CN101402758B - Non-halogen flame-proof polyvinyl composite and method of producing the same - Google Patents
Non-halogen flame-proof polyvinyl composite and method of producing the same Download PDFInfo
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- CN101402758B CN101402758B CN2008102261833A CN200810226183A CN101402758B CN 101402758 B CN101402758 B CN 101402758B CN 2008102261833 A CN2008102261833 A CN 2008102261833A CN 200810226183 A CN200810226183 A CN 200810226183A CN 101402758 B CN101402758 B CN 101402758B
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Abstract
The invention provides a non-halogen flame-retardant polyethylene composition and a preparation method thereof, which relates to the field of the flame-retardance modification of resins. The composition contains 100pbw (parts by weight) of polyethylene resin, 35 parts to 55 parts of non-halogen fire retardants and 8 parts to 20 parts of flame-retardant synergists. The non-halogen fire retardant is compounded by ammonium polyphosphate, melamine cyan urate and hydroxyphenol (diphenyl phosphate), wherein, the total amount of the ammonium polyphosphate and the melamine cyan urate accounts for 32pbw to 50pbw, and the weight ratio of the ammonium polyphosphate and the hydroxyphenol is 1:1 to 4:1; the hydroxyphenol (Diphenyl phosphate) accounts for 3pbw to 5pbw. The flame-retardant synergist can be graft copolymer of vinyl acetic ester and maleic anhydride, or graft copolymer of maleic anhydride and ethylene/octane, or ethylene/octane copolymer or polyphenyl ether. All components are mixed according to the parts by weight and then melted to obtain the polyethylene composition. Under the condition that FV-0 grade is ensured to reached, the polyethylene composition has high flame-retardant efficiency, generates no molten drop, creates small volume of smoke during burning and has good comprehensive mechanical properties.
Description
Technical field:
The present invention relates to a kind of flame-proof polyvinyl composite, further, relate to a kind of flame-proof polyethylene resin that utilizes the halogen-free flame retardants modification and preparation method thereof.
Background technology:
The polyethylene (PE) of using wide model is one of the world's five big general-purpose plastics, has light weight, nontoxic, and machine-shaping is convenient, and cheap, advantages such as resistance to chemical attack are widely used.But poly limiting oxygen index(LOI) very low (being about 17.5), flame retardant properties is poor, meets heat or very easily burning in discharge process, and produces a large amount of smog during burning, and the molten drop phenomenon is arranged.Therefore poly application has been subjected to very big restriction, need carry out certain flame-retardant modified to it.
Be used for poly fire-retardant means at present and be still to add halogenated flame retardant, the flame retardant effect of halogenated flame retardant in the fire retardant of all polymorphic types is best.But, human body there is bigger harm because its amount of being fuming can produce poisonous, corrosive gases greatly and in the combustion processes.Halogen-free flame retardants is extensive day by day with its low-smoke and the utilization of avirulent advantage, and the trend that replaces halogenated flame retardant is arranged.The halogen-free flameproof great majority are to add inorganic combustion inhibitor, expansion type flame retardant etc. at present.Inorganic combustion inhibitor commonly used mainly contains aluminium hydroxide, magnesium hydroxide, red phosphorus etc.Mineral-type fire retardant addition is big, and their polarity is big, and is bad with the consistency of material, and serious to the mechanical property damage of material, flame retardant effect is not obvious, the cost height.Though the flame retarding efficiency of red phosphorus is high, but neither well select because of the problem of color and consistency.Compare with the mineral-type fire retardant, the consistency of expansion type flame retardant and material is better, and the addition of requirement is little, and flame retardant effect is obvious, and the defective that can press down cigarette and overcome many molten drops when burning.Expansion type flame retardant generally is made up of three parts: (1) acid source (dewatering agent): be generally mineral acid or can original position generate sour salt when the burning heating, as phosphoric acid, phosphate amine salt etc.; (2) charcoal source (char-forming agent): be generally the polyol compound that is rich in carbon, as starch, tetramethylolmethane etc.; (3) source of the gas (whipping