CN104004384B - A kind of preparation method of hydrophobically modified filler - Google Patents
A kind of preparation method of hydrophobically modified filler Download PDFInfo
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Abstract
The invention discloses a kind of preparation method of hydrophobically modified filler, comprise the steps: step 1, by black liquid and inorganic filler aqueous dispersions mix and blend, utilize acid out technique that the organic compound in black liquor is separated out, obtain the slurry of organic coating inorganic filler; Step 2, slurry is dried at 105 DEG C, ball milling 0.5～2h under the rotating speed of 200～400rpm, crosses 200 mesh sieves, obtains dry powder; Step 3, dry powder is mixed with the mass ratio of 3:1～1:4 with finish, and add by different formulations the dispersant that accounts for finish quality 1%～20%, ball milling 0.5～2h under the rotating speed of 200～400rpm, obtains the hydrophobically modified filler of paste. It is cheap and easy to get that the present invention creates raw material, can reduce costs; In addition, hydrophobically modified filler of the present invention is applicable to fill SBS elastomeric material, can substitute the conventional filler precipitated calcium carbonate of SBS, significantly improves tensile strength, tearing strength and the wearability of material.<!--2-->
Description
Technical field
The present invention relates to macromolecular material filler reinforcement technical field, relate in particular to a kind of preparation side of hydrophobically modified fillerMethod.
Background technology
Black liquor in paper industry can bring a large amount of pollutions to environment, and vast environmental protection and scientific research personnel are black to processing in recent yearsLiquid, recycle organic matter wherein and inorganic matter and made and make great efforts and obtained progress. Chinese patent CN101328282A public affairsOpen a kind of organic modified montmorillonite as rubber reinforcing filler and preparation method thereof, utilized the lignin conduct in black liquidThe dressing agent of clay replaces traditional long-chain quaternary amine salt or nonionic surface active agent, has reached reinforcing effect, simultaneously for makingPaper waste water is recycled and has been proposed a solution route, but in preparation process, after being 2～3 with hydrochloric acid conditioning solution pH, needs to useDeionized water cyclic washing is neutral to approaching, and this can use a large amount of water, and it is large that energy consumption becomes, and manufactured new waste water simultaneously, and COD alsoBe difficult to reach discharge standard. Chinese patent CN101928466A discloses a kind of rubber reinforcing filler and preparation method thereof and application,Proposing to regulate in pH operation for the problem in is above 6～7 with sulfuric acid regulation solution pH, saves filtration and washing step, keeps awayExempt from the use of large water gaging, realized black liquor zero-emission. Above two patents all adopt the mixing method of wet method, are about to contain 20The organic decoration clay of～60% moisture adds in rubber, utilizes roller temperature to dehydrate. Wet method is mixing have been solved in dry mixing processThe problem that filler is reunited, has effectively improved fillers dispersed, but the dry operational sequence that increased of while later stage moisture content has reducedProduction efficiency, due to containing the water packing polarity different with rubber and different hydrophilic and oleophilic properties, go back Presence of an interface incompatible,The problem that reinforcing effect weakens, these problems have limited industrial applications and the popularization of this filler cheap and easy to get.
How to realize and in different rubber or elastomer, apply this class filler, do not cause burden can reach again to environment simultaneouslyThe difficult problem of scientific research personnel in application to desirable fillers dispersed and reinforcing effect. Following patent for solve filler withThe compatible problem in interface of rubber or elastomeric material is probed into. Wherein, Chinese patent CN103205141A discloses preparationThe method of maleic anhydride modified gum filler and the vulcanizate that comprises it, with maleic anhydride and the modifier ore deposit strong to hydrophilyThing filler carries out modification, make filling surface with lipophilic group and be applied to nonpolar natural rubber, ethylene propylene diene rubber andIn the acrylonitrile-butadiene rubber of polarity, though graft-modification method has the effect of interface compatibility of enhancing, have that percent grafting is little, grafting positionPut the problems such as uncertain, greatly affect the degree that is uniformly dispersed, and residual initator can cause to the cross-linking process of rubberImpact. Chinese patent CN103554555A discloses bagasse filler and preparation method and the rubber composite by this filler systemAnd preparation method, adopt ethylene-vinyl alcohol (EVOH) to be coated the bagasse fibre of polarity, alternative carbon black is used for strengthening nonpolarRubber raw rubber, the directly blend in banbury by EVOH and bagasse of this method, because the dispersion efficiency of banbury is not high, systemThe method of standby filler itself exists disperses inhomogeneous problem. Chinese patent CN1654549A discloses Coaseries kaolin and has prepared fourthThe method of base bottle closure of rubber reinforced filling, is applied to the chlorinated scoline of polarity with stearic acid surface modification Coaseries kaolinIn, this method is owing to participating in without decentralized medium the inhomogeneous problem of fillers dispersed that exists equally in modifying process. Chinese patentCN1296991 discloses the rubber composition of the rubber of hydroxyl and/or carboxyl and the oxidation of hydrophobization or silicates filler,Silica or silicates filler are carried out to hydrophobization processing with castor oil, remove solvent and dry after be applied to hydroxyl or carboxylicIn the rubber of base, but this method need with an organic solvent can cause environmental pollution, and course of reaction requirement is strict, and costHigh. Chinese patent CN103554581A discloses a kind of rubber containing reinforcement Iraq/Mongolia clay filler and preparation method thereof, Xiang NaIn rice clay aqueous slurry, successively add dispersant and modifier to grind respectively, after being dried, add again Silicon Containing Hydrogen wet goods to be coated and changeProperty, and be applied in nonpolar butadiene-styrene rubber, this method fillers dispersed is even, and reinforcing effect significantly and not causes environment dirtDye, but operating procedure is various, the Silicon Containing Hydrogen wet goods that coated modification is added has emollescence, can be to the mechanical performance of rubber andHardness impacts. Chinese patent CN1389497 discloses the production work of based article at the bottom of environment-friendly type SBS thermoplastic elastic body shoeSkill, first, by dry elastomer and compatilizer blend, adds other auxiliary agents successively, finally adds inorganic filler, compatilizer and bulletStrand between gonosome can tangle mutually, and carboxyl isopolarity group and inorganic filler surface on compatilizer strand can be changedLearn bonding, thereby promote the compatible of filler and matrix, take to add the rear a kind of material of cold burden, fall for solving powder lumping problemLow temperature makes finely dispersed method, and in this technique, the preparation process of compatilizer can contain organic solvent, can cause dirt to environmentDye, because the adding procedure of compatilizer and filler separates, in the situation that other auxiliary agents exist, may be unfavorable for filler and compatibleChemical bonding between agent, saying nothing of chemical bond by compatilizer and filler, incompatible to reach filler homodisperse in matrixEffect, and it is unsatisfactory to attempt to solve the method possibility of reuniting by cooling, and due to factors such as different polarity, some helpsAdding of agent or filler can be disturbed the dispersion of a kind of auxiliary agent between elastomer on the contrary, in addition in patent to machine construction, elasticityBody and machine clean level require strict, in actual mechanical process, can strengthen production cost.
Summary of the invention
For addressing the above problem, the object of the present invention is to provide a kind of preparation method of hydrophobically modified filler, it is comprehensiveUtilize organic principle and inorganic filler in black liquid, to realize the field that black liquid is recycled of expanding, reduce SBS bulletThe cost of gonosome filler, the problem of solution Environment Polluted by Papermaking Waste Water.
For achieving the above object, technical scheme of the present invention is:
A preparation method for hydrophobically modified filler, comprises the steps:
Step 1, by black liquid and inorganic filler aqueous dispersions mix and blend, utilize acid out technique to make having in black liquorOrganic compounds is separated out, and obtains the slurry of organic coating inorganic filler;
Step 2, slurry is dried at 105 DEG C, ball milling 0.5～2h under the rotating speed of 200～400rpm, crosses 200Mesh sieve, obtains dry powder;
Step 3, dry powder is mixed with the mass ratio of 3:1～1:4 with finish, and add and account for finish quality by different formulations1%～20% dispersant, ball milling 0.5～2h under the rotating speed of 200～400rpm, obtains the hydrophobically modified filler of paste.
