CN104893024B - The method that natural emulsion is blended with precipitated silica - Google Patents
The method that natural emulsion is blended with precipitated silica Download PDFInfo
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- CN104893024B CN104893024B CN201510366166.XA CN201510366166A CN104893024B CN 104893024 B CN104893024 B CN 104893024B CN 201510366166 A CN201510366166 A CN 201510366166A CN 104893024 B CN104893024 B CN 104893024B
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- natural emulsion
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/07—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media from polymer solutions
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
- Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction
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Abstract
The invention provides a kind of method that natural emulsion is blended with silica slurry, the method comprises the following steps: under normal temperature and pressure conditions, in natural emulsion aqueous solution, it is sequentially added into organic acid while stirring, it is stirred, it is subsequently adding emulsifying agent, proceeding stirring, maintaining solution ph in all whipping process is 5.5 7.0；Be subsequently adding silica slurry to be mixed and stirred for, in whipping process by add alkali-metal hydroxide solution maintenance system pH be 9 10.Liquid silica is mixed by the method with natural emulsion, makes silicon dioxide dispersibility and uniformity in rubber be improved the tire drag made little, and consumes less energy in mixing process.
Description
Technical field
The invention belongs to field of rubber preparation, relate in particular to the method being blended of natural emulsion and silica slurry.
Background technology
Precipitated hydrated silica mode of appearance is powdery, microballon, graininess, and also known as white carbon, due to the requirement of energy-saving and emission-reduction Yu environmental protection, increasing white carbon is applied to rubber for tire industry.Silicon dioxide is mixing with natural gum and rubber polymer as filler, it is applied to tire and can reduce resistance to rolling, improve wet and slippery performance, thus make that automobile oil consumption is low, reduce waste gas discharge, and improve silicon dioxide and natural gum hybrid technique is the important channel improving rubber quality.
White carbon is applied in tire the filler as rubber can improve the wearability of goods, tear-resistant intensity and hardness, but prior art generally uses white carbon directly to mix with natural gum, because dry product white carbon and dry glue mixing dispersion are poor, the heat of goods is high, abrasion height, tearing strength is low, and the tire drag made is big, and consumes the more energy in mixing process.
CN102775618A discloses a kind of Wet smelting method preparing natural rubber/nanometer silicon dioxide rubber compound, it is characterized in that with caoutchouc latex, with Ludox or nano silicon the dispersion in water be primary raw material liquid-liquid uniformly mix composition wet refining system, in stirring, heating in water bath is warming up to wet refining temperature, constant temperature stirs, adding flocculating agent makes natural rubber condense coprecipitated formation natural rubber/nanometer silica composite with nano-silicon dioxide particle, the most i.e. obtains natural rubber/nanometer silicon dioxide rubber compound.
CN103554377A discloses a kind of preparation method being realized nano silicon cladding by mini-emulsion polymerization, relates to atom transfer radical polymerization and mini-emulsion polymerization technical field.Its preparation method is as follows: first prepare macromole evocating agent to modify monomer surface, removes solvent and catalyst, then uses ATRP method to prepare graft copolymer with bromated monomer and silane coupler；Utilizing the copolymer that said method prepares separately as co-stabilizer or silane coupler, for mini-emulsion polymerization, the final particle diameter narrow distribution for preparing, relatively stable latex particle also achieves the requirement that nano silicon is coated with.
CN101899128A discloses the silica microsphere modified poly acrylate composite emulsion of a kind of hollow nano and the preparation method of thin film, with polyacrylate resin as matrix, hollow nano silicon dioxide microsphere prepared by template is filler, uses the dispersion of coupling agent treatment, ultrasound wave, emulsion polymerization and coating process to prepare.
WO2014/038650A1 discloses a kind of silicon dioxide/butadiene-styrene rubber complex, it is obtained by composite emulsion, described composite emulsion prepares in the following way: mix to obtain mixture by the microdispersed silica dispersion that surfactant and mean diameter are below 1 μm, the butadiene-styrene rubber latex mixing being then polymerized with emulsion by described mixture.
