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
- Publication number
- 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
- Authority
- CN
- China
- Prior art keywords
- halogen
- benzene sulfonate
- free flame
- flame retardants
- potassium phenylsulphonyl
- 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.)
- Granted
Links
Landscapes
- 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).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510519306.2A CN105038258B (en) | 2015-08-21 | 2015-08-21 | A kind of halogen-free flame retardants for containing 3 potassium phenylsulphonyl benzene sulfonates and its application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510519306.2A CN105038258B (en) | 2015-08-21 | 2015-08-21 | A kind of halogen-free flame retardants for containing 3 potassium phenylsulphonyl benzene sulfonates and its application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105038258A true CN105038258A (en) | 2015-11-11 |
| CN105038258B CN105038258B (en) | 2018-02-27 |
Family
ID=54445247
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510519306.2A Active CN105038258B (en) | 2015-08-21 | 2015-08-21 | A kind of halogen-free flame retardants for containing 3 potassium phenylsulphonyl benzene sulfonates and its application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105038258B (en) |
Citations (3)
| 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 |
-
2015
- 2015-08-21 CN CN201510519306.2A patent/CN105038258B/en active Active
Patent Citations (3)
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105038258B (en) | 2018-02-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101629007B (en) | Low smoke non-halogen flame retardant thermoplastic elastomer composite material and preparation method thereof | |
| CN107434878B (en) | High glow wire, boiling-resistant and flame-retardant polypropylene composite material and preparation method thereof | |
| CN105038088A (en) | Elastomer cable material for oil-resistant cold-resistant high-temperature-resistant electric automobile charge piles and preparation method thereof | |
| CN103289290B (en) | A kind of phosphorus system synergistic flame-retardant ABS compound material and preparation method thereof | |
| CN102250406B (en) | Polyethylene material with high flame resistance | |
| CN101550249A (en) | Halogen-free expandable fire retardant fiber glass reinforced polypropylene material and preparation method thereof | |
| CN102627805B (en) | Environmentally-friendly, high fire-resistant and high seawater-resistant polypropylene | |
| CN104530587A (en) | PVC composition specially used for high-rise buildings | |
| CN102911485B (en) | Flame-retardant chain-extended polybutylene terephthalate composition and preparation method thereof | |
| CN109265813A (en) | A kind of marine inflaming-retarding cable jacket material of salt spray proof and preparation method thereof | |
| CN104341678A (en) | Intumescent flame retardant waterproof polypropylene composite material | |
| CN104327441A (en) | Montmorillonite synergistic flame-retardant ABS composite material and preparation method thereof | |
| CN103087394B (en) | A kind of low-smoke halogen-free flame-proof cable material | |
| CN103396600B (en) | High-performance is containing organosilicon non halogen flame retardant polyolefin composite | |
| CN101161719B (en) | Special material for injection grade non-halogen flame-retardant wire plug and preparation method thereof | |
| CN102344626A (en) | Formula of flame-retardant plastic | |
| CN103613831A (en) | Nanometer environmental-protection halogen-free fire-retardation insulation material and preparation method thereof | |
| CN102816405B (en) | Low-smoke halogen-free flame-retardant thermoplastic elastomer and preparation method thereof | |
| CN104327462A (en) | Phosphorus-based synergistically flame-retardant PET/PBS alloy material and preparation method thereof | |
| CN104327474A (en) | Montmorillonite synergic flame-retardation PC/ABS alloy material and preparation method thereof | |
| CN103788614A (en) | Halogen-free flame retardant super-tough type polycarbonate material | |
| CN112724627B (en) | PC/ABS alloy material and application thereof | |
| CN101875775B (en) | Low-smoke zero-halogen flame-retardant polyphenyl ether composition and preparation method thereof | |
| CN104693730A (en) | High-flame-resistant high-toughness PC/PET alloy material | |
| CN105038258A (en) | Halogen-free flame retardant containing potassium 3-(phenylsulfonyl)benzene sulfonate and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |