CN103865024A - Preparation method of super-elastic polyurethane/montmorillonite nanocomposite - Google Patents
Preparation method of super-elastic polyurethane/montmorillonite nanocomposite Download PDFInfo
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- 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
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- C08K3/34—Silicon-containing compounds
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Abstract
The invention relates to a preparation method of a polyurethane/montmorillonite nanocomposite with super-elasticity, in particular to preparation under a mild (room temperature, manual stirring and no need of solvent) condition. According to the method, the cost and the energy consumption are greatly reduced, the production process is simplified, and the montmorillonite dispersed in the polymer has a peeling structure, so that real nano dispersion is realized. The composite prepared by the method can be widely applied to the fields of light industry, chemical industry, building materials and aviation.
Description
Technical field
The present invention relates to a kind of preparation method with super-elasticity urethane/montmorillonite nano complex, more specifically say a kind of gentle (room temperature, manual stir and without solvent) under condition, adopt the method for super-elasticity urethane/montmorillonite nano complex that prestripping method prepares.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, strong interaction between surface effects and nanoparticle and basal body interface, nano composite polymer-montmorillonoid material has and is better than the performance such as physics, chemistry of the conventional matrix material of same composition and has caused people's extensive concern.Urethanes is the synthetic materials between plastics and rafter glue, is to be formed by polyisocyanates (as, vulcabond OCN-R-NCO) and polyvalent alcohol (as, dibasic alcohol HO-R '-OH) reaction.Compare with polyether-type PU with polyester type, the polyurethane elastomer making take terminal hydroxyl polybutadiene liquid rubber as oligopolymer, both guaranteed 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 its at electronic industry, material of construction, elastomerics, epoxy resin roughening, prepare the field such as tackiness agent and coating and there are bright prospects.The high performance research of polyurethane elastomer is included in progressively and regulates its molecular chain structure and add mineral filler in polymerization process.
On the Chem Mater magazine of 1998, deliver first one piece of article about intercal type PU/MMT Nanocomposite (Zhen Wang, Thomas J.Pinnavaia.1998,10:3769-3771), by the prepolymer of methylenediphenyl diisocyanates difunctionality and organo montmorillonite are directly mixed with to intercal type PU/MMT Nanocomposite, research shows that have enhancement to elastic polyurethane/Nano composite material of montmorillonite mechanical property adding of polynite.Subsequently, the utilizations such as T.K.Chen are introduced the method for poly-hydroxyl caprolactone/Nano composite material of montmorillonite and have been synthesized 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).The impact of this research group intermolecular hydrogen bonding on matrix material and mechanical property with regard to polynite also studies in detail, the intermolecular hydrogen bonding of finding urethane reduces along with the increase of polynite content, but after massfraction reaches 5%, do not change, the matrix material that polynite massfraction is 1% in addition has best mechanical property.(Y.?I.Tien，Wei?K.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 that does not change 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 present invention's fluid rubber used; Preparation method presses substance law or solution polymerization, whole process need high-speed stirring, ultra-sonic oscillation, solvent system etc., but not the present invention's room temperature, common manual stirring, solvent-free system used.Chinese patent CN1362450A has reported 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, thereby obtain high, the good heat resistance of intensity and the good nano composite polyurethane-organic clay material of processibility.The prepared nano composite polyurethane-organic clay material of this invention is still that intercal type is compound, but not arrive exfoliated compound 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 that contains nano imvite and preparation method thereof, by by terminal hydroxyl polybutadiene liquid rubber, organo montmorillonite, tolylene diisocyanate, dibutyl tin laurate, be uniformly mixed, under vacuum, degassed reaction makes.The preparation method that this invention relates to adds a step mixing in system to make all raw materials, but not the prestripping method arriving involved in the present invention.Chinese patent CN1487027A discloses the preparation method of mass polymer/exfoliated nano-complex, by add organo montmorillonite grinding distribution in Cone crusher or colloidal mill at the polymkeric substance of liquid state or viscous state, obtains exfoliated mixture.The preparation method that this invention relates to utilizes mechanical mill to reach the even mixing of raw material and peeling off of montmorillonite layer, but not involved in the present invention to common craft be uniformly mixed.Chinese patent CN1523060A discloses kind 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 arriving 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 does not make under the condition of water and other organic solvents, the manual stirring of room temperature can realize, greatly reduce cost and energy consumption, simplify production technique, and the polynite being dispersed in polymkeric substance is lift-off structure, realize real nano-dispersed.