Further, described inorganic filler be a kind of in precipitated calcium carbonate, powdered whiting, imvite, kaolin orSeveral mixtures.
Further, described finish is the one in naphthenic oil, machine oil, paraffin oil.
Further, described dispersant is one or more in zinc stearate, calcium stearate, stearic acid, stearmideMixture.
Another technical scheme of the present invention is:
Use above-mentioned hydrophobically modified filler to prepare the method for the elastomer foamed material of SBS, comprise the steps:
Step 1, the SBS elastomer of plasticating;
Step 2, add hydrophobically modified filler, mixing 0.5～2h, then add respectively promoter, crosslinking agent, mixing evenlyRear discharging, last machine-shaping.
Compared to prior art, the present invention creates tool and has the following advantages:
1. utilize black liquid, inorganic filler, the finish main component as filler, raw material is cheap and easy to get, can reduce rubberThe cost of glue or elastomer reinforcing agent or filler;
2. the dispersant of using in hydrophobization processing procedure and covering are necessary group in SBS elastomer composite systemPoint, dispersant is simultaneously as releasing agent, and covering as plasticizer, has been simplified experimental procedure simultaneously;
3. rubber compounding process is without the participation of water, and in realizing black liquor zero-emission, process is to operating environmentPollute littlely, mixing time reduces, and can extend service life of machine.
In addition, hydrophobically modified filler of the present invention is applicable to fill SBS elastomeric material, can substitute the conventional filler of SBSPrecipitated calcium carbonate, significantly improves tensile strength, tearing strength and the wearability of material.
Brief description of the drawings
Fig. 1 is recipe step flow chart of the present invention.
Detailed description of the invention
In order to make object of the present invention, technical scheme and advantage clearer, below in conjunction with drawings and Examples, rightThe present invention is further elaborated. Should be appreciated that specific embodiment described herein is only in order to explain the present invention, andBe not used in restriction the present invention.
The preparation method of hydrophobically modified filler of the present invention, comprises the following steps:
Step 1, by black liquid and inorganic filler aqueous dispersions mix and blend, utilize acid out technique to make having in black liquorOrganic compounds is separated out, and obtains the slurry of organic coating inorganic filler;
Step 2, slurry is dried at 105 DEG C, ball milling 0.5～2h under the rotating speed of 200～400rpm, crosses 200Mesh sieve, obtains dry powder;
Step 3, dry powder is mixed with the mass ratio of 3:1～1:4 with finish, and add and account for finish quality by different formulations1%～20% dispersant, ball milling 0.5～2h under the rotating speed of 200～400rpm, obtains the hydrophobically modified filler of paste.
While using hydrophobically modified filler of the present invention to prepare the elastomer foamed material of SBS, the SBS elastomer of first plasticating, then addsEnter hydrophobically modified filler, mixing 0.5～2h, then add respectively promoter, crosslinking agent, and can add or not add blowing agent, mixing equalEven rear discharging, finally according to the machine-shaping of traditional SBS thermoplastic elastomer (TPE) processing method.
Wherein, described inorganic filler is one or more in precipitated calcium carbonate, powdered whiting, imvite, kaolinMixture. Described finish is the one in naphthenic oil, machine oil, paraffin oil. Described dispersant be zinc stearate, calcium stearate,The mixture of one or more in stearic acid, stearmide. Described plasticate and mixing service machine be mill, kneader,One in banbury. Described SBS elastomer is one or more the mixing in SBS, SEBS, high-phenylethylene, polystyreneThing. Described SBS elastic composite is particularly useful for making the end in footwear, the large end or other foaming products.
