CN105131500A - High- springback TPE thermoplastic elastomer and preparing method thereof - Google Patents
High- springback TPE thermoplastic elastomer and preparing method thereof Download PDFInfo
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Abstract
The invention discloses a high- springback TPE thermoplastic elastomer and a preparing method thereof. The thermoplastic elastomer is prepared from, by mass, 39%-49% of SEBS, 5%-10% of homopolymerization, 30%-40% of white oil, 5%-9% of simethicone, 4%-8% of calcium carbonate, 0.2%-0.4% of lubricating agents, and 0.2%-0.4% of antioxygen, and besides, elastic fibers are further added. By means of the high- springback TPE thermoplastic elastomer and the preparing method thereof, the elasticity resuming performance of a system is improved, and the overall shock resistance, creep resistance and the deformation resilience are improved. The high- springback TPE thermoplastic elastomer has excellent resilience, and is free of toxicity, environmentally friendly, good in machining performance, good in surface smooth degree, capable of being used for manufacturing medical grade products of high requirements and low in cost.
Description
Technical field
The present invention relates to a kind of thermoplastic elastomer and preparation method thereof, particularly a kind of high resilience TPE thermoplastic elastomer and preparation method thereof.
Background technology
Thermoplastic elastomer (TPE) is a kind of snappiness with rubber, high strength, high resilience, and having again can the material of feature of injection molding.There is environment-protecting asepsis safety, durometer level is wide, has excellent tint permanence, soft-touch, weathering resistance, fatigue resistance and temperature tolerance, processing characteristics is superior, need not sulfuration, can recycle and reduce costs, both can secondary injection molding, with body material coating and bondings such as PP, PE, PC, PS, ABS, also can be shaping separately.TPE outward appearance is true qualities, translucent or transparent round shaped grain or cylindrical particle, and surface is sub-face effect, and density is generally at 0.9-1.1g/cm
3.
Simultaneously TPE is again a kind of macromolecular material between rubber and thermoplastics characteristic, has the physical and mechanical properties of rubber and the performance of technical process of thermoplastics, is widely used in the fields such as automobile, electric, building, medical treatment.Along with the development of new technology, facilitate continuing to optimize and promoting of TPE performance, Application Areas is constantly expanded, especially automobile and medical field sought-after; In addition due to the raising of people's Environmental awareness, salvage material becomes an important factor of selection, and the PVC that the whole world is discarded becomes the major issue of environmental pollution, and restriction abroad uses PVC cry increasingly surging, also promotes the quick growth of TPE consumption.
The microtexture of TPE determines its performance, and not containing unsaturated link(age) in TPE material structure, Nature comparison is stablized, and has good heatproof (use temperature scope-50-100 DEG C), ageing-resistant, chemical resistant properties; Be the ethylene-stryene rigid chain segment of vitreous state containing normal temperature in TPE material structure, give the shape that material is fixing, ensure use properties, be also the divinyl soft segment of elastomeric state containing normal temperature, give the comfortable flexible touch of material and elasticity; TPE material does not introduce heavy metal in process of production, does not add poisonous phthalate softening agent, meets ROHS, REACH, EN71, PAHS and FDA environmental protection tests.It is the best materials replacing PVC; TPE material adopts direct injection moulding, handling ease, and shaping cycle is short, and useless goods reclaim easily, is the ideal material replacing rubber and silica gel; TPE material passes through the change of formula and proportioning, can provide physical property and the diversified material of hardness, to meet the optimum service requirements of variant production.
Styrenic TPE is a most popular class TPE, and be divinyl or isoprene and styrene block type multipolymer, its performance is closest to SBR rubber.About the output of current world styrenic TPE accounts for whole TPE half.Representational kind is vinylbenzene-divinyl-styrene block copolymer (SBS), and be widely used in shoe industry, major part instead of rubber; Purposes simultaneously in the industrial rubber articles such as adhesive plaster, offset plate is also in continuous expansion.SBS is also used as the anti-impact modifier of PS plastics in a large number, be also that the bituminous pavement of bituminous pavement road is wear-resisting, anticracking, anti-soft antiskid excellent properties-correcting agent.
SBS has good tensile strength and elasticity, rub resistance and excelling in fatigue property, and good and cheap, is mainly used in rubber overshoes, modifying asphalt, improvement agent for synthesis resin and tackiness agent etc.But the greatest problem that SBS exists is thermo-labile, the state such as American-European has carried out a series of improvement in performance to it for this reason, and wherein utilize SBS to obtain SEBS through saturated hydrogenation, shock strength can be made to increase substantially, weathering resistance and heat-resistant aging significantly improve.
