CN1167735C - Composition composed of liquid rubber and clay - Google Patents
Composition composed of liquid rubber and clay Download PDFInfo
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- CN1167735C CN1167735C CNB021491267A CN02149126A CN1167735C CN 1167735 C CN1167735 C CN 1167735C CN B021491267 A CNB021491267 A CN B021491267A CN 02149126 A CN02149126 A CN 02149126A CN 1167735 C CN1167735 C CN 1167735C
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Abstract
The present invention relates to a composition of liquid rubber / clay, which comprises the following components of raw materials by weigh: 10 to 99.8% of liquid rubber and 0.2 to 90% of organic modified laminated clay, wherein the liquid rubber is one of the liquid polybutadiene rubber and the liquid carboxyl-terminated nitrile rubber or a mixture of the liquid polybutadiene rubber and the carboxy nitrile rubber, and a clay sheet layer in the composition can reach a stripping and dispersed state. The composition has the advantages of simple preparation process and high production efficiency, can be used for directly preparing rubber / clay nanometer composite materials, and can be used as an additive agent for increasing the performance of other polymeric materials.
Description
Affiliated technical field
The present invention relates to the composition of a kind of polymkeric substance and clay, particularly the composition that obtains after class I liquid I rubber and the organo-clay blend.Composition of the present invention can directly prepare rubber/clay nanocomposites, also can be used as the additive that strengthens other macromolecular material performance and uses.
Background technology
Polymer/laminated clay nanometer composite material is the research focus of field of nanocomposite materials, because clay is dispersed in the polymkeric substance with the nanometer sheet form, given this class matrix material good mechanical performance, higher thermotolerance also has better gas-barrier and flame-retarding characteristic, has wide prospect in industrial application.In this matrix material, the dispersing morphology of clay in polymkeric substance has significant effects to its performance.
The clay dispersion form has compound, the intercal type and exfoliated of macroscopic view.Compound for macroscopic view, laminated clay generally keeps original state of aggregation, and polymkeric substance does not have intercalation in clay, just mechanically mixes with clay; For the intercalation decentralized, polyalcohol intercalation is to the sheet interlayer of clay, but laminated clay still keeps original crystal laminate structure, promptly still can occur the diffraction peak of layered crystal from x-ray diffraction pattern; This class intercalation dispersive clay content will arrive than higher degree, and some mechanical property of matrix material just can have more significantly raising.In the exfoliated dispersive matrix material, the sheet interlayer spacing of clay further increases, the electrostatic interaction of sheet interlayer diminishes up to disappearance, the laminate structure of clay is destroyed, at this moment the clay layer of nanoscale can be distributed in the polymeric matrix equably, and the clay dispersion of relatively small amount just can significantly improve the mechanical property of matrix material like this.The common relatively mixing of exfoliated matrix material or the intercal type of same clay content have better properties.Therefore, how preparing exfoliated polymer/clay composite material, that is to say the limellar stripping that how to make clay and evenly spread in the polymeric matrix in nanometer lamella mode, is the major issue in present technique field.
On general significance, general polymkeric substance (liquid or under fusion, solution state) but all intercalation form the intercal type mixture to the sheet interlayer of organo-clay.But because the difference of different polymer chemistry character, can intercalation and make the clay synusia peel off the dispersive polymkeric substance not have ubiquity.For example U.S. Pat 6,380, and 295 have described multiple organic polymer as carrier, mix the additive of back as polymer composites with organic modification montmonrillonite, relate to molten state or dissolution with solvents under polymkeric substance, be applied to the preparation of intercalation clay, U.S. Pat 6,242,500, US 6,057, and 396, US 5,877,248, US 5,760, and 121, US 5,698,624 with US 5,578, in the preparation of the organism intercalation clay matrix material described in 672, the interlamellar spacing of listed embodiment medium clay soil still is the intercal type dispersion state all less than 4.5nm.
Existing patent documentation (the Chinese patent CN 1242392A of method for preparing the thermoplastic polyalcohol/clay soil matrix material, CN1055706C) report, situ aggregation method is wherein arranged, simultaneously promptly, the clay/polymer composites that directly obtains intercalation or peel off, this preparation method's cost height at the polymer monomer polymeric, selection to organic intercalation agent has special requirement, complex process, particularly difficulty is transformed the polymer production equipment that has built up, is unfavorable for industrial-scale production in enormous quantities.
