Recyclable polymer and preparation method thereof

Abstract

The invention discloses a recyclable polymer and a preparation method thereof, and particularly discloses a polymer which has a repeating unit shown as a formula I, a repeating unit shown as a formula II, or repeating units shown as the formula I and the formula II. The polymer provided by the invention can be recycled, degradation sites are controllable, and the monomer utilization rate is high.

Description

Technical Field

[0001] This invention belongs to the field of polyolefin materials technology. Specifically, this invention relates to a recyclable polymer and its preparation method. Background Technology

[0002] Polar polyolefins are a class of high-performance materials designed by introducing functional groups containing heteroatoms (such as oxygen and nitrogen) into the traditional polyolefin polymer chain. This molecular-level chemical modification strategy effectively improves the comprehensive properties of polyolefin materials, including mechanical strength, interfacial compatibility, and adhesion, thereby significantly broadening their application scenarios and achieving multifunctionality. Therefore, the controllable and efficient introduction of polar functional groups into the polyolefin chain has always been a core research topic and challenge in the field of polyolefin materials science. Current research focuses on two synthetic routes: post-modification and polar monomer-olefin copolymerization, mainly to prepare side-chain polar polyolefins. For example, polyolefin elastomers (POEs), after free radical grafting, can be used as photovoltaic encapsulation films, which can effectively enhance the sealing performance and long-term weather resistance of solar modules, significantly extending their service life; ethylene-vinyl alcohol copolymers (EVOH), with their excellent gas barrier properties (especially against oxygen), excellent dyeability, and good print adhesion, have important value in high-requirement fields such as food and pharmaceutical packaging.

[0003] Polar polyolefins possess excellent properties and a wide range of applications, but these characteristics also present significant challenges to their recycling: the complex composition of post-consumer waste materials leads to low efficiency in physical separation and mechanical recycling. More critically, their polymer backbone structure is essentially composed of inert carbon-carbon bonds, lacking controllable breakage sites, making efficient and selective chemical recycling, especially closed-loop recycling, difficult. The increasing global consumption of polar polyolefins has exacerbated the problem of waste accumulation. Therefore, establishing an efficient and sustainable polar polyolefin recycling technology system has become a crucial scientific and engineering challenge that urgently needs to be addressed in the field of materials circular economy.

[0004] Currently, there have been a few breakthrough reports on methods for achieving closed-loop recycling of polar polyolefins, but it remains a huge challenge. Mecking et al. synthesized recyclable polyesters from bio-based palm oil, but the monomers are expensive, which is not conducive to large-scale industrial production. Tang et al. synthesized telechelic polyolefins with one hydroxyl end and one ester end through coordination chain transfer polymerization, achieving closed-loop recycling of ester-linked polyolefins, but their performance is lower than that of commercially available polar polyolefins.

[0005] Therefore, there is an urgent need in this field for a recyclable polar polyolefin material with controllable degradation sites and high utilization rate of telechelic macromolecular monomers, as well as a method for its preparation. Summary of the Invention

[0006] The technical problem to be solved by this invention is to overcome the difficulty in degrading traditional polyolefins in the prior art, and to provide a recyclable polymer and its preparation method. The recyclable polymer provided by this invention has controllable degradation sites and high monomer utilization.

[0007] In a first aspect, the present invention provides a polymer having repeating units as shown in Formula I, repeating units as shown in Formula II, or repeating units as shown in both Formula I and Formula II.

[0008]

[0009]

[0010] Where A is composed of repeating units and The random copolymer chain consists of repeating units. The molar content of the random copolymer chain is 0.5-25%;

[0011] L is composed of repeating units The polymer chain that makes up the polymer chain;

[0012] B and E are independent of C 1-10 Alkylene or C 6-10 Alpha-aryl;

[0013] p and q are independent integers from 1 to 20;

[0014] When the polymer has repeating units as shown in Formula I and Formula II, the molar content of the repeating units as shown in Formula I in the polymer is 1-98%;

[0015] The number-average molecular weight of the polymer is 25-200 kg / mol.

[0016] In some implementations, p and q are independent integers from 5 to 10, such as 6.

[0017] In some implementations, B and E are -(CH2)6-.

[0018] In some implementations, B and E are phenylene oxides.

[0019] In some implementations, A is composed of repeating units. and The random copolymer chain consists of repeating units. The molar content of the random copolymer chain is 5-15%, for example 6.5%, 9.7%, 10.1% or 13.4%.

[0020] In some embodiments, when the polymer has repeating units as shown in Formula I and Formula II, the molar content of the repeating units as shown in Formula I in the polymer is 10-90%, for example 19%, 56%, 68% or 88%.

[0021] In some embodiments, when the polymer has repeating units as shown in Formula I and Formula II, the repeating units The molar content of the polymer is 0-10%, for example 1.9%, 5.6%, 6.8% or 8.9%.

[0022] In some embodiments, when the polymer has repeating units as shown in Formula I and Formula II, the polymer is a block copolymer, such as a random block copolymer, and the repeating units as shown in Formula I and Formula II are randomly or disorderedly connected.

[0023] In some embodiments, the end group of the polymer connected to the carbonyl group in the polymer is -OC. 1-8 Alkyl group, with an H group on the other end.

[0024] In some embodiments, the end group of the polymer connected to the carbonyl group in the polymer is -OC. 1-4 Alkyl group, with an H group on the other end.

[0025] In some embodiments, the polymer has a carbonyl end group connected to the polymer that is -OMe or -OEt, and an H end group on the other side.

[0026] In some embodiments, the polymer is an elastomer.

[0027] In some embodiments, the polymer has a number-average molecular weight of 50-200 kg / mol, for example 61.3 kg / mol, 64.0 kg / mol, 70.8 kg / mol, 74.6 kg / mol, 83.3 kg / mol, 90.5 kg / mol, 95.3 kg / mol, 102.9 kg / mol, or 120.6 kg / mol.

[0028] In some embodiments, the polymer has a molecular weight distribution of 1.3-4.0, for example 1.4, 1.5, 1.6, 1.7, 1.8, 1.9 or 2.0.

[0029] In some embodiments, the polymer has a melting point of 49-120°C, such as 62°C, 67°C, 83°C, 101°C, 106°C, 110°C, 116°C, or 119°C.

[0030] In some embodiments, the polymer has repeating units as shown in Formula I;

[0031] A is composed of repeating units. and The random copolymer chain consists of repeating units. The molar content in the random copolymer chain is 0.5-25% (e.g., 5-15%).

[0032] B is -(CH2)6-; p is 6;

[0033] The polymer has a number-average molecular weight of 25-200 kg / mol (e.g., 50-140 kg / mol) and a molecular weight distribution of 1.3-4.0 (e.g., 1.2-2.0).

[0034] In some embodiments, the polymer has repeating units as shown in Formula I;

[0035] Where A is composed of repeating units and Random copolymer chains; repeating units The molar content of the random copolymer chain is 6.5%;

[0036] B is -(CH2)6-; p is 6;

[0037] The polymer has a number-average molecular weight of 102.9 kg / mol and a molecular weight distribution of 1.9.

[0038] In some embodiments, the polymer has repeating units as shown in Formula I;

[0039] Where A is composed of repeating units and Random copolymer chains; repeating units The molar content of the random copolymer chain is 9.7%;

[0040] B is -(CH2)6-; p is 6;

[0041] The polymer has a number-average molecular weight of 70.8 kg / mol and a molecular weight distribution of 1.7.

[0042] In some embodiments, the polymer has repeating units as shown in Formula I;

[0043] Where A is composed of repeating units and Random copolymer chains; repeating units The molar content of the random copolymer chain is 10.1%;

[0044] B is -(CH2)6-; p is 6;

[0045] The polymer has a number-average molecular weight of 120.6 kg / mol and a molecular weight distribution of 1.5.

[0046] In some embodiments, the polymer has repeating units as shown in Formula I;

[0047] Where A is composed of repeating units and Random copolymer chains; repeating units The molar content of the random copolymer chain is 13.4%;

[0048] B is -(CH2)6-; p is 6;

[0049] The polymer has a number-average molecular weight of 95.3 kg / mol and a molecular weight distribution of 1.6.

[0050] In some embodiments, the polymer has repeating units as shown in Formula II;

[0051] L is composed of repeating units The polymer chain that makes up the polymer chain;

[0052] E is -(CH2)6-; q is 6;

[0053] The polymer has a number-average molecular weight of 25-200 kg / mol (e.g., 50-140 kg / mol) and a molecular weight distribution of 1.3-4.0 (e.g., 1.2-2.0).

[0054] In some embodiments, the polymer has repeating units as shown in Formula II;

[0055] Where L consists of repeating units The polymer chain that makes up the polymer chain;

[0056] E-(CH2)6-; q is;

[0057] The polymer has a number-average molecular weight of 64.0 kg / mol and a molecular weight distribution of 1.4.

[0058] In some embodiments, the polymer has repeating units as shown in Formula I and Formula II;

[0059] Where A is composed of repeating units and The random copolymer chain consists of repeating units. The molar content in the random copolymer chain is 0.5-25% (e.g., 5-15%).

[0060] B is -(CH2)6-; p is 6;

[0061] L is composed of repeating units The polymer chain that makes up the polymer chain;

[0062] E is -(CH2)6-; q is 6;

[0063] The molar content of the repeating unit as shown in Formula I in the polymer is 1-98% (e.g., 10-90%).

