CN103044696A - Preparation method of thermoplastic vulcanized rubber - Google Patents
Preparation method of thermoplastic vulcanized rubber Download PDFInfo
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Abstract
The invention discloses a preparation method of thermoplastic vulcanized rubber, which comprises the following steps in sequence: (1) rubber and plastic premixed material preparation: melting and premixing rubber, a part of plastic, a filler and a processing aid, wherein the weight of the premixed plastic occupies 20-60 percent of total weight of plastic in the thermoplastic vulcanized rubber to be prepared; (2) dynamic vulcanization: adding a vulcanizing agent, an accelerant or an assistant crosslinker in the remixing material obtained in the step (1) and mixing for dynamic vulcanization; and (3) residual plastic, softening oil and anti-aging agent addition at the later stage: adding residual plastic, softening oil and an anti-aging agent and continuing to uniformly mix so as to obtain the thermoplastic vulcanized rubber, wherein the weight of the softening oil is 10-30 percent of total weight of the plastic. The thermoplastic vulcanized rubber prepared by the preparation method has the advantages of high liquidity, low hardness and low compression permanent deformation.
Description
Technical field
The present invention relates to the cross-linked rubber technical field, be specifically related to a kind of preparation method of thermoplastic sulfurized rubber.
Background technology
Thermoplastic sulfurized rubber refers to add rubber and vulcanizing agent in thermoplastic resin, in the mixing tank of high-temperature field and high shear field, with resin and rubber melt blending, it is crosslinked that rubber produces in-situ chemical simultaneously, shearing is scattered in the stable dispersion system of formation in the resin, thus a kind of novel elastomer of preparing.It mainly is comprised of two portions, and the one, plastics are as external phase, and the 2nd, rubber is as disperse phase.Usually, rubber needs softening oil or softening agent to cooperate with it, and vulcanizing agent and some auxiliary addition agents also are absolutely necessary.In addition, in order to reduce cost or to improve the performance of certain aspect, some mineral fillers also can be added.Because thermoplastic sulfurized rubber had both had the processing convenience of thermoplastics, the snappiness that has again thermoset rubber, excellent combination property, the moulding industrial flow is simple and easy, process-cycle and the recyclable recycling of energy have greatly been shortened, so its goods are widely used in each production field and progressively replace traditional rubber.
The traditional preparation method of thermoplastic sulfurized rubber is: the first melting mixing in high-temperature mixer with plastics and oxidation inhibitor, add again rubber mix, then adding processing aid, filler, softening oil mixes, add at last vulcanizing agent and promotor and carry out dynamic vulcanization while mixing, make thermoplastic sulfurized rubber, granulation after the cooling.To a certain extent, dynamic vulcanization technology is not suitable for the thermoplastic sulfurized rubber of preparation soft and high workability.This is because just must increase the content of rubber components for the cross-linked rubber that obtains soft, and the existence of a large amount of cross-linked rubber particles so that the elasticity of material increases, but mobilely obviously descends, thereby so that melt easily breaks, is difficult to realize extruding and injection moulding.If the minimizing rubber content, the hardness of material can obviously increase again, namely flexibility decrease.Taking into account soft and the high workability of thermoplastic sulfurized rubber, is the difficult point of preparation thermoplastic sulfurized rubber.
China Patent Publication No. is that the patent of invention of CN1916055A discloses a kind of method that improves fluidity of thermoplastic cross-linked rubber, it impels the PP in the thermoplastic sulfurized rubber to degrade by adding dicumyl peroxide, thereby it is mobile to improve product, although the flowability of thermoplastic sulfurized rubber has improved, take the loss product intensity as cost; Simultaneously, the affiliation that adds of dicumyl peroxide consumes the oxidation inhibitor that the dynamic vulcanization stage adds, and brings product aging loss of energy.Publication number is that the Chinese invention patent of CN101696279A discloses a kind of method for preparing thermoplastic elastomer through dynamic vulcanization, the method is by preparing a reactive step material, vulcanizing agent rubber master batch, promotor rubber master batch in advance, then expect that with three kinds the blended melting dynamic crosslinkings are with the preparation thermoplastic sulfurized rubber, although can effectively disperse vulcanizing agent, promotor, the shearing that guarantees simultaneously rubber phase disperses, but preparation technology is loaded down with trivial details, and the hardness of product is relatively high.Publication number is the preparation method that the Chinese invention patent of CN1508170A discloses a kind of thermoplastic sulfurized rubber, and the method with rubber and plastics premix, prepares the rubber rubber master batch first again, then carries out dynamic vulcanization, and the later stage is oil-filled.The method can produce the dynamic vulcanization process and suppress owing to being to add anti-aging agent in early stage, can't absorb the free radical that produces in the dynamic vulcanization process simultaneously; In addition, the method is unfavorable for the abundant dispersion in rubber of vulcanizing agent and promotor and other processing aid with the disposable adding of plastics, is unfavorable for the tight cure of rubber phase and shears dispersion, can't guarantee the mechanical property of the finished product.
