CN1597531A - Modified nanometer calcium carbonate and its preparation method - Google Patents
Modified nanometer calcium carbonate and its preparation method Download PDFInfo
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- CN1597531A CN1597531A CN 200410028166 CN200410028166A CN1597531A CN 1597531 A CN1597531 A CN 1597531A CN 200410028166 CN200410028166 CN 200410028166 CN 200410028166 A CN200410028166 A CN 200410028166A CN 1597531 A CN1597531 A CN 1597531A
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- calcium carbonate
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- resorcinol
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Abstract
A process for preparing the modified nano-calcium carbonate from the nano-calcium carbonate or stearic acid modified calcium carbonate includes such steps as proportionally adding resorcin or resorcin donor and methylene donor, and reacting at 80-120 deg.C for 0.5-2 hr.
Description
Technical field
The present invention relates to technical field of nano material, specifically relate to a kind of modified nano calcium carbonate and preparation method thereof.
Background technology
The principal character of nano composite material (Nanocomposites) be the one or more components in the compound system have at least one dimension with nano-scale (≤100nm) be evenly dispersed in the matrix of another component.The polymer/inorganic thing nano composite material that polymkeric substance and some inorganics nano-powder are formed, its polymkeric substance forms even and firm combining with the particles of inorganic material with nano-scale structure, the nanophase specific surface area is big, and phase spacing is little, there is special interaction, so its performance has the raising of highly significant than corresponding macroscopic view or micron order matrix material (for example, traditional Inorganic Fillers Filled polymer-modified), even qualitative leap appears, show brand-new performance or function.The development of polymer/inorganic thing nano composite material has represented a wide path of improving current material performance and development novel material significantly.
Macromolecular material (as rubber, plastics, coating, tackiness agent, polymer composite etc.) industry is extensive use of various mineral fillers (as lime carbonate, silicon-dioxide, talcum powder etc.), and traditional technology can only make it to reach the micron particles dispersion, can not produce significantly enhancing, toughness reinforcing and other modifying functions to polymkeric substance usually.In recent years along with the development of inorganic materials refinement technology, can make this class mineral filler reach nanoscale structures, thereby polymkeric substance is produced significantly enhancing toughening effect, and can improve other performances of polymkeric substance simultaneously, as thermotolerance, barrier, flame retardant resistance, ageing resistance etc., this has just opened up a new research field for the development of polymer science and technology.
Calcium carbonate superfine powder is a kind of suitability for industrialized production and the nano-calcium carbonate that obtains the cheapness with nano-scale of widespread use in macromolecular material industry.Under the situation of long time without surface modification, calcium carbonate superfine powder can produce serious agglomeration, is difficult to homodisperse in polymkeric substance, thereby is difficult to polymkeric substance is produced modified effect.At present, industrially many with stearic acid nano-calcium carbonate is carried out surface treatment, but only be physically modified, the effect of calcium carbonate granule and rubber matrix is very weak; Also useful coupling agent carries out modification to nano-calcium carbonate, but cost is higher.Other method of modifying is at present also rarely seen in industrial application, mainly is the cost height or is not easy to industrialization promotion.
Summary of the invention
The objective of the invention is shortcoming at existing calcium carbonate superfine powder process for modifying surface existence, a kind of preparation method of new modified nano calcium carbonate is provided, the modified nano calcium carbonate surface that obtains has coated one deck Resorcinol (or Resorcinol donor) and vulkacit H (or other methylene radical donors), and produce firm combination by modes such as hydrogen bonds, and can chemistry or physical bond take place with polymeric matrix (as vulcanized rubber, thermoplastic resin, thermosetting resin), thereby strengthen its interface combination, improve the over-all properties of material.
The present invention also aims to provide the modified nano calcium carbonate of described method preparation.
The preparation method of modified nano calcium carbonate of the present invention comprises:
100 parts of (mass parts, add 1～15 part of Resorcinol or Resorcinol donor and 1～25 part of methylene radical donor in nano-calcium carbonate or the stearic acid modified nano-calcium carbonate dry powder down together), reacted 0.5～2 hour down at 80～120 ℃, make modified nano calcium carbonate and (be called for short M-CaCO
3).Perhaps,
In 100 parts of (mass parts, down together) nano-calcium carbonates or stearic acid modified nano-calcium carbonate dry powder, add 1～25 part of Resorcinol and vulkacit H complex compound (RH), reacted 0.5～2 hour down, make modified nano calcium carbonate at 80～120 ℃.