agent): be generally nitrogenous many carbon compounds, as urea, trimeric cyanamide, polymeric amide etc.Development at present is comparatively ripe, most widely used expansion type flame retardant mainly is to be main raw material with ammonium polyphosphate (APP)/tetramethylolmethane (PER), its fire retardant mechanism is: when expansion type flame retardant is heated, form uniform expansion charcoal layer at material surface, play heat insulation, oxygen barrier at condensed phase, press down cigarette, anti-ly melt the effect of dripping, thereby play fire retardation.Present this widely used expanding fire retardant (IFR), relatively poor to the especially poly flame retarding efficiency of polyolefine, the subject matter that APP wherein exists in being applied to polyvinyl resin is that polyethylene itself is difficult for forming the charcoal layer, influences the flame retardant effect of expansion type flame retardant.The main fire retardation of APP is to be to form condensed phase, and its flame retardant effect depends on that polyphosphoric acid is dehydrated into the integrity of the thickness and the charcoal layer of the speed of charcoal, charcoal layer.Phenomenon during the polyethylene burning shows, APP among the existing IFR has played the effect of dehydration carbonization really in polyethylene incendiary process, but owing to become the speed of charcoal insufficient strength height and charcoal layer fast inadequately, the charcoal layer discontinuous, thereby cause formed knot charcoal along with poly molten drop drips, can not play the effect of isolated heat and oxygen, promptly not have the crucial fire-retardant effect of condensed phase.This illustrates that also polyethylene itself is not a kind of good carbon source, must add other material and do the charcoal source.In addition APP processing characteristics, water repelling property, with aspect poor-performing such as organism consistency.
So develop more fire-retardant synergistic series, multiple fire retardant, fire-retardant means synergistic are used, can remedy the defective of single flame resistant method, realize flame retardant effect preferably and can keep original performance of material simultaneously preferably.
Summary of the invention:
The inventor is according to expansion type flame-retarding system basal component " three sources " condensed phase thermolysis esterification, ester decomposition, aromatize and expand into the process of charcoal, adopt a kind of halogen-free expansion type flame-proof synergistic series, add the cooperative flame retardant component as becoming charcoal promotor, the thermolysis of quickening expansion type flame-retarding system is crosslinked, one-tenth charcoal speed, increase the residual carbon amount in fire-retardant, improve charcoal layer quality, the purpose that realize improving flame retarding efficiency, reduces the fire retardant addition also plays the effect that makes blend composition toughness reinforcing simultaneously.Thereby the original performance that keeps polythene material preferably, the effect that makes polyvinyl resin reach fire-retardant, press down cigarette, anti-molten drop.
Main purpose of the present invention provides a kind of non-halogen flame-proof polyvinyl composite, has good flame retardancy on the basis that keeps the original performance of polyvinyl resin.
Another object of the present invention provides the preparation method of described non-halogen flame-proof polyvinyl composite.
A kind of non-halogen flame-proof polyvinyl composite of the present invention, it includes the following component of blend: polyvinyl resin, 100 parts by weight; Halogen-free flame retardants 35～55 parts by weight are preferably 38～50 parts by weight; Flame retardancy synergists 8～20 parts by weight are preferably 10～18 parts by weight.
Polyvinyl resin in the above-described non-halogen flame-proof polyvinyl composite of the present invention is existing polyethylene kind in the prior art, comprises new LDPE (film grade) (LDPE), linear low density polyethylene (LLDPE), high density polyethylene(HDPE) (HDPE) etc.
Above-described halogen-free flame retardants is by (RDP) the composite mixture of forming of poly-sour ammonium (APP), melamine cyanurate (MC) and Resorcinol two (diphenyl phosphoesters).Wherein total consumption of APP and MC is preferably 36～46 parts at 32～50 parts; The weight ratio of APP and MC is just to play effective expandable flame retardant effect in 1: 1～4: 1, weight ratio is preferably 1: 1～and 3: 1.RDP is a buttery liquid, and consumption is difficult for too much, and consumption is preferably 2～4 parts at 3～5 parts.
