CN105175979A - High-resilience thermoplastic elastomer composition and preparation method thereof - Google Patents
High-resilience thermoplastic elastomer composition and preparation method thereof Download PDFInfo
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- CN105175979A CN105175979A CN201510704865.0A CN201510704865A CN105175979A CN 105175979 A CN105175979 A CN 105175979A CN 201510704865 A CN201510704865 A CN 201510704865A CN 105175979 A CN105175979 A CN 105175979A
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Abstract
The invention provides a high-resilience thermoplastic elastomer composition having remarkably-improved hand feeling. The high-resilience thermoplastic elastomer composition is used for preparation of high-strength high-resilience films and sheets. The high-resilience thermoplastic elastomer composition is prepared from, by weight, 40-60 parts of SEEPS block copolymer, 20-40 parts of mineral oil, 5-15 parts of metallocene polyolefin, 5-20 parts of polybutadiene, 3-15 parts of polystyrene and 3-10 parts of tackifying resin.
Description
Technical field
The invention belongs to polymeric material field, be specifically related to a kind of tool and be significantly improved the high resilience composition for thermoplastic elastomer and preparation method thereof of feel, for the preparation of film and sheet material.
Background technology
Thermoplastic elastomer normal temperature has the high rebound characteristics of rubber, under the high temperature conditions again can plasticizing forming, there is the processing characteristics that plastics are good, therefore can be widely used in needing high resilience, the medical device of easily processing, body articles for use and garment industry, such as: tourniquet, tubing, paper diaper pad, body-building pulling force rope/ring and some physical culture furnishings.
Styrene analog thermoplastic elastomer is easy to obtain because of its raw material, formula can scope of design wide, hardness adjustment is interval large and obtain increasing attention.Some goods in above-mentioned field, the Normal practice of employing styrenic elastomer is: do rubber phase with the styrene butadiene of hydrogenation/isopreene-styrene block polymkeric substance, tenderizer is made with mineral oil, coordinate properties-correcting agent (such as polypropylene, polystyrene etc.) and other additives.
United States Patent (USP) 6410129 discloses a kind of three components film formulation composition, includes
4033, mineral oil, vinyl aromatic resin.In the embodiment disclosed in this patent, film formulation comprises massfraction 55%
the mineral oil of the PS (polystyrene) and 30% of 4033,15%.But not easily processed by the composition of these material-mix, be easy to layering, obtained film/sheet material products feel is coarse; Product strength is poor in addition, easily splits in tension test repeatedly.
United States Patent (USP) 9056975 and Chinese patent CN103534310A disclose a kind of elastomer formulations being applicable to film and sheet material.Hydrogenation SEEPS segmented copolymer is comprised, polystyrene, oil & fat race hydrogenated resin in formula.Include in an embodiment disclosed in Chinese patent CN103534310A: massfraction 55%
4033 or JL-014, the oil of 15%, the polystyrene of 15% and the aliphatics hydrogenated resin of 15%
r1125, in this embodiment, improvement
4033 decrease content oily in formula, and obtained film and sheet material have better ultimate stress and Young's modulus.But the film creep loss obtained by this formula is large, and rebound resilience is poor; By adding aliphatic hydrogenated resin, decrease the content of polystyrene, and improve the processing characteristics of film and sheet material, but film obtained thus and sheet material also also exist feel difference, rebound resilience is not good, is needing the Application Areas of high strength, high resilience, and its application is restricted.
Therefore, this area need a kind of possess excellent handle and possess high resilience can composition for thermoplastic elastomer.
Summary of the invention
A kind of tool is the object of the present invention is to provide to be significantly improved the high resilience composition for thermoplastic elastomer of feel, for the preparation of the film had higher requirements to rebound resilience and feel and sheet material products.
Therefore, the invention provides a kind of high resilience composition for thermoplastic elastomer, its raw material comprises the component of following weight parts: SEEPS segmented copolymer 40-60 part, 20 ~ 40 parts, mineral oil, metallocene-polyolefin 5 ~ 15 parts, polyhutadiene 5-20 part, polystyrene 3-15 part and tackifying resin 3-10 part.