SEBS has the features such as ageing-resistant, safety non-toxic, environmental protection, in the industry cycle there is the title of " rubber gold ", be mainly used in drug packages, medical transfusion utensil, large span lubricating oil, food product pack, electric wire, sealing material, modifying plastics, high-grade asphalt modification and with the field such as the resilient material of human contact, belong to national strategy new industry and give priority to product.
But due to the block copolymer structure that SEBS is special, cause its processing characteristics generally poor, and the elastomeric rebound resilience of medical treatment that current traditional latex is produced and processing characteristics good not, and production cost is higher.
Summary of the invention
The object of the invention is the problems referred to above existed for prior art, propose a kind of asepsis environment-protecting, good processability, cost is low, and can be used for high resilience TPE thermoplastic elastomer of the medical grade product making high request and preparation method thereof.
Technical scheme of the present invention is: a kind of high resilience TPE thermoplastic elastomer is characterized in that the composition comprising following mass percent: the SEBS of 39 ~ 49%, the homopolymerization PP of 5 ~ 10%, the dimethyl silicone oil of 5 ~ 9%, the calcium carbonate of 4 ~ 8%, the lubricant of 0.2 ~ 0.4%, the oxidation inhibitor of 0.2 ~ 0.4%, surplus is white oil.
Described high resilience TPE thermoplastic elastomer also comprises the spandex fiber of 5 ~ 8%.
Chemical pipeline of the present invention is take SEBS as matrix with cold-resistant fiber glass reinforced polypropylene, add homopolymerization PP, white oil, dimethyl silicone oil, makes every mechanical property of material all be significantly improved, with the addition of spandex fiber in addition, calcium carbonate, lubricant and oxidation inhibitor, and the mass content defining each component, make the composition of material more rationally, performance is more perfect.Obtained thermoplastic elastomer has excellent rebound performance, asepsis environment-protecting, good processability, and surperficial smooth degree well, can be used for the medical grade product making high request.
Wherein SEBS is a kind of multiduty novel thermoplastic elastomer, it is the new modified elastomerics that in thermoplastic block copolymers styrene-butylene-styrene copolymer molecule, rubber segments polyhutadiene unsaturated double-bond is obtained through shortening, therefore has the stability more excellent than SBS and good thermotolerance.SEBS not only has excellent ageing-resistant performance, and has good mechanical property, not only has excellent resistance to ozone, resistance to oxidation, UV resistant and weather resistance, also has the lower temperature resistance of good oil resistant, chemicals-resistant corrodibility and excellence.Its product water white transparency, nontoxic, tasteless, tinctorial property is excellent, density is low and have stronger bonding force with other material.In addition, SEBS has good wear resistance and snappiness in use, and has the processing characteristics of thermoplastics, and can reclaim and re-use.
PP and polypropylene, the EB segment in PP and SEBS can be compatible, in SEBS compound, add PP, intensity and the mobility of compound can be improved, improve its hardness and shock resistance, and play the effect reduced costs, so the PP modified resin that to be SEBS desirable.When it and white oil is blended adds in SEBS, play reduction boundary stress, reduce the effect of system defect, obviously can improve processing characteristics and the use properties of SEBS.But the PP of different chemical structures is different on thermoplastic elastomer composite material impact, and wherein the molecular chain structure of homopolymerization PP is more regular, have higher degree of crystallinity and and more perfect crystalline structure, therefore its rigidity and hardness ratio random copolymerization PP and copolymerization PP higher.The tensile property of homopolymerization PP, bending property, hardness and other mechanical properties are all higher than random copolymerization PP and copolymerization PP.
The consistency of white oil and SEBS is good, due to poor with the PS block compatible in SEBS, so less on the impact of SEBS intensity.In SEBS, add another important reason of white oil is the network structure that PS section in SEBS and EB section can form physical crosslinking, its molecular entanglement is tightr, and white oil can destroy this entanglement, thus the reactive force reduced between macromole, make molecular chain submissive, increase flexibility and the mobility of material.
