CN101148518B - Application of apatite in anti-flaming composite material by using plastic as substrate - Google Patents
Application of apatite in anti-flaming composite material by using plastic as substrate Download PDFInfo
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- CN101148518B CN101148518B CN2007101351819A CN200710135181A CN101148518B CN 101148518 B CN101148518 B CN 101148518B CN 2007101351819 A CN2007101351819 A CN 2007101351819A CN 200710135181 A CN200710135181 A CN 200710135181A CN 101148518 B CN101148518 B CN 101148518B
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Abstract
The present invention is application of apatite in antiflaming plastic, and belongs to the field of composite material technology. Apatite with or without antiflaming synergist as the antiflaming agent is added into plastic matrix, and the mixture is prepared into the composite antiflaming material through in-situ polymerization and co-mixing extrusion or extruding reaction. In the composite antiflaming material, apatite accounts for 1-60 wt%, and the plastic is thermoplastic plastic, thermosetting plastic or plastic alloy. The present invention has low cost, simple technological process, excellent machining performance and other advantages, and may be applied widely.
Description
Technical field
The present invention relates to new purposes, the especially phosphatic rock application in the flame-proof composite material that with plastics is matrix of phosphatic rock.
Background technology
From the thirties in 20th century, after organic polymer material entered all respects of national economy every field and people's lives, the mankind began to face new fire threat.Reason is that this class material overwhelming majority is inflammable or combustible.Current, global fire hazard situation is very severe.At a rough estimate, the fire direct economic loss of industrially developed country is about the 0.1-0.2% of GDP at present, and indirect economic loss can reach 1% of GDP sometimes.
To inorganic additive flame retardant (as Al (OH)
3And Mg (OH)
2), that its fire retardation mainly shows is isolated to incendiary, cooling and dilution effect, be considered to the ideal green fire retardant, but this based flame retardant has a serious weakness, even to obtain the ideal flame retardant properties, need very high fire retardant loading level, even reach more than 60%, cause the mechanical property and the processing characteristics of matrix material to descend significantly, and make fire-retardant product occur quality problems such as macroscopic irregularity easily.Seek new inorganic combustion inhibitor ever more important.
Phosphatic rock exists extensively at nature, it is low that synthetic has a cost, technology is simple, each element ratio is controlled, advantages such as workability is strong, preparation and Application Areas about phosphatic rock almost all concentrates on biomaterial for medical purpose field or solid support material both at home and abroad, rare report in the material flame retardant area, only Z.A.Nagieb has reported the fire retardation of phosphatic rock in wooden oar, when addition is 4wt%, oxygen index can by 17 be increased to 23 (Polymer Degradation and Stability, 57:205-209).
Summary of the invention
The problem to be solved in the present invention: it is big to solve the used inorganic combustion inhibitor addition of present plastics flame retardant industry, the problem that the material property deterioration is serious.The present invention adopts the inorganic combustion inhibitor of phosphatic rock as plastic article industry, and phosphatic rock exists extensively at nature, and synthetic has advantages such as cost is low, and technology is simple, and each element ratio is controlled, and workability is strong.
The technical solution adopted for the present invention to solve the technical problems is: the application of phosphatic rock in flame retardant plastics, phosphatic rock is made flame-proof composite material as fire retardant material and plastics separately, or with phosphatic rock and fire retarding synergist is composite makes flame-proof composite material with plastics again.
A kind of use phosphatic rock or phosphatic rock and fire retarding synergist are composite as fire retardant, and matrix is the flame retardant of plastic matrix material.Wherein the general molecular formula of employed phosphatic rock is as follows:
A
m(XO
4)
n(CO
3)
r(F，OH，Cl)
p
Wherein A is Ca, Sr, Ba, Pb, Na, Ce, Y etc. one or more; X is P, As, V, Si etc. one or more; M, n,, r, p are arbitrarily more than or equal to zero integer.
It is that the oxygen of the aqueous vapor utilizing phosphatic rock to decompose in being subjected to thermal process to emit and carbon dioxide diluted material near surface and plastics decompose and discharge inflammable gas as the principle of fire retardant that the present invention uses phosphatic rock, reach the gas phase flame retardant effect, oxysalt that phosphatic rock decomposition simultaneously obtains and polymer unwinds resistates are combined closely and are formed the isolated heat of fine and close coverture and oxygen and inflammable gas propagation, reach the condensed phase flame retardant effect, cooperate the use of other fire retarding synergist, receive good synergistic effect, can be controlled at lower inorganic combustion inhibitor-phosphatic rock interpolation level, obtain the flame retardant effect of expection.
The present invention can be merged with plastic substrate preferably for making fire retardant, improves the mechanical property and the processing characteristics of flame-proof composite material, and the particle diameter of employed phosphatic rock is between 0.001um-50um, and particle diameter is preferably 0.05um-30um.