The preparation method of the super-elasticity urethane/montmorillonite nano complex the present invention relates to, comprises the steps:
(1), in aqueous systems, make organo montmorillonite;
(2) organo montmorillonite step (1) being made mixes with terminal hydroxy group divinyl fluid rubber, and common stirring is placed on a few hours in constant temperature oven, makes stripping-off liquid rubber/organic montmorillonite nano plural gel;
(3) in the nano-composite gel that contains prestripping montmorillonite layer making in step (2), add solidifying agent, chainextender, catalyzer etc., after evenly mixing, pour in polytetrafluoro mould, vacuum is taken out bubble, solidify a few hours, obtain super-elasticity polyurethane/organic montmorillonite nano mixture.
Advantage of the present invention is:
1, do not make water and organic solvent.The method the present invention relates to is directly mixed polymkeric substance with polynite, do not make water and organic solvent, has avoided environmental pollution, and has reduced production cost.
2, the preparation of the gentleness under normal temperature condition.The preparation process that the present invention relates to is simple, without high temperature, manual stirring, do not have particular requirement (to production unit, the stirrer using on general industry just can be realized), reduce energy consumption, for the industrial application aspect of fluid rubber provides bright prospects.
3, the present invention is directly dispersed into exfoliated nanoscale twins in advance by polynite, this fluid rubber/the montmorillonite nano complex that contains prestripping nanoscale twins, by directly adding linking agent curing reaction, obtains high performance urethane/montmorillonite nano complex easily.The method has overcome the autohemagglutination effect of montmorillonite layer in polyurethane matrix, is more conducive to the dispersion of peeling off of montmorillonite layer, is conducive to the raising of material property.
4, the urethane/montmorillonite nano complex the present invention relates to has super excellent elastic performance, the introducing of polynite improves polyurethane material elasticity-elongation at break and intensity simultaneously, overcome 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, formula and the explanation that use are not limitation of the present invention.
Embodiment 1:
(1) the polynite 10g that is 100mmol/100g by cation exchange capacity, the 500ml that adds water, 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 ℃, drips solution b, stir 4 hours simultaneously, naturally cool to room temperature, then suction filtration, washing (detecting to without bromide anion with 0.2% silver nitrate solution), can obtain organo montmorillonite after being dried.Its x-ray diffraction pattern is shown in Fig. 1, and near the interlamellar spacing of the diffraction peak explanation organo montmorillonite 2 θ are 3.4 ° is 2.55nm.
(2) by 0.40g organo montmorillonite and 40g Liquid Hydroxyl-Terminated Polybutadiene rubber (HTPB, hydroxyl value 0.60mmol/g) be at room temperature stirred to and mix by hand, be placed in constant temperature oven 8 hours (optimum temps 300-353K), make fluid rubber/montmorillonite nano complex that organo montmorillonite quality percentage composition is 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 to peel off state.
(3) at room temperature, after being mixed, 40.40g stripping-off liquid rubber/montmorillonite nano complex, 1.9g tolylene diisocyanate and 0.2g dibutyl tin laurate pour in polytetrafluoro mould, vacuum is taken out bubble, then in 80 ℃ solidify 6 hours, obtain urethane/montmorillonite nano complex.
Embodiment 2:
(1) the polynite 10g that is 100mmol/100g by cation exchange capacity, the 500ml that adds water, 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 ℃, drips solution b, stir 4 hours simultaneously, naturally cool to room temperature, then suction filtration, washing, to without bromide anion, can obtain organo montmorillonite after being dried with 0.2% silver nitrate solution detection.Its x-ray diffraction pattern is shown in Fig. 1, and near the interlamellar spacing of the diffraction peak explanation organo montmorillonite 2 θ are 3.4 ° is 2.55nm.
(2) by 1.24g organo montmorillonite and 40g Liquid Hydroxyl-Terminated Polybutadiene rubber (HTPB, hydroxyl value 0.60mmol/g) be at room temperature stirred to and mix by hand, be placed in constant temperature oven 8 hours (optimum temps 300-353K), make fluid rubber/montmorillonite nano complex that organo montmorillonite quality percentage composition is 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 to peel off state.