“Is Latex Surface Charge an
Important Parameter for Foam Stabilization?" Sarah L. Kettlewell et.al, Langmuir, 2007,23,11381-11386, have studied the surface charge material impact to foam stability of latex, be investigated the oriented impact on latex foam of latex particle simultaneously.
Earlier patent application CN102634083A of the present inventor discloses a kind of method that natural emulsion is blended with silica slurry, the method includes: under normal temperature and pressure conditions, natural emulsion is mixed and stirred for silica slurry, during mixing, adds organic acid and emulsifying agent according to the dry glue weight of natural emulsion respectively with 1～the 6 ‰ of silicon dioxide dry matter weight sum.But, in the method, natural emulsion, silica slurry, organic acid and emulsifying agent are to be simultaneously introduced, and cause the mixing dispersion difference of the blend prepared still to be difficult to meet the application of some high requirement.Pass through to quote at this to be expressly incorporated herein by full content of this patent application.
This area needs a kind of natural emulsion that disclosure satisfy that higher application requirement and the blend method of silica slurry badly.
Summary of the invention
On the basis of it is an object of the invention to previously study, it is provided that a kind of blending technology method being applied to natural emulsion and the improvement of silica slurry.
The present inventor is through further investigation and lot of experiments, it is provided that following technical scheme.
On the one hand, the invention provides a kind of method that natural emulsion is blended with silica slurry, the method comprises the following steps:
(1) under normal temperature and pressure conditions, adding organic acid, be stirred, be subsequently adding emulsifying agent, proceed stirring while stirring in natural emulsion aqueous solution, maintaining natural emulsion pH value of water solution in aforementioned all whipping process is 5.5-7.0；With
(2) it is subsequently adding silica slurry to be mixed and stirred for, maintains whole system pH to be 9-10 by the alkali-metal hydroxide solution of addition in whipping process；
Wherein, the dry glue weight that total addition is natural emulsion of described organic acid and emulsifying agent and the 1～6 ‰ of silicon dioxide dry matter weight sum.
The form that described natural emulsion aqueous solution can also replace with natural emulsion uses as raw material.Described natural emulsion aqueous solution can use natural emulsion: water volume ratio is that 1:1-5:1 mixed preparing forms.
Preferably, described organic acid is formic acid, acetic acid or the organic acid with amino-substituent.It is highly preferred that described organic acid uses as an aqueous solution, the concentration of organic acid is 0.05-0.5mol/L.
The present inventor through research it was unexpectedly found that, by adding organic acid to natural emulsion solution (aqueous solution) under conditions of being 5.5-7.0 at pH value, can be to the modifying surface of natural emulsion, make it have surface polar groups, then emulsifying agent is added, the one end making emulsifier molecules is connected with latex by described polar group, when adding silica slurry, it is possible to make silica dioxide granule effectively scatter with latex.It addition, in step (2), be 9-10 by maintaining whole reaction system pH, whole co-mixing system can be made to maintain charge stable, effectively prevent the generation of heterogeneous flocculation.
In a particularly preferred embodiment, described in have the organic acid of amino-substituent be the organic acid shown in following formula:
R1For polar group, such as carboxyl, hydroxyl, acyl group, carbonyl, oxygen carbonyl, alkoxyl, R2For C1-C6 alkyl, such as methyl, ethyl, n-pro-pyl, isopropyl etc..