Above-mentioned Resorcinol donor comprises the mixture or the compound of Resorcinol or derivatives thereof and organism (as stearic acid, resin) or inorganics (as silicon-dioxide or other fillers).
The methylene radical donor comprises wherein one or more mixtures of vulkacit H, modification vulkacit H, hexamethoxy methyl cyanuramide or its mixture.
The modified nano calcium carbonate surface of method for preparing has coated one deck Resorcinol (or Resorcinol donor) and vulkacit H (or other methylene radical donors), and produce firm combination by modes such as hydrogen bonds, strengthened the hydrophobicity on nano-calcium carbonate surface, make it be easy in polymkeric substance, disperse, reduced the reunion of nanoparticle; Under the polymer processing temperature, polymerization takes place and forms resol in surface coated Resorcinol (or Resorcinol donor) and vulkacit H (or other methylene radical donors), and with polymeric matrix (as vulcanized rubber, thermoplastic resin, thermosetting resin) chemistry or physical bond take place, thereby strengthened the interface combination, improved the over-all properties of nano composite material.
Modified nano calcium carbonate of the present invention can be applied to various polymkeric substance (as various rubber, plastics, coating, tackiness agent etc.) preparation polymer/inorganic thing nano composite material, be used to make various vulcanized rubber articles, plastics, coating, tackiness agent, water-proof material etc., have wide prospect in industrial application.
Embodiment
Embodiment 1
The preparation of modified nano calcium carbonate: in 100 gram nano-calcium carbonate dry powder, add 8.8 gram Resorcinols and 11.2 gram hexamethylenetetramines, under 100 ℃ in flask high speed stirring reaction 1 hour.Be cooled to room temperature and promptly get modified nano calcium carbonate M-CaCO
3
The preparation of rubber/modified nano calcium carbonate nano composite material: basic recipe (mass parts): natural rubber 100, M-CaCO
38, RH 5, stearic acid 2, zinc oxide 4, altax 0.5, accelerant CZ 1.5, antioxidant 4010NA 0.5, sulphur 2.Routinely the compounding rubber method mixing, the sulfuration and the test.
The nano combined cross-linked rubber of gained shows that by scanning electron microscope and transmissioning electric mirror test modified calcium carbonate is uniformly dispersed in this material, and the interface is fuzzy, illustrates that calcium carbonate granule has produced good binding with rubber matrix.Table 1 shows, NR/M-CaCO
3The comprehensive mechanical property of nano composite material obviously is better than filling unmodified nano-calcium carbonate system (NR/U-CaCO
3) and fill stearic acid modified nano-calcium carbonate (NR/CCR) system (CCR is the commodity nano-calcium carbonate, Enping City, Guangdong Guangping chemical industry Industrial Co., Ltd. product).M-CaCO is described
3Strengthening action to rubber significantly is better than U-CaCO
3And CCR, ageing-resistant performance also significantly improves simultaneously.The thermogravimetric analysis of table 2 (TGA) result shows that the adding of modified nano calcium carbonate of the present invention has significantly improved the thermostability of natural rubber vulcanized rubber, and its 5% weightless temperature increasing degree surpasses 30 ℃, obviously is better than U-CaCO
3And CCR.
Table 1 contains different nanometer CaCO
3The mechanical property of the natural rubber vulcanized rubber of (8 parts)
| Sample | 300% stress at definite elongation/MPa | Tensile strength/MPa | Tensile yield/% | Tensile set/% | Tear strength/kN/m | Shao Er A hardness | Thermal aging property rate of descent */% | Cross-linking density/V r |
| ??NR | 2.2 | ????30.0 | ????730 | ????29 | 28.1 | ???43 | 72 | ??0.284 |
| ??NR/M-CaCO 3 | 3.9 | ????26.0 | ????600 | ????8 | 44.5 | ???47 | 3 | ??0.303 |
| ??NR/U-CaCO 3 | 2.3 | ????26.5 | ????700 | ????29 | 24.2 | ???46 | 75 | ??0.277 |
| ??NR/CCR | 2.2 | ????20.2 | ????615 | ????6 | 33.7 | ???44 | 22 | ??0.282 |
* aging condition: 100 ℃ * 48h, aging before and after the rate of descent of tensile strength and tensile yield product.
