CN101134830A - Non-bittern expanding flame-proof material and method for making same - Google Patents
Non-bittern expanding flame-proof material and method for making same Download PDFInfo
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- CN101134830A CN101134830A CNA2007100298754A CN200710029875A CN101134830A CN 101134830 A CN101134830 A CN 101134830A CN A2007100298754 A CNA2007100298754 A CN A2007100298754A CN 200710029875 A CN200710029875 A CN 200710029875A CN 101134830 A CN101134830 A CN 101134830A
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Abstract
The present invention relates to one kind of no-halogen expanding fire retardant material and its preparation process. The no-halogen expanding fire retardant material consists of polypropylene and expanding fire retardant in 30-50 wt% of polypropylene. It is prepared through melting and rolling polypropylene at 160-170 deg.c, adding expanding fire retardant and additive and mixing for 8-15 min, hot pressing at 15 MPa and 180 deg.c for 2-5 min and cooling to set. The no-halogen expanding fire retardant material of the present invention has excellent fire retardant effect and high mechanical performance.
Description
Technical field
The present invention relates to fire retardant material, be specifically related to a kind of non-bittern expanding flame-proof material and preparation method thereof.
Background technology
At present, the fire retardant material of domestic employing mainly is the bromine series flame retardant material.But this bromine series flame retardant material is easy to generate pollution, is difficult to satisfy environmental requirement.Therefore, the novel Halogen of research and development, fire retardant material is very necessary efficiently.Developed a series of polypropylene bittern-free flame-proof materials at present abroad, these fire retardants are to be matrix with ammonium phosphate, are added with nitrogenous synergist, and adopt special process to make, and these fire retardant prices are too high, are difficult to the widespread use in China.
EUROPEAN PATENT OFFICE's EP0735119A1 open file discloses a kind of poly phosphorus-nitrogen expansion type fire retardant that is used for, and the add-on of this phosphorus-nitrogen expansion type fire retardant in polyethylene (PE) is 35%, and limiting oxygen index(LOI) (LOI) reaches 35, and UL-94 reaches the V-0 level.But this expansion type fire retardant flame retardant effect in the fire retardant material of forming with polyethylene is undesirable, on the other hand the own moisture-sensitive of this based flame retardant and cause the electric property of fire retardant material to descend.Has easy migration at the char-forming agent PER (tetramethylolmethane) among the conventional I FR (expansion type flame retardant), work in-process can generate shortcomings such as phosphoric acid ester with APP (polyphosphoric acid amine), people such as Liu Jun (" polymer material science and engineering ", 1999,15 (1): 73-79) having studied nitrogenous pyrrolotriazine derivatives is the influence of char-forming agent to PP (polypropylene) flame retardant properties, when APP and pyrrolotriazine derivatives were 5: 1, the LOI value of PP can reach 33.5.People such as Ou Yuxiang (" chemical industry progress ", 2004,23 (8): 857-860) studied MPP/PER/APP ternary IFR fire-retardant to PP (polypropylene), find as MPP (polyphosphoric acid melamine) when ternary IFR addition is 25%, the flame retardant resistance of PP promptly reaches the UL94V-0 level, and LOI is 30.7, increases with ternary IFR consumption, flame retarding efficiency (EFF) improves, and is up to about 30.The adding of ternary IFR has reduced the initial decomposition temperature of PP, improves charring rate, but in the thermal destruction volatile products of fire-retardant PP except that micromolecular compounds such as ammonia, water are arranged, also have trimeric cyanamide to emit, cause the human injury easily, bring pollution to environment.
Summary of the invention
For overcoming the above-mentioned shortcoming and defect of present technology, the invention provides a kind of is the low-smoke halogen-free expansion type fire retardant material of base-material with the polypropylene, and the present invention also provides the preparation method of described non-bittern expanding flame-proof material simultaneously.
Non-bittern expanding flame-proof material of the present invention comprises following component: polypropylene, expansion type flame retardant; Wherein, expansion type flame retardant weight is 30%～50% of polypropylene weight.
