CN117986477B - Functionalized polyolefin material and preparation method thereof - Google Patents
Functionalized polyolefin material and preparation method thereof Download PDFInfo
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- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 26
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- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 7
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
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- XFHJDMUEHUHAJW-UHFFFAOYSA-N n-tert-butylprop-2-enamide Chemical compound CC(C)(C)NC(=O)C=C XFHJDMUEHUHAJW-UHFFFAOYSA-N 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- YAXXOCZAXKLLCV-UHFFFAOYSA-N 3-dodecyloxolane-2,5-dione Chemical compound CCCCCCCCCCCCC1CC(=O)OC1=O YAXXOCZAXKLLCV-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical class ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 2
- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
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Abstract
The invention belongs to the field of high polymer materials, and particularly relates to a functionalized polyolefin material and a preparation method thereof. The preparation method provided by the invention comprises the following steps: a) Mixing a carbonyl-containing functional monomer and an N-hydroxyl compound in a solvent, wherein the carbonyl-containing functional monomer and the N-hydroxyl compound can be combined to form a charge transfer complex, and the solvent is a volatile solvent capable of simultaneously dissolving the carbonyl-containing functional monomer and the N-hydroxyl compound; then mixing the mixture with polyolefin powder, and removing the solvent to obtain premix; b) Carrying out melt blending on a precursor containing the premix to obtain a functionalized non-porous polyolefin material; or compacting, cold pressing and sintering the precursor containing the premix to obtain the functional porous polyolefin material. The preparation method provided by the invention can inhibit the occurrence of crosslinking side reaction while ensuring the grafting rate of the functional monomer, thereby obtaining the high-performance functional polyolefin material with high grafting rate and low crosslinking degree.
Description
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to a functionalized polyolefin material and a preparation method thereof.
Background
Polyolefins have found widespread use in recent years in medical devices, food packaging, automobiles, and many other products. Currently, medical devices and food packaging require functional products. But its miscibility, dyeability, hydrophilicity, printability are poor due to its surface inertness, which greatly limits its range of applications. Research has been carried out in the last 60 th century to improve a series of properties such as compatibility with other polar polymers, surface printability, hydrophilicity, and antibacterial properties by introducing polar monomers into the main chain of the polyolefin. The modified polyolefin has great potential in medical devices, active packaging and water filters. Compared with other alternative technologies, the melt grafting technology has the advantages of no solvent pollution, short reaction time, continuous process, low cost and the like, and becomes one of important means for preparing the functional polyolefin material.
In a melt grafting system, organic peroxide is a commonly adopted initiator, in the initiator system, as the polarity of polyolefin, monomer, initiator and other auxiliary agents is different, the polyolefin, monomer, initiator and other auxiliary agents are difficult to mix uniformly due to the shorter reaction time, so that the probability of occurrence of cross-linking side reaction is increased due to the peroxide-enriched area, the melt rheological behavior of the polyolefin is obviously changed by cross-linking (melt viscosity is increased and fluidity is lowered), and the secondary processing molding (extrusion) of the functionalized polyolefin is not facilitated; in addition, even if the reaction time is prolonged, the occurrence of crosslinking side reactions is caused, and the above problems cannot be solved. Therefore, the key problem to be solved in the preparation of the functionalized polyolefin material is to be solved by inhibiting the occurrence of the crosslinking side reaction while ensuring the grafting rate of the functional monomer.
Disclosure of Invention
In view of the above, the present invention aims to provide a functionalized polyolefin material and a preparation method thereof, wherein the preparation method provided by the present invention can inhibit the occurrence of a crosslinking side reaction while ensuring the grafting rate of a functional monomer, so as to obtain a high-performance functionalized polyolefin material with high grafting rate and low crosslinking degree.
The invention provides a preparation method of a functionalized polyolefin material, which comprises the following steps:
a) Mixing a carbonyl-containing functional monomer and an N-hydroxyl compound in a solvent, wherein the carbonyl-containing functional monomer and the N-hydroxyl compound are the carbonyl-containing functional monomer and the N-hydroxyl compound which can be combined to form a charge transfer compound, and the solvent is a volatile solvent capable of simultaneously dissolving the carbonyl-containing functional monomer and the N-hydroxyl compound; then mixing the mixture with polyolefin powder, and removing the solvent to obtain premix;
b) Carrying out melt blending on a precursor containing the premix to obtain a functionalized non-porous polyolefin material;
Or compacting, cold pressing and sintering the precursor containing the premix to obtain the functional porous polyolefin material.