In a kind of concrete embodiment, described metallocene-polyolefin is metallocene PE or metallocene polypropylene, and preferred described metallocene-polyolefin is that melting index is the metallocene PE of 1-3g/10min under test condition 190 DEG C and 2.16Kg.
In a kind of concrete embodiment, the molecular-weight average of described polyhutadiene is 80000 ~ 140000.
In a kind of concrete embodiment, 1,2-polybutadiene content >=90% in described polyhutadiene, softening temperature >=100 DEG C of polyhutadiene; 1,2-polybutadiene content >=93% in preferred polyhutadiene, softening temperature >=120 DEG C of polyhutadiene.
In a kind of concrete embodiment, the raw material preparing elastic composition comprises: SEEPS segmented copolymer 40-60%, mineral oil 20 ~ 40%, metallocene-polyolefin 5 ~ 15%, polyhutadiene 5-20%, polystyrene 3-15% and tackifying resin 3-10%, preferred SEEPS segmented copolymer 45-50%, mineral oil 20 ~ 35%, metallocene-polyolefin 5 ~ 12%, polyhutadiene 5-10%, polystyrene 4-10% and tackifying resin 7-10%.
In a kind of concrete embodiment, described SEEPS segmented copolymer comprise Kuraray company produce
series copolymer, preferably comprises
4033, more preferably comprising mass ratio is 1 ~ 10:1's
4033 Hes
4044.
In a kind of concrete embodiment, described mineral oil is saturated straight chain alkane and/or naphthenic hydrocarbon; Described tackifying resin is the aliphatics hydrocarbon resin of hydrogenation; And prepare in the raw material of described elastic composition and also comprise auxiliary agent, described auxiliary agent comprises antioxidant and/or slipping agent, preferred described antioxidant is the mixture of the Irganox168 of Irganox1010 and 0.1-0.4% of above-mentioned six kinds of main ingredient weight 0.05-0.4%, and preferred described slipping agent is the erucicamide of above-mentioned six kinds of main ingredient weight 0.05-0.2%.
In a kind of concrete embodiment, described metallocene-polyolefin is the SP1028 that Japanese Pu Ruiman Polymer Company produces, and described polyhutadiene is that Japanese JSR company produces
840.In a kind of concrete embodiment, the described raw material preparing elastic composition comprises by 40%
4033 and 10%
sEEPS, mineral oil 20%, the metallocene PE SP1028 of 4044 compositions are 12%, polyhutadiene RB840 is 6%, tackifying resin
h-142W be 7% and polystyrene GP5350 be 5%, and to account for above-mentioned raw materials gross weight mass percent be the auxiliary agent of 0.1 ~ 1%.
The present invention also provides a kind of preparation method of composition described above, comprise first by SEEPS segmented copolymer and mineral oil, add metallocene-polyolefin, polyhutadiene, tackifying resin, polystyrene and auxiliary agent again, fully add extrusion moulding in forcing machine after mixing.
In the present invention, metallocene-polyolefin is the polyolefine using metallocene (MAO) to produce for polymerizing catalyst.Therefore, it has significant different from the polyolefine that traditional Ziegler-Natta catalyst is polymerized (Z-N polyolefine) in performance.
Tackifying resin tool improves significantly the feature of copolymer resin Membranous lipid fluidity, and can reduce the content of oil.Adding of metallocene-polyolefin makes composition for thermoplastic elastomer have good elasticity and feel.Polyhutadiene and the blended mobility can improving composition for thermoplastic elastomer of SEEPS, and there is good rebound resilience.
Described SEEPS segmented copolymer is actual is this five block polymers of styrene-ethylene-ethylene/propylene-styrene, also referred to as hydrogenation SEEPS segmented copolymer.They obtain through hydrogenation derivation from the middle segment of isoprene/butadiene, has good elasticity and stability; Preferred SEEPS multipolymer is that Kuraray company produces
series, should
sEEPS has the vinylbenzene segment of 30% and the rubber segment of 70%, is more preferably
4033,
one or both in 4044.
