CN102627788B - Surface modifier formula for significantly reducing calcium carbonate oil absorption value - Google Patents
Surface modifier formula for significantly reducing calcium carbonate oil absorption value Download PDFInfo
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- CN102627788B CN102627788B CN 201110387649 CN201110387649A CN102627788B CN 102627788 B CN102627788 B CN 102627788B CN 201110387649 CN201110387649 CN 201110387649 CN 201110387649 A CN201110387649 A CN 201110387649A CN 102627788 B CN102627788 B CN 102627788B
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- Prior art keywords
- calcium carbonate
- surface modification
- surface modifier
- oil
- absorption value
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 title claims abstract description 62
- 229910000019 calcium carbonate Inorganic materials 0.000 title claims abstract description 31
- 238000010521 absorption reaction Methods 0.000 title claims abstract description 18
- 239000003607 modifier Substances 0.000 title abstract 5
- 238000012986 modification Methods 0.000 claims abstract description 28
- 230000004048 modification Effects 0.000 claims abstract description 28
- 239000000843 powder Substances 0.000 claims abstract description 24
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002131 composite material Substances 0.000 claims abstract description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 20
- 150000001875 compounds Chemical class 0.000 claims description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 14
- -1 polyoxyethylene Polymers 0.000 claims description 14
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 7
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 7
- 239000003921 oil Substances 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 239000010703 silicon Substances 0.000 claims description 7
- 229960004418 trolamine Drugs 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 abstract 1
- 229920013822 aminosilicone Polymers 0.000 abstract 1
- 229920001223 polyethylene glycol Polymers 0.000 abstract 1
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 26
- 229920005989 resin Polymers 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 6
- 229920006337 unsaturated polyester resin Polymers 0.000 description 4
- 239000002994 raw material Substances 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 238000010561 standard procedure Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
Abstract
The invention relates to a surface modifier formula for significantly reducing calcium carbonate oil absorption value. According to the formula, three surface modifiers of polyethylene glycol, triethanolamine and amino silicone oil are compounded; then, the composite surface modifier is heated to 50-95 DEG C and is added into a continuous powder surface modification machine according to a certain proportion of the weight of the calcium carbonate powder so as to carry out surface modification on calcium carbonate. DBP absorption value of the heavy calcium carbonate powder with its average granularity (D50) 5-10 microns after modified by the surface modifier formula can be reduced from 0.26ml/g-0.30ml/g before the modification to 0.13ml/g-0.17ml/g.
Description
1. technical field
The present invention relates to a kind of surface modification agent prescription that can significantly reduce the calcium carbonate oil-absorption(number), belong to powder surface modification and mineral material field.
2. background technology
Resin base artificial stone-like material is the novel organic/inorganic composite decorative building material that is composited by unsaturated polyester resin or Resins, epoxy and heavy calcium carbonate powder, has characteristics such as attractive in appearance, practical, safety, environmental protection, is kind with fastest developing speed among the artificial stone-like material.Water-ground limestone is the topmost filler of resin base artificial stone-like material, generally accounts for more than 75% of artificial stone-like material's quality, and loading level is more big, and resin demand is more few, and production cost is more low, also more environmental protection.Therefore, the loading level that increases water-ground limestone as far as possible is one of major technique developing direction of resin base rostone.
On the one hand because the inorganic nature of heavy calcium carbonate powder, poor with the consistency of organic resin, for the bonding force of the consistency that improves itself and organic resin and enhancing and organic resin with the quality index of guaranteeing matrix material, satisfy corresponding country or industry standard must be carried out surface modification to it; On the other hand, in order to increase the loading level of heavy calcium carbonate powder, also will be when improving itself and organic resin consistency big as far as possible its oil-absorption(number) of reduction.But existing calcium carbonate surface modifying prescription is mainly considered is the consistency that improves itself and organic resin.
The present invention is directed to the deficiency of existing heavy calcium carbonate powder surface modification prescription, proposes a kind of surface modification prescription that can take into account raising heavy calcium carbonate powder and unsaturated polyester resin or epoxy resin compatibility simultaneously and significantly reduce its oil-absorption(number).Make the unsaturated polyester resin based composites can not only significantly increase the loading level of water-ground limestone, and the mechanical property of material and other performances do not descend.
3. summary of the invention
Calcium carbonate surface modifying prescription of the present invention (kind, usage, consumption) is as follows:
(1) surface-modifying agent kind: polyoxyethylene glycol (molecular weight 200～3000), trolamine and amido silicon oil;
(2) usage: 1. (1) described three kinds of surface-modifying agents are carried out compoundly, compound (quality) is than for polyoxyethylene glycol: trolamine: amido silicon oil=0～50: 0～55: 0～50; 2. compound surface-treating agent is heated to 50～95 ℃, in the certain proportion adding continuous powdery surface modification machine by the calcium carbonate powder quality calcium carbonate is carried out surface modification.
(3) the compound surface-treating agent consumption is 0.2%～2.0% of calcium carbonate quality, specifically according to the product fineness of calcium carbonate or specific surface area size and decide.
With the heavy calcium carbonate powder of mean particle size (D50) 5～10 μ m after the surface modification agent prescription of the present invention modification, can be reduced to 0.13ml/g～0.17ml/g by the 0.26ml/g～0.30ml/g before the modification to the absorption value of DBP (dibutyl phthalate).
