CN101724187A - Rubber composition and preparation method thereof - Google Patents
Rubber composition and preparation method thereof Download PDFInfo
- Publication number
- CN101724187A CN101724187A CN200810225365A CN200810225365A CN101724187A CN 101724187 A CN101724187 A CN 101724187A CN 200810225365 A CN200810225365 A CN 200810225365A CN 200810225365 A CN200810225365 A CN 200810225365A CN 101724187 A CN101724187 A CN 101724187A
- Authority
- CN
- China
- Prior art keywords
- rubber
- composite powder
- rubber latex
- latex
- inorganic particulate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention provides a rubber composition and a preparation method thereof. The rubber composition comprises rubber and composite powder, wherein the total weight ratio of the composite powder to the rubber is 0.5:99.5-95:5; and the composite powder contains inorganic particles and rubber particles and is prepared by uniformly mixing a raw material containing irradiated or unirradiated rubber latex and inorganic particle slurry and then drying the mixture. The composite powder can well reinforce the rubber, so that the rubber composition has the advantages of very good tensile elongation, tensile breaking strength, tensile permanent deformation rate and the like; and at the same time, the preparation method for the rubber composition has the advantages of simple process, easy operation, low cost, wide application range and easy industrialization.
Description
Technical field
The present invention relates to a kind of modified rubber.Specifically, relate to a kind of rubber combination that adds composite powder and preparation method thereof.
Technical background
As everyone knows, in most cases, elastomeric material strengthens and can't use without filling.The strengthening agent that rubber industry is traditional is that carbon black and white carbon black, particularly carbon black occupy critical role in rubber industry always.But traditional strengthening agent has following shortcoming: (1) processing pollution is big, when filling in rubber, very easily produces and flies upward, and is difficult to guarantee the cleaning in operation workshop, and personnel's health is threatened.(2) because traditional strengthening agent disperses in rubber and to sneak into (or wedging) required time longer, so long processing time, mixing energy consumption is big.(3) the goods tone of black-reinforced is single, and the black of goods can't be changed.(4) because the carbon black dependency stronger to oil makes that the sooty price is higher.Therefore, seeking the alternative carbon black of a kind of novel strengthening agent is current urgent problem.
Provide a kind of composite powder that comprises organic elastic particle and inorganic rigid particle among the applicant's the Chinese patent ZL03109108.3 (CN 1239587C).This composite powder is well used in modifying plastics and preparation thermoplastic elastomer.
Adopt the composite powder among the above-mentioned Chinese patent ZL03109108.3 to come modified polypropene among the applicant's Chinese patent ZL03148381.X (CN 1233723C) and the Chinese patent ZL03148380.1 (CN 1233722C), when this modified polypropene toughness significantly improved, rigidity remained unchanged even also improves to some extent.
Adopt among the Chinese patent ZL200310101795.7 that the applicant asks (CN 1257939C) the composite powder that comprises organic elastic particle and clay among the above-mentioned Chinese patent ZL03109108.3 to make polymeric amide have good strong and unyielding property and improve thermotolerance simultaneously.
The described this composite powder of Chinese patent ZL03109108.3 is all well used in modifying plastics and preparation thermoplastic elastomer, still, never relates to the application in rubber.
Summary of the invention
The inventor finds by a large amount of experiments, the composite powder that this kind comprises organic elastic particle and inorganic rigid particle can substitute that carbon black comes reinforced rubber as strengthening agent in the prior art, its to rubber have good reinforcing effect, the salient features of the rubber combination that obtains all has to some extent to be improved, as hardness, elongation, breaking tenacity, tension set.
The purpose of this invention is to provide the rubber combination that comprises above-mentioned composite powder.Another object of the present invention provides the preparation method of described rubber combination.
Rubber combination of the present invention includes the following component of blend: rubber and composite powder; The ratio of composite powder gross weight and rubber gross weight is 0.5: 99.5～95: 5, is preferably 5: 95～90: 10, more preferably 10: 90～90: 10.
In rubber combination of the present invention, described rubber raw materials comprises a kind of or its combination in disclosed various types of natural rubbers of prior art and the synthetic rubber.
In rubber combination of the present invention, described composite powder is composited by rubber particles and inorganic particulate.Wherein the weight ratio of rubber particles and inorganic particulate is 99.9: 0.1～0.1: 99.9, is preferably 99: 1～1: 99, more preferably 85: 15～30: 70.
Wherein himself gel content of the rubber particles that contains of composite powder is 60% weight or higher, preferred 75% weight or higher.The median size of rubber particles is 20～2000nm, is preferably 30～1500nm, more preferably 50～500nm.The kind of described rubber particles is selected from least a in the following rubber kind: natural rubber, styrene-butadiene rubber(SBR), carboxylic styrene-butadiene rubber, paracril, carboxy nitrile rubber, polybutadiene rubber, chloroprene rubber, silicon rubber, esters of acrylic acid rubber, vinylpyridiene-styrene-butadiene rubber, Acrylester Butadiene Rubber, urethanes or viton etc.
Wherein the inorganic particulate that contains in the composite powder is 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 aluminum oxide (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.It is 0.2～500nm that its inorganic particulate particle has the one dimension mean sizes at least.
