CN116003689A - Modified polyolefin polymer and polyolefin film prepared from same - Google Patents
Modified polyolefin polymer and polyolefin film prepared from same Download PDFInfo
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Abstract
The invention relates to a modified polyolefin polymer and a polyolefin film prepared from the modified polyolefin polymer, wherein the polyolefin polymer comprises a polyolefin material and a polar monomer and/or a polar monomer polymer connected to the polyolefin material by chemical bonds, and the polar monomer is olefine acid ester. The polyolefin film surface prepared from the modified polyolefin polymer has high polarity, and can reduce corona energy consumption in the processing process, thereby reducing environmental hazard in the production process. Meanwhile, the polar groups can be uniformly distributed on the surface of the film so as to reduce the surface friction force of the film.
Description
Technical Field
The invention relates to a modified polyolefin polymer and a polyolefin film prepared from the modified polyolefin polymer, and belongs to the technical field of modification of polyolefin materials.
Background
The polyolefin material has excellent mechanical property, high light transmittance and low price, and can be widely applied to the fields of polyolefin packaging films, agricultural greenhouse film mulching films and the like.
In the processing process of the polyolefin film, the surface polarity of the polyolefin film is usually improved in a corona mode on the surface of the polyolefin film, so that the effect of improving the adhesion between the surface of the film and printing ink or hydrophilic coating of a greenhouse film is achieved, however, in the process, high energy consumption and high pollution are often generated due to corona; and can bring additional side effects, namely, the surface of the film is easy to break down by corona energy, so that the surface is adhered and difficult to open.
For example, in the production of PE film packaging bags, the bags are easy to adhere to each other due to corona treatment, and a plurality of bags are easy to be carried up when a mechanical arm adsorbs one bag, so that the continuous operation of the packaging bag production process is affected, and the packaging production line is stopped.
In order to solve this problem, the adhesion is usually reduced by adding an organic or inorganic opening aid. For example, in chinese patent CN112662049a, a multilayer coextrusion process is adopted to regulate and control the proportions of the opening auxiliary agent and the polymer material between different layers, so as to achieve the purpose of improving the anti-adhesion capability of the film. However, the process is complex, and the corona energy consumption in the production process is high, so that the production cost is increased, and high carbon emission and air pollution are generated.
Therefore, there is a need to develop a modified polyolefin polymer and a polyolefin film prepared from the same, which can effectively reduce environmental hazards in the corona production process, and at the same time, should have excellent surface properties, not be easy to adhere, and greatly improve the stability in the product preparation process.
Disclosure of Invention
The invention aims to develop a polyolefin polymer with low corona energy consumption and difficult adhesion and a preparation method thereof, and a polyolefin film prepared from the polyolefin polymer and a preparation method thereof, wherein the polyolefin polymer comprises a polyolefin material and a polar monomer and/or a polymer of the polar monomer connected with the polyolefin material by chemical bonds, and the polar monomer is an olefine acid ester. In the invention, polar monomer, initiator and polyolefin material are extruded through reaction, so that the polar monomer is connected with the polyolefin material through chemical bond to obtain modified polyolefin polymer, the polarity of the material is obviously improved, and corona is carried out on the modified polyolefin polymer on the basis to obtain the polyolefin film with high surface polarity. Through the technical scheme of the specific polar monomer of reaction extrusion grafting in this patent, required corona energy when reaching same surface polarity can be effectively reduced to the film of preparation is difficult for adhesion, and surface friction is lower, saves the use cost of smooth agent.
In a first aspect, the present invention relates to a modified polyolefin polymer comprising a polyolefin material and a polar monomer and/or a polymer of said polar monomer chemically bound thereto, wherein said polar monomer is an alkenoate, the hydrogen on the carbon of said alkenoate being optionally selected from halogen atoms, OH, C 1 -C 10 One or more substituents of the alkyl group.
