An anti-aging poly-α-olefin and its preparation method and application

Abstract

The present invention provides an anti-aging poly-α-olefin and its preparation method and application, belonging to the technical field of organic synthesis. The structural formula of the anti-aging poly-α-olefin provided by the present invention is: The preparation method is to mix an amino monomer or a sterically hindered phenol monomer with a hydrocarbon compound to obtain a mixed solution, then introduce an α-olefin compound into the mixed solution, and then sequentially add a cocatalyst and a catalyst for a polymerization reaction to obtain a target product. The introduction of a copolymerizable functional monomer into the poly-α-olefin by the present invention can effectively improve the light oxygen and thermal oxygen aging resistance of the polymer, and significantly inhibit the generation of surface cracks and the aging of the material during processes such as heating or irradiation of the sample. When the oxidation aging time exceeds 504 h and the ultraviolet aging time exceeds 168 h, the polymer does not undergo obvious aging.

Description

Technical Field

[0001] The present invention relates to the technical field of organic synthesis, and particularly relates to an anti-aging poly-α-olefin, a preparation method thereof, and an application thereof. Background Art

[0002] With the deepening of new industrialization, informatization, urbanization, and agricultural modernization and the continuous upgrading of the resident consumption structure, poly-α-olefins are applied in multiple fields such as automotive parts, energy, medical equipment, high-end pipes, and packaging. While the requirements for the service life of automotive parts by residents increase, the requirements for heat and light oxygen aging resistance of high-end pipes also increase. Currently, the anti-aging performance of polyolefin materials is mainly achieved by adding small molecule anti-aging auxiliaries containing hindered phenols and hindered amines. During use, these anti-aging agents are prone to agglomeration and overflow from the non-polar polyolefin matrix, resulting in attenuation or failure of the anti-aging performance, and even posing safety hazards. Some applications involve fields such as food and drug packaging, where the lower limit requirements for small molecule leachates are higher. Therefore, there is an urgent need to have higher stability and safety while ensuring the mechanical properties of the material itself, and to avoid the leaching of small molecule additives. The market demand for anti-aging olefin polymer materials will continue to grow and the requirements will be higher. However, the synthesis of poly-α-olefin materials that themselves meet the requirements of high heat resistance, excellent chemical stability, and ultraviolet absorption resistance remains a challenge.

[0003] Among poly-α-olefin materials, polypropylene (PP) is a thermoplastic synthetic resin with excellent properties. It is a colorless, translucent thermoplastic lightweight general-purpose plastic, with chemical resistance, heat resistance, electrical insulation, high-strength mechanical properties, and good high-abrasion processing performance. By controlling the conditions of the polymerization reaction and adding appropriate comonomers, properties such as UV resistance can be imparted to the material. Polybutene (PB) is a high-molecular-weight inert polymer, mainly polymerized from butene. Due to the high crystallinity and low melting point of PB, the material is endowed with good rigidity and strength, and the characteristics of being easy to process and form, making it suitable for packaging materials, electronic products, automotive parts, etc. In addition, by controlling the conditions of the polymerization reaction and adding appropriate comonomers, properties such as high-temperature resistance and UV resistance can be imparted to the material. Poly(4-methyl-1-pentene) (PMP) is a polymer material with high readability and practicality. Its structural formula is mainly composed of a cyclic molecule consisting of five carbon atoms, with a methyl group linked to one of the carbon atoms. Its unique structural formula has high thermal stability and chemical stability, and is widely used in the fields of aerospace, electronics and electrical appliances, etc. By controlling the conditions of the polymerization reaction and adding appropriate comonomers, properties such as UV resistance can be imparted to the material. Therefore, the excellent properties of PB, PP, and PMP make their application prospects in multiple fields such as packaging, electronics, and pipe materials emerging. However, since there are a large number of tertiary carbons in the main chain or side chain of these two types of polymers, the hydrogen on the tertiary carbon is unstable. Poly-α-olefins represented by polypropylene have poor light and heat tolerance, and are prone to photooxidative or thermal oxidative aging after absorbing energy, which greatly restricts their wide application in many fields. Although adding small-molecule antioxidants can improve the anti-aging ability, polyolefins themselves are non-polar and have poor compatibility with polar small-molecule antioxidants, and it is easy to cause aggregation and slippage of polar small molecules during processing and use, affecting the long-term and stability of the anti-aging performance. In order to effectively broaden the application fields of poly-α-olefins, improve their service life and performance stability, it is of great significance to develop poly-α-olefin materials with stable anti-aging properties.

[0004] In recent years, with the continuous innovation of synthetic catalyst technology, poly-α-olefin materials with novel structures and high-value applications have emerged. Among them, anti-aging poly-α-olefins not only retain the excellent properties of polymers but also exhibit high resistance to heat-oxygen aging and light aging, showing broad prospects for industrial application. Since polar functional groups can easily poison and deactivate olefin coordination polymerization catalysts, it is difficult to directly copolymerize to synthesize poly-α-olefins with anti-aging functional groups, which poses a great challenge to the direct synthesis of anti-aging poly-α-olefins. And these anti-aging macromolecules can also be further added to the poly-α-olefin matrix as anti-aging modifiers, which can effectively inhibit the slippage and aggregation of polar functional groups, thereby achieving better dispersibility and stability, avoiding the overflow problem of similar small molecule anti-aging agents, and further ensuring the performance stability of polyolefins and extending their service life.

[0005] In summary, there is almost no relevant research on poly-α-olefins with excellent anti-aging performance and their application as macromolecular anti-aging additives. Macroscopically, there is a lack of establishing the connection between structure and performance, and olefin polymer products with excellent comprehensive performance and their applications are urgently needed to be developed. Summary of the Invention

[0006] Based on the above, the present invention provides an anti-aging poly-α-olefin and its preparation method and application. By introducing amino monomers with heat-oxygen stability and ultraviolet stability, and optimizing the polymerization conditions, the synthesis of high-performance anti-aging polymers based on olefins is achieved.

[0007] To achieve the above object, the present invention provides the following technical solutions: An anti-aging poly-α-olefin has a structural formula shown in Formula I or Formula II:

[0008]

[0009] Wherein, R is selected from

[0010] The value range of n is 1 to 11.

[0011] The present invention also provides a preparation method of the anti-aging poly-α-olefin, including the following steps:

[0012] After mixing the copolymerization functional monomer with the hydrocarbon compound to obtain a mixed solution, then introducing an α-olefin compound into the mixed solution, and then successively adding a cocatalyst and a catalyst for polymerization reaction to obtain the anti-aging poly-α-olefin; the copolymerization functional monomer is an amino monomer or a sterically hindered phenol monomer. The reaction general formula is as follows:

[0013]

[0014] In some embodiments, the copolymerizable functional monomer includes 4-(2-propenyl)diphenylamine, 4-(3-butenyl)diphenylamine, 4-(4-pentenyl)diphenylamine, 4-(5-hexenyl)diphenylamine, 4-(6-heptenyl)diphenylamine, 4-(7-octenyl)diphenylamine, 3-carbazol-1-propene, 4-carbazol-1-butene, 5-carbazol-1-pentene, 6-carbazol-1-hexene, 7-carbazol-1-heptene, 8-carbazol-1-octene, 9-carbazol-1-nonene, 10-carbazol-1-decene, 11-carbazol-1-undecene, 4-(2-propenyl)-2,6-diisopropylbenzene, 4-(3-butenyl)-2,6-diisopropylphenol, 4-(4-pentenyl)-2,6-diisopropylphenol, 4-(5-hexenyl)-2,6-diisopropylphenol, 4-(6-heptenyl)-2,6-diisopropylphenol, 4-(7-octenyl)-2,6-diisopropylphenol, 4-(8-nonenyl)-2,6-diisopropylphenol, 4-(9-decenyl)-2,6-diisopropylphenol, 4-(10-undecenyl)-2,6-diisopropylphenol, 4-(2-propenyl)-2,2,6,6-tetramethylpiperidine, 4-(3-butenyl)-2,2,6,6-tetramethylpiperidine, 4-(4-pentenyl)-2,2,6,6-tetramethylpiperidine, 4-(5-hexenyl)-2,2,6,6-tetramethylpiperidine, 4-(6-heptenyl)-2,2,6,6-tetramethylpiperidine, 4-(7-octenyl)-2,2,6,6-tetramethylpiperidine, 4-(8-nonenyl)-2,2,6,6-tetramethylpiperidine, 4-(9-decenyl)-2,2,6,6-tetramethylpiperidine or 4-(10-undecenyl)-2,2,6,6-tetramethylpiperidine.

[0015] In some embodiments, the hydrocarbon compound includes at least one of toluene and its homologues, naphthalene and its homologues, alkanes and their homologues, and cycloalkanes and their homologues.

[0016] In some embodiments, the molar concentration of the copolymerizable functional monomer in the mixed solution is 1.0 - 0.01 mol / L.

[0017] In some embodiments, the α-olefin compound is butene or 4-methyl-1-pentene.

[0018] In some embodiments, the structural formula of the catalyst is as shown in Formula III, Formula IV, Formula V, Formula VI or Formula VII (i.e., the catalyst is one of Cat.1 - Cat.10):

[0019]

[0020] The cocatalyst is a boron-containing compound or an alkylaluminum;

[0021] The molar ratio of the catalyst to the cocatalyst is 100:1 to 3000:1.

