CN103627039A - Preparation method of nano MgO/polymer composite master rubber - Google Patents
Preparation method of nano MgO/polymer composite master rubber Download PDFInfo
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- CN103627039A CN103627039A CN201310485979.1A CN201310485979A CN103627039A CN 103627039 A CN103627039 A CN 103627039A CN 201310485979 A CN201310485979 A CN 201310485979A CN 103627039 A CN103627039 A CN 103627039A
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Abstract
The invention discloses a preparation method of nano MgO/polymer composite master rubber. The preparation method comprises the following operation steps: (1), stirring and mixing a dispersant, nano MgO and an emulsifier in water to prepare aqueous emulsion; (2), mixing the polymer emulsion with the aqueous emulsion; (3), adding flocculating agent liquor into the mixture of the polymer emulsion and the aqueous emulsion, and stirring and flocculating to obtain co-precipitates; (4), washing the co-precipitates with water and removing the flocculating agent; (5), drying the co-precipitates to obtain the nano MgO/polymer composite master rubber. The preparation method disclosed by the invention is simple and fine in dispersion. The prepared composite master rubber is added into rubber type CPE (Chlorinated Polyethylene) for manufacturing a cable, not only has an auxiliary vulcanization accelerating effect on the MgO, but also has good dispersion, good compatibility with the rubber material, does not easily absorb moisture, and can be used for improving the processing performance of a rubber compound and the ageing resistance of the vulcanized rubber.
Description
[technical field]
The present invention relates to the preparation method of the compound rubber master batch of a kind of nano-MgO/polymkeric substance.The method can be prepared nano-MgO homodisperse compound rubber master batch in polymkeric substance.This compound rubber master batch emphasis is applied to rubber industry, and wherein nano-MgO is mainly as the functional aid of rubber.
[technical background]
In recent years, rubber-type chlorinated polyethylene (hereinafter to be referred as CPE) is more and more extensive in the application of wires and cables industry, more than its consumption accounts for CPE85%, has greatly the trend of replacement chloroprene rubber (CR).The output of CPE is also with 40% speed increment.
As everyone knows, CPE itself does not have two keys, also the point that there is no crosslinking structure, by superoxide, be cross-linked completely, the radical that peroxide breakdown is produced at the high temperature in when sulfuration, captures the hydrogen on CPE long chain molecule and occurs the radical of CPE, under the help of vulcanization aid TAIC, the radical of two macromolecular chains is coupled together, form cross-linked structure, thereby make CPE sulfuration.Therefore, in rubber compounding, should not use acid Synergist S-421 95, prevent that acid Synergist S-421 95 from affecting the sulfuration of CPE on the destruction of superoxide.In this process, due to the effect of polar molecule, have the generation of HCl molecule, this HCl gas has not only hindered colloid sulfuration, and easily make CPE produce similar sponge-type porosity and its physical and mechanical properties is worsened, adding of active MgO overcome this problem effectively.In CPE, MgO is good acid-acceptor, vulcanization accelerator.
As acid-acceptor, vulcanization accelerator, MgO plays vital effect to Vulcanization Process of Rubber and vulcanizating glue physical performance, and its activity is crucial reference index.Particle diameter is less, and specific surface area is larger, and surface reaction activity is just higher, less on the mechanical property impact of sizing material, but its bad dispersibility in CPE and poor with the consistency of sizing material, and the easy moisture absorption while depositing.Therefore, to nano-MgO carry out modification with expectation obtain the auxiliary sulfuration of having of CPE special use promoter action, good dispersity, good and be difficult for the efficient MgO composition of the moisture absorption with sizing material consistency.
Compound rubber master batch had not only been conducive to environmental protection but also can conveniently feed intake precisely (reduce flying upward of powder, and the secondary pollution to product), guaranteed the accuracy of formula.Also can improve its dispersion effect in sizing material, improve and stabilized product quality.The pre-dispersed method providing due to prior art often needs a kind of thermoplastic polymer of polarity as pre-dispersed matrix, this just makes when pre-dispersed MgO and rubber mix, between the polar polymer that existence is introduced and rubber matrix, the poor problem of consistency, also can cause the rising of elastomeric material hardness simultaneously.This pre-dispersed method also causes the cost of the MgO that is finally applied to rubber also to have rising by a relatively large margin, because its preparation process is more complicated.Finally, due in disperseing the process of MgO pre-composition, still require the melting temperature of rubber higher, this remains the threat of oxidative degradation to the rubber that contains two keys.
[summary of the invention]
The object of the invention is: propose a kind of easy method that is easy to dispersed nano-MgO in industrialized polymkeric substance.This compound rubber master batch for CPE can play well auxiliary sulfuration promoter action, good dispersity, good and be difficult for the moisture absorption with sizing material consistency, said composition, except having the function of traditional MgO, can also be improved the processing characteristics of CPE rubber unvulcanizate and the ageing-resistant performance of cross-linked rubber.
