CN113292792A - rPP/POE/nano-silica composite material and preparation method and application thereof - Google Patents
rPP/POE/nano-silica composite material and preparation method and application thereof Download PDFInfo
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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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/08—Copolymers of ethene
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- C—CHEMISTRY; METALLURGY
- 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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- C—CHEMISTRY; METALLURGY
- 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
- C08K2201/006—Additives being defined by their surface area
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- C—CHEMISTRY; METALLURGY
- 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
- C08K2201/011—Nanostructured additives
Abstract
The invention discloses an rPP/POE/nano-silica composite material and a preparation method and application thereof. The composite material comprises rPP, POE and nano-SiO2And an antioxidant. The invention is prepared by mixing nano-SiO2Mixing and banburying with partial POE to obtain master batch; mixing rPP, an antioxidant, the rest POE and the master batch; then banburying through a mixer or melt extrusion through extensional rheology plasticizing extrusion equipment to obtain rPP/POE/nano-SiO2A composite material. The composite material effectively improves the mechanical property of rPP. The invention can effectively recycle the recycled polypropylene with high value.
Description
Technical Field
The invention belongs to the technical field of recycling and preparation of high polymer materials, and particularly relates to a high-performance low-cost rPP/POE/nano-silica composite material and a preparation method and application thereof.
Background
Polypropylene (PP) is one of the most common and widespread materials in the world, plastics being one of the most versatile. They are commonly used in packaging, household appliances, sports accessories, electronics, medicine and in automotive parts. The increase of the usage amount of the plastic also leads to the corresponding increase of the amount of the waste plastic, and because most of the plastic is extracted and synthesized from petroleum and is not degradable in the environment, the plastic causes great harm and pollution to organisms and the environment, and causes increasingly severe environmental problems. The waste polypropylene is exposed to light, oxygen and heat for a long time, so that the severe notch sensitivity is generated, and the mechanical property of the waste polypropylene is obviously reduced, so that the high-value recycling of the recycled polypropylene (rPP) becomes more important.
Many researchers have modified materials by toughening with a single elastomer, and although the impact strength of the mixture is slightly improved, some researchers have modified materials by adding a compatibilizer to improve the toughness due to the existence of two-phase compatibility. However, this component, while having better toughness, tends to be at the expense of the strength of the blend, and the addition of a compatibilizer adds cost and complexity to the process. In addition, most blending systems adopt traditional double-screw processing, when materials are melted and plasticized in a charging barrel, the materials are mainly under the action of a shear flow field, and fillers are mainly distributed and mixed, so that effective dispersive mixing is difficult to achieve, and the plasticizing and mixing effects of the blend are poor. Thus, effective performance enhancement of the blends is difficult to achieve.
Disclosure of Invention
To overcome the disadvantages and shortcomings of the prior art, the primary object of the present invention is to provide an rPP/POE/nano-silica composite (rPP/POE/nano-SiO)2)。
Another object of the present invention is to provide the rPP/POE/nano-SiO2A method for preparing a composite material.
Still another object of the present invention is to provide the rPP/POE/nano-SiO2Application of the composite material.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
rPP/POE/nano-SiO2The composite material comprises the following raw materials in parts by weight: 75-85 parts of rPP, 18-22 parts of POE and nano-SiO20.5-3 parts of antioxidant and 0-0.5 part of antioxidant; preferably comprisesThe raw materials comprise the following components in parts by weight: 80 parts of rPP, 20 parts of POE and nano-SiO20.5-3 parts of antioxidant and 0-0.5 part of antioxidant; more preferably comprises the following raw materials in parts by weight: 80 parts of rPP, 20 parts of POE and nano-SiO22-3 parts of antioxidant and 0.5 part of antioxidant.
Preferably, the rPP has a melt index of 13-14 g/10min (190 ℃/2.16kg), and further 13.3g/10min (190 ℃/2.16kg), and is a granule obtained by crushing, washing, drying, grounding, granulating and drying.
Preferably, the POE is an ethylene-octene copolymer with a melt index of 0.4-0.6 g/10min (190 ℃/2.16kg), and further is an ethylene-octene copolymer with a melt index of 0.5g/10min (190 ℃/2.16 kg).
Preferably, the nano-SiO2The average particle size is 10-15 nm, and the specific surface area is as follows: 200 +/-25 m2Fumed nanosilica of/G; further, average particle diameter 12nm, specific surface area: 200 +/-25 m2Fumed nanosilica of/G.
Preferably, the antioxidant is antioxidant 1010.
The rPP/POE/nano-SiO2The preparation method of the composite material comprises the following steps:
(1) mixing nano-SiO2Mixing and banburying with partial POE to obtain master batch;
(2) mixing rPP, an antioxidant, the rest POE and the master batch prepared in the step (1);
(3) banburying the material obtained by mixing in the step (2) by an internal mixer or melt extruding the material by an extensional rheological plastification extruding device to obtain rPP/POE/nano-SiO2A composite material.
Step (3) is preferably as follows: banburying the material obtained by mixing in the step (2) through an internal mixer, or melting and extruding through a stretching, rheological and plasticizing transportation device; then cooling, air drying, crushing and drying to obtain rPP/POE/nano-SiO2A composite material.
The banburying condition in the step (1) is preferably 100-180 ℃ and 40-80 rpm for 5-15 min; more preferably, the mixture is mixed at 150 ℃ and 60rpm for 10 min.
The mixing in step (2) is preferably carried out by a high-speed mixer.
The mixing condition is preferably that the mixture is mixed for 5-20 min at 800-1000 rpm; more preferably at 900rpm for 5 min.
The banburying condition in the step (3) is preferably that the banburying is carried out for 5-15 min at 150-200 ℃ and 40-80 rpm; more preferably, the mixture is mixed at 180 ℃ and 60rpm for 10 min.
The melt extrusion condition in the step (3) is preferably 100-180 ℃ and 5-45 rpm for mixing for 8-12 min; more preferably, the temperature of each stage is 100-160-180 ℃, and the mixing is carried out for 10min at 30 rpm.
rPP/POE/nano-SiO2The composite material is obtained by the preparation method.
The rPP/POE/nano-SiO2The composite material is applied in the fields of packaging, electric appliances and electronics.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the invention prepares rPP/POE/nano-SiO2The POE of the composite material of the blending system has similarity with the PP chain segment, and the two phases have better compatibility during melting and plasticizing, so that the composite material has better toughening effect compared with other mixtures.
(2) The invention adds the nano-SiO rigid particles2In the mixture, under the condition of low nano filler content, the strength of the composite material is effectively improved, and the impact strength is also obviously improved, so that the composite material with balanced rigidity and toughness is achieved. Because, when the composite material is subjected to impact stress, the propagation of cracks in the matrix absorbs energy. When the nano particles are added, the nano particles are more uniformly dispersed in the matrix under the action of the tensile flow field, and the nano particles can expand and refine cracks to generate more micro cracks and absorb more energy.
(3) The invention relates to rPP/POE/nano-SiO prepared by extensional rheology plasticizing conveying equipment2The mechanical property of the mixture is higher than that of the mixture processed under the traditional shear flow field, and the mixture is processed under 1 part of nano-SiO2Preparation at content under a tensile flow fieldCompared with the tensile strength and the notch impact strength under the traditional shear flow field, the composite material of the invention is respectively improved by 22 percent and 86 percent, and the mechanical property is obviously improved; and, in 2 parts nano-SiO2At the content, the impact strength is about 4 times of rPP and reaches about 2 times of new material polypropylene. This is because under the action of the stretching flow field, the fillers POE and nano-SiO2The dispersion and the mixing in the rPP matrix are more uniform; and the extensional rheological plasticizing conveying equipment has short processing flow and high heat transfer efficiency, thereby reducing the degradation of the waste polypropylene in the melting processing. Therefore, the invention can utilize a simple and effective process and equipment to recycle the recycled polypropylene with high value.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto. For process parameters not specifically noted, reference may be made to conventional techniques.
