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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- CN102295797A CN102295797A CN2010102095101A CN201010209510A CN102295797A CN 102295797 A CN102295797 A CN 102295797A CN 2010102095101 A CN2010102095101 A CN 2010102095101A CN 201010209510 A CN201010209510 A CN 201010209510A CN 102295797 A CN102295797 A CN 102295797A
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- 229920000098 polyolefin Polymers 0.000 title claims abstract description 56
- 239000000463 material Substances 0.000 title claims abstract description 50
- 239000003063 flame retardant Substances 0.000 title claims abstract description 30
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 229910052736 halogen Inorganic materials 0.000 title description 4
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims abstract description 50
- 239000005038 ethylene vinyl acetate Substances 0.000 claims abstract description 44
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000000758 substrate Substances 0.000 claims abstract description 13
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 claims abstract description 9
- 239000000654 additive Substances 0.000 claims abstract description 5
- 230000000996 additive effect Effects 0.000 claims abstract description 5
- 239000003999 initiator Substances 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 22
- 239000003963 antioxidant agent Substances 0.000 claims description 20
- 239000003795 chemical substances by application Substances 0.000 claims description 20
- 230000003078 antioxidant effect Effects 0.000 claims description 19
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 14
- 239000000314 lubricant Substances 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 150000007970 thio esters Chemical class 0.000 claims description 8
- 238000001125 extrusion Methods 0.000 claims description 7
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 7
- 239000000347 magnesium hydroxide Substances 0.000 claims description 7
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical group [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 6
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 4
- 239000012188 paraffin wax Substances 0.000 claims description 4
- 239000008188 pellet Substances 0.000 claims description 4
- -1 pentaerythritol ester Chemical class 0.000 claims description 4
- 239000000344 soap Substances 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 239000012796 inorganic flame retardant Substances 0.000 claims 5
- 239000002530 phenolic antioxidant Substances 0.000 claims 4
- 239000004712 Metallocene polyethylene (PE-MC) Substances 0.000 claims 2
- 150000001875 compounds Chemical class 0.000 claims 2
- 235000011330 Armoracia rusticana Nutrition 0.000 claims 1
- 240000003291 Armoracia rusticana Species 0.000 claims 1
- 239000003508 Dilauryl thiodipropionate Substances 0.000 claims 1
- 229920002943 EPDM rubber Polymers 0.000 claims 1
- 235000021355 Stearic acid Nutrition 0.000 claims 1
- 239000004595 color masterbatch Substances 0.000 claims 1
- 235000019304 dilauryl thiodipropionate Nutrition 0.000 claims 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 239000008117 stearic acid Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 10
- 239000002131 composite material Substances 0.000 abstract description 2
- 239000012745 toughening agent Substances 0.000 abstract 1
- 239000003112 inhibitor Substances 0.000 description 25
- 230000003647 oxidation Effects 0.000 description 14
- 238000007254 oxidation reaction Methods 0.000 description 14
- 238000002485 combustion reaction Methods 0.000 description 11
- 238000005469 granulation Methods 0.000 description 11
- 230000003179 granulation Effects 0.000 description 11
- 238000002844 melting Methods 0.000 description 9
- 230000008018 melting Effects 0.000 description 9
- 229920001296 polysiloxane Polymers 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- 239000000178 monomer Substances 0.000 description 5
- 230000000638 stimulation Effects 0.000 description 5
- 206010023126 Jaundice Diseases 0.000 description 4
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 150000002989 phenols Chemical class 0.000 description 4
- 230000036314 physical performance Effects 0.000 description 4
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 238000005453 pelletization Methods 0.000 description 3
- 235000019633 pungent taste Nutrition 0.000 description 3
- 239000004114 Ammonium polyphosphate Substances 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 2
- 229920001276 ammonium polyphosphate Polymers 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical class C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 239000012764 mineral filler Substances 0.000 description 2
- 229940059574 pentaerithrityl Drugs 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- HSLFISVKRDQEBY-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)cyclohexane Chemical compound CC(C)(C)OOC1(OOC(C)(C)C)CCCCC1 HSLFISVKRDQEBY-UHFFFAOYSA-N 0.000 description 1
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical group CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical group C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical group CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229960003328 benzoyl peroxide Drugs 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
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- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000007726 management method Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229920001526 metallocene linear low density polyethylene Polymers 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 229920006112 polar polymer Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
本发明公开了一种无卤阻燃聚烯烃材料及其制备方法和应用，该无卤阻燃聚烯烃材料包括至少含有乙烯-醋酸乙烯酯共聚物的聚烯烃基材、无卤阻燃剂、作为相容剂的接枝马来酸酐的乙烯-醋酸乙烯酯共聚物以及添加剂，其特征在于，所述无卤阻燃聚烯烃材料采用接枝马来酸酐的乙烯-醋酸乙烯酯共聚物作为相容剂。本发明的相容剂接枝率较高(～1％)，可以作为高分子相容剂和增韧剂，用于提高复合材料的界面相容性，对生产设备要求低，效率高，制得的聚烯烃材料有较好的性能，其强度及伸率均有明显的提高。The invention discloses a halogen-free flame-retardant polyolefin material and its preparation method and application. The halogen-free flame-retardant polyolefin material comprises a polyolefin substrate containing at least ethylene-vinyl acetate copolymer, a halogen-free flame retardant, The ethylene-vinyl acetate copolymer grafted with maleic anhydride as a compatibilizer and the additive are characterized in that the halogen-free flame-retardant polyolefin material adopts the ethylene-vinyl acetate copolymer grafted with maleic anhydride as a phase Toner. The compatibilizer grafting rate of the present invention is higher (～1%), can be used as macromolecular compatibilizer and toughening agent, be used for improving the interfacial compatibility of composite material, have low requirement to production equipment, high efficiency, easy to manufacture The obtained polyolefin material has good performance, and its strength and elongation are all 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)
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Cited By (5)
| 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 |
| CN120795443A (en) * | 2025-06-25 | 2025-10-17 | 上海贝思特管业有限公司 | Polyethylene and silica gel mixed material, preparation method and composite optical cable silicon core tube |
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 halogen-free flame-retardant polyolefin 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 halogen-free flame-retardant polyolefin 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 (5)
| 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 |
| CN120795443A (en) * | 2025-06-25 | 2025-10-17 | 上海贝思特管业有限公司 | Polyethylene and silica gel mixed material, preparation method and composite optical cable silicon core tube |
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