[0064] The polymer has a number-average molecular weight of 25-200 kg / mol (e.g., 50-100 kg / mol) and a molecular weight distribution of 1.2-2.1.

[0065] In some embodiments, the polymer has repeating units as shown in Formula I and Formula II; wherein, A is a repeating unit and Random copolymer chains; repeating units The molar content of the random copolymer chain is 10.1%;

[0066] B is -(CH2)6-; p is 6;

[0067] L is composed of repeating units The polymer chain that makes up the polymer chain;

[0068] E is -(CH2)6-; q is 6;

[0069] The repeating unit as shown in Formula I has a molar content of 19% in the polymer;

[0070] The polymer has a number-average molecular weight of 90.5 kg / mol and a molecular weight distribution of 1.3.

[0071] In some embodiments, the polymer has repeating units as shown in Formula I and Formula II; wherein, A is a repeating unit and Random copolymer chains; repeating units The molar content of the random copolymer chain is 10.1%;

[0072] B is -(CH2)6-; p is 6;

[0073] L is composed of repeating units The polymer chain that makes up the polymer chain;

[0074] E is -(CH2)6-; q is 6;

[0075] The repeating unit as shown in Formula I has a molar content of 56% in the polymer;

[0076] The polymer has a number-average molecular weight of 61.3 kg / mol and a molecular weight distribution of 2.0.

[0077] In some embodiments, the polymer has repeating units as shown in Formula I and Formula II; wherein, A is a repeating unit and Random copolymer chains; repeating units The molar content of the random copolymer is 10.1%;

[0078] B is -(CH2)6-; p is 6;

[0079] L is composed of repeating units The polymer chain that makes up the polymer chain;

[0080] E is -(CH2)6-; q is 6;

[0081] The repeating unit as shown in Formula I has a molar content of 68% in the polymer;

[0082] The polymer has a number-average molecular weight of 74.6 kg / mol and a molecular weight distribution of 1.8.

[0083] In some embodiments, the polymer has repeating units as shown in Formula I and Formula II; wherein, A is a repeating unit and Random copolymer chains; repeating units The molar content of the random copolymer is 10.1%;

[0084] B is -(CH2)6-; p is 6;

[0085] L is composed of repeating units The polymer chain that makes up the polymer chain;

[0086] E is -(CH2)6-; q is 6;

[0087] The repeating unit as shown in Formula I has a molar content of 88% in the polymer;

[0088] The polymer has a number-average molecular weight of 83.3 kg / mol and a molecular weight distribution of 1.7.

[0089] In a second aspect, the present invention provides a method for preparing a polymer as described in the first aspect of the present invention, comprising the following steps: in the presence of a Lewis acid catalyst, The polymer is obtained by polymerizing with a polyolefin, wherein the polyolefin is a polyolefin as shown in Formula III, a polyolefin as shown in Formula IV, or a polyolefin as shown in both Formula III and Formula IV.

[0090] ;

[0091] Wherein, A, L, B, p and q are defined as described in any of the embodiments of the first aspect of the present invention.

[0092] In some embodiments, the number-average molecular weight of the polyolefin as shown in Formula III or Formula IV is 1-20 kg / mol; preferably 1-10 kg / mol, for example 2.4 kg / mol, 4.6 kg / mol, 5.9 kg / mol, 6.0 kg / mol or 6.9 kg / mol.

[0093] In some embodiments, the polyolefins represented as of Formula III or Formula IV have a molecular weight distribution of 1.1-3.0, for example 1.1, 1.2, 1.3 or 1.4.

[0094] In some embodiments, the difunctionalization purity of the polyolefin as shown in Formula III or Formula IV is greater than 95%, for example 99%.

[0095] In some embodiments, in the polyolefin represented by Formula III, A is a repeating unit. and Random copolymer chains; repeating units The molar content of the random copolymer chain is 6.5%; p is 6;

[0096] The polyolefin shown in Formula III has a number-average molecular weight of 6.0 kg / mol and a molecular weight distribution of 1.2.

[0097] In some embodiments, in the polyolefin represented by Formula III, A is a repeating unit. and Random copolymer chains; repeating units The molar content of the random copolymer chain is 9.7%; p is 6;

[0098] The polyolefin shown in Formula III has a number-average molecular weight of 5.9 kg / mol and a molecular weight distribution of 1.3.

[0099] In some embodiments, in the polyolefin represented by Formula III, A is a repeating unit. and Random copolymer chains; repeating units The molar content of the random copolymer chain is 10.1%; p is 6;

[0100] The polyolefin shown in Formula III has a number-average molecular weight of 4.6 kg / mol and a molecular weight distribution of 1.2.

[0101] In some embodiments, in the polyolefin represented by Formula III, A is a repeating unit. and Random copolymer chains; repeating units The molar content of the random copolymer chain is 13.4%; p is 6;

[0102] The polyolefin shown in Formula III has a number-average molecular weight of 6.9 kg / mol and a molecular weight distribution of 1.4.

[0103] In some embodiments, in the polyolefin represented by Formula IV, L is composed of repeating units. The polymer chain is composed of a p-value of 6.

[0104] The polyolefin shown in Formula IV has a number-average molecular weight of 2.4 kg / mol and a molecular weight distribution of 1.1.

[0105] In some embodiments, when the polyolefin is a polyolefin of formula III or formula IV, the weight ratio of the polyolefin of formula III to that of formula IV is 1:(0.02-10), for example 1:0.07, 1:0.25, 1:0.4 or 1:2.3.

[0106] In some implementation schemes, It is hexamethylene diisocyanate (HDI).

[0107] In some implementation schemes, The molar ratio of the polyolefin to the polyolefin is (0.9-1.1):1, for example, 1:1.

[0108] In some embodiments, the organic solvent is C 6-10 Aromatic solvents, such as toluene.

[0109] In some embodiments, the Lewis acid catalyst is one or more of tetrabutyl titanate, dibutyltin dilaurate, and stannous octoate, preferably dibutyltin dilaurate.

[0110] In some embodiments, the molar ratio of the Lewis acid catalyst to the polyolefin is (0.001-0.005):1, for example, 0.002:1.

[0111] In some embodiments, the polymerization reaction is carried out at a temperature of 40-100°C. ° C, preferably 60-90 °C, more preferably 80 °C.

[0112] In some embodiments, the polymerization reaction takes 5-20 hours, preferably 10-15 hours, for example 12 hours.

[0113] In some embodiments, the polymerization reaction is carried out in an inert gas atmosphere, which may be nitrogen or argon, with nitrogen being preferred.

[0114] In some embodiments, the polymerization reaction further includes post-treatment. The post-treatment preferably includes the following steps: dissolving the crude polymer in a good solvent, precipitating it with a poor solvent, filtering, and drying to obtain the polymer.

[0115] In some embodiments, the benign solvent is C 6-10 Aromatic solvents, C 2-6 Ether solvents and C 1-6 One or more of alkane solvents; preferably one or more of toluene, mesitylene, tetrahydrofuran, dichloromethane, and chlorobenzene, more preferably mesitylene.

[0116] In some embodiments, the undesirable solvent is C 1-6 Alcohol solvents; preferably methanol.

[0117] In some embodiments, the method for preparing the polymer further includes a method for preparing the polyolefin as shown in Formula III. The method for preparing the polyolefin as shown in Formula III includes the following steps:

[0118] (1) In an organic solvent, in the presence of a palladium catalyst, acetyl chloride is reacted with a polyolefin as shown in formula VII-1 to obtain a polyolefin as shown in formula VI-1.

[0119] ;

[0120] Among them, R 4a for FG is ;R 1 R 2 and R 3 Independently for C 1-8 Alkyl or C 6-10 Aryl;

[0121] (2) In an organic solvent, in the presence of a reducing agent, the polyolefin shown in formula VI-1 is reduced to obtain the polyolefin shown in formula V-1.

[0122] ;

[0123] (3) In an organic solvent, in the presence of a deprotecting agent, the polyolefin shown in Formula V-1 is subjected to a deprotection reaction to obtain the polyolefin shown in Formula III;

[0124] ;

[0125] Wherein, A and p are defined as described in any embodiment of the present invention.

[0126] In some implementations, FG is Me3SiO-, Et3SiO-, t BuMe2SiO-、 i Pr3SiO- or t BuPh2SiO-, for example i Pr3SiO-.

[0127] In some embodiments, the number-average molecular weight of the polyolefin represented by Formula VII-1 is 1-20 kg / mol; preferably 1-10 kg / mol, for example 3.8 kg / mol, 4.9 kg / mol, 5.1 kg / mol or 5.3 kg / mol.

[0128] In some embodiments, the polyolefin represented by Formula VII-1 has a molecular weight distribution of 1.1-3.0, for example 1.2, 1.3 or 1.4.

[0129] In some embodiments, the polyolefin represented by formula VII-1 is any of the following:

[0130] (1) R 4a for A is composed of repeating units. and Random copolymer chains; repeating units The molar content of the random copolymer chain is 6.5%; the number-average molecular weight of the polyolefin as shown in Formula VII-1 is 5.3 kg / mol, and the molecular weight distribution is 1.2.

