CN103289286B - A kind of halogen-free flame retardant thermoplastic elastomer material and preparation method thereof - Google Patents
A kind of halogen-free flame retardant thermoplastic elastomer material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of Novel halogen-free flame-retardant thermoplastic elastomer material and preparation method thereof.Does this TPEE thermoplastic elastomer comprise: SEBS? 30 ~ 50 parts, polyphenylene oxide 15 ~ 30 parts, polyolefine 2 ~ 10 parts, polyolefin elastomer 2 ~ 5 parts, PEPA phosphinate, 10 ~ 20 parts; Secondary fire retardant 5 ~ 15 parts, fire retarding synergist 1 ~ 5 part, white oil 10 ~ 40 parts, other auxiliary agents 1 ~ 5 part.This material raw material SEBS and a part of white oil, polyphenylene oxide, polyolefine, secondary fire retardant, fire retarding synergist and other auxiliary agents is sent into homogenizer keep 40 ~ 100 DEG C of temperature high-speed stirring, mixing, send into screw rod through twin-screw extrusion owner feed system, PEPA phosphinate and remaining part white oil are sent into the blended granulation of twin screw extruder through side feeding and are formed.Does obtained flame-retardant TPE elastomer have good mechanical property and screen resilience, and passes through UL? the fire-retardant rank of 94V-0.
Description
Technical field
The invention belongs to industrial chemicals field, relate to a kind of Novel halogen-free flame-retardant thermoplastic elastomer material and preparation method thereof.
Background technology
SEBS is obtained through hydrogenation hydrogenation by thermoplastic elastomer SBS's (styrene-butadiene-styrene block copolymer), after SBS hydrogenation, structure becomes polystyrene (S)-polyethylene (E)-polybutene (B) polystyrene (S) segmented copolymer, therefore referred to as SEBS.In SEBS molecular structure, carbon-to-carbon double bond is hydrogenated saturated, and thus have the performances such as excellent weather-proof, anti-aging, heat-resisting, compression distortion, SEBS use temperature can reach 130 DEG C.Especially valuable is, and it has the weather resistance of excellent resistance to ozone, resistance to oxidation, UV resistant and open air, and has recyclable again by, the advantage such as the product properties that processes is even, size easily accurately controls.Thus the fields such as electrical equipment, cable, automobile making, building and daily necessities are widely used in.
Since in succession issuing from WEEE and RoHS two instructions, various countries increase the exploitation to halogen-free flame retardants, but halogen-free expansion fire retardant still faces many deficiencies so far, addition is still too high, still annoyings current academia with the poor precipitation problem brought of the consistency of material.
Because the fields such as electronic apparatus, automobile and precision instrument require high to the flame retardant properties of material, therefore be an important research direction about SEBS flame-retardant modified, the fire-retardant TPE product of what GE company of the U.S., Sabic company of Saudi Arabia etc. developed that flame retardant rating reaches UL94V-0 level in succession with SEBS is base.But its material surface color and luster is smooth not, the vertical combustion not by 1.6mm is tested, and its fancy price inhibits the further genralrlization in its market.And in the market in halogen-free flameproof TPE product, although some TPE product of existing market is cheap, its thermostability is poor, and ageing resistance, fire retardant resistance to migration are all not as the related products of the companies such as GE.Therefore, its application is very restricted.Because the SEBS research and development of China are started late, its modification particularly fire-retardant research also has larger gap with external.
Summary of the invention
Even if the object of the invention is, for existing above-mentioned deficiency, to provide a kind of Novel halogen-free flame-retardant thermoplastic elastomer material.
Another object of the present invention is to provide the preparation method of this halogen-free flame retardant thermoplastic elastomer material.
Another object of the present invention is to provide the halogen-free flame retardants PEPA phosphinate used in this halogen-free flame retardant thermoplastic elastomer material of preparation.
Object of the present invention realizes by following technical scheme:
A kind of halogen-free flameproof TPEE thermoplastic elastomer, comprises the component of following weight part:
Halogen-free flameproof TPEE thermoplastic elastomer of the present invention, preferably comprises the component of following weight part:
Wherein, described PEPA phosphinate structural formula is:
prepare by the following method: adopt aqueous phase synthesis method, by mol ratio be 1: 0.5-10 PEPA and Hypophosporous Acid, 50 be added to the water, with the stirring velocity of 300 ~ 600r/min, in 0 ~ 100 DEG C of stirring reaction 5 ~ 10 hours, then reaction product is carried out suction filtration, washing, in 150 DEG C of vacuum-dryings 2 ~ 3 hours, obtain PEPA hypophosphite fire retardant.
