CN105131500B - A kind of high rebound TPE thermoplastic elastomer (TPE) and preparation method thereof - Google Patents
A kind of high rebound TPE thermoplastic elastomer (TPE) and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of high rebound TPE thermoplastic elastomer (TPE)s and preparation method thereof, which includes the ingredient of following mass percent：39~49% SEBS, 5~10% homopolymerization PP, 30~40% white oil, 5~9% dimethicone, 4~8% calcium carbonate, 0.2~0.4% lubricant, 0.2~0.4% antioxidant.In addition to this it is also added into elastomer, improves the elastic recovery capability of system, modified whole shock resistance, creep resistant and deformation recovery capability.This material has excellent resilience performance, and asepsis environment-protecting, processing performance is good, and surface is smooth to be spent, and can be used for making the medical grade product of high request, and cost is relatively low.
Description
Technical field
The present invention relates to a kind of thermoplastic elastomer (TPE) and preparation method thereof, especially a kind of high rebound TPE thermoplastic elastic
Body and preparation method thereof.
Background technique
Thermoplastic elastomer (TPE) (TPE) is a kind of high resiliency with rubber, high-intensitive, high resilience, and has and can be molded
The material of the feature of processing.With environment-protecting and non-poisonous safety, hardness range is wide, there is an excellent coloring, soft-touch, weatherability,
Fatigue resistance and temperature tolerance, processing performance is superior, and without vulcanization, can be recycled reduces cost, both can with quadric injection mould at
Type can also be separately formed with the basis materials coating and bonding such as PP, PE, PC, PS, ABS.TPE appearance be true qualities, it is translucent or
Transparent round shaped grain or cylindrical particle, surface are sub- face effect, and density is generally in 0.9-1.1g/cm3。
TPE is a kind of high molecular material between rubber and thermoplastic characteristic again simultaneously, the physical machine with rubber
The performance of technical process of tool performance and thermoplastic is widely used in the fields such as automobile, electric, building, medical treatment.With
The development of new technology promotes continuing to optimize and being promoted for TPE performance, and application field is constantly expanded, especially automobile and medical treatment
Domain requirement is powerful；Additionally due to the raising of people's environmental consciousness, material recovery becomes a key factor of selection, the whole world
Discarded PVC becomes the major issue of environmental pollution, and foreign countries' limitation is increasingly surging using PVC cry, and it is fast to also promote TPE consumption
Speed increases.
The microstructure of TPE determines its performance, and unsaturated bond is free of in TPE material structure, and Nature comparison is stablized, had
Good heatproof (- 50-100 DEG C of use temperature range), ageing-resistant, chemical resistance；Containing room temperature in TPE material structure is glass
The ethylene-stryene rigid chain segment of state assigns material fixed shape, guarantees service performance, is also elastomeric state containing room temperature
Butadiene soft segment assigns the comfortable flexible touch of material and elasticity；TPE material does not introduce heavy metal in process of production,
Toxic phthalate plasticizer is not added, meets ROHS, REACH, EN71, PAHS and FDA environmental protection tests.It is to replace
The optimal material of PVC；TPE material uses direct injection molding, and handling ease, short molding cycle, it is to take that product recycling of giving up, which is easy,
For rubber and the ideal material of silica gel；The variation that TPE material passes through formula and proportion, it is possible to provide physical property and the diversified material of hardness
Material, to meet the optimum requirement of different product.
Phenylethylene TPE is most popular one kind TPE, is that butadiene or isoprene and styrene block type are copolymerized
Object, performance is closest to SBR rubber.The yield of world's phenylethylene TPE accounts for about whole TPE half or so at present.It is representative
Kind is styrene-butadiene-styrene block copolymer (SBS), is widely used in shoe industry, most of instead of rubber
Glue；The purposes in the industrial rubber articles such as adhesive plaster, offset plate is also constantly expanding simultaneously.SBS is also largely anti-as PS plastic
The bituminous pavement of impact modifying agent and bituminous pavement road is wear-resisting, anticracking, the excellent modifying agent for preventing soft antiskid.
SBS has good tensile strength and elasticity, rub resistance and excelling in fatigue property, and good and cheap, is mainly used for glue
Shoes, modified pitch, improvement agent for synthesis resin and adhesive etc..But greatest problem existing for SBS is thermo-labile, America and Europe etc. thus
State has carried out a series of performance improvements to it, wherein obtaining SEBS through saturated hydrogenation using SBS, shock strength can be made significantly to mention
Height, weatherability and heat-resistant aging significantly improve.