In a second aspect, the present invention relates to a process for preparing the above polyolefin polymer, said process comprising:
s1: dispersing an initiator in a polar monomer to form a mixed solution;
s2: adding the mixed solution obtained in the step S1 and a polymer material together or sequentially, carrying out reaction extrusion, cooling and granulating to obtain a modified polyolefin polymer;
in a third aspect, the present invention relates to a polyolefin film comprising the modified polyolefin polymer described above.
In a fourth aspect, the present invention relates to a process for the preparation of a polyolefin film, the process comprising: and plasticizing, extruding, cooling, shaping and corona the modified polyolefin polymer to obtain the polyolefin film.
Compared with the prior art, the invention has the following advantages:
the invention prepares a modified polyolefin polymer and a polyolefin film prepared by the modified polyolefin polymer and having high surface polarity and low surface friction at the same time in a simple and continuous mode. The energy consumption of the subsequent corona treatment can be obviously reduced, and the anti-adhesion capability of the surface of the corona treatment is enhanced. The polar monomer, the initiator and the polyolefin material are extruded through reaction, so that the polar monomer and/or the polymer of the polar monomer are/is connected with the polyolefin material through chemical bonds to obtain the modified polyolefin polymer, and the surface of the polyolefin film prepared from the modified polyolefin polymer has high polarity, so that the corona energy consumption in the processing process can be reduced, and the environmental hazard in the production process is reduced. Meanwhile, the polar groups can be uniformly distributed on the surface of the film so as to reduce the surface friction force of the film.
Drawings
FIG. 1A is a graph showing contact angles of DBM grafted polyethylene films at different corona strengths; fig. 1B is a contact angle of HEMA grafted polyethylene film at different corona intensities. The 0% sample is the contact angle of the ungrafted polyethylene film.
Fig. 2A is a non-linear fit of contact angles at different corona energies, fig. 2B is a corona energy saving for grafting different amounts of DBM polyethylene films compared to ungrafted modified PE at different corona energies, and 0% of the samples are ungrafted polyethylene films.
FIG. 3A shows the surface static friction coefficients of DBM grafted polyethylene films with different contents; FIG. 3B shows the surface static friction coefficients of HEMA grafted polyethylene films with different contents.
Detailed Description
The invention is further illustrated by the following examples, but it is to be noted that the scope of the invention is not limited thereto but is defined by the claims.
It is specifically noted that two or more aspects (or embodiments) disclosed in the context of the present specification may be arbitrarily combined with each other, and the resulting solutions are part of the original disclosure of the present specification, while also falling within the scope of the present invention.
The corona processing process refers to a process of ionizing, breaking down and discharging air by high voltage so as to carry polar groups such as carboxyl, hydroxyl, epoxy and the like on the surface of the polyolefin film and increase the polarity of the surface of the polyolefin film.
The invention relates to a modified polyolefin polymer, which comprises a polyolefin material and a polar monomer and/or a polymer of the polar monomer connected with the polyolefin material by a chemical bond, wherein the polar monomer is olefine acid ester; the hydrogen on the alkenyl acid ester carbon is optionally selected from halogen atoms, OH, C 1 -C 10 One or more substituents of the alkyl group.
According to some embodiments of the invention, the chemical bond connection is achieved by extrusion of the polar monomer, initiator and the polyolefin material by reaction.
According to some embodiments of the invention, the polyolefin material is selected from at least one of an ethylene homopolymer, an alpha olefin homopolymer, a metallocene-catalyzed ethylene and hexene copolymer or a metallocene-catalyzed ethylene and octene copolymer.
Further, the polyolefin material preferably has a density of 0.890 to 0.920g/cm 3 Metallocene linear low density polyethylene of (C) and a density of 0.915 to 0.935g/cm 3 At least one of the linear low density polyethylenes of (a).
According to some embodiments of the invention, the polar monomer is an olefin-based acid ester selected from the group consisting of olefin-based carboxylic acid esters, olefin-based sulfonic acid esters, or olefin-based phosphoric acid esters; preferred are olefin-based carboxylates.
