CN101824186A - Flame retarding polypropylene compound - Google Patents
Flame retarding polypropylene compound Download PDFInfo
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- CN101824186A CN101824186A CN200910213635A CN200910213635A CN101824186A CN 101824186 A CN101824186 A CN 101824186A CN 200910213635 A CN200910213635 A CN 200910213635A CN 200910213635 A CN200910213635 A CN 200910213635A CN 101824186 A CN101824186 A CN 101824186A
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Abstract
The invention relates to a flame retarding polypropylene compound, which belongs to the field of electrical and electronic materials, and is characterized by containing a brominated flame retardant and a phosphorus flame retardant which are in liquid state in the melting process of polypropylene. By the synergistic effect of the brominated flame retardant and the phosphorus flame retardant, the invention avoids using antimony inorganic synergistic flame retardants when reducing the dosage of the brominated flame retardant, and solves the problems in the technical field of the existing polypropylene flame retarding that the defects of the thin polypropylene product are increased and the mechanical property and the insulating property are reduced because of the large dosage of the brominated flame retardant and the agglomeration of the inorganic synergistic flame retardants. The flame retarding polypropylene compound has good flame retardancy, mechanical property and insulating property, and is mainly used for preparing thin products in electrical and electronic industries.
Description
Technical field
The present invention relates to a kind of flame-proof polypropelene composition, more particularly, the present invention relates to that a kind of flame retardant agent content is low, subsurface defect is few, be suitable for preparing the flame-proof polypropelene composition of thin products, belong to a kind of electric industry macromolecular material.
Background technology
Polypropylene flame redardant has advantages such as good processing characteristics, mechanical property, electric property, flame retardant properties and resistance toheat, has been widely used as outer casing member, connector and insulating mat spacing body etc. in the electronic and electrical equipment.For the existing a large amount of reports of the domestic and international patent of polypropylene flame redardant, the fire retardant that uses on polypropylene mainly comprises halogen antimony synergistic flame retardant, nitrogen flame retardant, phosphorus flame retardant, nitrogen phosphorus synergistic flame retardant and inorganic hydroxide fire retardant etc. at present.Along with the development of electronic and electrical equipment miniaturization, the polypropylene flame redardant product thickness of Shi Yonging is also more and more thinner thereon, make polypropylene reach original flame retardant rating under thinner thickness and just must add more fire retardant.For example, the polypropylene flame redardant product will be lower than the flame retardant rating more than UL 94 V-1 under the 1mm thickness, even the addition of most effective halogen antimony synergistic flame retardant is also more than 10wt%.The most fusing point of these fire retardants is higher than polyacrylic processing temperature, exists with solid-state form all the time in processing and use, has introduced a large amount of boundary defects to polypropylene articles, and mechanical property and electric property are declined to a great extent.Along with the polypropylene flame redardant products thickness reduces, the relative proportion of boundary defect increases, and the deterioration problem of goods mechanical property and electric property is even more serious.
Summary of the invention
The purpose of this invention is to provide that a kind of flame retardant agent content is low, subsurface defect is few, be suitable for preparing the flame-proof polypropelene composition of thin products, to solve the problems referred to above that exist in the existing polypropylene fire retardant technology.
The technical scheme that the present invention takes is as follows:
Flame-proof polypropelene composition of the present invention is a kind of bromide fire retardant that is in a liquid state in polyacrylic melt-processed process and polypropene composition of phosphorus flame retardant of containing.
