CN1206268C - Method for preparing powdered rubber in stuffing type with extra fine calcium carbonate - Google Patents
Method for preparing powdered rubber in stuffing type with extra fine calcium carbonate Download PDFInfo
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- CN1206268C CN1206268C CN 02152078 CN02152078A CN1206268C CN 1206268 C CN1206268 C CN 1206268C CN 02152078 CN02152078 CN 02152078 CN 02152078 A CN02152078 A CN 02152078A CN 1206268 C CN1206268 C CN 1206268C
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Abstract
The present invention provides a preparation method of filling type powdered rubber of superfine calcium carbonate. The preparation method comprises the following steps: mixing the components in the following proportions measured by rubber latex: 100 portions by weight of dry rubber, 0 to 250 portions by weight of superfine calcium carbonate powder, 0.2 to 8.0 portions by weight of surfactant, 0 to 70 portions by weight of operating oil, 0.5 to 3.0 portions by weight of antioxidant, 2.5 to 6.0 portions by weight of emulsifier, 2.0 to 5.0 portions by weight of coagulant and 300 to 2000 portions by weight of deionized water; emulsifying the superfine calcium carbonate powder; heating and coagulating latex; carrying out the post-treatment of coagulated matter. The powdered rubber prepared by the method of the present invention has the advantages of small addition of a coating agent, favorable coating effect and stable, reliable and convenient powdering technology; the powder preparation rate of the filling type powdered rubber of superfine calcium carbonate is above 99%; the particle size distribution of the prepared filling type powdered rubber of superfine calcium carbonate can be controlled by regulating coagulation conditions; a prepared product has the advantages of favorable physical and mechanical properties, no flying of dust, high fluidity and stable storage.
Description
The present invention relates to the preparation field of powdered rubber (Powdered Rubber), particularly a kind of method for preparing calcium carbonate superfine powder filled powder rubber (Ultra-fine calcium carbonate extendedpowdered rubber).
Background technology
Powdered rubber general reference particle diameter is less than 1.0mm, rubber particle with good fluidity, it is a kind of novel rubber raw materials, be used for substituting traditional niggerhead, adopt Special Equipment with inject, extrude, working method such as mold pressing or adopt existing rubber tooling to be processed into the cross-linked rubber goods with traditional working method, have the energy-and time-economizing, reduce facility investment, reduce production costs, help production process automatization control, improve mixing quality, reduce labor intensity, unusual effect such as non-environmental-pollution.The appearance of powdered rubber has been reformed traditional rubber processing with application, sets up brand-new technological process for rubber industry, can create higher economic benefit and social benefit.
Compare with traditional niggerhead, powdered rubber especially filled powder rubber has plurality of advantages; For example, the glue process of cutting that does not have piece glue with the technological process of powdered rubber processing cross-linked rubber, shorten mixing time and reduced power consumption, filler disperses more even in rubber matrix, when using some difficult mixing rubber such as chloroprene rubber, have the memory of shorter thermal history and heat still less, therefore can relax incipient scorch trend; In addition, the powdered rubber batching directly sends into forcing machine or the cross-linked rubber goods are produced in direct mold pressing, and this technological process can be exempted Banbury mixer and mill operation; Because filler is sneaked in the rubber in advance, so can eliminate flying upward of filler dust, makes surrounding environment more clean.
At present, the method for preparing powdered rubber mainly contains: mechanical crushing method, spray-drying process, cohesion coprecipitation method etc.Preceding two kinds of method equipment complexity, energy consumption is big, production cost height, and cohesion coprecipitation method processing unit is simple relatively, technological process is easy to control, and energy consumption is low, and rubber latex is easy to mix with the powder uniform filling, condenses can obtain filled powder rubber after coprecipitated.