Further, the polar monomer is an olefin-based carboxylate monomer having the following structure:
wherein R is 2 Selected from H or C 1 -C 20 Alkyl, COOR of (C) 4 、C 6 -C 30 At least one of aryl, silane and amino, R 1 、R 3 、R 4 、R 5 Selected from H or C respectively 1 -C 20 Alkyl, C of (2) 6 -C 30 At least one of an aromatic group, a silane group, and an amine group; preferably, R 2 Selected from H or C 1 -C 10 Alkyl, COOR of (C) 4 Silane group, amino group, C 6 -C 20 At least one of the aromatic groups, R 1 、R 3 、R 4 、R 5 Selected from H or C respectively 1 -C 10 Alkyl, silyl, amino, C 6 -C 20 At least one of aromatic groups; the hydrogen on the carbon of the alkyl, aryl, silyl, amino groups being optionally substituted by halogen atoms, alkoxy groups, C 1 -C 10 One or more substituents of the alkyl group.
More preferably, the polar monomer of the present invention is at least one selected from the group consisting of 2-hydroxyethyl acrylate, dibutyl maleate, diethyl maleate, dimethyl maleate, dioctyl maleate, t-butyl maleate, diamine maleate, dibenzyl maleate, trimethylsilyl maleate, oxypropyl bis (trimethylsiloxy) methylsilane acrylate, and triethoxysilylpropyl maleic acid.
Most preferably, the polar monomer is selected from one or more of diethyl maleate, dibutyl maleate, trimethylsilyl maleate, and oxypropyl bis (trimethylsiloxy) methylsilane acrylate.
According to some embodiments of the invention, the polar monomer comprises 0.5 to 50%, preferably 0.5 to 15% of the total mass of the modified polyolefin polymer.
The invention also relates to a process for the preparation of a modified polyolefin polymer, said process comprising:
s1: dispersing an initiator in a polar monomer to form a mixed solution;
s2: and (3) feeding the mixed solution obtained in the step (S1) and a polymer material, extruding through reaction, cooling and granulating to obtain the modified polyolefin polymer.
According to some embodiments of the invention, the polar monomer is grafted onto the polyolefin material by free radical polymerization by reactive extrusion under the action of an initiator to obtain a modified polyolefin polymer.
Further, the mixed solution obtained in the step S1 and the polymer material are fed into a double-screw extruder at one time, and are subjected to mixing, melting, reaction grafting and extrusion, and then are cooled and granulated.
Or, the mixed solution obtained in the step S1 and the polyolefin material are separated, added into a double-screw extruder through a syringe pump in the second stage, and then are mixed, melted, grafted and extruded, cooled and pelletized.
According to some embodiments of the invention, the reactive extrusion in step S2 employs a twin screw extruder having a screw speed of 20-1500rpm, preferably 50-1000rpm, more preferably 100-300rpm.
Further, the twin screw extruder of the present invention includes, but is not limited to: a Micro 27 twin-screw extruder manufactured by Leistritz, germany, which has a function of being switchable in the same direction/different directions; polyLab, euroLab co-rotating twin screw extruder manufactured by Thermo Fisher Scientific company; ZSK Mcc18 co-rotating parallel twin screw extruder from Coperion, germany, and the like.
According to some embodiments of the invention, the initiator is selected from one or more of acyl peroxides, alkyl peroxides, peresters, alkyl hydroperoxides, ketone peroxides, azo compounds. Preferably, the initiator is selected from one or more of benzoyl peroxide, azobisisobutyronitrile, dicumyl peroxide, di-tert-butyl peroxide, tert-butyl hydroperoxide, benzoic acid peroxide, 2, 5-dimethyl-2, 5-di-tert-butyl peroxyhexane.
According to some embodiments of the invention, the polar monomer comprises 0.5 to 50%, preferably 0.5 to 15% by mass of the polyolefin material; and/or the initiator accounts for 1-20% of the polar monomer.
According to some embodiments of the invention, the polymer has a melt index (190 ℃ C., 2.16 kg) of between 0.1g/10min and 5g/10min, preferably a melt index (190 ℃ C., 2.16 kg) of between 0.2g/10min and 4g/10 min.
