CN1800250A - Intercalated vermiculite/ natural rubber nanometer composite material and its preparation method - Google Patents
Intercalated vermiculite/ natural rubber nanometer composite material and its preparation method Download PDFInfo
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Abstract
The invention relates to an intercalation malacolite /natural rubber nanometer composite material and it's preparing method. It uses malacolite raw ore as material and shatters it then mixes it with the intercalation agent and the ion-free water, it uses ball crusher to crush them, washes, dries and shatters them to obtain the intercalation malacolite colloidal powder, wherein the malacolite (001) interlamellar spacing has been stayed to 4.38nm; it mixes the natural rubber and the intercalation malacolite and other matching agents to obtain the needed intercalation malacolite /natural rubber nanometer composite material.
Description
Technical field
The present invention relates to a kind of intercalated vermiculite/natural rubber nanometer composite material and preparation method thereof.Relate in particular to a kind of nano composite material that is composited by the intercalated vermiculite and the natural rubber of Prepared by Ball Milling and preparation method thereof.
Background technology
Vermiculite is the secondary metamorphic mineral of magniferous water aluminosilicate of a kind of 2: 1 type laminate structures, is mainly biotite and the phlogopite alteration product through the low temperature hot liquid effect, and its chemical formula is Mg
x(H
2O) { Mg
3-x[AlSi
3O
10] (OH)
2.The unit structure layer that the crystalline structure of vermiculite is made up of two-layer silicon-oxy tetrahedron stratum reticulare folder one deck magnesia octahedral layer constitutes, owing to often exist Al to substitute Si in the silicon-oxy tetrahedron, so the vermiculite structural sheet often is electronegativity, therefore exist positively charged ion to promote electrovalent balance between structural sheet, get final product exchangeable cation.Simultaneously the highlyest between the vermiculite structural sheet there is a two-layer water molecules, connected by exchangeable cation therebetween.This structure of vermiculite makes it have excellent ion exchangeable, thermal expansivity, adsorptivity and becomes a kind of important industrial mineral in the nonmetalliferous ore, is widely used in fields such as building, energy-saving and environmental protection, husbandry, gardening at present.
Along with improving and development of layered silicate (being mainly montmorillonite) polymer nanocomposites technology of preparing, vermiculite has been subjected to increasing attention because of having the crystalline structure and the interlayer cation exchangeability that are similar to montmorillonite, and it very likely becomes the important source material in the polymer nanocomposites from now on.Recently, occurred the research report of some relevant polymkeric substance/vermiculite nano composite materials both at home and abroad, but the correlative study of relevant intercalated vermiculite vermiculite/natural rubber nanometer composite material preparation does not appear in the newspapers as yet.
Summary of the invention
The object of the present invention is to provide a kind of intercalated vermiculite/natural rubber nanometer composite material and preparation method thereof, vermiculite can be dispersed in the natural rubber matrix being the nanometer lamella.The natural rubber that the present invention uses includes natural rubber preparation or deutero-derived product, as epoxy natural rubber, styrene butadiene rubbers (SBR), paracril (NBR), polyisoprene, polyhutadiene and chloroprene rubber (CR) etc.
Purpose of the present invention is achieved through the following technical solutions:
A kind of nano composite material of intercalated vermiculite/natural rubber is characterized in that, the feed composition and the content of described matrix material are as follows:
Material content (mass fraction)
Natural rubber 100
Intercalated vermiculite 5～40
Stearic acid 1～3
Promotor 1 0.5～1
Sulphur 1～3
Wherein, described intercalated vermiculite is meant that primary mineral of vermiculite is that raw material, quaternary ammonium salt are the intercalated vermiculite of intercalator, and promotor 1 is TMTD, and promotor 2 is tetramethyl-thiuram disulfide.
