CN103740031B - Sebs rubber composition and preparation method thereof - Google Patents
Sebs rubber composition and preparation method thereof Download PDFInfo
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- CN103740031B CN103740031B CN201310723582.1A CN201310723582A CN103740031B CN 103740031 B CN103740031 B CN 103740031B CN 201310723582 A CN201310723582 A CN 201310723582A CN 103740031 B CN103740031 B CN 103740031B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/04—Particle-shaped
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92695—Viscosity; Melt flow index [MFI]; Molecular weight
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92895—Barrel or housing
Abstract
The invention discloses a kind of SEBS rubber composition and preparation method thereof.This SEBS rubber composition includes following component: SEBS24～32% by weight percentage；PPO5～9%；C9 resin 1.3～3%；PP4～12%；Rubber filling oil 24～40%；Filler 25～35%；Other auxiliary agent 0.2～1.0%.The present invention is with SEBS as matrix material, by SEBS, PPO, rubber filling oil and the interaction of C9 resin, it is achieved the compatibility and the heat resistance of rubber composition dramatically increase；And make rubber composition have the permanent set at high temperature performance of excellence.This preparation method technique is simple simultaneously, low cost, it is easy to operate and control, being extremely suitable for industrial production.
Description
Technical field
The present invention relates to technical field of polymer materials, particularly relate to a kind of SEBS rubber composition and system thereof
Preparation Method.
Background technology
Thermoplastic elastomer (TPE) hydrogenated styrene-butadiene-styrene block copolymers (SEBS) be structure be polyphenyl
The triblock copolymer of ethylene (S)-polyethylene (E)/polybutene (B)-polystyrene (S).The SEBS of three block configuration
Key property be characterized as: polystyrene block is hard and strong at normal temperatures, with middle elastomeric blocks not phase
Holding, in phase-separated state, polystyrene block is coordinated phase region by van der Waals interaction, is scattered in elasticity base
Body mutually in, and form the network of physical crosslinking with elastomeric blocks, this with elastomeric segments as continuous phase, poly-
Styrene block is that the network structure of dispersion phase imparts the SEBS elastomer similar to conventional vulcanized rubbers
Energy.At present SEBS elastomer block hydrogenates the most completely so that it is have the weatherability of excellence, to ozone,
Ultraviolet, electric arc have the features such as good toleration, lower temperature resistance.Due to caoutchouc elasticity excellent for SEBS,
Weatherability, low-temperature type and environmental-protecting performance etc. so that SEBS obtains in many fields as mutual body material
With application, such as household electrical appliance, sports goods, automotive material, medical apparatus and instruments, building industry etc..
But, owing to SEBS is the bullet providing system using hard section polystyrene (PS) as physical crosslinking point
Property recover feature and mechanical property, therefore, compared with traditional vulcanite, the compression of this kind of elastomer is forever
Deformation, thermostability etc. are relatively poor for a long time, the glass transition temperature using temperature upper limit to be PS block due to it,
So the Compression Set performance of the most this kind of elastomer becomes very poor.
Polyphenylene oxide (PPO) is as a kind of resistant to elevated temperatures engineering plastics, and its glass transition temperature is between 220 DEG C,
And safety non-toxic.There is between PPO and PS the good compatibility, but the processing temperature of PPO is high, processing temperature
Degree typically need to reach 250-270 DEG C, and SEBS processing temperature is typically between 200 DEG C～230 DEG C, directly PPO
Join in SEBS material, by blending extrusion, PPO can be caused to melt not exclusively, do not reach optimal changing
Property effect.
Summary of the invention
It is an object of the invention to overcome the above-mentioned deficiency of prior art, it is provided that a kind of high heat-resisting, low compression is forever
The SEBS rubber composition of deformation for a long time, has solved SEBS material resistance to elevated temperatures in prior art poor, forever
The problem that compression for a long time is big.
Another object of the present invention is to provide a kind of technique simple, low cost, it is easy to operate and control
The preparation method of SEBS rubber composition.