Preferably, in the step a), the carbonyl-containing functional monomer is one or more of maleic anhydride, maleimide, acrylamide, N-t-butyl acrylamide, methacrylamide, N-t-butyl methacrylamide and acrylic acid.
Preferably, in step a), the N-hydroxy compound is one or more of N-hydroxyphthalimide, N-hydroxysuccinimide and N-hydroxysuccinimide.
Preferably, in step a), the polyolefin powder is a polyethylene powder and/or a polypropylene powder.
Preferably, in step a), the polyethylene in the polyethylene powder comprises one or more of high density polyethylene, low density polyethylene, linear low density polyethylene and ultra high molecular weight polyethylene.
Preferably, in the step b), the content of the carbonyl-containing functional monomer in the precursor is 1-10wt%.
Preferably, in the step b), the content of the N-hydroxyl compound in the precursor is 10-2000 ppm.
Preferably, in the step b), the temperature of the melt blending is 180-230 ℃.
Preferably, in the step b), the vibration frequency of the compaction is 30-200 Hz; and the vibration time of the compaction is 5-20 min.
Preferably, in the step b), the pressure of the cold pressing is 0-5 MPa; the cold pressing time is 10-25 min.
Preferably, in the step b), the sintering temperature is 160-200 ℃; the sintering time is 20-120 min.
Preferably, in the step b), the pore diameter of the functionalized porous polyolefin material is 25-100 μm; the porosity of the functionalized porous polyolefin material is 40-65%.
The invention provides a functional polyolefin material, which is prepared by the preparation method according to the technical scheme.
Compared with the prior art, the invention provides a functionalized polyolefin material and a preparation method thereof. The preparation method provided by the invention comprises the following steps: a) Mixing a carbonyl-containing functional monomer and an N-hydroxyl compound in a solvent, wherein the carbonyl-containing functional monomer and the N-hydroxyl compound are the carbonyl-containing functional monomer and the N-hydroxyl compound which can be combined to form a charge transfer compound, and the solvent is a volatile solvent capable of simultaneously dissolving the carbonyl-containing functional monomer and the N-hydroxyl compound; then mixing the mixture with polyolefin powder, and removing the solvent to obtain premix; b) Carrying out melt blending on a precursor containing the premix to obtain a functionalized non-porous polyolefin material; or compacting, cold pressing and sintering the precursor containing the premix to obtain the functional porous polyolefin material. The invention firstly combines carbonyl functional monomer and N-hydroxyl compound to form Charge Transfer Compound (CTC), then mixes the CTC with polyolefin powder base material to obtain premix, and then carries out melt blending or sintering to initiate grafting reaction to obtain the functional polyolefin material. In the preparation method provided by the invention, oxidation-reduction reaction can be generated after CTC is heated in the melt blending or sintering process to generate functional monomer free radicals and donor radicals (initiator free radicals), so that the initiator free radicals are generated in a relatively enriched area of the functional monomers, the grafting rate of the functional monomers is ensured, the occurrence of cross-linking side reaction is effectively inhibited, and the high-performance functional polyolefin material with high grafting rate and low cross-linking degree is obtained. Compared with the traditional organic peroxide initiating system, the preparation method can obtain the functionalized polyolefin material with similar or even higher monomer grafting rate by using fewer N-hydroxyl compounds and functional monomers, and the prepared functionalized polyolefin material has lower crosslinking degree, little change of melt rheological property and smaller influence on secondary processing and forming. In addition, the invention can design more effective N-hydroxyl compound according to the structure of polyolefin and the grafting reaction process, so that the grafting reaction can be carried out more efficiently.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only embodiments of the present invention, and that other drawings can be obtained according to the provided drawings without inventive effort for a person skilled in the art.
FIG. 1 is a torque comparison of the organic peroxide initiating system and the CTC initiating system provided in example 1 of the present invention;
FIG. 2 is a graph showing the comparison of the monomer grafting ratio of a CTC initiation system comprising two N-hydroxy compounds of different structures and functional monomers of the same structure, provided in example 2 of the present invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a preparation method of a functionalized polyolefin material, which comprises the following steps:
a) Mixing carbonyl functional monomer and N-hydroxyl compound in solvent, mixing with polyolefin powder, and removing solvent to obtain premix;
b) Carrying out melt blending on a precursor containing the premix to obtain a functionalized non-porous polyolefin material;
Or compacting, cold pressing and sintering the precursor containing the premix to obtain the functional porous polyolefin material.
