CN104817742A - Method for preparing thermoplastic epoxidized natural rubber through emulsion blending - Google Patents
Method for preparing thermoplastic epoxidized natural rubber through emulsion blending Download PDFInfo
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Abstract
The invention discloses a method for preparing thermoplastic epoxidized natural rubber through emulsion blending. According to the method, the thermoplastic epoxidized natural rubber is prepared through emulsion blending by blending epoxidized natural rubber latex and an aqueous polymer solution according to a certain ratio, employing latex prevulcanization technology, selecting a proper blending process and adding a compatibilizer capable of improving interaction of interfaces of two phases. The method provided by the invention has the following advantages: process is simple; no harm is posed to environment; automation degree is high; the prepared thermoplastic epoxidized natural rubber has excellent performances; the problems of complicated preparation process, a great amount of mechanical equipment, large occupied area, etc. in conventional thermalplastic elastomer blending methods are overcome; and the method has wide application prospects.
Description
Technical field
The present invention relates to the method for Polymer materialspreparation, particularly a kind of method adopting emulsion blending to prepare thermoplastic epoxyization natural rubber.
Background technology
Thermoplastic elastomer is a development in recent years the largest analog thermoplastic elastomer material, there is the dual property of rubber and plastics and broad characteristic, be widely used in and manufacture everyday articles and various industrial goods, rubber also can be replaced simultaneously to be used in a large number above the modification of interchangeable heat plastic resin and engineering plastics.This type of method for producing elastomers has mechanical blending method, dynamic vulcanization process etc., and the mixing equipment adopted comprises the equipment such as mixing roll, forcing machine or twin screw extruder.
At present, the main preparation methods of thermoplastic elastomer is dynamic vulcanization process.This method is the technology grown up the eighties, in the mixing tank of high-temperature field and high shear field by rubber and resin melting blended, under the effect of linking agent, make rubber In-situ sulphiding, and be scattered in resin and form stable dispersion system.The mainstream product of the dynamic vulcanization technology developed by Coran etc. is the EPDM/PP thermoplastic vulcanizates glue elastomer (TPV) that the commodity developed for 1981 are called Sentoprene, within 1985, the NBR/PP thermoplastic sulfurized rubber that a kind of commodity are called Geolast is released again in market, has since then in succession carried out years of researches exploitation to dynamic vulcanization process and based on the industrialization commodity of this method.
US Patent No. 20060293458 discloses a kind of process for preparation of thermoplastic elastomer of dynamic vulcanization, the method comprises processes following material melts under high shear conditions.: (A) at least one thermoplastic resin, (B) at least one can vulcanized rubber, (C) one or more solidifying agent, (D) at least one add in the thermoplastic engineering resin of solid particulate form, described solid particulate has the effective diameter being not less than 0.05mm, wherein before interpolation (C), period or afterwards but before the sulfuration of (B) completes substantially, described solid particulate (D) is added to (A), (B) in molten materials.This method provide and avoid the remarkable degraded of thermoplastic resin or undesirable crosslinked means, and provide and control the means of temperature of reaction in the solidification of rubber, sulfuration or crosslinked period; US Patent No. 7452940B2 discloses a kind of process for preparation of thermoplastic elastomer, the method mainly adopts the Twin screw extruder of synchronous rotary, prepare a kind of with TPO, can vulcanized rubber and the solidifying agent thermoplastic elastomer that is main base; Chinese patent CN103044696A discloses a kind of preparation method of thermoplastic sulfurized rubber, the method is carried out in Banbury mixer, mill or two steps type twin screw extruder, first carry out melt blending to add vulcanizing agent again and carry out dynamic crosslinking, last extruding pelletization obtains thermoplastic sulfurized rubber; Chinese patent 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 three kinds are expected that blended melting dynamic crosslinkings are to prepare thermoplastic sulfurized rubber, although can effectively dispersed sulfur agent, promotor, ensure the shearing dispersion of rubber phase simultaneously, but preparation technology is loaded down with trivial details, the hardness of product is relatively high.
But, above-mentioned existing process for preparation of thermoplastic elastomer all needs to use Special extruder of thermoplastic elastomer or other high temperature such as forcing machine, forming machine, High shear device, these equipment all can make plastics phase decomposition and produce objectionable impurities in preparation process, cause environmental pollution, and preparation process also have the shortcomings such as operation is loaded down with trivial details, mechanical means is many, floor space is large.
