Single-component organic Lewis acid-base pair and method for synthesizing polyacetal ether polyol

Abstract

The present invention belongs to the field of macromolecular and polymer synthesis. Aiming at the problems that the polymerization reaction of polyphthalaldehyde (POPD) generated by polycondensation of POPD monomer usually needs to be carried out at an ultra-low temperature (≤-40°C), the polymer has poor stability at room temperature and is easy to depolymerize, and the polymer needs to be end-capped after the reaction, the present invention provides a single-component organic Lewis acid-base pair having the structural formula: #imgabs0#n is the carbon chain length, R is any one of hydrogen, methyl, ethyl, butyl, phenyl or substituted phenyl; X is any one of halogen Cl, Br, I, acetate, trifluoroacetate, and succinate; R 1 、R 2 It is one or a combination of hydrogen, alkyl, cycloalkyl, aryl or substituted aryl; Y is a bridged skeleton. The single-component organic Lewis acid-base pair can achieve polymerization of o-phthalaldehyde and epoxy compounds under relatively mild conditions, and the obtained polymer does not need to be end-capped and can be purified for use.

Description

Technical Field

[0001] The invention belongs to the field of macromolecular and polymer synthesis, and particularly relates to a method for synthesizing polyacetal ether polyol by using a single-component organic Lewis acid-base pair and catalysis. Background Art

[0002] In the context of the urgent need to advance a truly sustainable circular economy, biodegradable and recyclable polymers appear to be the most promising candidates to replace chemically inert and environmentally persistent polymeric materials. Aldehyde monomers contain highly polar carbon-oxygen double bonds, which can be obtained through ionic polymerization to degradable polyaldehydes or polyacetals. The small change in the polymerization enthalpy when the carbon-oxygen double bond in the aldehyde group is converted to the acetal bond means that most aldehydes have an upper polymerization temperature (Tc), which is usually below room temperature. Among the numerous available aliphatic and aromatic aldehydes, polyphthalaldehyde (PPA), a terminal hemiacetal, can exhibit good thermal stability by end-capping.

[0003] In 1967, C.Aso [1－4] et al. first reported the preparation of cyclic poly(o-phthalaldehyde) and conducted detailed research on its reaction mechanism and morphology, which opened the door to the practical application of poly(o-phthalaldehyde). Initially, poly(o-phthalaldehyde) was widely studied and reported in the field of photoresist [5]. However, due to the harsh and long triggering conditions, its cost as a photoresist was high, and it was gradually eliminated.

[0004] Until 2010, Seo et al. [6] expanded the triggering depolymerization range of polyphthalaldehyde by controlling the end-capping modification of chain polyphthalaldehyde, making polyphthalaldehyde a focus material again. Because polyphthalaldehyde has an extremely low upper temperature limit Tc (-40℃), the polymer can be quickly converted into a monomer under the condition of removing the end group, and the monomeric polyphthalaldehyde cannot exist stably at room temperature and is easily volatilized with water vapor. The chain polyphthalaldehyde can be made stable at room temperature by end-capping modification. The chain polyphthalaldehyde after end-capping is used in deformation plastics. [6－7] , stimuli-responsive shell-core microcapsules [8] , Etchant in Thermal Lithography Probe [9－13] , thermal responsive materials

[14] , self-assembly materials

[15] Recently, it has also been extended to transient electronic devices.

[16] , substrate materials for graphene transfer

[17] Since then, o-phthalaldehyde has quickly become a cutting-edge material.

[0005] The preparation methods of poly(o-phthalaldehyde) are divided into anionic polymerization, cationic polymerization, γ-ray radiation polymerization and chelate catalytic polymerization. At present, the main preparation methods are anionic polymerization and cationic polymerization. Anionic polymerization mainly produces linear chain polymers. The chain poly(o-phthalaldehyde) mainly relies on trigger response to remove the end group and depolymerize into its constituent monomers. Cationic polymerization produces cyclic polymers. The cyclic poly(o-phthalaldehyde) opens the ring through acid trigger response and depolymerizes into its constituent monomers. Due to its upper limit polymerization temperature and rapid depolymerization problems, the polymerization reaction usually requires ultra-low temperature (≤-40°C). After the reaction, the polymer needs to be capped to prevent its rapid depolymerization. There are few methods for chemical modification or copolymerization of poly(o-phthalaldehyde) at room temperature.

[0006] [1]Aso C, Tagami S. Cyclopolymerization of o-phthalaldehyde[J]. Journal of Polymer Science Part B Polymer Letters, 1967, 5(3):217-220.

[0007] [2]AYaTemkin. Radiation-induced catalytic polymerization. Theory[J]. Journal of Polymer Science Part A (Polymer Physics), 1967, 5(1):211-223.

[0008] [3]Aso C, Tagami S, Kunitake T. Polymerization of aromaticaldehydes. Cationic cyclopolymerization of phthalaldehyde[J]. Journal of Polymer Science Part A: Polymer Chemistry, 1969, 7(2):497-511.

[0009] [4] Castetbon A. Polymerization of Aromatic Aldehydes. The Cyclopolymerization of Phthaldehyde and the Structure of the Polymer [J]. Macromolecules, 1969, 2(4): 414-419.

[0010] [5]Ito H,Willson C G.Chemical amplification in the design of drydeveloping resist materials [J].Polymer Engineering&Science,1983,23(18):1012-1018.

[0011] [6]Seo W,Phillips S T.Patterned plastics that change physicalstructure in response to applied chemical signals[J].Journal of the AmericanChemical Society,2010,132(27):9234-9235.

[0012] [7]Dilauro A M,Robbins J S,Phillips S T.Reproducible and ScalableSynthesis of End(phthalaldehydes)[J].Macromolecules,2013,46(8):2963-2968.

[0013] [8]Dilauro A M,Abbaspourrad A,Weitz D A,et al.Stimuli-ResponsiveCore-Shell Microcapsules with Tunable Rates of Release by Using aDepolymerizable Poly(phthalaldehyde)Membrane[J].Macromolecules,2013,46(9):3309-3313.

[0014] [9]Coulembier O,Knoll A,Pires D,et al.Probe-Based Nanolithography:Self-Amplified Depolymerization Media for Dry Lithography[J].Macromolecules,2010,43(1):572-574.

[0015]

[10] Knoll A W,Pires D,Coulembier O,et al.Probe-based 3Dnanolithography using self-amplified depolymerization polymers.[J].AdvancedMaterials,2014,22(1):3361-3365.