Table 2NR, NR/CCR, NR/M-CCR and NR/M-CaCO
3The TGA result of cross-linked rubber (atmosphere: nitrogen)
| Sample | ????NR | ????NR/U-CaCO 3 | ????NR/CCR | ????NR/M-CaCO 3 |
| 5% weightless temperature (℃) | ????275.76 | ????289.32 | ????298.89 | ????306.07 |
| 10% weightless temperature (℃) | ????329.68 | ????337.06 | ????337.98 | ????339.38 |
| Maximum weightless temperature (℃) | ????377.31 | ????377.20 | ????377.18 | ????377.45 |
Embodiment 2
The preparation of modified nano calcium carbonate: add 1.0 gram Resorcinols and 2.0 gram vulkacit Hs in 100 gram nano-calcium carbonate dry powder, 120 ℃ of high-speed stirring were reacted 1 hour in flask.Be cooled to room temperature and promptly get modified nano calcium carbonate M-CaCO
3
The preparation of rubber/modified nano calcium carbonate nano composite material: basic recipe (mass parts): paracril 100, M-CaCO
380, RH 6, stearic acid 2, zinc oxide 4, altax 0.5, accelerant CZ 1.5, antioxidant 4010NA 0.5, sulphur 1.5.The compounding rubber method is mixing routinely, sulfuration and test.
The test shows of mechanical property, M-CaCO under identical loading level
3Reinforcing effect to NBR is much better than CCR.When the two loading level during to 80phr, NBR/M-CaCO
3300% stress at definite elongation of cross-linked rubber, tear strength respectively 5 times, 2.5 times to NBR/CCR, and tension set has only the latter's 1/10th, shows good reinforcing effect; SEM observes and finds M-CaCO
3Dispersion in NBR is even than CCR; Thermogravimetric analysis (TGA) shows, when NBR fills 80phr M-CaCO
3The time, its maximum weightless temperature has improved nearly 13 ℃, has improved the thermostability of NBR significantly.
Embodiment 3
The preparation of modified nano calcium carbonate: in 100 gram nano-calcium carbonate dry powder, add 15.0 gram Resorcinol donor RS-11 (Resorcinol and silicon-dioxide are pressed 1: 1 mixture) and 25.0 gram hexamethoxy methyl cyanuramides, under 80 ℃,, be cooled to room temperature and promptly get modified nano calcium carbonate M-CaCO in flask high speed stirring reaction 2 hours
3
The preparation of rubber/modified nano calcium carbonate nano composite material: basic recipe (mass parts): paracril 100, M-CaCO
310, zinc dimethacrylate (ZDMA) 20, stearic acid 2, zinc oxide 4, altax 0.5, accelerant CZ 1.5, antioxidant 4010NA 0.5, sulphur 1.5, initiator (DCP) 2, the compounding rubber method is mixing routinely, sulfuration and test.Table 3 has been listed the NBR/ZDMA system and has been filled Different Ca CO
3Mechanical property.The comprehensive mechanical property that shows the NBR/M-CaCO3/ZDMA system obviously is better than other systems.
Table 3 paracril is filled 10 parts of CaCO
3With 40 parts of ZDMA mechanical properties of vulcanizate
300% stretches 500% surely stretches stretching surely and pulls apart by force that stretching stretches tears Shao Shi
Sample
Stress/MPa stress/MPa degree/MPa is long, and rate/A is hard for the % permanent strength
Distortion/(kNm
-1) degree
/％
NBR/ZDMA????????????3.3????????8.1????????22.2????540??????20????????67.0??????????72
NBR/M-CaCO
3/ZDMA???4.1????????13.0???????28.7????500??????22????????61.2??????????74
NBR/U-CaCO
3/ZDMA???3.7????????10.64??????22.0????500??????16????????53.8??????????74
NBR/CCR/ZDMA????????4.4????????9.4????????22.9????520??????30????????57.6??????????74
Embodiment 4
The preparation of modified nano calcium carbonate: in the stearic acid modified nano-calcium carbonate of 100g (CCR) dry powder, add 8.0 gram Resorcinols and 12.0 gram vulkacit Hs, under 80 ℃,, be cooled to room temperature and promptly get twice-modified nano-calcium carbonate M-CCR in flask high speed stirring reaction 2 hours.
The preparation of polymkeric substance/modified nano calcium carbonate nano composite material: basic recipe (mass parts): natural rubber 100, M-CCR 8, and RH 5, stearic acid 2, zinc oxide 4, altax 0.5, accelerant CZ 1.5, antioxidant 4010NA 0.5, sulphur 2.The compounding rubber method is mixing routinely, sulfuration and test.