In order to realize foregoing invention purpose, technical scheme is as follows:
A kind of SEBS rubber composition, includes following component according to percetage by weight:
And, the preparation method of a kind of SEBS rubber composition, comprise the steps:
Each component is weighed by the formula of above-mentioned SEBS rubber composition；
By PPO, C9 resin mixing treatment, rear extrusion, pelletize, obtain PPO master batch；
Rubber filling oil is mixed with SEBS, stands, obtain the swelling body of SEBS；
By PPO master batch, the swelling body of SEBS, PP and other auxiliary agent mix and blend, the rear filler that adds continues mixed
Closing, at a temperature of 210 DEG C～240 DEG C, extrusion, pelletize, obtain above-mentioned SEBS rubber composition.
Above-mentioned SEBS rubber composition has thermostability and the low compression set deformation behavior of excellence, concrete
Its by use SEBS as matrix material, and with polypropylene synergism so that SEBS building rubber compound
The mechanical property of thing gets a promotion with weatherability；By SEBS, PPO, rubber filling oil and C9 resin
Interact, it is achieved the compatibility and the heat resistance of rubber composition dramatically increase, and make rubber composition
Low compression set deformation nature excellent.
The preparation method of above-mentioned SEBS rubber composition, uses the mode that first segmentation mixing is blended again by each group
Divide and melt extrude, strengthen the dispersibility of each component so that the SEBS rubber composition stable performance of preparation.
The method technique is simple simultaneously, low cost, it is easy to operate and control, being extremely suitable for industrial production.
Accompanying drawing explanation
Fig. 1 is the process flow diagram of embodiment of the present invention SEBS rubber composition preparation method.
Detailed description of the invention
In order to make the technical problem to be solved in the present invention, technical scheme and beneficial effect clearer, with
Under in conjunction with the embodiments with accompanying drawing, the present invention is further elaborated.Should be appreciated that described herein
Specific embodiment only in order to explain the present invention, be not intended to limit the present invention.
The embodiment of the present invention provides a kind of SEBS rubber composition.This SEBS rubber composition, by weight
Percentage ratio includes following component:
Specifically, above-mentioned SEBS rubber composition is with SEBS as matrix material, this is because SEBS exists
There is under room temperature the high resiliency of rubber, at high temperature there is the mobility of plastics.SEBS is three block configuration,
Its two ends i.e. are polystyrene stiff plastic block PS, and centre is Ethylene/Butylene flexible blocks EB, and PS with
EB crosslinks formation network structure, but stiff plastic block PS is incompatible with flexible blocks EB and produce two
Phase structure.During machine-shaping, temperature is high, and the crosslinking points of PS phase is destroyed, every property of material
Can decline rapidly.Thus, for expanding the network structure of the rubber composition with SEBS as matrix, it is improved
Combination property, as the presently preferred embodiments, the molecular weight of above-mentioned SEBS is preferably number equal 240000～400000.
So, the high molecular of SEBS, it is possible not only to improve its mechanical property, and effectively prevents because of crosslinking points
Destroy and cause dissociating of SEBS network structure.
From the above mentioned, the PS phase non-refractory in SEBS, cause SEBS material thermal resistance poor, thus,
SEBS matrix adds resistant to elevated temperatures PPO, the resistance to elevated temperatures of SEBS material can be improved.But the processing of PPO
Temperature is high, typically need to reach 250-270 DEG C, and SEBS processing temperature is typically between 200 DEG C～230 DEG C, directly
PPO is joined in SEBS material, by blending extrusion, PPO can be caused to melt not exclusively, make further
Obtain PPO dispersive property in SEBS phase poor, do not reach optimal modified effect.Therefore, above-mentioned SEBS rubber
C9 resin is added in glue combination, this is because its processing temperature can be reduced after C9 resin is compatible with PPO so that
PPO melts in SEBS completely.As the presently preferred embodiments, C9 resin is preferably petroleum base anime,
Its fusing point is 120 DEG C～160 DEG C.Petroleum base anime is oligomer, and its molecular weight is low, compatibility good, hot
Stability is strong, and its fusing point is low, the most just can melt with PPO, and petroleum base anime
Having the good compatibility with SEBS, thus realize under relatively low processing temperature, PPO is at SEBS
Middle melting is complete.