[0022] In some embodiments, the boron-containing compound includes triethylammonium tetrakis(phenyl)borate, tributylammonium tetrakis(phenyl)borate, trimethylammonium tetrakis(phenyl)borate, tripropylammonium (phenyl)borate, trimethylammonium tetrakis(p-tolyl)borate, trimethylammonium tetrakis(o,p-dimethylphenyl)borate, tributylammonium tetrakis(p-trifluoromethylphenyl)borate, trimethylammonium tetrakis(p-trifluoromethylphenyl)borate, or tributylammonium tetrakis(pentafluorophenyl)borate;

[0023] The alkylaluminum includes trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylaluminum chloride, triisopropylaluminum, tri-sec-butylaluminum, tripentylaluminum, triisopentylaluminum, tricyclopentylaluminum, trihexylaluminum, trioctylaluminum, ethyldimethylaluminum, methyldiethylaluminum, triphenylaluminum, tri-p-tolylaluminum, methoxyaluminum, or dimethylmethoxyaluminum.

[0024] In some embodiments, the temperature of the polymerization reaction is 25 to 120 °C, and the time is 10 to 120 min.

[0025] In some embodiments, after the polymerization reaction, it further includes a step of separating the product; the specific steps of the separation are: after the reaction ends, adding a terminator to terminate the reaction, then adding an acidified precipitant, and then performing filtration, washing, and drying in sequence; the terminator is ethanol; the precipitant includes one or more of ethanol, methanol, petroleum ether, diethyl ether, n-hexane, acetone, n-pentane, tetrahydrofuran, or dichloromethane.

[0026] The copolymer obtained by copolymerizing an amino group and a sterically hindered phenol functional monomer with an olefin in the present invention has the characteristic of anti-aging performance. It should be particularly noted that this property can be maintained even under the condition of a low content of functional monomers in the copolymer. Therefore, the design and synthesis of amino monomers or sterically hindered phenol monomers are the key to preparing a series of excellent anti-aging polymers. At the same time, by designing a sterically hindered phenolic hydroxyl monomer or amino monomer and appropriately extending the number of carbon atoms between the olefin double bond and the functional group, the phenomenon of catalyst poisoning during the coordination process can be effectively avoided, the effective insertion of functional monomers during the copolymerization process can be achieved, and the reduction of catalytic activity can be avoided. In addition, a series of synthesized poly-α-olefins are characterized. High-temperature nuclear magnetic carbon spectroscopy is used to characterize the microscopic chemical structure of the polymer, high-temperature GPC is used to test the molecular weight and its distribution of the polymer, DSC is used to study the thermal behavior of the polymer, and an optical microscope is used to observe the surface morphology of the sample.

[0027] The present invention mainly uses amine monomers, sterically hindered phenol monomers and olefin compounds to form different reaction systems, optimizes the ratio of the main catalyst and the cocatalyst and the reaction temperature, and synthesizes a series of poly-α-olefins with thermal oxidation resistance of 24-504 h and ultraviolet aging resistance of 24-168 h. First, based on the fact that the catalyst has a certain degree of copolymerization ability with functionalized amino-olefin monomers or sterically hindered phenol-olefin monomers and 1-olefins, the effects of the concentration of functional monomers, polymerization time, temperature, different types of cocatalysts and the ratio of the main catalyst on the composition and properties of the polymer, as well as the effect of the content of functional groups on the anti-aging performance, are systematically studied to achieve efficient regulation of the anti-aging performance of poly-α-olefins. 13 The results of 13C NMR show that poly-α-olefins with different monomer insertion rates can be obtained with different initial concentrations of different functional monomers. The different aging degrees of the obtained copolymers are tested by different thermal oxidation aging and ultraviolet irradiation treatments. In addition, by blending poly-α-olefins with different degrees of anti-aging as macromolecular additives with poly-1-olefin without anti-aging additives, the anti-aging ability of poly-1-olefin can be effectively improved. Combining the surface morphology and characterization results of the samples, it shows that after the same aging treatment, the cracks on the surface of amino-functionalized poly-α-olefin are significantly less than those of untreated poly-α-olefin; the cracks on the surface of poly-α-olefin added with poly-α-olefin macromolecular additives are significantly less than those of untreated commercial polyolefin, indicating that this type of functionalized poly-α-olefin itself has high anti-aging performance, and at the same time can be used as an anti-aging agent for poly-α-olefin, which can not only improve the compatibility with the matrix, but also improve its aging resistance ability and avoid the aggregation and overflow of aging-resistant functional groups. In summary, the improvement of anti-aging performance plays a crucial role in broadening the wide application of poly-α-olefins in various fields.

[0028] In the anti-aging poly-α-olefin provided by the present invention, the insertion rate of the amine monomer is 0.5-5% (or the conversion rate is 40%-90%), T m = 50-240 °C, the weight-average molecular weight of the polymer is 5×10 3 - 50×10 4 g / mol, the PDI is between 2.1 and 3.2, and the activity is 60-90×10 5 kg polymer ·mmol Cat. -1 ·h -1 between. The thermal oxidation aging time of poly-α-olefin > 504 h, and the ultraviolet aging time > 168 h. When blended with commercial polyolefin products, the thermal oxidation aging time of the blend > 504 h, and the ultraviolet aging time > 168 h.

[0029] The present invention also provides an anti-aging polymer blend material, the raw materials of which include the anti-aging poly-α-olefin and a polymer; the proportion of the anti-aging poly-α-olefin in the anti-aging polymer blend material is 1-10 wt%.

[0030] The present invention discloses the following technical effects:

[0031] The present invention uses amino-functional monomers or sterically hindered phenol-type functional monomers and α-olefins to form different copolymerization reaction systems, and synthesizes a series of poly-α-olefins with anti-aging properties. According to the characteristics of efficient adjustability of the type and content of functional monomers, the anti-aging properties of poly-α-olefins can be efficiently controlled. The insertion rate of the polymer prepared by the present invention can be adjusted between 0.5% and 5%, and its molecular weight can be adjusted between 5×10 3 ~50×10 4 g / mol. Through the insertion rate, the mechanical properties and anti-aging properties of poly-α-olefins can be optimized. When the insertion rate reaches more than 0.55%, the polymer exhibits excellent anti-aging properties. For example, when the oxidation aging time exceeds 504 h and the ultraviolet aging time exceeds 168 h, the polymer does not show obvious aging.

[0032] The poly-α-olefin provided by the present invention is used as a macromolecular additive and blended with commercial polymers. By adjusting the ratio, a series of anti-aging blends are obtained. The dosage of the additive in the anti-aging blend prepared by the present invention can be adjusted between 1% and 10 wt%. When the additive content reaches more than 2%, the blend exhibits excellent anti-aging properties. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] In order to more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the following will briefly introduce the drawings required for use in the embodiments. Obviously, the drawings in the following description are only some embodiments of the present invention. For those of ordinary skill in the art, other drawings can be obtained based on these drawings without creative efforts.

[0034] Figure 1 13C NMR spectrum of the butene polymer obtained in Example 1 13 ;

[0035] Figure 2 GPC curves of the polymers obtained in Examples 1, 2, and 18 before and after 168 h of ultraviolet irradiation, where (a) is untreated PB, (b) is Example 1, (c) is Example 2, and (d) is Example 18;

[0036] Figure 3 GPC curves of the polymers obtained in Examples 1, 2, and 18 before and after 96 h of thermal-oxidative aging, where (a) is untreated PB, (b) is Example 1, (c) is Example 2, and (d) is Example 18;

[0037] Figure 4 OIT curves of the polymers obtained in Examples 1-3 at different thermal-oxidative aging times;

[0038] Figure 5 FT-IR partial enlarged views of the polymers obtained in Examples 10 - 12 at different thermo-oxidative aging times, where (a) is untreated PMP, (b) is Example 10, (c) is Example 11, and (d) is Example 12;

[0039] Figure 6 SEM images of the blend samples of the butene polymers obtained in Examples 13 and 15 and the polymer products in the prior art at different UV aging times. Detailed implementation manners

[0040] The various exemplary implementation manners of the present invention will now be described in detail. This detailed description should not be considered as a limitation of the present invention, but rather as a more detailed description of certain aspects, characteristics, and implementation schemes of the present invention.

[0041] It should be understood that the terms used in the present invention are only for describing specific implementation manners and are not used to limit the present invention. Additionally, for the numerical ranges in the present invention, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Any intermediate value within any stated value or stated range, as well as each smaller range between any other stated value or intermediate value within the stated range, is also included in the present invention. The upper and lower limits of these smaller ranges can be independently included or excluded from the range.

[0042] Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by those of ordinary skill in the art to which the present invention pertains. Although the present invention only describes preferred methods and materials, any methods and materials similar or equivalent to those described herein can also be used in the implementation or testing of the present invention. All documents mentioned in this specification are incorporated by reference to disclose and describe the methods and / or materials related to the documents. In case of conflict with any incorporated document, the content of this specification shall prevail.

[0043] Without departing from the scope or spirit of the present invention, various improvements and changes can be made to the specific implementation manners of the present invention specification, which are obvious to those skilled in the art. Other implementation manners obtained from the present invention specification are obvious to those skilled in the art. The present invention specification and examples are only exemplary.

[0044] Regarding the use of "comprising", "including", "having", "containing", etc. in this article, they are all open-ended terms, meaning including but not limited to.