The preferred feedstock component and the content of described matrix material are as follows:
Material content (mass fraction)
Natural rubber 100
Intercalated vermiculite 15
Zinc oxide 5
Promotor 1 0.7
Sulphur 2.5
The tensile strength of matrix material of the present invention, elongation at break, 300% tensile modulus, Shore A hardness, tear strength all have more significantly to be improved.The matrix material that wherein contains 15 parts of OVMT has optimum properties, and tensile strength and elongation at break have improved 235% and 88% than the bright sulfur natural rubber respectively
In addition, the present invention also announces the preparation method of the nano composite material of above-mentioned intercalated vermiculite/natural rubber, it is characterized in that, with the primary mineral of vermiculite is raw material, with the quaternary ammonium salt is intercalator, by ball milled vermiculite is carried out intercalation modifying and superfine grinding integrated, prepare a kind of intercalation type vermiculite superfine powder; The natural rubber of different proportionings and intercalated vermiculite are joined in the HAAKE torque rheometer hybrid process certain hour; Mixing evenly mixture and other Synergist S-421 95 in two roller mills then; At last on vulcanizing press the sulfuration, compressing tablet.
1) preparation intercalated vermiculite superfine powder
A. the vermiculite former state is pulverized and is weighed through airflow milling, adds quaternary ammonium salt, and the cation exchange capacity (CEC) that makes quaternary ammonium salt is 1～4 times of vermiculite cation exchange capacity (CEC), and adds 4～10 times of deionized waters to the vermiculite quality, mixes;
B. in grinding in ball grinder 15min～4 hour; With the sample that obtains after grinding, through centrifugal, filter, and with deionized water repetitive scrubbing 5～7 times, through Ag
+Detecting no white precipitate (AgBr) produces; Process sample centrifugal, that filter gained is dried and is ground to form powdery, obtains intercalated vermiculite;
2) preparation intercalated vermiculite/natural rubber nanometer composite material
A. natural rubber and intercalated vermiculite (OMVT) by ratio of quality and the number of copies 100: (5～40) join in the HAAKE torque rheometer, under 100～180 ℃ temperature, with rotating speed hybrid process 5～30min of 80～120rpm;
B. with step 2) mixture that obtains among a and other Synergist S-421 95 in two roller mills mixing evenly, its ratio of quality and the number of copies is: 1～3 part of stearic acid, 4～8 parts in zinc oxide, 10.5～1 parts of promotor, 20.3～0.8 parts of promotor, 1～3 part in sulphur;
C. the mixture of gained promptly gets the nano composite material of intercalated vermiculite/natural rubber with vulcanizing press sulfuration, compressing tablet.
In the described method, as preferred cetyl trimethylammonium bromide of the quaternary ammonium salt of intercalator or octadecyl trimethylammonium bromide;
Available stirring mill, vibration mill substitute described method steps 1) ball mill among the b;
The step 2 of aforesaid method) among a, natural rubber and the intercalated vermiculite mixing temperature in the HAAKE torque rheometer is 120 ℃, and hybrid process is 15min, and the rotating speed of HAAKE torque rheometer is 120rpm.
The step 2 of aforesaid method) among the c, with step 2) mixture that obtains among the b vulcanized 14 minutes under 140 ℃ temperature with vulcanizing press.
The present invention can make quaternary ammonium salt insert fast between the vermiculite structural sheet by ball milled, and make its (001) spacing increase to 4.38nm by the 1.46nm of raw ore, pass through the mixing of HAAKE torque rheometer and mill simultaneously, the state that can make vermiculite be the nanometer lamella is dispersed in the middle of the matrix of natural rubber, and its mechanical property has more significantly raising.
Description of drawings
Fig. 1 is the XRD figure of vermiculite raw material and intercalated vermiculite in the invention process example
Fig. 2 is an XRD figure in the invention process example 3
Fig. 3 is the physical and mechanical properties graphic representation of the matrix material of different umber vermiculites in the invention process example.
Embodiment
Embodiment 1:
The Shijiazhuang City silvery white vermiculite of mining industry Building Materials Factory of conquering east is pulverized through airflow milling, and crosses 100 mesh sieves and get raw material vermiculite (VMT), and its chemical constitution is: SiO
2: 41.2%, AL
2O
3: 12.68%, MgO:24.22%, CaO:0.96%, FeO:1.54%, Fe
2O
3: 4.06%, TiO
2: 1.33%, K
2O:5.97%, P
2O
5: 0.06%, H
2O:3%, Na
2O:1.6%, MnO:0.043%, TiO:5.097% burns and loses 6.71%.
