CN105038258B - A kind of halogen-free flame retardants for containing 3 potassium phenylsulphonyl benzene sulfonates and its application - Google Patents
A kind of halogen-free flame retardants for containing 3 potassium phenylsulphonyl benzene sulfonates and its application Download PDFInfo
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- CN105038258B CN105038258B CN201510519306.2A CN201510519306A CN105038258B CN 105038258 B CN105038258 B CN 105038258B CN 201510519306 A CN201510519306 A CN 201510519306A CN 105038258 B CN105038258 B CN 105038258B
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Abstract
The invention discloses a kind of halogen-free flame retardants for containing 3 potassium phenylsulphonyl benzene sulfonates and its application.The halogen-free flame retardants includes following component：The parts by weight of APP 8~16, the parts by weight of bipentaerythrite 3~8, the parts by weight of methyl vinyl silicone rubber 3~5, the parts by weight of 3 potassium phenylsulphonyl benzene sulfonate 0.1~0.4, the parts by weight of metal hydroxides 0.1~1.0.Fire retardant all components toxicity of the present invention is smaller; APP/bipentaerythrite this classical flame-retardant system is added in combination using methyl vinyl silicone rubber, 3 potassium phenylsulphonyl benzene sulfonates and metal hydroxides as auxiliary flame retardant; the total dosage of fire retardant is reduced 20%, reach a small amount of efficient effect.The methyl vinyl silicone rubber contained in fire retardant of the present invention, the fire retardant is added and its processing characteristics is improved when being kneaded in polyolefine material, obtained polyolefin flame-retardant material is white, is advantageous to industrial development and follow-up coloring work.
Description
Technical field
The invention belongs to high polymer material flame retardant area, and in particular to a kind of Halogen resistance of potassium phenylsulphonyl benzene sulfonate containing 3-
Fire agent and its application.
Background technology
Polyolefin belongs to combustible material, therefore is required for addition fire retardant fire-retardant to its in actual applications.It is domestic at present
Market mainly uses traditional halogenated flame retardant, and wherein bromine system flame retardant effect is best, but produces more cigarette, You Haihe during burning
Corrosive gas, it can be damaged to environment and human body.Therefore, bittern-free flame-proof material turns into the research and development focus of flame retardant area, and
Intumescent Retardant System is then a kind of novel environment friendly fire retardant applied to high molecular polymer generally acknowledged at present.
The combination of APP/pentaerythrite belongs to typical Intumescent Retardant System, its good flame retardation effect, but addition compared with
Greatly, flame retarding efficiency is relatively low, 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 being made up of two kinds or two or more components, and its flame retardant effect is better than each component
Flame retardant effect sum.At present, relatively conventional cooperative flame retardant system mainly has the collaboration of halogen phosphorus, the collaboration of halogen antimony, the collaboration of phosphorus nitrogen, phosphorus silicon
The systems such as collaboration, and to all less report of sulfur-containing organic compound synergistic flame-retardant system Chinese and foreign documents.If in addition, add metallization
Compound is generally the compound of the heavy metals such as transition metal, rare earth metal as synergistic flame retardant, and it has certain poison
The mankind and environment are had certain injury by property, thus heavy metal compound as synergist in halogen-free flameproof high polymer
Using certain limitation can be caused.
Silicon rubber oxygen index (OI) is high as the rubber of main chain compared with using carbon, and in burning, HRR is low, and flame propagation velocity is slow,
Without dripping off, toxic gas is hardly generated when and pure silicone rubber burns, can form the carbon silicon layer of ceramic on surface after combustion,
Internal combustible can be prevented to be contacted to external diffusion and with heat, oxygen.Therefore, under certain condition, silicon rubber can be used as synergistic to hinder
Agent is fired to use.
3- potassium phenylsulphonyl benzene sulfonates are as makrolon and its combustion inhibitor special of alloy material, without halogen, addition
0.05%-0.1% can make makrolon material reach UL-94V-0 levels (3.2mm), and not interfere with polycarbonate transparent
Property.
Antioxidant 1010 is a kind of multi-functional Hinered phenols antioxidant of macromolecular, is dissolved in benzene, acetone, chloroform but does not dissolve in
Water, nontoxic, pollution-free, nonflammable explosive, not colored, volatility is small, and resistance to extractable is good, and general dosage is 0.1%~0.5%.
It is widely used in polyethylene, polypropylene, polyformaldehyde, ABS resin, PS resins, PVC, engineering plastics, rubber and the production of other oil
Product, there is the antioxygenic property of brilliance to polypropylene, polyethylene, can effectively extend product useful life.Wherein, it resists with aiding in
Oxygen agent 168 is simultaneously used in polypropylene, can significantly improve its heat endurance.
