CN103865024B - A kind of preparation method of super-elasticity urethane/montmorillonite nano complex - Google Patents
A kind of preparation method of super-elasticity urethane/montmorillonite nano complex Download PDFInfo
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- CN103865024B CN103865024B CN201410074347.0A CN201410074347A CN103865024B CN 103865024 B CN103865024 B CN 103865024B CN 201410074347 A CN201410074347 A CN 201410074347A CN 103865024 B CN103865024 B CN 103865024B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/69—Polymers of conjugated dienes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/346—Clay
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
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Abstract
The present invention relates to a kind of preparation method with super-elasticity urethane/montmorillonite nano complex, especially gentle (room temperature, manual stir and without the need to solvent) to prepare under condition.This method greatly reduces cost and energy consumption, simplifies production technique, and to be dispersed in the Sino-German polynite of polymkeric substance be lift-off structure, achieves real nano-dispersed.The mixture having the inventive method to prepare can be widely used in the fields such as light industry, chemical industry, building materials, aviation.
Description
Technical field
The present invention relates to a kind of preparation method with super-elasticity urethane/montmorillonite nano complex, be more particularly a kind of gentle (room temperature, manual stir and without the need to solvent) under condition, the method for the super-elasticity urethane/montmorillonite nano complex adopting prestripping method to prepare.Super-elasticity urethane/montmorillonite nano complex that this prestripping method is prepared is widely used in the fields such as light industry, chemical industry, building materials, aviation.
Background technology
Due to nanometer size effect, surface effects and interaction strong between nanoparticle and basal body interface, nano composite polymer-montmorillonoid material has the performance such as physics, chemistry that is better than same composition conventional composites materials and causes the extensive concern of people.Urethanes is the synthetic materials between plastics and rafter glue, is to be reacted by polyisocyanates (e.g., vulcabond OCN-R-NCO) and polyvalent alcohol (e.g., dibasic alcohol HO-R '-OH) to form.Compare with polyether-type PU with polyester type, take terminal hydroxyl polybutadiene liquid rubber as the polyurethane elastomer that oligopolymer obtains, both ensure that the performance that polyurethane elastomer is good, there is again the characteristic of similar natural rubber, as resistance to air loss, water resistance etc., thus make it at electronic industry, material of construction, elastomerics, epoxy resin roughening, prepare the field such as tackiness agent and coating there are bright prospects.The high performance research of polyurethane elastomer is included in and progressively regulates its molecular chain structure in polymerization process and add mineral filler.
The ChemMater magazine of 1998 is delivered first one section of article (ZhenWang about intercal type PU/MMT Nanocomposite, ThomasJ.Pinnavaia.1998,10:3769-3771), by the prepolymer of methylenediphenyl diisocyanates difunctionality and organo montmorillonite are directly mixed with intercal type PU/MMT Nanocomposite, research shows that there is enhancement adding of polynite to elastic polyurethane/Nano composite material of montmorillonite mechanical property.Subsequently, T.K.Chen etc. utilize the method introducing poly-hydroxyl caprolactone/Nano composite material of montmorillonite to synthesize novel PU/MMT Nanocomposite, the introducing of a small amount of poly-hydroxyl caprolactone/montmorillonite composite material can make the over-all properties of PU/MMT Nanocomposite increase substantially (T.K.Chen, Y.I.Tien, K.H.Wei.Polymer, 2000,41:1345-1353).This research group also studies in detail the intermolecular hydrogen bonding of matrix material and the impact of mechanical property with regard to polynite, find that the intermolecular hydrogen bonding of urethane reduces along with the increase of polynite content, but do not change after massfraction reaches 5%, in addition polynite massfraction be 1% matrix material have best mechanical property.(Y.I.Tien，WeiK.H.Polymer，2001，2：3213-3221.)
