CN114409999A - Polypropylene composition and preparation method thereof - Google Patents
Polypropylene composition and preparation method thereof Download PDFInfo
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- CN114409999A CN114409999A CN202111677705.3A CN202111677705A CN114409999A CN 114409999 A CN114409999 A CN 114409999A CN 202111677705 A CN202111677705 A CN 202111677705A CN 114409999 A CN114409999 A CN 114409999A
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- polypropylene composition
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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
- C08L23/12—Polypropene
Abstract
The invention discloses a polypropylene composition and a preparation method thereof. The polypropylene composition comprises the following components in parts by weight: 55-90 parts of polypropylene resin, 1-5 parts of hyperbranched polymer, 5-10 parts of toughening agent, 5-10 parts of compatilizer, 0-30 parts of modified montmorillonite and 0.5-1 part of antioxidant. The polypropylene composition has good bonding performance by utilizing the hyperbranched polymer, and the hyperbranched polymer is added, so that the bonding performance of the material can be improved, the polypropylene composition can be directly bonded with metal in the forming process, an additional layer of tackifier material is not required, the process is simplified, and the cost is saved; on the other hand, the compatibility of the filler and the matrix resin can be improved, and the toughness and the rigidity of the material are improved. In addition, the modified montmorillonite is adopted, so that the compatibility of the montmorillonite and resin is improved, the mechanical property of the polypropylene composition is further improved, and the adhesion property with metal is also improved.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a polypropylene composition and a preparation method thereof.
Background
With the development of industries such as buildings, automobiles, decoration, furniture, information industry and the like and the improvement of requirements of people on living space environment, functional processing products such as safety glass, energy-saving hollow glass and the like are widely applied. Compared with single-layer glass, the hollow glass has better heat insulation and heat preservation effects and is more and more applied. The main materials of the hollow glass comprise glass, spacing bars, drying agents and the like. Traditional space bar is mostly the aluminium strip, because of metal coefficient of thermal conductivity is low, produces condensation easily, frosts and keeps warm shortcoming such as effect difference, the new warm limit space bar that arises of suitable fortune. At present, the materials are mostly PVC or PP, related documents and patents are consulted, and enterprises for producing the warm edge strips feed back that the materials are mostly imported at present, are easy to deform, poor in temperature resistance and high in price, cannot be directly bonded with metal aluminum strips, and can be bonded with metals only by adding an adhesive in a matching manner, but the process is complex and high in cost. Therefore, it is necessary to develop a material which can be bonded to a metal aluminum strip, and which is easy to process, excellent in heat resistance, and stable in size.
Disclosure of Invention
The invention aims to provide a polypropylene composition and a preparation method thereof aiming at the defects of the prior art. The polypropylene composition has better toughness, flexural modulus and adhesive property.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows: the polypropylene composition comprises the following components in parts by weight: 55-90 parts of polypropylene resin, 1-5 parts of hyperbranched polymer, 5-10 parts of toughening agent, 5-10 parts of compatilizer, 0-30 parts of modified montmorillonite and 0.5-1 part of antioxidant.
The hyperbranched polymer is a star-shaped or dendritic polymer, contains a large amount of active groups, and has good bonding performance, and the polypropylene composition can improve the bonding performance of materials on one hand, can be directly bonded with metal in molding without additionally adding a layer of tackifier-like material, so that the process can be simplified, and the cost can be saved; on the other hand, the compatibility of the montmorillonite and the matrix resin can be improved, and the toughness and the rigidity of the material are improved. In addition, as the content of the hyperbranched polymer increases, the toughness and peel strength of the material increase.
As a preferred embodiment of the present invention, the hyperbranched polymer is at least one of hyperbranched polyethyleneimine, hyperbranched polyester, hyperbranched unsaturated resin, and hyperbranched epoxy resin.
The molecular chain of the hyperbranched polymer contains more polar functional groups, such as amino, amide, ester, unsaturated groups or epoxy groups, has better compatibility with resin and fillers, and improves the performance of the whole material, such as mechanical performance, processing performance, adhesion and the like.
As a preferred embodiment of the present invention, the hyperbranched polymer has a degree of branching of 0.5 to 0.7.