4. embodiment
Embodiment one: polyoxyethylene glycol (molecular weight 200), trolamine and amido silicon oil is compound, stand-by by 35: 50: 15 mass ratio.Adopt the continuous powder surface modification machine of SLG-3/300 type as modified device; The globule size of modified heavy calcium carbonate powder raw material and be distributed as D
50=6.82 μ m, D
97=22.18 μ m, oil-absorption(number) (DBP) is 0.27ml/g.Compound surface-treating agent is moved into the chemical tank of surface modification machine and heat; treat to open the continuous powder surface modification machine of SLG-3/300 type after temperature reaches 80 ℃ and properties-correcting agent is metered into pump; beginning charging and 0.8% add compound surface-treating agent and carry out surface modification by what treat the modified heavy calcium carbonate quality; move and collect modified heavy calcium carbonate powder continuously; shut down behind the 30min, sampling is carried out oil-absorption(number) with dibutyl phthalate (DBP) by corresponding national standard method and is detected.
Embodiment two: polyoxyethylene glycol (molecular weight 200), trolamine and amido silicon oil is compound, stand-by by 30: 35: 35 mass ratio.Adopt the continuous powder surface modification machine of SLG-3/300 type as modified device; The globule size of modified heavy calcium carbonate powder raw material and be distributed as D
50=6.82 μ m, D
97=22.18 μ m, oil-absorption(number) (DBP) is 0.27ml/g.Compound surface-treating agent is moved into the chemical tank of surface modification machine and heat; treat to open the continuous powder surface modification machine of SLG-3/300 type after temperature reaches 80 ℃ and properties-correcting agent is metered into pump; beginning charging and 0.8% add compound surface-treating agent and carry out surface modification by what treat the modified heavy calcium carbonate quality; move and collect modified heavy calcium carbonate powder continuously; shut down behind the 30min, sampling is carried out oil-absorption(number) with dibutyl phthalate (DBP) by corresponding national standard method and is detected.
Embodiment three: polyoxyethylene glycol (molecular weight 200), trolamine and amido silicon oil is compound, stand-by by 35: 45: 20 mass ratio.Adopt the continuous powder surface modification machine of SLG-3/300 type as modified device; The globule size of modified heavy calcium carbonate powder raw material and be distributed as D
50=6.82 μ m, D
97=22.18 μ m, oil-absorption(number) (DBP) is 0.27ml/g.Compound surface-treating agent is moved into the chemical tank of surface modification machine and heat; treat to open the continuous powder surface modification machine of SLG-3/300 type after temperature reaches 80 ℃ and properties-correcting agent is metered into pump; beginning charging and 0.8% add compound surface-treating agent and carry out surface modification by what treat the modified heavy calcium carbonate quality; move and collect modified heavy calcium carbonate powder continuously; shut down behind the 30min, sampling is carried out oil-absorption(number) with dibutyl phthalate (DBP) by corresponding national standard method and is detected.
Table 1 is oil-absorption(number) (DBP) detected result of embodiment product.
Oil-absorption(number) (DBP) detected result of table 1 embodiment product
| Embodiment | One | Two | Three |
| Oil-absorption(number)/(ml/g) | 0.16 | 0.14 | 0.15 |
Claims (1)
1. surface modifying method that can significantly reduce the calcium carbonate oil-absorption(number) is characterized in that:
(1) surface-modifying agent is polyoxyethylene glycol, trolamine and the amido silicon oil of molecular weight 200～3000;
(2) (1) described three kinds of surface-modifying agents are carried out compound, composite quality is than for polyoxyethylene glycol: trolamine: amido silicon oil=35: 45: 20; Compound surface-treating agent is heated to 50～95 ℃ then, adds in the continuous powdery surface modification machine calcium carbonate powder is carried out surface modification.
(3) consumption of compound surface-treating agent is 0.8% of calcium carbonate quality.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 201110387649 CN102627788B (en) | 2011-11-29 | 2011-11-29 | Surface modifier formula for significantly reducing calcium carbonate oil absorption value |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110387649 CN102627788B (en) | 2011-11-29 | 2011-11-29 | Surface modifier formula for significantly reducing calcium carbonate oil absorption value |
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| CN102627788A CN102627788A (en) | 2012-08-08 |
| CN102627788B true CN102627788B (en) | 2013-07-17 |
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| CN 201110387649 Active CN102627788B (en) | 2011-11-29 | 2011-11-29 | Surface modifier formula for significantly reducing calcium carbonate oil absorption value |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103432958B (en) * | 2013-08-22 | 2014-11-05 | 郑四荣 | Calcium carbonate surface-active agent |
| CN105820600A (en) * | 2015-12-27 | 2016-08-03 | 湖北恒旭新材料科技股份有限公司 | Method for reducing oil absorption of heavy calcium carbonate powder |
| CN105968877B (en) * | 2016-07-26 | 2017-09-22 | 中国矿业大学(北京) | A kind of basic magnesite filler preparation method for filling unsaturated polyester resin |
| CN106431043B (en) * | 2016-09-13 | 2018-11-02 | 广西大学 | Strengthen the method using dual-functional group modifier modification lime stone under a kind of microwave field |
| CN116023802A (en) * | 2022-12-27 | 2023-04-28 | 池州市贵兴非矿新材料有限公司 | Modified heavy calcium carbonate with low oil absorption value |
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| CN1323947C (en) * | 2005-12-29 | 2007-07-04 | 上海耀华纳米科技有限公司 | Tech. for preparing super fine actived calcium carbonate with low oil absorpsion value |
| CN101914311B (en) * | 2010-07-30 | 2012-12-26 | 浙江常山金雄有限公司 | Calcium carbonate surface modifying method |
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Application publication date: 20120808 Assignee: Yunnan macro innovation Mstar Technology Ltd Assignor: China University of Mining & Technology, Beijing Contract record no.: 2016990000189 Denomination of invention: Surface modifier formula for significantly reducing calcium carbonate oil absorption value Granted publication date: 20130717 License type: Exclusive License Record date: 20160509 |
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