CN111378072A - Functionalized polyolefin wax and preparation method thereof - Google Patents
Functionalized polyolefin wax and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a functionalized polyolefin wax and a preparation method thereof. The method comprises the following steps: (1) polyolefin wax, linear low-density polyethylene and inert gas foaming agent are melted, stirred and mixed in a pressure vessel at the temperature of 150 ℃ and 180 ℃, and the microporous polyolefin wax particles are prepared by pressure spraying or mechanical crushing. (2) The microporous polyolefin wax particles, the swelling agent, the initiator and the functionalized monomer are stirred and mixed in a closed pressure container for 30 to 60 minutes at room temperature, and then the system is heated to 60 to 80 ℃ to swell for 8 to 12 hours. (3) And (3) stirring the closed system, heating to 80-125 ℃, reacting for 2-4 hours, vacuumizing for 1-2 hours, and discharging to obtain the functionalized polyolefin wax. The functional polyolefin wax prepared by the method has the advantages of high grafting efficiency, high grafting uniformity and controllable grafting rate and functionalization. The process uses less solvent, has low reaction temperature, is easy to control the reaction, is easy for industrial large-scale production, and is a preparation process and a method of the polyolefin wax which are green, environment-friendly, efficient and multifunctional.
Description
Technical Field
The invention belongs to the field of polyolefin wax production, and particularly relates to a functionalized polyolefin wax and a preparation method thereof.
Background
Polyolefin wax is a common name for low molecular weight polyolefin, and is mainly polyethylene wax and polypropylene wax because low molecular weight polyolefin is waxy at normal temperature. The polyolefin wax has molecular weight of one thousand to several tens of thousands, has the characteristics of no toxicity and no corrosion, and is widely applied to the fields of lubrication, dispersion, material appearance improvement and the like. The common polyolefin wax has low polarity and poor compatibility with various organic matters, and greatly limits the application of the polyolefin wax in certain fields. In order to increase the polarity of polyolefins, it is common practice to chemically modify polyolefin waxes. The chemical modification of polyolefin wax is to make polyolefin wax molecule have polar or reactive group by chemical reaction. The polarity of the polyolefin wax is improved after chemical modification, the reactivity is enhanced, and the solubility, the compatibility, the emulsibility, the coupling property and the like are correspondingly improved, so that the application range of the polyolefin wax is wider. Thus, the polarization or functionalization of polyolefin waxes is one of the hot areas of research.
Currently, polyolefin waxes are polarized or functionalized mainly by two chemical reactions, oxidation and grafting. The oxidized polyolefin wax is a product produced by subjecting a polyolefin wax to an oxidation reaction in a suitable environment under the action of an oxidizing agent. Many patents such as CN 1206719A, CN110317415A, CN109206637B, CN109206637A, etc. disclose methods for preparing oxidized polyethylene wax. Numerous documents (applied chemical, 2009, 38 (10): 1145-. Indeed, the oxidation process can provide the polyolefin wax with a certain functionality, but the oxidation process is currently limited to polyethylene wax, while the oxidation of polypropylene wax has certain limitations. In addition, the functional groups on the oxidized polyethylene wax molecule obtained by the oxidation method are mainly carbonyl, ester, carboxyl, hydroxyl and the like, and the functionality of the oxidized polyethylene wax is greatly limited. Moreover, the oxidized polyethylene wax has the defects of high randomness of polar group distribution, poor uniformity of polarity or functionalization, low oxidation efficiency (acid value), more colloid byproducts, yellowing of product color and the like, and the application of the oxidized polyethylene wax in certain fields is limited.