Chinese patent CN1376739A discloses the preparation method of a kind of nano imvite, polyurethane composition, utilize in-situ polymerization mechanism, under the prerequisite not changing existing operating procedure and synthetic route, prepare the nano montmorillonite/polyurethane composition of higher force performance.The raw material that this invention relates to is nano imvite/Aethoxy Sklerol or polyesterols mixture, does not relate to the fluid rubber that the present invention is used; Preparation method presses substance law or solution polymerization, whole process need high-speed stirring, ultra-sonic oscillation, solvent system etc., and non-invention room temperature used, commonly to stir by hand, solvent-free system.Chinese patent CN1362450A reports a kind of urethane/organic clay nano composite material and preparation method, utilize the method for monomer intercalation in-situ polymerization to make urethane and organic clay reach the compatible of molecular level, thus obtain high, the good heat resistance of intensity and the good nano composite polyurethane-organic clay material of processibility.Nano composite polyurethane-organic clay material obtained by this invention is still intercal type compound, but not the exfoliated compound arrived involved in the present invention, and do not relate to the present invention's fluid rubber used.Chinese patent CN1760301A discloses a kind of liquid rubber based adhesive containing nano imvite and preparation method thereof, by by terminal hydroxyl polybutadiene liquid rubber, organo montmorillonite, tolylene diisocyanate, dibutyl tin laurate, be uniformly mixed, degassed reaction obtains under vacuo.All raw materials are added a step mixing in system to obtain by the preparation method that this invention relates to, but not the prestripping method arrived involved in the present invention.Chinese patent CN1487027A discloses the preparation method of mass polymer/exfoliated nano-complex, by adding organo montmorillonite grinding distribution in Cone crusher or colloidal mill at the polymkeric substance of liquid or viscous state, obtains exfoliated mixture.The preparation method that this invention relates to utilizes mechanical mill to reach the Homogeneous phase mixing of raw material and the stripping of montmorillonite layer, but not involved in the present invention to common craft be uniformly mixed.Chinese patent CN1523060A discloses kind of an exfoliated polymer/Nanometer Composite Material Of Montmorillonite And Its Preparation Method, by by polymkeric substance and the direct melting mixing of organo montmorillonite, obtains the nano composite polymer-montmorillonoid material of exfoliated structure.What this invention related to extrudes melt intercalated method, but not the common prestripping method at ambient temperature arrived involved in the present invention.
Summary of the invention
The object of the present invention is to provide a kind of preparation method with super-elasticity urethane/montmorillonite nano complex, the method is under the condition not using water and other organic solvents, the manual stirring of room temperature can realize, greatly reduce cost and energy consumption, simplify production technique, and dispersion polynite is in the polymer lift-off structure, achieves real nano-dispersed.
The preparation method of the super-elasticity urethane/montmorillonite nano complex that the present invention relates to, comprises the steps:
(1) in aqueous systems, obtained organo montmorillonite;
(2) mixed with hydroxy-teminal butadiene fluid rubber by the organo montmorillonite that step (1) is obtained, normal agitation is evenly placed in constant temperature oven a few hours, obtained stripping-off liquid rubber/organic montmorillonite nano plural gel;
(3) solidifying agent, chainextender, catalyzer etc. are added in obtained the containing in the nano-composite gel of prestripping montmorillonite layer of step (2), pour in polytetrafluoro mould after Homogeneous phase mixing, vacuum takes out bubble, solidification a few hours, obtain super-elasticity polyurethane/organic montmorillonite nano mixture.
Advantage of the present invention is:
1, water and organic solvent is not used.Polymkeric substance directly mixes with polynite by the method that the present invention relates to, and does not use water and organic solvent, avoids environmental pollution, and reduce production cost.
2, the gentleness preparation under normal temperature condition.The preparation process that the present invention relates to simply, without the need to high temperature, craft stirs, do not have particular requirement (namely to production unit, the stirrer that general industry uses just can realize), reduce energy consumption, for the industrial application aspect of fluid rubber provides bright prospects.
3, polynite is directly dispersed into exfoliated nanoscale twins by the present invention in advance, this fluid rubber/montmorillonite nano complex containing prestripping nanoscale twins, by directly adding linking agent curing reaction, obtains high performance urethane/montmorillonite nano complex easily.The method overcome the autohemagglutination effect of montmorillonite layer in polyurethane matrix, the stripping advantageously in montmorillonite layer disperses, and is conducive to the raising of material property.
4, the urethane/montmorillonite nano complex that the present invention relates to has super excellent elastic performance, the introducing of polynite makes polyurethane material elasticity-elongation at break and intensity improve simultaneously, overcomes and can not play enhancing, toughness reinforcing problem to material property adding of mineral filler traditionally simultaneously.
