassium Inorganic materials 0.000 claims description 36
- 239000003963 antioxidant agent Substances 0.000 claims description 13
- 230000003078 antioxidant effect Effects 0.000 claims description 13
- 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 claims description 6
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 6
- 238000007731 hot pressing Methods 0.000 claims description 5
- 238000007599 discharging Methods 0.000 claims description 3
- 239000003112 inhibitor Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 238000003825 pressing Methods 0.000 claims description 3
- 239000002994 raw material Substances 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
- 239000012752 auxiliary agent Substances 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- 239000000945 filler Substances 0.000 claims description 2
- 229920001519 homopolymer Polymers 0.000 claims description 2
- 239000000314 lubricant Substances 0.000 claims description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 2
- 239000000347 magnesium hydroxide Substances 0.000 claims description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 2
- 239000000049 pigment Substances 0.000 claims description 2
- 230000003068 static effect Effects 0.000 claims description 2
- 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 abstract description 34
- 229920002379 silicone rubber Polymers 0.000 abstract description 11
- 239000004945 silicone rubber Substances 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 8
- HIHIPCDUFKZOSL-UHFFFAOYSA-N ethenyl(methyl)silicon Chemical compound C[Si]C=C HIHIPCDUFKZOSL-UHFFFAOYSA-N 0.000 abstract description 8
- 231100000419 toxicity Toxicity 0.000 abstract description 6
- 230000001988 toxicity Effects 0.000 abstract description 6
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
- 238000004040 coloring Methods 0.000 abstract 1
- -1 polyethylene Polymers 0.000 description 25
- 239000004743 Polypropylene Substances 0.000 description 15
- 229920001155 polypropylene Polymers 0.000 description 15
- 230000002195 synergetic effect Effects 0.000 description 11
- 239000004698 Polyethylene Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 229920000573 polyethylene Polymers 0.000 description 6
- 229920000515 polycarbonate Polymers 0.000 description 5
- 239000004417 polycarbonate Substances 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910000416 bismuth oxide Inorganic materials 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 229910001385 heavy metal Inorganic materials 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229940059574 pentaerithrityl Drugs 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 230000000979 retarding effect Effects 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 1
- HIVGXUNKSAJJDN-UHFFFAOYSA-N [Si].[P] Chemical compound [Si].[P] HIVGXUNKSAJJDN-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- GHPGOEFPKIHBNM-UHFFFAOYSA-N antimony(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Sb+3].[Sb+3] GHPGOEFPKIHBNM-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000012757 flame retardant agent Substances 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
- Fireproofing Substances (AREA)
Abstract
The invention discloses a halogen-free flame retardant containing potassium 3-(phenylsulfonyl)benzene sulfonate and an application thereof. The halogen-free flame retardant comprises the following components in parts by weight: 8-16 parts of ammonium polyphosphate, 3-8 parts of dipentaerythritol, 3-5 parts of methyl vinyl silicone rubber, 0.1-0.4 part of potassium 3-(phenylsulfonyl)benzene sulfonate and 0.1-1.0 part of metal hydroxide. The halogen-free flame retardant has the advantages and beneficial effects that all the components of the flame retardant have lower toxicity; the total dosage of the flame retardant is reduced by 20% and the effects of small quantity and high efficiency are achieved by combining the methyl vinyl silicone rubber, potassium 3-(phenylsulfonyl)benzene sulfonate and the metal hydroxide as auxiliary flame retardants and adding the three materials to a classic flame-retardant system ammonium polyphosphate/dipentaerythritol; the flame retardant contains the methyl vinyl silicone rubber, so that the processability of the flame retardant can be improved when the flame retardant is added to polyolefin materials for mixing; the prepared flame-retardant polyolefin materials are white, thus being beneficial to industrial production and subsequent coloring.
Description
Technical field
The invention belongs to macromolecular material flame retardant area, be specifically related to a kind of halogen-free flame retardants containing 3-potassium phenylsulphonyl benzene sulfonate and application thereof.