The invention also relates to a polyolefin film comprising the modified polyolefin polymer described above.
According to some embodiments of the invention, the polyolefin film of the invention has a coefficient of friction of 0.05 to 2.
According to some embodiments of the invention, the polyolefin film of the invention has a contact angle of 10 ° to 130 °, more preferably 20 ° to 120 °.
According to some embodiments of the invention, the polyolefin film of the invention has a light transmittance of not less than 70% and a haze of not more than 60%. The breaking elongation is more than 200 percent, and the breaking strength is more than 15MPa; further, the elongation at break is more than 350%, and the breaking strength is more than 20MPa.
The invention also relates to a preparation method of the polyolefin film, which comprises the following steps: and plasticizing, extruding, cooling, shaping and corona the modified polyolefin polymer to obtain the polyolefin film.
According to some embodiments of the invention, the polyolefin film of the invention is obtained after plasticizing, extruding, cooling, shaping, corona the modified polyolefin polymer by a single screw film blowing machine. The method saves more than 70% of corona energy when reaching the same surface polarity.
According to some embodiments of the invention, the temperature of the granulation and film blowing is 150 ℃ to 280 ℃, preferably 180 ℃ to 260 ℃, more preferably 200 ℃ to 240 ℃.
According to some embodiments of the invention, the modified polyolefin polymer is extruded through a single screw film blowing machine having a speed of rotation of 5 to 300rpm, preferably 10 to 200rpm.
According to some embodiments of the invention, the corona adopts an online film blowing corona mode, and the corona equipment is arranged at a traction section of the film blowing machine, wherein the traction speed is 0.1-20 m/s. Preferably 0.5 to 15m/s. The corona energy is adjustable from 0.01 to 100kW, preferably from 0.05 to 10kW, and more preferably from 0.1 to 5kW.
Experimental raw materials：
The metallocene linear low density polyethylene (mLLDPE) used in the invention is produced by Dow chemical production and has the brand XUS61530.02P.
Hydroxyethyl methacrylate (HEMA) used in the examples of the invention is an analytically pure product of the national pharmaceutical test, and dibutyl maleate (DBM) is an analytically pure product of aladine; the initiator used in the examples of the present invention was 2, 5-dimethyl-2, 5-di-t-butylperoxy hexane (hereinafter "Bifide five") which was an analytically pure product of the well-known, technical Co. The oxypropyl bis (trimethylsiloxy) methylsilane acrylate is selected from the microphone technology and has an analytically pure purity.
Test method and test equipment：
The invention adopts a small-sized suspension corona machine, a ceramic motor rod is arranged on a traction section of a film blowing cooling line, and the output power is 0-40kW. The traction speed is 0-20 m/min.
The invention adopts a co-rotating double-screw extruder of LabTech company, sweden, the diameter of the screw is 20mm, and the length-diameter ratio is 40.
The invention uses a single screw extruder from Collin technologies, germany, screw diameter 30mm, L/D=30.
Contact angle test: the test is carried out on a KRUSS DSA100 type contact angle measuring instrument in Germany, the test process is that a sample is paved on a sample table, proper liquid is selected, a small liquid drop of about 5L is extruded by a fine needle and hung on a needle head, the sample table is moved to lightly adhere the small liquid drop on the sample, after a set time, the sample table is photographed, and the included angle between the tangent line of the contact edge of the liquid drop and the sample in a photo and the plane of the sample is analyzed by software to obtain the measured contact angle.
Melt index (MFR) determination method: according to ISO 1133 standard, using Lloyd Davenport MFI-10/230 melt index instrument, measuring cylinder temperature 190 deg.C, weight load 2.16kg, die diameter 2.095mm, length 8mm, preheating time 4min, automatically cutting sample every set time, taking 5 times to average value, and expressing measurement result in grams per 10 minutes (g/10 min).
Transmittance and haze test: the test was performed on a Haze-gardi type transmission Haze meter from BYK corporation, germany, and the test was performed in transmission mode, typically with at least 5 times of testing of one sample, and the average was taken.