Hydrophobically modified filler in the present invention, is coated inorganic filler with the organic principle in black liquor, has with black liquorThe a large amount of carbochains that comprise in machine composition and the carbochain of finish are tangled mutually, and have concurrently with organic acid or acylate hydrophilic and closeOil characteristic makes lignin be able to stable and uniform to be dispersed in finish, and having realized hydrophobic finish has black liquor organic principle, black liquorMachine composition is to the stable double-coating of inorganic filler, and because the finish using is compatible to the butadiene segment in SBS elastomer,Thereby make hydrophobically modified filler and SBS elastomer there is good interface compatibility, can make the good SBS bullet of fillers dispersedGonosome composite.
Embodiment mono-
A preparation method for hydrophobically modified filler, by the mixed slurry of black liquor after treatment acid out and imvite 105At DEG C, dry, after ball milling sieves, obtain≤200 object dry powder, wherein, the quality of black liquor solid content and imvite in mixed slurryThan being 1:1; Dry powder, zinc stearate, naphthenic oil are mixed with the mass ratio of 1:2:13, ball milling 0.5h under the rotating speed of 200rpm,Obtain hydrophobically modified filler.
Above-mentioned hydrophobically modified filler is during for the preparation of the elastomer foamed material of SBS, and sizing compound formula is as follows: SBS100 part, dredge16 parts of water modified fillers, 3 parts, zinc oxide, 2 parts of Celogen Azs, 0.2 part of dual-tert-butyl peroxidating diisopropyl benzene. By SBSOn opening rubber mixing machine, plasticate, by above-mentioned formula mixing rear slice on opening rubber mixing machine, then in 170 DEG C of temperature, pressureUnder power 15MPa, foam, make foamed glue, the performance of test foamed glue. Wherein, performance data is in table 1.
Embodiment bis-
A preparation method for hydrophobically modified filler, by the mixed slurry of black liquor after treatment acid out and imvite 105At DEG C, dry, after ball milling sieves, obtain≤200 object dry powder, the mass ratio by dry powder, zinc stearate, naphthenic oil with 5:2:13Mix, ball milling 2h under the rotating speed of 300rpm, obtains hydrophobically modified filler.
Above-mentioned hydrophobically modified filler is during for the preparation of the elastomer foamed material of SBS, and sizing compound formula is as follows: SBS100 part, dredge20 parts of water modified fillers, 3 parts, zinc oxide, 2 parts of Celogen Azs, 0.2 part of dual-tert-butyl peroxidating diisopropyl benzene. By SBSOn opening rubber mixing machine, plasticate, by above-mentioned formula mixing rear slice on opening rubber mixing machine, then in 170 DEG C of temperature, pressureUnder power 15MPa, foam, make foamed glue, the performance of test foamed glue. Wherein, its performance data is in table 1.
Embodiment tri-
A preparation method for hydrophobically modified filler, by the mixed slurry of black liquor after treatment acid out and imvite 105At DEG C, dry, after ball milling sieves, obtain≤200 object dry powder, the mass ratio by dry powder, zinc stearate, naphthenic oil with 10:2:13Mix, ball milling 2h under the rotating speed of 400rpm, obtains hydrophobically modified filler.
Above-mentioned hydrophobically modified filler is during for the preparation of the elastomer foamed material of SBS, and sizing compound formula is as follows: SBS100 part, dredge25 parts of water modified fillers, 3 parts, zinc oxide, 2 parts of Celogen Azs, 0.2 part of dual-tert-butyl peroxidating diisopropyl benzene. By SBSOn opening rubber mixing machine, plasticate, by above-mentioned formula mixing rear slice on opening rubber mixing machine, then in 170 DEG C of temperature, pressureUnder power 15MPa, foam, make foamed glue, the performance of test foamed glue. Wherein, performance data is in table 1.
Embodiment tetra-
A preparation method for hydrophobically modified filler, by the mixed slurry of black liquor after treatment acid out and imvite 105At DEG C, dry, after ball milling sieves, obtain≤200 object dry powder, the mass ratio by dry powder, zinc stearate, naphthenic oil with 30:2:13Mix, ball milling 2h under the rotating speed of 300rpm, obtains hydrophobically modified filler.