At first, make slurry the cetyl trimethylammonium bromide of VMT sample and 2 times of CEC, the mixed stirring of deionized water.In ball mill, grind centrifugal, the filtration of sample process of taking out 15min grinding back respectively, use deionized water repetitive scrubbing 5 to 7 times, through Ag
+Detect no white precipitate (AgBr) and produce, drying through sample centrifugal, that filter gained and grinding to form powdery, obtain intercalated vermiculite (OVMT) at last.Fig. 1 is the XRD contrast collection of illustrative plates of sample VMT, VMT15m, and the d value of (001) face diffraction peak of VMT is that (001) spacing is 1.46nm among the figure.The d value of VMT15m is that the diffraction peak of 1.46nm disappears, and occurs the diffraction peak of 4.38nm simultaneously.After illustrating that the ball milled method is handled, the intercalator cetyl trimethylammonium bromide inserts between the structural sheet of vermiculite fully, thereby its interlamellar spacing is supportted greatly to 4.38nm by original 1.46nm, and the d value is disappeared for former (001) crystal face diffraction peak of 1.46nm.As seen utilize ball milled can obtain the complete intercalation type vermiculite of intercalation interlamellar spacing in 15 minutes for 4.38nm.
Be ratio of quality and the number of copies that 100: 5 natural rubber and intercalated vermiculite joins in the HAAKE torque rheometer again, under 120 ℃ temperature, with the rotating speed hybrid process 15min of 120rpm; Mixing evenly mixture and other Synergist S-421 95 in two roller mills then, wherein 2 parts of stearic acid, 5 parts in zinc oxide, 10.7 parts of promotor, 20.5 parts of promotor, 2.5 parts in sulphur; Under 140 ℃ temperature, vulcanize 14min with vulcanizing press at last, obtain nano composite material NRV5.Table 1 column data is the physical and mechanical properties contrast of bright sulfur natural rubber (NR) and NRV5.
The physical and mechanical properties contrast of table 1NR and NRV5
| Properties | NR | NRV5 |
| Tensile strength/MPa | 8.2 | 25.3 |
| Elongation at break/％ | 410 | 451 |
| Stress at 300％Elongation | 3.9 | 5.2 |
| Tear strength/(kN·m -1) | 31.4 | 35.8 |
| Shore Ahardness | 44.7 | 49.0 |
Embodiment 2:
Is ratio of quality and the number of copies that 100: 10 natural rubber and intercalated vermiculite joins in the HAAKE torque rheometer, under 120 ℃ temperature, with the rotating speed hybrid process 15min of 120rpm; Mixing evenly mixture and other Synergist S-421 95 in two roller mills then, wherein 2 parts of stearic acid, 5 parts in zinc oxide, 10.7 parts of promotor, 20.5 parts of promotor, 2.5 parts in sulphur; Under 140 ℃ temperature, vulcanize 14min with vulcanizing press at last, obtain nano composite material NRV10.Table 2 column data is the physical and mechanical properties contrast of bright sulfur natural rubber (NR) and NRV10.
The physical and mechanical properties contrast of table 1NR and NPV10
| Properties | NR | NRV10 |
| Tensile strength/MPa | 8.2 | 27.4 |
| Elongation at break/％ | 410 | 552 |
| Stress at 300％Elongation | 3.9 | 6.71 |
| Tear strength/(kN·m -1) | 31.4 | 36.5 |
| Shore Ahardness | 44.7 | 47.8 |
Embodiment 3:
Is ratio of quality and the number of copies that 100: 15 natural rubber and intercalated vermiculite joins in the HAAKE torque rheometer, under 120 ℃ temperature, with the rotating speed hybrid process 15min of 120rpm; Mixing evenly mixture and other Synergist S-421 95 in two roller mills then, wherein 2 parts of stearic acid, 5 parts in zinc oxide, 10.7 parts of promotor, 20.5 parts of promotor, 2.5 parts in sulphur; Under 140 ℃ temperature, vulcanize 14min with vulcanizing press at last, obtain nano composite material NRV15.Table 3 column data is the physical and mechanical properties contrast of bright sulfur natural rubber (NR) and NRV15.