[0016]

[11] Holzner F,Kuemin C,Paul P,et al.Directed Placement of GoldNanorods Using a R emovable Template for Guided Assembly[J].Nano Letters,2011,11(9):3957-3962.

[0017]

[12] Lin L C,Paul P,Holzner F,et al.Thermal Probe Maskless Lithographyfor 27.5nm Half-Pitch Si Technology[J].Nano Letters,2013,13(9):4485-4491.

[0018]

[13] Winter J D,Dove A P,Knoll A,et al.Control over molar mass,dispersity end groups and kinetics in cyclopolymerization of orthophthalaldehyde:Adapted choice of a phosphazeneorganocatalyst[J].PolymerChemistry,2013,5(3):706-711.

[0019]

[14] Kstler S,Zechner B,Trathnigg B,et al.Amphiphilic block copolymerscontaining thermally degradable poly(phthalaldehyde)blocks[J].Journal ofPolymer Science Part A Polymer Chemistry,2009,47(6):1499-1509.

[0020]

[15] Kaitz JA, Possanza CM, Song Y, et al. Depolymerizable, adaptive supramolecular polymer nanoparticles and networks[J]. Polymer Chemistry, 2014, 5(12):3788-3794.

[0021]

[16] Hernandez HL, Kang SK, Lee OP, et al. Triggered Transience ofMetastable Poly(phthalaldehyde)Advanced Materials, 2014, 26(45):7637.

[0022]

[17] Wood JD, Doidge GP, Carrion EA, et al. Annealing free, cleangraphene transfer using alternative polymer Nanotechnology, 2015, 26(5):055302. Summary of the Invention

[0023] To address the problems that the polymerization reaction of o-phthalaldehyde monomer to form poly-o-phthalaldehyde usually needs to be carried out at an ultra-low temperature (≤-40°C), the polymer has poor stability at room temperature and is easily depolymerized, and the polymer needs to be end-capped after the reaction, the present invention provides a single-component organic Lewis acid-base pair and a method for synthesizing polyacetal ether polyols. The developed single-component organic Lewis acid-base pair can be used as both an initiator and a catalyst, and can achieve polymerization of o-phthalaldehyde and an epoxy compound under relatively mild conditions (-20-45°C). Compared with a simple o-phthalaldehyde polymer, the resulting polymer does not require end-capping and can be purified for use. In addition, the system provided.

[0024] The technical solutions provided by the present invention are as follows:

[0025] (1) The present invention provides a single-component organic Lewis acid-base pair, wherein the single-component Lewis acid-base pair has a structural formula of any one of the following:

[0026]

[0027] In the above structural formula, n is the length of the carbon chain 1 to 4; R is any one of hydrogen, methyl, ethyl, butyl, phenyl or substituted phenyl; X is any one of halogen Cl, Br, I, acetate, trifluoroacetate, succinate; R 1 、R 2 is one or a combination of hydrogen, alkyl, cycloalkyl, aryl or substituted aryl; Y is a bridged skeleton, which is any one of the following structural formulas:

[0028]

[0029] Furthermore, the single-component organic Lewis acid-base pair has a structural formula of any one of the following:

[0030]

[0031]

[0032] The single-component organic Lewis acid-base pair and the chain transfer agent constitute a catalytic system, which can be used for catalytic synthesis of degradable polyacetal ether polyols.

[0033] (2) The present invention also provides a method for preparing a degradable polyacetal ether polyol, which uses the above-mentioned catalyst or system to catalyze the polymerization of dialdehyde monomers and epoxy monomers within a temperature range of -20-45°C.

[0034] Furthermore, the dialdehyde monomer is o-phthalaldehyde (OPA), which has the structural formula:

[0035]

[0036] The epoxy monomer is at least one of cyclohexene oxide (CHO), ethylene oxide (EO), propylene oxide (PO), 1,2-epoxyhexane (HO), epichlorohydrin (ECH), allyl glycidyl ether (AGE), butyl ethylene oxide (LO), butylene oxide (BO), n-butyl glycidyl ether (NBGE), styrene oxide (SO), furfuryl glycidyl ether (FGE), phenyl glycidyl ether (PGE), butyl glycidyl ether (BGE) and hexamethylcyclotrisiloxane (D3).

[0037]

[0038]

[0039] Furthermore, the single-component organic Lewis acid-base pair can be used in the presence of a chain transfer agent when preparing a polymer, thereby regulating the molecular weight of the prepared polymer (both high and low molecular weight polymers can be prepared), reducing the amount of catalyst used, reducing the molecular weight distribution of the polymer, and preparing a degradable polyacetal ether polyol with a functional group or a topological structure.

[0040] Furthermore, the chain transfer agent is any one of the following structures:

[0041]

[0042]

[0043] Furthermore, the structure of the degradable polyacetal ether polyol with functional groups is:

[0044] A represents a chain transfer agent structure.

[0045] Furthermore, the structure of the degradable polyacetal ether polyol having a topological structure is:

[0046]

[0047] Furthermore, in the preparation method of the degradable polyacetal ether polyol, the reaction temperature is controlled at -20 to 45°C, preferably -15 to 40°C, more preferably -20 to 35°C, more preferably -10 to 30°C, more preferably 0 to 25°C, 5 to 20°C.

[0048] Furthermore, in the preparation method of the degradable polyacetal ether polyol, the reaction time is controlled within 0.3 to 72 hours, preferably 1 to 70 hours, 2 to 68 hours, 3 to 64 hours, 4 to 60 hours, 6 to 48 hours, 10-36 hours, or 12 to 24 hours.

[0049] Furthermore, in the preparation method of the degradable polyacetal ether polyol, the molar ratio of the epoxy monomer, the dialdehyde monomer and the single-component organic Lewis acid-base pair is (20-3000):(20-1000):(0.01-1), preferably (100-2000):(100-2000):(0.05-1), more preferably (200-1000):(200-1000):(0.1-1), and more preferably 500:500:1.

[0050] Furthermore, in the preparation method of the degradable polyacetal ether polyol, the molar ratio of the epoxy monomer, the dialdehyde monomer, the chain transfer agent and the single-component organic Lewis acid-base pair is (100-2000):(100-2000):(1-0.01):(1-0.01), preferably (200-1800):(200-1800):(0.01-0.05):(0.01-0.05), and more preferably (500-1500):(500-1500):(0.01-0.03):(0.01-0.03).