[0045] During the preparation process, unless otherwise specified, all operations involved are carried out by professionals familiar with the technical field in an MBraun glove box or under the protection of inert gases such as nitrogen or argon using standard Schlenk techniques. At the same time, all solvents involved in the present invention are anhydrous and oxygen-free solvents after post-treatment. Additionally, during the preparation of the anti-aging poly-α-olefin, all operations sensitive to moisture and oxygen are carried out by professionals familiar with the technical field in an MBraun glove box or under the protection of nitrogen using standard Schlenk techniques.

[0046] All polymers in the examples need to be carried out under anhydrous and oxygen-free conditions. Glassware such as polymerization bottles, syringes, and ampoules involved in the reaction for weighing and transferring catalysts, cocatalysts, solutions, etc. have been treated under anhydrous and oxygen-free conditions.

[0047] The present invention has carried out relevant tests on the obtained polymers. Nuclear magnetic resonance spectroscopy ( 13 CNMR) was used to characterize the chemical structure of the polymers, differential scanning calorimetry (DSC) was used to characterize the thermal properties of the polymers, high-temperature gel permeation chromatography (GPC) was used to characterize the molecular weight and molecular weight distribution of the polymers, and Fourier transform infrared spectroscopy (FT-IR) was used to characterize the signal peaks of carbonyl functional groups in the polymers. Among them, the 1 H and 13 C NMR of the copolymers was measured on a Bruker-400 nuclear magnetic resonance spectrometer at 120 °C with TMS as the internal standard and deuterated ortho-dichlorobenzene or deuterated 1,1,2,2-tetrachloroethane as the solvent. The melting temperature (T m ) of the copolymers was measured by a differential scanning calorimeter (Q2000 DSC). The test conditions were as follows: under a nitrogen atmosphere, the heating / cooling rate was 10 °C / min. Gel permeation chromatography was measured using a (GPC) PL GPC-220 gel permeation chromatograph. The tester was RI-Laser, with PL EasiCal PS-1 as the standard sample, the packed column was Plgel 10μm MIXED-BLS, 1,2,4-trichlorobenzene (TCB) as the solvent (adding 0.05 wt% of 2,6-di-tert-butyl-4-methylphenol (BHT) as an antioxidant), the test temperature was 150 °C, and the flow rate was 1.0 mL / min. Fourier transform infrared spectroscopy was measured using a Nicolet 6700 infrared spectrometer.

[0048] To better understand the present invention, the content of the present invention will be further clarified below in conjunction with examples, but the content of the present invention is not limited to the following examples.

[0049] Example 1

[0050] A preparation method of an anti-aging poly-α-olefin in this embodiment includes the following steps (olefin coordination copolymerization using Cat.1 catalyst):

[0051] Using a Schlenk experimental device, and maintaining a vacuum of -101.325 KPa, add 30 mL of toluene solution and 2 mL (concentration of 0.25 mol / L) of toluene solution of 4-(7-octenyl)diphenylamine; then, introduce 1 atm of butene gas and stir for 5 min; after stabilization, add a total of 10 mL of toluene solutions of triisobutylaluminum and Cat.1 catalyst (the molar ratio of triisobutylaluminum to Cat.1 catalyst is 3000:1, and the concentration of triisobutylaluminum in the toluene solution is 1.5 mol / L), and stir and react for 10 min under the action of 600 rpm; after the polymerization ends, inject 0.1 mL of ethanol to terminate the polymerization. Finally, slowly pour the reaction solution drop by drop into a beaker containing 300 mL of ethanol / 37 wt% hydrochloric acid (volume ratio 100:1) for sedimentation, and then obtain the butene polymer through filtration, washing, and vacuum drying for subsequent characterization.

[0052] The obtained butene polymer is subjected to nuclear magnetic ( Figure 1 ) and DSC tests. The test results show that the insertion rate of 4-(7-octenyl)diphenylamine in the butene polymer polymerized in this embodiment is 0.43%, and the copolymerization activity is 88.4×10 5 g polymer ·mol Cat. -1 ·h -1 , the weight-average molecular weight is 33.3×10 4 g / mol, and the PDI is 3.1, indicating that the obtained butene polymer has obvious 4-(7-octenyl)diphenylamine insertion characteristics. The specific data are shown in Table 1.

[0053] The polymers are respectively subjected to accelerated thermal-oxidative aging treatment for different times (24 h, 72 h, 120 h, 168 h, 336 h, 504 h) and accelerated ultraviolet aging treatment for different times (24 h, 48 h, 72 h, 96 h, 120 h, 168 h) for subsequent characterization.

[0054] Take pictures of the butene polymers after the above aging treatment to observe the changes in surface morphology. The test results show that when the thermal-oxidative aging time is 336 h, cracks begin to appear in the butene polymer samples, indicating that the samples are aging at this time. FT-IR test shows that the intensity of the carbonyl absorption peak of the samples in this embodiment decreases significantly, indicating a decrease in the degree of thermal-oxidative aging. OIT( Figure 4)The test shows that the oxidation induction period of the samples in this example is significantly prolonged, and the oxidation induction curve drops significantly, indicating that the TPA group can effectively inhibit the aging of the samples. When the ultraviolet irradiation aging time is 168 h, aging cracks appear in the butene polymer.

[0055] Example 2

[0056] In this example, a preparation method of an anti-aging poly-α-olefin includes the following steps (olefin coordination copolymerization using Cat.1 catalyst):

[0057] Using a Schlenk experimental device, and maintaining a vacuum of -101.325 KPa, add 30 mL of toluene solution and 2 mL of toluene solution of 4-(7-octenyl) diphenylamine (concentration 0.5 mol / L); then, introduce 1 atm of butene gas and stir for 5 min; after stabilization, add a total of 10 mL of toluene solutions of triisobutylaluminum and Cat.1 catalyst (the molar ratio of triisobutylaluminum to Cat.1 catalyst is 3000:1, and the concentration of triisobutylaluminum in the toluene solution is 1.5 mol / L), and stir and react for 10 min under the action of 600 rpm; after the polymerization ends, inject 0.1 mL of ethanol to terminate the polymerization. Finally, slowly pour the reaction solution dropwise into a beaker containing 300 mL of ethanol / 37 wt% hydrochloric acid (volume ratio 100:1) for sedimentation, and then obtain the butene polymer through filtration, washing, and vacuum drying for subsequent characterization.

[0058] The above-obtained butene polymer is subjected to NMR and DSC tests. The test results show that the insertion rate of 4-(7-octenyl) diphenylamine in the butene polymer polymerized in this example is 1.42%, and the copolymerization activity is 84.6×10 5 g polymer ·mol Cat. -1 ·h -1 , the weight-average molecular weight is 18.7×10 4 g / mol, and the PDI is 2.4, indicating that the obtained butene polymer has the characteristic of a high insertion rate. The specific data are shown in Table 1.

[0059] The polymer is respectively subjected to accelerated thermal-oxidative aging treatment for different times (24 h, 72 h, 120 h, 168 h, 336 h, 504 h) and accelerated ultraviolet aging treatment for different times (24 h, 48 h, 72 h, 96 h, 120 h, 168 h) for subsequent characterization.

[0060] The butene polymer subjected to the above aging treatment was photographed to observe the change in surface morphology. The test results showed that when the thermo-oxidative aging time was 504 h, no cracks appeared in the sample of the butene polymer, indicating that the sample did not age at this time. FT-IR test showed that the intensity of the carbonyl absorption peak of the sample in this example decreased significantly, indicating a reduction in the degree of thermo-oxidative aging. OIT( Figure 4 ) test showed that the oxidation induction period of the sample in this example was significantly prolonged and the oxidation induction curve decreased significantly, indicating that the TPA group could effectively inhibit the aging of the sample. When the ultraviolet irradiation aging time was 168 h, no aging crack phenomenon appeared in the sample of the butene polymer.

[0061] Example 3

[0062] In this example, a method for preparing an anti-aging poly-α-olefin includes the following steps (olefin coordination copolymerization using Cat.1 catalyst):

[0063] Using a Schlenk experimental device and maintaining a vacuum of -101.325 KPa, 30 mL of toluene solution and 2 mL of toluene solution of 4-(7-octenyl)diphenylamine (concentration 0.75 mol / L) were added; then, 1 atm of butene gas was introduced and stirred for 5 min; after stabilization, a total of 10 mL of toluene solution of triisobutylaluminum and Cat.1 catalyst was added (the molar ratio of triisobutylaluminum to Cat.1 catalyst was 3000:1, and the concentration of triisobutylaluminum in the toluene solution was 1.5 mol / L), and the reaction was stirred at 600 rpm for 10 min; after the polymerization was completed, 0.1 mL of ethanol was injected to terminate the polymerization. Finally, the reaction solution was gradually poured dropwise into a beaker containing 300 mL of ethanol / 37 wt% hydrochloric acid (volume ratio 100:1) for precipitation, and then obtained the butene polymer through filtration, washing, and vacuum drying for subsequent characterization.

[0064] The above-obtained butene polymer was subjected to NMR and DSC tests. The test results showed that the insertion rate of 4-(7-octenyl)diphenylamine in the butene polymer polymerized in this example was 2.13%, and the copolymerization activity was 77.8×10 5 g polymer ·mol Cat. -1 ·h -1 , the weight-average molecular weight was 16.4×10 4 g / mol, and the PDI was 2.2, indicating that the obtained butene polymer had the characteristic of a high insertion rate. The specific data are shown in Table 1.

[0065] The polymer was subjected to accelerated thermal-oxidative aging treatment for different times (24 h, 72 h, 120 h, 168 h, 336 h, 504 h) and accelerated ultraviolet aging treatment for different times (24 h, 48 h, 72 h, 96 h, 120 h, 168 h), and awaited subsequent characterization.

