CN100363412C - Enhanced full vulcanizing polyolefine thermoplastic elastomer and preparation process thereof - Google Patents
Enhanced full vulcanizing polyolefine thermoplastic elastomer and preparation process thereof Download PDFInfo
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- CN100363412C CN100363412C CNB2004100803389A CN200410080338A CN100363412C CN 100363412 C CN100363412 C CN 100363412C CN B2004100803389 A CNB2004100803389 A CN B2004100803389A CN 200410080338 A CN200410080338 A CN 200410080338A CN 100363412 C CN100363412 C CN 100363412C
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Abstract
The present invention provides an enhanced fully vulcanized polyolefine thermoplastic elastomer and a preparation method thereof, which relates to the technical field of fully vulcanized thermoplastic elastomers. The fully vulcanized polyolefine thermoplastic elastomer comprises polyolefine resin and composite powder which are blended, wherein the ratio of the total weight of the composite powder to the total weight of the polyolefine resin is 30: 70 to 75: 25. The composite powder comprises powdered rubber particles with crosslinking structures and inorganic particles distributed among the rubber particles, wherein the weight ratio of the powdered rubber particles to the inorganic particles is 99: 1 to 20: 80. The composite powder is prepared by uniformly mixing and drying raw materials containing irradiated or unirradiated rubber latex or inorganic particle slurry, and the fully vulcanized polyolefine thermoplastic elastomer is prepared by melting and blending the composite powder and the polyolefine resin. The fully vulcanized polyolefine thermoplastic elastomer has the advantages of good tensile strength and wide application range because of the rubber particles in the composite powder and the inorganic particles uniformly dispersed in the polyolefine resin.
Description
Technical field
The present invention relates to thermoplastic elastomer, say further, relate to a kind of by obtaining high-intensity full vulcanizing polyolefine thermoplastic elastomer and preparation method thereof after the modification.
Background technology
Fully sulfurized thermoplastic elastomer is the type material of the development 1980s.It is by elastomerics and rigidity plastics under certain conditions, utilizes the method for dynamic vulcanization technology by mechanical blending to prepare.The rubber phase that this kind thermoplastic elastomer is fully crosslinked on phase is dispersed in the plastics substrate.Prepare fully sulfurized thermoplastic elastomer by dynamic vulcanization process, sulfuration at the simultaneous rubber of material blend, the size of rubber phase mainly rely on mechanical blending shear and chemical crosslink reaction between balance decide, so that the rubber phase particle diameter is difficult to accomplish is very little.This method all has very high requirement to vulcanizing agent, blending temperature, shearing rate, blend time and mutual cooperation etc., so the production technique more complicated, the median size of rubber phase and degree of crosslinking are difficult to control; And the special blending equipment that is applicable to dynamic vulcanization process of these method needs, so the production cost of this method is very high.
The inventor obtains a kind of fully vulcanized powder rubber (Chinese patent CN1152082C, September 18 2000 applying date, priority date December 3 in 1999) by great deal of experimental.This kind fully vulcanized powder rubber is by in rubber latex, behind the adding crosslinking coagent, carries out radiation vulcanization, and obtain after spray-dried.This kind powdered rubber and plastics can be made the little fully sulfurized thermoplastic elastomer of a kind of rubber phase median size by rubber plastic blend.This method is different from dynamic vulcanization process, uses general rubber plastic blend equipment and does not need special blending equipment, and technology is simple, and processing condition are easy to control, and are good for the particle diameter and the degree of crosslinking controllability of rubber phase.The prepared rubber phase particle diameter of rubber phase particle diameter ratio conventional dynamic vulcanization process of the fully sulfurized thermoplastic elastomer that obtains with this method is much smaller.
Utilize above-mentioned technology, the relevant patent that fully vulcanized powder rubber and polyolefin resin melt blending are prepared full vulcanizing polyolefine thermoplastic elastomer is seen the applicant's Chinese patent CN1154691C (application on April 18 calendar year 2001).The particle diameter of this full vulcanizing polyolefine thermoplastic elastomer rubber phase and gel content controllability are good, have the favorable mechanical performance.Especially have higher whiteness value, be easy to make light goods, also be easy to dye and make the goods of other color.But this kind full vulcanizing polyolefine thermoplastic elastomer insufficient strength height needs the elastomeric occasion of higher-strength inapplicable to some.
