CN1563165A - Ion crosslinking type flame retardant thermoplastic elastomer in low smoke and no halogen and preparation method - Google Patents
Ion crosslinking type flame retardant thermoplastic elastomer in low smoke and no halogen and preparation method Download PDFInfo
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- CN1563165A CN1563165A CN 200410017177 CN200410017177A CN1563165A CN 1563165 A CN1563165 A CN 1563165A CN 200410017177 CN200410017177 CN 200410017177 CN 200410017177 A CN200410017177 A CN 200410017177A CN 1563165 A CN1563165 A CN 1563165A
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Abstract
A thermoplastic elastomer is made of ionomer, vistanx, divalent or trivalent metal hydroxide, high polymer wax and assistant for plastic processing. The process of preparing the thermoplastic elastomer is simple and the produced product has excellent performance of low fuming and low temp is fire resistance.
Description
Technical field:
The present invention relates to a kind of ionomer type low-smoke halogen-free flame-retardant thermoplastic elastomer and preparation method, be specially adapted to the insulation and the sheath material of electric wire.
Technical background:
The ionomer polyolefine is confined to the research carried out of EXXON company of the later stage seventies.US3,974,241 and US4,220,573 disclose the mixture of being made up of transition metal ion and organic amine neutral polymkeric substance and crystalline polymer, adopting bigger complete neutral elastomerics and the partially crystalline polymer of sulfonation degree is body material, by ionomeric ionomer, obtains functional thermoplastic elastomer.Wherein elastomeric hardness and mechanical property are mediated by adding low molecule mineral oil and mineral filler.
The deficiency of these patents at first is exactly that the elastomerics that makes does not have flame retardant properties, makes its range of application be subjected to great limitation; Secondly since the bigger elastomerics of sulfonation degree since under the normal temperature its ion crystalline region bigger, the material hardness that obtains is bigger and elongation is smaller, generally reduces hardness by stearic acid or mineral wet goods softening agent, has reduced the mechanical property of material simultaneously.
The production method of the fire retardant polyolefin of being familiar with for everybody be with polyolefin resin with metal hydroxides, small molecules coupling agent, or metal hydroxides formed with the polyolefine Compound Machining after with the small molecules coupling agent treatment again.In addition, ionomer has good consistency owing to have polar group and polymer materials and mineral filler, thereby and under cold condition, have ionic cross-linked bond and make matrix material have the good mechanical performance, and, and make ionomer obtain increasingly extensive application at high temperature because thereby the fracture of ionic linkage makes material have good flowability and processing characteristics.
A kind of Halogen acid proof thermoplastic resin composition is disclosed in the CN1219550A patent.Added reactive compatibilizer in this invention in resin combination 1-20% weight.This reflection expanding material is: connect the reactive compatibilizer that obtains on the thermoplastic polymer of most modification as properties-correcting agent by the compound that will have a unsaturated link(age) at least and have a carboxyl in its molecule.Used unsaturated carboxylic compound is a Maleic Acid, Anhydrous, anhydrous methylene-succinic acid, anhydrous citraconic acid and anhydrous fumaric acid.The main effect of reactive compatibilizer in this invention is the acid resistance that improves composition.Magnesium hydroxide is carried out surface treatment by the small molecules surface treatment agent in this invention, thereby has improved the consistency of magnesium hydroxide and polymeric matrix greatly.Disclose a kind of flame retardant polyolefin jacket material of low-smoke zero-halogen low-toxicity in the CN1343737A patent, this sheath material has gone out the inorganic combustion inhibitor that wherein adds have been used outside the small molecules coupling agent treatment, has also added the fire-resistant synergistic order material of composition complexity.The CABLE MATERIALS complex procedures of this kind method preparation, and a large amount of retardant synergist, use surface-treated metal hydroxides and complicated base-material have all inevitably increased Financial cost greatly.