For better realization the present invention,
In the preferred ammonium polyphosphate of described expansion type flame retardant (APP), trimeric cyanamide (MEL), the tetramethylolmethane (PER) one or more;
Also can comprise additive in the described component; Wherein, described additive comprises one or more in zinc oxide, organic modification montmonrillonite (OMMT), the starch, and the weight of described additive is 0～20% of polypropylene weight; Wherein, further, the preferred zinc oxide of described additive, the weight of zinc oxide is 0.65%～3.9% of polypropylene weight; Described additive is preferred organic modification montmonrillonite also, and the weight of organic modification montmonrillonite is 1%～5% of polypropylene weight; But described additive is preferred starch also, and the weight of starch is 0～10% of polypropylene weight.
The preparation method of non-bittern expanding flame-proof material of the present invention comprises following technical process:
Get polypropylene, expansion type flame retardant, additive, then under 160 ℃～170 ℃ with polypropylene fusion bag roller, the mixture that adds expansion type flame retardant or expansion type flame retardant and additive again, mixing 8～15 minutes, and then 15Mpa, 180 ℃ of following hot pressing 2～5 minutes, cooling and shaping promptly;
Wherein, described expansion type flame retardant comprises one or more in ammonium polyphosphate, trimeric cyanamide, the tetramethylolmethane, and expansion type flame retardant weight is 30%～50% of polypropylene weight; Described additive comprises one or more in zinc oxide, organic modification montmonrillonite, the starch, and the weight of described additive is 0～20% of polypropylene weight.
The present invention proposes the additive preparation low smoke zero halogen flame retardant polypropylene material that adopts expansion type flame retardant and synergistic effect is arranged, compared with prior art, the present invention has the following advantages:
(1) experiment of the thermal weight loss of non-bittern expanding flame-proof material of the present invention shows that expansion type flame retardant has improved polypropylene maximum heat weight loss rate temperature, has increased the remaining rate of thermal weight loss; After being added with synergistic additive, system generates more surplus charcoal, forms stable polypropylene fire retardant protection charcoal layer;
(2) the scanning electron microscope morphology observation of non-bittern expanding flame-proof material of the present invention shows, burning carbon membrane aperture is less, and pore membrane is thicker, and good foaming effect is arranged;
(3) non-bittern expanding flame-proof material of the present invention, its oxygen index is 35 to the maximum, and tensile strength is greater than 26MPa, and flexural strength is greater than 52MPa, and shock strength is greater than 5.8KJ/m
2;
(4) the differential scanning calorimetric of non-bittern expanding flame-proof material of the present invention experiment shows that zinc oxide only plays katalysis in flame retardant systems, and along with the increase of zinc oxide dosage, the heat that the polypropylene flame redardant degraded discharges is constant substantially;
(5) it is little that non-bittern expanding flame-proof material of the present invention, goods reach the required fire retardant addition of V-0 level, and mechanical property is preferably arranged.Its fire retardant mechanism is to produce a kind of dense char layer between flame and material, and this charcoal layer can reduce the heating temperature of material greatly, because fire-retardant charcoal layer intercepts the effect of oxygen, the degree of oxidation of material reduces greatly simultaneously; Phosphorus nitrogen element in the organophosphorus nitrogen expansion type flame retardant molecule can dilute and stop the reaction of living radical in gas phase, thereby reaches fire-retardant purpose.
Description of drawings
Fig. 1 is the limiting oxygen index(LOI) figure of the embodiment of the invention 10～20 gained non-bittern expanding flame-proof materials;
Fig. 2 is the tensile strength index map of the embodiment of the invention 10～20 gained non-bittern expanding flame-proof materials;
Fig. 3 is the flexural strength index map of the embodiment of the invention 10～20 gained non-bittern expanding flame-proof materials;
Fig. 4 is the impact strength index figure of the embodiment of the invention 10～20 gained non-bittern expanding flame-proof materials.