Compared with the oxidation process for preparing the functionalized polyolefin wax, the grafting process for preparing the functionalized polyolefin wax greatly overcomes the defects and difficulties of the oxidation process. The methods for grafting polyolefin waxes are mainly the melt method (see patents CN103102454B, CN104448146B, JP59,191,706, U.S. Pat. No. 8,200,677: bonding, 2003, (6): 1-3 and the university of Qizihal, 2006, (6): 9-11), the solution method (see patent CN102167783A: high molecular materials and engineering, 2001, 17 (5): 30-33) and the solid phase grafting method (see patents CN1986588B, CN103772614A: chemical evolution, 2016, (9): 2941 and 2944). The melt grafting polyolefin wax has simple process and realizes continuous production, but the process has the defects of poor controllability of grafting reaction, serious side reaction, high requirement on equipment, low grafting rate (generally not higher than 1 percent), more unreacted monomer residue, serious environmental pollution caused by volatilization of the grafting monomer and the like. The solution grafting process can overcome some of the disadvantages of the melt industry, but because of the use of a large amount of solution, the post-treatment pressure is high, the cost is high, and the solvent has great pollution to the environment, the industrial production and application fields of the process are limited. The solid phase grafting process has relatively less solvent consumption, easy control of reaction, low production cost and less pollution, and can obtain polyolefin wax grafted products of different polarity via regulating the reaction time. The prior related patents are as follows: CN1986588B and CN103772614A, literature: chinese plastic, 2019, (6): 31-37 and petrochemical, 2017, (6): 731-738 et al, have the common limitations in the art of the preparation of polyolefin waxes and polyolefin solid phase graft copolymers, namely, the diffusion of the grafting monomer and initiator onto the graft material is not controllable, which severely results in low grafting efficiency and grafting yield, and poor grafting uniformity. The diffusion process of the grafting monomer and the initiator on the grafted object is closely related to the particle size of the grafted object, the shape of the particle size, the external air pressure, the swelling time and temperature and the solubility parameter of the swelling auxiliary agent. The controllable diffusion process of the grafting monomer and the initiator on the grafted object can improve the grafting efficiency and the grafting rate of the grafted object and the grafting uniformity.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims at the limitations of the prior art and provides a functionalized polyolefin wax and a preparation method thereof, which enable polyolefin wax particles grafted by a solid phase to have a certain void ratio and reasonable particle size by a physical foaming technology, and simultaneously adopt obvious stage control of a swelling process to change an uncontrollable diffusion process of a grafting monomer and an initiator in the grafted polyolefin wax into a controllable reaction process, so that the grafting efficiency, the grafting rate and the grafting uniformity of the polyolefin wax are greatly improved. The invention has the advantages of mild process conditions, controllable reaction, small environmental pollution and easy industrial production. The prepared functionalized polyolefin wax can be widely applied to compatilizers, adhesives, coupling agents and other fields requiring high polarity.
In order to solve the above technical problems, the present invention is solved by the following technical solutions.
A functionalized polyolefin wax, a method of making the functionalized polyolefin wax comprising the steps of: (1) polyolefin wax, linear low-density polyethylene and an inert gas foaming agent are put in a pressure container, melted, stirred and mixed uniformly, and then the mixture is sprayed under pressure/mechanically crushed to prepare microporous polyolefin wax particles; (2) uniformly stirring and mixing the microporous polyolefin wax particles, the swelling agent, the initiator and the functional monomer in a closed pressure container at room temperature, heating the system, and swelling; (3) and (3) stirring the closed swelling system, heating to 80-125 ℃, keeping the reaction for 2-4 hours, then vacuumizing, extracting for 1-2 hours, and discharging to obtain the functionalized polyolefin wax.
The preparation method of the functionalized polyolefin wax comprises the following steps: (1) polyolefin wax, linear low-density polyethylene and an inert gas foaming agent are put in a pressure container, melted, stirred and mixed uniformly, and then the mixture is sprayed under pressure/mechanically crushed to prepare microporous polyolefin wax particles; (2) uniformly stirring and mixing the microporous polyolefin wax particles, the swelling agent, the initiator and the functional monomer in a closed pressure container at room temperature, heating the system, and swelling; (3) and (3) stirring the closed swelling system, heating to 80-125 ℃, keeping the reaction for 2-4 hours, then vacuumizing, extracting for 1-2 hours, and discharging to obtain the functionalized polyolefin wax. Wherein the microporous polyolefin wax particles are prepared from the following raw materials in parts by weight: 80-95 parts of polyolefin wax; 5-20 parts of linear low-density polyethylene; 1-5 parts of inert gas.