In a particularly preferred embodiment, described emulsifying agent is the emulsifying agent shown in following formula:
Wherein R is methyl or ethyl；N is the integer of 1-3；X is 3-8, preferably 4-6；Y is 20-180, preferably 30-100；Z is 10-100, preferably 20-60；Z-For SO3 -Or PO3 2-, M+For alkali metal cation or NH4 +。
The inventors discovered that, the use of described emulsifying agent can make silicon dioxide the most mixing with natural emulsion, and dispersibility is more preferable, and the elastomeric material obtained has excellent wearability, and its abrasion are less than 20cm3/ 1.61Km, breaking strength is more than 30MPa, can be applicable to the relevant industries such as high-level Tire production and high-level shoemaking.
Described emulsifying agent can be obtained by typical polymerization methods.
Additionally or alternatively, emulsifying agent can also is that following emulsifying agent, and this states emulsifying agent by making following monomer mixture copolymerization obtain, and described monomer mixture includes following monomer or is made up of following monomer: (a) 70-95mol% methacrylic acid monomer；(b) 3-15mol% ethylenically unsaturated carboxylic acids or its anhydride；Monomer shown in (c) 1-10mol% following formula I；Monomer shown in (d) 0.2-5mol% Formula Il:
Formula (I)
Formula (II)
Wherein, n is the integer of 4-8, preferably 3-5, R1And R2It is C1-C4 straight or branched alkyl independently of one another, preferably C1-C3 alkyl, more preferably methyl or ethyl.
Described ethylenically unsaturated carboxylic acids or its anhydride are preferably such as itaconic acid, fumaric acid, maleic acid etc., itaconic anhydride, maleic anhydride etc..
The preparation of this emulsifying agent can be carried out by the typical polymerization methods of this area.
The polymerization that polymerization can use this area conventional is carried out, such as polymerisation in bulk, polymerisation in solution, emulsion polymerization or suspension polymerisation.The compound of described formula (I) and (II) can be commercially available, such as, can be purchased from Fluka company, it is also possible to obtains with reference to low-polyacrylate synthetic method.
In the step (1) of the inventive method, adding the mixing time after organic acid can be 1-4h, and adding the mixing time after emulsifying agent can be 1-4h；The mixing time of step (2) can be 2-5h.
Preferably, in described natural emulsion, dry glue is 10: 3～13 with the weight ratio of dry in silica slurry.
Preferably, organic acid and the emulsifying agent weight of described addition is respectively the dry glue in described natural emulsion and 0.5 of the dry matter weight sum in described silicon dioxide～3 ‰ and 0.5～3 ‰.
Preferably, the viscosity of described silica slurry is 100～600cP, and described silicon dioxide is precipitated hydrated silica.
In another aspect of the present invention, additionally provide the natural emulsion and silica slurry blend obtained according to said method.
In another aspect of the present invention, additionally provide and use described blend glue to be dry mixed through what dehydration obtained.
In still another aspect of the invention, it is provided that a kind of rubber product, glue is dry mixed by mixing acquisition described in its use.
The gel content of described natural emulsion can be 30～60% part by weight.
The solid content of described silica slurry can be 15～30%, preferably 24～25%.Solid content is that in serosity, solid gross mass obtains divided by the quality of all components of composition serosity.
After described natural emulsion mixes with silica slurry stirring, it is also possible to include importing material in-tank-solidification, wash the organic acid in solidfied material with water, then remove moisture, the solidfied material after dehydration is dried.
Present invention also offers the elastomeric material obtained by blended method of the present invention.
Detailed description of the invention
Following example are in order to illustrate the present invention, but do not limit the scope of the invention.
The method of testing of abrasion: BS 903:Part A9；The method of testing of breaking strength: ASTM D 412-1998A；The method of testing of heat: ASTM D 623-1999；The method of testing of tearing strength: ISO 34-1.