Summary of the invention
The inventor finds to utilize the Chinese patent application 03109108.3 that the applicant submits on April 3rd, 2003 after deliberation, and (with Chinese patent application 03109108.3 is that the international application of right of priority is PCT CN2004000309, the full vulcanizing polyolefine thermoplastic elastomer of a kind of composite powder that provides international filing date on April 5th, 2004) and the preparation of polyolefin resin melt blending has higher intensity than the full vulcanizing polyolefine thermoplastic elastomer of simple use fully vulcanized powder rubber preparation.
This composite powder that Chinese patent application 03109108.3 provided is by will be through irradiation or without the rubber latex of irradiation and inorganic particulate slurries etc., and even by the mixed of required dry weight, drying is prepared then.In the method that provides in the Chinese patent application 03109108.3, used inorganic particulate slurries are the suspension of inorganic particulate in water, inorganic particulate is suspended in the water with the state of primary particle substantially, and the latex particle in its used rubber latex also is suspended in the water with the state of primary particle substantially.The contriver find with the inorganic particulate slurries with mix through irradiation or without the rubber latex of irradiation, inorganic particulate and latex particle will intert and isolate mutually.Carry out spraying drying this moment, and both microcosmic composite structures just can be preserved, and theoretically, inorganic particulate is to be kept apart by rubber particles fully in the composite powder that obtains, and is distributed between the rubber particles, and keeps its size of particles.The full vulcanizing polyolefine thermoplastic elastomer that utilizes this kind composite powder and polyolefine to carry out the blend preparation, rubber particles and inorganic particulate homodisperse in polyolefin substrate forms disperse phase.By regulating the weight ratio of rubber and inorganic particulate in the composite powder, can realize improving the effect of the intensity of this thermoplastic elastomer: under the rubber content condition with higher, still can make fully sulfurized thermoplastic elastomer have tensile strength preferably.
Therefore, the purpose of this invention is to provide a kind of enhanced full vulcanizing polyolefine thermoplastic elastomer.
Another object of the present invention provides the preparation method of described full vulcanizing polyolefine thermoplastic elastomer.
A kind of enhanced full vulcanizing polyolefine thermoplastic elastomer of the present invention includes the following component of blend: polyolefin resin and composite powder.The ratio of composite powder gross weight and polyolefin resin gross weight is 30: 70～75: 25, is preferably 50: 50～75: 25.
Above-described polyolefin resin comprises the blend etc. of homopolymer, multipolymer and the polyolefin resin of polyolefin resin.Be preferably at least a in the following material: polypropylene, polypropylene copolymer, polyethylene or polyethylene and ethylene copolymers etc.
Above-described composite powder comprises the powdered rubber particle with crosslinking structure and is distributed in inorganic particulate between the powdered rubber particle.Wherein the weight ratio of rubber particles and inorganic particulate is 99: 1～20: 80, is preferably 99: 1～40: 60.
Inorganic particulate in the described composite powder can be by the available inorganic particulate of various prior aries, as long as its size range can reach the needed effect of invention within the scope of the invention, is not subjected to the restriction of itself substance classes.But except the inorganic particulate of chance water unstable.The individual particle of these inorganic particulates different can be sphere, elliposoidal, sheet shape, aciculiform or irregularly shaped.With three-dimensional perspective, it is 0.2～500nm that its individual particle has the one dimension mean sizes at least, is preferably 0.5～100nm.
Inorganic particulate in the above-described composite powder can be selected from one of following material or its combination: metal simple-substance or alloy, as gold and silver, copper, iron or its alloy separately etc.; Metal oxide is as aluminum oxide (Al
2O
3), magnesium oxide (MgO), titanium dioxide (TiO
2), ferric oxide (Fe
2O
3), Z 250 (Fe
3O
4), silver suboxide (Ag
2O), zinc oxide (ZnO) etc.; Metal or non-metal nitride are as aluminium nitride (AlN), silicon nitride (SiN
4) etc.; Non-metallic carbide is as silicon carbide (SiC) etc.; Nonmetal oxide is as silicon-dioxide (SiO
2) etc.; Metal hydroxides is as aluminium hydroxide (Al (OH)
3), magnesium hydroxide (Mg (OH)
2) etc.; Metallic salt comprises metal carbonate, silicate, vitriol etc., as lime carbonate (CaCO
3), barium sulfate (BaSO
4), calcium sulfate (CaSO
4), silver chloride (AgCl) etc.; Ore is as asbestos, talcum, kaolin, mica, feldspar, wollastonite, polynite etc.In the composite powder of full vulcanizing polyolefine thermoplastic elastomer of the present invention, inorganic particulate is preferably a kind of or its combination in metal oxide, metal hydroxides, the metal-salt.