[0131] (2) R 4a for A is composed of repeating units. and Random copolymer chains; repeating units The molar content of the random copolymer chain is 9.7%; the number-average molecular weight of the polyolefin as shown in Formula VII-1 is 5.1 kg / mol, and the molecular weight distribution is 1.3.

[0132] (3) R 4a for A is composed of repeating units. and Random copolymer chains; repeating units The molar content of the random copolymer chain is 10.1%; the number-average molecular weight of the polyolefin as shown in Formula VII-1 is 3.8 kg / mol, and the molecular weight distribution is 1.2.

[0133] (4) R 4a for A is composed of repeating units. and Random copolymer chains; repeating units The molar content of the random copolymer chain is 13.4%; the number-average molecular weight of the polyolefin as shown in Formula VII-1 is 4.9 kg / mol, and the molecular weight distribution is 1.4.

[0134] In step (1), the organic solvent may be C 6-10 Aromatic solvents and / or ether solvents, such as toluene and / or tetrahydrofuran.

[0135] In step (1), the palladium catalyst may be Pd(PPh3)4.

[0136] In step (1), the molar ratio of the palladium catalyst to the polyolefin as shown in Formula VII-1 can be (0.01-0.2):1; preferably 0.1:1.

[0137] In step (1), the molar ratio of the acetyl chloride to the polyolefin shown in formula VII-1 can be (3-10):1; preferably 6:1.

[0138] In step (1), the reaction temperature can be 80-150 ℃, for example 100 ℃.

[0139] In step (1), the reaction time can be 12-36 h, for example 24 h.

[0140] In some embodiments, the number-average molecular weight of the polyolefin as shown in Formula VI-1 is 1-20 kg / mol; preferably 1-10 kg / mol, for example 3.8 kg / mol, 4.9 kg / mol, 5.1 kg / mol or 5.3 kg / mol.

[0141] In some embodiments, the polyolefin represented by Formula VI-1 has a molecular weight distribution of 1.1-3.0, for example 1.2, 1.3 or 1.4.

[0142] In some embodiments, the difunctionalization purity of the polyolefin represented by Formula VI-1 is greater than 95%, for example 99%.

[0143] In some embodiments, in the polyolefin shown in Formula VI-1, A is a repeating unit. and Random copolymer chains; repeating units The molar content of the random copolymer chain is 6.5%; p is 6;

[0144] The polyolefin shown in Formula VI-1 has a number-average molecular weight of 5.3 kg / mol and a molecular weight distribution of 1.2.

[0145] In some embodiments, in the polyolefin shown in Formula VI-1, A is a repeating unit. and Random copolymer chains; repeating units The molar content of the random copolymer chain is 9.7%; p is 6;

[0146] The polyolefin shown in Formula VI-1 has a number-average molecular weight of 5.1 kg / mol and a molecular weight distribution of 1.3.

[0147] In some embodiments, in the polyolefin shown in Formula VI-1, A is a repeating unit. and Random copolymer chains; repeating units The molar content of the random copolymer chain is 10.1%; p is 6;

[0148] The polyolefin shown in Formula VI-1 has a number-average molecular weight of 3.8 kg / mol and a molecular weight distribution of 1.2.

[0149] In some embodiments, in the polyolefin shown in Formula VI-1, A is a repeating unit. and Random copolymer chains; repeating units The molar content of the random copolymer chain is 13.4%; p is 6;

[0150] The polyolefin shown in Formula VI-1 has a number-average molecular weight of 4.9 kg / mol and a molecular weight distribution of 1.4.

[0151] In some embodiments, the organic solvent in the reduction reaction is C 6-10 Aromatic solvents and C 1-6 Alcohol solvents, such as toluene and ethanol.

[0152] In some embodiments, the reducing agent in the reduction reaction is sodium borohydride, lithium borohydride, sodium cyanoborohydride, or sodium triacetylborohydride, preferably sodium borohydride.

[0153] In some embodiments, the reduction reaction is carried out at a temperature of 40-80 °C, preferably 60 °C.

[0154] In some embodiments, the reduction reaction takes 5-10 hours, preferably 4 hours.

[0155] In some embodiments, the organic solvent in the deprotection reaction is C 6-10 Aromatic solvents and / or ether solvents, such as toluene and / or tetrahydrofuran.

[0156] In some embodiments, the deprotecting agent is tetrabutylammonium fluoride or hydrochloric acid ethanol solution, such as a 1M tetrabutylammonium fluoride tetrahydrofuran solution.

[0157] In some embodiments, the deprotection reaction is carried out at a temperature of 50-100°C, for example, 80°C.

[0158] In some implementations, the deprotection reaction takes 5-24 hours, for example, 12 hours.

[0159] In some embodiments, the method for preparing the polymer further includes a method for preparing the polyolefin as shown in Formula IV. The method for preparing the polyolefin as shown in Formula IV includes the following steps:

[0160] (1) In an organic solvent, in the presence of a palladium catalyst, acetyl chloride is reacted with a polyolefin as shown in formula VII-2 to obtain a polyolefin as shown in formula VI-2;

[0161] ;

[0162] Among them, R 4b for FG is ;R 1 R 2 and R 3 Independently for C 1-8 Alkyl or C 6-10 Aryl;

[0163] (2) In an organic solvent, in the presence of a reducing agent, the polyolefin shown in formula VI-2 is reduced to obtain the polyolefin shown in formula V-2.

[0164] ;

[0165] (3) In an organic solvent, in the presence of a deprotecting agent, the polyolefin shown in formula V-2 is subjected to a deprotection reaction to obtain the polyolefin shown in formula IV;

[0166] ;

[0167] Wherein, L and q are defined as described in any embodiment of the present invention.

[0168] In some embodiments, the reaction conditions of steps (1), (2), and (3) in the method for preparing the polyolefin as shown in Formula IV are the same as the reaction conditions of each step in the method for preparing the polyolefin as shown in Formula III.

[0169] In some embodiments, the polyolefin represented by formula VII-2 is a polyolefin as follows:

[0170] R 4b for L represents a repeating unit. The polymer chain is composed of the following: the polyolefin as shown in Formula VII-2 has a number-average molecular weight of 2.6 kg / mol and a molecular weight distribution of 1.1.

[0171] In some embodiments, the polyolefin represented by formula VI-2 is a polyolefin as follows:

[0172] L is composed of repeating units The polymer chain is composed of q, which is 6.

[0173] The polyolefin shown in Formula VI-2 has a number-average molecular weight of 2.6 kg / mol and a molecular weight distribution of 1.1.

[0174] Thirdly, the present invention provides a polymer prepared by the preparation method described in the second aspect of the present invention.

[0175] Fourthly, the present invention provides a method for recycling a polymer as described in the first aspect of the present invention, comprising the following steps:

[0176] (1) In organic solvents, in catalysts In the presence of an alkali, the polymer is subjected to a hydrogenation degradation reaction in a hydrogen atmosphere to obtain the polyolefin as shown in Formula III, the polyolefin as shown in Formula IV, or the polyolefin as shown in Formula III and the polyolefin as shown in Formula IV as described above.

[0177] (2) The obtained polyolefin as shown in Formula III, polyolefin as shown in Formula IV, or polyolefin as shown in Formula III and polyolefin as shown in Formula IV are subjected to a repolymerization reaction to obtain the polymer.

[0178] In some embodiments, the organic solvent in the degradation reaction is C 6-10Aromatic solvents, such as toluene.

[0179] In some embodiments, the base in the degradation reaction is potassium tert-butoxide.

[0180] In some embodiments, the mass ratio of the catalyst to the polymer in the degradation reaction is (0.0005-0.002):1, for example, 0.001:1.

[0181] In some embodiments, the molar ratio of the base to the catalyst in the degradation reaction is (3-5):1, for example, 4:1.

[0182] In some embodiments, the degradation reaction is carried out under a high-pressure hydrogen system at a pressure of 30-50 bar, for example, 40 bar.

[0183] In some embodiments, the degradation reaction is carried out at a temperature of 100-200°C, preferably 140-180°C, for example 150-170°C.

[0184] In some embodiments, the degradation reaction takes 40-100 hours, for example 48-72 hours.

[0185] In some embodiments, the degradation reaction includes a post-treatment process, which includes the following steps: after the reaction is complete, an acidified alcohol solvent (e.g., a hydrochloric acid methanol solution, or for example, a 0.04 mol / L hydrochloric acid methanol solution) is added to the system, followed by sedimentation, filtration, and drying to obtain the polymer.

[0186] In some embodiments, the polymerization reaction conditions in the recycling method are as described in the second aspect of the invention.

[0187] Fifthly, the present invention provides a polyolefin as shown in Formula III, Formula IV, Formula VI-1, Formula VI-2, Formula VII-1, or Formula VII-2:

[0188] , , , , or ;

[0189] Among them, R 4a for ;R 4b for FG is ;R 1 R 2 and R 3 Independently for C1-8 Alkyl or C 6-10 Aryl groups; the definitions of A, L, p, and q are as described above.

[0190] In some embodiments, the polyolefin as shown in Formula III is any of the following:

[0191] (1) A is composed of repeating units and Random copolymer chains; repeating units The molar content of the random copolymer chain is 6.5%; p is 6;

[0192] The polyolefin shown in Formula III has a number-average molecular weight of 6.0 kg / mol and a molecular weight distribution of 1.2.