[0066] The butene polymer after the above aging treatment was photographed to observe the change in surface morphology. The test results showed that when the thermal-oxidative aging time was 504 h, no cracks appeared in the sample of the butene polymer, indicating that the sample did not age at this time. FT-IR test showed that the intensity of the carbonyl absorption peak of the sample in this example decreased significantly, indicating a decrease in the degree of thermal-oxidative aging. OIT( Figure 4 ) test showed that the oxidation induction period of the sample in this example was significantly prolonged and the oxidation induction curve decreased significantly, indicating that the TPA group could effectively inhibit the aging of the polymer. When the ultraviolet irradiation aging time was 168 h, no aging crack phenomenon appeared in the sample of the butene polymer.

[0067] Example 4

[0068] In this example, a preparation method of an anti-aging poly-α-olefin includes the following steps (olefin coordination copolymerization using Cat.2 catalyst):

[0069] Using a Schlenk experimental device and maintaining a vacuum of -101.325 KPa, 30 mL of toluene solution and 2 mL (concentration of 0.25 mol / L) of toluene solution of 4-(7-octenyl)diphenylamine were added; then, 25 mmol of 4-methyl-1-pentene was added and stirred for 5 min; after stabilization, a total of 10 mL of toluene solution of triisobutylaluminum and Cat.2 catalyst were added (the molar ratio of triisobutylaluminum to Cat.2 catalyst was 3000:1, and the concentration of triisobutylaluminum in the toluene solution was 1.5 mol / L), and the reaction was stirred at 600 rpm for 10 min; after the polymerization was completed, 0.1 mL of ethanol was injected to terminate the polymerization. Finally, the reaction solution was gradually poured into a beaker containing 300 mL of methanol / 37 wt% hydrochloric acid (volume ratio 100:1) for precipitation, and then obtained 4-methyl-1-pentene polymer through filtration, washing, and vacuum drying, awaiting subsequent characterization.

[0070] The obtained 4-methyl-1-pentene polymer was subjected to NMR and DSC tests. The test results showed that the insertion rate of 4-(7-octenyl)diphenylamine in the 4-methyl-1-pentene polymer polymerized in this example was 3.20%, the copolymerization conversion rate was 75.3%, the weight-average molecular weight was 11.9×10 4 g / mol, and the PDI was 2.4, indicating that the obtained 4-methyl-1-pentene polymer had the characteristics of a high insertion rate. The specific data is shown in Table 1.

[0071] The polymer was subjected to accelerated thermal-oxidative aging treatment for different times (24 h, 72 h, 120 h, 168 h, 336 h, 504 h) and accelerated ultraviolet aging treatment for different times (24 h, 48 h, 72 h, 96 h, 120 h, 168 h), and awaited subsequent characterization.

[0072] The 4-methyl-1-pentene polymer after the above aging treatment was photographed to observe the change in surface morphology. The test results showed that when the thermal-oxidative aging time was 504 h, no cracks appeared in the sample of the 4-methyl-1-pentene polymer, indicating that the sample did not age at this time. FT-IR test showed that the intensity of the carbonyl absorption peak of the sample in this example decreased significantly, indicating a decrease in the degree of thermal-oxidative aging. The OIT test showed that the oxidation induction period of the sample in this example was significantly prolonged and the oxidation induction curve decreased significantly, indicating that the TPA group could effectively inhibit the aging of the sample. When the ultraviolet irradiation aging time was 168 h, no aging crack phenomenon appeared in the sample of the 4-methyl-1-pentene polymer.

[0073] Example 5

[0074] In this example, a preparation method of an anti-aging poly-α-olefin includes the following steps (olefin coordination copolymerization using Cat.2 catalyst):

[0075] Using a Schlenk experimental device, under a vacuum of -101.325 KPa, 30 mL of toluene solution and 2 mL of toluene solution of 4-(7-octenyl)diphenylamine (concentration 0.5 mol / L) were added; then, 25 mmol of 4-methyl-1-pentene was added and stirred for 5 min; after stabilization, a total of 10 mL of toluene solution of triisobutylaluminum and Cat.2 catalyst was added (the molar ratio of triisobutylaluminum to Cat.2 catalyst was 3000:1, and the concentration of triisobutylaluminum in the toluene solution was 1.5 mol / L), and the reaction was stirred at 600 rpm for 10 min; after the polymerization ended, 0.1 mL of ethanol was injected to terminate the polymerization. Finally, the reaction solution was gradually poured dropwise into a beaker containing 300 mL of petroleum ether / 37 wt% hydrochloric acid (volume ratio 100:1) for sedimentation, and then obtained 4-methyl-1-pentene polymer through filtration, washing, and vacuum drying, and awaited subsequent characterization.

[0076] The obtained 4-methyl-1-pentene polymer was subjected to NMR and DSC tests. The test results showed that the insertion rate of 4-(7-octenyl)diphenylamine in the 4-methyl-1-pentene polymer polymerized in this example was 3.80%, the copolymerization conversion rate was 79.5%, the weight-average molecular weight was 10.9×10 4 g / mol, and the PDI was 2.7, indicating that the obtained 4-methyl-1-pentene polymer had the characteristic of a high insertion rate. The specific data is shown in Table 1.

[0077] The polymer was subjected to accelerated thermal-oxidative aging treatment for different times (24 h, 72 h, 120 h, 168 h, 336 h, 504 h) and accelerated ultraviolet aging treatment for different times (24 h, 48 h, 72 h, 96 h, 120 h, 168 h), and waited for subsequent characterization.

[0078] The above-aged 4-methyl-1-pentene polymer was photographed to observe the surface morphology changes. The test results showed that when the thermal-oxidative aging time was 504 h, there were no cracks in the 4-methyl-1-pentene polymer sample, indicating that the sample did not age at this time. FT-IR test showed that the intensity of the carbonyl absorption peak of the sample in this example decreased significantly, indicating a decrease in the degree of thermal-oxidative aging. The OIT test showed that the oxidation induction period of the sample in this example was significantly prolonged and the oxidation induction curve decreased significantly, indicating that the TPA group could effectively inhibit the aging of the sample. When the ultraviolet irradiation aging time was 168 h, there was no aging crack phenomenon in the 4-methyl-1-pentene polymer sample.

[0079] Example 6

[0080] In this example, a preparation method of an anti-aging poly-α-olefin includes the following steps (olefin coordination copolymerization using Cat.2 catalyst):

[0081] Using a Schlenk experimental device, and maintaining a vacuum of -101.325 KPa, 30 mL of toluene solution and 2 mL (concentration of 0.75 mol / L) of toluene solution of 4-(7-octenyl)diphenylamine were added; then, 25 mmol of 4-methyl-1-pentene was added and stirred for 5 min; after stabilization, a total of 10 mL of toluene solution of triisobutylaluminum and Cat.2 catalyst were added (the molar ratio of triisobutylaluminum to Cat.2 catalyst was 3000:1, and the concentration of triisobutylaluminum in the toluene solution was 1.5 mol / L), and the reaction was stirred at 600 rpm for 10 min; after the polymerization was completed, 0.1 mL of ethanol was injected to terminate the polymerization. Finally, the reaction solution was gradually poured into a beaker containing 300 mL of ethanol / 37 wt% hydrochloric acid (volume ratio 100:1) for sedimentation, and then obtained 4-methyl-1-pentene polymer through filtration, washing, and vacuum drying, and waited for subsequent characterization.

[0082] The above-obtained 4-methyl-1-pentene polymer was subjected to NMR and DSC tests. The test results showed that the insertion rate of 4-(7-octenyl)diphenylamine in the 4-methyl-1-pentene polymer polymerized in this example was 4.40%, the copolymerization conversion rate was 84.1%, and the weight-average molecular weight was 9.4×10 4g / mol, with a PDI of 2.8, indicating that the obtained 4-methyl-1-pentene polymer has the characteristic of a high insertion rate. The specific data is shown in Table 1.

[0083] The polymers were subjected to accelerated thermal-oxidative aging treatment for different times (24h, 72h, 120h, 168h, 336h, 504h) and accelerated ultraviolet aging treatment for different times (24h, 48h, 72h, 96h, 120h, 168h), pending subsequent characterization.

[0084] The above-aged 4-methyl-1-pentene polymer was photographed to observe the change in surface morphology. The test results showed that when the thermal-oxidative aging time was 504h, there were no cracks in the 4-methyl-1-pentene polymer sample, indicating that the sample did not age at this time. FT-IR test showed that the intensity of the carbonyl absorption peak of the sample in this example decreased significantly, indicating a decrease in the degree of thermal-oxidative aging. The OIT test showed that the oxidation induction period of the sample in this example was significantly prolonged and the oxidation induction curve decreased significantly, indicating that the TPA group could effectively inhibit the aging of the sample. When the ultraviolet irradiation aging time was 168h, there was no aging crack phenomenon in the 4-methyl-1-pentene polymer sample.