Embodiment
1
By distyrenated phenol (693g, 1 equivalent) and (+)-2,3-Epoxy-1-propanol allyl ether (492g, 2 equivalents) add to rustless steel autoclave together with potassium hydroxide KOH (2.26g), by airtight for autoclave and be heated to 105 DEG C, when all of (+)-2,3-Epoxy-1-propanol allyl ether is depleted, reaction mass is cooled down, take out product, this product is addition compound product, is transferred to another autoclave and is heated to 105 DEG C by this addition compound product of 1677g (1 equivalent).Then in 3 hours, add oxirane (2023g, 15 equivalents), after all oxirane are depleted, reaction mass are cooled down and adds a small amount of hydrochloric acid and carrys out catalyst neutralisation, i.e. obtain the emulsifying agent according to the present invention after filtration, be labeled as emulsifying agent A.
Embodiment
2
Under normal temperature and pressure conditions, while stirring, in 10kg natural emulsion aqueous solution, add 28.8g formic acid (CH2O2), stirring 1.5h, be subsequently adding 28.8g emulsifying agent A, proceed stirring, stir 1h, maintaining natural emulsion pH value of water solution in aforementioned all whipping process is 6.5, wherein can be by controlling the pH value of the addition speed maintenance system of formic acid；It is subsequently adding 14.4kg silica slurry (solid content is 25%, viscosity 300cP), is mixed and stirred for, stir 3h, whole system pH should be maintained to be 9.5 by the dilute potassium hydroxide solution of addition in whipping process.After stirring, importing hopper solidification, it is 6.0～8.0 that the mixture water after solidification is rinsed 2～3 times to rinsing water outlet pH value, makes the organic acid in mixture remove completely, uses centrifuge unwatering, is dried this solid mixture and obtains glue is dry mixed.Glue is dry mixed mixing according to the method for standard ISO2393-2008, the mechanical and physical performance of test gained rubber product.The results are shown in Table 1.
Comparative example
1
This comparative example is the embodiment in CN102634083A.By 10kg natural emulsion (gel content 60% mass ratio) and 14.4kg silica slurry, (solid content is 25%, viscosity 300cP) add in the reactor with agitating device, it is separately added into 28.8g formic acid (CH2O2) and 28.8g cetyl trimethylammonium bromide (CTAB, white powder) simultaneously.After stirring, importing hopper solidification, it is 6.0～8.0 that the mixture water after solidification is rinsed 2～3 times to rinsing water outlet pH value, makes the organic acid in mixture remove completely, uses centrifuge unwatering, is dried this solid mixture and obtains glue is dry mixed.Glue is dry mixed mixing according to the method for standard ISO2393-2008, the mechanical and physical performance of test gained rubber product.The results are shown in Table 1.
Table 1: the mechanical and physical performance parameter of product
By the data in upper table it can be seen that the mechanical and physical performance of the final rubber product obtained according to the embodiment 2 of blend method of the present invention, in addition to raw holding the most quite, all other parameter indexs are significantly better than that the rubber product of comparative example 1.Such those skilled in the art of having the technical effect that can not expect.
This written description uses the open present invention of example, including optimal mode, and also enables those skilled in the art manufacture and use the present invention.The present invention can patentable scope be defined by the claims, and can include other example that those skilled in the art expect.If other example this has the structural element of the literal language not differing from claims, or if other example this includes the equivalent structure element without substantial differences of the literal language with claims, other example the most this is intended to be within the scope of claims.Under not resulting in inconsistent degree, by with reference to by herein with reference to all references in place of be incorporated herein.
Claims (10)
1. the method that natural emulsion is blended with silica slurry, the method comprises the following steps:
(1) under normal temperature and pressure conditions, adding organic acid, be stirred, be subsequently adding emulsifying agent, proceed stirring while stirring in natural emulsion aqueous solution, maintaining natural emulsion pH value of water solution in aforementioned all whipping process is 5.5-7.0；With
(2) it is subsequently adding silica slurry to be mixed and stirred for, maintains whole system pH to be 9-10 by the alkali-metal hydroxide solution of addition in whipping process；
Wherein, the dry glue weight that total addition is natural emulsion of described organic acid and emulsifying agent and the 1～6 ‰ of silicon dioxide dry matter weight sum.