In the preparation method provided by the invention, in the step a), the carbonyl-containing functional monomer comprises one or more of Maleic Anhydride (MAH), maleimide (MI), acrylamide (AAM), N-tertiary butyl acrylamide (NTAAM), methacrylamide (MAM), N-tertiary butyl methacrylamide (NTMAM), acrylic Acid (AA) and other carbonyl-containing functional monomers.
In the preparation method provided by the invention, in the step a), the N-hydroxyl compound comprises one or more of N-hydroxyl compounds such as N-hydroxyphthalimide (NOP), N-hydroxysuccinimide (NHS) and N-hydroxysuccinimide.
In the preparation method provided by the invention, in the step a), the solvent is a volatile solvent capable of simultaneously dissolving the carbonyl functional monomer and the N-hydroxyl compound, and the volatile solvent comprises, but is not limited to, ethanol and/or acetone.
In the preparation method provided by the invention, in the step a), the rotation speed of mixing the carbonyl-containing functional monomer and the N-hydroxyl compound in the solvent is preferably 50-120 r/min, and can be specifically 50r/min, 60r/min, 70r/min, 80r/min, 90r/min, 100r/min, 110r/min or 120r/min; the mixing time is preferably 20-40 min, and specifically may be 20min, 25min, 30min, 35min or 40min.
In the preparation method provided by the invention, in the step a), the polyolefin powder is preferably polyethylene powder and/or polypropylene powder; the polyethylene in the polyethylene powder includes, but is not limited to, one or more of High Density Polyethylene (HDPE), low Density Polyethylene (LDPE), linear Low Density Polyethylene (LLDPE), and Ultra High Molecular Weight Polyethylene (UHMWPE); the purity grade of the polyolefin powder is preferably technical grade, food grade or medical grade; the particle size of the polyolefin powder is preferably 25-200 mu m.
In the preparation method provided by the invention, in the step a), the rotating speed for mixing the polyolefin powder is preferably 70-180 r/min, and specifically can be 70r/min, 80r/min, 90r/min, 100r/min, 110r/min, 120r/min, 130r/min, 140r/min, 150r/min, 160r/min, 170r/min or 180r/min; the mixing time is preferably 40-70 min, and specifically can be 40min, 45min, 50min, 55min, 60min, 65min or 70min.
In the preparation method provided by the invention, in the step a), the solvent is preferably removed by heating to volatilize the solvent; the heating temperature is preferably 40-60 ℃, and specifically can be 40 ℃, 45 ℃, 50 ℃, 55 ℃ or 60 ℃; the heating time is preferably 30-90 min, specifically 30min, 35min, 40min, 45min, 50min, 55min, 60min, 65min, 70min, 75min, 80min, 85min or 90min.
In the preparation method provided by the invention, in the step a), after the solvent removal is finished, the premix obtained is preferably mixed again; the speed of remixing is preferably 100-300 r/min, and can be specifically 100r/min, 120r/min, 150r/min, 170r/min, 200r/min, 230r/min, 250r/min, 270r/min or 300r/min; the time for remixing is preferably 30-100 min, and specifically may be 30min, 40min, 50min, 60min, 70min, 80min, 90min or 100min.
In the preparation method provided by the invention, in the step b), the content of the carbonyl-containing functional monomer in the precursor is preferably 1-10wt%, and specifically can be 1wt%, 2wt%, 3wt%, 4wt%, 5wt%, 6wt%, 7wt%, 8wt%, 9wt% or 10wt%; the content of the N-hydroxyl compound in the precursor is preferably 10-2000 ppm, and specifically may be 10ppm, 50ppm, 100ppm, 200ppm, 400ppm, 500ppm, 800ppm, 1000ppm, 1500ppm or 2000ppm.
In the preparation method provided by the invention, in the step b), the melt blending is preferably performed in an internal mixer; taking polyethylene powder as an example, linear Low Density Polyethylene (LLDPE) is adopted, the temperature of melt blending is preferably 180-230 ℃, and the LLDPE can be melted at the temperature to carry out grafting reaction in a short time, specifically 180 ℃, 185 ℃, 190 ℃, 195 ℃, 200 ℃, 205 ℃, 210 ℃, 215 ℃, 220 ℃, 225 ℃ or 230 ℃; the time of melt blending is preferably 3-15 min, and specifically can be 3min, 4min, 5min, 6min, 7min, 8min, 9min, 10min, 11min, 12min, 13min, 14min or 15min; the rotation speed of the melt blending screw is preferably 30-60 r/min, and can be specifically 30r/min, 35r/min, 40r/min, 45r/min, 50r/min, 55r/min or 60r/min.