Film tensile test: the test was performed according to ISO 527-3 using an Instron model 3344 material tester, version 2.31 Bluehill. The film was cut into Type 5 of ISO 527-3 standard in the direction of stretching (MD) and perpendicular to the direction of stretching (CD), and placed in a Blueboard BPS-100CB constant temperature and humidity cabinet (temperature 23 ℃ C., relative humidity 50%) of Shanghai-Heng-Hei scientific instruments Co., ltd for 24 hours. At the time of testing, the initial fixture spacing was 75mm, the test stretching rate was 100mm/min, and each sample was tested at least 5 times, and the average value was taken.
Examples
Example 1
The initiator was bi-di-pentad dispersed in monomeric DBM to make a 5% solution. The mixed polyolefin particles (mLLDPE) and a double-twin DBM solution are mixed, plasticized, reacted and extruded by using a co-rotating twin-screw extruder manufactured by LabTech company to prepare the grafted modified polyolefin material.
The extruder has 11 sections from a feeding port to a die, and the number of the sections is 1-11, wherein the section 1 only plays a role of feeding and cannot be heated. The temperatures of the sections 2 to 11 of the extruder are respectively as follows: 150 ℃,160 ℃,170 ℃,180 ℃,200 ℃,220 ℃,240 ℃,220 ℃,200 ℃ and 180 ℃ and the screw rotation speed is set at 200rpm. Feeding polyolefin mixture to the 1 st section of the double-screw extruder by using a weight-loss type feeder of the extruder, wherein the feeding speed is as follows: 10kg/h. The double-five DBM solution is injected into the 4 th section of a double-screw extruder by using an Optos Pump 2LMP metering Pump of the company Eldex Laboratories of the United states, and the feeding speed of the mixed solution is regulated so that the added DBM monomer accounts for 2%,5%,10% and 15% of the mass of PE.
Comparative example
The extrusion conditions for the comparative example were the same as in example 1, except that only mLLDPE was used, no monomer modification was added, designated PE-0%.
Example 2
The initiator was bi-di-pentad dispersed in monomer HEMA to make a 5% solution. Selecting a homodromous double-screw extruder, mixing the mixed polyolefin particles (mLLDPE) with a biwu HEMA solution, plasticizing, reacting and extruding to prepare the grafted modified polyolefin material. The extruder has 11 sections from a feeding port to a die, and the number of the sections is 1-11, wherein the section 1 only plays a role of feeding and cannot be heated. The temperatures of the sections 2 to 11 of the extruder are respectively as follows: 150 ℃,160 ℃,180 ℃,180 ℃,200 ℃,220 ℃,220 ℃,220 ℃,220 ℃ and 200 ℃, and the screw rotation speed is set at 200rpm. Feeding polyolefin mixture to the 1 st section of the double-screw extruder by using a weight-loss type feeder of the extruder, wherein the feeding speed is as follows: 10kg/h. The double-second-fifth HEMA solution was injected into the 4 th section of the twin-screw extruder by using an Optos Pump 2LMP metering Pump of the company Eldex Laboratories of the United states, and the feeding speed of the mixed solution was adjusted so that the amount of added HEMA monomer was 2% and 5% of the mass of PE. In the process of grafting HEMA, as the content of HEMA is continuously increased to more than 5%, a large number of crystal points are generated on the surface of the film, and the surface performance is greatly influenced. Thus, only 2% and 5% of the films were selected for subsequent testing.