Method the most according to claim 1, it is characterised in that described organic acid is formic acid, acetic acid or the organic acid with amino-substituent.
Method the most according to claim 1 and 2, it is characterised in that described emulsifying agent is the emulsifying agent shown in following formula:
Wherein R is methyl or ethyl, and n is the integer of 1-3, x be 3-8, y be 20-180, z be 10-100, Z-For SO3 -, M+For alkali metal cation or NH4 +。
Method the most according to claim 1 and 2, the most in step (1), adding the mixing time after organic acid is 1-4h, and adding the mixing time after emulsifying agent is 1-4h；The mixing time of step (2) is 2-5h.
Method the most according to claim 1 and 2, in wherein said natural emulsion, dry glue is 10: 3～13 with the weight ratio of dry in silica slurry.
Method the most according to claim 1 and 2, the organic acid of wherein said addition and emulsifying agent weight are respectively the dry glue in described natural emulsion and 0.5 of the dry matter weight sum in described silicon dioxide～3 ‰ and 0.5～3 ‰.
Method the most according to claim 1 and 2, the viscosity of wherein said silica slurry is 100～600cP, and described silicon dioxide is precipitated hydrated silica.
8. the natural emulsion obtained according to method in any one of the preceding claims wherein and the blend of silica slurry.
9. a glue is dry mixed, and it uses blend according to claim 8 to obtain through dehydration.
10. a rubber product, it uses the glue that is dry mixed according to claim 9 by mixing acquisition.
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| CN1421482A (en) * | 2001-11-22 | 2003-06-04 | 多元化学工程有限公司 | Wet natural rubber compound and producing process thereof |
| US20070173567A1 (en) * | 2006-01-20 | 2007-07-26 | Bridgestone Corporation | Method for producing a natural rubber master batch and a synthetic isoprene rubber master batch using biodegraded powder, a method for producing a natural rubber master batch and a synthetic isoprene rubber master batch using rubber powder and a filling agent and a method for producing a natural rubber master batch and a synthetic isoprene rubber master batch using biodegraded rubber powder and a filling agent |
| CN101307193A (en) * | 2007-05-16 | 2008-11-19 | 广东海洋大学 | Method for preparing nano SiO2/natural latex products |
| CN101402748A (en) * | 2007-10-01 | 2009-04-08 | 横滨橡胶株式会社 | Method for producing silicon dioxide-containing nature rubber composition and silicon dioxide-containing nature rubber composition produced with the method |
| CN102634083A (en) * | 2011-12-27 | 2012-08-15 | 确成硅化学股份有限公司 | Method for blending natural latex and silica slurry |
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- 2015-06-29 CN CN201510366166.XA patent/CN104893024B/en active Active
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|---|---|---|---|---|
| CN1421482A (en) * | 2001-11-22 | 2003-06-04 | 多元化学工程有限公司 | Wet natural rubber compound and producing process thereof |
| US20070173567A1 (en) * | 2006-01-20 | 2007-07-26 | Bridgestone Corporation | Method for producing a natural rubber master batch and a synthetic isoprene rubber master batch using biodegraded powder, a method for producing a natural rubber master batch and a synthetic isoprene rubber master batch using rubber powder and a filling agent and a method for producing a natural rubber master batch and a synthetic isoprene rubber master batch using biodegraded rubber powder and a filling agent |
| CN101307193A (en) * | 2007-05-16 | 2008-11-19 | 广东海洋大学 | Method for preparing nano SiO2/natural latex products |
| CN101402748A (en) * | 2007-10-01 | 2009-04-08 | 横滨橡胶株式会社 | Method for producing silicon dioxide-containing nature rubber composition and silicon dioxide-containing nature rubber composition produced with the method |
| CN102634083A (en) * | 2011-12-27 | 2012-08-15 | 确成硅化学股份有限公司 | Method for blending natural latex and silica slurry |
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