Organically-modified clay is directly sneaked in the fused polymkeric substance, the method for preparing the polyalcohol/clay soil matrix material also has report (CN1247206A), but because use is the clay powders of organic cation intercalation, the requirement that the comparison harshness is arranged for the equipment and the technology of matrix material processing, all need suitable coupling as screw rod long-width ratio, speed of rotation, processing temperature to forcing machine, generally speaking gained matrix material medium clay soil and not exclusively can be equably being dispersed in the polymkeric substance with the form of nanometer lamella has influenced performance of composites.Simultaneously, owing to use clay powders, increased the dust pollution in the course of processing.
Chinese patent CN 1079409C has reported and has utilized rubber latex to mix with the aqeous suspension of clay that breakdown of emulsion, flocculation agent prepare rubber/clay composite material in addition again, still exist technology many, will use the problem of multiple solvent simultaneously.
Bibliographical information Okada (Mater Sci ﹠amp; Engin, C3 1995,109-115) wait strong polar solvent and the hydrochloric acid reaction of using amino terminated liquid nitrile rubber, obtain holding the liquid acrylonitrile butadiene rubber solution of ammonium salt base, then with clay dispersion at aqueous phase, under brute force stirs, rubber solutions is joined in the clay water disperse phase, the liquid acrylonitrile butadiene rubber of end ammonium salt base will be inserted into interlayer by the positive ion permutoid reaction at two-phase interface.Similarly U.S. Pat 5,665,183 has been reported first preparation acid clay, carries out the intercalation technique of acid-base reaction then with the toluene solution of the liquid acrylonitrile butadiene rubber of holding the ammonium salt base.Prepared clay/the paracril of aforesaid method still is that intercal type is compound, but not exfoliated compound, and does not relate to the used fluid rubber of the present invention.
Chinese patent application CN1308101A has reported the preparation of silastic/clay matrix material, relates to silicon rubber or scion grafting silastic/clay matrix material, does not relate to the used fluid rubber of the present invention.
Summary of the invention
The composition that the purpose of this invention is to provide a kind of fluid rubber/clay, can overcome the shortcoming of prior art, and simplify production technique and control laminated clay more simply and effectively and in polymkeric substance, reach the dispersive state of peeling off, thereby obtain high performance polymer/clay nanocomposites, and widen the Application Areas of laminated clay in nano material.
The weight of fluid rubber of the present invention/clay composition raw material is formed and is comprised: fluid rubber 10-99.8%, organo-clay 0.2-90%; Described fluid rubber is any in liquid polybutadiene rubber and the liquid nbr carboxyl terminal (CTBN) or their mixture; Described organo-clay be through organic intercalation agent handle, the laminar silicic acid salts contg is greater than 70% laminated clay.Layered clay can be polynite; Described organic clay intercalator can be secondary amine, tertiary amine or four utmost point ammonium halides, and wherein said ammonium can be dodecyl to octadecyl ammonium; Described ammonium can be contain allyl group, acrylamido or propylene ester group dodecyl to the octadecyl ammonium halide.
The number-average molecular weight of fluid rubber of the present invention can be 500-8000, and wherein, the number-average molecular weight of described fluid rubber can be 800-6000.
The content of fluid rubber of the present invention can be 20-99.8%, and wherein, the content of described fluid rubber can be 40-99.8%.
The content of above-mentioned fluid rubber can be 60-99.8%, and wherein, the content of described fluid rubber can be 80-99.8%.
Consider the requirement of actual use, the preferable mixed weight per-cent of the present composition is: described fluid rubber accounts for 55-97%, organo-clay 3-45%, and the number-average molecular weight of fluid rubber is 1000-4000.
Fluid rubber of the present invention/clay blend composition is prepared by following method:
The organic modification of clay of laminar silicate is handled: at first be the clay of laminar silicate 0.1-40 weight part of 40-200meq./100g with a certain amount of cation exchange capacity, stir in 20-1500 part dispersion medium (as water) high speed, form stable suspension system, and sediment is wherein removed in sedimentation; Again 0.01-35 part cationite is dissolved in 50-600 part dispersion medium water and forms solution; Above-mentioned suspension system is warmed up to 70 ℃-90 ℃, drips above-mentioned solution, and 70 ℃-90 ℃ reactions 1-5 hour, solid-liquid separation, washing, drying can obtain organically-modified laminated clay then.
The organo-clay of metering is mixed with fluid rubber, be stirred to uniform mixing, can need not in the preparation process to heat, also can suitably heat under the fluid rubber pyrolysated condition not causing, can make composition of the present invention; The addition sequence of fluid rubber and organo-clay can exchange.