Above-mentioned bromide fire retardant is meant that fusing point is lower than the bromide fire retardant of polyacrylic melt processing temperature, this fire retardant can be fused into liquid state in the polypropylene fusion course of processing, with be dispersed in the polypropylene articles after the melt polypropylene blend, significantly reduced the boundary defect in the goods.The preferred fusing point of above-mentioned bromide fire retardant is at 70～200 ℃ bromide fire retardant.When the bromide fire retardant fusing point is lower than 70 ℃,, in the polypropylene fusion course of processing, is difficult to form effective shearing and disperses with melt polypropylene because of viscosity is low excessively.When the bromide fire retardant fusing point was higher than 200 ℃, because of can not be fused into liquid state in the polypropylene fusion course of processing, unable to get up reduced the boundary defect effect.Above-mentioned bromide fire retardant is any in tetrabromo-bisphenol-two (2,3-dibromopropyl ether), three (2,3-dibromo third), third chlorinated isocyanurates, hexabromocyclododecane, vinylformic acid pentabromo-benzyl ester and contract dibromoneopentyl glycol more preferably.Above-mentioned phosphorus flame retardant is meant that fusing point is lower than the phosphorus flame retardant of polyacrylic melt processing temperature, these phosphorus flame retardants substitute weisspiessglanz on the one hand, with the bromide fire retardant cooperative flame retardant, effectively reduce the usage quantity of bromide fire retardant, also reduced the boundary defect of introducing because of inorganic synergist; Be in a liquid state because of itself on the other hand or in poly-, can be fused into liquid state in the alkene melt-processed process, and be dispersed in the polypropylene articles after the melt polypropylene blend, also played the effect of minimizing boundary defect.Above-mentioned phosphorus flame retardant preferably contains the phosphate flame retardant of phenyl, be higher than aliphatic phosphate ester because contain the phosphoric acid ester of phenyl in decomposition temperature, more preferably any in triphenylphosphate, Resorcinol biphosphonate, dihydroxyphenyl propane two (diphenyl phosphoester), the diphenyl 2 ethylhexyl phosphate.Because the cooperative flame retardant effect of phosphorous flame-retardant is arranged, the mass percentage content of above-mentioned bromide fire retardant can be 4～9%, preferred 6～8%.When bromide fire retardant content is lower than 4%, be difficult to make the flame retardant rating of polypropylene at following UL 94 V-1 of 1mm thickness.When bromide fire retardant content is higher than 9%, make the mechanical property and the decreasing insulating of the following polypropylene articles of 1mm thickness bigger.The mass ratio of bromide fire retardant and phosphorus flame retardant is preferably 1/25～1/5 in the above-mentioned flame-proof polypropelene composition, when ratio is lower than 1/25 and when being higher than 1/5, all can not mention effective cooperative flame retardant effect.In order to reach better flame retardant effect, in the above-mentioned flame-proof polypropelene composition do not affect the mechanical properties and the situation of insulating property under, can also add a spot of inorganic synergist, these inorganic synergists are selected from polynite, magnesium hydroxide, aluminium hydroxide, zinc borate, zinc sulphide and molybdenum oxide, and mass percentage content can be 0.3～1%.Mass percentage content is lower than 0.3%, can not play the effect of cooperative flame retardant to polypropylene flame redardant, and mass percentage content is higher than 1%, can affect the mechanical properties and insulating property.
Compare with existing polypropylene fire retardant system, beneficial effect of the present invention is that the fire retardant that adopts exists with liquid state in polyacrylic melt-processed process, effectively reduced because of adding the boundary defect that solid-state fire retardant is introduced to polypropylene, make polypropylene when obtaining flame retardant properties, mechanical property and electrical insulation performance can also well be kept.And the present invention has also made full use of the cooperative flame retardant effect of bromide fire retardant and phosphorus flame retardant, greatly reduces the consumption of bromide fire retardant, and the fire retardant total amount is reduced to below the 10wt%, has also avoided the use of the inorganic synergistic flame retardant of weisspiessglanz.Flame-proof polypropelene composition of the present invention has good flame retardancy, mechanical property and insulating property, is mainly used in the thin products in the electric industry of preparation.
Embodiment
Further specify the present invention below by embodiment, therefore do not limit the present invention among the described scope of embodiments.Wherein tensile strength is pressed ASTM D638-2008 standard test, and shock strength is pressed ASTM D 256-2006 standard test, and flame retardant rating is pressed the evaluation of UL 94-2009 vertical combustion testing standard, and dielectric strength is pressed ASTM D149-1997 standard test.
Embodiment 1
With 9 kilograms of tetrabromo-bisphenols-two (2,3-dibromopropyl ether), the polypropylene of 0.36 kilogram triphenylphosphate and 90.64 kilograms melt extrudes at 170～210 ℃ through twin screw extruder and makes the polypropylene flame redardant pellet, again the polypropylene flame redardant pellet is injection molded into mechanics and flame-retardant standard batten through injection moulding machine at 170～210 ℃, by the standard test correlated performance, concrete data are listed in table 1.
