CN1523060A - Detaching type polymer/montmorillonite composite material and preparing method thereof - Google Patents
Detaching type polymer/montmorillonite composite material and preparing method thereof Download PDFInfo
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- CN1523060A CN1523060A CNA031271308A CN03127130A CN1523060A CN 1523060 A CN1523060 A CN 1523060A CN A031271308 A CNA031271308 A CN A031271308A CN 03127130 A CN03127130 A CN 03127130A CN 1523060 A CN1523060 A CN 1523060A
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- polypropylene
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Abstract
The present invention relates to a separable polymer/montmorillonite nano composite material and its preparation method. The selected polymer is polyamide, acid anhydridized polypropylene, acid anhydridized polyethylene, polyurethane, polystyrene, acid anhydridized ethylene-propylene rubber, nitrile rubber, SBR rubber or silicon rubber or polymer blend polypropylene/polyamide, polypropylene/acid anhydridized polypropylene, polyethylene/acid anhydridized polyethylene, polyamide/acid anhydrized polypropylene or polyurethane/acid anhydridized polypropylene, and the organic modified montmorillonite is formed from montmorillonite, cationite primary amine, secondary amine or tertiary amine. The dose of modification agent is seriously limited below the ion exchange capacity of montmorillonite, then the polymer and modified montmorillonite can be directly molten and mixed so as to obtain the invented product.
Description
Technical field
The invention belongs to a kind of exfoliated polymer/Nano composite material of montmorillonite; The invention still further relates to a kind of preparation method of exfoliated polymer/Nano composite material of montmorillonite.
Background technology
Adopt the layered inorganic component modification polymkeric substance of a small amount of 1-dimention nano size, rigidity, the intensity of polymkeric substance are obviously improved, and the material proportion and the transparency are more constant than substantially with polymer phase, also can increase substantially thermostability, flame retardant resistance and the barrier of polymkeric substance simultaneously.And polynite effectively peeling off and disperse that the raising of material property is had keying action in polymkeric substance.
The preparation method of nano composite polymer-montmorillonoid material has multiple, wherein, it is the most promising that scorification is considered to, because this method can be used traditional polymer processing or extrusion equipment and not have environmental pollution, this method is applicable to most polymers.It is conventionally believed that Organophilic Modification of Montmorillonite is the prerequisite of scorification, its purpose is to change the wetting ability on polynite surface and provides more favourable lipophilicity environment for polymer molecule or monomer enter the polynite bedding void.Yui, people such as T. think that (Langmuir 2002,18,891) should use the surfactant-modified polynite of a large amount of ammonium ions, so that as far as possible the inorganic cation between cheating engaging layer is displaced or increase the basic basal spacing of polynite.Use excessive properties-correcting agent to prepare organo montmorillonite among relevant patent CN1267682A and the CN1247206A.Yet we find at work, montmorillonite layer peel off the effect good between polynite and the polymkeric substance that depends on, when modified montmorillonoid, use more properties-correcting agent can increase the density of properties-correcting agent between cheating engaging layer, enter between cheating engaging layer or the effect between weakening polymkeric substance and the polynite thereby hinder polymkeric substance, be unfavorable for the dispersion of polynite.
Summary of the invention
The purpose of this invention is to provide a kind of exfoliated polymer/Nano composite material of montmorillonite;
Another object of the present invention provides a kind of preparation method of exfoliated polymer/Nano composite material of montmorillonite.
The present invention is limited in the strictness of cation modifier consumption below the ion-exchange capacity (CEC) of polynite, then with the direct melting mixing of the polynite of polymkeric substance and modification, obtains the nano composite polymer-montmorillonoid material with exfoliated structure.
The polymkeric substance of the preparation that the present invention selects is a polyamide 6, polyamide 66, polymeric amide 11, polymeric amide 12, polyamide 1010, the acid anhydrides polypropylene, the acid anhydrides polyethylene, Polyurethane, polystyrene, acid anhydrides ethylene-propylene rubber(EPR), paracril; styrene-butadiene rubber(SBR) or silastic polymer or polymer blend polypropylene/polymeric amide 11; polypropylene/polymeric amide 12; polypropylene/acid anhydrides polypropylene; polyethylene/acid anhydrides polyethylene; polyamide 6/acid anhydrides polypropylene; polyamide 66/acid anhydrides polypropylene; polymeric amide 11/ acid anhydrides polypropylene; polymeric amide 12/ acid anhydrides polypropylene; polyamide 1010/acid anhydrides polypropylene or Polyurethane/acid anhydrides polypropylene; Organo montmorillonite is made up of following component: 16～40 grams of polynite by weight, cationite are primary amine, swollen ammonium or tertiary amine 3.8～19.2 grams; Disperseing the WATER AS FLOW MEDIUM of polynite is 500～1500ml, the WATER AS FLOW MEDIUM 100～500ml of dispersible cationic exchanger; The ratio of cation modifier mole number and the ion-exchange capacity of polynite is less than 1;
Preparation process is as follows:
With cation exchange capacity be 50～150meq/100g polynite by weight 16～40 the gram, stir 0.5～2h in weight part 500～1000ml deionized water high speed, form stable suspension system, the cationite of 0.2CEC～1.0CEC is added in 100～500ml deionized water, temperature 60-90 ℃, add equimolar protonating agent hydrochloric acid or sulfuric acid again, emulsify at a high speed, form finely dispersed emulsion, and join in the suspension system of above-mentioned polynite, under high-speed stirring, mixed 10～60 minutes, precipitation, filter, vacuum-drying and pulverize organic montmorillonoid, the polynite of polymkeric substance or polymer blend and modification is 50～99 parts by weight: 1～50 part; In traditional mixed with polymers or extrusion equipment,, directly obtain exfoliated polymer/Nano composite material of montmorillonite respectively with polymkeric substance and organic montmorillonoid fusion intercalation.
The present invention is simple for process, need not to add extra equipment, and it is low to produce input cost, and instant effect is easy to promote.
Embodiment
Embodiment 1
With cation exchange capacity is polynite 24 grams of 120meq/100g, stirs 0.5h in 500ml deionized water high speed, forms stable suspension system.17.3 gram cationite stearylamines are added in the 500ml deionized waters, add and wait a mole protonating agent hydrochloric acid, emulsify at a high speed forms finely dispersed emulsion.Above-mentioned suspension and the emulsion that is heated to 60 ℃ mixed 10 minutes under high-speed stirring, and precipitation is filtered, vacuum-drying and pulverize organic montmorillonoid (OM1).With Polyurethane and organic montmorillonoid fusion intercalation, directly obtain nano composite polymer-montmorillonoid material PUS1 in traditional mixed with polymers or extrusion equipment, its wide-angle X-ray result (seeing attached list 1) shows that PUS1 has exfoliated structure.Change the cationite consumption and be respectively 1.0CEC, 1.5CEC, 2.0CEC, 2.5CEC, promptly be respectively 28.8 grams, 43.2 grams, 57.6 grams and 72 grams, and prepare corresponding Polyurethane/Nano composite material of montmorillonite PUS2, PUS3, PUS4, PUS5 result is as shown in table 1.The structure and the mechanical property that contrast them are seen Figure of description.
Table 1
Title Polyurethane PUS1 PUS2 PUS3 PUS4 PUS5
Tensile strength
29.9 29.5 33.2 31.9 29.6 30.6
(MPa)
Extension at break
270 255 330 273 297 280
Rate (%)
Tensile elasticity
242 652 608 557 543 523
Modulus (MPa)
Embodiment 2
With cation exchange capacity is polynite 40 grams of 50meq/100g, stirs 1h in 1000ml deionized water high speed, forms stable suspension system.12 gram cationite cetyl trimethylammonium bromides are added in the 200ml deionized waters, add and wait a mole protonating agent sulfuric acid, emulsify at a high speed forms finely dispersed emulsion.Above-mentioned suspension and the emulsion that is heated to 80 ℃ mixed 30 minutes under high-speed stirring, and precipitation is filtered, vacuum-drying and pulverize organic montmorillonoid.In traditional mixed with polymers or extrusion equipment with polyamide 6 and organic montmorillonoid fusion intercalation, directly obtain nano composite polymer-montmorillonoid material, (001) diffraction peak of polynite all disappears in its X-ray spectrogram, show polynite good dispersion in these polymkeric substance, have exfoliated structure.
