CN104231672A - Method for modifying packing, alpha-cristobalite powder, used for polymer material - Google Patents
Method for modifying packing, alpha-cristobalite powder, used for polymer material Download PDFInfo
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- CN104231672A CN104231672A CN201410501029.8A CN201410501029A CN104231672A CN 104231672 A CN104231672 A CN 104231672A CN 201410501029 A CN201410501029 A CN 201410501029A CN 104231672 A CN104231672 A CN 104231672A
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- powder
- cristobalite
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- aluminate coupling
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Abstract
The invention discloses a method for modifying a packing, alpha-cristobalite powder, used for a polymer material. A used activating agent is an aluminate coupling agent (DL-411A), and a used solvent is one of absolute ethyl alcohol, methylbenzene and DMF. The quality percentage content of the aluminate coupling agent is 3.8-4.4 percent, an aluminate coupling agent solution is recovered by a condensation pipe, and the heating temperature of the aluminate coupling agent solution in an electric jacket is 110 DEG C. The method has the beneficial effects of improving the hydrophobicity of alpha-cristobalite powder by modification, enabling powder particles to be easier to disperse in organic high-molecular polymers, and ensuring that the alpha-cristobalite powder serves as the polymer material packing to be possible.
Description
Technical field
The present invention relates to the filler modified technical field of macromolecular material, be specifically related to a kind of method of modifying of macromolecular material filler α-cristobalite powder.
Background technology
Quartz becomes the ideal filler of macromolecular material because of its stable physics and chemistry character.Quartz raw ore changes cristobalite into through removal of impurities, high-temperature calcination.The whiteness of cristobalite is high, and density is low, excellent property, as polymer carrier, is seldom studied by people.But cristobalite is directly used as filler, cannot be dispersed in polyvinyl chloride resin, the serious performance such as tensile strength, resistance to impact shock reducing polymer composite.Due to the wetting ability of silica powder surface, be difficult to compatible with organic polymer material, need to carry out hydrophobically modified to its surface for this reason, powder particle is more easily disperseed in organic high molecular polymer.
Summary of the invention
The object of the present invention is to provide a kind of method of modifying of macromolecular material filler α-cristobalite powder, the wetting ability solving current macromolecular material filler α-cristobalite powder surface causes difficult compatible with macromolecular material, the serious technical problem such as tensile strength, resistance to impact shock reducing polymer composite.
For solving the problems of the technologies described above, the present invention is achieved by the following technical solutions:
A method of modifying for macromolecular material filler α-cristobalite used powder, wherein: activator used is aluminate coupling agent (DL-411A), and concrete steps are as follows:
Step one, under room temperature condition, uses dissolution with solvents aluminate coupling agent, and load in round-bottomed flask, put into the dissolving in a solvent of the ultrasonic acceleration aluminate coupling agent of Ultrasonic Cleaners, the time is 8 min ~ 10min;
Step 2, will make α-cristobalite powder by oneself, put into the aluminate coupling agent solution prepared, ultrasonic disperse 28 min ~ 30min, makes reactant be thick shape, puts into electric mantle and heat, at 80 DEG C ~ 120 DEG C, heat 8h, take out the powder of the rear acquisition of reaction and get final product.
Preferably, described solvent is the one in dehydrated alcohol, toluene, DMF.
Preferably, described solvent is toluene.
The mass percentage content of described aluminate coupling agent is 3.8% ~ 4.4%.
Aluminate coupling agent solution prolong in described step 2 reclaims.
The Heating temperature of aluminate coupling agent solution in described step 2 in electric mantle is 110 DEG C.
Beneficial effect of the present invention: the method for modifying of a kind of macromolecular material filler α-cristobalite powder of the present invention, with aluminate coupling agent (DL-411A), surface modification is carried out to the α-cristobalite powder after ball milling, with the optimum addition of activation index determination coupling agent, contact angle, penetration period and infrared spectra is adopted to carry out the Characterization result of modification, found that, the optimum amount of coupling agent is 3.8%, and activation index reaches 97%.Found by the change of contact angle and penetration period, modified described α-cristobalite powder presents good lipophilicity, has occurred the characteristic peak do not had, show that modified effect is good in the infrared spectra of modified α-cristobalite powder powder.
Accompanying drawing explanation
Fig. 1 is the infrared spectra of unmodified α-cristobalite powder;
Fig. 2 is the infrared spectra of modified α-cristobalite powder.
Embodiment
For making the object, technical solutions and advantages of the present invention clearly, below in conjunction with drawings and Examples of the present invention, the technical scheme in the embodiment of the present invention is clearly and completely described, obviously, described embodiment is the present invention's part embodiment, instead of whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art, not making the every other embodiment obtained under creative work prerequisite, belong to the scope of protection of the invention.
In the embodiment of the present invention, to derive from Guiding County, Guizhou Province domestic for quartzy raw ore.When implementing the method for modifying of a kind of macromolecular material filler of the present invention α-cristobalite powder, first need to prepare α-cristobalite powder, preparation method is as follows:
Quartz original ore powder, under the high temperature of 1250 DEG C, adds mineralizer calcining, and the XRD of the powder after sintering detects transformation of crystal rate, determines to change α-cristobalite powder into.Be milled to micron order, and tested the character of powder.Result shows, the powder SiO after sintering
2content is up to more than 98%, and 95% changes α-cristobalite into, and the particle diameter after ball milling is less than 8 microns, and whiteness reaches more than 90.
