Vinyl polar polyolefin elastomer as well as preparation method and application thereof

Abstract

The invention provides a vinyl polar polyolefin elastomer as well as a preparation method and application thereof, and belongs to the technical field of functional polymer polyolefin materials. Wherein the vinyl polar polyolefin elastomer is a ternary random copolymer formed by copolymerizing a CH2 = CH2 monomer, a CH2 = CH-(CH2) n-CH3 monomer and a CH2 = CH-(CH2) m-X polar monomer or an acidified product of the ternary random copolymer; wherein the ternary random copolymer has a general formula structure shown as a formula (1): # imgabs0 # formula (1), n is an integer of 1-8, m is an integer of 0-10, and y represents the degree of polymerization and is 50-20000; # imgabs 1 # represents an interval symbol between the monomers; x is selected from at least one of-F,-Cl,-Br,-I,-CN,-C (= O) O-CH3, # imgabs2 # or # imgabs3 #, R1, R2 and R3 are respectively and independently selected from any one of C1-C16 alkyl and C1-C16 alkyl substituted phenyl, and at least one of R1, R2 and R3 is selected from C1-C16 alkyl; the acidified product has a general formula structure as shown in a formula (2): # imgabs4 #, wherein M is selected from at least one of-F,-Cl,-Br,-I,-CN,-OH,-C (= O) O-CH3 or-COOH.

Description

Technical Field

[0001] The present invention belongs to the technical field of functional polymer polyolefin materials, and in particular relates to a vinyl polar polyolefin elastomer and a preparation method and application thereof. Background Art

[0002] Polyolefins are an important class of synthetic polymers, which are widely used in life and industry due to their low cost, good chemical stability and good corrosion resistance. Polyolefin elastomers (POE) are random copolymers obtained by copolymerization of ethylene and α-olefins (such as 1-butene, 1-octene). The introduced α-olefin weakens the crystallization of the carbon-carbon main chain and forms elastic amorphous regions. Therefore, polyolefin elastomers are composed of a crystalline phase and an amorphous rubber phase, which gives the material thermoplasticity and high elasticity, and have important applications in toughened polypropylene, photovoltaic encapsulation films and other fields.

[0003] However, similar to other polyolefin materials, the non-polar properties of polyolefin elastomers limit their application in certain fields, such as toughening polar plastics. At present, the polarity is increased by introducing polar groups into polyolefin elastomers, such as introducing maleic anhydride into polyolefin elastomers through the method of blending and grafting, which can be used to toughen PA. However, blending and grafting are often accompanied by high temperature and high shear, which will cause chain scission of polyolefin elastomers and lead to performance degradation. Another method is to directly copolymerize olefins with polar monomers to obtain polar polyolefin elastomers. For example, polar linear low-density polyethylene is obtained by copolymerizing ethylene, octene and polar monomers using palladium (Pd) catalysts. Late transition metal catalysts have good tolerance for polar monomers, but poor selectivity for α-olefins; and the presence of polar comonomers significantly reduces the molecular weight of the copolymer, which is not conducive to the mechanical properties of the polymer. Therefore, it is necessary to provide a polar polyolefin elastomer material with multifunctionality, higher polymer molecular weight and better mechanical properties. Summary of the invention

[0004] In view of the above technical problems, the present disclosure provides a vinyl polar polyolefin elastomer and a preparation method and application thereof, in order to at least partially solve the above technical problems. In this regard, the technical solution provided by the present disclosure is as follows.

[0005] As a first aspect of the present disclosure, a vinyl polar polyolefin elastomer is provided, wherein the vinyl polar polyolefin elastomer is a CH2=CH2 monomer, CH2=CH-(CH2) n -CH3 monomer and CH2=CH-(CH2) m -X polar monomer copolymerization formed by terpolymer or its acidification product;

[0006] The ternary random copolymer has a general structure as shown in formula (1): Formula (1), wherein n is an integer of 1-8, m is an integer of 0-10, and y represents the degree of polymerization, which is 50-20000; represents the spacer symbol between monomers; X is selected from -F, -Cl, -Br, -I, -CN, -C(=O)O-CH3, or At least one of, R1, R2, R3 are each independently selected from C1-C 16 Alkyl, C1-C 16 Any of the alkyl-substituted phenyl groups, at least one of R1, R2, and R3 is selected from C1-C 16 alkyl;

[0007] The acidified product has the general structure shown in formula (2): Formula (2), wherein M is selected from at least one of -F, -Cl, -Br, -I, -CN, -OH, -C(=O)O-CH3 or -COOH.

[0008] As a second aspect of the present disclosure, a method for preparing a vinyl polar polyolefin elastomer is provided, comprising: converting CH2=CH-(CH2) n -CH3 monomer and CH2=CH-(CH2) m -X polar monomer, polymerization solvent, and scavenger are added into the reactor, CH2=CH2 monomer gas is introduced and the temperature is raised to the polymerization reaction temperature, and then the main catalyst and the co-catalyst are introduced to carry out polymerization reaction to obtain a ternary random copolymer; and optionally, the ternary random copolymer is acidified to obtain the above-mentioned vinyl polar polyolefin elastomer;

[0009] Wherein, n is an integer of 1-8, m is an integer of 0-10, and X is selected from -F, -Cl, -Br, -I, -CN, -C(=O)O-CH3, or At least one of, R1, R2, R3 are each independently selected from C1-C 16 Alkyl, C1-C 16 Any of the alkyl-substituted phenyl groups, at least one of R1, R2, and R3 is selected from C1-C 16 alkyl;

[0010] The main catalyst has a structure as shown in formula (3):

[0011] Formula (3), wherein R4 is selected from phenyl, C1-C4 alkyl substituted phenyl, 、N-C1-C 16 Alkyl, C1-C 16 At least one of the alkyl groups; R5 and R6 are each independently selected from Cl, C1-C16 Any one of alkyl, phenyl, and C1-C4 alkyl-substituted phenyl; R7 is selected from , , Any one of .

[0012] As a third aspect of the present disclosure, an application of a vinyl polar polyolefin elastomer is provided, and the application includes application in any field of packaging, automobile manufacturing, electrical appliance manufacturing, medical equipment, and photovoltaic film.

[0013] Based on the above technical solution, the present disclosure provides a vinyl polar polyolefin elastomer and a preparation method and application thereof, which have at least one of the following beneficial effects:

[0014] (1) In the embodiments of the present disclosure, ethylene monomer and α-olefin (CH2=CH-(CH2) n -CH3 monomer) and CH2=CH-(CH2) m -X polar monomers for copolymerization, using α-olefins to improve the mechanical and elastic properties of polymers, using CH2=CH-(CH2) m -X polar monomer is used to introduce polar functional groups into the polymer, so that the obtained ternary random copolymer or its acidified product can obtain a vinyl polar polyolefin elastomer with multifunctionality, higher polymer molecular weight and mechanical properties compared to the existing low polymer molecular weight (number average molecular weight below 100,000) copolymers.

[0015] (2) In the embodiments of the present disclosure, ethylene monomer, α-olefin (CH2=CH-(CH2) n -CH3 monomer) and CH2=CH-(CH2) m -X polar monomers, polymerization solvents, scavengers, etc. are added into the reactor, and copolymerization is carried out under relatively mild reaction conditions in the presence of specific titanium (Ti) catalysts and co-catalysts. The obtained terpolymer or its acidified product has a higher polymer molecular weight and excellent mechanical properties.

[0016] (3) In the embodiments of the present disclosure, the vinyl polar polyolefin elastomer can be applied to any field including packaging, automobile manufacturing, electrical appliance manufacturing, medical equipment, and photovoltaic film due to its high molecular weight and mechanical properties. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1 Graphs showing elongation at break and tensile strength of the vinyl polar polyolefin elastomer in Examples 1 to 5 of the present disclosure;

[0018] Figure 2This is a graph showing the test results of a 300% cyclic reciprocating test of a vinyl polar polyolefin elastomer in Example 2 of the present disclosure for ten times of fixed stretching;

[0019] Figure 3 This is a graph showing the test results of a 300% cyclic reciprocating test of a vinyl polar polyolefin elastomer in Example 4 of the present disclosure for ten times of fixed stretching;

[0020] Figure 4 This is a graph showing the test results of a 300% cyclic reciprocating test of a vinyl polar polyolefin elastomer in Example 5 of the present disclosure for ten times of fixed stretching;

[0021] Figure 5 Stress-strain curves of the blended materials in Application Example 1 and Comparative Example 1 are respectively obtained;

[0022] Figure 6 This is a scanning electron microscope (SEM) image of the blended material in Comparative Example 1;

[0023] Figure 7 This is a scanning electron microscope (SEM) image of the blended material in Application Example 1. DETAILED DESCRIPTION

[0024] Hereinafter, embodiments of the present disclosure will be described with reference to the accompanying drawings. However, it should be understood that these descriptions are exemplary only and are not intended to limit the scope of the present disclosure. In the following detailed description, for ease of explanation, many specific details are set forth to provide a comprehensive understanding of the embodiments of the present disclosure. However, it is apparent that one or more embodiments may also be implemented without these specific details. In addition, in the following description, descriptions of known structures and technologies are omitted to avoid unnecessary confusion of the concepts of the present disclosure.

[0025] The terms used herein are only for describing specific embodiments and are not intended to limit the present disclosure. The term "comprising" used herein indicates the existence of features, steps, operations, but does not exclude the existence or addition of one or more other features.

[0026] In the case of using expressions such as "at least one of A, B, and C, etc.", it should generally be interpreted in accordance with the meaning of the expression generally understood by those skilled in the art (for example, "a system having at least one of A, B, and C" should include but is not limited to a system having A alone, B alone, C alone, A and B, A and C, B and C, and / or A, B, C, etc.). In the case of using expressions such as "at least one of A, B, or C, etc.", it should generally be interpreted in accordance with the meaning of the expression generally understood by those skilled in the art (for example, "a system having at least one of A, B, or C" should include but is not limited to a system having A alone, B alone, C alone, A and B, A and C, B and C, and / or A, B, C, etc.).

[0027] It is shown in the related art that late transition metal catalysts have good tolerance for polar monomers, but poor selectivity for α-olefins; while early transition metal catalysts have poor tolerance for polar monomers, but have high activity and high insertion in catalyzing the copolymerization of ethylene and α-olefins. In order to achieve multifunctional and higher polymer molecular weight and mechanical properties of vinyl polar polyolefin elastomers, the present disclosure selects catalysts for catalyzing ethylene, α-olefins, and polar monomers, and finds that a specific titanium catalyst can achieve this purpose.

