CN1207333C - Method for raising compatibility of incompatible polyblend using inorganic nano particle - Google Patents
Method for raising compatibility of incompatible polyblend using inorganic nano particle Download PDFInfo
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- CN1207333C CN1207333C CN 03117284 CN03117284A CN1207333C CN 1207333 C CN1207333 C CN 1207333C CN 03117284 CN03117284 CN 03117284 CN 03117284 A CN03117284 A CN 03117284A CN 1207333 C CN1207333 C CN 1207333C
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Abstract
The present invention discloses a method for raising the compatibility of incompatible polyblends by using inorganic nano particles, which is characterized in that the inorganic nano particles are modified by alkyl amine salt or surface treating agents, melt blending is carried out to the inorganic nano particles with the proportion of 1 to 30% and two or more than two high polymers, or melt blending is carried out to the inorganic nano particles and one of the high polymers; after master batch is made, melt blending is carried out to the master batch and the other high polymer or more than one high polymesrs; a blending system obtained by the method of the present invention not only has the advantage of obvious disperse phase domain size reduction and is uniformly dispersed in a basal body, but also increases the compatibility of incompatible high polymers and improves the properties of modulus, strength, heat deflection temperature, etc. of blends. The present invention has the advantages of easy inorganic nano particle raw material obtaining, low cost, simple technical process and easy control and is suitable for various incompatible high polymer blending systems.
Description
One, technical field
The invention belongs to and improve the technical field that polyblend is a consistency, be specifically related to increase the method for incompatible poyblend compatibility with inorganic nano-particle.
Two, background technology
With the comprehensive performance of each superpolymer component of different types of superpolymer blend, learn from other's strong points to offset one's weaknesses, obtain comparatively ideal blend of over-all properties.But to really obtain the good blend of over-all properties, except that needing the physicals between the blend component to have the bigger difference, also requiring has consistency preferably between them, forming not separating on the macroscopic view, and be the heterogeneous system of heterogeneous structure on the microcosmic.Because the molecular structure of most of superpolymer, polarity, molecular weight etc. are widely different, even under powerful mechanical effect, the blend that can reach macroscopical homogeneous system still seldom.In order to change this present situation, people have carried out finding after a large amount of research, reduce if can make blend produce modal dispersed phase size, and the compatibilization that dispersity improves just can solve the inaccessible technique effect of simple mechanical way.
At present, the method that can produce compatibilization in polyblend system is a lot, and mainly contain following two kinds: 1, add segmented copolymer or graft copolymer as expanding material, as Radonjic G., J.Appl. at Polym.Sci., 1998:69 (13), 2625 reports in incompatible blend polypropylene and polystyrene, add styrene-butadiene-styrene block copolymer.This article claims to help like this increasing both consistencies, reduces the phase region size.But because the segmented copolymer of introducing is an elastomerics, thereby will reduce the tensile strength of system, performances such as rigidity inevitably in system.2, original position increase-volume, promptly in superpolymer melt blending process, functionalised polymers and other component reaction, thus form the effect that block or graft copolymer play increase-volume on the spot.For example peace doubly rich minister etc. at " Sumitomo Chemical ", 1989:(2) 56 the report in the triturating of super-toughened nylon (alloy), used the polymkeric substance of handling through maleic anhydride, the reaction of the terminal amido of its acid anhydrides side group and polymeric amide or the amide group of main chain can form the multipolymer that contains imide bond or new amido linkage in position.This class compatibilizing method requires body material must contain the functional group that can react accordingly obviously, and is then inapplicable to the incompatible blend that does not contain functional group, thereby do not have universality.
Three, summary of the invention
In view of the defective that prior art exists, the inventor try hard to provide a kind of new, have universality and can not reduce the compatibilizing method that polyblend is a mechanical property again.
Several years through the inventor are discovered, in polyblend system,, blend components is runs through entanglement mutually between approximate molecular chain or the molecular chain if phase farmland size can be reduced to nano level, then can improve the consistency between blend components, improve the performance of intermingling material.Because the dispersion size of inorganic particulate can reach several nanometers, and reach nanometer inorganic and have special surface effects, great specific surface area, if can make inconsistent superpolymer all be adsorbed on nanoparticle around or insert its interlayer, just can reduce the phase region size of blend, reach the purpose of increase-volume.Therefore the inventor proposes following technical scheme and reaches goal of the invention: promptly earlier inorganic nano-particle is carried out modification and handle, then with itself and inconsistent two or more superpolymer melt blending, or with its earlier with a kind of superpolymer melt blending wherein, after making masterbatch, again masterbatch and another kind of or more than one superpolymer melt blendings are got final product.