After obtaining α-cristobalite powder, modification is carried out to it, specific as follows:
embodiment 1
A method of modifying for macromolecular material filler α-cristobalite used powder, wherein: activator used is aluminate coupling agent (DL-411A), and concrete steps are as follows:
Step one, under room temperature condition, uses dissolution with solvents aluminate coupling agent, and load in round-bottomed flask, put into the ultrasonic acceleration aluminate coupling agent of Ultrasonic Cleaners and dissolve in a solvent, the time is 8 min ~ 10min;
Step 2, will make α-cristobalite powder by oneself, put into the aluminate coupling agent solution prepared, and ultrasonic disperse 28 min ~ 30min makes reactant be thick shape, puts into electric mantle and heat, at 110 DEG C, heats 8h, take out the powder of the rear acquisition of reaction and get final product.
Described solvent is toluene.
The mass percentage content of described aluminate coupling agent is 3.8%.
Aluminate coupling agent solution prolong in described step 2 reclaims.
With aforesaid method carry out α-cristobalite powder-modified after effect assessment:
(1) activity index contrast
Activation index evaluates powder-modified effect method the most intuitively, there is a large amount of Si-OH silica powder surface, the groups such as Si-OH......H, and in polarity, and silica powder volume density is comparatively large, very easily sedimentation in water.But modified through aluminate coupling agent, surfaces hydrophobic, is insoluble in water, the surface tension of modified α-cristobalite powder can sharply increase, thus swims in waterborne.
After taking the surface modification of 100g, α-cristobalite powder is in clean large beaker, slowly adds the distilled water of about 600ml, because modified powder is insoluble in water, and granularity is very thin, is easy under high velocity agitation permeate in air, so also need to seal beaker mouth with film, in high-speed stirring half an hour, leave standstill for some time, after clarification, get the powder granule that upper strata suspends, dry, weigh, can calculate the activation index of modified product, calculation formula is as follows:
Activation index=suspended sample quality (g)/product total mass (g) × 100%
When coupling agent consumption reaches 3.8%, solvent temperature is 110 DEG C, and the activation index of α-cristobalite powder is 97.3%.
(2) infrared spectra comparative analysis
As shown in accompanying drawing 1, accompanying drawing 2, select quality be 3.8% aluminate coupling agent surface modification is carried out to α-cristobalite powder, by the contrast of the infrared spectra of powder after before modified.
Accompanying drawing 1 and attached 2 contrasts known, at 3440cm
-1, 796cm
-1and 621cm
-1all there is obvious absorption peak, wherein 3440cm in place
-1roomy absorption peak is the hydrogen bond stretching vibration absorption peak of powder surface associated water molecule; 796cm
-1the sharp-pointed absorption peak at place is the characteristic peak of quartz, is the symmetrical stretching vibration peak of Si-O-Si; 621cm
-1be in aluminate coupling agent with alkynyl face outside the complete flexural vibration peak of C-H.The infared spectrum of modified α-cristobalite is at 2920cm
-1there is obvious absorption peak in place, is the characteristic peak of-CH2-stretching vibration; At 2850cm
-1also there is absorption peak in place, is the stretching vibration peak of C-H in aldehyde radical; Modified compared to before modified, modified powder 3440cm
-1the roomy absorption peak-to-peak type at place diminishes to some extent, illustrates that the part silicone hydroxyl of powder surface and aluminate coupling agent there occurs chemical reaction; At 1100cm
-1left and right, modified α-cristobalite powder absorption peak herein broadens, and absorption peak center offsets, 1100cm
-1it is the asymmetrical stretching vibration peak of Si-O or Al-O that place correspond to, and characteristic peak herein slightly broadens, reason is that the silicone hydroxyl of aluminate coupling agent and α-cristobalite powder surface there occurs chemical reaction, defines Al-O-Si chemical bond, causes the absorption peak wavelength at this place to broaden.By the infrared spectra contrast of powder after before modified, the silicone hydroxyl indicating aluminate coupling agent and α-cristobalite powder surface there occurs the combination of chemical bond.
(3) penetration period comparative analysis
Select quality be 3.8% aluminate coupling agent surface modification is carried out to α-cristobalite powder, use water, whiteruss and dibutyl phthalate three kinds of reagent, measure the penetration period in α-cristobalite powder before modification, as following table 1:
table 1 is the rear powder capillary time before modified
From upper table 1, in unmodified powder, the seepage velocity of water is exceedingly fast, and the seepage velocity of organic reagent is slow.In modified powder, the seepage velocity of water is slack-off, and the seepage velocity of organic reagent accelerates.