In the preparation process, stir and the prolongation churning time by suitable high speed machine, be more conducive to make the laminated clay powder in fluid rubber, to obtain disperseing more equably, thereby fluid rubber is had with the laminated clay powder contact and produce interaction more fully, and obtain the composition that laminated clay is better peeled off effect.
Preparation process of the present invention is simple, need not water and organic solvent.Fluid rubber intercalation of the present invention is in clay seam, can make the laminated structure of organic cation exchange modified layered clay form the state of peeling off, it is characterized by (001) of pairing x-ray diffraction pattern laminate clay but the completely dissolve of face diffraction peak confirms that clay exists with nanometer limellar stripping form.
In actual enforcement of the present invention, also can occur because of stir inhomogeneous or the laminated clay ratio too high, and can there be the laminated clay of part intercal type (not peeling off fully) in the composition that causes preparing, the diffraction peak that the laminated clay of a spot of intercal type from its x-ray diffraction pattern, can occur, but most exfoliated dispersive laminated clay still comprised in the prepared composition.
Organically-modified laminated clay is owing to the avidity of its surface with fluid rubber strengthens greatly than without organically-modified cationic laminated clay, and help very much in preparation of compositions of the present invention obtaining exfoliated laminated clay, if use without organically-modified cationic laminated clay (as sodium ion, type lithium ion laminated clay), then can only obtain intercal type fluid rubber/laminated clay composition.
Fluid rubber/clay composition of the present invention can carry out crosslinking reaction and directly prepare rubber/clay nanocomposites by adding linking agent (vulcanizer).
Fluid rubber/clay composition of the present invention can be used as the additive of reinforced polymeric material performance, and described polymer materials can comprise the blend of thermosetting polymer, thermoplastic polymer, rubber, elastomerics and above-mentioned materials.
The present invention handles organically-modified laminated clay by adopting fluid rubber, directly clay is dispersed into exfoliated nanometer lamella in advance.Fluid rubber/the clay composition of Xing Chenging not only can be by directly adding linking agent (vulcanizer) curing reaction like this, become high performance rubber/clay nanocomposites, but also can be with it as the additive (masterbatch) that strengthens other polymer materials performance, contain in this additive and peel off dispersive nanoclay lamella in advance, mode such as extrude by blend, screw rod and carry out processing, can easily the nanoclay lamella of peeling off be sneaked in the polymeric matrix, and more easily obtain high performance exfoliated polymer/clay nanocomposites.Preparation technology of the present invention is simple, production efficiency is high, and its application prospect is very wide.
Below in conjunction with embodiment technical scheme of the present invention and effect are further described.But employed concrete grammar, prescription and explanation are not limitation of the present invention.
Description of drawings
Fig. 1 is the octadecyl trimethylammonium bromide montmorillonite modified x-ray diffraction pattern of (fluid rubber adds preceding), and 2 θ are that near the diffraction peak 4 ° is the diffraction peak of montmorillonite layered structure d=1.9nm among the figure.
Fig. 2 is the x-ray diffraction pattern of embodiment 1 preparation composition; Fig. 3 is the x-ray diffraction pattern of embodiment 2 preparation compositions; Fig. 4 is the x-ray diffraction pattern of embodiment 3 preparation compositions; Fig. 5 is the x-ray diffraction pattern of embodiment 4 preparation compositions; Fig. 6 is the x-ray diffraction pattern of embodiment 5 preparation compositions.
Embodiment
Embodiment 1:
The preparation of organic modification montmonrillonite: with cation exchange capacity is polynite 10 grams of 80meq/100g, adds water 300 grams, and after being uniformly dispersed, high-speed stirring 30 minutes obtains suspension; 12 gram octadecyl trimethylammonium bromides are dissolved in the 150 gram water, make solution; Above-mentioned suspension is heated to 80-90 ℃, drips above-mentioned solution, stirs simultaneously 2 hours, naturally cools to room temperature, suction filtration then, and wash with water repeatedly, detecting to there not being bromide anion with 0.2% silver nitrate solution, drying can obtain organically-modified polynite.Its x-ray diffraction pattern is seen Fig. 1, is that the interlamellar spacing of the diffraction peak explanation organic modification montmonrillonite about 4 ° is 1.9nm at 2 θ.
With organic modification montmonrillonite 10 gram, with 40 gram Liquid Hydroxyl-Terminated Polybutadiene rubber (HTPB, number-average molecular weight 3200) at room temperature high speed machine be stirred to and mix, make composition of the present invention.The x-ray diffraction pattern of resulting composition is seen Fig. 2, and wherein (001) face diffraction peak (see figure 1) completely dissolve of laminated clay illustrates that polynite exists with the limellar stripping state.
