CN100443535C - Halogen-free reaction extruded expansible flame-proof polythene comprising organic metal complex and its preparation method - Google Patents
Halogen-free reaction extruded expansible flame-proof polythene comprising organic metal complex and its preparation method Download PDFInfo
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Abstract
The present invention discloses halogen-free extrusion and expansion type fire-retardant polyethene containing an organic metal complex. Containing an expansion type fire retardant and the organic metal complex, the polyethylene is characterized in that the expansion type fire retardant is an extrusion and expansion type fire retardant generated by compounding reactions and comprises the following components in weight percentages: 65 to 75% of polyethylene, 24.9 to 34.9% of the extrusion and expansion type fire retardant generated by compounding reactions and 0.1 to 1% of the organic metal complex. The present invention also discloses a preparation method. Containing fire-retardant basal particles for extrusion reactions, and compared with the common compounding type fire retardant, the extrusion and expansion type fire retardant generated by compounding reactions and adopted by the present invention has the advantages of better effect of carbon formation, higher efficiency of fire retardance, fewer preparation steps, simpler operation, shorter period and lower cost, so that the halogen-free extrusion and expansion type fire-retardant polyethene containing an organic metal complex disclosed by the present invention is easier to commercially produced in a large scale.
Description
One, technical field
The invention belongs to polyolefine flame retardant products and preparing technical field thereof, specifically, the present invention relates to higher halogen-free polyvinyl of a kind of flame retarding efficiency that contains organometallic complex and composite reaction extruded expansible flame-proof agent simultaneously and preparation method thereof.
Two, background technology
Polyethylene (PE) is as one of general-purpose plastics of output maximum, because it is in light weight, toxicity is low, and has good electric insulating quality and mechanical property, thereby is widely used in industries such as packing, building, traffic, home decoration and electric wire.But because of its limiting oxygen index(LOI) is very low, this shortcoming of very easily burning has had a strong impact on its widespread use aspect the high flame retardant rank.Therefore, improve poly flame retardant resistance is the direction that the scientific worker makes great efforts to study always.
Owing to can stoping polymer materials to be ignited by fire or suppress propagation of flame effectively, the interpolation fire retardant is widely used.At present, the fire retardant that adds in polyethylene is mainly halogen compounds, inorganic hydroxide and expansion type flame retardant etc.But regrettably, though halogen flame has advantages such as addition is few, flame retardant effect is remarkable, in flame-proof polyethylene, once occupied dominant position, but to produce poisonous, covering property gas during their combustion decomposition, and also can produce highly toxic bromo Er Ben Bing oxane and bromo diphenylene-oxide during some aryl bromide fire retardant burnings, this not only can threaten to people's life security, also pollutes the environment, and is now abandoned gradually; Though inorganic hydroxide wide material sources, inexpensive, but flame retarding efficiency is all lower, addition in polyolefine need reach 50-70% usually and just have flame retardant effect, because inorganic hydroxide and polyolefinic consistency are poor, under the so big situation of addition, influence the physical and mechanical properties of material undoubtedly again; And expansion type flame retardant, (" fire retardant material and technology " 1992 (4): that 15) introduces in the literary composition handles polyethylene with phosphorus-polyvalent alcohol-Cresol Formaldehyde Resin, the fire-retardant polyethylene of introducing in " fire retardant material and utilisation technology " book of Wang Yongqiang chief editor of polyaryl phosphoric acid ester oligopolymer in " new development of expansion type retardant polyethylene " as Mi Renxi; US4966931 is disclosed to be selected for use or with cyanurotriamide modified ammonium polyphosphate, 1,3, the 5-pyrrolotriazine derivatives is formed expanding halide-free fire-retardant polypropylene flame redardant or polyethylene, permitted Jingjing at " phosphorus series non-halogen Study of Flame Retardant progress " (" colloid and polymkeric substance " 2005 (23): the application of ammonium polyphosphate in polyolefine is fire-retardant of 39) introducing in the literary composition, though show low cigarette with the polyethylene after these expansion type flame retardants processing, nontoxic, characteristics such as good flame retardation effect and certain refractory drip, but still exist such or such problem to some extent: desirable not enough as flame retardant effect, dripping property of refractory is still waiting to improve, the addition of fire retardant is bigger, because of the water absorbability of ammonium polyphosphate can produce detrimentally affect etc. to flame retardant properties.