(3) at room temperature, after being mixed, 41.24g stripping-off liquid rubber/montmorillonite nano complex, 1.9g tolylene diisocyanate and 0.2g dibutyl tin laurate pour in polytetrafluoro mould, vacuum is taken out bubble, then in 80 ℃ solidify 6 hours, obtain urethane/montmorillonite nano complex.
Embodiment 3:
(1) the polynite 10g that is 100mmol/100g by cation exchange capacity, the 500ml that adds water, 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 ℃, drips solution b, stir 4 hours simultaneously, naturally cool to room temperature, then suction filtration, washing, to without bromide anion, can obtain organo montmorillonite after being dried with 0.2% silver nitrate solution detection.Its x-ray diffraction pattern is shown in Fig. 4, and near the interlamellar spacing of the diffraction peak explanation organo montmorillonite 2 θ are 2.3 ° is 3.57nm.
(2) by 0.40g organo montmorillonite and 40g Liquid Hydroxyl-Terminated Polybutadiene rubber (HTPB, hydroxyl value 0.60mmol/g) be at room temperature stirred to and mix by hand, be placed in constant temperature oven 8 hours (optimum temps 300-353K), make fluid rubber/montmorillonite nano complex that organo montmorillonite quality percentage composition is 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 to peel off state.Transmission electron microscope further illustrates montmorillonite layer and exists to peel off state in fluid rubber matrix, as shown in Figure 6.
(3) at room temperature, after being mixed, 40.40g stripping-off liquid rubber/montmorillonite nano complex, 1.9g tolylene diisocyanate and 0.2g dibutyl tin laurate pour in polytetrafluoro mould, vacuum is taken out bubble, then in 80 ℃ solidify 6 hours, obtain urethane/montmorillonite nano complex.
Embodiment 4:
(1) the polynite 10g that is 100mmol/100g by cation exchange capacity, the 500ml that adds water, 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 ℃, drips solution b, stir 4 hours simultaneously, naturally cool to room temperature, then suction filtration, washing,, is dried and can obtains organo montmorillonite to without bromide anion with 0.2% silver nitrate solution detection.Its x-ray diffraction pattern is shown in Fig. 4, and near the interlamellar spacing of the diffraction peak explanation organo montmorillonite 2 θ are 2.3 ° is 3.57nm.
(2) by 1.24g organo montmorillonite and 40g Liquid Hydroxyl-Terminated Polybutadiene rubber (HTPB, hydroxyl value 0.60mmol/g) be at room temperature stirred to and mix by hand, be placed in constant temperature oven 8 hours (optimum temps 300-353K), make fluid rubber/montmorillonite nano complex that organo montmorillonite quality percentage composition is 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 to peel off state.
(3) at room temperature, after being mixed, 41.24g stripping-off liquid rubber/montmorillonite nano complex, 1.9g tolylene diisocyanate and 0.2g dibutyl tin laurate pour in polytetrafluoro mould, vacuum is taken out bubble, then in 80 ℃ solidify 6 hours, obtain urethane, montmorillonite nano complex.
Embodiment 5:
(1) the polynite 10g that is 100mmol/100g by cation exchange capacity, the 500ml that adds water, 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 ℃, drips solution b, stir 4 hours simultaneously, naturally cool to room temperature, then suction filtration, washing,, is dried and can obtains organo montmorillonite to without bromide anion with 0.2% silver nitrate solution detection.Its x-ray diffraction pattern is shown in Fig. 4, and near the interlamellar spacing of the diffraction peak explanation organo montmorillonite 2 θ are 2.3 ° is 3.57nm.
(2) by 1.24g organo montmorillonite and 40g Liquid Hydroxyl-Terminated Polybutadiene rubber (HTPB, hydroxyl value 0.60mmol/g) be at room temperature stirred to and mix by hand, be placed in constant temperature oven 8 hours (optimum temps 300-353K), make fluid rubber/montmorillonite nano complex that organo montmorillonite quality percentage composition is 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 to peel off state.
(3) at room temperature, after being mixed, 41.24g stripping-off liquid rubber/montmorillonite nano complex, 2.3g tolylene diisocyanate and 0.2g dibutyl tin laurate pour in polytetrafluoro mould, vacuum is taken out bubble, then in 80 ℃ solidify 6 hours, obtain urethane/montmorillonite nano complex.