[0028] Specifically, as a first aspect of the present disclosure, a vinyl polar polyolefin elastomer is provided, wherein the vinyl polar polyolefin elastomer is a CH2=CH2 monomer, CH2=CH-(CH2) n -CH3 monomer and CH2=CH-(CH2) m -X polar monomer copolymerization formed by terpolymer or its acidification product;

[0029] The ternary random copolymer has a general structure as shown in formula (1): Formula (1), wherein n is an integer of 1-8, m is an integer of 0-10, and y represents the degree of polymerization, which is 50-20000; represents the spacer symbol between monomers; X is selected from -F, -Cl, -Br, -I, -CN, -C(=O)O-CH3, or At least one of, R1, R2, R3 are each independently selected from C1-C 16 Alkyl, C1-C 16 Any of the alkyl-substituted phenyl groups, at least one of R1, R2, and R3 is selected from C1-C 16 alkyl;

[0030] The acidified product has a general structure as shown in formula (2): Formula (2), wherein M is selected from at least one of -F, -Cl, -Br, -I, -CN, -OH, -C(=O)O-CH3 or -COOH.

[0031] In the embodiments of the present disclosure, ethylene monomer is mixed with α-olefin (CH2=CH-(CH2) n -CH3 monomer) and CH2=CH-(CH2) m -X polar monomers for copolymerization, in which α-olefins are used to improve the mechanical and elastic properties of the polymer, and CH2=CH-(CH2) m -X polar monomer is used to introduce polar functional groups into the final copolymer, so that the obtained terpolymer or its acidification product can obtain a vinyl polar polyolefin elastomer with multifunctionality, higher polymer molecular weight and mechanical properties compared to the existing low polymer molecular weight copolymer.

[0032] According to the embodiments of the present disclosure, the term "random copolymer" refers to the above-mentioned ethylene, (CH2=CH-(CH2) n -CH3 monomer) and CH2=CH-(CH2) m - A terpolymer formed by random copolymerization of a polar monomer X, or a copolymer formed by acidification with hydrochloric acid.

[0033] According to the embodiments of the present disclosure, formula (1) only represents that the random copolymer of the present disclosure is composed of CH2=CH2 monomer, CH2=CH-(CH2) n -CH3 monomer and CH2=CH-(CH2) m -X polar monomer (in formula (1) represented by the symbol " " " is separated) or has three repeating units, but it does not mean that the random copolymer disclosed in the present invention is polymerized by three monomers in an equal molar ratio, for example, a molar ratio of 1:1:1. In fact, due to the different copolymerization activities of the pre-transition metal catalyst (main catalyst) used in the preparation process when catalyzing the three different monomers used, the molar content of each monomer in the obtained random copolymer will be different.

[0034] According to the embodiment of the present disclosure, C1-C 16 Alkyl refers to a straight chain, branched or cyclic alkyl group having 1 to 16 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, n-hexyl, etc. or their isomeric forms.

[0035] According to embodiments of the present disclosure, the symbol "-" in the group represented by X means that the mentioned group is connected to the rest of the molecule at the atom where the symbol is located. For example, the group "-C(=O)O-CH3alkyl" means that the alkyl ester group is connected to the rest of the corresponding molecule through the carbonyl carbon (C) atom.

[0036] According to an embodiment of the present disclosure, m is an integer of 4-10, and X is selected from -C(=O)O-CH3, or At least one of; M is selected from at least one of -OH, -C(=O)O-CH3 or -COOH, so that when the vinyl polar polyolefin elastomer is used as a compatibilizer, the compatibility between the non-polar polymer and the polar filler can be improved, thereby further improving the mechanical properties and hydrophilicity of the polymer.

[0037] According to an embodiment of the present disclosure, in the vinyl polar polyolefin elastomer, CH2=CH-(CH2) n -The insertion ratio of CH3 monomer is 5.0-30%, CH2=CH-(CH2) m -The insertion ratio of the polar monomer of X is 0.5-3%. Among them, increasing the insertion ratio of the polar monomer can increase the surface properties of the vinyl polar polyolefin elastomer polymer, improve the mechanical properties of the vinyl polar polyolefin elastomer polymer, enhance the compatibility of the obtained vinyl polar polyolefin elastomer polymer with other polar materials, and also bring some new functions to the vinyl polar polyolefin elastomer polymer by using the polar group.

[0038] According to the embodiments of the present disclosure, the number average molecular weight of the vinyl polar polyolefin elastomer is 120,000-300,000, indicating that the polymer of the present disclosure has higher strength, rigidity and thermal stability; the polymer dispersibility index (PDI) is 1.9-3.5, and the polymer dispersibility index is relatively narrow, indicating that it has excellent mechanical properties.

[0039] According to the embodiments of the present disclosure, the tensile strength of the vinyl polar polyolefin elastomer can be 7.5 MPa-36.1 MPa, and the elongation at break is above 500%, and can even be as high as 1000%.