In the preparation method provided by the invention, in the step b), grafting reaction occurs between the functional monomer and polyolefin in the melt blending process; and after the melt blending is finished, obtaining the nonporous polyolefin material grafted with the functional monomer.
In the preparation method provided by the invention, in the step b), the vibration frequency of the tap is preferably 30-200 Hz, and can be specifically 30Hz, 50Hz, 70Hz, 100Hz, 120Hz, 150Hz, 170Hz or 200Hz; the vibration time of the compaction is preferably 5-20 min, and specifically may be 5min, 6min, 7min, 8min, 9min, 10min, 11min, 12min, 13min, 14min, 15min, 16min, 17min, 18min, 19min or 20min.
In the preparation method provided by the invention, in the step b), the pressure of the cold pressing is preferably 0-5 MPa, and specifically can be 0.5MPa, 1MPa, 1.5MPa, 2MPa, 2.5MPa, 3MPa, 3.5MPa, 4MPa, 4.5MPa or 5MPa; the cold pressing time is preferably 10-25 min, and specifically may be 10min, 12min, 15min, 17min, 20min, 23min or 25min.
In the preparation method provided by the invention, in the step b), the polyethylene powder is taken as an example of ultra-high molecular weight polyethylene (UHMWPE), the sintering temperature is preferably 160-200 ℃, and the temperature is slightly higher than the melting point of UHMWPE, so that powder particles can be bonded together, and pores are not blocked by melting, and specifically 160 ℃, 165 ℃, 170 ℃, 175 ℃, 180 ℃, 185 ℃, 190 ℃, 195 ℃ or 200 ℃; the sintering time is preferably 20-120 min, and specifically may be 20min, 30min, 40min, 50min, 60min, 70min, 80min, 90min, 100min, 110min or 120min.
In the preparation method provided by the invention, in the step b), in the sintering process, grafting reaction is carried out between the functional monomer and the polyolefin, and meanwhile, the polyolefin powder is mutually bonded to form a sintering neck, so that a three-dimensional porous structure is formed; after the sintering is finished, the porous polyolefin material grafted with the functional monomer is obtained. In the invention, the pore diameter of the functionalized porous polyolefin material is preferably 25-100 μm; the porosity of the functionalized porous polyolefin material is preferably 40-65%.
The invention also provides a functionalized polyolefin material which is prepared by the preparation method according to the technical scheme. According to the invention, the non-porous or porous polyolefin materials with different functions, such as antibacterial materials, filtering materials, blood purifying adsorbent materials and the like, can be prepared and obtained by adjusting the specific types and the preparation methods of the carbonyl-containing functional monomers according to actual demands.
The technical scheme provided by the invention is that firstly, a carbonyl-containing functional monomer and an N-hydroxyl compound are combined to form a Charge Transfer Compound (CTC), then the charge transfer compound is mixed with a polyolefin powder base material to obtain a premix, and then the premix is subjected to melt blending or sintering to initiate grafting reaction to obtain the functional polyolefin material. In the technical scheme provided by the invention, oxidation-reduction reaction can be generated after CTC is heated in the melt blending or sintering process to generate functional monomer free radicals and donor radicals (initiator free radicals), so that the initiator free radicals are generated in a relatively enriched area of the functional monomers, the grafting rate of the functional monomers is ensured, the occurrence of cross-linking side reaction is effectively inhibited, and the high-performance functional polyolefin material with high grafting rate and low cross-linking degree is obtained. Compared with the traditional organic peroxide initiating system, the preparation method can obtain the functionalized polyolefin material with similar or even higher monomer grafting rate by using fewer N-hydroxyl compounds and functional monomers, and the prepared functionalized polyolefin material has lower crosslinking degree, little change of melt rheological property and smaller influence on secondary processing and forming. In addition, the invention can design more effective N-hydroxyl compound according to the structure of polyolefin and the grafting reaction process, so that the grafting reaction can be carried out more efficiently.
For clarity, the following examples are provided in detail.