Inorganic nano-particle in the such scheme can be silicate, lime carbonate, silicon-dioxide or carbon black, and its particle diameter is 10～200 nanometers.Used silicate specifically can be polynite, kaolin, mica, talcum powder, vermiculite or graphite.What deserves to be explained is, therefore not have strict demand for its macroscopic particle diameter because silicate self just has special nano-lamellar structure.
When inorganic nano-particle being carried out modification and handle, if select silicate for use, it is to follow these steps to and condition is carried out that its modification is handled in the such scheme, and following component content is weight part:
(1) with 10～30 parts of stirring and dissolving of inorganic nano-particle in 20 times of solvents;
(2) 3～15 parts of alkylamine salts are continued to add wherein, and, filter 60～100 ℃ of following stir process of temperature 1～4 hour;
(3) modified inorganic nano-particle after will filtering is in the oven dry 2～6 hours down of 70～90 ℃ of temperature.
Wherein solvent be water, alcohol or ketone or can with water with other solvents of arbitrary proportion blended, alcohol etc. for example, but for the consideration of economy and environment aspect, the most preferred with water.Alkylamine salt is a hexanolactam salt, alkyl amino dodecane salt, alkyl cetylamine salt, alkyl stearylamine salt, at least a in ethanolamine salt or the triethanolamine salt.
In the such scheme when inorganic nano-particle being carried out modification and handles, if select for use be lime carbonate, silicon-dioxide or carbon black the time, it is directly to be 3～10% surface treatment agent with dried inorganic nano-particle and weight percent that its modification is handled, and stirring at normal temperatures gets final product.
Wherein surface treatment agent is any in stearic acid, sodium stearate, lead stearate, Zinic stearas, aluminic acid ester, phosphoric acid ester, silane coupling agent, the titanic acid ester.The aluminic acid ester can be two (oleic acid Diethylene Glycol ester group) aluminic acid isopropyl ester, two (three stearic acid tetramethylolmethane ester groups) aluminic acid isopropyl ester etc.; silane coupling agent can be g---aminopropyl trimethoxysilane, γ---(methacryloxypropyl) Trimethoxy silane etc., titanic acid ester can be sec.-propyl three (dioctyl phosphoryl) titanic acid ester, sec.-propyl three (dioctyl phosphoric acid ester acyl group) phthalate, sec.-propyl three oleoyl phthalates etc.
When increasing incompatible poyblend compatibility with inorganic nano-particle, its method one be with the inorganic nano-particle after the modification with weight percent be 1～30% with inconsistent two or more superpolymer, superpolymer fusion or 20～40 ℃ of blend more than the softening temperature 4～20 minutes.Its method two be with the inorganic nano-particle after the modification with weight percent be 1～30% earlier with a kind of superpolymer wherein, superpolymer fusion or 20～40 ℃ of blend more than the softening temperature 4～20 minutes, after making masterbatch, again with masterbatch and another kind of or more than one superpolymer, superpolymer fusion or 20～40 ℃ of blend more than the softening temperature 4～20 minutes.