The inventor is in order to solve the problem that expansion type flame retardant exists, once be to disclose a kind of halogen-free expanded flame-retardant polyethylene that contains organometallic complex in 200510022034.1 at application number, contained composite expansion type flame retardant and organometallic complex in this polyethylene simultaneously.Though because of containing autonomous synthetic pentaerythritol ester fire retardant in the composite expansion type flame retardant, thereby reduced ammonium polyphosphate, the addition of melamine phosphate, reduced the disadvantageous effect of ammonium polyphosphate water absorbability to the Flame Retardancy energy, improved the efficient of fire retardant, add the cooperative flame retardant effect that organometallic complex and composite expansion type flame retardant produce, not only improved the oxygen index flame retardant properties of polythene material greatly, also improved the vertical combustion that embodies dripping property of refractory greatly, having solved polythene material will reach in the comparatively difficult problem of high flame retardant rank electric and that building trade is required, but the processing step of synthesis of pentaerythritol ester fire retardant is many, preparation cycle is long, operation is comparatively complicated, is not suitable for suitability for industrialized production.
Three, summary of the invention
The objective of the invention is the problem at the prior art existence, a kind of organometallic complex and composite reaction extruded expansible flame-proof halogen-free polyvinyl of containing simultaneously is provided, the flame retardant amount that contains in this polyethylene is little, and dripping property of refractory is good.
Another object of the present invention provides the above-mentioned method that contains the halogen-free reaction extruded expansible flame-proof polythene of organometallic complex of preparation.
The halogen-free reaction extruded expansible flame-proof polythene that contains organometallic complex provided by the invention, as to reach the object of the invention, contain expanding fire retardant and organometallic complex in this polyethylene, it is characterized in that this expanding fire retardant is composite reaction extruded expansible flame-proof agent, each components contents is respectively by weight percentage: polyethylene 65～75%, composite reaction extruded expansible flame-proof agent 24.9～34.9%, organometallic complex 0.1～1%.
Wherein composite reaction extruded expansible flame-proof agent is by reaction extrusion type fire-retardant master granule and ammonium polyphosphate is composite forms, the content of each component in expansible flame-proof polythene is respectively by weight percentage: reaction extrusion type fire-retardant master granule 8.3～28%, ammonium polyphosphate 5～23.3%.And reaction extrusion type fire-retardant master granule is to be extruded through frit reaction by polyvalent alcohol, melamine compound and new LDPE (film grade) to form, wherein polyvalent alcohol and melamine compound were calculated in molar ratio as 1: 1～1: 2, and new LDPE (film grade) is 20% of fire-retardant master granule by weight percentage.
Polyvalent alcohol in the reaction extrusion type fire-retardant master granule is selected from any in tetramethylolmethane, dipentaerythritol, tripentaerythritol and the starch.Starch is any in W-Gum, tapioca (flour), the potato starch.
Melamine compound in the reaction extrusion type fire-retardant master granule is selected from any in melamine phosphate, trimeric cyanamide Diphosphonate and the trimeric cyanamide.
Wherein contained organometallic complex is by ' Synthesis that shows such as Hasan Mart by iron, cobalt, nickel, zinc or copper metal ion and methyl ethyl diketone, salicylaldoxime, salicylic aldehyde or salicylic aldehyde oligopolymer, characterization andthermal degradation of some copper (II), (Poly.Degrad.Stab.2004,83:255) method of Pi Luing prepares complexing and forms zinc (II) and cobalt (II) complexes witholigosalicylaldehyde '.
For reaching the method for the halogen-free reaction extruded expansible flame-proof polythene that contains organometallic complex that another purpose of the present invention provides, the processing step and the condition of this method are as follows:
(1) earlier polyvalent alcohol and melamine compound to be calculated in molar ratio as 1: 1～1: 2 mixed even for preparation feedback extrusion type fire-retardant master granule, add again and count 20% new LDPE (film grade) with the fire-retardant master granule gross weight and mix as vector resin, and this mixture put into twin screw extruder, 10～70 rev/mins of rotating speeds, extrude under temperature 160-300 ℃, pelletizing;
(2) composite mixing is carried out dried reaction extrusion type fire-retardant master granule and ammonium polyphosphate compositely in 8.3～28% and 5～23.3% the ratio of being respectively of the weight percent content in expansible flame-proof polythene, and mixes in high-speed mixer with 0.1～1% organometallic complex and 64～74% polyethylene;
(3) mixture after vacuum-drying will mix under 70～90 ℃ of temperature, dry 8～10 hours;
(4) melting mixing is put into twin screw extruder with dried mixture, extrudes at 150～190 ℃ of following melt blendings of temperature, and screw speed is controlled to be 50～100 rev/mins;
(5) the cooling and dicing melt blended material is extruded back naturally cooling pelletizing.