Described mineral oil, as tenderizer, can be at least one in the saturated straight chain alkane oil of different viscosity, naphthenic oil.More preferably, above-mentioned mineral oil is the straight-chain paraffin oil with high flash point.Such as: the two dragon of the 2071P that German Hansen & Rosenthal produces or Korea S produces
500N.
Described metallocene-polyolefin is metallocene PE or metallocene polypropylene, can obtain more stable processing characteristics and superior physicals when metallocene PE is applied to film production; In embodiments of the invention, the melting index of preferred metallocene PE is the Evolue of 1-3g/10min, such as PrimePolymer
tM-PSP1028.
Described polyhutadiene is syndiotactic 1, the 2-polyhutadiene that one has lower molecular weight and low-crystallinity (degree of crystallinity is 15 ~ 30%); Preferably the polyhutadiene per-cent of 1,2 structures is greater than 90%, and softening temperature is greater than 100 DEG C, and more preferably, the polyhutadiene per-cent of 1,2 structures is greater than 93, and softening temperature is greater than 120 DEG C.Such as Japanese JSR company
840.
Described polystyrene is General Purpose Polystyrenre, such as GP5350 and GP5500 of Tai Hua company; Polystyrene, as another component in elastic composition, can improve processing characteristics and other performances of elastic composition.
Described tackifying resin is the aliphatics hydrocarbon resin of hydrogenation, such as: Eastman Chemical
c-100W, C-115W, H-142W, wherein the softening temperature of H-142W is up to 142 DEG C; Suitable tackifier join in elastic composition, the addition of oil can be reduced, when maintaining same rigidity, improve the processing characteristics of elastic composition and the physicals of Elastic Film/sheet material obtained thus, therefore the preferred tackifying resin of the present invention is
h-142W, adding proportion is 3%.
Other described auxiliary agents include antioxidant, slipping agent etc.
According to oxidation inhibitor favourable in elastic composition of the present invention be: Irganox1010 and Irganox168, preferably, the Irganox168 of Irganox1010 and 0.1-0.4% of 0.05-0.4% is comprised in said composition, more preferably, the ratio of Irganox1010 is the ratio of 0.05%, Irganox168 is 0.2%.
According in elastic composition of the present invention advantageously slipping agent be: erucicamide.Preferably, in said composition, comprise the erucicamide of 0.05-0.2%, more preferably, in said composition, comprise the erucicamide of 0.1%.
According to elastic composition of the present invention needs in use, in composition, UV stablizer can be comprised, weighting agent, antiseptic-germicide, pigment etc.
Film prepared in accordance with the present invention can have the thickness of 0.05mm to 0.5mm.Preferably, the film of 0.05mm to 0.2mm is prepared.Sheet material prepared in accordance with the present invention can have the thickness of 0.5mm to 1mm or be greater than the thickness of 1mm.
Elastic composition of the present invention can adopt the method extruded continuously to be prepared.First SEEPS segmented copolymer is fully mixed to scale with mineral oil; add metallocene PE, polystyrene, polyhutadiene, tackifying resin and other auxiliary agents subsequently; join equably in twin screw extruder after abundant mixing, be cut into after column through dicing machine, fully dry.The temperature of twin screw extruder is set between 160 ~ 250 DEG C of scopes usually, is preferably 180 ~ 230 DEG C; Screw speed is set between 100 ~ 400 revs/min, preferably 200 ~ 350 revs/min.
After granulation, single screw extrusion machine is adopted above-mentioned granular elastic composition to be prepared into the sheet material of 0.8mm thickness.The temperature of forcing machine is set within the scope of 180-240 DEG C.
Embodiment
Below in conjunction with specific embodiment, the present invention is further illustrated, but scope of the present invention is not limited to these embodiments.
By the Example formulations listed by table 1, prepare this 10 kinds of elastic compositions successively, the adding proportion of each component of the digitized representation in table 1, in weight percent.
First SEEPS segmented copolymer is fully mixed to scale with mineral oil; add metallocene PE, polystyrene, polyhutadiene, tackifying resin and other auxiliary agents subsequently; join equably in twin screw extruder after abundant mixing, be cut into after column through dicing machine, fully dry.The temperature of twin screw extruder is set between 190 ~ 230 DEG C of scopes usually; Screw speed is set between 200 ~ 350 revs/min.Then single screw extrusion machine is adopted granular elastic composition to be prepared into the sheet material of 0.8mm thickness.The temperature of forcing machine is set within the scope of 190-240 DEG C.