For whether the consistency of checking the intermingling material for preparing with the inventive method obtains obvious improvement, the series of contrast material that the inventor will be done with the inorganic nano-particle polynite, at first test with wide-angle x-ray diffraction, its collection of illustrative plates is as shown in Figure 1: (1) polynite of being untreated, (2) modified montmorillonoid, (3) polypropylene/modified Nano composite material of montmorillonite, (4) polystyrene/Nano composite material of montmorillonite modified, (5) polypropylene/polystyrene/modified montmorillonoid matrix material.The result shows, the polynite of being untreated ° goes out peak 1.47nm in 2 θ=6.01, and modified montmorillonoid ° is located out peak 1.9nm in 2 θ=4.65, illustrates that the modified montmorillonoid interlamellar spacing increases; Polypropylene/modified Nano composite material of montmorillonite 2 θ=2.68 ° go out peak 3.3nm, and polystyrene/Nano composite material of montmorillonite modified 2 θ=2.82 ° go out peak 3.2nm, illustrate that polypropylene and polystyrene can both enter between cheating engaging layer; Polypropylene/polystyrene/modified montmorillonoid blend 2 θ=2.33 ° goes out peak 3.79nm, illustrates that polypropylene and polystyrene can enter between cheating engaging layer simultaneously, but also can enter same interlayer of polynite simultaneously.Secondly, will not add polynite again, be added with and be untreated polynite and be added with the polypropylene/polystyrene blend of modified montmorillonoid, and test with scanning electronic microscope, the photo of Huo Deing is seen Fig. 2 successively, Fig. 3, Fig. 4.The black cavity is the vestige that stays after the polystyrene disperse phase is etched away by toluene among the figure, therefrom can see the deployment conditions of polystyrene in matrix truly, be not add in the polypropylene/polystyrene blend with the unmodified processing polynite of interpolation to compare, the phase farmland size of disperse phase does not have obvious variation in the co-mixing system, and disperse phase is in matrix and disperses inequality, state not of uniform size; And added in the polypropylene/polystyrene blend of modified montmorillonoid, the phase farmland size of disperse phase obviously reduces, and is uniformly distributed in the matrix.This shows that inorganic nano particle modified polynite played tangible compatibilization in incompatible poyblend, helps disperse phase uniform distribution and reduce its phase farmland size in matrix.
Thereby the present invention has following advantage:
1, with the inventive method inorganic nano-particle is carried out modification after, mix and to interact with modified inorganic nano-particle with inconsistent two or more superpolymer again, and be enriched to around the inorganic nano-particle or enter its interlayer, thereby increased the entanglement of incompatible poyblend molecular chain greatly, improved the consistency between component.
2, because the inventive method introduces in incompatible blended polymer is inorganic nano-particle, thereby when improving the co-mixing system consistency, not only can obtain nano composite material, can also improve the modulus of blend, intensity, performances such as heat-drawn wire.
3, because the inventive method introduces in incompatible blended polymer is inorganic nano-particle, thereby not only raw material is easy to get, and compares with the segmented copolymers such as elastomerics SBS that prior art adds, and is with low cost.
4, the inventive method technological process is simple, is easy to control, applicable to various incompatible polyblend is.
Four, description of drawings
Fig. 1 is the wide-angle x-ray diffraction collection of illustrative plates of the series of contrast material done with the inorganic nano-particle polynite;
Fig. 2 is the scanning electron photomicrograph of polypropylene/polystyrene blend;
Fig. 3 is the scanning electron photomicrograph of polypropylene/polystyrene/unmodified processing polynite blend;
Fig. 4 is the scanning electron photomicrograph that the polynite blend is handled in polypropylene/polystyrene/modification.
Five, embodiment
Provide embodiment below so that the invention will be further described; but it is worthy of note; the embodiment that provides can not be interpreted as limiting the scope of the invention; person skilled in the art in this field to some nonessential improvement and adjustment that the present invention makes, must belong to protection scope of the present invention according to the content of the invention described above.
Embodiment one
Polynite 100 gram stirring and dissolving are restrained in the water in 2000; Add alkyl amino dodecane salt 35 grams, and stirred 2 hours down for 80 ℃, filter in temperature; Modified montmorillonoid after will filtering was then dried 4 hours down for 85 ℃ in temperature, and is standby.
Get polypropylene 26.6 grams, polystyrene 11.4 grams, modified montmorillonoid 2 grams promptly made the intermingling material that consistency is obviously improved in 5 minutes with 200 ℃ of melt blendings of temperature on torque rheometer.Modified montmorillonoid content is 5% in the intermingling material.
Embodiment two
Lime carbonate 100 grams of 80 nanometers, are mixed with 5 gram sec.-propyls, three oleoyl phthalates under the room temperature after 6 hours in 100 ℃ of following dryings of temperature.
Get polipropene 25 .2 gram, polystyrene 10.4 grams, modified calcium carbonate 12 grams with 200 ℃ of melt blendings of temperature 10 minutes, promptly make the intermingling material that consistency is obviously improved on torque rheometer.Modified calcium carbonate content is 30% in the intermingling material.