SEBS has the characteristics that ageing-resistant, safe and non-toxic, environmentally protective, in the industry cycle there is the title of " rubber gold ", main to use
In drug packages, medical transfusion utensil, large span lubricating oil, food packaging, wire and cable, sealing material, modifying plastics, high
Grade asphalt modification and with the fields such as the elastic material of human contact, belong to national strategy new industry and give priority to product.
But the block copolymer structure special due to SEBS, cause its processing performance generally poor, and tradition cream at present
The resilience and processing performance of the medical elastomer of glue production are but not good enough, and production cost is higher.
Summary of the invention
The purpose of the present invention is in view of the above-mentioned problems existing in the prior art, propose a kind of asepsis environment-protecting, processing performance
It is good, the high rebound TPE thermoplastic elastomer (TPE) of medical grade product and preparation method thereof at low cost, and can be used for making high request.
The technical scheme is that：It is characterized by comprising following quality hundred for a kind of high rebound TPE thermoplastic elastomer (TPE)
Divide the ingredient of ratio：39~49% SEBS, 5~10% homopolymerization PP, 5~9% dimethicone, 4~8% calcium carbonate,
0.2~0.4% lubricant, 0.2~0.4% antioxidant, surplus are white oil.
The high rebound TPE thermoplastic elastomer (TPE) further includes 5~8% elastomer.
Chemical pipeline of the present invention is that homopolymerization PP, white oil, diformazan is added using SEBS as matrix with cold-resistant fiber glass reinforced polypropylene
Base silicone oil makes every mechanical property of material all be significantly improved, is in addition added to elastomer, calcium carbonate, lubricant
And antioxidant, and define the mass content of each component, so that the composition of material is more reasonable, performance is more perfect.It is made
The thermoplastic elastomer (TPE) obtained has excellent resilience performance, and asepsis environment-protecting, processing performance is good, and surface is smooth to be spent, and can be used for making
The medical grade product of high request.
Wherein SEBS is a kind of multiduty novel thermoplastic elastomer, it is thermoplastic block copolymers styrene-fourth
Rubber segments polybutadiene unsaturated double-bond is through new modified elasticity prepared by catalytic hydrogenation in alkene-styrol copolymer molecule
Body, therefore there is the stability and good heat resistance more excellent than SBS.SEBS not only has excellent ageing-resistant performance, and
With preferable mechanical property, not only there is excellent resistance to ozone, resistance to oxidation, UV resistant and weather resistance, also have good
Oil resistant, chemicals-resistant corrosivity and excellent lower temperature resistance.Its product is colorless and transparent, nontoxic, tasteless, tinctorial property is excellent
It is different, density is low and has stronger bonding force with other materials.In addition, SEBS has preferable wearability and flexible when in use
Property, and the processing performance with thermoplastic, and can recycle and reuse.
PP, that is, polypropylene, PP can be compatible with the EB segment in SEBS, and PP is added in SEBS mixture, can improve mixed
The intensity and mobility for closing material, improve its hardness and shock resistance, and play the role of reducing cost, so PP is SEBS reason
The modified resin thought.It is added in SEBS when it is blended with white oil, plays the role of reduction boundary stress, reduce system defect, energy
Enough significantly improve the processing performance and service performance of SEBS.But the PP of different chemical structures is to thermoplastic elastomer composite material
Influence different, wherein the molecular chain structure of homopolymerization PP is more regular, crystallinity with higher and and more perfect crystal structure, because
This its rigidity and hardness are higher than random copolymerization PP and copolymerization PP.Tensile property, bending property, hardness and other power of homopolymerization PP
It learns performance and is all higher than random copolymerization PP and copolymerization PP.
The compatibility of white oil and SEBS are good, due to poor with the PS block compatible in SEBS, so to the shadow of SEBS intensity
Sound is smaller.It is the net that the PS section in SEBS will form physical crosslinking with EB sections that another important reason of white oil is added in SEBS
Network structure, molecular entanglement is closer, and white oil can destroy this entanglement, thus the effect between reducing macromolecular
Power increases the flexibility and mobility of material so that strand is submissive.