[0193] (2) A is composed of repeating units and Random copolymer chains; repeating units The molar content of the random copolymer chain is 9.7%; p is 6;

[0194] The polyolefin shown in Formula III has a number-average molecular weight of 5.9 kg / mol and a molecular weight distribution of 1.3.

[0195] (3) A is composed of repeating units and Random copolymer chains; repeating units The molar content of the random copolymer chain is 10.1%; p is 6;

[0196] The polyolefin shown in Formula III has a number-average molecular weight of 4.6 kg / mol and a molecular weight distribution of 1.2.

[0197] (4) A is composed of repeating units and Random copolymer chains; repeating units The molar content of the random copolymer chain is 13.4%; p is 6;

[0198] The polyolefin shown in Formula III has a number-average molecular weight of 6.9 kg / mol and a molecular weight distribution of 1.4.

[0199] In some embodiments, the polyolefin represented by Formula IV is a polyolefin as follows:

[0200] L is composed of repeating units The polymer chain is composed of q, which is 6; the number-average molecular weight of the polyolefin shown in Formula IV is 2.4 kg / mol, and the molecular weight distribution is 1.1.

[0201] In some embodiments, the polyolefin represented by formula VI-1 is any of the following:

[0202] (1) A is composed of repeating units and Random copolymer chains; repeating units The molar content of the random copolymer chain is 6.5%; p is 6;

[0203] The polyolefin shown in Formula VI-1 has a number-average molecular weight of 5.3 kg / mol and a molecular weight distribution of 1.2.

[0204] (2) A is composed of repeating units and Random copolymer chains; repeating units The molar content of the random copolymer chain is 9.7%; p is 6;

[0205] The polyolefin shown in Formula VI-1 has a number-average molecular weight of 5.1 kg / mol and a molecular weight distribution of 1.3.

[0206] (3) A is composed of repeating units and Random copolymer chains; repeating units The molar content of the random copolymer chain is 10.1%; p is 6;

[0207] The polyolefin shown in Formula VI-1 has a number-average molecular weight of 3.8 kg / mol and a molecular weight distribution of 1.2.

[0208] (4) A is composed of repeating units and Random copolymer chains; repeating units The molar content of the random copolymer chain is 13.4%; p is 6;

[0209] The polyolefin shown in Formula VI-1 has a number-average molecular weight of 4.9 kg / mol and a molecular weight distribution of 1.4.

[0210] In some embodiments, the polyolefin represented by formula VI-2 is a polyolefin as follows:

[0211] L is composed of repeating units The polymer chain is composed of q, which is 6.

[0212] The polyolefin shown in Formula VI-2 has a number-average molecular weight of 2.6 kg / mol and a molecular weight distribution of 1.1.

[0213] In some embodiments, the polyolefin represented by formula VII-1 is any of the following:

[0214] (1) R 4a for A is composed of repeating units. and Random copolymer chains; repeating units The molar content of the random copolymer chain is 6.5%; the number-average molecular weight of the polyolefin as shown in Formula VII-1 is 5.3 kg / mol, and the molecular weight distribution is 1.2.

[0215] (2) R 4a for A is composed of repeating units. and Random copolymer chains; repeating units The molar content of the random copolymer chain is 9.7%; the number-average molecular weight of the polyolefin as shown in Formula VII-1 is 5.1 kg / mol, and the molecular weight distribution is 1.3.

[0216] (3) R 4a for A is composed of repeating units. and Random copolymer chains; repeating units The molar content of the random copolymer chain is 10.1%; the number-average molecular weight of the polyolefin as shown in Formula VII-1 is 3.8 kg / mol, and the molecular weight distribution is 1.2.

[0217] (4) R 4a for A is composed of repeating units. and Random copolymer chains; repeating units The molar content of the random copolymer chain is 13.4%; the number-average molecular weight of the polyolefin as shown in Formula VII-1 is 4.9 kg / mol, and the molecular weight distribution is 1.4.

[0218] In some embodiments, the polyolefin represented by formula VII-2 is a polyolefin as follows:

[0219] R 4b for L represents a repeating unit. The polymer chain is composed of the following: the polyolefin as shown in Formula VII-2 has a number-average molecular weight of 2.6 kg / mol and a molecular weight distribution of 1.1.

[0220] the term

[0221] Unless otherwise specified herein, all terms and abbreviations shall have their conventional meanings as are known to those skilled in the art.

[0222] The term "alkyl" refers to a straight-chain or branched alkyl group having a specified number of carbon atoms (e.g., C1-8). Alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, isobutyl, sec-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, etc.

[0223] The term "alkylene" refers to the further substitution of one hydrogen atom of an alkyl group.

[0224] The term "alkoxy" refers to the group R. X -O-, where R X It is an alkyl group as defined above.

[0225] The term "halogen" refers to F, Cl, Br, and I.

[0226] The term "aryl" refers to an aryl group having a specified number of carbon atoms (e.g., C6~C5). 10 An aryl group is a cyclic group consisting solely of carbon atoms, which can be monocyclic or polycyclic and possess aromaticity (following Hückel's rule). The aryl group is linked to other segments of the molecule via an aromatic or non-aromatic ring. Aryl groups include, but are not limited to, phenyl and naphthyl groups.

[0227] The term "room temperature" refers to a temperature of 10-40 °C, preferably 25±5 °C.

[0228] It should be understood that, within the scope of this invention, the above-described technical features of this invention and the technical features specifically described below (such as in the embodiments) can be combined with each other to form new or preferred technical solutions. Due to space limitations, they will not be described in detail here.

[0229] Based on common knowledge in the field, the above-mentioned preferred conditions can be combined arbitrarily to obtain various preferred embodiments of the present invention.

[0230] The reagents and raw materials used in this invention are all commercially available.

[0231] (a) The positive and progressive effects of the present invention are as follows: the polar polymer provided by the present invention can be recycled, effectively solving the ecological environment and resource shortage problems caused by the single use and difficulty in recycling of traditional polar polyolefins.

[0232] (b) The polar polymer provided by the present invention is recyclable, which effectively solves the problems of complex operation and poor performance in the synthesis of closed-loop recyclable polyolefins.

[0233] (c) The method of the present invention can be used to prepare polar polymers with controllable degradation sites and mild degradation conditions, which effectively solves the ecological environment and resource shortage problems caused by the single use and difficulty in recycling of traditional polyolefins. Detailed Implementation

[0234] The present invention is further illustrated below by way of examples, but the invention is not limited to the scope of the examples described. Experimental methods not specifically described in the following examples were performed according to conventional methods and conditions, or as selected according to the product instructions. The number-average molecular weight and molecular weight distribution of the polymers in the following examples were determined by GPC, the polymer melting point was determined by DSC, and the tensile properties (e.g., elongation at break, tensile strength) were determined according to ASTM D638.

[0235] Example 1: Synthesis of Zn(R)2 (ethylene or ethylene octene copolymer)

[0236] Add 100 mL of toluene solvent to the reactor, and add 1 mmol of Zn((CH2)6OSiPr i 3)2 (prepared according to Example 1 of patent CN118599038A), ethylene at 5 atm was introduced until saturation, different amounts of octene were added, and 20 μmol of catalyst was added. And 24 μmol of cocatalyst Ph3CB(C6F5)4.

[0237] Polymerization was carried out at 80 °C, and ethylene or ethylene-octene copolymer Zn(R)2 was prepared according to the amount of octene in Table 1, which was used for the next reaction.

[0238]

[0239]

[0240] The octene insertion rate of 6.5% refers to the percentage of repeating units in the random copolymer chain. The molar content is 6.5%, repeating unit The molar content is 93.5%.

[0241] Example 2: Teleclaw polyolefin i Synthesis of Pr3SiO-(CH2)6-R-CO-CH3

[0242] After the polymerization reaction described in Example 1 was completed, 0.1 mmol Pd(PPh3)4, 6 mmol acetyl chloride, and 20 mL THF were added to the reaction system, and the reaction was carried out at 100 °C for 24 h. Then, the mixture was cooled to room temperature, ethanol was allowed to precipitate, and the mixture was washed and filtered to obtain the telechelic polyolefin.

[0243]

[0244]

[0245] tPO1: 1 H NMR(600MHz, tetrachloroethane-d2, 110 ℃, ppm), δ 3.76 (t, J= 6.4 Hz, 2H), 2.43 (t, J = 7.4 Hz, 2H), 2.15 (s, 3H), 1.61 (dd, J = 13.8,7.3 Hz, 4H), 1.35 (d, J = 1.6 Hz, 354H), 1.14 (d, J = 1.8 Hz, 21H).

[0246] tPO2: 1 H NMR(600MHz, tetrachloroethane-d2, 110 ℃, ppm), δ 3.76 (t, J= 6.5 Hz, 2H), 2.45 - 2.34 (m, 2H), 2.15 (s, 3H), 1.62 (dt, J = 13.8, 7.0 Hz,4H), 1.35 (s, 807H), 1.14 (d, J = 2.1 Hz, 21H), 0.96 (t, J = 7.0 Hz, 34H).

[0247] tPO3: 1 H NMR(600MHz, tetrachloroethane-d2, 110 ℃, ppm), δ 3.76 (t, J= 6.4 Hz, 2H), 2.46 - 2.33 (m, 2H), 2.15 (s, 3H), 1.70 - 1.57 (m, 4H), 1.41(d, J = 73.9 Hz, 807H), 1.14 (s, 21H), 0.96 (t, J = 6.8 Hz, 43H).