[0051] Furthermore, in the preparation method of the degradable polyacetal ether polyol, the molar ratio of the epoxy monomer, dialdehyde monomer, chain transfer agent, single-component organic Lewis acid-base pair and coupling agent is (100-2000):(100-2000):(1-0.01):(1-0.01):(1-0.01), preferably (200-1800):(200-1800):(0.01-0.05):(0.01-0.05):(0.01-0.05), more preferably (500-1500):(500-1500):(0.01-0.03):(0.01-0.03):(0.01-0.03).

[0052] Furthermore, a single-component organic Lewis acid-base pair PBB, o-phthalaldehyde, and propylene oxide are weighed into a pre-flame-dried pressure-resistant bottle equipped with a magnet, wherein the molar ratio of propylene oxide, o-phthalaldehyde, and the single-component organic Lewis acid-base pair PBB is (20-3000):(20-1000):1, the reaction temperature is controlled at -20-45°C, and the reaction time is controlled at 0.3-72h to obtain a functionalized degradable polyacetal ether polyol having a halogen at one end and a secondary hydroxyl at the other end.

[0053] Furthermore, a single-component organic Lewis acid-base pair PBB-1 and allyl alcohol (AA) are weighed into a pre-flame-dried pressure-resistant bottle equipped with a magnet, and the molar ratio of propylene oxide, o-phthalaldehyde, allyl alcohol and the single-component organic Lewis acid-base pair PBB-1 is (100-2000):(100-2000):(1-0.01):(1-0.01). The reaction temperature is controlled at -20-45°C, and the reaction time is controlled at 0.3-72h to obtain a functionalized degradable polyacetal ether polyol having an allyl group at one end and a secondary hydroxyl group at the other end.

[0054] Furthermore, a single-component organic Lewis acid-base pair PBB-3 and 3-trimethylsilyl-1-propynol (SAYA) are weighed into a pre-flame-dried pressure-resistant bottle equipped with a magnet, and the molar ratio of propylene oxide, o-phthalaldehyde, SAYA, and the single-component organic Lewis acid-base pair PBB-3 is (100-2000):(100-2000):(1-0.01):(1-0.01). The reaction temperature is controlled at -20-45°C, and the reaction time is controlled at 0.3-72h to obtain a functionalized degradable polyacetal ether polyol having a 3-trimethylsilyl-1-propynyl group at one end and a secondary hydroxyl group at the other end.

[0055] Furthermore, a single-component organic Lewis acid-base pair and p-aminobenzyl alcohol are weighed into a pre-flame-dried pressure-resistant bottle equipped with a magnet, and the molar ratio of propylene oxide, o-phthalaldehyde, p-aminobenzyl alcohol and the single-component organic Lewis acid-base pair is (100-2000):(100-2000):(1-0.01):(1-0.01). The reaction temperature is controlled at -20-45°C, and the reaction time is controlled at 0.3-72h to obtain a functionalized degradable polyacetal ether polyol having an amino group at one end and a secondary hydroxyl group at the other end.

[0056] Furthermore, the single-component organic Lewis acid-base pair PBB-6 and various chain transfer agents were weighed into a pre-flame-dried pressure-resistant bottle, and the pressure-resistant bottle was sealed and taken out of the glove box. The molar ratio of propylene oxide, o-phthalaldehyde, various chain transfer agents and the single-component organic Lewis acid-base pair PBB-6 was 100:100:1:0.01, the reaction temperature was controlled at 25° C., and the reaction time was controlled at 0.3 to 72 hours to obtain polymers that were various functionalized degradable polyacetal ether polyols.

[0057] Furthermore, in a glove box, a single-component organic Lewis acid-base pair and RAFT2 are weighed into a high-pressure reactor equipped with a magnet. After the reactor is sealed, the glove box is taken out and ethylene oxide is introduced. The molar ratio of propylene oxide, o-phthalaldehyde, RAFT2 and the single-component organic Lewis acid-base pair is (100-2000):(100-2000):(1-0.01):(1-0.01). The reaction temperature is controlled at -20-45°C and the reaction time is controlled at 0.3-72h to obtain a polymer that is a degradable polyacetal ether polyol with RFAT at one end and ethylene oxide at the other end.

[0058] Furthermore, the pressure of the ethylene oxide is 1-10 bar, preferably 2-9 bar, 3-8 bar, 4-7 bar, 5-6 bar.

[0059] Beneficial effects:

[0060] (1) The catalytic system provided by the present invention greatly expands the synthesis conditions, types and application scope of degradable polyacetal ether polyols.

[0061] (2) The polymerization process provided by the present invention can realize the preparation of various functionalized degradable polyacetal ether polyols under mild conditions.

[0062] (3) The molecular weight of the generated polymer is controllable (500-100000 g / mol) and the molecular weight distribution is narrow (≤1.18).

[0063] (4) It is possible to prepare degradable polyacetal ether polyols with various functionalizations and topological structures, which can greatly expand the application of this type of materials in the fields of biocompatibility, photolithography materials, degradable materials, click chemistry, free radical chemistry, supramolecular chemistry and polymer self-assembly. BRIEF DESCRIPTION OF THE DRAWINGS

[0064] Figure 1 The degradable polyacetal ether polyol prepared in Example 1 1 H NMR spectrum;

[0065] Figure 2 This is a representative GPC chart of the degradable polyacetal ether polyol prepared in Example 1;

[0066] Figure 3 The degradable polyacetal ether polyol prepared in Example 2 1 H NMR spectrum;

[0067] Figure 4 This is a representative GPC chart of the degradable polyacetal ether polyol prepared in Example 2;

[0068] Figure 5 The degradable polyacetal ether polyol prepared in Example 3 1 H NMR spectrum;

[0069] Figure 6 This is a representative GPC chart of the degradable polyacetal ether polyol prepared in Example 3;

[0070] Figure 7 The degradable polyacetal ether polyol prepared in Example 4 1 H NMR spectrum;

[0071] Figure 8 This is a representative GPC chart of the degradable polyacetal ether polyol prepared in Example 4.

[0072] Figure 9 Three degradable polyacetal ether polyols with topological structures prepared by the present invention. DETAILED DESCRIPTION

[0073] The present invention is further described in detail below with reference to specific embodiments.