Antioxidant 168 is a kind of auxiliary antioxidant, white powder, is dissolved in benzene, chloroform etc., is slightly soluble in ethanol, insoluble
Yu Shui, toxicity is low, volatility is low, heat endurance is good, anti-hydrolytic performance is excellent, often resists with phenols such as antioxidant 1010,1076
Oxidant is used in combination, and has preferable synergy, can improve processing characteristics, is widely used in polyethylene, polypropylene, poly- carbon
Acid esters, ABS resin etc..
Peng Huaqiao is in its thesis for the doctorate《The synthesis of the bicyclo cage shaped phosphonium flame retardant of different structure and its in polypropylene fire retardant
Application in modification》A kind of middle (1- oxo -4- methylene epoxides -2,6,7- three of fire retardant two containing phosphorus, element sulphur simultaneously of synthesis
Oxa- -1- phosphabicyclos [2.2.2] octane) thio-phenyl phosphonate ester (BCPPS) is polypropylene in formula：APP：Trimerization
Cyanamide phosphate：BCPPS=70:12:6:Anti-flaming polypropylene material can be made to reach UL-94V-0 when 12 (parts by weight ratio)
Level, this is that sulfur-containing compound synergistic anti-flaming polypropylene material is benefited our pursuits.But from addition, BCPPS is in synergistic
Performance is not very very good in APP/melamine phosphate flame-retardant system, and addition needs are more could to be met to require, not
It can play the fire resistance of sulfur-containing compound well, and need brand-new synthesis, if being applied to industrial production, its cost can be compared with
It is high.
Wu Na etc. is respectively in paper《The influence of Metal Oxides on Flame Retardancy of Polypropylene Intumescent Retardant System》With
《Effects of zinc and nickel salts in intumescent flame-retardant
polypropylene》It is middle to utilize main group metal compound bismuth oxide (III valencys), antimony oxide (III valencys), tin ash (IV valencys)
With transition metal zinc, nickel oxide and salt synergistic polypropylene/ammonium polyphosphate/double focusing pentaerythrite flame-retardant system, reach preferable
Synergistic.Wherein, compared to transistion metal compound it is generally necessary to which the addition of 1% order of magnitude, addition are 0.1% quantity
Advantageously, but bismuth oxide (III valencys) has stronger toxicity and contains face the main group metal compound bismuth oxide (III valencys) of level
Color, therefore its application as synergistic flame retardant is limited significantly.
The content of the invention
To solve, existing halogen-free expanded flame-retardant agent flame retarding efficiency is more relatively large than relatively low, addition and part has certain poison
Property, containing color the shortcomings of, primary and foremost purpose of the invention is to provide a kind of applied widely, efficient, environmentally friendly, cost-effective
The halogen-free flame retardants of the potassium phenylsulphonyl benzene sulfonate containing 3-.
Another object of the present invention is to provide the halogen-free flame retardants of the above-mentioned potassium phenylsulphonyl benzene sulfonate containing 3- in polyolefin
Application in material.
For achieving the above object, the present invention adopts the following technical scheme that：
A kind of halogen-free flame retardants of potassium phenylsulphonyl benzene sulfonate containing 3-, in parts by weight meter include following component：
Preferably, the halogen-free flame retardants of the potassium phenylsulphonyl benzene sulfonate containing 3- is counted including following components in parts by weight：
Preferably, the APP and bipentaerythrite weight ratio are 2:1~3:1, wherein most preferably scheme is 2:1.
Preferably, the metal hydroxides is magnesium hydroxide or aluminium hydroxide.
Application of the halogen-free flame retardants of the above-mentioned potassium phenylsulphonyl benzene sulfonate containing 3- in polyolefine material.
The specific preparation method of the application is as follows：
(1) various raw materials are weighed according to following percentage by weight：Polyolefin 75%~85%, the benzene sulfonic acid of benzenesulfonyl containing 3-
The halogen-free flame retardants 15%~25% and antioxidant 0.3~0.5% of potassium；
(2) polyolefin is added in two-roll mill and plastified, sequentially add antioxidant and the benzene sulfonic acid of benzenesulfonyl containing 3-
The halogen-free flame retardants of potassium is simultaneously kneaded 8~10min；
(3) discharging is positioned in mould, hot pressing 8~10 minutes in vulcanizing press, and then room temperature is cold-pressed 8~10 points
Clock, obtain a kind of halogen-free anti-flaming polyolefin material of potassium phenylsulphonyl benzene sulfonate containing 3-.