Background technology
Polyolefine belongs to inflammable material, therefore all needs to add fire retardant in actual applications fire-retardant to it.Domestic market mainly adopts traditional halogenated flame retardant, and wherein bromine system flame retardant effect is best, but produces more cigarette, harmful and corrosive gases during burning, works the mischief to environment and human body.Therefore, bittern-free flame-proof material becomes the research and development focus of flame retardant area, and Intumescent Retardant System is then a kind of novel environment friendly fire retardant being applied to high molecular polymer of generally acknowledging at present.
Ammonium polyphosphate/tetramethylolmethane combination belongs to typical Intumescent Retardant System, its good flame retardation effect, but addition is comparatively large, flame retarding efficiency is lower, has a strong impact on other performances of flame-retardant high-molecular system and increases its production cost.
Cooperative flame retardant refers to the flame-retardant system be made up of two kinds or two or more component, and its flame retardant effect is better than each component flame retardant effect sum.At present, comparatively common cooperative flame retardant system mainly contains the systems such as halogen phosphorus is collaborative, halogen antimony is collaborative, phosphorus nitrogen is collaborative, phosphorus silicon is collaborative, and to all less report of sulfur-containing organic compound synergistic flame-retardant system Chinese and foreign documents.In addition, if add metallic compound as synergistic flame retardant, then mostly be the compound of the such as heavy metal such as transition metal, rare earth metal, it has certain toxicity, have certain injury to the mankind and environment, therefore heavy metal compound can cause certain restriction as synergist in the application of halogen-free flameproof superpolymer.
Silicon rubber oxygen index is high compared with the rubber taking carbon as main chain, when burning, heat release rate is low, flame propagation velocity is slow, without drippage, and generate toxic gas hardly during pure silicone rubber burning, the carbon silicon layer of ceramic can be formed after combustion on surface, inner combustiblematerials can be stoped to external diffusion and contact with heat, oxygen.Therefore, under certain condition, silicon rubber can use as synergistic flame retardant.
3-potassium phenylsulphonyl benzene sulfonate is as the combustion inhibitor special of polycarbonate and alloy material thereof, not halogen-containing, adds 0.05%-0.1% and polycarbonate material can be made to reach UL-94V-0 level (3.2mm), and can not affect polycarbonate transparent.
Antioxidant 1010 is the multi-functional Hinered phenols antioxidant of a kind of macromole, and be dissolved in benzene, acetone, chloroform but water insoluble, nontoxic, pollution-free, nonflammable explosive, not painted, volatility is little, and resistance to extractable is good, and general consumption is 0.1% ~ 0.5%.It is widely used in polyethylene, polypropylene, polyoxymethylene, ABS resin, PS resin, PVC, engineering plastics, rubber and other petroleum productss, has remarkable antioxidant property, can effectively extend goods time limit of service to polypropylene, polyethylene.Wherein, itself and auxiliary antioxidant 168 in polypropylene, its thermostability can be significantly improved.
Antioxidant 168 is a kind of auxiliary antioxidants, white powder, be dissolved in benzene, chloroform etc., be slightly soluble in ethanol, water insoluble, toxicity is low, volatility is low, Heat stability is good, anti-hydrolytic performance are excellent, and normal and antioxidant 1010, the phenol antioxidant compound uses such as 1076, have good synergy, can processing characteristics be improved, be widely used in polyethylene, polypropylene, polycarbonate, ABS resin etc.
Peng Huaqiao synthesis one in its Ph D dissertation " synthesis of the bicyclo cage shaped phosphonium flame retardant of different structure and the application in polypropylene fire retardant modification thereof " contains phosphorus simultaneously, fire retardant two (the sub-methoxyl group-2 of 1-oxo-4-of element sulphur, 6, 7-trioxa-1-phosphabicyclo [2.2.2] octane) thio-phenyl phosphonic acid ester (BCPPS), at formula for polypropylene: anti-flaming polypropylene material can be made time ammonium polyphosphate: melamine phosphate: BCPPS=70:12:6:12 (parts by weight ratio) to reach UL-94V-0 level, this is benefiting our pursuits to sulfocompound synergistic anti-flaming polypropylene material.But, from addition, BCPPS performance in synergistic ammonium polyphosphate/melamine phosphate flame-retardant system is not very very good, addition needs morely just to meet the demands, well can not play the flame retardant properties of sulfocompound, and need brand-new synthesis, if be applied to industrial production, its cost can be higher.
Wu Na etc. utilize main group metal compound bismuth oxide (III valency), weisspiessglanz (III valency), tindioxide (IV valency) and transition metal zinc, nickel oxide and salt synergistic polypropylene/ammonium polyphosphate/double focusing tetramethylolmethane flame-retardant system respectively in paper " impact of Metal Oxides on Flame Retardancy of Polypropylene Intumescent Retardant System " and " Effectsofzincandnickelsaltsinintumescentflame-retardantp olypropylene ", reach good synergistic.Wherein, usually the addition of 1% order of magnitude is needed compared to transistion metal compound, addition be the main group metal compound bismuth oxide (III valency) of 0.1% order of magnitude advantageously, but bismuth oxide (III valency) has stronger toxicity and containing color, therefore greatly limit its application as synergistic flame retardant.
Summary of the invention
In order to solve, existing halogen-free expanded flame-retardant agent flame retarding efficiency is lower, addition is relatively large and part has certain toxicity, containing shortcomings such as colors, primary and foremost purpose of the present invention is to provide a kind of applied widely, efficient, environmental protection, the cost-effective halogen-free flame retardants containing 3-potassium phenylsulphonyl benzene sulfonate.
Another object of the present invention is to provide the above-mentioned application of halogen-free flame retardants in polyolefine material containing 3-potassium phenylsulphonyl benzene sulfonate.
For achieving the above object, the present invention adopts following technical scheme:
Containing a halogen-free flame retardants for 3-potassium phenylsulphonyl benzene sulfonate, meter comprises following component by weight:
Preferably, the described halogen-free flame retardants containing 3-potassium phenylsulphonyl benzene sulfonate is counted by weight and is comprised following component:
Preferably, described ammonium polyphosphate and dipentaerythritol weight ratio are 2:1 ~ 3:1, and wherein most preferably scheme is 2:1.
Preferably, described metal hydroxides is magnesium hydroxide or aluminium hydroxide.
The above-mentioned application of halogen-free flame retardants in polyolefine material containing 3-potassium phenylsulphonyl benzene sulfonate.
The concrete preparation method of described application is as follows:
(1) various raw material is taken according to following weight percent: polyolefine 75% ~ 85%, containing the halogen-free flame retardants 15% ~ 25% of 3-potassium phenylsulphonyl benzene sulfonate and antioxidant 0.3 ~ 0.5%;
(2) polyolefine is added in two roller mill and plastify, add antioxidant successively and containing the halogen-free flame retardants of 3-potassium phenylsulphonyl benzene sulfonate and mixing 8 ~ 10min;
(3) discharging is positioned in mould, hot pressing 8 ~ 10 minutes in vulcanizing press, and then room temperature is colded pressing 8 ~ 10 minutes, obtains a kind of halogen-free anti-flaming polyolefin material containing 3-potassium phenylsulphonyl benzene sulfonate.
In above-mentioned preparation method, polyolefine can be preferably 79.7 ~ 81.7wt%; halogen-free flame retardants containing 3-potassium phenylsulphonyl benzene sulfonate can be preferably 18 ~ 20wt%; antioxidant is the amount that this area is commonly used, and can realize the object of the invention in 0.3 ~ 0.5wt% scope.
Antioxidant described in step (1) is the antioxidant 1010 of mass ratio 1:1 and the composite of antioxidant 168.
Described in step (1), polyolefine is selected from polyolefin homopolymer, multipolymer and blend.
At least one auxiliary agent comprising toughner, compatilizer, lubricant, stablizer, static inhibitor, pigment, filler or strongthener can also be added mixing in above-mentioned steps (2).
Compared with prior art, the present invention has the following advantages and beneficial effect:
(1) the present invention reduces 20% containing the consumption of the halogen-free flame retardants of 3-potassium phenylsulphonyl benzene sulfonate compared to the usual consumption of this classical flame-retardant system of ammonium polyphosphate/dipentaerythritol, reaches a small amount of effect efficiently; In addition, add a small amount of metal hydroxides and obviously can strengthen flame retardant effect and avoid adding such as transition metal, rare earth metal etc. have hazardness heavy metal element to the mankind and environment, not only environmentally friendly but also can reduce costs.