Embodiment 2
With 4 kilogram three (2,3-dibromo third) polypropylene of third chlorinated isocyanurates, 0.8 kilogram Resorcinol biphosphonate and 95.2 kilograms melt extrudes at 170～210 ℃ through twin screw extruder and makes the polypropylene flame redardant pellet, again the polypropylene flame redardant pellet is injection molded into mechanics and flame-retardant standard batten through injection moulding machine at 170～210 ℃, by the standard test correlated performance, concrete data are listed in table 1.
Embodiment 3
The polypropylene of 6 kilograms of hexabromocyclododecanes, 0.96 jin dihydroxyphenyl propane two (diphenyl phosphoesters) and 93.04 kilograms melt extruded at 170～210 ℃ through twin screw extruder make the polypropylene flame redardant pellet, again the polypropylene flame redardant pellet is injection molded into mechanics and flame-retardant standard batten through injection moulding machine at 170～210 ℃, by the standard test correlated performance, concrete data are listed in table 1.
Embodiment 4
The polypropylene of 8 kilograms of vinylformic acid pentabromo-benzyl esters, 0.64 kilogram diphenyl 2 ethylhexyl phosphate and 91.36 kilograms melt extruded at 170～210 ℃ through twin screw extruder make the polypropylene flame redardant pellet, again the polypropylene flame redardant pellet is injection molded into mechanics and flame-retardant standard batten through injection moulding machine at 170～210 ℃, by the standard test correlated performance, concrete data are listed in table 1.
Embodiment 5
The polypropylene of 7 kilogram of one dibromoneopentyl glycol that contracts, 0.84 kilogram triphenyl phosphite and 92.16 kilograms melt extruded at 170～210 ℃ through twin screw extruder make the polypropylene flame redardant pellet, again the polypropylene flame redardant pellet is injection molded into mechanics and flame-retardant standard batten through injection moulding machine at 170～210 ℃, by the standard test correlated performance, concrete data are listed in table 1.
Embodiment 6
With 8.5 kilograms of tetrabromo-bisphenols-two (2,3-dibromopropyl ether), 1 kilogram 9, the 10-dihydro-9-oxy is assorted-and the polypropylene of 10-phospho hetero phenanthrene-10-oxide compound, 0.3 kilogram of polynite and 90.2 kilograms melt extrudes at 170～210 ℃ through twin screw extruder and makes the polypropylene flame redardant pellet, again the polypropylene flame redardant pellet is injection molded into mechanics and flame-retardant standard batten through injection moulding machine at 170～210 ℃, by the standard test correlated performance, concrete data are listed in table 1.
Embodiment 7
With 7.5 kilogram three (2,3-dibromo third) polypropylene of third chlorinated isocyanurates, 1 kilogram diphenyl 2 ethylhexyl phosphate, 0.9 kilogram of magnesium hydroxide, 0.2 kilogram of zinc borate and 90.3 kilograms melt extrudes at 170～210 ℃ through twin screw extruder and makes the polypropylene flame redardant pellet, again the polypropylene flame redardant pellet is injection molded into mechanics and flame-retardant standard batten through injection moulding machine at 170～210 ℃, by the standard test correlated performance, concrete data are listed in table 1.
Embodiment 8
With 7 kilograms of tetrabromo-bisphenols-two (2,3-dibromopropyl ether), the polypropylene of 1 kilogram of dihydroxyphenyl propane two (diphenyl phosphoester), 0.1 kilogram of antioxidant 1010,0.8 kilogram of aluminium hydroxide, 0.1 kilogram of molybdenum oxide and 91 kilograms melt extrudes at 170～210 ℃ through twin screw extruder and makes the polypropylene flame redardant pellet, again the polypropylene flame redardant pellet is injection molded into mechanics and flame-retardant standard batten through injection moulding machine at 170～210 ℃, by the standard test correlated performance, concrete data are listed in table 1.
