CN103740031A - Styrene-ethylene-butylene-styrene (SEBS) rubber composition and preparation method thereof - Google Patents
Styrene-ethylene-butylene-styrene (SEBS) rubber composition and preparation method thereof Download PDFInfo
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- CN103740031A CN103740031A CN201310723582.1A CN201310723582A CN103740031A CN 103740031 A CN103740031 A CN 103740031A CN 201310723582 A CN201310723582 A CN 201310723582A CN 103740031 A CN103740031 A CN 103740031A
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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
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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
- 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
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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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
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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
- 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
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Abstract
The invention discloses a styrene-ethylene-butylene-styrene (SEBS) rubber composition and a preparation method of the composition. The SEBS rubber composition comprises the following components by weight percent: 24-32% of SEBS, 5-9% of polyphenylene oxide (PPO), 1.3-3% of C9 resin, 4-12% of polypropylene (PP), 24-40% of rubber filling oil, 25-35% of a filler and 0.2-1.0% of other assistants. The SEBS is taken as a matrix material, and the compatibility and the heat resistance of the rubber composition can be significantly increased by the action of the SEBS, the PPO, the rubber filling oil and the C9 resin, and the rubber composition has excellent high-temperature compression and permanent deformation performances, and meanwhile, the preparation method is simple in process, low in cost, easy to operate and control and applicable to industrial production.
Description
Technical field
The present invention relates to technical field of polymer materials, relate in particular to a kind of SEBS rubber combination and preparation method thereof.
Background technology
Thermoplastic elastomer hydrogenated styrene-butadiene-styrene block copolymers (SEBS) is that structure is the triblock copolymer of polystyrene (S)-polyethylene (E)/polybutene (B)-polystyrene (S).The fundamental property of the SEBS of three block configurations is characterized as: polystyrene block is hard and strong at normal temperatures, incompatible with middle elastomeric blocks, be phase-separated state, polystyrene block is by the van der Waals interaction phase region that coordinates, be scattered in elastic matrix mutually in, and form the network of physical crosslinking with elastomeric blocks, and thisly take elastomeric segments as external phase, the network structure that polystyrene block is disperse phase has given SEBS the elastomer performance similar to traditional vulcanized rubber.The at present SEBS hydrogenation completely of gonosome block of being hit by a bullet, makes it have excellent weathering resistance, ozone, ultraviolet ray, electric arc is had to the features such as good tolerance, lower temperature resistance.Due to the good caoutchouc elasticity of SEBS, weathering resistance, low-temperature type and environmental-protecting performance etc., SEBS is applied in a lot of fields, as household electrical appliance, sports goods, automotive material, medicine equipment, construction industry etc. as mutual body material.
Yet, because SEBS usings hard section of polystyrene (PS) to provide recovery of elasticity feature and the mechanical property of system as physical crosslinking point, therefore, compare with traditional vulcanized rubber, the elastomeric Compression Set of this class, thermotolerance etc. are relatively poor, owing to being limited to the second-order transition temperature of PS block in its use temperature, so the elastomeric Compression Set performance of this class becomes very poor under comparatively high temps.
Polyphenylene oxide (PPO) is as a kind of resistant to elevated temperatures engineering plastics, and its second-order transition temperature is between 220 ℃, and safety non-toxic.Between PPO and PS, there is good consistency, but the processing temperature of PPO is high, processing temperature generally need reach 250-270 ℃, SEBS processing temperature is generally between 200 ℃～230 ℃, directly PPO is joined in SEBS material, by blending extrusion, can cause PPO to melt not exclusively, do not reach best modified effect.
Summary of the invention
The object of the invention is to overcome the above-mentioned deficiency of prior art, a kind of SEBS rubber combination of high heat-resisting, low Compression Set is provided, solved the problem that in prior art, SEBS material resistance to elevated temperatures is poor, permanent compression set is large.
Another object of the present invention is to provide a kind of technique simple, cost is low, the preparation method of the SEBS rubber combination being easy to operate and control.
In order to realize foregoing invention object, technical scheme of the present invention is as follows:
A SEBS rubber combination, comprises following component according to weight percentage:
And a kind of preparation method of SEBS rubber combination, comprises the steps:
By the formula of above-mentioned SEBS rubber combination, take each component;
By PPO, C9 resin mixing treatment, after extrude, granulation, obtain PPO master batch;
By rubber filling oil mix with SEBS, standing, obtain SEBS swelling body;
By PPO master batch, SEBS swelling body, PP and other auxiliary agent mix and blend, after add filler continue to mix, at 210 ℃～240 ℃ temperature, extrude, granulation, obtain above-mentioned SEBS rubber combination.
Above-mentioned SEBS rubber combination has excellent thermotolerance and low Compression Set characteristic, and concrete its passes through to use SEBS as body material, and acts synergistically with polypropylene, and the mechanical property of SEBS rubber combination and weathering resistance are got a promotion; By the interaction of SEBS, PPO, rubber filling oil and C9 resin, the consistency and the resistance toheat that realize rubber combination significantly increase, and make the low Compression Set excellent performance of rubber combination.
The preparation method of above-mentioned SEBS rubber combination, the mode that adopts first segmentation to mix blend is again extruded each component melts, strengthens the dispersiveness of each component, makes the SEBS rubber combination stable performance of preparation.The method technique is simple simultaneously, and cost is low, is easy to operate and control, and is very suitable for suitability for industrialized production.
Accompanying drawing explanation
Fig. 1 is embodiment of the present invention SEBS rubber combination preparation method's process flow diagram.
Embodiment
In order to make the technical problem to be solved in the present invention, technical scheme and beneficial effect clearer, below in conjunction with embodiment and accompanying drawing, the present invention is further elaborated.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention.
The embodiment of the present invention provides a kind of SEBS rubber combination.This SEBS rubber combination, comprises following component by weight percentage:
Particularly, above-mentioned SEBS rubber combination be take SEBS as body material, and this is because SEBS has the snappiness of rubber at normal temperatures, at high temperature has the mobility of plastics.SEBS is three block configurations, and its two ends are polystyrene hard plastic block PS, and centre is ethene-butylene flexible blocks EB, and PS and EB be cross-linked to form reticulated structure, produces two phase structure but hard plastic block PS is incompatible with flexible blocks EB.In machine-shaping process, temperature is high, and the cross-linking set of PS phase is destroyed, and the properties of material declines rapidly.Thus, for expanding, take the network structure of the rubber combination that SEBS is matrix, to improve its over-all properties, as preferred embodiment, the molecular weight of above-mentioned SEBS is preferably several equal 240000～400000.Like this, the high molecular of SEBS, not only can improve its mechanical property, and effectively prevents from causing dissociating of SEBS network structure because of the destruction of cross-linking set.
From the above mentioned, the PS phase non-refractory in SEBS, causes SEBS material thermal resistance poor, thus, adds resistant to elevated temperatures PPO in SEBS matrix, can improve the resistance to elevated temperatures of SEBS material.But the processing temperature of PPO is high, generally need reach 250-270 ℃, SEBS processing temperature is generally between 200 ℃～230 ℃, directly PPO is joined in SEBS material, pass through blending extrusion, can cause PPO to melt not exclusively, further make PPO SEBS mutually in dispersing property poor, do not reach best modified effect.Therefore, in above-mentioned SEBS building rubber compound, add C9 resin, this is because C9 resin can reduce its processing temperature after compatible with PPO, and PPO is melted completely in SEBS.As preferred embodiment, C9 resin is preferably petroleum base anine, and its fusing point is 120 ℃～160 ℃.Petroleum base anine is oligopolymer, its molecular weight is low, compatibility good, thermostability is strong, and its fusing point is low, at lower temperature, just can melt with PPO, and petroleum base anine and SEBS have good consistency, thereby realize under relatively low processing temperature, PPO melts completely in SEBS.
Further, for better realizing the consistency of PPO and C9 resin, above-mentioned PPO is Powdered, and its molecular weight for number equal 30000～350000, to be better scattered in C9 resin.In addition, because SEBS usings hard plastic block PS to provide elasticity and the mechanical property of system as physical crosslinking point, therefore, compare with traditional vulcanized rubber, the Compression Set of this class SEBS material is poor.By adding PPO, under high temperature, the PS in PPO and SEBS holds mutually, has improved the second-order transition temperature of PS in SEBS segmented copolymer, and the Compression Set of SEBS rubber combination is significantly improved.