The preparation method of the compound rubber master batch of nano-MgO/polymkeric substance the present invention relates to, its operation steps is as follows: (1) is uniformly mixed dispersion agent, nano-MgO, emulsifying agent and makes water miscible liquid in water, in this water miscible liquid, the mass concentration of dispersion agent is 0.2%～5%, the mass concentration of nano-MgO is 15%～40%:(2) polymer emulsion is mixed with water miscible liquid, the consumption of dispersion agent is 2%～10% of the dry state mixture weight that finally obtains, and the consumption of nano-MgO is 20%～80% of the dry state mixture weight that finally obtains; (3) flocculant solution is joined in polymer emulsion and water emulsion mixture, stir flocculation, obtain coprecipitated thing; (4) wash coprecipitated thing with water, remove flocculation agent; (5) coprecipitated thing drying, obtains the compound rubber master batch of nano-MgO/polymkeric substance.
The polymer emulsion that the present invention is used, as nature rubber latex, SBR emulsion, neoprene latex, acrylonitrile-butadiene rubber latex, polyvinyl chloride emulsion, ethylene-vinyl acetate emulsion, methyl vinyl silicone rubber emulsion, carboxy nitrile rubber emulsion or polyacrylate dispersion.
The dispersion agent that the present invention is used, as terephthalic acid calcium, terephthalic acid magnesium, terephthalic acid copper, terephthalic acid aluminium, terephthalic acid zinc, terephthalic acid lanthanum, terephthalic acid cerium, calcium phthalate, magnesium phthalate, phthalic acid copper, phthalic acid aluminium, zinc phthalate, m-phthalic acid calcium, m-phthalic acid magnesium, m-phthalic acid copper, m-phthalic acid aluminium, m-phthalic acid zinc etc.
The emulsifying agent that the present invention is used, as tween-80, Xylo-Mucine, carboxymethyl cellulose, Witco 1298 Soft Acid, Sodium dodecylbenzene sulfonate, sorbitan fatty acid ester, polyoxyethylene carboxylate etc.
The flocculation agent that the present invention is used, as calcium chloride water, sodium chloride aqueous solution, potassium chloride solution, dilute sulfuric acid aqueous solution, diluted hydrochloric acid aqueous solution or diluted nitric acid aqueous solution.
The drying temperature of the compound rubber master batch of nano-MgO/polymkeric substance of the present invention is at 50～120 ℃.
By method provided by the invention, prepare the compound rubber master batch of nano-MgO/polymkeric substance, with existing pre-dispersed method, compare, method is easy, is easy to industrialization.Can directly in the final stage of latex polymerization production polymkeric substance, be implemented.Because do not need high temperature hybrid process, so the oxidative degradation problem when considering rubber high temperature hybrid process.
Mixture rubber master batch prepared by the present invention can join in CPE the manufacture for electric wire.Compare with magnesium oxide, this compound rubber master batch not only have auxiliary sulfuration promoter action, good dispersity, good with sizing material consistency, be difficult for the moisture absorption, and can also improve the processing characteristics of CPE rubber unvulcanizate and the ageing-resistant performance of cross-linked rubber.
[embodiment]
The embodiment of the compound rubber master batch of nano-MgO/polymkeric substance of the present invention is below provided.
Embodiment 1
2 parts of dispersion agent terephthalic acid calcium, 150 parts of nano-MgOs, 0.3 part of tween-80 are joined in the water of 983 weight parts, open and stir until form water miscible liquid.500 parts of the styrene butadiene rubber latexes of above-mentioned 1000 parts of water miscible liquids and solid content 20% are mixed, at room temperature stir 1 hour, then 10% calcium chloride water is joined in mixture to system De-emulsification flocculent.With clear water washing 3 times, at 100 ℃, be dried 6 hours, obtain the compound rubber master batch of nano-MgO/styrene-butadiene rubber(SBR), wherein nano-MgO content is about 60%.
Embodiment 2
10 parts, dispersion agent terephthalic acid zinc, 200 parts of nano-MgOs, 0.5 part of Xylo-Mucine are joined in the water of 790 weight parts, open and stir until form water miscible liquid.400 parts, the paracril latex of above-mentioned 1000 parts of water miscible liquids and solid content 25% is mixed, at room temperature stir 1 hour, then diluted hydrochloric acid aqueous solution is joined in mixture to system De-emulsification flocculent.With clear water washing 3 times, at 80 ℃, be dried 12 hours, obtain the compound rubber master batch of nano-MgO/paracril, wherein nano-MgO content is about 64.5%.
Embodiment 3
20 parts, dispersion agent m-phthalic acid magnesium, 300 parts of nano-MgOs, 0.5 part of tween-80 are joined in the water of 680 weight parts, open and stir until form water miscible liquid.125 parts, the carboxy nitrile rubber latex of above-mentioned 1000 parts of water miscible liquids and solid content 40% is mixed, at room temperature stir 1 hour, then sodium-chlor and dilute sulfuric acid aqueous solution are joined in mixture to system De-emulsification flocculent.With clear water washing 3 times, at 100 ℃, be dried 8 hours, obtain the compound rubber master batch of nano-MgO/carboxy nitrile rubber, wherein nano-MgO content is about 81%.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, without departing from the inventive concept of the premise; can also make some improvements and modifications, these improvements and modifications also should be considered within the scope of protection of the present invention.