Described SEBS take polystyrene as end segment, the ethylene-butene copolymer that polyhutadiene hydrogenation obtains is the linear three block copolymer of middle spring block, its structural formula as shown in Figure 2, any one preferably in the styrene-ethylene/butylene-alkene block copolymer of basic, normal, high molecular weight, one or more further preferably in the A6150,6151 that produces of thermoplastic elastomer SEBSYH-601 or YH-602 that produce of Balin Branch Corp. SINOPEC and Ke Teng Polymer Co., Ltd.
Described polyolefine is selected from the one in polyethylene, polypropylene; Preferred molten index is the one in the polyethylene of 0.5 ~ 100g/10min, polypropylene; PP1003 or KH7726 of preferably Shanghai Secco Petrochemical Co., Ltd.'s production, and any one model in the LDPE of Shanghai Petrochemial Co Ltd, China Petrochemical Corp (Low Density Polyethylene) series product further.
Described secondary fire retardant is selected from the product of hydration metal hydroxides after silane coupling agent process or trimeric cyanamide, preferred D
98the product of hydration metal hydroxides between 5 ~ 20mm after silane coupling agent process or particle diameter D98 are less than the trimeric cyanamide of 10mm; Described fire retarding synergist is selected from one or more in boric acid, borax, zinc borate, boron trioxide, titanium oxide, silicon oxide, zinc oxide; Described white oil be selected from kinematic viscosity 5 ~ 120 high temperature resistant white oil or PIB white oil in one or more.
Other described auxiliary agents are selected from one or more in Hinered phenols or suffocated amine antioxidant, lubricant, uv-absorbing agent; One or more in the irgasfos 168 of preferred vapour bar (China) company limited, oxidation inhibitor 1098 and lubricant PalletS.
Halogen-free flameproof TPEE process for preparation of thermoplastic elastomer of the present invention, step is: the white oil of raw material SEBS and formula ratio 20% ~ 60%, polyphenylene oxide, polyolefine, secondary fire retardant, fire retarding synergist and other auxiliary agents are sent into homogenizer keep 40 ~ 100 DEG C of temperature at a high speed (40 ~ 100r/min) stir, mixing 2-4min, send into screw rod through twin-screw extrusion owner feed system, PEPA phosphinate and remaining part white oil are sent into the blended granulation of twin screw extruder through side feeding and are formed.
The twin screw extrusion process process of fire-retardant TPEE matrix material is: screw speed 10 ~ 200r/min; Head to charging opening temperature, 200 ~ 250 DEG C, a district, two 200 ~ 280 DEG C, districts, three 200 ~ 280 DEG C, districts, four 200 ~ 260 DEG C, districts, five 200 ~ 260 DEG C, districts, six 200 ~ 260 DEG C, districts, seven 200 ~ 260 DEG C, districts, charging opening 220 DEG C.
Prepare the halogen-free flame retardants PEPA phosphinate used in halogen-free flameproof TPEE thermoplastic elastomer, reacted by PEPA and Hypophosporous Acid, 50 and obtained, its structural formula is as follows:
The nmr spectrum of this material is shown in Fig. 1.
This PEPA phosphinate prepares by the following method: adopt aqueous phase synthesis method, by mol ratio be 1: 0.5-10 PEPA and Hypophosporous Acid, 50 be added to the water, with the stirring velocity of 300 ~ 600r/min, in 0 ~ 100 DEG C of stirring reaction 5 ~ 10 hours, then reaction product is carried out suction filtration, washing, in 150 DEG C of vacuum-dryings 2 ~ 3 hours, obtain PEPA hypophosphite fire retardant.
The invention has the beneficial effects as follows:
Use through reality, fire retardant material of the present invention has good flame retardant effect, UL-94V-0 grade standard (1.6mm) can be reached, add that it is not halogen-containing, LSZH, and main body fire retardant PEPA phosphinate can effectively be combined with matrix after silane coupling agent process, do not bring precipitation problem, its outstanding advantages all meets the environmental requirement of society.And this composition belongs to thermoplastic elastic material, not only rebound resilience, obdurability and weathering resistance are all fabulous, and can recycling use, meet circular economy concept.It can be widely used as sheath, the first-class electronic apparatus material of power plug into electric wire.Crude sense is not had, bracing wire smoother, uniform color by the product appearance that this composition makes.
Accompanying drawing explanation
Fig. 1 halogen-free flame retardants PEPA phosphinate nmr spectrum.
Fig. 2 SEBS structural formula,
Wherein, x, m, n all need to be greater than 1000, x/ (x+m+n) > 30%, simultaneously < 50%.
Embodiment
Below in conjunction with embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after the content of having read the present invention's instruction.
Embodiment 1:
Adopting aqueous phase synthesis method, is that PEPA and the Hypophosporous Acid, 50 of 1: 0.5 is added to the water, with the stirring velocity of 300r/min by mol ratio, in 40 DEG C of stirring reactions 10 hours, then reaction product is carried out suction filtration, washing, in 150 DEG C of dryings 2 hours, obtain PEPA hypophosphite fire retardant.Productive rate is about 65%, and fusing point is about 250 DEG C, and 1% thermosteresis temperature is 415 DEG C.