The powdered rubber particle with crosslinking structure that is comprised in the above composite powder is the rubber particles of equal phase structure.Be that single rubber particles all is a homogeneous on forming, particle inside is not found layering, is divided the phenomenon that equates uneven phase under the observation of existing microtechnique.Its gel content is 60 weight % or higher, preferred 75 weight % or higher; More preferably 80 weight % or higher.The gel content of rubber phase is the gel content that this kind has the rubber particles of crosslinking structure itself in Zhi Bei the full vulcanizing polyolefine thermoplastic elastomer thus.The kind of described powdered rubber particle is selected from least a in the following rubber kind: natural rubber, styrene-butadiene rubber(SBR), polybutadiene rubber, silicon rubber.
Composite powder described in the enhanced full vulcanizing polyolefine thermoplastic elastomer of the present invention include by powdered rubber particle and inorganic particulate form coacervate, the inside of this coacervate or its inside and surface are uniform-distribution with inorganic particulate, wherein the gel content of rubber particles self is 60% weight or higher, preferred 75% weight or higher, more preferably 80 weight % or higher.In addition, except including the coacervate of forming by powdered rubber particle and inorganic particulate, also might include discrete inorganic particulate in the composite powder.Especially when inorganic particulate content is higher, occur easily dispersing at coacervate inorganic particulate in addition.This coacervate of described composite powder still can keep in the composition that obtains behind itself and polyolefin resin melt blending.
Composite powder in the above enhanced full vulcanizing polyolefine thermoplastic elastomer of the present invention can adopt 03109108.3 kind of method that provides of Chinese patent application of submitting on April 3rd, 2003 according to the applicant to prepare.
Composite powder in this patent application (03109108.3) be by will through irradiation or without the slurries of the rubber latex of irradiation and inorganic particulate by corresponding to the mixed of required rubber particles and the ratio of inorganic particulate and stir, carry out drying then and make.
The disclosed method preparation for preparing fully vulcanized powder rubber of International Application No. WO 01/40356A1 (its disclosure all is incorporated herein for reference) that can adopt the applicant to submit on September 18th, 2000, different is before drying the latex after the irradiation to be mixed with the slurries of inorganic particulate.
In addition, the disclosed method preparation for preparing cross-linked powdered rubber of Chinese patent application 00130386.4 (its disclosure of CN 1353131A all is incorporated herein for reference) that described composite powder can also adopt the applicant to submit on November 3rd, 2000, different is before drying cross-linking type synthetic rubber latex to be mixed with the slurries of inorganic particulate.
Specifically, this composite powder is got by the method preparation that comprises one of following steps:
A. slurries and the cross-linking type synthetic rubber latex with inorganic particulate mixes, and obtains mixed emulsion, again with this mixed emulsion drying;
B. after adding or do not add under the situation of crosslinking coagent, adopting the energetic ray source to carry out radiation vulcanization rubber latex, the slurries of inorganic particulate and the rubber latex behind the irradiation are mixed, obtain mixed emulsion, again with this mixed emulsion drying.
In the preparation method of above composite powder, the slurries of inorganic particulate are the suspension of inorganic particulate in water, can directly adopt commercial slurries product, with need before rubber latex mixes to disperse through common dispersing apparatus (as high-shearing dispersion emulsifying machine, colloidal mill etc.), can in water, be uniformly dispersed to guarantee the solids in the slurries.If inorganic particulate does not have the slurries of commercial grade, also can make by oneself, promptly adopt common dispersing apparatus that inorganic particulate is become steady suspension with an amount of water-dispersion, and then mix with rubber latex.
Used inorganic particulate can be the available inorganic particulates of various prior aries among the preparation method of the above composite powder, as long as its size range can reach the needed effect of invention within the scope of the invention, be not subjected to the restriction of itself substance classes, but meet except the inorganic particulate of water unstable.The individual particle of these inorganic particulates different can be sphere, elliposoidal, sheet shape, aciculiform or irregularly shaped.With three-dimensional perspective, it is 0.2～500nm that its individual particle has the one dimension mean sizes at least, is preferably 0.5～100nm.