[0074] Examples 1 to 5

[0075] In a glove box, a single-component organic Lewis acid-base pair (PBB), o-phthalaldehyde, and propylene oxide were weighed into a pre-flame-dried pressure bottle equipped with a magnet. The molar ratio of propylene oxide, o-phthalaldehyde, and single-component organic Lewis acid-base pair was (20-30,000):(20-1,000):1. The pressure bottle was sealed and removed. The reaction temperature was controlled between -20°C and 45°C, and the reaction time was controlled between 0.3 and 72 hours. The specific operations of Examples 1 to 5 are as follows, and key data are summarized in Table 1.

[0076] Example 1

[0077] In a 10 mL pressure bottle, a single-component organic Lewis acid-base pair PBB (20 μmol, 11.8 mg, 1 equivalent) and o-phthalaldehyde (2 mmol, 268 mg, 100 equivalents) were added, followed by PO (2 mmol, 0.14 mL, 100 equivalents). The reaction mixture was stirred for 2.5 h at a temperature of 25 ° C. The number average molecular weight Mn measured by GPC was 21000 g / mol, and the molecular weight distribution was 2. is 1.08.

[0078] Example 2

[0079] In a 10 mL pressure bottle, a single-component organic Lewis acid-base pair PBB (20 μmol, 11.8 mg, 1 equivalent) and o-phthalaldehyde (2 mmol, 268 mg, 100 equivalents) were added, followed by PO (2 mmol, 0.14 mL, 100 equivalents). The reaction mixture was stirred for 6 h at 0 ° C. The number average molecular weight Mn measured by GPC was 20500 g / mol, and the molecular weight distribution was is 1.06.

[0080] Example 3

[0081] In a 10 mL pressure bottle, a single-component organic Lewis acid-base pair PBB (20 μmol, 11.8 mg, 1 equivalent) and o-phthalaldehyde (10 mmol, 1.34 g, 500 equivalents) were added, followed by PO (10 mmol, 0.7 mL, 500 equivalents). The reaction mixture was stirred for 3 h at a temperature of 25 ° C. The number average molecular weight Mn measured by GPC was 42500 g / mol, and the molecular weight distribution was is 1.12.

[0082] Example 4

[0083] In a 10 mL pressure bottle, a single-component organic Lewis acid-base pair PBB (10 μmol, 5.9 mg, 1 equivalent) and o-phthalaldehyde (10 mmol, 1.34 g, 1000 equivalents) were added, followed by PO (10 mmol, 0.7 mL, 1000 equivalents). The reaction mixture was stirred for 48 h at a temperature of 25 ° C. The number average molecular weight Mn measured by GPC was 24100 g / mol, and the molecular weight distribution was 2. is 1.14.

[0084] Example 5

[0085] In a 100 mL pressure bottle, a single-component organic Lewis acid-base pair PBB (10 μmol, 5.9 mg, 1 equivalent) and o-phthalaldehyde (10 mmol, 1.34 g, 1000 equivalents) were added, followed by PO (300 mmol, 21 mL, 30,000 equivalents). The reaction mixture was stirred for 72 h at a temperature of 25 ° C. The number average molecular weight Mn measured by GPC was 92100 g / mol, and the molecular weight distribution was 0. is 1.16.

[0086] Table 1 Summary of key data of Examples 1 to 5

[0087]

[0088] Examples 6 to 10

[0089] In a glove box, the single-component organic Lewis acid-base pair PBB-1 and allyl alcohol (AA) were weighed into a pre-flame-dried pressure bottle equipped with a magnet. The molar ratio of propylene oxide, o-phthalaldehyde, allyl alcohol, and the single-component organic Lewis acid-base pair was 2000:2000:1:0.1:0.1 to 100:100:1:0.01. The pressure bottle was sealed and removed from the container. The reaction temperature was controlled between -20°C and 45°C, and the reaction time was controlled between 0.3 and 72 hours. The specific operations for Examples 6 to 10 are as follows, and the key data are summarized in Table 2.

[0090] Example 6

[0091] In a 50 mL pressure bottle, a single-component Lewis acid-base pair PBB-1 (10 μmol, 5.1 mg, 0.01 equivalent), allyl alcohol (1 mmol, 68 μL, 1 equivalent), o-phthalaldehyde (0.1 mol, 13.4 g, 100 equivalents) were added in sequence, and then PO (0.1 mol, 7 mL, 100 equivalents) was added. The reaction mixture was stirred for 12 h at a reaction temperature of 0 ° C. The number average molecular weight Mn measured by GPC was 15000 g / mol, and the molecular weight distribution was 0. It is 1.13.

[0092] Example 7

[0093] In a 50 mL pressure bottle, a single-component Lewis acid-base pair PBB-1 (10 μmol, 5.1 mg, 0.05 equivalent), allyl alcohol (0.2 mmol, 13.7 μL, 1 equivalent), o-phthalaldehyde (20 mmol, 2.68 g, 100 equivalents) were added in sequence, and then PO (20 mmol, 2.4 mL, 100 equivalents) was added. The reaction mixture was stirred for 10 h at a reaction temperature of -20 ° C. The number average molecular weight Mn measured by GPC was 16500 g / mol, and the molecular weight distribution was 2. is 1.12.

[0094] Example 8

[0095] In a 10 mL pressure bottle, a single-component Lewis acid-base pair PBB-1 (10 μmol, 5.1 mg, 0.1 equivalent), allyl alcohol (0.1 mmol, 6.8 μL, 1 equivalent), and o-phthalaldehyde (10 mmol, 1.34 g, 100 equivalents) were added in sequence, and then PO (10 mmol, 0.7 mL, 100 equivalents) was added. The reaction mixture was stirred for 8 h at a reaction temperature of 25 ° C. The number average molecular weight Mn measured by GPC was 16800 g / mol, and the molecular weight distribution was 2. is 1.16.

[0096] Example 9

[0097] In a 10 mL pressure bottle, a single-component Lewis acid-base pair PBB-1 (10 μmol, 5.1 mg, 0.1 equivalent), allyl alcohol (0.1 mmol, 6.8 μL, 1 equivalent), and o-phthalaldehyde (20 mmol, 2.68 g, 200 equivalents) were added in sequence, and then PO (20 mmol, 1.4 mL, 200 equivalents) was added. The reaction mixture was stirred for 24 h at a reaction temperature of 25 ° C. The number average molecular weight Mn measured by GPC was 19000 g / mol, and the molecular weight distribution was 2. is 1.14.