The branching degree of the hyperbranched polymer influences the mechanical property and the adhesive property of the polypropylene composition. With the increase of the branching degree of the hyperbranched polymer, the impact strength and the bonding property of the polypropylene composition are enhanced, and the flexural modulus is slightly reduced. However, the degree of branching of the hyperbranched polymer is too high, the compatibility of the hyperbranched polymer and polypropylene is poor, and the mechanical property and the adhesive property of the material are reduced.
As a preferred embodiment of the invention, the modified montmorillonite is montmorillonite with the surface treated by acidification modification and/or quaternary ammonium salt modification; the D50 particle size of the modified montmorillonite is 2-5 μm; more preferably, the modified montmorillonite is montmorillonite with the surface subjected to acidification modification and quaternary ammonium salt modification treatment.
Montmorillonite is a sheet silicate with strong polarity, and after acid treatment, the montmorillonite has the advantages of passivation of polar bonds, increase of specific surface area and increase of aperture; meanwhile, after being treated by quaternary ammonium salt, the adsorption property of the resin is enhanced, the bonding property is improved, and the compatibility with resin can be improved. Compared with unmodified montmorillonite, the polypropylene composition prepared from the modified montmorillonite has obviously enhanced mechanical properties and metal bonding properties.
As a preferred embodiment of the present invention, the polypropylene resin has a melt flow rate of 1 to 5g/10min at 230 ℃ under test conditions of 2.16kg according to test standard ISO 1133-1-2011.
The invention selects the polypropylene resin with low melt flow rate to facilitate the extrusion molding of materials, and can avoid the unstable molding of low viscosity and high melt flow property of polypropylene.
As a preferred embodiment of the present invention, the toughening agent is at least one of POE, EVA, acrylic elastomer, EPDM; the melt flow rate of the toughening agent is 0.5-5g/10min under the test conditions of 190 ℃ and 2.16kg according to the test standard ISO 1133-1-2011.
As a preferred embodiment of the present invention, the compatibilizer is polypropylene grafted maleic anhydride.
As a preferred embodiment of the present invention, the antioxidant is a mixture of antioxidant 1010 and antioxidant 168; the mass ratio of the antioxidant 1010 to the antioxidant 168 is 1 (1-2).
In addition, the invention also claims a preparation method of the polypropylene composition, which comprises the following steps:
(1) uniformly mixing the hyperbranched polymer, the modified montmorillonite and the compatilizer, and then carrying out melt extrusion granulation to obtain a mixture;
(2) and mixing the mixture, the polypropylene resin, the toughening agent and the antioxidant, and carrying out melt extrusion and granulation to obtain the polypropylene composition.
As a preferred embodiment of the invention, in the step (2), the device for melt extrusion and granulation is a twin-screw extruder, the extrusion temperature of the twin-screw extruder is 180-210 ℃, and the length-diameter ratio is (38-42): 1, rotation speed 300 and 500 rpm.
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the invention, the hyperbranched polymer has good bonding performance, and is added into the polypropylene composition, so that on one hand, the bonding performance of the material can be improved, the material can be directly bonded with metal in the forming process, and an additional layer of tackifier-like material is not required to be added, so that the process is simplified, and the cost is saved; on the other hand, the compatibility of the filler and the matrix resin can be improved, and the toughness and the rigidity of the material are improved.
(2) In addition, the modified montmorillonite is adopted, so that the compatibility of the montmorillonite and resin is improved, the mechanical property of the polypropylene composition is further improved, and the adhesion property with metal is also improved.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to specific examples.
Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated. Unless otherwise indicated, reagents and materials used in the present invention are commercially available.
The examples and comparative examples of the invention employ the following raw materials:
polypropylene A: the melt flow rate measured at 230 ℃ under 2.16kg was 3g/10min, brand: PP K8003, purchased from the metallocene petrochemical industry;
polypropylene B: the melt flow rate measured at 230 ℃ under 2.16kg was 1g/10min, brand: PP EPS30R, available from the metallocene petrochemical industry;
polypropylene C: the melt flow rate measured at 230 ℃ under 2.16kg was 5g/10min, brand: PP K1005, available from yanshan petrochemical;
a toughening agent A: POE, melt flow rate measured at 190 ℃ under 2.16kg of 5g/10min, brand: POE 7447, available from DOW;
a toughening agent B: POE, melt flow rate measured at 190 ℃ under 2.16kg of 0.5g/10min, brand: POE 8150, available from DOW;
a toughening agent C: POE, melt flow rate at 190 ℃ under 2.16kg of 6g/10min, trade mark: POE LC610, available from LG;
hyperbranched polymer a: hyperbranched polyester, degree of branching 0.5, brand: hyper H102, available from wuhan Hyper branched;
hyperbranched polymer B: hyperbranched polyester, degree of branching 0.6, brand: hyper H103, available from wuhan Hyper branched;
hyperbranched polymer C: hyperbranched polyester, degree of branching 0.7, brand: hyper H104, available from wuhan Hyper branched;
hyperbranched polymer D: hyperbranched polyester, degree of branching 0.4, brand: hyper H101, purchased from wuhan Hyper branched;
hyperbranched polymer E: hyperbranched polyester, degree of branching 0.75, grade: hyper H105, available from wuhan Hyper branched;
modified montmorillonite A: montmorillonite of which the surface is modified by acidification and quaternary ammonium salt, D50 is 3um, and the mark is: DK4-D, available from Zhejiang Fenghong;
modified montmorillonite B: montmorillonite with the surface modified by acidification, D50 is 3um, and the mark is: DK4-S, available from Zhejiang Fenghong;
modified montmorillonite C: montmorillonite with the surface modified by quaternary ammonium salt, D50 is 3um, and the mark is: DK4-Y, available from Zhejiang Fenghong;
montmorillonite D: without modification, D50 was 3um, brand: DK4-1, available from Zhejiang Fenghong;
a compatilizer: polypropylene grafted maleic anhydride, commercially available, the inventive and comparative examples all used the same compatibilizer;
antioxidant: a mixture of antioxidant 1010 and antioxidant 168 in a mass ratio of 1:1, the same antioxidant was used in the inventive examples and comparative examples.
Examples 1 to 14 and comparative examples 1 to 5
The polypropylene compositions of examples 1 to 14 of the present invention are shown in Table 1, and the polypropylene compositions of comparative examples 1 to 5 are shown in Table 2.
The preparation method of the polypropylene composition disclosed in the embodiments 1-9, 11-14 and the comparative examples 2-4 of the invention comprises the following steps:
(1) uniformly mixing the hyperbranched polymer, the modified montmorillonite and the compatilizer, and then carrying out melt extrusion granulation to obtain a mixture;
(2) adding the mixture, the polypropylene resin, the toughening agent and the antioxidant into a double screw for mixing, and carrying out melt extrusion and granulation to obtain the polypropylene composition; the extrusion temperature of the double-screw extruder is 180-210 ℃, and the length-diameter ratio is 40: 1, rotation speed 300 and 500 rpm.
The preparation method of the polypropylene composition in the embodiment 10 of the invention comprises the following steps:
(1) uniformly mixing the hyperbranched polymer and the compatilizer, and then carrying out melt extrusion granulation to obtain a mixture;
(2) adding the mixture, the polypropylene resin, the toughening agent and the antioxidant into a double screw for mixing, and carrying out melt extrusion and granulation to obtain the polypropylene composition; the extrusion temperature of the double-screw extruder is 180-210 ℃.
Comparative example 1 of the present invention the preparation method of the polypropylene composition comprises:
(1) uniformly mixing the modified montmorillonite and the compatilizer, and then carrying out melt extrusion granulation to obtain a mixture;
(2) adding the mixture, the polypropylene resin, the toughening agent and the antioxidant into a double screw for mixing, and carrying out melt extrusion and granulation to obtain the polypropylene composition; the extrusion temperature of the double-screw extruder is 180-210 ℃.
The preparation method of the polypropylene composition of comparative example 5 of the present invention comprises:
(1) uniformly mixing the hyperbranched polymer, the unmodified montmorillonite and the compatilizer, and then carrying out melt extrusion granulation to obtain a mixture;
(2) adding the mixture, the polypropylene resin, the toughening agent and the antioxidant into a double screw for mixing, and carrying out melt extrusion and granulation to obtain the polypropylene composition; the extrusion temperature of the double-screw extruder is 180-210 ℃.
TABLE 1
TABLE 2
Examples of effects
The polypropylene compositions prepared in the examples and comparative examples were tested for their properties, and the specific test items and test methods were as follows:
(1) cantilever beam impact strength: testing according to GB/T1843-2008;
(2) flexural modulus: testing according to the standard GB/T9341-2008;
(3) peel strength: test standard GB/T2792-.
The results of the performance tests of the polypropylene compositions described in examples 1 to 14 and comparative examples 1 to 5 are shown in Table 3.
TABLE 3
According to the data in Table 3, the polypropylene compositions described in examples 1-14 have much higher Izod impact strength and peel strength than the polypropylene compositions prepared in comparative examples 1-5. According to examples 1-3, as the amount of hyperbranched polymer added increases, the Izod impact strength, flexural modulus and adhesive properties of the material increase; however, as can be seen from comparison of comparative examples 1 to 3 and examples 1 to 3, the addition of the hyperbranched polymer of the present invention can enhance the Izod impact strength, flexural modulus and adhesive properties of the material, but when the amount of the hyperbranched polymer is not within the range defined by the present invention, the Izod impact strength, flexural modulus and adhesive properties of the material are reduced. From the data of examples 2, 4-7, it can be seen that as the degree of branching of the hyperbranched polymer increases, the Izod impact strength, flexural modulus and adhesion properties of the material increase and then decrease, and that the properties of the material are best in the range of 0.5 to 0.7 of degree of branching. According to the data of the examples 2, 8-9 and the comparative example 5, compared with the unmodified montmorillonite, the modified montmorillonite can obviously enhance the mechanical property and the adhesive property of the material, and the montmorillonite subjected to surface acidification modification and quaternary ammonium salt modification treatment has the most obvious improvement on the property of the material. From the data of examples 2 and 10-12, it can be seen that the Izod impact strength, flexural modulus and adhesion property of the material increase with the increase of the addition amount of the modified montmorillonite, but the Izod impact strength and adhesion property of the material decrease significantly with the addition amount exceeding the range defined by the present invention.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. The polypropylene composition is characterized by comprising the following components in parts by weight: 55-90 parts of polypropylene resin, 1-5 parts of hyperbranched polymer, 5-10 parts of toughening agent, 5-10 parts of compatilizer, 0-30 parts of modified montmorillonite and 0.5-1 part of antioxidant.
2. The polypropylene composition according to claim 1, wherein the hyperbranched polymer is at least one of hyperbranched polyethyleneimine, hyperbranched polyester, hyperbranched unsaturated resin, and hyperbranched epoxy resin.
3. The polypropylene composition of claim 1, wherein the hyperbranched polymer has a degree of branching of from 0.5 to 0.7.
4. The polypropylene composition of claim 1, wherein the modified montmorillonite is montmorillonite whose surface is modified by acidification and/or quaternary ammonium salt; the D50 particle size of the modified montmorillonite is 2-5 μm.
5. The polypropylene composition of claim 1, wherein the polypropylene resin has a melt flow rate of 1 to 5g/min at 230 ℃ under a test condition of 2.16 kg.
6. The polypropylene composition of claim 1, wherein the toughening agent is at least one of POE, EVA, acrylic elastomer, EPDM; the melt flow rate of the toughening agent is 0.5-5g/min at 190 ℃ under the test condition of 2.16 kg.
7. The polypropylene composition of claim 1, wherein the compatibilizer is polypropylene grafted maleic anhydride.
8. The polypropylene composition of claim 1, wherein the antioxidant is a mixture of antioxidant 1010 and antioxidant 168.
9. A process for the preparation of a polypropylene composition according to any one of claims 1 to 7, comprising the steps of:
(1) uniformly mixing the hyperbranched polymer, the modified montmorillonite and the compatilizer, and then carrying out melt extrusion granulation to obtain a mixture;
(2) and mixing the mixture, the polypropylene resin, the toughening agent and the antioxidant, and carrying out melt extrusion and granulation to obtain the polypropylene composition.
10. The method for preparing the polypropylene composition according to claim 9, wherein the melt extrusion and granulation device in the step (2) is a twin-screw extruder, and the extrusion temperature of the twin-screw extruder is 180 to 210 ℃.
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Cited By (1)
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