CN102295797A - Zero-halogen flame-retardant polyolefin material and preparation method as well as application thereof - Google Patents
Zero-halogen flame-retardant polyolefin material and preparation method as well as application thereof Download PDFInfo
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Abstract
The invention discloses a zero-halogen flame-retardant polyolefin material and a preparation method as well as application thereof. The zero-halogen flame-retardant polyolefin material comprises a polyolefin substrate at least comprising ethylene-vinyl acetate copolymer, a zero-halogen flame retardant, ethylene-vinyl acetate copolymer grafted with maleic anhydride serving as a compatilizer and an additive, and is characterized in that: the ethylene-vinyl acetate copolymer grafted with maleic anhydride is used as a compatilizer for the zero-halogen flame-retardant polyolefin material. The grafting rate of the compatilizer is higher (about 1 percent), can be used as a high molecular compatilizer and toughening agent, is used for improving the interfacial compatibility of a composite material and has low requirement on production equipment and high efficiency; the prepared polyolefin material has high performance; and the strength and the extensibility of the material are obviously improved.
Description
Technical field
The present invention relates to a kind of halogen-free anti-flaming polyolefin material and its production and application.
Background technology
What European Union in 2002 formulated is " the electronic waste facture " of content with two instructions, one of them instruction for " about in electronic and electrical equipment, banning use of some objectionable impurities instruction " (ROHS).The ROHS command request, the Electrical and Electronic product that on July 1st, 2006 was thrown in European Union market later on must not contain 6 kinds of objectionable impuritiess such as lead, mercury, cadmium, sexavalent chrome, Polybrominated biphenyl and Poly Brominated Diphenyl Ethers.2004 beginning of the years, the Ministry of Information industry is according to relevant rules such as " promotion law on cleaner production ", " prevention and control of environmental pollution by solid wastes methods ", formulate " electronics and IT products prevention and cure of pollution management method " (being called for short " way "), " way " regulation, must not contain 6 kinds of objectionable impuritiess such as lead, mercury, cadmium, sexavalent chrome, Polybrominated biphenyl and Poly Brominated Diphenyl Ethers in the electronics and IT products after 1 day July in 2006, stipulate that simultaneously the electric equipment products that enters China must not contain above 6 kinds of objectionable impuritiess.Therefore development is present focus both domestic and external with the halogen-free anti-flaming polyolefin material that exploitation does not contain 6 kinds of objectionable impuritiess stipulating in the instruction.
The ethylene-vinyl acetate resistance toheat is good, and filling capacity is big, has good processing properties and good weathering resistance, and the performance of ethylene-vinyl acetate depends primarily on the content and the melt flow rate (MFR) of vinyl acetate in the multipolymer.Because ethylene-vinyl acetate is the thermoplastics that is polymerized by nonpolarity, crystalline vinyl monomer and strong polarity, noncrystalline Vinyl Acetate Monomer, with polar resin and non-polar resin good consistency is arranged all.But its inherent acetoxyl spatial obstacle that group forms makes its degree of crystallinity and second-order transition temperature and polyolefine that bigger difference arranged, and has influenced its thermostability, aging resistance and other physical and mechanical properties.So ethylene-vinyl acetate and polar copolymer and mineral filler consistency still remain to be improved.
The halogen-free anti-flaming polyolefin material of domestic-developed adopts the ethylene-vinyl acetate copolymer (EVA-g-MAH) of commercially available or fusion-grafting maleic anhydride as compatilizer mostly at present, because this compatilizer formula system is comparatively complicated, and the competition mutually of initiator and oxidation inhibitor, graft reaction and crosslinking reaction are carried out simultaneously in the production process, therefore the quality of compatilizer is than difficult control, if the improper meeting of control is to the performance generation adverse influence of the finished product.And the method for preparing the EVA-g-MAH compatilizer in the prior art also needs follow-uply to carry out electron rays or gamma-rays carries out radiation, and process is loaded down with trivial details and higher to equipment requirements.
Summary of the invention
The objective of the invention is to solve the problems of the technologies described above, a kind of halogen-free anti-flaming polyolefin material and its production and application is provided.