Above-mentioned hydrophobically modified filler is during for the preparation of the elastomer foamed material of SBS, and sizing compound formula is as follows: SBS100 part, dredge45 parts of water modified fillers, 3 parts, zinc oxide, 2 parts of Celogen Azs, 0.2 part of dual-tert-butyl peroxidating diisopropyl benzene. By SBSOn opening rubber mixing machine, plasticate, by above-mentioned formula mixing rear slice on opening rubber mixing machine, then in 170 DEG C of temperature, pressureUnder power 15MPa, foam, make foamed glue, the performance of test foamed glue. Performance data is in table 1.
Embodiment five
A preparation method for hydrophobically modified filler, by the mixed slurry of black liquor after treatment acid out and imvite 105At DEG C, dry, after ball milling sieves, obtain≤200 object dry powder, the mass ratio by dry powder, zinc stearate, naphthenic oil with 30:2:13Mix, ball milling 2h under the rotating speed of 300rpm, obtains hydrophobically modified filler.
Above-mentioned hydrophobically modified filler is as follows for the preparation of the sizing compound formula of SBS base vulcanizate (not foaming): SBS100 part,45 parts of hydrophobically modified fillers, 3 parts, zinc oxide, 0.2 part of dual-tert-butyl peroxidating diisopropyl benzene. By SBS at opening rubber mixing machineOn plasticate, by above-mentioned formula mixing rear slice on opening rubber mixing machine, then under 170 DEG C of temperature, pressure 15MPa, carry outSulfuration, makes vulcanizate, the performance of test vulcanizate.
Embodiment six
A preparation method for hydrophobically modified filler, by the mixed slurry of black liquor after treatment acid out and imvite 105At DEG C, dry, after ball milling sieves, obtain≤200 object dry powder, the mass ratio by dry powder, zinc stearate, naphthenic oil with 40:1:36Mix, ball milling 2h under the rotating speed of 300rpm, obtains hydrophobically modified filler.
Above-mentioned hydrophobically modified filler is as follows for the preparation of the sizing compound formula of the elastomer foamed material of SBS: SBS100 part, height50 parts of styrene, 38.5 parts of hydrophobically modified fillers, 2 parts, zinc oxide, 3 parts of Celogen Azs, dual-tert-butyl peroxidating diisopropyl0.35 part of base benzene. SBS and high-phenylethylene are plasticated on opening rubber mixing machine, mixing on opening rubber mixing machine by above-mentioned formulaRear slice then foams under 170 DEG C of temperature, pressure 15MPa, makes foamed glue, the performance of test foamed glue.
Table 1 adds the performance of the SBS foamed glue of the hydrophobically modified filler of different umbers
| Example | Filler umber/phr | Proportion/gcm-3 | Hardness (Shao Shi C) | Tensile strength/MPa | Percentage elongation/% |
| Without filler | 0 | 0.451±0.008 | 47±1 | 1.071±0.020 | 177±34 |
| Embodiment 1 | 16 | 0.254±0.010 | 28±1 | 0.680±0.025 | 285±20 |
| Embodiment 2 | 20 | 0.298±0.010 | 32±2 | 0.966±0.067 | 217±40 |
| Embodiment 3 | 25 | 0.480±0.028 | 47±1 | 1.473±0.063 | 298±2 |
| Embodiment 4 | 45 | 0.564±0.016 | 51±1 | 1.954±0.074 | 222±19 |
From the data in table 1, add hydrophobically modified filler to be conducive to the raising of SBS expanded material percentage elongation, compareUnloaded expanded material, in the time adding umber >=25 part of filler of the present invention, the tensile strength of SBS expanded material improves,In the time adding umber >=25 part of hydrophobically modified filler, hydrophobically modified filler has strengthening action to SBS elastomer.