Composite powder in the rubber combination of the present invention can adopt according to the method that provides among the Chinese patent ZL03109108.3 (CN1239587C) and prepare.Promptly by will be through irradiated or without irradiated rubber latex and inorganic particulate slurries etc., by required dry weight mixed and stir, the prepared composite powder of drying then.
Specifically, described composite powder is got by the method preparation that includes one of following steps:
A. with the slurries of the above inorganic particulate, mix, obtain mixed emulsion, again with this mixed emulsion drying with the cross-linking type synthetic rubber latex;
B. after adding or not adding under the situation of crosslinking coagent, adopting the high-energy radiation line source to carry out radiation vulcanization rubber latex, again with the slurries of inorganic particulate, mix with rubber latex behind the irradiation, obtain mixed emulsion, again with this mixed emulsion drying.
The ratio of the weight (dry weights of the slurries of inorganic particulate) of contained inorganic particulate is 99.9: 0.1～0.1: 99.9 in the slurries of weight of the rubber that above-described rubber latex or cross-linking type synthetic rubber latex are contained (being the solid content of rubber latex dry weight or rubber latex) and inorganic particulate, be preferably 99: 1～1: 99, more preferably 85: 15～30: 70.
Above-described inorganic particulate is can be by synthetic or the available inorganic particulate of other various technology, as long as its size range can reach the required effect of invention within the scope of the present invention, be not subjected to the restriction of itself substance classes, but meet except the inorganic particulate of water unstable.Specifically, inorganic particulate is selected from one of following material or its combination as mentioned above: metal simple-substance, metal alloy, metal oxide, metal or non-metal nitride, non-metallic carbide, nonmetal oxide, metal hydroxides, metallic salt, ore etc.Above-described its individual particle of inorganic particulate different can make sphere, elliposoidal, sheet shape, aciculiform, band shape or irregularly shaped.With three-dimensional perspective, it is 0.2～500nm that its individual particle has the one dimension mean sizes at least.
The above inorganic particulate slurries is the suspension of inorganic particulate in water, can directly adopt commercial slurries product, with need before rubber latex is mixed to disperse through common dispersing apparatus (as high-shear emulsifying agent, 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 conventional dispersing apparatus to make inorganic particulate and an amount of water formation steady suspension, mix with rubber latex then.
In the above-described method, can make it to mix through fully stirring in the rubber latex or crosslinking-type rubber latex behind the equilateral stirring of slurries limit adding a kind of (or multiple) irradiation of a kind of (or multiple) inorganic particulate.The solid content (drc) of rubber latex and the solid content (dry weights of the slurries of inorganic particulate) of inorganic particulate are not particularly limited.The drying means that is adopted in the described drying process is with the drying means during the preparation fully vulcanized powder rubber in Chinese patent ZL00816450.9 (WO 01/40356) and the Chinese patent 01801656.1 (WO 01/98395), 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 ℃.Consistent with the gel content of cross-linking type synthetic rubber latex in step a by the rubber content that the composite powder of above two kinds of method gained is contained, consistent with the gel content of rubber latex behind the irradiation in step b.
In the preparation method's of described composite powder step a, the cross-linking type synthetic rubber latex that uses is the cross-linking type synthetic rubber latex described in the applicant's the Chinese patent ZL 00130386.4 (CN 1145662C), 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 cross-linking type synthetic 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.The kind of cross-linking type synthetic rubber latex is selected from cross-linking type butylbenzene rubber latex, cross-linking type carboxylic styrene-butadiene rubber latex, cross-linking type content of polybutadiene rubber latex, crosslinking butadiene nitrile rubber latex, cross-linking type carboxy nitrile rubber latex, cross-linking type chloroprene rubber latex, crosslinking acrylate rubber latex etc.
Among the preparation method's of described composite powder the step b, to used rubber latex raw material without any restriction, rubber latex with preparation fully vulcanized powder rubber in Chinese patent ZL00816450.9 (WO 01/40356) and the Chinese patent 01801656.1 (WO01/98395) can be selected from natural rubber latex; styrene butadiene rubber latex; carboxylic styrene-butadiene rubber latex; paracril latex; carboxy nitrile rubber latex; content of polybutadiene rubber latex; chloroprene rubber latex; silicone rubber latex; the esters of acrylic acid rubber latex; vinylpyridiene-styrene-butadiene rubber latex; Acrylester Butadiene Rubber latex; urethanes latex and fluoroelastomer latex etc.
In fact used rubber latex comprises the crosslinking-type rubber latex among the above-described step a among the described composite powder preparation process b, that is to say that crosslinking-type rubber latex can prepare composite powder of the present invention (as described in step a) without irradiation, also can prepare composite powder of the present invention (as step b) through irradiation.Just the gel content of the composite powder kind rubber that obtains of the latter is higher than the former.
Among preparation method's step b of described composite powder, to the irradiance method of the irradiance method of rubber latex (comprise energetic ray line source that crosslinking coagent, irradiation dose, irradiation are used etc.) with preparation fully vulcanized powder rubber in Chinese patent ZL00816450.9 (WO01/40356) and the Chinese patent 01801656.1 (WO 01/98395).Crosslinking coagent can be do not used at rubber latex, 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 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 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 0.1～10% weight of dried glue weight in the latex with the kind and different variation of prescription of rubber latex.Be 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 preparation method's step b of described composite powder, 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.
