CN105131449A - Expanded antiflaming environment-friendly polystyrene - Google Patents
Expanded antiflaming environment-friendly polystyrene Download PDFInfo
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- CN105131449A CN105131449A CN201510621076.0A CN201510621076A CN105131449A CN 105131449 A CN105131449 A CN 105131449A CN 201510621076 A CN201510621076 A CN 201510621076A CN 105131449 A CN105131449 A CN 105131449A
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Abstract
An expanded antiflaming environment-friendly polystyrene is prepared from polystyrene resin, expandable graphite, ammonium polyphosphate, surfactant, dispenser and antioxidant, wherein the expandable graphite and ammonium polyphosphate are mixed into a fire retardant mixture at high speed in proportion, then the surfactant is added in proportion, and then mixing is performed in a high-speed mixer to obtain compound fire retardant. The low-price expandable graphite and ammonium polyphosphate serve as a compound fire retardant, an antiflaming effect at a difficult-to-burn of a V-0 level is obtained by changing distribution ratios and blending and extruding respective components, antiflaming efficiency is further improved, smoke release amount is reduced, no halogen and no toxicity exist, no environment pollution is generated, and the expanded antiflaming environment-friendly polystyrene can be widely applied to materials of buildings and electronics.
Description
Technical field
The present invention relates to a kind of modified polystyrene, specifically a kind of by expansible black lead and ammonium polyphosphate mixing, form flame-retardant mixture, and then add the expandable flame retardant environment-friendly type polystyrene that tensio-active agent carries out high-speed mixing.
Background technology
Polystyrene (PS) is the resin be polymerized by vinylbenzene (SM), is one of five large synthetic resins that consumption is maximum in the world.Thermal conductivity is higher, better heat stability, its stretch and flexural strength the highest in general-purpose plastics, shaping convenient, cheap, have at building trade, packaging field, electronic enterprises etc. and apply comparatively widely.But plastics have a fatal weakness to be exactly inflammable, and polystyrene is no exception, vigorous combustion when meeting fire, adjoint has melting drip phenomenon, and has a large amount of heat release, and very easily initiation fire, seriously limits the scope of application of polystyrene.Along with the raising of living standard and the continuous progress of science and technology, p-poly-phenyl ethene carries out flame-retardant modifiedly becoming a megatrend.
The fire retardant kind of polystyrene is more, is generally divided into response type and addition type two class.Reactive flame retardant refers in the process of varying with temperature, and the group with fire retardation can be received on macromolecular chain, and the flame retardant resistance of matrix itself is improved.It has the advantages such as stability is good, flame retarding efficiency is high, persistence is good, but the process of synthesis fire retardant is complicated, also has the generation of by product.Therefore, prevailing or additive flame retardant in life is produced, because halogenated flame retardant has good flame retardant properties, therefore it occupies an leading position in additive flame retardant for a long time, as TDE, bromination alkane, brominated epoxy resin etc., but can release poisonous or mordant gas in fire-retardant process, smoke release is large, again brings harm to people.Many countries have proposed or have implemented the regulation limiting the use of or forbid halogenated flame retardant.Therefore, the use of environment friendly flame retardant receives the favor of people.
What rise is phosphorus system, nitrogen system, silicon system and expansion based flame retardant thereupon.Among these fire retardants, the widest of people is the fire retardant with synergistic effect.But the ratio between fire retardant decides again the power of synergistic effect, thus determine the quality of flame retardant of plastic performance.
As prior art CN103333423A discloses " a kind of Compound flame-retardant polystyrene composition and preparation method thereof ".Fire retardant described in it is expansible black lead, ammonium polyphosphate, calcium carbonate and become the mixture of charcoal promotor, by matrix, fire retardant and various auxiliary agent blending extrusion, can obtain the good polyphenylacetylene combination of flame retardant properties, its limiting oxygen index(LOI) reaches about 30%.But the synergistic effect do not discussed between expansible black lead and ammonium polyphosphate and proportionlity.