Further, for preferably realizing the compatibility of PPO Yu C9 resin, above-mentioned PPO is powder, and
Its molecular weight is number equal 30000～350000, in order to be preferably scattered in C9 resin.Further, since SEBS
It is elasticity and the mechanical property that system is provided using stiff plastic block PS as physical crosslinking point, therefore, with biography
The vulcanite of system is compared, and the Compression Set of this kind of SEBS material is poor.By adding PPO, under high temperature,
PS phase mutual tolerance in PPO with SEBS, improves the glass transition temperature of PS in SEBS block copolymer,
The Compression Set making SEBS rubber composition is significantly improved.
For improving the flexibility of SEBS, elasticity and increasing SEBS mobility in the course of processing, above-mentioned
SEBS adds rubber filling oil.As the presently preferred embodiments, this rubber filling oil is cycloalkane rubber oil or stone
Cerul rubber oil, it has suitable arene content and high naphthene content, it is possible to be filled in SEBS in a large number
In, thus form uniform swelling body with SEBS, it is ensured that the mobility of the course of processing.At specific embodiment
In, this rubber filling oil is paraffin oil.
Further, for preventing from improving resistance to elevated temperatures and the Compression Set of SEBS rubber composition
While energy, its mechanical property can reduce, and for improving the mobility adding compositions in man-hour, above-mentioned SEBS
Rubber composition adds PP.Preferably, PP is HOPP or COPP, and its melt index
It is 0.5～12g/10min (230 DEG C/2.16KG).In a particular embodiment, PP is HOPP, this be because of
For HOPP only with propylene as monomer, degree of crystallinity is high so that it is heat-resisting quantity and hardness ratio COPP
Excellent.
For improving mechanics and the thermodynamic property of SEBS material further, simultaneously because filler low cost, in work
Industry metaplasia is produced during the SEBS rubber composition of the present embodiment more economical, economical, above-mentioned SEBS rubber composition
Middle interpolation filler.As the presently preferred embodiments, this filler is preferably natural stratiform sodio silicate, hollow glass
Microballon, calcium carbonate, one or more mixture talcous, and this filler should be and process without surface
Filler.This is because the filler after surface treated is the most oxidizable aging, cause SEBS rubber group
Compound is unstable, reduces its yields.In a particular embodiment, calcium carbonate elected as by this filler.
It addition, be to prevent each component of SEBS rubber composition of the embodiment of the present invention under high temperature in the course of processing
Aoxidize, aging or degraded cause material internal defect, in above-mentioned SEBS rubber composition add antioxidant
And heat stabilizer, meanwhile, the embodiment of the present invention obtains little and equal by adding nucleator in the mixed melting stage
Even PP spherocrystal, is favorably improved PP nucleation rate and the quality of SEBS rubber composition.
Specifically, other auxiliary agent above-mentioned includes following component according to percetage by weight:
Antioxidant 0.05～0.3%；
Nucleator 0.1～0.3%；
Heat stabilizer 0～0.5%.
Wherein, above-mentioned antioxidant derives from commercially available, such as antioxidant 1010, irgasfos 168 etc., thermally-stabilised
Agent is the product such as zinc stearate, barium stearate, and nucleator is glucitol derivative or organic phosphoric acid product salt.
Above-mentioned SEBS rubber composition, by using SEBS as matrix material, and with polypropylene and filler
Synergism so that the mechanical property of rubber composition gets a promotion with weatherability.Meanwhile, PPO is first passed through
Dissolve each other with C9 resin, reduce the processing temperature of PPO；And rubber filling oil is mixed with SEBS, obtain
Elastic and the flexible good swelling body of SEBS, then by compatible with body swelling with SEBS for PPO-C9 mixture,
Not only make PPO in the course of processing be melted in completely in SEBS, improve the compatible of SEBS rubber composition
Property and heat resistance, and make the low compression set deformation nature of rubber composition excellent.