The preparation method of rubber combination of the present invention is: will comprise described rubber and described composite powder in interior component by the mixing rubber combination that makes of described amount.The weight ratio of composite powder and rubber raw materials is 0.5: 99.5～95: 5, is preferably 5: 95～90: 10, more preferably 10: 90～90: 10.
The calendering process that the present invention prepares rubber combination adopts existing rubber mixing-milling technique in the prior art.Employed mixing facilities 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.
The present invention prepares the influence that rubber combination is not subjected to vulcanization system, can vulcanize in the sulfur cross-linking system of routine or non-sulfur cross-linking system.The present invention prepares the influence that rubber combination is not subjected to sulfuration process, can compression molding, injection sulfurization, sulfurizing pot vulcanization, individual vulcanizer sulfuration, the sulfuration of congruent melting salt, fluidized bed vulcanization, microwave vulcanization and energetic ray sulfuration etc.
Owing to contain rubber particles in the rubber combination, can improve the deficiency of rubber raw materials performance, owing to contain inorganic particulate in the rubber combination, promptly can substitute the carbon black reinforced rubber simultaneously, can give rubber some special performances again, as magnetic, flame retardant resistance etc.Preparation method's technology that must this rubber combination provided by the present invention is simple, easy handling, and cost is low, use is wide, is easy to industrialization.
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
Sodium-based montmorillonite (chemical plant, Qinghe, Zhangjiakou, Hebei produces, and the lamella mean thickness is 1nm) is mixed by the concentration of 5% weight with water, disperse, place for some time through the high-shear dispersion machine.Commercially available styrene butadiene rubber latex (Shanghai Gaoqiao petro-chemical corporation produces, the trade mark: butylbenzene-7723, and solid content is 34%, the gel content of rubber particles is 82% in the latex, average particle size is 100nm).Styrene-butadiene latex and sodium-based montmorillonite slurries are cooperated in 70: 30 ratios of dry weight separately, stirred one 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) montmorillonite Composite powder of collection in cyclonic separator (
Composite powder 1).
Embodiment 2
With solid content is that (Shanghai Gaoqiao petro-chemical corporation produces, and the trade mark: butylbenzene-5050) 4Kg places container, drips Viscoat 295 54g under stirring on the limit, after being added dropwise to complete, continues to stir one hour for the commercially available styrene butadiene rubber latex of 45% weight.Use cobalt-60 radiosterilize afterwards, dosage is 0.5Mrad, and dose rate is 50Gy/min.After the irradiation in the latex gel content of rubber particles be 85%, average particle size is 100nm.Latex behind the irradiation and sodium-based montmorillonite slurries (with embodiment 1) cooperate in 70: 30 ratios of dry weight separately, stirred one 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 ℃, collection dried styrene-butadiene rubber(SBR)/montmorillonite Composite powder in cyclonic separator (
Composite powder 2).
Embodiment 3
With solid content is that (Lanhua Latex Research and Development Centre, the trade mark: butyronitrile-26) 4Kg places container, drips Viscoat 295 72g under stirring on the limit, after being added dropwise to complete, continues to stir one hour for the commercially available paracril latex of 45% weight.Use cobalt-60 radiosterilize afterwards, dosage is 1Mrad, and dose rate is 50Gy/min.After the irradiation in the latex gel content of rubber particles be 86%, average particle size is 100nm.Latex behind the irradiation and sodium-based montmorillonite slurries (with embodiment 1) cooperate in 70: 30 ratios of dry weight separately, stirred one 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 ℃, collection dried paracril/montmorillonite Composite powder in cyclonic separator (
Composite powder 3).
Embodiment 4
With paracril latex behind the irradiation among the embodiment 3 and calcium carbonate serosity (nano Tyke, Beijing nanosecond science and technology company limited, size on its particle one dimension of calcium carbonate particles cooperates in 40～60nm) 40: 60 ratios in dry weight separately, stirred one 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 ℃, in cyclonic separator, collect dried spray-dried paracril/lime carbonate composite powder (
Composite powder 4).
Embodiment 5
With paracril latex behind the irradiation among the embodiment 3 and magnesium hydroxide slurry (Yixing City auxiliary chemicals factory, solid content 12.5%, median size≤100nm) in ratios cooperations in 40: 60 of dry weight separately, stirred one hour, then mixed solution is passed through the spray-dryer spraying drying, the inlet temperature of spray-dryer is 140～160 ℃, and temperature out is 40～60 ℃, in cyclonic separator, collect dried spray-dried paracril/magnesium hydroxide composite powder (
Composite powder 5).
Embodiment 6
Paracril latex behind the irradiation among the embodiment 3, magnesium hydroxide slurry (with embodiment 5) and sodium-based montmorillonite slurries (with embodiment 1) are cooperated in 40: 54: 6 ratios of dry weight separately, stirred one 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 ℃, in cyclonic separator, collect dried spray-dried paracril calcium carbonate/magnesium hydroxide/sodium-based montmorillonite composite powder (
Composite powder 6).