[0098] Example 10

[0099] In a 100 mL pressure bottle, a single-component Lewis acid-base pair PBB-1 (10 μmol, 5.1 mg, 0.1 equivalent), allyl alcohol (0.1 mmol, 6.8 μL, 1 equivalent), o-phthalaldehyde (200 mmol, 26.8 g, 2000 equivalents) were added in sequence, and then PO (200 mmol, 14 mL, 2000 equivalents) was added. The reaction mixture was stirred for 72 h at 0 ° C. The number average molecular weight Mn measured by GPC was 79200 g / mol, and the molecular weight distribution was 2. is 1.16.

[0100] Table 2 Summary of key data of Examples 6 to 10

[0101]

[0102] Examples 11 to 15

[0103] In a glove box, a single-component organic Lewis acid-base pair (PBB-3) and 3-trimethylsilyl-1-propynol (SAYA) were weighed into a pre-flame-dried pressure bottle equipped with a magnet. The molar ratio of propylene oxide, o-phthalaldehyde, SAYA, and the single-component organic Lewis acid-base pair was 2000:2000:1:0.1:0.1 to 100:100:1:0.01. The pressure bottle was sealed and removed from the container. The reaction temperature was controlled between -20°C and 45°C, and the reaction time was controlled between 0.3 and 72 hours. The specific operations for Examples 11 to 15 are as follows, and key data are summarized in Table 3.

[0104] Example 11

[0105] In a 50 mL pressure bottle, a single-component Lewis acid-base pair PBB-3 (10 μmol, 4.7 mg, 0.01 equivalent), SAYA (1 mmol, 148 μL, 1 equivalent), o-phthalaldehyde (0.1 mol, 13.4 g, 100 equivalents) were added in sequence, and then PO (0.1 mol, 7 mL, 100 equivalents) was added. The reaction mixture was stirred for 8 h at a reaction temperature of 25 ° C. The number average molecular weight Mn measured by GPC was 18000 g / mol, and the molecular weight distribution was 1. is 1.15.

[0106] Example 12

[0107] In a 50 mL pressure bottle, a single-component Lewis acid-base pair PBB-3 (10 μmol, 4.7 mg, 0.05 equivalent), SAYA (0.2 mmol, 30 μL, 1 equivalent), o-phthalaldehyde (20 mmol, 2.68 g, 100 equivalents) were added in sequence, and then PO (20 mmol, 2.4 mL, 100 equivalents) was added. The reaction mixture was stirred for 5 h at a reaction temperature of 0 ° C. The number average molecular weight Mn measured by GPC was 16200 g / mol, and the molecular weight distribution was 0. It is 1.13.

[0108] Example 13

[0109] In a 10 mL pressure bottle, a single-component Lewis acid-base pair PBB-3 (10 μmol, 4.7 mg, 0.1 equivalent), SAYA (0.1 mmol, 15 μL, 1 equivalent), and o-phthalaldehyde (10 mmol, 1.34 g, 100 equivalents) were added in sequence, and then PO (10 mmol, 0.7 mL, 100 equivalents) was added. The reaction mixture was stirred for 3 h at a reaction temperature of -20 ° C. The number average molecular weight Mn measured by GPC was 16300 g / mol, and the molecular weight distribution was 0. It is 1.17.

[0110] Example 14

[0111] In a 10 mL pressure bottle, a single-component Lewis acid-base pair PBB-3 (10 μmol, 4.7 mg, 0.1 equivalent), SAYA (0.1 mmol, 15 μL, 1 equivalent), o-phthalaldehyde (20 mmol, 2.68 g, 200 equivalents) was added in sequence, and then PO (20 mmol, 1.4 mL, 200 equivalents) was added. The reaction mixture was stirred for 48 h at a reaction temperature of 25 ° C. The number average molecular weight Mn measured by GPC was 18600 g / mol, and the molecular weight distribution was 2. is 1.14.

[0112] Example 15

[0113] In a 100 mL pressure bottle, a single-component Lewis acid-base pair PBB-3 (10 μmol, 4.7 mg, 0.1 equivalent), SAYA (0.1 mmol, 15 μL, 1 equivalent), and o-phthalaldehyde (200 mmol, 26.8 g, 2000 equivalents) were added in sequence, and then PO (200 mmol, 14 mL, 2000 equivalents) was added. The reaction mixture was stirred for 72 h at a reaction temperature of 25 ° C. The number average molecular weight Mn measured by GPC was 85600 g / mol, and the molecular weight distribution was 2. is 1.16.

[0114] Table 3 Summary of key data of Examples 11 to 15

[0115]

[0116] Examples 16 to 20

[0117] In a glove box, a single-component organic Lewis acid-base pair and p-aminobenzyl alcohol were weighed into a pre-flame-dried pressure bottle equipped with a magnet. The molar ratio of propylene oxide, o-phthalaldehyde, p-aminobenzyl alcohol, and the single-component organic Lewis acid-base pair was 2000:2000:1:0.1:0.1 to 100:100:1:0.01:0.01. The pressure bottle was sealed and removed from the container. The reaction temperature was controlled between -20°C and 45°C, and the reaction time was controlled between 0.3 and 72 hours. The specific operations for Examples 16 to 20 are as follows, and key data are summarized in Table 4.

[0118] Example 16

[0119] In a 50 mL pressure bottle, a single-component Lewis acid-base pair PBB-5 (10 μmol, 7.0 mg, 0.01 equivalent), p-aminobenzyl alcohol (1 mmol, 123 mg, 1 equivalent), and o-phthalaldehyde (0.1 mol, 13.4 g, 100 equivalents) were added in sequence, and then PO (0.1 mol, 7 mL, 100 equivalents) was added. The reaction mixture was stirred for 6 h at a reaction temperature of 0 ° C. The number average molecular weight Mn measured by GPC was 16700 g / mol, and the molecular weight distribution was 0. It is 1.13.

[0120] Example 17

[0121] In a 50 mL pressure bottle, a single-component Lewis acid-base pair PBB-5 (10 μmol, 7.0 mg, 0.05 equivalent), p-aminobenzyl alcohol (0.2 mmol, 24.6 mg, 1 equivalent), and o-phthalaldehyde (20 mmol, 2.68 g, 100 equivalents) were added in sequence, and then PO (20 mmol, 2.4 mL, 100 equivalents) was added. The reaction mixture was stirred for 5 h at a reaction temperature of 25 ° C. The number average molecular weight Mn measured by GPC was 17400 g / mol, and the molecular weight distribution was 2. It is 1.13.