Embodiment 3
With cation exchange capacity is polynite 16 grams of 150meq/100g, stirs 2h in 1000ml deionized water high speed, forms stable suspension system.14.4 gram cationite cetyl trimethylammonium bromides are added in the 300ml deionized waters, add and wait a mole protonating agent sulfuric acid, emulsify at a high speed forms finely dispersed emulsion.Above-mentioned suspension and the emulsion that is heated to 90 ℃ mixed 60 minutes under high-speed stirring, and precipitation is filtered, vacuum-drying and pulverize organic montmorillonoid.In traditional mixed with polymers or extrusion equipment with polyamide 66 and organic montmorillonoid fusion intercalation, directly obtain nano composite polymer-montmorillonoid material, (001) diffraction peak of polynite all disappears in its X-ray spectrogram, show polynite good dispersion in these polymkeric substance, have exfoliated structure.
Embodiment 4
With cation exchange capacity is polynite 16 grams of 120meq/100g, stirs 2h in 1000ml deionized water high speed, forms stable suspension system.Respectively with 0.2,0.4,0.6,0.8 and the cationite stearylamine of 1.0 times of CEC quantity (its weight is respectively 3.8 grams, 7.7 grams, 11.5 grams, 15.4 gram and 19.2 grams) be respectively in the adding 500ml deionized water, mole protonating agent hydrochloric acid such as add again, emulsify at a high speed forms finely dispersed emulsion.Above-mentioned suspension and the emulsion that is heated to 60 ℃ mixed 30 minutes under high-speed stirring, and precipitation is filtered, vacuum-drying and pulverize organic montmorillonoid.In traditional mixed with polymers or extrusion equipment with acid anhydrides polypropylene and organic montmorillonoid fusion intercalation, directly obtain a series of acid anhydrides composite nanometer-level polypropylene/montmorillonoid materials, (001) diffraction peak of polynite all disappears in its X-ray spectrogram, show polynite good dispersion in these polymkeric substance, have exfoliated structure.
Embodiment 5
With cation exchange capacity is polynite 14 grams of 150meq/100g, stirs 2h in 1500ml deionized water high speed, forms stable suspension system.10.5 gram cationite cetyl trimethylammonium bromides are added in the 500ml deionized waters, add and wait a mole protonating agent sulfuric acid, emulsify at a high speed forms finely dispersed emulsion.Above-mentioned suspension and the emulsion that is heated to 90 ℃ mixed 50 minutes under high-speed stirring, and precipitation is filtered, vacuum-drying and pulverize organic montmorillonoid.In traditional mixed with polymers or extrusion equipment with organic montmorillonoid and polymeric amide 11 melting mixing, correspondingly obtain nano composite polymer-montmorillonoid material, (001) diffraction peak of polynite all disappears in its X-ray spectrogram, show polynite good dispersion in these polymkeric substance, have exfoliated structure.
Embodiment 6
With cation exchange capacity is polynite 14 grams of 150meq/100g, stirs 2h in 1500ml deionized water high speed, forms stable suspension system.10.5 gram cationite cetyl trimethylammonium bromides are added in the 500ml deionized waters, add and wait a mole protonating agent sulfuric acid, emulsify at a high speed forms finely dispersed emulsion.Above-mentioned suspension and the emulsion that is heated to 90 ℃ mixed 50 minutes under high-speed stirring, and precipitation is filtered, vacuum-drying and pulverize organic montmorillonoid.In traditional mixed with polymers or extrusion equipment with organic montmorillonoid and polymeric amide 12 melting mixing, correspondingly obtain nano composite polymer-montmorillonoid material, (001) diffraction peak of polynite all disappears in its X-ray spectrogram, show polynite good dispersion in these polymkeric substance, have exfoliated structure.