Comparative example 1
(Shanghai Gaoqiao petro-chemical corporation produces with the styrene butadiene rubber latex among the embodiment 1, the trade mark: butylbenzene-7723) do not sneak into montmorillonite slurry, directly by 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) powder of collection in cyclonic separator (
Powdered rubber 1).
Comparative example 2
Paracril latex behind the irradiation among the embodiment 3 is not sneaked into montmorillonite slurry, directly by the spray-dryer spraying drying, the inlet temperature of spray-dryer is 140～160 ℃, and temperature out is 40～60 ℃, the dried paracril powder of collection in cyclonic separator (
Powdered rubber 2).
Two, the preparation of rubber combination
Embodiment 7
With preparation-obtained among the embodiment 1
Composite powder 130g and styrene-butadiene rubber(SBR) (Jilin chemical industry company limited, the trade mark 1500) 120g is after two roller mills mix, parts by weight in styrene-butadiene rubber(SBR) are 100 parts, technology adds vulcanization system (related vulcanization aid is commercially available) routinely, and its proportioning is: 4 parts in zinc oxide, 2 parts of stearic acid, 1.5 parts of accelerant CZs, 0.5 part of altax, 1.5 parts of oxidation inhibitor 4010NA, 1.5 parts in sulphur.Obtain the composition of composite powder and rubber, press sulfurizing time T down at 170 ℃ then
90Sulfuration is made the standard batten with the vulcanized rubber print then, carries out every Mechanics Performance Testing, and its result is as shown in table 1.
Embodiment 8
With the styrene-butadiene rubber(SBR) 90g among the embodiment 7 with
Composite powder 160g is after two roller mills mix, and technology adds the vulcanization system of identical proportioning among the embodiment 7 routinely, makes after the sulfuration and makes the standard batten, carries out every Mechanics Performance Testing, and its result is as shown in table 1.
Embodiment 9
With the styrene-butadiene rubber(SBR) 60g among the embodiment 7 with
Composite powder 190g is after two roller mills mix, and technology adds the vulcanization system of embodiment 7 identical proportionings routinely, makes after the sulfuration and makes the standard batten, carries out every Mechanics Performance Testing, and its result is as shown in table 1.
Embodiment 10
With the styrene-butadiene rubber(SBR) 90g among the embodiment 7 with
Composite powder 260g is after two roller mills mix, and technology adds the vulcanization system of embodiment 7 identical proportionings routinely, makes after the sulfuration and makes the standard batten, carries out every Mechanics Performance Testing, and its result is as shown in table 1.
Comparative example 3
With the styrene-butadiene rubber(SBR) 90g among the embodiment 7,
Powdered rubber 142g and sodium-based montmorillonite (with embodiment 1) 18g is after two roller mills mix, and technology adds the vulcanization system of embodiment 7 identical proportionings routinely, makes after the sulfuration and makes the standard batten, carries out every Mechanics Performance Testing, and its result is as shown in table 1.
Comparative example 4
Technology adds the vulcanization system through embodiment 7 identical proportionings in styrene-butadiene rubber(SBR) (with embodiment 7) 150g routinely, makes after the sulfuration and makes the standard batten, carries out every Mechanics Performance Testing, and its result is as shown in table 1.
Table 1
| Project | Styrene-butadiene rubber(SBR) | Composite powder 1 | Composite powder 2 | Powdered rubber 1 | Sodium-based montmorillonite | Tensile break strength (MPa) | Tension fracture elongation rate (%) |
| Embodiment 7 | ????80 | ???20 | ??- | ??- | ??- | ??1.85 | ??389 |
| Embodiment 8 | ????60 | ???40 | ??- | ??- | ??- | ??3.28 | ??449 |
| Embodiment 9 | ????40 | ???60 | ??- | ??- | ??- | ??3.82 | ??498 |
| Embodiment 10 | ????60 | ???- | ??40 | ??- | ??- | ??6.19 | ??632 |
| Project | Styrene-butadiene rubber(SBR) | Composite powder 1 | Composite powder 2 | Powdered rubber 1 | Sodium-based montmorillonite | Tensile break strength (MPa) | Tension fracture elongation rate (%) |
| Comparative example 3 | ????60 | ???- | ??- | ??28 | ??12 | ??2.29 | ??338 |
| Comparative example 4 | ????100 | ???- | ??- | ??- | ??- | ??1.77 | ??406 |
| Testing standard | ????- | ???- | ??- | ??- | ??- | ??ASTM??D-412 | ???ASTM???D-412 |
Annotate: each component content is parts by weight in the table 1
The embodiment that lists from table 1 and the result of comparative example add an amount of composite powder and can make the tensile break strength of this rubber and tension fracture elongation rate obviously improve as can be seen in styrene-butadiene rubber(SBR).