The present invention adopts following technical scheme to solve the problems of the technologies described above:
A kind of halogen-free anti-flaming polyolefin material, this halogen-free anti-flaming polyolefin material comprises the polyolefin substrate that contains ethylene-vinyl acetate copolymer at least, halogen-free flame retardants, as the ethylene-vinyl acetate copolymer and the additive of the grafted maleic anhydride of compatilizer, it is characterized in that, described halogen-free anti-flaming polyolefin material adopts the ethylene-vinyl acetate copolymer of grafted maleic anhydride as compatilizer, and the ethylene-vinyl acetate copolymer of described grafted maleic anhydride is made by following method:
1) ethylene-vinyl acetate, maleic anhydride, initiator, oxidation inhibitor and rheological agent are prepared burden by weight ratio, mix in high-speed mixer, the weight part proportioning is:
100 parts of ethylene-vinyl acetates;
0.6～2.4 part of maleic anhydride;
0.06～0.24 part of initiator;
0.3～0.7 part in oxidation inhibitor;
0.01～0.10 part of rheological agent;
2) expressing technique: after mixing of materials is even, material is thrown in the twin screw extruder, extrusion temperature is 75-160 ℃, and engine speed is 150r/min～500r/min, reacts 1～3 minute, through tie rod, cooling, pelletizing, the dry pellet that gets.
Preferably, in the described step 1), the consumption of maleic anhydride is 1.2～1.6 weight parts, and the consumption of initiator is 0.13～0.16 weight part.
Described polyolefin substrate can be any existing polyolefin substrate that contains EVA at least, as ethylene-vinyl acetate copolymer (EVA), or ethylene-vinyl acetate copolymer and other polyolefine, one or more blended mixtures in metallocene PE, terpolymer EP rubber and the ethylene-octene copolymer (POE) for example: the weight percentage of the vinyl acetate in the preferred ethylene-vinyl acetate copolymer is 18～28%, and the melting index scope of this ethylene-vinyl acetate copolymer is 2～4g/10min.
Described halogen-free flame retardants can be organophosphorus, as ammonium polyphosphate (APP), organophosphorus-nitrogen series, as trimeric cyanamide, and organic fire-retardant such as tetramethylolmethane; Also can be inorganic combustion inhibitor, as borates such as metal hydroxidess such as aluminium hydroxide, magnesium hydroxide and zinc borates.
Preferable, described halogen-free flame retardants is an inorganic combustion inhibitor, and described inorganic combustion inhibitor is selected from one or more the mixture in aluminium hydroxide, magnesium hydroxide and the zinc borate.
Preferable, described initiator is 2,5-dimethyl-2,5-bis(t-butylperoxy) hexane or 1,1-bis(t-butylperoxy) cyclohexane.
Preferable, described rheological agent is an organopolysiloxane, and the molecular weight ranges of described organopolysiloxane is 200～300g/mol.
Preferably, described oxidation inhibitor is selected from one or both the mixture in Hinered phenols antioxidant and the thioesters kind antioxidant.
Further preferred, described Hinered phenols antioxidant is [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester; Described thioesters kind antioxidant is a Tyox B.
Preferable, described additive is selected from one or more the mixture in lubricant and the Halogen Masterbatch.
Preferable, described lubricant is selected from one or both the mixture in divalence metallic soap of stearic acid salt and the paraffin.
Preferable, in the weight of described polyolefin substrate, the weight of compatilizer is 30～40% of polyolefin substrate weight.
Preferably, comprise following components by part by weight in the described halogen-free anti-flaming polyolefin material:
Compatilizer: 5～15 parts of the ethylene-vinyl acetate copolymers of grafted maleic anhydride;
Polyolefin substrate: 20～30 parts of ethylene-vinyl acetate copolymers, 5～10 parts of metallocene PEs;
Oxidation inhibitor: 1～2 part;
Halogen-free flame retardants: inorganic combustion inhibitor: 90～130 parts of the mixtures of aluminium hydroxide and magnesium hydroxide;
Lubricant: 0.8～1.6 part of divalence metallic soap of stearic acid salt, 0.6～1.5 part in paraffin;
0～5 part of Halogen Masterbatch.
Further preferred, comprise the Hinered phenols antioxidant of 0.5 weight part and the thioesters kind antioxidant of 0.5～1.5 weight part in the described oxidation inhibitor.
Another object of the present invention provides above-mentioned halogen-free anti-flaming polyolefin preparation methods.
Halogen-free anti-flaming polyolefin preparation methods of the present invention comprises and adopts the existing machinery production technology with above-mentioned each component blend, extrudes granulation and make above-mentioned halogen-free anti-flaming polyolefin material.