The elastomer is polyurethane fiber, has deep drawing quality, low elastic modulus and elastic recovery rate.Polyurethane
The macromolecular of block copolymer is alternately made of the short segment (hard segment) of flexible very big long-chain-segment (soft chain segment) and rigidity
's.Using soft chain segment as matrix, and hard segment dispersion is embedded in wherein.Flexible soft chain segment is made of aliphatic polyester or polyethers, can be with
Regard the spring for being easy stretching, extension as；And rigid chain segment is then made of carbamate and urea groups, such as same rigidity
Bead.Since singly-bound each in soft chain segment makees different degrees of interior rotation around its adjacent singly-bound, thus shape is having many bends or curves
Long-chain-segment as a mixed and disorderly ball of string, its form constantly changes.Macromolecular has very big adaptability under external force
And length also has very big stretching, extension leeway, so have the characteristic of deep drawing quality and elastic recovery rate.
Elastomer can realize the winding to calcium carbonate in system, additionally it is possible to realize to crystal region and noncrystalline domain
The elastic connection of domain and extrinsic region while enhancing each microstructure part switching performance of system, can also improve system
Elastic recovery capability, high efficiency buffer and recovery, modified whole shock resistance, creep resistant and deformation are carried out to extraneous stress impact
Recovery capability etc..
The calcium carbonate is porous calcium carbonate, and porous calcium carbonate is since its density is small, small in size, specific surface area and pore-body
Product is big, has mechanical and thermal stability, can be used as the filler of thermoplastic elastomer (TPE).The partial size of the porous calcium carbonate is 1.0
~1.2 μm, aperture is 32~40nm, specific surface area 5m2/g。
It is pre-processed using surface of the coupling agent to the sodium carbonate, is then put into production technology again.It is even
Connection agent can be improved the compatibility, wellability and dispersibility of calcium carbonate and TPE.Preprocess method is：By calcium carbonate in 90-100
Dry 2h at DEG C；Coupling agent and cyclohexanone are hybridly prepared into the treatment fluid that mass fraction is 1.5%；It is added in treatment fluid dry
(its mass ratio is calcium carbonate to calcium carbonate after dry: treatment fluid=1: 10), being passed through nitrogen protection, high-speed stirred is changed under constant temperature
Property calcium carbonate mixed solution；Mixed liquor is filtered, is washed repeatedly with acetone calcium carbonate 3 times, puts it into constant temperature oven 80-90 DEG C
Drying, obtains modified calcium carbonate.
After processing, coupling agent forms one layer of cover film in calcium carbonate surface, improves calcium carbonate granule and matrix plastic
Compatibility, and due to the unique microstructure of coupling agent, there is good coupling efficiency to polymer and coupling agent, passes through coupling agent
The bonding action of active group and matrix plastic exposed terminated groups can make the macromolecular chain in matrix plastic overcome the stress of micropore
Obstacle and enter in the micropore of calcium carbonate surface so that the combination of calcium carbonate and matrix plastic is more secured, bonded area
Bigger, combination degree is deeper, thus improves its dispersibility and bonding force in SEBS matrix, and improve calcium carbonate with
The compatibility of SEBS system, to significantly enhance the processing performance and mechanical performance of material entirety.
The coupling agent is KH550, KH560, at least one of KH570.
The lubricant is calcium stearate, zinc stearate, polyethylene wax or di-2-ethylhexylphosphine oxide dialkyldithiocarbamacompositions
At least one of ester.These lubricants are added in the material can significantly improve the smooth degree of material surface.
The antioxidant is antioxidant 1010, antioxidant 1076, at least one of irgasfos 168 or antioxidant 1098.
Preferably, antioxidant is irgasfos 168.Irgasfos 168 can prevent SEBS/PP blend aging, and will not
What, which generates, on the performance of blend influences.
A kind of high rebound TPE process for preparation of thermoplastic elastomer, includes the following steps：
1) it is uniformly mixed after sixty minutes in the high speed mixer for being 500rpm with white oil investment revolving speed by SEBS, stands 0.5
Hour, other components are blended into, mixing 4min is caused uniformly, and discharging obtains mixture；
2) mixture is put into double screw extruder hopper；
4) double screw extruder engine speed 30-40HZ, main feeding 10-20HZ are set, die temperature is 195-215 DEG C,
Extruding pelletization, it is dry to constant-quality.