In sum, the preparation method of existing thermoplastic sulfurized rubber is further improved.
Summary of the invention
The object of the invention is to overcome the defective of above-mentioned prior art, a kind of preparation method of thermoplastic sulfurized rubber is provided, it can make the thermoplastic sulfurized rubber of high workability, soft, low compression set.
For achieving the above object, the present invention adopts following technical scheme:
A kind of preparation method of thermoplastic sulfurized rubber is characterized in that may further comprise the steps in turn:
(1) preparation rubber and plastics Preblend: with rubber and partly plastic, filler, processing aid melting premix, the weight that participates in the plastics of premix accounts for the 20-60% of plastics gross weight in the thermoplastic sulfurized rubber to be prepared;
(2) dynamic vulcanization: in the Preblend of step (1), add vulcanizing agent, promotor or additional crosslinker, be mixed into the Mobile state sulfuration;
(3) later stage adds leftover and plastic, softening oil and anti-aging agent: add remaining plastics, softening oil and anti-aging agent, continue to mix, namely obtain thermoplastic sulfurized rubber, the weight of softening oil is the 10-30% of plastics gross weight.
Preferably, the temperature of melting premix is 180-220 ℃ in the step (1), and the dynamic vulcanization time is 5-10min in the step (2).
Three steps of preparation method of the present invention all can be carried out on Banbury mixer, mill, two steps type twin screw extruder continuously, the loaded down with trivial details preparation technology who has avoided minute rubber master batch processed or masterbatch to bring.Because the stroke of single twin screw extruder is short, relatively be difficult to guarantee dynamic vulcanization time of growing, therefore, preparation method of the present invention preferably carries out in the two steps type twin screw extruder.The upper rank of two steps type twin screw extruder are single screw extrusion machine, can run up, and transporting molten and compacting be mixed material all; The lower rank of two steps type twin screw extruder are twin screw extruder, can realize the processing requirement of the dynamic vulcanization of long period.Specifically: add rubber and partly plastic, filler, assistant engineer's auxiliary agent melting premix on the upper rank of two steps type forcing machine, add in the middle vulcanizing agent, promotor or additional crosslinker; Crosslinked at the enterprising Mobile state of the extruding zone on lower rank; Postmedian on lower rank adds leftover and plastic and anti-aging agent at last, extrudes rear water-cooled granulation, obtains thermoplastic sulfurized rubber.
Prescription used in the present invention is the prescription of the thermoplastic sulfurized rubber of routine in the prior art, and concrete various components are as follows:
Described rubber is one or more mixing in chloroprene rubber, natural rubber, trans-isoprene, terpolymer EP rubber, cis-1,4-polybutadiene rubber, ethylene-vinyl acetate copolymer, chlorinated polyethylene rubber, acrylic elastomer, paracril, the styrene-butadiene rubber(SBR).
Described plastics are one or more mixing in polyethylene, polystyrene, polyvinyl chloride, polypropylene, acrylonitrile-butadiene-styrene copolymer, styrene-acrylonitrile copolymer, the polymethylmethacrylate.
Described filler is one or more mixing in White Carbon black, carbon black, potter's clay, tripoli, the kaolin.
Described vulcanizing agent is organo-peroxide or Sulfur or resol.
Described organo-peroxide is dibenzoyl peroxide, 1,1-two (tert-pentyl peroxy) hexanaphthene, tert butyl peroxy benzoate, 1, two (t-butylperoxy di-isopropyl) benzene, 1 of 4-, two (t-butylperoxy di-isopropyl) benzene, 2 of 3-, 5-dimethyl-2, two (tert-butyl peroxy base) hexanes, 2 of 5-, 5-dimethyl-2, two (tert-butyl peroxy the base)-3-hexins of 5-, ethyl-3,3-two (tert-butyl peroxy base) butyric ester, ethyl-3, one or more mixing in 3-two (tert-pentyl peroxy) butyric ester.