Inorganic particulate can be selected from one of following material or its combination: metal simple-substance or alloy, as gold and silver, copper, iron or its alloy separately etc.; Metal oxide is as aluminum oxide (Al
2O
3), magnesium oxide (MgO), titanium dioxide (TiO
2), ferric oxide (Fe
2O
3), Z 250 (Fe
3O
4), silver suboxide (Ag
2O), zinc oxide (ZnO) etc.; Metal or non-metal nitride are as aluminium nitride (AlN), silicon nitride (SiN
4) etc.; Non-metallic carbide is as silicon carbide (SiC) etc.; Nonmetal oxide is as silicon-dioxide (SiO
2) etc.; Metal hydroxides is as aluminium hydroxide (Al (OH)
3), magnesium hydroxide (Mg (OH)
2) etc.; Metallic salt comprises metal carbonate, silicate, vitriol etc., as lime carbonate (CaCO
3), barium sulfate (BaSO
4), calcium sulfate (CaSO
4), silver chloride (AgCl) etc.; Ore is as asbestos, talcum, kaolin, mica, feldspar, wollastonite, polynite etc.In the composite powder of full vulcanizing polyolefine thermoplastic elastomer of the present invention, inorganic particulate is preferably a kind of or its combination in metal oxide, metal hydroxides, the metal-salt.
The ratio of the weight (dry weights of inorganic particulate slurries) of contained inorganic particulate is 99: 1～20: 80 in weight of contained rubber in rubber latex described in the above-described composite powder preparation method or the crosslinking-type rubber latex (being the solid content of rubber latex dry weight or rubber latex) and the inorganic particulate slurries, is preferably 99: 1～40: 60.
In the method for described composite powder, the inorganic particulate slurries can be added while stirring in the rubber latex or crosslinking-type rubber latex behind the irradiation, make it to mix through fully stirring.The concentration of rubber latex and the concentration of inorganic nano-particle slurries are had no special requirements.Generally for inorganic particulate is fully disperseed in water, the concentration of inorganic particulate slurries is suitable, should not surpass the critical gel strength of this inorganic particulate in water.The solid content of rubber latex (drc) is generally 20～70% weight, is preferably 30～60% weight, more preferably 40～50% weight.
Drying means when preparing fully vulcanized powder rubber in the International Patent Application WO 01/98395 that the drying means that is adopted is submitted to June 15 calendar year 2001 with International Patent Application WO 01/40356A1 and the applicant (priority application is the Chinese patent application CN 1383439A that submitted on June 15th, 2000) in described drying process, be that drying process can be carried out with spray-dryer, inlet temperature can be controlled at 100～200 ℃, and temperature out can be controlled at 20～80 ℃.
The inventor discovers have some synthetic rubber latex between the rubber molecule certain cross can take place in the synthetic process, thereby make resulting rubber latex have certain crosslinking degree by experiment.We are referred to as cross-linking type synthetic rubber latex (or being referred to as cross-linking type synthetic rubber latex).Cross-linking type synthetic rubber latex described in the Chinese patent application of submitting on November 3rd, 2000 as the applicant 00130386.4 (CN 1353131A), the gel content of this cross-linking type synthetic rubber latex (cross-linking type synthetic rubber latex) should be 80% weight or higher, is preferably 85% weight or higher.For this crosslinking-type rubber latex,, need not further cross-linking radiation and get final product drying and obtain rubber powder because the crosslinking degree of self is higher.In the preparation method a of composite powder of the present invention, use this cross-linking type synthetic rubber latex as the latex raw material.The kind of cross-linking type synthetic rubber latex is selected from cross-linking type butylbenzene rubber latex, cross-linking type content of polybutadiene rubber latex etc.
Among the preparation method b of described composite powder, to used rubber latex raw material without any restriction, for example can use the rubber latex that is used to prepare fully vulcanized powder rubber in International Patent Application WO 01/40356A1 and the International Application No. WO 01/98395, as natural rubber latex, styrene butadiene rubber latex, content of polybutadiene rubber latex, silicone rubber latex etc.