Example 3
The initiator bis-di-penta was dispersed in the monomer oxypropyl bis (trimethylsiloxy) methylsilane (MPTM) to make a 5% solution. Selecting a homodromous double-screw extruder, mixing the mixed polyolefin particles (mLLDPE) with a biwu-acrylic acid oxypropyl bis (trimethylsiloxy) methylsilane solution, plasticizing, reacting and extruding to prepare the grafted modified polyolefin material. The extruder has 11 sections from a feeding port to a die, and the number of the sections is 1-11, wherein the section 1 only plays a role of feeding and cannot be heated. The temperatures of the sections 2 to 11 of the extruder are respectively as follows: 150 ℃,160 ℃,180 ℃,180 ℃,200 ℃,220 ℃,220 ℃,220 ℃,220 ℃ and 200 ℃, and the screw rotation speed is set at 200rpm. Feeding polyolefin mixture to the 1 st section of the double-screw extruder by using a weight-loss type feeder of the extruder, wherein the feeding speed is as follows: 10kg/h. The bifive MPTM solution was injected into section 4 of a twin screw extruder using an Optos Pump 2LMP metering Pump from America Eldex Laboratories, where the specific processing parameters for examples 1-3 and comparative examples are shown in Table one.
Table one processing parameters of HEMA, DBM reactive extrusion grafted polyolefin
Example 4
8 particles of examples 1-3, comparative example, polyLab HAAKE, thermo Fisher technology Co., USA TM Film blowing was performed in a rheomix OS PTW16 co-rotating twin screw extruder (screw diameter 16mm, l/d=40) having four heating sections numbered 1 to 4 from the feed inlet to the outlet, respectively, and a film blowing die having a die diameter of 60mm and a die gap of 0.8mm with a heating function was provided, the screw rotation speed was set to 50rpm, and the temperatures of the respective sections were set to: and (3) cooling, shaping, drafting and rolling at 190 ℃,200 ℃ and 200 ℃ to form a film. On the basis, corona was carried out at 0 to 0.5kW for each sample except for example 3, and specific corona and winding conditions are shown in Table II.
Corona parameters of a PE film
Haze and transmittance test
8 kinds of particles in examples 1 to 3 and comparative example were selected and prepared into corresponding films according to the method of example 4, and haze and transmittance were measured, and the results are shown in Table three.
Table three PE filmHaze and transmittance test
As shown in the table, the transmittance was relatively good for the above modified films. In the case of the modified monomer DBM, the haze of the modified film increased significantly from 11.9% to 51.2% with increasing grafting. HEMA has less effect on haze. Increasing from 11.9 to 23.6%. The effect of the oxypropyl bis (trimethylsiloxy) methylsilane of example 3 was similar to that of DBM, grafting 5% and haze increased to 42.3%. After grafting different amounts of modified monomer, the elongation at break is slightly reduced, but the overall reduction is not large. The thickness of the DBM graft modified film is about 50 μm, while the thickness of the unmodified film is 64 μm, considering the influence of thickness. Therefore, the mechanical properties of the film are not obviously reduced after the polyethylene is grafted.
Contact angle test
All the films of examples 1 to 3 and comparative examples were subjected to contact angle measurement, and the results are shown in FIG. 1.
As shown in fig. 1, the surface contact angle of the ungrafted PE film gradually decreased with increasing corona intensity, indicating that more polar groups were generated. For PE-g-DBM grafted with DBM, the contact angle of the surface gradually decreases from 100 DEG to 90 DEG with increasing grafting amount at 0kW, and for oxypropyl bis (trimethylsiloxy) methylsilane acrylate, after 5% grafting, the contact angle decreases to 81.2 deg.
The difference between grafted and ungrafted contact angles becomes more pronounced with increasing corona energy, at 0.1kW, when the contact angle of 0% pe-g-DBM is 93 °, while the contact angle of 15% pe-g-DBM is significantly reduced to around 62 °. At higher corona intensities, the decrease in contact angle of PE-g-DBM was no longer apparent with increasing grafting amount of DBM. At 0.4kW, the drop is only from 70 ° to around 61 °. It is demonstrated that grafting of polar monomer DBM can significantly reduce the contact angle of the modified PE film at lower corona strengths.
Similarly, for modified films incorporating HEMA grafting, the contact angle decreased significantly with increasing grafting amount of HEMA at 0.2 kW. From 78 deg. down to 45 deg.. Compared with DBM, HEMA has higher monomer activity, high grafting efficiency and lower contact angle.