Example 1
A preparation method of a functionalized polyolefin material, which comprises the following steps:
step 1: premix (CTC initiation system) was prepared: adding acetone into Maleic Anhydride (MAH) and N-hydroxyphthalimide (NOP) and stirring to dissolve the mixture, wherein the rotating speed of stirring equipment (DF-101S heat collection type constant temperature heating magnetic stirrer) is 90r/min, and the stirring time is 30min; adding LLDPE powder (powder of the name of Mao petrochemical DAFA7042 with the particle size of 200 μm) into the solution, mechanically stirring to uniformly mix LLDPE, MAH, NOP, wherein the rotating speed of stirring equipment is 160r/min, and the stirring time is 50min; then drying in an oven to volatilize acetone completely, wherein the drying temperature is 60 ℃, the drying time is 60min, then carrying out secondary mechanical stirring, the rotating speed of stirring equipment is 200r/min, and the stirring time is 60min, thus obtaining LLDPE/MAH/NOP premix; the amounts of LLDPE, MAH and NOP used are detailed in Table 1;
Step 2: placing LLDPE/MAH/NOP premix into an internal mixer to carry out melt blending for grafting reaction, wherein the melt blending temperature is 200 ℃, the reaction time is 10min, and the screw rotating speed is 60r/min; after the melt blending is finished, the prepared functionalized polyolefin material (LLDPE-g-MAH) is taken out from an internal mixer, sheared by a pair of scissors and naturally cooled.
As a control LLDPE-g-MAH prepared with a conventional organic peroxide initiating system (dicumyl peroxide (DCP)).
Step 1: premix (organic peroxide initiation system) was prepared: adding acetone into Maleic Anhydride (MAH) and dicumyl peroxide (DCP) and stirring to dissolve the acetone, wherein the rotating speed of stirring equipment is 90r/min, and the stirring time is 30min; adding LLDPE powder (having a particle size of 200 μm) into the above solution, mechanically stirring to uniformly mix LLDPE, MAH, DCP, wherein the rotation speed of stirring equipment is 160r/min, and the stirring time is 50min; then drying in an oven to volatilize acetone completely, wherein the drying temperature is 60 ℃, the drying time is 60min, then carrying out secondary mechanical stirring, the rotating speed of stirring equipment is 200r/min, and the stirring time is 60min, thus obtaining LLDPE/MAH/DCP premix; the amounts of LLDPE, MAH and DCP used are given in Table 1.
Step 2: placing LLDPE/MAH/DCP premix into an internal mixer to carry out melt blending for grafting reaction, wherein the melt blending temperature is 200 ℃, the reaction time is 10min, and the screw rotating speed is 60r/min; after the melt blending is finished, the prepared functionalized polyolefin material (LLDPE-g-MAH) is taken out from an internal mixer, sheared by a pair of scissors and naturally cooled.
Further, the grafting ratio and gel content (the portion of the polyethylene which swells but does not dissolve in the heated xylene solvent after crosslinking) of LLDPE-g-MAH prepared by using the CTC (NOP/MAH) initiation system and the organic peroxide (DCP) initiation system in this example were measured as follows
A. the grafting ratio testing method comprises the following steps:
By infra-red spectrometry
Uniformly mixing 1%, 2%, 3% and 4% of dodecyl succinic anhydride with LLDPE, adding the mixture into a torque rheometer at a screw speed of 60rpm at 200 ℃, taking out the mixture from a reaction chamber after mixing for 10 minutes, and cooling the mixture at room temperature for later use;
converting the mass fraction of the dodecyl succinic anhydride in LLDPE into the grafting rate DG of the maleic anhydride in the LLDPE, calculating the absorbance A of an anhydride ring characteristic peak in an infrared spectrum of a blending sample with each proportion according to a formula (1), obtaining a standard curve and a formula (2) by linear fitting with the A and the DG, and substituting the A of each grafted polymer into the formula (2) to calculate the DG;
（1）；
（2）；
Note that: The absorbance of the characteristic peaks on the anhydride ring and LLDPE, respectively.
B. Gel content testing method:
Accurately weighing 0.5g of sample and cutting into pieces After the sample is wrapped by a 100-mesh copper net (the mass of the copper net is m 1), weighing the copper net and the mass of the sample is m 2, placing the copper net and the sample in boiling xylene (and adding 3 wt% of antioxidant) for dissolution for 12 hours, then drying the copper net and the sample in a vacuum oven at 145 ℃ for 2 hours, weighing the copper net and the sample again, recording the mass of the copper net and the sample as m 3, and the Gel Content (GC) is calculated as shown in the following formula:
（3）。
the specific results are shown in table 2 below:
TABLE 1 raw material consumption and preparation conditions for four groups of test samples of the two initiating systems
TABLE 2 grafting and gel content of LLDPE-g-MAH prepared by different initiation systems
As can be seen from Table 2, when the grafting ratio of the CTC (NOP/MAH) initiating system is equivalent to that of the conventional DCP initiating system, the gel content of the graft polymer of the CTC (NOP/MAH) initiating system is significantly reduced as compared with that of the conventional DCP initiating system.