Embodiment 2:
The preparation of organic modification montmonrillonite: with cation exchange capacity is polynite 10 grams of 90meq/100g, adds water 300 grams, and after being uniformly dispersed, high-speed stirring 30 minutes obtains suspension; 12 gram octadecyl trimethylammonium bromides are dissolved in the 150 gram water, make solution; Above-mentioned suspension is heated to 80-90 ℃, drips above-mentioned solution, stirs simultaneously 2 hours, naturally cools to room temperature, suction filtration then, and wash with water repeatedly, detecting to there not being bromide anion with 0.2% silver nitrate solution, drying can obtain organically-modified polynite.
With organic modification montmonrillonite 10 grams, mix with at room temperature manual being stirred to of 40 gram Liquid Hydroxyl-Terminated Polybutadiene rubber (HTPB, number-average molecular weight 3200), make composition of the present invention.The x-ray diffraction pattern of resulting composition is seen Fig. 3, and wherein laminated clay d (001) face diffraction peak almost completely disappears, and illustrates that most of polynite exists with the limellar stripping state; At 2 θ is the polynite signal that the little wide diffraction peak about 4 ° is not peeled off fully for part.
Embodiment 3:
The preparation of organic modification montmonrillonite: with cation exchange capacity is polynite 10 grams of 85meq/100g, adds water 300 grams, and after being uniformly dispersed, high-speed stirring 30 minutes obtains suspension; 12 gram octadecyl trimethylammonium bromides are dissolved in the 150 gram water, make solution; Above-mentioned suspension is heated to 80-90 ℃, drips above-mentioned solution, stirs simultaneously 2 hours, naturally cools to room temperature, suction filtration then, and wash with water repeatedly, detecting to there not being bromide anion with 0.2% silver nitrate solution, drying can obtain organically-modified polynite.
With organic modification montmonrillonite 10 grams, mix with at room temperature manual being stirred to of 10 gram Liquid Hydroxyl-Terminated Polybutadiene rubber (HTPB, number-average molecular weight 3200), make composition of the present invention.The x-ray diffraction pattern of resulting composition is seen Fig. 4, wherein not completely dissolve of laminated clay d=1.9nm diffraction peak, and its reason is the too high levels of polynite, fluid rubber can not fully make it to peel off.
Embodiment 4:
The preparation of organic modification montmonrillonite: with cation exchange capacity is polynite 10 grams of 100meq/100g, adds water 300 grams, and after being uniformly dispersed, high-speed stirring 30 minutes obtains suspension; 12 gram cetyl trimethylammonium bromides are dissolved in the 150 gram water, make solution; Above-mentioned suspension is heated to 80-90 ℃, drips above-mentioned solution, stirs simultaneously 2 hours, naturally cools to room temperature, suction filtration then, and wash with water repeatedly, detecting to there not being bromide anion with 0.2% silver nitrate solution, drying can obtain organically-modified polynite.
With organic modification montmonrillonite 10 grams, with 90 gram liquid carboxyl terminated potybutadiene rubbers (CTPB, number-average molecular weight 3000), at room temperature manual being stirred to mixes, and makes composition of the present invention.The x-ray diffraction pattern of resulting composition is seen Fig. 5, and (001) face diffraction peak wherein almost completely disappears, and illustrates that polynite exists with the limellar stripping state.
Embodiment 5:
The preparation of organic modification montmonrillonite: with cation exchange capacity is polynite 10 grams of 100meq/100g, adds water 300 grams, and after being uniformly dispersed, high-speed stirring 30 minutes obtains suspension; 12 gram cetyl trimethylammonium bromides are dissolved in the 150 gram water, make solution; Above-mentioned suspension is heated to 80-90 ℃, drips above-mentioned solution, stirs simultaneously 2 hours, naturally cools to room temperature, suction filtration then, and wash with water repeatedly, detecting to there not being bromide anion with 0.2% silver nitrate solution, drying can obtain organically-modified polynite.
With organic modification montmonrillonite 10 grams, with 90 gram liquid nbr carboxyl terminals (CTBN, number-average molecular weight 3200), at room temperature high speed machine is stirred to and mixes, and makes composition of the present invention.The x-ray diffraction pattern of resulting composition is seen Fig. 6, and (001) face diffraction peak completely dissolve wherein illustrates that polynite exists with the limellar stripping state.
