CN100509938C - Halogen-free flame-proof resin composition and preparation method thereof - Google Patents
Halogen-free flame-proof resin composition and preparation method thereof Download PDFInfo
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- CN100509938C CN100509938C CNB2006101193204A CN200610119320A CN100509938C CN 100509938 C CN100509938 C CN 100509938C CN B2006101193204 A CNB2006101193204 A CN B2006101193204A CN 200610119320 A CN200610119320 A CN 200610119320A CN 100509938 C CN100509938 C CN 100509938C
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- halogen
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- resin composition
- flame retardant
- proof resin
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- 239000011342 resin composition Substances 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims description 9
- 239000003063 flame retardant Substances 0.000 claims abstract description 37
- 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 claims abstract description 26
- 239000000203 mixture Substances 0.000 claims abstract description 18
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000004698 Polyethylene Substances 0.000 claims abstract description 16
- -1 polyethylene Polymers 0.000 claims abstract description 15
- 229920000573 polyethylene Polymers 0.000 claims abstract description 15
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical class C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 30
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- 239000004727 Noryl Substances 0.000 claims description 9
- 229920001207 Noryl Polymers 0.000 claims description 9
- 239000006057 Non-nutritive feed additive Substances 0.000 claims description 8
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 8
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 claims description 7
- 238000005538 encapsulation Methods 0.000 claims description 6
- 229920001903 high density polyethylene Polymers 0.000 claims description 6
- 239000004700 high-density polyethylene Substances 0.000 claims description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 230000004927 fusion Effects 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000005453 pelletization Methods 0.000 claims description 3
- 239000003112 inhibitor Substances 0.000 claims description 2
- 229920001684 low density polyethylene Polymers 0.000 claims description 2
- 239000004702 low-density polyethylene Substances 0.000 claims description 2
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical group NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 238000001746 injection moulding Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 229910052736 halogen Inorganic materials 0.000 abstract description 5
- 150000002367 halogens Chemical class 0.000 abstract description 5
- 238000012856 packing Methods 0.000 abstract description 3
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 abstract description 3
- 229920001400 block copolymer Polymers 0.000 abstract description 2
- 238000000034 method Methods 0.000 abstract description 2
- 239000002671 adjuvant Substances 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 239000003094 microcapsule Substances 0.000 abstract 1
- 229920013638 modified polyphenyl ether Polymers 0.000 abstract 1
- 239000000047 product Substances 0.000 description 16
- 239000000463 material Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 6
- 238000012545 processing Methods 0.000 description 4
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229920006124 polyolefin elastomer Polymers 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 206010009866 Cold sweat Diseases 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229920000412 polyarylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
Abstract
The invention discloses a non-halogen flame-retarded resin composition, which comprises the following parts: PE, MPPO, SEBS, non-halogen flame-retarded agent, non-halogen red phosphorus, nitrogen-system flame retardant and manufacturing adjuvant. The making method comprises the following steps: putting polyethylene, modified polyphenyl ether, hydrogenated phenylethene-butadiene block copolymer and composition of micro-capsule clad red phosphorus and nitrogen-system flame retardant into high-speed blender; dispersing; fusing and squeezing through double-screw squeezer; cooling; cutting; drying; packing. The invention is fit for making kinds of flexible and semi-hard product.
Description
Affiliated technical field
The present invention relates to a kind of polymeric composition, particularly relate to a kind of halogen-free fire-proof resin composition and preparation method thereof.
Background technology
Continuous development along with science and technology, the range of application of resin combination is more and more wider, simultaneously, also its corresponding various chemistry, physicals are had higher requirement, as: flame retardant resistance, chemical resistant properties, thermotolerance, shock-resistance, flexibility, electric property and environmental-protecting performance or the like preferably.
In order to improve the chemical property of composition, Chinese patent CN1711317A has disclosed a kind of " resin combination that is used for the electric wire and cable covering material ", and it comprises polyarylene ether resin, a together upright thing polystyrene, olefin type elastomer, hydrogenated styrene-Ding ethylene block copolymer and phosphoric acid ester halogen-free flame retardants.Although said composition has good weathering resistance, thermotolerance, compression deformability and excellent mechanical property, and have environmental-protecting performance preferably.But, must add certain amount and just can reach the required flame retardant effect of electric wire, thereby fire retardant is very easily separated out from product surface because its phosphate flame retardant phosphorus content that adopts is low.Cause product surface to be clamminess, be stained with dirt easily.Fire retardant separate out use and the outward appearance that not only influences goods, more seriously, the water resistance of composition is reduced, influence electric property.In addition, in said composition, also adopted olefin type elastomer newly developed in recent years, though it has excellent balance, owing to be subject to processing the influence of aspects factors such as performance, the slipperiness of product, water-intake rate etc. are also all not too use up people's will after the moulding.And manufacturing cost also improves greatly.
Summary of the invention
In order to address the above problem and deficiency, providing a kind of can effectively prevent to separate out, and can reduce product cost again, improves halogen-free fire-proof resin composition of processing characteristics and preparation method thereof exactly in the present invention.