[0040] As a second aspect of the present disclosure, a method for preparing a vinyl polar polyolefin elastomer is provided, comprising: converting CH2=CH-(CH2) n -CH3 monomer and CH2=CH-(CH2) m-X polar monomer, polymerization solvent, and scavenger are added into the reactor, CH2=CH2 monomer gas is introduced and the temperature is raised to the polymerization reaction temperature, and then the main catalyst and the co-catalyst are introduced to carry out polymerization reaction to obtain a ternary random copolymer; and optionally, the ternary random copolymer is subjected to acidification treatment to obtain a vinyl polar polyolefin elastomer; wherein n is an integer of 1-8, m is an integer of 0-10, and X is selected from -F, -Cl, -Br, -I, -CN, -C(=O)O-CH3, or At least one of, R1, R2, R3 are each independently selected from C1-C 16 Alkyl, C1-C 16 Any of the alkyl-substituted phenyl groups, at least one of R1, R2, and R3 is selected from C1-C 16 The main catalyst has a structure as shown in formula (3): Formula (3), wherein R4 is selected from phenyl, C1-C4 alkyl substituted phenyl, 、N-C1-C 16 Alkyl, C1-C 16 At least one of the alkyl groups; R5 and R6 are each independently selected from Cl, C1-C 16 Any one of alkyl, phenyl, and C1-C4 alkyl-substituted phenyl; R7 is selected from , , Any one of .

[0041] In the embodiments of the present disclosure, ethylene monomer, α-olefin (CH2=CH-(CH2) n -CH3 monomer) and CH2=CH-(CH2) m -X polar monomers, polymerization solvents, scavengers, etc. are added into the reactor, and copolymerization is carried out under relatively mild reaction conditions in the presence of specific titanium (Ti) catalysts and co-catalysts. The obtained terpolymer or its acidified product has a higher polymer molecular weight and excellent mechanical properties.

[0042] According to an embodiment of the present disclosure, the co-catalyst is selected from any one of B(C6F5)3, [Ph3C][B(C6F5)4], and [PhNH(CH3)2][B(C6F5)4].

[0043] According to an embodiment of the present disclosure, the cleaning agent is selected from C1-C 16 Alkyl aluminoxane, C1-C 16 Alkyl aluminum, C1-C4 alkyl substituted aluminum chloride, C1-C4 alkyl substituted phenyl aluminum, C6-C 18 Any one of the aryl aluminums. Specifically, C1-C 16The alkylaluminoxane is selected from any one of methylaluminoxane, ethylaluminoxane, butylaluminoxane and hexylaluminoxane. 16 The alkylaluminum is selected from any one of trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, triisopropylaluminum, triisobutylaluminum, tripentylaluminum, trihexylaluminum, tricyclohexylaluminum, and trioctylaluminum. The C1-C4 alkyl-substituted aluminum chloride is selected from any one of diethylaluminum chloride. The C1-C4 alkyl-substituted phenylaluminum is selected from any one of triphenylaluminum and tri-p-tolylaluminum. 18 The aryl aluminum is selected from any one of tribenzyl aluminum, ethyl dibenzyl aluminum, ethyl di-p-tolyl aluminum and diethylbenzyl aluminum. The present disclosure adopts a scavenger mainly to remove active hydrogen, moisture, oxygen and other possible poisons of the main catalyst in the ethylene polymerization process. The scavenger reacts with these poisons to remove them from the reaction system, thereby keeping the main catalyst active.

[0044] According to an embodiment of the present disclosure, the polymerization solvent is selected from at least one of toluene, xylene, chlorobenzene, n-hexane, n-heptane, and methylcyclohexane. Since the polymerization reaction of the present disclosure is carried out in a solution, it can also be called a solution polymerization reaction.

[0045] According to an embodiment of the present disclosure, the polymerization temperature is 0-180°C, for example, 10°C, 20°C, 30°C, 50°C, 100°C, 120°C, 150°C, 180°C, etc., within which the main catalyst and the co-catalyst can stably exist and exert catalytic performance. The ethylene pressure is 1-35atm, preferably 3-30atm, more preferably 3-15atm, and further preferably 3-9atm. The polymerization time is 0.1h-12h, preferably 0.1-2h, for example, 0.1h, 0.5h, 2h, 4h, 6h, 8h, 10h, 12h.

[0046] According to an embodiment of the present disclosure, CH2=CH-(CH2) n -CH3 monomer and CH2=CH-(CH2) m - The concentration of the polar monomers X is independently 0.01-10 mol / L, wherein CH2=CH-(CH2) n The concentration of -CH3 monomer is preferably 0.1-4 mol / L, CH2=CH-(CH2) m The concentration of the -X polar monomer is preferably 0.1-2 mol / L.

[0047] According to an embodiment of the present disclosure, during the solution polymerization process, the sweeping agent reacts with CH2=CH-(CH2) mThe molar ratio of -X is 1.05-1.2:1. The amount of the main catalyst can be 1.0-200 μmol, and the molar ratio of the co-catalyst to the main catalyst is (1-20):1, CH2=CH-(CH2) n -The molar ratio of CH3 monomer to main catalyst is (2000-100000):1, CH2=CH-(CH2) m -The molar ratio of the polar monomer to the main catalyst is (2000-50000): 1, and the co-catalyst used is CH2=CH-(CH2) m -X polar monomer molar ratio is (1.05-3): 1. For example, when the concentration of the main catalyst used is 2.5 μmol, CH2=CH-(CH2) n -CH3 monomer concentration is 40mmol, CH2=CH-(CH2) m The concentration of -X polar monomer was 8 mmol.

[0048] According to the embodiments of the present disclosure, the present disclosure provides a method for realizing CH2=CH2 monomer, CH2=CH-(CH2) n -CH3 monomer and CH2=CH-(CH2) m The reactor for the copolymerization of -X polar monomers is not particularly limited, as long as it can provide the desired copolymerization reaction site. Preferably, the polymerization reaction of the present disclosure can be carried out in a reactor. More preferably, the reactor is in an inert atmosphere, such as a nitrogen atmosphere. The reaction temperature of the reactor can be provided by a water bath heating or an oil bath heating system.