Embodiment 11
With preparation-obtained among the embodiment 3
Composite powder 330g and paracril (Lanzhou chemical industry company limited, the trade mark: 2702) 120g is after two roller mills mix, weight fraction in paracril is 100 parts, technology adds vulcanization system (related vulcanization aid is commercially available) routinely, and its proportioning is: 5 parts in zinc oxide, 1 part of stearic acid, 0.5 part of accelerant CZ, 1.5 parts of altaxs, oxidation inhibitor 4010NA1.5 part, 1.5 parts in sulphur.Obtain the composition of composite powder and rubber, press sulfurizing time T down at 160 ℃ then
90Sulfuration is made the standard batten with the vulcanized rubber test piece then, carries out every Mechanics Performance Testing, and its result is as shown in table 2.
Embodiment 12
With the paracril 90g among the embodiment 11 with
Composite powder 360g is after two roller mills mix, and technology adds the vulcanization system of identical proportioning among the embodiment 11 routinely, makes after the sulfuration and makes the standard batten, carries out every Mechanics Performance Testing, and its result is as shown in table 2.
Embodiment 13
With the paracril 60g among the embodiment 11 with
Composite powder 390g is after two roller mills mix, and technology adds the vulcanization system of identical proportioning among the embodiment 11 routinely, makes after the sulfuration and makes the standard batten, carries out every Mechanics Performance Testing, and its result is as shown in table 2.
Embodiment 14
With the paracril 30g among the embodiment 11 with
Composite powder 3120g is after two roller mills mix, and technology adds the vulcanization system of identical proportioning among the embodiment 11 routinely, makes after the sulfuration and makes the standard batten, carries out every Mechanics Performance Testing, and its result is as shown in table 2.
Comparative example 5
With the paracril 90g among the embodiment 11,
Powdered rubber 242g and sodium-based montmorillonite (with embodiment 1) 18g is after two roller mills mix, and technology adds the vulcanization system of identical proportioning among the embodiment 11 routinely, makes after the sulfuration and makes the standard batten, carries out every Mechanics Performance Testing, and its result is as shown in table 2.
Comparative example 6
Technology adds the vulcanization system with embodiment 11 identical proportionings in paracril (with embodiment 11) 150g routinely, makes after the sulfuration and makes the standard batten, carries out every Mechanics Performance Testing, and its result is as shown in table 2.
Table 2
Annotate: each component content is parts by weight in the table 2
The embodiment that lists from table 2 and the result of comparative example add an amount of composite powder and can make tensile modulus, tensile break strength, tension fracture elongation rate, tensile set, angle tear strength, the shore hardness A of this rubber that raising is in various degree arranged as can be seen in paracril.
Embodiment 15
With preparation-obtained among the embodiment 4
Composite powder 430g and paracril (Lanzhou chemical industry company limited, the trade mark: 2702) 120g is after two roller mills mix, weight fraction in paracril is 100 parts, technology adds vulcanization system (related vulcanization aid is commercially available) routinely, and its proportioning is: 5 parts in zinc oxide, 1 part of stearic acid, 0.5 part of accelerant CZ, 1.5 parts of altaxs, oxidation inhibitor 4010NA1.5 part, 1.5 parts in sulphur.Obtain composite powder and rubber composite, press sulfurizing time T down at 160 ℃ then
90Sulfuration is made the standard batten with the vulcanized rubber test piece then, carries out every Mechanics Performance Testing, and its result is as shown in table 3.
Embodiment 16
With the paracril 90g among the embodiment 15 with
Composite powder 460g is after two roller mills mix, and technology adds the vulcanization system of identical proportioning among the embodiment 15 routinely, makes after the sulfuration and makes the standard batten, carries out every Mechanics Performance Testing, and its result is as shown in table 3.
Embodiment 17
With the paracril 60g among the embodiment 15 with
Composite powder 490g is after two roller mills mix, and technology adds the vulcanization system of identical proportioning among the embodiment 15 routinely, makes after the sulfuration and makes the standard batten, carries out every Mechanics Performance Testing, and its result is as shown in table 3.
Embodiment 18
With the paracril 30g among the embodiment 15 with
Composite powder 4120g is after two roller mills mix, and technology adds the vulcanization system of identical proportioning among the embodiment 15 routinely, makes after the sulfuration and makes the standard batten, carries out every Mechanics Performance Testing, and its result is as shown in table 3.
Comparative example 7
With the paracril 90g among the embodiment 15,
Powdered rubber 2(westernization factory is covered in the Inner Mongol for 24g and nano-calcium carbonate, median size 30nm) 36g is after two roller mills mix, and technology adds the vulcanization system of identical proportioning among the embodiment 15 routinely, makes after the sulfuration and makes the standard batten, carry out every Mechanics Performance Testing, its result is as shown in table 3.
Table 3
Annotate: each component content is parts by weight in the table 3
The embodiment that lists from table 3 and the result of comparative example add an amount of composite powder and can make tensile modulus, tensile break strength, tension fracture elongation rate, tensile set, angle tear strength, the shore hardness A of this rubber that raising is in various degree arranged as can be seen in paracril.