Claims (15)
1, a kind of composition of fluid rubber/clay is characterized in that the weight composition of described composition comprises: fluid rubber 10-99.8%, organically-modified laminated clay 0.2-90%; Described fluid rubber is any in liquid polybutadiene rubber or the liquid nbr carboxyl terminal or their mixture; Described organically-modified laminated clay is the laminated clay of handling through the organic intercalation agent modification.
2, fluid rubber/clay composition according to claim 1 is characterized in that described liquid polybutadiene rubber is Liquid Hydroxyl-Terminated Polybutadiene rubber or liquid carboxyl terminated potybutadiene rubber.
3, fluid rubber/clay composition according to claim 1, the number-average molecular weight that it is characterized in that described fluid rubber is 500-8000.
4, fluid rubber/clay composition according to claim 3, the number-average molecular weight that it is characterized in that described fluid rubber is 800-6000.
5, fluid rubber/clay composition according to claim 4, the number-average molecular weight that it is characterized in that described fluid rubber is 1000-4000.
6, the composition of fluid rubber/clay according to claim 1, it is characterized by described laminated clay is polynite.
7, fluid rubber/clay composition according to claim 1 is characterized in that described organic intercalation agent is secondary amine, tertiary amine or level Four ammonium halide.
8, a kind of fluid rubber/clay composition according to claim 7 is characterized in that described organic intercalation agent is that dodecyl is to octadecyl ammonium.
9, a kind of fluid rubber/clay composition according to claim 8, its feature are to contain the dodecyl of allyl group, acrylamido or propylene ester group to the octadecyl ammonium halide at described organic intercalation agent.
10, fluid rubber/clay composition according to claim 1, the content that it is characterized by described fluid rubber is 20-99.8%.
11, fluid rubber/clay composition according to claim 10, the content that it is characterized by described fluid rubber is 40-99.8%.
12, fluid rubber/clay composition according to claim 11, the content that it is characterized by described fluid rubber is 60-99.8%.
13, fluid rubber/clay composition according to claim 12, the content that it is characterized by described fluid rubber is 80-99.8%.
14, the application of the described fluid rubber/clay composition of claim 1 is characterized by that described fluid rubber/clay composition directly prepares rubber/clay nanocomposites by adding linking agent and carrying out crosslinking reaction or as the additive of reinforced polymeric material performance.
15, the application of fluid rubber/clay composition according to claim 14 is characterized by the blend that described polymer materials comprises thermosetting polymer, thermoplastic polymer, rubber, elastomerics or above-mentioned materials.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021491267A CN1167735C (en) | 2002-11-27 | 2002-11-27 | Composition composed of liquid rubber and clay |
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| Application Number | Priority Date | Filing Date | Title |
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| CNB021491267A CN1167735C (en) | 2002-11-27 | 2002-11-27 | Composition composed of liquid rubber and clay |
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| CN1414029A CN1414029A (en) | 2003-04-30 |
| CN1167735C true CN1167735C (en) | 2004-09-22 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10370523B2 (en) | 2017-04-03 | 2019-08-06 | Fina Technology, Inc. | Insulating glass sealants based on polyurethanes and organically-modified nanoclays |
| US11466118B2 (en) | 2019-11-22 | 2022-10-11 | Fina Technology, Inc. | Chain end hydroxyl functionalized branched polyfarnesenes obtained by radical polymerization |
| US11634531B2 (en) | 2016-01-06 | 2023-04-25 | Fina Technology, Inc. | Curable polyfarnesene-based compositions |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1308386C (en) * | 2004-10-19 | 2007-04-04 | 北京化工大学 | Modified clay and rubber composite material preparation method |
| CN100374524C (en) * | 2005-08-19 | 2008-03-12 | 上海工程技术大学 | Liquid rubber based adhesive containing Nano montmorillonite and preparation method |
| CN109568155B (en) * | 2018-12-26 | 2021-06-04 | 南京林业大学 | Skin moisturizer based on liquid natural rubber and preparation method thereof |
-
2002
- 2002-11-27 CN CNB021491267A patent/CN1167735C/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11634531B2 (en) | 2016-01-06 | 2023-04-25 | Fina Technology, Inc. | Curable polyfarnesene-based compositions |
| US10370523B2 (en) | 2017-04-03 | 2019-08-06 | Fina Technology, Inc. | Insulating glass sealants based on polyurethanes and organically-modified nanoclays |
| US11466118B2 (en) | 2019-11-22 | 2022-10-11 | Fina Technology, Inc. | Chain end hydroxyl functionalized branched polyfarnesenes obtained by radical polymerization |
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| CN1414029A (en) | 2003-04-30 |
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