Accompanying drawing explanation
The X-ray diffraction spectrogram of Fig. 1 Cetyltrimethylammonium bromide modified montmorillonoid
The X-ray diffraction spectrogram of fluid rubber/montmorillonite nano complex prepared by Fig. 2 embodiment 1
The X-ray diffraction spectrogram of fluid rubber/montmorillonite nano complex prepared by Fig. 3 embodiment 2
The X-ray diffraction spectrogram of Fig. 4 DDA modified montmorillonoid
The X-ray diffraction spectrogram of fluid rubber/montmorillonite nano complex prepared by Fig. 5 embodiment 3
The transmission electron microscope picture of fluid rubber/montmorillonite nano complex prepared by Fig. 6 embodiment 3
The X-ray diffraction spectrogram of fluid rubber/montmorillonite nano complex prepared by Fig. 7 embodiment 4
The X-ray diffraction spectrogram of fluid rubber/montmorillonite nano complex prepared by Fig. 8 embodiment 6
The transmission electron microscope picture of fluid rubber/montmorillonite nano complex prepared by Fig. 9 embodiment 6
Embodiment
Below in conjunction with embodiment, technical scheme of the present invention and effect are further described.But the concrete grammar used, formula and explanation are not limitation of the present invention.
Embodiment 1:
(1) by cation exchange capacity be the polynite 10g of 100mmol/100g, add water 500ml, and after being uniformly dispersed, high-speed stirring 1 hour, obtains suspension a; 3.93g Cetyltrimethylammonium bromide is dissolved in 50ml water, makes solution b; Above-mentioned suspension a is heated to 80 DEG C, drips solution b, stir 4 hours simultaneously, naturally cool to room temperature, then suction filtration, washing (detecting extremely without bromide anion with 0.2% silver nitrate solution), can obtain organo montmorillonite after drying.Its x-ray diffraction pattern is shown in Fig. 1, is that diffraction peak near 3.4 ° illustrates that the interlamellar spacing of organo montmorillonite is 2.55nm at 2 θ.
(2) by 0.40g organo montmorillonite and 40g Liquid Hydroxyl-Terminated Polybutadiene rubber (HTPB, hydroxyl value 0.60mmol/g) at room temperature manual being stirred to mix, be placed in constant temperature oven 8 hours (optimum temps 300-353K), obtained organo montmorillonite mass percentage is the fluid rubber/montmorillonite nano complex of 1%.The x-ray diffraction pattern of gained nano-complex is shown in Fig. 2, and the completely dissolve substantially of wherein polynite (001) face diffraction peak, illustrates that montmorillonite layer is present in the matrix of fluid rubber with stripping state.
(3) at room temperature, pour in polytetrafluoro mould after 40.40g stripping-off liquid rubber/montmorillonite nano complex, 1.9g tolylene diisocyanate and 0.2g dibutyl tin laurate are mixed, vacuum takes out bubble, then in 80 DEG C of solidifications 6 hours, urethane/montmorillonite nano complex is obtained.
Embodiment 2:
(1) by cation exchange capacity be the polynite 10g of 100mmol/100g, add water 500ml, and after being uniformly dispersed, high-speed stirring 1 hour, obtains suspension a; 3.93g Cetyltrimethylammonium bromide is dissolved in 50ml water, makes solution b; Above-mentioned suspension a is heated to 80 DEG C, drips solution b, stir 4 hours simultaneously, naturally cool to room temperature, then suction filtration, washing, detect to without bromide anion with 0.2% silver nitrate solution, after drying, can organo montmorillonite be obtained.Its x-ray diffraction pattern is shown in Fig. 1, is that diffraction peak near 3.4 ° illustrates that the interlamellar spacing of organo montmorillonite is 2.55nm at 2 θ.
(2) by 1.24g organo montmorillonite and 40g Liquid Hydroxyl-Terminated Polybutadiene rubber (HTPB, hydroxyl value 0.60mmol/g) at room temperature manual being stirred to mix, be placed in constant temperature oven 8 hours (optimum temps 300-353K), obtained organo montmorillonite mass percentage is the fluid rubber/montmorillonite nano complex of 3%.The x-ray diffraction pattern of gained nano-complex is shown in Fig. 3, and the completely dissolve substantially of wherein polynite (001) face diffraction peak, illustrates that montmorillonite layer is present in the matrix of fluid rubber with stripping state.
(3) at room temperature, pour in polytetrafluoro mould after 41.24g stripping-off liquid rubber/montmorillonite nano complex, 1.9g tolylene diisocyanate and 0.2g dibutyl tin laurate are mixed, vacuum takes out bubble, then in 80 DEG C of solidifications 6 hours, urethane/montmorillonite nano complex is obtained.