Table 1
The sheet material that each embodiment listed by table 1 and comparative example composition obtain, impact briquetting is dumbbell shaped testing plate, and the performance is after tested listed in table 2.
In the result of the performance test of table 2, material has carried out two test periods.One-period, for material is stretched to 200% from 0%, then stops after 30 seconds, removes loading force, make it be returned to complete relaxed state lower 60 seconds, then carry out the test of second period.Second period is the repetition of period 1.Related definition in material properties test result is as follows:
Ultimate stress " I ": in first test period, material is stretched to the tensile stress of 200% from 0%;
Loss stress " I ": after material extending to 200%, tensile stress when stopping after 30 seconds;
Ultimate stress " II ": in second test period, material is stretched to the tensile stress of 200% from 0%;
Loss stress " II ": after material extending to 200%, tensile stress when stopping after 30 seconds;
Total loss: the loss per-cent between ultimate stress " I " and ultimate stress " II ";
Creep loss " I ": in the period 1, the loss per-cent between ultimate stress " I " and loss stress " I ";
Creep loss " II ": in second cycle, the loss per-cent between ultimate stress " II " and loss stress " II ";
Surely reply is stretched: two all after dates (be stabilized in 0%, pause 60 seconds), the strain of test material and the per-cent of initial length.
Table 2
Those skilled in the art are known, and in above-mentioned table 2, it is best that hardness and melting index are in a rational scope, and the data of tensile strength and elongation at break are the bigger the better, and tensile set data are the smaller the better; Ultimate stress represent material extending to 200% time tensile stress, the larger material that represents of its data more not easily pulls; Loss stress represents material under that loading condition, the hold facility of stress; Total loss represent that material is in its elastic maintenance situation after twice stretching, and data are the smaller the better; Creep loss represents material its elasticity maintenance situation under that loading condition, and data are the smaller the better; Surely stretch reply similar with tensile set, its data are the smaller the better; And the quality of feel is the feel sophistication according to material, smooth degree and whether has the sensation that is similar to silicon rubber and determine.Wherein, have following data for the rebound performance of exosyndrome material, total loss and creep loss are from the angle of force value to characterize elasticity, and tensile set and surely to stretch recovery be characterize elasticity from the angle of deformation.
As can be seen from test above, the preferred embodiments of the present invention, under the prerequisite balancing Drawing abillity and tensile strength, obtain the formula of the film/sheet material simultaneously with better rebound resilience and feel.The SEEPS of different molecular weight is relatively more remarkable to the intensity effect of obtained sheet material, and the SEEPS of high molecular has better intensity, but mobility is poor, and rebound resilience is also poor; As can be seen from embodiment 1 ~ 3, by being used in conjunction with each other of the hydrogenation SEEPS segmented copolymer of different molecular weight, especially mass ratio is adopted to be 1 ~ 10:1's
4033 Hes
4044, being balanced well of the processing characteristics of sheet material and tensile strength can be made.
As can be seen from embodiment and comparative example relatively, containing in the formula of polyhutadiene, the tensile set of sheet material and surely stretch recovery data and be all starkly lower than not containing the formula of polyhutadiene, its rebound resilience is good; In addition, the elastic composition containing polyhutadiene, its creep loss is less, illustrates that said composition material has better resistance to fatigue and elasticity.In the present invention's experiment, another finds significantly to be exactly that the sheet material that the formula being added with metallocene PE obtains, under rebound resilience hardly affected prerequisite, its feel is fine and smooth, smooth, have the sensation being similar to silicon rubber.And if interpolation is Z-N polyethylene (comparative example 5), then the sheet material of gained not only has no the improvement of feel, and also has an impact to the rebound resilience of sheet material to a certain extent.