Wherein the feed zone temperature of extruder can be 180-195 DEG C, and compression section temperature can be 200-220 DEG C, plasticizing
Duan Wendu 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 carry out unit conversion and meet the following conditions：RPM=120*F/P, F refer to HZ
Number, P refer to the number of poles of three-phase motor.
Finished product is uniformly mixed sampling, with injection molding machine sample preparation.Finally material is tested for the property, wherein density according to
ISO1183 test, tensile strength and elongation at break are tested according to ISO37, and tearing strength is tested according to ISO34, compressive deformation
Rate is tested according to ISO815.
Beneficial effects of the present invention：
This material has excellent resilience performance, and asepsis environment-protecting, processing performance is good, and surface is smooth to be spent, and can be used for making
The medical grade product for making high request, due to using SEBS system, can large-scale serial production, the medical bullet of more traditional latex production
Property body, there is simple production process, pollute small, at low cost advantage.
Specific embodiment
With reference to embodiment, the present invention is furture elucidated, it should be understood that following specific embodiments are only used for
It is bright the present invention rather than limit the scope of the invention.
Embodiment 1
A kind of high rebound TPE thermoplastic elastomer (TPE), specifically includes the ingredient of following mass percent：47% SEBS, 5%
Homopolymerization PP, 7% dimethicone, 4% calcium carbonate, 0.4% lubricant, 0.2% antioxidant, surplus is white oil.
Wherein lubricant is calcium stearate, and antioxidant is antioxidant 1010.
The performance test data of the material is listed in Table 1 below.
Embodiment 2
A kind of high rebound TPE thermoplastic elastomer (TPE), specifically includes the ingredient of following mass percent：45% SEBS, 6%
Homopolymerization PP, 9% dimethicone, 6% calcium carbonate, 0.3% lubricant, 0.4% antioxidant, surplus is white oil.
Wherein lubricant is zinc stearate, and antioxidant is antioxidant 1076.
The performance test data of the material is listed in Table 1 below.
Embodiment 3
A kind of high rebound TPE thermoplastic elastomer (TPE), specifically includes the ingredient of following mass percent：39% SEBS,
10% homopolymerization PP, 5% dimethicone, 8% calcium carbonate, 0.2% lubricant, 0.3% antioxidant, surplus are white
Oil.
Wherein lubricant is polyethylene wax, and antioxidant is antioxidant 1098.
The performance test data of the material is listed in Table 1 below.
Table 1
| Test item | Unit | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| Density | g/cm3 | 0.99 | 0.99 | 0.97 |
| Tensile strength | MPa | 5 | 4 | 5 |
| Elongation at break | % | 400 | 415 | 420 |
| Tearing strength | KN/m | 26 | 26 | 28 |
| Compressive deformation | % | 48 | 50 | 50 |
Embodiment 4
A kind of high rebound TPE thermoplastic elastomer (TPE), specifically includes the ingredient of following mass percent：47% SEBS, 5%
Homopolymerization PP, 7% dimethicone, 4% calcium carbonate, 0.4% lubricant, 0.2% antioxidant, surplus is white oil.
The high rebound TPE thermoplastic elastomer (TPE) further includes 6% elastomer.The elastomer is that polyurethane is fine
Dimension.
Wherein lubricant is calcium stearate, and antioxidant is antioxidant 1010.
The results are shown in Table 2 for the performance test data of the material.
Embodiment 5
A kind of high rebound TPE thermoplastic elastomer (TPE), specifically includes the ingredient of following mass percent：45% SEBS, 6%
Homopolymerization PP, 9% dimethicone, 6% calcium carbonate, 0.3% lubricant, 0.4% antioxidant, surplus is white oil.
The high rebound TPE thermoplastic elastomer (TPE) further includes 5% elastomer.The elastomer is that polyurethane is fine
Dimension.
Wherein lubricant is calcium stearate, and antioxidant is antioxidant 1076.
The results are shown in Table 2 for the performance test data of the material.
Embodiment 6
A kind of high rebound TPE thermoplastic elastomer (TPE), specifically includes the ingredient of following mass percent：39% SEBS,
10% homopolymerization PP, 5% dimethicone, 8% calcium carbonate, 0.2% lubricant, 0.3% antioxidant, surplus are white
Oil.