Embodiment 19
With preparation-obtained among the embodiment 2
Composite powder 1With ethylene-propylene diene copolymer (Japanese JSR company produces, the trade mark: EP57P) and oxidation inhibitor RD (chemical plant, Nanjing) mix, be 100 parts in the weight fraction of rubber, it specifically consists of: 62.5 parts of ethylene-propylene diene copolymers,
Composite powder 1Be 37.5 parts, 1 part of oxidation inhibitor RD.Adopt the ZSK-25 twin screw extruder blend granulation of German WP company, each section of forcing machine temperature is respectively: 185 ℃, 200 ℃, 200 ℃, 200 ℃, 200 ℃ and 200 ℃ (head temperature).Pellet is made print through compression molding, puts into plastics bag through vacuum plastic sealing, uses cobalt-60 radiosterilize afterwards, and dosage is 5Mrad, and dose rate is 50Gy/min.Make the standard batten at last and carry out every Mechanics Performance Testing, its result is as shown in table 4.
Comparative example 8
After ethylene-propylene rubber(EPR) pellet among the embodiment 19 and oxidation inhibitor mixed, through with identically among the embodiment 19 extrude, compressing tablet, irradiation technique condition make the standard batten, carries out various Mechanics Performance Testings, the results are shown in table 4.
Table 4
| Project | Ethylene-propylene diene copolymer | ?? Compound?? Powder 1 | 300% tensile modulus (MPa) | Tensile break strength (MPa) | Tension fracture elongation rate (%) | Tensile set (%) | Angle tear strength (MPa) | Shore hardness A |
| Embodiment 19 | ??62.5 | ??37.5 | ??1.71 | ??4.56 | ??370 | ??30 | 22.8 | ??61 |
| Comparative example 8 | ??100 | ??- | ??1.46 | ??2.09 | ??278 | ??12 | 16.9 | ??62 |
| Testing standard | ??- | ??- | ??ASTM??D-412 | ??ASTM??D-412 | ??ASTM??D-412 | ??ASTM??D-412 | ASTMD-1004 | ??ASTM??D-2240 |
Annotate: each component content is parts by weight in the table 4
The embodiment that lists from table 4 and the result of comparative example add an amount of composite powder and can make the tensile modulus, tensile break strength, tension fracture elongation rate, tensile set, angle tear strength etc. of this rubber that raising is in various degree arranged as can be seen in terpolymer EP rubber.
Embodiment 20
With preparation-obtained among the embodiment 5
Composite powder 5With EVA (acetate-vinyl acetate between to for plastic ester elastomer, the production of Bayer company, the trade mark: Levamelt 500,50%) and antioxidant 1010 (Switzerland vapour Ba Jiaji production) mix VA content:, weight fraction in rubber is 100 parts, and it specifically consists of: EVA is 44.4 parts
Composite powder 5Be 55.6 parts, antioxidant 1010 is 0.3 part.Adopt the mixed Banbury mixer of Hakke, blending temperature is respectively 160 ℃, and rotating speed is 50rpm, and the blend time is 10min.Discharging is put into plastics bag after vacuum plastic sealing is used cobalt-60 radiosterilize afterwards after compression molding is made print, and dosage is 6Mrad, and dose rate is 50Gy/min.Make the standard batten at last and carry out every Mechanics Performance Testing, its result is as shown in table 5.
Embodiment 21
Remove among the embodiment 20
Composite powder 5Change into
Composite powder 6In addition, other condition is identical with embodiment 18.Make the standard batten behind, mold pressing mixed through Banbury mixer, the irradiation and carry out every Mechanics Performance Testing, its result is as shown in table 5.
Comparative example 9
EVA among the embodiment 20 is mixed with oxidation inhibitor, and other condition is identical with embodiment 20.Make into the standard batten behind, mold pressing mixed through Banbury mixer, the irradiation and carry out every Mechanics Performance Testing, its result is as shown in table 5.
Table 5
| Project | Styrene-butadiene rubber(SBR) | ?? Compound?? Powder 5 | ???? Compound???? Powder 6 | 100% tensile modulus (MPa) |
| Embodiment 20 | ????44.4 | ??55.6 | ????- | ??5.21 |
| Embodiment 21 | ????44.4 | ??- | ????55.6 | ??4.85 |
| Comparative example 9 | ????100 | ??- | ????- | ??0.94 |
| Testing standard | ????- | ??- | ????- | ??ASTM?D-412 |
Annotate: each component content is parts by weight in the table 5
The embodiment that lists from table 5 and the result of comparative example add an amount of composite powder and can make the tensile modulus of this rubber be significantly improved as can be seen in EVA.
Claims (10)
1. rubber combination includes the following component of blend: rubber and composite powder, and wherein the ratio of composite powder gross weight and rubber gross weight is 0.5: 99.5～95: 5, is preferably 5: 95～90: 10; Wherein said rubber is natural rubber or synthetic rubber, and 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 the cross-linking type synthetic rubber latex;
B. after adding or not adding under the situation of crosslinking coagent, adopting the high-energy radiation line source to carry out radiation vulcanization rubber latex, again 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; Described 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, ore; It is 0.2～500nm that its inorganic particulate particle has the one dimension mean sizes at least;
The weight ratio of contained inorganic particulate is 99.9: 0.1～0.1: 99.9 in the weight of the rubber that described rubber latex or cross-linking type synthetic rubber latex are contained and the slurries of inorganic particulate, is preferably 99: 1～1: 99.