Mechanical property and the processing characteristics of the present invention in order not reduce flame-proof composite material, simultaneously can make the flame-proof composite material of preparation that good fire retardancy is arranged again, phosphatic rock proportion in whole matrix material is 1wt%-60wt%, and preferred proportion is 5wt%-25wt%.
Phosphatic rock described in the present invention can join in the various plastic substrates and use, and comprises thermoplastics, thermosetting resin or various polyblend as the plastics of body material; Described thermosetting resin comprises ABS (acrylonitrile-butadiene-styrene copolymer), PE (polyethylene), PP (polypropylene), PC (polycarbonate), PBT (polybutylene terephthalate), PET (polyethylene terephthalate).
The preparation method of flame-proof composite material of the present invention has following three kinds of methods: situ aggregation method, blend extrusion molding and extrusion reaction method.
Situ aggregation method described in the present invention is that phosphatic rock is mixed with plastics synthon and other auxiliary agents, and technology polymerization routinely in polymerization reaction kettle prepares flame-proof composite material by the in-situ polymerization mode, i.e. the method for in-situ polymerization.
Blend extrusion molding described in the present invention is that phosphatic rock is mixed with plastics and other properties-correcting agent, extrudes the preparation flame-proof composite material through blend on the twin screw extrusion equipment, i.e. the method that blend is extruded.
Extrusion reaction method described in the present invention is mixed phosphatic rock with the plastics that can carry out chemical modification and other auxiliary agents, extrude the preparation flame-proof composite material through high molecular weight reactive modification, blend on forcing machine, i.e. the method that reaction is extruded.
The invention has the beneficial effects as follows that the present invention has advantages such as cost is low, and technology is simple, and workability is strong, can be widely used in flame retardant plastics goods field.
Embodiment
Below by embodiment the present invention is specifically described; what be worth to propose is that following examples only are used for that the present invention will be further described; can not be interpreted as limiting the scope of the invention; and nonessential improvement and adjustment that present technique field professional makes according to the invention described above content should belong to protection scope of the present invention.
Embodiment 1-4
In reactor, press table 1 proportioning and add terephthalic acid (PTA), ethylene glycol (EG), phosphorus containing fire retardant copolyester monomer (DOP), other raw materials, other raw materials comprise oxidation inhibitor, lubricant and dispersion agent, usage quantity is suitable with the general employed amount of plastics-production, pressurize and be warming up to 245-269 ℃ and carry out esterification, reaction time of esterification 2-3h; After esterification finishes, temperature control is at 230-270 ℃, add spent glycol dispersive apatite powder (AP) in advance, after distilling out unnecessary ethylene glycol, rough vacuum polycondensation 1-1.5h, temperature 269-283 ℃, continue to be warming up to 283-290 ℃ then, and under high vacuum condition, carry out polycondensation 1-2h and get final product.Prepare respectively according to this operating process and to contain phosphatic rock 0,5,10, the flame-proof composite material of 15wt%.Each sample oxygen index sees Table 1.The fusion drip phenomenon obviously improves.
Table 1
| PTA (part) | EG (part) | DOP (part) | AP (part) | Other raw material (part) | LOI (part) |
| 2200 | 1240 | 333 | 0 | 30 | 28 |
| 2200 | 1240 | 333 | 150 | 30 | 28.5 |
| 2200 | 1240 | 333 | 320 | 30 | 30 |
| 2200 | 1240 | 333 | 510 | 30 | 32 |
Embodiment 5-10
By the listed proportioning of table 2 new LDPE (film grade) (LDPE), ammonium polyphosphate (APP), aluminium hydroxide (ATH), phosphatic rock (AP) and other raw material are joined the high-speed mixer thorough mixing respectively, other raw materials comprise oxidation inhibitor, lubricant and dispersion agent, usage quantity is suitable with the general employed amount of plastics-production, under 160-220 ℃, extrude then, obtain flame-proof composite material in the twin screw extruder blend.Each sample oxygen index sees Table 2.
Table 2
| LDPE (part) | APP (part) | ATH (part) | AP (part) | Other raw material (part) | LOI(％) |
| 60 | 20 | 30 | 0 | 5 | 27.7 |
| 60 | 20 | 20 | 10 | 5 | 28.2 |
| 60 | 20 | 15 | 15 | 5 | 28.7 |
| 60 | 20 | 10 | 20 | 5 | 29.2 |
| 60 | 20 | 5 | 25 | 5 | 29.6 |
| 60 | 20 | 0 | 30 | 5 | 29.7 |
Embodiment 11-16
Just ethylene vinyl acetate (EVA), new LDPE (film grade) (LDPE), linking agent, elastomerics, aluminium hydroxide (ATH), phosphatic rock (AP) and other raw material join the high-speed mixer thorough mixing by the listed proportioning of table 3 respectively, other raw materials comprise oxidation inhibitor, lubricant and dispersion agent, the control feeding temperature is 90-100 ℃ on dual-screw-stem machine, 120-130 ℃ of fluxing zone temperature, 90-110 ℃ of metering zone temperature, die head temperature 140-150 ℃, through blended cross linking reaction extruding pelletization, obtain flame-proof composite material.Each sample oxygen index sees Table 3.
