CN111621114B - Modified polypropylene furniture composite material and preparation method and application thereof - Google Patents
Modified polypropylene furniture composite material and preparation method and application thereof Download PDFInfo
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- CN111621114B CN111621114B CN202010516257.8A CN202010516257A CN111621114B CN 111621114 B CN111621114 B CN 111621114B CN 202010516257 A CN202010516257 A CN 202010516257A CN 111621114 B CN111621114 B CN 111621114B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/14—Copolymers of propene
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- 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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
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Abstract
The invention provides a modified polypropylene furniture composite material, a preparation method and application thereof, wherein the composite material comprises the following components: copolymerized polypropylene, polyethylene, a toughening agent, a compatilizer and a filler; the filler comprises organic modified montmorillonite, and the organic modifier is selected from aliphatic diisocyanate and aliphatic diamine. The invention uses aliphatic diisocyanate and aliphatic diamine to carry out organic modification treatment on the montmorillonite, on one hand, the lipophilicity of the montmorillonite is improved, on the other hand, the organic modified montmorillonite can react with the compatilizer containing anhydride groups in the polypropylene composite material during melt extrusion, not only can the low-temperature toughness of the polypropylene composite material be improved, but also the interaction between the montmorillonite and the polypropylene material can be further improved, and the composite material is endowed with long-term weather resistance. The composite material has excellent rigidity and toughness, and can be applied to the field of special-shaped furniture with high requirements on rigidity and toughness.
Description
Technical Field
The invention belongs to the technical field of polypropylene composite materials, and particularly relates to a modified polypropylene furniture composite material, a preparation method thereof and application thereof in the field of special-shaped furniture.
Background
Polypropylene (PP-polypropylene) is a thermoplastic synthetic resin with excellent performance, has the advantages of small specific gravity, no toxicity, easy processing, impact strength, flexibility resistance and the like, and is an excellent building material and furniture base material. In five general-purpose plastics, the yield is second to polyethylene and polyvinyl chloride, the domestic consumption is second to the polyethylene position, but the weather resistance of polypropylene is poor, and because a large amount of unstable tertiary carbon atoms exist on the chain, the hydrogen on the tertiary carbon atoms can be removed into tertiary carbon free radicals only by small energy under the aerobic condition, the active tertiary carbon free radicals can spontaneously further initiate the polypropylene chain to break, the consequence is molecular degradation, the relative quality of macromolecules is reduced, and then the products and the products are discolored, hardened and cracked, thereby greatly limiting the application of the polypropylene in the fields of building materials and furniture which have requirements on appearance and mechanical properties.
There are several methods for improving the weatherability of polypropylene, among which the cost is low, it is simpler to operate to dope inorganic filler in polypropylene material, montmorillonite is clay composed of silicate sheets with nanometer thickness, and because of its wide source and low price, it is one of the most commonly used inorganic fillers in polypropylene. The basic structural unit of the montmorillonite is a layered structure formed by clamping one alundum octahedron between two silicon-oxygen tetrahedrons and sharing oxygen atoms, and the surfaces of the sheets have surplus negative charges, so that the montmorillonite sheets usually absorb hydrated cations such as sodium, potassium, calcium and the like to show water and oil repellency, so when the polypropylene weather resistance is improved by the montmorillonite, the montmorillonite needs to be subjected to hydrophobic modification firstly, for example, patent CN03115233.3 discloses a preparation method of a polypropylene/montmorillonite intercalation type nano composite material, a cation exchanger of the organic modified montmorillonite is 16-18 carbon alkyl ammonium salt or di-16-18 carbon alkyl ammonium salt, and in the polypropylene/montmorillonite intercalation type nano composite material prepared by the invention, the organic modified montmorillonite is uniformly dispersed in the polypropylene substrate; the patent CN00104624.1 discloses a polypropylene/montmorillonite nanocomposite and a preparation method thereof, the invention adopts a liquid phase intercalation method to prepare the polypropylene/montmorillonite nanocomposite, namely, the interlayer spacing of montmorillonite is enlarged through ion exchange reaction in a liquid phase reactor, simultaneously PP molecular chains and grafting monomers subjected to polarity treatment are inserted and dispersed in a liquid phase state, montmorillonite particles are uniformly dispersed in a PP matrix, and the combination of polypropylene and montmorillonite nano-scale is formed, thus obtaining the polypropylene/montmorillonite nanocomposite. The patent adopts an organic reagent to modify montmorillonite, improves the affinity of montmorillonite and organic materials, and improves the dispersion performance of montmorillonite in organic resin, but the intercalation montmorillonite prepared by the method cannot fully exert the advantages of nano-montmorillonite, but rather makes the polypropylene composite material easier to brittle fracture and poor creep resistance.