Embodiment 7
With cation exchange capacity is polynite 14 grams of 150meq/100g, stirs 2h in 1500ml deionized water high speed, forms stable suspension system.10.5 gram cationite cetyl trimethylammonium bromides are added in the 500ml deionized waters, add and wait a mole protonating agent sulfuric acid, emulsify at a high speed forms finely dispersed emulsion.Above-mentioned suspension and the emulsion that is heated to 90 ℃ mixed 50 minutes under high-speed stirring, and precipitation is filtered, vacuum-drying and pulverize organic montmorillonoid.In traditional mixed with polymers or extrusion equipment with organic montmorillonoid and polyamide 1010 melting mixing, correspondingly obtain nano composite polymer-montmorillonoid material, (001) diffraction peak of polynite all disappears in its X-ray spectrogram, show polynite good dispersion in these polymkeric substance, have exfoliated structure.
Embodiment 8
With cation exchange capacity is polynite 14 grams of 150meq/100g, stirs 2h in 1500ml deionized water high speed, forms stable suspension system.10.5 gram cationite cetyl trimethylammonium bromides are added in the 500ml deionized waters, add and wait a mole protonating agent sulfuric acid, emulsify at a high speed forms finely dispersed emulsion.Above-mentioned suspension and the emulsion that is heated to 90 ℃ mixed 50 minutes under high-speed stirring, and precipitation is filtered, vacuum-drying and pulverize organic montmorillonoid.In traditional mixed with polymers or extrusion equipment with organic montmorillonoid and acid anhydrides polyethylene melting mixing, correspondingly obtain nano composite polymer-montmorillonoid material, (001) diffraction peak of polynite all disappears in its X-ray spectrogram, show polynite good dispersion in these polymkeric substance, have exfoliated structure.
Embodiment 9
With cation exchange capacity is polynite 14 grams of 150meq/100g, stirs 2h in 1500ml deionized water high speed, forms stable suspension system.10.5 gram cationite cetyl trimethylammonium bromides are added in the 500ml deionized waters, add and wait a mole protonating agent sulfuric acid, emulsify at a high speed forms finely dispersed emulsion.Above-mentioned suspension and the emulsion that is heated to 90 ℃ mixed 50 minutes under high-speed stirring, and precipitation is filtered, vacuum-drying and pulverize organic montmorillonoid.In traditional mixed with polymers or extrusion equipment with organic montmorillonoid and polystyrene melting mixing, correspondingly obtain nano composite polymer-montmorillonoid material, (001) diffraction peak of polynite all disappears in its X-ray spectrogram, show polynite good dispersion in these polymkeric substance, have exfoliated structure.
Embodiment 10
With cation exchange capacity is polynite 14 grams of 150meq/100g, stirs 2h in 1500ml deionized water high speed, forms stable suspension system.10.5 gram cationite cetyl trimethylammonium bromides are added in the 500ml deionized waters, add and wait a mole protonating agent sulfuric acid, emulsify at a high speed forms finely dispersed emulsion.Above-mentioned suspension and the emulsion that is heated to 90 ℃ mixed 50 minutes under high-speed stirring, and precipitation is filtered, vacuum-drying and pulverize organic montmorillonoid.In traditional mixed with polymers or extrusion equipment with organic montmorillonoid and acid anhydrides ethylene-propylene rubber(EPR) melting mixing, correspondingly obtain nano composite polymer-montmorillonoid material, (001) diffraction peak of polynite all disappears in its X-ray spectrogram, show polynite good dispersion in these polymkeric substance, have exfoliated structure.
Embodiment 11
With cation exchange capacity is polynite 14 grams of 150meq/100g, stirs 2h in 1500ml deionized water high speed, forms stable suspension system.10.5 gram cationite cetyl trimethylammonium bromides are added in the 500ml deionized waters, add and wait a mole protonating agent sulfuric acid, emulsify at a high speed forms finely dispersed emulsion.Above-mentioned suspension and the emulsion that is heated to 90 ℃ mixed 50 minutes under high-speed stirring, and precipitation is filtered, vacuum-drying and pulverize organic montmorillonoid.In traditional mixed with polymers or extrusion equipment with organic montmorillonoid and paracril melting mixing, correspondingly obtain nano composite polymer-montmorillonoid material, (001) diffraction peak of polynite all disappears in its X-ray spectrogram, show polynite good dispersion in these polymkeric substance, have exfoliated structure.