For improving flexibility, the elasticity of SEBS and increasing the mobility of SEBS in the course of processing, in above-mentioned SEBS, add rubber filling oil.As preferred embodiment, this rubber filling oil is naphthenic hydrocarbon rubber oil or paraffinic base rubber oil, and it has suitable aromaticity content and high naphthene content, can be filled in a large number in SEBS, thereby form uniform swelling body with SEBS, guaranteed the mobility of the course of processing.In specific embodiment, this rubber filling oil is paraffin oil.
Further, for preventing that its mechanical property can reduce when improving the resistance to elevated temperatures and Compression Set performance of SEBS rubber combination, and for improving the mobility that adds composition in man-hour, in above-mentioned SEBS rubber combination, add PP.Preferably, PP is homo-polypropylene or Co-polypropylene, and its melting index is 0.5～12g/10min (230 ℃/2.16KG).In specific embodiment, PP is homo-polypropylene, and this is that degree of crystallinity is high because homo-polypropylene only be take propylene as monomer, makes its high thermal resistance and hardness ratio Co-polypropylene excellent.
For further improving mechanics and the thermomechanical property of SEBS material, simultaneously because filler cost is low, more economical, economical when the SEBS of suitability for industrialized production the present embodiment rubber combination, in above-mentioned SEBS rubber combination, add filler.As preferred embodiment, this filler is preferably natural stratiform sodium base silicate, hollow glass micropearl, calcium carbonate, talcous one or more mixture, and this filler should be without surface-treated filler.This is because the filler after surface treatment is oxidizable aging in air, causes SEBS rubber combination unstable, reduces its good article rate.In specific embodiment, this filler is elected calcium carbonate as.
In addition, for preventing that each component of SEBS rubber combination of the embodiment of the present invention is oxidized under high temperature in the course of processing, aging or degraded causes material internal defect, in above-mentioned SEBS rubber combination, add oxidation inhibitor and thermo-stabilizer, simultaneously, the embodiment of the present invention, by adding nucleator to obtain little and uniform PP spherocrystal in the mixed melting stage, contributes to improve the quality of PP nucleation rate and SEBS rubber combination.
Particularly, above-mentioned other auxiliary agent comprises following component according to weight percentage:
Oxidation inhibitor 0.05～0.3%;
Nucleator 0.1～0.3%;
Thermo-stabilizer 0～0.5%.
Wherein, above-mentioned oxidation inhibitor all derives from commercially available, and as antioxidant 1010, irgasfos 168 etc., thermo-stabilizer is the products such as Zinic stearas, barium stearate, and nucleator is glucitol derivative or organic phosphoric acid product salt.
Above-mentioned SEBS rubber combination, by usining SEBS as body material, and acts synergistically with polypropylene and filler, and the mechanical property of rubber combination and weathering resistance are got a promotion., first by PPO and C9 resin, dissolve each other meanwhile, reduce the processing temperature of PPO; And rubber filling oil is mixed with SEBS, obtain elasticity and flexible good SEBS swelling body, again by PPO-C9 mixture and compatible with SEBS swelling body, not only make PPO in the course of processing be melted in SEBS completely, improve consistency and the resistance toheat of SEBS rubber combination, and make the low Compression Set excellent performance of rubber combination.
Correspondingly, the embodiment of the present invention also provides the preparation method of above-mentioned SEBS rubber combination, and its technical process as shown in Figure 1.The method comprises the following steps:
S01. by the formula of above-mentioned SEBS rubber combination, take each component;
S02. by PPO, C9 resin mixing treatment, after extrude, granulation, obtain PPO master batch;
S03. rubber filling oil is mixed with SEBS, standing, obtain SEBS swelling body;
S04. by PPO master batch, SEBS swelling body, PP and other auxiliary agent mix and blend, after add filler to continue to mix, at 210 ℃～240 ℃ temperature, extrude, granulation, obtain above-mentioned SEBS rubber combination.
In above-mentioned steps S02, for improving PPO and C9 resin compatible, mixing treatment is carried out in super mixer.
In above-mentioned steps S03, for the PS that the improves SEBS dispersiveness in composition, first rubber filling oil is mixed with SEBS, and standing 1～4 hour, rubber oil is absorbed fully by SEBS.