[0248] tPO4: 1H NMR(600MHz, tetrachloroethane-d2, 110 ℃, ppm), δ 3.76 (t, J= 6.7 Hz, 2H), 2.49 - 2.33 (m, 2H), 2.15 (s, 3H), 1.62 (dq, J = 14.3, 7.1 Hz, 4H), 1.36 (s, 563H), 1.15 (d, J = 2.2 Hz, 21H), 0.97 (t, J = 6.9 Hz, 36H).

[0249] tPO5: 1 H NMR(600MHz, tetrachloroethane-d2, 110 ℃, ppm), δ 3.76 (t, J= 6.6 Hz, 2H), 2.46 - 2.34 (m, 2H), 2.15 (s, 3H), 1.61 (p, J = 7.0 Hz, 4H),1.55 - 1.23 (m, 898H), 1.14 (d, J = 2.2 Hz, 21H), 0.97 (t, J = 6.8 Hz, 70H).

[0250] Example 3: Synthesis of the telechelic polyolefin HO-(CH2)6-R-CH(CH3)OH

[0251] The polyolefin tPO2 (6 g) obtained in Example 2 was added to the reactor, along with 100 mL of toluene, 5 mL of ethanol, and sodium borohydride (10 equivalents). The mixture was stirred at 60 °C for 4 h. After the reaction was complete, the mixture was cooled to room temperature, and 2 mL of acetic acid was added to quench the reaction. 500 mL of methanol was added for precipitation, followed by washing and filtration. The resulting solid was dissolved in 100 mL of toluene, and 4 mL of a 1M tetrabutylammonium fluoride (TBAF) tetrahydrofuran solution was added. The mixture was stirred at 80 °C for 12 h, and 500 mL of methanol was added for precipitation. The mixture was washed and filtered to obtain 5.5 g of telechelic polyolefin tPO7.

[0252] tPO6, tPO8, tPO9 and tPO10 were prepared using the same method as tPO7.

[0253]

[0254]

[0255] tPO6: 1H NMR(600MHz, tetrachloroethane-d2, 110 ℃, ppm), δ 3.83 (q, J= 6.0 Hz, 1H), 3.67 (t, J = 6.6 Hz, 2H), 1.63 (p, J = 6.7 Hz, 2H), 1.36 (s,353H), 1.28 - 1.20 (m, 3H).

[0256] tPO7: 1 H NMR(600MHz, tetrachloroethane-d2, 110 ℃, ppm), δ 3.97 - 3.77(m, 1H), 3.67 (t, J = 6.5 Hz, 2H), 1.69 - 1.58 (m, 2H), 1.57 - 1.10 (m,876H), 1.08 - 0.89 (m, 38H).

[0257] tPO8: 1 H NMR(600MHz, tetrachloroethane-d2, 110 ℃, ppm), δ 3.87 (d, J= 46.0 Hz, 1H), 3.67 (t, J = 6.5 Hz, 2H), 1.72 - 1.60 (m, 2H), 1.35 (s,809H), 0.96 (t, J = 6.7 Hz, 48H).

[0258] tPO9: 1 H NMR(600MHz, tetrachloroethane-d2, 110 ℃, ppm), δ 3.97 - 3.78(m, 1H), 3.67 (t, J = 6.6 Hz, 2H), 1.63 (t, J = 7.0 Hz, 2H), 1.36 (s, 618H),0.97 (t, J = 6.8 Hz, 38H).

[0259] tPO10: 1 H NMR(600MHz, tetrachloroethane-d2, 110 ℃, ppm), δ 3.96 -3.78 (m, 1H), 3.67 (t, J = 6.6 Hz, 2H), 1.68 - 1.58 (m, 2H), 1.35 (s, 962H),0.97 (t, J = 6.9 Hz, 75H).

[0260] Application Example: Preparation of High-Performance Recyclable Polymers Using Telechelic Polyolefins

[0261] Preparation of controllable degradation and recycling polymers

[0262] Example 4:

[0263] A method for preparing a controllable degradation and recycling polymer is as follows: A 100 mL Schlenk reaction tube is used. Under nitrogen protection, tPO6 (6.1 g, molecular weight 2.4 kg / mol), 20 mL of toluene, hexamethylene diisocyanate (420 mg), and the catalyst dibutyltin dilaurate (3.2 mg) are added sequentially. The temperature is raised to a predetermined temperature of 90°C, and the reaction is stopped after a predetermined time of 12 h. The system is then allowed to return to room temperature. The polymer is dissolved in a suitable amount of the good solvent trimethylbenzene, and then precipitated in the poor solvent methanol. The solid residue is collected by filtration and vacuum dried to obtain the polymer M. The obtained polymer M... n = 64.0 kg / mol, PDI = 1.4. The resulting polymer T m = 119 ℃, the elongation at break in the stress-strain curve is 1525%, and the tensile strength is 23.3 MPa.

[0264] 1 H NMR(600MHz, tetrachloroethane-d2, 110 ℃, ppm), δ 4.83 (q, J = 6.5Hz, 1H), 4.52 (d, J = 23.5 Hz, 2H), 4.10 (t, J = 6.8 Hz, 2H), 3.19 (p, J =6.0 Hz, 4H), 1.67 (q, J = 10.2, 8.6 Hz, 4H), 1.62 - 1.51 (m, 8H), 1.51 - 1.18 (m, 366H).

[0265] Example 5:

[0266] A method for preparing a controllable degradation and recycling polymer is as follows: A 100 mL Schlenk reaction tube is used. Under nitrogen protection, 12.0 g of tPO7 (molecular weight 6.0 kg / mol), 20 mL of toluene, 336 mg of hexamethylene diisocyanate, and 2.6 mg of dibutyltin dilaurate catalyst are added sequentially. The mixture is heated to a predetermined temperature of 80°C and reacted for a predetermined time of 12 h. The system is then allowed to return to room temperature. The polymer is dissolved in a suitable amount of the good solvent trimethylbenzene, then precipitated in the poor solvent methanol. The solid residue is collected by filtration and vacuum dried to obtain the polymer M. The obtained polymer M...n = 102.9 kg / mol, PDI = 1.9. The resulting polymer T m = 83 ℃, the elongation at break in the stress-strain curve is 1546%, and the tensile strength is 30.8 MPa.

[0267] Example 6:

[0268] A method for preparing a controllable degradation and recycling polymer is as follows: A 100 mL Schlenk reaction tube is used. Under nitrogen protection, tPO8 (5.9 g, molecular weight 5.9 kg / mol), 20 mL of toluene, hexamethylene diisocyanate (168 mg), and the catalyst dibutyltin dilaurate (1.3 mg) are added sequentially. The temperature is raised to a predetermined temperature of 80°C, and the reaction is stopped after a predetermined time of 12 h. The system is then allowed to return to room temperature. The polymer is dissolved in a suitable amount of the good solvent trimethylbenzene, and then precipitated in the poor solvent methanol. The solid residue is collected by filtration and vacuum dried to obtain the polymer M. The obtained polymer M... n = 70.8 kg / mol, PDI = 1.7.

[0269] Example 7:

[0270] A method for preparing a controllable degradation and recycling polymer is as follows: A 100 mL Schlenk reaction tube is used. Under nitrogen protection, tPO9 (27.5 g, molecular weight 4.6 kg / mol), 20 mL of toluene, hexamethylene diisocyanate (1.0 g), and the catalyst dibutyltin dilaurate (7.6 mg) are added sequentially. The temperature is raised to a predetermined temperature of 80°C, and the reaction is stopped after a predetermined time of 12 h. The system is then allowed to return to room temperature. The polymer is dissolved in a suitable amount of the good solvent trimethylbenzene, and then precipitated in the poor solvent methanol. The solid residue is collected by filtration and vacuum dried to obtain the polymer M. The obtained polymer M... n = 120.6 kg / mol, PDI = 1.5. The resulting polymer T m = 62 ℃, the elongation at break in the stress-strain curve is 1659%, and the tensile strength is 25.1 MPa.

[0271] Example 8:

[0272] A method for preparing a controllable degradation and recycling polymer is as follows: A 100 mL Schlenk reaction tube is used. Under nitrogen protection, tPO10 (6.9 g, molecular weight 6.9 kg / mol), 20 mL of toluene, hexamethylene diisocyanate (168 mg), and the catalyst dibutyltin dilaurate (1.3 mg) are added sequentially. The temperature is raised to a predetermined temperature of 80°C, and the reaction is stopped after a predetermined time of 12 h. The system is then allowed to return to room temperature. The polymer is dissolved in a suitable amount of the good solvent trimethylbenzene, and then precipitated in the poor solvent methanol. The solid residue is collected by filtration and vacuum dried to obtain the polymer M. The obtained polymer M... n = 95.3 kg / mol, PDI = 1.6. The resulting polymer T m = 49 ℃, the elongation at break in the stress-strain curve is 3048%, and the tensile strength is 9.3 MPa.