Described spandex fiber is polyurethane fiber, has deep drawing quality, low elastic modulus and elastic recovery rate.The macromole of block polymers of polyurethane is alternately made up of the short chain section (hard segment) of the very large long-chain-segment (soft chain segment) of flexibility and rigidity.Take soft chain segment as matrix, and hard segment dispersion is embedded in wherein.Flexible soft chain segment is made up of aliphatic polyester or polyethers, can be regarded as a spring easily stretched; Rigid chain segment is then made up of carbamate and urea groups, as same rigidity bead.Because singly-bound each in soft chain segment is done to rotate in various degree around its adjacent singly-bound, thus the sinuate long-chain-segment of profile resembles a mixed and disorderly ball of string, and its form constantly changes.Macromole has very large adaptability under external force and length also has very large stretching, extension leeway, so there is the characteristic of deep drawing quality and elastic recovery rate.
Spandex fiber can realize the winding to calcium carbonate in system, can also realize being connected the elasticity of crystal region with amorphous regions and extrinsic region, while enhancing system each microtexture part switching performance, the elastic recovery capability of system can also be improved, stress impact carries out high efficiency buffer and recovery to external world, the shock resistance of modification entirety, creep resistance and deformation restorability etc.
Described calcium carbonate is porous calcium carbonate, porous calcium carbonate because its density is little, volume is little, specific surface area and volume of voids large, there is machinery and thermostability, can as the weighting agent of thermoplastic elastomer.The particle diameter of this porous calcium carbonate is 1.0 ~ 1.2 μm, and aperture is 32 ~ 40nm, and specific surface area is 5m
2/ g.
Use coupling agent to carry out pre-treatment to the surface of described sodium carbonate, and then put in production technique.Coupling agent can improve the consistency of calcium carbonate and TPE, wetting property and dispersiveness.Pretreatment process is: by calcium carbonate dry 2h at 90-100 DEG C; Coupling agent and pimelinketone are hybridly prepared into the treatment solution that massfraction is 1.5%; In treatment solution, adding dried calcium carbonate, (its mass ratio is calcium carbonate: treatment solution=1: 10), passes into nitrogen protection, and under constant temperature, high-speed stirring obtains modified calcium carbonate mixing solutions; Filter mixed solution, with acetone repetitive scrubbing calcium carbonate 3 times, put it into 80-90 DEG C of oven dry in constant temperature oven, obtain modified calcium carbonate.
After process, coupling agent defines one deck mulch film at calcium carbonate surface, improve the consistency of calcium carbonate granule and matrix plastic, again due to the microtexture of coupling agent uniqueness, good coupling usefulness is had to polymkeric substance and coupling agent, by the bonding action of coupling agent active group and matrix plastic exposed terminated groups, the macromolecular chain in matrix plastic can be made to overcome the stress obstacle of micropore and enter in the micropore of calcium carbonate surface, thus make the combination of calcium carbonate and matrix plastic more firm, bonded area is larger, combination degree is darker, thus its dispersiveness in SEBS matrix and bounding force is improved, and improve the consistency of calcium carbonate and SEBS system, thus significantly enhance processing characteristics and the mechanical property of material monolithic.
Described coupling agent is at least one in KH550, KH560, KH570.
Described lubricant is at least one in calcium stearate, Zinic stearas, polyethylene wax or methylene-bis dialkyl dithio amino formate.Add the smooth degree that these lubricants can significantly improve material surface in the material.
Described oxidation inhibitor is antioxidant 1010, antioxidant 1076, at least one in irgasfos 168 or oxidation inhibitor 1098.
Preferably, oxidation inhibitor is irgasfos 168.Irgasfos 168 can prevent SEBS/PP blend aging, and can not produce what impact to the performance of blend.
A kind of high resilience TPE process for preparation of thermoplastic elastomer, comprises the following steps:
1) SEBS and white oil being dropped into rotating speed is after mixing 60 minutes in the high speed mixer of 500rpm, leaves standstill 0.5 hour, then is mixed into other components, and mixing 4min causes evenly, and discharging, obtains mixture;
2) mixture is put into twin screw extruder hopper;
4) set twin screw extruder engine speed 30-40HZ, main feeding 10-20HZ, die temperature is 195-215 DEG C, and extruding pelletization, is dried to constant-quality.
Wherein the feed zone temperature of forcing machine can be 180-195 DEG C, and compression section temperature can be 200-220 DEG C, and fluxing zone temperature can be 195-215 DEG C, and homogenizing zone temperature can be 195-215 DEG C.
In above-mentioned parameter, Speed unit HZ and rpm carries out unit conversion and meets the following conditions: RPM=120*F/P, F refer to HZ number, and P refers to the number of poles of three-phase machine.