Preferable, described halogen-free anti-flaming polyolefin preparation methods comprises the steps: oxidation inhibitor, inorganic combustion inhibitor, lubricant and the compatilizer of half mass parts and polyolefin substrate behind high speed kneader thorough mixing, extrude air-cooled granulation at twin screw extruder; This particle and residue oxidation inhibitor, inorganic combustion inhibitor and lubricant further behind high speed kneader thorough mixing, are extruded at twin screw extruder again, and air-cooled granulation gets halogen-free anti-flaming polyolefin material of the present invention.
Because flame retardant amount is bigger in the preferred embodiment of the present invention, so adopt reinforced method of two steps, to disperse inhomogeneously when having avoided once adding, the problem of processing difficulties is convenient to suitability for industrialized production, and the performance for preparing material meets the requirements.
The present invention is mainly by preparing new EVA-g-MAH as compatilizer, the percentage of grafting of this EVA-g-MAH is higher, and the degree that side reaction such as crosslinked takes place is less, therefore can improve the consistency between base material component and the filling components greatly, thereby improve the performance of polyolefine material, can be used as high molecular compatible agent and toughner.
The present invention selects for use maleic anhydride as grafted monomer, and its advantage is: maleic anhydride monomer can not form long grafted chain under the grafting condition, and one has avoided polyolefinic overall performance to descend; It two has avoided the polarity of grafts excessive, causes the viscosifying power with the polyene hydrocarbon phase to descend; It three has prevented owing to monomeric homopolymerization reduces percentage of grafting.
Present method adopts reaction to extrude the fusion-grafting method, and it is simple to have an operating procedure, and facility investment is few, but serialization operation, production cost is low, by selecting suitable initiator and consumption and suitable reaction extrusion process condition, has overcome the side reaction in the melting graft reaction simultaneously.
Unusual effect of the present invention is: the present invention carries out graft reaction by the polar monomer maleic anhydride to ethylene-vinyl acetate, can on the ethylene-vinyl acetate molecular chain, introduce polar group, improve the performance of ethylene-vinyl acetate, make it become the expanding material of polyolefine and other polar polymers or mineral filler, both enlarge the application of ethylene-vinyl acetate, improved the added value of ethylene-vinyl acetate again.Can be used as high molecular compatible agent and toughner.The present invention can be used for improving the interface compatibility of matrix material, is used for the expanding material of polymer alloy and the compatilizer of macromolecular material and inorganic materials, as fire retardant material etc.For example the ethylene-vinyl acetate grafted maleic anhydride can improve inorganic combustion inhibitor magnesium hydroxide and poly composite performance, and does not have the grafted ethylene-vinyl acetate to compare performance to be improved largely.The comprehensive performance is better, has broad application prospects.The present invention does not need follow-uply to carry out electron rays or gamma-rays carries out radiation, and is not high to equipment requirements, but because the serialization operation, reaction efficiency is higher, and the percentage of grafting of products obtained therefrom can reach about 1%, and melting index can reach 2～4g/10min.
Embodiment
Further describe technical scheme of the present invention below by specific embodiment.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.
The preparation of embodiment 1 EVA-g-MAH
Initiator 160g and rheological agent (rheological agent is that molecular weight ranges is the organopolysiloxane of 200～300g/mol) 50g adding are mixed with among ethylene-vinyl acetate copolymer (A type) 100Kg of maleic anhydride, mix back granulation in 90～160 ℃ of temperature ranges of twin screw extruder at high-speed mixer and promptly obtain EVA-g-MAH.
The preparation of embodiment 2 EVA-g-MAH
Initiator 150g and rheological agent (rheological agent is that molecular weight ranges is the organopolysiloxane of 200～300g/mol) 50g adding are mixed with among ethylene-vinyl acetate copolymer (A type) 100Kg of maleic anhydride, mix back granulation in 90～160 ℃ of temperature ranges of twin screw extruder at high-speed mixer and promptly obtain EVA-g-MAH.
The preparation of embodiment 3 EVA-g-MAH
Initiator 100g and rheological agent (rheological agent is that molecular weight ranges is the organopolysiloxane of 200～300g/mol) 50g adding are mixed with among ethylene-vinyl acetate copolymer (A type) 100Kg of maleic anhydride, mix back granulation in 90～160 ℃ of temperature ranges of twin screw extruder at high-speed mixer and promptly obtain EVA-g-MAH.
The preparation of embodiment 4 EVA-g-MAH
Initiator 160g and rheological agent (rheological agent is that molecular weight ranges is the organopolysiloxane of 200～300g/mol) 50g adding are mixed with among ethylene-vinyl acetate copolymer (Type B) 100Kg of maleic anhydride, mix back granulation in 90～160 ℃ of temperature ranges of twin screw extruder at high-speed mixer and promptly obtain EVA-g-MAH.