[0273] Example 9:

[0274] A method for preparing a controllable degradation and recycling polymer is as follows: A 100 mL Schlenk reaction tube is used. Under nitrogen protection, tPO6 (4.2 g, molecular weight 2.4 kg / mol), tPO9 (1.8 g, molecular weight 4.6 kg / mol), 20 mL of toluene, hexamethylene diisocyanate (353 mg), and the catalyst dibutyltin dilaurate (2.8 mg) are added sequentially. The temperature is raised to a predetermined temperature of 90°C, and the reaction is stopped after a predetermined time of 12 h. The system is then allowed to return to room temperature. The polymer is dissolved in a suitable amount of the good solvent trimethylbenzene, and then precipitated in the poor solvent methanol. The solid residue is collected by filtration and vacuum dried to obtain the polymer M. The obtained polymer M... n = 90.5 kg / mol, PDI = 1.3. Based on the molar ratio of the two tPOs at the time of reaction, the PE units in the resulting polymer ( The molar percentage of POE units is 81%. The molar percentage of octene was 19%, and the octene insertion rate in the resulting polymer was 1.9%. The resulting polymer T... m = 116 ℃, the elongation at break in the stress-strain curve is 1447%, and the tensile strength is 27.5 MPa.

[0275] Example 10:

[0276] A method for preparing a controllable degradation and recycling polymer is as follows: A 100 mL Schlenk reaction tube is used. Under nitrogen protection, tPO6 (1.8 g, molecular weight 2.4 kg / mol), tPO9 (4.2 g, molecular weight 4.6 kg / mol), 20 mL of toluene, hexamethylene diisocyanate (278 mg), and the catalyst dibutyltin dilaurate (2.2 mg) are added sequentially. The temperature is raised to a predetermined temperature of 90°C, and the reaction is stopped after a predetermined time of 12 h. The system is then allowed to return to room temperature. The polymer is dissolved in a suitable amount of the good solvent trimethylbenzene, and then precipitated in the poor solvent methanol. The solid residue is collected by filtration and vacuum dried to obtain the polymer M. The obtained polymer M... n = 61.3 kg / mol, PDI = 2.0. Based on the molar ratio of the two tPOs at the time of reaction, the PE units in the resulting polymer ( The molar percentage is 44%, and the POE unit ( The molar percentage of octene was 56%, and the octene insertion rate in the resulting polymer was 5.6%. The resulting polymer T... m = 110 ℃, the elongation at break in the stress-strain curve is 1599%, and the tensile strength is 35.7 MPa.

[0277] Example 11:

[0278] A method for preparing a controllable degradation and recycling polymer is as follows: A 100 mL Schlenk reaction tube is used. Under nitrogen protection, tPO6 (1.2 g, molecular weight 2.4 kg / mol), tPO9 (4.8 g, molecular weight 4.6 kg / mol), 20 mL of toluene, hexamethylene diisocyanate (259 mg), and the catalyst dibutyltin dilaurate (2.0 mg) are added sequentially. The temperature is raised to a predetermined temperature of 90°C, and the reaction is stopped after a predetermined time of 12 h. The system is then allowed to return to room temperature. The polymer is dissolved in a suitable amount of the good solvent trimethylbenzene, and then precipitated in the poor solvent methanol. The solid residue is collected by filtration and vacuum dried to obtain the polymer M. The obtained polymer M... n = 74.6 kg / mol, PDI = 1.8. Based on the molar ratio of the two tPOs at the time of reaction, the PE units in the resulting polymer ( The molar percentage is 32%, and the POE unit ( The molar percentage of octene was 68%, and the octene insertion rate in the resulting polymer was 6.8%. The resulting polymer T... m = 106 ℃.

[0279] Example 12:

[0280] A method for preparing a controllable degradation and recycling polymer is as follows: A 100 mL Schlenk reaction tube is used. Under nitrogen protection, tPO6 (0.4 g, molecular weight 2.4 kg / mol), tPO9 (5.6 g, molecular weight 4.6 kg / mol), 20 mL of toluene, hexamethylene diisocyanate (233 mg), and the catalyst dibutyltin dilaurate (1.8 mg) are added sequentially. The temperature is raised to a predetermined temperature of 90°C, and the reaction is stopped after a predetermined time of 12 h. The system is then allowed to return to room temperature. The polymer is dissolved in a suitable amount of the good solvent trimethylbenzene, and then precipitated in the poor solvent methanol. The solid residue is collected by filtration and vacuum dried to obtain the polymer M. The obtained polymer M... n = 83.3 kg / mol, PDI = 1.7. Based on the molar ratio of the two tPOs at the time of reaction, the PE units in the resulting polymer ( The molar percentage is 12%, POE unit ( The molar percentage of octene was 88%, and the octene insertion rate in the resulting polymer was 8.9%. The resulting polymer T... m = 101 ℃.

[0281] The data is as follows:

[0282]

[0283]

[0284]

[0285]

[0286] The polymers prepared in Examples 9-12 are random block copolymers, with PE units ( ) and POE unit ( () is a random or unordered link.

[0287] Example 13: Degradation of POE polymer

[0288] In a glove box, 6.0 g of the polymer obtained in Example 5 was weighed and placed in a 260 mL glass liner. Toluene (50 mL) and catalyst were added sequentially. (60 mg), potassium tert-butoxide (42.6 mg). The mixture was placed in a high-pressure reactor with a glass liner, sealed, and then removed from the glove box. Hydrogen gas was introduced at 40 bar, and the reaction was continued at 150°C for 72 hours. After the reaction, the mixture was cooled to room temperature (25°C), and residual hydrogen gas was slowly released. 100 mL of a methanol solution of HCl (0.04 M) was added to the reaction system, allowing it to settle. The solid residue was collected by filtration and vacuum dried to obtain the polymer monomer tPO7-1, with a number-average molecular weight M.n = 6.0 kg / mol.

[0289] Preparation of controllable degradation and recycling of polyolefins

[0290] Example 14:

[0291] A method for preparing a controllable degradation and recycling polymer is as follows: A 300 mL Schlenk reaction tube is used. Under nitrogen protection, tPO9 (27.5 g, molecular weight 4.6 kg / mol), 120 mL of toluene, hexamethylene diisocyanate (1 g), and the catalyst dibutyltin dilaurate (18 mg) are added sequentially. The temperature is raised to a predetermined temperature of 80°C, and the reaction is stopped after a predetermined time of 12 h. The system is then allowed to return to room temperature. The polymer is dissolved in a suitable amount of the good solvent trimethylbenzene, and then precipitated in the poor solvent methanol. The solid residue is collected by filtration and vacuum dried to obtain polymer H-PO-1. The resulting polymer M... n =120.6 kg / mol, PDI = 1.5. The elongation at break in the stress-strain curve is 1659%, and the tensile strength is 25.1 MPa.

[0292] In a glove box, weigh 18.0 g of H-PO-1 polymer and place it in a 260 mL glass liner. Then add toluene (100 mL) and catalyst sequentially. (180 mg), potassium tert-butoxide (128 mg). The mixture was placed in a high-pressure reactor with a glass liner, sealed, and then removed from the glove box. Hydrogen gas was introduced at 40 bar, and the reaction was continued at 150°C for 72 hours. After the reaction, the mixture was cooled to room temperature (25°C), and residual hydrogen gas was slowly released. 400 mL of a methanol solution of HCl (0.04 M) was added to the reaction system, allowing it to settle. The solid residue was collected by filtration and vacuum dried to obtain the polymer monomer tPO9-1 (16.7 g), with a number-average molecular weight M. n = 4.6 kg / mol.

[0293] Second cycle: A 300 mL Schlenk reaction tube was used. Under nitrogen protection, tPO9-1 (16 g, molecular weight 4.6 kg / mol), 70 mL of toluene, hexamethylene diisocyanate (0.588 g), and the catalyst dibutyltin dilaurate (10 mg) were added sequentially. The temperature was raised to the predetermined temperature of 80 °C, and the reaction was stopped after the predetermined time of 12 h. The system was then allowed to return to room temperature. The polymer was dissolved in a suitable amount of the good solvent trimethylbenzene, and then precipitated in the poor solvent methanol. The solid residue was collected by filtration and vacuum dried to obtain polymer H-PO-2. The obtained polymer M... n= 179.0 kg / mol, PDI = 1.5. The elongation at break in the stress-strain curve is 1631%, and the tensile strength is 25.6 MPa.

[0294] In a glove box, weigh 8.0 g of H-PO-2 polymer and place it in a 260 mL glass liner. Then add toluene (50 mL) and catalyst sequentially. (80 mg), potassium tert-butoxide (57 mg). The mixture was placed in a high-pressure reactor with a glass liner, sealed, and then removed from the glove box. Hydrogen gas was introduced at 40 bar, and the reaction was continued at 150°C for 72 hours. After the reaction, the mixture was cooled to room temperature (25°C), and the residual hydrogen gas was slowly released. 200 mL of a methanol solution of HCl (0.04 M) was added to the reaction system, allowing it to settle. The solid residue was collected by filtration and vacuum dried to obtain the polymer monomer tPO9-2 (7.5 g), with a number-average molecular weight M. n = 4.6 kg / mol.

[0295] Third cycle: A 100 mL Schlenk reaction tube was used. Under nitrogen protection, tPO9-2 (7 g, molecular weight 4.6 kg / mol), 30 mL of toluene, hexamethylene diisocyanate (0.257 g), and the catalyst dibutyltin dilaurate (4 mg) were added sequentially. The temperature was raised to the predetermined temperature of 80 °C, and the reaction was stopped after the predetermined time of 12 h. The system was then allowed to return to room temperature. The polymer was dissolved in a suitable amount of the good solvent trimethylbenzene, and then precipitated in the poor solvent methanol. The solid residue was collected by filtration and vacuum dried to obtain polymer H-PO-3. The obtained polymer M... n = 71.2 kg / mol, PDI = 1.5. The elongation at break in the stress-strain curve is 1664%, and the tensile strength is 24.8 MPa.