Finished product is mixed sampling, uses injection moulding machine sample preparation.Finally carry out performance test to material, its Midst density is tested according to ISO1183, and tensile strength and elongation at break are tested according to ISO37, and tear strength is tested according to ISO34, and compression deformation rate is tested according to ISO815.
Beneficial effect of the present invention:
This material has excellent rebound performance, asepsis environment-protecting, good processability, surperficial smooth degree well, can be used for the medical grade product making high request, owing to adopting SEBS system, can large-scale mass production, the medical elastomerics that more traditional latex is produced, has production technique simple, pollute little, the advantage that cost is low.
Embodiment
Below in conjunction with embodiment, illustrate the present invention further, following embodiment should be understood and be only not used in for illustration of the present invention and limit the scope of the invention.
Embodiment 1
A kind of high resilience TPE thermoplastic elastomer, specifically comprise the composition of following mass percent: the SEBS of 47%, the homopolymerization PP of 5%, the dimethyl silicone oil of 7%, the calcium carbonate of 4%, the lubricant of 0.4%, the oxidation inhibitor of 0.2%, surplus is white oil.
Wherein lubricant is calcium stearate, and oxidation inhibitor is antioxidant 1010.
The performance test data of this material is listed in table 1.
Embodiment 2
A kind of high resilience TPE thermoplastic elastomer, specifically comprise the composition of following mass percent: the SEBS of 45%, the homopolymerization PP of 6%, the dimethyl silicone oil of 9%, the calcium carbonate of 6%, the lubricant of 0.3%, the oxidation inhibitor of 0.4%, surplus is white oil.
Wherein lubricant is Zinic stearas, and oxidation inhibitor is antioxidant 1076.
The performance test data of this material is listed in table 1.
Embodiment 3
A kind of high resilience TPE thermoplastic elastomer, specifically comprise the composition of following mass percent: the SEBS of 39%, the homopolymerization PP of 10%, the dimethyl silicone oil of 5%, the calcium carbonate of 8%, the lubricant of 0.2%, the oxidation inhibitor of 0.3%, surplus is white oil.
Wherein lubricant is polyethylene wax, and oxidation inhibitor is oxidation inhibitor 1098.
The performance test data of this material is listed in table 1.
Table 1
| Test event | Unit | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| Density | g/cm 3 | 0.99 | 0.99 | 0.97 |
| Tensile strength | MPa | 5 | 4 | 5 |
| Elongation at break | ％ | 400 | 415 | 420 |
| Tear strength | KN/m | 26 | 26 | 28 |
| Compression set | ％ | 48 | 50 | 50 |
Embodiment 4
A kind of high resilience TPE thermoplastic elastomer, specifically comprise the composition of following mass percent: the SEBS of 47%, the homopolymerization PP of 5%, the dimethyl silicone oil of 7%, the calcium carbonate of 4%, the lubricant of 0.4%, the oxidation inhibitor of 0.2%, surplus is white oil.
Described high resilience TPE thermoplastic elastomer also comprises the spandex fiber of 6%.Described spandex fiber is polyurethane fiber.
Wherein lubricant is calcium stearate, and oxidation inhibitor is antioxidant 1010.
The results are shown in Table 2 for the performance test data of this material.
Embodiment 5
A kind of high resilience TPE thermoplastic elastomer, specifically comprise the composition of following mass percent: the SEBS of 45%, the homopolymerization PP of 6%, the dimethyl silicone oil of 9%, the calcium carbonate of 6%, the lubricant of 0.3%, the oxidation inhibitor of 0.4%, surplus is white oil.
Described high resilience TPE thermoplastic elastomer also comprises the spandex fiber of 5%.Described spandex fiber is polyurethane fiber.
Wherein lubricant is calcium stearate, and oxidation inhibitor is antioxidant 1076.
The results are shown in Table 2 for the performance test data of this material.
Embodiment 6
A kind of high resilience TPE thermoplastic elastomer, specifically comprise the composition of following mass percent: the SEBS of 39%, the homopolymerization PP of 10%, the dimethyl silicone oil of 5%, the calcium carbonate of 8%, the lubricant of 0.2%, the oxidation inhibitor of 0.3%, surplus is white oil.
Described high resilience TPE thermoplastic elastomer also comprises the spandex fiber of 8%.Described spandex fiber is polyurethane fiber.