The high rebound TPE thermoplastic elastomer (TPE) further includes 8% elastomer.The elastomer is that polyurethane is fine
Dimension.
Wherein lubricant is calcium stearate, and antioxidant is antioxidant 1098.
The results are shown in Table 2 for the performance test data of the material.
Table 2
| Test item | Unit | Embodiment 4 | Embodiment 5 | Embodiment 6 |
| Density | g/cm3 | 0.99 | 0.99 | 0.97 |
| Tensile strength | MPa | 5 | 6 | 6 |
| Elongation at break | % | 470 | 470 | 480 |
| Tearing strength | KN/m | 30 | 29 | 30 |
| Compressive deformation | % | 42 | 42 | 42 |
Embodiment 7
A kind of high rebound TPE thermoplastic elastomer (TPE), specifically includes the ingredient of following mass percent：43% SEBS, 7%
Homopolymerization PP, 5% dimethicone, 4.5% calcium carbonate, 0.2% lubricant, 0.3% antioxidant, surplus be it is white
Oil.
The high rebound TPE thermoplastic elastomer (TPE) further includes 5% elastomer.The elastomer is that polyurethane is fine
Dimension.
Wherein lubricant is zinc stearate, and antioxidant is irgasfos 168.
The calcium carbonate is porous calcium carbonate, and calcium carbonate microparticle partial size is 1.0 μm, aperture 32nm, and specific surface area is
5m2/g。
To be pretreated by coupling agent KH550, pre-treatment step is the calcium carbonate：Calcium carbonate is dry at 90 DEG C
2h；Coupling agent KH550 and cyclohexanone are hybridly prepared into the treatment fluid that mass fraction is 1.5%；Drying is added in treatment fluid
(its mass ratio is calcium carbonate to calcium carbonate afterwards: treatment fluid=1: 10), being passed through nitrogen protection, high-speed stirred is modified under constant temperature
Calcium carbonate mixed solution；Mixed liquor is filtered, is washed repeatedly with acetone calcium carbonate 3 times, 80 DEG C of drying in constant temperature oven are put it into,
Obtain modified calcium carbonate.
The results are shown in Table 3 for the performance test data of the material.
Embodiment 8
A kind of high rebound TPE thermoplastic elastomer (TPE), specifically includes the ingredient of following mass percent：43% SEBS, 7%
Homopolymerization PP, 5% dimethicone, 4.5% calcium carbonate, 0.2% lubricant, 0.3% antioxidant, surplus be it is white
Oil.
The high rebound TPE thermoplastic elastomer (TPE) further includes 5% elastomer.The elastomer is that polyurethane is fine
Dimension.
Wherein lubricant is zinc stearate, and antioxidant is antioxidant 1010.
The calcium carbonate is porous calcium carbonate, and calcium carbonate microparticle partial size is 1.1 μm, aperture 35nm, and specific surface area is
8m2/g。
To be pretreated by coupling agent KH560, pre-treatment step is the calcium carbonate：Calcium carbonate is dry at 95 DEG C
2h；Coupling agent KH560 and cyclohexanone are hybridly prepared into the treatment fluid that mass fraction is 1.5%；Drying is added in treatment fluid
(its mass ratio is calcium carbonate to calcium carbonate afterwards: treatment fluid=1: 10), being passed through nitrogen protection, high-speed stirred is modified under constant temperature
Calcium carbonate mixed solution；Mixed liquor is filtered, is washed repeatedly with acetone calcium carbonate 3 times, 85 DEG C of drying in constant temperature oven are put it into,
Obtain modified calcium carbonate.
The results are shown in Table 3 for the performance test data of the material.
Embodiment 9
A kind of high rebound TPE thermoplastic elastomer (TPE), specifically includes the ingredient of following mass percent：43% SEBS, 7%
Homopolymerization PP, 5% dimethicone, 4.5% calcium carbonate, 0.2% lubricant, 0.3% antioxidant, surplus be it is white
Oil.
The high rebound TPE thermoplastic elastomer (TPE) further includes 5% elastomer.The elastomer is that polyurethane is fine
Dimension.
Wherein lubricant is zinc stearate, and antioxidant is the mixture of irgasfos 168 and antioxidant 1098.
