CN102391589A - Preparation method of surface halogenation modified vulcanized rubber powder/polyvinyl chloride blended compound - Google Patents
Preparation method of surface halogenation modified vulcanized rubber powder/polyvinyl chloride blended compound Download PDFInfo
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- CN102391589A CN102391589A CN2011101852927A CN201110185292A CN102391589A CN 102391589 A CN102391589 A CN 102391589A CN 2011101852927 A CN2011101852927 A CN 2011101852927A CN 201110185292 A CN201110185292 A CN 201110185292A CN 102391589 A CN102391589 A CN 102391589A
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Abstract
The invention discloses a preparation method of a surface halogenation modified vulcanized rubber powder/polyvinyl chloride blended compound, which is characterized by comprising the following steps: adding 100 parts of vulcanized rubber powder (of which the average particle size is smaller than or equal to 100 mu m), 200-500 parts of solvent and 1.0-10 parts of halogenating agent into a reactor provided with a stirrer, a thermometer and a heater, reacting at 5-50 DEG C for 0.5-4 hours, filtering, and drying to obtain the surface halogenation modified vulcanized rubber powder; and evenly mixing 10-50 parts of modified vulcanized rubber powder, 25-58 parts of polyvinyl chloride and 25-32 parts of plasticizer in a high-speed mixer, and thermoforming with a flat vulcanizing machine at 180-200 DEG C under the pressure of 10-15Mpa, thereby obtaining the surface halogenation modified vulcanized rubber powder/polyvinyl chloride blended compound.
Description
Technical field
The present invention relates to the preparation method of a kind of surperficial halogenation modification vulcanized rubber powder/polychloroethylene blended mixture, belong to the regenerated using field of waste rubber.
Background technology
Along with the human society modernization process, the interior automobile of worldwide uses increasingly extensive, makes with the tire for vehicles to be the rubber item consumption cumulative year after year of main body.The consequent is all to have every day a large amount of junked tires to produce.These waste rubber goods are not easy degraded under field conditions (factors) very much, if let alone to stack, not only occupy a large amount of valuable soils, but also grow mosquito, influence the environmental health and the places of cultural interest.On the other hand, rubber itself is one type of more rare material, even the waste rubber goods are still keeping elastomeric characteristic preferably, if not to these waste or used vulcanized rubber materials reasonable use in addition, also be a kind of huge waste of resource.
The development and use of waste or used vulcanized rubber have continued decades, and have obtained undeniable achievement, are the preparation and the application of regenerated rubber by what people were familiar with wherein.As everyone knows; Regenerated rubber is to utilize the depleted vulcanized rubber; Handle through pulverizing, heating, mechanical shearing, and combine the chain transfer of organic polysulfide (regeneration activator), make the rubber waste from elastic stage; " reduction " becomes plasticity and viscous state, and rubber structure also is degraded to branched structure and linear structure from three-dimensional network.Here it is, and many before this countries have continued to use " high temperature desulfurizing " technology of decades.Regenerated rubber through " sulfur removal technology " obtains forms crosslinking structure with sulphur or other vulcanizing agent effect again under cure conditions, obtain more rudimentary elastomeric article.In production practice, a small amount of regenerated rubber is mixed use with original untreated rubber, can satisfy the needs of rudimentary goods in some.Yet this dependence high temperature desulfurizing mode prepares the technology of regenerated rubber, and not only energy consumption is very high, but also owing to produce waste water, waste gas, forms serious secondary pollution.In recent years, constantly strengthen with environmental protection consciousness along with being becoming tight energy day, above-mentioned traditional " regenerated rubber " method is limited successively, and this technology is eliminated in some developed country.
At present, the developing direction of vulcanized rubber powder product is mainly aspect several:
1) non-surface-treated rubber powder powder product.The preparation of this type rubber powder is to rely on crushing mechanism will discard vulcanized rubber article to process suitable fragment earlier, then under low temperature or normal temperature through grinding or the powder of suitable fineness further processed the vulcanized rubber fragment by disintegrating apparatus.This vulcanized rubber powder that only relies on physical method to obtain, its surface is still three-dimensional net structure basically, and surfactivity is lower, and the bonding force of they and untreated rubber or other macromolecular material is less, is difficult to attractive purposes generally speaking.In order to improve the surfactivity of this type of rubber powder, can rubber powder be pulverized as much as possible, make it to become the powder of granularity very tiny (particle diameter is little of several microns, even near nano level).Because the particle of powder is more little; Its specific surface area is just big more; The surfactivity that is had is just big more, so the bonding force that in the rubber compounding system, produces through physical adsorption and intermolecular forces between rubber powder particle and the rubber polymer is just strong more, and the better product properties of acquisition thus.Like Chinese patent CN00813897.4 and CN00106144.5; CN201020172641.2; CN201020172635.7: U.S. Pat 2005107484 documents such as (A1) has proposed the process method and the application example of the meticulous or hyperfine cross-linked rubber powders of some preparations.The characteristics of these methods are through the improvement of equipment or the adjustment of technology vulcanized rubber to be prepared into tiny as far as possible powder body material.But, a rule is arranged in the powder body material processing industry, promptly no matter how equipment and technology are improved, and seek out ultramicrofine powder body material, have all crossed over not high energy consumption and expensive this road bank, and the situation of vulcanized rubber powder also is like this.Expect more tiny powder, will more pulverize number of times, corresponding energy consumption is just higher; And workloads such as consequent powder conveying, classification, circulation are just more complicated, also will take into account ultrafine dust simultaneously to fly upward the environmental improvement that brings, and its running cost is low certainly not to get off.Therefore, the simple particle diameter that reduces rubber powder that relies on, not too economical certainly.