The mixture of gained (NR/M-CCR) sulfuration and by scanning electron microscope and transmissioning electric mirror test, find that M-CCR is uniformly dispersed in this material, and particle surface is fuzzy, illustrate that calcium carbonate granule combines with the rubber matrix generation, its performance obviously is better than NR/CCR system (seeing Table 4), comprehensive mechanical property the best when wherein M-CCR is 8 parts.
Table 4 is filled 8 parts of Different Ca CO
3The time natural rubber vulcanized rubber performance
300% decides stretching pulls apart by force and stretches permanent change to tear strong Shao A warm air old crosslinked close
Sample
Stretch and answer the long rate of dynamics/MPa/% shape/% degree hardness voltinism can descend degree/Vr
Rate/% falls in/MPa/kN/m
NR????????????2.2??????30.0?????730?????29????????28.1????43????????72??????????0.28
NR/CCR????????2.2??????20.2?????615?????6?????????33.7????44????????22??????????0.28
NR/M-CCR??????3.6??????23.4?????597?????8?????????42.1????45????????6???????????0.30
Embodiment 5
The preparation of modified nano calcium carbonate: in 100 gram nano-calcium carbonate dry powder, add 15.0 gram Resorcinol and hexamethylenetetramine complex compound RH, under 80 ℃,, be cooled to room temperature and promptly get modified nano calcium carbonate M-CaCO in flask high speed stirring reaction 2 hours
3
The preparation of polymkeric substance/modified nano calcium carbonate nano composite material: basic recipe (mass parts): natural rubber 100, M-CCR 8, and RH 5, stearic acid 2, zinc oxide 4, altax 0.5, accelerant CZ 1.5, antioxidant 4010NA 0.5, sulphur 2.The compounding rubber method is mixing routinely, sulfuration and test.
This system (NR/M-CaCO
3) comprehensive mechanical property (seeing Table 5) obviously be better than filling stearic acid modified nano-calcium carbonate system (NR/CCR), in addition, NR/M-CaCO
3The cross-linking density of system improves than NR and NR/CCR system, declaratives M-CaCO
3Participated in the crosslinking reaction of natural rubber, produced certain combining with rubber matrix.
Table 5 natural rubber is filled 8 parts of Different Ca CO
3The time mechanical properties of vulcanizate
300% decides stretching pulls apart by force and stretches permanent change to tear the hard warm air of Qiang Shao A crosslinked close
Sample
Stretch and answer the long rate of dynamics/MPa/% shape/% degree/kN/m degree aging degree/V
r
/ MPa can descend
Rate/%
NR?????????????2.2????????30.0??????730???????29????????28.1?????43??????72???????0.284
NR/CCR?????????2.2????????20.2??????615???????6?????????33.7?????44??????22???????0.282
NR/M-CaCO
3????3.6????????23.4??????597???????8?????????42.1?????45??????6????????0.297
Claims (5)
1, a kind of preparation method of modified nano calcium carbonate, it is characterized in that: in 100 mass parts nano-calcium carbonates or stearic acid modified nano-calcium carbonate dry powder, add 1～15 part of Resorcinol or Resorcinol donor and 1～25 part of methylene radical donor, reacted 0.5～2 hour down at 80～120 ℃, make modified nano calcium carbonate.
2, the preparation method of modified nano calcium carbonate according to claim 1 is characterized in that described Resorcinol donor comprises the mixture or the compound of Resorcinol or derivatives thereof and organism stearic acid, resin or inorganics silicon-dioxide.
3, the preparation method of modified nano calcium carbonate according to claim 1 and 2 is characterized in that the methylene radical donor comprises wherein one or more mixtures of vulkacit H, modification vulkacit H, hexamethoxy methyl cyanuramide or its mixture.
4, a kind of preparation method of modified nano calcium carbonate, it is characterized in that: in 100 mass parts nano-calcium carbonates or stearic acid modified nano-calcium carbonate dry powder, add 1～25 part of Resorcinol and vulkacit H complex compound, reacted 0.5～2 hour down at 80～120 ℃, make modified nano calcium carbonate.
5, a kind of modified nano calcium carbonate is characterized in that it being that method by claim 1 or 4 prepares.