In above-mentioned steps S04, first, by PPO master batch, SEBS swelling body, PP and other auxiliary agent mix and blend 5～15 minutes, make the abundant compatible dispersion of organic constituent, after add again mineral filler and in super mixer, mix 3～10 minutes, obtain mixture; Afterwards, mixture is added in forcing machine, at 210 ℃～240 ℃ temperature, extrude, granulation, obtain above-mentioned SEBS rubber combination.
Wherein, as long as the forcing machine using in above-mentioned steps can realize is extruded, the function of granulation, and its kind is not limited at this.Meanwhile, as long as the mixing tank that above-mentioned steps is used can make PPO evenly mix with C9 resin, its kind is not limited yet.
The preparation method of above-mentioned SEBS rubber combination, the mode that adopts first segmentation to mix blend is again extruded each component melts, strengthens the dispersiveness of each component, makes the SEBS rubber combination stable performance of preparation.This preparation method's technique is simple simultaneously, and cost is low, be easy to operate and control, and the good article rate of producing is high, is very suitable for suitability for industrialized production.
The formula and preparation method thereof of SEBS rubber combination of now take is example, and the present invention is further elaborated.Wherein, the related SEBS number-average molecular weight of following each embodiment and comparative example is 240000; PPO weight-average molecular weight or number-average molecular weight are 30000; PP is for all occupying polypropylene PPH, and melting index is 0.5g/10min (230 ℃/2.16KG); Rubber filling oil is the two imperial 150N of Korea S; Oxidation inhibitor is 1010 and 168 mixture; Nucleator is Millad3905; Thermo-stabilizer is Zinic stearas.
Embodiment 1～5
In embodiment 1～5, each SEBS rubber combination concrete component by weight percentage sees the following form 1.
In above-described embodiment 1～5, the preparation method of each SEBS rubber combination is identical, includes following steps:
S1. whole components of each SEBS rubber combination in above-described embodiment 1～5 are taken to each component in the concrete ratio in table 1 respectively;
S2. the PPO taking and C9 resin are added in homogenizer and are stirred, after send into blend at 260 ℃ of temperature in twin screw extruder, extrude, granulation, obtain PPO master batch;
S3. the rubber filling oil taking is joined in homogenizer, after add SEBS standing 2～3h, obtain SEBS swelling body;
S4. in SEBS swelling body, add successively PP, PPO master batch, oxidation inhibitor, nucleator and the thermo-stabilizer taking, in high-speed stirring, stir 10min, after add the filler taking, continue to stir 5min, obtain mixture; Mixture is joined in twin screw extruder, at 220 ℃～230 ℃ temperature, extrude, granulation, dry, obtain SEBS rubber combination.
Comparative example 1～2
In comparative example 1～2, each SEBS rubber combination concrete component by weight percentage sees the following form 1.
In above-mentioned comparative example 1～2, the preparation method of each SEBS rubber combination is identical, includes following steps:
D1. whole components of each SEBS rubber combination in above-mentioned comparative example 1～2 are taken to each component in the concrete ratio in table 1 respectively;
D2. the rubber filling oil taking is joined in homogenizer, after add SEBS standing 2～3h, obtain SEBS swelling body;
D3. in SEBS swelling body, add successively PP, PPO, C9 resin, oxidation inhibitor, nucleator and the thermo-stabilizer taking, in high-speed stirring, stir 10min, after add the filler taking, continue to stir 5min, obtain mixture; Mixture is joined in twin screw extruder, at 220 ℃～230 ℃ temperature, extrude, granulation, dry, obtain SEBS rubber combination.
Table 1
Performance test:
Above-described embodiment 1～5 and the SEBS building rubber compound matter sample of comparative example 1～2 preparation are carried out to following performance test, and concrete physicals test item is as follows:
(1) hardness: according to ASTM D-2240 standard testing, read the Shore durometer number postponing after 15s
(2) tensile property: according to ASTM D-412 standard testing, draw speed 500mm/min, respectively test tensile strength, elongation at break, 100% tensile modulus
(3) compression set: according to ASTM D-395 standard testing, probe temperature: 100 ℃, the test duration: 72h.
(4) outward appearance: the outward appearance of visual inspection sample.