Embodiment 3:
(1) by cation exchange capacity be the polynite 10g of 100mmol/100g, add water 500ml, and after being uniformly dispersed, high-speed stirring 1 hour, obtains suspension a; 6.31g DDA is dissolved in 50ml water, makes solution b; Above-mentioned suspension a is heated to 80 DEG C, drips solution b, stir 4 hours simultaneously, naturally cool to room temperature, then suction filtration, washing, detect to without bromide anion with 0.2% silver nitrate solution, after drying, can organo montmorillonite be obtained.Its x-ray diffraction pattern is shown in Fig. 4, is that diffraction peak near 2.3 ° illustrates that the interlamellar spacing of organo montmorillonite is 3.57nm at 2 θ.
(2) by 0.40g organo montmorillonite and 40g Liquid Hydroxyl-Terminated Polybutadiene rubber (HTPB, hydroxyl value 0.60mmol/g) at room temperature manual being stirred to mix, be placed in constant temperature oven 8 hours (optimum temps 300-353K), obtained organo montmorillonite mass percentage is the fluid rubber/montmorillonite nano complex of 1%.The x-ray diffraction pattern of gained nano-complex is shown in Fig. 5, and the completely dissolve substantially of wherein polynite (001) face diffraction peak, illustrates that montmorillonite layer is present in the matrix of fluid rubber with stripping state.Transmission electron microscope further illustrates montmorillonite layer to be existed with stripping state in fluid rubber matrix, as shown in Figure 6.
(3) at room temperature, pour in polytetrafluoro mould after 40.40g stripping-off liquid rubber/montmorillonite nano complex, 1.9g tolylene diisocyanate and 0.2g dibutyl tin laurate are mixed, vacuum takes out bubble, then in 80 DEG C of solidifications 6 hours, urethane/montmorillonite nano complex is obtained.
Embodiment 4:
(1) by cation exchange capacity be the polynite 10g of 100mmol/100g, add water 500ml, and after being uniformly dispersed, high-speed stirring 1 hour, obtains suspension a; 6.31g DDA is dissolved in 50ml water, makes solution b; Above-mentioned suspension a is heated to 80 DEG C, drips solution b, stir 4 hours simultaneously, naturally cool to room temperature, then suction filtration, washing, detect extremely without bromide anion with 0.2% silver nitrate solution, drying can obtain organo montmorillonite.Its x-ray diffraction pattern is shown in Fig. 4, is that diffraction peak near 2.3 ° illustrates that the interlamellar spacing of organo montmorillonite is 3.57nm at 2 θ.
(2) by 1.24g organo montmorillonite and 40g Liquid Hydroxyl-Terminated Polybutadiene rubber (HTPB, hydroxyl value 0.60mmol/g) at room temperature manual being stirred to mix, be placed in constant temperature oven 8 hours (optimum temps 300-353K), obtained organo montmorillonite mass percentage is the fluid rubber/montmorillonite nano complex of 3%.The x-ray diffraction pattern of gained nano-complex is shown in Fig. 7, and the completely dissolve substantially of wherein polynite (001) face diffraction peak, illustrates that montmorillonite layer is present in the matrix of fluid rubber with stripping state.
(3) at room temperature, pour in polytetrafluoro mould after 41.24g stripping-off liquid rubber/montmorillonite nano complex, 1.9g tolylene diisocyanate and 0.2g dibutyl tin laurate are mixed, vacuum takes out bubble, then in 80 DEG C of solidifications 6 hours, urethane, montmorillonite nano complex is obtained.
Embodiment 5:
(1) by cation exchange capacity be the polynite 10g of 100mmol/100g, add water 500ml, and after being uniformly dispersed, high-speed stirring 1 hour, obtains suspension a; 6.31g DDA is dissolved in 50ml water, makes solution b; Above-mentioned suspension a is heated to 80 DEG C, drips solution b, stir 4 hours simultaneously, naturally cool to room temperature, then suction filtration, washing, detect extremely without bromide anion with 0.2% silver nitrate solution, drying can obtain organo montmorillonite.Its x-ray diffraction pattern is shown in Fig. 4, is that diffraction peak near 2.3 ° illustrates that the interlamellar spacing of organo montmorillonite is 3.57nm at 2 θ.
(2) by 1.24g organo montmorillonite and 40g Liquid Hydroxyl-Terminated Polybutadiene rubber (HTPB, hydroxyl value 0.60mmol/g) at room temperature manual being stirred to mix, be placed in constant temperature oven 8 hours (optimum temps 300-353K), obtained organo montmorillonite mass percentage is the fluid rubber/montmorillonite nano complex of 3%.The x-ray diffraction pattern of gained nano-complex is shown in Fig. 7, and the completely dissolve substantially of wherein polynite (001) face diffraction peak, illustrates that montmorillonite layer is present in the matrix of fluid rubber with stripping state.