2) surperficial machinery-chemical method modification
Under regeneration activator or peptizer participation, vulcanized rubber powder is placed on the mechanical shearing that carries out in rubber mixing machine or the twin screw extruder repeatedly, make the fracture of vulcanized rubber powder surface portion generation S-S key and S-C key, so obtain the rubber powder modified thing of part " desulfurization ".Like Chinese patent CN201020000817.6 and the described process method of CN201020000819.5.The rubber powder product of the so-called mechanical-chemical method of this type process modification, its surface have produced and untreated rubber bonded condition, can its part be added in the untreated rubber prescription to the needed rubber item of preparation people.But the maximum characteristic of these class methods is exactly that rubber powder will carry out repetitious mechanical shearing or rolls.Therefore, produce in batches if will implement mechanical-chemical method modified glue powder, mechanical energy consumption is still very high.
3) chemical modification of vulcanized rubber powder
Go up some active structures through chemical means on vulcanized rubber powder surface " connecing "; Make rubber powder under cure conditions, have an opportunity with rubbery system in main substance combine through chemical reaction; Perhaps make vulcanized rubber powder good bonding force arranged, produce better product properties thus with the Polymer Systems outside some rubber.As, Chinese patent CN95105209.8 and CN03146994.9; CN200610125315.4: U.S. Pat 20107816446 document descriptions such as grade this type of chemical modification method.They generally all are to utilize alkene class or polyenoid class monomer at vulcanized rubber powder generation graft reaction, make vulcanized rubber powder obtain to help the functional group of follow-up chemically crosslinked or physical bond.Yet the monomer of this type of graft reaction generally all is volatile and to the irritant organic liquid of human body, some reaction is still carried out in poisonous and hazardous organic solvents such as aromatic hydrocarbons or hydrochloric ether.Therefore, the modifying process operation easier of this type rubber powder is bigger, has no small potential safety hazard and environmental exposure.
Summary of the invention
The present invention the objective of the invention is to prior art deficiency and put forward the preparation method of a kind of surperficial halogenation modification vulcanized rubber powder/polychloroethylene blended mixture; Be characterized in water or lower aliphatic ketone medium; Through of the reaction of tricarbimide halo derivatives to vulcanized rubber powder; Introduce halogen atom to the vulcanized rubber powder surface, thereby vulcanized rubber powder polarity is improved.With the PVC RESINS blend by a certain percentage of halogenation modification vulcanized rubber powder and plasticizer-containing, prepare composite rubber-plastic material again.
The object of the invention is realized that by following technical measures wherein said raw material umber is parts by weight except that specified otherwise.
Preparing method's method of surface halogenation modification vulcanized rubber powder/polychloroethylene blended mixture may further comprise the steps:
(1) preparation of surperficial halogenation modification vulcanized rubber powder
With 100 parts of the vulcanized rubber powders of median size≤100 μ m, 200～500 parts of solvents, 1.0～10 parts of addings of halogenating agent have in the reactor drum of whisking appliance, TM and heating unit; In 5～50 ℃ of reactions of temperature, 0.5～4h; Through filtering, drying makes the vulcanized rubber powder of surperficial halogenation modification.
(2) preparation of surperficial halogenation modification vulcanized rubber powder/polyvinyl chloride blend
With 10～50 parts of modification vulcanized rubber powders, 25～58 parts of SE, 25～32 parts in softening agent; Mix through impeller; 180～200 ℃ of temperature, pressure 10～15Mpa is hot-forming through vulcanizing press, obtains surperficial halogenation modification vulcanized rubber powder/polychloroethylene blended mixture.
Solvent is any in water, acetone or the methylethylketone.
Halogenating agent is a trichloroisocyanuric acid, at least a in Surchlor GR 60 and the chlorobromide isocyanuric acid.