In a preferred embodiment, the inert gas is one of nitrogen and carbon dioxide, preferably nitrogen.
In a preferred embodiment, the functionalized polyolefin wax is prepared from the following raw materials in parts by mass: microporous polyolefin wax particles 100; 1-10 parts of swelling agent; 0.1-0.5 of initiator; 1-10 functional monomers.
In a preferred embodiment, the swelling agent is a solvent with solubility parameter delta (cal.cm-3) 1/2 of 8.0 +/-1.5, and is preferably one or a mixture of diethyl ether, acetone, carbon tetrachloride, benzene and xylene.
In a preferred embodiment, the initiator is a peroxide with a half-life (t 1/2) of 1 hour and a decomposition temperature of 80-130 ℃, and is preferably one or a mixture of dibenzoyl peroxide, tert-butyl peroxybenzoate and 2, 2-di (tert-butylperoxy) butane.
In a preferred embodiment, the functional monomer is a compound having an unsaturated double bond, and is preferably one or a mixture of several of acrylic acid and its ester derivatives, maleic anhydride and its derivatives, unsaturated silanes, unsaturated diacids or esters, epoxy-containing compounds, oxazoline-containing compounds, and styrene.
In a preferred embodiment, the polyolefin wax is one or more of chemically synthesized polyethylene wax, thermally cracked polyethylene wax, synthesized polypropylene wax, thermally cracked polypropylene wax, oligomer or by-product thereof in the synthesis of polyolefin resin, and fischer-tropsch wax.
In a preferred embodiment, the linear low density polyethylene is produced by copolymerizing ethylene and α -olefin, and has a weight average molecular weight Mw of 20000-50000, a molecular weight distribution index (Mw/Mn) of 4.0-5.0, a resin particle size of 5-300 mesh, and a melt index of 40-100g/10min (190 ℃,2.16 Kg).
In a preferred embodiment, the linear low density polyethylene has a melt index of 50 to 60g/10min (190 ℃,2.16Kg), and the α -olefin is selected from one or more of butene, hexene, and octene.
In a preferred embodiment, the preparation process is as follows: (1) polyolefin wax, linear low-density polyethylene and an inert gas foaming agent are put in a pressure container to be melted, stirred and mixed at the temperature of 180 ℃ under the stirring speed of 200-; (2) the microporous polyolefin wax particles, the swelling agent, the initiator and the functional monomer are stirred and mixed in a closed pressure container for 30 to 60 minutes at room temperature, the stirring speed is 20 to 100 revolutions per minute, and then the system is heated to 60 to 80 ℃ and swelled for 8 to 12 hours. (3) And (3) stirring the closed system, heating the closed system to 80-125 ℃, keeping the stirring speed at 50-200 rpm for 2-4 hours, then vacuumizing, extracting for 1-2 hours, and discharging to obtain the functionalized polyolefin wax.
Compared with the prior art, the invention has the following beneficial effects: the invention provides a functionalized polyolefin wax and a preparation method thereof, which leads polyolefin wax particles grafted by a solid phase to have certain void ratio and reasonable particle size by a physical foaming technology, and simultaneously adopts obvious stage control of a swelling process to lead a grafting monomer and an initiator to be changed into a controllable reaction process from an uncontrollable diffusion process in the grafted polyolefin wax, thus greatly improving the grafting efficiency, the grafting ratio and the grafting uniformity of the polyolefin wax. The invention has the advantages of mild process conditions, controllable reaction, small environmental pollution and easy industrial production. The prepared functionalized polyolefin wax can be widely applied to compatilizers, adhesives, coupling agents and other fields requiring high polarity.
Drawings
FIG. 1 is an SEM photograph of the surface of polyolefin wax particles (sample No. PEW-0-1) according to the present invention.
FIG. 2 is an SEM photograph of the surface of polyolefin wax particles (sample No. PEW-1) in the present invention.