Technical scheme of the present invention is achieved in that a kind of halogen-free fire-proof resin composition, comprises polyethylene (PE), Noryl (MPPO), hydrogenated styrene-butadiene block copolymer (SEBS) and halogen-free flame retardants and processing aid.Wherein, polyethylene is 1-15 weight %, Noryl is that 15-50 weight %, hydrogenated styrene-butadiene block copolymer are 15-45 weight %, halogen-free flame retardants is the mixture of micro encapsulation encapsulated red phosphorus and nitrogen flame retardant, the red phosphorus that coats is 1-10 weight %, the nitrogen flame retardant is 5-20 weight %, and processing aid is 5-28 weight %.During preparation with polyethylene, Noryl, hydrogenated styrene-butadiene block copolymer, the mixture of micro encapsulation encapsulated red phosphorus and nitrogen flame retardant, drop into high-speed mixer by required weight %, after the dispersing and mixing, through the twin screw extruder fusion, extrude, cooling, pelletizing, drying and packing.
Further technical scheme of the present invention is achieved in that a kind of halogen-free fire-proof resin composition, and wherein, polyethylene can be chosen wantonly in high density polyethylene(HDPE), new LDPE (film grade) and linear polyethylene.The nitrogen flame retardant can first-selected melamine cyanurate nitrogen flame retardant, and, can also in processing aid, add the oxidation inhibitor of 0.05-0.3 weight %.Mixture of the present invention is suitable for the making of various soft and semi-rigid products, as: the coating of electric wire, supply lead injection plug etc.
Beneficial effect of the present invention is: owing to adopted the polyethylene that does not contain polarity gene, have good chemical stability, fabulous electrical property and lower temperature resistance can be applicable to the making of various products at-40 ℃ of life-time service.Particularly, after other components of the present invention mix, has more superiority: the flowability that increases material in the processing, improve processing characteristics, can either guarantee the slipperiness of product surface in process of production, also accelerate the extruded velocity of goods simultaneously, enhance productivity; Improve water tolerance, guarantee the electric performance stablity in hot and humid environment; Increase the wear resistance of product surface, be difficult for producing scratch, blushing in the use; The acid-and base-resisting and the solvent-proof corrosive nature of product have been improved; The starting material wide material sources greatly reduce cost.
Because Noryl of the present invention has good thermotolerance and flame retardant resistance, excellent electrical insulating property, physical strength height, very low water absorbability and good advantage such as dimensional stability.Making applicable to various soft, semi-rigid goods.
Because Halogen micro encapsulation encapsulated red phosphorus and nitrogen flame retardant that the present invention adopts are solid flame retardant, have fundamentally solved the problem of separating out of fire retardant.Simultaneously, because the ignition-proof element phosphorus content is very high in the encapsulated red phosphorus, reach more than 70% usually, so flame retarding efficiency is higher than other phosphorus flame retardants, cooperates the nitrogen flame retardant again, promptly usage quantity is very low also can obtain required flame retardant resistance.Make and to meet that fire does not drip behind the finished product, thermostability by force, not halogen-containing, cost is low, environmental protection, products appearance is beautiful, is smooth to the touch, no precipitate.
The invention will be further described below in conjunction with each embodiment.
Embodiment
Embodiment one
Use halogen-free fire-proof resin composition, preparation is applicable to material such as soft electric wire coating, supply lead injection plug.The starting material of composition can directly be bought from market, and table 1 has been listed the part composition trade mark and the production firm that can supply the present invention to select for use in detail.
Table 1: the trade mark of composition and production firm
Embodiment two
Use halogen-free fire-proof resin composition, prepare a kind of supply lead injection plug material.Following component is dropped into high-speed mixer: the polyethylene of 1-15 weight %, 15-50 weight % Noryl, 15-45 weight % hydrogenated styrene-butadiene block copolymer, and halogen-free flame retardants.Halogen-free flame retardants is the mixture of micro encapsulation encapsulated red phosphorus and nitrogen flame retardant, wherein, and 1-10 weight % encapsulated red phosphorus, 5-20 weight % nitrogen flame retardant and 5-28 weight % processing aid.After the dispersing and mixing, through the twin screw extruder fusion, extrude, cooling, pelletizing, drying and packing.Preparation flow is simple, continuous, high, the constant product quality of production efficiency.The plug material that makes has good thermotolerance and flame retardant resistance, excellent electrical insulating property, stronger wear resistance.And outward appearance is beautiful, is smooth to the touch, no precipitate.The weight % of mixture each component can be according to the purposes of product, particular performances, and the material of different production firms adjusts, when weight % adopted the proportioning of table 2, the product performance index that records was referring to table 3.