[0296] In a glove box, weigh 7.0 g of H-PO-3 polymer and place it in a 260 mL glass liner. Then add toluene (50 mL) and catalyst sequentially. (70 mg), potassium tert-butoxide (52 mg). The mixture was placed in a high-pressure reactor with a glass liner, sealed, and then removed from the glove box. Hydrogen gas was introduced at 40 bar, and the reaction was continued at 150°C for 72 hours. After the reaction, the mixture was cooled to room temperature (25°C), and the residual hydrogen gas was slowly released. 100 mL of a methanol solution of HCl (0.04 M) was added to the reaction system, allowing it to settle. The solid residue was collected by filtration and vacuum dried to obtain the polymer monomer tPO9-3 (6.5 g), with a number-average molecular weight M. n = 4.6 kg / mol.

[0297] All documents mentioned in this invention are incorporated herein by reference as if each document were individually incorporated by reference. Furthermore, it should be understood that after reading the foregoing teachings of this invention, those skilled in the art can make various alterations or modifications to this invention, and these equivalent forms also fall within the scope defined by the appended claims.

Claims

1. A polymer having repeating units as shown in Formula I, repeating units as shown in Formula II, or repeating units as shown in both Formula I and Formula II; 、 ； in, A is composed of repeating units. and The random copolymer chain consists of repeating units. The molar content of the random copolymer chain is 0.5-25%; L is composed of repeating units The polymer chain that makes up the polymer chain; B and E are independent of C 1-10 Alkylene or C 6-10 Alpha-aryl; p and q are independent integers from 1 to 20; When the polymer has repeating units as shown in Formula I and Formula II, the molar content of the repeating units as shown in Formula I in the polymer is 1-98%; The number-average molecular weight of the polymer is 25-200 kg / mol.

2. The polymer according to claim 1, characterized in that, The polymer satisfies at least one of the following conditions: (1) p and q are independent integers from 5 to 10, for example, 6; (2) B and E are -(CH2)6-; (3) A is composed of repeating units and The random copolymer chain consists of repeating units. The molar content of the random copolymer chain is 5-15%, for example 6.5%, 9.7%, 10.1% or 13.4%; (4) When the polymer has repeating units as shown in Formula I and Formula II, the molar content of the repeating units as shown in Formula I in the polymer is 10-90%, for example 19%, 56%, 68% or 88%; (5) When the polymer has repeating units as shown in Formula I and Formula II, the repeating units The molar content of the polymer is 0-10%, for example 1.9%, 5.6%, 6.8% or 8.9%; (6) In the polymer, the end group connected to the carbonyl group in the polymer is -OC. 1-8 Alkyl group, with H as the terminal group on the other side; preferably, the terminal group connected to the carbonyl group of the polymer is -OMe or -OEt, with H as the terminal group on the other side; (7) The number average molecular weight of the polymer is 50-200 kg / mol, for example 61.3 kg / mol, 64.0 kg / mol, 70.8 kg / mol, 74.6 kg / mol, 83.3 kg / mol, 90.5 kg / mol, 95.3 kg / mol, 102.9 kg / mol or 120.6 kg / mol; (8) The molecular weight distribution of the polymer is 1.3-4.0, for example 1.4, 1.5, 1.6, 1.7, 1.8, 1.9 or 2.0; (9) The melting point of the polymer is 49-120°C, for example 62°C, 67°C, 83°C, 101°C, 106°C, 110°C, 116°C or 119°C.

3. The polymer as described in claim 1 or 2, characterized in that, The polymer is any one of the following: (1) The polymer has repeating units as shown in Formula I; A is composed of repeating units. and The random copolymer chain consists of repeating units. The molar content of the random copolymer chain is 0.5-25%; B is -(CH2)6-; p is 6; The polymer has a number-average molecular weight of 25-200 kg / mol and a molecular weight distribution of 1.3-4.

0. (2) The polymer has repeating units as shown in Formula II; L is composed of repeating units The polymer chain that makes up the polymer chain; E is -(CH2)6-; q is 6; The polymer has a number-average molecular weight of 25-200 kg / mol and a molecular weight distribution of 1.3-4.

0. (3) The polymer has repeating units as shown in Formula I and Formula II; Where A is composed of repeating units and The random copolymer chain consists of repeating units. The molar content of the random copolymer chain is 0.5-25%; B is -(CH2)6-; p is 6; L is composed of repeating units The polymer chain that makes up the polymer chain; E is -(CH2)6-; q is 6; The molar content of the repeating unit as shown in Formula I in the polymer is 1-98%; The polymer has a number-average molecular weight of 25-200 kg / mol and a molecular weight distribution of 1.2-2.

1.

4. The polymer according to claim 1, characterized in that, The polymer is any one of the following: (1) The polymer has repeating units as shown in Formula I; Where A is composed of repeating units and Random copolymer chains; repeating units The molar content of the random copolymer chain is 6.5%; B is -(CH2)6-; p is 6; The polymer has a number-average molecular weight of 102.9 kg / mol and a molecular weight distribution of 1.

9. (2) The polymer has repeating units as shown in Formula I; Where A is composed of repeating units and Random copolymer chains; repeating units The molar content of the random copolymer chain is 9.7%; B is -(CH2)6-; p is 6; The polymer has a number-average molecular weight of 70.8 kg / mol and a molecular weight distribution of 1.

7. (3) The polymer has repeating units as shown in Formula I; Where A is composed of repeating units and Random copolymer chains; repeating units The molar content of the random copolymer chain is 10.1%; B is -(CH2)6-; p is 6; The polymer has a number-average molecular weight of 120.6 kg / mol and a molecular weight distribution of 1.

5. (4) The polymer has repeating units as shown in Formula I; Where A is composed of repeating units and Random copolymer chains; repeating units The molar content of the random copolymer chain is 13.4%; B is -(CH2)6-; p is 6; The polymer has a number-average molecular weight of 95.3 kg / mol and a molecular weight distribution of 1.

6. (5) The polymer has repeating units as shown in Formula II; Where L is composed of repeating units The polymer chain that makes up the polymer chain; E is -(CH2)6-; q is 6; The polymer has a number-average molecular weight of 64.0 kg / mol and a molecular weight distribution of 1.

4. (6) The polymer has repeating units as shown in Formula I and Formula II; wherein, A is a repeating unit and Random copolymer chains; repeating units The molar content of the random copolymer chain is 10.1%; B is -(CH2)6-; p is 6; L is composed of repeating units The polymer chain that makes up the polymer chain; E is -(CH2)6-; q is 6; The repeating unit as shown in Formula I has a molar content of 19% in the polymer; The polymer has a number-average molecular weight of 90.5 kg / mol and a molecular weight distribution of 1.

3. (7) The polymer has repeating units as shown in Formula I and Formula II; wherein, A is a repeating unit and Random copolymer chains; repeating units The molar content of the random copolymer is 10.1%; B is -(CH2)6-; p is 6; L is composed of repeating units The polymer chain that makes up the polymer chain; E is -(CH2)6-; q is 6; The repeating unit as shown in Formula I has a molar content of 56% in the polymer; The polymer has a number-average molecular weight of 61.3 kg / mol and a molecular weight distribution of 2.

0. (8) The polymer has repeating units as shown in Formula I and Formula II; wherein, A is a repeating unit and Random copolymer chains; repeating units The molar content of the random copolymer is 10.1%; B is -(CH2)6-; p is 6; L is composed of repeating units The polymer chain that makes up the polymer chain; E is -(CH2)6-; q is 6; The repeating unit as shown in Formula I has a molar content of 68% in the polymer; The polymer has a number-average molecular weight of 74.6 kg / mol and a molecular weight distribution of 1.

8. (9) The polymer has repeating units as shown in Formula I and Formula II; wherein, A is a repeating unit and Random copolymer chains; repeating units The molar content of the random copolymer is 10.1%; B is -(CH2)6-; p is 6; L is composed of repeating units The polymer chain that makes up the polymer chain; E is -(CH2)6-; q is 6; The repeating unit as shown in Formula I has a molar content of 88% in the polymer; The polymer has a number-average molecular weight of 83.3 kg / mol and a molecular weight distribution of 1.

7.