In addition, monitoring the torque in real time during the grafting reaction (the magnitude of the torque of the rotor of the internal mixer depends on the melt viscosity, which is positively correlated with the degree of crosslinking of the LLDPE); the monitoring results of the amounts of the materials corresponding to the group 2 of the table 1 are shown in fig. 1, and fig. 1 is a torque comparison chart of the organic peroxide initiating system and the CTC initiating system provided in the embodiment 1 of the present invention, and as shown in fig. 1, the torque of the CTC initiating system in the molten state in the reaction process is significantly lower than that of the conventional DCP initiating system, which indicates that the crosslinking side reaction of the LLDPE in the CTC (NOP/MAH) initiating system is effectively inhibited.
Example 2
Step 1: preparing premix: adding acetone into Maleic Anhydride (MAH) and N-hydroxysuccinimide (NHS) and stirring to dissolve, wherein the rotating speed of stirring equipment (DF-101S heat collection type constant temperature heating magnetic stirrer) is 90r/min, and the stirring time is 30min; adding LLDPE powder (a powder with a particle size of 200 μm and a chemical name of DAFA 7042:7042) into the solution, mechanically stirring to uniformly mix LLDPE, MAH, NHS, wherein the rotating speed of stirring equipment (DF-101S heat collection type constant temperature heating magnetic stirrer) is 160r/min, and the stirring time is 50min; then drying in an oven to volatilize acetone completely, wherein the drying temperature is 60 ℃, the drying time is 60min, then carrying out secondary mechanical stirring, the rotating speed of stirring equipment is 200r/min, and the stirring time is 60min, thus obtaining LLDPE/MAH/NHS premix; the LLDPE/MAH/NHS premix has a MAH content of 4wt% and a NHS content of 10, 50, 100, 400, 800ppm for a total of 5 groups of experiments.
Step 2: placing LLDPE/MAH/NHS premix into an internal mixer to carry out melt blending for grafting reaction, wherein the melt blending temperature is 200 ℃, the reaction time is 10min, and the screw rotating speed is 60r/min; after the melt blending is finished, the prepared functionalized polyolefin material (LLDPE-g-MAH) is taken out from an internal mixer, sheared by a pair of scissors and naturally cooled.
Further, the grafting ratio of LLDPE-g-MAH prepared by using a CTC (NHS/MAH) initiation system in this example was measured and compared with that of LLDPE-g-MAH prepared by using a CTC (NOP/MAH) initiation system under the same preparation conditions, and as a result, as shown in FIG. 2, FIG. 2 is a graph showing the comparison of the monomer grafting ratio of a CTC initiation system composed of two different N-hydroxy compounds of the structure provided in example 2 of the present invention and a functional monomer of the same structure.
As can be seen from FIG. 2, CMC initiation systems composed of different N-hydroxy compounds resulted in different grafting rates of monomers, mainly because the dissociation energy of the O-H bond of NHS < the dissociation energy of the O-H bond of NOP (BDE O-H) resulted in the hydrogen abstraction capacity of nitroxide NOP > nitroxide NHS, and therefore the grafting rate of NOP initiation systems was higher.
Example 3
A preparation method of a functionalized polyolefin material, which comprises the following steps:
Step 1: preparing premix: adding acetone into methacrylamide (MAM) and N-hydroxyphthalimide (NOP) and stirring to dissolve the methacrylamide and the N-hydroxyphthalimide, wherein the rotating speed of stirring equipment (DF-101S heat collection type constant temperature heating magnetic stirrer) is 90r/min, and the stirring time is 30min; adding LLDPE powder (powder of the name of Mao petrochemical DAFA7042 with the particle size of 200 μm) into the solution, mechanically stirring to uniformly mix LLDPE, MAM, NOP, wherein the rotating speed of stirring equipment is 160r/min, and the stirring time is 50min; then drying in an oven to volatilize acetone completely, wherein the drying temperature is 60 ℃ and the drying time is 50min, then carrying out secondary mechanical stirring, wherein the rotating speed of stirring equipment is 200r/min, and the stirring time is 60min, so as to obtain LLDPE/MAM/NOP premix; the LLDPE/MAH/NOP premix has a MAM content of 2.5wt% and a NOP content of 200ppm.
Step 2: placing LLDPE/MAM/NOP premix into an internal mixer to carry out melt blending for grafting reaction, wherein the melt blending temperature is 200 ℃, the reaction time is 10min, and the screw rotating speed is 60r/min; after the melt blending is finished, the prepared functionalized polyolefin material (LLDPE-g-MAM) is taken out of an internal mixer, sheared by a pair of scissors and naturally cooled.
As a control LLDPE-g-MAH was prepared with a conventional organic peroxide initiating system (dicumyl peroxide (DCP)).
Step 1: premix (organic peroxide initiation system) was prepared: adding acetone into methacrylamide (MAM) and dicumyl peroxide (DCP) and stirring to dissolve the mixture, wherein the rotating speed of stirring equipment (DF-101S heat collection type constant temperature heating magnetic stirrer) is 90r/min, and the stirring time is 30min; adding LLDPE powder (powder of the name of Mao petrochemical DAFA7042 with the particle size of 200 μm) into the solution, mechanically stirring to uniformly mix LLDPE, MAM, DCP, wherein the rotating speed of stirring equipment is 160r/min, and the stirring time is 50min; then drying in an oven to volatilize acetone completely, wherein the drying temperature is 60 ℃, the drying time is 60min, then carrying out secondary mechanical stirring, the rotating speed of stirring equipment is 200r/min, and the stirring time is 60min, thus obtaining LLDPE/MAM/DCP premix; the content of MAM in the LLDPE/MAM/DCP premix is 2.5 wt percent and the content of DCP is 1 weight percent.
Step 2: placing LLDPE/MAM/DCP premix into an internal mixer to carry out melt blending for grafting reaction, wherein the melt blending temperature is 200 ℃, the reaction time is 10min, and the screw rotating speed is 60r/min; after the melt blending is finished, the prepared functionalized polyolefin material (LLDPE-g-MAM) is taken out of an internal mixer, sheared by a pair of scissors and naturally cooled.
Further, the grafting ratio and melt index of LLDPE-g-MAM prepared by using CTC (NOP/MAM) initiation system of this example were measured and compared with LLDPE-g-MAM prepared by using conventional organic peroxide initiation system (dicumyl peroxide (DCP)), and the melt index (MFR) test method was as follows:
Under the same load (2.16 kg), the test temperature was 230 ℃, a section was cut every 30s, and the melt mass flow rate was calculated according to formula (5):
；
Wherein t tref: reference time (600 s); m: cutting off the mass (g); t: interval time(s) of the shut-off.
The specific results are shown in table 3 below:
TABLE 3 grafting and melt index of LLDPE-g-MAM prepared by different initiation systems
As can be seen from Table 3, the melt index of the grafted polymer obtained by the CTC initiating system is far higher than that of the DCP initiating system, and is relatively close to that of 1.113g/10min of the original LLDPE, which indicates that the cross-linking side reaction of the CTC initiating system in the grafting reaction is far lower than that of the traditional organic peroxide initiating system (dicumyl peroxide (DCP)), so that the influence of the CTC initiating system on the processing fluidity of the LLDPE after grafting modification is less, and the secondary addition work forming of the functionalized LLDPE material is more facilitated.
Example 4
A preparation method of a functional porous polyolefin material, which comprises the following steps:
Step 1: preparing premix: adding acetone into methacrylamide (MAM) and N-hydroxyphthalimide (NOP) and stirring to dissolve the methacrylamide and the N-hydroxyphthalimide, wherein the rotating speed of stirring equipment (DF-101S heat collection type constant temperature heating magnetic stirrer) is 90r/min, and the stirring time is 30min; adding UHMWPE powder (oil U050 with particle diameter of 200 μm) into the above solution, mechanically stirring to make UHMWPE, MAM, NOP parts uniformly mixed, stirring at rotation speed of 160r/min for 50min; then drying in an oven to volatilize acetone completely, wherein the drying temperature is 60 ℃, the drying time is 60min, then carrying out secondary mechanical stirring, the rotating speed of stirring equipment is 200r/min, and the stirring time is 60min, so as to obtain UHMWPE/MAM/NOP premix; the UHMWPE/MAM/NOP premix has a MAM content of 4wt% and a NOP content of 200ppm.
Step 2: vibration: placing UHMWPE/MAM/NOP premix in a mold, placing the mold on a vibrator, compacting the premix in the mold, and vibrating at 150Hz for 15min.
Step 3: cold pressing: the die was placed in a tablet press and cold pressed at 2MPa for 10min.