Wherein lubricant is calcium stearate, and oxidation inhibitor is oxidation inhibitor 1098.
The results are shown in Table 2 for the performance test data of this material.
Table 2
| Test event | Unit | Embodiment 4 | Embodiment 5 | Embodiment 6 |
| Density | g/cm 3 | 0.99 | 0.99 | 0.97 |
| Tensile strength | MPa | 5 | 6 | 6 |
| Elongation at break | ％ | 470 | 470 | 480 |
| Tear strength | KN/m | 30 | 29 | 30 |
| Compression set | ％ | 42 | 42 | 42 |
Embodiment 7
A kind of high resilience TPE thermoplastic elastomer, specifically comprise the composition of following mass percent: the SEBS of 43%, the homopolymerization PP of 7%, the dimethyl silicone oil of 5%, the calcium carbonate of 4.5%, the lubricant of 0.2%, the oxidation inhibitor of 0.3%, surplus is white oil.
Described high resilience TPE thermoplastic elastomer also comprises the spandex fiber of 5%.Described spandex fiber is polyurethane fiber.
Wherein lubricant is Zinic stearas, and oxidation inhibitor is irgasfos 168.
Described calcium carbonate is porous calcium carbonate, and calcium carbonate microparticle particle diameter is 1.0 μm, and aperture is 32nm, and specific surface area is 5m
2/ g.
Described calcium carbonate is pretreated through coupling agent KH550, and pre-treatment step is: by calcium carbonate dry 2h at 90 DEG C; Coupling agent KH550 and pimelinketone are hybridly prepared into the treatment solution that massfraction is 1.5%; In treatment solution, adding dried calcium carbonate, (its mass ratio is calcium carbonate: treatment solution=1: 10), passes into nitrogen protection, and under constant temperature, high-speed stirring obtains modified calcium carbonate mixing solutions; Filter mixed solution, with acetone repetitive scrubbing calcium carbonate 3 times, put it into 80 DEG C of oven dry in constant temperature oven, obtain modified calcium carbonate.
The results are shown in Table 3 for the performance test data of this material.
Embodiment 8
A kind of high resilience TPE thermoplastic elastomer, specifically comprise the composition of following mass percent: the SEBS of 43%, the homopolymerization PP of 7%, the dimethyl silicone oil of 5%, the calcium carbonate of 4.5%, the lubricant of 0.2%, the oxidation inhibitor of 0.3%, surplus is white oil.
Described high resilience TPE thermoplastic elastomer also comprises the spandex fiber of 5%.Described spandex fiber is polyurethane fiber.
Wherein lubricant is Zinic stearas, and oxidation inhibitor is antioxidant 1010.
Described calcium carbonate is porous calcium carbonate, and calcium carbonate microparticle particle diameter is 1.1 μm, and aperture is 35nm, and specific surface area is 8m
2/ g.
Described calcium carbonate is pretreated through coupling agent KH560, and pre-treatment step is: by calcium carbonate dry 2h at 95 DEG C; Coupling agent KH560 and pimelinketone are hybridly prepared into the treatment solution that massfraction is 1.5%; In treatment solution, adding dried calcium carbonate, (its mass ratio is calcium carbonate: treatment solution=1: 10), passes into nitrogen protection, and under constant temperature, high-speed stirring obtains modified calcium carbonate mixing solutions; Filter mixed solution, with acetone repetitive scrubbing calcium carbonate 3 times, put it into 85 DEG C of oven dry in constant temperature oven, obtain modified calcium carbonate.
The results are shown in Table 3 for the performance test data of this material.
Embodiment 9
A kind of high resilience TPE thermoplastic elastomer, specifically comprise the composition of following mass percent: the SEBS of 43%, the homopolymerization PP of 7%, the dimethyl silicone oil of 5%, the calcium carbonate of 4.5%, the lubricant of 0.2%, the oxidation inhibitor of 0.3%, surplus is white oil.
Described high resilience TPE thermoplastic elastomer also comprises the spandex fiber of 5%.Described spandex fiber is polyurethane fiber.
Wherein lubricant is Zinic stearas, and oxidation inhibitor is the mixture of irgasfos 168 and oxidation inhibitor 1098.
Described calcium carbonate is porous calcium carbonate, and calcium carbonate microparticle particle diameter is 1.2 μm, and aperture is 40nm, and specific surface area is 10m
2/ g.