The physical and mechanical properties contrast of table 3NR and NRV15
| Properties | NR | NRV15 |
| Tensile strength/MPa | 8.2 | 27.5 |
| Elongation at break/％ | 410 | 772 |
| Stress at 300％Elongation | 3.9 | 7.6 |
| Tear strength/(kN·m -1) | 31.4 | 36.9 |
| Shore Ahardness | 44.7 | 50.7 |
Fig. 2 is the XRD figure of vermiculite (15 parts)/natural rubber nano composite material, the diffraction peak of (001) crystal face of visible organic intercalation vermiculite almost disappears among the figure, illustrate that the structure crystal layer almost is stripped from fully because of having more weak bonding force on organic intercalation vermiculite (001) direction by effects such as the mixing in the nano composite material preparation process, sulfurations.
In addition, in experiment, from the SEM figure of vermiculite/natural rubber nanometer composite material, also observe, the vermiculite lamella is dispersed in the natural rubber matrix uniformly, and have preferably and align, can be observed the natural rubber matrix simultaneously and be inserted between vermiculite layers, and the intermediateness that its structural sheet is peeled off.The thickness of vermiculite lamella is between 50～200nm in the natural rubber matrix, illustrates that the melting mixing method has organic intercalation vermiculite structural sheet to peel off effect preferably
Embodiment 4:
Is ratio of quality and the number of copies that 100: 20 natural rubber and intercalated vermiculite joins in the HAAKE torque rheometer, under 120 ℃ temperature, with the rotating speed hybrid process 15min of 120rpm; Mixing evenly mixture and other Synergist S-421 95 in two roller mills then, wherein 2 parts of stearic acid, 5 parts in zinc oxide, 10.7 parts of promotor, 20.5 parts of promotor, 2.5 parts in sulphur; Under 140 ℃ temperature, vulcanize 14min with vulcanizing press at last, obtain nano composite material NRV20.Table 4 column data is the physical and mechanical properties contrast of bright sulfur natural rubber (NR) and NRV20.
The physical and mechanical properties contrast of table 4NR and NRV20
| Properties | NR | NRV20 |
| Tensile strength/MPa | 8.2 | 26.7 |
| Elongation at break/％ | 410 | 464 |
| Stress at 300％Elongation | 3.9 | 8.4 |
| Tear strength/(kN·m -1) | 31.4 | 38.2 |
| Shore Ahardness | 44.7 | 51.1 |
Embodiment 5:
Is ratio of quality and the number of copies that 100: 30 natural rubber and intercalated vermiculite joins in the HAAKE torque rheometer, under 120 ℃ temperature, with the rotating speed hybrid process 15min of 120rpm; Mixing evenly mixture and other Synergist S-421 95 in two roller mills then, wherein 2 parts of stearic acid, 5 parts in zinc oxide, 10.7 parts of promotor, 20.5 parts of promotor, 2.5 parts in sulphur; Under 140 ℃ temperature, vulcanize 14min with vulcanizing press at last, obtain nano composite material NRV30.Table 5 column data is the physical and mechanical properties contrast of bright sulfur natural rubber (NR) and NRV30.
The physical and mechanical properties contrast of table 5NR and NRV30
| Properties | NR | NRV30 |
| Tensile strength/MPa | 8.2 | 26.4 |
| Elongation at break/％ | 410 | 483 |
| Stress at 300％Elongation | 3.9 | 7.5 |
| Tear strength/(kN·m -1) | 31.4 | 43.4 |
| Shore Ahardness | 44.7 | 59.1 |
Embodiment 6:
Is ratio of quality and the number of copies that 100: 40 natural rubber and intercalated vermiculite joins in the HAAKE torque rheometer, under 120 ℃ temperature, with the rotating speed hybrid process 15min of 120rpm; Mixing evenly mixture and other Synergist S-421 95 in two roller mills then, wherein 2 parts of stearic acid, 5 parts in zinc oxide, 10.7 parts of promotor, 20.5 parts of promotor, 2.5 parts in sulphur; Under 140 ℃ temperature, vulcanize 14min with vulcanizing press at last, obtain nano composite material NRV40.Table 6 column data is the physical and mechanical properties contrast of bright sulfur natural rubber (NR) and NRV40.