[0122] Example 18

[0123] In a 10 mL pressure bottle, a single-component Lewis acid-base pair PBB-5 (10 μmol, 7.0 mg, 0.1 equivalent), p-aminobenzyl alcohol (0.1 mmol, 12.3 mg, 1 equivalent), and o-phthalaldehyde (10 mmol, 1.34 g, 100 equivalents) were added in sequence, and then PO (10 mmol, 0.7 mL, 100 equivalents) was added. The reaction mixture was stirred for 12 h at a reaction temperature of -20 ° C. The number average molecular weight Mn measured by GPC was 15600 g / mol, and the molecular weight distribution was 0. is 1.12.

[0124] Example 19

[0125] In a 10 mL pressure bottle, a single-component Lewis acid-base pair PBB-5 (10 μmol, 7.0 mg, 0.1 equivalent), p-aminobenzyl alcohol (0.1 mmol, 12.3 mg, 1 equivalent), and o-phthalaldehyde (20 mmol, 2.68 g, 200 equivalents) were added in sequence, and then PO (20 mmol, 1.4 mL, 200 equivalents) was added. The reaction mixture was stirred for 24 h at a reaction temperature of 45 ° C. The number average molecular weight M was measured by GPC. n 26100 g / mol, molecular weight distribution is 1.16.

[0126] Example 20

[0127] In a 100 mL pressure bottle, a single-component Lewis acid-base pair PBB-6 (10 μmol, 6.6 mg, 0.1 equivalent), p-aminobenzyl alcohol (0.1 mmol, 12.3 mg, 1 equivalent), and o-phthalaldehyde (200 mmol, 26.8 g, 2000 equivalents) were added in sequence, and then PO (200 mmol, 14 mL, 2000 equivalents) was added. The reaction mixture was stirred for 48 h at a reaction temperature of 25 ° C. The number average molecular weight Mn measured by GPC was 73100 g / mol, and the molecular weight distribution was 2. It is 1.18.

[0128] Table 4 Summary of key data of Examples 16 to 20

[0129]

[0130] Examples 21 to 38

[0131] In a glove box, a single-component organic Lewis acid-base pair (PBB-6) and various chain transfer agents were weighed into a pre-flame-dried pressure bottle equipped with a magnet. The molar ratio of propylene oxide, o-phthalaldehyde, various chain transfer agents, and single-component organic Lewis acid-base to PBB-6 was 100:100:1:0.01. The pressure bottle was sealed and removed from the container. The reaction temperature was controlled at 25°C, and the reaction time was controlled between 0.3 and 72 hours. The specific procedures for Examples 21 to 38 are as follows; key data are summarized in Table 5.

[0132] Example 21

[0133] In a 50 mL pressure bottle, a single-component Lewis acid-base pair PBB-6 (10 μmol, 6.6 mg, 0.01 equivalent), benzyl alcohol (1 mmol, 103 μL, 1 equivalent), o-phthalaldehyde (0.1 mol, 13.4 g, 100 equivalents) was added in sequence, and then PO (0.1 mol, 7 mL, 100 equivalents) was added. The reaction mixture was stirred for 4 h at a reaction temperature of 25 ° C. The number average molecular weight Mn measured by GPC was 13700 g / mol, and the molecular weight distribution was 0. It is 1.18.

[0134] Example 22

[0135] In a 50 mL pressure bottle, a single-component Lewis acid-base pair PBB-6 (10 μmol, 6.6 mg, 0.01 equivalent), allyl alcohol (1 mmol, 68 μL, 1 equivalent), and o-phthalaldehyde (0.1 mol, 13.4 g, 100 equivalents) were added in sequence, and then PO (0.1 mol, 7 mL, 100 equivalents) was added. The reaction mixture was stirred for 4 h at a reaction temperature of 25 ° C. The number average molecular weight Mn measured by GPC was 14600 g / mol, and the molecular weight distribution was 0.01%. is 1.16.

[0136] Example 23

[0137] In a 50 mL pressure bottle, a single-component Lewis acid-base pair PBB-6 (10 μmol, 6.6 mg, 0.01 equivalent), p-aminobenzyl alcohol (1 mmol, 123 mg, 1 equivalent), and o-phthalaldehyde (0.1 mol, 13.4 g, 100 equivalents) were added in sequence, and then PO (0.1 mol, 7 mL, 100 equivalents) was added. The reaction mixture was stirred for 2.5 h at a reaction temperature of 25 ° C. The number average molecular weight Mn measured by GPC was 14200 g / mol, and the molecular weight distribution was 1. is 1.16.

[0138] Example 24

[0139] In a 50 mL pressure bottle, a single-component Lewis acid-base pair PBB-6 (10 μmol, 6.6 mg, 0.01 equivalent), 3-(trimethylsilyl)propargyl alcohol (1 mmol, 148 μL, 1 equivalent), and o-phthalaldehyde (0.1 mol, 13.4 g, 100 equivalents) were added in sequence, and then PO (0.1 mol, 7 mL, 100 equivalents) was added. The reaction mixture was stirred for 4 h at a reaction temperature of 25 ° C. The number average molecular weight Mn measured by GPC was 17400 g / mol, and the molecular weight distribution was 2. is 1.14.

[0140] Example 25

[0141] In a 50 mL pressure bottle, a single-component Lewis acid-base pair PBB-6 (10 μmol, 6.6 mg, 0.01 equivalent), furfuryl alcohol (1 mmol, 86 μL, 1 equivalent), and o-phthalaldehyde (0.1 mol, 13.4 g, 100 equivalents) were added in sequence, and then PO (0.1 mol, 7 mL, 100 equivalents) was added. The reaction mixture was stirred for 24 h at a reaction temperature of 25 ° C. The number average molecular weight Mn measured by GPC was 17800 g / mol, and the molecular weight distribution was 2. It is 1.18.