Above-described flame retardancy synergists is selected from least a in the material: maleic anhydride grafted ethene-vinyl acetate copolymer (EVA-g-MAH), maleic anhydride grafted ethene-octene copolymer (POE-g-MAH), ethylene-octene copolymer (POE), poly-2,6-dimethyl-1, the 4-phenylate (is a polyphenylene oxide, PPO).
The subject matter that exists in being applied to polyvinyl resin of APP in the expansion type flame retardant is that polyethylene itself is difficult for forming the charcoal layer as previously mentioned, influence the flame retardant effect of expansion type flame retardant, in addition APP processing characteristics, water repelling property, with aspect poor-performing such as organism compatibility performance.In polyethylene, become problems such as charcoal is bad in order to solve APP, the present invention adopts the expansion type flame retardant of the Halogen of APP, MC and RDP composition that PE is carried out the halogen-free flameproof modification, adopt the short char-forming agent as expansion type flame retardant such as flame retardancy synergists PPO simultaneously, improve into the charcoal effect.
In this halogen-free flameproof intumescent system, APP and MC exist as the acid source and the source of the gas of expanding fire retardant respectively.While is as the RDP of acid source, its good thermal stability reacts in the thermal decomposition process of cooperative flame retardant polyethylene system, discharges aqueous vapor, and overcome the defective of conventional expanded type flame-retardant system (APP-PER) thermotolerance, wet poor stability, effectively improve flame retardant effect.The use of RDP has promoted the formation of expansion charcoal layer, has reduced the consumption of fire retardant, the flame retardant properties of synergy polyvinyl resin.
Above listed elastomerics and described other component blend such as PPO as flame retardancy synergists, especially the tough effect that can play the interface increase-volume, not only the mechanical property of this expandable flame retardant system there is to a certain degree improvement, simultaneously because the flame retardant resistance of PPO itself is fine, flame retardant properties to this system also has promoter action, from and can reduce the consumption of fire retardant relatively.Flame retardancy synergists such as the above PPO can also as carbon source and APP, the MC of expansion type flame retardant and RDP is collaborative be used in addition.When material combustion, because elastomericss such as POE, PPO are as the carbon source of expanding fire retardant, under lower temperature, acid source APP, RDP produce the acid that can be used as dewatering agent.Under the high-temperature, under the effect of acid, PPO is dehydrogenated to charcoal slightly, and water vapour that produces in the reaction process and the non-flammable gases of emitting as the MC decomposition of source of the gas make the system that is in molten state expanded foamed.When reacting approaching finishing, system gel and curing form porous foam charcoal layer at last.Help to form early fine and close expansion charcoal layer like this, effect of heat insulation with improve every the gas-tight property of matter, improve flame retarding efficiency.
In order to make Zero halogen flame resistance polyethylene resin combination of the present invention possess antistatic property, also including in polyvinyl resin in the polyethylene composition of the present invention is 100 parts by weight, 2.0～5.0 weight parts, is preferably the static inhibitor of 3.0～4.0 weight parts.Consider and the fire retardant coupling that described static inhibitor is a non-ionic antistatic agent.It is preferably a kind of in the following static inhibitor: mainly contain the static inhibitor of the ethylene oxide adduct of lipid acid, mainly contain the static inhibitor of polyhydric alcohol fatty acid ester, mainly contain the static inhibitor of hydroxyethyl aliphatic amide; Preferred static inhibitor is that main component is the static inhibitor of the ethylene oxide adduct of lipid acid.Other contained components of above-mentioned static inhibitor are common added Synergist S-421 95 etc. in the static inhibitor preparation.