Compared with the prior art the present invention has the following advantages:
1. react the extrusion type fire-retardant master granule owing to containing in the composite reaction extruded expansible flame-proof agent of the present invention through autonomous synthetic, thereby generally compound flame retardant has better one-tenth charcoal effect, flame retarding efficiency is higher.
2. because reaction extrusion type fire-retardant master granule of the present invention, its preparation process is few, and is simple to operate, and the cycle is short, with low cost, thereby make the halogen-free reaction extruded expansible flame-proof polythene that contains organometallic complex provided by the invention be easier to large-scale industrial production.
3. because the organometallic complex that the present invention adds also can produce the cooperative flame retardant effect with the reaction extruded expansible flame-proof agent, thereby also can improve the oxygen index flame retardant properties of polythene material, solved polythene material and will reach in electric and high flame retardant rank that building trade the is required problem of difficulty comparatively.
Four, description of drawings
Accompanying drawing is the infared spectrum of the prepared reaction extrusion type fire-retardant master granule of the embodiment of the invention 2.
Five, embodiment
Provide embodiment below, so that the present invention is carried out concrete description.Need this explanation be that following enforcement only is used for that the present invention is further described, can not be interpreted as limiting the scope of the invention, the person skilled in the art in this field can do some nonessential improvement and adjustment to the present invention according to the invention described above content.
Embodiment 1,8,9,13
(1) earlier dipentaerythritol and melamine phosphate to be calculated in molar ratio as 1: 2 mixed even for preparation feedback extrusion type fire-retardant master granule, add again and count 20% new LDPE (film grade) with the fire-retardant master granule gross weight and mix as vector resin, and this mixture put into twin screw extruder, 40 rev/mins of rotating speeds, extrude under temperature 160-190 ℃, pelletizing, drying;
(2) the reaction extrusion type fire-retardant master granule behind the composite combination drying and the compound proportion of ammonium polyphosphate, and blended organometallic complex kind, ratio and poly addition see Table 1 respectively in high-speed mixer;
(3) mixture after drying will mix under 70 ℃ of temperature, dry 9 hours;
(4) melting mixing is put into twin screw extruder with dried mixture, and the temperature in each district of forcing machine is controlled to be 150 ℃, 160 ℃, 170 ℃, 170 ℃, 160 ℃, 150 ℃ following melt blendings respectively and extrudes, and screw speed is controlled to be 90 rev/mins;
(5) the cooling and dicing melt blended material is extruded back naturally cooling pelletizing.
Embodiment 2,5～7
(1) earlier tetramethylolmethane and melamine phosphate to be calculated in molar ratio as 1: 1.2 mixed even for preparation feedback extrusion type fire-retardant master granule, add again and count 20% new LDPE (film grade) with the fire-retardant master granule gross weight and mix as vector resin, and this mixture put into twin screw extruder, 50 rev/mins of rotating speeds, extrude under temperature 260-290 ℃, pelletizing, drying;
(2) composite mixing is respectively the listed ratio of table 1 with dried reaction extrusion type fire-retardant master granule and ammonium polyphosphate in the weight percent content in expansible flame-proof polythene and carries out compositely, and mixes in high-speed mixer with the organometallic complex and the polyethylene of the listed kind of table 1, ratio;
(3) mixture after drying will mix under 80 ℃ of temperature, dry 8 hours;
(4) melting mixing is put into twin screw extruder with dried mixture, and the temperature in each district of forcing machine is controlled to be 170 ℃, 180 ℃, 190 ℃, 190 ℃, 180 ℃, 170 ℃ following melt blendings respectively and extrudes, and screw speed is controlled to be 100 rev/mins;
(5) the cooling and dicing melt blended material is extruded back naturally cooling pelletizing.
Embodiment 3,10,12
(1) earlier dipentaerythritol and trimeric cyanamide to be calculated in molar ratio as 1: 1 mixed even for preparation feedback extrusion type fire-retardant master granule, add again and count 20% new LDPE (film grade) with the fire-retardant master granule gross weight and mix as vector resin, and this mixture put into twin screw extruder, 10 rev/mins of rotating speeds, extrude under temperature 270-300 ℃, pelletizing, drying;
(2) the reaction extrusion type fire-retardant master granule behind the composite combination drying and the compound proportion of ammonium polyphosphate, and blended organometallic complex kind, ratio and poly addition see Table 1 respectively in high-speed mixer;
(3) mixture after vacuum-drying will mix under 90 ℃ of temperature, dry 10 hours;
Following melting mixing and cooling and dicing step are controlled to be 50 rev/mins except that screw speed, and all the other are with embodiment 1, slightly.