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| CN 200410028166 CN1597531A (en) | 2004-07-21 | 2004-07-21 | Modified nanometer calcium carbonate and its preparation method |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1331754C (en) * | 2005-07-20 | 2007-08-15 | 哈尔滨工业大学 | Nanometer conductive calcium carbonate and its production thereof |
| CN100362058C (en) * | 2005-12-20 | 2008-01-16 | 中国地质大学（武汉） | Dry process mechanical force and chemical modification method of superfine calcium carbonate |
| CN101250338B (en) * | 2008-04-01 | 2010-11-10 | 中国科学院化学研究所 | Modified inorganic nano-particle as well as preparation method and use thereof |
| CN101891909A (en) * | 2010-07-14 | 2010-11-24 | 西南石油大学 | Multifunctional nano CaCO3 reinforced nitrile rubber |
| CN102898112A (en) * | 2011-07-29 | 2013-01-30 | 上海圣济国际贸易有限公司 | Novel environmentally friendly material of composite calcium carbonate |
| CN104693482A (en) * | 2015-04-03 | 2015-06-10 | 浙江宇翔生物科技有限公司 | Rubber multi-function additive efficient modulus fortifier and preparation method thereof |
| TWI510432B (en) * | 2010-04-09 | 2015-12-01 | Omya Int Ag | Use of surface modified calcium carbonate in adhesives, sealants and/or caulks |
| CN106967310A (en) * | 2017-05-05 | 2017-07-21 | 南宁市三通专用化学助剂技术有限公司 | One kind paint dedicated modified calcium carbonate of class and preparation method thereof |
| CN107033630A (en) * | 2017-04-24 | 2017-08-11 | 确成硅化学股份有限公司 | A kind of preparation method of silicon rubber white carbon |
| CN109503929A (en) * | 2018-12-10 | 2019-03-22 | 深圳市欧科力科技有限公司 | A kind of environment-friendly type composite plastic and preparation method thereof |
| CN110437500A (en) * | 2019-08-15 | 2019-11-12 | 浙江宇翔生物科技有限公司 | A kind of rubber processing aids and its production technology improving rubber stiffness |
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2004
- 2004-07-21 CN CN 200410028166 patent/CN1597531A/en active Pending
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1331754C (en) * | 2005-07-20 | 2007-08-15 | 哈尔滨工业大学 | Nanometer conductive calcium carbonate and its production thereof |
| CN100362058C (en) * | 2005-12-20 | 2008-01-16 | 中国地质大学（武汉） | Dry process mechanical force and chemical modification method of superfine calcium carbonate |
| CN101250338B (en) * | 2008-04-01 | 2010-11-10 | 中国科学院化学研究所 | Modified inorganic nano-particle as well as preparation method and use thereof |
| TWI510432B (en) * | 2010-04-09 | 2015-12-01 | Omya Int Ag | Use of surface modified calcium carbonate in adhesives, sealants and/or caulks |
| CN101891909A (en) * | 2010-07-14 | 2010-11-24 | 西南石油大学 | Multifunctional nano CaCO3 reinforced nitrile rubber |
| CN101891909B (en) * | 2010-07-14 | 2011-11-16 | 西南石油大学 | Multifunctional nano CaCO3 reinforced nitrile rubber |
| CN102898112A (en) * | 2011-07-29 | 2013-01-30 | 上海圣济国际贸易有限公司 | Novel environmentally friendly material of composite calcium carbonate |
| CN104693482A (en) * | 2015-04-03 | 2015-06-10 | 浙江宇翔生物科技有限公司 | Rubber multi-function additive efficient modulus fortifier and preparation method thereof |
| CN107033630A (en) * | 2017-04-24 | 2017-08-11 | 确成硅化学股份有限公司 | A kind of preparation method of silicon rubber white carbon |
| CN107033630B (en) * | 2017-04-24 | 2019-03-29 | 确成硅化学股份有限公司 | A kind of preparation method of silicon rubber white carbon black |
| CN106967310A (en) * | 2017-05-05 | 2017-07-21 | 南宁市三通专用化学助剂技术有限公司 | One kind paint dedicated modified calcium carbonate of class and preparation method thereof |
| CN106967310B (en) * | 2017-05-05 | 2019-02-01 | 南宁市三通专用化学助剂技术有限公司 | Dedicated modified calcium carbonate of a kind of paint class and preparation method thereof |
| CN109503929A (en) * | 2018-12-10 | 2019-03-22 | 深圳市欧科力科技有限公司 | A kind of environment-friendly type composite plastic and preparation method thereof |
| CN110437500A (en) * | 2019-08-15 | 2019-11-12 | 浙江宇翔生物科技有限公司 | A kind of rubber processing aids and its production technology improving rubber stiffness |
| CN110437500B (en) * | 2019-08-15 | 2021-09-07 | 浙江蓝色海洋生物科技有限公司 | Rubber processing aid for improving rubber rigidity and production process thereof |
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