CN103087551A - Surface modification method for improving hydrophobicity and temperature resistance of calcium carbonate for plastics - Google Patents
Surface modification method for improving hydrophobicity and temperature resistance of calcium carbonate for plastics Download PDFInfo
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- CN103087551A CN103087551A CN2013100575428A CN201310057542A CN103087551A CN 103087551 A CN103087551 A CN 103087551A CN 2013100575428 A CN2013100575428 A CN 2013100575428A CN 201310057542 A CN201310057542 A CN 201310057542A CN 103087551 A CN103087551 A CN 103087551A
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- calcium carbonate
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Abstract
The invention provides an organic surface modification method for improving the hydrophobicity and temperature resistance of calcium carbonate for plastics. The method is characterized in that one or more organic silicon material compounds are used to act on calcium carbonate particles to modify the surface of the calcium carbonate by a wet method in which the organic silicon material and the calcium carbonate are mixed with deionized water as a diluting agent and a dry method which utilizes ball mill, Raymond mill or fluid jet mill and other crushing equipment. Thus, the hydrophobicity and temperature resistance of calcium carbonate can be remarkably improved. The method has the advantages of mild reaction condition, no environmental pollution and low cost, and is simple to operate and convenient to prepare.
Description
Technical field
The invention belongs to the organic surface modifying method of calcium carbonate, say more specifically calcium carbonate powders is carried out organic-capping, thereby improve its hydrophobicity and durothermic method.
Background technology
Calcium carbonate because have that low price, color and luster are good, easy coloring, hardness are low, thermostability and chemical stability is good, easily dry, nontoxic, nonirritant, the advantage such as tasteless, so used in a large number in plastic working.But directly the joining in resin system of calcium carbonate, the mechanical property of plastic material is descended comprehensively, this has just limited the additional proportion of calcium carbonate, has also just limited the large-scale application of calcium carbonate.If but in advance calcium carbonate is carried out surface modification treatment, and can alleviate calcium carbonate to the detrimentally affect of filled plastics mechanical property, the pure matrix plastic of some Performance Ratio also will be got well.Application practice for many years shows, not only can reduce the material cost of plastics through the calcium carbonate (popular title method is activated calcium carbonate) of surface organic modification processing, can also improve the shock resistance of plastics and the printing performance on surface.
When calcium carbonate was applied to the plastics field, hydrophobic performance and heat resistance were to weigh two very important indexs of calcium carbonate quality.If hydrophobicity is poor, the calcium carbonate surface by polar group (as-OH) coat, make it easily produce reunion because of polar adsorption or the moisture absorption, when being used for plastic applications, calcium carbonate occurring and add difficulty, easily bond in transport pipe, also be easy to stop up screen cloth, even join smoothly in mixing roll, also be difficult to disperse equably the loading level that this can have a strong impact on the production efficiency of plastics and reduce calcium carbonate when mixing in system.If the temperature tolerance of calcium carbonate is poor, calcium carbonate easy Yin Wendu when mixing raises, cause the organic modifiers volatilization on calcium carbonate surface or the moisture evaporation of titanium pillaring solution, this can cause plastics the defectives such as gap, bulge to occur, has a strong impact on intensity and the outward appearance of plastics.
The hydrophobic characterizing method of calcium carbonate:
1) floating method
Inject clear water (water temperature and room temperature approach) in transparent beaker, be sprinkling upon on the water surface with the appropriate calcium carbonate of little bale-out, observe its sedimentation situation, sedimentation is slower, and hydrophobicity is better; Otherwise hydrophobicity is poorer.
2) pressed disc method
Appropriate calcium carbonate is poured in compression mold, it is compressed, strikes off with scraper, and form concave surface.Then drip the globule on its surface with dropper, observe globule seepage and spread condition.Seepage and diffusion are slower, and hydrophobicity is better; Otherwise hydrophobicity is poorer.
The stable on heating characterizing method of calcium carbonate:
Be tiled in respectively the calcium carbonate powders of 5-10 gram to be detected in watch-glass, be placed in simultaneously baking oven, after baking 20-60 minute (being generally 30 minutes) that (is generally 250-500 degree centigrade) under assigned temperature, take out all calcium carbonate, be placed in loft drier coolingly, take out all surface ware after being cooled to normal temperature, in one line, its colour-change situation of visual detection is mainly to see the xanthochromia degree.Take blank sample as object of reference, xanthochromia is more serious, and the expression temperature tolerance is poorer, and color is whiter, and the expression temperature tolerance is better.
Stearic acid and derivative, titanic acid ester etc. are mostly selected in traditional calcium carbonate surface modifying agent, although they can be in problems such as in varying degrees solution dispersiveness, hydrophobicitys, these materials all are difficult to reach simultaneously hydrophobicity and durothermic requirement.