Embodiment
Effects more of the present invention embodiment preferably below is provided, and further specifying the present invention, but protection scope of the present invention is not limited in this.
Embodiment 1:
Be to add 100gPP earlier on two roller warm-up mills of 160～170 ℃ in the roller temperature, behind the fusion bag roller, add 20gAPP, 10gPER and 10gMEL, mixing 8min, fire retardant is fully disperseed in PP, in 15MPa180 ℃ vulcanizing press hot pressing 3min, cooling and shaping 5min is promptly in the cold-smoothing plate vulcanizer of 15MPa again.Its oxygen index of halogen-free expansion type flame-proof polypropylene that present embodiment makes is 33, and tensile strength, flexural strength, shock strength are respectively 20.87MPa, 50.64MPa, 4.42KJ/m
2
Each raw material and proportioning see Table 1, are respectively 8,10,9,9,15,11,13 from the mixing time of embodiment 2 to 9,9min, and hot pressing time is respectively 2,3,3,3,5,4,3,5min, other steps and condition are with embodiment 1.
Table 1 embodiment 2～9
The flame retardant properties and the mechanical property of embodiment 2～9 prepared non-bittern expanding flame-proof materials are seen as follows
Table 2:
The flame retardant properties and the mechanical property of table 2 embodiment 2～9 materials
Embodiment 10:
Be to add 100gPP earlier on two roller warm-up mills of 160～170 ℃ in the roller temperature, behind the fusion bag roller, add 20gAPP, 9gPER, 1g starch and 10gMEL, mixing 9min, after fire retardant is fully disperseed in PP, in the vulcanizing press hot pressing 3min of 180 ℃ of 15MPa, cooling and shaping 5min in the cold-smoothing plate vulcanizer of 15MPa again.Its oxygen index of halogen-free expansion type flame-proof polypropylene that present embodiment makes is 33, and tensile strength, flexural strength, shock strength and embodiment 1 are together.
Embodiment 11～20
Each raw material and proportioning see Table 3, and the preparation method is with embodiment 10.
Table 3 embodiment 11～20
The limiting oxygen index(LOI) of the non-bittern expanding flame-proof material of embodiment 10～20 gained is seen accompanying drawing 1, and the mechanical property index is seen accompanying drawing 2～4.By Fig. 1～4 as seen, its oxygen index is 35 to the maximum, and tensile strength is greater than 26MPa, and flexural strength is greater than 52MPa, and shock strength is greater than 5.8KJ/m
2, as seen, the non-bittern expanding flame-proof material of gained of the present invention has preferable performance.
Embodiment 21:
Be to add 100gPP earlier on two roller warm-up mills of 160～170 ℃ in the roller temperature, behind the fusion bag roller, add 20gAPP, 10gPER and 1.3gZnO, mixing 10min, after fire retardant is fully disperseed in PP, in the vulcanizing press hot pressing 3min of 180 ℃ of 15MPa, cooling and shaping 5min in the cold-smoothing plate vulcanizer of 15MPa again.Its oxygen index of halogen-free expansion type flame-proof polypropylene that present embodiment makes is 34, and tensile strength, flexural strength, shock strength are respectively 26.27MPa, 52.1MPa, 5.85KJ/m
2
Embodiment 22～25
Each raw material and consumption thereof see Table 4, and the preparation method is with embodiment 21.
Table 4
Embodiment 26:
Be to add 100gPP earlier on two roller warm-up mills of 160～170 ℃ in the roller temperature, behind the fusion bag roller, add 20gAPP, 10gPER, 1.3g ZnO and 1gOMMT, mixing 10min, after fire retardant is fully disperseed in PP, in the vulcanizing press hot pressing 3min of 180 ℃ of 15MPa, cooling and shaping 5min in the cold-smoothing plate vulcanizer of 15MPa again.Its oxygen index of halogen-free expansion type flame-proof polypropylene that present embodiment makes is 35, and tensile strength, flexural strength, shock strength are respectively 27.01MPa, 54.24MPa, 5.92KJ/m
2
Each raw material and consumption thereof see Table 5, and the preparation method is with embodiment 26.