5. A method for preparing the polymer according to any one of claims 1-4, characterized in that, The preparation method includes the following steps: in an organic solvent, in the presence of a Lewis acid catalyst, The polymer is obtained by polymerizing with a polyolefin, wherein the polyolefin is a polyolefin as shown in Formula III, a polyolefin as shown in Formula IV, or a polyolefin as shown in both Formula III and Formula IV. 、 。 6. The method for preparing the polymer according to claim 5, characterized in that, The preparation method satisfies at least one of the following conditions: (1) The number average molecular weight of the polyolefin as shown in Formula III or Formula IV is 1-20 kg / mol; preferably 1-10 kg / mol, for example 2.4 kg / mol, 4.6 kg / mol, 5.9 kg / mol, 6.0 kg / mol or 6.9 kg / mol; (2) The molecular weight distribution of the polyolefin as shown in Formula III or Formula IV is 1.1-3.0, for example 1.1, 1.2, 1.3 or 1.4; (3) The difunctional purity of the polyolefin as shown in Formula III or Formula IV is greater than 95%, for example 99%; (4) When the polyolefin is a polyolefin of formula III or formula IV, the weight ratio of the polyolefin of formula III to that of formula IV is 1: (0.02-10), for example 1: 0.07, 1: 0.25, 1: 0.4 or 1: 2.3; (5) It is hexamethylene diisocyanate; (6) The molar ratio of the polyolefin to the polyolefin is (0.9-1.1):1, for example, 1:1; (7) The organic solvent is C 6-10 Aromatic solvents, such as toluene; (8) The Lewis acid catalyst is one or more of tetrabutyl titanate, dibutyltin dilaurate and stannous octoate, preferably dibutyltin dilaurate; (9) The molar ratio of the Lewis acid catalyst to the polyolefin is (0.001-0.005):1, for example, 0.002:1; (10) The reaction temperature of the polymerization reaction is 40-100 °C. ° C, preferably 60-90 °C, more preferably 80 °C; (11) The reaction time of the polymerization reaction is 5-20 h, preferably 10-15 h, for example 12 h.

7. The method for preparing the polymer according to claim 5, characterized in that, The method for preparing the polymer further includes a method for preparing the polyolefin as shown in Formula III or Formula IV; the method for preparing the polyolefin as shown in Formula III includes the following steps: (1) In an organic solvent, in the presence of a palladium catalyst, acetyl chloride is reacted with a polyolefin as shown in formula VII-1 to obtain a polyolefin as shown in formula VI-1. ； Among them, R 4a for FG is ;R 1 R 2 and R 3 Independently for C 1-8 Alkyl or C 6-10 Aryl; (2) In an organic solvent, in the presence of a reducing agent, the polyolefin shown in formula VI-1 is reduced to obtain the polyolefin shown in formula V-1. ； (3) In an organic solvent, in the presence of a deprotecting agent, the polyolefin shown in Formula V-1 is subjected to a deprotection reaction to obtain the polyolefin shown in Formula III; ； The method for preparing the polyolefin as shown in Formula IV includes the following steps: (1) In an organic solvent, in the presence of a palladium catalyst, acetyl chloride is reacted with a polyolefin as shown in formula VII-2 to obtain a polyolefin as shown in formula VI-2; ； Among them, R 4b for FG is ;R 1 R 2 and R 3 Independently for C 1-8 Alkyl or C 6-10 Aryl; (2) In an organic solvent, in the presence of a reducing agent, the polyolefin shown in formula VI-2 is reduced to obtain the polyolefin shown in formula V-2. ； (3) In an organic solvent, in the presence of a deprotecting agent, the polyolefin shown in formula V-2 is subjected to a deprotection reaction to obtain the polyolefin shown in formula IV; 。 8. A polymer, characterized in that, The polymer is prepared by any one of the preparation methods described in 5-7.

9. A method for recycling the polymer as described in any one of claims 1-4, characterized in that, It includes the following steps: (1) In organic solvents, in catalysts In the presence of an alkali, the polymer is subjected to a hydrogenation degradation reaction in a hydrogen atmosphere to obtain a polyolefin as shown in Formula III, a polyolefin as shown in Formula IV, or a combination of the polyolefins shown in Formula III and Formula IV. 、 ； Wherein, A, L and p are as defined in any one of claims 1-4; (2) The obtained polyolefin as shown in Formula III, polyolefin as shown in Formula IV, or polyolefin as shown in Formula III and polyolefin as shown in Formula IV are subjected to a repolymerization reaction to obtain the polymer.

10. The method for recycling the polymer as described in claim 9, characterized in that, The recycling method satisfies at least one of the following conditions: (1) In the degradation reaction, the organic solvent is C 6-10 Aromatic solvents, such as toluene; (2) In the degradation reaction, the base is potassium tert-butoxide; (3) In the degradation reaction, the mass ratio of the catalyst to the polymer is (0.0005-0.002):1, for example, 0.001:1; (4) In the degradation reaction, the molar ratio of the base to the catalyst is (3-5):1, for example, 4:1; (5) The degradation reaction is carried out under a high-pressure hydrogen system at a pressure of 30-50 bar, for example 40 bar; (6) The reaction temperature of the degradation reaction is 100-200℃, preferably 140-180℃, for example 150-170℃; (7) The reaction time of the degradation reaction is 40-100 hours, for example 48-72 hours; (8) The degradation reaction includes post-treatment, which includes the following steps: after the reaction is completed, an acidified alcohol solvent (e.g., hydrochloric acid methanol solution) is added to the system, the system is precipitated, filtered, and dried to obtain the polymer; (9) The reaction conditions for the polymerization reaction are as described in claim 5 or 6.

11. A polyolefin of formula III, formula IV, formula VI-1, formula VI-2, formula VII-1 or formula VII-2: , , , , or ; in, R 4a for ;R 4b for FG is ;R 1 R 2 and R 3 Independently for C 1-8 Alkyl or C 6-10 Aryl; A, L, p and q as defined in any one of claims 1-4.

12. The polyolefin as claimed in claim 11, characterized in that, The polyolefin represented by Formula III is any one of the following: (1) A is composed of repeating units and Random copolymer chains; repeating units The molar content of the random copolymer chain is 6.5%; p is 6; The polyolefin shown in Formula III has a number-average molecular weight of 6.0 kg / mol and a molecular weight distribution of 1.

2. (2) A is composed of repeating units and Random copolymer chains; repeating units The molar content of the random copolymer chain is 9.7%; p is 6; The polyolefin shown in Formula III has a number-average molecular weight of 5.9 kg / mol and a molecular weight distribution of 1.

3. (3) A is composed of repeating units and Random copolymer chains; repeating units The molar content of the random copolymer chain is 10.1%; p is 6; The polyolefin shown in Formula III has a number-average molecular weight of 4.6 kg / mol and a molecular weight distribution of 1.

2. (4) A is composed of repeating units and Random copolymer chains; repeating units The molar content of the random copolymer chain is 13.4%; p is 6; The polyolefin shown in Formula III has a number-average molecular weight of 6.9 kg / mol and a molecular weight distribution of 1.

4. Alternatively, the polyolefin represented by Formula IV is a polyolefin as follows: L is composed of repeating units The polymer chain is composed of q, which is 6; the number-average molecular weight of the polyolefin shown in Formula IV is 2.4 kg / mol, and the molecular weight distribution is 1.

1. Alternatively, the polyolefin represented by formula VI-1 may be any of the following: (1) A is composed of repeating units and Random copolymer chains; repeating units The molar content of the random copolymer chain is 6.5%; p is 6; The polyolefin shown in Formula VI-1 has a number-average molecular weight of 5.3 kg / mol and a molecular weight distribution of 1.

2. (2) A is composed of repeating units and Random copolymer chains; repeating units The molar content of the random copolymer chain is 9.7%; p is 6; The polyolefin shown in Formula VI-1 has a number-average molecular weight of 5.1 kg / mol and a molecular weight distribution of 1.

3. (3) A is composed of repeating units and Random copolymer chains; repeating units The molar content of the random copolymer chain is 10.1%; p is 6; The polyolefin shown in Formula VI-1 has a number-average molecular weight of 3.8 kg / mol and a molecular weight distribution of 1.

2. (4) A is composed of repeating units and Random copolymer chains; repeating units The molar content of the random copolymer chain is 13.4%; p is 6; The polyolefin shown in Formula VI-1 has a number-average molecular weight of 4.9 kg / mol and a molecular weight distribution of 1.

4. Alternatively, the polyolefin represented by formula VI-2 may be a polyolefin as follows: L is composed of repeating units The polymer chain is composed of q, which is 6. The polyolefin shown in Formula VI-2 has a number-average molecular weight of 2.6 kg / mol and a molecular weight distribution of 1.

1. Alternatively, the polyolefin represented by formula VII-1 may be any of the following: (1) R 4a for A is composed of repeating units. and Random copolymer chains; repeating units The molar content of the random copolymer chain is 6.5%; the number-average molecular weight of the polyolefin as shown in Formula VII-1 is 5.3 kg / mol, and the molecular weight distribution is 1.

2. (2) R 4a for A is composed of repeating units. and Random copolymer chains; repeating units The molar content of the random copolymer chain is 9.7%; the number-average molecular weight of the polyolefin as shown in Formula VII-1 is 5.1 kg / mol, and the molecular weight distribution is 1.

3. (3) R 4a for A is composed of repeating units. and Random copolymer chains; repeating units The molar content of the random copolymer chain is 10.1%; the number-average molecular weight of the polyolefin as shown in Formula VII-1 is 3.8 kg / mol, and the molecular weight distribution is 1.

2. (4) R 4a for A is composed of repeating units. and Random copolymer chains; repeating units The molar content of the random copolymer chain is 13.4%; the number-average molecular weight of the polyolefin as shown in Formula VII-1 is 4.9 kg / mol, and the molecular weight distribution is 1.

4. Alternatively, the polyolefin represented by formula VII-2 may be a polyolefin as follows: R 4b for L represents a repeating unit. The polymer chain is composed of the following: the polyolefin as shown in Formula VII-2 has a number-average molecular weight of 2.6 kg / mol and a molecular weight distribution of 1.1.

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