The preparation of embodiment 5 EVA-g-MAH
Initiator 160g and rheological agent (rheological agent is that molecular weight ranges is the organopolysiloxane of 200～300g/mol) 70g adding are mixed with among ethylene-vinyl acetate copolymer (Type B) 100Kg of maleic anhydride, mix back granulation in 90～160 ℃ of temperature ranges of twin screw extruder at high-speed mixer and promptly obtain EVA-g-MAH.
The preparation of embodiment 6 EVA-g-MAH
Initiator 160g and rheological agent (rheological agent is that molecular weight ranges is the organopolysiloxane of 200～300g/mol) 100g adding are mixed with among ethylene-vinyl acetate copolymer (Type B) 100Kg of maleic anhydride, mix back granulation in 90～160 ℃ of temperature ranges of twin screw extruder at high-speed mixer and promptly obtain EVA-g-MAH.
The physical performance index of embodiment 1-6 sees Table 1
Table 1
| Physical performance index | 1# | 2# | 3# | 4# | 5# | 6# |
| Tensile strength MPa | 22.2 | 20.0 | 17.4 | 30.2 | 30.7 | 29.2 |
| Elongation at break % | 790 | 790 | 830 | 740 | 740 | 740 |
| 150 ℃ of * 5Kg of melting index | 0.95 | 1.18 | 2.11 | 0.82 | 0.92 | 0.98 |
The preparation of embodiment 7 halogen-free anti-flaming polyolefin materials
The ethylene-vinyl acetate copolymer of the grafted maleic anhydride that the method for embodiment 1-6 is obtained is applied to use the halogen-free anti-flaming polyolefin system of inorganic combustion inhibitor, by following polyolefine material prescription:
Compatilizer: 5～15 parts of the ethylene-vinyl acetate copolymers of grafted maleic anhydride;
Polyolefin substrate: 20～30 parts of ethylene-vinyl acetate copolymers, 5～10 parts of metallocene PEs;
Oxidation inhibitor: 1～2 part;
Halogen-free flame retardants: inorganic combustion inhibitor: 90～130 parts of the mixtures of aluminium hydroxide and magnesium hydroxide;
Lubricant: 0.8～1.6 part of divalence metallic soap of stearic acid salt, 0.6～1.5 part in paraffin;
0～5 part of Halogen Masterbatch.
Wherein, comprise the Hinered phenols antioxidant of 0.5 weight part and the thioesters kind antioxidant of 0.5～1.5 weight part in the described oxidation inhibitor.
Employing is prepared as follows the halogen-free anti-flaming polyolefin material that method makes: oxidation inhibitor, inorganic combustion inhibitor, lubricant and the compatilizer of half mass parts and polyolefin substrate behind high speed kneader thorough mixing, are extruded air-cooled granulation at twin screw extruder; This particle and residue oxidation inhibitor, inorganic combustion inhibitor and lubricant further behind high speed kneader thorough mixing, are extruded at twin screw extruder again, and air-cooled granulation gets halogen-free anti-flaming polyolefin material of the present invention, and its physical performance index sees Table 2.
Table 2
| Physical performance index | 1# | 2# | 3# | 4# | 5# | 6# |
| Tensile strength MPa | 10.9 | 10.9 | 10.2 | 12.3 | 12.7 | 11.8 |
| Elongation at break % | 190 | 180 | 200 | 140 | 150 | 140 |
| 150 ℃ of * 21.6Kg of melting index | 3.88 | 4.13 | 5.64 | 3.38 | 2.88 | 3.33 |
From the result, the consumption of initiator serves as preferred with about 0.15～0.17 part, and the consumption of rheological agent serves as preferred with 0.06～0.08.
The optimum amount experiment of embodiment 8 maleic anhydride monomers and initiator
Adopt 2 by the advance copy invention, 5-dimethyl-2,5-bis(t-butylperoxy) hexane is as initiator; Expressing technique is: extrusion temperature is 75～160 ℃, and engine speed is 150r/min～500r/min, reacts 1～3 minute.
1, the consumption of maleic anhydride is explored:
Get 100 parts ethylene-vinyl acetate, 0.4 part of oxidation inhibitor, get maleic anhydride, 0.15 part of initiator by table 1, in high-speed mixer, mix, after mixing of materials is even, material is thrown in the twin screw extruder, extrusion temperature is 160 ℃, and engine speed is 400r/min, reacts 1～3 minute, through tie rod, cooling, pelletizing, the dry pellet that gets, the results are shown in Table 3.