From the decrease of the contact angle, it can be known that the polar monomer can be grafted by the reactive extrusion method in the invention, thereby effectively reducing the surface polarity of the PE film.
Corona energy
According to the results of the fitting of the nonlinear data obtained by the points in fig. 1A, as shown in fig. 2A, and according to the results of fig. 2A, the corona energy saving results, which are obtained by obtaining the same contact angle after grafting different amounts of DBM relative to ungrafted linear low density polyethylene and achieving ungrafted linear low density polyethylene, are calculated, are shown in fig. 2B.
As shown in fig. 2, the corona energy required to reach the same surface contact angle is greatly reduced as the amount of DBM grafting increases, as shown in fig. 2B, the saved corona energy is significantly improved as the amount of DBM grafting increases compared to ungrafted mLLDPE, and the effect is more pronounced at higher corona energies. At 0.5kW, compared with ungrafted mLLDPE, 15% of mLLDPE-g-DBM grafted can save corona energy of 0.42kW, and the saving efficiency reaches 84%.
Surface friction test
When all the grafted films of example 4 were subjected to surface friction test, and the relationship between the static friction coefficient and the grafting amount obtained respectively was shown in fig. 3, it can be seen that, at 0kW, the surface friction coefficient of the modified film significantly decreased with an increase in the grafting amount of the grafted monomer DBM. The static coefficient of friction of the PE-g-DBM film grafted with 15% at 0kW was reduced from 0.82 to 0.36. While the surface friction of the PE film tends to increase more significantly with the corona, from 0.82 at 0kW to 1.1 at 0.5 kW. The grafting of DBM can obviously inhibit the trend of increasing the surface friction force, and at 0.5kW, the surface friction force of the PE-g-DBM grafted with 15% is only 0.37, and compared with 0kW, the surface friction force of the PE-g-DBM grafted with 0kW can be kept stable. The introduction of DBM can greatly reduce the influence of corona on the friction force of the film surface, so that the anti-adhesion performance of the DBM is greatly enhanced. In FIG. 3B, the coefficient of friction is also reduced after grafting only 2% HEMA compared to the ungrafted modified film, but the surface friction of the modified film is significantly increased after grafting 5% HEMA. This is probably due to the higher grafting activity of HEMA, resulting in crosslinking of the PE film surface and uneven distribution on the film.
Any numerical value recited in this disclosure includes all values incremented by one unit from the lowest value to the highest value if there is only a two unit interval between any lowest value and any highest value. For example, if the amount of one component, or the value of a process variable such as temperature, pressure, time, etc., is stated to be 50-90, it is meant in this specification that values such as 51-89, 52-88 … …, and 69-71, and 70-71 are specifically recited. For non-integer values, 0.1, 0.01, 0.001 or 0.0001 units may be considered as appropriate. This is only a few examples of the specific designations. In a similar manner, all possible combinations of numerical values between the lowest value and the highest value enumerated are to be considered to be disclosed in this application.
It should be noted that the above-described embodiments are only for explaining the present invention and do not constitute any limitation of the present invention. The invention has been described with reference to exemplary embodiments, but it is understood that the words which have been used are words of description and illustration, rather than words of limitation. Modifications may be made to the invention as defined in the appended claims, and the invention may be modified without departing from the scope and spirit of the invention. Although the invention is described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, as the invention extends to all other means and applications which perform the same function.
Claims (13)
1. A modified polyolefin polymer comprising a polyolefin material and a polar monomer and/or a polymer of said polar monomer chemically bound thereto, wherein said polar monomer is an alkenoate, the hydrogen on the carbon of said alkenoate being optionally selected from halogen atoms, OH, C 1 -C 10 One of the alkyl groupsOr a plurality of substituents.
2. The modified polyolefin polymer of claim 1, wherein the polyolefin material is selected from at least one of an ethylene homopolymer, an alpha olefin homopolymer, a metallocene-catalyzed ethylene and hexene copolymer, or a metallocene-catalyzed ethylene and octene copolymer; preferably, the polyolefin material has a density of 0.890-0.920g/cm 3 Metallocene linear low density polyethylene of (C) and a density of 0.915 to 0.935g/cm 3 At least one of the linear low density polyethylenes of (a).