Table 5 embodiment 27～29
Claims (7)
1. a non-bittern expanding flame-proof material is characterized in that, comprises following component: polypropylene, expansion type flame retardant; Wherein, expansion type flame retardant weight is 30%～50% of polypropylene weight.
2. a kind of non-bittern expanding flame-proof material according to claim 1 is characterized in that described expansion type flame retardant comprises one or more in ammonium polyphosphate, trimeric cyanamide, the tetramethylolmethane.
3. a kind of non-bittern expanding flame-proof material according to claim 1 and 2 is characterized in that, also comprises additive in the component; Wherein, described additive comprises one or more in zinc oxide, organic modification montmonrillonite, the starch, and the weight of described additive is 0～20% of polypropylene weight.
4. a kind of non-bittern expanding flame-proof material according to claim 3 is characterized in that described additive is a zinc oxide, and the weight of zinc oxide is 0.65%～3.9% of polypropylene weight.
5. a kind of non-bittern expanding flame-proof material according to claim 3 is characterized in that described additive is an organic modification montmonrillonite, and the weight of organic modification montmonrillonite is 1%～5% of polypropylene weight.
6. a kind of non-bittern expanding flame-proof material according to claim 3 is characterized in that described additive is a starch, and the weight of starch is 0～10% of polypropylene weight.
7. the preparation method of the described a kind of non-bittern expanding flame-proof material of claim 1 is characterized in that, comprises following technical process:
Get polypropylene, expansion type flame retardant, additive, then under 160 ℃～170 ℃ with polypropylene fusion bag roller, the mixture that adds expansion type flame retardant or expansion type flame retardant and additive again, mixing 8～15 minutes, and then 15Mpa, 180 ℃ of following hot pressing 2～5 minutes, cooling and shaping promptly;
Wherein, described expansion type flame retardant comprises one or more in ammonium polyphosphate, trimeric cyanamide, the tetramethylolmethane, and expansion type flame retardant weight is 30%～50% of polypropylene weight; Described additive comprises one or more in zinc oxide, organic modification montmonrillonite, the starch, and the weight of described additive is 0～20% of polypropylene weight.
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101928430A (en) * | 2010-10-14 | 2010-12-29 | 北京东方绿达科技发展有限责任公司 | Novel flame redundant material and preparation method thereof |
| CN101735514B (en) * | 2009-12-29 | 2011-10-05 | 青岛国恩科技发展有限公司 | Flame-retardant polypropylene material and preparation method |
| CN102977580A (en) * | 2012-12-14 | 2013-03-20 | 青岛中科润美润滑材料技术有限公司 | Preparation process of flame-retardant microencapsulated alloy |
| CN102993679A (en) * | 2012-12-14 | 2013-03-27 | 青岛中科润美润滑材料技术有限公司 | Method for preparing flame-retardant microencapsulation alloy |
| CN103013085A (en) * | 2012-12-14 | 2013-04-03 | 青岛华电高压电气有限公司 | Method for producing flame-retardant microencapsulation alloy |
| RU2491317C2 (en) * | 2011-09-21 | 2013-08-27 | Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования Кабардино-Балкарский государственный университет им. Х.М. Бербекова | Fire-resistant nanocomposite and method of its obtaining |
| CN103333406A (en) * | 2013-06-05 | 2013-10-02 | 华南理工大学 | Modified intumescent flame-retardant polypropylene composition and preparation method thereof |