As prior art CN100419028 discloses " having fire-retardant and polymer-based carbon functional composite material that is conducting function concurrently ".Described fire retardant is expansible black lead and auxiliary flame retardant (triethyl phosphate, red phosphorus and ammonium polyphosphate), simply discuss the ratio between expansible black lead and auxiliary flame retardant, but do not illustrate the proportionlity between expansible black lead and ammonium polyphosphate.
As prior art CN103467807A discloses " a kind of halogen-free flameproof PE water service pipe ".Which use fire retardant expansible black lead, ammonium polyphosphate, magnesium hydroxide, PETO etc.Although obtain the good PE water service pipe of flame retardant properties, also specifically do not set forth ratio and synergistic effect between expansible black lead and ammonium polyphosphate.
Summary of the invention
The particular problem that the present invention will solve inquires into ratio between expansible black lead and ammonium polyphosphate and both synergistic effects, obtains the good a kind of expandable flame retardant environment-friendly type polystyrene of flame retardant properties simultaneously.
In order to solve the problem, the technical solution used in the present invention is as follows.
A kind of expandable flame retardant environment-friendly type polystyrene, composition and the content thereof of polystyrene described in it by mass parts are: the polystyrene resin of 60 ~ 80 parts; The expansible black lead of 5 ~ 25 parts; The ammonium polyphosphate of 5 ~ 25 parts; The tensio-active agent of 2 ~ 3 parts; The dispersion agent of 3 ~ 5 parts; The oxidation inhibitor of 2 ~ 3 parts, wherein, expansible black lead and ammonium polyphosphate are fire retardants, and both mass ratioes are 1: 3 ~ 4: 1.
Further, the composition of described polystyrene and content thereof are polystyrene resin, 22.5 parts of expansible black leads, 7.5 parts of ammonium polyphosphates of 70 parts by mass parts, 2.5 parts of tensio-active agents, 4 dispersion agents and 3 oxidation inhibitor; Wherein, expansible black lead and ammonium polyphosphate are fire retardants, and both composite mass ratioes are 3: 1.
In technique scheme, described fire retardant carries out composite making by expansible black lead and ammonium polyphosphate, preparation method is 20 ~ 40 by the mass parts total addition level of expansible black lead and ammonium polyphosphate, and then the tensio-active agent of 2 ~ 3 parts is added by mass parts, be placed in high-speed mixer to mix, obtain compound flame retardant.Described expansible black lead granularity is 50 ~ 100 orders, and expansion multiplying power is 300 ~ 400ml/g, and initial expansion temperature is 150 ~ 200 DEG C; Described ammonium polyphosphate is II type ammonium polyphosphate, polymerization degree n >=1000, and granularity is 50 ~ 100 orders; Described tensio-active agent is the one in silane resin acceptor kh-550 and KH-570; Described dispersion agent is the one in stearic acid, whiteruss, barium stearate; Described oxidation inhibitor is the one in sulfur-bearing oxidation inhibitor, polyphenol antioxidant 1010 and polyphenol antioxidant 168.
Realize the technical scheme of a kind of expandable flame retardant environment-friendly type polystyrene that the invention described above provides, expansion based flame retardant graphite and phosphorus flame retardant ammonium polyphosphate is adopted to carry out composite, discussion compound proportion is between the two on the impact of its synergistic effect, and obtain best formula, further increase flame retarding efficiency and thermostability.
In technique scheme of the present invention, add expansible black lead and ammonium polyphosphate two kinds of fire retardants, wherein expansible black lead heat expanding volume becomes large, increases the spacing of matrix and thermal source; Ammonium polyphosphate heat is decomposed into NH
3, H
2the non-flammable gases such as O, reduce further matrix ambient oxygen concentration, and the cohesiveness such as polyphosphoric acid, metaphosphoric acid material can be produced, well dilator can be bonded together, generate fine and close layer of charcoal, serve the effect that gas phase is fire-retardant and condensed phase is fire-retardant, and then polystyrene thermostability is improved, reach good flame retardant effect.