FIG. 3 shows the IR spectra of polyolefin wax particles before and after functionalization according to the present invention.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
The embodiments described below by referring to the drawings, in which the same or similar reference numerals denote the same or similar elements or elements having the same or similar functions throughout, are exemplary only for explaining the present invention, and are not construed as limiting the present invention.
Description of the test methods:
testing of a scanning electron microscope:
and (3) spraying gold on the surfaces of the polyolefin wax particles, and testing under a field emission scanning electron microscope. The diameters of the open pores on the surface of the microporous polyolefin wax particles were characterized, and the open pore ratio was calculated using the sum of the areas of all the open pores in the scanning field and/or the area of the scanning field.
Characterization of the polyolefin wax infrared spectrum:
melting purified microporous polyolefin wax, making into 1-2 mm thick sheet, and testing infrared spectrogram by Fourier infrared spectroscopy (reflection method).
Measurement of swelling degree:
the swelling degree is determined by volume method, measuring the volume of polyolefin wax particles before and after swelling and soaking with colorimetric cylinder
And (4) calculating. Wherein:
4) the method for calculating the grafting rate and the grafting efficiency comprises the following steps:
the graft ratio and the graft efficiency were calculated by weighing the change in the mass of the polyolefin wax before and after the reaction according to the formula.
Comparative example 1:
the synthetic polyethylene wax of 900 g and the linear low density polyethylene (LLDPE-8250) of 150 g are put into a pressure vessel with electric heating, heated to 180 ℃, melted, stirred and mixed evenly, and then pressure spray granulation is carried out to obtain the polyethylene wax particles of 15 meshes. 100g of polyethylene hydrocarbon wax particles, 5 g of dimethylbenzene, 0.3 g of dibenzoyl peroxide and 5 g of maleic anhydride are put into a closed pressure vessel with electric heating, stirred and heated to 80 ℃, the stirring speed is 100 r/min, the reaction is kept for 3 hours, then the mixture is vacuumized and extracted for 1.5 hours, and the functionalized polyethylene wax PEW-0-1 is obtained.
Comparative example 2:
the synthetic polyethylene wax of 900 g and the linear low density polyethylene (LLDPE-8250) of 150 g are put into a pressure vessel with electric heating, heated to 180 ℃, melted, stirred and mixed evenly, and then pressure spray granulation is carried out to obtain the polyethylene wax particles of 15 meshes. Then 100g of polyethylene hydrocarbon wax particles, 5 g of dimethylbenzene, 0.3 g of dibenzoyl peroxide and 5 g of maleic anhydride are stirred and mixed in a closed pressure container at room temperature for 45 minutes, the stirring speed is 60 revolutions per minute, then the system is heated to 60 ℃, after swelling for 10 hours, the closed system is stirred and heated to 80 ℃, the stirring speed is 150 revolutions per minute, reaction is kept for 3 hours, then vacuum extraction is carried out for 1.5 hours, and discharging is carried out, thus obtaining the functionalized polyethylene wax PEW-0-2.
Comparative example 3:
the preparation method comprises the steps of putting 900 g of synthetic polypropylene wax and 150 g of linear low density polyethylene (LLDPE-8250) into a pressure container with electric heating, heating to 180 ℃, melting, stirring and uniformly mixing, and mechanically crushing and granulating to obtain 15-mesh polypropylene wax particles. 100g of polypropylene olefin wax particles, 5 g of dimethylbenzene, 0.3 g of dibenzoyl peroxide and 5 g of maleic anhydride are put into a closed pressure container with electric heating, stirred and heated to 120 ℃, the stirring speed is 100 r/min, the reaction is kept for 3 hours, and then the mixture is vacuumized, extracted for 1.5 hours and discharged, thus obtaining the functional polypropylene wax PPW-0-1.