Table 3
| Maleic anhydride | Initiator | Color | Smell | Smooth degree | Melting index |
| 0.4 | 0.15 | White | Non-stimulated gas | More smooth | 2.71 |
| 0.8 | 0.15 | White | Non-stimulated gas | Smooth even | 3.06 |
| 1.2 | 0.15 | Jaundice | Stimulation is arranged slightly | Smooth even | 3.30 |
| 1.6 | 0.15 | Jaundice | Stimulation is arranged slightly | Smooth even | 3.45 |
| 2.0 | 0.15 | Yellow | Pungency gas | Smooth even | 3.61 |
| 2.4 | 0.15 | Yellow | Pungency gas | Smooth even | 3.81 |
From the result, the consumption of maleic anhydride serves as preferred with 1.2～1.6 parts.(melting index unit is g/10min)
2, the consumption of initiator is explored:
Get 100 parts ethylene-vinyl acetate, 0.4 part of oxidation inhibitor, 1.5 parts maleic anhydride, get initiator by table 2, in high-speed mixer, mix, material is thrown in the twin screw extruder, extrusion temperature is 160 ℃, engine speed is 400r/min, reacted 1～3 minute, and, the results are shown in Table 4 through tie rod, cooling, pelletizing, the dry pellet that gets.
Table 4
| Maleic anhydride | Initiator | Color | Smell | Smooth degree | Melting index |
| 1.5 | 0.07 | White | Pungency gas | Smooth even | 4.36 |
| 1.5 | 0.10 | White | Stimulation is arranged slightly | Smooth even | 3.90 |
| 1.5 | 0.13 | Jaundice | Stimulation is arranged slightly | Smooth even | 3.56 |
| 1.5 | 0.16 | Jaundice | Stimulation is arranged slightly | Smooth even | 3.35 |
| 1.5 | 0.19 | Yellow | Non-stimulated gas | More smooth | 2.93 |
| 1.5 | 0.22 | Yellow | Non-stimulated gas | Coarse ring shape | 2.20 |
From the result, the consumption of initiator serves as preferred with 0.13～0.16 part.(melting index unit is g/10min)
Claims (9)
1. halogen-free anti-flaming polyolefin material, this halogen-free anti-flaming polyolefin material comprises the polyolefin substrate that contains ethylene-vinyl acetate copolymer at least, halogen-free flame retardants, as the ethylene-vinyl acetate copolymer and the additive of the grafted maleic anhydride of compatilizer, it is characterized in that, described halogen-free anti-flaming polyolefin material adopts the ethylene-vinyl acetate copolymer of grafted maleic anhydride as compatilizer, and the ethylene-vinyl acetate copolymer of described grafted maleic anhydride is made by following method:
1) ethylene-vinyl acetate, maleic anhydride, initiator, oxidation inhibitor and rheological agent are prepared burden by weight ratio, mix in high-speed mixer, the weight part proportioning is:
100 parts of ethylene-vinyl acetates,
0.6～2.4 part of maleic anhydride,
0.06～0.24 part of initiator,
0.3～0.7 part in oxidation inhibitor,
0.01～0.10 part of rheological agent;
2) expressing technique: after mixing of materials is even, material is thrown in the twin screw extruder, extrusion temperature is 75～160 ℃, and engine speed is 150r/min～500r/min, reacts 1～3 minute, through tie rod, cooling, pelletizing, the dry pellet that gets.
2. halogen-free anti-flaming polyolefin material as claimed in claim 1, it is characterized in that described polyolefin substrate is ethylene-vinyl acetate copolymer or ethylene-vinyl acetate copolymer and is selected from one or more blended mixtures in metallocene PE, terpolymer EP rubber and the ethylene-octene copolymer.
3. halogen-free anti-flaming polyolefin material as claimed in claim 1 is characterized in that, described halogen-free flame retardants is an inorganic combustion inhibitor, and described inorganic combustion inhibitor is selected from one or more the mixture in aluminium hydroxide, magnesium hydroxide and the zinc borate.
4. halogen-free anti-flaming polyolefin material as claimed in claim 1 is characterized in that, described additive is selected from one or more the mixture in oxidation inhibitor, lubricant and the Halogen Masterbatch.