(3) at room temperature, pour in polytetrafluoro mould after 41.24g stripping-off liquid rubber/montmorillonite nano complex, 2.3g tolylene diisocyanate and 0.2g dibutyl tin laurate are mixed, vacuum takes out bubble, then in 80 DEG C of solidifications 6 hours, urethane/montmorillonite nano complex is obtained.
Embodiment 6:
Other conditions are identical with embodiment 3, organo montmorillonite and being blended in high-speed shearing machine of fluid rubber are carried out, velocity of shear is 60r/min, shear time 10 minutes, Fig. 8 is seen through x-ray diffraction pattern, the completely dissolve substantially of wherein polynite (001) face diffraction peak, illustrates that montmorillonite layer is present in the matrix of fluid rubber with stripping state.Transmission electron microscope further illustrates montmorillonite layer to be existed with stripping state in fluid rubber matrix, as shown in Figure 9.
The mechanical performance data of obtained urethane/montmorillonite nano complex is listed in table 1, known by the test data in table 1, no matter mixing of organo montmorillonite and fluid rubber be manual stirring (embodiment 3) or standard machinery stirs (embodiment 6), the basic indifference of mechanical property of final obtained urethane/montmorillonite nano complex.Therefore, the preparation method of super-elasticity urethane/montmorillonite nano complex that this patent relates to, its great advantage to be in preparation process only to need to stir by hand (room temperature, without the need to solvent) just can realize material property optimization, has so not only saved cost but also environmental protection.
The mechanical performance compare of table 1 urethane/montmorillonite nano complex and conventional polyurethanes
Note: (1) isocyanate index R=NCO/OH: represent add tolylene diisocyanate in system-NCO and terminal hydroxyl polybutadiene liquid rubber-ratio of the amount of substance of OH.
(2) test bars specification is 20 × 5.0 × 1.0mm
3, the sample of often kind of material is no less than five, and the mechanical performance index of resulting materials is all mean value.
Claims (1)
1. a preparation method for super-elasticity urethane/montmorillonite nano complex, comprises the following steps:
(1) by cation exchange capacity be the polynite 10g of 100mmol/100g, add water 500ml, and after being uniformly dispersed, high-speed stirring 1 hour, obtains suspension a; 6.31g DDA is dissolved in 50ml water, makes solution b; Above-mentioned suspension a is heated to 80 DEG C, drips solution b, stir 4 hours simultaneously, naturally cool to room temperature, then suction filtration, washing, detect to without bromide anion with 0.2% silver nitrate solution, after drying, can organo montmorillonite be obtained;
(2) by the Liquid Hydroxyl-Terminated Polybutadiene rubber of 0.40g organo montmorillonite and 40g hydroxyl value 0.60mmol/g, at room temperature manual being stirred to mixes, be placed in the constant temperature oven 8 hours of temperature 300-353K, obtained organo montmorillonite mass percentage is the fluid rubber/montmorillonite nano complex of 1%;
(3) at room temperature, pour in polytetrafluoro mould after 40.40g stripping-off liquid rubber/montmorillonite nano complex, 1.9g tolylene diisocyanate and 0.2g dibutyl tin laurate are mixed, vacuum takes out bubble, then in 80 DEG C of solidifications 6 hours, urethane/montmorillonite nano complex is obtained.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1487027A (en) * | 2003-07-11 | 2004-04-07 | 中国科学院广州化学研究所 | Prepn of bulk polymer/peel-off nano montmorillonoid compound |
| CN1523060A (en) * | 2003-09-03 | 2004-08-25 | 中国科学院长春应用化学研究所 | Detaching type polymer/montmorillonite composite material and preparing method thereof |
| CN1760301A (en) * | 2005-08-19 | 2006-04-19 | 上海工程技术大学 | Liquid rubber based adhesive containing Nano montmorillonite and preparation method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1487027A (en) * | 2003-07-11 | 2004-04-07 | 中国科学院广州化学研究所 | Prepn of bulk polymer/peel-off nano montmorillonoid compound |
| CN1523060A (en) * | 2003-09-03 | 2004-08-25 | 中国科学院长春应用化学研究所 | Detaching type polymer/montmorillonite composite material and preparing method thereof |
| CN1760301A (en) * | 2005-08-19 | 2006-04-19 | 上海工程技术大学 | Liquid rubber based adhesive containing Nano montmorillonite and preparation method |
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| "固体核磁共振研究蒙脱土的有机插层改性";朱建君 等;《光谱实验室》;20110725;第28卷(第4期);2135-2139 * |
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