Correspondingly, the embodiment of the present invention also provides for the preparation method of above-mentioned SEBS rubber composition, its technique
Flow process is as shown in Figure 1.The method comprises the following steps:
S01. each component is weighed by the formula of above-mentioned SEBS rubber composition；
S02. by PPO, C9 resin mixing treatment, rear extrusion, pelletize, obtain PPO master batch；
S03. rubber filling oil mixed with SEBS, stand, obtain the swelling body of SEBS；
S04. by PPO master batch, the swelling body of SEBS, PP and other auxiliary agent mix and blend, filler is added afterwards
Continuing mixing, at a temperature of 210 DEG C～240 DEG C, extrusion, pelletize, obtain above-mentioned SEBS rubber composition.
In above-mentioned steps S02, for improving PPO Yu C9 resin compatible, mixing treatment is at super mixer
In carry out.
In above-mentioned steps S03, for improving the PS phase dispersibility in the composition of SEBS, first rubber is filled out
Oil-filled mix with SEBS, and stand 1～4 hour, make rubber oil sufficiently be absorbed by SEBS.
In above-mentioned steps S04, first by PPO master batch, the swelling body of SEBS, PP and other auxiliary agent mix and blend
5～15 minutes, make organic component be fully compatible dispersion, after add inorganic filler mixed in super mixer
Close 3～10 minutes, obtain mixed material；Afterwards, mixed material is added in extruder, at 210 DEG C～240 DEG C
At a temperature of extrude, pelletize, obtain above-mentioned SEBS rubber composition.
Wherein, as long as the extruder used in above-mentioned steps can realize extrusion, the function of pelletize, its kind exists
This is not limited.Meanwhile, as long as the blender that above-mentioned steps is used can make PPO with C9 resin uniform
Mixing, its kind is not limited.
The preparation method of above-mentioned SEBS rubber composition, uses the mode that first segmentation mixing is blended again by each group
Divide and melt extrude, strengthen the dispersibility of each component so that the SEBS rubber composition stable performance of preparation.
This preparation method technique is simple simultaneously, low cost, it is easy to operate and control, and the yields produced is high, non-
It is adapted to industrialized production.
Now as a example by formula of SEBS rubber composition and preparation method thereof, the present invention is carried out the most in detail
Describe in detail bright.Wherein, following each embodiment is 240000 with the SEBS number-average molecular weight involved by comparative example；
PPO weight average molecular weight or number-average molecular weight are 30000；PP is for all to occupy polypropylene PPH, and melt index is
0.5g/10min(230℃/2.16KG)；Rubber filling oil is Korea S double dragon 150N；Antioxidant is 1010 and 168
Mixture；Nucleator is Millad3905；Heat stabilizer is zinc stearate.
Embodiment 1～5
In embodiment 1～5, each SEBS rubber composition concrete component by weight percentage see table 1.
In above-described embodiment 1～5, the preparation method of each SEBS rubber composition is identical, all comprises the following steps:
S1. whole components of SEBS rubber composition each in above-described embodiment 1～5 are pressed in table 1 respectively
Concrete ratio weighs each component；
S2. PPO with the C9 resin weighed is added in homogenizer and stir, send into twin screw afterwards
In extruder at a temperature of 260 DEG C be blended, extrusion, pelletize, obtain PPO master batch；
S3. joining in homogenizer by the rubber filling oil weighed, rear addition SEBS also stands 2～3h,
Obtain the swelling body of SEBS；
S4. be sequentially added in the swelling body of SEBS weigh PP, PPO master batch, antioxidant, nucleator and
Heat stabilizer, stirs 10min in high-speed stirred, adds the filler weighed afterwards, continues stirring 5min,
Mixed material；Mixed material is joined in double screw extruder, extrude at a temperature of 220 DEG C～230 DEG C,
Pelletize, be dried, obtain SEBS rubber composition.