The physical and mechanical properties contrast of table 6NR and NRV40
| Properties | NR | NRV40 |
| Tensile strength/MPa | 8.2 | 23.1 |
| Elongation at break/％ | 410 | 453 |
| Stress at 300％Elongation | 3.9 | 10.1 |
| Tear strength/(kN·m -1) | 31.4 | 45.7 |
| Shore Ahardness | 44.7 | 63.6 |
Fig. 3 is the physical and mechanical properties curve of the matrix material of different umber vermiculites among the present invention, the result shows the adding along with OVMT, and the tensile strength of matrix material, elongation at break, 300% tensile modulus, Shore A hardness, tear strength have all had tangible improvement.Wherein tensile strength and elongation at break reach maximum value 27.5Mpa and 772% when OVMT content is 15 parts, have improved 235% and 88% than the bright sulfur natural rubber respectively.This two tops performance descended to some extent when OVMT surpassed 15 parts, mainly was because OVMT content is more, added the man-hour particulate and easily reunited, and the dispersiveness in NR descends, due to the interfacial interaction between particulate and the matrix is affected.300% tensile modulus of matrix material, Shore A hardness, tear strength present progressively enhanced trend along with the increase of OVMT content.Analysis-by-synthesis, the matrix material that contains 15 parts of OVMT has optimum properties.
Claims (7)
1. an intercalated vermiculite/natural rubber nanometer composite material is characterized in that, the feed composition and the content of described matrix material are as follows:
The feed composition mass fraction
Natural rubber 100
Intercalated vermiculite 5～40
Stearic acid 1～3
Zinc oxide 4～8
Promotor 1 0.5～1
Promotor 2 0.3～0.8
Sulphur 1～3
Wherein, described intercalated vermiculite is meant that primary mineral of vermiculite is that raw material, quaternary ammonium salt are the intercalated vermiculite of intercalator; Promotor 1 is TMTD, and promotor 2 is tetramethyl-thiuram disulfide.
2. as claim 1 described a kind of intercalated vermiculite/natural rubber nanometer composite material, it is characterized in that the feed composition and the content of described matrix material are as follows:
The feed composition mass fraction
Natural rubber 100
Intercalated vermiculite 15
Stearic acid 2
Zinc oxide 5
Promotor 1 0.7
Promotor 2 0.5
Sulphur 2.5.
3. the preparation method of an intercalated vermiculite/natural rubber nanometer composite material is characterized in that, said method comprising the steps of:
1) preparation intercalated vermiculite superfine powder
A. the vermiculite former state adds quaternary ammonium salt through pulverizing and weighing, and the cation exchange capacity that makes quaternary ammonium salt is 1～4 times of the vermiculite cation exchange capacity, and adds 4～10 times of deionized waters to the vermiculite quality, mixes;
B. in grinding in ball grinder 15min～4 hour; With the sample that obtains after grinding, through centrifugal, filter, and with deionized water repetitive scrubbing 5～7 times, through Ag
+Detecting no white precipitate (AgBr) produces; Through centrifugal, filtration, the sample oven dry of gained also grinds to form powdery, obtains intercalated vermiculite again;
2) preparation intercalated vermiculite/natural rubber nanometer composite material
A. the intercalated vermiculite of natural rubber and step 1) gained by ratio of quality and the number of copies 100: (5～40) join in the HAAKE torque rheometer, under 100～180 ℃ temperature, with rotating speed hybrid process 5～30min of 80～120rpm;
B. with step 2) mixture that obtains among a and other Synergist S-421 95 in two roller mills mixing evenly, its ratio of quality and the number of copies is: 1～3 part of stearic acid, 4～8 parts in zinc oxide, promotor 1 are that 0.5～1 part, promotor 2 are 1～3 part of 0.3～0.8 part, sulphur;
C. the mixture of gained promptly gets the nano composite material of intercalated vermiculite/natural rubber with vulcanizing press sulfuration, compressing tablet.