Embodiment three
Polynite 90 gram stirring and dissolving are restrained in the water in 1800; Add alkyl stearylamine salt 31 grams and ethanolamine salt 11 grams, and stirred 2.5 hours down for 70 ℃, filter in temperature; Modified montmorillonoid after will filtering then was 70 ℃ of oven dry of temperature 6 hours, and is standby.
Get polymethylmethacrylate 150 grams, modified montmorillonoid 50 grams, 200 ℃ of melt blendings make masterbatch on twin screw extruder.Masterbatch contains modified montmorillonoid 25%; 200 ℃ of melt blendings on twin screw extruder with masterbatch and polypropylene, polymethylmethacrylate and new LDPE (film grade) promptly make the intermingling material that consistency is obviously improved again.The ratio of polypropylene, polymethylmethacrylate and new LDPE (film grade) is 70/30/10 in the intermingling material, and polynite content is 10%.
Embodiment four
90 nano kaolines, 100 gram stirring and dissolving are restrained in the water in 2000; Add alkyl cetylamine salt 40 grams, and stirred 3 hours down for 90 ℃, filter in temperature; Modified kaolin after will filtering was then dried 3 hours down for 90 ℃ in temperature, and is standby.
Get each 225 gram of polymethylmethacrylate and polystyrene, modified kaolin 10 grams, 210 ℃ of melt blending granulations on twin screw extruder promptly make the intermingling material that consistency is obviously improved.Kaolin content is 2% in the intermingling material.
Embodiment five
With 50 nano silicons, 100 grams, after under 100 ℃ dry 6 hours, mix with 10 gram aminopropyl trimethoxysilane under the room temperature.
Get polystyrene 10.4 gram, nylon-6 25.2 grams, improved silica 3.2 grams with 250 ℃ of melt blendings of temperature 8 minutes, promptly make the intermingling material that consistency is obviously improved on torque rheometer.Improved silica content is 8% in the intermingling material.
Embodiment six
With 150 nano silicons, 100 grams, after under 100 ℃ dry 6 hours, mix with 3 gram sec.-propyl three (dioctyl phosphoric acid ester acyl group) titanic acid ester under the room temperature.
Get polystyrene 10.4 gram, nylon-6 25.2 grams, improved silica 2 grams with 250 ℃ of melt blendings of temperature 12 minutes, promptly make the intermingling material that consistency is obviously improved on torque rheometer.Improved silica content is 5.3% in the intermingling material.
Embodiment seven
Vermiculite 50 gram stirring and dissolving are restrained in the water in 1000; Add alkyl cetylamine salt 10 grams, and stirred 1.5 hours down for 75 ℃, filter in temperature; PERFORMANCE OF MODIFIED VERMICULITE after will filtering then was 75 ℃ of oven dry of temperature 5 hours, and is standby.
Get polymethylmethacrylate 150 grams, PERFORMANCE OF MODIFIED VERMICULITE 50 grams, 240 ℃ of melt blendings make masterbatch on twin screw extruder, and it is 25% that masterbatch contains vermiculite; With masterbatch and polypropylene, polymethylmethacrylate 240 ℃ of melt blendings on twin screw extruder, promptly make the intermingling material that consistency is obviously improved again.Polypropylene and polymethylmethacrylate ratio are 70/30 in the intermingling material, and PERFORMANCE OF MODIFIED VERMICULITE content is 5%.
Embodiment eight
With 200 nanometer carbon blacks, 100 grams, after under 100 ℃ dry 6 hours, mix with 9 gram g-aminopropyl trimethoxysilane under the room temperature.
Get polystyrene 9.6 gram, nylon-6 38.4 grams, modification carbon black 2 grams, under 250 ℃ on torque rheometer with 250 ℃ of melt blendings of temperature 15 minutes, promptly make the intermingling material that consistency is obviously improved.The modification carbon black content is 4% in the intermingling material.