Comparative example 1～2
In comparative example 1～2, each SEBS rubber composition concrete component by weight percentage see table 1.
In above-mentioned comparative example 1～2, the preparation method of each SEBS rubber composition is identical, all comprises the following steps:
D1. whole components of each SEBS rubber composition in above-mentioned comparative example 1～2 are pressed in table 1 respectively
Concrete ratio weighs each component；
D2. joining in homogenizer by the rubber filling oil weighed, rear addition SEBS also stands 2～3h,
Obtain the swelling body of SEBS；
D3. be sequentially added in the swelling body of SEBS weigh PP, PPO, C9 resin, antioxidant, nucleation
Agent and heat stabilizer, stir 10min in high-speed stirred, add the filler weighed afterwards, continues stirring 5min,
Obtain mixed material；Mixed material is joined in double screw extruder, extrude at a temperature of 220 DEG C～230 DEG C,
Pelletize, be dried, obtain SEBS rubber composition.
Table 1
Performance test:
The SEBS rubber composition sample of above-described embodiment 1～5 with comparative example 1～2 preparation is carried out following performance
Test, concrete physical property detection project is as follows:
(1) hardness: according to ASTM D-2240 standard testing, read the Shore durometer number after postponing 15s
(2) tensile property: according to ASTM D-412 standard testing, draw speed 500mm/min, survey respectively
Examination hot strength, elongation at break, 100% stretch modulus
(3) compression set: according to ASTM D-395 standard testing, test temperature: 100 DEG C, during test
Between: 72h.
(4) outward appearance: the outward appearance of perusal sample.
The performance test knot of the SEBS rubber composition sample that above-described embodiment 1～5 is prepared with comparative example 1～2
Fruit see table 2.
Table 2
Can be concluded that by upper table 2
(1) from embodiment 1 and comparative example 1, after adding PPO in SEBS, 100 DEG C of temperature
Under the conditions of the compression set of SEBS rubber composition reduce 41.7%, show that the addition of PPO can be bright
Show and improve material Compression Set performance.
(2) from embodiment 2 and comparative example 2, the pressure of the SEBS rubber composition of PPO master batch is added
Compression permanent deformation reduces by 12.8% than the compression set that PPO directly joins SEBS rubber composition,
And its outward appearance has bigger difference, show directly PPO to be joined in SEBS rubber composition and can be caused
PPO is not sufficiently mixed in SEBS rubber composition.
(3) from embodiment 1,2,3, along with the increase of PPO content, SEBS rubber composition
Compression set starts to reduce, when PPO content joins 9 parts, and the compression set change of material
Tend towards stability.
(4) from embodiment 3,4, along with increasing of PP content, the hardness of SEBS rubber composition is bright
Aobvious increase, mechanical property improves, and permanent compression set increases, and shows the PP low pressure to material of low content
Contracting permanent deformation is favourable.
(5) from embodiment 2,5, the increase of nucleator makes the compression of SEBS rubber composition permanent
Deformation is improved, this is because the beneficially PP that there was added of nucleator quickly forms little and uniform spherocrystal,
Further speed up the formation of SEBS compositions.
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all at this
Any amendment, equivalent and the improvement etc. made within bright spirit and principle, should be included in the present invention
Protection domain within.
Claims (7)
1. a SEBS rubber composition, is made up of the component of following percetage by weight:
Wherein, the number-average molecular weight of described SEBS is 240000～400000；
Wherein, described PPO and described C9 resin need to first carry out being blended, extrude, pelletize, makes PPO
Master batch, after being mixed and made into the swelling body of SEBS by described rubber filling oil with described SEBS, then by described simultaneously
The swelling body of PPO master batch, SEBS, PP and the stirring mixing of other auxiliary agent, rear addition described filler continuation mixing,
At a temperature of 210 DEG C～240 DEG C, extrusion, pelletize, form described SEBS rubber composition.