Described calcium carbonate is pretreated through coupling agent KH570, and pre-treatment step is: by calcium carbonate dry 2h at 100 DEG C; Coupling agent KH570 and pimelinketone are hybridly prepared into the treatment solution that massfraction is 1.5%; In treatment solution, adding dried calcium carbonate, (its mass ratio is calcium carbonate: treatment solution=1: 10), passes into nitrogen protection, and under constant temperature, high-speed stirring obtains modified calcium carbonate mixing solutions; Filter mixed solution, with acetone repetitive scrubbing calcium carbonate 3 times, put it into 90 DEG C of oven dry in constant temperature oven, obtain modified calcium carbonate.
The results are shown in Table 3 for the performance test data of this material.
Table 3
| Test event | Unit | Embodiment 7 | Embodiment 8 | Embodiment 9 |
| Density | g/cm 3 | 0.99 | 0.99 | 0.97 |
| Tensile strength | MPa | 7 | 8 | 8 |
| Elongation at break | ％ | 500 | 505 | 515 |
| Tear strength | KN/m | 35 | 33 | 35 |
| Compression set | ％ | 34 | 33 | 33 |
Embodiment 10
A kind of high resilience TPE thermoplastic elastomer, specifically comprise the composition of following mass percent: the SEBS of 39%, the homopolymerization PP of 8%, the dimethyl silicone oil of 5.4%, the porous calcium carbonate of 8%, the calcium stearate of 0.2%, the irgasfos 168 of 0.4%, surplus is white oil.
Described high resilience TPE thermoplastic elastomer also comprises the polyurethane fiber of 5%.
Above-mentioned TPE process for preparation of thermoplastic elastomer, comprises the following steps:
1) take SEBS, homopolymerization PP, white oil, dimethyl silicone oil, polyurethane fiber, porous calcium carbonate, calcium stearate and irgasfos 168 according to the mass ratio of above-mentioned each component, wherein porous calcium carbonate can through coupling agent pre-treatment,
2) SEBS and white oil being dropped into rotating speed is after mixing 60 minutes in the high speed mixer of 500rpm, leaves standstill 0.5 hour, then is mixed into other components, and mixing 4min causes evenly, and discharging, obtains mixture,
3) mixture is put into twin screw extruder hopper, selects the screw combinations of Strong shear,
4) set twin screw extruder parameter, engine speed 40HZ, main feeding 15HZ, die temperature is 195 DEG C, and extruding pelletization, is dried to constant-quality.
Finished product is mixed sampling, uses injection moulding machine sample preparation.Finally carry out performance test to material, testing method and test condition are all listed in table 4.Test data the results are shown in table 5.
Embodiment 11
A kind of high resilience TPE thermoplastic elastomer, specifically comprise the composition of following mass percent: the SEBS of 40%, the homopolymerization PP of 5%, the dimethyl silicone oil of 9%, the porous calcium carbonate of 4.3%, the Zinic stearas of 0.3%, the irgasfos 168 of 0.4%, surplus is white oil.
Described high resilience TPE thermoplastic elastomer also comprises the polyurethane fiber of 8%.
Above-mentioned TPE process for preparation of thermoplastic elastomer, comprises the following steps:
1) take SEBS, homopolymerization PP, white oil, dimethyl silicone oil, polyurethane fiber, porous calcium carbonate, Zinic stearas and irgasfos 168 according to the mass ratio of above-mentioned each component, wherein porous calcium carbonate can through coupling agent pre-treatment,
2) SEBS and white oil being dropped into rotating speed is after mixing 60 minutes in the high speed mixer of 500rpm, leaves standstill 0.5 hour, then is mixed into other components, and mixing 4min causes evenly, and discharging, obtains mixture,
3) mixture is put into twin screw extruder hopper, selects the screw combinations of Strong shear,
4) set twin screw extruder parameter, engine speed 30HZ, main feeding 20HZ, die temperature is 200 DEG C, and extruding pelletization, is dried to constant-quality.
Finished product is mixed sampling, uses injection moulding machine sample preparation.Finally carry out performance test to material, testing method and test condition are all listed in table 4.Test data the results are shown in table 5.
Embodiment 12
A kind of high resilience TPE thermoplastic elastomer, specifically comprise the composition of following mass percent: the SEBS of 39%, the homopolymerization PP of 6.5%, the dimethyl silicone oil of 5%, the porous calcium carbonate of 4%, the polyethylene wax of 0.2%, the irgasfos 168 of 0.3%, surplus is white oil.
Described high resilience TPE thermoplastic elastomer also comprises the polyurethane fiber of 5%.
Above-mentioned TPE process for preparation of thermoplastic elastomer, comprises the following steps:
1) take SEBS, homopolymerization PP, white oil, dimethyl silicone oil, polyurethane fiber, porous calcium carbonate, polyethylene wax and irgasfos 168 according to the mass ratio of above-mentioned each component, wherein porous calcium carbonate can through coupling agent pre-treatment,
2) SEBS and white oil being dropped into rotating speed is after mixing 60 minutes in the high speed mixer of 500rpm, leaves standstill 0.5 hour, then is mixed into other components, and mixing 4min causes evenly, and discharging, obtains mixture,
3) mixture is put into twin screw extruder hopper, selects the screw combinations of Strong shear,
4) set twin screw extruder parameter, engine speed 30HZ, main feeding 10HZ, die temperature is 205 DEG C, and extruding pelletization, is dried to constant-quality.
Finished product is mixed sampling, uses injection moulding machine sample preparation.Finally carry out performance test to material, testing method and test condition are all listed in table 4.Test data the results are shown in table 5.
Embodiment 13
A kind of high resilience TPE thermoplastic elastomer, specifically comprise the composition of following mass percent: the SEBS of 49%, the homopolymerization PP of 5%, the dimethyl silicone oil of 5.5%, the porous calcium carbonate of 4%, the methylene-bis dialkyl dithio amino formate of 0.3%, the irgasfos 168 of 0.2%, surplus is white oil.
Described high resilience TPE thermoplastic elastomer also comprises the polyurethane fiber of 6%.
Above-mentioned TPE process for preparation of thermoplastic elastomer, comprises the following steps:
1) SEBS, homopolymerization PP, white oil, dimethyl silicone oil, polyurethane fiber, porous calcium carbonate, methylene-bis dialkyl dithio amino formate and irgasfos 168 is taken according to the mass ratio of above-mentioned each component, wherein porous calcium carbonate can through coupling agent pre-treatment
2) SEBS and white oil being dropped into rotating speed is after mixing 60 minutes in the high speed mixer of 500rpm, leaves standstill 0.5 hour, then is mixed into other components, and mixing 4min causes evenly, and discharging, obtains mixture,
3) mixture is put into twin screw extruder hopper, selects the screw combinations of Strong shear,
4) set twin screw extruder parameter, engine speed 35HZ, main feeding 15HZ, die temperature is 210 DEG C, and extruding pelletization, is dried to constant-quality.
Finished product is mixed sampling, uses injection moulding machine sample preparation.Testing method and test condition are all listed in table 4.Test data the results are shown in table 5.
Embodiment 14
Above-mentioned TPE thermoplastic elastomer, specifically comprise the composition of following mass percent: the SEBS of 41%, the homopolymerization PP of 10%, the dimethyl silicone oil of 6.3%, the porous calcium carbonate of 5%, the calcium stearate of 0.4% and methylene-bis dialkyl dithio amino formate mixture, the irgasfos 168 of 0.3%, surplus is white oil.
Described high resilience TPE thermoplastic elastomer also comprises the polyurethane fiber of 7%.
A kind of high resilience TPE process for preparation of thermoplastic elastomer, comprises the following steps:
1) SEBS, homopolymerization PP, white oil, dimethyl silicone oil, polyurethane fiber, porous calcium carbonate, calcium stearate and methylene-bis dialkyl dithio amino formate mixture and irgasfos 168 is taken according to the mass ratio of above-mentioned each component, wherein porous calcium carbonate can through coupling agent pre-treatment
2) SEBS and white oil being dropped into rotating speed is after mixing 60 minutes in the high speed mixer of 500rpm, leaves standstill 0.5 hour, then is mixed into other components, and mixing 4min causes evenly, and discharging, obtains mixture,
3) mixture is put into twin screw extruder hopper, selects the screw combinations of Strong shear,
4) set twin screw extruder parameter, engine speed 35HZ, main feeding 20HZ, die temperature is 215 DEG C, and extruding pelletization, is dried to constant-quality.
Finished product is mixed sampling, uses injection moulding machine sample preparation.Finally carry out performance test to material, testing method and test condition are all listed in table 4.Test data the results are shown in table 5.
Comparative example 1
Have chosen market like product and carry out performance test at identical conditions, test data the results are shown in table 5.