Therefore, also need to provide a kind of in preparation process, avoid plastics phase decomposition, objectionable impurities environmental pollution can not be produced and preparation process is simple, mechanical means is few, floor space is little process for preparation of thermoplastic elastomer.
Summary of the invention
The object of the present invention is to provide a kind of method adopting emulsion blending to prepare thermoplastic epoxyization natural rubber.
Specifically, by epoxidized natural latex and aqueous solutions of polymers are carried out blended according to certain component ratio, adopt prevulcanized latex technology, and select suitable blending technology, add and can improve the interactional expanding material of two-phase interface, thus prepare thermoplastic epoxyization natural rubber by emulsion dispersion.
Specific embodiment of the invention step is as follows:
1), by epoxidized natural latex carry out pre-treatment, by high speed centrifugation, filter and remove non-rubber component, be then made into the emulsion of certain mass concentration, and emulsion is carried out ultrasonication, filtration, obtain the epoxidized natural latex of suitable particle diameter;
2), by polyvinyl alcohol dissolution, the polyvinyl alcohol solution of certain mass concentration is made into;
3), part 2 is got) polyvinyl alcohol solution that is equipped with is diluted to certain mass concentration, and add 1 ~ 20ml methyl methacrylate under certain conditions, after the reaction regular hour, obtain the polyvinyl alcohol graft copolymerized product of suitable particle diameter;
4), by step 3) after the polyvinyl alcohol graft copolymerized product Soxhlet extraction method that obtains carries out purifying, be made into certain density polyvinyl alcohol graft copolymerized reaction mixture;
5), by 1) epoxidized natural latex prepared, with 2) polyvinyl alcohol solution prepared mixes by certain mass ratio, and add 4) the polyvinyl alcohol graft copolymerized thing solution prepared is as expanding material, mixed emulsion is placed in ultrasonic field stir, add after vulcanization system carries out prevulcanized, obtain thermoplastic epoxyization nature rubber latex;
6), by 5) the thermoplastic epoxyization nature rubber latex of gained stirs, filtering and standing, after shaping and later stage sulfuration, obtains thermoplastic epoxyization natural rubber.
Step 1 of the present invention) the total solids level of epoxidized natural latex be the epoxidized natural latex of 30 ~ 40%, after removing non-rubber component by high speed centrifugation, filtration, be made into the emulsion that mass concentration is 25 ~ 35%, the epoxidized natural latex particle dia after ultrasonication is 150 ~ 200nm;
Step 2 of the present invention) the weight-average molecular weight of polyvinyl alcohol be 11803 ~ 13539, and be that solvent dissolves at 60 ~ 70 DEG C with water by it, be made into the polyvinyl alcohol solution that mass concentration is 20 ~ 25%;
Step 3 of the present invention) reaction conditions be get part 2) polyvinyl alcohol solution that is equipped be diluted to 10 ~ 15%; H is added at 60 ~ 70 DEG C
2o
2be oxidized 1 ~ 25 minute, add 1 ~ 20ml methyl methacrylate, react 0.5 ~ 3 hour at 70 ~ 90 DEG C; The polyvinyl alcohol graft copolymerized product that particle diameter is 70 ~ 120nm is obtained after reaction;
Step 4 of the present invention) the concentration of polyvinyl alcohol graft copolymerized thing solution be 5 ~ 10%;
Step 5 of the present invention) epoxidized natural latex: polyvinyl alcohol solution: the mass ratio of polyvinyl alcohol graft copolymerized thing solution is 15: 85: 5 ~ 50: 50: 5.
Therefore, a kind of method adopting emulsion blending to prepare thermoplastic epoxyization natural rubber of the present invention, preferably adopts following implementation step:
1), the epoxidized natural latex of total solids level 30 ~ 40% is carried out pre-treatment, by high speed centrifugation, filter and remove non-rubber component, then the emulsion that mass concentration is 25 ~ 35% is made into, and emulsion is carried out ultrasonication, filtration, obtaining particle dia is the epoxidized natural latex of 150 ~ 200nm;
2) be, by the polyvinyl alcohol of weight-average molecular weight 11803 ~ 13539 with water that solvent dissolves at 60 ~ 70 DEG C, be made into the polyvinyl alcohol solution that mass concentration is 20 ~ 25%.