[0085] Example 7

[0086] A preparation method of an anti-aging poly-α-olefin in this example includes the following steps (olefin coordination copolymerization using Cat.1 catalyst):

[0087] Using a Schlenk experimental device, and maintaining a vacuum of -101.325 KPa, 30 mL of toluene solution and 2 mL (concentration of 0.25 mol / L) of toluene solution of 11-carbazol-1-undecene were added; then, 1 atm of butene gas was introduced and stirred for 5 min; after stabilization, a total of 10 mL of toluene solution of triisobutylaluminum and Cat.1 catalyst was added (the molar ratio of triisobutylaluminum to Cat.1 catalyst was 3000:1, and the concentration of triisobutylaluminum in the toluene solution was 1.5 mol / L), and the reaction was stirred at 600 rpm for 10 min; after the polymerization was completed, 0.1 mL of ethanol was injected to terminate the polymerization. Finally, the reaction solution was gradually poured dropwise into a beaker containing 300 mL of ethanol / 37 wt% hydrochloric acid (volume ratio 100:1) for sedimentation, and then obtained butene polymer through filtration, washing, and vacuum drying, pending subsequent characterization.

[0088] The above-obtained butene polymer was subjected to NMR and DSC tests. The test results showed that the insertion rate of the butene polymer polymerized in this example was 0.45%, and the copolymerization activity was 65.4×10 5 g polymer ·mol Cat. -1·h -1 with a weight-average molecular weight of 37.6×10 4 g / mol and a PDI of 2.7, indicating that the obtained butene polymer has obvious insertion characteristics of 11-carbazole-1-undecene. The specific data are shown in Table 1.

[0089] The polymers were subjected to accelerated thermal-oxidative aging treatment for different times (24 h, 72 h, 120 h, 168 h, 336 h, 504 h) and accelerated ultraviolet aging treatment for different times (24 h, 48 h, 72 h, 96 h, 120 h, 168 h) for subsequent characterization.

[0090] The butene polymers after the above aging treatment were photographed to observe the changes in surface morphology. The test results showed that when the thermal-oxidative aging time was 504 h, no cracks appeared in the butene polymer samples, indicating that the samples did not age at this time. FT-IR test showed that the intensity of the carbonyl absorption peak of the samples in this example decreased significantly, indicating a decrease in the degree of thermal-oxidative aging. OIT test showed that the oxidation induction period of the samples in this example was significantly extended and the oxidation induction curve decreased significantly, indicating that the Cz group could effectively inhibit the aging of the samples. When the ultraviolet irradiation aging time was 168 h, no aging crack phenomenon appeared in the butene polymer samples.

[0091] Example 8

[0092] A preparation method of an anti-aging poly-α-olefin in this example includes the following steps (olefin coordination copolymerization using Cat.1 catalyst):

[0093] Using a Schlenk experimental device, and maintaining a vacuum of -101.325 KPa, 30 mL of toluene solution and 2 mL (concentration of 0.5 mol / L) of toluene solution of 11-carbazole-1-undecene were added; then, 1 atm of butene gas was introduced and stirred for 5 min; after stabilization, a total of 10 mL of toluene solution of triisobutylaluminum and Cat.1 catalyst were added (the molar ratio of triisobutylaluminum to Cat.1 catalyst was 3000:1, and the concentration of triisobutylaluminum in the toluene solution was 1.5 mol / L), and the reaction was stirred at 600 rpm for 10 min; after the polymerization was completed, 0.1 mL of ethanol was injected to terminate the polymerization. Finally, the reaction solution was gradually poured into a beaker containing 300 mL of ethanol / 37 wt% hydrochloric acid (volume ratio 100:1) for precipitation, and then obtained the butene polymer after filtration, washing, and vacuum drying for subsequent characterization.

[0094] The obtained butene polymer was subjected to NMR and DSC tests. The test results showed that the insertion rate of the butene polymer polymerized in this example was 1.11%, and the copolymerization activity was 63.5×10 5 g polymer ·molCat. -1 ·h -1 , the weight-average molecular weight is 34.2×10 4 g / mol, and the PDI is 2.6, indicating that the obtained butene polymer has obvious high insertion characteristics of 11-carbazole-1-undecene. The specific data are shown in Table 1.

[0095] The polymers were subjected to accelerated thermal-oxidative aging treatment for different times (24 h, 72 h, 120 h, 168 h, 336 h, 504 h) and accelerated ultraviolet aging treatment for different times (24 h, 48 h, 72 h, 96 h, 120 h, 168 h), and then waited for subsequent characterization.

[0096] The butene polymers after the above aging treatments were photographed to observe the changes in surface morphology. The test results showed that when the thermal-oxidative aging time was 504 h, there were no cracks in the samples of the butene polymer, indicating that the samples did not age at this time. FT-IR test showed that the intensity of the carbonyl absorption peak of the samples in this example decreased significantly, indicating a decrease in the degree of thermal-oxidative aging. OIT test showed that the oxidation induction period of the samples in this example was significantly prolonged and the oxidation induction curve decreased significantly, indicating that the Cz group could effectively inhibit the aging of the samples. When the ultraviolet irradiation aging time was 168 h, there was no aging crack phenomenon in the samples of the butene polymer.

[0097] Example 9

[0098] A preparation method of an anti-aging poly-α-olefin in this example includes the following steps (olefin coordination copolymerization using Cat.1 catalyst):

[0099] Using a Schlenk experimental device, and maintaining a vacuum of -101.325 KPa, 30 mL of toluene solution and 2 mL (concentration of 0.75 mol / L) of toluene solution of 11-carbazole-1-undecene were added; then, 1 atm of butene gas was introduced and stirred for 5 min; after stabilization, a total of 10 mL of toluene solution of triisobutylaluminum and Cat.1 catalyst were added (the molar ratio of triisobutylaluminum to Cat.1 catalyst was 3000:1, and the concentration of triisobutylaluminum in the toluene solution was 1.5 mol / L), and the reaction was stirred at 600 rpm for 10 min; after the polymerization was completed, 0.1 mL of ethanol was injected to terminate the polymerization. Finally, the reaction solution was gradually poured dropwise into a beaker containing 300 mL of ethanol / 37 wt% hydrochloric acid (volume ratio 100:1) for sedimentation, and then obtained the butene polymer after filtration, washing, and vacuum drying, and waited for subsequent characterization.

[0100] The above-obtained butene polymer was subjected to NMR and DSC tests. The test results showed that the insertion rate of the butene polymer polymerized in this example was 1.67%, and the copolymerization activity was 60.7×105 g polymer ·mol Cat. -1 ·h -1 , the weight-average molecular weight is 23.2×10 4 g / mol, and the PDI is 2.1, indicating that the obtained butene polymer has obvious high insertion characteristics of 11-carbazole-1-undecene. The specific data are shown in Table 1.

[0101] The polymers were respectively subjected to accelerated thermal-oxidative aging treatment for different times (24 h, 72 h, 120 h, 168 h, 336 h, 504 h) and accelerated ultraviolet aging treatment for different times (24 h, 48 h, 72 h, 96 h, 120 h, 168 h), and waited for subsequent characterization.

[0102] The butene polymers after the above aging treatment were photographed to observe the changes in surface morphology. The test results showed that when the thermal-oxidative aging time was 504 h, no cracks appeared in the samples of the butene polymer, indicating that the samples did not age at this time. FT-IR test showed that the intensity of the carbonyl absorption peak of the samples in this example decreased significantly, indicating a decrease in the degree of thermal-oxidative aging. The OIT test showed that the oxidation induction period of the samples in this example was significantly prolonged and the oxidation induction curve decreased significantly, indicating that the Cz group could effectively inhibit the aging of the samples. When the ultraviolet irradiation aging time was 168 h, no aging crack phenomenon appeared in the samples of the butene polymer.

[0103] Example 10

[0104] In this example, a preparation method of an anti-aging poly-α-olefin includes the following steps (olefin coordination copolymerization using Cat.2 catalyst):

[0105] Using a Schlenk experimental device, and maintaining a vacuum of -101.325 KPa, 30 mL of toluene solution and 2 mL of toluene solution of 11-carbazole-1-undecene (concentration of 0.25 mol / L) were added; then, 25 mmol of 4-methyl-1-pentene was added and stirred for 5 min; after stabilization, a total of 10 mL of toluene solution of triisobutylaluminum and Cat.2 catalyst were added (the molar ratio of triisobutylaluminum to Cat.2 catalyst was 3000:1, and the concentration of triisobutylaluminum in the toluene solution was 1.5 mol / L), and the reaction was stirred at 600 rpm for 10 min; after the polymerization was completed, 0.1 mL of ethanol was injected to terminate the polymerization. Finally, the reaction solution was slowly poured dropwise into a beaker containing 300 mL of ethanol / 37 wt% hydrochloric acid (volume ratio 100:1) for sedimentation, and then obtained 4-methyl-1-pentene polymer after filtration, washing, and vacuum drying, and waited for subsequent characterization.

[0106] The obtained 4-methyl-1-pentene polymer was subjected to NMR and DSC tests. The test results showed that the insertion rate of 11-carbazol-1-undecene in the 4-methyl-1-pentene polymer polymerized in this example was 0.70%, the copolymerization conversion rate was 72.7%, and the weight-average molecular weight was 11.9×10 4 g / mol, and the PDI was 2.4, indicating that the obtained 4-methyl-1-pentene polymer had the insertion characteristics of 11-carbazol-1-undecene. The specific data are shown in Table 1.

[0107] The polymers were respectively subjected to accelerated thermal-oxidative aging treatment for different times (24 h, 72 h, 120 h, 168 h, 336 h, 504 h) and accelerated ultraviolet aging treatment for different times (24 h, 48 h, 72 h, 96 h, 120 h, 168 h) for subsequent characterization.