Comparative example 4:
the preparation method comprises the steps of putting 900 g of synthetic polypropylene wax and 150 g of linear low density polyethylene (LLDPE-8250) into a pressure container with electric heating, heating to 180 ℃, melting, stirring and uniformly mixing, and mechanically crushing and granulating to obtain 15-mesh polypropylene wax particles. Then 100g of polypropylene olefin wax particles, 5 g of dimethylbenzene, 0.3 g of dibenzoyl peroxide and 5 g of maleic anhydride are stirred and mixed in a closed pressure container for 45 minutes at room temperature, the stirring speed is 60 revolutions per minute, then the system is heated to 70 ℃, after swelling for 10 hours, the closed system is stirred and heated to 120 ℃, the stirring speed is 150 revolutions per minute, reaction is kept for 3 hours, then vacuum extraction is carried out for 1.5 hours, and discharging is carried out, thus obtaining the functional polypropylene hydrocarbon wax PPW-0-2.
Example 1
Putting 900 g of synthetic polyethylene wax and 150 g of linear low density polyethylene (LLDPE-8250) into a pressure container with electric heating, introducing 4 g of nitrogen, heating to 180 ℃, melting, stirring and uniformly mixing at the stirring speed of 500 revolutions per molecule for 45 minutes, and then carrying out pressure spray granulation to obtain 15-mesh polyethylene wax particles. Then 100g of polyethylene hydrocarbon wax particles, 5 g of dimethylbenzene, 0.3 g of dibenzoyl peroxide and 5 g of maleic anhydride are stirred and mixed in a closed pressure container at room temperature for 45 minutes, the stirring speed is 60 revolutions per minute, then the system is heated to 60 ℃, after swelling for 10 hours, the closed system is stirred and heated to 80 ℃, the stirring speed is 150 revolutions per minute, reaction is kept for 3 hours, then vacuum extraction is carried out for 1.5 hours, and discharging is carried out, thus obtaining the functionalized polyethylene wax PEW-1.
Example 2
Putting 900 g of synthetic polyethylene wax and 150 g of linear low density polyethylene (LLDPE-8250) into a pressure container with electric heating, introducing 5 g of nitrogen, heating to 180 ℃, melting, stirring and uniformly mixing at the stirring speed of 500 revolutions per molecule for 45 minutes, and then carrying out pressure spray granulation to obtain 15-mesh polyethylene wax particles. Then 100g of polyethylene hydrocarbon wax particles, 5 g of dimethylbenzene, 0.3 g of dibenzoyl peroxide and 5 g of maleic anhydride are stirred and mixed in a closed pressure container at room temperature for 45 minutes, the stirring speed is 60 revolutions per minute, then the system is heated to 60 ℃, after swelling for 10 hours, the closed system is stirred and heated to 80 ℃, the stirring speed is 150 revolutions per minute, reaction is kept for 3 hours, then vacuum extraction is carried out for 1.5 hours, and discharging is carried out, thus obtaining the functionalized polyethylene wax PEW-2.
Example 3
Putting 900 g of synthetic polyethylene wax and 150 g of linear low density polyethylene (LLDPE-8250) into a pressure container with electric heating, introducing 5 g of nitrogen, heating to 180 ℃, melting, stirring and uniformly mixing at the stirring speed of 500 revolutions per molecule for 45 minutes, and then carrying out pressure spray granulation to obtain 15-mesh polyethylene wax particles. Then 100g of polyethylene hydrocarbon wax particles, 5 g of dimethylbenzene, 0.3 g of dibenzoyl peroxide and 5 g of maleic anhydride are stirred and mixed in a closed pressure container at room temperature for 45 minutes, the stirring speed is 60 revolutions per minute, then the system is heated to 70 ℃, after swelling is carried out for 10 hours, the closed system is stirred and heated to 80 ℃, the stirring speed is 150 revolutions per minute, reaction is kept for 3 hours, then vacuum extraction is carried out for 1.5 hours, and discharging is carried out, thus obtaining the functionalized polyethylene wax PEW-3.