(2) sulfurous organic compound synergistic fire-retardant in passing Chinese and foreign documents less report, even if mention being mostly all again synthesize to adapt to the fire-retardant use of polyolefine material.The present invention utilizes the 3-potassium phenylsulphonyl benzene sulfonate being widely used in polycarbonate to carry out synergistic, not only greatly expands the range of application of 3-potassium phenylsulphonyl benzene sulfonate but also save the cost of development being applicable to the fire-retardant sulfur-bearing fire retardant of polyolefine material.
(3) the present invention is containing the methyl vinyl silicone rubber contained in the halogen-free flame retardants of 3-potassium phenylsulphonyl benzene sulfonate; sizing material processing characteristics can be improved when making this fire retardant add mixing in polymer materials; and the polyolefin flame-retardant material prepared is white, is conducive to industrial development and follow-up painted work.
(4) halogen-free flame retardants flame-retardant system toxicity of the present invention is low, can not produce harmful halogen gas when adding the polymer combustion of halogen-free flame retardants of the present invention.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail.
The amount of each feed composition of reference examples 1-12 and embodiment 1-18 as shown in table 1,2, reference examples 1-12 and embodiment 1-18 preparation technology as follows:
(1) various raw material is taken according to table 1 and table 2 respectively;
(2) (PE Processing temperature is 125 DEG C ~ 135 DEG C polypropylene or polyethylene to be added plasticizing in two roller mill, polypropylene processing temperature is 170 ~ 180 DEG C), add antioxidant successively and containing the halogen-free flame retardants of 3-potassium phenylsulphonyl benzene sulfonate and mixing 8 ~ 10min;
(3) discharging is positioned in mould, hot pressing 8 ~ 10 minutes (polyethylene hot pressing temperature is 160 DEG C ~ 180 DEG C, and polypropylene hot pressing temperature is 170 DEG C ~ 190 DEG C) in vulcanizing press, then room temperature is colded pressing 8 ~ 10 minutes, then depanning obtains sheet material, carries out UL-94 test.
The blended formula of table 1 anti-flaming polypropylene material (wt%) and UL-94 test result
Note: antioxidant 1010 and the antioxidant 168 of to be mass ratio the be 1:1 of the antioxidant in table.
The blended formula of table 2 fire-retardant polyethylene material (wt%) and UL-94 test result
Note: antioxidant 1010 and the antioxidant 168 of to be mass ratio the be 1:1 of the antioxidant in table.
From reference examples 1-7 in table 1 and embodiment 1-14, reference examples 2 compare as a rule 1 illustrate add methyl vinyl silicone rubber after, fire retardant its flame retardant properties when identical addition has obvious raising, thus illustrate that methyl vinyl silicone rubber has good synergistic flame retardant resistance to ammonium polyphosphate/dipentaerythritol, but fire retardant to be added when total amount reduces to 20% from 22% just nonrated (reference examples 3), reference examples 4 fire retardant addition total amount compared with 3 is constant, but flame retardant properties improves more obvious after adding 0.2%3-potassium phenylsulphonyl benzene sulfonate again, effect just better (embodiment 1-6) after adding metal hydroxides again when the total consumption of fire retardant is identical in an embodiment.According to reference examples 5-7, if do not have methyl vinyl silicone rubber or 3-potassium phenylsulphonyl benzene sulfonate, even if the complete reservation of other components, the flame retardant resistance of polypropylene flameretardant material all can be deteriorated.
Embodiment 7-14 demonstrates the ratio of ammonium polyphosphate/dipentaerythritol system and the endpoint value (embodiment 7,8) of consumption respectively; the endpoint value (embodiment 9,10) of methyl vinyl silicone rubber consumption; the endpoint value (embodiment 11,12) of 3-potassium phenylsulphonyl benzene sulfonate consumption, the endpoint value (embodiment 13,14) of metal hydroxides consumption.
Table 2 is that a kind of halogen-free flame retardants containing 3-potassium phenylsulphonyl benzene sulfonate is applied to poly fire-retardant situation.
From above-mentioned formula data and analyze, a kind of halogen-free flame retardants excellent flame retardancy containing 3-potassium phenylsulphonyl benzene sulfonate of the present invention, and rarely have report before this.