In technique scheme of the present invention, when carrying out composite with suitable ratio, it is V-0 rank that its limiting oxygen index(LOI) can reach more than 30%, UL-94; Smoke release reduces, without melting drip phenomenon; The layer of charcoal produced is thick and closely knit, and these are all the effects due to synergistic effect.And in whole fire-retardant process, not having poisonous gas to produce, Heat liberation unit is little, environmentally friendly, and cheap.In fields such as building, automobile, electronic apparatus and packagings, there is very large development prospect.
Accompanying drawing explanation
Fig. 1 be the present invention test in polystyrene, add equal parts (30 parts) different ratios fire retardant after measured limiting oxygen index(LOI) figure.
Embodiment
Below the specific embodiment of the present invention is made further instructions, but the present invention is not limited to these embodiments.
Embodiment 1
Implement a kind of technical scheme of expandable flame retardant environment-friendly type polystyrene, composition and the content thereof of polystyrene described in it by mass parts are: polystyrene (PS) resin of 70 parts; The expansible black lead (EG) of 24 parts; The ammonium polyphosphate (APP) of 6 parts; The tensio-active agent of 2.5 parts; The dispersion agent of 4 parts; The oxidation inhibitor of 3 parts.
Wherein, the mass ratio between expansible black lead and ammonium polyphosphate is 4: 1.
Expansible black lead, ammonium polyphosphate and tensio-active agent KH-550 in above-mentioned formula are mixed 10 minutes with 800r/min in high-speed mixer, takes out and dry at 80 DEG C in an oven, obtain compound flame retardant; Again composite good fire retardant and PS, dispersant liq paraffin, antioxidant 1010 are placed in high-speed mixer and mix 15 minutes with 800r/min again, then extruding pelletization in twin screw extruder, each section of temperature of forcing machine is respectively: 190 DEG C, an interval; Two 205 DEG C, intervals; Three 220 DEG C, intervals; Four 215 DEG C, intervals; Head 210 DEG C; After detect through injection moulding machine injection moulding batten, according to the limiting oxygen index(LOI) performance of GB/T2406.2-2009 test bars, according to the horizontal vertical combustionproperty of GB/T2408-2008 test bars.
The oxygen index value of obtained polystyrene based composites is 30.2%, and the flame retardant effect through UL-94 standard testing can reach V-0 rank and not have melting drip phenomenon, and there is synergistic effect between the two.
Embodiment 2
Implement a kind of technical scheme of expandable flame retardant environment-friendly type polystyrene, the composition of polystyrene described in it and content thereof are polystyrene (PS) resins of 70 parts by mass parts; The expansible black lead (EG) of 22.5 parts; The ammonium polyphosphate (APP) of 7.5 parts; The tensio-active agent of 2.5 parts; The dispersion agent of 4 parts; The oxidation inhibitor of 3 parts.
Wherein, the mass ratio between expansible black lead and ammonium polyphosphate is 3: 1.
Above-mentioned formula is shaping according to the complete processing in embodiment 1, obtained environmental-protection flame-retardant polystyrene based composites.
The oxygen index value of obtained polystyrene based composites is 31.8%, and the flame retardant effect through UL-94 standard testing can reach V-0 rank and not have melting drip phenomenon.The synergistic effect highly significant of known EG and the APP under this ratio of comparative example 1.
Above-described embodiment uses halogen-free environment-friendlyflame flame retardant expansible black lead and ammonium polyphosphate, not only environmentally friendly pollution-free, and only used two kinds of composite flame retardant propertiess of product that just can make of fire retardant and be greatly improved; Obtain the optimum compound proportion example between two kinds of fire retardants by experiment, achieving unforeseeable synergistic effect, is fail in prior art to reach.