In fact used rubber latex comprises the crosslinking-type rubber latex among the above-described method a among the described composite powder preparation method b, that is to say that crosslinking-type rubber latex can prepare composite powder of the present invention (as described in method a) without irradiation, also can prepare composite powder of the present invention (as method b) through irradiation.Just the gel content of the composite powder kind rubber that obtains of the latter is higher than the former.
The median size of rubber particles is 20-2000nm in the above rubber latex, is preferably 30～1500nm, more preferably 50～500nm.Because the gel content of rubber particles is 60% weight or higher in the rubber latex in the method for the described composite powder of preparation behind the irradiation, the gel content of rubber particles is 80% weight or higher in the crosslinking-type rubber latex, so be difficult for adhesion between the rubber particles of dry back, especially with inorganic particulate slurries combination drying after just more be difficult for adhesion.Therefore the primary particle median size of powdered rubber particle can be consistent substantially with the particle diameter in its latex in the described composite powder, is 20-2000nm, is preferably 30～1500nm, more preferably 50～500nm.
Among the preparation method b of above-described composite powder, for the irradiance method of the irradiance method of rubber latex (comprise energetic ray source that crosslinking coagent, irradiation dose, irradiation are used etc.) with preparation fully vulcanized powder rubber in International Patent Application WO 01/40356A1 and the International Application No. WO 01/98395.In rubber latex, crosslinking coagent can be do not used, also crosslinking coagent can be used.Used crosslinking coagent is selected from simple function group crosslinking coagent, two functional group's crosslinking coagents, trifunctional crosslinking coagent, four-functional group crosslinking coagent or more polyfunctional group crosslinking coagent and arbitrary combination thereof.The example of described simple function group crosslinking coagent includes, but is not limited to: (methyl) Octyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) glycidyl acrylate; The example of described two functional group's crosslinking coagents includes, but is not limited to: 1,4-butyleneglycol two (methyl) acrylate, 1,6-hexylene glycol two (methyl) acrylate, Diethylene Glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, Vinylstyrene; The example of described trifunctional crosslinking coagent includes, but is not limited to: trimethylolpropane tris (methyl) acrylate, tetramethylolmethane three (methyl) acrylate; The example of described four-functional group crosslinking coagent includes, but is not limited to: tetramethylolmethane four (methyl) acrylate, ethoxyquin tetramethylolmethane four (methyl) acrylate; The example of described more polyfunctional group crosslinking coagent includes, but is not limited to: Dipentaerythritol five (methyl) acrylate.In this article, " (methyl) acrylate " refers to acrylate or methacrylic ester.These crosslinking coagents can use in the mode of arbitrary combination, as long as they help sulfuration under irradiation.
The add-on of the above crosslinking coagent is generally the 0.1-10% weight of dried glue weight in the latex with the kind and different variation of prescription of rubber latex, is preferably 0.5-9% weight, more preferably 0.7-7% weight.
The energetic ray source is selected from cobalt source, ultraviolet or high-energy electron accelerator among the preparation method b of composite powder of the present invention, preferred cobalt source.The dosage of irradiation can be 0.1～30Mrad, preferred 0.5～20Mrad.The dosage of irradiation is relevant with prescription with the kind of rubber latex.Generally speaking, irradiation dose should make the gel content behind the rubber latex radiation vulcanization reach 60% weight or higher, preferred 75% weight or higher, more preferably 80% weight or higher.
Gel content by the contained rubber of composite powder of the above two kinds of method gained is consistent with the gel content of cross-linking type synthetic rubber latex in method a, and is consistent with the gel content of rubber latex behind the irradiation in method b.
The described composite powder that the method for spraying altogether through the above rubber latex and inorganic particulate slurries etc. prepares, its powder particle has special state of aggregation: include the special coacervate of being made up of rubber particles and inorganic particulate in the described composite powder, the structure of this coacervate is that inorganic particulate single or that reunite is wrapped up by the rubber particles of reunion, wherein the gel content of rubber particles self is 60% weight or higher, preferred 75% weight or higher, more preferably 80% weight or higher.The inorganic particulate that also might include the single of discrete (not being wrapped in the rubber particles) in addition in the composite powder or reunite except including the coacervate of being made up of rubber particles and inorganic particulate promptly can also include the inorganic particulate that is free in the single or reunion outside the described special coacervate in the composite powder.Especially when inorganic particulate content is higher, occur easily dispersing at coacervate inorganic particulate in addition.