Example 4
Putting 900 g of synthetic polyethylene wax and 150 g of linear low density polyethylene (LLDPE-8250) into a pressure container with electric heating, introducing 5 g of nitrogen, heating to 180 ℃, melting, stirring and uniformly mixing at the stirring speed of 500 revolutions per molecule for 45 minutes, and then carrying out pressure spray granulation to obtain 15-mesh polyethylene wax particles. Then 100g of polyethylene hydrocarbon wax particles, 5 g of dimethylbenzene, 0.3 g of dibenzoyl peroxide and 5 g of maleic anhydride are stirred and mixed in a closed pressure container at room temperature for 45 minutes, the stirring speed is 60 revolutions per minute, then the system is heated to 70 ℃, after swelling is carried out for 10 hours, the closed system is stirred and heated to 80 ℃, the stirring speed is 150 revolutions per minute, reaction is kept for 4 hours, then vacuum extraction is carried out for 1.5 hours, and discharging is carried out, thus obtaining the functionalized polyethylene wax PEW-4.
Example 5:
the preparation method comprises the steps of putting 900 g of synthetic polypropylene wax and 150 g of linear low density polyethylene (LLDPE-8250) into a pressure container with electric heating, introducing 3 g of nitrogen, heating to 180 ℃, melting, stirring and mixing uniformly at the stirring speed of 500 revolutions per molecule for 45 minutes, and then mechanically crushing and granulating to obtain 15-mesh polypropylene wax particles. Then 100g of polypropylene olefin wax particles, 5 g of dimethylbenzene, 0.3 g of dibenzoyl peroxide and 5 g of maleic anhydride are stirred and mixed in a closed pressure container for 45 minutes at room temperature, the stirring speed is 60 revolutions per minute, then the system is heated to 70 ℃, after swelling for 10 hours, the closed system is stirred and heated to 120 ℃, the stirring speed is 150 revolutions per minute, reaction is kept for 3 hours, then vacuum extraction is carried out for 1.5 hours, and discharging is carried out, thus obtaining the functional polypropylene hydrocarbon wax PPW-1.
Example 6:
the preparation method comprises the steps of putting 900 g of synthetic polypropylene wax and 150 g of linear low density polyethylene (LLDPE-8250) into a pressure container with electric heating, introducing 5 g of nitrogen, heating to 180 ℃, melting, stirring and mixing uniformly at the stirring speed of 500 revolutions per molecule for 45 minutes, and then mechanically crushing and granulating to obtain 15-mesh polypropylene wax particles. Then 100g of polypropylene olefin wax particles, 5 g of dimethylbenzene, 0.3 g of dibenzoyl peroxide and 5 g of maleic anhydride are stirred and mixed in a closed pressure container for 45 minutes at room temperature, the stirring speed is 60 revolutions per minute, then the system is heated to 70 ℃, after swelling for 10 hours, the closed system is stirred and heated to 120 ℃, the stirring speed is 150 revolutions per minute, reaction is kept for 3 hours, then vacuum extraction is carried out for 1.5 hours, and discharging is carried out, thus obtaining the functional polypropylene hydrocarbon wax PPW-2.
Example 7:
the preparation method comprises the steps of putting 900 g of synthetic polypropylene wax and 150 g of linear low density polyethylene (LLDPE-8250) into a pressure container with electric heating, introducing 5 g of nitrogen, heating to 180 ℃, melting, stirring and mixing uniformly at the stirring speed of 500 revolutions per molecule for 45 minutes, and then mechanically crushing and granulating to obtain 15-mesh polypropylene wax particles. Then 100g of polypropylene olefin wax particles, 5 g of dimethylbenzene, 0.3 g of dibenzoyl peroxide and 5 g of maleic anhydride are stirred and mixed in a closed pressure container for 45 minutes at room temperature, the stirring speed is 60 revolutions per minute, then the system is heated to 80 ℃, after swelling for 10 hours, the closed system is stirred and heated to 120 ℃, the stirring speed is 150 revolutions per minute, reaction is kept for 3 hours, then vacuum extraction is carried out for 1.5 hours, and discharging is carried out, thus obtaining the functional polypropylene hydrocarbon wax PPW-3.