[0108] The 4-methyl-1-pentene polymer subjected to the above aging treatment was photographed to observe the change in surface morphology. The test results showed that when the thermal-oxidative aging time was 504 h, there were no cracks in the sample of the 4-methyl-1-pentene polymer, indicating that the sample did not age at this time. FT-IR( Figure 5 ) test showed that the intensity of the carbonyl absorption peak of the sample in this example decreased significantly, indicating a decrease in the degree of thermal-oxidative aging. The OIT test showed that the oxidation induction period of the sample in this example was significantly prolonged and the oxidation induction curve decreased significantly, indicating that the Cz group could effectively inhibit the aging of the sample. When the ultraviolet irradiation aging time was 168 h, there was no aging crack phenomenon in the sample of the 4-methyl-1-pentene polymer.

[0109] Example 11

[0110] A preparation method of an anti-aging poly-α-olefin in this example includes the following steps (olefin coordination copolymerization using Cat.2 catalyst):

[0111] Using a Schlenk experimental apparatus and maintaining a vacuum of -101.325 KPa, 30 mL of toluene solution and 2 mL of toluene solution of 11-carbazole-1-undecene (concentration 0.5 mol / L) were added; then, 25 mmol of 4-methyl-1-pentene was added and stirred for 5 min; after stabilization, a total of 10 mL of toluene solution of triisobutylaluminum and Cat.2 catalyst (molar ratio of triisobutylaluminum to Cat.2 catalyst was 3000:1, and the concentration of triisobutylaluminum in the toluene solution was 1.5 mol / L) was added, and the reaction was stirred at 600 rpm for 10 min; after the polymerization ended, 0.1 mL of ethanol was injected to terminate the polymerization. Finally, the reaction solution was gradually poured dropwise into a beaker containing 300 mL of ethanol / 37 wt% hydrochloric acid (volume ratio 100:1) for sedimentation, and then obtained 4-methyl-1-pentene polymer through filtration, washing, and vacuum drying, awaiting subsequent characterization.

[0112] The obtained 4-methyl-1-pentene polymer was subjected to NMR and DSC tests. The test results showed that the insertion rate of 11-carbazole-1-undecene in the 4-methyl-1-pentene polymer polymerized in this example was 1.20%, the copolymerization conversion rate was 77.3%, the weight-average molecular weight was 10.3×10 4 g / mol, and the PDI was 2.4, indicating that the obtained 4-methyl-1-pentene polymer had the characteristic of a high insertion rate. The specific data are shown in Table 1.

[0113] The polymer was subjected to accelerated thermal-oxidative aging treatment for different times (24 h, 72 h, 120 h, 168 h, 336 h, 504 h) and accelerated ultraviolet aging treatment for different times (24 h, 48 h, 72 h, 96 h, 120 h, 168 h), awaiting subsequent characterization.

[0114] The aged 4-methyl-1-pentene polymer was photographed to observe the change in surface morphology. The test results showed that when the thermal-oxidative aging time was 504 h, there were no cracks in the sample of 4-methyl-1-pentene polymer, indicating that the sample did not age at this time. FT-IR ( Figure 5 ) test showed that the intensity of the carbonyl absorption peak of the sample in this example decreased significantly, indicating a decrease in the degree of thermal-oxidative aging. The OIT test showed that the oxidation induction period of the sample in this example was significantly extended and the oxidation induction curve decreased significantly, indicating that the Cz group could effectively inhibit the aging of the sample. When the ultraviolet irradiation aging time was 168 h, there was no aging crack phenomenon in the sample of 4-methyl-1-pentene polymer.

[0115] Example 12

[0116] The preparation method of an anti-aging poly-α-olefin in this example includes the following steps (olefin coordination copolymerization using Cat.2 catalyst):

[0117] Using a Schlenk experimental setup and maintaining a vacuum of -101.325 KPa, 30 mL of toluene solution and 2 mL of toluene solution of 11-carbazole-1-undecene (concentration 0.75 mol / L) were added; then, 25 mmol of 4-methyl-1-pentene was added and stirred for 5 min; after stabilization, a total of 10 mL of toluene solution of triisobutylaluminum and Cat.2 catalyst were added (the molar ratio of triisobutylaluminum to Cat.2 catalyst was 3000:1, and the concentration of triisobutylaluminum in the toluene solution was 1.5 mol / L), and the mixture was stirred and reacted for 10 min under the action of 600 rpm; after the polymerization ended, 0.1 mL of ethanol was injected to terminate the polymerization. Finally, the reaction solution was gradually poured dropwise into a beaker containing 300 mL of ethanol / 37 wt% hydrochloric acid (volume ratio 100:1) for sedimentation, and then obtained 4-methyl-1-pentene polymer through filtration, washing, and vacuum drying, to be characterized later.

[0118] The 4-methyl-1-pentene polymer obtained above was subjected to NMR and DSC tests. The test results showed that the insertion rate of 11-carbazole-1-undecene in the 4-methyl-1-pentene polymer polymerized in this example was 1.90%, the copolymerization conversion rate was 83.1%, the weight-average molecular weight was 7.9×10 4 g / mol, and the PDI was 2.9, indicating that the obtained 4-methyl-1-pentene polymer had the characteristic of a high insertion rate. The specific data are shown in Table 1.

[0119] The polymers were respectively subjected to accelerated thermal-oxidative aging treatment for different times (24 h, 72 h, 120 h, 168 h, 336 h, 504 h) and accelerated ultraviolet aging treatment for different times (24 h, 48 h, 72 h, 96 h, 120 h, 168 h), to be characterized later.

[0120] The 4-methyl-1-pentene polymer after the above aging treatment was photographed to observe the change in surface morphology. The test results showed that when the thermal-oxidative aging time was 504 h, there were no cracks in the sample of the 4-methyl-1-pentene polymer, indicating that the sample did not age at this time. FT-IR( Figure 5 ) test showed that the intensity of the carbonyl absorption peak of the sample in this example decreased significantly, indicating a decrease in the degree of thermal-oxidative aging. The OIT test showed that the oxidation induction period of the sample in this example was significantly prolonged and the oxidation induction curve decreased significantly, indicating that the Cz group could effectively inhibit the aging of the sample. When the ultraviolet irradiation aging time was 168 h, there was no aging crack phenomenon in the sample of the 4-methyl-1-pentene polymer.

[0121] Example 13

[0122] In this embodiment, a preparation method of an anti-aging poly-α-olefin includes the following steps (olefin coordination copolymerization using Cat.5 catalyst):

[0123] Using a Schlenk experimental device, and maintaining a vacuum of -101.325 KPa, add 30 mL of toluene solution and 2 mL (concentration of 1.75 mol / L) of toluene solution of 4-(7-octenyl)diphenylamine; then, introduce 1 atm of butene gas and stir for 5 min; after stabilization, add a total of 10 mL of toluene solutions of triisobutylaluminum and Cat.5 catalyst (the molar ratio of triisobutylaluminum to Cat.5 catalyst is 3000:1, and the concentration of triisobutylaluminum in the toluene solution is 1.5 mol / L), and stir and react for 10 min under the action of 600 rpm; after the polymerization is completed, inject 0.1 mL of ethanol to terminate the polymerization. Finally, slowly pour the reaction solution drop by drop into a beaker containing 300 mL of ethanol / 37 wt% hydrochloric acid (volume ratio 100:1) for sedimentation, and then obtain butene polymer through filtration, washing, and vacuum drying.

[0124] The butene polymer obtained above is subjected to NMR and DSC tests. The test results show that the insertion rate of 4-(7-octenyl)diphenylamine in the butene polymer polymerized in this embodiment is 1.97%, and the copolymerization activity is 73.7×10 5 g polymer ·mol Cat. -1 ·h -1 , the weight-average molecular weight is 18.3×10 4 g / mol, and the PDI is 2.7, indicating that the obtained butene polymer has obvious 4-(7-octenyl)diphenylamine insertion characteristics. The specific data are shown in Table 1.

[0125] Mix the butene polymer and BEAULON TM product (purchased from Mitsui Chemicals, Japan) in a mixer for 5 min according to a mass ratio of 5:95, and directly extrude it into an injection molding machine to prepare anti-aging butene blend samples. The blends are respectively subjected to accelerated thermal-oxidative aging treatment for different times (24 h, 72 h, 120 h, 168 h, 336 h, 504 h) and accelerated ultraviolet aging treatment for different times (24 h, 48 h, 72 h, 96 h, 120 h, 168 h) for subsequent characterization.

[0126] The blend after the above aging treatment was photographed to observe the change in surface morphology. The test results showed that when the thermo-oxidative aging time was 504 h, no cracks appeared in the sample, indicating that the sample did not age at this time. FT-IR test showed that the intensity of the carbonyl absorption peak of the sample in this example decreased significantly, indicating a reduction in the degree of thermo-oxidative aging. OIT test showed that the oxidation induction period of the sample in this example was significantly prolonged and the oxidation induction curve decreased significantly, indicating that the TPA group could effectively inhibit the aging of the sample. When the ultraviolet irradiation aging time was 168 h, no aging crack phenomenon occurred in the sample( Figure 6 ).