Embodiment 12
With cation exchange capacity is polynite 14 grams of 150meq/100g, stirs 2h in 1500ml deionized water high speed, forms stable suspension system.10.5 gram cationite cetyl trimethylammonium bromides are added in the 500ml deionized waters, add and wait a mole protonating agent sulfuric acid, emulsify at a high speed forms finely dispersed emulsion.Above-mentioned suspension and the emulsion that is heated to 90 ℃ mixed 50 minutes under high-speed stirring, and precipitation is filtered, vacuum-drying and pulverize organic montmorillonoid.In traditional mixed with polymers or extrusion equipment with organic montmorillonoid and styrene-butadiene rubber(SBR) melting mixing, correspondingly obtain nano composite polymer-montmorillonoid material, (001) diffraction peak of polynite all disappears in its X-ray spectrogram, show polynite good dispersion in these polymkeric substance, have exfoliated structure.
Embodiment 13
With cation exchange capacity is polynite 14 grams of 150meq/100g, stirs 2h in 1500ml deionized water high speed, forms stable suspension system.10.5 gram cationite cetyl trimethylammonium bromides are added in the 500ml deionized waters, add and wait a mole protonating agent sulfuric acid, emulsify at a high speed forms finely dispersed emulsion.Above-mentioned suspension and the emulsion that is heated to 90 ℃ mixed 50 minutes under high-speed stirring, and precipitation is filtered, vacuum-drying and pulverize organic montmorillonoid.In traditional mixed with polymers or extrusion equipment with organic montmorillonoid and silastic polymer melting mixing, correspondingly obtain nano composite polymer-montmorillonoid material, (001) diffraction peak of polynite all disappears in its X-ray spectrogram, show polynite good dispersion in these polymkeric substance, have exfoliated structure.
Embodiment 14
With cation exchange capacity is polynite 40 grams of 50meq/100g, stirs 1h in 1000ml deionized water high speed, forms stable suspension system.12 gram cationite cetyl trimethylammonium bromides are added in the 200ml deionized waters, add and wait a mole protonating agent sulfuric acid, emulsify at a high speed forms finely dispersed emulsion.Above-mentioned suspension and the emulsion that is heated to 80 ℃ mixed 30 minutes under high-speed stirring, and precipitation is filtered, vacuum-drying and pulverize organic montmorillonoid.In traditional mixed with polymers or extrusion equipment with 89 parts of polypropylene, 10 parts of polymeric amide 11 and 1 part of organic montmorillonoid fusion intercalation, directly obtain nano composite polymer-montmorillonoid material, (001) diffraction peak of polynite all disappears in its X-ray spectrogram, show polynite good dispersion in these polymkeric substance, have exfoliated structure.
Embodiment 15
With cation exchange capacity is polynite 16 grams of 150meq/100g, stirs 2h in 1000ml deionized water high speed, forms stable suspension system.14.4 gram cationite cetyl trimethylammonium bromides are added in the 300ml deionized waters, add and wait a mole protonating agent sulfuric acid, emulsify at a high speed forms finely dispersed emulsion.Above-mentioned suspension and the emulsion that is heated to 90 ℃ mixed 60 minutes under high-speed stirring, and precipitation is filtered, vacuum-drying and pulverize organic montmorillonoid.In traditional mixed with polymers or extrusion equipment with 80 parts of polypropylene, 15 parts of polymeric amide 12 and 10 parts of organic montmorillonoid fusion intercalations, directly obtain nano composite polymer-montmorillonoid material, (001) diffraction peak of polynite all disappears in its X-ray spectrogram, show polynite good dispersion in these polymkeric substance, have exfoliated structure.