Claims (5)
1. the preparation method of the compound rubber master batch of nano-MgO/polymkeric substance, its operation steps is as follows:
(1) dispersion agent, nano-MgO, emulsifying agent are uniformly mixed and make water miscible liquid in water, in this water miscible liquid, the mass concentration of dispersion agent is 0.2%～5%, and the mass concentration of nano-MgO is 15%～50%;
(2) polymer emulsion is mixed with water miscible liquid, the consumption of dispersion agent is 0.1%～5% of the dry state mixture weight that finally obtains, and the consumption of nano-MgO is 40%～85% of the dry state mixture weight that finally obtains;
(3) flocculant solution is joined in polymer emulsion and water emulsion mixture, stir flocculation, obtain coprecipitated thing;
(4) wash coprecipitated thing with water, remove flocculation agent;
(5) coprecipitated thing drying, obtains the compound rubber master batch of nano-MgO/polymkeric substance.
2. the preparation method of the compound rubber master batch of nano-MgO/polymkeric substance according to claim 1, is characterized in that: polymer emulsion is nature rubber latex, SBR emulsion, neoprene latex, acrylonitrile-butadiene rubber latex, polyvinyl chloride emulsion, ethylene-vinyl acetate emulsion, methyl vinyl silicone rubber emulsion, carboxy nitrile rubber emulsion or polyacrylate dispersion.
3. the preparation method of the compound rubber master batch of nano-MgO/polymkeric substance according to claim 1, is characterized in that: dispersion agent is terephthalic acid calcium, terephthalic acid magnesium, terephthalic acid copper, terephthalic acid aluminium, terephthalic acid zinc, terephthalic acid lanthanum, terephthalic acid cerium, calcium phthalate, magnesium phthalate, phthalic acid copper, phthalic acid aluminium, zinc phthalate, m-phthalic acid calcium, m-phthalic acid magnesium, m-phthalic acid copper, m-phthalic acid aluminium, m-phthalic acid zinc etc.
4. the preparation method of the compound rubber master batch of nano-MgO/polymkeric substance according to claim 1, is characterized in that: emulsifying agent is tween-80, Xylo-Mucine, carboxymethyl cellulose, Witco 1298 Soft Acid, Sodium dodecylbenzene sulfonate, sorbitan fatty acid ester, polyoxyethylene carboxylate etc.
5. the preparation method of the compound rubber master batch of nano-MgO/polymkeric substance according to claim 1, is characterized in that: flocculation agent is calcium chloride water, sodium chloride aqueous solution, potassium chloride solution, dilute sulfuric acid aqueous solution, diluted hydrochloric acid aqueous solution or diluted nitric acid aqueous solution.6, the preparation method of the compound rubber master batch of nano-MgO/polymkeric substance according to claim 1, is characterized in that: the drying temperature of compound rubber master batch is at 50～120 ℃.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111777774A (en) * | 2020-07-16 | 2020-10-16 | 株洲安宝麟锋新材料有限公司 | Acid-free preparation method of wet mixing rubber material |
| CN112875749A (en) * | 2021-02-25 | 2021-06-01 | 江苏爱特恩高分子材料有限公司 | Method for preparing high-dispersion titanium dioxide by recycling alkali-reduced wastewater |
| CN112919684A (en) * | 2021-03-01 | 2021-06-08 | 江苏爱特恩高分子材料有限公司 | Method for preparing ultra-dispersed titanium dioxide by recycling alkali-reduction wastewater resources |
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| CN1358787A (en) * | 2000-12-12 | 2002-07-17 | 海尔科化工程塑料国家工程研究中心有限公司 | Nano ridigity modiifying agent and preparation method |
| CN101115785A (en) * | 2005-02-03 | 2008-01-30 | 株式会社普利司通 | Method for producing rubber-filler master batch |
| JP2011256373A (en) * | 2010-05-11 | 2011-12-22 | Sumitomo Rubber Ind Ltd | Composite and method of manufacturing the same |
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- 2013-10-17 CN CN201310485979.1A patent/CN103627039A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1358787A (en) * | 2000-12-12 | 2002-07-17 | 海尔科化工程塑料国家工程研究中心有限公司 | Nano ridigity modiifying agent and preparation method |
| CN101115785A (en) * | 2005-02-03 | 2008-01-30 | 株式会社普利司通 | Method for producing rubber-filler master batch |
| JP2011256373A (en) * | 2010-05-11 | 2011-12-22 | Sumitomo Rubber Ind Ltd | Composite and method of manufacturing the same |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111777774A (en) * | 2020-07-16 | 2020-10-16 | 株洲安宝麟锋新材料有限公司 | Acid-free preparation method of wet mixing rubber material |
| CN112875749A (en) * | 2021-02-25 | 2021-06-01 | 江苏爱特恩高分子材料有限公司 | Method for preparing high-dispersion titanium dioxide by recycling alkali-reduced wastewater |
| CN112919684A (en) * | 2021-03-01 | 2021-06-08 | 江苏爱特恩高分子材料有限公司 | Method for preparing ultra-dispersed titanium dioxide by recycling alkali-reduction wastewater resources |
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Application publication date: 20140312 |