Embodiment 9
With 6.5 kilograms of hexabromocyclododecanes, 0.8 jin Resorcinol biphosphonate, 1 kilogram of magnesium hydroxide, 0.05 kilogram of silane coupling agent KH550,0.1 kilogram of antioxidant 1010 and and 91.65 kilograms polypropylene melt extrude at 170～210 ℃ through twin screw extruder and make the polypropylene flame redardant pellet, again the polypropylene flame redardant pellet is injection molded into mechanics and flame-retardant standard batten through injection moulding machine at 170～210 ℃, by the standard test correlated performance, concrete data are listed in table 1.
Comparative example 1
The polypropylene of 13 kilograms of TDE, 3.5 kilograms antimonous oxide, 0.05 kilogram of silane coupling agent KH550 and 83.45 kilograms melt extruded at 170～210 ℃ through twin screw extruder make the polypropylene flame redardant pellet, again the polypropylene flame redardant pellet is injection molded into mechanics and flame-retardant standard batten through injection moulding machine at 170～210 ℃, by the standard test correlated performance, concrete data are listed in table 1.
Comparative example 2
The polypropylene of 16 kilograms of decabromodiphenyl oxides, 5 kilograms antimonous oxide, 0.05 kilogram of silane coupling agent KH550 and 78.95 kilograms melt extruded at 170～210 ℃ through twin screw extruder make the polypropylene flame redardant pellet, again the polypropylene flame redardant pellet is injection molded into mechanics and flame-retardant standard batten through injection moulding machine at 170～210 ℃, by the standard test correlated performance, concrete data are listed in table 1.
The performance data of table 1 flame-proof polypropelene composition
| Embodiment | Tensile strength (MPa) | Shock strength (J/m) | UL 94 flame retardant ratings (0.8mm is thick) | Dielectric strength (vol/mil) |
| Pure PP | ??33.02 | ??16.19 | Not fire-retardant | ??2210 |
| Embodiment 1 | ??31.61 | ??14.82 | ??V0 | ??1596 |
| Embodiment 2 | ??35.66 | ??13.28 | ??V1 | ??1556 |
| Embodiment 3 | ??34.34 | ??12.59 | ??V0 | ??1482 |
| Embodiment 4 | ??32.50 | ??13.16 | ??V0 | ??1549 |
| Embodiment 5 | ??32.78 | ??12.86 | ??V1 | ??1621 |
| Embodiment 6 | ??34.08 | ??13.76 | ??V0 | ??1502 |
| Embodiment 7 | ??35.62 | ??13.97 | ??V0 | ??1515 |
| Embodiment 8 | ??31.20 | ??14.20 | ??V0 | ??1659 |
| Embodiment 9 | ??34.81 | ??13.47 | ??V0 | ??1487 |
| Comparative example 1 | ??36.11 | ??9.16 | ??V1 | ??1023 |
| Comparative example 2 | ??35.65 | ??8.55 | ??V1 | ??981 |
Claims (10)
1. a flame-proof polypropelene composition is characterized in that containing bromide fire retardant and the phosphorus flame retardant that is in a liquid state in polyacrylic melt-processed process.
2. flame-proof polypropelene composition according to claim 1 is characterized in that described bromide fire retardant is a fusing point at 70～200 ℃ bromide fire retardant.
3. flame-proof polypropelene composition according to claim 1, it is characterized in that described bromide fire retardant is a tetrabromo-bisphenol-two (2,3-dibromopropyl ether), three (2,3-dibromo third), third chlorinated isocyanurates, hexabromocyclododecane, vinylformic acid pentabromo-benzyl ester and any in the dibromoneopentyl glycol that contract.
4. flame-proof polypropelene composition according to claim 1 is characterized in that described phosphorus flame retardant is the phosphoric acid ester that contains phenyl.
5. flame-proof polypropelene composition according to claim 1 is characterized in that described phosphorus flame retardant is any in triphenylphosphate, Resorcinol biphosphonate, dihydroxyphenyl propane two (diphenyl phosphoester), the diphenyl 2 ethylhexyl phosphate.
6. according to the described flame-proof polypropelene composition of claim 1 to 5, the mass percentage content that it is characterized in that described bromide fire retardant is 4～9%.