Therefore, the development of the polypropylene composite material with good weather resistance and excellent low-temperature toughness plays a key role in the popularization of the polypropylene material in the fields of building materials and furniture.
Disclosure of Invention
The invention aims to solve the technical problems and provides a modified polypropylene furniture composite material and a preparation method thereof, wherein the aliphatic diisocyanate and the aliphatic diamine are used for organically treating montmorillonite to prepare the organic modified montmorillonite with an amino chain end functional group, the organic modification treatment mode improves the lipophilicity of the montmorillonite on one hand, and enables the organic modified montmorillonite to be extruded out with a compatilizer containing an anhydride group in the polypropylene composite material to form an imide bond when the organic modified montmorillonite is extruded in a melting way, so that the low-temperature toughness of the polypropylene composite material can be improved, the interaction between the montmorillonite and the polypropylene material can be further improved, the montmorillonite is prevented from being separated out to influence the attractiveness of a polypropylene composite material product, and the composite material is endowed with long-term weather resistance.
In order to realize the purpose, the invention adopts the specific technical scheme that:
a modified polypropylene furniture composite comprising the following components: copolymerized polypropylene, polyethylene, a toughening agent, a compatilizer and a filler; the filler comprises organic modified montmorillonite, and the organic modifier is selected from aliphatic diisocyanate and aliphatic diamine.
A modified polypropylene furniture composite material comprises the following components in parts by weight: 100 parts of polypropylene copolymer, 15-25 parts of polyethylene, 10-15 parts of toughening agent, 10-20 parts of compatilizer and 20-35 parts of filler; the filler is organic modified montmorillonite, and the modifier comprises 60-120 parts of aliphatic diisocyanate and 60-80 parts of aliphatic diamine.
The aliphatic diisocyanate is selected from at least one of Hexamethylene Diisocyanate (HDI), 2, 4-trimethylhexamethylene diisocyanate (TMDI) and L-lysine diisocyanate.
The aliphatic diamine is selected from at least one of n-butylamine, hexamethylenediamine, decamethylenediamine and octamethylenediamine.
The compatilizer comprises at least one of maleic anhydride grafted polyethylene, maleic anhydride grafted polypropylene and ethylene-methyl acrylate-glycidyl methacrylate random terpolymer.
The melt index of the maleic anhydride grafted polyethylene and/or the maleic anhydride grafted polypropylene is 5-15g/10 min; the grafting rate of the maleic anhydride grafted polyethylene and/or the maleic anhydride grafted polypropylene is 3-5%.
Preferably, the compatilizer is a composition of maleic anhydride grafted polypropylene and ethylene-methyl acrylate-glycidyl methacrylate random terpolymer, and the weight ratio of the two is 1-3: 1.
The average grain diameter of the montmorillonite is 30-80 nm.