Embodiment 3
Implement a kind of technical scheme of expandable flame retardant environment-friendly type polystyrene, composition and the content thereof of polystyrene described in it by mass parts are: polystyrene (PS) resin of 70 parts; The expansible black lead (EG) of 20 parts; The ammonium polyphosphate (APP) of 10 parts; The tensio-active agent of 2.5 parts; The dispersion agent of 4 parts; The oxidation inhibitor of 3 parts.
Wherein, the mass ratio between expansible black lead and ammonium polyphosphate is 2: 1.
Above-mentioned formula is shaping according to the complete processing in embodiment 1, obtained environmental-protection flame-retardant polystyrene based composites.
The oxygen index value of obtained polystyrene based composites is 30.6%, and the flame retardant effect through UL-94 standard testing can reach V-0 rank and not have melting drip phenomenon.Comparative example 1 and embodiment 2 known under this formula EG and APP have synergistic effect effect, but relatively its synergistic effect of embodiment 2 is more weak.
Embodiment 4
Implement a kind of technical scheme of expandable flame retardant environment-friendly type polystyrene, composition and the content thereof of polystyrene described in it by mass parts are: polystyrene (PS) resin of 70 parts; The expansible black lead (EG) of 15 parts; The ammonium polyphosphate (APP) of 15 parts; The tensio-active agent of 2.5 parts; The dispersion agent of 4 parts; The oxidation inhibitor of 3 parts.
Wherein, the mass ratio between expansible black lead and ammonium polyphosphate is 1: 1.
Above-mentioned formula is shaping according to the complete processing in embodiment 1, obtained environmental-protection flame-retardant polystyrene based composites.
The oxygen index value of obtained polystyrene based composites is 28.2%, and the flame retardant effect through UL-94 standard testing can reach V-0 rank and not have melting drip phenomenon.Comparative example 1 and the known synergistic effect under this formula between EG and APP of embodiment 2 not remarkable.
Embodiment 5
Implement a kind of technical scheme of expandable flame retardant environment-friendly type polystyrene, composition and the content thereof of polystyrene described in it by mass parts are: polystyrene (PS) resin of 70 parts; The expansible black lead (EG) of 10 parts; The ammonium polyphosphate (APP) of 20 parts; The tensio-active agent of 2.5 parts; The dispersion agent of 4 parts; The oxidation inhibitor of 3 parts.
Mass ratio wherein between expansible black lead and ammonium polyphosphate is 1: 2.
Above-mentioned formula is shaping according to the complete processing in embodiment 1, obtained environmental-protection flame-retardant polystyrene based composites.
The oxygen index value of obtained polystyrene based composites only has 26.0%, and the flame retardant effect through UL-94 standard testing can reach V-0 rank and not have melting drip phenomenon.Comparative example 1 and embodiment 2 is known there is not synergistic effect between EG and APP under this formula.
Embodiment 6
Implement a kind of technical scheme of expandable flame retardant environment-friendly type polystyrene, composition and the content thereof of polystyrene described in it by mass parts are: polystyrene (PS) resin of 70 parts; The expansible black lead (EG) of 7.5 parts; The ammonium polyphosphate (APP) of 22.5 parts; The tensio-active agent of 2.5 parts; The dispersion agent of 4 parts; The oxidation inhibitor of 3 parts.
Wherein, the mass ratio between expansible black lead and ammonium polyphosphate is 1: 3.
Above-mentioned formula is shaping according to the complete processing in embodiment 1, obtained environmental-protection flame-retardant polystyrene based composites.
The oxygen index value of obtained polystyrene based composites is only 24.6%, and the flame retardant effect through UL-94 standard testing reaches V-0 rank and do not have melting drip phenomenon.Comparative example 1 and embodiment 2 known under this formula EG and APP there is not synergistic effect.