[0142] Example 26

[0143] In a 50 mL pressure bottle, a single-component Lewis acid-base pair PBB-6 (10 μmol, 6.6 mg, 0.01 equivalent), 2-azidoethanol (1 mmol, 76 μL, 1 equivalent), and o-phthalaldehyde (0.1 mol, 13.4 g, 100 equivalents) were added in sequence, and then PO (0.1 mol, 7 mL, 100 equivalents) was added. The reaction mixture was stirred for 4 h at a reaction temperature of 25 ° C. The number average molecular weight Mn measured by GPC was 18500 g / mol, and the molecular weight distribution was 2. is 1.15.

[0144] Example 27

[0145] In a 50 mL pressure bottle, a single-component Lewis acid-base pair PBB-6 (10 μmol, 6.6 mg, 0.01 equivalent), 2-(dibenzylamino)ethanol (1 mmol, 241 mg, 1 equivalent), and o-phthalaldehyde (0.1 mol, 13.4 g, 100 equivalents) were added in sequence, and then PO (0.1 mol, 7 mL, 100 equivalents) was added. The reaction mixture was stirred for 5 h at a reaction temperature of 25 ° C. The number average molecular weight Mn measured by GPC was 18300 g / mol, and the molecular weight distribution was 2. It is 1.17.

[0146] Example 28

[0147] In a 50 mL pressure bottle, a single-component Lewis acid-base pair PBB-6 (10 μmol, 6.6 mg, 0.01 equivalent), N-(2-hydroxyethyl) acrylamide (1 mmol, 104 μL, 1 equivalent), and o-phthalaldehyde (0.1 mol, 13.4 g, 100 equivalents) were added in sequence, and then PO (0.1 mol, 7 mL, 100 equivalents) was added. The reaction mixture was stirred for 5 h at a reaction temperature of 25 ° C. The number average molecular weight Mn measured by GPC was 18300 g / mol, and the molecular weight distribution was 2. is 1.16.

[0148] Example 29

[0149] In a 50 mL pressure bottle, a single-component Lewis acid-base pair PBB-6 (10 μmol, 6.6 mg, 0.01 equivalent), N-Boc-ethanolamine (1 mmol, 155 μL, 1 equivalent), and o-phthalaldehyde (0.1 mol, 13.4 g, 100 equivalents) were added in sequence, and then PO (0.1 mol, 7 mL, 100 equivalents) was added. The reaction mixture was stirred for 5 h at a reaction temperature of 25 ° C. The number average molecular weight Mn measured by GPC was 19200 g / mol, and the molecular weight distribution was 2. is 1.14.

[0150] Example 30

[0151] In a 50 mL pressure bottle, a single-component Lewis acid-base pair PBB-6 (10 μmol, 6.6 mg, 0.01 equivalent), tert-butyl 2-glycolate (1 mmol, 132 mg, 1 equivalent), and o-phthalaldehyde (0.1 mol, 13.4 g, 100 equivalents) were added in sequence, and then PO (0.1 mol, 7 mL, 100 equivalents) was added. The reaction mixture was stirred for 2 h at a reaction temperature of 25 ° C. The number average molecular weight Mn measured by GPC was 17900 g / mol, and the molecular weight distribution was 0.001%. is 1.12.

[0152] Example 31

[0153] In a 50 mL pressure bottle, a single-component Lewis acid-base pair PBB-6 (10 μmol, 6.6 mg, 0.01 equivalent), 4,5-dimethoxy-2-nitrobenzyl alcohol (1 mmol, 213 mg, 1 equivalent), and o-phthalaldehyde (0.1 mol, 13.4 g, 100 equivalents) were added in sequence, and then PO (0.1 mol, 7 mL, 100 equivalents) was added. The reaction mixture was stirred for 6 h at a reaction temperature of 25 ° C. The number average molecular weight Mn measured by GPC was 18200 g / mol, and the molecular weight distribution was 2. is 1.15.

[0154] Example 32

[0155] In a 50 mL pressure bottle, a single-component Lewis acid-base pair PBB-6 (10 μmol, 6.6 mg, 0.01 equivalent), ethylene glycol (1 mmol, 56 μL, 1 equivalent), o-phthalaldehyde (0.1 mol, 13.4 g, 100 equivalents) was added in sequence, and then PO (0.1 mol, 7 mL, 100 equivalents) was added. The reaction mixture was stirred for 4 h at a reaction temperature of 25 ° C. The number average molecular weight Mn measured by GPC was 17300 g / mol, and the molecular weight distribution was 2. is 1.14.

[0156] Example 33

[0157] In a 50 mL pressure bottle, a single-component Lewis acid-base pair PBB-6 (10 μmol, 6.6 mg, 0.01 equivalent), 1,2-propylene glycol (1 mmol, 73 μL, 1 equivalent), and o-phthalaldehyde (0.1 mol, 13.4 g, 100 equivalents) were added in sequence, and then PO (0.1 mol, 7 mL, 100 equivalents) was added. The reaction mixture was stirred for 2 h at a reaction temperature of 25 ° C. The number average molecular weight Mn measured by GPC was 17600 g / mol, and the molecular weight distribution was 0.01%. It is 1.11.

[0158] Example 34

[0159] In a 50 mL pressure bottle, a single-component Lewis acid-base pair PBB-6 (10 μmol, 6.6 mg, 0.01 equivalent), 2-butyl-2-ethyl-1,3-propanediol (1 mmol, 160 mg, 1 equivalent), and o-phthalaldehyde (0.1 mol, 13.4 g, 100 equivalents) were added in sequence, and then PO (0.1 mol, 7 mL, 100 equivalents) was added. The reaction mixture was stirred for 72 h at a reaction temperature of 25 ° C. The number average molecular weight Mn measured by GPC was 18000 g / mol, and the molecular weight distribution was 2. is 1.15.

[0160] Example 35

[0161] In a 50 mL pressure bottle, a single-component Lewis acid-base pair PBB-6 (10 μmol, 6.6 mg, 0.01 equivalent), glycerol (1 mmol, 73 μL, 1 equivalent), and o-phthalaldehyde (0.1 mol, 13.4 g, 100 equivalents) were added in sequence, and then PO (0.1 mol, 7 mL, 100 equivalents) was added. The reaction mixture was stirred for 19 h at a reaction temperature of 25 ° C. The number average molecular weight Mn measured by GPC was 18100 g / mol, and the molecular weight distribution was 2. is 1.14.