Summary of the invention
The present invention propose to adopt one or more organosilicon materials, and calcium carbonate is carried out organically-modified processing, obtains having the method for the calcium carbonate of high hydrophobicity and high temperature tolerance.
We realize above-mentioned purpose by the following technical solutions:
1) appropriate deionized water is joined in treatment trough with high-speed stirring apparatus, start stirring, rotating speed is 1000 rev/mins to 3000 rev/mins;
One or more organosilicon materials that 2) will measure join in treatment trough;
3) slowly add the calcium carbonate (calcium carbonate is the calcium carbonate without organically-modified processing) of metering, pull an oar and processed 20-30 minute, rotating speed is 2000 rev/mins to 3000 rev/mins;
4) calcium carbonate slurry is dried in the baking oven of 100-150 degree centigrade after, then carry out comminution by gas stream, make required height and dredge
The calcium carbonate product of water-based and high temperature tolerance.
Above-described organosilicon material is that viscosity is 1-500cst, contains one or both compound of hydroxy-terminated polysiloxane, terminal methyl hydrogen containing siloxane, and molecular formula is respectively:
Terminal methyl hydrogen containing siloxane: (CH
3)
3SiO[SiO (H) (CH
3)] nSi (CH
3)
3N=15-50
Hydroxy-terminated polysiloxane: HO (CH
3)
2SiO[SiO (CH
3)
2] nSi (CH
3)
2OH n=10-30
Embodiment
Embodiment 1:
Getting 400 ml deionized water joins in the glass beaker of 1000 milliliters with high-speed stirring apparatus, start stirring (rotating speed is 1000 rev/mins), slowly add the calcium carbonate (calcium carbonate is without organically-modified calcium carbonate) of 200 grams, pull an oar and process 30 minutes (rotating speed is 3000 rev/mins); Calcium carbonate is baked to complete drying in the baking ovens of 120 degree, calcium carbonate is pulverized with small-sized micronizer mill after cooling, make required calcium carbonate sample.
Embodiment 2:
Getting 400 ml deionized water joins in the glass beaker of 1000 milliliters with high-speed stirring apparatus, start stirring (rotating speed is 1000 rev/mins), add 4 gram stearic acid, being stirred to stearic acid dissolves fully, slowly add the calcium carbonate (calcium carbonate is without organically-modified calcium carbonate) of 200 grams, pull an oar and process 30 minutes (rotating speed is 3000 rev/mins); Calcium carbonate is baked to complete drying in the baking ovens of 120 degree, calcium carbonate is pulverized with small-sized micronizer mill after cooling, make required calcium carbonate sample.
Embodiment 3
Getting 400 ml deionized water joins in the glass beaker of 1000 milliliters with high-speed stirring apparatus, start stirring (rotating speed is 1000 rev/mins), add 4 gram titanic acid ester, stirred 5 minutes, slowly add the calcium carbonate (calcium carbonate is without organically-modified calcium carbonate) of 200 grams, pull an oar and process 30 minutes (rotating speed is 3000 rev/mins); Calcium carbonate is baked to complete drying in the baking ovens of 120 degree, calcium carbonate is pulverized with small-sized micronizer mill after cooling, make required calcium carbonate sample.
Embodiment 4
Getting 400 ml deionized water joins in the glass beaker of 1000 milliliters with high-speed stirring apparatus, start stirring (rotating speed is 1000 rev/mins), add 4 gram terminal methyl hydrogen containing siloxanes, stirred 5 minutes, slowly add the calcium carbonate (calcium carbonate is without organically-modified calcium carbonate) of 200 grams, pull an oar and process 30 minutes (rotating speed is 3000 rev/mins); Calcium carbonate is baked to complete drying in the baking ovens of 120 degree, calcium carbonate is pulverized with small-sized micronizer mill after cooling, make required calcium carbonate sample.
Embodiment 5
Getting 400 ml deionized water joins in the glass beaker of 1000 milliliters with high-speed stirring apparatus, start stirring (rotating speed is 1000 rev/mins), add, 1 gram hydroxy-terminated polysiloxane, add again 3 gram terminal methyl hydrogen containing siloxanes, stirred 5 minutes, and slowly added the calcium carbonate (calcium carbonate is without organically-modified calcium carbonate) of 200 grams, pull an oar and process 30 minutes (rotating speed is 3000 rev/mins); Calcium carbonate is baked to complete drying in the baking ovens of 120 degree, calcium carbonate is pulverized with small-sized micronizer mill after cooling, make required calcium carbonate sample.
Embodiment 6
Getting 400 ml deionized water joins in the glass beaker of 1000 milliliters with high-speed stirring apparatus, start stirring (rotating speed is 1000 rev/mins), add 2 gram hydroxy-terminated polysiloxanes, add again 2 gram terminal methyl hydrogen containing siloxanes, stirred 5 minutes, slowly add the calcium carbonate (calcium carbonate is without organically-modified calcium carbonate) of 200 grams, pull an oar and process 30 minutes (rotating speed is 3000 rev/mins); Calcium carbonate is baked to complete drying in the baking ovens of 120 degree, calcium carbonate is pulverized with small-sized micronizer mill after cooling, make required calcium carbonate sample.