| Starting material | Weight % |
| PE | 1～13 |
| SEBS | 18.5～44 |
| MPPO | 24～47.5 |
| Encapsulated red phosphorus | 4～6 |
| MCA | 10.9～13.5 |
| 1010 | 0.05～0.3 |
| White oil | 3.4～14 |
Table 3: product physicals and testing method
| Test event | Testing method | Performance |
| Tensile strength MPa | GB/T?1040 | 10.5～18 |
| Elongation % | GB/T?1040 | 75～280 |
| Hardness Shao A | GB/T?2411 | 81～96 |
| Density g/cm3 | GB/T?1033 | 1.10 |
| 20 ℃ of volume specific resistance Ω .cm | GB/T?1410 | 3.0*10 13～5.0*10 13 |
| Flame retardant rating | UL94 | 3.2mm?V-0 |
Embodiment three
Use halogen-free fire-proof resin composition, the preparation wire gage is that the electric wire of 1.38*2.80mm coats material.The proportioning of composition is: the high density polyethylene(HDPE) of 4-12 weight %, the hydrogenated styrene-butadiene block copolymer of the Noryl of 30-45 weight %, 18-30 weight %, 1-4 weight % encapsulated red phosphorus, 9-14 weight % nitrogen flame retardant and 9-21 weight % processing aid.After tested, the every performance index excellence of product sees table 4 for details.
Table 4: the physicals of wire rod and testing method
| Test event | Performance | Testing standard |
| Tensile strength MPa | 15.50～21.00 | UL1581 |
| Elongation % | 100～230 | UL1581 |
| Hardness Shao A | 92～97 | GB/T?2411 |
| Density g/cm 3 | 1.10 | GB/T?1033 |
| Flame retardant rating VW-1 | By | UL1581 |
Claims (6)
1. halogen-free fire-proof resin composition, it is characterized in that comprising polyethylene, Noryl, hydrogenated styrene-butadiene block copolymer, halogen-free flame retardants and processing aid, wherein, polyethylene is 1-15 weight %, Noryl is that 15-50 weight %, hydrogenated styrene-butadiene block copolymer are 15-45 weight %, halogen-free flame retardants is the mixture of micro encapsulation encapsulated red phosphorus and nitrogen flame retardant, the red phosphorus that coats is 1-10 weight %, the nitrogen flame retardant is 5-20 weight %, and processing aid is 5-28 weight %.
2. halogen-free fire-proof resin composition according to claim 1 is characterized in that described polyethylene is the arbitrary class in high density polyethylene(HDPE), new LDPE (film grade), the linear polyethylene.
3. halogen-free fire-proof resin composition according to claim 1 is characterized in that described nitrogen flame retardant is a melamine cyanurate nitrogen flame retardant.
4. halogen-free fire-proof resin composition according to claim 1 is characterized in that described processing aid contains oxidation inhibitor, is 0.05-0.3 weight %.
5. the preparation method of the described halogen-free fire-proof resin composition of claim 1, it is characterized in that polyethylene, Noryl, hydrogenated styrene-butadiene block copolymer, the mixture of micro encapsulation encapsulated red phosphorus and nitrogen flame retardant, % drops into high-speed mixer by weight, after the dispersing and mixing, through the twin screw extruder fusion, extrude, cooling, pelletizing, drying.
6. the described halogen-free fire-proof resin composition of claim 1 is applicable to the purposes of the coating and the injection moulding of electric wire.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006101193204A CN100509938C (en) | 2006-12-08 | 2006-12-08 | Halogen-free flame-proof resin composition and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006101193204A CN100509938C (en) | 2006-12-08 | 2006-12-08 | Halogen-free flame-proof resin composition and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1970610A CN1970610A (en) | 2007-05-30 |
| CN100509938C true CN100509938C (en) | 2009-07-08 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNB2006101193204A Expired - Fee Related CN100509938C (en) | 2006-12-08 | 2006-12-08 | Halogen-free flame-proof resin composition and preparation method thereof |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101397399B (en) * | 2007-09-26 | 2011-03-02 | 比亚迪股份有限公司 | Flame retardant polyphenylene ether resin composition and preparation method thereof |
| CN101161719B (en) * | 2007-09-30 | 2010-12-15 | 上海金发科技发展有限公司 | Special material for injection grade non-halogen flame-retardant wire plug and preparation method thereof |
| JP5095426B2 (en) * | 2008-01-23 | 2012-12-12 | 矢崎総業株式会社 | Covered wire and wire harness |
| KR20110003435A (en) * | 2008-04-09 | 2011-01-12 | 스미토모덴키고교가부시키가이샤 | Flame-retardant tube and heat-shrinkable tube made by using the same |
| CN101831134B (en) * | 2010-05-10 | 2012-02-01 | 宁波市青湖弹性体科技有限公司 | Thermoplastic halogen-free flame retarding elastomer composition for electric wire and cable covering materials |
| KR101482027B1 (en) * | 2011-12-15 | 2015-01-21 | 제일모직주식회사 | Low hardness thermoplastic elastomer and diaphragm usign the same |
| JP5494688B2 (en) * | 2012-02-03 | 2014-05-21 | 住友電気工業株式会社 | Halogen-free flame retardant insulated wire |
-
2006
- 2006-12-08 CN CNB2006101193204A patent/CN100509938C/en not_active Expired - Fee Related
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| CN1970610A (en) | 2007-05-30 |
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Granted publication date: 20090708 |