Described promotor is one or more mixing in dithiocarbamate(s), xanthogenic acid salt, guanidine class, Thiourea, sulfenamide, thiurams, aldehyde amines, the metal halide class.
Described additional crosslinker is triallyl cyanurate, triallyl isocyanurate, N, one or more mixing in N-phenyl-bismaleimide, ethyleneglycol dimethyacrylate, dimethacrylate vinyl glycol ester, trimethylammonium vinylformic acid trishydroxymethyl propyl ester, three vinylformic acid trishydroxymethyl propyl ester, the allyl methacrylate(AMA).
Described anti-aging agent is one or more mixing among antioxidant A, antioxidant D, antioxidant 2246, antioxidant 4010, antioxidant 264, antioxidant 1010, antioxidant 1076, antioxidant 245, photostabilizer UV-9, photostabilizer UV-327, photostabilizer UV-328, photostabilizer UV-329, the photostabilizer UV-531.
Described softening oil is one or more mixing in naphthenic oil, paraffin oil, the Vaseline.
Described processing aid is stearic acid or polyethylene wax or above two kinds of mixing.
It is very even that the premix technology of rubber and plastics can make rubber and partly plastic mix, further add plastics after, whole plastics and rubber will form uniform form in the short period of time.Because the process time of dynamic vulcanization is shorter, rubber edge sulfuration limit disperses among traditional preparation method, causes rubber and plastic not mix; Perhaps have a mind to prolong the dynamic vulcanization time for the mixedness that increases rubber and plastic, thereby thereby caused filler and various auxiliary agents to plastics mutually in migration affect product property.Partly plastic and rubber premix have been avoided above-mentioned shortcoming, so that rubber just well disperses before dynamic vulcanization, have also created condition for the mutually reverse of rubber plastic.The good distribution of rubber particles also provides prerequisite for the high workability of cross-linked rubber.
The in batches adding technology of plastics is conducive to the abundant dispersions in rubber such as vulcanizing agent and promotor, thereby guarantees the tight cure of rubber phase and shear dispersion.Among the tradition preparation method, various auxiliary agents inevitably migrate into plastics mutually in, reduced and fully the contacting of rubber phase; Simultaneously, each organo-peroxide also can cause the degraded of plastics.Plastics add in batches, can reduce above-mentioned behavior; Simultaneously the later stage adds plastics, can make rubber phase further shear refinement, be scattered in plastics mutually in, thereby improve the flowability of thermoplastic sulfurized rubber.
Oil-filled finger of later stage adds after dynamic vulcanization is finished and accounts for the softening oil that is equivalent to plastic content 10-30%, and this part oil has small part to infiltrate in the rubber particles, but major part remain in plastics mutually in.The adding of softening oil, in the situation that consumption is few, can the plasticising cross-linked rubber, thus can obviously reduce hardness and the compression set of cross-linked rubber, and improve mobile.
Later stage adds protective agent and can avoid these hot oxygen or photostabilizer to the inhibition of dynamic vulcanization process, avoids these auxiliary agents to be consumed in advance in the course of processing; The simultaneously adding of anti-aging agent also can absorb the free radical that produces in the dynamic vulcanization process, the plastics of avoiding the later stage to add are degraded, and has therefore guaranteed the mechanical property of the finished product.
In sum, the invention has the beneficial effects as follows:
1, the employing plastics add technology, partly plastic rubber premix technology in batches, the later stage is oil-filled and add the anti-aging agent technology can effectively increase the sulfuration of rubber phase and shear dispersion, can effectively improve the flowability of thermoplastic sulfurized rubber, the hardness for preparing simultaneously product is low, compression set is little, and the specific performance parameter sees Table one;
2, the serialization production that preparation method of the present invention can be on Banbury mixer, mill, two steps type twin screw extruder has the advantages such as equipment is applied widely, preparation technology is simple, production cost is low.
Embodiment
Below by the implementation example the present invention is described in further detail.Following processing aid is selected stearic acid or polyethylene vinegar, and anti-aging agent is selected antioxidant 1010 or antioxidant 168 or photostabilizer UV-9 or photostabilizer UV-327.