The gordian technique for preparing powdered rubber with the cohesion coprecipitation method is a coating.The effect of coating is the surface coverage thin film at the powdered rubber particle, thereby rubber particles is isolated, and therefore requires coating that good film-forming properties must be arranged.At first, preparing the used separant of powdered rubber with the cohesion coprecipitation method is inorganic powder such as water glass, silica, white carbon black, carbon black, lime carbonate, talcum powder etc., but isolation effect is undesirable.The coating starch xanthate of the exploitation same period has good coating buffer action owing to can crosslinked action take place to rubber particles, but prepared powdered rubber can mouldy, variable color and aging in storage process.Developed water-soluble polymers or poly-dielectric medium coating such as polyvinyl alcohol, polyacrylic acid sodium salt, modified-cellulose etc. afterwards, but this class coating poor water resistance is incompatible with rubber matrix, thus bigger to the performance impact of powdered rubber cross-linked rubber goods.Preparing powdered rubber with macromolecule resin as coating is the new technology that development in recent years is got up.Owing to good film-forming properties is arranged on the rubber particles surface and certain consistency is arranged with rubber matrix by molecular designing synthetic macromolecule resin, so not only rubber particles is had significant coating isolation effect, and the detrimental effect of product property is greatly reduced.
Calcium carbonate superfine powder is a rubber industry packing strengthening agent commonly used, is particularly useful for making higher white of requirement of strength or colorful rubber goods, and it is lower and have a strengthening action to fill cost.But because the particle of calcium carbonate superfine powder is very thin, with rubber mixing process in be difficult for sneaking into rubber matrix, dispersion effect after sneaking into is relatively poor, and the dust from flying of sneaking in the process is bigger, production environment and surrounding environment there is serious pollution, with calcium carbonate superfine powder filled powder rubber no white dust from flying in accumulating, the course of processing of cohesion coprecipitation method preparation, be a kind of environment-friendly rubber raw material therefore.
When preparing the calcium carbonate superfine powder filled powder rubber with macromolecule resin as coating, macromolecule resin and calcium carbonate superfine powder are isolated the coating of rubber particles synergy, so products therefrom has good flowability.But macromolecule resin has cohesive action to the calcium carbonate superfine powder particle, make part calcium carbonate superfine powder particle form particle diameter bigger be difficult to the dispersive granule, on the other hand, macromolecule resin is non-rubber material after all, and the effect of the two has adverse influence to mechanical properties of vulcanizate.
Summary of the invention
The objective of the invention is to overcome have now utilizes macromolecule resin to prepare the deficiency of calcium carbonate superfine powder filled powder rubber as coating, a kind of powdered rubber that is suitable for preparing the calcium carbonate superfine powder filled-type of four glue kinds is provided, comprises the method for powder natural rubber, powder styrene butadiene rubber, Powdered acrylonitrile-butadiene rubber, powdered polychloroprene rubber.
Purpose of the present invention is achieved through the following technical solutions: the preparation method of this calcium carbonate superfine powder filled powder rubber comprises the steps:
(1) gets the raw materials ready
Measure contained dried glue by latex: calcium carbonate superfine powder: tensio-active agent: process oil: anti-aging agent: fatty acid alkali metal salt emulsifying agent: flocculation agent: the weight ratio of deionized water is 100: 0～250: 0.2～8.0: 0～70: 0.5～3.0: 2.5～6.0: 2.0～5.0: 300～2000 proportion ingredient;
(2) emulsification of calcium carbonate superfine powder
The water and the tensio-active agent that add metering in the tempering tank that agitator is housed after stirring, add the calcium carbonate superfine powder of metering in stirring, continued to mix 5～30 minutes, obtain calcium carbonate superfine powder suspension;
(3) thermal treatment of latex
The deionized water that in latex, adds metering, the solid content of regulating latex is 5～25%, in stirring, above-mentioned calcium carbonate superfine powder suspension is joined in the latex, heating in water bath system to 60 after mixing～95 ℃, the concentration that adds metering is 5% the fatty acid alkali metal salt emulsifying agent and the hot water suspension of anti-aging agent, if contain process oil in the prescription, adds the process oil of metering in stirring, continue to stir 10～30 minutes, constitute the powdered system;
(4) agglomeration process
Under high-speed stirring, add the flocculation agent aqueous solution of metering in the powdered system after the thermal treatment of above-mentioned process, the cohesion of system generation powdery is coprecipitated, keeps 70～90 ℃ of system temperatures, and slaking is discharge after 10～30 minutes;
(5) aftertreatment of condensation product
Condensation product is entered in industrial centrifugal machine or other dewatering units, with tap water washing, dehydration three to four times, last centrifuge dehydration to material water ratio is 30～50%, and in the vibratory screening apparatus of the pulverizer of being with rake teeth, sieve, the wet particle product of gained is dried to moisture content below 1% with 60～130 ℃ in drying plant such as ebullated bed, pneumatic dryer, obtaining particle diameter is the calcium carbonate superfine powder filled powder rubber of 0.2～1.0mm.