[0049] More specifically, the method for preparing a vinyl polar polyolefin elastomer comprises: converting CH2=CH-(CH2) n -CH3 monomer and CH2=CH-(CH2) m -X polar monomer, n-heptane (polymerization solvent) and scavenger are added to the polymerization reactor, CH2=CH2 monomer gas is introduced, and after heating to the specified temperature, the required main catalyst and co-catalyst are injected, and the ethylene pressure is adjusted to the specified pressure. After polymerization for a certain period of time, a ternary random copolymer is obtained. Subsequently, a large amount of hydrochloric acid acetone solution is added to quench, and a white polymer is obtained by filtration, which is further extracted by a Soxhlet extractor to remove the residual CH2=CH-(CH2) n -CH3 monomer and CH2=CH-(CH2) m -X polar monomer, thereby obtaining the acidified product of the terpolymer.

[0050] As a third aspect of the present disclosure, an application of a vinyl polar polyolefin elastomer is provided, and the application includes application in any field of packaging, automobile manufacturing, electrical appliance manufacturing, medical equipment, and photovoltaic film.

[0051] In order to further illustrate the technical solution of the present disclosure, the following is a detailed description of the vinyl polar polyolefin elastomer provided by the present disclosure and its preparation method and application in combination with the examples. However, it should be understood that these examples are only used for the purpose of illustrating to help understand the concept of the present disclosure, rather than limiting the scope of protection of the present disclosure, and the scope of protection of the present disclosure is not limited to the following examples.

[0052] The present disclosure has no particular limitation on the sources of the raw materials in the following examples, and the raw materials may be prepared by methods well known to those skilled in the art or purchased from the market.

[0053] The data given in the examples include the specific process and parameters of the copolymerization of olefin monomers. The polymerization process is carried out in an inert atmosphere or environment without water or oxygen. All sensitive substances are stored in a glove box or refrigerator at -30°C. All solvents are strictly dried and dehydrated. Unless otherwise specified, all other raw materials are used directly after purchase.

[0054] Example 1

[0055] Ethylene, 1-octene and (CH2=CH-(CH2)9-OSiMe3 polar monomer (abbreviated as: m-OSiMe3) are used as raw materials to prepare vinyl polar polyolefin elastomer, and the specific preparation process is as follows.

[0056] In a glove box, under a nitrogen atmosphere, a 350 mL reactor was added with n-heptane solvent, wherein the molar number of 1-octene (Oct) monomer was 20 mmol, and the molar number of m-OSiMe3 polar monomer was 8 mmol, and a scavenger (triisobutylaluminum) equivalent to 1.1 equivalents of m-OSiMe3 polar monomer was added to the reactor. Then, the ethylene gas source pipeline was connected to pass ethylene (abbreviated as E monomer) gas into the reactor, and the reactor was heated to 30°C by water bath heating under magnetic stirring, and 2.5 μmol of the main catalyst dissolved in 1 mL of toluene and 1.5 equivalents of the co-catalyst [Ph3C][B(C6F5)4] were added to the reactor, and the ethylene pressure was adjusted to 8 atm and the reaction was carried out under magnetic stirring for 10 minutes. After the reaction is completed, the excess gas is released, and then the reactor is opened. 50 mL of acetone hydrochloride is added to the reaction solution to quench it. Finally, it is filtered under reduced pressure and the solid product is dried in a vacuum oven at 50°C for 24 hours to obtain a white solid, which is the desired vinyl polar polyolefin elastomer E / Oct(0.5) / m-OSiMe3(0.2), where the molar concentration of each monomer is indicated in brackets after the corresponding comonomer. The structure of the main catalyst is shown in the following formula (3-1). Calculate the product yield (i.e., the mass of the copolymer obtained during the polymerization time (g)) and the reaction activity (in g·mol -1 ·h -1 , that is, the mass of copolymer produced by polymerization per mole of catalyst per hour). The specific test results are shown in Table 1.

[0057] Main catalyst of formula (3-1).

[0058] Example 2

[0059] Example 2: A vinyl polar polyolefin elastomer is prepared by the same method as in Example 1, with the only difference being that when the total reactant volume is 40 mL, the molar number of 1-octene (Oct) monomer is 40 mmol, and the molar number of m-OSiMe3 polar monomer is 8 mmol, and the obtained vinyl polar polyolefin elastomer is E / Oct(1) / m-OSiMe3(0.2).

[0060] Example 3

[0061] Example 3: A vinyl polar polyolefin elastomer is prepared by the same method as in Example 1, with the only difference being that when the total reactant volume is 40 mL, the molar number of 1-octene (Oct) monomer is 20 mmol, and the molar number of CH2=CH-(CH2)8-COOSiMe3 polar monomer (abbreviated as m-COOSiMe3) is 8 mmol, and the obtained vinyl polar polyolefin elastomer is E / Oct(0.5) / m-COOSiMe3(0.2).

[0062] Example 4

[0063] Example 4: A vinyl polar polyolefin elastomer is prepared by the same method as in Example 1, with the only difference being that when the total reactant volume is 40 mL, the molar number of 1-octene (Oct) monomer is 40 mmol, and the molar number of CH2=CH-(CH2)8-COOSiMe3 polar monomer (abbreviated as m-COOSiMe3) is 8 mmol, and the obtained vinyl polar polyolefin elastomer is E / Oct(1) / m-COOSiMe3(0.2).