3), part 2 is got) 20 ~ 25% polyvinyl alcohol solutions that are equipped with are diluted to 10 ~ 15%, at 60 ~ 70 DEG C, add H
2o
2be oxidized 1 ~ 25 minute, add 1 ~ 20ml methyl methacrylate, react 0.5 ~ 3 hour at 70 ~ 90 DEG C, after reaction, obtain the polyvinyl alcohol graft copolymerized thing that particle diameter is 70 ~ 120nm;
4), by step 3) acquisition polyvinyl alcohol graft copolymerized product Soxhlet extraction method carry out purifying after, be made into the polyvinyl alcohol graft copolymerized reaction mixture of 5 ~ 10%.
5), by 1) epoxidized natural latex and 2 prepared) polyvinyl alcohol prepared mixes, and add 4) the polyvinyl alcohol graft copolymerized thing solution prepared as expanding material, epoxidized natural latex: polyvinyl alcohol solution: the mass ratio of polyvinyl alcohol graft copolymerized thing solution is 15: 85: 5 ~ 50: 50: 5.Mixed emulsion is placed in ultrasonic field, adds vulcanization system and carry out prevulcanized at 40 ~ 60 DEG C, stirring velocity 50 ~ 600 revs/min, obtain thermoplastic epoxyization nature rubber latex;
6), by 5) gained thermoplastic epoxyization nature rubber latex stirs filtering and standing after 0.5 ~ 1h, after shaping and later stage sulfuration, obtains thermoplastic epoxyization natural rubber.
Key problem in technology point of the present invention
Key problem in technology point of the present invention is:
(1) the present invention have selected the moderate polyvinyl alcohol of molecular weight as plastics phase, and molecular weight is most important for the aqueous polymer solution viscosity forming certain mass concentration;
(2) the present invention selects size distribution to carry out blended at the epoxidized natural latex of certain limit and polyvinyl alcohol solution, and suitable size has important effect for the formation of later stage thermoplastic epoxyization natural rubber structure and morphology;
(3) present invention employs a kind of specific polyvinyl alcohol graft copolymerized product as expanding material, this expanding material can improve the combination degree of two-phase interface, improves the consistency of two-phase in Blending Processes;
(4) the present invention strictly controls the mass ratio of epoxidized natural latex, polyvinyl alcohol solution, polyvinyl alcohol graft copolymerized reaction mixture, thus obtains thermoplastic epoxyization nature rubber latex.
Beneficial effect of the present invention
The present invention adopts emulsion blending to prepare thermoplastic epoxyization natural rubber, has following unusual effect:
1, the product performance of preparation are excellent, and epoxidized natural latex is good with aqueous solutions of polymers dispersion effect in Blending Processes;
2, the expanding material introduced plays a part to connect two-phase, makes both better combine by interfacial energy;
3, because epoxidized natural latex is without solidifying granulation supervisor, avoid the destruction of rubber molecule, therefore, prepared material property is excellent, intensity good; Meanwhile, optimize preparation technology's flow process, technique simply, reliable, level of automation is high, improves the quality stability of preparation efficiency and product;
4, whole preparation process uses water as solvent, to environment without harm;
5, overcome that the preparation section that existing thermoplastic elastomer blending method exists is loaded down with trivial details, mechanical means is many, large etc. the problem of floor space, have broad application prospects.
Accompanying drawing explanation
Fig. 1 is the transmission electron microscope picture of embodiment, wherein Fig. 1 (a), Fig. 1 (b), Fig. 1 (c) is embodiment 1 respectively, embodiment 2, the transmission electron microscope picture of embodiment 3, it is the transmission electron microscope photo after prepared thermoplastic epoxyization nature rubber latex is diluted to 1%o, in figure, black particles is epoxy natural rubber, ash colored particle is polyvinyl alcohol, as can be seen from the figure, adding polyvinyl alcohol graft copolymerized thing makes epoxidized natural latex particle have good dispersiveness as expanding material, polyvinyl alcohol particle is as matrix parcel epoxy natural rubber particle, two-phase forms island structure,
Fig. 2 is the scanning electron microscope (SEM) photograph of embodiment, wherein Fig. 2 (a), Fig. 2 (b), Fig. 2 (c) are the scanning electron microscope (SEM) photograph of embodiment 1, embodiment 2, embodiment 3 respectively, this sample breaks through freezing extraction, observe after section boiling water is etched away polyvinyl alcohol, as can be seen from the figure, from embodiment 1 to embodiment 3, phase structure completes from two-phase continuously to the transformation of island structure, in island structure, epoxidized natural latex particle as disperse phase be dispersed in polyvinyl alcohol matrix mutually in;
Fig. 3 is the stress-strain test figure of embodiment 1, and curve meets stress-strain change in elastomeric stretch process, and rupture stress is 4.57Mpa, and breaking strain is 334.7%, 100% stress at definite elongation is 3.29Mpa, and 300% stress at definite elongation is 4.38Mpa.