5. as arbitrary described halogen-free anti-flaming polyolefin material in the claim 1～4, it is characterized in that in the weight of described halogen-free anti-flaming polyolefin material, the consumption of described compatilizer is 30～40% of a polyolefin substrate weight.
6. halogen-free anti-flaming polyolefin material as claimed in claim 1 is characterized in that, described halogen-free anti-flaming polyolefin material comprises following components by part by weight:
Compatilizer: 5～15 parts of the ethylene-vinyl acetate copolymers of grafted maleic anhydride;
Polyolefin substrate: 20～30 parts of ethylene-vinyl acetate copolymers, 5～10 parts of metallocene PEs;
Oxidation inhibitor: 1～2 part of composite antioxidant, wherein Hinered phenols antioxidant: thioesters kind antioxidant=0.5: 0.5～1.5 part;
Halogen-free flame retardants: inorganic combustion inhibitor: 90～130 parts of the mixtures of aluminium hydroxide and magnesium hydroxide;
Lubricant: 0.8～1.6 part of divalence metallic soap of stearic acid salt, 0.6～1.5 part in paraffin;
0～5 part of Halogen Masterbatch.
7. the halogen-free anti-flaming polyolefin material described in claim 6 is characterized in that, described oxidation inhibitor comprises Hinered phenols antioxidant and thioesters kind antioxidant, and the weight ratio of Hinered phenols antioxidant and thioesters kind antioxidant is 1: 1～3.
8. the halogen-free anti-flaming polyolefin material described in claim 7 is characterized in that, described Hinered phenols antioxidant is a pentaerythritol ester, and described thioesters kind antioxidant is a Tyox B.
9. arbitrary described halogen-free anti-flaming polyolefin preparation methods in the claim 1～8, comprise the following steps: part oxidation inhibitor, inorganic combustion inhibitor, lubricant and compatilizer and polyolefin substrate behind high speed kneader thorough mixing, extrude air-cooled granulation at twin screw extruder; This particle and residue oxidation inhibitor, inorganic combustion inhibitor and lubricant further behind high speed kneader thorough mixing, are extruded at twin screw extruder again, and air-cooled granulation gets described halogen-free anti-flaming polyolefin material.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102604206A (en) * | 2012-02-06 | 2012-07-25 | 金发科技股份有限公司 | Superfine talcum powder-polypropylene filled master batch, preparation method and equipment thereof |
| CN108794691A (en) * | 2018-06-29 | 2018-11-13 | 重庆文理学院 | Non-crosslinked polyolefin composition for cable |
| CN112012016A (en) * | 2020-06-15 | 2020-12-01 | 江苏北化新橡新材料科技有限公司 | Environment-friendly halogen-free polyolefin composite material for textilene mesh cloth and preparation method thereof |
| CN116285082A (en) * | 2023-03-22 | 2023-06-23 | 江苏益帆高分子材料有限公司 | Low-smoke halogen-free cable material with rubber improving irradiation crosslinking physical property and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101037495A (en) * | 2007-04-05 | 2007-09-19 | 辽宁大学 | Branching method of ethylene-acetic acid ethylene ester to maleic anhydride |
| CN101100537A (en) * | 2006-07-07 | 2008-01-09 | 中国科学院上海应用物理研究所 | Low-smoke halide-free fireproof polyolefine material and its preparation method and application |
-
2010
- 2010-06-24 CN CN 201010209510 patent/CN102295797B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101100537A (en) * | 2006-07-07 | 2008-01-09 | 中国科学院上海应用物理研究所 | Low-smoke halide-free fireproof polyolefine material and its preparation method and application |
| CN101037495A (en) * | 2007-04-05 | 2007-09-19 | 辽宁大学 | Branching method of ethylene-acetic acid ethylene ester to maleic anhydride |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102604206A (en) * | 2012-02-06 | 2012-07-25 | 金发科技股份有限公司 | Superfine talcum powder-polypropylene filled master batch, preparation method and equipment thereof |
| CN108794691A (en) * | 2018-06-29 | 2018-11-13 | 重庆文理学院 | Non-crosslinked polyolefin composition for cable |
| CN112012016A (en) * | 2020-06-15 | 2020-12-01 | 江苏北化新橡新材料科技有限公司 | Environment-friendly halogen-free polyolefin composite material for textilene mesh cloth and preparation method thereof |
| CN116285082A (en) * | 2023-03-22 | 2023-06-23 | 江苏益帆高分子材料有限公司 | Low-smoke halogen-free cable material with rubber improving irradiation crosslinking physical property and preparation method thereof |
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