Softening agent is phthalic acid two (a 2-ethylhexyl), any in dimixo-octyl phthalate or the Witcizer 300.
Surperficial halogenation modification vulcanized rubber powder/polychloroethylene blended mixture that the preparation method of surface halogenation modification vulcanized rubber powder/polychloroethylene blended mixture prepares.
Surface halogenation modification vulcanized rubber powder/polychloroethylene blended mixture can replace some rubber items to use, thereby has expanded the regenerated using of vulcanized rubber.
Performance test
Surperficial halogenation modification vulcanized rubber powder/polychloroethylene blended composite materials with aforesaid method makes carries out the physical and mechanical properties test according to GB/T528-1998 to compound sizing material test piece, and the result sees for details shown in the table 1.The result shows that by the compound sizing material of surperficial halogenation modification vulcanized rubber powder preparation, the compound sizing material for preparing than unmodified rubber powder has the better material performance.
The present invention has the following advantages:
1) elastomer material that utilizes the vulcanized rubber powder preparation to have certain purposes is reused waste rubber.
2) surface chemical modification of vulcanized rubber powder is carried out in water, acetone or methylethylketone medium, does not relate to toxic media such as aromatic hydrocarbons or hydrochloric ether, and operating environment is relatively more friendly, and simple.
Embodiment
Following while, embodiment specifically described the present invention; Be necessary to be pointed out that at this present embodiment only is used for the present invention is further specified; Can not be interpreted as the restriction to protection domain of the present invention, the number of techniques personnel in this field can make some nonessential improvement and adjustment according to the content of the invention described above.
Embodiment 1
(1) preparation of surperficial halogenation modification vulcanized rubber powder
With 100 parts of the vulcanized rubber powders of median size≤100 μ m, 200 parts of methylethylketones, 1.0 parts of trichloroisocyanuric acids; Adding has in the reactor drum of whisking appliance, TM and heating unit, in 5 ℃ of reactions of temperature 1.5h, through filtering; Drying makes the vulcanized rubber powder of surperficial halogenation modification.
(2) preparation of surperficial halogenation modification vulcanized rubber powder/polyvinyl chloride blend
The preparation of experiment sizing compound formula test piece A: with 10 parts of modification vulcanized rubber powders; 58 parts of SE; 32 parts of phthalic acids two (2-ethylhexyl) mix through impeller, through vulcanizing press 180 ℃ of temperature; Pressure 10Mpa is hot-forming, obtains surperficial halogenation modification vulcanized rubber powder/polychloroethylene blended mixture.
The preparation of contrast experiment's sizing compound formula test piece B: adopt the unmodified vulcanized rubber powder of equivalent to replace modified glue powder, all the other same A.Embodiment 2
(1) preparation of surperficial halogenation modification vulcanized rubber powder
With 100 parts of the vulcanized rubber powders of median size≤100 μ m, 350 parts of deionized waters, 5.0 parts of chlorobromide isocyanuric acids; Adding has in the reactor drum of whisking appliance, TM and heating unit, in 35 ℃ of reactions of temperature 4h, through filtering; Drying makes the vulcanized rubber powder of surperficial halogenation modification.
(2) preparation of surperficial halogenation modification vulcanized rubber powder/polyvinyl chloride blend
The preparation of experiment sizing compound formula test piece A: with 35 parts of modification vulcanized rubber powders; 37 parts of SE; 28 parts of dimixo-octyl phthalates mix through impeller, through vulcanizing press 180 ℃ of temperature; Pressure 12Mpa is hot-forming, obtains surperficial halogenation modification vulcanized rubber powder/polychloroethylene blended mixture.
The preparation of contrast experiment's sizing compound formula test piece B: adopt the unmodified vulcanized rubber powder of equivalent to replace modified glue powder, all the other same A.
Embodiment 3
(1) preparation of surperficial halogenation modification vulcanized rubber powder
With 100 parts of the vulcanized rubber powders of median size≤100 μ m, 400 parts of deionized waters, 10 parts of Surchlor GR 60s; Adding has in the reactor drum of whisking appliance, TM and heating unit, in 45 ℃ of reactions of temperature 1h, through filtering; Drying makes the vulcanized rubber powder of surperficial halogenation modification.
(2) preparation of surperficial halogenation modification vulcanized rubber powder/polyvinyl chloride blend
The preparation of experiment sizing compound formula test piece A: with 40 parts of modification vulcanized rubber powders; 30 parts of SE; 30 parts of Witcizer 300s mix through impeller, through vulcanizing press 190 ℃ of temperature; Pressure 14Mpa is hot-forming, obtains surperficial halogenation modification vulcanized rubber powder/polychloroethylene blended mixture.
The preparation of contrast experiment's sizing compound formula test piece B: adopt the unmodified vulcanized rubber powder of equivalent to replace modified glue powder, all the other same A.