The calcium carbonate is porous calcium carbonate, and calcium carbonate microparticle partial size is 1.2 μm, aperture 40nm, and specific surface area is
10m2/g。
To be pretreated by coupling agent KH570, pre-treatment step is the calcium carbonate：Calcium carbonate is done at 100 DEG C
Dry 2h；Coupling agent KH570 and cyclohexanone are hybridly prepared into the treatment fluid that mass fraction is 1.5%；It is added in treatment fluid dry
(its mass ratio is calcium carbonate to calcium carbonate after dry: treatment fluid=1: 10), being passed through nitrogen protection, high-speed stirred is changed under constant temperature
Property calcium carbonate mixed solution；Mixed liquor is filtered, is washed repeatedly with acetone calcium carbonate 3 times, 90 DEG C of bakings in constant temperature oven are put it into
It is dry, obtain modified calcium carbonate.
The results are shown in Table 3 for the performance test data of the material.
Table 3
| Test item | Unit | Embodiment 7 | Embodiment 8 | Embodiment 9 |
| Density | g/cm3 | 0.99 | 0.99 | 0.97 |
| Tensile strength | MPa | 7 | 8 | 8 |
| Elongation at break | % | 500 | 505 | 515 |
| Tearing strength | KN/m | 35 | 33 | 35 |
| Compressive deformation | % | 34 | 33 | 33 |
Embodiment 10
A kind of high rebound TPE thermoplastic elastomer (TPE), specifically includes the ingredient of following mass percent：39% SEBS, 8%
Homopolymerization PP, 5.4% dimethicone, 8% porous calcium carbonate, 0.2% calcium stearate, 0.4% irgasfos 168,
Surplus is white oil.
The high rebound TPE thermoplastic elastomer (TPE) further includes 5% polyurethane fiber.
Above-mentioned TPE process for preparation of thermoplastic elastomer, includes the following steps：
1) SEBS, homopolymerization PP, white oil, dimethicone, polyurethane fiber, more is weighed according to the mass ratio of above-mentioned each component
Hole calcium carbonate, calcium stearate and irgasfos 168, wherein porous calcium carbonate can be pre-processed by coupling agent,
2) it is uniformly mixed after sixty minutes in the high speed mixer for being 500rpm with white oil investment revolving speed by SEBS, stands 0.5
Hour, other components are blended into, mixing 4min is caused uniformly, and discharging obtains mixture,
3) mixture is put into double screw extruder hopper, selects the screw combinations of Strong shear,
4) double screw extruder parameter is set, engine speed 40HZ, main feeding 15HZ, die temperature is 195 DEG C, and extrusion is made
Grain, it is dry to constant-quality.
Finished product is uniformly mixed sampling, with injection molding machine sample preparation.Finally material is tested for the property, test method and test
Condition is listed in Table 4 below.Test data result is listed in table 5.
Embodiment 11
A kind of high rebound TPE thermoplastic elastomer (TPE), specifically includes the ingredient of following mass percent：40% SEBS, 5%
Homopolymerization PP, 9% dimethicone, 4.3% porous calcium carbonate, 0.3% zinc stearate, 0.4% irgasfos 168,
Surplus is white oil.
The high rebound TPE thermoplastic elastomer (TPE) further includes 8% polyurethane fiber.
Above-mentioned TPE process for preparation of thermoplastic elastomer, includes the following steps：
1) SEBS, homopolymerization PP, white oil, dimethicone, polyurethane fiber, more is weighed according to the mass ratio of above-mentioned each component
Hole calcium carbonate, zinc stearate and irgasfos 168, wherein porous calcium carbonate can be pre-processed by coupling agent,
2) it is uniformly mixed after sixty minutes in the high speed mixer for being 500rpm with white oil investment revolving speed by SEBS, stands 0.5
Hour, other components are blended into, mixing 4min is caused uniformly, and discharging obtains mixture,
3) mixture is put into double screw extruder hopper, selects the screw combinations of Strong shear,
4) double screw extruder parameter is set, engine speed 30HZ, main feeding 20HZ, die temperature is 200 DEG C, and extrusion is made
Grain, it is dry to constant-quality.
Finished product is uniformly mixed sampling, with injection molding machine sample preparation.Finally material is tested for the property, test method and test
Condition is listed in Table 4 below.Test data result is listed in table 5.