In order to make polyolefine resin composition of the present invention possess weather resistance, flame-proof polyvinyl composite of the present invention, can also contain in polyvinyl resin is 100 parts by weight, 0.1～0.4 parts by weight, is preferably the composite antioxidant of 0.1～0.3 parts by weight.Composite antioxidant is the mixture of Hinered phenols antioxidant and phosphite ester kind antioxidant or is the mixture of Hinered phenols antioxidant and monothioester kind antioxidant, wherein the weight ratio of Hinered phenols antioxidant and phosphite ester kind antioxidant or Hinered phenols antioxidant and monothioester kind antioxidant is 1: 1～2: 1, is preferably 1: 1～1.5: 1.
Hinered phenols antioxidant is preferably four [β-(3,5-di-t-butyl-4-hydroxy phenyl) propionic acid] pentaerythritol ester in the above-described polyethylene composition; Phosphite ester kind antioxidant is preferably (2,4-di-tert-butyl-phenyl) tris phosphite or two (2,4-di-tert-butyl-phenyl) pentaerythritol diphosphites; The monothioester kind antioxidant is preferably Tyox B.
In order to improve the blended avidity of fire retardant and flame retardancy synergists and polyvinyl resin system, improve the mechanical property of its flame-retardant modified back material.Non-halogen flame-proof polyvinyl composite of the present invention wherein also can include coupling agent, and described coupling agent is a titanate coupling agent.Titanate coupling agent described in the present invention is preferably sec.-propyl three (different perester radical) titanic acid ester, sec.-propyl three (dioctyl phosphoric acid ester acyl group) titanic acid ester, sec.-propyl three (dioctylphyrophosphoric acid ester acyl group) titanic acid ester.Described coupling agent is 3～5%wt of halogen-free flame retardants gross weight.
In addition, flame-proof polyvinyl composite of the present invention also includes common agent commonly used in other polyvinyl resin processing technologies, as coupling agent thinner (as white oil), compatilizer etc.It adds consumption and is common consumption.
The preparation method of non-halogen flame-proof polyvinyl composite of the present invention comprises described each component by described amount thorough mixing, obtains described non-halogen flame-proof polyvinyl composite through the melt-mixing method of common polyvinyl resin.
Specifically can be: above-mentioned each component is joined mixing equipment by described consumption, in homogenizer, carrying out thorough mixing under the mixing condition usually.Wherein the homogenizer rotating speed is generally 800～1000r/min.With said mixture through the twin screw extruder melt blending, extrude, granulation, obtain flame-proof polyethylene resin combination of the present invention.Wherein the various operating parameterss of twin screw extruder are the operating parameters that common polyvinyl resin adds man-hour during melt blending.As: the screw rod velocity of rotation is common velocity of rotation, can be preferably 900～1200r/min; Main spout feed rate can be preferably 300～600r/min; The processing temperature of melt blending is the common blending temperature of polyvinyl resin, generally can be 150～170 ℃.Material through melt blending extrude, granulation, obtain non-halogen flame-proof polyvinyl composite of the present invention.
In order to obtain the better mixing effect, the mixing of each component can be divided into some steps, promptly preferably include the preparation method of following steps:
1. with described other component except that fire retardant, comprise polyvinyl resin, flame retardancy synergists, coupling agent, perhaps also have components such as thinner, be fully mixed in high-speed mixer by described amount and mix, coupling agent fully is coated on polymer surfaces thus.Usually can select high mixer rotating speed 800～1000r/min for use, mix 8 minutes～12 minutes;
2. halogen-free flame retardants is joined in the above-mentioned mixture that mixes, in high-speed mixer, be fully mixed to and mix.Usually can select high mixer rotating speed 800～1000r/min for use, mix 5～7 fens clock times.For reaching the better mixing effect, can be more preferably under being 65～75 ℃ condition, temperature mixes, and fire retardant and polymkeric substance carry out can cooling off behind the thorough mixing;
3. above-mentioned gained mixture is obtained described non-halogen flame-proof polyvinyl composite through melt blending.