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not restricted to the described embodiments; change, the modification done under other any does not deviate from spirit of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (9)
1. containing a halogen-free flame retardants for 3-potassium phenylsulphonyl benzene sulfonate, it is characterized in that, the described halogen-free flame retardants containing 3-potassium phenylsulphonyl benzene sulfonate is counted by weight and is comprised following component:
2. the halogen-free flame retardants containing 3-potassium phenylsulphonyl benzene sulfonate according to claim 1, is characterized in that, the described halogen-free flame retardants containing 3-potassium phenylsulphonyl benzene sulfonate is counted by weight and comprised following component:
3. the halogen-free flame retardants containing 3-potassium phenylsulphonyl benzene sulfonate according to claim 1, it is characterized in that, described ammonium polyphosphate and dipentaerythritol weight ratio are 2:1 ~ 3:1.
4. the halogen-free flame retardants containing 3-potassium phenylsulphonyl benzene sulfonate according to claim 1, it is characterized in that, described metal hydroxides is magnesium hydroxide or aluminium hydroxide.
5. the application of halogen-free flame retardants in polyolefine material containing 3-potassium phenylsulphonyl benzene sulfonate described in any one of Claims 1-4.
6. the application of halogen-free flame retardants in polyolefine material containing 3-potassium phenylsulphonyl benzene sulfonate according to claim 5, it is characterized in that, the concrete grammar of described application is as follows:
(1) various raw material is taken according to following weight percent: polyolefine 75% ~ 85%, containing the halogen-free flame retardants 15% ~ 25% of 3-potassium phenylsulphonyl benzene sulfonate and antioxidant 0.3 ~ 0.5%;
(2) polyolefine is added in two roller mill and plastify, add antioxidant successively and containing the halogen-free flame retardants of 3-potassium phenylsulphonyl benzene sulfonate and mixing 8 ~ 10min;
(3) discharging is positioned in mould, hot pressing 8 ~ 10 minutes in vulcanizing press, and then room temperature is colded pressing 8 ~ 10 minutes, obtains a kind of halogen-free anti-flaming polyolefin material containing 3-potassium phenylsulphonyl benzene sulfonate.
7. the application of halogen-free flame retardants in polyolefine material containing 3-potassium phenylsulphonyl benzene sulfonate according to claim 6, it is characterized in that, described in step (1), polyolefine material is selected from polyolefin homopolymer, multipolymer and blend.
8. the application of halogen-free flame retardants in polyolefine material containing 3-potassium phenylsulphonyl benzene sulfonate according to claim 6; it is characterized in that, antioxidant described in step (1) is the antioxidant 1010 of mass ratio 1:1 and the composite of antioxidant 168.
9. the application of halogen-free flame retardants in polyolefine material containing 3-potassium phenylsulphonyl benzene sulfonate according to claim 6; it is characterized in that, it is mixing also to add at least one auxiliary agent comprising toughner, compatilizer, lubricant, stablizer, static inhibitor, pigment, filler or strongthener in step (2).
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Citations (3)
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| CN101948581A (en) * | 2010-08-31 | 2011-01-19 | 杭州高新绝缘材料有限公司 | Intumescent flame retardant polyethylene containing organosilicon compound |
| CN103173884A (en) * | 2011-12-21 | 2013-06-26 | 上海杰事杰新材料(集团)股份有限公司 | Halogen-free flame-retardant polypropylene fiber and preparation method thereof |
| CN103421241A (en) * | 2013-07-23 | 2013-12-04 | 中国科学院宁波材料技术与工程研究所 | Flame-retardant polyolefine compound |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101948581A (en) * | 2010-08-31 | 2011-01-19 | 杭州高新绝缘材料有限公司 | Intumescent flame retardant polyethylene containing organosilicon compound |
| CN103173884A (en) * | 2011-12-21 | 2013-06-26 | 上海杰事杰新材料(集团)股份有限公司 | Halogen-free flame-retardant polypropylene fiber and preparation method thereof |
| CN103421241A (en) * | 2013-07-23 | 2013-12-04 | 中国科学院宁波材料技术与工程研究所 | Flame-retardant polyolefine compound |
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