Embodiment 12
A kind of high rebound TPE thermoplastic elastomer (TPE), specifically includes the ingredient of following mass percent：39% SEBS,
6.5% homopolymerization PP, 5% dimethicone, 4% porous calcium carbonate, 0.2% polyethylene wax, 0.3% antioxidant
168, surplus is white oil.
The high rebound TPE thermoplastic elastomer (TPE) further includes 5% polyurethane fiber.
Above-mentioned TPE process for preparation of thermoplastic elastomer, includes the following steps：
1) SEBS, homopolymerization PP, white oil, dimethicone, polyurethane fiber, more is weighed according to the mass ratio of above-mentioned each component
Hole calcium carbonate, polyethylene wax and irgasfos 168, wherein porous calcium carbonate can be pre-processed by coupling agent,
2) it is uniformly mixed after sixty minutes in the high speed mixer for being 500rpm with white oil investment revolving speed by SEBS, stands 0.5
Hour, other components are blended into, mixing 4min is caused uniformly, and discharging obtains mixture,
3) mixture is put into double screw extruder hopper, selects the screw combinations of Strong shear,
4) double screw extruder parameter is set, engine speed 30HZ, main feeding 10HZ, die temperature is 205 DEG C, and extrusion is made
Grain, it is dry to constant-quality.
Finished product is uniformly mixed sampling, with injection molding machine sample preparation.Finally material is tested for the property, test method and test
Condition is listed in Table 4 below.Test data result is listed in table 5.
Embodiment 13
A kind of high rebound TPE thermoplastic elastomer (TPE), specifically includes the ingredient of following mass percent：49% SEBS, 5%
Homopolymerization PP, 5.5% dimethicone, 4% porous calcium carbonate, 0.3% di-2-ethylhexylphosphine oxide dialkyl dithio amino first
Acid esters, 0.2% irgasfos 168, surplus are white oil.
The high rebound TPE thermoplastic elastomer (TPE) further includes 6% polyurethane fiber.
Above-mentioned TPE process for preparation of thermoplastic elastomer, includes the following steps：
1) SEBS, homopolymerization PP, white oil, dimethicone, polyurethane fiber, more is weighed according to the mass ratio of above-mentioned each component
Hole calcium carbonate, di-2-ethylhexylphosphine oxide dialkyl dithio amino formate and irgasfos 168, wherein porous calcium carbonate can be by coupling
Agent pretreatment,
2) it is uniformly mixed after sixty minutes in the high speed mixer for being 500rpm with white oil investment revolving speed by SEBS, stands 0.5
Hour, other components are blended into, mixing 4min is caused uniformly, and discharging obtains mixture,
3) mixture is put into double screw extruder hopper, selects the screw combinations of Strong shear,
4) double screw extruder parameter is set, engine speed 35HZ, main feeding 15HZ, die temperature is 210 DEG C, and extrusion is made
Grain, it is dry to constant-quality.
Finished product is uniformly mixed sampling, with injection molding machine sample preparation.Test method and test condition are listed in Table 4 below.Test number
Table 5 is listed according to result.
Embodiment 14
Above-mentioned TPE thermoplastic elastomer (TPE), specifically includes the ingredient of following mass percent：41% SEBS, 10% it is equal
Poly- PP, 6.3% dimethicone, 5% porous calcium carbonate, 0.4% calcium stearate and di-2-ethylhexylphosphine oxide dialkyl dithio
Carbamic acid ester admixture, 0.3% irgasfos 168, surplus are white oil.
The high rebound TPE thermoplastic elastomer (TPE) further includes 7% polyurethane fiber.
A kind of high rebound TPE process for preparation of thermoplastic elastomer, includes the following steps：
1) SEBS, homopolymerization PP, white oil, dimethicone, polyurethane fiber, more is weighed according to the mass ratio of above-mentioned each component
Hole calcium carbonate, calcium stearate and di-2-ethylhexylphosphine oxide dialkyl dithio amino formate mixture and irgasfos 168, wherein porous carbon
Sour calcium can be pre-processed by coupling agent,
2) it is uniformly mixed after sixty minutes in the high speed mixer for being 500rpm with white oil investment revolving speed by SEBS, stands 0.5
Hour, other components are blended into, mixing 4min is caused uniformly, and discharging obtains mixture,
3) mixture is put into double screw extruder hopper, selects the screw combinations of Strong shear,
4) double screw extruder parameter is set, engine speed 35HZ, main feeding 20HZ, die temperature is 215 DEG C, and extrusion is made
Grain, it is dry to constant-quality.