This special state of aggregation of described composite powder, promptly inorganic particulate is wrapped in the coacervate of forming in the rubber particles of reunion, still can keep in the composition that obtains behind itself and plastics melt blending.In enhanced full vulcanizing polyolefine thermoplastic elastomer of the present invention, rubber particles and inorganic particulate are formed the gathering that coacervate has reduced inorganic particulate, make rubber particles and inorganic particulate in the polyolefin resin matrix, all can well disperse, Li San inorganic particulate and coacervate can produce certain synergistic effect simultaneously, obtain result preferably, make prepared full vulcanizing polyolefine thermoplastic elastomer have good intensity.
The preparation method of enhanced full vulcanizing polyolefine thermoplastic elastomer of the present invention is: polyolefin resin and the above-described composite powder melt blending by the general-purpose plastics processor is made Thermoplastic Elastomer, Olefinic.Wherein the weight ratio of composite powder and polyolefin resin is 30: 70～75: 25, preferred 50: 50～75: 25.
In preparation process, the blending temperature of material is the temperature that polyolefin resin is processed used melt blending in the prior art, can decide according to the melt temperature of matrix polyolefin resin, select in the scope that should not only guarantee the complete fusion of polyolefin plastics but also polyolefine is decomposed.In addition, according to the processing needs, can in the blend material, add the conventional auxiliary agent and the expanding material of polyolefin resin processing in right amount.In the blend process, this composite powder and the disposable blend of polyolefin plastics can be extruded, also a part of composite powder and polyolefin plastics blend can be made master batch, and then carry out the secondary blend with the composite powder that is left and extrude.The employed melt blending equipment of present method is the general blending equipment of rubber and plastic processing industry kind, can make mill, Banbury mixer, single screw extrusion machine or twin screw extruder etc.
Enhanced full vulcanizing polyolefine thermoplastic elastomer of the present invention owing to rubber particles and inorganic particulate homodisperse in matrix in the composite powder, can make fully sulfurized thermoplastic elastomer of the present invention have good tensile.This method technology is simple, and easy handling is used.
Embodiment
Further describe the present invention below in conjunction with embodiment, scope of the present invention is not subjected to the restriction of these embodiment.Scope of the present invention proposes in claims.
One, the preparation of composite powder
Embodiment 1
With solid content is commercially available styrene-butadiene latex (the orchidization production of 45% weight, the trade mark: butylbenzene-50, gel content 88.9%) with calcium carbonate serosity (Fine Chemical Factory of Beijing University of Chemical Technology, solid content 47.3%, mean sizes 40～60nm) on its granular one dimension, by proportionings mixing in 90: 10 of dry weight separately, stirred 1 hour, then mixed solution is passed through the spray-dryer spraying drying, the inlet temperature of spray-dryer is 140 ℃-160 ℃, temperature out is 40 ℃-60 ℃, the dried styrene-butadiene rubber(SBR) lime carbonate composite powder of collection in cyclonic separator (
Multiple Close powder 1).
Embodiment 2
Except described styrene butadiene rubber latex and calcium carbonate serosity by 80: 20 of dry weight separately, all the other conditions are all with embodiment 1.Spray-dried styrene-butadiene rubber(SBR) lime carbonate composite powder (
Composite powder 2).
Embodiment 3
Except described styrene butadiene rubber latex and calcium carbonate serosity by 70: 30 of dry weight separately, all the other conditions are all with embodiment 1.Spray-dried styrene-butadiene rubber(SBR) lime carbonate composite powder (
Composite powder 3).
Embodiment 4
Except described styrene butadiene rubber latex and calcium carbonate serosity by 50: 50 of dry weight separately, all the other conditions are all with embodiment 1.Spray-dried styrene-butadiene rubber(SBR) lime carbonate composite powder (
Composite powder 4).
Two, the preparation of composite powder fully sulfurized thermoplastic elastomer
Embodiment 5
With polypropylene (Daqing Huake Co., Ltd. produce, melting index is 0.4g/10min) with obtain with embodiment 1
Composite powder 1Weight ratio with 50/50 mixes in high-speed mixer, and at the ZSK-25 type twin screw extruder extruding pelletization with German WP company, each section of forcing machine temperature is respectively: 170 ℃, 190 ℃, 200 ℃, 210 ℃, 220 ℃ and 210 ℃ (head temperature).Pellet is made the standard batten with injection moulding, carry out every performance test, the results are shown in Table 1 for the full sulfuration polypropylene thermoplastic elastomer that records.