Embodiment 7
Getting 400 ml deionized water joins in the glass beaker of 1000 milliliters with high-speed stirring apparatus, start stirring (rotating speed is 1000 rev/mins), add 3 gram hydroxy-terminated polysiloxanes, add again 1 gram terminal methyl hydrogen containing siloxane, stirred 5 minutes, slowly add the calcium carbonate (calcium carbonate is without organically-modified calcium carbonate) of 200 grams, pull an oar and process 30 minutes (rotating speed is 3000 rev/mins); Calcium carbonate is baked to complete drying in the baking ovens of 120 degree, calcium carbonate is pulverized with small-sized micronizer mill after cooling, make required calcium carbonate sample.
Embodiment 8
Getting 400 ml deionized water joins in the glass beaker of 1000 milliliters with high-speed stirring apparatus, start stirring (rotating speed is 1000 rev/mins), add 4 gram hydroxy-terminated polysiloxanes, stirred 5 minutes, slowly add the calcium carbonate (calcium carbonate is without organically-modified calcium carbonate) of 200 grams, pull an oar and process 30 minutes (rotating speed is 3000 rev/mins); Calcium carbonate is baked to complete drying in the baking ovens of 120 degree, calcium carbonate is pulverized with small-sized micronizer mill after cooling, make required calcium carbonate sample.
Performance Detection
1, hydrophobicity
The calcium carbonate that makes is detected by aforesaid hydrophobicity characterizing method, and comparing result is as follows:
2, temperature tolerance detects
The calcium carbonate that makes is detected by aforesaid temperature tolerance characterizing method, and comparing result is as follows:
| The calcium carbonate sample | Temperature tolerance |
| Example 1 | Object of reference |
| Example 2 | Serious xanthochromia |
| Example 3 | Xanthochromia |
| Example 4 | Slightly in object of reference |
| Example 5 | Be better than object of reference |
| Example 6 | Be much better than object of reference |
| Example 7 | Be much better than object of reference |
| Example 8 | Be much better than object of reference |
Can be found out by above-mentioned experimental result: after adopting organic surface modifying method of the present invention to carry out the surface organic modification processing to calcium carbonate, can significantly improve hydrophobic performance and the heat resistance of calcium carbonate.
Claims (1)
1. one kind is improved plastics calcium carbonate hydrophobicity and durothermic surface modifying method.It is characterized in that: first the special organosilicon material with appropriate viscosity joins in appropriate amount of deionized water, starts stirring (rotating speed 300-3000 rev/min), then adds the calcium carbonate powders without organically-modified processing, pulls an oar and processes 5-30 minute; Calcium carbonate slurry is baked to complete drying in the baking oven of 100-150 degree centigrade, calcium carbonate is pulverized with small-sized micronizer mill after cooling, make required calcium carbonate;
Described organosilicon material is one or both the compound that contains hydroxy-terminated polysiloxane, terminal methyl hydrogen containing siloxane, and molecular formula is respectively:
Terminal methyl hydrogen containing siloxane: (CH
3)
3SiO[SiO (H) (CH
3)]
nSi (CH
3)
3N=15-50
Hydroxy-terminated polysiloxane: HO (CH
3)
2SiO[SiO (CH
3)
2]
nSi (CH
3)
2OH n=10-30
The consumption of organosilicon material is the 0.5-5.0% of weight of calcium carbonate;
Described calcium carbonate is the calcium carbonate powders without any organically-modified processing.
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|---|---|---|---|
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105255218A (en) * | 2015-10-26 | 2016-01-20 | 广西华纳新材料科技有限公司 | Surface treatment method of special nanometer calcium carbonate for polyurethane sealant |
| CN106675109A (en) * | 2016-11-11 | 2017-05-17 | 恩平燕怡新材料有限公司 | Preparation method of high-activity nano calcium carbonate subjected to surface bioactive treatment |
| CN114889278A (en) * | 2022-04-13 | 2022-08-12 | 惠州市道科包装材料有限公司 | Polyethylene type recyclable packaging material and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105255218A (en) * | 2015-10-26 | 2016-01-20 | 广西华纳新材料科技有限公司 | Surface treatment method of special nanometer calcium carbonate for polyurethane sealant |
| CN106675109A (en) * | 2016-11-11 | 2017-05-17 | 恩平燕怡新材料有限公司 | Preparation method of high-activity nano calcium carbonate subjected to surface bioactive treatment |
| CN114889278A (en) * | 2022-04-13 | 2022-08-12 | 惠州市道科包装材料有限公司 | Polyethylene type recyclable packaging material and preparation method thereof |
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Application publication date: 20130508 |