Finished product is uniformly mixed sampling, with injection molding machine sample preparation.Finally material is tested for the property, test method and test
Condition is listed in Table 4 below.Test data result is listed in table 5.
Comparative example 1
It has chosen market similar product to be tested for the property under the same conditions, test data result is listed in table 5.
Table 4
| Test item | Unit | Test method | Test condition |
| Density | g/cm3 | ISO1183 | / |
| Tensile strength | MPa | ISO37 | V=500mm/min |
| Elongation at break | % | ISO37 | V=500mm/min |
| Tearing strength | KN/m | ISO34 | V=500mm/min |
| Compressive deformation | % | ISO815 | 22h, 70 DEG C |
Note：V is test rate
Table 5
| Test item | Unit | Embodiment 10 | Embodiment 11 | Embodiment 12 | Embodiment 13 | Embodiment 14 | Comparative example 1 |
| Density | g/cm3 | 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 |
| Tearing strength | KN/m | 34 | 33 | 34 | 35 | 35 | 32 |
| Compressive deformation | % | 34 | 33 | 33 | 34 | 33 | 60 |
In view of the numerous embodiments of the scheme of the present invention, each embodiment experimental data is huge numerous, is not suitable for arranging one by one herein
Explanation is lifted, but the content verified required for each embodiment and obtained final conclusion are close, so herein not to each reality
The verifying content for applying example is explained one by one.
This place embodiment is not exhaustive claimed midpoint of technical range and in embodiment technology
In scheme to single or multiple technical characteristics it is same replacement be formed by new technical solution, equally all the present invention claims
In the range of protection；Simultaneously the present invention program it is all enumerate or unlisted embodiment in, in the same embodiment each
Parameter is merely representative of an example (i.e. a kind of feasible scheme) for its technical solution, and between parameters and is not present stringent
Cooperation and qualified relation, wherein each parameter can be replaced mutually when stating and asking without prejudice to axiom and the present invention, special declaration
Except.
The technical means disclosed in the embodiments of the present invention is not limited to the technical means disclosed in the above technical means, and further includes
Technical solution consisting of any combination of the above technical features.The foregoing is a specific embodiment of the present invention, should refer to
Out, for those skilled in the art, without departing from the principle of the present invention, can also make several
Improvements and modifications, these modifications and embellishments are also considered to be within the scope of the present invention.
Claims (6)
1. a kind of high rebound TPE thermoplastic elastomer (TPE), it is characterised in that it includes the ingredient of following mass percent：39~49%
SEBS, 5~10% homopolymerization PP, 5~9% dimethicone, 4~8% porous calcium carbonate, 0.2~0.4% lubricant,
0.2~0.4% antioxidant, 5~8% polyurethane fiber, surplus are white oil；The calcium carbonate is to pre-process by coupling agent
's.
2. a kind of high rebound TPE thermoplastic elastomer (TPE) according to claim 1, it is characterised in that：The calcium carbonate microparticle
Partial size be 1.0~1.2 μm, aperture be 32~40nm, specific surface area be 5~10m2/g。
3. a kind of high rebound TPE thermoplastic elastomer (TPE) according to claim 1, it is characterised in that：The coupling agent is
At least one of KH550, KH560, KH570.
4. a kind of high rebound TPE thermoplastic elastomer (TPE) according to claim 1, it is characterised in that：The lubricant is hard
At least one of resin acid calcium, zinc stearate, polyethylene wax or di-2-ethylhexylphosphine oxide dialkyl dithio amino formate.
5. a kind of high rebound TPE thermoplastic elastomer (TPE) according to claim 1, it is characterised in that：The antioxidant is anti-
Oxygen agent 1010, antioxidant 1076, one or more of irgasfos 168 or antioxidant 1098.
6. a kind of high rebound TPE process for preparation of thermoplastic elastomer as described in claim 1, it is characterised in that including following
Step：
SEBS is uniformly mixed with white oil, is blended into other components, is uniformly mixed and obtains mixture；
By mixture through screw extruder extruding pelletization；Wherein extruder engine speed 30-40HZ, main feeding 10-20HZ, die orifice
Temperature is 195-215 DEG C.
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