Table 4
| Test event | Unit | Testing method | Test condition |
| Density | g/cm 3 | ISO1183 | / |
| Tensile strength | MPa | ISO37 | V＝500mm/min |
| Elongation at break | ％ | ISO37 | V＝500mm/min |
| Tear strength | KN/m | ISO34 | V＝500mm/min |
| Compression set | ％ | ISO815 | 22h，70℃ |
Note: V is test rate
Table 5
| Test event | Unit | Embodiment 10 | Embodiment 11 | Embodiment 12 | Embodiment 13 | Embodiment 14 | Comparative example 1 |
| Density | g/cm 3 | 0.99 | 0.99 | 0.97 | 0.98 | 0.98 | 0.97 |
| Tensile strength | MPa | 7 | 7 | 8 | 7 | 8 | 3 |
| Elongation at break | ％ | 502 | 510 | 510 | 515 | 520 | 350 |
| Tear strength | KN/m | 34 | 33 | 34 | 35 | 35 | 32 |
| Compression set | ％ | 34 | 33 | 33 | 34 | 33 | 60 |
In view of the present invention program's embodiment is numerous, each embodiment experimental data is huge numerous, be not suitable for particularize herein to illustrate, but the content of the required checking of each embodiment is all close with the final conclusion obtained, so do not illustrate one by one the checking content of each embodiment herein.
The technical scope mid point value non-limit part that this place embodiment is protected application claims and in embodiment technical scheme to the new technical scheme that the equal replacement of single or multiple technical characteristic is formed, equally all in the scope of protection of present invention; Simultaneously in all embodiments enumerated or do not enumerate of the present invention program, parameters in the same embodiment only represents an example (i.e. a kind of feasible scheme) of its technical scheme, and between parameters, there is not strict cooperation and qualified relation, wherein each parameter can be replaced, except special declaration mutually when stating ask without prejudice to axiom and the present invention.
Technique means disclosed in the present invention program is not limited only to the technique means disclosed in above-mentioned technique means, also comprises the technical scheme be made up of above technical characteristic arbitrary combination.The above is the specific embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications are also considered as protection scope of the present invention.
Claims (10)
1. one kind high resilience TPE thermoplastic elastomer, it is characterized in that it comprises the composition of following mass percent: the SEBS of 39 ~ 49%, the homopolymerization PP of 5 ~ 10%, the dimethyl silicone oil of 5 ~ 9%, the calcium carbonate of 4 ~ 8%, the lubricant of 0.2 ~ 0.4%, the oxidation inhibitor of 0.2 ~ 0.4%, surplus is white oil.
2. one according to claim 1 high resilience TPE thermoplastic elastomer, characterized by further comprising the spandex fiber of 5 ~ 8%.
3. one according to claim 2 high resilience TPE thermoplastic elastomer, is characterized in that: described spandex fiber is polyurethane fiber.
4. one according to claim 1 high resilience TPE thermoplastic elastomer, is characterized in that: described calcium carbonate is porous calcium carbonate.
5. one according to claim 4 high resilience TPE thermoplastic elastomer, is characterized in that: the particle diameter of described calcium carbonate microparticle is 1.0 ~ 1.2 μm, and aperture is 32 ~ 40nm, and specific surface area is 5 ~ 10m2/g.
6. the one high resilience TPE thermoplastic elastomer according to claim 1 or 4 or 5, is characterized in that: described calcium carbonate is for pretreated through coupling agent.
7. one according to claim 6 high resilience TPE thermoplastic elastomer, is characterized in that: described coupling agent is at least one in KH550, KH560, KH570.
8. one according to claim 1 high resilience TPE thermoplastic elastomer, is characterized in that: described lubricant is at least one in calcium stearate, Zinic stearas, polyethylene wax or methylene-bis dialkyl dithio amino formate.
9. one according to claim 1 high resilience TPE thermoplastic elastomer, is characterized in that: described oxidation inhibitor is antioxidant 1010, antioxidant 1076, one or more in irgasfos 168 or oxidation inhibitor 1098.
10. a high resilience TPE process for preparation of thermoplastic elastomer, is characterized in that comprising the following steps:
1) SEBS is mixed with white oil, then be mixed into other components, mix and obtain mixture;
2) by mixture through screw extrusion press extruding pelletization; Wherein forcing machine engine speed 30-40HZ, main feeding 10-20HZ, die temperature is 195-215 DEG C.
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