[0064] Example 5

[0065] Example 5: A vinyl polar polyolefin elastomer is prepared by the same method as in Example 1, with the only difference being that, when the total reactant volume is 40 mL, the molar number of 1-octene (Oct) monomer is 80 mmol, and the molar number of CH2=CH-(CH2)8-COOSiMe3 polar monomer (abbreviated as m-COOSiMe3) is 8 mmol, and the obtained vinyl polar polyolefin elastomer is E / Oct(2) / m-COOSiMe3(0.2).

[0066] Example 6

[0067] Example 6: A vinyl polar polyolefin elastomer is prepared by the same method as in Example 1, with the only difference being that when the total reactant volume is 40 mL, the molar number of 1-octene (Oct) monomer is 80 mmol, and the molar number of CH2=CH-(CH2)8-COOSiMe3 polar monomer (abbreviated as m-COOSiMe3) is 20 mmol, and the obtained vinyl polar polyolefin elastomer is E / Oct(2) / m-COOSiMe3(0.5).

[0068] Example 7

[0069] Example 7 The same method as in Example 1 was used to prepare a vinyl polar polyolefin elastomer, except that the molar number of 1-octene (Oct) monomer was 20 mmol, and CH2=CH-(CH2)9-OSi t BuMe2 polar monomer (abbreviated as m-OSi t The molar number of BuMe2) is 8 mmol, and the obtained vinyl polar polyolefin elastomer is E / Oct(0.5) / m-OSi t BuMe2(0.2).

[0070] Example 8

[0071] Example 8 The same method as in Example 1 was used to prepare a vinyl polar polyolefin elastomer, except that the molar number of 1-octene (Oct) monomer was 40 mmol, and CH2=CH-(CH2)9-OSi t BuMe2 polar monomer (abbreviated as m-OSi t The molar number of BuMe2) is 8 mmol, and the obtained vinyl polar polyolefin elastomer is E / Oct(1) / m-OSi t BuMe2(0.2).

[0072] Example 9

[0073] Example 9 The same method as in Example 1 was used to prepare a vinyl polar polyolefin elastomer, except that the molar number of 1-octene (Oct) monomer was 20 mmol, and CH2=CH-(CH2)8-COOSi was 20 mmol when the total reactant volume was 40 mL. t BuMe2 polar monomer (abbreviated as m-COOSi t The molar number of BuMe2) is 8 mmol, and the obtained vinyl polar polyolefin elastomer is E / Oct(0.5) / m-COOSi t BuMe2(0.2).

[0074] Example 10

[0075] Example 10: A vinyl polar polyolefin elastomer was prepared by the same method as in Example 1, except that: when the total reactant volume was 40 mL, the molar number of 1-octene (Oct) monomer was 40 mmol, and CH2=CH-(CH2)8-COOSi t BuMe2 polar monomer (abbreviated as m-COOSi tThe molar number of BuMe2) is 8 mmol, and the obtained vinyl polar polyolefin elastomer is E / Oct(1) / m-COOSi t BuMe2(0.2).

[0076] Embodiment 11

[0077] Example 11: A vinyl polar polyolefin elastomer is prepared by the same method as in Example 1, with the only difference being that when the total reactant volume is 40 mL, the molar number of 1-octene (Oct) monomer is 20 mmol, and the molar number of CH2=CH-(CH2)8-COOCH3 polar monomer (abbreviated as m-COOCH3) is 8 mmol, and the obtained vinyl polar polyolefin elastomer is E / Oct(0.5) / m-COOCH3(0.2).

[0078] Example 12

[0079] Example 12: A vinyl polar polyolefin elastomer is prepared by the same method as in Example 1, with the only difference being that the reaction temperature is 120°C.

[0080] The mechanism routes for preparing the vinyl polar polyolefin elastomers in the above-mentioned Examples 1 to 11 are as follows:

[0081]

[0082] Among them, the formula The ethylene monomer (E) represented by the formula represents 1-octene monomer (Oct), Represents a polar monomer, wherein X represents -CH2OSiMe3, -COOSiMe3, -CH2OSi t BuMe2, -COOCH3 or -COOSi t BuMe2, M represents -CH2OH, -COOH or -COOCH3, and y is the degree of polymerization, which can be in the range of 50~20000.

[0083] The monomer insertion ratio (i.e., the percentage of 1-octene monomer (Oct) or polar monomer in the obtained copolymer polymer chain, and the higher the insertion ratio, the higher the proportion of the monomer in the polymer chain of the vinyl polar polyolefin elastomer). The specific monomer insertion ratio is measured by 1 H NMR or 13 C NMR spectra were measured in deuterated tetrachloroethane (C2D2Cl4) at 120°C.

[0084] The obtained vinyl polar polyolefin elastomer can be characterized by high temperature gel permeation chromatography (GPC) (trichlorobenzene as solvent, test temperature 150o C) Measure the number average molecular weight (M n ) and polydispersity index (PDI), and can also be measured by differential scanning calorimetry (DSC, scanning temperature range -50-150 o C, the heating rate is 10 o C / min) to measure the melting point T of the product m and glass transition temperature T g The specific test results are shown in Table 1 below.