Embodiment 6:
Other conditions are identical with embodiment 3, being blended in high-speed shearing machine of organo montmorillonite and fluid rubber carried out, velocity of shear is 60r/min, shear time 10 minutes, see Fig. 8 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 to peel off state.Transmission electron microscope further illustrates montmorillonite layer and exists to peel off state in fluid rubber matrix, as shown in Figure 9.
The mechanical performance data that makes urethane/montmorillonite nano complex is listed in table 1, known by the test data in table 1, no matter organo montmorillonite is that manual stirring (embodiment 3) or standard machinery stir (embodiment 6), the basic indifference of mechanical property of the urethane/montmorillonite nano complex finally making with mixing of fluid rubber.Therefore, the preparation method of super-elasticity urethane/montmorillonite nano complex that this patent relates to, its great advantage is in preparation process only to need manual stirring (room temperature, without 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 to 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 every kind of material is no less than five, and the mechanical performance index of resulting materials is all mean value.
Claims (10)
1. a preparation method for super-elasticity urethane/montmorillonite nano complex, order comprises the following steps:
(1), in aqueous systems, make organo montmorillonite;
(2) organo montmorillonite step (1) being made mixes with terminal hydroxy group divinyl fluid rubber, and under room temperature, manual stirring is placed on a few hours in constant temperature oven, makes stripping-off liquid rubber/organic montmorillonite nano plural gel;
(3) in the nano-composite gel that contains prestripping montmorillonite layer making in step (2), add solidifying agent, chainextender, catalyzer etc., after evenly mixing, pour in polytetrafluoro mould, vacuum is taken out bubble, solidify a few hours, obtain super-elasticity polyurethane/organic montmorillonite nano mixture.
2. preparation method according to claim 1, the preparation method who it is characterized in that organo montmorillonite in described step (1) is: 1-50 part purifying sodium-based montmorillonite is mixed with 100-5000 part deionized water, mechanical stirring 0.5-10 hour at 50-90 ℃, obtain the suspension of homogeneous phase, then the organic modifiers aqueous solution that slowly dropping has prepared in this suspension, temperature of reaction remains on 50-90 ℃, mechanical stirring 2-24 hour, then filtering and washing is to halogen-free ionic, vacuum-drying also grinds powdered, through 200 mesh standard sieve screenings.
3. preparation method according to claim 2, is characterized in that described organic modifiers is that ten alkyl are to octadecyl trimethyl-ammonium halide, two ten alkyl to octadecyl dimethyl ammonium halide.
4. preparation method according to claim 1, is characterized in that in described step (2), fluid rubber is terminal hydroxyl polybutadiene liquid rubber, and number-average molecular weight is 500-8000.
5. preparation method according to claim 1, is characterized in that the consumption of fluid rubber in described step (2) is 100 parts, and the consumption of organo montmorillonite is 0.2-90 part.
6. preparation method according to claim 1, is characterized in that in described step (2), constant temperature oven temperature is 300-333K, and constant temperature time is 4-12 hour.
7. preparation method according to claim 1, it is characterized in that the solidifying agent in described step (3) is tolylene diisocyanate (TDI), ditan-4,4'-vulcabond (MDI), six methylene diisocyanates (HDI) and derivative thereof, hardener dose is 2-50 part.
8. preparation method according to claim 1, is characterized in that the chainextender in described step (3) is ethylene glycol or glycerol, and chainextender consumption is 0-10 part.
9. preparation method according to claim 1, is characterized in that the catalyzer in described step (3) is dibutyl tin laurate, stannous octoate, triethylenediamine, and catalyst levels is 0-1 part.
10. preparation method according to claim 1, is characterized in that in described step (3), solidification value is 300-353K, and be 1-12 hour set time.
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| CN109535375A (en) * | 2018-11-29 | 2019-03-29 | 广东石油化工学院 | A kind of preparation method of the two-dimensional nano piece enhancing compound polyurethane material of height removing |
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| 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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| 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 |
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| CN109535375A (en) * | 2018-11-29 | 2019-03-29 | 广东石油化工学院 | A kind of preparation method of the two-dimensional nano piece enhancing compound polyurethane material of height removing |
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