2. rubber combination according to claim 1, the ratio that it is characterized in that described composite powder gross weight and rubber gross weight is 5: 95～90: 10.
3. rubber combination according to claim 1 is characterized in that the weight ratio of contained inorganic particulate in the slurries of the weight of the rubber that rubber latex among the described composite powder preparation method or cross-linking type synthetic rubber latex are contained and inorganic particulate is 99: 1～1: 99.
4. rubber combination according to claim 1 is characterized in that the inorganic particulate among the described composite powder preparation method is selected from one of following material or combination: 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 or polynite.
5. rubber combination according to claim 1 is characterized in that the gel content of the cross-linking type synthetic rubber latex described in the step a among the described composite powder preparation method is 80% weight or higher.
6. rubber combination according to claim 5 is characterized in that the cross-linking type synthetic rubber latex described in the step a is selected from cross-linking type butylbenzene rubber latex, cross-linking type carboxylic styrene-butadiene rubber latex, cross-linking type content of polybutadiene rubber latex, crosslinking butadiene nitrile rubber latex, cross-linking type carboxy nitrile rubber latex, cross-linking type chloroprene rubber latex or crosslinking acrylate rubber latex among the described composite powder preparation method.
7. rubber combination according to claim 1 is characterized in that the rubber latex described in the step b is selected from natural rubber latex, styrene butadiene rubber latex, carboxylic styrene-butadiene rubber latex, paracril latex, carboxy nitrile rubber latex, content of polybutadiene rubber latex, chloroprene rubber latex, silicone rubber latex, esters of acrylic acid rubber latex, vinylpyridiene-styrene-butadiene rubber latex, Acrylester Butadiene Rubber latex, urethanes latex or fluoroelastomer latex among the described composite powder preparation method.
8. rubber combination according to claim 1 is characterized in that the curdled milk content of rubber in the described composite powder is 60% weight or higher, is preferably 75% weight or higher.
9. rubber combination according to claim 1 is characterized in that the median size of rubber particles in the described composite powder is 20～2000nm, is preferably 30～1500nm, more preferably 50～500nm.
10. preparation method who prepares each described rubber combination of claim 1～9, it is characterized in that with comprise described rubber and described composite powder in interior component by the mixing rubber combination that makes of described amount.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008102253659A CN101724187B (en) | 2008-10-31 | 2008-10-31 | Rubber composition and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008102253659A CN101724187B (en) | 2008-10-31 | 2008-10-31 | Rubber composition and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101724187A true CN101724187A (en) | 2010-06-09 |
| CN101724187B CN101724187B (en) | 2011-08-31 |
Family
ID=42445782
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008102253659A Active CN101724187B (en) | 2008-10-31 | 2008-10-31 | Rubber composition and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101724187B (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102108171A (en) * | 2011-04-07 | 2011-06-29 | 铁岭福神橡胶密封有限责任公司 | Formula of high-strength fluororubber product material |
| CN102558866A (en) * | 2011-12-12 | 2012-07-11 | 彭朕财 | Liquid transparent toughening agent for plastics |
| CN103289144A (en) * | 2013-06-17 | 2013-09-11 | 海南大学 | Nano ferroferric oxide/natural composite magnetic latex and preparation method thereof |
| CN104629127A (en) * | 2015-01-26 | 2015-05-20 | 安徽国华电缆集团有限公司 | Sheathing material for modified cables and preparation method thereof |
| CN105504604A (en) * | 2015-12-31 | 2016-04-20 | 崇夕山 | Tear-resistant rubber gasket for motorcycle engine |
| CN105860163A (en) * | 2014-12-04 | 2016-08-17 | 陈薇 | Environment-friendly modified natural rubber material |
| CN106032434A (en) * | 2015-03-18 | 2016-10-19 | 中国石油化工股份有限公司 | Powder rubber and vulcanized powder rubber, and preparation methods of powder rubber and vulcanized powder rubber |
| CN106402561A (en) * | 2016-10-28 | 2017-02-15 | 当涂县金龙机械有限公司 | Anti-radiation ternary fluorine rubber non-metallic compensator and preparation method thereof |
| CN107686660A (en) * | 2017-10-25 | 2018-02-13 | 陆建文 | A kind of high-temperature resistant rubber sole |
| CN109312138A (en) * | 2016-07-05 | 2019-02-05 | 电化株式会社 | Acrylic rubber composition |
| TWI658079B (en) * | 2015-06-19 | 2019-05-01 | 日商大金工業股份有限公司 | Compositions and shaped articles made of fluoropolymers |
| CN110903521A (en) * | 2019-11-25 | 2020-03-24 | 西安和光明宸科技有限公司 | Preparation method of rubber for automobile tires |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19815453A1 (en) * | 1998-04-07 | 1999-10-21 | Pku Pulverkautschuk Union Gmbh | Powdery, filler-containing rubber powders, process for their production and use |