Claims (8)
1. an expandable flame retardant environment-friendly type polystyrene, composition and the content thereof of polystyrene described in it by mass parts are: the polystyrene resin of 60 ~ 80 parts; The expansible black lead of 5 ~ 25 parts; The ammonium polyphosphate of 5 ~ 25 parts; The tensio-active agent of 2 ~ 3 parts; The dispersion agent of 3 ~ 5 parts; The oxidation inhibitor of 2 ~ 3 parts; Wherein, expansible black lead and ammonium polyphosphate are fire retardants, and both mass ratioes are 1: 3 ~ 4: 1.
2. expandable flame retardant environment-friendly type polystyrene as claimed in claim 1, described polystyrene further forms and content is polystyrene resin, 22.5 parts of expansible black leads, 7.5 parts of ammonium polyphosphates of 70 parts by mass parts, 2.5 parts of tensio-active agents, 4 dispersion agents and 3 oxidation inhibitor, wherein, expansible black lead and ammonium polyphosphate are fire retardants, and both composite mass ratioes are 3: 1.
3. expandable flame retardant environment-friendly type polystyrene as claimed in claim 1 or 2, described fire retardant carries out composite making by expansible black lead and ammonium polyphosphate, preparation method is 20 ~ 40 by the mass parts total addition level of expansible black lead and ammonium polyphosphate, and then the tensio-active agent of 2 ~ 3 parts is added by mass parts, be placed in high-speed mixer to mix, obtain compound flame retardant.
4. expandable flame retardant environment-friendly type polystyrene as claimed in claim 1 or 2, described expansible black lead granularity is 50 ~ 100 orders, and expansion multiplying power is 300 ~ 400ml/g, and initial expansion temperature is 150 ~ 200 DEG C.
5. expandable flame retardant environment-friendly type polystyrene as claimed in claim 1 or 2, described ammonium polyphosphate is II type ammonium polyphosphate, polymerization degree n >=1000, and granularity is 50 ~ 100 orders.
6. expandable flame retardant environment-friendly type polystyrene as claimed in claim 1 or 2, described tensio-active agent is the one in silane resin acceptor kh-550 and KH-570.
7. expandable flame retardant environment-friendly type polystyrene as claimed in claim 1 or 2, described dispersion agent is the one in stearic acid, whiteruss, barium stearate.
8. expandable flame retardant environment-friendly type polystyrene as claimed in claim 1 or 2, described oxidation inhibitor is the one in sulfur-bearing oxidation inhibitor, polyphenol antioxidant 1010 and polyphenol antioxidant 168.
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| CN108178883A (en) * | 2018-02-01 | 2018-06-19 | 哈尔滨理工大学 | A kind of halogen-free flameproof polystyrene of fire retardant selective distribution and preparation method thereof |
| CN108841043A (en) * | 2018-07-13 | 2018-11-20 | 广州广化塑料管道有限公司 | Pvc material nanosizing coating modification composite flame-retardant agent and preparation method thereof |
| CN109233064A (en) * | 2018-09-28 | 2019-01-18 | 杭州通宇实业有限公司 | A kind of composite polyethylene solid wall pipe and preparation method thereof |
| CN110330262A (en) * | 2019-07-18 | 2019-10-15 | 成都硕屋科技有限公司 | A kind of fire proofing material of high-strength fireproof and preparation method thereof |
| CN115746444A (en) * | 2022-11-29 | 2023-03-07 | 哈尔滨理工大学 | Halogen-free synergistic flame-retardant polyolefin cable sheath material and preparation method thereof |
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Cited By (5)
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| CN110330262A (en) * | 2019-07-18 | 2019-10-15 | 成都硕屋科技有限公司 | A kind of fire proofing material of high-strength fireproof and preparation method thereof |
| CN115746444A (en) * | 2022-11-29 | 2023-03-07 | 哈尔滨理工大学 | Halogen-free synergistic flame-retardant polyolefin cable sheath material and preparation method thereof |
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