Embodiment 4,11,14
(1) earlier tapioca (flour) and trimeric cyanamide Diphosphonate to be calculated in molar ratio as 1: 1.5 mixed even for preparation feedback extrusion type fire-retardant master granule, add again and count 20% new LDPE (film grade) with the fire-retardant master granule gross weight and mix as vector resin, and this mixture put into twin screw extruder, 70 rev/mins of rotating speeds, extrude under temperature 220-250 ℃, pelletizing, drying;
(2) the reaction extrusion type fire-retardant master granule behind the composite combination drying and the compound proportion of ammonium polyphosphate, and blended organometallic complex kind, ratio and poly addition see Table 1 respectively in high-speed mixer;
(3) mixture after vacuum-drying will mix in vacuum drying oven, under 70 ℃ of temperature, dry 8 hours;
Following melting mixing and cooling and dicing step are controlled to be 70 rev/mins except that screw speed, and all the other are with embodiment 1, slightly.
For whether the reaction extrusion type fire-retardant master granule of investigating the present invention's preparation esterification has taken place in melt extruding process, the inventor gets 1.5g with embodiment 2 prepared reaction extrusion type fire-retardant master granules, place Soxhlet extractor,, get resistates with refluxing toluene extracting 80 hours.Resistates is tested the gained infared spectrum see accompanying drawing.From accompanying drawing, 1086 and 1046cm
-1New absorption peak appears in the place, thereby confirms at extrusion esterification to have taken place.
Table 1
Annotate: AcAc is a methyl ethyl diketone; OSA is the oligopolymer salicylic aldehyde; SAO is a salicylaldoxime; SA is a salicylic aldehyde.
In addition, in order to investigate poly flame retardant properties provided by the invention, the inventor also will be wherein heating platen after embodiment 5, the 6 melting mixing obtained flame-retardant polyethylene vacuum-dryings, cut into behind the standard batten of 130 * 6.5 * 3mm and 130 * 13 * 3mm and pure polyethylene, the polyethylene that only added halogen-free expansion fire retardant and only added organometallic complex respectively carry out following contrast combustionproperty test:
1. limiting oxygen index determination
Press the program test of GB2406-93 specified standards with JF-3 type oxygen index instrument.
2. vertical combustion is measured
Press the program test of GB2408-96 specified standards with CZF-2 structural synthesis vertical combustion instrument.
Test result sees Table 2.
Table 2
| Description of materials | Oxygen index | Vertical combustion (3mm) |
| Pure PE | 17.8 | Do not pass through |
| PE/IFR | 27.4 | FV-0 |
| PE/CuSAO | 18.6 | Do not pass through |
| PE/IFR/CuSA | 28.3 | FV-0 |
| PE/IFR/CuSAO | 28.7 | FV-0 |
Annotate: PE is a polyethylene; IFR is composite reaction extruded expansible flame-proof agent; The fire retardant total addition level is 30wt%; The IFR addition is 29.8wt% among the PE/IFR; The CuSAO addition is 0.2wt% among the PE/CuSAO.
In order to investigate poly one-tenth charcoal provided by the invention, carry out the thermogravimetric test comparison with adding the polyethylene of composite reaction extruded expansible flame-proof agent and the polyethylene of polyvalent alcohol/trimeric cyanamide compounds/ammonium polyphosphate simple blend.Adopt the anti-Q500 type thermal analyzer of speeding to measure their thermostability in air atmosphere, heated perimeter is room temperature～600 ℃, and temperature rise rate is 10 ℃/min, and gas flow rate is 80ml/min, and amount of samples is about 7mg, and test result sees Table 3.
Table 3
Claims (4)
1, a kind of halogen-free reaction extruded expansible flame-proof polythene that contains organometallic complex, contain expanding fire retardant and organometallic complex in this polyethylene, it is characterized in that this expanding fire retardant is composite reaction extruded expansible flame-proof agent, each components contents is respectively by weight percentage: polyethylene 65～75%, composite reaction extruded expansible flame-proof agent 24.9～34.9%, organometallic complex 0.1～1%, wherein composite reaction extruded expansible flame-proof agent is by reaction extrusion type fire-retardant master granule and ammonium polyphosphate is composite forms, the content of each component in expansible flame-proof polythene is respectively by weight percentage: reaction extrusion type fire-retardant master granule 8.3～28%, ammonium polyphosphate 5～23.3%, and reaction extrusion type fire-retardant master granule is by polyvalent alcohol, melamine compound and new LDPE (film grade) are extruded through frit reaction and are formed, wherein polyvalent alcohol and melamine compound were calculated in molar ratio as 1: 1～1: 2, and new LDPE (film grade) is 20% of fire-retardant master granule by weight percentage; Organometallic complex is to be formed by iron, cobalt, nickel, zinc or copper metal ion and methyl ethyl diketone, salicylaldoxime, salicylic aldehyde or the complexing of salicylic aldehyde oligopolymer.