Embodiment 6
Removing will
Composite powder 1Replace with
Composite powder 2Outward, all the other are all identical with embodiment 5, and the results are shown in Table 1 for the full sulfuration polypropylene thermoplastic elastomer that records.
Embodiment 7
Removing will
Composite powder 1Replace with
Composite powder 3Outward, all the other are all identical with embodiment 5, and the results are shown in Table 1 for the full sulfuration polypropylene thermoplastic elastomer that records.
Embodiment 8
Removing will
Composite powder 1Replace with
Composite powder 4Outward, all the other are all identical with embodiment 5, and the results are shown in Table 1 for the full sulfuration polypropylene thermoplastic elastomer that records.
Comparative Examples 1
Removing will
Composite powder 1Change into outside the butylbenzene powdered rubber (the China Petrochemical Industry Beijing Chemical Research Institute produces, trade mark VP-101, particle diameter 100nm, gel content 88.9% weight), other are with embodiment 1.Pellet is made the standard batten with injection moulding, carry out every performance test, the results are shown in Table 1 for the full sulfuration polypropylene thermoplastic elastomer that records.
Table 1
| Tensile break strength | Tension fracture elongation rate | Compression set (22 hours, 23 ℃) | Shore hardness | |
| Unit | MPa | ％ | ％ | HD |
| Embodiment 5 | 19.0 | -- | 16.0 | 47-- |
| Embodiment 6 | 19.6 | -- | 18.5 | 47 |
| Embodiment 7 | 18.0 | 248 | -- | 47-- |
| Embodiment 8 | 17.3 | 182 | -- | 49-- |
| Comparative Examples 1 | 16.4 | -- | 15.8 | 47 |
| Testing standard | ASTM D412 | ASTM D412 | ASTM D395-98 | ASTM D2240-95 |
Claims (17)
1. enhanced full vulcanizing polyolefine thermoplastic elastomer includes the following component of blend: polyolefin resin and composite powder, and the ratio of composite powder gross weight and polyolefin resin gross weight is 30: 70～75: 25; Wherein said composite powder comprises the powdered rubber particle with crosslinking structure and is distributed in inorganic particulate between the rubber particles; The gel content of the powdered rubber particle in the described composite powder is 60% weight or higher, to have the one dimension mean sizes at least be 0.2～500nm to the inorganic particulate particle in the described composite powder, and inorganic particulate is selected from one of following material or its combination: metal simple-substance, metal alloy, metal oxide, metal or non-metal nitride, non-metallic carbide, nonmetal oxide, metal hydroxides, metallic salt and ore; The weight ratio of powdered rubber particle and inorganic particulate is 99: 1～20: 80.
2. full vulcanizing polyolefine thermoplastic elastomer according to claim 1, the ratio of wherein said composite powder gross weight and polyolefin resin gross weight is 50: 50～75: 25.
3. full vulcanizing polyolefine thermoplastic elastomer according to claim 1, the powdered rubber particle is the rubber particles of equal phase structure in the wherein said composite powder.
4. full vulcanizing polyolefine thermoplastic elastomer according to claim 1, the weight ratio of contained powdered rubber particle and inorganic particulate is 99: 1～40: 60 in the wherein said composite powder.
5. full vulcanizing polyolefine thermoplastic elastomer according to claim 1, to have the one dimension mean sizes at least be 0.5～100nm to inorganic particulate in the wherein said composite powder.
6. full vulcanizing polyolefine thermoplastic elastomer according to claim 1, inorganic particulate is selected from one of following material or its combination in the wherein said composite powder: gold and silver, copper, iron, au-alloy, silver alloys, copper alloy, iron alloy, aluminum oxide, magnesium oxide, titanium dioxide, ferric oxide, Z 250, silver suboxide, zinc oxide, aluminium nitride, silicon nitride, silicon carbide, silicon-dioxide, aluminium hydroxide, magnesium hydroxide, lime carbonate, barium sulfate, calcium sulfate, silver chloride, asbestos, talcum, kaolin, mica, feldspar, wollastonite and polynite.
7. full vulcanizing polyolefine thermoplastic elastomer according to claim 1, inorganic particulate is selected from one of metal-salt, metal hydroxides, metal oxide or its combination in the wherein said composite powder.