Fig. 4 is the stress-strain test figure of embodiment 2, and curve meets stress-strain change in elastomeric stretch process, and rupture stress is 5.52Mpa, and breaking strain is 286.9%, 100% stress at definite elongation is 4.23Mpa.
Fig. 5 is the stress-strain test figure of embodiment 3, and curve meets stress-strain change in elastomeric stretch process, and rupture stress is 6.38Mpa, and breaking strain is 190.75%, 100% stress at definite elongation is 5.93Mpa.
Fig. 6 is the stress-strain curve diagram of polyvinyl alcohol, wherein this test sample result is by polyvinyl alcohol solution through plastic film mulch drying and moulding, then tests after cut-parts and obtained, and rupture stress is 7.67Mpa, breaking strain is 200.95%, 100% stress at definite elongation is 6.2Mpa.
Fig. 7 is the stress-strain curve diagram of epoxy natural rubber, and wherein this test sample result is by epoxy natural rubber emulsion through plastic film mulch drying and moulding, then tests after cut-parts and obtained.
Embodiment
[embodiment 1]
1), non-rubber component is removed in the fresh epoxidation natural rubber latex high speed centrifugation of total solids level 30%, filtration, then the emulsion of mass concentration 25% is made into, emulsion is carried out ultrasonication, filtration, obtains the epoxidized natural latex of particle diameter integrated distribution at about 150nm, for subsequent use;
2) be, by weight-average molecular weight the water-soluble swollen 24h post-heating of polyvinyl alcohol of 11803 to 80 DEG C, open electric blender and stir after 1.5h and be cooled to room temperature, obtained massfraction is the polyvinyl alcohol solution of 20%, for subsequent use;
3), part 2 is got) 20% polyvinyl alcohol solution prepared is diluted to 10%, at 70 DEG C, add H
2o
2be oxidized 15 minutes, add 8ml methyl methacrylate, react 2 hours at 80 DEG C, after reaction, obtain the polyvinyl alcohol graft copolymerized thing of particle diameter integrated distribution at about 70nm, for subsequent use;
4), by 3) after the polyvinyl alcohol graft copolymerized thing Soxhlet extraction method prepared carries out purifying, be mixed with the polyvinyl alcohol graft copolymerized thing solution of 5%, for subsequent use;
5), by 1) epoxidized natural latex and 2 prepared) polyvinyl alcohol solution prepared carries out blended, adding step 4) the polyvinyl alcohol graft copolymerized thing solution prepared is as expanding material, epoxidized natural latex: polyvinyl alcohol solution: the mass ratio of polyvinyl alcohol graft copolymerized thing solution is 50: 50: 5, mixed emulsion is placed in ultrasonic field, stir by electric blender, stir speed (S.S.) 80r/min, vulcanization system is added when being warming up to 35 DEG C, then stop heating after being warming up to 60 DEG C of stirring 2.5h, obtain thermoplastic epoxyization nature rubber latex; Whole process system will seal isolated air;
6), by 5) the thermoplastic epoxyization nature rubber latex that obtains at room temperature carries out plastic film mulch or shaping, as needs rapid shaping can carry out air-cooled or cryodrying to make product dried shaping faster, the sulfuration 6h under the environment of 70 DEG C of warm air dryings of the goods after drying and moulding is obtained thermoplastic epoxyization natural rubber.