The preparation method of the organic modified montmorillonite comprises the following steps:
s1, adding montmorillonite into deionized water, stirring and dispersing uniformly, performing centrifugal separation, adding a hydrochloric acid solution into the precipitate, acidifying, and finally washing with deionized water until no Cl exists - Vacuum drying to obtain acidified montmorillonite;
s2, dispersing the acidified montmorillonite prepared in the step S1 in an anhydrous organic solution of aliphatic diisocyanate, stirring and reacting under vacuum, filtering a reaction product under a vacuum condition, and washing off excessive aliphatic diisocyanate by using an anhydrous organic solvent;
s3, dispersing the solid product obtained in the step S2 into an anhydrous organic solvent of aliphatic diamine again, stirring and reacting under a vacuum condition, filtering the reaction product under the vacuum condition, washing off excessive aliphatic diamine by using the organic solvent, and drying under the vacuum condition for later use;
step S2, the stirring reaction speed is 800-1200r/min, the stirring reaction time is 10-40min, the concentration of the aliphatic diisocyanate in the anhydrous organic solution of the aliphatic diisocyanate is 40-80 wt%, and the organic solvent of the anhydrous organic solution of the aliphatic diisocyanate includes but is not limited to at least one of benzene, toluene, acetone, ethyl acetate and diethyl ether.
Step S3, the stirring rotation speed is 800-.
The toughening agent comprises at least one of polyethylene terephthalate, polytrimethylene terephthalate and polybutylene terephthalate.
The toughening agents are terminated with carboxyl groups and/or anhydrides.
The polypropylene is classified into homo-polypropylene and co-polypropylene; the copolymerized polypropylene is divided into random copolymerized polypropylene and block copolymerized polypropylene, the random copolymerized polypropylene is obtained by copolymerizing propylene monomer and a small amount of ethylene (1-4%) monomer under the action of heating, pressurizing and catalyst, and the ethylene monomer is randomly and randomly distributed in the long chain of the propylene; the block copolymerization polypropylene has high ethylene content, generally 7-15%, wherein the probability of connecting two ethylene monomers and three monomers is very high, namely, the ethylene monomers only exist in a block phase, and the regularity of the polypropylene is not influenced.
The copolymerized polypropylene comprises at least one of random copolymerized polypropylene and block copolymerized polypropylene, and the melt index of the copolymerized polypropylene is 5-15g/10 min.
The polyethylene has a melt index of 10-15g/10 min.
The molecular weight of polypropylene, polyethylene is an important characteristic.
A preparation method of a modified polypropylene furniture composite material comprises the following steps:
t1, uniformly mixing the polypropylene copolymer, the polyethylene, the toughening agent, the compatilizer and the filler in a high-speed mixer;
t2, adding the mixture obtained in the step T1 into a double-screw extruder, and carrying out melt extrusion molding to obtain the polypropylene composite material;
step T2, the length-diameter ratio of the double-screw extruder is 50-55:1, and the extrusion temperature is 180-; and a material plasticizing area and a melt conveying area of the double-screw extruder are provided with vacuumizing devices, and the vacuum degree is-0.1 MPa- (-0.05) MPa.
The invention also provides the application of the modified polypropylene furniture composite material, which belongs to the field of special-shaped furniture with high requirements on rigidity and toughness, such as egg chairs, swan chairs, uterine chairs and the like.
Compared with the prior art, the invention has the beneficial effects that:
the invention uses aliphatic diisocyanate and aliphatic diamine to carry out organic treatment on montmorillonite to prepare the organic modified montmorillonite with amino chain end functional groups, the organic treatment improves the lipophilicity of montmorillonite on one hand, and on the other hand, the organic modified montmorillonite can carry out extrusion reaction with a compatilizer containing anhydride groups in the polypropylene composite material to form imide bonds when the organic modified montmorillonite is melt extruded, thereby not only improving the low-temperature toughness of the polypropylene composite material, but also further improving the interaction between the montmorillonite and the polypropylene material, preventing the montmorillonite from being separated out to influence the beauty of the polypropylene composite material product, and endowing the composite material with long-term weather resistance.