Unmodified α-cristobalite powder surface is polarity, and the water capacity is wetting powder easily, and the wettability of organic reagent is poor; And modified α-cristobalite powder surface hydrophobicity, organic reagent is easy to wetting powder, and the wettability of water is poor, illustrate that α-cristobalite powder is modified through aluminate coupling agent, powder surface coupled agent molecule institute is coated, surface is become nonpolar (hydrophobicity) from polarity, and the hydrophobic oleophilic oil of modified α-cristobalite powder significantly improves.
(4) contact angle analysis
Select quality be 3.8% aluminate coupling agent surface modification is carried out to α-cristobalite powder and contact angle detection is carried out, as following table 2 to the α-cristobalite powder before modified:
table 2 is rear powder contact angle before modified
| Powder sample | Contact angle (K) |
| Unmodified | 6.87 |
| Modified | 0.51 |
α-cristobalite powder is modified through aluminate coupling agent, and coupling agent is coated on powder surface, and surface presentation goes out hydrophobicity.And water is polar liquid, when modified powder contacts with water, water cannot wet granulate surface, and contact angle becomes large, and corresponding K value diminishes.Powder surface presents wetting ability before modified, is easy to adsorbed water molecule, and unmodified powder is easy to soak with the water molecules in polarity, and contact angle diminishes, and correspond to K value and becomes large.According to the change of K value, show powder-modified respond well.
embodiment 2
Compared with embodiment 1, other conditions are constant, and solvent used is dehydrated alcohol, and the activation index of α-cristobalite powder is 31.5%.
embodiment 3
Compared with embodiment 1, other conditions are constant, and solvent used is DMF, and the activation index of α-cristobalite powder is 45.6%.
Modified α-cristobalite powder and polyvinyl chloride resin is adopted to prepare matrix material.To its processing characteristics, mechanical property and thermostability carry out detection find, when the addition of modification α-cristobalite filler is 10%, rheological property and thermostability the highest, difficulty of processing is minimum.Found by the SEM picture in material transverse section, the dispersiveness of filler in polyvinyl chloride resin is best, best with the interface cohesion effect of PVC matrix, makes the tensile strength of matrix material, resistance to impact shock is improved.
Above embodiment only in order to technical scheme of the present invention to be described, is not intended to limit; Although with reference to previous embodiment to invention has been detailed description, those of ordinary skill in the art is to be understood that: it still can be modified to the technical scheme described in previous embodiment, or carries out equivalent replacement to wherein some or all of technical characteristic; And these amendments or replacement, do not make the essence of appropriate technical solution depart from the scope of embodiment of the present invention technical scheme.
Claims (6)
1. a method of modifying for macromolecular material filler α-cristobalite used powder, is characterized in that: activator used is aluminate coupling agent (DL-411A), and concrete steps are as follows:
Step one, under room temperature condition, uses dissolution with solvents aluminate coupling agent, and load in round-bottomed flask, put into the dissolving in a solvent of the ultrasonic acceleration aluminate coupling agent of Ultrasonic Cleaners, the time is 8 min ~ 10min;
Step 2, will make α-cristobalite powder by oneself, put into the aluminate coupling agent solution prepared, ultrasonic disperse 28 min ~ 30min, makes reactant be thick shape, puts into electric mantle and heat, at 80 DEG C ~ 120 DEG C, heat 8h, take out the powder of the rear acquisition of reaction and get final product.
2. the method for modifying of macromolecular material filler α-cristobalite used powder as claimed in claim 1, described solvent is the one in dehydrated alcohol, toluene, DMF.
3. the method for modifying of macromolecular material filler α-cristobalite used powder as claimed in claim 1, described solvent is toluene.
4. the method for modifying of macromolecular material filler α-cristobalite used powder as claimed in claim 1, the mass percentage content of described aluminate coupling agent is 3.8% ~ 4.4%.
5. the method for modifying of macromolecular material filler α-cristobalite used powder as claimed in claim 1, the solvent prolong in described step 2 reclaims.
6. the method for modifying of macromolecular material filler α-cristobalite used powder as claimed in claim 1, the Heating temperature in electric mantle of the solvent in described step 2 is 110 DEG C.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2019128473A1 (en) * | 2017-12-27 | 2019-07-04 | 江苏亨通光电股份有限公司 | High-density pressure-resistant optical fiber bundle cable for use in datacenter |
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| CN102993780A (en) * | 2012-11-20 | 2013-03-27 | 山东鲲鹏新材料科技股份有限公司 | Long-chain fatty acid-modified quartz material and preparation method thereof |
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| US4594271A (en) * | 1984-12-24 | 1986-06-10 | U.S. Philips Corporation | Process for coating inorganic particles with condensating polymers |
| CN1831049A (en) * | 2005-09-15 | 2006-09-13 | 成都理工大学 | Method for producing compound and modified quartz powder by using aluminate ester and methyl acryloxyl silicane |
| CN101955693A (en) * | 2010-08-26 | 2011-01-26 | 成都理工大学 | Method for compositely modifying microcrystal muscovite powder by using boronic acid ester and epoxy silane |
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| WO2019128473A1 (en) * | 2017-12-27 | 2019-07-04 | 江苏亨通光电股份有限公司 | High-density pressure-resistant optical fiber bundle cable for use in datacenter |
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Application publication date: 20141224 |