Claims (9)
1, a kind of method that increases incompatible poyblend compatibility with inorganic nano-particle, it is characterized in that earlier inorganic nano-particle being carried out modification handles, be 1～30% ratio and inconsistent two or more superpolymer melt blending with it with weight percent then, or with its with weight percent be 1～30% ratio earlier with a kind of superpolymer melt blending wherein, after making masterbatch, again masterbatch and another kind of or more than one superpolymer melt blendings are got final product, used inorganic nano-particle is a silicate, lime carbonate, silicon-dioxide or carbon black, its particle diameter are 10～200 nanometers.
2, the method that increases incompatible poyblend compatibility with inorganic nano-particle according to claim 1, it is characterized in that when inorganic nano-particle is silicate, it is to follow these steps to and condition is carried out that its modification is handled, and following component content is weight part:
(1) with 10～30 parts of stirring and dissolving of inorganic nano-particle in 20 times of solvents;
(2) 3～15 parts of alkylamine salts are continued to add wherein, and, filter 60～100 ℃ of following stir process of temperature 1～4 hour;
(3) modified inorganic nano-particle after will filtering is in the oven dry 2～6 hours down of 70～90 ℃ of temperature.
3, according to claim 2ly increase the method for incompatible poyblend compatibility with inorganic nano-particle, it is characterized in that solvent be water, alcohol or ketone or with water with arbitrary proportion blended solvent alcohol.
4, according to claim 2 or the 3 described methods that increase incompatible poyblend compatibility with inorganic nano-particle, it is characterized in that alkylamine salt is a hexanolactam salt, alkyl amino dodecane salt, alkyl cetylamine salt, alkyl stearylamine salt, at least a in ethanolamine salt or the triethanolamine salt.
5, the method that increases incompatible poyblend compatibility with inorganic nano-particle according to claim 1, it is characterized in that when inorganic nano-particle is lime carbonate, silicon-dioxide or carbon black, it is directly to be 1～10% surface treatment agent with dried inorganic nano-particle and weight percent that its modification is handled, and stirring at normal temperatures gets final product.
6, according to claim 5ly increase the method for incompatible poyblend compatibility, it is characterized in that surface treatment agent is any in stearic acid, sodium stearate, lead stearate, Zinic stearas, aluminic acid ester, phosphoric acid ester, silane coupling agent, the titanic acid ester with inorganic nano-particle.
7, according to claim 1 or 2 or 3 or the 5 or 6 described methods that increase incompatible poyblend compatibility with inorganic nano-particle, it is characterized in that inorganic nano-particle after the modification is at superpolymer fusion or more than the softening temperature 20～40 ℃, with inconsistent two or more superpolymer blend 4～20 minutes.
8, the method that increases incompatible poyblend compatibility with inorganic nano-particle according to claim 4, it is characterized in that inorganic nano-particle after the modification is at superpolymer fusion or more than the softening temperature 20～40 ℃, with inconsistent two or more superpolymer blend 4～20 minutes.
9, according to claim 1 or 2 or 3 or the 5 or 6 described methods that increase incompatible poyblend compatibility with inorganic nano-particle, it is characterized in that inorganic nano-particle after the modification is at superpolymer fusion or more than the softening temperature 20～40 ℃, earlier with a kind of superpolymer blend wherein 4～20 minutes, after making masterbatch, again with masterbatch and another kind of or more than one superpolymer, superpolymer fusion or 20～40 ℃ of blend more than the softening temperature 4～20 minutes.
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| EP1682608A2 (en) | 2003-11-04 | 2006-07-26 | Huntsman Advanced Materials (Switzerland) GmbH | Two component curable compositions |
| CN101094885A (en) | 2004-12-30 | 2007-12-26 | 3M创新有限公司 | Polymer blends including surface-modified nanoparticles and methods of making the same |
| CN103360693B (en) * | 2013-07-30 | 2016-05-11 | 四川大学 | A kind of method of preparing incompatible polyblend |
| CN105220270A (en) * | 2015-10-30 | 2016-01-06 | 无锡市长安曙光手套厂 | A kind of polyester fiber and preparation method thereof |
| CN110527278B (en) * | 2019-08-30 | 2020-11-20 | 北京化工大学 | Nano particle compatibilizer based on carbon quantum dots and preparation method and application thereof |
| CN113402221B (en) * | 2021-02-18 | 2023-06-27 | 浙江大东吴集团建材构配件有限公司 | High-strength high-heat-preservation concrete and production process thereof |
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