Embodiment 4
(1) preparation of surperficial halogenation modification vulcanized rubber powder
With 100 parts of the vulcanized rubber powders of median size≤100 μ m, 300 parts of deionized waters, 200 parts in acetone; 4 parts of trichloroisocyanuric acids, 4 parts of chlorobromide isocyanuric acids, adding has in the reactor drum of whisking appliance, TM and heating unit; In 50 ℃ of reactions of temperature 0.5h; Through filtering, drying makes the vulcanized rubber powder of surperficial halogenation modification.
(2) preparation of surperficial halogenation modification vulcanized rubber powder/polyvinyl chloride blend
The preparation of experiment sizing compound formula test piece A: with 50 parts of modification vulcanized rubber powders; 25 parts of SE; 25 parts of phthalic acids two (2-ethylhexyl) mix through impeller, through vulcanizing press 200 ℃ of temperature; Pressure 15Mpa is hot-forming, obtains surperficial halogenation modification vulcanized rubber powder/polychloroethylene blended mixture.
The preparation of contrast experiment's sizing compound formula test piece B: adopt the unmodified vulcanized rubber powder of equivalent to replace modified glue powder, all the other same A.
The concurrent mixture of above-mentioned four embodiment and Comparative Examples acquisition is processed test piece test, the result sees for details shown in the table 1.
Table 1 is that the physical and mechanical properties of surperficial halogenation modification vulcanized rubber powder/polychloroethylene blended mixture embodiment and Comparative Examples compares
Claims (6)
1. the preparation method of surperficial halogenation modification vulcanized rubber powder/polychloroethylene blended mixture is characterized in that this method may further comprise the steps, and is by weight:
(1) preparation of surperficial halogenation modification vulcanized rubber powder
With 100 parts of the vulcanized rubber powders of median size≤100 μ m, 200～500 parts of solvents, 1.0～10 parts of addings of halogenating agent have in the reactor drum of whisking appliance, TM and heating unit; In 5～50 ℃ of reactions of temperature, 0.5～4h; Through filtering, drying makes the vulcanized rubber powder of surperficial halogenation modification;
(2) preparation of surperficial halogenation modification vulcanized rubber powder/polyvinyl chloride blend
With 10～50 parts of modification vulcanized rubber powders, 25～58 parts of SE, 25～32 parts in softening agent; Mix through impeller; 180～200 ℃ of temperature, pressure 10～15Mpa is hot-forming through vulcanizing press, obtains surperficial halogenation modification vulcanized rubber powder/polychloroethylene blended mixture.
2. the preparation method of surperficial according to claim 1 halogenation modification vulcanized rubber powder/polychloroethylene blended mixture, the solvent that it is characterized in that modified-reaction is any in water, acetone or the methylethylketone.
3. the preparation method of surperficial according to claim 1 halogenation modification vulcanized rubber powder/polychloroethylene blended mixture is characterized in that properties-correcting agent is trichloroisocyanuric acid, at least a in Surchlor GR 60 and the chlorobromide isocyanuric acid.
4. the preparation method of surperficial according to claim 1 halogenation modification vulcanized rubber powder/polychloroethylene blended mixture; It is characterized in that softening agent is phthalic acid two (a 2-ethylhexyl) in the blended complex, any in dimixo-octyl phthalate or the Witcizer 300.
5. surperficial halogenation modification vulcanized rubber powder/polychloroethylene blended mixture of preparing of method according to claim 1.
6. like the said surperficial halogenation modification vulcanized rubber powder of claim 5/polychloroethylene blended composite materials, it is characterized in that this blended complex can replace some rubber items to use, thereby expanded the regenerated using of vulcanized rubber.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113788976A (en) * | 2021-09-15 | 2021-12-14 | 成都盛帮密封件股份有限公司 | Latex product surface treating agent and preparation method and application thereof |
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| CN101948595A (en) * | 2010-10-26 | 2011-01-19 | 曾广胜 | Waste rubber powder/PVC thermoplastic elastomer material and preparation process thereof |
| CN102010531A (en) * | 2010-11-17 | 2011-04-13 | 安徽安大中鼎橡胶技术开发有限公司 | Modified-surface activated waste vulcanizate powder |
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Patent Citations (2)
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| CN101948595A (en) * | 2010-10-26 | 2011-01-19 | 曾广胜 | Waste rubber powder/PVC thermoplastic elastomer material and preparation process thereof |
| CN102010531A (en) * | 2010-11-17 | 2011-04-13 | 安徽安大中鼎橡胶技术开发有限公司 | Modified-surface activated waste vulcanizate powder |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113788976A (en) * | 2021-09-15 | 2021-12-14 | 成都盛帮密封件股份有限公司 | Latex product surface treating agent and preparation method and application thereof |
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