Embodiment 2:
Adopting aqueous phase synthesis method, is that PEPA and the Hypophosporous Acid, 50 of 1: 10 is added to the water, with the stirring velocity of 600r/min by mol ratio, in 60 DEG C of stirring reactions 5 hours, then reaction product is carried out suction filtration, washing, in 150 DEG C of dryings 3 hours, obtain PEPA hypophosphite fire retardant.Productive rate is about 80%, and fusing point is about 255 DEG C, and 1% thermosteresis temperature is 420 DEG C.
Embodiment 3 ~ 11 the following example is contrasted by form 1 ~ 2 and lists
The white oil of 20 ~ 60% of raw material SEBS and formula ratio, polyphenylene oxide, polyolefine, secondary fire retardant, fire retarding synergist and other auxiliary agents are sent into homogenizer keep 40 ~ 60 DEG C of temperature at a high speed (40 ~ 100r/min) stir, mixing 2-4min, send into screw rod through twin-screw extrusion owner feed system, PEPA phosphinate and remaining part white oil are sent into the blended granulation of twin screw extruder through side feeding and are formed.
The technological process of double-screw extruding pelletizing is: screw speed 100 ~ 120r/min; Head to charging opening temperature, 190 ~ 210 DEG C, a district, two 190 ~ 210 DEG C, districts, three 190 ~ 210 DEG C, districts, four 195 ~ 215 DEG C, districts, five 195 ~ 215 DEG C, districts, six 195 ~ 215 DEG C, districts, seven 195 ~ 215 DEG C, districts, head 190 ~ 210 DEG C.
Table 1
Table 2
Table note: in table 1 and table 2, polypropylene and poly melting index are respectively 10 and 17g/10min, and manufacturer is Yanshan Petrochemical.The W 4600 A171 silane coupling agent process of connection carbonizer company of the U.S., its particle diameter D98 < 10, the trimeric cyanamide KH-560 coupling agent treatment of same company, its particle diameter D98 < 8.The manufacturer of YH503 is Yueyang petrochemical industry.The manufacturer of A1654 and A1650 is Ke Teng company of the U.S..The manufacturer of PPO is blue star chemical industry.The manufacturer of lubricant is Wa Ke company.The manufacturer of other auxiliary agents is Ciba company limited of the U.S..
Claims (14)
1. a halogen-free flame-retardant thermoplastic elastomer, is characterized in that the component comprising following weight part:
Wherein, described polyolefine is selected from the one in polyethylene, polypropylene,
Described PEPA phosphinate structural formula is:
prepare by the following method: adopt aqueous phase synthesis method, be that PEPA and the Hypophosporous Acid, 50 of 1:0.5-10 is added to the water by mol ratio, with the stirring velocity of 300 ~ 600r/min, in 0 ~ 100 DEG C of stirring reaction 5 ~ 10 hours, then reaction product is carried out suction filtration, washing, in 150 DEG C of vacuum-dryings 2 ~ 3 hours, obtain PEPA phosphinate.
2. halogen-free flame-retardant thermoplastic elastomer according to claim 1, is characterized in that the component comprising following weight part:
3. halogen-free flame-retardant thermoplastic elastomer according to claim 1, it is characterized in that described SEBS take polystyrene as end segment, the ethylene-butene copolymer that polyhutadiene hydrogenation obtains is the linear three block copolymer of middle spring block.
4. halogen-free flame-retardant thermoplastic elastomer according to claim 3, it is characterized in that described SEBS is selected from the vinylbenzene-ethylene/butylene-alkene block copolymer of basic, normal, high molecular weight any one.
5. halogen-free flame-retardant thermoplastic elastomer according to claim 4, it is characterized in that described SEBS be selected from Balin Branch Corp. SINOPEC produce thermoplastic elastomer SEBSYH-601 or 602 and Ke Teng Polymer Co., Ltd produce A6150,6151 in one or more.
6. halogen-free flame-retardant thermoplastic elastomer according to claim 1, is characterized in that described polyolefine is selected from the one in polyethylene that melting index is 0.5 ~ 100g/10min, polypropylene.
7. halogen-free flame-retardant thermoplastic elastomer according to claim 1, it is characterized in that described polyolefine is selected from PPS1003 or KH7726 of Shanghai Secco Petrochemical Co., Ltd.'s production, and any one model in the LDPE of Shanghai Petrochemial Co Ltd, China Petrochemical Corp (Low Density Polyethylene) series product.
8. halogen-free flame-retardant thermoplastic elastomer according to claim 1, is characterized in that described secondary fire retardant is selected from the product of hydration metal hydroxides after silane coupling agent process or trimeric cyanamide; Described fire retarding synergist is selected from one or more in boric acid, borax, zinc borate, boron trioxide, titanium oxide, silicon oxide, zinc oxide; Described white oil be selected from kinematic viscosity 5 ~ 120 high temperature resistant white oil or PIB white oil in one or more.
9. halogen-free flame-retardant thermoplastic elastomer according to claim 8, is characterized in that described secondary fire retardant is selected from D
98the product of hydration metal hydroxides between 5 ~ 20mm after silane coupling agent process or particle diameter D
98be less than the trimeric cyanamide of 10mm.
10. halogen-free flame-retardant thermoplastic elastomer according to claim 1, is characterized in that one or more that other described auxiliary agents are selected from Hinered phenols or suffocated amine antioxidant, lubricant, uv-absorbing agent.
11. halogen-free flame-retardant thermoplastic elastomers according to claim 1, is characterized in that one or more that other described auxiliary agents are selected from the vapour bar irgasfos 168 of (China) company limited, oxidation inhibitor 1098 and lubricant PalletS.
The preparation method of 12. halogen-free flame-retardant thermoplastic elastomers according to claim 1, it is characterized in that step is: the white oil of raw material SEBS and formula ratio 20% ~ 60%, polyphenylene oxide, polyolefine, secondary fire retardant, fire retarding synergist and other auxiliary agents are sent into homogenizer and keeps 40 ~ 100 DEG C of temperature 40 ~ 100r/min to stir, mixing 2-4min, send into screw rod through twin-screw extrusion owner feed system, PEPA phosphinate and remaining part white oil are sent into the blended granulation of twin screw extruder through side feeding and are formed.
13. 1 kinds, for the preparation of the halogen-free flame retardants PEPA phosphinate of halogen-free flame-retardant thermoplastic elastomer according to claim 1, is characterized in that: reacted by PEPA and Hypophosporous Acid, 50 and obtained, its structural formula is as follows:
14. halogen-free flame retardants PEPA phosphinates according to claim 13, it is characterized in that this PEPA phosphinate prepares by the following method: adopt aqueous phase synthesis method, be that PEPA and the Hypophosporous Acid, 50 of 1:0.5-10 is added to the water by mol ratio, with the stirring velocity of 300 ~ 600r/min, in 0 ~ 100 DEG C of stirring reaction 5 ~ 10 hours, then reaction product is carried out suction filtration, washing, in 150 DEG C of vacuum-dryings 2 ~ 3 hours, obtain PEPA phosphinate.
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| CN104277408B (en) * | 2014-09-30 | 2017-06-06 | 广东省石油化工研究院 | Halogen-free flameproof oligocene ether content plug material and preparation method thereof |
| CN104672884A (en) * | 2015-02-12 | 2015-06-03 | 衡阳恒飞电缆有限责任公司 | Material for cables and preparation method of material |
| CN104962029A (en) * | 2015-08-04 | 2015-10-07 | 上海至正道化高分子材料股份有限公司 | Oil-resistant TPE (thermoplastic elastomer) halogen-free flame-retardant cable material and preparation method thereof |
| CN105273352A (en) * | 2015-11-09 | 2016-01-27 | 安徽韧达高分子材料有限公司 | Halogen-free flame-retardant TPE material and preparation method thereof |
| CN105273413B (en) * | 2015-11-09 | 2018-04-13 | 安徽韧达高分子材料有限公司 | A kind of soft high intensity TPE material and preparation method thereof |
| CN105623179A (en) * | 2015-12-10 | 2016-06-01 | 上海至正道化高分子材料股份有限公司 | Anti-yellowing halogen-free flame retardant thermoplastic elastomer and preparation method thereof |
| CN106189042A (en) * | 2016-08-31 | 2016-12-07 | 苏州亨利通信材料有限公司 | One has fire-retardant TPE cable material of heat conductivility and preparation method thereof |
| CN106589756A (en) * | 2016-12-06 | 2017-04-26 | 佛山市高明区生产力促进中心 | Novel TPE (thermoplastic elastomer) material |
| CN110746733B (en) * | 2019-09-25 | 2022-12-02 | 广东格瑞新材料股份有限公司 | Halogen-free and sulfur-free TPE damping material and preparation method thereof |
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| EP1882717A1 (en) * | 2006-07-28 | 2008-01-30 | DSMIP Assets B.V. | Toughened halogen free flame retardant polyester composition |
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Address after: 225500, Ma 986 Road, Jiangyan Economic Development Zone, Jiangsu, Taizhou, China Patentee after: 5ELEM HI-TECH CORPORATION Address before: 225500, Ma 986 Road, Jiangyan Economic Development Zone, Jiangsu, Taizhou, China Patentee before: Five lines material science and Technology (Jiangsu) Co., Ltd. |