Above-described embodiment 1～5 sees the following form 2 with the performance test results of the SEBS building rubber compound matter sample of comparative example 1～2 preparation.
Table 2
By upper table 2, can be drawn to draw a conclusion:
(1) from embodiment 1 and comparative example 1, in SEBS, add after PPO, under 100 ℃ of temperature condition, the compression set of SEBS rubber combination has reduced by 41.7%,, show can obviously improve material Compression Set performance adding of PPO.
(2) from embodiment 2 and comparative example 2, add the compression set of the SEBS rubber combination of PPO master batch to reduce by 12.8% than the compression set that directly PPO is joined to SEBS rubber combination, and its outward appearance has larger difference, show directly PPO to be joined in SEBS rubber combination and can cause PPO not fully to be mixed in SEBS rubber combination.
(3) from embodiment 1,2,3, along with the increase of PPO content, the compression set of SEBS rubber combination starts to reduce, and when PPO content joins 9 parts, the compression set of material variation tends towards stability.
(4) from embodiment 3,4, along with increasing of PP content, the hardness of SEBS rubber combination obviously increases, and mechanical property improves, and permanent compression set increases, and shows that the PP of low levels is favourable to the low Compression Set of material.
(5) from embodiment 2,5, the increase of nucleator is improved the compression set of SEBS rubber combination, and this is because adding of nucleator is conducive to PP and forms fast little and uniform spherocrystal is further accelerated the formation of SEBS composition.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any modifications of doing within the spirit and principles in the present invention, be equal to and replace and improvement etc., within all should being included in protection scope of the present invention.
Claims (9)
1. a SEBS rubber combination, percentage ratio comprises following component by weight:
2. SEBS rubber combination as claimed in claim 1, is characterized in that, the number-average molecular weight of described SEBS is 240000～400000.
3. SEBS rubber combination as claimed in claim 2, is characterized in that, described C9 resin is petroleum base anine, and its fusing point is 120 ℃～160 ℃.
4. SEBS rubber combination as claimed in claim 3, is characterized in that, the number-average molecular weight of described PPO is 30000～350000.
5. the SEBS rubber combination as described in claim 1～4 any one, is characterized in that, described PP is homo-polypropylene or Co-polypropylene, and its melting index is 0.5～12g/10min (230 ℃/2.16KG).
6. the SEBS rubber combination as described in claim 1～4 any one, is characterized in that, described rubber filling oil is naphthenic hydrocarbon rubber oil or paraffinic base rubber oil.
7. the SEBS rubber combination as described in claim 1～4 any one, is characterized in that, described filler is natural stratiform sodium base silicate, hollow glass micropearl, calcium carbonate, talcous one or more mixture.
8. SEBS rubber combination as claimed in claim 1, is characterized in that, other described auxiliary agent comprises following component according to weight percentage:
Oxidation inhibitor 0.05～0.3%;
Nucleator 0.1～0.3%;
Thermo-stabilizer 0～0.5%.
9. the preparation method of the SEBS rubber combination as described in claim 1～8 any one, comprises the steps:
Formula by the arbitrary described SEBS rubber combination of claim 1～8 takes each component;
By described PPO, C9 resin mixing treatment, after extrude, granulation, obtain PPO master batch;
By described rubber filling oil mix with SEBS, standing, obtain SEBS swelling body;
Described PPO master batch, SEBS swelling body, PP and other auxiliary agent are uniformly mixed, after add described filler to continue to mix, at 210 ℃～240 ℃ temperature, extrude, granulation, obtain described SEBS rubber combination.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
| CN104693510A (en) * | 2015-02-11 | 2015-06-10 | 宁波汉德汽车配件有限公司 | Preparation material of scratch-resistant screen wiper rubber sheet and preparation method thereof |
| WO2017012334A1 (en) * | 2015-07-21 | 2017-01-26 | 南通普力马弹性体技术有限公司 | Thermoplastic styrene-based elastomer composition with high elongation and low permanent deformation at given elongation |
| 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 |
| CN114806191A (en) * | 2022-03-11 | 2022-07-29 | 金发科技股份有限公司 | Styrene elastomer TPS material composition and preparation and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
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| 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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| CN103740031B (en) | 2016-09-14 |
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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. |