Embodiment 1
A kind of preparation method of thermoplastic sulfurized rubber, it may further comprise the steps in turn:
(1) preparation rubber and plastics Preblend: 60 parts of ethylene-propylene diene copolymers (EPDM), 20 parts of polypropylene (PP), 5 parts of filler White Carbon blacks and 0.5 part of processing aid are put in 180 ℃ of two roller mills, mix, play triangle bag twice, obtain rubber plastic Preblend.
(2) dynamic vulcanization: 2 parts of organo-peroxide dicumyl peroxides (DCP) and 1 part of additional crosslinker triallyl cyanurate (TAIC) are joined in the rubber plastic Preblend, mix the Mobile state sulfuration of going forward side by side, the dynamic vulcanization time is 5-10 minute.
(3) after dynamic vulcanization is finished, add 20 parts of PP, 20 parts of naphthenic oils, 1 part of anti-aging agent, mix, discharge obtains rubber and plastic than ethylene-propylene diene copolymer/polypropylene (EPDM/PP) thermoplastic sulfurized rubber that is 60/40.
Embodiment 2
A kind of preparation method of thermoplastic sulfurized rubber, it may further comprise the steps in turn:
(1) preparation rubber and plastics Preblend: 70 parts of butadiene-styrene rubbers (SBR), 15 parts of polypropylene (PP), 10 parts of filler White Carbon blacks and 0.5 part of processing aid are put in 200 ℃ of Banbury mixeies, mixed, obtain rubber plastic Preblend.
(2) dynamic vulcanization: 3 parts of Sulfurs and 1 part of promotor thiocarbamyl sulfenamide are joined in the rubber plastic Preblend, mix the Mobile state sulfuration of going forward side by side, the dynamic vulcanization time is 5-10 minute.
(3) after dynamic vulcanization is finished, add 15 parts of PP, 15 parts of white oils, 1 part of anti-aging agent, mix, discharge obtains rubber and plastic than butadiene-styrene rubber/polypropylene (SBR/PP) thermoplastic sulfurized rubber that is 70/30.
Embodiment 3
A kind of preparation method of thermoplastic sulfurized rubber, it may further comprise the steps in turn:
(1) preparation rubber and plastics Preblend: 65 parts of ethylene-propylene diene copolymers (EPDM), 20 parts of polypropylene (PP), 5 parts of filler White Carbon blacks and 0.5 part of processing aid are put into first charging opening on rank on the two steps type twin screw extruder, carried out the melting premix of rubber and plastics at screw rod place, upper rank.Each section of two steps type twin screw extruder Temperature Setting is 180-220 ℃.
(2) with 2 parts of organo-peroxides 2,5-dimethyl-2, second charging opening on 5-(two tert-butyl peroxy bases) hexane and 1 part of additional crosslinker triallyl cyanurate (TAIC) rank on the two steps type twin screw extruder adds, and carries out dynamic vulcanization at screw rod place, lower rank.
(3) under the two steps type twin screw extruder screw rod place on rank in after stroke partly add 15 parts of PP, 10 parts of naphthenic oils, 1 part of anti-aging agent, mix, extrude, the water-cooled granulation, obtain rubber and plastic than ethylene-propylene diene copolymer/polypropylene (EPDM/PP) thermoplastic sulfurized rubber that is 65/35.
Embodiment 4
A kind of preparation method of thermoplastic sulfurized rubber, it may further comprise the steps in turn:
(1) preparation rubber and plastics Preblend: 65 parts of cis-1,4-polybutadiene rubbers (BR), 15 parts of polypropylene (PP), 15 parts of filler carbon blacks and 0.5 part of processing aid are put into 180 ℃ of two roller mills, mix, play triangle bag twice, obtain rubber plastic Preblend.
(2) 4 vulcanizing agent brominated phenolic resins are joined in the rubber plastic Preblend, mix and carry out
Dynamic vulcanization.The dynamic vulcanization time is 5-10 minute.
(3) after dynamic vulcanization is finished, add 20 parts of PP, 20 parts of naphthenic oils, 1 part of anti-aging agent, mix, discharge obtains rubber and plastic than cis-butadiene cement/polypropylene (BR/PP) thermoplastic sulfurized rubber that is 65/35.