Hydrophobically modified filler in the present invention, is coated inorganic filler with the organic principle in black liquor, has with black liquorThe a large amount of carbochains that comprise in machine composition and the carbochain of finish are tangled mutually, and have concurrently with organic acid or acylate hydrophilic and closeOil characteristic makes lignin be able to stable and uniform to be dispersed in finish, and having realized hydrophobic finish has black liquor organic principle, black liquorMachine composition is to the stable double-coating of inorganic filler, and because the finish using is compatible to the butadiene segment in SBS elastomer,Thereby make hydrophobically modified filler and SBS elastomer there is good interface compatibility, can make the good SBS bullet of fillers dispersedGonosome composite.
The present invention creates tool and has the following advantages:
4. utilize black liquid, inorganic filler, the finish main component as filler, raw material is cheap and easy to get, can reduce rubberThe cost of glue or elastomer reinforcing agent or filler;
5. the dispersant of using in hydrophobization processing procedure and covering are necessary group in SBS elastomer composite systemPoint, dispersant is simultaneously as releasing agent, and covering as plasticizer, has been simplified experimental procedure simultaneously;
6. rubber compounding process is without the participation of water, and in realizing black liquor zero-emission, process is to operating environmentPollute littlely, mixing time reduces, and can extend service life of machine.
Experimental result shows, hydrophobically modified filler of the present invention is applicable to fill SBS elastomeric material, can substitute SBS normalUse filler precipitated calcium carbonate, significantly improve tensile strength, tearing strength and the wearability of material.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all in essence of the present inventionAny amendment of doing within god and principle, be equal to replacement and improvement etc., within protection scope of the present invention all should be included in.
Claims (5)
1. a preparation method for hydrophobically modified filler, is characterized in that, comprises the steps:
Step 1, by black liquid and inorganic filler aqueous dispersions mix and blend, utilize acid out technique to make organising in black liquorCompound is separated out, and obtains the slurry of organic coating inorganic filler;
Step 2, slurry is dried at 105 DEG C, ball milling 0.5～2h under the rotating speed of 200～400rpm, crosses 200 mesh sieves,To dry powder;
Step 3, dry powder is mixed with the mass ratio of 3: 1～1: 4 with finish, and by different formulations add account for finish quality 1%～20% dispersant, ball milling 0.5～2h under the rotating speed of 200～400rpm, obtains the hydrophobically modified filler of paste;
Organic principle in black liquor is coated inorganic filler, with a large amount of carbochains of comprising in black liquor organic principle and finishCarbochain is tangled mutually, and the hydrophilic and oil-wet behavior having concurrently with organic acid or acylate makes lignin be able to stable and uniform pointBe dispersed in finish, realized hydrophobic finish to black liquor organic principle, black liquor organic principle to the stable double-coating of inorganic filler.
2. the preparation method of hydrophobically modified filler according to claim 1, is characterized in that: described inorganic filler is lightweightThe mixture of one or more in calcium carbonate, powdered whiting, imvite, kaolin.
3. the preparation method of hydrophobically modified filler according to claim 2, is characterized in that: described finish be naphthenic oil,One in machine oil, paraffin oil.
4. the preparation method of hydrophobically modified filler according to claim 3, is characterized in that: described dispersant is stearic acidThe mixture of one or more in zinc, calcium stearate, stearic acid, stearmide.
5. use the hydrophobically modified filler described in claim 1 to prepare the method for the elastomer foamed material of SBS, its feature existsIn, comprise the steps:
Step 1, the SBS elastomer of plasticating;
Step 2, add hydrophobically modified filler, mixing 0.5～2h, then add respectively promoter, crosslinking agent, blowing agent, mixing allEven rear discharging, last machine-shaping.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101328282A (en) * | 2008-07-22 | 2008-12-24 | 湖南师范大学 | Organic modified montmorillonite used as rubber reinforcing agent and preparation thereof |
| CN103421142A (en) * | 2013-07-18 | 2013-12-04 | 贺州学院 | Ground calcium carbonate powder surface modification method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101328282A (en) * | 2008-07-22 | 2008-12-24 | 湖南师范大学 | Organic modified montmorillonite used as rubber reinforcing agent and preparation thereof |
| CN103421142A (en) * | 2013-07-18 | 2013-12-04 | 贺州学院 | Ground calcium carbonate powder surface modification method |
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