Embodiment 16
With cation exchange capacity is polynite 16 grams of 120meq/100g, stirs 2h in 1000ml deionized water high speed, forms stable suspension system.3.8 gram cationite stearylamine adds in the 500ml deionized water, adds to wait a mole protonating agent hydrochloric acid again, emulsify at a high speed forms finely dispersed emulsion.Above-mentioned suspension and the emulsion that is heated to 60 ℃ mixed 30 minutes under high-speed stirring, and precipitation is filtered, vacuum-drying and pulverize organic montmorillonoid.In traditional mixed with polymers or extrusion equipment with 80 parts of polypropylene, 15 parts of acid anhydrides polypropylene and 5 parts of organic montmorillonoid fusion intercalations, directly obtain a series of acid anhydrides composite nanometer-level polypropylene/montmorillonoid materials, (001) diffraction peak of polynite all disappears in its X-ray spectrogram, show polynite good dispersion in these polymkeric substance, have exfoliated structure.
Embodiment 17
With cation exchange capacity is polynite 14 grams of 150meq/100g, stirs 2h in 1500ml deionized water high speed, forms stable suspension system.10.5 gram cationite cetyl trimethylammonium bromides are added in the 500ml deionized waters, add and wait a mole protonating agent sulfuric acid, emulsify at a high speed forms finely dispersed emulsion.Above-mentioned suspension and the emulsion that is heated to 90 ℃ mixed 50 minutes under high-speed stirring, and precipitation is filtered, vacuum-drying and pulverize organic montmorillonoid.In traditional mixed with polymers or extrusion equipment with 5 parts of organic montmorillonoids and 60 parts of polyethylene, 35 parts of acid anhydrides polyethylene melting mixing, correspondingly obtain nano composite polymer-montmorillonoid material, (001) diffraction peak of polynite all disappears in its X-ray spectrogram, show polynite good dispersion in these polymkeric substance, have exfoliated structure.
Embodiment 18
With cation exchange capacity is polynite 14 grams of 150meq/100g, stirs 2h in 1500ml deionized water high speed, forms stable suspension system.10.5 gram cationite cetyl trimethylammonium bromides are added in the 500ml deionized waters, add and wait a mole protonating agent sulfuric acid, emulsify at a high speed forms finely dispersed emulsion.Above-mentioned suspension and the emulsion that is heated to 90 ℃ mixed 50 minutes under high-speed stirring, and precipitation is filtered, vacuum-drying and pulverize organic montmorillonoid.In traditional mixed with polymers or extrusion equipment, 10 parts of organic montmorillonoids are mixed with 70 parts of polyamide 6s, 20 parts of acid anhydrides polypropylene fusions, correspondingly obtain nano composite polymer-montmorillonoid material, (001) diffraction peak of polynite all disappears in its X-ray spectrogram, show polynite good dispersion in these polymkeric substance, have exfoliated structure.
Embodiment 19
With cation exchange capacity is polynite 14 grams of 150meq/100g, stirs 2h in 1500ml deionized water high speed, forms stable suspension system.10.5 gram cationite cetyl trimethylammonium bromides are added in the 500ml deionized waters, add and wait a mole protonating agent sulfuric acid, emulsify at a high speed forms finely dispersed emulsion.Above-mentioned suspension and the emulsion that is heated to 90 ℃ mixed 50 minutes under high-speed stirring, and precipitation is filtered, vacuum-drying and pulverize organic montmorillonoid.In traditional mixed with polymers or extrusion equipment, 5 parts of organic montmorillonoids are mixed with 80 parts of polyamide 66s, 15 parts of acid anhydrides polypropylene fusions, correspondingly obtain nano composite polymer-montmorillonoid material, (001) diffraction peak of polynite all disappears in its X-ray spectrogram, show polynite good dispersion in these polymkeric substance, have exfoliated structure.
Embodiment 20
With cation exchange capacity is polynite 14 grams of 150meq/100g, stirs 2h in 1500ml deionized water high speed, forms stable suspension system.10.5 gram cationite cetyl trimethylammonium bromides are added in the 500ml deionized waters, add and wait a mole protonating agent sulfuric acid, emulsify at a high speed forms finely dispersed emulsion.Above-mentioned suspension and the emulsion that is heated to 90 ℃ mixed 50 minutes under high-speed stirring, and precipitation is filtered, vacuum-drying and pulverize organic montmorillonoid.In traditional mixed with polymers or extrusion equipment, 10 parts of organic montmorillonoids are mixed with 11,30 parts of acid anhydrides polypropylene fusions of 60 parts of polymeric amide, correspondingly obtain nano composite polymer-montmorillonoid material, (001) diffraction peak of polynite all disappears in its X-ray spectrogram, show polynite good dispersion in these polymkeric substance, have exfoliated structure.