Comparative Examples 1:
Adopt conventional art to prepare rubber and plastic than ethylene-propylene diene copolymer/polypropylene (EPDM/PP) thermoplastic sulfurized rubber that is 60/40, specific operation process is as follows:
60 parts of ethylene-propylene diene copolymers (EPDM), 40 parts of polypropylene (PP), 5 parts of filler White Carbon blacks and 0.5 part of processing aid, 2 parts of machine superoxide dicumyl peroxide (DCP) and 1 part of additional crosslinker triallyl cyanurate (TAIC), 20 parts of naphthenic oils, 1 part of anti-aging agent are joined 180 ℃ of two roller mills, mix, play the triangle bag twice, discharge obtains rubber and plastic than ethylene-propylene diene copolymer/polypropylene (EPDM/PP) thermoplastic sulfurized rubber that is 60/40.
Comparative Examples 2:
Adopt conventional art to prepare rubber and plastic than butadiene-styrene rubber/polypropylene (BR/PP) thermoplastic sulfurized rubber that is 70/30, specific operation process is as follows:
70 parts of butadiene-styrene rubbers (BR), 30 parts of polypropylene (PP), 10 parts of filler White Carbon blacks and 0.5 part of processing aid, 3 parts of Sulfurs and 1 part of promotor thiocarbamyl sulfenamide, 15 parts of white oils, 1 part of anti-aging agent are joined in 180 ℃ of Banbury mixeies, mix, play the triangle bag twice, discharge obtains rubber and plastic than butadiene-styrene rubber/polypropylene (BR/PP) thermoplastic sulfurized rubber that is 70/30.
Comparative Examples 3:
Adopt conventional art to prepare rubber and plastic than ethylene-propylene diene copolymer/polypropylene (EPDM/PP) thermoplastic sulfurized rubber that is 70/30, specific operation process is as follows:
With 70 parts of ethylene-propylene diene copolymers (EPDM), 30 parts of polypropylene (PP), 5 parts of filler White Carbon blacks and 0.5 part of processing aid, 2 parts of organo-peroxides 2,5-dimethyl-2,5-(two tert-butyl peroxy bases) hexane and 1 part of additional crosslinker triallyl cyanurate (TAIC), 10 parts of naphthenic oils, 1 part of anti-aging agent join the common double screw extrusion press after mixing.Extruder temperature is set as 180-190 ℃.Extrude, the water-cooled granulation, obtain rubber and plastic than ethylene-propylene diene copolymer/polypropylene (EPDM/PP) thermoplastic sulfurized rubber that is 70/30.Because rubber ratio is larger, mix abundant not, in the extrusion through the normal off bar, the extrudate surface irregularity.
Choose embodiment 1,2,3 product is got part material compressing tablet and is cut out sample as measuring picture, according to the respective country standard, carries out performance test.Simultaneously it performance with Comparative Examples 1,2,3 product is compared.Concrete outcome sees Table 1.
Table 1:
| ? | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative Examples 1 | Comparative Examples 2 | Comparative Examples 3 |
| Hardness (Shore D) | 40 | 30 | 36 | 58 | 45 | 51 |
| Tensile strength MPa | 7.2 | 6.5 | 6.8 | 7.0 | 6.6 | 6.7 |
| Elongation at break % | 330 | 400 | 385 | 315 | 386 | 354 |
| Tensile set % | 15 | 13 | 14 | 29 | 26 | 24 |
| Compression set % | 27 | 33 | 30 | 42 | 47 | 45 |
| Melt flow rate (MFR) | 7.2 | 6.4 | 5.7 | 1.3 | 2.1 | 0.9 |
The condition of wherein measuring compression set be the test condition of 70 ℃ * 22h, melt flow rate (MFR) be g/10min (230 ℃, 5Kg).As can be seen from Table 1, embodiment 1,2 compares with Comparative Examples, and its hardness, tensile set, compression set are less than Comparative Examples 1,2; And tensile strength and melt flow rate (MFR) are higher than Comparative Examples 1,2.Embodiment 3 is identical with the situation of Comparative Examples 3, and simultaneously, it is stable that embodiment 3 extrudes situation, is easy to check rod, the product smooth surface.Comparative Examples 3 is extruded easily disconnected bar, product surface irregularity.Generally speaking, the prepared cross-linked rubber of preparation method of the comparative descriptions thermoplastic sulfurized rubber of the present invention of above-mentioned situation has high flowability, soft, low compression set, thereby its overall performance is better than the thermoplastic sulfurized rubber that traditional technology is prepared.