[embodiment 2]
1), non-rubber component is removed in the fresh epoxidation natural rubber latex high speed centrifugation of total solids level 35%, filtration, then the emulsion of mass concentration 30% is made into, emulsion is carried out ultrasonication, filtration, obtains the epoxidized natural latex of particle diameter integrated distribution at about 180nm, for subsequent use;
2) be, by weight-average molecular weight the water-soluble swollen 24h post-heating of polyvinyl alcohol of 13251 to 80 DEG C, open electric blender and stir after 1.5h and be cooled to room temperature, obtained massfraction is the polyvinyl alcohol solution of 20%, for subsequent use;
3), part 2 is got) 20% polyvinyl alcohol solution prepared is diluted to 10%, at 70 DEG C, add H
2o
2be oxidized 15 minutes, add 8ml methyl methacrylate, react 2 hours at 80 DEG C, after reaction, obtain the polyvinyl alcohol graft copolymerized thing of particle diameter integrated distribution at about 70nm, for subsequent use;
4), by 3) after the polyvinyl alcohol graft copolymerized thing Soxhlet extraction method prepared carries out purifying, be mixed with the polyvinyl alcohol graft copolymerized thing solution of 8%, for subsequent use;
5), by 1) epoxidized natural latex and 2 prepared) polyvinyl alcohol solution prepared carries out blended, adding step 4) the polyvinyl alcohol graft copolymerized thing solution prepared is as expanding material, epoxidized natural latex: polyvinyl alcohol solution: the mass ratio of polyvinyl alcohol graft copolymerized thing solution is 40: 60: 5, mixed emulsion is placed in ultrasonic field, stir by electric blender, stir speed (S.S.) 80r/min, vulcanization system is added when being warming up to 35 DEG C, then stop heating after being warming up to 60 DEG C of stirring 2.5h, obtain thermoplastic epoxyization nature rubber latex; Whole process system will seal isolated air;
6), by 5) the thermoplastic epoxyization nature rubber latex that obtains at room temperature carries out plastic film mulch or shaping, as needs rapid shaping can carry out air-cooled or cryodrying to make product dried shaping faster, the sulfuration 6h under the environment of 70 DEG C of warm air dryings of the goods after drying and moulding is obtained thermoplastic epoxyization natural rubber.
[embodiment 3]
1), non-rubber component is removed in the fresh epoxidation natural rubber latex high speed centrifugation of total solids level 40%, filtration, then the emulsion of mass concentration 35% is made into, emulsion is carried out ultrasonication, filtration, obtains the epoxidized natural latex of particle diameter integrated distribution at about 200nm, for subsequent use;
2) be, by weight-average molecular weight the water-soluble swollen 24h post-heating of polyvinyl alcohol of 13539 to 80 DEG C, open electric blender and stir after 1.5h and be cooled to room temperature, obtained massfraction is the polyvinyl alcohol solution of 25%, for subsequent use;
3), part 2 is got) 25% polyvinyl alcohol solution prepared is diluted to 15%, at 70 DEG C, add H
2o
2be oxidized 15 minutes, add 10ml methyl methacrylate, react 3 hours at 80 DEG C, after reaction, obtain the polyvinyl alcohol graft copolymerized thing of particle diameter integrated distribution at about 120nm, for subsequent use;
4), by 3) after the polyvinyl alcohol graft copolymerized thing Soxhlet extraction method prepared carries out purifying, be mixed with the polyvinyl alcohol graft copolymerized thing solution of 10%, for subsequent use;
5), by 1) epoxidized natural latex and 2 prepared) polyvinyl alcohol solution prepared carries out blended, adding step 4) the polyvinyl alcohol graft copolymerized thing solution prepared is as expanding material, epoxidized natural latex: polyvinyl alcohol solution: the mass ratio of polyvinyl alcohol graft copolymerized thing solution is 20: 80: 5, mixed emulsion is placed in ultrasonic field, stir by electric blender, stir speed (S.S.) 80r/min, vulcanization system is added when being warming up to 35 DEG C, then stop heating after being warming up to 60 DEG C of stirring 2.5h, obtain thermoplastic epoxyization nature rubber latex; Whole process system will seal isolated air;
6), by 5) the thermoplastic epoxyization nature rubber latex that obtains at room temperature carries out plastic film mulch or shaping, as needs rapid shaping can carry out air-cooled or cryodrying to make product dried shaping faster, the sulfuration 6h under the environment of 70 DEG C of warm air dryings of the goods after drying and moulding is obtained thermoplastic epoxyization natural rubber.