4. the preparation method of intercalated vermiculite/natural rubber nanometer composite material as claimed in claim 3 is characterized in that, in the described method, as preferred cetyl trimethylammonium bromide of the quaternary ammonium salt of intercalator or octadecyl trimethylammonium bromide.
5. the preparation method of intercalated vermiculite/natural rubber nanometer composite material as claimed in claim 3, it is characterized in that, the step 2 of described method) among a, natural rubber and the intercalated vermiculite mixing temperature in the HAAKE torque rheometer is 120 ℃, hybrid process is 15min, and the rotating speed of HAAKE torque rheometer is 120rpm.
6. the preparation method of intercalated vermiculite/natural rubber nanometer composite material as claimed in claim 3 is characterized in that, the step 2 of described method) among the c, with step 2) mixture that obtains among the b vulcanized 14 minutes under 140 ℃ temperature with vulcanizing press.
7. the preparation method of intercalated vermiculite/natural rubber nanometer composite material as claimed in claim 3 is characterized in that, with stirring mill, vibration mill alternative steps 1) ball mill among the b.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100457813C (en) * | 2006-11-17 | 2009-02-04 | 中国地质大学（北京） | Duprene rubber/vermicultie namo composite material and its preparing method |
| CN101875732A (en) * | 2010-07-06 | 2010-11-03 | 南京信息工程大学 | Rubber, vermiculite and barium ferric oxide composite material and preparation method thereof |
| CN104804440A (en) * | 2015-06-02 | 2015-07-29 | 郑州轻工业学院 | Preparation method of silastic/vermiculite compound material and silastic/vermiculite compound material prepared by preparation method |
| CN105585851A (en) * | 2016-03-16 | 2016-05-18 | 王社兵 | High temperature resistance and impact resistance variable frequency cable |
| CN107021502A (en) * | 2017-04-26 | 2017-08-08 | 无锡永高新材料科技有限公司 | A kind of method of dry method quick preparing intercalation type vermiculite |
| CN107099062A (en) * | 2017-04-26 | 2017-08-29 | 无锡永高新材料科技有限公司 | A kind of nano composite material of vermiculite and natural rubber and preparation method thereof |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100457813C (en) * | 2006-11-17 | 2009-02-04 | 中国地质大学（北京） | Duprene rubber/vermicultie namo composite material and its preparing method |
| CN101875732A (en) * | 2010-07-06 | 2010-11-03 | 南京信息工程大学 | Rubber, vermiculite and barium ferric oxide composite material and preparation method thereof |
| CN104804440A (en) * | 2015-06-02 | 2015-07-29 | 郑州轻工业学院 | Preparation method of silastic/vermiculite compound material and silastic/vermiculite compound material prepared by preparation method |
| CN104804440B (en) * | 2015-06-02 | 2018-06-05 | 郑州轻工业学院 | The preparation method of silicon rubber/vermiculite Composite and its silicon rubber/vermiculite Composite obtained |
| CN105585851A (en) * | 2016-03-16 | 2016-05-18 | 王社兵 | High temperature resistance and impact resistance variable frequency cable |
| CN107021502A (en) * | 2017-04-26 | 2017-08-08 | 无锡永高新材料科技有限公司 | A kind of method of dry method quick preparing intercalation type vermiculite |
| CN107099062A (en) * | 2017-04-26 | 2017-08-29 | 无锡永高新材料科技有限公司 | A kind of nano composite material of vermiculite and natural rubber and preparation method thereof |
| CN112174122A (en) * | 2020-09-30 | 2021-01-05 | 李素红 | Antibacterial graphene nano knife and preparation method and application thereof |
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