Polyolefin can be preferably 79.7~81.7wt% in above-mentioned preparation method, the nothing of the potassium phenylsulphonyl benzene sulfonate containing 3-
Halogen fire retardant can be preferably 18~20wt%, and antioxidant is amount commonly used in the art, all may be used in 0.3~0.5wt% scopes
To realize the object of the invention.
Antioxidant described in step (1) is mass ratio 1:1 antioxidant 1010 and the compounding of antioxidant 168.
Polyolefin described in step (1) is selected from polyolefin homopolymer, copolymer and blend.
Can also be added in above-mentioned steps (2) including toughener, compatilizer, lubricant, stabilizer, antistatic additive, pigment,
At least one auxiliary agent including filler or reinforcing material is kneaded.
Compared with prior art, the present invention has advantages below and beneficial effect：
(1) dosage of the halogen-free flame retardants of the potassium phenylsulphonyl benzene sulfonate of the invention containing 3- is compared to APP/bis- season penta
The usual dosage of this classical flame-retardant system of tetrol reduces 20%, reaches a small amount of efficient effect；In addition, add a small amount of metallic hydrogen
Oxide can be remarkably reinforced flame retardant effect and avoid adding transition metal, rare earth metal etc. to the mankind and environment with danger
The heavy metal element of property is done harm to, both environmentally friendly and can enough reduced cost.
(2) the fire-retardant report less in passing Chinese and foreign documents of sulfurous organic compound synergistic, even if it is all mostly to close again to refer to
Into to adapt to the fire-retardant use of polyolefine material.The present invention utilizes the 3- benzenesulfonyl benzene sulfonic acids for having been widely used for makrolon
Potassium carries out synergistic, not only expands the application of 3- potassium phenylsulphonyl benzene sulfonates significantly but also saves fire-retardant suitable for polyolefine material
The development cost of sulfur-bearing fire retardant.
(3) methyl vinyl silicone rubber contained in the halogen-free flame retardants of the potassium phenylsulphonyl benzene sulfonate of the invention containing 3-, makes
The fire retardant adds can improve sizing material processing characteristics when being kneaded in polymeric material, and the polyolefin flame-retardant material being prepared is
White, be advantageous to industrial development and follow-up coloring work.
(4) halogen-free flame retardants flame-retardant system toxicity of the present invention is low, when adding the polymer combustion of halogen-free flame retardants of the present invention
Harmful halogen gas will not be produced.
Embodiment
With reference to embodiment, the present invention is described in further detail.
The amount of reference examples 1-12 and each raw material components of embodiment 1-18 is as shown in table 1,2, reference examples 1-12 and embodiment 1-
18 preparation technologies are as follows：
(1) various raw materials are weighed according to Tables 1 and 2 respectively；
(2) will be plastified in polypropylene or polyethylene addition two-roll mill (PE Processing temperature is 125 DEG C~135 DEG C,
Polypropylene processing temperature is 170~180 DEG C), sequentially add the halogen-free flameproof of antioxidant and the potassium phenylsulphonyl benzene sulfonate containing 3-
Agent is simultaneously kneaded 8~10min；
(3) discharging is positioned in mould, and (polyethylene hot pressing temperature is 160 DEG C within 8~10 minutes for hot pressing in vulcanizing press
~180 DEG C, polypropylene hot pressing temperature is 170 DEG C~190 DEG C), then room temperature is cold-pressed 8~10 minutes, and sheet material is made in then depanning,
Carry out UL-94 tests.
The anti-flaming polypropylene material of table 1 blending formula (wt%) and UL-94 test results
Note：Antioxidant in table is that mass ratio is 1:1 antioxidant 1010 and antioxidant 168.
The fire-retardant polyethylene material of table 2 blending formula (wt%) and UL-94 test results
Note：Antioxidant in table is that mass ratio is 1:1 antioxidant 1010 and antioxidant 168.