Table 1 embodiment result
| Mechanical property | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| Rupture stress (MPa) | 4.57 | 5.52 | 6.38 |
| Breaking strain (%) | 334.7 | 286.9 | 190.7 |
| 100% stress at definite elongation (MPa) | 3.29 | 4.23 | 5.93 |
| 300% stress at definite elongation (MPa) | 3.79 | - | - |
| Shearing resistance (N) | 26.7 | 37.0 | 54.2 |
| Hardness | 72 | 80 | 83 |
Table 1 lists the mechanical property result of embodiment, along with the increase of plastics phase, from embodiment 1 to embodiment 3, elastomeric rupture stress increases gradually, can be seen by breaking strain, the breaking strain of embodiment, all more than 100%6, meets the general definition for thermoplastic elastomer in the world, and can find in conjunction with stress-strain(ed) curve in Figure of description, three kinds of embodiments all meet stress-strain(ed) curve change in thermoplastic elastomer drawing process.
Claims (2)
1. adopt emulsion blending to prepare a method for thermoplastic epoxyization natural rubber, it is characterized in that its preparation process is as follows:
1) epoxidized natural latex is carried out pre-treatment, by high speed centrifugation, filter and remove non-rubber component, be then made into the emulsion of certain mass concentration, and emulsion is carried out ultrasonication, filtration, obtain the epoxidized natural latex of suitable particle diameter; The total solids level of described epoxidized natural latex is 30 ~ 40%, and after removing non-rubber component by high speed centrifugation, filtration, be made into the emulsion that mass concentration is 25 ~ 35%, the epoxidized natural latex particle dia after ultrasonication is 150 ~ 200nm;
2) by polyvinyl alcohol dissolution, the polyvinyl alcohol solution of certain mass concentration is made into; The weight-average molecular weight of described polyvinyl alcohol is 11803 ~ 13539, and is that solvent dissolves at 60 ~ 70 DEG C with water by it, is made into the polyvinyl alcohol solution that mass concentration is 20 ~ 25%;
3) part steps 2 is got) polyvinyl alcohol solution that is equipped with is diluted to certain mass concentration, and add methyl methacrylate under certain conditions, after the reaction regular hour, obtain the polyvinyl alcohol graft copolymerized product of suitable particle diameter; Described reaction conditions is by step 2) polyvinyl alcohol solution that is equipped with is diluted to 10 ~ 15%, at 60 ~ 70 DEG C, add H
2o
2be oxidized 1 ~ 25 minute, add 1 ~ 20ml methyl methacrylate, react 0.5 ~ 3 hour at 70 ~ 90 DEG C; The suitable particle diameter of described polyvinyl alcohol graft copolymerized thing is 70 ~ 120nm;
4) by step 3) acquisition polyvinyl alcohol graft copolymerized product Soxhlet extraction method carry out purifying after, be made into certain density polyvinyl alcohol graft copolymerized reaction mixture; The concentration of described polyvinyl alcohol graft copolymerized thing solution is 5 ~ 10%;
5) by 1) epoxidized natural latex and 2 prepared) polyvinyl alcohol prepared mixes, and add polyvinyl alcohol graft copolymerized thing solution as expanding material, epoxidized natural latex, polyvinyl alcohol solution, polyvinyl alcohol graft copolymerized thing solution are mixed by certain mass ratio, mixed emulsion is placed in ultrasonic field stir, obtains thermoplastic epoxyization nature rubber latex;
6) by step 5) after the thermoplastic epoxyization nature rubber latex prepared stirs, filtering and standing, obtains thermoplastic epoxyization natural rubber after shaping and later stage sulfuration.
2. a kind of method adopting emulsion blending to prepare thermoplastic epoxyization natural rubber according to claim 1, is characterized in that step 5) described in epoxidized natural latex: polyvinyl alcohol solution: the mass ratio of polyvinyl alcohol graft copolymerized thing solution is 15: 85: 5 ~ 50: 50: 5.
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| CN1709956A (en) * | 2004-12-10 | 2005-12-21 | 海南省国营立才农场 | Modified nano matural rubber |
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| CN103442907A (en) * | 2011-03-11 | 2013-12-11 | 埃克森美孚化学专利公司 | Dynamically vulcanized thermoplastic elastomer film |
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2014
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| CN1709956A (en) * | 2004-12-10 | 2005-12-21 | 海南省国营立才农场 | Modified nano matural rubber |
| CN101821335A (en) * | 2007-10-11 | 2010-09-01 | 埃克森美孚化学专利公司 | Produce the efficient mixing process of composition for thermoplastic elastomer |
| CN103442907A (en) * | 2011-03-11 | 2013-12-11 | 埃克森美孚化学专利公司 | Dynamically vulcanized thermoplastic elastomer film |
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