[0162] Example 36

[0163] In a 50 mL pressure bottle, a single-component Lewis acid-base pair PBB-6 (10 μmol, 6.6 mg, 0.01 equivalent), hydroxyethyl acrylate (1 mmol, 105 μL, 1 equivalent), and o-phthalaldehyde (0.1 mol, 13.4 g, 100 equivalents) were added in sequence, and then PO (0.1 mol, 7 mL, 100 equivalents) was added. The reaction mixture was stirred for 2 h at a reaction temperature of 25 ° C. The number average molecular weight Mn measured by GPC was 18500 g / mol, and the molecular weight distribution was 2. It is 1.13.

[0164] Example 37

[0165] In a 50 mL pressure bottle, a single-component Lewis acid-base pair PBB-6 (10 μmol, 6.6 mg, 0.01 equivalent), 2-hydroxyethyl methacrylate (1 mmol, 121 μL, 1 equivalent), and o-phthalaldehyde (0.1 mol, 13.4 g, 100 equivalents) were added in sequence, and then PO (0.1 mol, 7 mL, 100 equivalents) was added. The reaction mixture was stirred for 2 h at a reaction temperature of 25 ° C. The number average molecular weight Mn measured by GPC was 18800 g / mol, and the molecular weight distribution was 2. is 1.12.

[0166] Example 38

[0167] In a 50 mL pressure bottle, a single-component Lewis acid-base pair PBB-6 (10 μmol, 6.6 mg, 0.01 equivalent), 3-amino-1-propanol (1 mmol, 76.5 μL, 1 equivalent), and o-phthalaldehyde (0.1 mol, 13.4 g, 100 equivalents) were added in sequence, and then PO (0.1 mol, 7 mL, 100 equivalents) was added. The reaction mixture was stirred for 6 h at a reaction temperature of 25 ° C. The number average molecular weight Mn measured by GPC was 16300 g / mol, and the molecular weight distribution was 2. It is 1.17.

[0168] Table 5 Summary of key data of Examples 21 to 38

[0169]

[0170]

[0171] Example 39

[0172] In a 50 mL high-pressure reactor, a single-component Lewis acid-base pair PBB-CyC4 (10 μmol, 13.74 mg, 0.01 equivalent), RAFT2 (1 mmol, 476.8 mg, 1 equivalent), and o-phthalaldehyde (0.1 mol, 13.4 g, 100 equivalents) were added in sequence, and then propylene oxide (0.1 mol, 7 mL, 100 equivalents) was added. The pressure of ethylene oxide was 10 bar, and the reaction mixture was stirred for 12 h. The reaction temperature was 25 ° C. GPC measured the number average molecular weight Mn to be 16700 g / mol, and the molecular weight distribution was It is 1.11.

[0173] Table 6 Summary of key data of Example 39

[0174]

[0175] The embodiments described above are merely descriptions of preferred implementations of the present invention and are not intended to limit the scope of the present invention. Without departing from the spirit of the present invention, various modifications and improvements made to the technical solutions of the present invention by ordinary technicians in this field should fall within the scope of protection determined by the claims of the present invention.

Claims

1. A single-component organic Lewis acid-base pair, characterized in that: The single-component Lewis acid-base pair has the following structural formula: In the above structural formula, n is the carbon chain length of 1 to 4; R is any one of hydrogen, methyl, ethyl, butyl, phenyl or substituted phenyl; X is Cl, Br, I, CH3COO - ,CF3COO - , - OOC-CH2-CH2-COO - Any of the following; R 1 、R 2 is one or a combination of hydrogen, alkyl, cycloalkyl, aryl or substituted aryl; Y is a bridging skeleton, which is any one of the following structural formulas:

2. The single-component organic Lewis acid-base pair according to claim 1, characterized in that: The single-component Lewis acid-base pair is any one of the following structures:

3. A method for preparing a degradable polyacetal ether polyol, characterized in that: The single-component Lewis acid-base pair described in claim 1 is used as an initiator to catalyze the polymerization of dialdehyde monomer and epoxy monomer in the temperature range of -20-45°C to synthesize the degradable polyacetal ether polyol.

4. The preparation method according to claim 3, characterized in that The invention also includes a chain transfer agent. The single-component Lewis acid-base pair and the chain transfer agent are mixed. The single-component Lewis acid-base pair is used as a catalyst to catalyze the polymerization of the dialdehyde monomer and the epoxy monomer.

5. The preparation method according to claim 3, characterized in that The dialdehyde monomer is o-phthalaldehyde.

6. The preparation method according to claim 3, characterized in that The epoxy monomer is at least one of cyclohexene oxide, ethylene oxide, propylene oxide, 1,2-epoxyhexane, epichlorohydrin, allyl glycidyl ether, butyl ethylene oxide, butylene oxide, n-butyl glycidyl ether, styrene oxide, furfuryl glycidyl ether, phenyl glycidyl ether, butyl glycidyl ether and hexamethylcyclotrisiloxane.

7. The preparation method according to claim 4, characterized in that The chain transfer agent is any one of the following: allyl alcohol, propargyl alcohol, 3-trimethylsilyl-propargyl alcohol, ethanolamine, 6-hydroxy-1-n-hexylamine, p-aminobenzyl alcohol, p-methylaminobenzyl alcohol, 2-amino-1,3-propanediol, 4,5-dimethoxy-2-nitrobenzyl alcohol, 2-(dibenzylamino)ethanol, N-(2-hydroxyethyl)acrylamide, 2-furanethanol, N-(tert-butyloxycarbonyl)ethanolamine, tert-butyl glycolate, tert-butyl Dimethylsilanol, 2-azidoethanol, hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 4-cyano-4-[(dodecylsulfanylthiocarbonyl)sulfanyl]pentanol, 4-ester-4-[(dodecylsulfanylthiocarbonyl)sulfanyl]butanol, 2-ester-2-[(ethoxysulfanylthiocarbonyl)sulfanyl]ethanol, 2-ester-2-[(4-methylaminopyridylsulfanylthiocarbonyl)sulfanyl]ethanol.

8. The preparation method according to claim 3, characterized in that The molar ratio of the epoxy monomer, the dialdehyde monomer and the single-component organic Lewis acid-base pair is (20-3000):(20-1000):(0.01-1).

9. The preparation method according to claim 4, characterized in that The molar ratio of the epoxy monomer, the dialdehyde monomer, the chain transfer agent and the single-component organic Lewis acid-base pair is (100-2000):(100-2000):(0.01-1):(0.01-1).

10. The preparation method according to claim 3, characterized in that The reaction time is controlled between 0.3 and 72 hours.

Images