From reference examples 1-7 in table 1 and embodiment 1-14, reference examples 2 add methyl ethylene compared to the explanation of reference examples 1
After silicon rubber, fire retardant its fire resistance in identical addition has obvious raising, so as to illustrate methyl ethylene silicon rubber
Glue has preferable synergistic anti-flammability to APP/bipentaerythrite, but fire retardant total amount of adding is reduced to from 22%
(reference examples 3) just nonrated when 20%, the fire retardant addition total amount compared with 3 of reference examples 4 is constant, but adds 0.2%
Fire resistance is improved more apparent after 3- potassium phenylsulphonyl benzene sulfonates, and gold is added when the total dosage of fire retardant is identical in embodiment
Effect is with regard to more preferable (embodiment 1-6) after belonging to hydroxide.It can be seen from reference examples 5-7, if without methyl ethylene silicon rubber
Glue or 3- potassium phenylsulphonyl benzene sulfonates, even if other components completely retain, the anti-flammability of polypropylene flameretardant material can all be deteriorated.
The endpoint value of ratio and dosage that embodiment 7-14 has separately verified APP/bipentaerythrite system (is implemented
Example 7,8), the endpoint value (embodiment 9,10) of methyl vinyl silicone rubber dosage, the end points of 3- potassium phenylsulphonyl benzene sulfonate dosages
It is worth (embodiment 11,12), the endpoint value (embodiment 13,14) of metal hydroxides dosage.
Table 2 is applied to the fire-retardant situation of polyethylene for a kind of halogen-free flame retardants of potassium phenylsulphonyl benzene sulfonate containing 3-.
Data and its analysis from above-mentioned formula, a kind of halogen-free flameproof of the potassium phenylsulphonyl benzene sulfonate containing 3- of the present invention
Agent excellent flame retardancy, and be rarely reported before this.
Above-described embodiment is the preferable embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any Spirit Essences without departing from the present invention with made under principle change, modification, replacement, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (9)
- A kind of 1. halogen-free flame retardants of potassium phenylsulphonyl benzene sulfonate containing 3-, it is characterised in that the benzene sulfonic acid of benzenesulfonyl containing 3- The halogen-free flame retardants of potassium is counted in parts by weight to be made up of following component：
- 2. the halogen-free flame retardants of the potassium phenylsulphonyl benzene sulfonate according to claim 1 containing 3-, it is characterised in that described to contain 3- The halogen-free flame retardants of potassium phenylsulphonyl benzene sulfonate is counted composed of the following components in parts by weight：
- 3. the halogen-free flame retardants of the potassium phenylsulphonyl benzene sulfonate according to claim 1 containing 3-, it is characterised in that the poly- phosphorus Sour ammonium is 2 with bipentaerythrite weight ratio:1~3:1.
- 4. the halogen-free flame retardants of the potassium phenylsulphonyl benzene sulfonate according to claim 1 containing 3-, it is characterised in that the metal Hydroxide is magnesium hydroxide or aluminium hydroxide.
- 5. the halogen-free flame retardants of the potassium phenylsulphonyl benzene sulfonate containing 3- described in any one of Claims 1-4 is in polyolefine material Application.
- 6. the halogen-free flame retardants of the potassium phenylsulphonyl benzene sulfonate according to claim 5 containing 3- answering in polyolefine material With, it is characterised in that the specific method of the application is as follows：(1) various raw materials are weighed according to following percentage by weight：Polyolefin 75%~80%, the potassium phenylsulphonyl benzene sulfonate containing 3- Halogen-free flame retardants 15%~20% and antioxidant 0.3~0.5%；(2) polyolefin is added in two-roll mill and plastified, sequentially add antioxidant and the potassium phenylsulphonyl benzene sulfonate containing 3- Halogen-free flame retardants is simultaneously kneaded 8~10min；(3) discharging is positioned in mould, hot pressing 8~10 minutes in vulcanizing press, and then room temperature is cold-pressed 8~10 minutes, is obtained To a kind of halogen-free anti-flaming polyolefin material of potassium phenylsulphonyl benzene sulfonate containing 3-.
- 7. the halogen-free flame retardants of the potassium phenylsulphonyl benzene sulfonate according to claim 6 containing 3- answering in polyolefine material With, it is characterised in that polyolefine material described in step (1) is selected from polyolefin homopolymer, copolymer and blend.
- 8. the halogen-free flame retardants of the potassium phenylsulphonyl benzene sulfonate according to claim 6 containing 3- answering in polyolefine material With, it is characterised in that antioxidant described in step (1) is mass ratio 1:1 antioxidant 1010 and antioxidant 168 are answered Match somebody with somebody.
- 9. the halogen-free flame retardants of the potassium phenylsulphonyl benzene sulfonate according to claim 6 containing 3- answering in polyolefine material With, it is characterised in that it is additionally added including toughener, compatilizer, lubricant, stabilizer, antistatic additive, pigment, fills out in step (2) At least one auxiliary agent including material or reinforcing material is kneaded.
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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 |
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- 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 |
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