| CN105862490A (en) * | 2016-04-05 | 2016-08-17 | 华南理工大学 | Environment-friendly type flame retardant paper and preparation method thereof |
| CN105885229A (en) * | 2016-05-31 | 2016-08-24 | 陈加福 | Halogen-free flame-retardant polypropylene compound and preparation method thereof |
| CN106560487A (en) * | 2016-01-08 | 2017-04-12 | 福建泉州市朝闻鞋业有限公司 | Halogen-free flame-retardant polypropylene compound and preparation method thereof |
| CN106700227A (en) * | 2015-11-12 | 2017-05-24 | 北京化工大学 | Polypropylene nanometer montmorillonite intumescent flame-retardant composite and preparation method thereof |
| CN107815017A (en) * | 2017-11-02 | 2018-03-20 | 南京工业大学连云港工业技术研究院 | Expansion type flame retardant and its preparation method |
| CN107988644A (en) * | 2017-12-05 | 2018-05-04 | 安徽益邦新材料科技股份有限公司 | A kind of preparation method of fire-retardant container bag |
| CN112961431A (en) * | 2021-02-07 | 2021-06-15 | 陈瑞英 | High-temperature-resistant flame-retardant insulating material and preparation method thereof |
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2007
- 2007-08-24 CN CNA2007100298754A patent/CN101134830A/en active Pending
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101735514B (en) * | 2009-12-29 | 2011-10-05 | 青岛国恩科技发展有限公司 | Flame-retardant polypropylene material and preparation method |
| CN101928430A (en) * | 2010-10-14 | 2010-12-29 | 北京东方绿达科技发展有限责任公司 | Novel flame redundant material and preparation method thereof |
| CN101928430B (en) * | 2010-10-14 | 2012-06-13 | 北京东方绿达科技发展有限责任公司 | Novel flame redundant material and preparation method thereof |
| RU2491317C2 (en) * | 2011-09-21 | 2013-08-27 | Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования Кабардино-Балкарский государственный университет им. Х.М. Бербекова | Fire-resistant nanocomposite and method of its obtaining |
| CN102977580A (en) * | 2012-12-14 | 2013-03-20 | 青岛中科润美润滑材料技术有限公司 | Preparation process of flame-retardant microencapsulated alloy |
| CN102993679A (en) * | 2012-12-14 | 2013-03-27 | 青岛中科润美润滑材料技术有限公司 | Method for preparing flame-retardant microencapsulation alloy |
| CN103013085A (en) * | 2012-12-14 | 2013-04-03 | 青岛华电高压电气有限公司 | Method for producing flame-retardant microencapsulation alloy |
| CN103333406B (en) * | 2013-06-05 | 2016-01-06 | 华南理工大学 | A kind of modified expanded flame-proof polypropelene composition and preparation method thereof |
| CN103333406A (en) * | 2013-06-05 | 2013-10-02 | 华南理工大学 | Modified intumescent flame-retardant polypropylene composition and preparation method thereof |
| CN106700227A (en) * | 2015-11-12 | 2017-05-24 | 北京化工大学 | Polypropylene nanometer montmorillonite intumescent flame-retardant composite and preparation method thereof |
| CN106560487A (en) * | 2016-01-08 | 2017-04-12 | 福建泉州市朝闻鞋业有限公司 | Halogen-free flame-retardant polypropylene compound and preparation method thereof |
| CN105862490A (en) * | 2016-04-05 | 2016-08-17 | 华南理工大学 | Environment-friendly type flame retardant paper and preparation method thereof |
| CN105885229A (en) * | 2016-05-31 | 2016-08-24 | 陈加福 | Halogen-free flame-retardant polypropylene compound and preparation method thereof |
| CN107815017A (en) * | 2017-11-02 | 2018-03-20 | 南京工业大学连云港工业技术研究院 | Expansion type flame retardant and its preparation method |
| CN107988644A (en) * | 2017-12-05 | 2018-05-04 | 安徽益邦新材料科技股份有限公司 | A kind of preparation method of fire-retardant container bag |
| CN112961431A (en) * | 2021-02-07 | 2021-06-15 | 陈瑞英 | High-temperature-resistant flame-retardant insulating material and preparation method thereof |
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Open date: 20080305 |