Table 3
| EVA (part) | LDPE (part) | ATH (part) | AP (part) | Other raw material (part) | LOI(％) |
| 50 | 20 | 60 | 0 | 5 | 30.2 |
| 50 | 20 | 50 | 10 | 5 | 30.5 |
| 50 | 20 | 40 | 20 | 5 | 31.6 |
| 50 | 20 | 30 | 30 | 5 | 32.9 |
| 50 | 20 | 20 | 40 | 5 | 33.1 |
| 50 | 20 | 0 | 60 | 5 | 33.3 |
Claims (3)
1. flame-proof composite material, it is characterized in that: employed fire retardant is phosphatic rock or phosphatic rock and fire retarding synergist is composite forms, the matrix of material is ABS, PE, PP, PC, PBT or PET, described fire retarding synergist is one or more a mixture of aluminium hydroxide, magnesium hydroxide, aluminosilicate, boron flame retardant, Sb system fire retardant, phosphonium flame retardant, expansion type flame retardant or fire resistant fluid polycrystalline macromolecule, and described phosphatic rock proportion in whole matrix material is 8.7wt%-60wt%.
2. a kind of flame-proof composite material according to claim 1 is characterized in that: described phosphatic rock particle diameter is between 0.001um-50um.
3. a kind of flame-proof composite material according to claim 2 is characterized in that: the preferred 0.05um-30um of described phosphatic rock particle diameter.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007101351819A CN101148518B (en) | 2007-11-02 | 2007-11-02 | Application of apatite in anti-flaming composite material by using plastic as substrate |
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|---|---|---|---|
| CN2007101351819A CN101148518B (en) | 2007-11-02 | 2007-11-02 | Application of apatite in anti-flaming composite material by using plastic as substrate |
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| CN101148518B true CN101148518B (en) | 2011-03-23 |
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| CN102532793B (en) * | 2011-12-27 | 2014-04-02 | 彭朕财 | Plastic grain-removal brightener and preparation method thereof |
| CN106995580A (en) * | 2017-03-27 | 2017-08-01 | 佛山汇沐化学科技有限公司 | A kind of high Antibacterial flame retardant plastic its preparation method |
| CN114574996B (en) * | 2022-03-28 | 2024-01-12 | 杭州成江纺织有限公司 | Flame-retardant composite polyester filament yarn and processing technology thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1847308A (en) * | 2005-04-04 | 2006-10-18 | 信越化学工业株式会社 | Flame retardant and an epoxy resin composition comprising the same for encapsulating semiconductor devices |
| KR100759066B1 (en) * | 2007-07-02 | 2007-09-19 | 주식회사 대겸 | Preparation method of incombustible polystyrene using waste expanded polystyrene |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1847308A (en) * | 2005-04-04 | 2006-10-18 | 信越化学工业株式会社 | Flame retardant and an epoxy resin composition comprising the same for encapsulating semiconductor devices |
| KR100759066B1 (en) * | 2007-07-02 | 2007-09-19 | 주식회사 대겸 | Preparation method of incombustible polystyrene using waste expanded polystyrene |
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Assignee: Jiangsu AGT New Material Technology Co.,Ltd. Assignor: Shi Mingdong Contract record no.: 2011320000549 Denomination of invention: Application of apatite in anti-flaming composite material by using plastic as substrate Granted publication date: 20110323 License type: Exclusive License Open date: 20080326 Record date: 20110411 |
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Effective date of registration: 20160628 Address after: 213000 Jiangsu city of Changzhou Province, Wujin District Wujin Road Economic Development Zone Patentee after: Changzhou Hui Xin new Mstar Technology Ltd Address before: 213102 Changhong Road, Changzhou Town, Wujin District, Jiangsu, China Patentee before: Shi Mingdong |
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Address after: 213000 Daoxiang Road, Wujin Economic Development Zone, Changzhou City, Jiangsu Province Patentee after: Changzhou Weimao New Material Technology Co., Ltd. Address before: 213000 Daoxiang Road, Wujin Economic Development Zone, Changzhou City, Jiangsu Province Patentee before: Changzhou Hui Xin new Mstar Technology Ltd |