2, the halogen-free reaction extruded expansible flame-proof polythene that contains organometallic complex according to claim 1 is characterized in that reacting polyvalent alcohol in the extrusion type fire-retardant master granule and is selected from tetramethylolmethane, dipentaerythritol, tripentaerythritol and the starch any.
3, the halogen-free reaction extruded expansible flame-proof polythene that contains organometallic complex according to claim 1 and 2 is characterized in that reacting melamine compound in the extrusion type fire-retardant master granule and is selected from melamine phosphate, trimeric cyanamide Diphosphonate and the trimeric cyanamide any.
4, a kind of each described method that contains the halogen-free reaction extruded expansible flame-proof polythene of organometallic complex for preparing claim 1～3, the processing step and the condition of this method are as follows:
(1) earlier polyvalent alcohol and melamine compound to be calculated in molar ratio as 1: 1～1: 2 mixed even for preparation feedback extrusion type fire-retardant master granule, add again and count 20% new LDPE (film grade) with the fire-retardant master granule gross weight and mix as vector resin, and this mixture put into twin screw extruder, 10～70 rev/mins of rotating speeds, extrude under temperature 160-300 ℃, pelletizing;
(2) composite mixing is carried out dried reaction extrusion type fire-retardant master granule and ammonium polyphosphate compositely in 8.3～28% and 5～23.3% the ratio of being respectively of the weight percent content in expansible flame-proof polythene, and mixes in high-speed mixer with 0.1～1% organometallic complex and 65～75% polyethylene;
(3) mixture after vacuum-drying will mix under 70～90 ℃ of temperature, dry 8～10 hours;
(4) melting mixing is put into twin screw extruder with dried mixture, extrudes at 150～190 ℃ of following melt blendings of temperature, and screw speed is controlled to be 50～100 rev/mins;
(5) the cooling and dicing melt blended material is extruded back naturally cooling pelletizing.
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| CN102382253A (en) * | 2010-08-31 | 2012-03-21 | 比亚迪股份有限公司 | Organic complex and preparation method thereof as well as flame-retarding material and preparation method thereof |
| BE1023119B1 (en) * | 2015-05-22 | 2016-11-23 | Nmc Sa | Polymer compositions with improved fire resistance |
| CN108219253A (en) * | 2018-01-19 | 2018-06-29 | 广西大学 | A kind of expansion type flame retardant of fire retardant low-density polyethylene |
| CN112194833A (en) * | 2020-09-30 | 2021-01-08 | 淮安丹文化工科技有限公司 | Intumescent flame-retardant polyethylene containing organic metal complex and preparation method thereof |
| CN115109338B (en) * | 2022-07-08 | 2023-10-03 | 维希艾环保新材料(上海)股份有限公司 | Flame-retardant antirust film and preparation method thereof |
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| JPH1025379A (en) * | 1996-07-11 | 1998-01-27 | Mitsui Petrochem Ind Ltd | Vulcanizable flame retardant rubber composition |
| CN1335332A (en) * | 2001-08-28 | 2002-02-13 | 巴陵石化岳阳石油化工总厂 | Expanding fire retardant composition without halide for polyolefine |
| CN1506398A (en) * | 2002-12-12 | 2004-06-23 | 中国科学技术大学 | Prepn of halogen-free fireproof polypropylene cable material |
| CN1757667A (en) * | 2005-11-08 | 2006-04-12 | 四川大学 | Halogen-free expansion type retardant polyethylene contg. organic metal complex |
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Patent Citations (4)
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|---|---|---|---|---|
| JPH1025379A (en) * | 1996-07-11 | 1998-01-27 | Mitsui Petrochem Ind Ltd | Vulcanizable flame retardant rubber composition |
| CN1335332A (en) * | 2001-08-28 | 2002-02-13 | 巴陵石化岳阳石油化工总厂 | Expanding fire retardant composition without halide for polyolefine |
| CN1506398A (en) * | 2002-12-12 | 2004-06-23 | 中国科学技术大学 | Prepn of halogen-free fireproof polypropylene cable material |
| CN1757667A (en) * | 2005-11-08 | 2006-04-12 | 四川大学 | Halogen-free expansion type retardant polyethylene contg. organic metal complex |
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