Described latex is natural rubber (NR) latex, styrene-butadiene rubber(SBR) (SBR) latex, paracril (NBR) latex or chloroprene rubber (CR) latex.
Described calcium carbonate superfine powder is Bai Yanhua NA, Bai Yanhua DD, and Bai Yanhua CC-R, its loading level are 0～250 part.
Described process oil is rubber industry process oil commonly used or extending oil, as: machine oil, Viscotrol C, aromatic hydrocarbon oil, third fractional oil, high sulfone wet goods.
Described tensio-active agent is nonionic surface active agent or aniorfic surfactant, as: dodecyl Soxylat A 25-7, octadecyl Soxylat A 25-7, octyl phenyl Soxylat A 25-7, nonyl phenyl Soxylat A 25-7, polysorbas20, polysorbate60, tween 80, polyvinyl alcohol, peregal " O ", lauric acid sodium sulfate, sodium oleyl sulfate, ammonium laurate, potassium laurate etc.; Effect nonionic surface active agent preferably wherein.
Described fatty acid alkali metal salt emulsifying agent is for being dissolved in synthetic fatty acid potassium, the sodium fat synthesis of hot water below 90 ℃, as: potassium stearate, sodium stearate, potassium oleate, sodium oleate etc., mentioned emulsifier can 60～90 ℃ down with flocculation agent in calcium, magnesium, aluminum ion generate water-fast divalent metal salt on the spot, the latter plays the coating buffer action to rubber particles.
The latex solid content of the powdered system in the thermal treatment of described step (three) latex is 7～15%.
Described anti-aging agent is the general anti-aging agent of rubber, as antioxidant 4010, antioxidant 4010NA, antioxidant 264, and anti-aging agent 2264 etc.
Described flocculation agent is the mixture of aluminum chloride, aluminum nitrate, Tai-Ace S 150, calcium chloride, nitrocalcite, magnesium chloride, magnesium nitrate or above-mentioned substance and hydrochloric acid, sulfuric acid, acetate.
The optimum drying temperature range of wet particle product is 70～120 ℃ in the aftertreatment of described step (five) condensation product.
Action principle of the present invention is: the calcium carbonate superfine powder tensio-active agent that this preparation method uses is nonionic surface active agent, and used coating is a fatty acid alkali metal salt; Compare with anion surfactant, a little less than the surface adsorption effect of nonionic surface active agent to the calcium carbonate superfine powder particle, used water is washed away it from powdered rubber; Calcium carbonate superfine powder has certain buffer action to the powdered rubber particle, in the powdered system, add the small amounts of water soluble fatty acid alkali metal salt, then with water-soluble divalent metal salt cohesion, fatty acid alkali metal salt generates insoluble divalent metal salt immediately, the latter be covered in the macroscopic particle that rubber and calcium carbonate superfine powder constitute the surface and with its isolation; Calcium carbonate superfine powder filled powder rubber particle through washing is substantially free of tensio-active agent, the content of lipid acid divalent metal salt also seldom, therefore the calcium carbonate superfine powder filled powder rubber with this technology preparation is very pure, thereby the physical and mechanical properties that has guaranteed its cross-linked rubber is not damaged by impurity.