Above-described embodiment only is preferred implementation of the present invention, can not limit protection scope of the present invention with this, and the variation of any unsubstantiality that those skilled in the art does on basis of the present invention and replacement all belong to protection scope of the present invention.
Claims (10)
1. the preparation method of a thermoplastic sulfurized rubber is characterized in that may further comprise the steps in turn:
(1) preparation rubber and plastics Preblend: with rubber and partly plastic, filler, processing aid melting premix, the weight that participates in the plastics of premix accounts for the 20-60% of plastics gross weight in the thermoplastic sulfurized rubber to be prepared;
(2) dynamic vulcanization: in the Preblend of step (1), add vulcanizing agent, promotor or additional crosslinker, be mixed into the Mobile state sulfuration;
(3) later stage adds leftover and plastic, softening oil and anti-aging agent: add remaining plastics, softening oil and anti-aging agent, continue to mix, namely obtain thermoplastic sulfurized rubber, the weight of softening oil is the 10-30% of plastics gross weight.
2. the preparation method of thermoplastic sulfurized rubber as claimed in claim 1 is characterized in that: the temperature of melting premix is 180-220 ℃ in the step (1), and the dynamic vulcanization time is 5-10min in the step (2).
3. the preparation method of thermoplastic sulfurized rubber as claimed in claim 1, it is characterized in that: the method is to carry out in Banbury mixer, mill or two steps type twin screw extruder; The concrete grammar that carries out in the two steps type twin screw extruder is, add rubber and partly plastic, filler, assistant engineer's auxiliary agent melting premix on the upper rank of two steps type twin screw extruder, add in the middle vulcanizing agent, promotor or additional crosslinker, crosslinked at the enterprising Mobile state of extruding zone on the lower rank of two steps type twin screw extruder; Postmedian on lower rank adds leftover and plastic and anti-aging agent at last, extrudes rear water-cooled granulation, obtains thermoplastic sulfurized rubber.
4. the preparation method of thermoplastic sulfurized rubber as claimed in claim 1, it is characterized in that: described rubber is one or more mixing in chloroprene rubber, natural rubber, trans-isoprene, terpolymer EP rubber, cis-1,4-polybutadiene rubber, ethylene-vinyl acetate copolymer, chlorinated polyethylene rubber, acrylic elastomer, paracril, the styrene-butadiene rubber(SBR).
5. the preparation method of thermoplastic sulfurized rubber as claimed in claim 1 is characterized in that: described plastics be polyethylene, polystyrene, polyvinyl chloride, polypropylene, acrylonitrile-butadiene-styrene copolymer, styrene-acrylonitrile copolymer, polymethylmethacrylate, in one or more mixing.
6. the preparation method of thermoplastic sulfurized rubber as claimed in claim 1, it is characterized in that: described filler is one or more mixing in White Carbon black, carbon black, potter's clay, tripoli, the kaolin.
7. the preparation method of thermoplastic sulfurized rubber as claimed in claim 1, it is characterized in that: described vulcanizing agent is organo-peroxide or Sulfur or resol.
8. the preparation method of thermoplastic sulfurized rubber as claimed in claim 1, it is characterized in that: described promotor is one or more mixing in dithiocarbamate(s), xanthogenic acid salt, guanidine class, Thiourea, sulfenamide, thiurams, aldehyde amines, the metal halide class; Described additional crosslinker is triallyl cyanurate, triallyl isocyanurate, N, one or more mixing in N-phenyl-bismaleimide, ethyleneglycol dimethyacrylate, dimethacrylate vinyl glycol ester, trimethylammonium vinylformic acid trishydroxymethyl propyl ester, three vinylformic acid trishydroxymethyl propyl ester, the allyl methacrylate(AMA).
9. the preparation method of thermoplastic sulfurized rubber as claimed in claim 1, it is characterized in that: described anti-aging agent is one or more mixing among antioxidant A, antioxidant D, antioxidant 2246, antioxidant 4010, antioxidant 264, antioxidant 1010, antioxidant 1076, antioxidant 245, photostabilizer UV-9, photostabilizer UV-327, photostabilizer UV-328, photostabilizer UV-329, the photostabilizer UV-531.
10. the preparation method of thermoplastic sulfurized rubber as claimed in claim 1, it is characterized in that: described softening oil is one or more mixing in naphthenic oil, paraffin oil, the Vaseline.
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