[0085] Table 1

[0086]

[0087] Note: :V 总 =40 mL, T=30°C, ethylene pressure=8 atm, polymerization time=10 min; g·mol -1 ·h -1 ; (Indicates that per 1 mole of polymer, CH2=CH-(CH2) m -X polar monomer and CH2=CH-(CH2) n - molar insertion ratio of CH3 monomer); and polydispersity index PDI measured by GPC; Measured by DSC.

[0088] As can be seen from Table 1, the vinyl polar polyolefin elastomer prepared by the method provided by the present invention has a relatively high molecular weight, and the number average molecular weight is above 120,000, and the highest can reach 279,000. At the same time, the dispersion index (PDI) range of the vinyl polar polyolefin elastomer obtained by the present invention is relatively narrow, mainly concentrated in 1.9-3.5.

[0089] Furthermore, the mechanical properties of the vinyl polar polyolefin elastomers obtained in the above Examples 1 to 5 were tested. The specific testing method is: the vinyl polar polyolefin elastomers prepared in the above Examples 1 to 5 were made into dumbbell-shaped specimens (length 25 mm×width 2 mm×thickness 0.5 mm), and the mechanical properties were tested by a universal testing machine (UTM2502). The obtained tensile strength and elongation at break results are shown as follows: Figure 1 shown.

[0090] Figure 1 This is a graph of the elongation at break and tensile strength of the vinyl polar polyolefin elastomer in Examples 1 to 5 of the present disclosure.

[0091] like Figure 1As shown, the vinyl polar polyolefin elastomers in Examples 1 to 5 of the present disclosure all have excellent mechanical properties, wherein the tensile strength of the vinyl polar polyolefin elastomer is between 7.5 MPa and 36.1 MPa, and the elongation at break is all above 500%, and some can even be as high as 1000% or more, with excellent elasticity.

[0092] Furthermore, the vinyl polar polyolefin elastomers in the above-mentioned Examples 1 to 5 were subjected to ten 300% constant stretching cycles. The specific test results are as follows: Figure 2-Figure 4 shown.

[0093] Figure 2 This is a graph showing the test results of a 300% cyclic reciprocating test of a vinyl polar polyolefin elastomer in Example 2 of the present disclosure for ten times of fixed stretching; Figure 3 This is a graph showing the test results of a 300% cyclic reciprocating test of a vinyl polar polyolefin elastomer in Example 4 of the present disclosure for ten times of fixed stretching; Figure 4 This is a graph showing the test results of ten cycles of 300% stretching of the vinyl polar polyolefin elastomer in Example 5 of the present disclosure.

[0094] like Figure 2-Figure 4 As shown, in ten 300% cycle experiments, the vinyl polar polyolefin elastomer maintained an elastic recovery of 37%-80%, indicating that it has good elastic and mechanical properties, and is expected to be used in various applications, such as packaging materials, automobile manufacturing materials, electrical manufacturing materials, medical device manufacturing materials or photovoltaic film manufacturing materials, etc.

[0095] Furthermore, vinyl polar polyolefin elastomers contain polar groups, which can be used as compatibilizers to increase the compatibilization of high-density polyethylene (HDPE, a non-polar polymer) and calcium carbonate (a polar filler) to improve the mechanical properties of the composites.

[0096] Application Example 1

[0097] The vinyl polar polyolefin elastomer obtained in Example 2 was weighed according to the weight ratio of E / Oct(1) / m-OSiMe3(0.2), HDPE and CaCO3 of 5:55:40, and mixed with 0.2% antioxidant 2,6-di-tert-butyl-p-cresol. The mixed materials were transported to a twin-screw extruder for blending at an extruder operating temperature of 180°C and a mixing time of 6 minutes, thereby obtaining a blend of E / Oct(1) / m-OSiMe3(0.2)-compatibilized HDPE and CaCO3 (HDPE / CaCO3 / E / Oct(1) / m-OSiMe3(0.2)(55 / 40 / 5)).

[0098] Comparative Example 1

[0099] The same method as in Application Example 1 was used to prepare a blend of HDPE and CaCO3, with the only difference being that instead of using the vinyl polar polyolefin elastomer E / Oct(1) / m-OSiMe3 (0.2), only HDPE and CaCO3 were blended in a twin-screw extruder to obtain a blend of HDPE and CaCO3, wherein the weight ratio of HDPE to CaCO3 was 60:40, referred to as HDPE / CaCO3 (60 / 40).

[0100] The blended materials prepared in the above-mentioned application example 1 and comparative example 1 were subjected to stress-strain curve test and brittle fracture scanning electron microscope characterization, and the specific comparison results are as follows: Figure 5-Figure 7 shown.

[0101] Figure 5 The stress-strain curves of the blended materials in Application Example 1 and Comparative Example 1 are respectively: Figure 6 This is a scanning electron microscope (SEM) image of the blended material in Comparative Example 1. Figure 7 This is a scanning electron microscope (SEM) image of the blended material in Application Example 1.

[0102] like Figure 5 As shown in FIG. 1 , after adding the vinyl polar polyolefin elastomer E / Oct(1) / m-OSiMe3 (0.2), the elongation at break is greatly improved while the tensile strength remains almost unchanged. Figure 6 and Figure 7 It can be seen from the SEM image shown that when the vinyl polar polyolefin elastomer E / Oct(1) / m-OSiMe3(0.2) is not added, the obtained HDPE / CaCO3 blend material has severe phase separation, which leads to poor mechanical properties; while when the vinyl polar polyolefin elastomer E / Oct(1) / m-OSiMe3(0.2) is added, the obtained HDPE / CaCO3 / E / Oct(1) / m-OSiMe3(0.2) blend material has a uniform structure, evenly dispersed CaCO3, and no obvious phase separation, so its mechanical properties are higher.