The present invention compared with prior art has following outstanding advantage:
1) adopt of the present inventionly when generating lipid acid divalent metal salt coating technology on the spot and preparing the calcium carbonate superfine powder filled powder rubber, the coating add-on is less, and covered effect is good, and the powdered process stabilizing is reliable, easy;
2) adopt the powder formation rate of pulverizing technology calcium carbonate superfine powder filled powder rubber of the present invention to reach more than 99%;
3) adopt the size distribution of the prepared calcium carbonate superfine powder filled powder rubber of the present invention to control, can prepare the calcium carbonate superfine powder filled powder rubber of multiple size distribution by customer requirements by regulating coherence condition;
4) adopt the prepared calcium carbonate superfine powder filled powder rubber of the present invention not have dust from flying, good fluidity, stable storing.
5) adopt the physical and mechanical properties of the prepared calcium carbonate superfine powder filled powder rubber cross-linked rubber of the present invention good, be significantly higher than the cross-linked rubber of corresponding niggerhead/calcium carbonate superfine powder through mechanically milling gained rubber unvulcanizate, process easy, do not have filler grain to fly upward in the mixing process, mixing environment more cleans.
Embodiment
Below by embodiment the present invention is done further concrete description, but embodiments of the present invention are not limited thereto.
Embodiment
(1) gets the raw materials ready
Get the raw materials ready by the proportioning in the table 1.
The reagent dosage of table 1 embodiment and processing condition
(2) emulsification of calcium carbonate superfine powder
Press prescription listed in the table 1, add 50 kg water and tensio-active agent OP-10 in 100 liters of steel basins, middling speed stirs, after treating that OP-10 all dissolves, in stirring, add calcium carbonate superfine powder, continue to stir 10～30 minutes, make calcium carbonate superfine powder and surfactant soln form uniform suspension.
(3) thermal treatment of latex
The deionized water that in latex, adds metering, the solid content of regulating latex is 7～15%, in stirring, above-mentioned calcium carbonate superfine powder suspension is joined in the latex, heating in water bath system to 70 after mixing～90 ℃, press prescription listed in the table 1, the concentration that adds metering is 5% the fatty acid alkali metal salt emulsifying agent and the hot water suspension of anti-aging agent, continues to stir 10～30 minutes, constitutes the powdered system.
(4) agglomeration process
Press prescription listed in the table 1, the concentration that adds metering in above-mentioned powdered system is 10% calcium chloride water, (600～1000rpm), after the system for the treatment of all was condensed into particle, the reduction stirring velocity was to middle stirring at low speed (300～500rpm) for vigorous stirring simultaneously.Slaking is discharge after 10～30 minutes.Keeping system temperature in this process is 70～90 ℃.
(5) aftertreatment of condensation product
Condensation product is entered in the industrial centrifugal machine, with tap water washing, dehydration three to four times, last centrifuge dehydration to material water ratio is 30～50%, and in band rake teeth vibratory screening apparatus, sieve, the wet particle product of gained is dried to moisture content below 1% under 70～120 ℃, obtain the calcium carbonate superfine powder filled powder rubber of suitable particle diameter, its size distribution is as shown in table 2, and physical and mechanical properties is as shown in table 3; By table 2 as seen, can prepare the powdered rubber that particle diameter meets industrial requirements by the present invention, by table 3 as seen, the physical and mechanical properties of above-mentioned powdered rubber is good.
The size distribution of table 2 calcium carbonate superfine powder filled powder rubber
Sequence number NO.1 NO.2 NO.3 NO.4 NO.5 NO.6 NO.7 NO.8
Rubber kind NR NR SBR SBR NBR NBR CR CR
≤0.45mm(％) 10.5 36.3 20.3 52.6 55.6 65.4 45.6 55.8
≤0.9mm(％) 98.2 99.3 98.6 99.8 100 100 100 100
＞0.9mm(％) 1.8 0.7 1.4 0.2 0 0 0 0
The physical and mechanical properties of table 3 calcium carbonate superfine powder filled powder rubber
NO. NO. NO. NO. NO. NO. NO. NO.