Embodiment 21
With cation exchange capacity is polynite 14 grams of 150meq/100g, stirs 2h in 1500ml deionized water high speed, forms stable suspension system.10.5 gram cationite cetyl trimethylammonium bromides are added in the 500ml deionized waters, add and wait a mole protonating agent sulfuric acid, emulsify at a high speed forms finely dispersed emulsion.Above-mentioned suspension and the emulsion that is heated to 90 ℃ mixed 50 minutes under high-speed stirring, and precipitation is filtered, vacuum-drying and pulverize organic montmorillonoid.In traditional mixed with polymers or extrusion equipment, 15 parts of organic montmorillonoids are mixed with 12,30 parts of acid anhydrides polypropylene fusions of 55 parts of polymeric amide, correspondingly obtain nano composite polymer-montmorillonoid material, (001) diffraction peak of polynite all disappears in its X-ray spectrogram, show polynite good dispersion in these polymkeric substance, have exfoliated structure.
Embodiment 22
With cation exchange capacity is polynite 14 grams of 150meq/100g, stirs 2h in 1500ml deionized water high speed, forms stable suspension system.10.5 gram cationite cetyl trimethylammonium bromides are added in the 500ml deionized waters, add and wait a mole protonating agent sulfuric acid, emulsify at a high speed forms finely dispersed emulsion.Above-mentioned suspension and the emulsion that is heated to 90 ℃ mixed 50 minutes under high-speed stirring, and precipitation is filtered, vacuum-drying and pulverize organic montmorillonoid.In traditional mixed with polymers or extrusion equipment, 8 parts of organic montmorillonoids are mixed with 68 parts of polyamide 1010s, 24 parts of acid anhydrides polypropylene fusions, correspondingly obtain nano composite polymer-montmorillonoid material, (001) diffraction peak of polynite all disappears in its X-ray spectrogram, show polynite good dispersion in these polymkeric substance, have exfoliated structure.
Embodiment 23
With cation exchange capacity is polynite 14 grams of 150meq/100g, stirs 2h in 1500ml deionized water high speed, forms stable suspension system.10.5 gram cationite cetyl trimethylammonium bromides are added in the 500ml deionized waters, add and wait a mole protonating agent sulfuric acid, emulsify at a high speed forms finely dispersed emulsion.Above-mentioned suspension and the emulsion that is heated to 90 ℃ mixed 50 minutes under high-speed stirring, and precipitation is filtered, vacuum-drying and pulverize organic montmorillonoid.In traditional mixed with polymers or extrusion equipment, 6 parts of organic montmorillonoids are mixed with 76 parts of Polyurethanes, 18 parts of acid anhydrides polypropylene fusions, correspondingly obtain nano composite polymer-montmorillonoid material, (001) diffraction peak of polynite all disappears in its X-ray spectrogram, show polynite good dispersion in these polymkeric substance, have exfoliated structure.
Claims (4)
1. one kind prepares exfoliated polymer and Nano composite material of montmorillonite, and polymkeric substance is a polyamide 6, polyamide 66, polymeric amide 11, polymeric amide 12, polyamide 1010, the acid anhydrides polypropylene, the acid anhydrides polyethylene, Polyurethane, polystyrene, acid anhydrides ethylene-propylene rubber(EPR), paracril; styrene-butadiene rubber(SBR) or silastic polymer or polymer blend polypropylene/polymeric amide 11; polypropylene/polymeric amide 12; polypropylene/acid anhydrides polypropylene; polyethylene/acid anhydrides polyethylene; polyamide 6/acid anhydrides polypropylene; polyamide 66/acid anhydrides polypropylene; polymeric amide 11/ acid anhydrides polypropylene; polymeric amide 12/ acid anhydrides polypropylene; polyamide 1010/acid anhydrides polypropylene or Polyurethane/acid anhydrides polypropylene; Organic modification montmonrillonite, be made up of following component: (by weight) polynite 16～40 grams, cationite are primary amine, secondary ammonium or tertiary amine 3.8～19.2 grams; Disperseing the WATER AS FLOW MEDIUM of polynite is 500～1500ml, the WATER AS FLOW MEDIUM 100～500ml of dispersible cationic exchanger; The ratio of cation modifier mole number and the ion-exchange capacity of polynite is less than 1.