3. The modified polyolefin polymer of claim 1 or 2, wherein the chemical bond connection is achieved by reactive extrusion of the polar monomer, initiator and polyolefin material.
4. The modified polyolefin polymer of any of claims 1-3, wherein the polar monomer is an olefin-based acid ester selected from the group consisting of an olefin-based carboxylic acid ester, an olefin-based sulfonic acid ester, and an olefin-based phosphoric acid ester; preferred are olefin-based carboxylates.
5. The modified polyolefin polymer of claim 4, wherein the polar monomer is an olefin-based carboxylate monomer having the structure:
wherein R is 2 Selected from H or C 1 -C 20 Alkyl, COOR of (C) 4 、C 6 -C 30 At least one of aryl, silane and amino, R 1 、R 3 、R 4 、R 5 Selected from H or C respectively 1 -C 20 Alkyl, C of (2) 6 -C 30 At least one of an aromatic group, a silane group, and an amine group; preferably, R 2 Selected from H or C 1 -C 10 Alkyl, COOR of (C) 4 Silane group, amino group, C 6 -C 20 At least one of the aromatic groups, R 1 、R 3 、R 4 、R 5 Selected from H or C respectively 1 -C 10 Alkyl, silyl, amino, C 6 -C 20 At least one of aromatic groups; the hydrogen on the carbon of the alkyl, aryl, silyl, amino groups being optionally substituted by halogen atoms, alkoxy groups, C 1 -C 10 One or more substituents of the alkyl group. More preferably, the polar monomer is selected from at least one of 2-hydroxyethyl acrylate, dibutyl maleate, diethyl maleate, dimethyl maleate, dioctyl maleate, tert-butyl maleate, diamine maleate, dibenzyl maleate, oxypropyl bis (trimethylsiloxy) methylsilane triethoxysilylpropyl maleic acid; most preferably, the polar monomer is selected from one or more of diethyl maleate, dibutyl maleate, oxypropyl bis (trimethylsiloxy) methylsilane acrylate.
6. The modified polyolefin polymer of any of claims 1-5, wherein the polar monomer comprises from 0.5 to 50% of the total mass of the modified polyolefin polymer.
7. A process for preparing the modified polyolefin polymer of any of claims 1-6, the process comprising:
s1: dispersing an initiator in a polar monomer to form a mixed solution;
s2: and (3) feeding the mixed solution obtained in the step (S1) and a polymer material together or sequentially, carrying out reaction extrusion, cooling and granulating to obtain the modified polyolefin polymer.
8. The method for producing a modified polyolefin polymer according to claim 7, wherein the initiator is one or more selected from the group consisting of acyl peroxides, alkyl peroxides, peresters, alkyl hydroperoxides, ketone peroxides, azo compounds; preferably, the initiator is selected from one or more of benzoyl peroxide, azobisisobutyronitrile, dicumyl peroxide, di-tert-butyl peroxide, tert-butyl hydroperoxide, benzoic acid peroxide, 2, 5-dimethyl-2, 5-di-tert-butyl peroxyhexane.
9. The method for producing a modified polyolefin polymer according to claim 7 or 8, wherein the polar monomer is 0.5 to 50%, preferably 0.5 to 15% by mass of the polyolefin material; and/or the initiator comprises 1% -20% of the polar monomer.
10. A polyolefin film comprising the modified polyolefin polymer of claims 1-6.
11. The polyolefin film according to claim 10, wherein the polyolefin film has a coefficient of friction of 0.05 to 2.
12. The polyolefin film according to claim 10 or 11, wherein the polyolefin film has a contact angle of 10 ° to 130 °, further preferably 20 ° to 120 °.
13. A process for preparing the polyolefin film according to any of claims 10 to 12, the process comprising: and plasticizing, extruding, cooling, shaping and corona the modified polyolefin polymer to obtain the polyolefin film.
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