Sequence number
1 2 3 4 5 6 7 8
Rubber kind NR NR SBR SBR NBR NBR CR CR
Vulkameter t
10, min
6.0 5.5 5.0 5.0 6.0 6.0 10.0 9.6
(150℃)
Vulkameter t
90, min
8.0 8.0 7.5 7.5 9.0 9.0 22.5 21.6
(150℃)
Tensile strength, MPa 18.2 13.4 11.5 10.2 14.7 10.3 15.6 14.8
Tensile yield, % 610 500 660 480 660 430 550 540
100% stress at definite elongation,
2.5 3.8 2.3 3.1 2.6 4.8 1.3 1.5
MPa
300% stress at definite elongation,
5.8 7.2 4.2 4.8 5.6 7.0 5.6 5.8
MPa
Hardness (Shao A) spends 66 76 73 81 64 75 55 57
Setafter break, % 58 60 42 61 27 30 36 40
Tear strength, N/m 77.5 73.4 28 32 30 32.2 32.5 33.6
Annotate:
1. the sulfurizing formula of calcium carbonate superfine powder filled-type powder natural rubber: rubber (not containing calcium carbonate superfine powder) 100, calcium carbonate superfine powder variable, zinc oxide 5, stearic acid 2, sulphur 2.25, accelerator NS 0.7.
2. the sulfurizing formula of calcium carbonate superfine powder filled-type powder styrene butadiene rubber: rubber (not containing calcium carbonate superfine powder) 100, calcium carbonate superfine powder variable, zinc oxide 3, stearic acid 1, sulphur 1.75, accelerator NS 1.0.
3. the sulfurizing formula of calcium carbonate superfine powder filled-type Powdered acrylonitrile-butadiene rubber: rubber (not containing calcium carbonate superfine powder) 100, calcium carbonate superfine powder variable, zinc oxide 4, stearic acid 1.5, sulphur 1.75, altax 1.5, promotor T.T 0.2.
4. the sulfurizing formula of calcium carbonate superfine powder filled-type powdered polychloroprene rubber: rubber (not containing calcium carbonate superfine powder) 100, calcium carbonate superfine powder variable, zinc oxide 5, magnesium oxide 4, stearic acid 0.5.
Claims (10)
1, a kind of preparation method of calcium carbonate superfine powder filled powder rubber is characterized in that comprising the steps:
(1) gets the raw materials ready
Measure contained dried glue by latex: calcium carbonate superfine powder: tensio-active agent: process oil: anti-aging agent: fatty acid alkali metal salt emulsifying agent: flocculation agent: the weight ratio of deionized water is 100: 100～250: 0.2～8.0: 0～70: 0.5～3.0: 2.5～6.0: 2.0～5.0: 300～2000 proportion ingredient;
(2) emulsification of calcium carbonate superfine powder
The water and the tensio-active agent that add metering in the tempering tank that agitator is housed after stirring, add the calcium carbonate superfine powder of metering in stirring, continued to mix 5～30 minutes, obtain calcium carbonate superfine powder suspension;
(3) thermal treatment of latex
The deionized water that in latex, adds metering, the solid content of regulating latex is 7～15%, in stirring, above-mentioned calcium carbonate superfine powder suspension is joined in the latex, heating in water bath system to 60 after mixing～95 ℃, the concentration that adds metering is 5% the fatty acid alkali metal salt emulsifying agent and the hot water suspension of anti-aging agent, continue to stir 10～30 minutes, constitute the powdered system;
(4) agglomeration process
Under high-speed stirring, add the flocculation agent aqueous solution of metering in the powdered system after the thermal treatment of above-mentioned process, the cohesion of system generation powdery is coprecipitated, keeps 70～90 ℃ of system temperatures, and slaking is discharge after 10～30 minutes;
(5) aftertreatment of condensation product
Condensation product is entered in industrial centrifugal machine or other dewatering units, with tap water washing, dehydration three to four times, last centrifuge dehydration to material water ratio is 30～50%, and in the vibratory screening apparatus of the pulverizer of being with rake teeth, sieve, the wet particle product of gained is dried to moisture content below 1% with 60～130 ℃ in drying plant, obtaining particle diameter is the calcium carbonate superfine powder filled powder rubber of 0.2～1.0mm.