In addition in order to prevent humidity, in order to avoid influence flame retardant effect, among the non-halogen flame-proof polyvinyl composite preparation method of the present invention, preferably with halogen-free flame retardants with before described other components are mixed in 95～100 ℃ of bakings 2～3 hours down.
Non-halogen flame-proof polyvinyl composite of the present invention compared with the prior art, advantage is that the fire retardant addition is few, the flame retarding efficiency height, it is little that burning does not produce the molten drop and the amount of being fuming, comprehensive mechanical property is good guaranteeing to reach under the condition of FV-0 level (GB/T4609-93), and has antistatic, ageing resistance.
Embodiment:
Below in conjunction with embodiment, further specify the present invention.
Raw material:
Polyvinyl resin:
1.
New LDPE (film grade)(LDPE), Beijing Yanshan Petro-Chemical Industry Corporation chemical plant produces, the trade mark: AC-100, density 0.9225g/cm
3, melt flow rate (MFR) 2.0g/10min, granular.
2.
Ammonium polyphosphate(APP): the fire-retardant chemical industry of Hangzhou Jie Ersi company limited produces, and the trade mark: JLS-APP101, its phosphorus content are 28～30%, and nitrogen content is 17～20%.
3.
Melamine cyanurate(MC): Hangzhou JLS Flame Retardants Chemical Co., Ltd. produces, the trade mark: JLS-MC25.
4.
Resorcinol (bis phosphoric acid diphenyl ester)(RDP): U.S. rising sun Rui Da company produces, the trade mark: FyrolflexRDP.
5.
Maleic anhydride grafted ethene-vinyl acetate copolymer(EVA-g-MAH): Nanjing moral crust chemical industry company limited produces the trade mark: EVA-G-1, percentage of grafting 1.10%, melt flow rate (MFR) 1-15g/10min, VA content 28%.
6.
Maleic anhydride grafted ethene-octene copolymer(POE-g-MAH): Nanjing moral crust chemical industry company limited produces, and the trade mark is: POE-G-1, percentage of grafting are 0.9%, and melt flow rate (MFR) is 0.5～2.5g/10min.
7.
Polyphenylene oxide(PPO): chemical name is poly-2,6-dimethyl-1,4-phenylate, and U.S. GE company produces the trade mark: NP190X-111.
8.
Antioxidant 1010: four [β-(3,5-di-t-butyl-4-hydroxy phenyl) propionic acid] pentaerythritol ester, Jia Zhuo company in Shanghai produces.
9.
Oxidation inhibitor 168: (2, the 4-di-tert-butyl-phenyl) tris phosphite, Jia Zhuo company in Shanghai produces.
10.
Static inhibitor: main ingredient is the non-ionic antistatic agent of the ethylene oxide adduct of lipid acid, and Beijing Chemical Research Institute branch produces, trade mark ASA-51.
Testing method:
Mechanics Performance Testing: the test of mechanical properties such as according to GB/T1040-92, GB/T9341-2000, GB/T1043-93 stretch respectively, bending, impact.
The combustionproperty test: measure according to the limiting oxygen index determination standard of GB/T2406-1993 and the vertical combustion method of GB/T4609-1996.