[0127] Example 14

[0128] The preparation method of an anti-aging poly-α-olefin in this example includes the following steps (olefin coordination copolymerization using Cat.8 catalyst):

[0129] Using a Schlenk experimental device and maintaining a vacuum of -101.325 KPa, 30 mL of toluene solution and 2 mL (concentration of 0.75 mol / L) of toluene solution of 4-(7-octenyl)diphenylamine were added; then, 25 mmol of 4-methyl-1-pentene was added and stirred for 5 min; after stabilization, a total of 10 mL of toluene solution of triisobutylaluminum and Cat.8 catalyst were added (the molar ratio of triisobutylaluminum to Cat.8 catalyst was 3000:1, and the concentration of triisobutylaluminum in the toluene solution was 1.5 mol / L), and the reaction was stirred at 600 rpm for 10 min; after the polymerization was completed, 0.1 mL of ethanol was injected to terminate the polymerization. Finally, the reaction solution was gradually poured dropwise into a beaker containing 300 mL of ethanol / 37 wt% hydrochloric acid (volume ratio 100:1) for sedimentation, and then obtained 4-methyl-1-pentene polymer through filtration, washing, and vacuum drying.

[0130] The obtained 4-methyl-1-pentene polymer was subjected to NMR and DSC tests. The test results showed that the insertion rate of 4-(7-octenyl)diphenylamine in the 4-methyl-1-pentene polymer polymerized in this example was 9.20%, the copolymerization conversion rate was 82.7%, the weight-average molecular weight was 9.5×10 4 g / mol, and the PDI was 2.4, indicating that the obtained 4-methyl-1-pentene polymer had the characteristics of a high insertion rate. The specific data is shown in Table 1.

[0131] The 4-methyl-1-pentene polymer and TPX MX002 product (purchased from Mitsui Chemicals, Japan) were blended in a mixer for 5 min at a mass ratio of 2:98, and then directly extruded into an injection molding machine to prepare 4-methyl-1-pentene blend splines. The blends were subjected to accelerated thermal-oxidative aging treatment for different times (24 h, 72 h, 120 h, 168 h, 336 h, 504 h) and accelerated ultraviolet aging treatment for different times (24 h, 48 h, 72 h, 96 h, 120 h, 168 h) for subsequent characterization.

[0132] The blends after the above aging treatments were photographed to observe the surface morphology changes. The test results showed that when the thermal-oxidative aging time was 504 h, no cracks appeared in the samples of the 4-methyl-1-pentene blend, indicating that the samples did not age at this time. FT-IR test showed that the intensity of the carbonyl absorption peak of the samples in this example decreased significantly, indicating a decrease in the degree of thermal-oxidative aging. OIT test showed that the oxidation induction period of the samples in this example was significantly prolonged and the oxidation induction curve decreased significantly, indicating that the TPA group could effectively inhibit the aging of the samples. When the ultraviolet irradiation aging time was 168 h, no aging crack phenomenon appeared in the samples of the 4-methyl-1-pentene blend.

[0133] Example 15

[0134] A preparation method of an anti-aging poly-α-olefin in this example includes the following steps (olefin coordination copolymerization using Cat.9 catalyst):

[0135] Using a Schlenk experimental device and maintaining a vacuum of -101.325 KPa, 30 mL of toluene solution and 2 mL (concentration of 1.75 mol / L) of toluene solution of 11-carbazol-1-undecene were added; then, 1 atm of butene gas was introduced and stirred for 5 min; after stabilization, a total of 10 mL of toluene solution of triisobutylaluminum and Cat.9 catalyst were added (the molar ratio of triisobutylaluminum to Cat.9 catalyst was 3000:1, and the concentration of triisobutylaluminum in the toluene solution was 1.5 mol / L), and the reaction was stirred at 600 rpm for 10 min; after the polymerization was completed, 0.1 mL of ethanol was injected to terminate the polymerization. Finally, the reaction solution was gradually poured dropwise into a beaker containing 300 mL of ethanol / 37 wt% hydrochloric acid (volume ratio 100:1) for sedimentation, and then obtained butene polymer after filtration, washing, and vacuum drying.

[0136] The obtained butene polymer was subjected to NMR and DSC tests. The test results showed that the insertion rate of the butene polymer polymerized in this example was 1.66%, and the copolymerization activity was 59.3×10 5 g polymer ·mol Cat. -1 ·h-1 , with a weight-average molecular weight of 17.7×10 4 g / mol and a PDI of 2.5, indicating that the obtained butene polymer has an obvious high insertion characteristic of 11-carbazole-1-undecene. The specific data are shown in Table 1.

[0137] The butene polymer and BEAULON TM product (purchased from Mitsui Chemicals, Japan) were blended in a mixer for 5 min according to a mass ratio of 10:90, and then directly extruded into an injection molding machine to prepare an anti-aging butene blend sample. The blend was subjected to accelerated thermal-oxidative aging treatment for different times (24 h, 72 h, 120 h, 168 h, 336 h, 504 h) and accelerated ultraviolet aging treatment for different times (24 h, 48 h, 72 h, 96 h, 120 h, 168 h) for subsequent characterization.

[0138] The aged butene blend was photographed to observe the change in surface morphology. The test results showed that when the thermal-oxidative aging time was 504 h, no cracks appeared in the butene blend sample, indicating that no aging occurred at this time. FT-IR test showed that the intensity of the carbonyl absorption peak of the sample in this example decreased significantly, indicating a decrease in the degree of thermal-oxidative aging. OIT test showed that the oxidation induction period of the sample in this example was significantly extended and the oxidation induction curve decreased significantly, indicating that the Cz group could effectively inhibit the aging of the sample. When the ultraviolet irradiation aging time was 168 h, no aging crack phenomenon occurred in the butene polymer sample ( Figure 6 ).

[0139] Example 16

[0140] A method for preparing an anti-aging poly-α-olefin in this example includes the following steps (olefin coordination copolymerization using Cat.10 catalyst):

[0141] Using a Schlenk experimental device and maintaining a vacuum of -101.325 KPa, 30 mL of toluene solution and 2 mL (concentration of 0.75 mol / L) of toluene solution of 11-carbazole-1-undecene were added; then, 25 mmol of 4-methyl-1-pentene was added and stirred for 5 min; after stabilization, a total of 10 mL of toluene solution of triisobutylaluminum and Cat.10 catalyst were added (the molar ratio of triisobutylaluminum to Cat.10 catalyst was 3000:1, and the concentration of triisobutylaluminum in the toluene solution was 1.5 mol / L), and the reaction was stirred at 600 rpm for 10 min; after the polymerization was completed, 0.1 mL of ethanol was injected to terminate the polymerization. Finally, the reaction solution was slowly poured dropwise into a beaker containing 300 mL of ethanol / 37 wt% hydrochloric acid (volume ratio 100:1) for sedimentation, and then obtained 4-methyl-1-pentene polymer through filtration, washing, and vacuum drying.

[0142] The obtained 4-methyl-1-pentene polymer was subjected to NMR and DSC tests. The test results showed that the insertion rate of 11-carbazole-1-undecene in the 4-methyl-1-pentene polymer polymerized in this example was 8.80%, the copolymerization conversion rate was 86.8%, the weight-average molecular weight was 10.3×10 4 g / mol, and the PDI was 2.9, indicating that the obtained 4-methyl-1-pentene polymer had the characteristic of a high insertion rate. The specific data are shown in Table 1.

[0143] The 4-methyl-1-pentene polymer and the TPX MX002 product (purchased from Mitsui Chemicals, Japan) were blended in a mixer for 5 min according to a mass ratio of 10:90, and then directly extruded into an injection molding machine to prepare 4-methyl-1-pentene blend splines. The blends were subjected to accelerated thermal-oxidative aging treatment for different times (24 h, 72 h, 120 h, 168 h, 336 h, 504 h) and accelerated ultraviolet aging treatment for different times (24 h, 48 h, 72 h, 96 h, 120 h, 168 h) for subsequent characterization.

[0144] The blends subjected to the above aging treatments were photographed to observe the changes in surface morphology. The test results showed that when the thermal-oxidative aging time was 504 h, no cracks appeared in the samples of the 4-methyl-1-pentene blend, indicating that the samples did not age at this time. FT-IR test showed that the intensity of the carbonyl absorption peak of the samples in this example decreased significantly, indicating a decrease in the degree of thermal-oxidative aging. The OIT test showed that the oxidation induction period of the samples in this example was significantly prolonged and the oxidation induction curve decreased significantly, indicating that the Cz group could effectively inhibit the aging of the samples. When the ultraviolet irradiation aging time was 168 h, no aging crack phenomenon appeared in the samples of the 4-methyl-1-pentene blend.

[0145] Example 17

[0146] In this example, a method for preparing an anti-aging poly-α-olefin includes the following steps (olefin coordination copolymerization using Cat.1 catalyst):

[0147] Using a Schlenk experimental setup and maintaining a vacuum of -101.325 KPa, 30 mL of toluene solution and 2 mL of toluene solution of 4-(7-octenyl)-2,6-diisopropylphenol (with a concentration of 0.75 mol / L) were added; then, 1 atm of propylene gas was introduced and stirred for 5 min; after stabilization, a total of 10 mL of toluene solution of triisobutylaluminum and Cat.1 catalyst were added (the molar ratio of triisobutylaluminum to Cat.1 catalyst was 3000:1, and the concentration of triisobutylaluminum in the toluene solution was 1.5 mol / L), and the reaction was stirred at 600 rpm for 10 min; after the polymerization ended, 0.1 mL of ethanol was injected to terminate the polymerization. Finally, the reaction solution was slowly poured dropwise into a beaker containing 300 mL of ethanol / 37 wt% hydrochloric acid (volume ratio 100:1) for precipitation, and then obtained the propylene polymer through filtration, washing, and vacuum drying for subsequent characterization.