The inventor unexpectedly discovers that the organic modified montmorillonite has the function of improving the toughness of the composite material by the synergistic toughening agent while improving the weather resistance of the polypropylene composite material, so that the composite material has excellent rigidity and good toughness, and the material is suitable for being used as special-shaped furniture, such as egg chairs, swan chairs, uterine chairs and the like.
Detailed Description
The present invention will be further described with reference to the following examples, but the present invention is not limited to the descriptions in the following. Unless otherwise specified, "parts" in the examples of the present invention are parts by weight. All reagents used are commercially available in the art.
Example 1
Preparation of organic modified montmorillonite
S1, adding 50 parts of montmorillonite (with average particle size of 40nm) into 100 parts of deionized water, stirring and dispersing uniformly, performing centrifugal separation, and adding a hydrochloric acid solution (pH value of an acidification system) into the precipitateValue up to 4.0), acidifying for 30min, and washing with deionized water until AgNO is used 3 Detecting no white precipitate, and vacuum drying at 60 deg.C for 2 hr to obtain dried acidified montmorillonite;
s2, dispersing the acidified montmorillonite prepared in the step S1 in 120 parts of 50 wt% hexamethylene diisocyanate anhydrous toluene solution, stirring and reacting at 800r/min under-0.05 MPa vacuum condition for 40min, filtering the final mixture under vacuum condition, and washing off residual hexamethylene diisocyanate on filter residues by using anhydrous toluene;
s3, dispersing the filter residue obtained in the step S2 in 120 parts of anhydrous toluene solution with the concentration of 50 wt% of hexamethylene diamine again, stirring and reacting for 20min at 800r/min under the vacuum condition of-0.05 MPa, filtering the final mixture under the vacuum condition, washing off excessive hexamethylene diamine by using toluene, and drying in vacuum at 60 ℃ for later use;
preparation of modified polypropylene furniture composite material
The formula is as follows: 100 parts of block copolymerization polypropylene of an ethylene monomer and a propylene monomer with a melt index of 10g/10min, 15 parts of polyethylene with a melt index of 10g/10min, 15 parts of carboxyl-terminated polybutylene terephthalate, 15 parts of maleic anhydride grafted polypropylene with a melt index of 12g/10min and a grafting rate of 5%, 5 parts of ethylene-methyl acrylate-glycidyl methacrylate and 30 parts of the prepared organic modified montmorillonite.
T1, adding the materials in the formula into a high-speed mixer and uniformly mixing;
and T2, adding the mixture obtained in the step T1 into a double-screw extruder with the length-diameter ratio of 50:1, and carrying out melt extrusion molding at the extrusion temperature of 180-230 ℃ to obtain the polypropylene composite material, wherein 4 vacuumizing devices are arranged in a material plasticizing area and a melt conveying area of the double-screw extruder, and the vacuum degrees are all-0.08 MPa.
Example 2
The rest is the same as the example 1, except that the dosage of the organic modified montmorillonite in the formula is 20 parts.
Example 3
The rest is the same as the example 1, except that the dosage of the organic modified montmorillonite in the formula is 35 parts.
Example 4
The rest is the same as the example 1, except that the amount of the organic modified montmorillonite in the formula is 15 parts.
Example 5
The rest is the same as the example 1, except that the amount of the organic modified montmorillonite in the formula is 40 parts.
Example 6
The procedure was repeated as in example 1 except that 10 parts of maleic anhydride-grafted polypropylene and 10 parts of ethylene-methyl acrylate-glycidyl methacrylate were used in the formulation.
Example 7
The procedure was repeated as in example 1 except that the maleic anhydride-grafted polypropylene in the formulation had a grafting ratio of 3%.
Comparative example 1
The rest is the same as example 1, except that montmorillonite which is not organically modified is used in the formulation.
The composite materials prepared in the above examples and comparative examples were subjected to the following performance tests:
and (3) performance testing:
and (3) testing low-temperature toughness: the samples (80X 10X 4mm, notch depth: 2mm) were placed at-20 ℃ for 12 hours and then removed quickly, and the notch impact strength was tested according to GB/T1843-1996 within 10 seconds, and the results are shown in the following table.
Notched izod impact strength: the samples (80X 10X 4mm, notch depth: 2mm) were tested for notch impact strength at 23 ℃ according to the standard GB/T1843-1996, the results of which are given in the table below.
Bending property: the tests were carried out with reference to the standard GB/T9341-2000, with sample sizes of 80X 10X 4mm, and the results are given in the following table.
Tensile property: the tests were carried out according to the standard GB/T1040-1992, using type I specimens, at a tensile speed of 5 mm/min, and the results are given in the following table.
And (3) weather resistance test: ultraviolet indoor artificial accelerated aging test: the irradiance of the fluorescent ultraviolet lamps with the wavelength of 340nm and 313nm is controlled to be 0.68W/m 2 Irradiating and exposing for 3h at the temperature of (60 +/-3) DEG C in the blackboard, condensing and exposing for 3h under the non-irradiation condition at the condensation temperature of (50 +/-3) DEG C, and finally blowing for 10min (simulating four-level wind), wherein the circulation is carried out once every 370 min; the test protocol was 144h to test the notched strength retention, and the results are given in the following table.
TABLE 1
The invention uses aliphatic diisocyanate and aliphatic diamine to carry out organic treatment on montmorillonite to prepare the organic modified montmorillonite with amino chain end functional groups, the organic treatment improves the lipophilicity of montmorillonite on one hand, and on the other hand, the organic modified montmorillonite can carry out extrusion reaction with a compatilizer containing anhydride groups in the polypropylene composite material to form imide bonds when the organic modified montmorillonite is melt extruded, thereby not only improving the low-temperature toughness of the polypropylene composite material, but also further improving the interaction between the montmorillonite and the polypropylene material, preventing the montmorillonite from being separated out to influence the beauty of the polypropylene composite material product, and endowing the composite material with long-term weather resistance.
The inventor unexpectedly discovers that the organic modified montmorillonite has the function of improving the toughness of the composite material by the synergistic toughening agent while improving the weather resistance of the polypropylene composite material, so that the composite material has excellent rigidity and good toughness, and the material is suitable for being used as special-shaped furniture, such as egg chairs, swan chairs, uterine chairs and the like.
The above detailed description is specific to one possible embodiment of the present invention, and the embodiment is not intended to limit the scope of the present invention, and all equivalent implementations or modifications without departing from the scope of the present invention should be included in the technical scope of the present invention.
Claims (6)
1. The modified polypropylene furniture composite material is characterized by comprising the following components in parts by weight: 100 parts of polypropylene copolymer, 15-25 parts of polyethylene, 10-15 parts of toughening agent, 10-20 parts of compatilizer and 20-35 parts of filler; the filler is organic modified montmorillonite, and the organic modifier comprises 60-120 parts of aliphatic diisocyanate and 60-80 parts of aliphatic diamine;
the copolymerized polypropylene is a random copolymer and/or a block copolymer of ethylene and propylene monomers; the toughening agent is terminated by carboxyl and/or anhydride and is selected from at least one of polyethylene terephthalate, polytrimethylene terephthalate and polybutylene terephthalate;
the aliphatic diisocyanate is selected from at least one of Hexamethylene Diisocyanate (HDI), 2, 4-trimethylhexamethylene diisocyanate (TMDI) and L-lysine diisocyanate;
the aliphatic diamine is at least one selected from hexamethylenediamine, decamethylenediamine and octamethylenediamine;
the preparation method of the organic modified montmorillonite comprises the following steps:
s1, adding montmorillonite into deionized water, stirring and dispersing uniformly, performing centrifugal separation, adding a hydrochloric acid solution into the precipitate, acidifying, and finally washing with deionized water until no Cl exists - Vacuum drying to obtain acidified montmorillonite;
s2, dispersing the acidified montmorillonite prepared in the step S1 in an anhydrous organic solution of aliphatic diisocyanate, stirring and reacting under vacuum, filtering a reaction product under a vacuum condition, and washing off excessive aliphatic diisocyanate by using an anhydrous organic solvent;
s3, dispersing the solid product obtained in the step S2 into an anhydrous organic solvent of aliphatic diamine again, stirring and reacting under a vacuum condition, filtering the reaction product under the vacuum condition, washing off excessive aliphatic diamine by using the organic solvent, and drying under the vacuum condition for later use.
2. The modified polypropylene furniture composite material according to claim 1, wherein the compatibilizer is at least one selected from the group consisting of maleic anhydride grafted polyethylene, maleic anhydride grafted polypropylene, and ethylene-methyl acrylate-glycidyl methacrylate random terpolymer, and the graft ratio of the maleic anhydride grafted polyethylene and/or the maleic anhydride grafted polypropylene is 3 to 5%.
3. The modified polypropylene furniture composite of claim 2, wherein the compatibilizer is a combination of maleic anhydride grafted polypropylene and ethylene-methyl acrylate-glycidyl methacrylate random terpolymer in a weight ratio of 1-3: 1.
4. A process for the preparation of a modified polypropylene furniture composite according to any one of claims 1 to 3 comprising the steps of:
t1, uniformly mixing the polypropylene copolymer, the polyethylene, the toughening agent, the compatilizer and the filler in a high-speed mixer;
and T2, adding the mixture obtained in the step T1 into a double-screw extruder, and carrying out melt extrusion molding to obtain the polypropylene furniture composite material.
5. The method for preparing the modified polypropylene furniture composite material as claimed in claim 4, wherein the length/diameter ratio of the twin-screw extruder in the step T2 is 50-55:1, and the extrusion temperature is 180-230 ℃; and/or a material plasticizing area and a melt conveying area of the double-screw extruder are provided with vacuumizing devices, and the vacuum degree is-0.1 MPa- (-0.05) MPa.
6. Use of the modified polypropylene furniture composite material according to any one of claims 1 to 3 in the field of shaped furniture.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1613905A (en) * | 2004-09-16 | 2005-05-11 | 上海交通大学 | Preparation of polypropylene / organic montmorillonite nanometer composite material |
| CN101225226A (en) * | 2008-01-28 | 2008-07-23 | 浙江大学 | Method for preparing water-dispersion montmorillonite/organic block polyurethane nano composite material and uses thereof |
| CN101307129A (en) * | 2007-05-17 | 2008-11-19 | 宁波星箭航天机械厂 | Polyurethane/organic montmorillonite nano composite material and method for preparing same |
| CN106366456A (en) * | 2016-08-29 | 2017-02-01 | 合肥会通新材料有限公司 | Low-filling high-performance nanomontmorillonite-reinforced polypropylene composite material and preparation method thereof |
| CN110628134A (en) * | 2019-10-15 | 2019-12-31 | 合肥学院 | Nano montmorillonite modified polypropylene composite material and preparation method thereof |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1613905A (en) * | 2004-09-16 | 2005-05-11 | 上海交通大学 | Preparation of polypropylene / organic montmorillonite nanometer composite material |
| CN101307129A (en) * | 2007-05-17 | 2008-11-19 | 宁波星箭航天机械厂 | Polyurethane/organic montmorillonite nano composite material and method for preparing same |
| CN101225226A (en) * | 2008-01-28 | 2008-07-23 | 浙江大学 | Method for preparing water-dispersion montmorillonite/organic block polyurethane nano composite material and uses thereof |
| CN106366456A (en) * | 2016-08-29 | 2017-02-01 | 合肥会通新材料有限公司 | Low-filling high-performance nanomontmorillonite-reinforced polypropylene composite material and preparation method thereof |
| CN110628134A (en) * | 2019-10-15 | 2019-12-31 | 合肥学院 | Nano montmorillonite modified polypropylene composite material and preparation method thereof |
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