2, the preparation method of calcium carbonate superfine powder filled powder rubber according to claim 1 is characterized in that: described latex is natural rubber latex, styrene butadiene rubber latex, paracril latex or chloroprene rubber latex.
3, the preparation method of calcium carbonate superfine powder filled powder rubber according to claim 1 is characterized in that: described calcium carbonate superfine powder is Bai Yanhua NA, Bai Yanhua DD, Bai Yanhua CC-R.
4, the preparation method of calcium carbonate superfine powder filled powder rubber according to claim 1 is characterized in that: described process oil is rubber industry process oil commonly used or extending oil.
5, the preparation method of calcium carbonate superfine powder filled powder rubber according to claim 1 is characterized in that: described tensio-active agent is nonionic surface active agent or aniorfic surfactant.
6, the preparation method of calcium carbonate superfine powder filled powder rubber according to claim 1 is characterized in that: described fatty acid alkali metal salt emulsifying agent is for being dissolved in synthetic fatty acid potassium, the sodium fat synthesis of hot water below 90 ℃.
7, the preparation method of calcium carbonate superfine powder filled powder rubber according to claim 1 is characterized in that: the latex solid content of the powdered system in the thermal treatment of described step (three) latex is 7～15%.
8, the preparation method of calcium carbonate superfine powder filled powder rubber according to claim 1 is characterized in that: described anti-aging agent is the general anti-aging agent of rubber.
9, the preparation method of calcium carbonate superfine powder filled powder rubber according to claim 1 is characterized in that: described flocculation agent is the mixture of aluminum chloride, aluminum nitrate, Tai-Ace S 150, calcium chloride, nitrocalcite, magnesium chloride, magnesium nitrate or above-mentioned substance and hydrochloric acid, sulfuric acid, acetate.
10, the preparation method of calcium carbonate superfine powder filled powder rubber according to claim 1 is characterized in that: the optimum drying temperature range of wet particle product is 70～120 ℃ in the aftertreatment of described step (five) condensation product.
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| CN 02152078 CN1206268C (en) | 2002-11-29 | 2002-11-29 | Method for preparing powdered rubber in stuffing type with extra fine calcium carbonate |
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| CN 02152078 CN1206268C (en) | 2002-11-29 | 2002-11-29 | Method for preparing powdered rubber in stuffing type with extra fine calcium carbonate |
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| CN1415648A CN1415648A (en) | 2003-05-07 |
| CN1206268C true CN1206268C (en) | 2005-06-15 |
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1300223C (en) * | 2004-06-02 | 2007-02-14 | 中国石油天然气股份有限公司 | Method for producing powdered rubber |
| CN100417681C (en) * | 2004-10-27 | 2008-09-10 | 中国石油化工股份有限公司 | High-strength wholly-vulcanised polyolefinic thermoplastic elastomer and its preparation method |
| CN102653605B (en) * | 2012-05-11 | 2013-07-24 | 云南省热带作物科学研究所 | Method for preparing powdered natural rubber by fresh latex |
| CN104211837B (en) * | 2014-07-15 | 2016-05-04 | 华南理工大学 | A kind of preparation method of carbon black extended SBR rubber master batch |
| CN106280142B (en) * | 2016-08-25 | 2018-12-11 | 浙江孚诺林化工新材料有限公司 | A kind of preparation method of 26 type fluorubber mixture of powder |
| CN107522909A (en) * | 2017-09-25 | 2017-12-29 | 安徽依采妮纤维材料科技有限公司 | A kind of preparation method of calcium carbonate superfine powder modified rubber material |
| CN107619508A (en) * | 2017-09-25 | 2018-01-23 | 芜湖凯奥尔环保科技有限公司 | A kind of rubber composite |
| CN107488280A (en) * | 2017-09-30 | 2017-12-19 | 广西华洋矿源材料有限公司 | A kind of preparation method of calcium carbonate superfine powder and rubber composite |
| CN111909398B (en) * | 2020-07-27 | 2022-08-19 | 浙江天晨胶业股份有限公司 | Powdered styrene butadiene rubber and preparation method thereof |
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