Disclosed material mainly contains 2 deficiencies in the above patent, the one, the material of a large amount of metal hydroxidess is filled by low-smoke halide-free fireproof composite polyolefine material system, with a spot of these mineral fillers of small molecules coupling agent treatment, general treating processes is difficult to accomplish even processing, promptly be difficult to make inorganic material surface evenly to cover the small molecules coupling agent, this makes material in use unavoidably occur the stress cracking phenomenon usually too early.And heavy addition small molecules coupling agent does not also gear to actual circumstances, and is extremely uneconomical on the one hand, will damage the mechanical property of material on the other hand, will reduce significantly as tensile strength.The 2nd, low-smoke halide-free fireproof composite polyolefine material is general main to be a large amount of materials of filling of aluminium hydroxide, magnesium hydroxide or their mixture.These two kinds of fillers that use do not have enhancement to material property, cause commercially available low-smoke halogen-free polyolefin material under the situation of the elongation at break that keeps being fit to, and tensile strength is all lower.With commercially available black low-smoke non-halogen flame-retardant material is example, and such as the UCC DFDA1642 trade mark, LOI is 37, and tensile strength is 11.5Mpa, and elongation at break is also lower, only is 165%.With commercially available true qualities low-smoke non-halogen flame-retardant material is example, and as the megolon S571 of the Britain Scapa Polymer Company trade mark, LOI is 35, and tensile strength is 11Mpa, and elongation at break is 160%.
In addition, widely used flame-proof elastomer material generally is to adopt the PVC material, it has good flame retardant property and cryogenic mechanics performance, but owing to contain a large amount of halogens in the PVC material, in the removal process of burning and a large amount of waste products, brought serious day by day problem for environment, owing to the pay attention to day by day of countries in the world, press for a kind of substitute products of PVC material in recent years for environmental problem.
Summary of the invention:
Purpose of the present invention is at above-mentioned the deficiencies in the prior art, the requirement of the replacement PVC material that proposes according to environmental protection, a kind of novel ionomer type low-smoke halogen-free flame-retardant thermoplastic elastomer material has been proposed, raw materials used being easy to get, machine-shaping is convenient, has good low-smoke and flame retardant characteristic and mechanical property.
The present invention proposes a kind of novel ionomer type low-smoke halogen-free flame-retardant thermoplastic elastomer, its weight is formed and is comprised: the macromolecule wax of the polyolefin resin of the ionomer of 30-70 part, 30-70 part, the divalence of 120-170 part or trivalent metal hydroxides, 2-15 part, the plastic processing additives of 1-10 part.
Wherein ionomer adopts following method preparation: the rubber that will contain conjugated double bond dissolves in non-polar solvent, forming weight ratio is the homogeneous solution of 3-15%, solvent temperature is 50-80 ℃, be cooled to room temperature adding 0.02-0.2mol/100g rubber acetylsulfuric acid then and introduce sulfonic acid group by substitution reaction, the transition metal alkali or the salt that add 0.02-0.25mol/100g rubber after half an hour neutralize, neutralization reaction carries out taking out reaction product after half an hour, and wherein degree of neutralization is greater than 95%.Obtain ionomer by washing drying then.
The rubber of the conjugated double bond that the present invention adopts has Ethylene-Propylene-Diene Monomer (EPDM) (EPDM), natural rubber, polyisoprene rubber, styrene-butadiene rubber(SBR) or isoprene-isobutylene rubber.
The non-polar solvent that the present invention adopts has toluene, dimethylbenzene, hexanaphthene or normal hexane.
Transition metal alkali or salt that the present invention adopts are meant iron, zinc, cobalt, nickel, copper metal base or salt.
The polyolefin resin that the present invention adopts has polyethylene, polypropylene, ethylene vinyl acetate (EVA) or their mixture.
The metal hydroxides that the present invention adopts has aluminium hydroxide, magnesium hydroxide or their mixture, and the median size of metal hydroxides powder is 0.7 μ m～20 μ m.
The macromolecule wax that the present invention adopts has polyethylene wax, Poly Propylene Wax or their mixture, and viscosity-average molecular weight is 1000-3000.
The plastic processing additives that the present invention selects for use has antioxidant, ultraviolet absorber, tinting material, softening agent etc.Selected auxiliary agent can not obviously influence the flame retardant properties and the mechanical property of material.
Ionomer type low-smoke halogen-free flame-retardant thermoplastic elastomer preparation method of the present invention comprises:
(1) prepares ionomer according to the method described above;
(2) it is mixing even to put into Banbury mixer by ionomer, polyolefine, metal hydroxides, macromolecule wax and five kinds of components of plastic processing additives of above-mentioned composition, and melting temperature is 150-170 ℃, and mixing time is 8 minutes, can obtain finished product.
The novel ionomer type low-smoke halogen-free flame-retardant thermoplastic elastomer that the present invention obtains, compare with traditional thermoplastic elastomer to have and do not need crosslinkedly can have the good mechanical performance, complete processing is easy, and has higher oxygen index, has good flame retardancy; Have the elongation at break height with traditional halogen-free flame-retardant cable material contrast, breaking tenacity is big, has good toughness and flexibility; With normally used PVC material contrast, have not halogen-containing, heavy metal and other any toxic ingredient, eco-friendly characteristics.The ionomer type low-smoke halogen-free flame-retardant thermoplastic elastomer that the present invention obtains is ionomer type matrix material tensile strength at normal temperatures, elongation at break, breaking down field strength are bigger, dielectric loss constant is little, has good fire-retardant low cigarette characteristic, under hot conditions, the ionomer bond rupture has good flowability and processing characteristics, not halogen-containing, heavy metal and other any toxic ingredient, being specially adapted to electric wire, optical cable, indoor decoration, automobile, electronics line etc. has the field of strict demand to use to fire-retardant and elasticity.
Embodiment:
The present invention will be described in more details technical scheme of the present invention by following concrete embodiment, but the present invention is not limited to embodiment proposed below.
The judgement criteria that the present invention uses is as follows:
The mechanical property evaluation method adopts the IEC60811 standard; The oxygen index judgement criteria adopts the ASTM2863 standard.
Embodiment 1, ionomeric preparation:
Get the EPDM (therein ethylene content is 69%, and propylene content is 30.5%, and ethylidene norbornene content is 0.5%) of 50 grams, under 70 ℃ of conditions, be dissolved in 600 milliliters of hexanaphthenes and obtain uniform EPDM cyclohexane solution.Be cooled to room temperature then, under well-beaten condition, add the 0.03mol acetylsulfuric acid, obtain sulfonated EPDM after continuing to stir half an hour, after interpolation 0.04mol zinc acetate continues to stir half an hour under the well-beaten condition, obtain zine ion neutral sulfonated epdm ionomer then.By washing, drying, obtain pure ionomer then.
Embodiment 2:
Obtain ionomer according to embodiment 1, the ionomer that obtains 15 grams and polypropylene 15 grams and aluminium hydroxide 48 grams and Poly Propylene Wax 1.5 were restrained in Haake torque rheometer uniform mixing 8 minutes, mixing temperature is 170 ℃.The oxygen index of gained ionomer type low-smoke halogen-free flame-retardant thermoplastic elastomer is 37, and tensile strength and elongation at break are 14Mpa and 380%.
Embodiment 3:
Obtain ionomer according to embodiment 1.With the ionomer that obtains 15 grams and polyethylene 15 grams and the aluminium hydroxide 48 that not have to handle restrains and polyethylene wax 1.5 restrained in Haake torque rheometer uniform mixing 8 minutes, mixing temperature is 170 ℃.The oxygen index of gained ionomer type low-smoke halogen-free flame-retardant thermoplastic elastomer is 37, and tensile strength and elongation at break are 13Mpa and 280%.
Embodiment 4:
Obtain ionomer according to embodiment 1.With the ionomer that obtains 15 grams and EVA15 gram and the aluminium hydroxide 48 that not have to handle restrains and polyethylene wax 1.5 restrained in Haake torque rheometer uniform mixing 8 minutes, mixing temperature is 170 ℃.The oxygen index of gained ionomer type low-smoke halogen-free flame-retardant thermoplastic elastomer is 37, and tensile strength and elongation at break are 12Mpa and 480%.
Performance compares:
Above-mentioned three the resulting ionomer type of the embodiment low-smoke halogen-free flame-retardant thermoplastic elastomers of the present invention all have good room temperature and cryogenic mechanics performance, acid-proof alkaline, flame retardant properties and excellent high temperature process performance.
Claims (9)
1, a kind of ionomer type low-smoke halogen-free flame-retardant thermoplastic elastomer is characterized in that the weight composition comprises: the macromolecule wax of the polyolefin resin of the ionomer of 30-70 part, 30-70 part, the divalence of 120-170 part or trivalent metal hydroxides, 2-15 part, the plastic working additive of 1-10 part;
Wherein ionomer adopts following method preparation: the rubber that will contain conjugated double bond dissolves in non-polar solvent, forming weight ratio is the homogeneous solution of 3-15%, solvent temperature is 50-80 ℃, be cooled to room temperature adding 0.02-0.2mol/100g rubber acetylsulfuric acid then and introduce sulfonic acid group by substitution reaction, the transition metal alkali or the salt that add 0.02-0.25mol/100g rubber after half an hour neutralize, neutralization reaction carries out taking out reaction product after half an hour, wherein degree of neutralization obtains ionomer by washing drying then greater than 95%.
2, a kind of ionomer type low-smoke halogen-free flame-retardant thermoplastic elastomer according to claim 1 is characterized in that the rubber of the conjugated double bond that adopts has Ethylene-Propylene-Diene Monomer (EPDM) (EPDM), natural rubber, polyisoprene rubber, styrene-butadiene rubber(SBR) or isoprene-isobutylene rubber.
3, a kind of ionomer type low-smoke halogen-free flame-retardant thermoplastic elastomer according to claim 1 is characterized in that the non-polar solvent that adopts has toluene, dimethylbenzene, hexanaphthene or normal hexane.
4, a kind of ionomer type low-smoke halogen-free flame-retardant thermoplastic elastomer according to claim 1 is characterized in that transition metal alkali or salt have iron, zinc, cobalt, nickel, copper metal base or salt.
5, a kind of ionomer type low-smoke halogen-free flame-retardant thermoplastic elastomer according to claim 1 is characterized in that thermoplastic resin has polyethylene, polypropylene, ethylene vinyl acetate or their mixture.
6, a kind of ionomer type low-smoke halogen-free flame-retardant thermoplastic elastomer according to claim 1 is characterized in that metal hydroxides has aluminium hydroxide, magnesium hydroxide or their mixture.
7, a kind of ionomer type low-smoke halogen-free flame-retardant thermoplastic elastomer according to claim 1 is characterized in that described macromolecule wax has polyethylene wax, Poly Propylene Wax or their mixture.
8, a kind of ionomer type low-smoke halogen-free flame-retardant thermoplastic elastomer according to claim 1 is characterized in that described plastic processing additives includes antioxidant, ultraviolet absorber, tinting material, softening agent.
9, a kind of ionomer type low-smoke halogen-free flame-retardant thermoplastic elastomer preparation method, the preparation method is as follows for its feature:
(1) prepares ionomer in accordance with the method for claim 1;
(2) it is mixing even to put into Banbury mixer by ionomer, polyolefine, metal hydroxides, macromolecule wax and five kinds of components of plastic processing additives of above-mentioned composition, and melting temperature is 150-170 ℃, and mixing time is 5-10 minute, can obtain finished product.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 200410017177 CN1266209C (en) | 2004-03-25 | 2004-03-25 | Ion crosslinking type flame retardant thermoplastic elastomer in low smoke and no halogen and preparation method |
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| Application Number | Priority Date | Filing Date | Title |
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| CN 200410017177 CN1266209C (en) | 2004-03-25 | 2004-03-25 | Ion crosslinking type flame retardant thermoplastic elastomer in low smoke and no halogen and preparation method |
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| CN1563165A true CN1563165A (en) | 2005-01-12 |
| CN1266209C CN1266209C (en) | 2006-07-26 |
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| CN 200410017177 Expired - Fee Related CN1266209C (en) | 2004-03-25 | 2004-03-25 | Ion crosslinking type flame retardant thermoplastic elastomer in low smoke and no halogen and preparation method |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101211681B (en) * | 2006-12-29 | 2010-09-15 | 财团法人工业技术研究院 | Fireproof electric wire and cable |
| CN101174492B (en) * | 2006-10-10 | 2011-04-13 | 日立电线株式会社 | Non-halogen fire resistant wire with excellent process at ends |
| CN102675706A (en) * | 2011-03-07 | 2012-09-19 | 陈明玉 | Composite component and polymer interior decoration material |
| CN104788868A (en) * | 2015-04-24 | 2015-07-22 | 福建师范大学泉港石化研究院 | Method for preparing rubber from metal salt containing concentration water through coordination crosslinking |
| CN105895229A (en) * | 2016-07-04 | 2016-08-24 | 苏州宝兴电线电缆有限公司 | Large-cross-section copper-clad aluminum EV vehicle-mounted high-voltage cable |
| CN111995838A (en) * | 2020-07-17 | 2020-11-27 | 中北大学 | Modified and regenerated ABS/HIPS (acrylonitrile-butadiene-styrene/high impact polystyrene) blend material by utilizing ionic crosslinking and preparation method thereof |
-
2004
- 2004-03-25 CN CN 200410017177 patent/CN1266209C/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101174492B (en) * | 2006-10-10 | 2011-04-13 | 日立电线株式会社 | Non-halogen fire resistant wire with excellent process at ends |
| CN101211681B (en) * | 2006-12-29 | 2010-09-15 | 财团法人工业技术研究院 | Fireproof electric wire and cable |
| CN102675706A (en) * | 2011-03-07 | 2012-09-19 | 陈明玉 | Composite component and polymer interior decoration material |
| CN102675706B (en) * | 2011-03-07 | 2015-03-25 | 陈明玉 | Composite component and polymer interior decoration material |
| CN104788868A (en) * | 2015-04-24 | 2015-07-22 | 福建师范大学泉港石化研究院 | Method for preparing rubber from metal salt containing concentration water through coordination crosslinking |
| CN104788868B (en) * | 2015-04-24 | 2016-08-24 | 福建师范大学泉港石化研究院 | A kind of preparation method of the coordination crosslinking rubber containing water of crystallization slaine |
| CN105895229A (en) * | 2016-07-04 | 2016-08-24 | 苏州宝兴电线电缆有限公司 | Large-cross-section copper-clad aluminum EV vehicle-mounted high-voltage cable |
| CN111995838A (en) * | 2020-07-17 | 2020-11-27 | 中北大学 | Modified and regenerated ABS/HIPS (acrylonitrile-butadiene-styrene/high impact polystyrene) blend material by utilizing ionic crosslinking and preparation method thereof |
| CN111995838B (en) * | 2020-07-17 | 2022-11-08 | 中北大学 | Regenerated ABS/HIPS blending material modified by ionic crosslinking and preparation method thereof |
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| CN1266209C (en) | 2006-07-26 |
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Assignee: Ningbo Jinhai Plastic Mould Co., Ltd. Assignor: Shanghai Jiao Tong University Contract fulfillment period: 2008.4.29 to 2013.4.29 contract change Contract record no.: 2009990000462 Denomination of invention: Ion crosslinking type flame retardant thermoplastic elastomer in low smoke and no halogen and preparation method Granted publication date: 20060726 License type: Exclusive license Record date: 2009.5.11 |
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Free format text: EXCLUSIVE LICENSE; TIME LIMIT OF IMPLEMENTING CONTACT: 2008.4.29 TO 2013.4.29; CHANGE OF CONTRACT Name of requester: NINGBO JINHAI MOLD + PLASTIC CO., LTD. Effective date: 20090511 |
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Granted publication date: 20060726 Termination date: 20120325 |