To sum up, by preparing in the styrene analog thermoplastic elastomer composite formula of film/sheet material common, low-molecular-weight polyhutadiene composition is added, the rebound resilience of the material that can improve and fatigue resistance; By adding metallocene-polyolefin, the good elastic composition formula of feel can be obtained.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, for a person skilled in the art, the present invention can have various modifications and variations.Within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. a high resilience composition for thermoplastic elastomer, its raw material comprises the component of following weight parts: SEEPS segmented copolymer 40-60 part, 20 ~ 40 parts, mineral oil, metallocene-polyolefin 5 ~ 15 parts, polyhutadiene 5-20 part, polystyrene 3-15 part and tackifying resin 3-10 part.
2. composition according to claim 1, it is characterized in that, described metallocene-polyolefin is metallocene PE or metallocene polypropylene, and preferred described metallocene-polyolefin is that melting index is the metallocene PE of 1-3g/10min under test condition 190 DEG C and 2.16Kg.
3. composition according to claim 1, it is characterized in that, the molecular-weight average of described polyhutadiene is 80000 ~ 140000.
4. composition according to claim 1, is characterized in that, 1,2-polybutadiene content >=90% in described polyhutadiene, softening temperature >=100 DEG C of polyhutadiene; 1,2-polybutadiene content >=93% in preferred polyhutadiene, softening temperature >=120 DEG C of polyhutadiene.
5. composition according to claim 1, it is characterized in that, the raw material preparing elastic composition comprises: SEEPS segmented copolymer 40-60%, mineral oil 20 ~ 40%, metallocene-polyolefin 5 ~ 15%, polyhutadiene 5-20%, polystyrene 3-15% and tackifying resin 3-10%, preferred SEEPS segmented copolymer 45-50%, mineral oil 20 ~ 35%, metallocene-polyolefin 5 ~ 12%, polyhutadiene 5-10%, polystyrene 4-10% and tackifying resin 7-10%.
6. composition according to claim 1, is characterized in that, described SEEPS segmented copolymer comprises that Kuraray company produces
series copolymer, preferably comprises
4033, more preferably comprising mass ratio is 1 ~ 10:1's
4033 Hes
4044.
7. composition according to claim 1, it is characterized in that, described mineral oil is saturated straight chain alkane and/or naphthenic hydrocarbon; Described tackifying resin is the aliphatics hydrocarbon resin of hydrogenation;
And prepare in the raw material of described elastic composition and also comprise auxiliary agent, described auxiliary agent comprises antioxidant and/or slipping agent, preferred described antioxidant is the mixture of the Irganox168 of Irganox1010 and 0.1-0.4% of above-mentioned six kinds of main ingredient weight 0.05-0.4%, and preferred described slipping agent is the erucicamide of above-mentioned six kinds of main ingredient weight 0.05-0.2%.
8. according to composition described in any one in claim 1 ~ 7, it is characterized in that, described metallocene-polyolefin is the SP1028 that Japanese Pu Ruiman Polymer Company produces, and described polyhutadiene is that Japanese JSR company produces
840.
9. composition according to claim 8, is characterized in that, the described raw material preparing elastic composition comprises by 40%
4033 and 10%
sEEPS, mineral oil 20%, the metallocene PE SP1028 of 4044 compositions are 12%, polyhutadiene RB840 is 6%, tackifying resin
h-142W be 7% and polystyrene GP5350 be 5%, and to account for above-mentioned raw materials gross weight mass percent be the auxiliary agent of 0.1 ~ 1%.
10. the preparation method as composition as described in any one in claim 1 ~ 9, comprise first by SEEPS segmented copolymer and mineral oil, add metallocene-polyolefin, polyhutadiene, tackifying resin, polystyrene and auxiliary agent again, fully add extrusion moulding in forcing machine after mixing.
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| WO2018036132A1 (en) * | 2016-08-24 | 2018-03-01 | 南通普力马弹性体技术有限公司 | Solvent-bonding twisting-resistant transparent transfusion tube material |
| CN108727767A (en) * | 2018-06-26 | 2018-11-02 | 南通普力马弹性体技术有限公司 | Thermoplastic elastic material and film |
| CN113785011A (en) * | 2019-04-26 | 2021-12-10 | 艾维恩股份有限公司 | Thermoplastic elastomer gel |
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Application publication date: 20151223 |