2. SEBS rubber composition as claimed in claim 1, it is characterised in that described C9 resin is
Petroleum base anime, its fusing point is 120 DEG C～160 DEG C.
3. SEBS rubber composition as claimed in claim 1, it is characterised in that the number of described PPO is equal
Molecular weight is 30000～350000.
4. the SEBS rubber composition as described in any one of claims 1 to 3, it is characterised in that described PP
For HOPP or COPP, its melt index is 0.5～12g/10min, 230 DEG C/2.16KG.
5. the SEBS rubber composition as described in any one of claims 1 to 3, it is characterised in that described rubber
Oil filled by glue is cycloalkane rubber oil or paraffinic base rubber oil.
6. the SEBS rubber composition as described in any one of claims 1 to 3, it is characterised in that described in fill out
Material for natural stratiform sodio silicate, hollow glass micropearl, calcium carbonate, talcous one or more
Mixture.
7. the preparation method of the SEBS rubber composition as described in any one of claim 1～6, including as follows
Step:
Each component is weighed by the formula of the arbitrary described SEBS rubber composition of claim 1～6；
By described PPO, C9 resin mixing treatment, rear extrusion, pelletize, obtain PPO master batch；
Described rubber filling oil is mixed with SEBS, stands, obtains the swelling body of SEBS；
By the stirring mixing of described PPO master batch, the swelling body of SEBS, PP and other auxiliary agent, fill out described in addition afterwards
Material continues mixing, and at a temperature of 210 DEG C～240 DEG C, extrusion, pelletize, obtain described SEBS rubber composition.
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| CN104403194A (en) * | 2014-11-10 | 2015-03-11 | 苏州新区枫盛塑料制品厂 | Thermoplastic elastomer formula |
| CN104693510B (en) * | 2015-02-11 | 2016-10-26 | 宁波汉德汽车配件有限公司 | A kind of scratch-resistant rain brush film prepare material and preparation method thereof |
| CN104987646A (en) * | 2015-07-21 | 2015-10-21 | 南通普力马弹性体技术有限公司 | Thermoplastic styrenic elastomer composition with high elongation and low stretching permanent deformation |
| CN113278446A (en) * | 2021-05-24 | 2021-08-20 | 贝源新材料科技(广东)有限公司 | Preparation method of environment-friendly naphthenic rubber oil |
| CN114806191B (en) * | 2022-03-11 | 2023-06-23 | 金发科技股份有限公司 | Styrene elastomer TPS material composition and preparation and application thereof |
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| CN102634159A (en) * | 2012-04-25 | 2012-08-15 | 益阳达普林科技有限公司 | SEBS (styrenic block copolymer) thermoplastic elastomer and preparation method thereof |
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| CN1628150A (en) * | 2002-01-31 | 2005-06-15 | 克拉通聚合物研究有限公司 | Blockcopolymer compositions, having improved mechanical properties and processability and styrenic blockcopolymer to be used in them |
| CN101747581A (en) * | 2008-12-12 | 2010-06-23 | 第一毛织株式会社 | Thermoplastic elastomer composition |
| CN102634159A (en) * | 2012-04-25 | 2012-08-15 | 益阳达普林科技有限公司 | SEBS (styrenic block copolymer) thermoplastic elastomer and preparation method thereof |
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Effective date of registration: 20190124 Address after: 523000 Block E, 20 Xinglang Road, Jiucun Village, Huangjiang Town, Dongguan City, Guangdong Province Patentee after: Putmei Rubber and Plastic Raw Materials (Dongguan) Co., Ltd. Address before: 518000 A19 Building of Jiangshi Xinwei Fourth Industrial Zone, Gongming Town, Guangming New District, Shenzhen City, Guangdong Province Patentee before: SHENZHEN PUTEMEI RUBBER PLASTIC MATERIAL CO., LTD. |