8. full vulcanizing polyolefine thermoplastic elastomer according to claim 1, the gel content of the powdered rubber particle in the wherein said composite powder is 75% weight or higher.
9. full vulcanizing polyolefine thermoplastic elastomer according to claim 1, the kind of the powdered rubber particle in the wherein said composite powder are selected from least a in the following rubber kind: natural rubber, styrene-butadiene rubber(SBR), polybutadiene rubber, silicon rubber.
10. full vulcanizing polyolefine thermoplastic elastomer according to claim 1, comprise the coacervate form of forming by powdered rubber particle and inorganic particulate in the wherein said composite powder, the structure of this coacervate is that inorganic particulate single or that reunite is wrapped up by the rubber particles of reunion, and wherein the gel content of rubber particles self is 60% weight or higher.
11. full vulcanizing polyolefine thermoplastic elastomer according to claim 10 includes the inorganic particulate that is not wrapped in the single or reunion in the powdered rubber particle in the wherein said composite powder.
12. according to the described full vulcanizing polyolefine thermoplastic elastomer of one of claim 1～11, wherein said composite powder is got by the method preparation that includes one of following steps:
A. with the slurries of inorganic particulate, mix, obtain mixed emulsion, again with this mixed emulsion drying with cross-linking type synthetic rubber latex; Or
B. after adding or not adding under the situation of crosslinking coagent, adopting the energetic ray source to carry out radiation vulcanization rubber latex, with the slurries of inorganic particulate, mix with rubber latex behind the irradiation, obtain mixed emulsion, again with this mixed emulsion drying;
Above-described inorganic particulate slurries are the suspension of inorganic particulate in water, and wherein to have the one dimension mean sizes at least be 0.2～500nm to the inorganic particulate particle;
In described rubber latex or the cross-linking type synthetic rubber latex in the weight of contained rubber and the inorganic particulate slurries weight ratio of contained inorganic particulate be 99: 1～20: 80.
13. full vulcanizing polyolefine thermoplastic elastomer according to claim 12, the gel content of the cross-linking type synthetic rubber latex among the wherein said composite powder preparation method described in the step a is 80% weight or higher.
14. full vulcanizing polyolefine thermoplastic elastomer according to claim 12, the described cross-linking type synthetic rubber of step a latex is selected from cross-linking type butylbenzene rubber latex, cross-linking type content of polybutadiene rubber latex among the wherein said composite powder preparation method.
15. according to the full vulcanizing polyolefine thermoplastic elastomer that claim 12 is stated, the described rubber latex of step b is selected from natural rubber latex, styrene butadiene rubber latex, content of polybutadiene rubber latex, silicone rubber latex among the wherein said composite powder preparation method.
16. full vulcanizing polyolefine thermoplastic elastomer according to claim 1, wherein said polyolefin resin comprises polypropylene, polypropylene copolymer, polyethylene or polyethylene and ethylene copolymers.
17. preparation method who prepares the described full vulcanizing polyolefine thermoplastic elastomer of one of claim 1～16, wherein described polyolefine and described composite powder melt blending are made full vulcanizing polyolefine thermoplastic elastomer, wherein the ratio of powder gross weight and polyolefin resin gross weight is 30: 70～75: 25.
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| CN102050973B (en) * | 2009-10-30 | 2012-11-21 | 中国石油化工股份有限公司 | Tread rubber composite material and preparation method thereof |
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|---|---|---|---|---|
| US4250082A (en) * | 1978-05-20 | 1981-02-10 | Chemische Werke Huls Aktiengesellschaft | Process for the preparation of a pulverulent filled rubber |
| CN1140728A (en) * | 1995-06-29 | 1997-01-22 | 三井石油化学工业株式会社 | Olefin thermoplastic elastomer compositions |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4250082A (en) * | 1978-05-20 | 1981-02-10 | Chemische Werke Huls Aktiengesellschaft | Process for the preparation of a pulverulent filled rubber |
| CN1140728A (en) * | 1995-06-29 | 1997-01-22 | 三井石油化学工业株式会社 | Olefin thermoplastic elastomer compositions |
| CN1282754A (en) * | 1995-06-29 | 2001-02-07 | 三井化学株式会社 | Olefine hydrocarbon thermo plastic elastic body composition |
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