[0148] The obtained propylene polymer was subjected to NMR and DSC tests. The test results showed that the insertion rate of the propylene polymer obtained in this example was 2.10%, and the copolymerization activity was 72.5×10 5 g polymer ·mol Cat. -1 ·h -1 , the weight-average molecular weight was 12.3×10 4 g / mol, and the PDI was 2.1, indicating that the obtained propylene polymer had obvious high-insertion characteristics of 4-(7-octenyl)-2,6-diisopropylphenol. The specific data are shown in Table 1.

[0149] The propylene polymer and Prime Polypro TM product (purchased from Mitsui Chemicals, Japan) were blended in a mixer for 5 min according to a mass ratio of 10:90, and directly extruded into an injection molding machine to prepare propylene blend splines. The blends were subjected to accelerated thermal-oxidative aging treatment for different times (24 h, 72 h, 120 h, 168 h, 336 h, 504 h) and accelerated ultraviolet aging treatment for different times (24 h, 48 h, 72 h, 96 h, 120 h, 168 h) for subsequent characterization

[0150] The above-aged propylene blends were photographed to observe the surface morphology changes. The test results showed that when the thermal-oxidative aging time was 504 h, the samples of the propylene blends did not show cracks, indicating that the samples did not age at this time. FT-IR test showed that the intensity of the carbonyl absorption peak of the samples in this example decreased significantly, indicating a reduced degree of thermal-oxidative aging. OIT test showed that the oxidation induction period of the samples in this example was significantly prolonged and the oxidation induction curve decreased significantly, indicating that the BHT group could effectively inhibit the aging of the samples. When the ultraviolet irradiation aging time was 168 h, the samples of the propylene blends did not show aging crack phenomena.

[0151] Example 18

[0152] In this example, a method for preparing an anti-aging poly-α-olefin includes the following steps (olefin coordination copolymerization using Cat.1 catalyst):

[0153] Using a Schlenk experimental device, and maintaining a vacuum of -101.325 KPa, add 30 mL of toluene solution and 2 mL (concentration of 0.75 mol / L) of toluene solution of 4-(7-octenyl)-2,2,6,6-tetramethylpiperidine; then, introduce 1 atm of butene gas and stir for 5 min; after stabilization, add a total of 10 mL of toluene solutions of triisobutylaluminum and Cat.1 catalyst (the molar ratio of triisobutylaluminum to Cat.1 catalyst is 3000:1, and the concentration of triisobutylaluminum in the toluene solution is 1.5 mol / L), and stir and react for 10 min under the action of 600 rpm; after the polymerization is completed, inject 0.1 mL of ethanol to terminate the polymerization. Finally, slowly pour the reaction solution dropwise into a beaker containing 300 mL of ethanol / 37 wt% hydrochloric acid (volume ratio 100:1) for sedimentation, and then obtain the butene polymer through filtration, washing, and vacuum drying for subsequent characterization.

[0154] The above-obtained butene polymer was subjected to NMR and DSC tests. The test results showed that the insertion rate of the butene polymer polymerized in this example was 2.60%, and the copolymerization activity was 63.7×10 5 g polymer ·mol Cat. -1 ·h -1 , the weight-average molecular weight was 11.7×10 4 g / mol, and the PDI was 2.7, indicating that the obtained butene polymer had obvious high-insertion characteristics of 4-(7-octenyl)-2,2,6,6-tetramethylpiperidine. The specific data are shown in Table 1.

[0155] The polymers were respectively subjected to accelerated thermal-oxidative aging treatment for different times (24 h, 72 h, 120 h, 168 h, 336 h, 504 h) and accelerated ultraviolet aging treatment for different times (24 h, 48 h, 72 h, 96 h, 120 h, 168 h) for subsequent characterization.

[0156] The above-aged butene polymer was photographed to observe the changes in surface morphology. The test results showed that when the thermo-oxidative aging time was 504 h, no cracks appeared in the butene polymer sample, indicating that the sample did not age at this time. FT-IR test showed that the intensity of the carbonyl absorption peak of the sample in this example decreased significantly, indicating a decrease in the degree of thermo-oxidative aging. The OIT test showed that the oxidation induction period of the sample in this example was significantly prolonged and the oxidation induction curve decreased significantly, indicating that the TMP group could effectively inhibit the aging of the sample. When the ultraviolet irradiation aging time was 168 h, no aging crack phenomenon appeared in the butene polymer sample.

[0157] Table 1 Performance data of the α-olefin polymers prepared in Examples 1-18 a

[0158]

[0159] Note: a: Reaction conditions: Cat. = 3-10 μmol, [B] / Hf = 100-500, temperature = 25-60 °C; b: Addition amount of the amino-functional monomer; c: Measured by high-temperature GPC; d: Calculated by 13C NMR; e: Measured by DSC; f: Calculated by polymerization activity; g: Copolymerization conversion rate.

[0160] From the data in Table 1, it can be seen that as the insertion rate of the amino group increases (compared with Examples 1, 2, and 3), the molecular weight distribution of the polymer gradually narrows. This may be because the addition of the comonomer inhibits the transfer of active centers to a certain extent. However, through relevant characterizations, it can be seen that the introduction of the amino monomer can effectively inhibit the aging behavior. Through Figure 2 and Figure 3 it can be seen that the blended product also has obvious anti-aging performance.

[0161] The preparation method of the olefin polymer with excellent anti-aging performance provided by the present invention broadens the wide application of olefin polymers in multiple fields and has very important practical significance.

[0162] The above are only the preferred embodiments of the present invention. It should be noted that for those of ordinary skill in the art, without departing from the principle of the present invention, several improvements and refinements can be made, and these improvements and refinements should also be regarded as the protection scope of the present invention.

Claims

1. A method for preparing an anti-aging poly-α-olefin, characterized in that: The following steps are involved: After mixing the copolymerizable functional monomer with the hydrocarbon compound to obtain a mixed solution, an α-olefin compound is introduced into the mixed solution, and then a co-catalyst and a catalyst are added in sequence to perform a polymerization reaction to obtain the anti-aging polyα-olefin; The copolymer functional monomers include 4-(2-propenyl)diphenylaniline, 4-(3-butenyl)diphenylaniline, 4-(4-pentenyl)diphenylaniline, 4-(5-hexenyl)diphenylaniline, 4-(6-heptenyl)diphenylaniline, 4-(7-octenyl)diphenylaniline, 3-carbazole-1-propene, 4-carbazole-1-butene, 5-carbazole-1-pentene, 6-carbazole-1-hexene, 7-carbazole-1-heptene, 8-carbazole-1-octene, 9-carbazole-1-nonene, 10-carbazole-1-decene, 11-carbazole-1-undecene, 4-(2-propenyl)-2,6-diisopropylphenol, 4-(3-butenyl)-2,6-diisopropylphenol, 4-(4-pentenyl)-2,6-diisopropylphenol, 4-(5-hexenyl)-2,6-diisopropylphenol, 4-(6-heptenyl)-2,6-diisopropylphenol, 4- (7-octenyl)-2,6-diisopropylphenol, 4-(8-nonenyl)-2,6-diisopropylphenol, 4-(9-decenyl)-2,6-diisopropylphenol, 4-(10-undecenyl)-2,6-diisopropylphenol, 4-(2-propenyl)-2,2,6,6-tetramethylpiperidine, 4-(3-butenyl)-2,2,6,6-tetramethylpiperidine, 4-(4-pentenyl)-2,2,6,6-tetramethylpiperidine methylpiperidine, 4-(5-hexenyl)-2,2,6,6-tetramethylpiperidine, 4-(6-heptenyl)-2,2,6,6-tetramethylpiperidine, 4-(7-octenyl)-2,2,6,6-tetramethylpiperidine, 4-(8-nonenyl)-2,2,6,6-tetramethylpiperidine, 4-(9-decenyl)-2,2,6,6-tetramethylpiperidine or 4-(10-undecenyl)-2,2,6,6-tetramethylpiperidine; The α-olefin compound is butene or 4-methyl-1-pentene; The structural formula of the catalyst is shown in Formula III, Formula IV, Formula V, Formula VI or Formula VII: Formula III, Formula IV, Formula V, Formula VI, Formula VII; Wherein, in formula III, R1=2- i Pr-Ph, t Bu or CH3, R2=H or CH3; in formula V, R3=R4=CH3 or Ph, R5=CH3 or tBu; The co-catalyst is an alkyl aluminum; The molar ratio of the catalyst to the co-catalyst is 100:1 to 3000:1; The anti-aging poly-α-olefin has a structural formula shown in Formula I or Formula II: ， ， Formula I Formula II; Among them, R is selected from ; The value range of n is 1~7.

2. The method for preparing anti-aging poly-α-olefin according to claim 1, characterized in that: The hydrocarbon compound includes at least one of toluene and its homologues, naphthalene and its homologues, alkanes and its homologues, and cycloalkanes and its homologues.

3. The method for preparing anti-aging poly-α-olefin according to claim 1, characterized in that: The molar concentration of the copolymerizable functional monomer in the mixed solution is 1.0-0.01 mol / L.

4. The method for preparing anti-aging poly-α-olefin according to claim 1, characterized in that: The polymerization reaction temperature is 25-120° C. and the reaction time is 10-120 min.

5. The method for preparing anti-aging poly-α-olefin according to claim 1, characterized in that: After the polymerization reaction is completed, the step of separating the product is also included.

6. An anti-aging polymer blend material, characterized in that: The raw materials include the anti-aging poly-α-olefin and polymer as claimed in claim 1.

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