The preparation process of embodiment and Comparative Examples:
With polyvinyl resin, halogen-free flame retardants (is ammonium polyphosphate (APP), melamine cyanurate (MC), two (diphenyl phosphoester) mixtures (RDP) of Resorcinol), flame retardancy synergists (is ethylene vinyl acetate grafted maleic anhydride (EVA-g-MAH), maleic anhydride grafted ethene-octene copolymer (POE-g-MAH), a kind of in the polyphenylene oxide (PPO)), static inhibitor (ASA-51), composite antioxidant (mixture of antioxidant 1010 and oxidation inhibitor 168), each component of titanate coupling agent (NDZ101) takes by weighing according to quantity.At first, comprise components such as polyvinyl resin, flame retardancy synergists, coupling agent, be fully mixed in high-speed mixer by described amount and mix that high mixer rotating speed 900r/min mixed 10 minutes with described other component except that fire retardant; Halogen-free flame retardants is joined in the above-mentioned mixture that mixes, be fully mixed in high-speed mixer and mix, high mixer rotating speed 900r/min mixes 6 fens clock times.The material that mixes is added twin screw extruder, and the screw rod velocity of rotation is 1000r/min, and main spout feed rate is 400r/min.Wherein one to seven district's temperature is 155 ℃ ℃, 160 ℃, 165 ℃, 170 ℃, 165 ℃, 160 ℃, 155 ℃ (head) on the forcing machine, and pressure is to melt extrude granulation under the condition of 1.0～1.2MPa.
Make pellet put into baking oven in 80 ℃ down oven dry be injection molded into the standard batten with injection moulding machine after 8 hours.Injection temperature is set at 190 ℃.With the standard batten, carry out every Mechanics Performance Testing.
In embodiment and the Comparative Examples in each assembly side the consumption of coupling agent be the 4%wt of halogen-free flame retardants gross weight wherein, other each component prescriptions see Table 1.Each routine test result sees Table 2.Experimental data by embodiment 1,2,3 from table 2 as seen, two (diphenyl phosphoester) three actings in conjunction of ammonium polyphosphate, melamine cyanurate and Resorcinol in the halogen-free flame retardants, and be combined with flame retardancy synergists and make that the flame retardant effect of polyvinyl resin is good, and has the good mechanical performance.
Table 1
Table 2
Indicate: all battens all do not have to melt to drip and produce among the embodiment, and comparative example 2,3,4 has the molten drop phenomenon.
Claims (11)
1. non-halogen flame-proof polyvinyl composite, it includes the following component of blend:
Polyvinyl resin 100 parts by weight
Halogen-free flame retardants 35～55 parts by weight
Flame retardancy synergists 8～20 parts by weight
The above halogen-free flame retardants is the mixture that ammonium polyphosphate, melamine cyanurate and Resorcinol two (diphenyl phosphoester) are formed; Wherein the total amount of ammonium polyphosphate and melamine cyanurate is 32～50 parts by weight, and both weight ratios are 1: 1～4: 1;
The above flame retardancy synergists is selected from least a in the following material: maleic anhydride grafted ethene vinyl acetate, maleic anhydride grafted ethene-octene copolymer, ethylene-octene copolymer, polyphenylene oxide.
2. non-halogen flame-proof polyvinyl composite according to claim 1, it includes the following component of blend:
Polyvinyl resin 100 parts by weight
Halogen-free flame retardants 38～50 parts by weight
Flame retardancy synergists 10～18 parts by weight
The total amount of ammonium polyphosphate and melamine cyanurate is 36～46 parts by weight in the wherein said halogen-free flame retardants, and both weight ratios are 1: 1～3: 1.
3. according to each described non-halogen flame-proof polyvinyl composite of claim 1～2, wherein include the fire retardant surface treatment agent, surface treatment agent is a titanate coupling agent, and the content of surface treatment agent is 3～5%wt of described halogen-free flame retardants gross weight.
4. non-halogen flame-proof polyvinyl composite according to claim 3, titanate coupling agent wherein are selected from least a in the following material: sec.-propyl three (different perester radical) titanic acid ester, sec.-propyl three (dioctyl phosphoric acid ester acyl group) titanic acid ester, sec.-propyl three (dioctylphyrophosphoric acid ester acyl group) titanic acid ester.
5. according to each described non-halogen flame-proof polyvinyl composite of claim 1～2, wherein including in polyvinyl resin is 100 parts by weight, the static inhibitor of 2.0～5.0 weight parts; Described static inhibitor is a non-ionic antistatic agent.
6. non-halogen flame-proof polyvinyl composite according to claim 5, wherein said static inhibitor are 3.0～4.0 parts by weight in polyvinyl resin 100 parts by weight; Described static inhibitor is selected from a kind of in the following static inhibitor: mainly contain the static inhibitor of the ethylene oxide adduct of lipid acid, mainly contain the static inhibitor of polyhydric alcohol fatty acid ester, mainly contain the static inhibitor of hydroxyethyl aliphatic amide.
7. according to each described non-halogen flame-proof polyvinyl composite of claim 1～2, wherein containing in polyvinyl resin is 100 parts by weight, 0.1 the composite antioxidant of～0.4 parts by weight, described composite antioxidant is the mixture of Hinered phenols antioxidant and phosphite ester kind antioxidant or is the mixture of Hinered phenols antioxidant and monothioester kind antioxidant that wherein the weight ratio of Hinered phenols antioxidant and phosphite ester kind antioxidant or Hinered phenols antioxidant and monothioester kind antioxidant is 1: 1～2: 1.
8. non-halogen flame-proof polyvinyl composite according to claim 7, wherein the weight ratio of Hinered phenols antioxidant and phosphite ester kind antioxidant or Hinered phenols antioxidant and monothioester kind antioxidant is 1: 1～1.5: 1.
9. non-halogen flame-proof polyvinyl composite according to claim 7, wherein oxidation inhibitor is 100 parts by weight in polyvinyl resin, is 0.1～0.3 parts by weight.
10. non-halogen flame-proof polyvinyl composite according to claim 7, wherein said Hinered phenols antioxidant are four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester; Phosphite ester kind antioxidant is (2, the 4-di-tert-butyl-phenyl) tris phosphite or two (2, the 4-di-tert-butyl-phenyl) pentaerythritol diphosphites; The monothioester kind antioxidant is a Tyox B.
11. the preparation method according to each described non-halogen flame-proof polyvinyl composite of claim 1～10 comprises described each component by described amount thorough mixing, obtains described non-halogen flame-proof polyvinyl composite through melt blending.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101629006B (en) * | 2009-07-09 | 2011-04-20 | 广州市合诚化学有限公司 | Zero halogen flame resistance polyethylene breathable film and preparation method and application thereof |
| CN102504396A (en) * | 2011-11-25 | 2012-06-20 | 成都亨通光通信有限公司 | Intumescent flame retardant (IFR) |
| CN103242642A (en) * | 2012-02-08 | 2013-08-14 | 东莞市聚恩特新材料有限公司 | Halogen free flame retardation thermoplastic metal conductor insulation coated composite material |
| CN102643472A (en) * | 2012-04-19 | 2012-08-22 | 上海新上化高分子材料有限公司 | Chemically-crosslinkable polyethylene insulating plastic for medium/high-voltage power cables and preparation method thereof |
| CN105504519A (en) * | 2016-01-25 | 2016-04-20 | 上海捷棉新材料科技有限公司 | Halogen-free environment-friendly flame-retardant polyolefin master batch for replacing bromine-containing flame retardant and preparation method of master batch |
| CN109721806A (en) * | 2017-10-30 | 2019-05-07 | 江苏亨通电力电缆有限公司 | Environment protection heat-proof type fireproofing cable material without halide |
| CN109721793A (en) * | 2017-10-30 | 2019-05-07 | 华东理工大学 | Halogen-free type highly effective flame-retardant cable material of polyolefin |
| CN113462308A (en) * | 2021-07-27 | 2021-10-01 | 深圳市卓汉材料技术有限公司 | Topological conductive foam material and construction method thereof |
| CN114163717B (en) * | 2021-12-29 | 2023-08-18 | 广东中德电缆有限公司 | PPO reinforced flame-retardant EVA-based polyolefin material and preparation method thereof |
| CN114989513A (en) * | 2022-04-20 | 2022-09-02 | 李平 | Halogen-free environment-friendly flame-retardant polyethylene material and preparation method thereof |
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