Example 8:
the preparation method comprises the steps of putting 900 g of synthetic polypropylene wax and 150 g of linear low density polyethylene (LLDPE-8250) into a pressure container with electric heating, introducing 5 g of nitrogen, heating to 180 ℃, melting, stirring and mixing uniformly at the stirring speed of 500 revolutions per molecule for 45 minutes, and then mechanically crushing and granulating to obtain 15-mesh polypropylene wax particles. Then 100g of polypropylene olefin wax particles, 5 g of dimethylbenzene, 0.3 g of dibenzoyl peroxide and 5 g of maleic anhydride are stirred and mixed in a closed pressure container for 45 minutes at room temperature, the stirring speed is 60 revolutions per minute, then the system is heated to 80 ℃, after swelling for 10 hours, the closed system is stirred and heated to 120 ℃, the stirring speed is 150 revolutions per minute, reaction is kept for 4 hours, then vacuum extraction is carried out for 1.5 hours, and discharging is carried out, thus obtaining the functional polypropylene hydrocarbon wax PPW-4.
The properties of the materials prepared in examples 1 to 8 and comparative examples 1 to 4 are shown in Table 1. FIGS. 1 and 2 show SEM photographs of the surface of polyolefin wax particles (sample No. PEW-0-1) and functionalized (sample No. EW-1). FIG. 3 shows the infrared spectra of the polyolefin wax before and after functionalization.
TABLE 1 Properties of functional polyolefin waxes prepared in examples 1-8 and comparative η examples 1-4
| Numbering of polyolefin waxes | Degree of swelling η% | Graft ratio GP | Grafting efficiency GE |
| PEW-0-1 | 2.2 | 0.56 | 3.1 |
| PEW-0-2 | 3.8 | 0.92 | 4.6 |
| PPW-0-1 | 1.4 | 0.37 | 2.2 |
| PPW-0-2 | 2.9 | 0.61 | 3.3 |
| PEW-1 | 5.6 | 1.5 | 7.5 |
| PEW-2 | 7.2 | 2.0 | 8.8 |
| PEW-3 | 9.8 | 3.1 | 9.1 |
| PEW-4 | 9.5 | 3.8 | 9.3 |
| PPW-1 | 4.1 | 0.91 | 4.4 |
| PPW-2 | 5.6 | 1.6 | 5.5 |
| PPW-3 | 6.8 | 1.91 | 7.7 |
| PPW-4 | 7.0 | 2.1 | 7.9 |
As can be seen from Table 1, the examples using the technical solution of the present invention have higher swelling ratio than the comparative examples, resulting in significantly higher grafting yield and efficiency of the functionalized polyolefin. As can be seen from FIGS. 1 to 3, the microporous polyolefin wax particles can be obtained and functionalized by the technical scheme of the invention.
The scope of the present invention includes, but is not limited to, the above embodiments, and the present invention is defined by the appended claims, and any alterations, modifications, and improvements that may occur to those skilled in the art are all within the scope of the present invention.
Claims (10)
1. A functionalized polyolefin wax, wherein the preparation method of the functionalized polyolefin wax comprises the following steps:
polyolefin wax, linear low-density polyethylene and an inert gas foaming agent are put in a pressure container, melted, stirred and mixed uniformly, and then the mixture is sprayed under pressure/mechanically crushed to prepare microporous polyolefin wax particles;
uniformly stirring and mixing the microporous polyolefin wax particles, the swelling agent, the initiator and the functional monomer in a closed pressure container at room temperature, heating the system, and swelling;
and (3) stirring the closed swelling system, heating to 80-125 ℃, keeping the reaction for 2-4 hours, then vacuumizing, extracting for 1-2 hours, and discharging to obtain the functionalized polyolefin wax.