The rPP used in the following examples, from the waste catering box, purchased from zhangzhou, land and sea environmental protection industry development limited, melt index: 13.3g/10min (190 ℃/2.16 kg).
POE was purchased from dow chemical company, designation 8157, melt index: 0.5g/10min (190 ℃/2.16 kg).
nano-SiO2Purchased from Woundplast corporation (Germany) under the trade designation AEROSIL 200, average particle size: 12nm, specific surface area: 200 +/-25 m2/G。
Antioxidant 1010 was purchased from basf (germany).
The Brabender internal mixer is model number DDRV501, manufacturer Brabender Instruments, Inc., USA.
See chinese patent CN101219565A for a device based on extensional rheology plasticization transportation (also called extensional rheology plasticization extrusion device, abbreviated as extensional rheology extruder).
Example 1
The embodiment provides rPP/POE/nano-SiO based on a Brabender internal mixer2Composite materials and methods for making the same.
The respective raw materials were dried in an air-blast drying oven at 60 ℃ for 8 hours.
Mixing the materials according to the formula proportion shown in the table 1: wherein the content of the first and second substances,
examples 1 to 4 are: preparing rPP/POE/nano-SiO2When the composite material is prepared by adopting a two-step method, nano-SiO is weighed firstly2Mixing the master batch with POE (polyolefin elastomer) with the mass of 2/5 in a formula table in a Brabender internal mixer at 150 ℃ for 10min to prepare a master batch, wherein the rotating speed of a rotor is 60 revolutions per minute; mixing rPP, antioxidant 1010, the prepared master batch and the rest POE in a high-speed mixer (900rpm) for 5 min; then adding the mixture into a Brabender internal mixer for melting and mixing for 10min, wherein the temperature of each section of the internal mixer is 180-180 ℃, and the rotating speed of a rotor is 60 r/min; cooling, air drying, crushing and drying to obtain the material.
Comparative examples 1 and 2 are: mixing the raw materials in a high-speed mixer (900rpm) for 5 min; then adding the mixture into a Brabender internal mixer for melting and mixing for 10min, wherein the temperature of each section of the internal mixer is 180-180 ℃, and the rotating speed of a rotor is 60 r/min; cooling, air drying, crushing and drying to obtain the material.
TABLE 1 formulation of blends with different base ratios
Example 2
This example provides an rPP/POE/nano-SiO based on an extensional rheology extruder2Composite materials and methods for making the same.
The raw materials were dried in an air-blast drying oven at 60 ℃ for 8 hours.
Mixing the ingredients according to the formula proportion shown in table 2, wherein:
examples 5 to 8 are: preparing rPP/POE/nano-SiO2When the composite material is prepared by adopting a two-step method, nano-SiO is weighed firstly2Mixing the master batch with POE (polyolefin elastomer) with the mass of 2/5 in a formula table in a Brabender internal mixer at 150 ℃ for 10min to prepare a master batch, wherein the rotating speed of a rotor is 60 revolutions per minute; mixing rPP, antioxidant 1010, the prepared master batch and the rest POE in a high-speed mixer (900rpm) for 5 min; then adding the mixture into an extensional rheological extruder for melt mixingMixing for 10min, wherein the temperature of each section of the extruder is 100-; and extruding, cooling, crushing and drying to obtain the material.
Comparative example 3 is: mixing the raw materials in a high-speed mixer (900rpm) for 5 min; then adding the mixture into a stretching rheological extruder for melt mixing for 10min, wherein the temperature of each section of the extruder is 100-; and extruding, cooling, crushing and drying to obtain the material.
TABLE 2 formulation of blends of different base ratios
Effects of the embodiment
The composite materials prepared in example 1 and example 2 were subjected to tensile and impact property tests in accordance with GB/T1040-2006 and GB/T1043-2000, the results of which are shown in Table 3.
Table 3 mechanical property table of composite material under each component proportion
As can be seen from Table 3, the impact strength of the mixture as a function of nano-SiO was melt blended in a Brabender internal mixer2Is increased with an increase in; based on the extensional rheological plasticizing conveying equipment, the impact strength of the mixture is changed along with nano-SiO2The mechanical property of the mixture under the action of the stretching flow field is higher than that under the action of the shearing flow field.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. rPP/POE/nano silicon dioxideThe composite material is characterized by comprising the following raw materials in parts by mass: 75-85 parts of rPP, 18-22 parts of POE and nano-SiO20.5-3 parts of antioxidant and 0-0.5 part of antioxidant.
2. The rPP/POE/nano-silica composite material of claim 1, which is characterized by comprising the following raw materials in parts by mass: 80 parts of rPP, 20 parts of POE and nano-SiO20.5-3 parts of antioxidant and 0-0.5 part of antioxidant.
3. The rPP/POE/nano-silica composite material according to claim 2, which is characterized by comprising the following raw materials in parts by mass: 80 parts of rPP, 20 parts of POE and nano-SiO22-3 parts of antioxidant and 0.5 part of antioxidant.
4. The rPP/POE/nano-silica composite material according to any one of claims 1 to 3, wherein:
the melt index of the rPP is 13-14 g/10min at 190 ℃ under the condition of 2.16 kg;
the melt index of the POE is 0.4-0.6 g/10min at 190 ℃ under the condition of 2.16 kg;
the nano-SiO2The average particle size is 10-15 nm, and the specific surface area is as follows: 200 +/-25 m2Fumed nanosilica of/G.
5. The rPP/POE/nanosilica composite of claim 4, wherein:
the melt index of the rPP is 13.3g/10min at 190 ℃ under the condition of 2.16 kg;
the melt index of the POE is 0.5g/10min at 190 ℃ under the condition of 2.16 kg;
the nano-SiO2Average particle diameter 12nm, specific surface area: 200 +/-25 m2Fumed nanosilica of/G.
6. The rPP/POE/nano-silica composite material according to any one of claims 1 to 3, wherein: the antioxidant is antioxidant 1010.
7. The method for preparing rPP/POE/nano-silica composite material according to any one of claims 1 to 6, which comprises the following steps:
(1) mixing nano-SiO2Mixing and banburying with partial POE to obtain master batch;
(2) mixing rPP, an antioxidant, the rest POE and the master batch prepared in the step (1);
(3) banburying the material obtained by mixing in the step (2) by an internal mixer or melt extruding the material by an extensional rheological plastification extruding device to obtain rPP/POE/nano-SiO2A composite material.
8. The method of preparing rPP/POE/nano-silica composite material according to claim 7, wherein: the step (3) is as follows: banburying the material obtained by mixing in the step (2) through an internal mixer, or melting and extruding through a stretching, rheological and plasticizing transportation device; then cooling, air drying, crushing and drying to obtain rPP/POE/nano-SiO2A composite material.
9. The method for preparing rPP/POE/nano-silica composite material according to claim 7 or 8, wherein:
the banburying condition in the step (1) is that the mixture is mixed for 5-15 min at 100-180 ℃ and 40-80 rpm;
the mixing condition in the step (2) is mixing for 5-20 min at 800-1000 rpm;
the banburying condition in the step (3) is that the mixture is mixed for 5-15 min at 150-200 ℃ and 40-80 rpm;
the melt extrusion in the step (3) is carried out under the conditions of 100-180 ℃ and 5-45 rpm for 8-12 min.
10. The rPP/POE/nano-silica composite material as claimed in any one of claims 1 to 3, which is used in the fields of packaging, electrical appliances and electronics.
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