Step 4: sintering: and taking out the die, putting the die into a sintering furnace, heating to 165 ℃ and sintering for 25min, and naturally cooling to room temperature after the sintering is finished to obtain the functional porous polyolefin material (UHMWPE-g-MAM).
Step 5: and (3) demolding, wherein the pore diameter of the generated functional porous polyolefin material (UHMWPE-g-MAM) is 25-100 microns (the pore diameter is measured by an optical microscope), and the porosity is 40-65% (the porosity is measured by a mercury intrusion method).
Example 5
A preparation method of a functional porous polyolefin material, which comprises the following steps:
Step 1: preparing premix: adding acetone into methacrylic acid (MAA) and N-hydroxyphthalimide (NOP) and stirring to dissolve the mixture, wherein the rotating speed of stirring equipment (DF-101S heat collection type constant temperature heating magnetic stirrer) is 90r/min, and the stirring time is 30min; adding UHMWPE powder (oil U050 with particle diameter of 200 μm) into the above solution, mechanically stirring to make UHMWPE, MAA, NOP parts uniformly mixed, stirring at rotation speed of 160r/min for 50min; then putting the mixture into an oven for drying to volatilize acetone completely, wherein the drying temperature is 60 ℃, the drying time is 1h, then carrying out secondary mechanical stirring, the rotating speed of stirring equipment is 200r/min, and the stirring time is 60min, so as to obtain UHMWPE/MAA/NOP premix; the UHMWPE/MAA/NOP premix has a MAA content of 4wt% and a NOP content of 200ppm.
Step 2: vibration: placing UHMWPE/MAA/NOP premix in a mold, placing the mold on a vibrator, compacting the premix in the mold, and vibrating at 150Hz for 15min.
Step 3: cold pressing: the die was placed in a tablet press and cold pressed at 2MPa for 10min.
Step 4: sintering: and taking out the die, putting the die into a sintering furnace, heating to 165 ℃ and sintering for 25min, and naturally cooling after the sintering is finished to obtain the functional porous polyolefin material (UHMWPE-g-MAA).
Step 5: and (3) demolding, wherein the pore diameter of the generated functional porous polyolefin material (UHMWPE-g-MAA) is 25-100 microns (the pore diameter is measured by an optical microscope), and the porosity is 40-65% (the porosity is measured by a mercury intrusion method).
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. A method for preparing a functionalized polyolefin material, comprising the steps of:
a) Mixing a carbonyl-containing functional monomer and an N-hydroxyl compound in a solvent, wherein the carbonyl-containing functional monomer is maleic anhydride, the N-hydroxyl compound is N-hydroxyphthalimide, and the solvent is a volatile solvent capable of simultaneously dissolving the carbonyl-containing functional monomer and the N-hydroxyl compound; then mixing the mixture with polyolefin powder, and removing the solvent to obtain premix;
b) Carrying out melt blending on a precursor containing the premix to obtain a functionalized non-porous polyolefin material;
Or compacting, cold pressing and sintering the precursor containing the premix to obtain the functional porous polyolefin material;
In the step b), the content of the carbonyl-containing functional monomer in the precursor is 2-4wt%, and the content of the N-hydroxyl compound in the precursor is 100-400 ppm.
2. The method according to claim 1, wherein in step a), the polyolefin powder is a polyethylene powder and/or a polypropylene powder.
3. The method of claim 2, wherein in step a) the polyethylene in the polyethylene powder comprises one or more of high density polyethylene, low density polyethylene, linear low density polyethylene and ultra high molecular weight polyethylene.
4. The method according to claim 1, wherein in step b), the content of the N-hydroxy compound in the precursor is 200ppm.
5. The method according to claim 1, wherein in step b), the temperature of the melt blending is 180-230 ℃.
6. The method according to claim 1, wherein in step b), the vibration frequency of the tap is 30 to 200hz; and the vibration time of the compaction is 5-20 min.
7. The method according to claim 1, wherein in step b), the cold pressing pressure is 0 to 5mpa; the cold pressing time is 10-25 min.
8. The method according to claim 1, wherein in step b), the sintering temperature is 160-200 ℃; the sintering time is 20-120 min.
9. The method according to claim 1, wherein in step b), the pore size of the functionalized porous polyolefin material is 25-100 μm; the porosity of the functionalized porous polyolefin material is 40-65%.
10. A functionalized polyolefin material, characterized in that it is prepared according to the preparation method of any one of claims 1 to 9.
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