2. A method for preparing a functionalized polyolefin wax, comprising the steps of:
polyolefin wax, linear low-density polyethylene and an inert gas foaming agent are put in a pressure container, melted, stirred and mixed uniformly, and then the mixture is sprayed under pressure/mechanically crushed to prepare microporous polyolefin wax particles;
uniformly stirring and mixing the microporous polyolefin wax particles, the swelling agent, the initiator and the functional monomer in a closed pressure container at room temperature, heating the system, and swelling;
stirring the closed swelling system, heating to 80-125 ℃, keeping reacting for 2-4 hours, then vacuumizing, extracting for 1-2 hours, and discharging to obtain the functionalized polyolefin wax;
wherein the microporous polyolefin wax particles are prepared from the following raw materials in parts by weight: 80-95 parts of polyolefin wax; 5-20 parts of linear low-density polyethylene; 1-5 parts of inert gas.
3. The preparation method of the functionalized polyolefin wax according to claim 2, wherein the functionalized polyolefin wax is prepared from the following raw materials in parts by mass: microporous polyolefin wax particles 100; 1-10 parts of swelling agent; 0.1-0.5 of initiator; 1-10 functional monomers.
4. The method for preparing a functionalized polyolefin wax according to claim 3, wherein the swelling agent is a solvent with solubility parameter δ (cal.cm-3) 1/2 of 8.0 ± 1.5, preferably one or more of diethyl ether, acetone, carbon tetrachloride, benzene and xylene.
5. The method of claim 3, wherein the initiator is a peroxide having a half-life (t 1/2) of 1 hour and a decomposition temperature of 80-130 ℃, and is preferably one or a mixture of dibenzoyl peroxide, tert-butyl peroxybenzoate, and 2, 2-di (tert-butylperoxy) butane.
6. The method of claim 3, wherein the functional monomer is a compound having an unsaturated double bond, preferably one or a mixture of acrylic acid and its ester derivatives, maleic anhydride and its derivatives, unsaturated silanes, unsaturated diacids or esters, epoxy-containing compounds, oxazoline-containing compounds, and styrene.
7. The method of claim 2, wherein the polyolefin wax is one or more of a chemically synthesized polyethylene wax, a thermally cracked polyethylene wax, a synthesized polypropylene wax, a thermally cracked polypropylene wax, an oligomer or a byproduct thereof obtained by synthesizing a polyolefin resin, and a Fischer-Tropsch wax.
8. The method of claim 2, wherein the linear low density polyethylene is prepared by copolymerizing ethylene and α -olefin, and has a weight average molecular weight Mw of 20000-50000, a molecular weight distribution index (Mw/Mn) of 4.0-5.0, a resin particle size of 5-300 mesh, and a melt index of 40-100g/10min (190 ℃,2.16 Kg).
9. The method of claim 8, wherein the linear low density polyethylene has a melt index of 50-60g/10min (190 ℃,2.16Kg), and the α -olefin is selected from one or more of butene, hexene, and octene.
10. The method for preparing the functionalized polyolefin wax according to claim 2, wherein the specific process of the preparation is as follows: (1) polyolefin wax, linear low-density polyethylene and an inert gas foaming agent are put in a pressure container to be melted, stirred and mixed at the temperature of 180 ℃ under the stirring speed of 200-; (2) stirring and mixing the microporous polyolefin wax particles, the swelling agent, the initiator and the functionalized monomer in a closed pressure container at room temperature for 30-60 minutes at the stirring speed of 20-100 revolutions per minute, and then heating the system to 60-80 ℃ for swelling for 8-12 hours; (3) and (3) stirring the closed system, heating the closed system to 80-125 ℃, keeping the stirring speed at 50-200 rpm for 2-4 hours, then vacuumizing, extracting for 1-2 hours, and discharging to obtain the functionalized polyolefin wax.
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| CN114920881A (en) * | 2022-05-25 | 2022-08-19 | 合肥工业大学 | HDPE/PEW-g- (MAH-co-HEMA) micro powder for powder coating and preparation method thereof |
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| CN114920881A (en) * | 2022-05-25 | 2022-08-19 | 合肥工业大学 | HDPE/PEW-g- (MAH-co-HEMA) micro powder for powder coating and preparation method thereof |
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