| CN1239587C (en) * | 2003-04-03 | 2006-02-01 | 中国石油化工股份有限公司 | Composite powder, its preparation method and application |
| EP1648959B1 (en) * | 2003-07-30 | 2010-11-24 | PolyOne Corporation | Nucleated thermoplastic elastomer compositions and related methods |
-
2008
- 2008-10-31 CN CN2008102253659A patent/CN101724187B/en active Active
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102108171A (en) * | 2011-04-07 | 2011-06-29 | 铁岭福神橡胶密封有限责任公司 | Formula of high-strength fluororubber product material |
| CN102558866A (en) * | 2011-12-12 | 2012-07-11 | 彭朕财 | Liquid transparent toughening agent for plastics |
| CN103289144A (en) * | 2013-06-17 | 2013-09-11 | 海南大学 | Nano ferroferric oxide/natural composite magnetic latex and preparation method thereof |
| CN105860163A (en) * | 2014-12-04 | 2016-08-17 | 陈薇 | Environment-friendly modified natural rubber material |
| CN104629127A (en) * | 2015-01-26 | 2015-05-20 | 安徽国华电缆集团有限公司 | Sheathing material for modified cables and preparation method thereof |
| CN106032434A (en) * | 2015-03-18 | 2016-10-19 | 中国石油化工股份有限公司 | Powder rubber and vulcanized powder rubber, and preparation methods of powder rubber and vulcanized powder rubber |
| CN106032434B (en) * | 2015-03-18 | 2019-12-20 | 中国石油化工股份有限公司 | Powder rubber and vulcanized powder rubber and preparation method thereof |
| TWI658079B (en) * | 2015-06-19 | 2019-05-01 | 日商大金工業股份有限公司 | Compositions and shaped articles made of fluoropolymers |
| US11072700B2 (en) | 2015-06-19 | 2021-07-27 | Daikin Industries, Ltd. | Composition comprising fluoropolymer and molded article |
| CN105504604A (en) * | 2015-12-31 | 2016-04-20 | 崇夕山 | Tear-resistant rubber gasket for motorcycle engine |
| CN109312138B (en) * | 2016-07-05 | 2021-07-09 | 电化株式会社 | Acrylic rubber composition |
| CN109312138A (en) * | 2016-07-05 | 2019-02-05 | 电化株式会社 | Acrylic rubber composition |
| US10982029B2 (en) | 2016-07-05 | 2021-04-20 | Denka Company Limited | Acrylic rubber composition |
| CN106402561A (en) * | 2016-10-28 | 2017-02-15 | 当涂县金龙机械有限公司 | Anti-radiation ternary fluorine rubber non-metallic compensator and preparation method thereof |
| CN107686660A (en) * | 2017-10-25 | 2018-02-13 | 陆建文 | A kind of high-temperature resistant rubber sole |
| CN110903521A (en) * | 2019-11-25 | 2020-03-24 | 西安和光明宸科技有限公司 | Preparation method of rubber for automobile tires |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101724187B (en) | 2011-08-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101724187B (en) | Rubber composition and preparation method thereof | |
| CN102050973B (en) | Tread rubber composite material and preparation method thereof | |
| CN102050972A (en) | Modified rubber composition and preparation method thereof | |
| CN1239587C (en) | Composite powder, its preparation method and application | |
| Arayapranee et al. | Application of rice husk ash as fillers in the natural rubber industry | |
| CN1305951C (en) | Elastomer composites, elastomer blends and methods | |
| CN1844270A (en) | Nano antibacterial powdered paint and its micro-suspension one-step preparation therefor | |
| CN101084258B (en) | Modified natural rubber masterbatch and method for production thereof, and rubber composition and tire | |
| Moonchai et al. | Comparative properties of natural rubber vulcanisates filled with defatted rice bran, clay and calcium carbonate | |
| CN102732063A (en) | Modified fly ash, preparation method thereof, and preparation apparatus thereof | |
| CN1386786A (en) | Rubber composition and tyre contg. said composition | |
| Onyeagoro | Cure characteristics and physico-mechanical properties of carbonized bamboo fibre filled natural rubber vulcanizates | |
| CN102796294A (en) | Preparation method of calcium carbonate modified butylbenzene/natural rubber composite material | |
| CN102675918A (en) | Preparation method of low-yellowness antibacterial calcium carbonate functional composite powder for ventilated membrane | |
| CN103965530B (en) | A kind of rubber combination and preparation method thereof and its cross-linked rubber | |
| CN106867099A (en) | A kind of composite and preparation method thereof | |
| CN100387651C (en) | Ultrathin composite powder reinforced polyformaldehyde materials and method for preparing same | |
| CN104311927A (en) | Synthetic rubber with high mechanical property for color sorter and preparation method of synthetic rubber | |
| CN1233722C (en) | Polypropylene composition and preparation process thereof | |
| CN111393727A (en) | Wear-resistant rare earth rubber material and preparation method thereof | |
| CN1168770C (en) | Method for preparing powdered rubber with carbon black stuffing | |
| CN1233723C (en) | Toughened polypropylene composition and preparation process thereof | |
| CN100363412C (en) | Enhanced full vulcanizing polyolefine thermoplastic elastomer and preparation process thereof | |
| CN1597753A (en) | Nitrile polymer mixer used for magnetic sealing | |
| CN1106030A (en) | Unorganic particles coated with elastic material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |