CN102898737A - Macromolecular flame-retardant elastomer environment-friendly material and preparation method thereof - Google Patents
Macromolecular flame-retardant elastomer environment-friendly material and preparation method thereof Download PDFInfo
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- CN102898737A CN102898737A CN2012103652578A CN201210365257A CN102898737A CN 102898737 A CN102898737 A CN 102898737A CN 2012103652578 A CN2012103652578 A CN 2012103652578A CN 201210365257 A CN201210365257 A CN 201210365257A CN 102898737 A CN102898737 A CN 102898737A
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Abstract
The invention provides a macromolecular flame-retardant elastomer environment-friendly material and a preparation method thereof. The macromolecular flame-retardant elastomer environment-friendly material consists of thermoplastic styrene elastomer, polypropylene, polyethylene octene co-elastomer, a phosphorus nitrogen series composite flame retardant, a flame-retardant synergist, a compatilizer, white oil, an antioxidant and a coloring agent. The preparation method comprises the following steps of: mixing the raw materials in a ratio, extruding, drawing, granulating, and thus obtaining the material. The material has good physical property, and is suitable for making low-voltage wires such as electronic wires, earphone wires, audio wires, universal serial bus (USB) wires, computer flat cables and signal wires on the premise that good flame-retardant performance is ensured.
Description
Technical field
The invention belongs to polymeric material field, particularly a kind of high molecular fire retardant elastomerics environmental protection material and preparation method thereof.
Background technology
At present, one of material of usage quantity maximum is polyvinyl chloride (PVC) in the electric wire industry, and it is the material of a kind of halogen system, and chlorinity is up to 50% macromolecular material, in the electric wire manufacturing processed, also added other a large amount of harmful modified materials, made the inadequate environmental protection of PVC material.The PVC material can produce halocarbon and other toxic gases (such as dioxin) etc. when burning.When presence of fire, very harmful to human body, and make people's death by suffocation.The environmental-protecting performance aspect of PVC material is not enough and the hazardness of fire, and to the application of PVC, American-European all states (such as the U.S., Germany, Britain, Switzerland etc.) and Japan and other countries are held the strongest opposition attitude.The legislative bodies that these are national and coordination organization have worked out blue law, the industrial application of restriction PVC material, and the functional materials of the exploitation environmental protection of trying every possible means replaces PVC as early as possible.
In the prior art, well-known halogen-free low-smoke flame retardant material is take polyolefin resin as base material, and filler metal oxyhydroxide is done fire retardant material, mixes plasticizing forming at some functional agents of interpolation together, processes with chemistry or physical method.This type of halogen-free low-smoke flame retardant material is mainly used in the cable of all kinds, various uses, such as high-low pressure power cable, control cables, telecommunication cable, shipboard cable, vehicular cable, electronic cable etc.When materials is applied to the low pressure wire rod such as electric wire, electric wire, signal wire, earphone cord, tone frequency channel wire, USB line of electronic apparatus, its material behavior exists four aspects not enough: the one, and the fire-retardant and infill system that halogen-free low-smoke flame retardant material uses is the metal hydroxides material, fill content up to more than 65%, cause the product line wood property to descend, in the follow-up use course of processing, be prone to outward appearance phenomenons such as scraping white scratch; The 2nd, because metal hydroxides material flame retarding efficiency is not high, use to produce that some structures are comparatively complicated, during the electric wire of wall thickness, the wire rod flame retardant test can reach the flame retardant rating of UL1581:VW-1, just can't be by the flame retardant rating test of UL1581:VW-1 but keep away thin wire rod at some; The 3rd, a large amount of metal hydroxides materials are filled by this type of low-smoke halide-free fireproof composite polyolefine material system, and hardness is large, and Shao Shi A can't satisfy the low pressure wire rods such as electric wire and signal wire to the requirement of flexibility often more than 90; The 4th, a large amount of metal hydroxides materials are filled by this type of low-smoke halide-free fireproof composite polyolefine material system, and the cost cost is higher, and difficulty is used in marketing.
Summary of the invention
For solving the problems of the technologies described above, the invention provides effectively fire-retardant high molecular fire retardant elastomerics environmental protection material and preparation method thereof.
The present invention realizes in the following way:
A kind of high molecular fire retardant elastomerics environmental protection material is made of thermoplastic styrene class elastomerics, polypropylene, polyethylene octene elastomer, phosphorus nitrogen series composite flame retardant, retardant synergist, compatilizer, white oil, oxidation inhibitor, lubricant and tinting material;
Its mass fraction ratio is:
Thermoplastic styrene class elastomerics 35 ~ 55,
Polypropylene 5 ~ 20,
Polyethylene octene elastomer 5 ~ 10,
Phosphorus nitrogen series composite flame retardant 15 ~ 25,
Retardant synergist 3 ~ 10,
Compatilizer 2 ~ 10,
White oil 10 ~ 55,
Oxidation inhibitor 0.05 ~ 0.15,
Tinting material 0.05 ~ 0.15.
As further improvement in the technical proposal, described thermoplastic styrene class elastomerics is that one or several the arbitrary ratio in styrene-ethylene-styrol copolymer, styrene-butadiene-styrene block copolymer, styrene-ethylene-isoprene-styrene block copolymer, the styrene isoprene styrene block copolymer (SIS) is mixed.
As further improvement in the technical proposal, described phosphorus nitrogen series composite flame retardant is that one or more the arbitrary ratio in the ammonium polyphosphate, trimeric cyanamide, terpolycyantoamino-formaldehyde resin, pentaerythritol bis (dihydrogen phosphate) melamine salt, tetramethylolmethane, tritolyl phosphate, trioctyl phosphate, triphenylphosphate, Resorcinol two (diphenyl phosphoester) is mixed.
As further improvement in the technical proposal, described retardant synergist is that one or more the arbitrary ratio in the solid-state siloxanes, nano organic montmorillonite, silicone, antimonous oxide, zinc borate, silicon-dioxide, molybdenum dioxide, bismuth oxide, cupric oxide, magnesium oxide of ultra-high molecular weight is mixed.
As further improvement in the technical proposal, described compatilizer is the ethylene-vinyl acetate copolymer grafted maleic anhydride, ethylene-vinyl acetate copolymer grafting methyl methacrylate, the SIS/SEBS grafted maleic anhydride, SIS/SEBS grafting methyl methacrylate, the grafted low density polyethylene maleic anhydride, high-density polycthylene grafted maleic anhydride, polypropylene grafted maleic anhydride, the grafted low density polyethylene methyl methacrylate, high-density polycthylene grafted methyl methacrylate, polypropylene grafted methyl methacrylate, the linear low density polyethylene grafted maleic anhydride, linear low density polyethylene grafting methyl methacrylate, arbitrary ratio of one or more in the atactic styrene-maleic anhydride copolymer is mixed.
The selected additive of the technical program is the common plastics additive that helps to promote physicals and the flame retardant properties of material.
Low Density Polyethylene in the technical program and linear low density polyethylene refer to that density is generally 0.910 ~ 0.925g/cm
3Polyethylene and linear polyethylene.
Prepare the method for above-mentioned high molecular fire retardant elastomerics environmental protection material, may further comprise the steps:
(1) be that 35 ~ 55:5 ~ 20:5 ~ 10:15 ~ 25:3 ~ 10:2 ~ 10:10 ~ 55:0.05 ~ 0.15:0.05 ~ 0.15 mixes thermoplastic styrene class elastomerics, polypropylene (PP), polyethylene octene elastomer (POE), phosphorus nitrogen series composite flame retardant, retardant synergist, compatilizer, white oil, oxidation inhibitor, tinting material in mass ratio; Mixing condition is to stir 5 ~ 10min under the rotating speed of 1100 ~ 1350rpm/min;
(2) under 170 ℃ ~ 210 ℃, extrude, traction, granulation, obtain high molecular fire retardant elastomerics environmental protection material.
Compared with prior art, the present invention has following beneficial effect:
1, the heavy metal such as not leaded, the cadmium of the material produced of the present invention, mercury is not halogen-containing, meets ROHS standard and WEEE requirement, is a kind of green material.
2, the tensile strength of material produced of the present invention is high, unit elongation is large, soft, have good fire-retardant, low cigarette, characteristic and the excellent processing characteristics of environmental protection.
3, the material of the present invention's production is applicable to make the low dc voltage electric wire, electric wire, and earphone cord, tone frequency channel wire, the USB line, computer line bank, the low pressure wire rods such as signal wire, wire product all can reach the flame retardant rating of UL1581:VW-1.
4, the material metal oxide content of the present invention's production is few, greatly reduces manufacturing cost.
Embodiment
Defective for prior art exists will be described in further detail the present invention for the ease of it will be appreciated by those skilled in the art that below:
Embodiment one:
According to ratio of quality and the number of copies, take by weighing 40 parts of styrene-ethylene-styrol copolymers (SEBS), 10 parts of polypropylene (PP), 5 parts of polyethylene octene elastomer (POE), 5 parts of silicone, 15 parts of pentaerythritol bis (dihydrogen phosphate) melamine salt, 3 parts of zinc borates, 40 parts of white oils, 0.1 part in oxidation inhibitor, 0.1 part of tinting material.Above-mentioned load weighted each starting material rotating speed with 1150rpm/min in the high-speed mixing stirrer was evenly mixed 8 minutes, then add 5 parts of ethylene-vinyl acetate copolymer grafted maleic anhydrides (EVA-g-MAH), then remix 2 minutes is extruded at twin screw extruder, granulation, cooling.Extrude processing temperature between 180 ℃ to 220 ℃, head and die temperature are 220 ℃.
The present invention adds white oil for improving material softer hardness, can adopt polypropylene material for regulating tensile strength and scrape abrasion resistance, simultaneously, use the common body of polyethylene octene to be main raw material for improving anti-shear-stress and rebound performance, the high molecular fire retardant elastomerics environmental protection material of making, prepare specimen with injection moulding machine, the melting index that records sample by ASTM D1238 standard be 10.5g/10min (200 ℃/2.16kg), Shore A hardness by ASTM D1124 standard testing sample is 80, tensile strength and elongation at break by ASTM D412 standard testing sample are 12.8MPa and 386%, extrude UL1581 2.0mm wire and cable standard at forcing machine, copper wire is the sample of 0.12mmX20, the tensile strength and the elongation at break that record wire rod by the UL1581 standard are 12.5MPa and 360%, by VW-1 burning grade.
Embodiment two:
According to ratio of quality and the number of copies, take by weighing 35 parts of styrene-butadiene-styrene block copolymers (SBS), 5 parts of polypropylene (PP), 10 parts of polyethylene octene elastomer (POE), 15 parts of ammonium polyphosphates, 10 parts of trimeric cyanamides, 5 parts of silicone, 5 parts of zinc borates, 30 parts of white oils, 0.1 part in oxidation inhibitor, 0.1 part of tinting material.Load weighted each starting material were evenly mixed 10 minutes in the high-speed mixing stirrer, then add 5 parts of SIS/SEBS grafted maleic anhydrides (SEBS-g-MAH), then remix 2 minutes is extruded at twin screw extruder, granulation, cooling.Extrude processing temperature between 180 ℃ to 220 ℃, head and die temperature are 220 ℃.
The present invention adds white oil for improving material softer hardness, can adopt polypropylene material for regulating tensile strength and scrape abrasion resistance, simultaneously, use the common body of polyethylene octene to be main raw material for improving anti-shear-stress and rebound performance, the high molecular fire retardant elastomerics environmental protection material of making, prepare specimen with injection moulding machine, the melting index that records sample by ASTM D1238 standard be 5.3g/10min (200 ℃/2.16kg), Shore A hardness by ASTM D1124 standard testing sample is 85, tensile strength and elongation at break by ASTM D412 standard testing sample are 11.4MPa and 378%, on forcing machine, extrude UL1581 2.0mm wire and cable standard, copper wire is the sample of 0.12mmX20, the tensile strength and the elongation at break that record wire rod by the UL1581 standard are 11.0MPa and 353%, by VW-1 burning grade.
Embodiment three:
According to ratio of quality and the number of copies, take by weighing 40 parts of styrene-ethylene-styrol copolymers (SEBS), 10 parts of styrene-butadiene-styrene block copolymers (SBS), 5 parts of polypropylene (PP), 10 parts of polyethylene octene elastomer (POE), 15 parts of ammonium polyphosphates, 10 parts of trimeric cyanamides, 5 parts of silicone, 2 parts of silicon-dioxide, 50 parts of white oils, 0.1 part in oxidation inhibitor, 0.1 part of tinting material evenly mixes load weighted each starting material 10 minutes in the high-speed mixing stirrer, then adds 7.5 parts of ethylene-vinyl acetate copolymer grafting methyl methacrylates (EVA-g-MMA), remix 2 minutes, then extrude granulation, cooling at twin screw extruder.Extrude processing temperature between 180 ℃ to 220 ℃, head and die temperature are 220 ℃.
The present invention adds white oil for improving material softer hardness, can adopt polypropylene material for regulating tensile strength and scrape abrasion resistance, simultaneously, use the common body of polyethylene octene to be main raw material for improving anti-shear-stress and rebound performance, the high molecular fire retardant elastomerics environmental protection material of making, prepare specimen with injection moulding machine, the melting index that records sample by ASTM D1238 standard be 14.7g/10min (200 ℃/2.16kg), Shore A hardness by ASTM D1124 standard testing sample is 70, tensile strength and elongation at break by ASTM D412 standard testing sample are 10.3MPa and 482%, on forcing machine, extrude UL1581 2.0mm wire and cable standard, copper wire is the sample of 0.12mmX20, the tensile strength and the elongation at break that record wire rod by the UL1581 standard are 9.4MPa and 455%, by VW-1 burning grade.
In the present invention, except composition and content that above-mentioned three embodiment adopt, other concrete composition and content can also be arranged.Such as, styrene-ethylene-styrol copolymer, styrene-butadiene-styrene block copolymer is thermoplastic styrene class elastomerics, can adopt other thermoplastic styrene class elastomerics such as styrene-ethylene-isoprene-styrene block copolymers, any composition in the styrene isoprene styrene block copolymer (SIS), arbitrary ratio that also can be above-mentioned Multiple components is mixed, for the concrete content of above-mentioned thermoplastic styrene class elastomerics, also can be the arbitrary value between 35 ~ 55, such as 20 parts or 55 parts etc., because its effect is consistent with above-mentioned two embodiment effects, therefore not to repeat here.For polypropylene, its concrete content also can be arbitrary value between 5 ~ 20 parts, as 8 parts or 15 parts or 20 parts all can, because its effect is consistent with above-mentioned two embodiment effects, therefore not to repeat here.For the polyethylene octene elastomer, can adopt polyethylene octene elastomer commonly used in the industry, such as the POE8402 type of du pont company production or 8999 type polyethylene octene elastomer of LG-DOW company production etc., its concrete content also can 5 ~ 10 between arbitrary value, such as 6 parts or 8 parts etc., because its effect is consistent with above-mentioned two embodiment effects, therefore not to repeat here.For the ammonium polyphosphate as the phosphorus nitrogen series composite flame retardant, trimeric cyanamide, pentaerythritol bis (dihydrogen phosphate) melamine salt, can adopt other phosphorus nitrogen series composite flame retardant such as terpolycyantoamino-formaldehyde resins, tetramethylolmethane, tritolyl phosphate, trioctyl phosphate, triphenylphosphate, any composition in the Resorcinol two (diphenyl phosphoester), arbitrary ratio that also can be above-mentioned Multiple components is mixed, concrete content for the phosphorus nitrogen series composite flame retardant, also can be the arbitrary value between 15 ~ 25, such as 20 parts or 24 parts etc., because its effect is consistent with above-mentioned two embodiment effects, therefore not to repeat here.For for the silicone of retardant synergist, zinc borate, silicon-dioxide, can adopt any composition in the solid-state siloxanes, nano organic montmorillonite, antimonous oxide, molybdenum dioxide, bismuth oxide, cupric oxide, magnesium oxide of other retardant synergists such as ultra-high molecular weight, arbitrary ratio that also can be above-mentioned Multiple components is mixed, for concrete content, also can be arbitrary value between 3 ~ 10, such as 5 parts or 8 parts etc., because its effect is consistent with above-mentioned two embodiment effects, therefore not to repeat here.For the ethylene-vinyl acetate copolymer grafted maleic anhydride as compatilizer, ethylene-vinyl acetate copolymer grafting methyl methacrylate, the SIS/SEBS grafted maleic anhydride, also can adopt other compatilizers such as SIS/SEBS grafting methyl methacrylate, the grafted low density polyethylene maleic anhydride, high-density polycthylene grafted maleic anhydride, polypropylene grafted maleic anhydride, the grafted low density polyethylene methyl methacrylate, high-density polycthylene grafted methyl methacrylate, polypropylene grafted methyl methacrylate, the linear low density polyethylene grafted maleic anhydride, linear low density polyethylene grafting methyl methacrylate, any composition in the atactic styrene-maleic anhydride copolymer, arbitrary ratio that also can be above-mentioned Multiple components is mixed, for the concrete content of compatilizer, also can be the arbitrary value between 2 ~ 10, such as 2 parts or 5 parts etc., because its effect is consistent with above-mentioned two embodiment effects, therefore not to repeat here.For white oil, its concrete content also can be arbitrary value between 10 ~ 55, and such as 10 parts or 20 parts or 55 parts etc., because its effect is consistent with above-mentioned two embodiment effects, therefore not to repeat here.For oxidation inhibitor, can select oxidation inhibitor commonly used in the industry, the oxidation inhibitor SK-100 that produces such as Linfen, Shandong three Feng Huagong company limiteds or the phosphite ester kind antioxidant 168 of the China's exploitation eighties or composite antioxidant 215,225 etc., its concrete content also can be arbitrary value between 0.05 ~ 0.15, such as 0.05 part or 0.15 part etc., because its effect is consistent with above-mentioned two embodiment effects, therefore not to repeat here.For tinting material, can select tinting material commonly used in the industry, the SJ36W type tinting material of producing such as Wenzhou Li Haoda chemical industry company limited etc., its concrete content also can be the arbitrary value between 0.05 ~ 0.15, such as 0.05 part or 0.15 part etc., because its effect is consistent with above-mentioned two embodiment effects, therefore not to repeat here.
The above embodiment has only expressed embodiments of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to claim of the present invention.Should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.
Claims (7)
1. a high molecular fire retardant elastomerics environmental protection material is characterized in that: be made of thermoplastic styrene class elastomerics, polypropylene, polyethylene octene elastomer, phosphorus nitrogen series composite flame retardant, retardant synergist, compatilizer, white oil, oxidation inhibitor and tinting material;
Its mass fraction ratio is:
Thermoplastic styrene class elastomerics 35 ~ 55,
Polypropylene 5 ~ 20,
Polyethylene octene elastomer 5 ~ 10,
Phosphorus nitrogen series composite flame retardant 15 ~ 25,
Retardant synergist 3 ~ 10,
Compatilizer 2 ~ 10,
White oil 10 ~ 55,
Oxidation inhibitor 0.05 ~ 0.15,
Tinting material 0.05 ~ 0.15.
2. high molecular fire retardant elastomerics environmental protection material according to claim 1, it is characterized in that, described thermoplastic styrene class elastomerics is that one or several the arbitrary ratio in styrene-ethylene-styrol copolymer, styrene-butadiene-styrene block copolymer, styrene-ethylene-isoprene-styrene block copolymer, the styrene isoprene styrene block copolymer (SIS) is mixed.
3. high molecular fire retardant elastomerics environmental protection material according to claim 1, it is characterized in that, described phosphorus nitrogen series composite flame retardant is that one or more the arbitrary ratio in the ammonium polyphosphate, trimeric cyanamide, terpolycyantoamino-formaldehyde resin, pentaerythritol bis (dihydrogen phosphate) melamine salt, tetramethylolmethane, tritolyl phosphate, trioctyl phosphate, triphenylphosphate, Resorcinol two (diphenyl phosphoester) is mixed.
4. high molecular fire retardant elastomerics environmental protection material according to claim 1, it is characterized in that, described retardant synergist is that one or more the arbitrary ratio in the solid-state siloxanes, nano organic montmorillonite, silicone, antimonous oxide, zinc borate, silicon-dioxide, molybdenum dioxide, bismuth oxide, cupric oxide, magnesium oxide of ultra-high molecular weight is mixed.
5. high molecular fire retardant elastomerics environmental protection material according to claim 1, it is characterized in that, described compatilizer is the ethylene-vinyl acetate copolymer grafted maleic anhydride, ethylene-vinyl acetate copolymer grafting methyl methacrylate, the SIS/SEBS grafted maleic anhydride, SIS/SEBS grafting methyl methacrylate, the grafted low density polyethylene maleic anhydride, high-density polycthylene grafted maleic anhydride, polypropylene grafted maleic anhydride, the grafted low density polyethylene methyl methacrylate, high-density polycthylene grafted methyl methacrylate, polypropylene grafted methyl methacrylate, the linear low density polyethylene grafted maleic anhydride, linear low density polyethylene grafting methyl methacrylate, arbitrary ratio of one or more in the atactic styrene-maleic anhydride copolymer is mixed.
6. prepare the method for high molecular fire retardant elastomerics environmental protection material claimed in claim 1, it is characterized in that, may further comprise the steps:
(1) with mass ratio be 35 ~ 55:5 ~ 20:5 ~ 10:15 ~ 25:3 ~ 10:2 ~ 10:10 ~ 55:0.05 ~ 0.15:0.05 ~ 0.15 thermoplastic styrene class elastomerics,, polypropylene, polyethylene octene elastomer, phosphorus nitrogen series composite flame retardant, retardant synergist, compatilizer, white oil, oxidation inhibitor, tinting material mix;
(2) under 170 ℃ ~ 210 ℃, extrude, traction, granulation, obtain high molecular fire retardant elastomerics environmental protection material.
7. preparation method according to claim 6 is characterized in that, mixing condition is rotating speed 1100 ~ 1350rpm/min in the described step (1), churning time 5 ~ 10min.
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