[0103] The specific embodiments described above further illustrate the purpose, technical solutions and beneficial effects of the present disclosure. It should be understood that the above description is only a specific embodiment of the present disclosure and is not intended to limit the present disclosure. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present disclosure should be included in the protection scope of the present disclosure.

Claims

1. A vinyl polar polyolefin elastomer, characterized in that: The vinyl polar polyolefin elastomer is a CH2=CH2 monomer, CH2=CH-(CH2) n -CH3 monomer and CH2=CH-(CH2) m -X polar monomer copolymerization formed by terpolymer or its acidification product; The ternary random copolymer has a general structure as shown in formula (1): Formula (1), wherein n is an integer of 1-8, m is an integer of 0-10, and y represents the degree of polymerization, which is 50-20000; represents the spacer symbol between monomers; X is selected from -F, -Cl, -Br, -I, -CN, -C(=O)O-CH3, or At least one of, R1, R2, R3 are each independently selected from C1-C 16 Alkyl, C1-C 16 Any of the alkyl-substituted phenyl groups, at least one of R1, R2, and R3 is selected from C1-C 16 alkyl; The acidified product has a general structure as shown in formula (2): Formula (2), wherein M is selected from at least one of -F, -Cl, -Br, -I, -CN, -OH, -C(=O)O-CH3 or -COOH.

2. The vinyl polar polyolefin elastomer according to claim 1, characterized in that The m is an integer of 4-10, and X is selected from -C(=O)O-CH3, or At least one of the following; M is selected from at least one of -OH, -C(=O)O-CH3 or -COOH.

3. The vinyl polar polyolefin elastomer according to claim 1, characterized in that In the vinyl polar polyolefin elastomer, the CH2=CH-(CH2) n -The insertion ratio of CH3 monomer is 5.0-30%, and the CH2=CH-(CH2) m The insertion ratio of -X polar monomer is 0.5-3%.

4. The vinyl polar polyolefin elastomer according to claim 1, characterized in that The number average molecular weight of the vinyl polar polyolefin elastomer is 120,000-300,000, and the polymer dispersibility index is 1.9-3.

5.

5. A method for preparing a vinyl polar polyolefin elastomer, characterized in that: The preparation method comprises: CH2=CH-(CH2) n -CH3 monomer and CH2=CH-(CH2) m -X polar monomer, polymerization solvent, and scavenger are added into the reactor, CH2=CH2 monomer gas is introduced and the temperature is raised to the polymerization reaction temperature, and then the main catalyst and the co-catalyst are introduced to carry out polymerization reaction to obtain a ternary random copolymer; and Optionally, the terpolymer is subjected to acidification treatment to obtain the vinyl polar polyolefin elastomer as described in any one of claims 1 to 4; Wherein, n is an integer of 1-8, m is an integer of 0-10, and X is selected from -F, -Cl, -Br, -I, -CN, -C(=O)O-CH3, or At least one of, R1, R2, R3 are each independently selected from C1-C 16 Alkyl, C1-C 16 Any of the alkyl-substituted phenyl groups, at least one of R1, R2, and R3 is selected from C1-C 16 alkyl; The main catalyst has a structure as shown in formula (3): Formula (3), wherein R4 is selected from phenyl, C1-C4 alkyl substituted phenyl, 、N-C1-C 16 Alkyl, C1-C 16 At least one of the alkyl groups; R5 and R6 are each independently selected from Cl, C1-C 16 Any one of alkyl, phenyl, and C1-C4 alkyl-substituted phenyl; R7 is selected from , , Any one of .

6. The preparation method according to claim 5, characterized in that: The co-catalyst is selected from , , Any one of; The cleaning agent is selected from C1-C 16 Alkyl aluminoxane, C1-C 16 Alkyl aluminum, C1-C4 alkyl substituted aluminum chloride, C1-C4 alkyl substituted phenyl aluminum, C6-C 18 Any of aryl aluminum; The polymerization solvent is selected from at least one of toluene, xylene, chlorobenzene, n-hexane, n-heptane and methylcyclohexane.

7. The preparation method according to claim 5, characterized in that: The polymerization reaction temperature is 0-180° C., the ethylene pressure is 1-35 atm, and the time is 0.1 h-12 h.

8. The preparation method according to claim 5 or 7, characterized in that: The CH2=CH-(CH2) n -CH3 monomer and CH2=CH-(CH2) m The concentration of the -X polar monomers is independently 0.01-10 mol / L.

9. The preparation method according to claim 8, characterized in that: The cleaning agent and the CH2=CH-(CH2) m -The molar ratio of X is 1.05-1.2:1; The molar ratio of the co-catalyst to the main catalyst is (1-20):1; the CH2=CH-(CH2) n -The molar ratio of CH3 monomer to main catalyst is (2000-100000):1, the CH2=CH-(CH2) m -X polar monomer and main catalyst ratio is (2000-50000): 1, the co-catalyst and CH2=CH-(CH2) m The ratio of -X polar monomer is (1.05-3):

1.

10. A use of the vinyl polar polyolefin elastomer according to any one of claims 1 to 4, characterized in that: The application includes application in any field of packaging, automobile manufacturing, electrical appliance manufacturing, medical equipment, and photovoltaic film.

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