7. according to the described flame-proof polypropelene composition of claim 1 to 5, the mass percentage content that it is characterized in that described bromide fire retardant is 6～8%.
8. according to the described flame-proof polypropelene composition of claim 1 to 7, the mass ratio that it is characterized in that described bromide fire retardant and phosphorus flame retardant is 1/25～1/5.
9. according to the described flame-proof polypropelene composition of claim 1 to 8, it is characterized in that going back at least a inorganic synergist in montmorillonoid-containing, magnesium hydroxide, aluminium hydroxide, zinc borate, zinc sulphide and the molybdenum oxide.
10. flame-proof polypropelene composition according to claim 9 is characterized in that described inorganic synergist mass percentage content is 0.3～1%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910213635A CN101824186A (en) | 2009-12-09 | 2009-12-09 | Flame retarding polypropylene compound |
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| CN200910213635A CN101824186A (en) | 2009-12-09 | 2009-12-09 | Flame retarding polypropylene compound |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104004270A (en) * | 2014-06-17 | 2014-08-27 | 青岛职业技术学院 | Low-halogen polypropylene flame-resistant materials and preparing method thereof |
| CN107177361A (en) * | 2017-06-02 | 2017-09-19 | 冯新平 | A kind of environment-friendlyflame flame retardant and its preparation technology |
| CN107735445A (en) * | 2015-07-29 | 2018-02-23 | 出光狮王塑料株式会社 | High reflection flame resistance thermoplastic resin compositions, formed body and lighting machine reflecting plate |
| CN109233101A (en) * | 2018-09-10 | 2019-01-18 | 金发科技股份有限公司 | A kind of heat-proof combustion-resistant polypropene composition and preparation method thereof |
| CN109689750A (en) * | 2016-09-19 | 2019-04-26 | 乐天化学株式会社 | The flame-retardant expanded product for being used to prepare the resin combination of the flame-retardant expanded product of polyolefins and being formed by it |
| CN111471181A (en) * | 2020-05-13 | 2020-07-31 | 宁波公牛精密制造有限公司 | Phosphorus-nitrogen flame retardant, preparation method thereof and polypropylene composite material containing phosphorus-nitrogen flame retardant |
| CN112143094A (en) * | 2019-06-28 | 2020-12-29 | 合肥杰事杰新材料股份有限公司 | Regenerated polyolefin plastic composition and preparation method and application thereof |
-
2009
- 2009-12-09 CN CN200910213635A patent/CN101824186A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104004270A (en) * | 2014-06-17 | 2014-08-27 | 青岛职业技术学院 | Low-halogen polypropylene flame-resistant materials and preparing method thereof |
| CN107735445A (en) * | 2015-07-29 | 2018-02-23 | 出光狮王塑料株式会社 | High reflection flame resistance thermoplastic resin compositions, formed body and lighting machine reflecting plate |
| CN109689750A (en) * | 2016-09-19 | 2019-04-26 | 乐天化学株式会社 | The flame-retardant expanded product for being used to prepare the resin combination of the flame-retardant expanded product of polyolefins and being formed by it |
| CN107177361A (en) * | 2017-06-02 | 2017-09-19 | 冯新平 | A kind of environment-friendlyflame flame retardant and its preparation technology |
| CN109233101A (en) * | 2018-09-10 | 2019-01-18 | 金发科技股份有限公司 | A kind of heat-proof combustion-resistant polypropene composition and preparation method thereof |
| CN112143094A (en) * | 2019-06-28 | 2020-12-29 | 合肥杰事杰新材料股份有限公司 | Regenerated polyolefin plastic composition and preparation method and application thereof |
| CN112143094B (en) * | 2019-06-28 | 2022-04-26 | 合肥杰事杰新材料股份有限公司 | Regenerated polyolefin plastic composition and preparation method and application thereof |
| CN111471181A (en) * | 2020-05-13 | 2020-07-31 | 宁波公牛精密制造有限公司 | Phosphorus-nitrogen flame retardant, preparation method thereof and polypropylene composite material containing phosphorus-nitrogen flame retardant |
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Application publication date: 20100908 |