2. according to claims 1 described a kind of exfoliated polymer and Nano composite material of montmorillonite, it is characterized in that described cationite is the primary amine stearylamine.
3. according to claims 1 described a kind of exfoliated polymer and Nano composite material of montmorillonite, it is characterized in that described cationite is the tertiary amine cetyl trimethylammonium bromide.
4. the preparation method of claims 1 described exfoliated polymer and Nano composite material of montmorillonite, the polymkeric substance of selection is a polyamide 6, polyamide 66, polymeric amide 11, polymeric amide 12, polyamide 1010, the acid anhydrides polypropylene, the acid anhydrides polyethylene, Polyurethane, polystyrene, acid anhydrides ethylene-propylene rubber(EPR), paracril; styrene-butadiene rubber(SBR) or silicon rubber or polymer blend polypropylene/polymeric amide 11; polypropylene/polymeric amide 12; polypropylene/acid anhydrides polypropylene; polyethylene/acid anhydrides polyethylene; polyamide 6/acid anhydrides polypropylene; polyamide 66/acid anhydrides polypropylene; polymeric amide 11/ acid anhydrides polypropylene; polymeric amide 12/ acid anhydrides polypropylene; polyamide 1010/acid anhydrides polypropylene or Polyurethane/acid anhydrides polypropylene; Organic modification montmonrillonite, be made up of following component: (by weight) polynite 16～40 grams, cationite are primary amine, secondary ammonium or tertiary amine 3.8～19.2 grams; Disperseing the WATER AS FLOW MEDIUM of polynite is 500～1500ml, the WATER AS FLOW MEDIUM 100～500ml of dispersible cationic exchanger; The ratio of cation modifier mole number and the ion-exchange capacity of polynite is less than 1, and the polynite of polymkeric substance or polymer blend and modification is 50～99 parts by weight: 1～50 part;
Preparation process is as follows:
With cation exchange capacity be 50～150meq/100g polynite by weight 16～40 the gram, stir 0.5～2h in weight part 500～1000ml deionized water high speed, form stable suspension system, the cationite of 0.2～1.0 times of polynite ion-exchange capacity is added in 100～500ml deionized water, temperature 60-90 ℃, add equimolar protonating agent hydrochloric acid or sulfuric acid again, emulsify at a high speed, form finely dispersed emulsion, and join in the suspension system of above-mentioned polynite, under high-speed stirring, mixed 10～60 minutes, precipitation, filter, vacuum-drying and pulverize organic montmorillonoid, the polynite of polymkeric substance or polymer blend and modification is 50～99 parts by weight: 1～50 part; Extrude fusion intercalation, directly obtain exfoliated polymer/Nano composite material of montmorillonite.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031271308A CN100386384C (en) | 2003-09-03 | 2003-09-03 | Detaching type polymer/montmorillonite composite material and preparing method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031271308A CN100386384C (en) | 2003-09-03 | 2003-09-03 | Detaching type polymer/montmorillonite composite material and preparing method thereof |
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| Publication Number | Publication Date |
|---|---|
| CN1523060A true CN1523060A (en) | 2004-08-25 |
| CN100386384C CN100386384C (en) | 2008-05-07 |
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Assignee: Changzhou Tiansheng Neo-material Co., Ltd. Assignor: Changchun Institue of Applied Chemistry, Chinese Academy of Sciences Contract fulfillment period: 2008.7.28 to 2013.7.27 Contract record no.: 2009320000342 Denomination of invention: Detaching type polymer/montmorillonite composite material and preparing method thereof Granted publication date: 20080507 License type: Exclusive license Record date: 2009.3.13 |
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